CN111454061A - Polycarbosilane non-melting pretreatment and cracking conversion method for three-dimensional ceramic - Google Patents
Polycarbosilane non-melting pretreatment and cracking conversion method for three-dimensional ceramic Download PDFInfo
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Abstract
A polycarbosilane non-melting pretreatment and a method for converting polycarbosilane into three-dimensional ceramic by cracking relate to the preparation of ceramic materials. Firstly synthesizing a three-dimensional silicon carbide polymer precursor, preparing SiC (Al, rGO) p ceramic particles by pyrolysis under the protection of inert atmosphere, ball-milling and uniformly mixing the SiC (Al, rGO) p ceramic particles with precursor powder, drying the mixture, tabletting the mixture to form a product, then sintering the product at high temperature to obtain 3D-SiC (Al, rGO) ceramic, and finally modifying the surface morphology of the ceramic. The three-dimensional ceramic material contains four elements of Si, C, O and Al, and the Al is uniformly distributed in SiO in an atomic statexCyIn the amorphous phase, β -SiC nanocrystals are embedded in SiO of composite rGOxCy/CfreeIn the amorphous phase, SiO is present2And (4) microcrystals. The cross-linking degree and the molecular weight of the precursor are expanded to form a three-dimensional network structure, so that the evaporation of small molecular gas during cracking is reduced, the fracture toughness and the high temperature resistance stability of the ceramic are improved, and the application fields of severe environments such as high temperature are met.
Description
Technical Field
The invention relates to preparation of ceramic materials, in particular to a method for pretreating polycarbosilane without melting and converting polycarbosilane into three-dimensional ceramic through cracking.
Background
Silicon carbide (SiC), as an advanced ceramic material, has excellent properties such as good mechanical properties, wide band gap, high electron mobility, chemical stability, high temperature resistance, corrosion resistance, etc., and also exhibits excellent properties under severe environmental conditions such as high temperature, high frequency, high power, etc., is often used for manufacturing corrosion-resistant materials, wear-resistant materials, high-temperature structural components, diodes, etc., and has wide applications in the fields of microelectronic systems, machinery, petroleum, chemical industry, metallurgy, aerospace, national defense, etc.
The method comprises the steps of repeatedly soaking the silicon carbide composite ceramic body in phenolic resin and silica sol, performing heat treatment for 1-4 hours at 1450-1550 ℃ under the protection of normal pressure nitrogen to obtain the soaking reinforced silicon carbide processable complex phase ceramic, the method comprises the steps of dissolving, stirring, evaporating, drying and the like, cracking under the protection of 1050-1100 ℃ inert atmosphere to obtain SiC/TiC composite powder, performing hot-pressing sintering at 1500-1600 ℃ to obtain the SiC/TiC composite ceramic, the method comprises the steps of performing reaction sintering on silicon carbide particles and molding resin to obtain the silicon carbide ceramic, performing ball-milling sintering at 1800 ℃ and using graphite-alumina powder as a sintering aid, adding a graphite-alumina powder as a sintering aid, performing spray sintering at 1650 ℃, and performing ball-milling at the temperature of 1650-1650 ℃ to obtain the silicon carbide ceramic, and performing ball-milling under the conditions that the high-temperature sintering additive is difficult to produce.
A precursor conversion method for preparing inorganic ceramic material by thermal decomposition and conversion of organic polymer has the unique advantages of designability of molecular structure, low preparation temperature, no sintering additive, controllable ceramic components, high purity, good product performance and the like, is a breakthrough in the important research of advanced ceramic preparation technology, and has wide application prospect in the aspect of preparing low-dimensional (such as fiber, film and coating) ceramic of silicon carbide, Chinese patent CN 109456065A discloses a preparation method of silicon carbide ceramic fiber, a one-pot method for synthesizing boron-containing silicon carbide precursor, and high-temperature-resistant silicon carbide ceramic fiber prepared by melt spinning and ultraviolet crosslinking, Chinese patent CN 110105070A discloses a method for preparing continuous silicon carbide fiber with controllable electric property and wide range by using aluminum powder containing phenyl polycarbosilane precursor, and Chinese patent Z L201410099387.0 discloses a method for preparing SiC/Al continuous silicon carbide fiber by using polycarbosilane, SiC particles and taking the polycarbosilane as raw materials through a precursor conversion method2O3Chinese patent CN 109111574A discloses a preparation method of Si-Al-C-O fiber, a polyaluminum carbosilane precursor is prepared from polycarbosilane and 8-hydroxyquinoline aluminum at high temperature and high pressure, and Si-Al-C-O fiber is obtained by melt spinning and sinteringBut has certain difficulty in preparing silicon carbide three-dimensional ceramics. The low molecular weight polycarbosilane precursor is not easy to form at normal temperature and is difficult to convert into three-dimensional ceramics. The polycarbosilane can release a large amount of H in the pyrolysis process2、CH4Chinese patent Z L201711494377.7 discloses a method for preparing graphene/silicon carbide monolithic ceramics by high-temperature pyrolysis of a graphene oxide-vinyltriethoxysilane-polycarbosilane precursor, a breakthrough is made in the field of precursor ceramics, but the comprehensive performance of the obtained monolithic ceramics is not good.A blending and cracking method is disclosed in Chinese patent CN 110467467A, so that the graphene/silicon carbide monolithic ceramics has high ceramic yield and low linear shrinkage, but the high-temperature cracking of the silicon carbide precursor inevitably generates a large amount of small-molecule gases, the surface of the ceramic has more pores and defects on a micro scale, the high temperature resistance and fracture toughness need to be improved, and the application of the silicon carbide ceramic is limited.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a simple and economic polycarbosilane non-melting pretreatment and cracking conversion method for three-dimensional ceramics, which is suitable for industrial production.
The invention also aims to provide a high-temperature-resistant 3D-SiC (Al, rGO) ceramic material which is prepared by adopting the polycarbosilane non-melting pretreatment and cracking conversion method thereof to obtain the three-dimensional ceramic and has high ceramic yield, high fracture toughness and low linear shrinkage.
The polycarbosilane non-melting pretreatment and cracking conversion method for three-dimensional ceramics comprises the following steps:
1) synthesis of three-dimensional silicon carbide polymer precursor
Polycarbosilane (PCS) and aluminum acetylacetonate (Al (acac)3) Dissolving the components in an organic solvent together, building a distillation device, quickly heating up under the protection of inert atmosphere to evaporate the organic solvent, then preserving heat, heating up and preserving heat for the second time to obtain a highly cross-linked hyperbranched aluminum-containing polycarbosilane solid, cooling, adding the organic solvent, dissolving and filtering to form a golden yellow transparent organic solution, pouring Graphene Oxide (GO) powder into deionized water to obtain a turbid aqueous solution, and performing ultrasonic dispersion on the organic solution and the aqueous solution respectively to obtain a hyperbranched aluminum-containing polycarbosilane solution and a graphene oxide dispersion solution; adding a Kansted platinum catalyst into a hyperbranched aluminum-containing polycarbosilane solution, adding Vinyl Triethoxysilane (VTES) crosslinking infusible pretreating agent and dilute hydrochloric acid into a graphene oxide dispersion liquid to adjust the solution to acidity, mixing the two solutions, placing the mixture in a beaker for water bath heating reaction, performing magnetic stirring, standing after the reaction is finished, taking out an upper layer product, performing reduced pressure distillation to obtain a precursor aluminum-containing polycarbosilane-vinyl triethoxysilane-graphene oxide (PACS-VTES-GO, PAVG for short) solid polymer, and grinding to obtain precursor PAVG powder;
in the step 1), the mass ratio of the polycarbosilane to the aluminum acetylacetonate powder is preferably (40-60): 3, the organic reagent is preferably xylene, the inert atmosphere is preferably argon, the flow rate is preferably 20-50 m L/min, the rapid temperature rise is preferably performed at the temperature rise rate of 4-6 ℃/min to 145-155 ℃, the heat preservation time is preferably 0.5-2 h, the second temperature rise is preferably performed at the temperature rise rate of 2-4 ℃/min to 305-315 ℃, the heat preservation time is preferably 4-6 h, the mass ratio of the hyperbranched aluminum-containing polycarbosilane to the graphene oxide powder is preferably (80-120): 1, the volume ratio of the organic solution, the aqueous solution, the vinyltriethoxysilane crosslinking non-melting pretreatment agent and the Carlst platinum catalyst is preferably (30-50): 2 (5): 1, the concentration of the dilute hydrochloric acid is preferably 3-10 wt%, the pH value is preferably adjusted to 1-3, the water bath heating temperature is preferably 50 ℃, (50): 2-5): 0.35-4 h, and the magnetic stirring time is preferably 0.4-4 h.
2) Preparation of SiC (Al, rGO) p ceramic particles
Putting a part of PAVG powder of a precursor obtained in the step 1) in a graphite paper boat under the protection of inert atmosphere to perform high-temperature cracking in a tubular furnace to obtain cracked SiC (Al, rGO) p ceramic particles;
in the step 2), the inert atmosphere is preferably argon, the gas flow rate is preferably 60-150 m L/min, the pyrolysis temperature is preferably 1300 ℃, the heating rate is preferably 3-5 ℃/min, and the heat preservation time is preferably 1-30 min.
3) Preparation of 3D-SiC (Al, rGO) ceramic
Adding the rest PAVG powder of the precursor in the step 1) and alcohol into the SiC (Al, rGO) p ceramic particles obtained in the step 2), performing ball milling, uniformly mixing, drying, performing tabletting molding, putting into an inert atmosphere tube furnace, and performing high-temperature sintering again to obtain 3D-SiC (Al, rGO) ceramic;
in the step 3), the mass of the cracked SiC (Al, rGO) p ceramic particles and the precursor PAVG powder is preferably (5-50): 10, the ball milling time is preferably 8-10 h, the tabletting and forming pressure is preferably 30-50 MPa, the pressure maintaining time is preferably 15-25 s, the inert atmosphere is preferably argon, the gas flow rate is preferably 60-150 m L/min, the high-temperature sintering temperature is preferably 1200-1400 ℃, the temperature rise rate is preferably 3-5 ℃/min, and the heat preservation time is preferably 5-35 min.
4) Surface morphology modification of 3D-SiC (Al, rGO) ceramic
And (3) dipping the 3D-SiC (Al, rGO) ceramic obtained in the step (3) into liquid polycarbosilane, and sintering in an inert atmosphere tubular furnace again to obtain the 3D-SiC (Al, rGO) ceramic material with a more compact surface appearance.
In the step 4), the soaking time is preferably 20-30 h, the inert atmosphere is preferably argon, the gas flow rate is preferably 60-150 m L/min, the sintering temperature is preferably the same as the sintering temperature in the step 3), the temperature rise rate is preferably 3-5 ℃/min, and the heat preservation time is preferably 1-30 min.
The 3D-SiC (Al, rGO) ceramic material contains four elements of Si, C, O and Al, and the Al is uniformly distributed in SiO in an atomic statexCyIn the amorphous phase, β -SiC nanocrystals are embedded in SiO of composite rGOxCy/CfreeIn the amorphous phase, SiO is present2And (4) microcrystals.
The polymer precursor is prepared by taking aluminum acetylacetonate and vinyl triethoxysilane as crosslinking non-melting pretreatment agents, and performing non-melting pretreatment on polycarbosilane with a silicon-hydrogen bond and graphene oxide containing hydroxyl in a system to form an aluminum-containing polycarbosilane-vinyl triethoxysilane-graphene oxide three-dimensional network structure polymer. In the invention, by utilizing the characteristics of adjustable molecular structure, easy molding and conversion into inorganic ceramic of polycarbosilane, a novel and economic crosslinking infusible pretreatment modification technology and a cracking conversion ceramic method are developed, the crosslinking degree and molecular weight of a precursor are expanded to form a three-dimensional network structure, the evaporation of small molecular gas during cracking is reduced, the fracture toughness and high temperature resistance stability of the ceramic are improved, and a light high-strength 3D-SiC (Al, rGO) ceramic material with high ceramic yield, high fracture toughness and low linear shrinkage is provided for the application fields of severe environments such as high temperature.
Compared with the prior art, the invention has the following outstanding beneficial effects:
(1) the high-temperature-resistant 3D-SiC (Al, rGO) ceramic prepared by the invention is compact and crack-free, has excellent performances such as high ceramic yield (> 90%), low linear shrinkage (< 5%), high hardness and high fracture toughness, comprehensively strengthens the performance of the traditional silicon carbide polymer precursor ceramic, and has important significance for expanding the application of the ceramic in complex severe environments.
(2) The invention adopts Al (acac)3And VTES as crosslinking non-melting pretreating agent, and treating PCS with non-melting pretreatment to consume part of Si-H bonds on PCS chain to generate stable Si-O-Al bonds and Si-C bonds6The PCS three-dimensional space network structure with rGO/VTES as a pivot greatly improves the molecular weight of a precursor, and introduces aluminum atoms and a graphene lamellar structure to improve the ceramic yield, high-temperature resistance stability, fracture toughness and hardness, reduce the shrinkage rate, eliminate cracks and the like, thereby providing the PCS three-dimensional space network structure for solving the problems of the existing silicon carbide precursor ceramicA new scheme is provided.
(3) The polycarbosilane crosslinking infusible pretreatment and the cracking conversion of the polycarbosilane crosslinking infusible pretreatment into 3D-SiC (Al, rGO) ceramic provided by the invention have simple and economic two-step process, the ceramic property can be regulated and controlled by adjusting the technical parameters such as the proportion of cracking ceramic/precursor, sintering temperature and the like, and the invention is convenient for popularization to realize industrial production.
Drawings
FIG. 1 is a graph of 3D-SiC (Al, rGO) ceramic sample samples prepared at different sintering temperatures of 1200 deg.C, 1300 deg.C, and 1400 deg.C.
FIG. 2 is an infrared (FTIR) spectrum of PCS, PACS and PAVG as powder samples. In FIG. 2, the abscissa is the wave number (cm)-1)。
FIG. 3 is a graph of the linear shrinkage of 3D-SiC (Al, rGO) ceramics and the yield of the ceramics as a function of different sintering temperatures (1200 deg.C, 1300 deg.C, 1400 deg.C). In FIG. 3, the ordinate represents the linear shrinkage (%) and the ceramic yield (%) and the abscissa represents the ceramic sintering temperature (. degree. C.).
FIG. 4 is an X-ray diffraction (XRD) pattern of 3D-SiC (Al, rGO) ceramic at different sintering temperatures (1200 deg.C, 1300 deg.C, 1400 deg.C) and SiC (Al, rGO) p ceramic particles with a cracking temperature of 1300 deg.C. In fig. 4, the abscissa is 2 θ (°).
FIG. 5 is a Raman (Raman) spectrum of 3D-SiC (Al, rGO) ceramics at different sintering temperatures (1200 deg.C, 1300 deg.C, 1400 deg.C). In FIG. 5, the abscissa is the Raman shift (cm)-1)。
FIG. 6 is a series of 3D-SiC (Al, rGO) ceramic surface Scanning Electron Microscope (SEM) images. In fig. 6, (a) corresponds to a sintering temperature of 1200 ℃; (b) the corresponding sintering temperature is 1300 ℃; (c) the corresponding sintering temperature is 1400 ℃; (d) the surface morphology of the ceramic material is modified to correspond to 3D-SiC (Al, rGO) ceramic with the sintering temperature of 1300 ℃.
Detailed Description
The above-described scheme will be further explained with reference to specific embodiments.
The 3D-SiC (Al, rGO) ceramic prepared by the invention is black, has good integrity, compact and smooth surface and no visible cracks or holes. The structural general formula of the polymer precursor PAVG is as follows:
FIG. 1 shows the graph of 3D-SiC (Al, rGO) ceramic samples prepared by sintering at 1200 deg.C, 1300 deg.C, 1400 deg.C. An infrared (FTIR) spectrum (figure 2) of the precursor PAVG shows that Si-C (780 cm) exists in the system-1)、Si–CH2–Si(1020cm-1)、Si–O–Si(1080cm-1)、Si–O–C(1100cm-1)、Si–CH3(1250cm-1)、C＝C(1600cm-1)、Si–H(2100cm-1) The 3D-SiC (Al, rGO) ceramic of the present invention has characteristics in a graph (FIG. 3) of linear shrinkage and ceramic yield versus different sintering temperatures (1200 ℃, 1300 ℃, 1400 ℃) in which the ceramic yield decreases and the linear shrinkage increases as the sintering temperature increases, and the SiC (Al, rGO) p ceramic particles and the 3D-SiC (Al, rGO) ceramic have characteristics in an X-ray diffraction (XRD) diagram (FIG. 4) in which (111)/(220)/(311) crystal plane diffraction peaks ascribed to β -SiC are present at 2 theta 35.6 DEG/60.1 DEG/71.7 DEG, and the intensities of the three peaks gradually increase as the sintering temperature increases, and β -SiC crystal peaks in the 3D-SiC (Al, rGO) ceramic are stronger than those of (Al, rGO) p ceramic, and SiO is present at 2 theta 20.9 DEG/26.6 DEG2The (100)/(011) crystal plane diffraction peak of (A) only appears in 3D-SiC (Al, rGO) ceramics, and the intensity of the peak is weakened along with the increase of the sintering temperature. The 3D-SiC (Al, rGO) ceramic has the following characteristics in the Raman (Raman) spectrum (fig. 5): at 1350cm-1(peak D) and 1600cm-1(G peak) there is a characteristic peak, which is respectively assigned to amorphous carbon and graphitization degree, and the ratio of D peak to G peak increases with the increase of sintering temperature. The 3D-SiC (Al, rGO) ceramic has the following characteristics in a Scanning Electron Microscope (SEM) image (fig. 6): the surface of the 3D-SiC (Al, rGO) ceramic is compact, and particles on the surface of the ceramic gradually increase and enlarge along with the increase of the sintering temperature; the surface of the 3D-SiC (Al, rGO) ceramic subjected to precursor impregnation and cracking is more compact.
Table 1 shows the hardness and fracture toughness of 3D-SiC (Al, rGO) ceramics at different sintering temperatures (1200 ℃, 1300 ℃, 1400 ℃).
TABLE 1
Specific preparation method examples are given below.
Example 1
1. 2g of PCS powder and 0.12g of acetylacetone aluminum powder are dissolved in 40m of L xylene and then poured into a 150m of L three-necked bottle, a distillation device is built, argon is introduced for protection, the flow rate is 35m of L/min, the temperature is rapidly increased to 150 ℃ at the speed of 5 ℃/min under the magnetic stirring of 200rpm, the xylene is evaporated to dryness, and the temperature is kept for 1 h;
2. heating the electric jacket to 310 ℃ at the speed of 3 ℃/min and preserving heat for 5 hours to obtain highly crosslinked hyperbranched aluminum-containing polycarbosilane solid, cooling, pouring a proper amount of xylene into the bottle for dissolving and filtering to obtain 40m L golden yellow transparent solution;
3. dispersing 0.02g of graphene oxide powder in 40m L deionized water, and respectively ultrasonically dispersing the aqueous solution and the xylene solution obtained in the step 2 for 30 min;
4. adding 1m L Karsted platinum catalyst into a xylene solution, adding 2m L of vinyltriethoxysilane cross-linking infusible pretreating agent and a proper amount of dilute hydrochloric acid (5 wt%) into an aqueous solution, and adjusting the pH of the solution to 1-3;
5. the two solutions of step 4 were mixed in a beaker and reacted for 30min at 60 ℃ water bath conditions with a magnetic stirring rate of 30 rpm. After rotary evaporation, obtaining black solid and grinding the black solid to obtain PAVG powder;
6. putting the PAVG powder obtained in the step 5 into a crucible to be cracked at 1300 ℃, wherein the heating rate is 4 ℃/min, the heat preservation time is 1min, and the argon flow rate is 100m L/min, so that cracked SiC (Al, rGO) p ceramic particles are obtained, taking 0.6g of SiC (Al, rGO) p ceramic particles, 0.4g of PAVG powder, 4g of agate grinding balls and a proper amount of alcohol, ball-milling for 9h, and drying to obtain SiC (Al, rGO) p/PAVG powder;
7. weighing 0.5g of SiC (Al, rGO) p/PAVG powder obtained in the step 6, keeping the pressure for 20s under the pressure of 40MPa, pressing the powder into a wafer shape by using a die, putting the wafer shape into a tube furnace, heating the wafer shape to 1200 ℃ at the heating rate of 4 ℃/min, sintering the wafer shape, keeping the temperature for 5min, keeping the argon flow rate at 100m L/min, and cooling the wafer along with the furnace to obtain the 3D-SiC (Al, rGO) ceramic.
Example 2
1. 2g of PCS powder and 0.12g of acetylacetone aluminum powder are dissolved in 40m of L xylene and then poured into a 150m of L three-necked bottle, a distillation device is built, argon is introduced for protection, the flow rate is 35m of L/min, the temperature is rapidly increased to 150 ℃ at the speed of 5 ℃/min under the magnetic stirring of 200rpm, the xylene is evaporated to dryness, and the temperature is kept for 1 h;
2. heating the electric jacket to 310 ℃ at the speed of 3 ℃/min and preserving heat for 5 hours to obtain highly crosslinked hyperbranched aluminum-containing polycarbosilane solid, cooling, pouring a proper amount of xylene into the bottle for dissolving and filtering to obtain 40m L golden yellow transparent solution;
3. dispersing 0.02g of graphene oxide powder in 40m L deionized water, and respectively ultrasonically dispersing the aqueous solution and the xylene solution obtained in the step 2 for 30 min;
4. adding 1m L Karsted platinum catalyst into a xylene solution, adding 2m L of vinyltriethoxysilane cross-linking infusible pretreating agent and a proper amount of dilute hydrochloric acid (5 wt%) into an aqueous solution, and adjusting the pH of the solution to 1-3;
5. the two solutions of step 4 were mixed in a beaker and reacted for 30min at 60 ℃ water bath conditions with a magnetic stirring rate of 30 rpm. After rotary evaporation, obtaining black solid and grinding the black solid to obtain PAVG powder;
6. putting the PAVG powder obtained in the step 5 into a crucible to be cracked at 1300 ℃, wherein the heating rate is 4 ℃/min, the heat preservation time is 1min, and the argon flow rate is 100m L/min, so that cracked SiC (Al, rGO) p ceramic particles are obtained, taking 0.6g of SiC (Al, rGO) p ceramic particles, 0.4g of PAVG powder, 4g of agate grinding balls and a proper amount of alcohol, ball-milling for 9h, and drying to obtain SiC (Al, rGO) p/PAVG powder;
7. weighing 0.5g of SiC (Al, rGO) p/PAVG powder obtained in the step 6, keeping the pressure for 20s under the pressure of 40MPa, pressing the powder into a wafer shape by using a die, putting the wafer shape into a tube furnace, heating the wafer shape to 1300 ℃ at the heating rate of 4 ℃/min, sintering the wafer shape, keeping the temperature for 5min, keeping the argon flow rate at 100m L/min, and cooling the wafer along with the furnace to obtain the 3D-SiC (Al, rGO) ceramic.
8. And (3) dipping the 3D-SiC (Al, rGO) ceramic obtained in the step (7) in liquid PCS for 24h, putting the liquid PCS in a tubular furnace, heating to 1300 ℃ at a heating rate of 4 ℃/min, sintering, keeping the temperature for 5min, and keeping the argon flow rate at 100m L/min to obtain the 3D-SiC (Al, rGO) ceramic with a more compact surface appearance.
Example 3
1. 2g of PCS powder and 0.12g of acetylacetone aluminum powder are dissolved in 40m of L xylene and then poured into a 150m of L three-necked bottle, a distillation device is built, argon is introduced for protection, the flow rate is 35m of L/min, the temperature is rapidly increased to 150 ℃ at the speed of 5 ℃/min under the magnetic stirring of 200rpm, the xylene is evaporated to dryness, and the temperature is kept for 1 h;
2. heating the electric jacket to 310 ℃ at the speed of 3 ℃/min and preserving heat for 5 hours to obtain highly crosslinked hyperbranched aluminum-containing polycarbosilane solid, cooling, pouring a proper amount of xylene into the bottle for dissolving and filtering to obtain 40m L golden yellow transparent solution;
3. dispersing 0.02g of graphene oxide powder in 40m L deionized water, and respectively ultrasonically dispersing the aqueous solution and the xylene solution obtained in the step 2 for 30 min;
4. adding 1m L Karsted platinum catalyst into a xylene solution, adding 2m L of vinyltriethoxysilane cross-linking infusible pretreating agent and a proper amount of dilute hydrochloric acid (5 wt%) into an aqueous solution, and adjusting the pH of the solution to 1-3;
5. the two solutions of step 4 were mixed in a beaker and reacted for 30min at 60 ℃ water bath conditions with a magnetic stirring rate of 30 rpm. After rotary evaporation, obtaining black solid and grinding the black solid to obtain PAVG powder;
6. putting the PAVG powder obtained in the step 5 into a crucible to be cracked at 1300 ℃, wherein the heating rate is 4 ℃/min, the heat preservation time is 1min, and the argon flow rate is 100m L/min, so that cracked SiC (Al, rGO) p ceramic particles are obtained, taking 0.6g of SiC (Al, rGO) p ceramic particles, 0.4g of PAVG powder, 4g of agate grinding balls and a proper amount of alcohol, ball-milling for 9h, and drying to obtain SiC (Al, rGO) p/PAVG powder;
7. weighing 0.5g of SiC (Al, rGO) p/PAVG powder obtained in the step 6, keeping the pressure for 20s under the pressure of 40MPa, pressing the powder into a wafer shape by using a die, placing the wafer into a tubular furnace, heating the wafer to 1400 ℃ at the heating rate of 4 ℃/min, sintering the wafer, keeping the temperature for 5min, keeping the argon flow rate at 100m L/min, and cooling the wafer along with the furnace to obtain the 3D-SiC (Al, rGO) ceramic.
The above embodiments are only examples of the inventionThe described preferred embodiments should not be considered as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention. The invention takes PCS as raw material and takes Al (acac)3And VTES is a crosslinking non-melting pretreating agent, GO is a crosslinking non-melting pretreating auxiliary agent, a silicon carbide ceramic precursor PAVG with a three-dimensional network structure is prepared by utilizing a crosslinking non-melting pretreating modification technology, SiC (Al, rGO) p ceramic particles are obtained through high-temperature cracking, wherein the SiC (Al, rGO) p ceramic particles with the cracking temperature of 1300 ℃ have the best comprehensive performance, and therefore the ceramic particles are mixed with PAVG precursor powder in a ball milling mode, 3D-SiC (Al, rGO) ceramic is obtained through a further precursor conversion process, and finally the surface morphology of the ceramic is modified through a liquid PCS impregnation pyrolysis method, so that the ceramic is further densified, and the 3D-SiC (Al, rGO) ceramic material with excellent comprehensive performance can be obtained. The PAVG precursor obtained after the polycarbosilane is subjected to non-melting pretreatment has high molecular weight and high crosslinking degree, so that the escape of small molecular gas during cracking is greatly improved, the ceramic yield of the precursor is improved, and the shrinkage rate is reduced. The Al-O-Si network structure of the 3D-SiC (Al, rGO) ceramic at the grain boundary can block crack propagation, the sliding effect of graphene and particles and micropores generated by ball-milling and re-sintering can help to relax stress, and aluminum atoms can achieve the purpose of particle dispersion toughening, which are beneficial to improving the fracture toughness of the precursor ceramic. In addition, aluminum atoms can inhibit SiOxCyThe decomposition of the phase further hinders the growth of β -SiC microcrystals, thereby improving the hardness and the high temperature resistance stability of the precursor ceramic.
Claims (10)
1. A polycarbosilane non-melting pretreatment and cracking conversion method for three-dimensional ceramics are characterized by comprising the following steps:
1) synthesis of three-dimensional silicon carbide polymer precursor
Dissolving polycarbosilane and aluminum acetylacetonate in an organic solvent together, building a distillation device, quickly heating to evaporate the organic solvent and preserving heat under the protection of inert atmosphere, heating and preserving heat for the second time to obtain a highly-crosslinked hyperbranched aluminum-containing polycarbosilane solid, cooling, adding the organic solvent, dissolving and filtering to form a golden yellow transparent organic solution, pouring graphene oxide powder into deionized water to obtain a turbid aqueous solution, and performing ultrasonic dispersion on the organic solution and the aqueous solution respectively to obtain a hyperbranched aluminum-containing polycarbosilane solution and a graphene oxide dispersion solution; adding a Kansted platinum catalyst into a hyperbranched aluminum-containing polycarbosilane solution, adding a vinyltriethoxysilane crosslinking infusible pretreating agent and dilute hydrochloric acid into a graphene oxide dispersion solution to adjust the solution to acidity, mixing the two solutions, placing the two solutions in a beaker for water bath heating reaction, simultaneously performing magnetic stirring, standing after the reaction is finished, taking out an upper layer product, performing reduced pressure distillation to obtain a precursor aluminum-containing polycarbosilane-vinyltriethoxysilane-graphene oxide solid polymer, and grinding to obtain precursor powder;
2) preparation of SiC (Al, rGO) p ceramic particles
Putting a part of precursor powder obtained in the step 1) in a graphite paper boat under the protection of inert atmosphere to carry out high-temperature cracking in a tubular furnace to obtain cracked SiC (Al, rGO) p ceramic particles;
3) preparation of 3D-SiC (Al, rGO) ceramic
Adding the rest precursor powder obtained in the step 1) and alcohol into the SiC (Al, rGO) p ceramic particles cracked in the step 2), performing ball milling, uniformly mixing, drying, performing tabletting molding, putting into an inert atmosphere tube furnace, and performing high-temperature sintering again to obtain 3D-SiC (Al, rGO) ceramic;
4) surface morphology modification of 3D-SiC (Al, rGO) ceramic
And (3) dipping the 3D-SiC (Al, rGO) ceramic obtained in the step (3) into liquid polycarbosilane, and sintering in an inert atmosphere tubular furnace again to obtain the 3D-SiC (Al, rGO) ceramic material with a more compact surface appearance.
2. The method for the non-melting pretreatment and the pyrolysis conversion of the polycarbosilane into the three-dimensional ceramic according to claim 1, wherein in the step 1), the mass ratio of the polycarbosilane to the acetylacetone aluminum powder is (40-60): 3.
3. The method for the non-melting pretreatment and the pyrolysis conversion of three-dimensional ceramics by polycarbosilane as claimed in claim 1, wherein in step 1), the organic solvent is xylene, the inert atmosphere is argon at a flow rate of 20-50 m L/min, the rapid temperature rise is preferably carried out at a temperature rise rate of 4-6 ℃/min to 145-155 ℃, the holding time is preferably 0.5-2 h, the second temperature rise is preferably carried out at a temperature rise rate of 2-4 ℃/min to 305-315 ℃, and the holding time is preferably 4-6 h.
4. The method for the non-melting pretreatment and the pyrolysis conversion of the polycarbosilane into the three-dimensional ceramic according to claim 1, wherein in the step 1), the mass ratio of the hyperbranched aluminum-containing polycarbosilane to the graphene oxide powder is (80-120): 1; the volume ratio of the organic solution, the aqueous solution, the vinyltriethoxysilane crosslinking non-melting pretreatment agent and the platinum catalyst is (30-50): 2-5): 1; the concentration of the dilute hydrochloric acid is 3-10 wt%, and the pH value is preferably adjusted to 1-3 when the dilute hydrochloric acid is adjusted to be acidic; the water bath heating temperature is preferably 50-70 ℃, the magnetic stirring speed is preferably 25-35 rpm, and the heat preservation time is preferably 0.4-0.6 h.
5. The method for the non-melting pretreatment and the pyrolysis conversion of the three-dimensional ceramic by the polycarbosilane as claimed in claim 1, wherein in the step 2), the inert atmosphere is argon, the gas flow rate is 60-150 m L/min, the pyrolysis temperature is preferably 1300 ℃, the heating rate is preferably 3-5 ℃/min, and the heat preservation time is preferably 1-30 min.
6. The method for non-melting pretreatment and pyrolysis conversion of three-dimensional ceramics by polycarbosilane according to claim 1, wherein in step 3), the mass ratio of the pyrolyzed SiC (Al, rGO) p ceramic particles to the precursor powder is (5-50): 10, the ball milling time is preferably 8-10 h, the pressure for tabletting formation is preferably 30-50 MPa, the pressure holding time is preferably 15-25 s, the inert atmosphere is preferably argon, and the gas flow rate is preferably 60-150 m L/min.
7. The method for non-melting pretreatment and pyrolysis conversion of three-dimensional ceramics by polycarbosilane as claimed in claim 1, wherein in step 3), the temperature of the high-temperature sintering is 1200-1400 ℃, the heating rate is 3-5 ℃/min, and the holding time is 5-35 min.
8. The method for the non-melting pretreatment and the pyrolysis conversion of the three-dimensional ceramic by the polycarbosilane as claimed in claim 1, wherein in the step 4), the immersion time is 20-30 h, the inert atmosphere is preferably argon, and the gas flow rate is preferably 60-150 m L/min.
9. The method for the non-melting pretreatment and the pyrolysis conversion of the three-dimensional ceramic by the polycarbosilane as claimed in claim 1, wherein in the step 4), the sintering temperature is equal to the sintering temperature in the step 3), the heating rate is 3-5 ℃/min, and the holding time is 1-30 min.
10. The 3D-SiC (Al, rGO) ceramic material prepared by the polycarbosilane non-melting pretreatment and cracking conversion three-dimensional ceramic method as claimed in claim 1, wherein the 3D-SiC (Al, rGO) ceramic material contains four elements of Si, C, O and Al, and Al is uniformly distributed in SiO in atomic statexCyIn the amorphous phase, β -SiC nanocrystals are embedded in SiO of composite rGOxCy/CfreeIn the amorphous phase, SiO is present2And (4) microcrystals.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112552052A (en) * | 2020-12-22 | 2021-03-26 | 珠海亿特立新材料有限公司 | Microwave-assisted silicon carbide porous ceramic, aluminum silicon carbide composite preparation method and aluminum silicon carbide composite |
| CN112979316A (en) * | 2021-04-08 | 2021-06-18 | 华南理工大学 | SiAlOC ceramic and synthesis method thereof |
| CN113372107A (en) * | 2021-07-08 | 2021-09-10 | 铜陵四拓智能装备科技有限公司 | Preparation process of low-thermal-expansion composite material |
| CN114736485A (en) * | 2022-04-14 | 2022-07-12 | 咸阳师范学院 | Resin-based ceramic friction material and preparation method and application thereof |
| CN114874020A (en) * | 2022-05-13 | 2022-08-09 | 厦门大学 | Carbon fiber reinforced silicon carbide ceramic matrix porous composite material and preparation method thereof |
| CN115180950A (en) * | 2022-07-28 | 2022-10-14 | 中南大学 | Multi-carbide/silicon carbide nano composite ceramic and preparation method thereof |
| CN115745614A (en) * | 2022-11-29 | 2023-03-07 | 厦门大学 | Nano-metal toughened silicon carbide ceramic material and preparation method thereof |
| CN115894069A (en) * | 2022-11-29 | 2023-04-04 | 厦门大学 | Porous silicon carbide high-temperature heat insulation tile and preparation method thereof |
| CN116143524A (en) * | 2023-02-24 | 2023-05-23 | 厦门大学 | Three-dimensional reticular silicon carbide nanowire and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129151A (en) * | 2017-12-31 | 2018-06-08 | 厦门大学 | A kind of graphene/carbon SiClx nano composite structure layered ceramic and preparation method thereof |
| CN110467467A (en) * | 2019-09-03 | 2019-11-19 | 厦门大学 | A kind of bulky silicon carbide polymer precursor is ceramic and blending cracks preparation method again |
| CN110922191A (en) * | 2019-12-20 | 2020-03-27 | 厦门大学 | Silicon carbide polymer precursor ceramic defect healing method |
-
2020
- 2020-04-07 CN CN202010266375.8A patent/CN111454061B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129151A (en) * | 2017-12-31 | 2018-06-08 | 厦门大学 | A kind of graphene/carbon SiClx nano composite structure layered ceramic and preparation method thereof |
| CN110467467A (en) * | 2019-09-03 | 2019-11-19 | 厦门大学 | A kind of bulky silicon carbide polymer precursor is ceramic and blending cracks preparation method again |
| CN110922191A (en) * | 2019-12-20 | 2020-03-27 | 厦门大学 | Silicon carbide polymer precursor ceramic defect healing method |
Non-Patent Citations (2)
| Title |
|---|
| YANGPENG DUAN: "Effects of aluminium content on the molecular structure and properties of polyaluminocarbosilane for SiC fibre fabrication", 《CERAMICS INTERNATIONAL》 * |
| YUXI YU: "Synthesis and Characterization of Ceramic Precursor Aluminum-Containing Polycarbosilane and its Pyrolysis", 《JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS》 * |
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|---|---|---|---|---|
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| CN112979316A (en) * | 2021-04-08 | 2021-06-18 | 华南理工大学 | SiAlOC ceramic and synthesis method thereof |
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| CN113372107B (en) * | 2021-07-08 | 2023-01-31 | 铜陵四拓智能装备科技有限公司 | Preparation process of low-thermal-expansion composite material |
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| CN114874020A (en) * | 2022-05-13 | 2022-08-09 | 厦门大学 | Carbon fiber reinforced silicon carbide ceramic matrix porous composite material and preparation method thereof |
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| CN115745614A (en) * | 2022-11-29 | 2023-03-07 | 厦门大学 | Nano-metal toughened silicon carbide ceramic material and preparation method thereof |
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