CN111454061B - A kind of polycarbosilane non-melting pretreatment and its pyrolysis transformation three-dimensional ceramic method - Google Patents

A kind of polycarbosilane non-melting pretreatment and its pyrolysis transformation three-dimensional ceramic method Download PDF

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CN111454061B
CN111454061B CN202010266375.8A CN202010266375A CN111454061B CN 111454061 B CN111454061 B CN 111454061B CN 202010266375 A CN202010266375 A CN 202010266375A CN 111454061 B CN111454061 B CN 111454061B
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姚荣迁
黄雯燕
郑艺浓
廖亮
蓝思琦
罗涛
郭鹏焕
朱烨琦
李万翔
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Zhongke Desheng Changzhou Electronic Technology Co ltd
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Abstract

一种聚碳硅烷不熔化预处理及其裂解转化三维陶瓷方法,涉及陶瓷材料制备。先合成三维碳化硅聚合物先驱体,在惰性气氛保护下高温裂解制备SiC(Al,rGO)p陶瓷颗粒,与先驱体粉末球磨混匀后烘干,压片成型后再次高温烧结得到3D‑SiC(Al,rGO)陶瓷,最后对陶瓷的表面形貌修饰。所述三维陶瓷材料含有Si、C、O、Al四种元素,Al以原子状态均匀分布于SiOxCy无定形相中,β‑SiC纳米晶镶嵌于复合rGO的SiOxCy/Cfree无定形相中,存在SiO2微晶。扩展先驱体的交联度与分子量以形成三维网络结构,减少裂解时小分子气体的蒸发,提高陶瓷断裂韧性与耐高温稳定性,满足高温等恶劣环境应用领域。

Figure 202010266375

The invention discloses a non-melting pretreatment of polycarbosilane and a method for pyrolysis and transformation of three-dimensional ceramics, relating to the preparation of ceramic materials. The 3D silicon carbide polymer precursor was synthesized first, and SiC(Al,rGO)p ceramic particles were prepared by high-temperature pyrolysis under the protection of inert atmosphere, which was mixed with the precursor powder by ball milling, dried, and sintered at high temperature to obtain 3D-SiC. (Al,rGO) ceramics, and finally the surface morphology of the ceramics was modified. The three-dimensional ceramic material contains four elements, Si, C, O, and Al. Al is uniformly distributed in the SiO x C y amorphous phase in an atomic state, and the β-SiC nanocrystals are embedded in the SiO x C y /C free of the composite rGO. In the amorphous phase, SiO2 crystallites are present. Expand the crosslinking degree and molecular weight of the precursor to form a three-dimensional network structure, reduce the evaporation of small molecular gases during cracking, improve the fracture toughness and high temperature stability of ceramics, and meet the application fields of high temperature and other harsh environments.

Figure 202010266375

Description

Polycarbosilane non-melting pretreatment and cracking conversion method for three-dimensional ceramic
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.
At present, the silicon carbide ceramic can be obtained by preparation methods such as normal pressure sintering, hot pressing sintering, reaction sintering and the like. Chinese patent ZL 201110347554.5 discloses a preparation method of an impregnated reinforced silicon carbide machinable complex-phase ceramic, wherein graphite, yttrium oxide and alumina powder are used as sintering aids, the graphite, yttrium oxide and alumina powder are sintered at normal pressure to obtain a silicon carbide complex-phase ceramic matrix, and the silicon carbide complex-phase ceramic matrix is repeatedly impregnated with phenolic resin and silica sol and then is subjected to heat treatment for 1-4 hours at 1450-1550 ℃ under the protection of nitrogen at normal pressure to obtain the impregnated reinforced silicon carbide machinable complex-phase ceramic. Chinese patent ZL 201510515890.4 discloses a method for preparing SiC/TiC composite ceramic by a precursor method, which comprises the steps of dissolving polycarbosilane and titanium powder serving as raw materials, stirring, evaporating, drying and the like, cracking at 1050-1100 ℃ under the protection of inert atmosphere to obtain SiC/TiC composite powder, and performing hot-pressing sintering at 1500-1600 ℃ to obtain the SiC/TiC composite ceramic. Chinese patent ZL 201510580537.4 discloses a method for producing silicon carbide ceramics by reacting and sintering silicon carbide particles with a molding resin. Chinese patent ZL 201510369345.9 discloses a high-thermal-conductivity reaction-sintered silicon carbide ceramic material and a preparation method thereof, wherein graphene, carbon powder, a surfactant, a dispersant and a binder are used as sintering aids, and the silicon particles are paved under the vacuum condition of 1650-1800 ℃ for reaction sintering after ball milling, spray granulation and press forming to obtain the silicon carbide ceramic. However, the method has the problems of high sintering temperature, high production cost, difficulty in mass production and the like, or the addition of a sintering aid is often required, so that impurity phases are easily introduced to influence the product performance.
The precursor conversion method is a method and a process for preparing an inorganic ceramic material by carrying out thermal decomposition and conversion on an organic polymer, and has the unique advantages of designability of molecular structure, lower preparation temperature, no sintering additive, controllable ceramic components, high purity, good product performance and the like. The precursor conversion method is a breakthrough of the great research of the advanced ceramic preparation technology, and has wide application prospect in the aspect of preparing silicon carbide low-dimensional (such as fiber, film and coating) ceramic. Chinese patent CN 109456065A discloses a preparation method of silicon carbide ceramic fiber, a boron-containing silicon carbide precursor is synthesized by a one-pot method, and the high-temperature resistant silicon carbide ceramic fiber is prepared by melt spinning and ultraviolet crosslinking. Chinese patent CN 110105070A discloses a method for preparing continuous silicon carbide fiber with controllable electrical property and wide range by using a phenyl-containing polycarbosilane precursor. Chinese patent ZL 201410099387.0 discloses a method for preparing SiC/Al by taking polycarbosilane, SiC particles and aluminum powder as raw materials through precursor conversion method2O3A method for complex phase ceramic coating. At present, inorganic elements in the silicon carbide precursor ceramic material are expanded to partial metal elements, such as Al, Ti and the like. Chinese patent CN 109111574A discloses a preparation method of Si-Al-C-O fiber, which comprises the steps of preparing a polyaluminum carbosilane precursor from polycarbosilane and 8-hydroxyquinoline aluminum at high temperature and high pressure, and carrying out melt spinning and sintering to obtain the Si-Al-C-O fiber. Chinese patent ZL 201010617739.9 discloses a method for preparing compact silicon carbide/titanium carbide complex phase ceramic by using cyclopentadienyl titanium dichloride and hyperbranched polycarbosilane precursor. Although the advantages of the precursor conversion method are remarkable, certain difficulties exist 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、CH4And small molecular gases such as SiO and CO shrink the ceramic, so that the internal defects exist, the mechanical properties such as ceramic fracture toughness are poor, a large number of cracks are generated, and finally the ceramic is seriously damaged and cannot be molded. Chinese patent ZL 201711494377.7 discloses a method for preparing graphene/silicon carbide monolithic ceramic by high-temperature pyrolysis of graphene oxide-vinyltriethoxysilane-polycarbosilane precursorThe method makes a new breakthrough in the field of precursor ceramics, but the obtained monolithic ceramics have poor comprehensive performance. Chinese patent CN 110467467 a discloses a blending and re-cracking method, which enables graphene/silicon carbide monolithic ceramics to have higher ceramic yield and lower linear shrinkage, but the high-temperature cracking of the silicon carbide precursor still inevitably generates a large amount of small molecular gas, the ceramic surface still has many holes and defects on the microscopic scale, and the high temperature resistance and fracture toughness need to be improved, which limits the application of silicon carbide ceramics. Therefore, in order to further improve the structure/function integration level of the silicon carbide three-dimensional ceramic, reduce the holes and shrinkage of the ceramic and improve the fracture toughness of the ceramic, the key point is to carry out non-melting pretreatment modification on the silicon carbide precursor.
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; in the hyperbranched polymer containingAdding a Kansted platinum catalyst into an aluminum polycarbosilane solution, adding a 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 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-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 acetylacetone aluminum powder is preferably (40-60): 3; the organic reagent is preferably xylene; the inert atmosphere is preferably argon, and the flow rate is preferably 20-50 mL/min; the rapid heating is preferably carried out at a heating rate of 4-6 ℃/min to 145-155 ℃, and the heat preservation time is preferably 0.5-2 h; the second heating is preferably carried out at a heating rate of 2-4 ℃/min to 305-315 ℃, and 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 platinum catalyst is preferably (30-50): 2-5): 1; the concentration of the dilute hydrochloric acid is preferably 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.
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, and the gas flow rate is preferably 60-150 mL/min; the high-temperature cracking 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 pressure of the tabletting molding is preferably 30-50 MPa, and the pressure maintaining time is preferably 15-25 s; the inert atmosphere is preferably argon, and the gas flow rate is preferably 60-150 mL/min; the temperature of the secondary high-temperature sintering is preferably 1200-1400 ℃, the heating 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; argon is preferably selected as the inert atmosphere, and the gas flow rate is preferably 60-150 mL/min; the sintering temperature is preferably equal to the sintering temperature in the step 3), the heating 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, beta-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 the rGO/VTES as the pivot greatly improves the molecular weight of the precursor, and introduces aluminum atoms and a graphene lamellar structure, so that the ceramic yield, high-temperature stability, fracture toughness and hardness can be improved, the shrinkage rate can be reduced, cracks can be eliminated, and a new scheme is provided for solving the problems of the existing silicon carbide precursor ceramic.
(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. 2The 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:
Figure BDA0002441401640000051
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) And the like. The 3D-SiC (Al, rGO) ceramic of the invention has the following characteristics in the linear shrinkage rate and the relation curve chart (figure 3) of the ceramic yield and different sintering temperatures (1200 ℃, 1300 ℃, 1400 ℃): with the increase of the sintering temperature, the ceramic yield is reduced, and the linear shrinkage rate is increased. The SiC (Al, rGO) p ceramic particles and 3D-SiC (Al, rGO) ceramics have the following characteristics in an X-ray diffraction (XRD) pattern (fig. 4): the (111)/(220)/(311) crystal plane diffraction peak belonging to beta-SiC exists at the 2 theta position of 35.6 degrees/60.1 degrees/71.7 degrees, the intensities of the three peaks are gradually increased along with the increase of the sintering temperature, and the beta-SiC crystal peak in the 3D-SiC (Al, rGO) ceramic is stronger than that in the SiC (Al, rGO) p ceramic; the 2 theta is attributed to SiO at 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
Figure BDA0002441401640000061
Specific preparation method examples are given below.
Example 1
1. 2g of PCS powder and 0.12g of acetylacetone aluminum powder are dissolved in 40mL of dimethylbenzene and then poured into a 150mL three-necked bottle, a distillation device is built, argon is introduced for protection, the flow rate is 35mL/min, the temperature is rapidly increased to 150 ℃ at the speed of 5 ℃/min under the magnetic stirring of 200rpm, the dimethylbenzene 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 5h to obtain the highly crosslinked hyperbranched aluminum-containing polycarbosilane solid. After cooling, pouring a proper amount of dimethylbenzene into the bottle for dissolving and filtering to obtain 40mL of golden yellow transparent solution;
3. dispersing 0.02g of graphene oxide powder in 40mL of deionized water, and respectively ultrasonically dispersing the aqueous solution and the xylene solution obtained in the step 2 for 30 min;
4. adding 1mL of Kanst platinum catalyst into a xylene solution, adding 2mL 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 value 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. and (3) 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 100mL/min, so that the 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 9 hours, 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 tubular 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 100mL/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 40mL of dimethylbenzene and then poured into a 150mL three-necked bottle, a distillation device is built, argon is introduced for protection, the flow rate is 35mL/min, the temperature is rapidly increased to 150 ℃ at the speed of 5 ℃/min under the magnetic stirring of 200rpm, the dimethylbenzene 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 5h to obtain the highly crosslinked hyperbranched aluminum-containing polycarbosilane solid. After cooling, pouring a proper amount of dimethylbenzene into the bottle for dissolving and filtering to obtain 40mL of golden yellow transparent solution;
3. dispersing 0.02g of graphene oxide powder in 40mL of deionized water, and respectively ultrasonically dispersing the aqueous solution and the xylene solution obtained in the step 2 for 30 min;
4. adding 1mL of Kanst platinum catalyst into a xylene solution, adding 2mL 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 value 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. and (3) 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 100mL/min, so that the 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 9 hours, 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 100mL/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 100mL/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 40mL of dimethylbenzene and then poured into a 150mL three-necked bottle, a distillation device is built, argon is introduced for protection, the flow rate is 35mL/min, the temperature is rapidly increased to 150 ℃ at the speed of 5 ℃/min under the magnetic stirring of 200rpm, the dimethylbenzene 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 5h to obtain the highly crosslinked hyperbranched aluminum-containing polycarbosilane solid. After cooling, pouring a proper amount of dimethylbenzene into the bottle for dissolving and filtering to obtain 40mL of golden yellow transparent solution;
3. dispersing 0.02g of graphene oxide powder in 40mL of deionized water, and respectively ultrasonically dispersing the aqueous solution and the xylene solution obtained in the step 2 for 30 min;
4. adding 1mL of Kanst platinum catalyst into a xylene solution, adding 2mL 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 value 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. and (3) 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 100mL/min, so that the 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 9 hours, 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 shape in a tubular furnace, raising the temperature to 1400 ℃ at the temperature rise speed of 4 ℃/min, sintering, keeping the temperature for 5min, keeping the argon flow speed at 100mL/min, and cooling along with the furnace to obtain the 3D-SiC (Al, rGO) ceramic.
The above-described embodiments are merely preferred embodiments of the present invention, and should not be construed 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, and 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, so that the SiC (Al, rGO) p ceramic particles and the SiC (Al, rGO) p ceramic particles are mixed to obtain the silicon carbide ceramic precursor PAVGPAVG precursor powder is subjected to ball milling and mixing, 3D-SiC (Al, rGO) ceramic is obtained through a further precursor conversion process, and finally the surface appearance 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 beta-SiC microcrystals, thereby improving the hardness and the high temperature resistance stability of the precursor ceramic.

Claims (7)

1.一种聚碳硅烷不熔化预处理及其裂解转化三维陶瓷方法,其特征在于包括以下步骤:1. a polycarbosilane non-melting pretreatment and a three-dimensional ceramic method for pyrolysis conversion thereof, characterized in that comprising the following steps: 1)三维碳化硅聚合物先驱体的合成1) Synthesis of 3D SiC polymer precursors 将聚碳硅烷与乙酰丙酮铝共同溶解于有机溶剂中,搭建蒸馏装置,在惰性气氛保护下,快速升温将有机溶剂蒸出后保温,再进行第二次升温、保温,获得高度交联的超支化含铝聚碳硅烷固体,冷却后加入有机溶剂,溶解并过滤形成金黄色透明的有机溶液,另将氧化石墨烯粉末倒入去离子水中得混浊的水溶液,将上述有机溶液和水溶液分别超声分散,得超支化含铝聚碳硅烷溶液和氧化石墨烯分散液;在超支化含铝聚碳硅烷溶液中加入卡斯特铂金催化剂,在氧化石墨烯分散液中加入乙烯基三乙氧基硅烷交联不熔化预处理剂以及稀盐酸将溶液调节至酸性,将两种溶液混合置于烧杯中水浴加热反应,同时进行磁力搅拌,反应结束后静置,将上层产物取出进行减压蒸馏,得到先驱体含铝聚碳硅烷-乙烯基三乙氧基硅烷-氧化石墨烯固态聚合物,研磨后得先驱体粉末;所述聚碳硅烷与乙酰丙酮铝粉末质量比为(40~60)︰3;Dissolve polycarbosilane and aluminum acetylacetonate together in an organic solvent, set up a distillation apparatus, and under the protection of an inert atmosphere, rapidly heat up the organic solvent to steam out and then keep warm, and then perform a second heating and heat preservation to obtain a highly cross-linked overrun. The aluminum-containing polycarbosilane solid was dissolved, an organic solvent was added after cooling, dissolved and filtered to form a golden-yellow transparent organic solution, and the graphene oxide powder was poured into deionized water to obtain a turbid aqueous solution, and the above-mentioned organic solution and the aqueous solution were ultrasonically dispersed. , to obtain hyperbranched aluminum-containing polycarbosilane solution and graphene oxide dispersion; add Castel platinum catalyst to the hyperbranched aluminum-containing polycarbosilane solution, add vinyltriethoxysilane to the graphene oxide dispersion The solution is adjusted to acidity by combining the non-melting pretreatment agent and dilute hydrochloric acid, and the two solutions are mixed and placed in a beaker for heating reaction in a water bath, while magnetic stirring is performed. The aluminum-containing polycarbosilane-vinyltriethoxysilane-graphene oxide solid polymer is ground, and the precursor powder is obtained; the mass ratio of the polycarbosilane to the aluminum acetylacetonate powder is (40-60): 3; 所述超支化含铝聚碳硅烷与氧化石墨烯粉末质量比为(80~120)︰1;所述有机溶液、水溶液、乙烯基三乙氧基硅烷交联不熔化预处理剂以及卡斯特铂金催化剂体积比为(30~50)︰(30~50)︰(2~5)︰1;所述稀盐酸浓度为3~10wt%,所述调节至酸性是调节至pH值1~3;所述水浴加热温度为50~70℃,磁力搅拌速度为25~35rpm,保温时间为0.4~0.6h;The mass ratio of the hyperbranched aluminum-containing polycarbosilane to the graphene oxide powder is (80-120): 1; the organic solution, the aqueous solution, the vinyltriethoxysilane cross-linking infusible pretreatment agent and the caster The volume ratio of platinum catalyst is (30-50): (30-50): (2-5): 1; the concentration of the dilute hydrochloric acid is 3-10wt%, and the adjustment to acidity is to adjust to pH 1-3; The heating temperature of the water bath is 50-70°C, the magnetic stirring speed is 25-35rpm, and the holding time is 0.4-0.6h; 2)SiC(Al,rGO)p陶瓷颗粒的制备2) Preparation of SiC(Al,rGO)p ceramic particles 将一部分步骤1)得到的先驱体粉末在惰性气氛保护下,置于石墨纸舟中于管式炉内进行高温裂解,得到裂解后的SiC(Al,rGO)p陶瓷颗粒;Part of the precursor powder obtained in step 1) is placed in a graphite paper boat under the protection of an inert atmosphere for high temperature cracking in a tube furnace to obtain cracked SiC(Al,rGO)p ceramic particles; 3)3D-SiC(Al,rGO)陶瓷的制备3) Preparation of 3D-SiC(Al,rGO) ceramics 将剩余的步骤1)先驱体粉末以及酒精加入步骤2)裂解后的SiC(Al,rGO)p陶瓷颗粒中,球磨混合均匀后烘干,压片成型后放入惰性气氛管式炉内,再次高温烧结得到3D-SiC(Al,rGO)陶瓷;The remaining step 1) precursor powder and alcohol are added to the cracked SiC(Al,rGO)p ceramic particles in step 2), ball-milled and mixed evenly, dried, pressed into tablets and placed in an inert atmosphere tube furnace, and then again High temperature sintering to obtain 3D-SiC(Al,rGO) ceramics; 所述裂解后的SiC(Al,rGO)p陶瓷颗粒与先驱体粉末的质量比为(5~50)︰10;所述球磨时间为8~10h;所述压片成型的压力为30~50MPa,保压时间为15~25s;所述惰性气氛为氩气,气体流速为60~150mL/min;The mass ratio of the cracked SiC(Al,rGO)p ceramic particles to the precursor powder is (5-50):10; the ball milling time is 8-10h; the pressure of the tablet forming is 30-50MPa , the pressure holding time is 15-25s; the inert atmosphere is argon, and the gas flow rate is 60-150mL/min; 4)3D-SiC(Al,rGO)陶瓷的表面形貌修饰4) Surface Morphology Modification of 3D-SiC(Al,rGO) Ceramics 将步骤3)得到的3D-SiC(Al,rGO)陶瓷浸渍于液态聚碳硅烷中,再次置于惰性气氛管式炉内烧结,即得表面形貌更致密的3D-SiC(Al,rGO)陶瓷材料。The 3D-SiC(Al,rGO) ceramic obtained in step 3) was immersed in liquid polycarbosilane, and then sintered in an inert atmosphere tube furnace to obtain 3D-SiC(Al,rGO) with a denser surface morphology. Ceramic material. 2.如权利要求1所述一种聚碳硅烷不熔化预处理及其裂解转化三维陶瓷方法,其特征在于在步骤1)中,所述有机溶剂为二甲苯;所述惰性气氛为氩气,流速20~50mL/min;所述快速升温以4~6℃/min的升温速率加热至145~155℃,保温时间为0.5~2h;所述第二次升温以2~4℃/min的升温速率加热至305~315℃,保温时间为4~6h。2. a kind of polycarbosilane non-melting pretreatment as claimed in claim 1 and its pyrolysis conversion three-dimensional ceramic method, it is characterized in that in step 1), described organic solvent is xylene; Described inert atmosphere is argon, The flow rate is 20-50mL/min; the rapid temperature rise is heated to 145-155°C at a heating rate of 4-6°C/min, and the holding time is 0.5-2h; the second temperature rise is heated at a temperature of 2-4°C/min The rate is heated to 305~315℃, and the holding time is 4~6h. 3.如权利要求1所述一种聚碳硅烷不熔化预处理及其裂解转化三维陶瓷方法,其特征在于在步骤2)中,所述惰性气氛为氩气,气体流速为60~150mL/min;所述高温裂解的温度为1300℃,升温速率为3~5℃/min,保温时间为1~30min。3. a kind of polycarbosilane infusible pretreatment as claimed in claim 1 and its pyrolysis conversion three-dimensional ceramic method, it is characterized in that in step 2), described inert atmosphere is argon, and gas flow rate is 60~150mL/min The temperature of the high-temperature cracking is 1300°C, the heating rate is 3~5°C/min, and the holding time is 1~30min. 4.如权利要求1所述一种聚碳硅烷不熔化预处理及其裂解转化三维陶瓷方法,其特征在于在步骤3)中,所述再次高温烧结的温度为1200~1400℃,升温速率为3~5℃/min,保温时间为5~35min。4. a kind of polycarbosilane non-melting pretreatment as claimed in claim 1 and its pyrolysis conversion three-dimensional ceramic method, it is characterized in that in step 3), the temperature of described high temperature sintering again is 1200~1400 ℃, and the heating rate is 3~5℃/min, the holding time is 5~35min. 5.如权利要求1所述一种聚碳硅烷不熔化预处理及其裂解转化三维陶瓷方法,其特征在于在步骤4)中,所述浸渍的时间为20~30h;所述惰性气氛为氩气,气体流速为60~150mL/min。5. A kind of polycarbosilane non-melting pretreatment as claimed in claim 1 and its pyrolysis conversion three-dimensional ceramic method, characterized in that in step 4), the immersion time is 20 ~ 30h; the inert atmosphere is argon Gas, the gas flow rate is 60 ~ 150mL/min. 6.如权利要求1所述一种聚碳硅烷不熔化预处理及其裂解转化三维陶瓷方法,其特征在于在步骤4)中,所述烧结温度等温于步骤3)的烧结温度,升温速率为3~5℃/min,保温时间为1~30min。6. a kind of polycarbosilane non-melting pretreatment as claimed in claim 1 and its pyrolysis conversion three-dimensional ceramic method, it is characterized in that in step 4), described sintering temperature is isothermal at the sintering temperature of step 3), and the heating rate is 3~5℃/min, the holding time is 1~30min. 7.如权利要求1所述一种聚碳硅烷不熔化预处理及其裂解转化三维陶瓷方法制备的3D-SiC(Al,rGO)陶瓷材料,其特征在于所述3D-SiC(Al,rGO)陶瓷材料含有Si、C、O、Al四种元素,Al以原子状态均匀分布于SiOxCy无定形相中,β-SiC纳米晶镶嵌于复合rGO的SiOxCy/Cfree无定形相中,存在SiO2微晶。7. The 3D-SiC (Al, rGO) ceramic material prepared by infusible pretreatment of polycarbosilane and its pyrolysis transformation three-dimensional ceramic method as claimed in claim 1, characterized in that the 3D-SiC (Al, rGO) The ceramic material contains four elements, Si, C, O, and Al. Al is uniformly distributed in the SiO x C y amorphous phase in the atomic state, and β-SiC nanocrystals are embedded in the SiO x C y /C free amorphous phase of the composite rGO. , there are SiO2 crystallites.
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