CN116023147A - Polycarbosilane and silicon composition, application thereof, siC ceramic and SiC ceramic matrix composite - Google Patents
Polycarbosilane and silicon composition, application thereof, siC ceramic and SiC ceramic matrix composite Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 129
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 119
- 239000010703 silicon Substances 0.000 title claims abstract description 119
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a polycarbosilane and silicon composition for adjusting the residual carbon content in SiC ceramic converted from polycarbosilane, which at least comprises polycarbosilane and silicon simple substance. The mole content of the simple substance silicon is less than or equal to the mole content of residual carbon in the SiC ceramic obtained after the pyrolysis of the polycarbosilane. The polycarbosilane and silicon composition can reduce the content of residual carbon in a precursor polycarbosilane ceramic product, is not limited by diffusion factors, can remove residual carbon in SiC ceramics with different forms, has no gas phase by-product in the carbon removal process, and can improve the crystallinity of the obtained SiC ceramics. The invention provides SiC ceramic prepared from a polycarbosilane and silicon composition and a preparation method thereof. The invention also provides application of the polycarbosilane and silicon composition.
Description
Technical Field
The invention relates to the technical field of silicon carbide ceramics, in particular to a silicon carbide raw material polycarbosilane and silicon composition and application thereof, siC ceramics and SiC ceramic matrix composite materials.
Background
Silicon carbide (SiC) ceramics have the advantages of excellent high-temperature oxidation resistance, abrasion resistance, chemical corrosion resistance, neutron irradiation resistance and the like, so that the silicon carbide (SiC) ceramics are widely applied to the fields of high-end science and technology and national defense and military.
At present, siC ceramics are generally prepared by a precursor conversion method, and specifically are formed by cracking and converting polycarbosilane precursors containing elements such as silicon, carbon, hydrogen and the like. The method has the following advantages: the method comprises the steps of realizing the regulation and control of the composition, structure and performance of SiC ceramics through the molecular design of polycarbosilane; because of the soluble and fusible properties of the polymer materials, the ceramic material can be molded by adopting general material processing technology and equipment; can realize ceramization at lower temperature, and reduce the production energy consumption and the cost.
Polycarbosilanes are polymers having a linear or branched structure with a backbone composed of silicon and carbon atoms to which hydrogen or other organic groups are attached. Carbon residues are unavoidable during the pyrolytic conversion thereof into SiC ceramics due to the introduction of organic groups. Although the order of the residual carbon increases with increasing heat treatment temperature, it is still independent of the converted SiC ceramic and does not pass sp 3 The hybridization being interconnected with Si or other atoms by chemical bonds, but C and C being interconnected in sp 2 The presence of hybridization, so is also known as "free carbon", "free carbon" or "sp 2 -hybrid carbon.
The presence of residual carbon has a critical impact on the crystallinity, microstructure and properties of the precursor-converted SiC. In addition, from the development history of SiC fibers, the presence of residual carbon is disadvantageous in improving the high temperature stability thereof, but a proper amount of residual carbon is important for maintaining the high temperature strength of the fibers because it forms a cage-like network around SiC crystals, which can prevent explosive growth of SiC crystal grains and maintain the fiber strength.
In SiC ceramic products, the content of residual carbon depends firstly on the structure of the precursor polymer, which has the following law: an increase in the number of substituents and an increase in the residual carbon content; the unsaturated group introduces a higher content of residual carbon than the saturated group; the residual carbon content increases with increasing carbon atom content in the substituent; in addition, the thermal stability of the organic groups in the precursor structure also affects the residual carbon content.
In the prior art, a gas phase method is mainly adopted to reduce or adjust the conversion of precursor polycarbosilaneResidual carbon content in the porcelain. In the process of preparing SiC fibers from polycarbosilane, as in the Chinese patent application CN104529462A, the obtained polycarbosilane non-melted fibers are placed in a high temperature furnace, heated to 1000 ℃ at a speed of 100-150 ℃ per hour under the protection of nitrogen, wherein H with a hydrogen concentration of 50-70 vol% is introduced at a flow rate of 800-1000 mL/min in a temperature range of 400-1000 DEG C 2 /N 2 Carrying out pyrolysis and decarbonization treatment on the mixed gas, and when the temperature reaches 1000 ℃, carrying out H 2 /N 2 The mixed gas is replaced by nitrogen, the temperature is raised to 1300-1600 ℃ at the speed of 100-200 ℃/h under the protection of nitrogen, and the heat is preserved for 1-2 h, thus obtaining the SiC fiber with near stoichiometric ratio.
For example, chinese patent application CN102976325a uses vaporizable organosilicon polymer generated during the synthesis of polycarbosilane as raw material, and prepares β -SiC ultra-fine powder by gas phase pyrolysis; the decarburization process is heat treatment at 500-800 deg.c in oxygen atmosphere for 1-4 hr. For another example, chinese patent application CN108238799a describes a method for preparing a silicon-containing ceramic coating from a polycarbosilane solution, in which a reducing gas is filled in a temperature range of 300-1000 ℃ for decarburization treatment during the pyrolysis, and the reducing gas atmosphere is a mixed atmosphere formed by hydrogen or ammonia and an inert gas.
The gas phase method is limited by the diffusion and infiltration of gas, so that the residual carbon content in the SiC ceramic is regulated by the gas phase method, and the SiC ceramic is mainly suitable for fine materials such as fibers, micro powder, coatings and the like.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a polycarbosilane and silicon composition which can reduce the content of residual carbon in a precursor polycarbosilane ceramic product, is not limited by diffusion factors, can remove residual carbon in SiC ceramics with different forms, has no gas phase by-product in the carbon removal process and can improve the crystallinity of the obtained SiC ceramics. The invention also provides application of the polycarbosilane and silicon composition, and SiC ceramic matrix composite prepared from the polycarbosilane and silicon composition.
In order to achieve the above object, the present invention provides the following technical solutions:
a polycarbosilane and silicon composition for adjusting the residual carbon content of a polycarbosilane converted into SiC ceramic comprises at least polycarbosilane and a silicon simple substance.
In polycarbosilanes and silicon compositions, the polycarbosilanes are linear or branched structure polymers having a backbone composed of silicon and carbon atoms to which are attached hydrogen or other organic groups.
The principle of reducing and adjusting residual carbon in SiC ceramic formed by converting precursor polycarbosilane is as follows: the silicon simple substance can directly form SiC with carbon with equal molar weight under a high-temperature environment, and residual carbon in the SiC converted by the precursor polycarbosilane can be reduced or removed through the introduction of the silicon simple substance.
Further, the molar content of the simple substance silicon is smaller than or equal to the molar content of residual carbon in the SiC ceramic obtained after pyrolysis of the polycarbosilane.
In order to remove residual carbon in the SiC ceramic, the molar content of elemental silicon may be higher than the molar amount of residual carbon in the polycarbosilane converted SiC ceramic; but this in turn leads to the residue of elemental silicon. Therefore, preferably, the molar content of the elemental silicon is less than or equal to the molar content of residual carbon in the SiC ceramic obtained after pyrolysis of polycarbosilane. As a further preferred aspect, the molar content of the elemental silicon is equal to the molar content of residual carbon in the SiC ceramic obtained after pyrolysis of the polycarbosilane, such that the elemental silicon can form SiC directly with an equimolar amount of carbon in a high temperature environment.
Wherein the high temperature environment is an inert atmosphere with the temperature of more than 1000 ℃; to accelerate the reaction rate, the temperature should preferably be higher than 1400 ℃.
Further, the polycarbosilane includes at least one of structural units represented by the following formulas (1), (2), (3) and (4):
wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are independently selected from one of C1-C6 alkyl and unsaturated groups; meanwhile, at least one group of R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 is an unsaturated group, and the structural unit where it is located is required to be present in the polycarbosilane.
The simple substances of silicon need to be uniformly distributed in the polycarbosilane, and on one hand, the simple substances of silicon need to be well dispersed in the polycarbosilane; on the other hand, the particle size of the simple substance silicon is as small as possible.
When the silicon simple substance is uniformly dispersed in the polycarbosilane, the uniform and stable distribution of the silicon simple substance can be realized by combining a plurality of methods such as solvent dilution, mechanical dispersion, dispersant stabilization, chemical modification and the like.
In the solvent dilution method, a polar aprotic solvent such as tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether, etc. which also has good solubility for polycarbosilane is used. In the mechanical dispersion, physical methods such as ultrasonic, ball milling, stirring and the like can be adopted; in the dispersant stabilization method, a surfactant or a silane coupling agent such as cetyltrimethylammonium bromide, aminopropyl triethoxysilane may be selected.
In the chemical modification, si-O-Si, si-O-C, si-NH and other connecting structures can be introduced on the surface of the silicon simple substance, so that the dispersibility of the silicon simple substance in an organic solvent and polycarbosilane is improved, for example: si-OH groups formed by the easy oxidation of the surface of the simple substance silicon and containing-Si-Cl groups containing-Si-OR groups (R is an alkyl OR unsaturated group) containing-Si-OAc groups OR-Si-N (CH) 3 ) 2 Condensing the compound of the group, thereby introducing the organic group into the silicon simple substance through the Si-O-Si structure; si-OH groups and SOCl 2 、SO 2 Cl 2 The reaction of RCOCl and the like can form Si-Cl groups, the Si-Cl groups have high activity and can be combined with HO-, NH-containing groups 2 -a compound of alike groups, whereby organic groups are introduced into the elemental silicon through Si-O-C, si-NH alike structures.
Further, the average grain diameter of the simple substance silicon is smaller than 200nm, namely the simple substance silicon is silicon powder with the average grain diameter smaller than 200nm.
Further, the average grain diameter of the simple substance silicon is smaller than 80nm, and the simple substance silicon is silicon powder with the average grain diameter smaller than 80nm.
Further, the average grain diameter of the simple substance silicon is smaller than 50nm, and the simple substance silicon is silicon powder with the average grain diameter smaller than 50nm.
For nano-sized silicon powder, the particle size is small, the specific surface is large, the surface energy is high, and the agglomeration is generated due to the fact that moisture is easily absorbed in the storage process, so that the nano-sized silicon powder is not easy to well disperse in weak-polarity polycarbosilane. As described above, the invention can introduce organic groups into the silicon simple substance through at least one connecting structure of Si-O-Si, si-O-C or Si-NH on the surface of the silicon simple substance by carrying out chemical grafting modification treatment on the silicon simple substance, thereby improving the dispersibility of the silicon simple substance in an organic solvent and polycarbosilane.
Further, the polycarbosilane and silicon composition also comprises SiC ceramic powder; the mass fraction of the SiC ceramic powder is 10-30%,
the polycarbosilane and silicon composition further comprises a thermal decomposition type free radical initiator, such as tert-butyl peroxybenzoate, dibenzoyl peroxide or cumene hydroperoxide, and the mass fraction of the thermal decomposition type free radical initiator is preferably 0.5-2%.
The invention also provides application of the polycarbosilane and silicon composition, and the polycarbosilane and silicon composition is pyrolyzed and converted into SiC ceramic, and the application at least comprises;
is applied to the preparation of SiC ceramic matrix composite materials and porous SiC ceramics,
is applied to filling of ceramic or graphite materials,
is applied to preparing protective coatings of carbon materials or metals,
applied to the connection of ceramic or ceramic matrix composite materials,
the method is applied to the field of energy storage.
When the method is applied to the preparation of SiC ceramic matrix composite materials, the polycarbosilane and silicon composition can directly impregnate fibers, then the fibers are pyrolyzed and converted into a SiC ceramic matrix, and densification is realized by repeated impregnation-cracking for a plurality of cycles.
When the method is applied to the preparation of SiC ceramic matrix composite materials, the polycarbosilane and silicon composition can directly impregnate fibers, then the fibers are pyrolyzed and converted into a SiC ceramic matrix, and the impregnation-pyrolysis is repeated for a plurality of cycles to realize densification; wherein the fibers include, but are not limited to, linear fiber bundles, planar fiber cloths, three-dimensional fiber preforms.
When the method is applied to preparing porous SiC ceramic, the foaming microsphere can be dispersed in a polycarbosilane and silicon composition, and the composition is heated for pyrolysis, so that the SiC ceramic is converted from the polycarbosilane and silicon composition while the microsphere is foamed and pore-formed.
When the method is applied to filling of ceramic or graphite materials, the polycarbosilane and silicon composition can be filled at the pores of the ceramic or graphite materials, or the ceramic and graphite are soaked in the polycarbosilane and silicon composition and then pyrolyzed and converted into SiC ceramic for filling.
When applied to a protective coating of carbon material or metal, the polycarbosilane and silicon composition can be coated on the surface of the carbon material or metal material by a coating or spin coating process, and then pyrolytically converted into a SiC ceramic coating.
When applied to the joining of ceramic or ceramic matrix composites, polycarbosilane and silicon compositions are applied to the joint and then pyrolysed to convert to SiC ceramics for joining.
When applied in the energy storage field, the molar content of the added elemental silicon is preferably higher than the molar content of the residual carbon, because silicon has a high energy storage density, which can increase the energy density of the battery.
The viscosity or solvent content, the rate of temperature rise, the content of elemental silicon, the additive components, and the impregnation or pyrolysis cycle of the polycarbosilane and silicon composition can be adjusted as desired during different applications.
The invention also provides SiC ceramic, which is formed by pyrolysis and conversion of the polycarbosilane and silicon composition.
The invention also provides a SiC ceramic matrix composite material, which is prepared by impregnating the fiber with the polycarbosilane and silicon composition, then performing pyrolysis to convert the fiber-reinforced SiC ceramic matrix composite material, and performing repeated impregnation of the polycarbosilane and silicon composition and pyrolysis to realize densification.
Further, the fibers include at least one of linear fiber bundles, planar fiber cloth, or three-dimensional fiber preform.
When the polycarbosilane and silicon composition is applied to the preparation of the SiC ceramic matrix composite material, the polycarbosilane and silicon composition can directly impregnate fibers, then the fibers are pyrolyzed and converted into a SiC ceramic matrix, and the impregnation-pyrolysis is repeated for a plurality of cycles to realize densification; wherein the fibers include, but are not limited to, linear fiber bundles, planar fiber cloths, three-dimensional fiber preforms.
Further, after the linear fiber bundles are immersed in the polycarbosilane and silicon composition, a tubular member is formed by winding or braiding, and the tubular member is heated to crosslink and solidify the polycarbosilane therein under the negative pressure condition, and then is thermally decomposed to more than 1400 ℃.
Application of polycarbosilane and silicon composition to tubular SiC f When the SiC composite material is prepared, the preparation process is as follows: after the linear fiber bundles are immersed in the polycarbosilane and silicon composition, a tubular piece is formed on a core mold through winding or braiding, the tubular piece is placed in a vacuum bag film, the tubular piece is heated to crosslink and solidify the polycarbosilane therein under the negative pressure condition, and then the polycarbosilane is pyrolyzed to be more than 1400 ℃, so that the ceramic can be realized, and the residual carbon in the pyrolysis product of the polycarbosilane reacts with simple substance silicon to form SiC.
Wherein the polycarbosilane is liquid polycarbosilane containing unsaturated groups, such as allyl, vinyl or ethynyl, and the C/Si ratio of the ceramic product is not higher than 1.2.
Based on the technical scheme, compared with the prior art, the invention has the following technical effects:
(1) According to the polycarbosilane and silicon composition provided by the invention, the silicon simple substance is introduced into the polycarbosilane, so that the removal of residual carbon in SiC ceramic converted from the polycarbosilane can be realized, and compared with a gas phase method for fine structures such as fibers, micro powder and coatings, the application range is wider.
(2) According to the polycarbosilane and silicon composition provided by the invention, the molar content of the simple substance silicon is controlled to be smaller than or equal to the molar content of residual carbon in SiC ceramic obtained after the polycarbosilane is pyrolyzed, so that the content of the residual carbon can be adjusted.
(3) According to the polycarbosilane and silicon composition provided by the invention, silicon simple substance reacts with residual carbon to generate SiC, so that on one hand, no gas phase product overflows and no quality loss exists, and the ceramic yield can be ensured; on the other hand, the crystallinity of the ceramic can be improved.
Drawings
Fig. 1 is an XRD spectrum of SiC ceramics prepared in example 1, example 2 and comparative example 1 of the present invention.
FIG. 2 is a Raman spectrum of the SiC ceramics prepared in example 2 and comparative example 1 of the present invention.
FIG. 3 is a transmission electron microscopic image of the SiC ceramics prepared in example 2 and comparative example 1 of the present invention.
FIG. 4 is a SiC prepared in example 5 of the present invention f Internal topography of SiC tubular member.
FIG. 5 is a Raman spectrum of the SiC ceramic prepared in comparative example 2 of the present invention.
Detailed Description
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated in the appended drawings. The drawings illustrate preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
A polycarbosilane and silicon composition for adjusting the residual carbon content of a polycarbosilane converted into SiC ceramic comprises at least polycarbosilane and a silicon simple substance.
Wherein the mole content of the simple substance silicon is less than or equal to the mole content of residual carbon in SiC ceramic obtained after the pyrolysis of polycarbosilane.
Wherein the polycarbosilane comprises at least one of structural units represented by the following formula (1), formula (2), formula (3) and formula (4):
wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are independently selected from one of C1-C6 alkyl and unsaturated groups; meanwhile, at least one group of R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 is an unsaturated group, and the structural unit where it is located is required to be present in the polycarbosilane.
Preferably, the polycarbosilane is a liquid polycarbosilane containing unsaturated groups such as allyl, vinyl or ethynyl groups having a C/Si ratio of not more than 1.2 in the ceramic product.
Preferably, the silicon simple substance is subjected to chemical grafting treatment, and at least one connecting structure of Si-O-Si, si-O-C or Si-NH is contained on the surface of the silicon simple substance.
Preferably, the average particle size of the elemental silicon is less than 200nm. Further preferably, the average particle size of the elemental silicon is less than 80nm. Further preferably, the average particle size of the elemental silicon is less than 50nm.
Preferably, the polycarbosilane and silicon composition further comprises SiC ceramic powder, and the mass fraction of the SiC ceramic powder is 10-30%.
Preferably, the polycarbosilane and silicon composition further comprises a thermally decomposed radical initiator.
The polycarbosilane and silicon composition are pyrolyzed and converted into SiC ceramic, and the application of the SiC ceramic at least comprises; the method is applied to the preparation of SiC ceramic matrix composite materials and porous SiC ceramics; the method is applied to filling of ceramic or graphite materials; the method is applied to preparing a protective coating of carbon materials or metals; the method is applied to the connection of ceramic or ceramic matrix composite materials; the method is applied to the field of energy storage.
After the SiC ceramic matrix composite is prepared by impregnating the polycarbosilane and silicon composition with fibers, performing pyrolysis to convert the fiber-reinforced SiC ceramic matrix composite, and performing repeated impregnation of the polycarbosilane and silicon composition and pyrolysis to realize densification. The fibers comprise at least one of linear fiber bundles, planar fiber cloths, or three-dimensional fiber preforms.
After the linear fiber bundles are immersed in the polycarbosilane and silicon composition, a tubular member is formed by winding or braiding, and the tubular member is heated to crosslink and solidify the polycarbosilane therein under the negative pressure condition, and then is thermally decomposed to more than 1400 ℃.
Example 1
A SiC ceramic is prepared by the following method:
0.45g of silica powder with an average particle diameter of 50nm is added into 10mL of tetrahydrofuran, and ball milling is performed at a high speed for 10h. Then 10.0g of allyl-containing liquid polycarbosilane (structural formula { [ SiCH ] 2 H 2 ] 0.9 [SiCH 2 H(CH 2 CH＝CH 2 )] 0.1 } n The method comprises the steps of carrying out a first treatment on the surface of the Ceramic yield 75wt%; the ceramic product had a C content of 33.09wt%, an O content of 1.53wt% and a C/Si ratio of 1.18). After the ball milling is continued for 10 hours, the silicon carbide balls are separated, and then tetrahydrofuran is decompressed and extracted.
Placing the liquid polycarbosilane and nano silicon powder composition into a high-temperature tube furnace, replacing three times of gas, protecting by high-purity argon, heating to 1600 ℃ at a speed of 3 ℃/min, and preserving heat for 1h; and naturally cooling to prepare the SiC ceramic.
XRD spectra of SiC ceramics prepared in this example are shown in FIG. 1. From the XRD spectrum of FIG. 1, it can be calculated that the average grain size of the SiC ceramic prepared in this example is
Example 2
A SiC ceramic is prepared by the following method:
0.9g of silica powder with an average particle diameter of 50nm is added into 20mL of tetrahydrofuran, and ball milling is performed at a high speed for 10h. Then 10.0g of allyl-containing liquid polycarbosilane (structural formula { [ SiCH ] 2 H 2 ] 0.9 [SiCH 2 H(CH 2 CH＝CH 2 )] 0.1 } n The method comprises the steps of carrying out a first treatment on the surface of the Ceramic yield 75wt%; the ceramic product had a C content of 33.09wt%, an O content of 1.53wt% and a C/Si ratio of 1.18). After the ball milling is continued for 10 hours, the silicon carbide balls are separated, and then tetrahydrofuran is decompressed and extracted.
Placing the liquid polycarbosilane and nano silicon powder composition into a high-temperature tube furnace, replacing three times of gas, protecting by high-purity argon, heating to 1600 ℃ at a speed of 3 ℃/min, and preserving heat for 1h; and naturally cooling to prepare the SiC ceramic.
XRD spectra, raman spectra and transmission electron microscope images of the SiC ceramics prepared in the embodiment refer to figures 1 to 3 respectively. From the XRD spectrum of FIG. 1, it can be calculated that the average grain size of the SiC ceramic prepared in this example is
Example 3
A SiC ceramic is prepared by the following method:
1.12g of silica powder with an average particle diameter of 80nm is added into 25mL of tetrahydrofuran, and ball milling is performed for 10h at a high speed. Then 10.0g of a vinyl-containing liquid polycarbosilane (structural formula: { [ SiCH ] 2 H 2 ] 0.88 [SiCH 2 H(C≡CH)] 0.12 } n The method comprises the steps of carrying out a first treatment on the surface of the Ceramic yield 78wt%; the ceramic product had a C content of 33.79wt%, an O content of 1.63wt% and a C/Si ratio of 1.22). After the ball milling is continued for 10 hours, the silicon carbide balls are separated, and then tetrahydrofuran is decompressed and extracted.
Placing the liquid polycarbosilane and nano silicon powder composition into a high-temperature tube furnace, replacing three times of gas, protecting by high-purity argon, heating to 1600 ℃ at a speed of 2 ℃/min, and preserving heat for 1h; and naturally cooling to prepare the SiC ceramic. The raman spectrum did not find the D, G peak associated with residual carbon.
Example 4
A SiC ceramic is prepared by the following method:
0.78g of silica powder with an average particle diameter of 200nm is added into 20mL of tetrahydrofuran, and ball milling is performed at a high speed for 10h. Then 10.0g of a vinyl-containing liquid polycarbosilane (structural formula: { [ SiCH ] 2 H 2 ] 0.91 [SiCH 2 H(CH＝CH 2 )] 0.09 } n The method comprises the steps of carrying out a first treatment on the surface of the Ceramic yield 80wt%; the ceramic product had a C content of 32.47wt%, an O content of 1.33wt% and a C/Si ratio of 1.15). After ball milling for 10 hours, separating the silicon carbide balls, and then carrying out four-step ball millingThe hydrogen furan is decompressed and extracted.
Placing the liquid polycarbosilane and nano silicon powder composition into a high-temperature tube furnace, replacing three times of gas, protecting with high-purity argon, heating to 1400 ℃ at a speed of 2 ℃/min, and preserving heat for 3 hours; and naturally cooling to prepare the SiC ceramic. The raman spectrum did not find the D, G peak associated with residual carbon.
Example 5
SiC (silicon carbide) f SiC tubular member (SiC ceramic matrix composite) prepared by the following method:
4.5g of silica powder with an average particle diameter of 50nm is added into 100mL of tetrahydrofuran, and ball milling is performed for 10h at a high speed. Then 50.0g of allyl-containing liquid polycarbosilane (structural formula: { [ SiCH ] 2 H 2 ] 0.9 [SiCH 2 H(CH 2 CH＝CH 2 )] 0.1 } n The method comprises the steps of carrying out a first treatment on the surface of the Ceramic yield 75wt%; the ceramic product had a C content of 33.09wt%, an O content of 1.53wt%, and a C/Si ratio of 1.18), 0.04g of cetyltrimethylammonium bromide and 0.5g of t-butyl peroxybenzoate.
And (3) after ball milling is continued for 10 hours, separating the silicon carbide balls, and then decompressing and extracting tetrahydrofuran to obtain slurry prepared from liquid polycarbosilane, nano silicon, thermal decomposition type free radical initiator and dispersing agent. On an automatic winder, siC fibers were passed through the slurry prepared above and then wound on a graphite mandrel. After the winding is completed, the material is placed in a vacuum bag. The vacuum bag was placed in an oven at 120 ℃ and evacuated.
And after 2 hours, solidifying the liquid polycarbosilane, stopping heating, and removing the vacuum bag film after cooling. Transferring the fiber winding piece into a high-temperature tube furnace, replacing three times of gas, protecting with high-purity argon, then heating to 1500 ℃ at a speed of 3 ℃/min, and preserving the temperature for 1h. And cooling and taking out. Then soaking the mixture in the prepared slurry, and carrying out vacuum impregnation. After the impregnation is completed, the mixture is taken out and put into a high-temperature tube furnace, and then is cracked according to the above procedure. Continuously repeating the vacuum impregnation-pyrolysis for 6 periods until the weight gain rate is lower than 2wt%, and removing the graphite core mould to prepare SiC f SiC tubular member.
FIG. 4 shows the SiC obtained in this example f SiC tubular formThe internal morphology of the part is shown in FIG. 4, siC prepared in this example f The inside of the SiC tubular member is dense. At the SiC f In the SiC tubular member, the SiC fiber content was 55.1% by weight.
Example 6
SiC (silicon carbide) f SiC tubular member (SiC ceramic matrix composite) prepared by the following method:
4.5g of silica powder with an average particle diameter of 50nm is added into 100mL of tetrahydrofuran, and ball milling is performed for 10h at a high speed. Then 5.0g of SiC powder with the average particle size of 150nm is added, and ball milling is continued for 5 hours. A further 50.0g of allyl-containing liquid polycarbosilane (structural formula { [ SiCH ] 2 H 2 ] 0.9 [SiCH 2 H(CH 2 CH＝CH 2 )] 0.1 } n The method comprises the steps of carrying out a first treatment on the surface of the Ceramic yield 75wt%; the ceramic product had a C content of 33.09wt%, an O content of 1.53wt%, and a C/Si ratio of 1.18), 0.1g of aminopropyl triethoxysilane, and 0.5g of t-butyl peroxybenzoate.
And (3) after ball milling is continued for 10 hours, separating the silicon carbide balls, and then decompressing and extracting tetrahydrofuran to obtain slurry prepared from liquid polycarbosilane, nano silicon, nano SiC powder, a thermal decomposition type free radical initiator and a dispersing agent. On an automatic winder, siC fibers were passed through the slurry prepared above and then wound on a graphite mandrel. After the winding is completed, the material is placed in a vacuum bag. The vacuum bag was placed in an oven at 120 ℃ and evacuated.
And after 2 hours, solidifying the liquid polycarbosilane, stopping heating, and removing the vacuum bag film after cooling. Transferring the fiber winding piece into a high-temperature tube furnace, replacing three times of gas, protecting with high-purity argon, then heating to 1500 ℃ at a speed of 3 ℃/min, and preserving the temperature for 1h. And cooling and taking out. Then soaking the mixture in the prepared slurry, and carrying out pressure impregnation. After the impregnation is completed, the mixture is taken out and put into a high-temperature tube furnace, and then is cracked according to the above procedure. Continuously repeating the vacuum impregnation-pyrolysis for 4 periods until the weight gain rate is lower than 2wt%, and removing the graphite core mould to prepare SiC f SiC tubular member. The SiC is f The inside of the SiC tubular member was dense, and the SiC fiber content was 55.3wt%.
Comparative example 1
The SiC ceramic is prepared by the following preparation method:
10.0g of allyl-containing liquid polycarbosilane (structural formula: { [ SiCH ] 2 H 2 ] 0.9 [SiCH 2 H(CH 2 CH＝CH 2 )] 0.1 } n ) Placing the mixture in a high-temperature tube furnace, replacing the gas for three times, protecting the gas by high-purity argon, then heating to 1600 ℃ at a speed of 3 ℃/min, and preserving the heat for 1h; and naturally cooling to prepare the SiC ceramic. Wherein, the ceramic yield is 75wt%; the ceramic product has a C content of 33.09wt% and an O content of 1.53wt%; the C/Si ratio was 1.18.
XRD spectra, raman spectra and transmission electron microscope spectra of the SiC ceramic prepared in comparative example 1 are respectively referred to FIGS. 1 to 3. From the XRD spectrum of FIG. 1, it can be calculated that the average grain size of the SiC ceramic prepared in comparative example 1 is
Comparative example 2
A SiC ceramic is prepared by the following method:
0.9g of silica powder having an average particle diameter of 1 μm was added to 20mL of tetrahydrofuran, and ball-milled at a high speed for 10 hours. Then 10.0g of allyl-containing liquid polycarbosilane (structural formula { [ SiCH ] 2 H 2 ] 0.9 [SiCH 2 H(CH 2 CH＝CH 2 )] 0.1 } n The method comprises the steps of carrying out a first treatment on the surface of the Ceramic yield 75wt%; the ceramic product had a C content of 33.09wt%, an O content of 1.53wt% and a C/Si ratio of 1.18). After the ball milling is continued for 10 hours, the silicon carbide balls are separated, and then tetrahydrofuran is decompressed and extracted.
Placing the liquid polycarbosilane and nano silicon powder composition into a high-temperature tube furnace, replacing three times of gas, protecting by high-purity argon, heating to 1600 ℃ at a speed of 3 ℃/min, and preserving heat for 1h; and naturally cooling to prepare the SiC ceramic. The raman spectrum of the SiC ceramic prepared in comparative example 2 is referred to fig. 5.
As can be seen from example 1, example 2 and comparative example 1, after the addition of the elemental silicon, the XRD diffraction peak associated with SiC was enhanced, which is manifested by a decrease in half-width, an increase in grain size, a decrease or even disappearance of D and G peaks associated with residual carbon, and a disappearance of graphite structure under TEM electron microscope, indicating that the addition of the elemental silicon effectively removed the residual carbon in the precursor polycarbosilane converted ceramic.
From examples 2 to 4, it is clear that the nanosized elemental silicon is not selective for the precursor structure when removing residual carbon from the precursor polycarbosilane-converted SiC ceramic.
As can be seen from comparative example 2, the D peak and G peak associated with the residual carbon are still strong, indicating that the effect of the nano-sized elemental silicon is better than that of the micro-sized elemental silicon when the residual carbon in the precursor polycarbosilane-converted SiC ceramic is removed.
From examples 5 and 6, it is known that slurries formed from polycarbosilane and elemental silicon and the like can be used for preparing SiC ceramic matrix composites.
Performance tests in the above examples and comparative examples were performed using the following instruments:
x-ray diffraction (XRD): testing by using a D8 advanced type X-ray diffractometer of Bruker company, germany;
raman spectroscopy: testing with a laser confocal microscopic Raman spectrometer of the company LAbRAMHR Evolution of Horiba Japan;
transmission Electron Microscope (TEM): talos F200X-type transmission electron microscope test of Thermo Scientific company in the United states was adopted;
scanning Electron Microscope (SEM): the test was carried out by using a field emission scanning electron microscope of Hitachi, japan, S-4800.
The foregoing is merely illustrative and explanatory of the invention as it is described in more detail and is not thereby to be construed as limiting the scope of the invention. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the invention, and that these obvious alternatives fall within the scope of the invention.
Claims (14)
1. The polycarbosilane and silicon composition is characterized by being used for adjusting the content of residual carbon in the conversion of the polycarbosilane into SiC ceramic, and at least comprises polycarbosilane and silicon simple substance.
2. The polycarbosilane and silicon composition of claim 1 wherein the mole content of elemental silicon is less than or equal to the mole content of residual carbon in the SiC ceramic obtained after pyrolysis of the polycarbosilane.
3. The polycarbosilane and silicon composition of claim 1, wherein the polycarbosilane comprises at least one structural unit of the following formulas (1), (2), (3) and (4):
wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are independently selected from one of C1-C6 alkyl and unsaturated groups; meanwhile, at least one group of R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 is an unsaturated group, and the structural unit where it is located is required to be present in the polycarbosilane.
4. The polycarbosilane and silicon composition of claim 1, wherein the elemental silicon is chemically grafted to contain at least one Si-O-Si, si-O-C, or Si-NH linkage on the surface of the elemental silicon.
5. The polycarbosilane and silicon composition of claim 1 wherein the average particle size of the elemental silicon is less than 200nm.
6. The polycarbosilane and silicon composition of claim 1 wherein the average particle size of the elemental silicon is less than 80nm.
7. The polycarbosilane and silicon composition of claim 1 wherein the average particle size of the elemental silicon is less than 50nm.
8. The polycarbosilane and silicon composition of claim 1 further comprising SiC ceramic powder; the mass fraction of the SiC ceramic powder is 10-30%.
9. The polycarbosilane and silicon composition of claim 1 further comprising a thermally decomposed free radical initiator.
10. Use of a polycarbosilane and silicon composition, characterized in that it is pyrolytically converted into SiC ceramic according to any one of claims 1 to 9, comprising at least;
is applied to the preparation of SiC ceramic matrix composite materials and porous SiC ceramics,
is applied to filling of ceramic or graphite materials,
is applied to preparing protective coatings of carbon materials or metals,
applied to the connection of ceramic or ceramic matrix composite materials,
the method is applied to the field of energy storage.
SiC ceramic, characterized in that it is formed by the pyrolytic conversion of a polycarbosilane according to any one of claims 1 to 9 with a silicon composition.
SiC ceramic matrix composite, characterized in that after impregnating the polycarbosilane and silicon composition according to any one of claims 1-9 with fibres, it is thermally pyrolysed to a fibre reinforced SiC ceramic matrix composite, densification is achieved by repeated impregnation of the polycarbosilane and silicon composition and thermal decomposition.
13. The SiC ceramic matrix composite of claim 12, wherein the fibers comprise at least one of linear fiber bundles, planar fiber cloth, or three-dimensional fiber preform.
14. The SiC ceramic matrix composite of claim 13, wherein the linear fiber bundles are impregnated with the polycarbosilane and silicon composition and then wound or woven to form a tubular member, and the tubular member is heated under negative pressure to crosslink the polycarbosilane and cure it, and then pyrolyzed to above 1400 ℃.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807347A (en) * | 2006-01-26 | 2006-07-26 | 中国科学院上海硅酸盐研究所 | Boride-silicon carbide multiple phase ceramic and its preparation method |
| CN1850730A (en) * | 2006-05-26 | 2006-10-25 | 中国科学院上海硅酸盐研究所 | Method for preparing carbon-fiber reinforced silicon carbonate base composite by gas-phase siliconizing technology |
| CN101157556A (en) * | 2007-09-26 | 2008-04-09 | 中南大学 | Method for preparing nano SiC particle reinforced MoSi2 radical composite material by polymer cracking-reaction hot-pressing |
| CN103474666A (en) * | 2013-07-23 | 2013-12-25 | 江苏华东锂电技术研究院有限公司 | Preparation method for negative electrode active material of lithium ion battery |
| CN107556011A (en) * | 2017-08-23 | 2018-01-09 | 中国建筑材料科学研究总院 | SiCf/ SiC ceramic matrix composite material and preparation method thereof |
| CN108424160A (en) * | 2018-03-28 | 2018-08-21 | 中国航发北京航空材料研究院 | A kind of preparation method of short cycle silicon carbide fiber reinforced silicon carbide composite material |
| CN110078516A (en) * | 2019-05-14 | 2019-08-02 | 西北工业大学 | The quasi-isotropic SiC of high-volume fractional short fiber reinforcedfThe preparation method of/SiC ceramic matrix composite material |
| CN110087822A (en) * | 2016-12-27 | 2019-08-02 | 三菱铝株式会社 | The manufacturing method of the solder piece of solder without soldering acid, solder without soldering acid method and heat exchanger |
| CN111908934A (en) * | 2020-07-31 | 2020-11-10 | 中国航发北京航空材料研究院 | Preparation method of in-situ reaction SiC composite material in fiber bundle |
| CN112745135A (en) * | 2021-01-08 | 2021-05-04 | 武汉科技大学 | Magnesium oxide-silicon carbide-carbon porous ceramic filter and preparation method thereof |
-
2022
- 2022-12-14 CN CN202211630724.5A patent/CN116023147A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807347A (en) * | 2006-01-26 | 2006-07-26 | 中国科学院上海硅酸盐研究所 | Boride-silicon carbide multiple phase ceramic and its preparation method |
| CN1850730A (en) * | 2006-05-26 | 2006-10-25 | 中国科学院上海硅酸盐研究所 | Method for preparing carbon-fiber reinforced silicon carbonate base composite by gas-phase siliconizing technology |
| CN101157556A (en) * | 2007-09-26 | 2008-04-09 | 中南大学 | Method for preparing nano SiC particle reinforced MoSi2 radical composite material by polymer cracking-reaction hot-pressing |
| CN103474666A (en) * | 2013-07-23 | 2013-12-25 | 江苏华东锂电技术研究院有限公司 | Preparation method for negative electrode active material of lithium ion battery |
| CN110087822A (en) * | 2016-12-27 | 2019-08-02 | 三菱铝株式会社 | The manufacturing method of the solder piece of solder without soldering acid, solder without soldering acid method and heat exchanger |
| CN107556011A (en) * | 2017-08-23 | 2018-01-09 | 中国建筑材料科学研究总院 | SiCf/ SiC ceramic matrix composite material and preparation method thereof |
| CN108424160A (en) * | 2018-03-28 | 2018-08-21 | 中国航发北京航空材料研究院 | A kind of preparation method of short cycle silicon carbide fiber reinforced silicon carbide composite material |
| CN110078516A (en) * | 2019-05-14 | 2019-08-02 | 西北工业大学 | The quasi-isotropic SiC of high-volume fractional short fiber reinforcedfThe preparation method of/SiC ceramic matrix composite material |
| CN111908934A (en) * | 2020-07-31 | 2020-11-10 | 中国航发北京航空材料研究院 | Preparation method of in-situ reaction SiC composite material in fiber bundle |
| CN112745135A (en) * | 2021-01-08 | 2021-05-04 | 武汉科技大学 | Magnesium oxide-silicon carbide-carbon porous ceramic filter and preparation method thereof |
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