CN102093055B - Method for preparing silicon carbide/titanium carbide composite ceramics - Google Patents
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- CN102093055B CN102093055B CN2010106177399A CN201010617739A CN102093055B CN 102093055 B CN102093055 B CN 102093055B CN 2010106177399 A CN2010106177399 A CN 2010106177399A CN 201010617739 A CN201010617739 A CN 201010617739A CN 102093055 B CN102093055 B CN 102093055B
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Abstract
The invention provides a method for preparing silicon carbide/titanium carbide composite ceramics, belonging to the field of inorganic non-metallic materials. The method comprises the following steps: under the protection of inert atmosphere, adding titanocene dichloride and hyperbranched polycarbosilane to a solvent to obtain solution; and depriving the solvent in the solution, ensuring the residues to under cracking reaction in the inert atmosphere and obtaining the silicon carbide/titanium carbide composite ceramics immediately after the reaction is completed. The problem that the mechanical property and high temperature resistance of the composite ceramics are degraded because oxygen is introduced in the process of preparing the silicon carbide/titanium carbide composite ceramics by the existing precursor pyrolysis method is solved by the method provided by the invention, the used process is simple, the cost is low and the prepared silicon carbide/titanium carbide composite ceramics have high yield.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material, relate to a kind of preparation method of silicon carbide/carbon titanium complex phase ceramic.
Background technology
Silicon carbide ceramics has broad-band gap, high heat conductance, HMP, high electron mobility, high disruptive critical voltage and good characteristics such as chemicalstability; Become the ideal material of extreme electronics device such as development high-frequency high-power, high temperature resistant, anti-irradiation and circuit, all have a wide range of applications aspect many in communication, automobile, Aeronautics and Astronautics, national defence etc.The precursor conversion method is the main method of preparation silicon carbide ceramics; By Yajima of northeastern Japan university etc. (1, Yajima S.Development of asilicon carbide fiber of high tensile strength [J] .Nature; 1976,261 (5562): 683-685) in 1976 years initiatives.The common precursor of silicon carbide ceramics is a Polycarbosilane, also is called the Yajima Polycarbosilane.According to document (2, Cao F; Li X D; PengP, et al.Structural evolution and ass-ociated properties on conversion from Si-C-O-Al ceramicfibers to Si-C-Al fibers by sintering [J] .J Mater Chem, 2002; 12 (3), 606-610; 3, Hasegawa Yoshio.Factors affecting the thermal stability of continuous SiC fibres [J] .Compo Sci Technol 1990; 37 (1-3): 37-54) report, there is the Si-C-O phase in the silicon carbide ceramics that is prepared by polycarbosilane precusor, when working temperature is higher than 1200 ℃; Si-C-O phase decomposition and carborundum grain are grown up; Produce a large amount of holes, cause mechanical property sharply to descend, thereby influence its resistance to elevated temperatures.At present; The main method that improves silicon carbide ceramics superhigh temperature resistant performance is in silicon carbide ceramics, to introduce heterogeneous element; The grain growth of two phases or multiphase mixture pottery is slower than one-component ceramic under the high temperature, and heterogeneous element gets into carborundum grain, but because of the ligancy difference; Crystal such as the carbide of its formation can suppress silit grain growing under hot conditions, reach the purpose that improves silit superhigh temperature resistant performance.Ube company adds titanium elements in precursor, prepared silicon carbide ceramics fiber use temperature up to 1500 ℃ about.Therefore, silicon carbide/carbon titanium complex phase ceramic is for silicon carbide ceramics, and its resistance to elevated temperatures significantly improves.
At present, the main method of preparation silicon carbide/carbon titanium complex phase ceramic is the precursor conversion method, prepares silicon carbide/carbon titanium complex phase ceramic through the direct cracking of titaniferous precursor.Be at first Japanese scholar (4, Song Y C, Hasegawa Y, Yang S J, et al.Ceramic fibres from polymer precursor containing Si-O-Ti bonds [J] .J Mater Sci, 1988,23:1911-1920; 5, Song Y, Feng C, Tan Z, et al.Structure and properties of polytitanocarbosilane asthe precursor of SiC-TiC fibre [J] J Mater Sci Lett, 1990,9:1310-1313; 6, Hasegawa Yoshio; Feng C X; Song Y C, et al.Ceramic fibres from polymer precursor containing Si-O-Ti bonds [J] .JMater Sci, 1991; 26:3657-3664) with solid-state Yajima Polycarbosilane and tetrabutyl titanate in xylene solution, under the inert atmosphere protection prepared in reaction spinning with gathering titanium carbon silane.Gather the crystallite that the split product of titanium carbon silane when 1400 ℃ and 1700 ℃ is silit and titanium carbide (7, Yajima S; Iwai T; Yamamura T; Et al.Synthesis of a polytitanocarbosilaneand its conversion into inorganic compounds [J] Mater Chem, 1981,16:1349-1355.).In addition; The introducing of titanium can suppress at high temperature crystallization of silit (8, Ishikawa T; Yamamura T; Okamura K.Productionmechanism of Polytitanocarbosilane and its conversion ofthe polymer into inorganic materials [J] J Mater Sci, 1992,27:6627-6634).At normal temperatures, the Yajima Polycarbosilane is solid-state, has the complex construction of branching, cyclisation and a small amount of Si-Si key, and the average structure formula is-[SiH (CH
3)-CH
2]
n-.Because the hydrogen on the silicon-hydrogen bond in the oxygen attack Polycarbosilane of butyl(tetra)titanate; Nucleophilic substitution reaction takes place; The form of titanium atom with chemical bond is incorporated in the Polycarbosilane, at high temperature gathers the cracking of titanium carbon silane, the uncombined carbon reduction titanium oxide of formation forms titanium carbide.The effusion of gases such as carbon monoxide, silicon monoxide is arranged under the high temperature, form hole, make fibrous texture become loose, with the mechanical property of influence pottery at fiber surface.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of silicon carbide/carbon titanium complex phase ceramic.
The preparation method of said a kind of silicon carbide/carbon titanium complex phase ceramic may further comprise the steps:
1) under inert atmosphere protection, with getting solution in cyclopentadienyl titanium dichloride and the hyperbranched Polycarbosilane adding solvent;
2) with the solvent removal in the step 1) gained solution, residuum carries out scission reaction under inert atmosphere, and reaction promptly gets silicon carbide/carbon titanium complex phase ceramic after finishing.
In step 1), the mass ratio of said cyclopentadienyl titanium dichloride and hyperbranched Polycarbosilane can be (0.1～1): 1; Said solvent can be DMSO 99.8MIN., N, trichloromethane, methylene dichloride, THF or normal hexane; The massfraction of cyclopentadienyl titanium dichloride can be 1%～10% in the said solution; The average structure formula of said hyperbranched Polycarbosilane is-[SiHR-CH
2]
n-, wherein R is Wasserstoffatoms, alkyl, alkenyl or alkynyl, n>=3.
In step 2) in, said solvent removal can adopt vacuum decompression distillatory method.The temperature of said scission reaction can be 1200～1800 ℃, and the time of scission reaction can be 10～120min.
The present invention adopts hyperbranched Polycarbosilane and cyclopentadienyl titanium dichloride blend, prepares a kind of hyperbranched Polycarbosilane/cyclopentadienyl titanium dichloride hydridization precursor of anaerobic.Used hyperbranched Polycarbosilane is liquid at normal temperatures, mainly contains SiH
3CH
2, SiH
2(CH
2)
2, SiH (CH
2)
3, Si (CH
2)
4Four kinds of structural units have the super branched molecule structure, compare with the Yajima Polycarbosilane, and silicon-hydrogen bond content is higher.Cyclopentadienyl titanium dichloride in hyperbranched Polycarbosilane/cyclopentadienyl titanium dichloride hydridization precursor not only can be used as the titanium source and prepares the titanium carbide pottery, and crosslinking reaction that can the hyperbranched Polycarbosilane of catalysis, thereby improves the ceramic yield of hyperbranched Polycarbosilane.Therefore, hyperbranched Polycarbosilane/cyclopentadienyl titanium dichloride hydridization precursor is applicable to the silicon carbide/carbon titanium complex phase ceramic that preparation is fine and close.The invention solves in the existing Stainless Steel via Precursor Pyrolysis silicon carbide/carbon titanium complex phase ceramic process; The problem that complex phase ceramic mechanical property that causes because introduce oxygen and resistance to elevated temperatures descend; Used technology is simple, and is with low cost, and the silicon carbide/carbon titanium complex phase ceramic productive rate that makes is high.
Compared with prior art, advantage of the present invention is following:
1) cyclopentadienyl titanium dichloride not only can be used as the titanium source and prepares the titanium carbide pottery, and crosslinking reaction that can the hyperbranched Polycarbosilane of catalysis, thereby improves the ceramic yield of hyperbranched Polycarbosilane, is convenient to obtain fine and close silicon carbide/carbon titanium complex phase ceramic.
2) titanium carbide can suppress the growth of silit crystallite crystal grain, improves the fire-resistant oxidation resistant performance of matrix material.
3) content through cyclopentadienyl titanium dichloride in the control hydridization precursor, thus realize the controlled of titanium content in the complex phase ceramic.
4) anaerobic in hyperbranched Polycarbosilane/cyclopentadienyl titanium dichloride hydridization precursor reduces overflowing of gas in the Pintsch process process, and the ceramic dense degree is high, and is simple to operate, is easy to through engineering approaches.
Description of drawings
Fig. 1 is the TGA spectrogram of precursor.In Fig. 1, X-coordinate be temperature (℃), ordinate zou is ceramic yield (%); Curve a is hyperbranched Polycarbosilane/cyclopentadienyl titanium dichloride hydridization precursor TGA; Curve b is hyperbranched Polycarbosilane TGA.
Fig. 2 is the X-ray diffraction spectrogram of precursor split product.In Fig. 2; X-coordinate be diffraction angle 2 θ (°); Ordinate zou is diffraction intensity (a.u.); Curve a is that hyperbranched Polycarbosilane/cyclopentadienyl titanium dichloride hydridization precursor is at 1400 ℃ of cracking 120min split products; Curve b be hyperbranched Polycarbosilane at 1400 ℃ of cracking 120min split products, ▲ be silit,
is titanium carbide.
Embodiment
Embodiment 1
1) under inert atmosphere protection, dissolve cyclopentadienyl titanium dichloride with N, stir, add hyperbranched Polycarbosilane again, the mass ratio of cyclopentadienyl titanium dichloride, hyperbranched Polycarbosilane and N is 1: 1: 15;
2) the mixture vacuum decompression distillation with the step 1) gained removes solvent;
3) with step 2) mixture of gained under inert atmosphere, at 1400 ℃ of following cracking 120min, make silicon carbide/carbon titanium complex phase ceramic.
The average structure formula of hyperbranched Polycarbosilane is-[SiH
1.7(CH
3)
0.2(CH
2CH=CH
2)
0.1-CH
2]
n-, measure (referring to Fig. 1) by thermogravimetry (TGA), the ceramic yield of 1400 ℃ of hyperbranched Polycarbosilane/cyclopentadienyl titanium dichloride hydridization precursor is 81.1%, and the ceramic yield of 1400 ℃ of hyperbranched Polycarbosilanes of raw material is 68.9%; The silicon carbide/carbon titanium complex phase ceramic chemical constitution of preparation is SiC thus
1.120Ti
0.203X-ray diffraction spectrum figure shows: the silicon B-carbide crystallite of its formation and titanium carbide crystallite grain-size are respectively 15nm and 51nm, and the split product formation grain-size of the hyperbranched Polycarbosilane of raw material under 1400 ℃ is the silicon B-carbide crystallite (referring to Fig. 2) of 31nm.
Embodiment 2
1) under inert atmosphere protection, dissolve cyclopentadienyl titanium dichloride with THF, stir, add hyperbranched Polycarbosilane again, the mass ratio of cyclopentadienyl titanium dichloride, hyperbranched Polycarbosilane and THF is 1: 3.3: 65;
2) the mixture vacuum decompression distillation with the step 1) gained removes solvent;
3) with step 2) mixture of gained under inert atmosphere, at 1300 ℃ of following cracking 10min, make silicon carbide/carbon titanium complex phase ceramic.
The average structure formula of raw materials used hyperbranched Polycarbosilane is-[SiH
1.5(CH
3)
0.5-CH
2]
n-, to measure by thermogravimetry (TGA), the ceramic yield of 1300 ℃ of hyperbranched Polycarbosilane/cyclopentadienyl titanium dichloride hydridization precursor is 76.4%, and the ceramic yield of 1300 ℃ of hyperbranched Polycarbosilanes of raw material is 67.5%; The silicon carbide/carbon titanium complex phase ceramic chemical constitution of preparation is SiC thus
1.250Ti
0.068, the silicon B-carbide crystallite of formation and titanium carbide crystallite grain-size are respectively 12nm and 30nm, and the split product formation grain-size of the hyperbranched Polycarbosilane of raw material under 1300 ℃ is the silicon B-carbide crystallite of 21nm.
Embodiment 3
1) under inert atmosphere protection, dissolve cyclopentadienyl titanium dichloride with trichloromethane, stir, add hyperbranched Polycarbosilane again, the mass ratio of cyclopentadienyl titanium dichloride, hyperbranched Polycarbosilane and trichloromethane is 1: 2: 30.
2) the mixture vacuum decompression distillation with the step 1) gained removes solvent.
3) with step 2) mixture of gained under inert atmosphere, at 1400 ℃ of following cracking 30min, make silicon carbide/carbon titanium complex phase ceramic.
The average structure formula of the hyperbranched Polycarbosilane of employed raw material is-[SiH
1.5(CH
3)
0.3(C ≡ CH)
0.2-CH
2]
n-, to measure by thermogravimetry (TGA), the ceramic yield of 1400 ℃ of hyperbranched Polycarbosilane/cyclopentadienyl titanium dichloride hydridization precursor is 82.1%, and the ceramic yield of 1400 ℃ of hyperbranched Polycarbosilanes of raw material is 72.9%; The silicon carbide/carbon titanium complex phase ceramic chemical constitution of preparation is SiC thus
1.150Ti
0.099, the silicon B-carbide crystallite of formation and titanium carbide crystallite grain-size are respectively 16nm and 48nm, and the split product formation grain-size of the hyperbranched Polycarbosilane of raw material under 1400 ℃ is the silicon B-carbide crystallite of 28nm.
Embodiment 4
1) under inert atmosphere protection, dissolve cyclopentadienyl titanium dichloride with methylene dichloride, stir, add hyperbranched Polycarbosilane again, the mass ratio of cyclopentadienyl titanium dichloride, hyperbranched Polycarbosilane and methylene dichloride is 1: 3.3: 35.
2) the mixture vacuum decompression distillation with the step 1) gained removes solvent.
3) with step 2) mixture of gained under inert atmosphere, at 1600 ℃ of following cracking 30min, make silicon carbide/carbon titanium complex phase ceramic.
The average structure formula of the hyperbranched Polycarbosilane of employed raw material is-[SiH
1.6(C H
3)
0.3(CH
2CH=CH
2)
0.1-CH
2]
n-, to measure by thermogravimetry (TGA), the ceramic yield of 1600 ℃ of hyperbranched Polycarbosilane/cyclopentadienyl titanium dichloride hydridization precursor is 74.8%, and the ceramic yield of 1600 ℃ of hyperbranched Polycarbosilanes of raw material is 66.2%; The silicon carbide/carbon titanium complex phase ceramic chemical constitution of preparation is SiC thus
1.350Ti
0.064, the silicon B-carbide crystallite of formation and titanium carbide crystallite grain-size are respectively 22nm and 60nm, and the split product formation grain-size of the hyperbranched Polycarbosilane of raw material under 1600 ℃ is the silicon B-carbide crystallite of 36nm.
Embodiment 5
1) under inert atmosphere protection, use the dmso solution cyclopentadienyl titanium dichloride, stir, add hyperbranched Polycarbosilane again, the mass ratio of cyclopentadienyl titanium dichloride, hyperbranched Polycarbosilane and DMSO 99.8MIN. is 1: 2: 10.
2) the mixture vacuum decompression distillation with the step 1) gained removes solvent.
3) with step 2) mixture of gained under inert atmosphere, at 1800 ℃ of following cracking 60min, make silicon carbide/carbon titanium complex phase ceramic.
The average structure formula of the hyperbranched Polycarbosilane of employed raw material is-[SiH
1.6(CH
3)
0.4-CH
2]
n-, to measure by thermogravimetry (TGA), the ceramic yield of 1800 ℃ of hyperbranched Polycarbosilane/cyclopentadienyl titanium dichloride hydridization precursor is 66.8%, and the ceramic yield of 1800 ℃ of hyperbranched Polycarbosilanes of raw material is 58.2%; The silicon carbide/carbon titanium complex phase ceramic chemical constitution of preparation is SiC thus
1.120Ti
0.108, the silicon B-carbide crystallite of formation and titanium carbide crystallite grain-size are respectively 24nm and 75nm, and the split product formation grain-size of the hyperbranched Polycarbosilane of raw material under 1800 ℃ is the silicon B-carbide crystallite of 46nm.
Embodiment 6
1) under inert atmosphere protection, use the n-hexane dissolution cyclopentadienyl titanium dichloride, stir, add hyperbranched Polycarbosilane again, the mass ratio of cyclopentadienyl titanium dichloride, hyperbranched Polycarbosilane and normal hexane is 1: 10: 80.
2) the mixture vacuum decompression distillation with the step 1) gained removes solvent.
3) with step 2) mixture of gained under inert atmosphere, at 1200 ℃ of following cracking 120min, make silicon carbide/carbon titanium complex phase ceramic.
The average structure formula of the hyperbranched Polycarbosilane of employed raw material liquid is-[SiH
2-CH
2]
n-, to measure by thermogravimetry (TGA), the ceramic yield of hyperbranched Polycarbosilane in the time of 1200 ℃/cyclopentadienyl titanium dichloride hydridization precursor is 75.2%, and the ceramic yield of 1200 ℃ of hyperbranched Polycarbosilanes of raw material is 70.6%; The silicon carbide/carbon titanium complex phase ceramic chemical constitution of preparation is SiC thus
1.12Ti
0.022, the silicon B-carbide crystallite of formation and titanium carbide crystallite grain-size are respectively 5nm and 10nm, and the split product formation grain-size of the hyperbranched Polycarbosilane of raw material under 1200 ℃ is the silicon B-carbide crystallite of 11nm.
Claims (4)
1. the preparation method of a silicon carbide/carbon titanium complex phase ceramic is characterized in that may further comprise the steps:
1) under inert atmosphere protection, with getting solution in cyclopentadienyl titanium dichloride and the hyperbranched Polycarbosilane adding solvent; The mass ratio of said cyclopentadienyl titanium dichloride and hyperbranched Polycarbosilane is 0.1～1: 1; The average structure formula of said hyperbranched Polycarbosilane is-[SiHR-CH
2]
n-, wherein R is Wasserstoffatoms, alkyl, alkenyl or alkynyl, n>=3;
2) with the solvent removal in the step 1) gained solution, residuum carries out scission reaction under inert atmosphere, and reaction promptly gets silicon carbide/carbon titanium complex phase ceramic after finishing, and the temperature of said scission reaction is 1200～1800 ℃, and the time of scission reaction is 10～120min.
2. the preparation method of a kind of silicon carbide/carbon titanium complex phase ceramic as claimed in claim 1 is characterized in that in step 1), and said solvent is DMSO 99.8MIN., N, trichloromethane, methylene dichloride, THF or normal hexane.
3. the preparation method of a kind of silicon carbide/carbon titanium complex phase ceramic as claimed in claim 1 is characterized in that in step 1), and the massfraction of cyclopentadienyl titanium dichloride is 1%～10% in the said solution.
4. the preparation method of a kind of silicon carbide/carbon titanium complex phase ceramic as claimed in claim 1 is characterized in that in step 2) in, said solvent removal is to adopt vacuum decompression distillatory method.
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| CN102503425A (en) * | 2011-10-12 | 2012-06-20 | 厦门大学 | Preparation method of silicon carbide/zirconium carbide composite ceramic |
| CN103275327B (en) * | 2013-06-15 | 2015-05-13 | 厦门大学 | Method for preparing liquid anaerobic polytitanocarbosilane |
| US20170088674A1 (en) * | 2014-08-14 | 2017-03-30 | Institute Of Process Engineering, Chinese Academy Of Sciences | Polymetallocarbosilane from organic metal catalyzed polymerization and uses thereof |
| CN114591087A (en) * | 2020-12-03 | 2022-06-07 | 中国科学院上海硅酸盐研究所 | Complex-phase silicon carbide conductive ceramic taking MAX-phase titanium aluminum carbide as auxiliary agent and preparation method thereof |
| CN115180950B (en) * | 2022-07-28 | 2023-05-19 | 中南大学 | Multi-carbide/silicon carbide nano multiphase ceramic and preparation method thereof |
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| EP1452488B1 (en) * | 2001-10-11 | 2005-03-09 | Universidad de Sevilla | Method of producing silicon carbide ceramics from plant precursors |
| CN1793054A (en) * | 2005-11-11 | 2006-06-28 | 中国人民解放军国防科学技术大学 | Process for preparing heat guarding plate of Cf/SiC high temp, resistant and washing resistant by pioneer method |
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