CN101054309A - Method for preparing porous silicon carbonitride by oxygen-free sol-gel reaction - Google Patents
Method for preparing porous silicon carbonitride by oxygen-free sol-gel reaction Download PDFInfo
- Publication number
- CN101054309A CN101054309A CN 200710057495 CN200710057495A CN101054309A CN 101054309 A CN101054309 A CN 101054309A CN 200710057495 CN200710057495 CN 200710057495 CN 200710057495 A CN200710057495 A CN 200710057495A CN 101054309 A CN101054309 A CN 101054309A
- Authority
- CN
- China
- Prior art keywords
- silane
- dichlorosilane
- acid amides
- gel
- porous silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Ceramic Products (AREA)
Abstract
The present invention discloses a method for preparing porous silicon carbonitride through a sol-gel reaction without oxygen containing and belongs to the field of ceramics preparation technology. Said mehtod comprises the following steps: mixing dichlorosilane and trichlorosilane together according to different molar ratios; mixing the mixed chlorosilane with imides according to a certain molar ratio; reacting at 10-150 DEG C and at an atmosphere of argon, nitrogen or mixture of them to form a gel; drying and then thermal pyrolyzing the gel, followed with heat preservation and colling, to get a porous silicon carbonitride porcelain. As compared with conventional methods, said invention possesses the advantages that said method can prepare directly porous silicon carbonitride porcelain with pore size of 0.01-100 mu m and porosity rate of 92% without using a template, wherein the both the pore size and the porosity rate are controllable. The produced porous silicon carbonitride porcelain possesses excellent high-temperature resistance, oxidation resistance and chemical resistance, as well as excellent permeability, and is applicable broad to the fields of high-efficience adsorption, advanced catalysis, optoelectronic device and high-tech energy.
Description
Technical field
The present invention relates to a kind of mixed chlorosilane and inferior acid amides of adopting by the method for preparing porous silicon carbonitride by oxygen-free sol-gel reaction, belong to the ceramics processing field.
Background technology
Porous ceramics is widely used in various fields such as Metal smelting, petrochemical complex, molecular sieve, chemisorption, sewage disposal, lithium ion battery and opto-electronic devices.Traditional porous ceramics is oxide-base synthesize ceramic or mineral material, and its preparation method is confined to template.But property that oxide ceramics is high temperature resistant (＜1000 ℃), resistance of oxidation and resistance to chemical attack are all very limited, can not satisfy the requirement of materials used under the extreme environment of ultrahigh-temperature deep-etching.Owing to the existence of template, be difficult to prepare the pottery of high porosity (＞90%), this has limited its Application Areas greatly.Carbonitride of silicium has superpower high thermal resistance (1600～2000 ℃), oxidation-resistance and resistance to chemical corrosion, high temperature and creep resistance excellent specific properties such as (high temperature almost do not have creep), is the ideal material that extreme environment uses.Current, only there is external a few researchist to adopt polysilane to prepare the porous carbon silicon nitride ceramics by hard template method, its void content and aperture all depend on template to a great extent, also do not prepare void content and surpass 80% porous carbon silicon nitride ceramics, and need carry out the complicated template procedure that goes.
Summary of the invention
The object of the present invention is to provide a kind of method that adopts mixed chlorosilane and inferior acid amides by preparing porous silicon carbonitride by oxygen-free sol-gel reaction.This method has been avoided the complicated template procedure that goes, and the porous carbon silicon nitride ceramics of preparation has high void content and reaches 92%.
For achieving the above object, the present invention is realized by following technical proposals: a kind of method by preparing porous silicon carbonitride by oxygen-free sol-gel reaction.It is characterized in that comprising following detailed process:, mixed in 1: 20 in molar ratio～20: 1 with wherein a kind of of trichlorosilane alkane, trichloromethyl silane, trieline silane and trichlorophenyl silane a kind of and dimethyldichlorosilane(DMCS), dichloromethyl hydrogen silane, divinyl dichlorosilane, diphenyl dichlorosilane, methyl ethylene dichlorosilane, dichloroethylene hydrogen silane, dichloromethyl phenylsilane and ethenylphenyl dichlorosilane wherein.Mixed chlorosilane was mixed with trimethyl silicon based carbonization two inferior acid amides, the silica-based carbonization two inferior acid amides of trivinyl or the silica-based carbonization two inferior acid amides of triphenyl in 12: 1 in molar ratio～1: 12, reaction forms gel in 10～150 ℃ of following argon gas, nitrogen or their mixed atmosphere, gel is dry down at 50～250 ℃, the gained xerogel is 500～2000 ℃ of following thermo-crackings, 1～100 ℃/min of temperature rise rate, soaking time 1～20h, 1～100 ℃/min of rate of temperature fall, directly forming the aperture is the porous carbon silicon nitride ceramics of 0.01～100 μ m.
The mol ratio of above-mentioned trichlorosilane alkane, trichloromethyl silane, trieline silane or trichlorophenyl silane and dimethyldichlorosilane(DMCS), dichloromethyl hydrogen silane, divinyl dichlorosilane, diphenyl dichlorosilane, methyl ethylene dichlorosilane, dichloroethylene hydrogen silane, dichloromethyl phenylsilane or ethenylphenyl dichlorosilane 5: 1～1: 2; Mixed chlorosilane and trimethyl silicon based carbonization two inferior acid amides, the silica-based carbonization two inferior acid amides of trivinyl or the silica-based carbonization two inferior acid amides of triphenyl 5: 1 in molar ratio～1: 3.
The invention has the advantages that with traditional method and compare that it is 0.01～100 μ m, void content 92% porous carbon silicon nitride ceramics that present method is not directly prepared the aperture by template, pore size and void content are all controlled in the process.Prepared porous carbon silicon nitride ceramics has good high temperature resistant, oxidation-resistance and resistance to chemical corrosion, has widely in efficient absorption, advanced catalysis, opto-electronic device, energy high-tech sector and uses.In addition, present technique can also be expanded to other systems and prepare porous ceramics.
Description of drawings
Fig. 1: the SEM photo that makes the porous carbon silicon nitride ceramics for the embodiment of the invention one.
Fig. 2: the SEM photo that makes the porous carbon silicon nitride ceramics for the embodiment of the invention two.
Fig. 3: the SEM photo that makes the porous carbon silicon nitride ceramics for the embodiment of the invention three.
Fig. 4: the SEM photo that makes the porous carbon silicon nitride ceramics for the embodiment of the invention four.
Embodiment
Embodiment one: in 35 ℃ of following argon gas atmosphere, with 1ml dimethyldichlorosilane(DMCS) and 0.07ml trichlorosilane alkane and the trimethyl silicon based carbonization two inferior acid amides hybrid reactions formation gels of 1.41ml, gel is dry down at 150 ℃, the gained xerogel is 1200 ℃ of following thermo-crackings, 5 ℃/min of temperature rise rate, soaking time 2h, 5 ℃/min of rate of temperature fall reduces to 20 ℃.Make the porous carbon silicon nitride ceramics of mean pore size 2.5 μ m, void content 13.8%.
Embodiment two: in 35 ℃ of following nitrogen atmospheres, with 1ml diphenyl dichlorosilane and 0.14ml trichloromethyl silane and the trimethyl silicon based carbonization two inferior acid amides hybrid reactions formation gels of 2.5ml, gel is dry down at 150 ℃, the gained xerogel is 1200 ℃ of following thermo-crackings, 5 ℃/min of temperature rise rate, soaking time 2h, 5 ℃/min of rate of temperature fall reduces to 20 ℃.Make mean pore size 1 μ m, void content 26% porous carbon silicon nitride ceramics.As shown in Figure 1.
Embodiment three: in 35 ℃ of following argon gas atmosphere, with 1ml dichloroethylene hydrogen silane and 0.7ml trieline silane and the trimethyl silicon based carbonization two inferior acid amides hybrid reactions formation gels of 3.1ml, gel is dry down at 150 ℃, the gained xerogel is 1200 ℃ of following thermo-crackings, 5 ℃/min of temperature rise rate, soaking time 2h, 5 ℃/min of rate of temperature fall reduces to 20 ℃.Make mean pore size 0.4 μ m, void content 45% porous carbon silicon nitride ceramics.
Embodiment four: in 35 ℃ of following argon gas atmosphere, with 1ml dichloromethyl hydrogen silane and 1.2ml trieline silane and the trimethyl silicon based carbonization two inferior acid amides hybrid reactions formation gels of 5.5ml, gel is dry down at 150 ℃, the gained xerogel is 1200 ℃ of following thermo-crackings, 5 ℃/min of temperature rise rate, soaking time 2h, 5 ℃/min of rate of temperature fall reduces to 20 ℃.Make mean pore size 2 μ m, void content 92% porous carbon silicon nitride ceramics.As shown in Figure 2.
Embodiment five: in 35 ℃ of following argon gas atmosphere, with 1ml ethenylphenyl dichloro silicon and 0.07ml trieline silane and the trimethyl silicon based carbonization two inferior acid amides hybrid reactions formation gels of 1.41ml, gel is dry down at 150 ℃, the gained xerogel is 1200 ℃ of following thermo-crackings, 10 ℃/min of temperature rise rate, soaking time 4h, 5 ℃/min of rate of temperature fall reduces to 20 ℃.Make the porous carbon silicon nitride ceramics of the average 1.5 μ m in aperture, void content 6%.
Embodiment six: in 35 ℃ of following argon gas and nitrogen mixture atmosphere, with 1ml ethenylphenyl dichloro silicon and 0.07ml trieline silane and the trimethyl silicon based carbonization two inferior acid amides hybrid reactions formation gels of 1.41ml, gel is dry down at 150 ℃, the gained xerogel is 1200 ℃ of following thermo-crackings, 10 ℃/min of temperature rise rate, soaking time 4h, 10 ℃/min of rate of temperature fall reduces to 20 ℃.Make the porous carbon silicon nitride ceramics of mean pore size 10 μ m, void content 35%.As shown in Figure 3.
Embodiment seven: in 35 ℃ of following argon gas atmosphere, with 1ml dichloromethyl hydrogen silane and 1.2ml trieline silane and the silica-based carbonization two inferior acid amides hybrid reactions formation gels of 5.5ml trivinyl, gel is dry down at 150 ℃, the gained xerogel is 1200 ℃ of following thermo-crackings, 20 ℃/min of temperature rise rate, soaking time 2h, 20 ℃/min of rate of temperature fall reduces to 20 ℃.Make mean pore size 60 μ m, void content 90% porous carbon silicon nitride ceramics.As shown in Figure 4.
Embodiment eight: in 35 ℃ of following argon gas atmosphere, with 1ml methyl ethylene dichlorosilane and 1.2ml trichlorophenyl silane and the silica-based carbonization two inferior acid amides hybrid reactions formation gels of 5.5ml triphenyl, gel is dry down at 150 ℃, the gained xerogel is 1200 ℃ of following thermo-crackings, 10 ℃/min of temperature rise rate, soaking time 2h, 20 ℃/min of rate of temperature fall reduces to 20 ℃.Make mean pore size 40 μ m, void content 85% porous carbon silicon nitride ceramics.
Claims (2)
1. the method for a preparing porous silicon carbonitride by oxygen-free sol-gel reaction, it is characterized in that comprising following detailed process: with trichlorosilane alkane, trichloromethyl silane, trieline silane and trichlorophenyl silane a kind of and dimethyldichlorosilane(DMCS) wherein, the dichloromethyl hydrogen silane, the divinyl dichlorosilane, diphenyl dichlorosilane, the methyl ethylene dichlorosilane, the dichloroethylene hydrogen silane, wherein a kind of of dichloromethyl phenylsilane and ethenylphenyl dichlorosilane, mixed in 1: 20 in molar ratio～20: 1, with mixed chlorosilane and trimethyl silicon based carbonization two inferior acid amides, silica-based carbonization two inferior acid amides of trivinyl or the silica-based carbonization two inferior acid amides of triphenyl mixed in 12: 1 in molar ratio～1: 12, at 10～150 ℃ of following argon gas, reaction forms gel in nitrogen or their mixed atmosphere, gel is dry down at 50～250 ℃, the gained xerogel is 500～2000 ℃ of following thermo-crackings, 1～100 ℃/min of temperature rise rate, soaking time 1～20h, 1～100 ℃/min of rate of temperature fall, directly forming the aperture is the porous carbon silicon nitride ceramics of 0.01～100 μ m.
2. by the method for the described preparing porous silicon carbonitride by oxygen-free sol-gel reaction of claim 1, it is characterized in that: the mol ratio of trichlorosilane alkane, trichloromethyl silane, trieline silane or trichlorophenyl silane and dimethyldichlorosilane(DMCS), dichloromethyl hydrogen silane, divinyl dichlorosilane, diphenyl dichlorosilane, methyl ethylene dichlorosilane, dichloroethylene hydrogen silane, dichloromethyl phenylsilane or ethenylphenyl dichlorosilane 5: 1～1: 2; Mixed chlorosilane and trimethyl silicon based carbonization two inferior acid amides, the silica-based carbonization two inferior acid amides of trivinyl or the silica-based carbonization two inferior acid amides mol ratios of triphenyl 5: 1～1: 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710057495 CN101054309A (en) | 2007-05-30 | 2007-05-30 | Method for preparing porous silicon carbonitride by oxygen-free sol-gel reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710057495 CN101054309A (en) | 2007-05-30 | 2007-05-30 | Method for preparing porous silicon carbonitride by oxygen-free sol-gel reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101054309A true CN101054309A (en) | 2007-10-17 |
Family
ID=38794388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710057495 Pending CN101054309A (en) | 2007-05-30 | 2007-05-30 | Method for preparing porous silicon carbonitride by oxygen-free sol-gel reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101054309A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774593A (en) * | 2009-01-14 | 2010-07-14 | 西南科技大学 | Ordered porous silica and silicon carbonitride and preparation method and application thereof |
| CN104229768A (en) * | 2014-07-01 | 2014-12-24 | 江西师范大学 | Method for preparing porous carbon with three-dimensional structure |
-
2007
- 2007-05-30 CN CN 200710057495 patent/CN101054309A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774593A (en) * | 2009-01-14 | 2010-07-14 | 西南科技大学 | Ordered porous silica and silicon carbonitride and preparation method and application thereof |
| CN104229768A (en) * | 2014-07-01 | 2014-12-24 | 江西师范大学 | Method for preparing porous carbon with three-dimensional structure |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5770275A (en) | Molecular sieving silica membrane fabrication process | |
| US5935646A (en) | Molecular sieving silica membrane fabrication process | |
| KR101218508B1 (en) | Ceramic-carbon composites and its process | |
| CN100395211C (en) | Method for preparing porous silicon carbide ceramic with high porosity | |
| Sun et al. | Preparation of reticulated MAX‐phase support with morphology‐controllable nanostructured ceria coating for gas exhaust catalyst devices | |
| CN107082628B (en) | Preparation method of porous ceramic support based on molecular sieve membrane synthesis residual liquid | |
| CN111454061A (en) | Polycarbosilane non-melting pretreatment and cracking conversion method for three-dimensional ceramic | |
| CN108187712B (en) | Non-metal boron nitride catalyst, preparation and application thereof, and regeneration method | |
| Hector | Materials synthesis using oxide free sol–gel systems | |
| CN113716966B (en) | SiCN ceramic aerogel and preparation method and application thereof | |
| CN107746285B (en) | Three-dimensional porous nitride nano ceramic and preparation method thereof | |
| CN104130004A (en) | Preparation method of high-strength block-shaped porous alumina nano-ceramic | |
| CN106192371B (en) | A kind of high temperature resistant 3Al2O3-2SiO2The preparation method of-SiBNC carbon fiber composite coatings | |
| CN102218270A (en) | Phenyl decorated organic-inorganic hybridization millipore silicon dioxide film preparation method | |
| JP4858954B2 (en) | Mesoporous silicon carbide film and method for manufacturing the same | |
| CN108752038A (en) | It is a kind of with can be thermally cured Polycarbosilane preparation foam silicon carbide ceramics | |
| CN102351182A (en) | Preparation method of ultra-long silicon carbide nano-wires | |
| CN110282632B (en) | Preparation method of multifunctional flexible silica-based aerogel | |
| CN111807368A (en) | Preparation method of high-temperature-resistant ultralow-density silicon carbide nanotube aerogel | |
| CN113666375B (en) | Green preparation method of beta-silicon carbide with high specific surface area | |
| CN101054309A (en) | Method for preparing porous silicon carbonitride by oxygen-free sol-gel reaction | |
| CN112537961B (en) | Preparation method of polymer precursor ceramic aerogel | |
| Kaur et al. | High surface area SiC (O)‐based ceramic by pyrolysis of poly (ethylene glycol) methacrylate‐modified polycarbosilane | |
| CN112299871A (en) | Preparation method of porous ceramic containing silicon carbide film | |
| Hasegawa | Porous reduced ceramic monoliths derived from silicon-and titanium-based preceramic polymer gels |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |