CN1654319A - Preparation method for silicon oxide carbide - Google Patents
Preparation method for silicon oxide carbide Download PDFInfo
- Publication number
- CN1654319A CN1654319A CN200510038120.1A CN200510038120A CN1654319A CN 1654319 A CN1654319 A CN 1654319A CN 200510038120 A CN200510038120 A CN 200510038120A CN 1654319 A CN1654319 A CN 1654319A
- Authority
- CN
- China
- Prior art keywords
- cross
- silicon oxide
- linking type
- type polysiloxane
- oxide carbide
- 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.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 72
- 229910052814 silicon oxide Inorganic materials 0.000 title claims description 68
- 238000002360 preparation method Methods 0.000 title claims description 27
- -1 polysiloxane Polymers 0.000 claims abstract description 66
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 58
- 239000002245 particle Substances 0.000 claims abstract description 56
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000000839 emulsion Substances 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000004224 protection Effects 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004132 cross linking Methods 0.000 claims description 50
- 239000007908 nanoemulsion Substances 0.000 claims description 22
- 238000005336 cracking Methods 0.000 claims description 19
- 239000002105 nanoparticle Substances 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- WDCKRYQAVLUEDJ-UHFFFAOYSA-N methyl(oxo)silicon Chemical compound C[Si]=O WDCKRYQAVLUEDJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000015556 catabolic process Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000000280 densification Methods 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- 238000001035 drying Methods 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical class C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 description 1
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 1
- 241000248771 Amphiops mater Species 0.000 description 1
- 229910014571 C—O—Si Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- MCAPDUSPBSEQQO-UHFFFAOYSA-N O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1.CC=C Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1.CC=C MCAPDUSPBSEQQO-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910003923 SiC 4 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Nanometer emulsion of cross-linked polysiloxane is diluted with water to the concentration of 0.1-2 % and painted onto copper net or silicon base board with carbon film sprayed, and after drying in the air, the copper net or silicon base board is cracked at 600-1300 deg.c for 1-2.5 hr under the protection of N2, Ar, etc. to obtain nanometer silicon oxycarbide particles on the copper net or compact silicon oxycarbide film on the surface of the silicon base board. Or, the nanometer emulsion of cross-linked polysiloxane may be demulsified to obtain cross-linked polysiloxane powder, and the cross-linked polysiloxane powder may be pyrolyzed to obtain silicon oxycarbide particles, which are porous or compact depending on different conditions. The present invention has the advantages of easily obtained material, low cost, and controllable size of obtained silicon oxycarbide particles.
Description
Technical field
The present invention relates to the preparation method of silicon oxide carbide nano particle or coating.
Background technology
In pottery and glass industry, inorganic oxide is the very important material of a class, is widely studied for many years, and has obtained widespread use at many industrial circles, and wherein, silicon-dioxide is major ingredient wherein under most occasions.And silicon oxide carbide is a kind of glass material of carbon elements, can be by the pyrolysis and getting in inert atmosphere of silicone resin or methyl siliconic acid, carbon atom directly is connected with Siliciumatom in the silicon oxide carbide molecule, this makes the performance of silicon oxide carbide and silicon-dioxide have many differences [Baney R H, Chi F K.EP 107943 (1984) .].
More existing reports about silicon oxide carbide particle and porous particle: under atmosphere of inert gases, can obtain silicon oxide carbide glass material [BaneyR H, Chi F K.EP 107943 (1984) from the organosilicon precursor that contains Si-O and Si-C through high temperature (600～1000 ℃) thermo-cracking; Fery V, Pachaly B, Zeller N.US 4833220 (1989); Fery V, Pachaly B, Zeller N.US 5015605 (1991); Lipowitz J, Freeman H A, Chen R T, et al.AdvCeram Mat, 1987,2:121.]; It is RSiO from structure that people such as Frey have introduced a kind of in the patent of their application
3/2Silicone resin make the method for silicon oxide carbide glass material, they have described the method for making porousness silicon oxide carbide material from the methyl alkoxy disilane in other a patent.Pachaly has prepared a kind of the have polysiloxane of the narrow distribution of particle diameter or the spheroidal particle of silicon oxide carbide simultaneously, and wherein spherical silicon oxide carbide particulate median size is 2 μ m[PachalyB.US 5130400 (1992) .].
Forefathers adopt solid
29Si NMR, XPS and Raman spectrum etc. have carried out comparatively deep research to structure, composition and the performance of silicon oxide carbide material, and the result shows that along with the difference of thermo-cracking condition, in the chemical constitution of silicon oxide carbide, following several compositions all can exist: SiO
4, SiCO
3, SiC
2O
2, SiC
3O and SiC
4[Zhang H, PantanoC G.J Am Ceram Soc, 1990,73:958; Renlund G M, Prochazka S, Doremus RH.J Mater Res, 1991,6:2723; Soraru G D, D ' Andrea G, Campostrini R, et al.J Am Ceram Soc, 1995,78:379; Soraru G D, D ' Andrea G, Glisenti A.Mater Let, 1996,27:1; Radovanovic E, Gozzi M F, Goncalves M C, et al.J Non-Crystlline Solids, 1999,248:37; Burns G T, Taylor R B, Xu Y, etal.Chem Mater, 1992,4:1313.]; Also may exist simultaneously with CH
2Or the H element of the form of CH connection, and carbon-oxygen bond, as C=O or C-O-Si etc.
Electrical insulation capability and thermal stability that silicon oxide carbide has excellence are good; can be used as heat insulator or material for core; be particularly suitable under high temperature or high-voltage situation, using; for example: be used for power equipment; propping material (as nozzle, valve and tubing etc.) as protection overcoat, coil or isolator; high strength glass, the coating of ferroelectric material and nuke rubbish etc.Also can be used as the starting material of powder sintered pottery, filler as ceramic coating or tackiness agent, the surface can be used as ion exchange resin, catalyzer and biological mould etc. carrier after hydride modified processing, and [the Seyferth D such as carrier of chromatographic column, Stewart R M.Appl Organomet Chem, 1997,11:813; Greil P.J Am Ceram Soc, 1995,78:835.].
Though the molecule of silicon oxide carbide can be obtained by silicone resin or methyl siliconic acid colloidal high temperature pyrolysis under inert atmosphere, but the particle diameter of the particle diameter that obtains in this way is generally 1～5 μ m, is difficult to obtain the nano-sized carbon silicon oxide particle of particle diameter below 100nm.Therefore preparing the nano-sized carbon silicon oxide particle with a kind of simple method is a job highly significant.Simultaneously, silicon oxide carbide porous particles or film also have very important use, and the research of its preparation method also highly significant.
We are crosslinked organosilicon nanometer microsphere [the Zhang D M of tens nanometers with particle diameter for this patent, Jiang X Q, YangC Z.J Appl Polym Sci.2003,89:3587.] be raw material, its thermo-cracking is prepared nano-sized carbon silicon oxide particle, silicon oxide carbide coating or porousness silicon oxide carbide microballoon.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of silicon oxide carbide nano particle, porousness silicon oxide carbide particle or silicon oxide carbide coating.
Basic thought of the present invention is: adopting particle diameter is that the cross-linking type polysiloxane nanoemulsions of tens nanometers is a raw material, and the method by high temperature pyrolysis prepares silicon oxide carbide.Can obtain the silicon oxide carbide of different shape by the control of cracking condition, as ball shaped nano silicon oxide carbide particle, porousness silicon oxide carbide particle or silicon oxycarbide films etc.
Therefore technical scheme of the present invention is as follows:
A kind of preparation method of silicon oxide carbide, it comprises the steps:
1. be that cross-linking type polysiloxane nanoemulsions thin up to cross-linking type polysiloxane quality percentage composition below 100 nanometers is 0.1～2% with the average grain particle diameter, preferably 0.3～0.5%,
2. the cross-linking type polysiloxane nanoemulsions with the dilution of step 1 gained is coated in carrier surface, dries.For the ease of analyzing, we are coated in it on transmission electron microscope copper mesh or silicon substrate that is sprayed with carbon film,
3. with the loaded cross-linked type polysiloxane nanoemulsions particulate carrier of step 2 gained; as copper mesh or silicon substrate; at rare gas element; as protections such as nitrogen or argon gas down; 600～1300 ℃ of cracking 1～2.5 hour, promptly obtaining particle diameter on copper mesh was the silicon oxide carbide nano particle of 10～60 nanometers or the silicon oxide carbide film that obtains densification on the silicon substrate surface.
The described cross-linking type polysiloxane of step 1 nanoemulsions can be by Zhang D M, Jiang X Q, Yang C Z.JAppl Polym Sci.2003, the reported method preparation of 89:3587. institute.
Cross-linking type polysiloxane nanometer (about the particle diameter 50nm) emulsion of dilution applied be fixed on when carrying out high temperature pyrolysis on the copper mesh, in thermal cracking processes, cross-linking type polysiloxane nanoparticle conversion is inorganic silicon oxide carbide, can lose a large amount of CO
2And H
2Small molecules products such as O, weight diminishes, it is big that density becomes, so volume will reduce greatly, should obtain particle diameter in theory and be the particle about 10nm, and the silicon oxide carbide particle grain size that transmission electron microscope (TEM) analysis revealed obtains is 10～60nm, this is because in the specimen preparation process, if there is more cross-linking type polysiloxane nano particle to be deposited in together, in thermal cracking processes, it is one that particle can and gather mutually, will produce the bigger silicon oxide carbide particle of diameter like this.And on silicon substrate, because the organic silicon granule that applies is more, be deposited in together, inter-adhesive between the particle in the high temperature pyrolysis process, obtained uniform silicon oxycarbide films.If this organic silicon emulsion is coated in the other materials surface, hot crackedly can form one deck silicon oxycarbide films on the surface equally.
Method of the present invention also can make the porousness silicon oxide carbide, and concrete grammar is as follows.
A kind of preparation method of silicon oxide carbide, it comprises the steps:
1. be ethanol or the Virahol breakdown of emulsion that cross-linking type polysiloxane nanoemulsions below 100 nanometers adds 3～10 times of quality of quality of the emulsion with the average grain particle diameter, collect cross-linking type polysiloxane powder,
2. cross-linking type polysiloxane powder is washed with water the back oven dry,
With the cross-linking type polysiloxane powder of step 2 gained in inert gasses, as protections such as nitrogen or argon gas down,, promptly get particle diameter and be 50～150 microns porousness silicon oxide carbide particle 600～800 ℃ of cracking 1～2.5 hour.
Among the preparation method of above-mentioned silicon oxide carbide; with the cross-linking type polysiloxane powder of the cleaning of step 2 gained, oven dry in inert gasses; about 2.5 hours, then make irregularly shaped, hard dense carbon silicon oxide particle 1300 ℃ of cracking down as protections such as nitrogen or argon gas.
With cross-linking type polysiloxane nanoemulsions breakdown of emulsion, can obtain the aggregate of cross-linking type polysiloxane nano particle.This aggregate is carried out pyrolysis about 600～800 ℃, can obtain particle diameter is the porousness silicon oxide carbide particle of 50～150 μ m, within it portion many diameters are arranged is the spherical silicon oxide carbide particle of 1.5～4.5 μ m; And when cracking temperature is 1300 ℃, the block carbon silicon oxide particle that obtains for densification.
Analyze and can find through scanning electronic microscope (SEM), through the pyrolysis about 600～800 ℃/2h, original nanometer small-particle has been assembled and has been macroscopic porousness ball-type thing, and diameter is about 50～150 μ m; Further analyze and find that the littler bead of many particle diameters is contained in the inside of porousness bead, its particle size range is 1.5～4.5 μ m, and median size is 3 μ m.This can illustrate cross-linking type polysiloxane nano particle when pyrolysis, and the contiguous mutual melting of particle meeting becomes macrobead, can be clear that the product of this fusion process in SEM figure.Yet, when pyrolysis temperature rises to 1300 ℃, behind pyrolysis 2.5h under this temperature, sem analysis is found: variation has taken place again in the form of product, and at first from appearance, product is hard black small-particle, hardness is very big, very difficult grinding diminishes, and after the amplification, bead or the porous product that picture produces also do not occur when 600～800 ℃ of pyrolysis.
Silicon oxide carbide nano particle that the present invention obtains or film can be used for the finishing of material, or thermotolerance filler, additive etc., or other adaptable occasions; And many skies property silicon oxide carbide particle can be used as the carrier of medicine, biological enzyme or catalyzer etc. or other adaptable occasions.
Technological merit of the present invention is: the polysiloxane emulsion that can obtain with the organic silicon emulsion polymerization is a raw material, and raw material is simple and easy to, low price; With the polysiloxane in the emulsion crosslinked after; its shape size is kept; and in conjunction with pyrolysis temperature; can control the silicon oxide carbide particulate size that obtains after the pyrolysis; under different condition; can obtain particle diameter is the silicon oxide carbide nano particle of 10～60nm, perhaps obtains porousness silicon oxide carbide particle or fine and close silicon oxide carbide particle, perhaps obtains the silicon oxide carbide film attached to carrier surface.
Description of drawings
Fig. 1 is the TEM photo of the cross-linking type polysiloxane emulsion of peroxide crosslinking, amplifies 50,000 times.
Fig. 2 is the TEM photo of the silicon oxide carbide that obtains behind 800 ℃ of cracking 1h, amplifies 50,000 times.
Fig. 3 is the TEM photo of the silicon oxide carbide that obtains behind 800 ℃ of cracking 2h, amplifies 50,000 times.
The silicon oxide carbide SEM figure that Fig. 4 obtains behind 800 ℃ of cracking 2h for cross-linking type polysiloxane aggregate amplifies 40 times.
The silicon oxide carbide SEM figure that Fig. 5 obtains behind 800 ℃ of cracking 2h for cross-linking type polysiloxane aggregate amplifies 2000 times.
The silicon oxide carbide SEM figure of Fig. 6 for obtaining behind 1300 ℃ of cracking 2.5h of cross-linking type polysiloxane aggregate amplifies 50 times.
The silicon oxide carbide SEM figure of Fig. 7 for obtaining behind 1300 ℃ of cracking 2.5h of cross-linking type polysiloxane aggregate amplifies 5000 times.
Fig. 8 amplifies 2000 times for the silicon oxide carbide SEM figure that the cross-linking type polysiloxane emulsion obtains behind 1300 ℃ of cracking 2.5h on the silicon substrate.
Fig. 9 amplifies 1000 times for the SEM figure of cross-linking type polysiloxane emulsion after the silicon oxide carbide film surface that obtains behind 1300 ℃ of cracking 2.5h on the silicon substrate is destroyed.Really there is silicon oxycarbide films to exist above the particle of the white explanation silicon substrate among the figure.
Embodiment
The preparation of embodiment 1. polysiloxane nanoemulsions
The preparation method is as follows for the polysiloxane nanoemulsions: with 78.0 gram octamethylcyclotetrasiloxanes, 13.5 the stearic alcohol ether of gram polyoxyethylene (EO=25), 7.5 gram polyoxyethylene (EO=40) nonylphenyl ether, 6.0 gram polyoxyethylene (EO=40) lauryl alcohol, 30g ethylene glycol and 120 gram distilled water join thermometer are housed, in the 500ml four-necked bottle of reflux condensing tube and agitator, put into the thermostat(t)ed water bathtub, stir down material is heated to 80 ℃, add 10.0 gram mass concentration then and be 25.0% the KOH aqueous solution, constant temperature is at 80 ± 0.5 ℃ of following stirring reaction 8h, finish reaction, cool, adding mass concentration then is that 25% aqueous acetic acid is neutralized to pH=7.
The preparation of embodiment 2. cross-linking type polysiloxane nanoemulsions
Peroxide crosslinking: with 47.0 gram octamethylcyclotetrasiloxanes, 31.0g methyl ethylene cyclotetrasiloxane, 13.5 the stearic alcohol ether of gram polyoxyethylene (EO=25), 7.5 gram polyoxyethylene (EO=40) nonylphenyl ether, 6.0 gram polyoxyethylene (EO=40) lauryl alcohol, 40g ethylene glycol and 110 gram water join thermometer are housed, in the 500ml four-necked bottle of reflux condensing tube and agitator, put into the thermostat(t)ed water bathtub, stir down material is heated to 80 ℃, add 10.0 gram mass concentration then and be 25.0% the KOH aqueous solution, constant temperature cools off then at 80 ± 0.5 ℃ of following stirring reaction 8h, and adding mass concentration is that 25% aqueous acetic acid is neutralized to pH=7.In reaction system, add mass concentration again and be 10% K
2S
2O
8The aqueous solution 20 grams are at N
2Protection is down in 80 ℃ of stirring reaction 10hr, adds mass concentration then and be 10% K
2S
2O
8The aqueous solution 10 grams again in 80 ℃ of stirring reaction 8hr, finish reaction.
Tem analysis shows that the median size of cross-linking type polysiloxane particle wherein is 50nm (Fig. 1).
The preparation of embodiment 3. cross-linking type polysiloxane nanoemulsions
ND-22 is crosslinked: the polydimethylsiloxane nanoemulsions 10mL that gets preparation among the embodiment 1, join in the 100ml beaker, use the 20mL distilled water diluting, under magnetic stirrer, be added dropwise to the aqueous solution that the 10mL mass concentration for preparing in advance is 3.0% diethylin Union carbide A-162 then in room temperature, dropwise and continue to stir 30min, a week is placed in room temperature in product sealing back.
The preparation of embodiment 4. silicon oxide carbide nano particles
Is 0.3% with the cross-linking type polysiloxane nanoemulsions that obtains among the embodiment 2 with distilled water diluting to organosilicon concentration, with dropper it is dripped on the copper mesh that is sprayed with carbon film, placed one day in room temperature, again copper mesh is placed in the tube furnace, speed with 12 ℃/min under argon gas atmosphere is heated to 800 ℃, and under this temperature, be incubated 1.0 hours, and allow it lower the temperature naturally then and be cooled to below 100 ℃, sample is taken out from burner hearth.
Tem analysis shows that the silicon oxide carbide particulate median size of generation is 10～40nm (Fig. 2).
The preparation of embodiment 5. silicon oxide carbide nano particles
Is 0.5% with the cross-linking type polysiloxane nanoemulsions that obtains among the embodiment 2 with distilled water diluting to organosilicon concentration, with dropper it is dripped on the copper mesh that is sprayed with carbon film, placed one day in room temperature, again copper mesh is placed in the tube furnace, speed with 12 ℃/min under argon gas atmosphere is heated to 800 ℃, and under this temperature, be incubated 2.0 hours, and allow it lower the temperature naturally then and be cooled to below 100 ℃, sample is taken out from burner hearth.
Tem analysis shows that the silicon oxide carbide particulate median size of generation is 10～60nm (Fig. 3).
The preparation of embodiment 6. cross-linking type polysiloxane powder
With the cross-linking type polysiloxane nanoemulsions 100ml that obtains among the embodiment 2 800ml ethanol breakdown of emulsion, centrifugal settling is used ethanol and distilled water wash respectively for several times with throw out, places 120 ℃ of bakings of baking oven 2.0 hours then, obtains cross-linking type polysiloxane powder.
The preparation of embodiment 7. cross-linking type polysiloxane powder
With the cross-linking type polysiloxane nanoemulsions 100ml that obtains among the embodiment 2 800ml Virahol breakdown of emulsion, centrifugal settling is used ethanol and distilled water wash respectively for several times with throw out, places 120 ℃ of bakings of baking oven 2.0 hours then, obtains cross-linking type polysiloxane powder.
The preparation of embodiment 8. porousness silicon oxide carbide particulate
The cross-linking type polysiloxane powder that obtains among the embodiment 6 is placed on places a tube furnace in the crucible, speed with 12 ℃/min under argon gas atmosphere is heated to 800 ℃, and under this temperature, be incubated 1.0 hours, and allow it lower the temperature naturally then and be cooled to below 100 ℃, sample is taken out from burner hearth.
Sem analysis shows that having obtained the irregular spheric median size of outward appearance is the porousness silicon oxide carbide particle of 100 μ m, within it portion have many diameters be 1.5～4.5 μ m spherical silicon oxide carbide particle (Fig. 4, Fig. 5).
XPS analysis shows that the elementary composition ratio of product is Si: C: O=1: 1.48: 1.91.
The preparation of embodiment 9. silicon oxide carbide particulate
The cross-linking type polysiloxane nanoemulsions 100ml that obtains among the embodiment 2 is placed in the 500ml large beaker; place in 100 ℃ of baking ovens and dry moisture content; take out; the solid that obtains is pulverized a little; using hot wash three times; place 120 ℃ of bakings of baking oven 2.0 hours again; take out; the cooling back is levigate with mortar; the organosilicon powder that this method is obtained is placed on and places tube furnace in the crucible; under nitrogen protection, be heated to 1300 ℃ and kept 2.5 hours in this temperature with the speed of 200 ℃/h, pyrolysis finish relief its lower the temperature naturally and be cooled to below 100 ℃, sample is taken out from burner hearth.
Sem analysis show obtain for fine and close block carbon silicon oxide particle (Fig. 6, Fig. 7).
XPS analysis shows that the elementary composition ratio of product is Si: C: O=1: 1.27: 1.98.
The preparation of embodiment 10. silicon oxide carbide coatings
S' 0.5% the aqueous solution with the cross-linking type polysiloxane nanoemulsions that obtains among the embodiment 2 with distilled water diluting, then will be wherein through the silicon substrate submergence of hydrophilic treatment such as hydrogen peroxide and acid, take out after 5 minutes, the vertical placement removed excess liquid a moment, make silicon chip surface keep the thin liquid of one deck, horizontal positioned places two days natural airings of watch-glass then; Place it in then in the tube furnace, under nitrogen atmosphere, be heated to 1300 ℃ and kept 2.5 hours in this temperature with the speed of 200 ℃/h, pyrolysis finish relief its lower the temperature naturally and be cooled to below 100 ℃, sample is taken out from burner hearth.
Sem analysis show the silicon oxycarbide films that formed one deck densification on the surface of silicon substrate (Fig. 8, Fig. 9).
Claims (5)
1. the preparation method of a silicon oxide carbide is characterized in that it comprises the steps:
1. be that cross-linking type polysiloxane nanoemulsions thin up to cross-linking type polysiloxane quality percentage composition below 100 nanometers is 0.1～2% with the average grain particle diameter,
2. the cross-linking type polysiloxane nanoemulsions with the dilution of step 1 gained is coated on the carrier, dry,
3. with the carrier that is coated with cross-linking type polysiloxane nano particle of step 2 gained; under the inert gasses protection; 600～1300 ℃ of cracking 1～2.5 hour, promptly obtaining particle diameter on copper mesh was the silicon oxide carbide nano particle of 10～60 nanometers or the silicon oxide carbide film that obtains densification on the silicon substrate surface.
2. preparation method according to claim 1 is characterized in that: step 1 is to be 0.3～0.5% with cross-linking type polysiloxane nanoemulsions thin up to cross-linking type polysiloxane quality percentage composition.
3. preparation method according to claim 1 is characterized in that: the described carrier of step 2 is copper mesh or the silicon substrate that is sprayed with carbon film.
4. the preparation method of a silicon oxide carbide is characterized in that it comprises the steps:
1. be ethanol or the Virahol breakdown of emulsion that cross-linking type polysiloxane nanoemulsions below 100 nanometers adds 3～10 times of quality of quality of the emulsion with the average grain particle diameter, collect cross-linking type polysiloxane powder,
2. cross-linking type polysiloxane powder is washed with water the back oven dry,
With the cross-linking type polysiloxane powder of step 2 gained in inert gasses, as protections such as nitrogen or argon gas down,, promptly get particle diameter and be 50～150 microns porousness silicon oxide carbide particle 600～800 ℃ of cracking 1～2.5 hour.
5. according to the preparation method of the described silicon oxide carbide of claim 3; it is characterized in that: with the cross-linking type polysiloxane powder of the cleaning of step 2 gained, oven dry under the inert gasses protection 1300 ℃ of cracking 2.5 hours, then make irregularly shaped, hard dense carbon silicon oxide particle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100381201A CN1298622C (en) | 2005-01-17 | 2005-01-17 | Preparation method for silicon oxide carbide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100381201A CN1298622C (en) | 2005-01-17 | 2005-01-17 | Preparation method for silicon oxide carbide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1654319A true CN1654319A (en) | 2005-08-17 |
| CN1298622C CN1298622C (en) | 2007-02-07 |
Family
ID=34894412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100381201A Expired - Fee Related CN1298622C (en) | 2005-01-17 | 2005-01-17 | Preparation method for silicon oxide carbide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1298622C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073297A (en) * | 2013-02-22 | 2013-05-01 | 厦门大学 | Preparation method of SiCO ceramic nanospheres |
| CN108899495A (en) * | 2018-06-22 | 2018-11-27 | 哈尔滨工业大学 | Lithium ion battery silicon oxocarbon group negative electrode material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3917898A1 (en) * | 1989-06-01 | 1990-12-06 | Wacker Chemie Gmbh | METHOD FOR PRODUCING SPHERICAL, MONODISPERSE ORGANOPOLYSILOXANE OR SILICON OXYCARBIDE |
| US5162480A (en) * | 1990-12-14 | 1992-11-10 | Union Carbide Chemicals & Plastics Technology Corporation | Self-curing ceramicizable polysiloxanes |
-
2005
- 2005-01-17 CN CNB2005100381201A patent/CN1298622C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073297A (en) * | 2013-02-22 | 2013-05-01 | 厦门大学 | Preparation method of SiCO ceramic nanospheres |
| CN108899495A (en) * | 2018-06-22 | 2018-11-27 | 哈尔滨工业大学 | Lithium ion battery silicon oxocarbon group negative electrode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1298622C (en) | 2007-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Loy et al. | Bridged polysilsesquioxanes. Highly porous hybrid organic-inorganic materials | |
| Costa et al. | Infrared and thermogravimetric study of high pressure consolidation in alkoxide silica gel powders | |
| Nitta et al. | Surface modified spin-on xerogel films as interlayer dielectrics | |
| CN1146965C (en) | Silane-based nanoporous silica thin films | |
| CN100351211C (en) | Ceramic moulded body comprising a photocatalytic coating and method for producing the same | |
| Kim et al. | Synthesis of size controlled spherical silica nanoparticles via sol-gel process within hydrophilic solvent | |
| CN1803715A (en) | Method for preparing silicon carbide fiber reinforced silicon carbide composite material | |
| CN1955228A (en) | Durable hard coating containing silicon nitride | |
| JP6485244B2 (en) | Spherical silicon oxycarbide powder and method for producing the same | |
| CN1616468A (en) | Multi-functional cyclic siloxane compound, siloxane-based polymer prepared from the compound and process for preparing dielectric film by using the polymer | |
| JP2018511905A (en) | Silicon carbon nanostructure composite | |
| CN1035280A (en) | Stablize zircon its preparation method and the application in Chemical Composition | |
| CN1355858A (en) | Low dielectric mano-porous material obtainable from polymer decomposition | |
| Katayama et al. | Characterization and mechanical properties of flexible dimethylsiloxane‐based inorganic/organic hybrid sheets | |
| CN1298622C (en) | Preparation method for silicon oxide carbide | |
| CN1836017A (en) | Coating composition and low dielectric siliceous material produced by using same | |
| Darmawan et al. | Hydrophobic silica films derived from methyltriethoxysilane (MTES): Effect of pH and calcination temperature | |
| KR20210037493A (en) | METHOD FOR FABRICATING AMORPHOUS SiC BLOCK | |
| JPH0741365A (en) | Preparation of high-density boron carbide ceramics | |
| CN1865350A (en) | Organic-inorganic hybridized nano composite material resisting atomic oxygen denudation and its preparation method | |
| CN112299871A (en) | Preparation method of porous ceramic containing silicon carbide film | |
| CN109574674B (en) | Poly-silicon aluminum carbon nitrogen ceramic microsphere and preparation method and application thereof | |
| CN101603207B (en) | Method for preparing network branched silicon nitride single crystal nanostructure with high purity and high yield | |
| JP4929835B2 (en) | Method for producing surface-coated hexaboride particles | |
| TWI294467B (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |