CN1193929C - One-dimension nano structure of silicon nitride and silicon carbide and its preparing method - Google Patents
One-dimension nano structure of silicon nitride and silicon carbide and its preparing method Download PDFInfo
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- CN1193929C CN1193929C CN03152915.1A CN03152915A CN1193929C CN 1193929 C CN1193929 C CN 1193929C CN 03152915 A CN03152915 A CN 03152915A CN 1193929 C CN1193929 C CN 1193929C
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- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000002086 nanomaterial Substances 0.000 title claims description 47
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title abstract description 50
- 229910010271 silicon carbide Inorganic materials 0.000 title abstract description 48
- 229910052581 Si3N4 Inorganic materials 0.000 title abstract description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 229910020711 Co—Si Inorganic materials 0.000 claims abstract description 17
- 229910018098 Ni-Si Inorganic materials 0.000 claims abstract description 12
- 229910018529 Ni—Si Inorganic materials 0.000 claims abstract description 12
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 10
- 229910017082 Fe-Si Inorganic materials 0.000 claims abstract description 9
- 229910017133 Fe—Si Inorganic materials 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 58
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 56
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 51
- 239000002070 nanowire Substances 0.000 claims description 35
- 229910052786 argon Inorganic materials 0.000 claims description 29
- 235000013312 flour Nutrition 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 28
- 229910052742 iron Inorganic materials 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 20
- 229910045601 alloy Inorganic materials 0.000 claims description 16
- 239000000956 alloy Substances 0.000 claims description 16
- 239000002127 nanobelt Substances 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 239000012300 argon atmosphere Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 10
- 238000003746 solid phase reaction Methods 0.000 claims description 10
- 238000010671 solid-state reaction Methods 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims description 2
- 229910000676 Si alloy Inorganic materials 0.000 abstract description 11
- 239000002243 precursor Substances 0.000 abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000012071 phase Substances 0.000 abstract description 8
- 239000007790 solid phase Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000010000 carbonizing Methods 0.000 abstract 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910021484 silicon-nickel alloy Inorganic materials 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- SICLLPHPVFCNTJ-UHFFFAOYSA-N 1,1,1',1'-tetramethyl-3,3'-spirobi[2h-indene]-5,5'-diol Chemical compound C12=CC(O)=CC=C2C(C)(C)CC11C2=CC(O)=CC=C2C(C)(C)C1 SICLLPHPVFCNTJ-UHFFFAOYSA-N 0.000 description 3
- KSIIOJIEFUOLDP-UHFFFAOYSA-N [Si].[Fe].[Ni] Chemical compound [Si].[Fe].[Ni] KSIIOJIEFUOLDP-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- AIOWANYIHSOXQY-UHFFFAOYSA-N cobalt silicon Chemical compound [Si].[Co] AIOWANYIHSOXQY-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
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- 239000010431 corundum Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000608 laser ablation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
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- 229910052582 BN Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
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- 238000000280 densification Methods 0.000 description 1
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- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- -1 nisiloy Chemical compound 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a method for growing a one-dimensional nanometer structure of silicon nitride and silicon carbide, which uses metal alloy particles with 20 to 80% of silicon as catalyst and provides a silicon source. The present invention uses gas or solid containing nitrogen or carbon as a carbon source. Particles containing silicon alloy are azotized or carbonized in a tubular furnace at a high temperature, and a one-dimensional nanometer structure of silicon nitride and silicon carbide is obtained. A temperature range for azotizing or carbonizing the particles containing silicon alloy in the tubular furnace at a hight temperature is from 1200 to 1600 DEG C. Metal alloy particles containing silicon are mainly Fe-Si, Ni-Si, Co-Si, Fe-Ni-Si, Fe-Co-Si, etc. The method of the present invention introduces a key step that components required for products are respectively provided from two channels of gas phase (or solid phase) precursors and catalysts, and chemical reaction occurs in catalyst liquid drops for generating target products.
Description
One, technical field
The present invention relates to Si
3N
4With novel one dimension Nano structures such as SiC nano wire, nano belt, nanometer rod.The present invention also relates to utilize cheap silicon-containing alloy particle as catalyzer and provide Si source, gas phase or solid phase precursor to provide nitrogenous source, carbon source to carry out prepared in reaction to comprise Si
3N
4Novel method with SiC kind one-dimensional nanostructure.
Two, background technology
In recent years, one dimension Nano structure (nanotube, nano wire, nanometer rod) is because its great scientific value and potential application prospect have caused people's very big interest.Theoretical and experimental study shows that all one-dimensional nano structure material has the performance of a series of excellences, as the character such as electricity, optics and magnetics of high mechanical strength, uniqueness.Therefore, people competitively adopt various technological lines to synthesize various one dimension Nano structures with property.
Si
3N
4With SiC be important high temperature resistant structure ceramics, owing to have high temperature resistant, advantages such as chemical stability good, intensity is high, hardness is big, wear-resistant, shock resistance, anticorrosive, light weight and good heat conductivity, have wide application prospects in various fields such as machinery, electronics, chemical industry, aerospace, military projects.Traditional Si
3N
4Pottery is made by macrobead, heterogeneous powder, causes that its fragility is big, toughness and intensity is relatively poor, thereby has been subjected to certain restriction on using.One dimension silicon nitride and nanometer silicon carbide structure can be controlled ceramics component, structure simultaneously because its specific surface area is big, chemically reactive is high and distinctive quantum confined effect on the microstructure level, make it show the performance more more superior than body phase material.One dimension Si
3N
4Can significantly reduce Si with the SiC nanostructure
3N
4With the sintering densification degree of SiC pottery, the intensity of made structure unit and reliability are also higher, and can overcome fragility effectively, improve snappiness and processability.The one dimension SiC nanostructure will have huge potential application in high frequency, superpower and high-temperature electronic device.At present, unidimensional Si
3N
4Become a big focus of present material research field with the SiC nanostructure.
Existing Si
3N
4Mainly be divided into five classes with SiC one dimension Nano structure synthetic technology thinking: a) carbon nanotube confinement growth method, with the carbon nanotube is template, make the oxide compound and the halide reaction of itself and silicon, in argon atmospher, obtain SiC nano wire and nanometer rod (X.H.Sun, et al.J.Am.Chem.Soc.124 (2002) 14464-14471 ﹠amp; H.Dai, et al.Nature375 (1995) 796-798), in a large amount of nitrogen atmosphere, obtain Si
3N
4Nano wire (W.Q.Han, et al.Appl.Phys.Lett71 (1997) 2271-2273) 1287-1289).B) hydrothermal synthesis method (Q.Lu, et al.Appl.Phys.Lett.75 (1995) 507-509 ﹠amp; G.Z.Shen, et al.Chem.Phys.Lett.375 (2003) 177-184).C) arc discharge method, laser ablation method promptly at high temperature synthesize (W.S.Shi, et al.J.Am.Ceram.Soc.83 (2000) 3228-3230) such as SiC nano wires with arc-over or laser ablation technology.D) chemical Vapor deposition process.E) carbothermic method.
At some above-mentioned preparation Si
3N
4In the method for SiC one dimension Nano structure, chemical Vapor deposition process and carbothermic method are owing to have that technology is simple, low cost and other advantages has obtained extensive employing.The report that document is also more the work of association area.X.C.Wu etc. are in a large amount of nitrogen atmospheres, in 1450 ℃ of heating SiO
2The mixed powder of nanoparticle and gac obtains α-Si simultaneously
3N
4And the nanometer rod of γ-SiC (X.C.Wu, et al.Mater.Res.Bull.36 (2001) 847-852).H.Y.Kim etc. are catalyzer with gallium (Ga), gan (GaN) and iron (Fe), at 1100 ℃, have obtained directed SiC nano wire in methane and the nitrogen atmosphere on silicon substrate, the Si of catalysis synthesis of high content under 1200 ℃ and ammonia atmosphere
3N
4Nano wire (H.Y.Kim, et al.Chem.Commun.2 (2003) 256-257 ﹠amp; H.Y.Kim, et al.Chem.Phys.Lett.372 (2003) 269-274).H.Cui etc. adopt microwave plasma enhanced chemical Vapor deposition process, utilize microwave plasma heating silicon substrate in ammonia atmosphere, and growth obtains needle-like Si on silicon substrate
3N
4Nano wire (H.Cui, et al.J.Mater.Res.16 (2001) 3111-3115).L.D.Zhang etc. are at 1420～1650 ℃, and heating contains the SiO of carbon nano-particles
2, select for use argon gas atmosphere can obtain SiO
2The SiC nano wire of parcel selects for use nitrogen atmosphere then can obtain Si
3N
4Nano wire (L.D.Zhang, et al.Mater.Sci.Eng.A.286 (2000) 34-38).C.C.Tang etc. use ammonia boron nitride silex glass down at 1350 ℃, make the fabulous Si of degree of crystallinity
3N
4Nanometer rod (C.C.Tang, et al.Jpn.J.Appl.Phys.Part 2,41 (2002) 589-591).Y.J.Zhang etc. heat Si powder or Si and SiO about 1200 ℃ in nitrogen or ammonia
2Mixed powder, all obtained Si under the situation of non-metal catalyst having
3N
4Nano wire (Y.J.Zhang, et al.J.Cryst.Growth.233 (2001) 803-808).The commercial SiC that is easy to get of usefulness such as Wu.Z.S is a reaction raw materials, and catalyzer is metallic iron (Fe), and reaction at high temperature obtains acicular SiC nano wire (Z.S.Wu.et.alAppl.Phys.Lett.80 (2002) 3829-3831).
Above-mentioned chemical Vapor deposition process and carbothermic method prepare Si
3N
4Mainly be divided into two classes with the reaction mechanism of SiC one dimension Nano structure: a class is Vapor-Liquid-Solid (VLS) growth mechanism (H.Y.Kim, et al.Chem.Phys.Lett.372 (2003) 269-274).Principal feature is: one, appropriate catalyst must be arranged, and catalyzer is in liquid state during nanostructure growth, so need suitable temperature.It two must have nitrogenous, carbonaceous precursor, and precursor constantly enters catalyzer by dissociating or reacting after generating the target product species on catalyzer drop surface, separates out, generates one dimension Nano structure reach supersaturation in the catalyzer drop after.Another kind of is Vapor-Solid (VS) growth mechanism (X.C.Wu, et al.Mater.Res.Bull.36 (2001) 847-852).This mechanism and the difference of above-mentioned VLS growth mechanism mainly are not need to be in liquid catalyzer, separate out one dimension Nano structures such as obtaining nano wire, nanometer rod by the reaction between the gas phase.
Three, summary of the invention
The cheap industrial raw material iron silica flour (Fe-Si) that the purpose of this invention is to provide a kind of utilization prepares Si
3N
4Novel method and new technology path with novel one dimension Nano structures such as SiC nano wire, nano belt, nanometer rod.Specifically, the less particle of the particle diameter that makes with the iron silica flour mechanical ball milling of industrial cheapness is as " catalyzer " and provide Si source, the commercial gas phase that is easy to get or solid phase precursor to provide nitrogenous source, carbon source to react to obtain Si
3N
4With SiC kind one-dimensional nanostructure.The alloy particles such as iron silicon, nisiloy, cobalt silicon and ternary alloy thereof that the present invention also aims to make with other approach are " catalyzer ", also can obtain Si by direct nitrogenize or carbonization
3N
4With novel one dimension Nano structures such as SiC.
One dimension silicon nitride of the present invention and nanometer silicon carbide structure preparation method, be to be " catalyzer " and the silicon source is provided with siliceous 20～80% metal alloy particle, gas or solid with nitrogenous or carbon are nitrogenous source and carbon source, and (1200～1600 ℃) nitrogenize or carbonization silicon-containing alloy particle obtain unidimensional Si under the high temperature
3N
4With SiC nano wire, nano belt and nanometer rod.Siliceous metal alloy particle can be the industrial cheap raw material iron silica flour of handling through mechanical ball milling, also can be the binary or the siliceous metal alloy particle of ternary that make by solid state reaction and liquid phase method, comprise Fe-Si, Ni-Si, Co-Si, Fe-Ni-Si, Fe-Co-Si, Ni-Co-Si etc.Its general formula is Fe
xSi
100-x, Ni
ySi
100-y, Co
zSi
100-z, Fe
aNi
bSi
100-a-b, Fe
aCo
bSi1
00-a-b, x, y, z get 20～80, and a+b gets 20～80, and size of particles is 20～200nm, and silicon content is 20～80%.
The present invention and existingly prepare Si by the VLS method
3N
4The main difference of comparing with the SiC technological line is, present method has been introduced respectively provides product required constituent element respectively from gas phase (or solid phase) precursor and two channels of " catalyzer " alloy, and this key link of chemical reaction generation target product takes place in the catalyzer drop.Present method is that the VLS mechanism of our expansion that proposes is at Si
3N
4Extension (K.F.Huo, et al.Appl.Phys.Lett.80 (2002) 3611-3613, Q.Wu, J.Mater.Chem.13 (2003) 2024-2027) with the SiC system.Specifically that is to say, obtain Si at iron silicon alloy " catalyzer " particle internal reaction from the silicon in the iron silica flour with from the nitrogen in gas phase or the solid phase precursor, carbon
3N
4And SiC, as the Si that generates
3N
4When in " catalyzer " drop, reaching supersaturation, just, under different condition, form the one dimension Si of different shape so that liquid-solid interface can minimum mode be separated out from certain crystal face with the SiC species
3N
4With the SiC nanostructure.
The present invention is achieved through the following technical solutions:
1. device required for the present invention mainly contains body of heater, gas distributing system and vacuum system three parts and forms, the relation of its each several part is as follows with effect: the reaction chamber that (1) is made by alundum tube or stainless steel tube places in the tube furnace, the corundum boat that is placed with siliceous " catalyzer " powder places the reaction chamber center, the temperature of vitellarium can be regulated and control, and is beneficial to Si
3N
4Growth with the SiC one dimension Nano structure.(2) gas distributing system is made up of gas circuit and mass flowmeter, is connected to an end of growth room, utilizes it can regulate Si
3N
4Kind, flow and proportioning with SiC one dimension Nano structure growth room gas.(3) vacuum system, utilize it can be before heating up in the growth room applying argon gas and vacuumizing repeatedly, get rid of oxidized possibility under " catalyzer " nanoparticle high temperature in the growth room, also can regulate vacuum tightness and reacting gas pressure in the growth room simultaneously.
2. siliceous " catalyzer " alloy particle of the present invention's employing is mainly Fe-Si, Ni-Si, Co-Si, Fe-Ni-Si, Fe-Co-Si, Ni-Co-Si etc.Its general formula is Fe
xSi
100-x, Ni
ySi
100-y, Co
zSi
100-z, Fe
aNi
bSi
100-a-bAnd Fe
aCo
bSi
100-a-b, x, y, z get 20-80, and a+b gets 20～80.
3. siliceous " catalyzer " alloy particle of the present invention's employing is from the cheap raw material of industry, also can use for reference solid state reaction (Hu Zheng etc., Chinese patent ZL.96117127.8, T.Shimoo, et al.J.Mater.Sci.34 (1999) 5525-5532) etc. method prepares above-mentioned siliceous " catalyzer " alloy particle.
4. invention prepares Si
3N
4Carry out under 1200～1600 ℃ of high temperature with the method for SiC one dimension Nano structure.
5. the Si that provides is provided
3N
4Comprise Si with the SiC one dimension Nano structure
3N
4With SiC nano wire, nanometer rod and nano belt.Nanowire diameter provided by the present invention is at 20～80nm, and length reaches micron dimension, and the nanometer rod diameter is at 30～120nm, and length reaches 300～1000nm, and the nano belt width is at 20～80nm, and thickness is at 5～20nm, and length reaches micron dimension.
6. the present invention can pass through the amount and the temperature of reaction of the precursor of the siliceous Nanoalloy diameter of particle of control and silicon content and nitrogenous or carbon, obtains Si respectively
3N
4Account for the product of main body with the wherein a certain one dimension Nano structure of SiC nano wire, nanometer rod and nano belt.
7. the present invention prepares Si
3N
4The method of nanostructure is that siliceous nanometer " catalyzer " alloy particle that will make earlier places above-mentioned growth room, and roasting is 1～3 hour under 500～700 ℃, atmosphere of hydrogen, is warmed up to 1200～1500C then, feeds N
2/ NH
3(10%NH
3) gas mixture carries out nitrogenizing reaction and obtain, and also can feed N simultaneously
2/ NH
3And SiH
4Gas.
8. the present invention prepares the method for SiC nanostructure, is that siliceous nanometer " catalyzer " alloy particle that will make earlier and active carbon powder mix and be placed in the above-mentioned growth room, 1300～1600 ℃ down reaction obtaining the SiC nanostructure.Also can feed N simultaneously
2/ NH
3(10%NH
3) and gaseous state or solid carbon-contg precursor, promptly pre-reaction material can contain nitrogenous source and carbon source simultaneously, thereby obtains the SiCN nanostructure.
9. also can be solid-state, solid-state N source be ammonium chloride (NH to the N source among the present invention
4Cl) or urea (CO (NH
2)
2); The C source can be solid-state or gaseous state, and solid-state carbon source comprises gac, powdered graphite or other high carbonaceous organic materials, and gaseous carbon source comprises CH
4, CO, C
2H
4, C
2H
2Deng low-carbon (LC) hydrocarbonylation thing.
10. optimum temps of the present invention is 1300～1350 ℃.
Characteristics of the present invention are as follows:
1. present method has been introduced respectively provides product required constituent element respectively from gas phase (or solid phase) precursor and two channels of " catalyzer " alloy, and this key link of chemical reaction generation target product takes place in the catalyzer drop.Present method is that the VLS mechanism of the expansion that proposes of our research group is at Si
3N
4Extension (K.F.Huo, et al.Appl.Phys.Lett.80 (2002) 3611-3613, Q.Wu, J.Mater.Chem.13 (2003) 2024-2027) with the SiC system.At Si
3N
4Expansion and extension with the SiC system.Made the one dimension Si of variform with this method
3N
4With the SiC structure, comprise nano belt, nano wire, nanometer rod.
2. the technological line of preparation nanostructure provided by the invention may extend into the preparation of some novel double elements or multicomponent compound nano structure, and the present invention simultaneously provides new selection for the nanostructure of some system of preparation (poisonous as precursor or be difficult to obtain system).
3. provided by the present invention cheap industrial raw material is converted into the preparation technology of the 1-dimention nano mechanism of high added value, cost is low, is suitable for industrial mass production.
Four, description of drawings
Fig. 1: the present invention Si that grows
3N
4Testing apparatus synoptic diagram with the SiC one dimension Nano structure.
(1) source of the gas; (2) pressure maintaining valve; (3) flow stabilizing valve; (4) mass flowmeter; (5) stop,threeway; (6) vacuum system; (7) O type shack; (8) growth room; (9) corundum boat; (10) beds; (11) heating and temperature controlling system; (12) acetone or water; (13) reaction back gas leads to stink cupboard.
Fig. 2: the TEM photo of the iron silicon alloy " catalyzer " that mechanical ball milling industrial iron silica flour obtained in 300 hours among the present invention.
Fig. 3: the iron silicon alloy " catalyzer " that obtained in 300 hours with mechanical ball milling industrial iron silica flour with the inventive method is at 1300 ℃ of Si that make
3N
4The TEM photo of nano wire.
Fig. 4: the iron silicon alloy " catalyzer " that obtained in 300 hours with mechanical ball milling industrial iron silica flour with the inventive method is at 1350 ℃ of Si that make
3N
4The TEM photo of nano belt.
Fig. 5: with the inventive method with the iron nickel silicon alloy particle that obtains by solid state reaction at 1400 ℃ of Si that make
3N
4The HRTEM photo of nano belt
Fig. 6: is that " catalyzer " is at 1300 ℃ of Si that make with the inventive method with the nickel silicon alloy particle
3N
4The TEM photo of nano wire.
Fig. 7: iron silicon alloy " catalyzer " powder that obtained in 300 hours with mechanical ball milling industrial iron silica flour with the inventive method is at 1250 ℃ of Si that make
3N
4The TEM photo of nanometer rod.
Fig. 8: with the inventive method with the cobalt silicon alloy particle that obtains by solid state reaction at 1380 ℃ of Si that make
3N
4The HRTEM photo of nano belt.
Fig. 9: with the inventive method with the cobalt silicon alloy particle that obtains by solid state reaction at 1300 ℃ of Si that make
3N
4The HRTEM photo of nano wire.
Figure 10: the iron silicon alloy " catalyzer " that obtained in 600 hours with mechanical ball milling industrial iron silica flour with the inventive method is at the TEM photo of 1350 ℃ of SiC nano wires that make.
Figure 11: the iron silicon alloy " catalyzer " that obtained in 600 hours with mechanical ball milling industrial iron silica flour with the inventive method is at the TEM photo of 1300 ℃ of SiC nanometer rod that make.
Figure 12: with the inventive method with the nickel silicon alloy particle that obtains by solid state reaction HRTEM photo at 1300 ℃ of SiC nano wires that make.
Figure 13: the SiC nano structure that makes with the inventive method the EDS power spectrum.
Figure 14: the Si that makes with the inventive method
3N
4The nano structure the EDS power spectrum.
Five, embodiment
Embodiment 1 with the industrial iron silica flour at 1300 ℃ of Si that make
3N
4Nano wire.
300 purpose industrial iron silica flours were obtained the particle (see figure 2) of size 30～180nm in 300 hours through mechanical ball milling, place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3～5 times with mechanical pump repeatedly then, the temperature rise rate with 10 ℃ of per minutes under argon atmosphere is warmed up to 1300 ℃.Stop applying argon gas, feed the N of 300sccm
2/ NH
3(4%NH
3) gas mixture, reacted 2 hours down at 1300 ℃.Obtain the Si that diameter is about 20～100nm in the beds district
3N
4Nano wire.(see figure 3)
Embodiment 2 with the industrial iron silica flour at 1350 ℃ of Si that make
3N
4Nano wire.
300 purpose industrial iron silica flours were obtained the particle (see figure 2) of size 30～180nm in 300 hours through mechanical ball milling, place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3～5 times with mechanical pump repeatedly then, the temperature rise rate with 10 ℃ of per minutes under argon atmosphere is warmed up to 1350 ℃.Stop applying argon gas, feed the N of 500sccm
2/ NH
3(4%NH
3) gas mixture, reacted 2 hours down at 1350 ℃, obtain the Si of width at 20～80nm in the beds district
3N
4Nano belt.(see figure 4).Identical at 1200 ℃ with reaction result under 1450 ℃ of temperature.
Embodiment 3 makes Si with the iron nickel silicon alloy particle that solid state reaction obtains at 1300 ℃
3N
4Nano wire.
To pass through Si
3N
4Place the alundum tube central zone with the iron nickel silicon alloy particle that obtains through ball milling again after Si and the metal Fe-Ni alloy high-temp solid state reaction, applying argon gas and find time 3 times with mechanical pump repeatedly then, the temperature rise rate with 10 ℃ of per minutes under argon atmosphere is warmed up to 1300 ℃.Stop applying argon gas, feed the N of 400sccm
2/ NH
3(4%NH
3) gas mixture, 1300 ℃ of down reactions 3 hours, obtain obtaining the Si of width in the beds district at 20～100nm in the beds district
3N
4Nano belt.(see figure 5)
According to above-mentioned reaction conditions, the condition of preparation Fe-Si, Ni-Si, Co-Si, Fe-Ni-Si, Fe-Co-Si, Ni-Co-Si is same as described above.Size of particles is 20～200nm, and silicon content is that 20～80% scope has a plurality of samples, a wider range of covering.The result is basic identical.
The Fe-Si powdered alloy that industrial 200 purposes are siliceous obtained the particle of size 50～240nm in 300 hours through mechanical ball milling, place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3～5 times with mechanical pump repeatedly then, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1400 ℃.Stop applying argon gas, feed the N of 200sccm
2/ NH
3(4%NH
3) gas mixture, reacted 2 hours down at 1400 ℃, obtain diameter in the beds district at 40～180nm, length is the Si of 300～1000nm
3N
4The nanometer rod (see figure 6).
To make the nisiloy particulate by nickel powder and the silica flour method by mechanical ball milling and place the alundum tube central zone, applying argon gas and find time 3～5 times repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1300 ℃.Stop applying argon gas, feed the N of 200sccm
2/ NH
3(10%NH
3) gas mixture, reacted 3 hours down at 1300 ℃.Obtain the Si that diameter is about 20～140nm in the beds district
3N
4The nano wire (see figure 7).
To place the alundum tube central zone by cobalt powder and the silica flour method system cobalt nisiloy particulate by mechanical ball milling, applying argon gas and find time 3～5 times repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1380 ℃.Stop applying argon gas, feed the N of 500sccm
2/ NH
3(10%NH
3) gas mixture, reacted 3 hours down at 1380 ℃.Obtain the Si of width at 20～120nm in the beds district
3N
4The nano belt (see figure 8).
To place the alundum tube central zone by cobalt powder and the silica flour method system cobalt nisiloy particulate by mechanical ball milling, applying argon gas and find time 3～5 times repeatedly then with mechanical pump, the temperature rise rate with 10 ℃ of per minutes under argon atmosphere is warmed up to 1300 ℃.Stop applying argon gas, feed the N of 200sccm
2/ NH
3(10%NH
3) gas mixture, reacted 3 hours down at 1380 ℃.Obtain the Si of width at 20～120nm in the beds district
3N
4The nano wire (see figure 9).
Industrial iron silica flour obtained the particle of size 20～150nm in 600 hours through mechanical ball milling, place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3～5 times with mechanical pump repeatedly then, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1250 ℃.Stop applying argon gas, feed the CO gas of 100sccm, reacted 2 hours down, obtain diameter in the beds district in the SiC of 30～120nm nano wire (see figure 10) at 1350 ℃.
Industrial iron silica flour obtained the particle of size 20～150nm 30～180nm in 600 hours through mechanical ball milling, place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3～5 times repeatedly then with mechanical pump, under argon atmosphere, be warmed up to 1300 ℃ and stop applying argon gas, feed the CH of 100sccm with the temperature rise rate of 15 ℃ of per minutes
4H with 200sccm
2, reacted 2 hours down at 1300 ℃, obtain diameter in the beds district in the SiC of 20～120nm nanometer rod (Figure 11).
To make the nisiloy particulate by nickel powder and the silica flour method by mechanical ball milling, particle diameter 50～200nm, place the alundum tube central zone, applying argon gas and find time 3～5 times repeatedly then with mechanical pump, the temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1300 ℃.Stop applying argon gas, feed the CH of 80sccm
4H with 200sccm
2, reacted 2 hours down at 1300 ℃, obtain diameter in the beds district at the SiC of 20～120nm nano wire (seeing Figure 12).
The different temperature condition of above-mentioned reaction: as identical with reaction result under 1450 ℃ of temperature at 1200 ℃.
Above-mentioned silicon-containing alloy also can be the siliceous metal alloy particle of the binary that makes by solid state reaction and liquid phase method or ternary such as Fe-Si, Ni-Si, Co-Si, Fe-Ni-Si, Fe-Co-Si, Ni-Co-Si, silicon content can be 20～80%, a wider range of covering.According to above-mentioned reaction conditions, the SiC nanostructure of preparation is same as described above.
Claims (9)
1. growth of one-dimensional Si
3N
4With the method for SiC nanostructure, it is characterized in that being " catalyzer " and the silicon source is provided with siliceous 20～80% metal alloy particle, be nitrogenous source and carbon source with the gas or the solid of nitrogenous or carbon, under the high temperature in tube furnace nitrogenize or carbonization silicon-containing alloy particle obtain Si
3N
4With the SiC one dimension Nano structure, under the high temperature in tube furnace the temperature range of nitrogenize or carbonization silicon-containing alloy particle be 1200-1600 ℃.
2. growth of one-dimensional Si according to claim 1
3N
4With the method for SiC nanostructure, it is characterized in that siliceous metal alloy particle is mainly Fe-Si, Ni-Si, Co-Si, Fe-Ni-Si, Fe-Co-Si, Ni-Co-Si, its general formula is Fe
xSi
100-x, Ni
ySi
100-y, Co
zSi
100-z, Fe
aNi
bSi
100-a-b, Fe
aCo
bSi
100-a-b, x, y, z get 20-80, and a+b gets 20-80.
3. growth of one-dimensional Si according to claim 1
3N
4Method with the SiC nanostructure, it is characterized in that can be by the particle of the siliceous Fe-Si alloy particle diameter 50～240nm of control, place the alundum tube central zone with this as catalyzer, applying argon gas and find time 3～5 times repeatedly then with mechanical pump, temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1400 ℃, stop applying argon gas, feed the N of 200sccm
2/ NH
3Gas mixture contains 4%NH
3, 400 ℃ were reacted 2 hours down, obtained diameter in the beds district at 40～180nm, and length is the Si of 300～1000nm
3N
4Nanometer rod.
4. one dimension Si according to claim 1
3N
4Preparation method with the SiC nanostructure, it is characterized in that making the nisiloy particulate with nickel powder and the silica flour method by mechanical ball milling, particle diameter 50～200nm, place the alundum tube central zone, applying argon gas and find time 3～5 times repeatedly then with mechanical pump, temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1300 ℃, stops applying argon gas, feeds the CH of 80sccm
4H with 200sccm
2, reacted 2 hours down at 1300 ℃, obtain diameter in the beds district at the SiC of 20～120nm nano wire.
5. growth of one-dimensional Si according to claim 1
3N
4Method with the SiC nanostructure, it is characterized in that siliceous metal alloy particle can be industrial cheap raw material iron silica flour, also can be the binary or the siliceous metal alloy particle of ternary that make by solid state reaction and liquid phase method, size of particles is 20-200nm, and silicon content is 20～80%.
6. growth of one-dimensional Si according to claim 1
3N
4With SiC nanostructure preparation method, it is characterized in that gasiform N source is N
2And NH
3, gaseous state C source refers to CH
4, CO, C
2H
4, C
2H
2Low-carbon (LC) hydrocarbonylation thing, solid-state C source are gac or powdered graphite or other high carbonaceous organic materials.
7. growth of one-dimensional Si according to claim 1
3N
4With the method for SiC nanostructure, it is characterized in that optimum temps is 1300-1350 ℃.
8. growth of one-dimensional Si according to claim 1
3N
4With the method for SiC nanostructure, it is characterized in that pre-reaction material can contain nitrogenous source and carbon source simultaneously, thereby obtain the SiCN nanostructure.
9, growth of one-dimensional Si according to claim 1
3N
4Method with the SiC nanostructure, it is characterized in that and to place the alundum tube central zone by cobalt powder and the silica flour method system cobalt nisiloy particulate by mechanical ball milling, applying argon gas and find time 3～5 times repeatedly then with mechanical pump, temperature rise rate with 15 ℃ of per minutes under argon atmosphere is warmed up to 1380 ℃, stop applying argon gas, feed the N of 500sccm
2/ NH
3Gas mixture contains 10%NH
3, reacted 3 hours down at 1380 ℃, obtain the Si of width at 20～120nm in the beds district
3N
4Nano belt.
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| CN103496679B (en) * | 2013-10-18 | 2015-08-19 | 武汉科技大学 | A kind of beta-silicon nitride powder and preparation method thereof |
| CN103754879B (en) * | 2014-01-24 | 2015-05-20 | 扬州大学 | Method for preparing 3C-SiC nanoparticles 2nm in grain size through laser ablation process |
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| CN109879285B (en) * | 2019-03-21 | 2022-03-22 | 武汉工程大学 | Silicon carbide nano material and preparation method thereof |
| CN114751764B (en) * | 2021-02-09 | 2023-06-09 | 海南大学 | Multifunctional ceramic nanofiber sponge and preparation method thereof |
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