CN105752952B - A kind of method for preparing overlength beta-silicon nitride nanowire in porous body or powder shaped carborundum Polycarbosilane surface in situ and ex situ - Google Patents
A kind of method for preparing overlength beta-silicon nitride nanowire in porous body or powder shaped carborundum Polycarbosilane surface in situ and ex situ Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 132
- 229920003257 polycarbosilane Polymers 0.000 title claims abstract description 78
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 64
- 239000002070 nanowire Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 32
- 238000011066 ex-situ storage Methods 0.000 title claims abstract description 31
- 229910010271 silicon carbide Inorganic materials 0.000 title abstract 4
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 29
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 54
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 238000000498 ball milling Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 5
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 10
- 229910000077 silane Inorganic materials 0.000 description 10
- 239000007787 solid Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- IKXDEFIEGAVNOZ-UHFFFAOYSA-N [SiH4].[C] Chemical compound [SiH4].[C] IKXDEFIEGAVNOZ-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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Abstract
A kind of method for preparing overlength beta-silicon nitride nanowire in porous body or powder shaped carborundum Polycarbosilane surface in situ and ex situ, it is related to a kind of preparation method of beta-silicon nitride nanowire.The invention aims to solve existing preparation overlength silicon nitride nano-material, to there is reaction condition more harsh, causes security low, it is necessary to catalyst, causes purity low, the high technical problem of equipment requirement height, complex process, cost.Method：First, porous body or powder shaped carborundum Polycarbosilane are prepared；2nd, it is heat-treated, that is, the method for completing to prepare overlength beta-silicon nitride nanowire in porous body or powder shaped carborundum Polycarbosilane surface in situ and the wall ex situ of porcelain Noah's ark four.Advantage：Once, in the overlength beta-silicon nitride nanowire up to several millimeters of even Centimeter Level ranks can be prepared under normal pressure, and overlength beta-silicon nitride nanowire is presented linear；2nd, operating process is relatively simple, safety coefficient is high.Present invention is mainly used for prepare overlength beta-silicon nitride nanowire.
Description
Technical field
The present invention relates to a kind of preparation method of beta-silicon nitride nanowire.
Background technology
Silicon nitride is widely used in high-temperature structural material because of the premium properties such as its high temperature resistant, anti-oxidant, while because
Its broad-band gap, electrical insulating property be good and the performance such as medium heat transfer is applied but also as semi-conducting material.One-dimensional silicon nitride
Nano material generally has excellent physical and chemical performance, has in fields such as composite, nano-devices before important application
Scape.The current method for preparing beta-silicon nitride nanowire has a lot, as polymer cracking method, carbothermic method, chemical vapour deposition technique,
Template etc..Wherein polymer cracking method is relatively conventional, but at present on being closed under a nitrogen atmosphere using Polycarbosilane as presoma
Report into beta-silicon nitride nanowire is less, and existing most preparation methods are only capable of synthesizing one that length is tens to hundred microns
Tie up silicon nitride nano-material, relative to the nano wire of these microscopic dimensions, overlength beta-silicon nitride nanowire will in basic research and
Special field of nanometer devices obtains new application.
At present, it is only a small number of to reach text prepared by the overlength beta-silicon nitride nanowire of several millimeters of even Centimeter Levels on length
Offer report, the document of 2008 " F. Gao, W. Yang, Y. Fan, L. An, Nanotechnology, 19 (10),
105602. " be exactly to be raw material using poly-aluminium silazane and copper is that catalyst can be up under the conditions of 1550 DEG C of flowing nitrogens
Several millimeters of beta-silicon nitride nanowire, 2012 document " L.W. Lin, Y.H. He. CrystEngComm, 14 (9),
3250-3256. " is exactly with SiO or Si and SiO2Mixture is silicon source, CH4For carbon source, N2For nitrogen source, in 1400 ~ 1550 DEG C
The overlength beta-silicon nitride nanowire up to several millimeters can be obtained with 3h is incubated under 1.1atm ~ 1.5atm air pressure.Although the side of the above
Method can prepare the overlength beta-silicon nitride nanowire up to several millimeters, but two problems of generally existing：（1）Need catalysis
Agent, such as copper, iron and nickel, this can cause the nano wire purity obtained not high, influence the subsequent applications of nano wire；（2）React bar
Part is more harsh, such as pressurizes, is passed through flammable gas, causes processing safety relatively low, higher etc. to equipment requirement.
The content of the invention
The invention aims to solve existing preparation overlength silicon nitride nano-material, to there is reaction condition more harsh, leads
Cause security low, it is necessary to catalyst, causes purity low, the high technical problem of equipment requirement height, complex process, cost, and provide
A kind of side that overlength beta-silicon nitride nanowire is prepared in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ
Method.
It is a kind of to be received in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ preparation overlength silicon nitride
The method of rice noodles, is specifically realized by the following steps：
First, porous body or powder shaped carborundum-Polycarbosilane are prepared：SiC powder is added in amphene, poly- carbon is added
Silane, is 60 DEG C of constant temperature ball milling 5h ~ 20h in temperature, is then transferred in freeze drier and is freezed and dried 24h ~ 48h,
Obtain porous body or powder shaped carborundum-Polycarbosilane；The volume ratio of SiC powder and amphene described in step one is (1
~4):20；The mass ratio of SiC powder and Polycarbosilane described in step one is 20: (1~5)；
2nd, it is heat-treated：Porous body or powder shaped carborundum-Polycarbosilane are fitted into porcelain Noah's ark, then porcelain Noah's ark is put
Enter in tube furnace, nitrogen be continually fed into 50mL/min ~ 400mL/min flow velocitys, make in tube furnace in nitrogen protection, then with
1 DEG C/min ~ 10 DEG C/min programming rates are 1300 ~ 1500 DEG C from room temperature to temperature, and are 1300 ~ 1500 DEG C in temperature
Under the conditions of be incubated 1h ~ 6h, being then down to temperature as 1300 ~ 1500 DEG C from temperature using 1 DEG C/min ~ 10 DEG C/min cooling rates again is
500 DEG C, then cool to room temperature with the furnace, that is, complete in porous body or powder shaped carborundum-Polycarbosilane surface in situ and porcelain side
The wall ex situ of boat four prepares overlength beta-silicon nitride nanowire.
Advantage of the present invention：First, the present invention is freeze-dried acquisition again mainly using SiC and PCS as raw material after constant temperature ball milling
Porous body or powder, through simple preparation method in can just be prepared under normal pressure up to several millimeters of even Centimeter Level ranks
Overlength beta-silicon nitride nanowire, and overlength beta-silicon nitride nanowire is presented linear；2nd, operating process is relatively simple, safety coefficient
High and amphene can be recycled, so as to reduce cost；3rd, because overlength beta-silicon nitride nanowire prepared by the present invention is up to number milli
Rice even Centimeter Level rank, therefore can apply to the fields such as composite, nanoelectronic component, can also further open up
Open up the practical ranges of nano wire.
Brief description of the drawings
Fig. 1 is the photo in kind for the product that the step 2 of embodiment 1 is obtained；
Fig. 2 is the SEM figures of overlength beta-silicon nitride nanowire prepared by embodiment 1；
Fig. 3 is the XRD for the overlength beta-silicon nitride nanowire that embodiment 1 is obtained.
Embodiment
Embodiment one：Present embodiment is one kind on porous body or powder shaped carborundum-Polycarbosilane surface
The method that in situ and ex situ prepares overlength beta-silicon nitride nanowire, is specifically realized by the following steps：
First, porous body or powder shaped carborundum-Polycarbosilane are prepared：SiC powder is added in amphene, poly- carbon is added
Silane, is 60 DEG C of constant temperature ball milling 5h ~ 20h in temperature, is then transferred in freeze drier and is freezed and dried 24h ~ 48h,
Obtain porous body or powder shaped carborundum-Polycarbosilane；The volume ratio of SiC powder and amphene described in step one is (1
~4):20；The mass ratio of SiC powder and Polycarbosilane described in step one is 20: (1~5)；
2nd, it is heat-treated：Porous body or powder shaped carborundum-Polycarbosilane are fitted into porcelain Noah's ark, then porcelain Noah's ark is put
Enter in tube furnace, nitrogen be continually fed into 50mL/min ~ 400mL/min flow velocitys, make in tube furnace in nitrogen protection, then with
1 DEG C/min ~ 10 DEG C/min programming rates are 1300 ~ 1500 DEG C from room temperature to temperature, and are 1300 ~ 1500 DEG C in temperature
Under the conditions of be incubated 1h ~ 6h, being then down to temperature as 1300 ~ 1500 DEG C from temperature using 1 DEG C/min ~ 10 DEG C/min cooling rates again is
500 DEG C, then cool to room temperature with the furnace, that is, complete in porous body or powder shaped carborundum-Polycarbosilane surface in situ and porcelain side
The wall ex situ of boat four prepares overlength beta-silicon nitride nanowire.
Present embodiment mainly using SiC and PCS as raw material, after constant temperature ball milling again be freeze-dried acquisition porous body or
Powder, through simple preparation method in can just be prepared under normal pressure up to several millimeters even Centimeter Level ranks overlength nitrogenize
Silicon nanowires, and overlength beta-silicon nitride nanowire is presented linear.
Present embodiment operating process is relatively simple, safety coefficient is high and amphene can be recycled, so as to reduce cost.
Overlength beta-silicon nitride nanowire prepared by present embodiment can apply to the neck such as composite, nanoelectronic component
Domain, can also further expand the practical ranges of nano wire.
Embodiment two：The difference of present embodiment and embodiment one is：SiC powder described in step one
The particle diameter of body is.Other are identical with embodiment one.
Embodiment three：One of present embodiment and embodiment one or two difference is：Institute in step one
The porous body stated or powder are shaped as porous body or powder.Other are identical with embodiment one or two.
Embodiment four：One of present embodiment and embodiment one to three difference is：Will in step one
SiC powder is added in amphene, adds Polycarbosilane, is 60 DEG C of constant temperature ball milling 8h in temperature, is then transferred to freeze drier
It is middle to be freezed and dried 30h, that is, obtain porous body or powder；The volume ratio of SiC powder and amphene described in step one
For 1:10；The mass ratio of SiC powder and Polycarbosilane described in step one is 10: 1.Other with embodiment one to
Three is identical.
Embodiment five：One of present embodiment and embodiment one to four difference is：Will in step one
SiC powder is added in amphene, adds Polycarbosilane, is 60 DEG C of constant temperature ball milling 10h in temperature, is then transferred to freeze drier
It is middle to be freezed and dried 32h, that is, obtain porous body or powder；The volume ratio of SiC powder and amphene described in step one
For 3:25；The mass ratio of SiC powder and Polycarbosilane described in step one is 20: 3.Other with embodiment one to
Four is identical.
Embodiment six：One of present embodiment and embodiment one to five difference is：Will in step one
SiC powder is added in amphene, adds Polycarbosilane, is 60 DEG C of constant temperature ball milling 12h in temperature, is then transferred to freeze drier
It is middle to be freezed and dried 34h, that is, obtain porous body or powder；The volume ratio of SiC powder and amphene described in step one
For 3:20；The mass ratio of SiC powder and Polycarbosilane described in step one is 50:9.Other and embodiment one to five
It is identical.
Embodiment seven：One of present embodiment and embodiment one to six difference is：Will in step one
SiC powder is added in amphene, adds Polycarbosilane, is 60 DEG C of constant temperature ball milling 15h in temperature, is then transferred to freeze drier
It is middle to be freezed and dried 36h, that is, obtain porous body or powder；The volume ratio of SiC powder and amphene described in step one
For 9:50；The mass ratio of SiC powder and Polycarbosilane described in step one is 5:1.Other and embodiment one to six
It is identical.
Embodiment eight：One of present embodiment and embodiment one to seven difference is：In step 2 first
It is passed through nitrogen and keeps 75mL/min flow velocitys, then again using 2 DEG C/min programming rates from room temperature to temperature as 1350 DEG C, and
5h is incubated under conditions of temperature is 1350 DEG C, being then down to temperature as 1350 DEG C from temperature using 2 DEG C/min cooling rates again is
500℃.Other are identical with embodiment one to seven.
Embodiment nine：One of present embodiment and embodiment one to eight difference is：In step 2 first
It is passed through nitrogen and keeps 100mL/min flow velocitys, then again using 3 DEG C/min programming rates from room temperature to temperature as 1400 DEG C,
And 3h is incubated under conditions of temperature is 1400 DEG C, temperature is then down to from temperature as 1400 DEG C using 3 DEG C/min cooling rates again
For 500 DEG C.Other are identical with embodiment one to eight.
Embodiment ten：One of present embodiment and embodiment one to nine difference is：In step 2 first
It is passed through nitrogen and keeps 200mL/min flow velocitys, then again using 4 DEG C/min programming rates from room temperature to temperature as 1450 DEG C,
And 3h is incubated under conditions of temperature is 1450 DEG C, temperature is then down to from temperature as 1450 DEG C using 4 DEG C/min cooling rates again
For 500 DEG C.Other are identical with embodiment one to nine.
Embodiment 11：One of present embodiment and embodiment one to ten difference is：In step 2
First it is passed through nitrogen and keeps 300mL/min flow velocitys, then again using 5 DEG C/min programming rates from room temperature to temperature as 1470
DEG C, and 2h is incubated under conditions of temperature is 1470 DEG C, temperature is then down to from temperature as 1470 DEG C using 5 DEG C/min cooling rates again
Spend for 500 DEG C.Other are identical with embodiment one to ten.
Present invention is not limited only to the content of the respective embodiments described above, the group of one of them or several embodiments
Contract sample can also realize the purpose of invention.
Using following verification experimental verifications effect of the present invention
Embodiment 1：It is a kind of to prepare overlength in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ
The method of beta-silicon nitride nanowire, is specifically realized by the following steps：
First, porous body or powder shaped carborundum-Polycarbosilane are prepared：SiC powder is added in amphene, poly- carbon is added
Silane, is 60 DEG C of constant temperature ball milling 20h in temperature, is then transferred in freeze drier and is freezed and dried 48h, obtain porous
Base substrate or powder shaped carborundum-Polycarbosilane, at the same time, the white solid i.e. amphene scraped from the wall of freeze drier four can be with
Recycle；The volume ratio of SiC powder and amphene described in step one is 1:5；SiC powder and poly- carbon described in step one
The mass ratio of silane is 5:1；
2nd, it is heat-treated：Porous body or powder shaped carborundum-Polycarbosilane are fitted into porcelain Noah's ark, then porcelain Noah's ark is put
Enter in tube furnace, nitrogen is continually fed into 50mL/min flow velocitys, make in nitrogen protection in tube furnace, then again with 1 DEG C/min
Programming rate from room temperature to temperature be 1400 DEG C, and temperature be 1400 DEG C under conditions of be incubated 6h, then again with 1 DEG C/
Min cooling rates are 1400 DEG C from temperature, and to be down to temperature be 500 DEG C, then cools to room temperature with the furnace, that is, complete in porous body or
Powder shaped carborundum-Polycarbosilane surface in situ and the wall ex situ of porcelain Noah's ark four prepare overlength beta-silicon nitride nanowire.
The particle diameter of SiC powder is described in the step one of embodiment 1。
Fig. 1 is the photo in kind for the product that the step 2 of embodiment 1 is obtained, and what as seen in Figure 1 prepared by embodiment 1 surpasses
Long silicon nitride nano line length has reached several millimeters of even centimetre ranks, understands this implementation in porous body or powder by measurement
The overlength silicon nitride nano line length of body shape carborundum-Polycarbosilane superficial growth is about 2mm, in the growth of the wall surface of porcelain Noah's ark four
Overlength silicon nitride nano line length be about 5mm, it is most long up to 1cm.
Fig. 2 is the SEM figures for the overlength beta-silicon nitride nanowire that embodiment 1 is obtained, as shown in Figure 2 beta-silicon nitride nanowire purity
Very high, diameter is evenly distributed, and product is main linearly to exist.
Fig. 3 is the XRD for the overlength beta-silicon nitride nanowire that embodiment 1 is obtained, as shown in Figure 3 overlength beta-silicon nitride nanowire
Mainly with α-Si3N4In the presence of.
Embodiment 2：It is a kind of to prepare overlength in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ
The method of beta-silicon nitride nanowire, is specifically realized by the following steps：
First, porous body or powder shaped carborundum-Polycarbosilane are prepared：SiC powder is added in amphene, poly- carbon is added
Silane, is 60 DEG C of constant temperature ball milling 18h in temperature, is then transferred in freeze drier and is freezed and dried 45h, obtain porous
Base substrate or powder shaped carborundum-Polycarbosilane, at the same time, the white solid i.e. amphene scraped from the wall of freeze drier four can be with
Recycle；The volume ratio of SiC powder and amphene described in step one is 1:5；SiC powder and poly- carbon described in step one
The mass ratio of silane is 20:3；
2nd, it is heat-treated：Porous body or powder shaped carborundum-Polycarbosilane are fitted into porcelain Noah's ark, then porcelain Noah's ark is put
Enter in tube furnace, nitrogen is continually fed into 75mL/min flow velocitys, make in nitrogen protection in tube furnace, then again with 3 DEG C/min
Programming rate from room temperature to temperature be 1400 DEG C, and temperature be 1400 DEG C under conditions of be incubated 5h, then again with 3 DEG C/
Min cooling rates are 1400 DEG C from temperature, and to be down to temperature be 500 DEG C, then cools to room temperature with the furnace, that is, complete in porous body or
Powder shaped carborundum-Polycarbosilane surface in situ and the wall ex situ of porcelain Noah's ark four prepare overlength beta-silicon nitride nanowire.
The particle diameter of SiC powder is described in the step one of embodiment 2。
Embodiment 3：It is a kind of to prepare overlength in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ
The method of beta-silicon nitride nanowire, is specifically realized by the following steps：
First, porous body or powder shaped carborundum-Polycarbosilane are prepared：SiC powder is added in amphene, poly- carbon is added
Silane, is 60 DEG C of constant temperature ball milling 15h in temperature, is then transferred in freeze drier and is freezed and dried 42h, that is, obtain many
Hole base substrate or powder shaped carborundum-Polycarbosilane, at the same time, the white solid i.e. amphene scraped from the wall of freeze drier four can
To recycle；The volume ratio of SiC powder and amphene described in step one is 1:5；SiC powder described in step one is with gathering
The mass ratio of carbon silane is 10:1；
2nd, it is heat-treated：Porous body or powder shaped carborundum-Polycarbosilane body are fitted into porcelain Noah's ark, then by porcelain Noah's ark
Be put into tube furnace, nitrogen be continually fed into 100mL/min flow velocitys, make in tube furnace in nitrogen protection, then again with 5 DEG C/
Min programming rates are 1400 DEG C from room temperature to temperature, and are incubated 4h under conditions of temperature is 1400 DEG C, then again with 5
DEG C/min cooling rates from temperature are 1400 DEG C to be down to temperature are 500 DEG C, then cool to room temperature with the furnace, that is, complete in porous body
Or powder surface is in situ and the wall ex situ of porcelain Noah's ark four prepares overlength beta-silicon nitride nanowire.
The particle diameter of SiC powder is described in the step one of embodiment 3。
Embodiment 4：It is a kind of to prepare overlength in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ
The method of beta-silicon nitride nanowire, is specifically realized by the following steps：
First, porous body or powder shaped carborundum-Polycarbosilane are prepared：SiC powder is added in amphene, poly- carbon is added
Silane, is 60 DEG C of constant temperature ball milling 12h in temperature, is then transferred in freeze drier and is freezed and dried 40h, that is, obtain many
Hole base substrate or powder shaped carborundum-Polycarbosilane, at the same time, the white solid i.e. amphene scraped from the wall of freeze drier four can
To recycle；The volume ratio of SiC powder and amphene described in step one is 1:5；SiC powder described in step one is with gathering
The mass ratio of carbon silane is 20:1；
2nd, it is heat-treated：Porous body or powder shaped carborundum-Polycarbosilane are fitted into porcelain Noah's ark, then porcelain Noah's ark is put
Enter in tube furnace, nitrogen is continually fed into 150mL/min flow velocitys, make in nitrogen protection in tube furnace, then again with 7 DEG C/min
Programming rate from room temperature to temperature be 1400 DEG C, and temperature be 1400 DEG C under conditions of be incubated 3h, then again with 7 DEG C/
Min cooling rates are 1400 DEG C from temperature, and to be down to temperature be 500 DEG C, then cools to room temperature with the furnace, that is, complete in porous body or
Powder shaped carborundum-Polycarbosilane surface in situ and the wall ex situ of porcelain Noah's ark four prepare overlength beta-silicon nitride nanowire.
The particle diameter of SiC powder is described in the step one of embodiment 4。
Embodiment 5：It is a kind of to prepare overlength in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ
The method of beta-silicon nitride nanowire, is specifically realized by the following steps：
First, porous body or powder shaped carborundum-Polycarbosilane are prepared：SiC powder is added in amphene, poly- carbon is added
Silane, is 60 DEG C of constant temperature ball milling 10h in temperature, is then transferred in freeze drier and is freezed and dried 38h, that is, obtain many
Hole base substrate or powder shaped carborundum-Polycarbosilane, at the same time, the white solid i.e. amphene scraped from the wall of freeze drier four can
To recycle；The volume ratio of SiC powder and amphene described in step one is 1:10；SiC powder described in step one with
The mass ratio of Polycarbosilane is 5:1；
2nd, it is heat-treated：Porous body or powder shaped carborundum-Polycarbosilane are fitted into porcelain Noah's ark, then porcelain Noah's ark is put
Enter in tube furnace, nitrogen be continually fed into 200mL/min flow velocitys, make in tube furnace in nitrogen protection, then again with 10 DEG C/
Min programming rates are 1400 DEG C from room temperature to temperature, and are incubated 2h under conditions of temperature is 1400 DEG C, then again with 10
DEG C/min cooling rates from temperature are 1400 DEG C to be down to temperature are 500 DEG C, then cool to room temperature with the furnace, that is, complete in porous body
Or powder shaped carborundum-Polycarbosilane surface in situ and the wall ex situ of porcelain Noah's ark four prepare overlength beta-silicon nitride nanowire.
The particle diameter of SiC powder is described in the step one of embodiment 5。
Embodiment 6：It is a kind of to prepare overlength in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ
The method of beta-silicon nitride nanowire, is specifically realized by the following steps：
First, porous body or powder shaped carborundum-Polycarbosilane are prepared：SiC powder is added in amphene, poly- carbon is added
Silane, is 60 DEG C of constant temperature ball milling 8h in temperature, is then transferred in freeze drier and is freezed and dried 36h, that is, obtain many
Hole base substrate or powder shaped carborundum-Polycarbosilane, at the same time, the white solid i.e. amphene scraped from the wall of freeze drier four can
To recycle；The volume ratio of SiC powder and amphene described in step one is 1:10；SiC powder described in step one with
The mass ratio of Polycarbosilane is 10:1；
2nd, it is heat-treated：Porous body or powder shaped carborundum-Polycarbosilane are fitted into porcelain Noah's ark, then porcelain Noah's ark is put
Enter in tube furnace, nitrogen is continually fed into 300mL/min flow velocitys, make in nitrogen protection in tube furnace, then again with 6 DEG C/min
Programming rate from room temperature to temperature be 1400 DEG C, and temperature be 1400 DEG C under conditions of be incubated 3h, then again with 6 DEG C/
Min cooling rates are 1400 DEG C from temperature, and to be down to temperature be 500 DEG C, then cools to room temperature with the furnace, that is, complete in porous body or
Powder shaped carborundum-Polycarbosilane surface in situ and the wall ex situ of porcelain Noah's ark four prepare overlength beta-silicon nitride nanowire.
The particle diameter of SiC powder is described in the step one of embodiment 6。
Claims (10)
1. a kind of prepare overlength silicon nitride nano in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ
The method of line, it is characterised in that it is completed according to the following steps：
First, porous body or powder shaped carborundum-Polycarbosilane are prepared：SiC powder is added in amphene, poly- carbon silicon is added
Alkane, is 60 DEG C of constant temperature ball milling 5h~20h in temperature, be then transferred in freeze drier freezed and be dried in vacuo 24h~
48h, that is, obtain porous body or powder shaped carborundum-Polycarbosilane；The volume ratio of SiC powder and amphene described in step one
For (1~4):20；The mass ratio of SiC powder and Polycarbosilane described in step one is 20:(1~5)；
2nd, it is heat-treated：Porous body or powder shaped carborundum-Polycarbosilane are fitted into porcelain Noah's ark, then porcelain Noah's ark is put into pipe
In formula stove, nitrogen is continually fed into 50mL/min~400mL/min flow velocitys, made in nitrogen protection in tube furnace, then with 1
DEG C/min~10 DEG C/min programming rates from room temperature to temperature be 1300~1500 DEG C, and temperature be 1300~1500 DEG C
Under conditions of be incubated 1h~6h, be then down to again using 1 DEG C/min~10 DEG C/min cooling rates from temperature as 1300~1500 DEG C
Temperature is 500 DEG C, then cools to room temperature with the furnace, that is, is completed in porous body or powder shaped carborundum-Polycarbosilane surface in situ
And the wall ex situ of porcelain Noah's ark four prepares overlength beta-silicon nitride nanowire.
2. one kind is in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ according to claim 1
The method for preparing overlength beta-silicon nitride nanowire, it is characterised in that the particle diameter of SiC powder described in step one is 0.1 μm~1 μm.
3. one kind is in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ according to claim 1
The method for preparing overlength beta-silicon nitride nanowire, it is characterised in that SiC powder is added in amphene in step one, poly- carbon silicon is added
Alkane, is 60 DEG C of constant temperature ball milling 8h in temperature, is then transferred in freeze drier and is freezed and dried 30h, that is, obtain porous
Base substrate or powder；The volume ratio of SiC powder and amphene described in step one is 1:10；SiC powder described in step one with
The mass ratio of Polycarbosilane is 10:1.
4. one kind is in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ according to claim 1
The method for preparing overlength beta-silicon nitride nanowire, it is characterised in that SiC powder is added in amphene in step one, poly- carbon silicon is added
Alkane, is 60 DEG C of constant temperature ball milling 10h in temperature, is then transferred in freeze drier and is freezed and dried 32h, that is, obtain porous
Base substrate or powder；The volume ratio of SiC powder and amphene described in step one is 3:25；SiC powder described in step one with
The mass ratio of Polycarbosilane is 20:3.
5. one kind is in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ according to claim 1
The method for preparing overlength beta-silicon nitride nanowire, it is characterised in that SiC powder is added in amphene in step one, poly- carbon silicon is added
Alkane, is 60 DEG C of constant temperature ball milling 12h in temperature, is then transferred in freeze drier and is freezed and dried 34h, that is, obtain porous
Base substrate or powder；The volume ratio of SiC powder and amphene described in step one is 3:20；SiC powder described in step one with
The mass ratio of Polycarbosilane is 50:9.
6. one kind is in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ according to claim 1
The method for preparing overlength beta-silicon nitride nanowire, it is characterised in that SiC powder is added in amphene in step one, poly- carbon silicon is added
Alkane, is 60 DEG C of constant temperature ball milling 15h in temperature, is then transferred in freeze drier and is freezed and dried 36h, that is, obtain porous
Base substrate or powder；The volume ratio of SiC powder and amphene described in step one is 9:50；SiC powder described in step one with
The mass ratio of Polycarbosilane is 5:1.
7. one kind is in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ according to claim 1
The method for preparing overlength beta-silicon nitride nanowire, it is characterised in that nitrogen is first passed through in step 2 and 75mL/min flow velocitys are kept, so
Afterwards again using 2 DEG C/min programming rates from room temperature to temperature as 1350 DEG C, and 5h is incubated under conditions of temperature is 1350 DEG C,
Then it is 500 DEG C to be down to temperature as 1350 DEG C from temperature using 2 DEG C/min cooling rates again.
8. one kind is in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ according to claim 1
The method for preparing overlength beta-silicon nitride nanowire, it is characterised in that nitrogen is first passed through in step 2 and 100mL/min flow velocitys are kept, so
Afterwards again using 3 DEG C/min programming rates from room temperature to temperature as 1400 DEG C, and 3h is incubated under conditions of temperature is 1400 DEG C,
Then it is 500 DEG C to be down to temperature as 1400 DEG C from temperature using 3 DEG C/min cooling rates again.
9. one kind is in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ according to claim 1
The method for preparing overlength beta-silicon nitride nanowire, it is characterised in that nitrogen is first passed through in step 2 and 200mL/min flow velocitys are kept, so
Afterwards again using 4 DEG C/min programming rates from room temperature to temperature as 1450 DEG C, and 3h is incubated under conditions of temperature is 1450 DEG C,
Then it is 500 DEG C to be down to temperature as 1450 DEG C from temperature using 4 DEG C/min cooling rates again.
10. one kind is in porous body or powder shaped carborundum-Polycarbosilane surface in situ and ex situ according to claim 1
The method for preparing overlength beta-silicon nitride nanowire, it is characterised in that nitrogen is first passed through in step 2 and 300mL/min flow velocitys are kept, so
Afterwards again using 5 DEG C/min programming rates from room temperature to temperature as 1470 DEG C, and 2h is incubated under conditions of temperature is 1470 DEG C,
Then it is 500 DEG C to be down to temperature as 1470 DEG C from temperature using 5 DEG C/min cooling rates again.
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