CN105502315B - A kind of method that ex situ in situ grows overlength silicon nitride nano-material simultaneously - Google Patents
A kind of method that ex situ in situ grows overlength silicon nitride nano-material simultaneously Download PDFInfo
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- CN105502315B CN105502315B CN201610060579.XA CN201610060579A CN105502315B CN 105502315 B CN105502315 B CN 105502315B CN 201610060579 A CN201610060579 A CN 201610060579A CN 105502315 B CN105502315 B CN 105502315B
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 55
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 49
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000011066 ex-situ storage Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000011065 in-situ storage Methods 0.000 title abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 141
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 95
- 229910052757 nitrogen Inorganic materials 0.000 claims description 70
- 239000000377 silicon dioxide Substances 0.000 claims description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 229910052573 porcelain Inorganic materials 0.000 claims description 26
- 229910002804 graphite Inorganic materials 0.000 claims description 25
- 239000010439 graphite Substances 0.000 claims description 25
- 235000013312 flour Nutrition 0.000 claims description 24
- 239000011812 mixed powder Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 19
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229910021487 silica fume Inorganic materials 0.000 claims description 7
- 239000002070 nanowire Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910003978 SiClx Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001709 polysilazane Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 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
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- C01B21/0685—Preparation by carboreductive nitridation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/10—One-dimensional structures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Products (AREA)
Abstract
A kind of method that ex situ in situ grows overlength silicon nitride nano-material simultaneously, is related to a kind of preparation method of silicon nitride nano-material.The present invention is to need catalyst to solve the preparation method of current overlength silicon nitride nano-material, cause product purity not high, influence the high-temperature behavior and subsequent applications, reaction condition of nano wire more harsh, such as pressurize, be passed through flammable gas, cause processing safety relatively low, the technical problem higher to equipment requirement.The present invention：First, prefabricated powder is prepared；2nd, calcine.Operating process of the present invention is relatively simple, equipment requirement is low, safety coefficient is high etc..The present invention is applied to prepare overlength silicon nitride nano-material.
Description
Technical field
The present invention relates to a kind of preparation method of silicon nitride nano-material.
Background technology
High temperature resistant, anti-oxidant, broad-band gap relative to block materials, electrical insulating property be good and the Optimality such as medium heat transfer
Can, the performance of one-dimensional silicon nitride nano-material more attracts the sight of researcher, this mainly due to its special pattern with it is micro-
Caused by structure, while also making it that there is important application prospect in fields such as composite, nano-devices.It is current to prepare one
The method of dimension silicon nitride nano-material has a lot, such as carbothermic method, polymer cracking method, chemical vapour deposition technique, template
Deng.But it is less on the report in the original location with ex situ grown silicon nitride nano material simultaneously at present, and existing most prepare
Method is only capable of synthesizing the one-dimensional silicon nitride nano-material that length is tens to hundreds of microns, relative to receiving for these microscopic dimensions
Rice material, the preparation of overlength silicon nitride nano-material will expand it in basic research and the application of special field of nanometer devices
Prospect.
At present on the preparation method of overlength silicon nitride nano-material report it is less, the document of 2005 " W.Yang,
Z.Xie,J.Li,H.Miao,L.Zhang,L.An,Journal of the American Ceramic Society,88(6),
1647-1650. " is using liquid polysilazane as raw material, and prior to 260 DEG C progress curing process further take out grinding and and FeCl2Mixing
It is uniform to obtain several millimeters of nano wire in progress reaction under 1250 DEG C of condition of nitrogen gas, but contrast test is found, if being not added with catalysis
Agent is by the generation without nano wire；Document " L.W.Lin, Y.H.He.CrystEngComm, 14 (9), 3250- of 2012
3256. " with inflammable CH4For carbon source, SiO or Si and SiO2Mixture is silicon source in N2Under the conditions of be heated to 1400-1550 DEG C
(1.1~1.5atm), which is incubated 3h, under pressurized conditions can obtain the overlength beta-silicon nitride nanowire up to several millimeters.Although the above
Method successfully prepares the overlength silicon nitride nano-material up to several millimeters, but two problems of generally existing：(1) need to urge
Agent, such as iron, this can cause product purity not high, influence the high-temperature behavior and subsequent applications of nano wire；(2) reaction condition compared with
For harshness, such as pressurize, be passed through flammable gas, cause processing safety relatively low, it is higher etc. to equipment requirement.
The content of the invention
The present invention is to need catalyst to solve the preparation method of current overlength silicon nitride nano-material, causes product pure
Degree is not high, influences the high-temperature behavior and subsequent applications, reaction condition of nano wire more harsh, causes processing safety relatively low, right
The higher technical problem of equipment requirement, and a kind of original position-ex situ is provided while growing the method for overlength silicon nitride nano-material.
The method that a kind of original position-ex situ of the present invention grows overlength silicon nitride nano-material simultaneously is to enter according to the following steps
Capable：
First, prefabricated powder is prepared：Silica flour and silicon dioxide powder are well mixed, silicon-silica mixed powder is obtained, then will
Graphite and silicon-silica mixed powder are fitted into ball grinder together, the ball under conditions of rotating speed is 180r/min~300r/min
6h~30h is ground, the prefabricated powder of carbon-silicon is obtained；Described silica flour and the mol ratio of silicon dioxide powder are 1:1；In described graphite
The mol ratio of element silicon is 3 in carbon and silicon-silica mixed powder:1；
2nd, the prefabricated powder of carbon-silicon prepared by step one is put into porcelain Noah's ark, then porcelain Noah's ark is put into tube furnace,
With 1~10 DEG C/min heating rate from room temperature to 300 DEG C under conditions of nitrogen protection, it is in nitrogen protection and temperature
10min is incubated under conditions of 300 DEG C, then is heated up under conditions of nitrogen protection with 1~10 DEG C/min heating rate from 300 DEG C
Be to be incubated 10min under conditions of 800 DEG C in nitrogen protection and temperature to 800 DEG C, then under conditions of nitrogen protection with 1~
10 DEG C/min heating rate is warming up to 1500 DEG C from 800 DEG C, nitrogen protection and temperature be 1500 DEG C under conditions of insulation 1~
6h, is then cooled to 500 DEG C, furnace cooling with 1~10 DEG C/min rate of temperature fall under conditions of nitrogen protection from 1500 DEG C
To room temperature, that is, complete in powder surface original position and the wall ex situ of porcelain Noah's ark four while obtaining overlength silicon nitride nano-material.
The present invention is pre- with acquisition carbon-silicon after ball milling through weighing mainly using silica flour, silicon dioxide powder and graphite as raw material
Powder processed, through simple preparation method in can just prepare the overlength silicon nitride nano-material up to several millimeters grades under normal pressure.
Operating process is relatively simple, equipment requirement is low, safety coefficient is high etc..Overlength nano material prepared by the present invention can not only be applied
In fields such as nanoelectronic components, its application prospect in fragile material can also be further expanded.It is prepared by the present invention
Micron-sized graphite powder, nano level silicon and silicon dioxide powder etc. are employed during nano wire, but in actual fabrication process, can be with
The graphite, silicon, silicon-dioxide powdery of any particle diameter are selected, when selected particle diameter is different by selecting different ball milling parameters to obtain
Well mixed inorganic mixed material, can also obtain well-grown and up to several millimeters according to the similar method of the present invention afterwards
Overlength silicon nitride nano-material.
Brief description of the drawings
Fig. 1 is the photo in kind for testing an overlength silicon nitride nano-material prepared；
Fig. 2 is the SEM figures for testing an i.e. growth in situ overlength silicon nitride nano-material in beta-silicon nitride powder surface prepared；
Fig. 3 is the SEM figures for testing the overlength silicon nitride nano-material grown in one in the wall ex situ of porcelain Noah's ark four；
Fig. 4 is to test a beta-silicon nitride powder surface i.e. XRD for growth in situ overlength silicon nitride nano-material prepared.
Embodiment
Embodiment one：Present embodiment is that a kind of original position-ex situ grows overlength silicon nitride nano-material simultaneously
Method, be specifically according to the following steps to carry out：
First, prefabricated powder is prepared：Silica flour and silicon dioxide powder are well mixed, silicon-silica mixed powder is obtained, then will
Graphite and silicon-silica mixed powder are fitted into ball grinder together, the ball under conditions of rotating speed is 180r/min~300r/min
6h~30h is ground, the prefabricated powder of carbon-silicon is obtained；Described silica flour and the mol ratio of silicon dioxide powder are 1:1；In described graphite
The mol ratio of element silicon is 3 in carbon and silicon-silica mixed powder:1；
2nd, the prefabricated powder of carbon-silicon prepared by step one is put into porcelain Noah's ark, then porcelain Noah's ark is put into tube furnace,
With 1~10 DEG C/min heating rate from room temperature to 300 DEG C under conditions of nitrogen protection, it is in nitrogen protection and temperature
10min is incubated under conditions of 300 DEG C, then is heated up under conditions of nitrogen protection with 1~10 DEG C/min heating rate from 300 DEG C
Be to be incubated 10min under conditions of 800 DEG C in nitrogen protection and temperature to 800 DEG C, then under conditions of nitrogen protection with 1~
10 DEG C/min heating rate is warming up to 1500 DEG C from 800 DEG C, nitrogen protection and temperature be 1500 DEG C under conditions of insulation 1~
6h, is then cooled to 500 DEG C, furnace cooling with 1~10 DEG C/min rate of temperature fall under conditions of nitrogen protection from 1500 DEG C
To room temperature, that is, complete in powder surface original position and the wall ex situ of porcelain Noah's ark four while obtaining overlength silicon nitride nano-material.
Embodiment two：The difference of present embodiment and embodiment one is：In step one during ball milling
The mass ratio of ball material is (30~5):1.Other are identical with embodiment one.
Embodiment three：The difference of present embodiment and embodiment one or two is：Described in step one
Silica flour be industrial silica fume, particle diameter be 0.05 μm~0.15 μm.Other are identical with embodiment one or two.
Embodiment four：The difference of present embodiment and embodiment one to three is：Described in step one
Silicon dioxide powder particle diameter be 0.02 μm~0.05 μm.Other are identical with embodiment one to three.
Embodiment five：The difference of present embodiment and embodiment one to four is：Described in step one
Graphite particle diameter be 10 μm~20 μm.Other are identical with embodiment one to four.
Embodiment six：The difference of present embodiment and embodiment one to five is：Described in step 2
Nitrogen protection be specially：Condition using flow velocity as 50mL/min~400mL/min is passed through nitrogen.Other and embodiment
One to five is identical.
Beneficial effects of the present invention are verified by tests below：
Experiment one：This experiment is a kind of method that original position-ex situ grows overlength silicon nitride nano-material simultaneously, is specifically
Carry out according to the following steps：
First, prefabricated powder is prepared：Silica flour and silicon dioxide powder are well mixed, silicon-silica mixed powder is obtained, then will
Graphite and silicon-silica mixed powder are fitted into ball grinder together, the ball milling 6h under conditions of rotating speed is 300r/min, obtain
The prefabricated powder of carbon-silicon；Described silica flour and the mol ratio of silicon dioxide powder are 1:1；Carbon and silicon-dioxy in described graphite
The mol ratio of element silicon is 3 in SiClx mixed powder:1；
2nd, the prefabricated powder of carbon-silicon prepared by step one is put into porcelain Noah's ark, then porcelain Noah's ark is put into tube furnace,
It it is 300 DEG C in nitrogen protection and temperature with 3 DEG C/min heating rate from room temperature to 300 DEG C under conditions of nitrogen protection
Under conditions of be incubated 10min, then with 3 DEG C/min heating rate be warming up to 800 DEG C from 300 DEG C under conditions of nitrogen protection,
10min is incubated under conditions of nitrogen protection and temperature is 800 DEG C, then with 5 DEG C/min liter under conditions of nitrogen protection
Warm speed is warming up to 1500 DEG C from 800 DEG C, is incubated 2h under conditions of nitrogen protection and temperature is 1500 DEG C, is then protected in nitrogen
500 DEG C are cooled to from 1500 DEG C with 5 DEG C/min rate of temperature fall under conditions of shield, room temperature is cooled to the furnace, that is, completed in powder
Surface in situ and the wall ex situ of porcelain Noah's ark four obtain overlength silicon nitride nano-material simultaneously.
The mass ratio of ball material in step one during ball milling is 30:1；Silica flour described in step one is industrial silica fume, particle diameter
For 0.10 μm；The particle diameter of silicon dioxide powder described in step one is 0.025 μm；The particle diameter of graphite described in step one is 20
μm；Nitrogen described in step 2, which is protected, is specially：Condition using flow velocity as 50mL/min is passed through nitrogen.
Experiment two：This experiment is a kind of method that original position-ex situ grows overlength silicon nitride nano-material simultaneously, is specifically
Carry out according to the following steps：
First, prefabricated powder is prepared：Silica flour and silicon dioxide powder are well mixed, silicon-silica mixed powder is obtained, then will
Graphite and silicon-silica mixed powder are fitted into ball grinder together, the ball milling 10h under conditions of rotating speed is 280r/min, obtain
The prefabricated powder of carbon-silicon；Described silica flour and the mol ratio of silicon dioxide powder are 1:1；Carbon and silicon-dioxy in described graphite
The mol ratio of element silicon is 3 in SiClx mixed powder:1；
2nd, the prefabricated powder of carbon-silicon prepared by step one is put into porcelain Noah's ark, then porcelain Noah's ark is put into tube furnace,
It it is 300 DEG C in nitrogen protection and temperature with 4 DEG C/min heating rate from room temperature to 300 DEG C under conditions of nitrogen protection
Under conditions of be incubated 10min, then with 4 DEG C/min heating rate be warming up to 800 DEG C from 300 DEG C under conditions of nitrogen protection,
10min is incubated under conditions of nitrogen protection and temperature is 800 DEG C, then with 4 DEG C/min liter under conditions of nitrogen protection
Warm speed is warming up to 1500 DEG C from 800 DEG C, is incubated 2h under conditions of nitrogen protection and temperature is 1500 DEG C, is then protected in nitrogen
500 DEG C are cooled to from 1500 DEG C with 4 DEG C/min rate of temperature fall under conditions of shield, room temperature is cooled to the furnace, that is, completed in powder
Surface in situ and the wall ex situ of porcelain Noah's ark four obtain overlength silicon nitride nano-material simultaneously.
The mass ratio of ball material in step one during ball milling is 25:1；Silica flour described in step one is industrial silica fume, particle diameter
For 0.05 μm~0.15 μm；The particle diameter of silicon dioxide powder described in step one is 0.02 μm~0.05 μm；Described in step one
Graphite particle diameter be 10 μm~20 μm；Nitrogen described in step 2, which is protected, is specially：Using flow velocity as 75mL/min condition
It is passed through nitrogen.
Experiment three：This experiment is a kind of method that original position-ex situ grows overlength silicon nitride nano-material simultaneously, is specifically
Carry out according to the following steps：
First, prefabricated powder is prepared：Silica flour and silicon dioxide powder are well mixed, silicon-silica mixed powder is obtained, then will
Graphite and silicon-silica mixed powder are fitted into ball grinder together, the ball milling 15h under conditions of rotating speed is 240r/min, obtain
The prefabricated powder of carbon-silicon；Described silica flour and the mol ratio of silicon dioxide powder are 1:1；Carbon and silicon-dioxy in described graphite
The mol ratio of element silicon is 3 in SiClx mixed powder:1；
2nd, the prefabricated powder of carbon-silicon prepared by step one is put into porcelain Noah's ark, then porcelain Noah's ark is put into tube furnace,
It it is 300 DEG C in nitrogen protection and temperature with 5 DEG C/min heating rate from room temperature to 300 DEG C under conditions of nitrogen protection
Under conditions of be incubated 15min, then with 5 DEG C/min heating rate be warming up to 800 DEG C from 300 DEG C under conditions of nitrogen protection,
15min is incubated under conditions of nitrogen protection and temperature is 800 DEG C, then with 5 DEG C/min liter under conditions of nitrogen protection
Warm speed is warming up to 1500 DEG C from 800 DEG C, is incubated 2h under conditions of nitrogen protection and temperature is 1500 DEG C, is then protected in nitrogen
500 DEG C are cooled to from 1500 DEG C with 5 DEG C/min rate of temperature fall under conditions of shield, room temperature is cooled to the furnace, that is, completed in powder
Surface in situ and the wall ex situ of porcelain Noah's ark four obtain overlength silicon nitride nano-material simultaneously.
The mass ratio of ball material in step one during ball milling is 20:1；Silica flour described in step one is industrial silica fume, particle diameter
For 0.05 μm~0.15 μm；The particle diameter of silicon dioxide powder described in step one is 0.02 μm~0.05 μm；Described in step one
Graphite particle diameter be 10 μm~20 μm；Nitrogen described in step 2, which is protected, is specially：Using flow velocity as 100mL/min condition
It is passed through nitrogen.
Experiment four：This experiment is a kind of method that original position-ex situ grows overlength silicon nitride nano-material simultaneously, is specifically
Carry out according to the following steps：
First, prefabricated powder is prepared：Silica flour and silicon dioxide powder are well mixed, silicon-silica mixed powder is obtained, then will
Graphite and silicon-silica mixed powder are fitted into ball grinder together, the ball milling 20h under conditions of rotating speed is 200r/min, obtain
The prefabricated powder of carbon-silicon；Described silica flour and the mol ratio of silicon dioxide powder are 1:1；Carbon and silicon-dioxy in described graphite
The mol ratio of element silicon is 3 in SiClx mixed powder:1；
2nd, the prefabricated powder of carbon-silicon prepared by step one is put into porcelain Noah's ark, then porcelain Noah's ark is put into tube furnace,
It it is 300 DEG C in nitrogen protection and temperature with 6 DEG C/min heating rate from room temperature to 300 DEG C under conditions of nitrogen protection
Under conditions of be incubated 20min, then with 6 DEG C/min heating rate be warming up to 800 DEG C from 300 DEG C under conditions of nitrogen protection,
20min is incubated under conditions of nitrogen protection and temperature is 800 DEG C, then with 6 DEG C/min liter under conditions of nitrogen protection
Warm speed is warming up to 1500 DEG C from 800 DEG C, is incubated 2h under conditions of nitrogen protection and temperature is 1500 DEG C, is then protected in nitrogen
500 DEG C are cooled to from 1500 DEG C with 6 DEG C/min rate of temperature fall under conditions of shield, room temperature is cooled to the furnace, that is, completed in powder
Surface in situ and the wall ex situ of porcelain Noah's ark four obtain overlength silicon nitride nano-material simultaneously.
The mass ratio of ball material in step one during ball milling is 30:1；Silica flour described in step one is industrial silica fume, particle diameter
For 0.05 μm~0.15 μm；The particle diameter of silicon dioxide powder described in step one is 0.02 μm~0.05 μm；Described in step one
Graphite particle diameter be 10 μm~20 μm；Nitrogen described in step 2, which is protected, is specially：Using flow velocity as 200mL/min condition
It is passed through nitrogen.
Experiment five：This experiment is a kind of method that original position-ex situ grows overlength silicon nitride nano-material simultaneously, is specifically
Carry out according to the following steps：
First, prefabricated powder is prepared：Silica flour and silicon dioxide powder are well mixed, silicon-silica mixed powder is obtained, then will
Graphite and silicon-silica mixed powder are fitted into ball grinder together, the ball milling 30h under conditions of rotating speed is 180r/min, obtain
The prefabricated powder of carbon-silicon；Described silica flour and the mol ratio of silicon dioxide powder are 1:1；Carbon and silicon-dioxy in described graphite
The mol ratio of element silicon is 3 in SiClx mixed powder:1；
2nd, the prefabricated powder of carbon-silicon prepared by step one is put into porcelain Noah's ark, then porcelain Noah's ark is put into tube furnace,
It it is 300 DEG C in nitrogen protection and temperature with 7 DEG C/min heating rate from room temperature to 300 DEG C under conditions of nitrogen protection
Under conditions of be incubated 25min, then with 7 DEG C/min heating rate be warming up to 800 DEG C from 300 DEG C under conditions of nitrogen protection,
25min is incubated under conditions of nitrogen protection and temperature is 800 DEG C, then with 7 DEG C/min liter under conditions of nitrogen protection
Warm speed is warming up to 1500 DEG C from 800 DEG C, is incubated 2h under conditions of nitrogen protection and temperature is 1500 DEG C, is then protected in nitrogen
500 DEG C are cooled to from 1500 DEG C with 7 DEG C/min rate of temperature fall under conditions of shield, room temperature is cooled to the furnace, that is, completed in powder
Surface in situ and the wall ex situ of porcelain Noah's ark four obtain overlength silicon nitride nano-material simultaneously.
The mass ratio of ball material in step one during ball milling is 30:1；Silica flour described in step one is industrial silica fume, particle diameter
For 0.05 μm~0.15 μm；The particle diameter of silicon dioxide powder described in step one is 0.02 μm~0.05 μm；Described in step one
Graphite particle diameter be 10 μm~20 μm；Nitrogen described in step 2, which is protected, is specially：Using flow velocity as 400mL/min condition
It is passed through nitrogen.
Fig. 1 is the photo in kind for testing an overlength silicon nitride nano-material prepared, is as can be seen from the figure prepared
Silicon nitride length has reached several millimeters of ranks.
Fig. 2 is the SEM figures for testing an i.e. growth in situ overlength silicon nitride nano-material in beta-silicon nitride powder surface prepared, from
The silicon nitride nano-material of it can be seen from the figure that growth in situ is mainly presented with banding.
Fig. 3 is the SEM figures for testing the overlength silicon nitride nano-material grown in one in the wall ex situ of porcelain Noah's ark four, from figure
Presented it can be seen that the overlength silicon nitride nano-material of ex situ growth is main with cylindric, prism-shaped, banding etc..
Fig. 4 is to test a beta-silicon nitride powder surface i.e. XRD for growth in situ overlength silicon nitride nano-material prepared, from
It can be seen from the figure that product is main with α-Si3N4In the presence of.
Claims (4)
1. a kind of method that original position-ex situ grows overlength silicon nitride nano-material simultaneously, it is characterised in that original position-ex situ is same
The method of Shi Shengchang overlength silicon nitride nano-materials is carried out according to the following steps：
First, prefabricated powder is prepared：Silica flour and silicon dioxide powder are well mixed, silicon-silica mixed powder is obtained, then by graphite
It is fitted into together in ball grinder with silicon-silica mixed powder, the ball milling 6h under conditions of rotating speed is 180r/min~300r/min
~30h, obtains the prefabricated powder of carbon-silicon；Described silica flour and the mol ratio of silicon dioxide powder are 1:1；Carbon member in described graphite
The mol ratio of element silicon is 3 in element and silicon-silica mixed powder:1；The particle diameter of graphite described in step one is 10 μm~20
μm；
2nd, the prefabricated powder of carbon-silicon prepared by step one is put into porcelain Noah's ark, then porcelain Noah's ark is put into tube furnace, in nitrogen
It it is 300 DEG C in nitrogen protection and temperature with 1~10 DEG C/min heating rate from room temperature to 300 DEG C under conditions of protection
Under conditions of be incubated 10min, then with 1~10 DEG C/min heating rate be warming up to 800 from 300 DEG C under conditions of nitrogen protection
DEG C, nitrogen protection and temperature be 800 DEG C under conditions of be incubated 10min, then nitrogen protection under conditions of with 1~10 DEG C/
Min heating rate is warming up to 1500 DEG C from 800 DEG C, is incubated 1~6h under conditions of nitrogen protection and temperature is 1500 DEG C, so
500 DEG C are cooled to from 1500 DEG C with 1~10 DEG C/min rate of temperature fall under conditions of nitrogen protection afterwards, room is cooled to the furnace
Temperature, that is, complete in powder surface original position and the wall ex situ of porcelain Noah's ark four while obtaining overlength silicon nitride nano-material；In step 2
Described nitrogen is protected：Condition using flow velocity as 50mL/min~400mL/min is passed through nitrogen.
2. the method that a kind of original position-ex situ according to claim 1 grows overlength silicon nitride nano-material simultaneously, it is special
The mass ratio for levying ball material when being ball milling in step one is (30~5):1.
3. the method that a kind of original position-ex situ according to claim 1 grows overlength silicon nitride nano-material simultaneously, it is special
Levy and be that the silica flour described in step one is industrial silica fume, particle diameter is 0.05 μm~0.15 μm.
4. the method that a kind of original position-ex situ according to claim 1 grows overlength silicon nitride nano-material simultaneously, it is special
Levy and be the particle diameter of the silicon dioxide powder described in step one for 0.02 μm~0.05 μm.
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