CN105502315A - Method for synchronously growing ultralong silicon nitride nanomaterials in situ and ex situ - Google Patents
Method for synchronously growing ultralong silicon nitride nanomaterials in situ and ex situ Download PDFInfo
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- CN105502315A CN105502315A CN201610060579.XA CN201610060579A CN105502315A CN 105502315 A CN105502315 A CN 105502315A CN 201610060579 A CN201610060579 A CN 201610060579A CN 105502315 A CN105502315 A CN 105502315A
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 57
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 52
- 238000011066 ex-situ storage Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000011065 in-situ storage Methods 0.000 title abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 10
- 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 75
- 229910052757 nitrogen Inorganic materials 0.000 claims description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 26
- 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
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- FRIKWZARTBPWBN-UHFFFAOYSA-N [Si].O=[Si]=O Chemical compound [Si].O=[Si]=O FRIKWZARTBPWBN-UHFFFAOYSA-N 0.000 claims description 24
- 235000013312 flour Nutrition 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 23
- 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 17
- 238000010792 warming Methods 0.000 claims description 16
- 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
- 238000002360 preparation method Methods 0.000 abstract description 13
- 239000002070 nanowire Substances 0.000 abstract description 7
- 238000001354 calcination Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 206010037660 Pyrexia Diseases 0.000 description 1
- 229910004298 SiO 2 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005336 cracking Methods 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
- 239000011159 matrix material 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
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
Abstract
The invention provides a method for synchronously growing ultralong silicon nitride nanomaterials in situ and ex situ, relates to a preparation method for a silicon nitride nanomaterial, and aims to solve technical problems that the purity of products is low due to the fact that the current ultralong silicon nitride nanometer material preparation method needs catalysts, high-temperature performance and subsequent applications of nanowires are influenced, reaction conditions are severe, and due to pressurizing and flammable gas feeding, the operation security is low, and requirements on equipment are high. The method comprises the following steps: 1, preparing prefabricated powders; 2, calcining. The method for synchronously growing the ultralong silicon nitride nanomaterials in situ and ex situ has a simple operation process, low requirements on equipment, high security coefficient and the like, and is applied to preparation of ultralong silicon nitride nanomaterials.
Description
Technical field
The present invention relates to a kind of preparation method of silicon nitride nano-material.
Background technology
Relative to block materials high temperature resistant, anti-oxidant, broad-band gap, electrical insulating property are good and the premium properties such as moderate fever conduction, the performance of one dimension silicon nitride nano-material attracts the sight of investigator more, this mainly causes due to its special pattern and microstructure, also makes it have important application prospect in the field such as matrix material, nano-device simultaneously.The current method preparing one dimension silicon nitride nano-material has a lot, as carbothermic method, polymer cracking method, chemical Vapor deposition process, template etc.But at present about less with the report of grown silicon nitride nano material while of ex situ in position, and existing majority system Preparation Method only can synthesize the one dimension silicon nitride nano-material that length is tens to hundreds of micron, relative to the nano material of these microscopic dimensions, the preparation of overlength silicon nitride nano-material will expand its application prospect in fundamental research and special field of nanometer devices.
At present about the preparation method of overlength silicon nitride nano-material report less, the document " W.Yang, Z.Xie, J.Li; H.Miao; L.Zhang, L.An, JournaloftheAmericanCeramicSociety; 88 (6); 1647-1650. " of 2005 for raw material, is cured process prior to 260 DEG C with liquid polysilazane, then takes out grinding and and FeCl
2mix and carry out reacting the nano wire obtaining several millimeters under 1250 DEG C of condition of nitrogen gas, but simultaneous test finds, if do not add catalyzer will not have the generation of nano wire; The document " L.W.Lin, Y.H.He.CrystEngComm, 14 (9), 3250-3256. " of 2012 is with inflammable CH
4for carbon source, SiO or Si and SiO
2mixture is that silicon comes from N
2be heated to (1.1 ~ 1.5atm) under 1400-1550 DEG C of pressurized conditions under condition be incubated 3h and can obtain the overlength beta-silicon nitride nanowire reaching several millimeters.Although above method successfully prepares the overlength silicon nitride nano-material reaching several millimeters, but ubiquity two problems: (1) needs catalyzer, as iron etc., this can cause product purity not high, affects high-temperature behavior and the subsequent applications of nano wire; (2) reaction conditions is comparatively harsh, as pressurization, passes into flammable gas etc., causes processing safety lower, more high to equipment requirements.
Summary of the invention
The present invention is that the preparation method in order to solve current overlength silicon nitride nano-material needs catalyzer, cause product purity not high, affect the high-temperature behavior of nano wire and subsequent applications, reaction conditions is comparatively harsh, cause processing safety lower, the technical problem higher to equipment requirements, and provide a kind of original position-ex situ to grow the method for overlength silicon nitride nano-material simultaneously.
The method that a kind of original position-ex situ of the present invention grows overlength silicon nitride nano-material is simultaneously carried out according to the following steps:
One, prefabricated powder is prepared: silica flour and silicon dioxide powder are mixed, obtain silicon-silicon-dioxide powder mix, again graphite is loaded in ball grinder together with silicon-silicon-dioxide powder mix, be ball milling 6h ~ 30h under the condition of 180r/min ~ 300r/min at rotating speed, obtain the prefabricated powder of carbon-silicon; Described silica flour and the mol ratio of silicon dioxide powder are 1:1; In described graphite, in carbon and silicon-silicon-dioxide powder mix, the mol ratio of element silicon is 3:1;
Two, the prefabricated powder of carbon-silicon step one prepared puts into porcelain Noah's ark, again porcelain Noah's ark is put into tube furnace, under the condition of nitrogen protection with the temperature rise rate of 1 ~ 10 DEG C/min from room temperature to 300 DEG C, 10min is incubated under nitrogen protection and temperature are the condition of 300 DEG C, 800 DEG C are warming up to the temperature rise rate of 1 ~ 10 DEG C/min from 300 DEG C again under the condition of nitrogen protection, 10min is incubated under nitrogen protection and temperature are the condition of 800 DEG C, then under the condition of nitrogen protection, 1500 DEG C are warming up to the temperature rise rate of 1 ~ 10 DEG C/min from 800 DEG C, 1 ~ 6h is incubated under nitrogen protection and temperature are the condition of 1500 DEG C, then under the condition of nitrogen protection, 500 DEG C are cooled to the rate of temperature fall of 1 ~ 10 DEG C/min from 1500 DEG C, cool to room temperature with the furnace, namely complete and obtain overlength silicon nitride nano-material in powder surface original position and porcelain Noah's ark wall ex situ simultaneously.
The present invention mainly with silica flour, silicon dioxide powder and graphite for raw material, through weigh and ball milling after obtain the prefabricated powder of carbon-silicon, just can prepare under normal pressure through simple preparation method and reach several millimetre-sized overlength silicon nitride nano-material.Operating process is comparatively simple, equipment requirements is low, safety coefficient is high.Overlength nano material prepared by the present invention not only can be applied to the fields such as nanoelectronic components and parts, can also expand further its application prospect in hard brittle material.The present invention have employed micron-sized Graphite Powder 99, nano level silicon and silicon dioxide powder etc. when preparing nano wire, but in actual fabrication process, the graphite of any particle diameter, silicon, silicon-dioxide powdery can be selected, when selected particle diameter being different by selecting different ball milling parameter to obtain the inorganic mixing raw material mixed, also can obtaining well-grown according to the method that the present invention is similar afterwards and reaching the overlength silicon nitride nano-material of several millimeters.
Accompanying drawing explanation
Fig. 1 is the photo in kind of overlength silicon nitride nano-material prepared by test one;
Fig. 2 is the silicon nitride powder surface of test one preparation and the SEM figure of growth in situ overlength silicon nitride nano-material;
Fig. 3 is the SEM figure at the overlength silicon nitride nano-material of porcelain Noah's ark wall ex situ growth in test one;
Fig. 4 is the silicon nitride powder surface of test one preparation and the XRD figure of growth in situ overlength silicon nitride nano-material.
Embodiment
Embodiment one: present embodiment is a kind of method that original position-ex situ grows overlength silicon nitride nano-material simultaneously, specifically carries out according to the following steps:
One, prefabricated powder is prepared: silica flour and silicon dioxide powder are mixed, obtain silicon-silicon-dioxide powder mix, again graphite is loaded in ball grinder together with silicon-silicon-dioxide powder mix, be ball milling 6h ~ 30h under the condition of 180r/min ~ 300r/min at rotating speed, obtain the prefabricated powder of carbon-silicon; Described silica flour and the mol ratio of silicon dioxide powder are 1:1; In described graphite, in carbon and silicon-silicon-dioxide powder mix, the mol ratio of element silicon is 3:1;
Two, the prefabricated powder of carbon-silicon step one prepared puts into porcelain Noah's ark, again porcelain Noah's ark is put into tube furnace, under the condition of nitrogen protection with the temperature rise rate of 1 ~ 10 DEG C/min from room temperature to 300 DEG C, 10min is incubated under nitrogen protection and temperature are the condition of 300 DEG C, 800 DEG C are warming up to the temperature rise rate of 1 ~ 10 DEG C/min from 300 DEG C again under the condition of nitrogen protection, 10min is incubated under nitrogen protection and temperature are the condition of 800 DEG C, then under the condition of nitrogen protection, 1500 DEG C are warming up to the temperature rise rate of 1 ~ 10 DEG C/min from 800 DEG C, 1 ~ 6h is incubated under nitrogen protection and temperature are the condition of 1500 DEG C, then under the condition of nitrogen protection, 500 DEG C are cooled to the rate of temperature fall of 1 ~ 10 DEG C/min from 1500 DEG C, cool to room temperature with the furnace, namely complete and obtain overlength silicon nitride nano-material in powder surface original position and porcelain Noah's ark wall ex situ simultaneously.
Embodiment two: the difference of present embodiment and embodiment one is: the mass ratio of the ball material in step one during ball milling is (30 ~ 5): 1.Other are identical with embodiment one.
Embodiment three: the difference of present embodiment and embodiment one or two is: the silica flour described in step one is industrial silica fume, particle diameter is 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: the particle diameter of the silicon dioxide powder described in step one is 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: the particle diameter of the graphite described in step one is 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: the nitrogen protection described in step 2 is specially: be that the condition of 50mL/min ~ 400mL/min passes into nitrogen with flow velocity.Other are identical with embodiment one to five.
By following verification experimental verification beneficial effect of the present invention:
Test one: this test is a kind of method that original position-ex situ grows overlength silicon nitride nano-material simultaneously, specifically carries out according to the following steps:
One, prefabricated powder is prepared: silica flour and silicon dioxide powder are mixed, obtain silicon-silicon-dioxide powder mix, again graphite is loaded in ball grinder together with silicon-silicon-dioxide powder mix, be ball milling 6h under the condition of 300r/min at rotating speed, obtain the prefabricated powder of carbon-silicon; Described silica flour and the mol ratio of silicon dioxide powder are 1:1; In described graphite, in carbon and silicon-silicon-dioxide powder mix, the mol ratio of element silicon is 3:1;
Two, the prefabricated powder of carbon-silicon step one prepared puts into porcelain Noah's ark, again porcelain Noah's ark is put into tube furnace, under the condition of nitrogen protection with the temperature rise rate of 3 DEG C/min from room temperature to 300 DEG C, 10min is incubated under nitrogen protection and temperature are the condition of 300 DEG C, 800 DEG C are warming up to the temperature rise rate of 3 DEG C/min from 300 DEG C again under the condition of nitrogen protection, 10min is incubated under nitrogen protection and temperature are the condition of 800 DEG C, then under the condition of nitrogen protection, 1500 DEG C are warming up to the temperature rise rate of 5 DEG C/min from 800 DEG C, 2h is incubated under nitrogen protection and temperature are the condition of 1500 DEG C, then under the condition of nitrogen protection, 500 DEG C are cooled to the rate of temperature fall of 5 DEG C/min from 1500 DEG C, cool to room temperature with the furnace, namely complete and obtain overlength silicon nitride nano-material in powder surface original position and porcelain Noah's ark wall ex situ simultaneously.
The mass ratio of the ball material in step one during ball milling is 30:1; Silica flour described in step one is industrial silica fume, and particle diameter is 0.10 μm; The particle diameter of the silicon dioxide powder described in step one is 0.025 μm; The particle diameter of the graphite described in step one is 20 μm; Nitrogen protection described in step 2 is specially: be that the condition of 50mL/min passes into nitrogen with flow velocity.
Test two: this test is a kind of method that original position-ex situ grows overlength silicon nitride nano-material simultaneously, specifically carries out according to the following steps:
One, prefabricated powder is prepared: silica flour and silicon dioxide powder are mixed, obtain silicon-silicon-dioxide powder mix, again graphite is loaded in ball grinder together with silicon-silicon-dioxide powder mix, be ball milling 10h under the condition of 280r/min at rotating speed, obtain the prefabricated powder of carbon-silicon; Described silica flour and the mol ratio of silicon dioxide powder are 1:1; In described graphite, in carbon and silicon-silicon-dioxide powder mix, the mol ratio of element silicon is 3:1;
Two, the prefabricated powder of carbon-silicon step one prepared puts into porcelain Noah's ark, again porcelain Noah's ark is put into tube furnace, under the condition of nitrogen protection with the temperature rise rate of 4 DEG C/min from room temperature to 300 DEG C, 10min is incubated under nitrogen protection and temperature are the condition of 300 DEG C, 800 DEG C are warming up to the temperature rise rate of 4 DEG C/min from 300 DEG C again under the condition of nitrogen protection, 10min is incubated under nitrogen protection and temperature are the condition of 800 DEG C, then under the condition of nitrogen protection, 1500 DEG C are warming up to the temperature rise rate of 4 DEG C/min from 800 DEG C, 2h is incubated under nitrogen protection and temperature are the condition of 1500 DEG C, then under the condition of nitrogen protection, 500 DEG C are cooled to the rate of temperature fall of 4 DEG C/min from 1500 DEG C, cool to room temperature with the furnace, namely complete and obtain overlength silicon nitride nano-material in powder surface original position and porcelain Noah's ark wall ex situ simultaneously.
The mass ratio of the ball material in step one during ball milling is 25:1; Silica flour described in step one is industrial silica fume, and particle diameter is 0.05 μm ~ 0.15 μm; The particle diameter of the silicon dioxide powder described in step one is 0.02 μm ~ 0.05 μm; The particle diameter of the graphite described in step one is 10 μm ~ 20 μm; Nitrogen protection described in step 2 is specially: be that the condition of 75mL/min passes into nitrogen with flow velocity.
Test three: this test is a kind of method that original position-ex situ grows overlength silicon nitride nano-material simultaneously, specifically carries out according to the following steps:
One, prefabricated powder is prepared: silica flour and silicon dioxide powder are mixed, obtain silicon-silicon-dioxide powder mix, again graphite is loaded in ball grinder together with silicon-silicon-dioxide powder mix, be ball milling 15h under the condition of 240r/min at rotating speed, obtain the prefabricated powder of carbon-silicon; Described silica flour and the mol ratio of silicon dioxide powder are 1:1; In described graphite, in carbon and silicon-silicon-dioxide powder mix, the mol ratio of element silicon is 3:1;
Two, the prefabricated powder of carbon-silicon step one prepared puts into porcelain Noah's ark, again porcelain Noah's ark is put into tube furnace, under the condition of nitrogen protection with the temperature rise rate of 5 DEG C/min from room temperature to 300 DEG C, 15min is incubated under nitrogen protection and temperature are the condition of 300 DEG C, 800 DEG C are warming up to the temperature rise rate of 5 DEG C/min from 300 DEG C again under the condition of nitrogen protection, 15min is incubated under nitrogen protection and temperature are the condition of 800 DEG C, then under the condition of nitrogen protection, 1500 DEG C are warming up to the temperature rise rate of 5 DEG C/min from 800 DEG C, 2h is incubated under nitrogen protection and temperature are the condition of 1500 DEG C, then under the condition of nitrogen protection, 500 DEG C are cooled to the rate of temperature fall of 5 DEG C/min from 1500 DEG C, cool to room temperature with the furnace, namely complete and obtain overlength silicon nitride nano-material in powder surface original position and porcelain Noah's ark wall ex situ simultaneously.
The mass ratio of the ball material in step one during ball milling is 20:1; Silica flour described in step one is industrial silica fume, and particle diameter is 0.05 μm ~ 0.15 μm; The particle diameter of the silicon dioxide powder described in step one is 0.02 μm ~ 0.05 μm; The particle diameter of the graphite described in step one is 10 μm ~ 20 μm; Nitrogen protection described in step 2 is specially: be that the condition of 100mL/min passes into nitrogen with flow velocity.
Test four: this test is a kind of method that original position-ex situ grows overlength silicon nitride nano-material simultaneously, specifically carries out according to the following steps:
One, prefabricated powder is prepared: silica flour and silicon dioxide powder are mixed, obtain silicon-silicon-dioxide powder mix, again graphite is loaded in ball grinder together with silicon-silicon-dioxide powder mix, be ball milling 20h under the condition of 200r/min at rotating speed, obtain the prefabricated powder of carbon-silicon; Described silica flour and the mol ratio of silicon dioxide powder are 1:1; In described graphite, in carbon and silicon-silicon-dioxide powder mix, the mol ratio of element silicon is 3:1;
Two, the prefabricated powder of carbon-silicon step one prepared puts into porcelain Noah's ark, again porcelain Noah's ark is put into tube furnace, under the condition of nitrogen protection with the temperature rise rate of 6 DEG C/min from room temperature to 300 DEG C, 20min is incubated under nitrogen protection and temperature are the condition of 300 DEG C, 800 DEG C are warming up to the temperature rise rate of 6 DEG C/min from 300 DEG C again under the condition of nitrogen protection, 20min is incubated under nitrogen protection and temperature are the condition of 800 DEG C, then under the condition of nitrogen protection, 1500 DEG C are warming up to the temperature rise rate of 6 DEG C/min from 800 DEG C, 2h is incubated under nitrogen protection and temperature are the condition of 1500 DEG C, then under the condition of nitrogen protection, 500 DEG C are cooled to the rate of temperature fall of 6 DEG C/min from 1500 DEG C, cool to room temperature with the furnace, namely complete and obtain overlength silicon nitride nano-material in powder surface original position and porcelain Noah's ark wall ex situ simultaneously.
The mass ratio of the ball material in step one during ball milling is 30:1; Silica flour described in step one is industrial silica fume, and particle diameter is 0.05 μm ~ 0.15 μm; The particle diameter of the silicon dioxide powder described in step one is 0.02 μm ~ 0.05 μm; The particle diameter of the graphite described in step one is 10 μm ~ 20 μm; Nitrogen protection described in step 2 is specially: be that the condition of 200mL/min passes into nitrogen with flow velocity.
Test five: this test is a kind of method that original position-ex situ grows overlength silicon nitride nano-material simultaneously, specifically carries out according to the following steps:
One, prefabricated powder is prepared: silica flour and silicon dioxide powder are mixed, obtain silicon-silicon-dioxide powder mix, again graphite is loaded in ball grinder together with silicon-silicon-dioxide powder mix, be ball milling 30h under the condition of 180r/min at rotating speed, obtain the prefabricated powder of carbon-silicon; Described silica flour and the mol ratio of silicon dioxide powder are 1:1; In described graphite, in carbon and silicon-silicon-dioxide powder mix, the mol ratio of element silicon is 3:1;
Two, the prefabricated powder of carbon-silicon step one prepared puts into porcelain Noah's ark, again porcelain Noah's ark is put into tube furnace, under the condition of nitrogen protection with the temperature rise rate of 7 DEG C/min from room temperature to 300 DEG C, 25min is incubated under nitrogen protection and temperature are the condition of 300 DEG C, 800 DEG C are warming up to the temperature rise rate of 7 DEG C/min from 300 DEG C again under the condition of nitrogen protection, 25min is incubated under nitrogen protection and temperature are the condition of 800 DEG C, then under the condition of nitrogen protection, 1500 DEG C are warming up to the temperature rise rate of 7 DEG C/min from 800 DEG C, 2h is incubated under nitrogen protection and temperature are the condition of 1500 DEG C, then under the condition of nitrogen protection, 500 DEG C are cooled to the rate of temperature fall of 7 DEG C/min from 1500 DEG C, cool to room temperature with the furnace, namely complete and obtain overlength silicon nitride nano-material in powder surface original position and porcelain Noah's ark wall ex situ simultaneously.
The mass ratio of the ball material in step one during ball milling is 30:1; Silica flour described in step one is industrial silica fume, and particle diameter is 0.05 μm ~ 0.15 μm; The particle diameter of the silicon dioxide powder described in step one is 0.02 μm ~ 0.05 μm; The particle diameter of the graphite described in step one is 10 μm ~ 20 μm; Nitrogen protection described in step 2 is specially: be that the condition of 400mL/min passes into nitrogen with flow velocity.
Fig. 1 is the photo in kind of overlength silicon nitride nano-material prepared by test one, and the silicon nitride length as can be seen from the figure prepared reaches several millimeters of ranks.
Fig. 2 is the silicon nitride powder surface of test one preparation and the SEM figure of growth in situ overlength silicon nitride nano-material, and as can be seen from the figure the silicon nitride nano-material of growth in situ mainly presents with band shape.
Fig. 3 is the SEM figure at the overlength silicon nitride nano-material of porcelain Noah's ark wall ex situ growth in test one, and the overlength silicon nitride nano-material of as can be seen from the figure ex situ growth mainly presents with cylindric, prism-shaped, band shape etc.
Fig. 4 is the silicon nitride powder surface of test one preparation and the XRD figure of growth in situ overlength silicon nitride nano-material, and as can be seen from the figure product is mainly with α-Si
3n
4exist.
Claims (6)
1. original position-ex situ grows a method for overlength silicon nitride nano-material simultaneously, it is characterized in that the method that original position-ex situ grows overlength silicon nitride nano-material is simultaneously carried out according to the following steps:
One, prefabricated powder is prepared: silica flour and silicon dioxide powder are mixed, obtain silicon-silicon-dioxide powder mix, again graphite is loaded in ball grinder together with silicon-silicon-dioxide powder mix, be ball milling 6h ~ 30h under the condition of 180r/min ~ 300r/min at rotating speed, obtain the prefabricated powder of carbon-silicon; Described silica flour and the mol ratio of silicon dioxide powder are 1:1; In described graphite, in carbon and silicon-silicon-dioxide powder mix, the mol ratio of element silicon is 3:1;
Two, the prefabricated powder of carbon-silicon step one prepared puts into porcelain Noah's ark, again porcelain Noah's ark is put into tube furnace, under the condition of nitrogen protection with the temperature rise rate of 1 ~ 10 DEG C/min from room temperature to 300 DEG C, 10min is incubated under nitrogen protection and temperature are the condition of 300 DEG C, 800 DEG C are warming up to the temperature rise rate of 1 ~ 10 DEG C/min from 300 DEG C again under the condition of nitrogen protection, 10min is incubated under nitrogen protection and temperature are the condition of 800 DEG C, then under the condition of nitrogen protection, 1500 DEG C are warming up to the temperature rise rate of 1 ~ 10 DEG C/min from 800 DEG C, 1 ~ 6h is incubated under nitrogen protection and temperature are the condition of 1500 DEG C, then under the condition of nitrogen protection, 500 DEG C are cooled to the rate of temperature fall of 1 ~ 10 DEG C/min from 1500 DEG C, cool to room temperature with the furnace, namely complete and obtain overlength silicon nitride nano-material in powder surface original position and porcelain Noah's ark wall ex situ simultaneously.
2. a kind of original position-ex situ according to claim 1 grows the method for overlength silicon nitride nano-material simultaneously, and the mass ratio of ball material when it is characterized in that ball milling in step one is (30 ~ 5): 1.
3. a kind of original position-ex situ according to claim 1 grows the method for overlength silicon nitride nano-material simultaneously, it is characterized in that the silica flour described in step one is industrial silica fume, and particle diameter is 0.05 μm ~ 0.15 μm.
4. a kind of original position-ex situ according to claim 1 grows the method for overlength silicon nitride nano-material simultaneously, it is characterized in that the particle diameter of the silicon dioxide powder described in step one is 0.02 μm ~ 0.05 μm.
5. a kind of original position-ex situ according to claim 1 grows the method for overlength silicon nitride nano-material simultaneously, it is characterized in that the particle diameter of the graphite described in step one is 10 μm ~ 20 μm.
6. a kind of original position-ex situ according to claim 1 grows the method for overlength silicon nitride nano-material simultaneously, it is characterized in that the nitrogen protection described in step 2 is specially: be that the condition of 50mL/min ~ 400mL/min passes into nitrogen with flow velocity.
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| CN201610060579.XA CN105502315B (en) | 2016-01-28 | 2016-01-28 | A kind of method that ex situ in situ grows overlength silicon nitride nano-material simultaneously |
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| CN107342403A (en) * | 2017-06-09 | 2017-11-10 | 江永斌 | Nano material containing silicon nitride and its production and use |
| CN110436934A (en) * | 2019-07-09 | 2019-11-12 | 南昌大学 | A kind of preparation method of alpha-phase silicon nitride powder, overlength beta-silicon nitride nanowire |
| CN112607715A (en) * | 2020-12-29 | 2021-04-06 | 黑龙江冠瓷科技有限公司 | Preparation method of high-purity alpha-phase silicon nitride nanowire |
| CN112624766A (en) * | 2020-12-29 | 2021-04-09 | 哈尔滨工业大学 | Preparation method of silicon nitride @ silicon carbide @ boron nitride composite fiber felt |
| CN112624767A (en) * | 2020-12-29 | 2021-04-09 | 黑龙江冠瓷科技有限公司 | Preparation method of silicon carbide/silicon nitride composite fiber felt |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107342403A (en) * | 2017-06-09 | 2017-11-10 | 江永斌 | Nano material containing silicon nitride and its production and use |
| CN107342403B (en) * | 2017-06-09 | 2019-11-12 | 江永斌 | Nano material and its preparation method and application containing silicon nitride |
| CN110436934A (en) * | 2019-07-09 | 2019-11-12 | 南昌大学 | A kind of preparation method of alpha-phase silicon nitride powder, overlength beta-silicon nitride nanowire |
| CN110436934B (en) * | 2019-07-09 | 2022-02-11 | 南昌大学 | Preparation method of high alpha-phase silicon nitride powder and ultra-long silicon nitride nanowire |
| CN112607715A (en) * | 2020-12-29 | 2021-04-06 | 黑龙江冠瓷科技有限公司 | Preparation method of high-purity alpha-phase silicon nitride nanowire |
| CN112624766A (en) * | 2020-12-29 | 2021-04-09 | 哈尔滨工业大学 | Preparation method of silicon nitride @ silicon carbide @ boron nitride composite fiber felt |
| CN112624767A (en) * | 2020-12-29 | 2021-04-09 | 黑龙江冠瓷科技有限公司 | Preparation method of silicon carbide/silicon nitride composite fiber felt |
| CN112607715B (en) * | 2020-12-29 | 2021-12-10 | 哈尔滨工业大学 | Preparation method of high-purity alpha-phase silicon nitride nanowire |
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