CN1724466A - Process for synthesizing based si-based one-dimensional nano material - Google Patents
Process for synthesizing based si-based one-dimensional nano material Download PDFInfo
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- CN1724466A CN1724466A CN 200510012187 CN200510012187A CN1724466A CN 1724466 A CN1724466 A CN 1724466A CN 200510012187 CN200510012187 CN 200510012187 CN 200510012187 A CN200510012187 A CN 200510012187A CN 1724466 A CN1724466 A CN 1724466A
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Abstract
A process for synthesizing one-dimension Si-base nano-material includes such steps as providing polyazane as raw material, cross-linking and solidifying at 150-180 deg. C in protective atmosphere to obtain non- crystalline SiCN solid, ball grinding While adding catalyst chosen from FeCL2,Al,Cu and Ni, and thermo-decomposing in alumina ceramic cruicible at 1250-1700 deg. C in the protective atmosphere.
Description
Technical field
The present invention relates to a kind of new low-dimensional materials preparation method, belong to technical field of material.
Background technology
Nano material has unique effects such as surface effects, volume effect and quantum size, thereby embodies the various performances that are better than traditional material at aspects such as electricity, mechanics, magnetics, optics.Nanotechnology makes nano material and technology thereof become one of focus of present scientific research in the successful Application in fields such as fine ceramics, microtronics, biotechnology, chemical industry, medical science and wide application prospect thereof, is the Industrial Revolution again of new millennium.In the research of nanometer material science, the preparation science of nano material occupies very consequence in the research of current nanometer material science, and the microtexture and the performance of nano material had significant effects.
Low-dimensional Si
3N
4Material has very high intensity, and is in light weight, good heat shock resistance and resistance of oxidation, thereby have very widely at a lot of industrial circles and to use.Simultaneously, Si
3N
4Also be a kind of wide semi-conductor (5.3ev) that can be with, can be with its electricity and optical property, prepare the nano electron device that can under high temperature and high radiation environment, use thereby can reduce it by means such as doping.Up to the present, synthetic Si
3N
4The method of nano wire has: carbothermic reduction under the hot conditions and direct nitrogenizing reaction method, the combustion reactions method under the high nitrogen pressure environment; CVD and microwave plasma heating method.There is synthesis condition harshness (as High Temperature High Pressure) in these methods or shortcoming such as combined coefficient is on the low side or synthesis device costs an arm and a leg.The SiC low-dimension nano material has good characteristics such as high rigidity, high tenacity, high-wearing feature, high temperature resistant, low thermal coefficient of expansion, thereby, particularly has very tempting application prospect aspect preparation nano photoelectronic devices, high-intensity fine small size composite element and slim composite element, the nano surface reinforced composite at the preparation high performance composite.Silicon carbide also is a kind of semiconductor material of broad-band gap simultaneously, have characteristics such as high disruptive critical voltage, high heat conductance, high carrier saturation drift velocity, be third generation wide bandgap semiconductor materials, be mainly used in high temperature, high frequency, high-power, photoelectron and radioprotective device.The method for preparing the SiC low-dimension nano material of existing report has template (as the carbon nanotube template etc.), carbothermic method, chemical vapor deposition (CVD), sol-gel method and arc discharge method etc.Shortcomings such as all there is complex process in the synthesis technique major part of these reports, and equipment price costliness and synthetic product are impure.Therefore, synthetic this basic research work of low-dimension nano material still is faced with great challenge.
Summary of the invention
It is simple to the objective of the invention is to propose a kind of equipment and synthesis technique, the product purity height, and have the method for the new synthetic low-dimension nano material of good repeatability, promptly by the synthetic low-dimension nano material of organic precursor pyrolysis.The growth mechanism of the nano-material of this method preparation is different with traditional gas-solid (Vapor-Solid:VS) growth mechanism gentle liquid-solid (Vapor-Liquid-Solid:VLS) mechanism, is solid-liquid gas-solid (Solid-Liquid-Gas-Solid:LSGS) mechanism.This mechanism is very beneficial for low-dimension nano material is carried out doping treatment, thereby regulates and control its electricity and optical property, prepares the nano electron device that can use under high temperature and high radiation environment.
The method of a kind of synthetic Si base monodimension nanometer material that the present invention proposes is characterized in that: described method adopts the synthetic Si base of organic precursor pyrolysis low-dimension nano material, may further comprise the steps:
(1) crosslinked at low temperature solidifies: initial feed adopts poly-silicon nitrogen tabernaemontanus bulrush, and 250-280 ℃ of insulation carried out crosslinking curing in 0.5-2 hour, and protective atmosphere is nitrogen or ammonia, obtains translucent non-crystalline state SiCN solid;
(2) high-energy ball milling is pulverized: carry out dry ball milling in the nylon resin ball grinder of will above-mentioned translucent SiCN solid packing in high energy ball mill and pulverize abrasive material employing Si
3N
4Or the SiC ball, the ball milling time is 10-15 hour, introduces catalyzer in the time of ball milling, makes that non-crystalline state SiCN powder and catalyst mix are even;
(3) high temperature pyrolysis: the mixture behind the high-energy ball milling that takes a morsel is packed into and is carried out high temperature pyrolysis in the alumina-ceramic crucible; under 1250～1700 ℃ of pyrolysis temperatures, be incubated 1～4 hour; can obtain the low-dimension nano material of different-shape and chemical ingredients, protective atmosphere is nitrogen or ammonia.
In aforesaid method, the described catalyzer of step 2 is FeCl
2, any among Al, Cu, the Ni.
In aforesaid method, the described catalyst consumption of step 2 is 1-5wt%.
Method of the present invention has the following advantages:
1) equipment is simple, and is with low cost;
2) synthesis technique is simple, and controllability is strong, simply control the low-dimension nano material that some key process parameters in the synthesis technique can obtain to have different chemical component and pattern, and technological process has very high repeatability;
3) synthetic product purity height, synthetic low-dimension nano material any surface finish is not polluted;
4) the present invention's method of preparing nano material is very beneficial for nano material is carried out doping treatment, and performances such as this light for the regulation and control nano material, electricity, heat, magnetic are very favorable, provide the foundation for nano material preparation becomes nano-device;
5) method for preparing nano material of most of report can only be synthesized the low-dimension nano material of single shape, and the present invention prepares the method for nano material can be prepared different-shape by the several key process parameters of simple control low-dimension nano material such as nano wire, nano belt and nanometer rod etc.
Description of drawings
Fig. 1 raw material is Polyureasilazane, and catalyzer is FeCl
2, 2 hours synthetic single crystalline Si of insulation under 1250 ℃ of pyrolysis temperatures
3N
4Nano wire SEM figure.
Fig. 2 raw material is Polyureasilazane, and catalyzer is Al, in 1 hour synthetic single crystalline Si of 1350 ℃ of insulations
3N
4Nano wire SEM figure.
Fig. 3 raw material is Polyureasilazane and Al[OCH (CH
3)
2]
3, catalyzer is FeCl
2, have the adulterated single crystalline Si of Al at 2 hours synthetic of 1250 ℃ of insulations
3N
4Nano wire SEM figure.
Fig. 4 raw material is Polyureasilazane, and catalyzer is FeCl
2, at 2 hours synthetic monocrystal SiC nanometer rod SEM figure of 1700 ℃ of insulations.
Fig. 5 raw material is Polyureasilazane, and Al and Fe mixed catalytic are in 2 hours synthetic single crystalline Si of 1350 ℃ of insulations
3N
4Nanometer dendrite SEM figure.
Below in conjunction with embodiment technical scheme of the present invention is described further:
Embodiment 1
Initial feed adopts a kind of poly-silicon nitrogen tabernaemontanus bulrush (Polyureasilazane), and 260 ℃ of insulations were carried out crosslinking curing in 0.5 hour, and protective atmosphere is the N of 0.1MPa
2Gas obtains translucent non-crystalline state SiCN solid.Translucent SiCN solid packed into carry out dry ball milling in the nylon resin ball grinder pulverize in high energy ball mill, abrasive material adopts Si
3N
4Ball, the ball milling time is 12 hours.Introduce the FeCl of 3wt% in the time of ball milling
2Powder makes that as catalyzer non-crystalline state SiCN powder and catalyst mix are even.Get mixture behind the 2g high-energy ball milling then and pack into and carry out high temperature pyrolysis in the alumina-ceramic crucible in tube furnace, Si was synthesized in insulation in 2 hours under 1250 ℃ of pyrolysis temperatures
3N
4Monocrystal nanowire.Protective atmosphere is the mobile N of 0.1MPa
2Gas, gas flow rate are 200ml/min.Synthetic Si
3N
4Monocrystal nanowire as shown in Figure 1.Single monocrystal nanowire even thickness, mean diameter is approximately 30nm, and length can reach several mm, and size is even between the nano wire, and any surface finish is not polluted.
Embodiment 2
Initial feed adopts a kind of liquid state to gather silicon nitrogen tabernaemontanus bulrush (Polysilazane), and 250 ℃ of insulations were carried out crosslinking curing in 0.6 hour, and protective atmosphere is the N of 0.1MPa
2Gas obtains translucent non-crystalline state SiCN solid.Translucent SiCN solid packed into carry out dry ball milling in the nylon resin ball grinder pulverize in high energy ball mill, abrasive material adopts Si
3N
4Ball, the ball milling time is 10 hours.The Al powder of introducing 5wt% in the time of ball milling makes that as catalyzer non-crystalline state SiCN powder and catalyst mix are even.Get mixture behind the 3g high-energy ball milling then and pack into and carry out high temperature pyrolysis in the alumina-ceramic crucible in tube furnace, Si was synthesized in insulation in 1 hour under 1350 ℃ of pyrolysis temperatures
3N
4Monocrystal nanowire.Protective atmosphere is the mobile ammonia of 0.1MPa, and gas flow rate is 200ml/min.Synthetic Si
3N
4Monocrystal nanowire as shown in Figure 2.Single monocrystal nanowire even thickness, mean diameter is approximately 70nm, and length reaches several mm, and size is even between the nano wire, and any surface finish is not polluted.
Embodiment 3
Initial feed adopts two kinds of poly-silicon nitrogen tabernaemontanus bulrush (Polyureasilazane and Al[OCH (CH
3)
2]
3), the back is a kind of be solid state powder, at first with these two kinds of powder (Polyureasilazane:Al[OCH (CH by weight
3)
2]
3) be in nylon resin ball grinder to mix at 2: 1, carried out crosslinking curing in 0.5 hour 280 ℃ of insulations then, protective atmosphere is the N of 0.1MPa
2Gas obtains translucent non-crystalline solids particle.Solid particulate packed into carry out dry ball milling in the nylon resin ball grinder pulverize in high energy ball mill, abrasive material adopts the SiC ball, and the ball milling time is 14 hours.Introduce the FeCl of 3wt% in the time of ball milling
2As catalyzer, make that non-crystalline state powder and catalyst mix are even.Get mixture behind the 4g high-energy ball milling then and pack into and carry out high temperature pyrolysis in the alumina-ceramic crucible in tube furnace, insulation was synthesized and has been had the adulterated Si of Al in 2 hours under 1250 ℃ of pyrolysis temperatures
3N
4Monocrystal nanowire.Protective atmosphere is the mobile N of 0.1MPa
2Gas, gas flow rate are 200ml/min.Synthetic Si
3N
4Monocrystal nanowire as shown in Figure 3.Single monocrystal nanowire even thickness, crooked circlewise, mean diameter is approximately 40nm, and size is even between the nano wire, and any surface finish is not polluted, for finding first.
Embodiment 4
Initial feed adopts a kind of liquid state to gather silicon nitrogen tabernaemontanus bulrush (Polyureasilazane), and 270 ℃ of insulations were carried out crosslinking curing in 1 hour, and protective atmosphere is the N of 0.1MPa
2Gas obtains translucent non-crystalline state SiCN solid.Translucent SiCN solid packed into carry out dry ball milling in the nylon resin ball grinder pulverize in high energy ball mill, abrasive material adopts Si
3N
4Ball, the ball milling time is 13 hours.Introduce the FeCl of 1wt% in the time of ball milling
2As catalyzer, make that non-crystalline state SiCN powder and catalyst mix are even.Get mixture behind the 2g high-energy ball milling then and pack into and carry out high temperature pyrolysis in the 99 alumina-ceramic crucibles in tube furnace, the monocrystal SiC nanometer rod was synthesized in insulation in 2 hours under 1700 ℃ of pyrolysis temperatures.Protective atmosphere is the mobile N of 0.1MPa
2Gas, gas flow rate are 200ml/min.Synthetic monocrystal SiC nano wire as shown in Figure 4.Single monocrystal nano rod thickness is more even, and diameter is approximately 80～200nm, and length reaches tens μ m, and size is even between the nano wire, and any surface finish is not polluted.
Embodiment 5
Initial feed adopts a kind of liquid state to gather silicon nitrogen tabernaemontanus bulrush (Polyureasilazane), and 260 ℃ of insulations were carried out crosslinking curing in 1 hour, and protective atmosphere is the N of 0.1MPa
2Gas obtains translucent non-crystalline state SiCN solid.Translucent SiCN solid packed into carry out dry ball milling in the nylon resin ball grinder pulverize in high energy ball mill, abrasive material adopts Si
3N
4Ball, the ball milling time is 10 hours.The Al of introducing 3wt% and iron powder powder make that as mixed catalyst non-crystalline state SiCN powder and catalyst mix are even in the time of ball milling.Get mixture behind the 3g high-energy ball milling then and pack into and carry out high temperature pyrolysis in the alumina-ceramic crucible in tube furnace, single crystalline Si has been synthesized in insulation self-assembly in 2 hours under 1350 ℃ of pyrolysis temperatures
3N
4Nanometer dendrite.Protective atmosphere is the mobile N of 0.1MPa
2Gas, gas flow rate are 200ml/min.The synthetic single crystalline Si
3N
4Nanometer dendrite as shown in Figure 5.Synthetic nanometer dendrite length can reach hundreds of μ m, and the dendrite that is about the 40nm even thickness is arranged in thickness with equidistant self-assembly very uniformly and is about on the main shaft of 200nm.This self-assembled structures is expected to be prepared into grating and optical splitter.
Claims (3)
1, a kind of method of synthetic Si base monodimension nanometer material is characterized in that: described method adopts the synthetic Si base of organic precursor pyrolysis low-dimension nano material, may further comprise the steps:
(1) crosslinked at low temperature solidifies: initial feed adopts poly-silicon nitrogen tabernaemontanus bulrush, and 250-280 ℃ of insulation carried out crosslinking curing in 0.5-2 hour, and protective atmosphere is nitrogen or ammonia, obtains translucent non-crystalline state SiCN solid;
(2) high-energy ball milling is pulverized: carry out dry ball milling in the nylon resin ball grinder of will above-mentioned translucent SiCN solid packing in high energy ball mill and pulverize abrasive material employing Si
3N
4Or the SiC ball, the ball milling time is 10-15 hour, introduces catalyzer in the time of ball milling, makes that non-crystalline state SiCN powder and catalyst mix are even;
(3) high temperature pyrolysis: the mixture behind the high-energy ball milling that takes a morsel is packed into and is carried out high temperature pyrolysis in the alumina-ceramic crucible; under 1250～1700 ℃ of pyrolysis temperatures, be incubated 1～4 hour; can obtain the low-dimension nano material of different-shape and chemical ingredients, protective atmosphere is nitrogen or ammonia.
2, in accordance with the method for claim 1, it is characterized in that: the described catalyzer of step 2 is FeCl
2, any among Al, Cu, the Ni.
3, in accordance with the method for claim 1, it is characterized in that: the described catalyst consumption of step 2 is 1-5wt%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102148160A (en) * | 2011-01-19 | 2011-08-10 | 青岛大学 | Method for preparing P-type SiC nanowire filed-effect tube |
| CN101609735B (en) * | 2009-07-21 | 2011-08-31 | 中国地质大学（北京） | Method for preparing high purity, high density and high yield Si3N4/SiO2 coaxial nano-cable array |
| CN101603207B (en) * | 2009-07-21 | 2011-11-09 | 中国地质大学（北京） | Method for preparing network branched silicon nitride single crystal nanostructure with high purity and high yield |
| CN108341674A (en) * | 2018-02-05 | 2018-07-31 | 郑州大学 | A kind of polymer precursor Ceramic Composite aeroge and its microwave synthesis method |
| CN108706588A (en) * | 2018-07-03 | 2018-10-26 | 宁波工程学院 | A kind of big flakiness ratio N doping SiC nanobelts and preparation method thereof |
| CN111320484A (en) * | 2020-04-01 | 2020-06-23 | 西北工业大学 | Preparation method of isotropic silicon nitride whisker reinforced nitride composite material antenna housing |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3840781A1 (en) * | 1988-12-03 | 1990-06-07 | Hoechst Ag | FIBER COMPOSITE CERAMICS AND METHOD FOR THEIR PRODUCTION |
| DE3840773A1 (en) * | 1988-12-03 | 1990-06-07 | Hoechst Ag | SINTERABLE CERAMIC POWDER, METHOD FOR THE PRODUCTION THEREOF, SILICON NITRIDE CERAMIC PRODUCED THEREOF, METHOD FOR THE PRODUCTION AND THE USE THEREOF |
-
2005
- 2005-07-15 CN CNB2005100121878A patent/CN1312028C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101609735B (en) * | 2009-07-21 | 2011-08-31 | 中国地质大学（北京） | Method for preparing high purity, high density and high yield Si3N4/SiO2 coaxial nano-cable array |
| CN101603207B (en) * | 2009-07-21 | 2011-11-09 | 中国地质大学（北京） | Method for preparing network branched silicon nitride single crystal nanostructure with high purity and high yield |
| CN102148160A (en) * | 2011-01-19 | 2011-08-10 | 青岛大学 | Method for preparing P-type SiC nanowire filed-effect tube |
| CN102148160B (en) * | 2011-01-19 | 2013-03-06 | 青岛大学 | Method for preparing P-type SiC nanowire filed-effect tube |
| CN108341674A (en) * | 2018-02-05 | 2018-07-31 | 郑州大学 | A kind of polymer precursor Ceramic Composite aeroge and its microwave synthesis method |
| CN108341674B (en) * | 2018-02-05 | 2020-07-31 | 郑州大学 | Polymer precursor ceramic composite aerogel and microwave synthesis method thereof |
| CN108706588A (en) * | 2018-07-03 | 2018-10-26 | 宁波工程学院 | A kind of big flakiness ratio N doping SiC nanobelts and preparation method thereof |
| CN108706588B (en) * | 2018-07-03 | 2022-02-22 | 宁波工程学院 | N-doped SiC nanobelt with large width-thickness ratio and preparation method thereof |
| CN111320484A (en) * | 2020-04-01 | 2020-06-23 | 西北工业大学 | Preparation method of isotropic silicon nitride whisker reinforced nitride composite material antenna housing |
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| CN1312028C (en) | 2007-04-25 |
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