CN100445199C - Preparation method of silicon nitride nano wire and nano band powder material - Google Patents
Preparation method of silicon nitride nano wire and nano band powder material Download PDFInfo
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- CN100445199C CN100445199C CNB2006100375811A CN200610037581A CN100445199C CN 100445199 C CN100445199 C CN 100445199C CN B2006100375811 A CNB2006100375811 A CN B2006100375811A CN 200610037581 A CN200610037581 A CN 200610037581A CN 100445199 C CN100445199 C CN 100445199C
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Abstract
A process for preparing Si3N4 nanowires (30 nm in diameter) and nanobands (40-80 nm in width and 20 nm in thickness) includes such steps as proportional reaction between SiCl4, NaN3 and Na at 400-500 deg.C, washing, filtering, and drying.
Description
Technical field:
The present invention relates to the preparation method of beta-silicon nitride nanowire or nano belt powder body material.
Background technology
Silicon nitride ceramics because have that height ratio is strong, height ratio mould, high temperature resistant, anti-oxidant and advantages such as wear-resistant and anti-thermal shock, have broad application prospects as structured material and functional materials.The high temperature that particularly in modern technologies, often runs into, at a high speed, the applied environment of strong corrosive medium, make silicon nitride material also have a lot of special using values.Though its range of application constantly enlarges, there are shortcomings such as preparation cost height, high-temperature behavior reduction and inherent fragility, limited its application to a great extent.The fine ceramics goods of Nano powder of silicon nitride preparation and subsequent development are the focuses that competitively research and develop countries in the world.In view of being raw material agglomerating ceramic with Nano powder of silicon nitride, (1～100nm) goes up control ceramics component and structure, helps giving full play to Si at the nanostructure level
3N
4The potential performance of stupalith., specific surface area minimum because of its particle grain diameter and chemically reactive can be big, can significantly reduce the sintering densification degree and the save energy of material, burn till and shrink unanimity and uniform crystal particles, defective is little, the intensity of prepared structure unit and reliability are also higher, and can overcome fragility, have good processability.Silicon nitride one-dimensional nano line and silicon nitride nano band, its physical and mechanical properties is different from general nano particle again, has big potentiality aspect raising stupalith intensity and the toughness.
Do not find natural silicon nitride at occurring in nature.In the many decades in the past, the synthetic research for silicon nitride has developed multiple preparation method.Such as carbothermic method, self-propagating high-temperature combustion method (HSH), chemical vapor deposition (CVD), the pyrolysis of organic precursor thing etc.In addition, utilize laser irradiation from SiH in addition
2Cl
2And NH
3Mixed gas prepares 15-110nm Si
3N
4Amorphous particle, the using plasma method makes silica flour and N
2The prepared in reaction particle diameter is α-Si of 20-30nm
3N
4(48-77%) and β-Si
3N
4(20-39%) powder.Seeking low-costly and in high volume and synthesizing fast in the flow of research of high quality silicon nitride nano-material, a research topic that receives much attention is to explore by silicon tetrachloride (SiCl
4) rapid reaction that causes at low temperatures with the different nitrogen sources raw material prepares silicon nitride nano-material.For example, SiCl
4With ammonia (NH
3) reacting at heated filament-flow reactor to obtain beta-silicon nitride powder.Similarly, the sodium hexafluorisilicate thermolysis produces silicon tetrafluoride (SiF
4), at high temperature with reaction NH
3Or nitrogen reaction can prepare silicon nitride materials such as containing mutually particulate state of α and β, whisker, fiber.Adopt magnesium nitride (Mg
3N
2) as the solid nitrogenous source, in 600 ℃ of seal pots with SiCl
4Reaction can be prepared α-Si
3N
4Nano wire.Adopt sodiumazide as the solid nitrogenous source, under the excessive slightly situation of sodiumazide, with SiCl
4Reaction can be prepared dendroid and corynebacterium silicon nitride α and β mixed powder mutually.
" U.S.'s pottery meeting will " has reported the β-Si that grows in (Si/Al/Mg/Y) melt of 1680 ℃
3N
4Crystalline research, and find that the silicon nitride speed of growth is relevant with the composition of this melt with the crystal length-to-diameter ratio." advanced material " reported employing SiCl
4Liquid is brilliant and nanorod growth media as silicon nitride nano, and wherein silicon nitride α and beta-phase seed crystal are by SiCl
4With NaN
3On-the-spot synthetic under about 670 ℃.Chinese invention patent application CN1491885 discloses a kind of silicon nitride and silicon carbide one dimension Nano structure and preparation method thereof, be to be catalyzer and the silicon source is provided with siliceous 20～80% metal alloy particle, gas or solid with nitrogenous or carbon are nitrogenous source and carbon source, under the high temperature in tube furnace nitrogenize or carbonization silicon-containing alloy particle obtain Si
3N
4One dimension Nano structure, wherein the temperature range of nitrogenize or carbonization silicon-containing alloy particle is 1200-1600 ℃ in the pyritous tube furnace.Another Chinese invention patent application CN1562735 discloses a kind of method of preparing silicon nitride powder material under low temperature, adopts SiCl
4Do the silicon source, with NaN
3Make nitrogenous source, carry out chemical exchange reaction in stainless steel cauldron, through cleaning, suction filtration, oven dry, its chemical equation is: 3SiCl to reaction product
4+ 12NaN
3=Si
3N
4+ 12NaCl+16N
2
Summary of the invention:
The preparation method who the purpose of this invention is to provide a kind of beta-silicon nitride nanowire or nano belt powder body material, operation is simple, safety, and obtained product is pure, the yield height.
For reaching above-mentioned purpose, the present invention adopts following technical scheme: the preparation method of beta-silicon nitride nanowire of the present invention or nano belt powder body material, and with SiCl
4For the silicon source, with NaN
3For nitrogenous source and add sodium Metal 99.5, temperature is that 400-600 ℃, system autogenous pressure are reaction 0.5-6 hour under the condition of 5-40MPa in reactor, and product is through washing, separation and dry white powder product;
Chemical reaction of the present invention can be represented with following reaction equation:
3SiCl
4+n?NaN
3+(12-n)Na＝Si
3N
4+12NaCl+(1.5n-2)N
2 (1)
Wherein n satisfies 1.334≤n≤11.998.Calculate according to reaction normal free energy and enthalpy, obtain following relation:
ΔG°＝-3391-187.52*n kJ/mol (2)
ΔH°＝-3617-21.71*n kJ/mol (3)
Wherein n satisfies 2≤n≤4 best results.
In proper range, regulate and control SiCl
4, NaN
3, Na ratio, can obtain the silicon nitride of different-shape.The SiCl that is added
4, NaN
3, Na mass ratio be 1: 0.4～0.5: 0.36～0.4 o'clock, can make beta-silicon nitride nanowire; The SiCl that is added
4, NaN
3, Na mass ratio be 1: 0.25-0.38: during 0.40-0.45, can obtain the silicon nitride nano band.
In order to realize the present invention better, in described reactor, feed rare gas element and also carry out reacting by heating again after the sealing.Described rare gas element preferred nitrogen or argon gas.
As preferred version, described temperature of reaction is 450～500 ℃; Described reaction system autogenous pressure is about 15-25MPa; The described reaction times is 0.5-5 hour.
The centrifugation behind washing and absolute ethanol washing of described product, 80 ℃ of following dryings 24 hours in vacuum drying oven then.
SiCl
4With NaN
3Mix, just vigorous reaction can take place more than 100 ℃, form polysilicon, sodium-chlor and a small amount of silicon nitride, produce a large amount of nitrogen simultaneously.Sodiumazide is a kind of cheap solid nitrogenous source, be heated to 410 ℃ separately and be decomposed to form sodium Metal 99.5 and nitrogen, be a kind of easy blast and highly toxic substance, in the self-propagating high-temperature synthesizing silicon nitride, be commonly used for auxiliary nitrogenous source of solid and catalyzer, so that increase the α-Si in the product
3N
4Content.Reduce NaN
3Consumption also uses a large amount of sodium Metal 99.5s to replace, and sodium Metal 99.5 fusing point low (97.82 ℃) not only changes chemical reaction and relaxes reaction environment as reactant, solvent and heat absorbent, can also avoid the danger of exploding, and improves reaction safety; Simultaneously, sodium Metal 99.5 is also as silicon nitride nano crystals growth media, thereby can prepare comparison pure nano line and nano belt.In the present invention, sodium Metal 99.5 consumption difference all has significant effects, reaction system pressure difference, β-Si in the product to reaction and product
3N
4And α-Si
3N
4The ratio difference also has a significant impact the product pattern.The optimum range that experiment showed, n is 2≤n≤4.
The colourless liquid SiCl that the present invention is used
4Be analytical reagent, white crystalline solid NaN
3With metal Na be chemically pure reagent.Metal Na is taken out from kerosene, blots with filter paper, is cut into small pieces.SiCl
4And NaN
3Before use without special processing.By the proportioning weighing NaN that designs in advance
3Add about 60ml stainless steel cauldron with metal Na, add the SiCl of metering again
4Operation is to charge at ambient temperature in the glove box of dry argon gas to carry out.The reactor of sealing is put into well formula crucible oven, under predetermined temperature (400-600 ℃) isothermal reaction 0.5-6 hour, makes it naturally cooling then, drives still and takes out reaction product.Product is removed by product sodium-chlor through distilled water wash, absolute ethanol washing and centrifugation, in 80 ℃ times dry 24 hours, can obtain the white powder sample in vacuum drying oven, and weighing is also calculated productive rate, and the product silicon nitride is with respect to raw material SiCl
4Total recovery all more than 90%.
For n=2,3 and 4, Δ G ℃ be respectively-3766 ,-3954 and-4141kJ/mol, Δ H ° be respectively-3660 ,-3682 and-3704kJ/mol, illustrate that above-mentioned reaction is a spontaneous reaction, and emit a large amount of reaction heat.But in initial reaction stage, all in the sodium Metal 99.5 of liquid state, this reaction is and SiCl for the formation of silicon nitride and nucleation
4Only and NaN
3It is different reacting and not having the participation of sodium Metal 99.5.Liquid metal sodium also is a kind of reactant and temporary transient thinner and heat absorbent except that crystallization and growing environment are provided, and is nano wire and nano belt shape thereby relax reaction and help the product crystalline growth.The present invention has also studied the influence of excess metal sodium to the product pattern, finds that unfavorable on the contrary for beta-silicon nitride nanowire and nano belt formation, its product pattern mostly is nano particle and nanometer stub when excessive to amounts of reactants 3-8 times of sodium Metal 99.5.This illustrates that nanocrystalline growth follows chemical reaction, may react local superheating and cause.For the response situation that is lower than 400 ℃, reaction produces a part of by product polycrysalline silcon, brings impurity to product, and making purifies becomes complicated.Because of sending out reaction and, not having polysilicon in the product, react completely, more than 400 ℃ with respect to SiCl more than 1 hour
4Product silicon nitride yield is more than 90%, but also there is certain influence in the reaction times to the product pattern.Product proportioning and reaction pressure have certain relation, because reaction is to carry out in the reactor of sealing, how much formation of reaction system gas makes pressure change within the specific limits.Estimate that according to perfect gas during n=4, the preparation feedback peak pressure is no more than 220 normal atmosphere.
The products therefrom sample structure is used MSAL-XD2 type X-light powder diffractometer (40kV, 20mA, λ=1.5406
) analyze, 2 θ are 10-80 ° of scope.With Technai-10 type and JEM-2010HR type transmission electron microscope observation product pattern,, analyze its composition with EDX with the microstructure of electron diffraction investigation microcell material.The sample that electron microscopy observation, electron diffraction and EDX analyze, be with the product powder by ultrasonic dispersing in dehydrated alcohol, drop in then on the special-purpose carbon film copper mesh of TEM and observe.The product sample also uses JSM-6330F type field emission scanning electron microscope to observe pattern and uses EDX to analyze its composition, and its sample preparation is directly to adopt the product powder distribution on the double faced adhesive tape and be bonded on the sample copper platform and observe behind the metal spraying.FTIR analyzes and adopts Nicolet type infrared spectrometer, and the product powder uses the sample preparation of KBr compressing tablet.ESCALAB 250 model (Thermao Electron Corp.) X-gamma spectrometer is adopted in the analysis of X-ray energy spectrum, is excitation light source with the K α line of aluminium, and carbon (bound energy C1s 285.5eV) is interior mark.
Description of drawings:
Fig. 1. the beta-silicon nitride nanowire x-ray diffraction pattern.
Fig. 2. beta-silicon nitride nanowire FTIR spectrogram.
Fig. 3. beta-silicon nitride nanowire transmission electron microscope photo (a), and electron diffraction pattern (b).
Fig. 4. beta-silicon nitride nanowire electron scanning micrograph (a) and EDX analysis of spectra (b).
Fig. 5. the beta-silicon nitride nanowire TEM photo that under different condition, prepares.(a) 400 ℃ 1 hour, n=4; (b) 500 ℃ 5 hours, n=4; (c) 500 ℃ 1 hour, n=3; (d) 500 ℃ 5 hours, n=3.
Fig. 6. silicon nitride nano band x-ray diffraction pattern.
Fig. 7. silicon nitride nano band TEM photo (a, b) and EDS spectrum.
Fig. 8. silicon nitride nano band FTIR spectrum.
Fig. 9. beta-silicon nitride nanowire (a) and nano belt (b) X-ray energy spectrum.
The characterization result of the beta-silicon nitride nanowire that obtained in 5 hours 450 ℃ of reactions when Fig. 1-4 has showed n=4.
Wherein Fig. 1 is the X-ray diffraction style of product powder.17 diffraction envelopes of indexing are corresponding to β-Si
3N
4Diffracted ray, the lattice parameter that calculates thus is a=7.590 and c=2.904
, (thick line, a=7.634, c=2.921 are consistent with JCPDS card# 82-0710
); All the other more weak diffraction peaks are all corresponding to α-Si
3N
4(fine rule, JCPDS card# 83-0700).There is not the impurity signal.The prepared product of this explanation is the crystallization silicon nitride.According to β-Si
3N
4The strong and α-Si of diffracted ray
3N
4More weak feature can judge that the main thing of product is β-Si mutually
3N
4Adopt the method for estimation of relevant document, obtain α-Si
3N
4/ β-Si
3N
4Mass ratio equals 0.1598, and β-Si in the product is described
3N
4Account for 86.2%, α-Si
3N
4Account for 13.8%.
Fig. 2 has provided the FTIR spectrogram of this sample.Among the figure 445.6,578.2,858.2,990.7 and 1047cm
-1Demonstrate very strong absorption, illustrate that product is a silicon nitride.Wherein 858.2 and 445.6,578.2cm
-1Correspond respectively to the stretching vibration and the formation vibration of Si-N key.990.7cm
-1Corresponding to the asymmetrical stretching vibration of Si-N key.1047cm
-1Stretching vibration corresponding to the N-Si-O key.These absorption peaks all are the characteristic absorbance of silicon nitride.The existence of Si-O key derives from the oxidation of material surface and the purification process hydrolysis takes place, thereby forms a small amount of Si-OH and N-H key.So, at 1635cm
-1A more weak absorption peak corresponding to the N-H key can be seen in the position.As for 3439cm
-1Absorption on every side, corresponding to the absorption of O-H key, it mainly forms reason is the moisture that sample absorbs in air.
Fig. 3 has provided the transmission electron microscope photo and the electron diffraction pattern of this sample.Shown in accompanying drawing 3a, the beta-silicon nitride nanowire mean diameter is about 30nm, and length is bigger, and length/diameter ratio is about 25.Electron diffraction provides clear spot among the accompanying drawing 3b, illustrates that the beta-silicon nitride nanowire crystallization is fine, according to calculating, and its d-value and β-Si
3N
4Be consistent, and with above-mentioned X-diffraction in β-Si
3N
4Consistent.
Fig. 4 has provided the beta-silicon nitride nanowire electron scanning micrograph and the EDX analysis of spectra of this sample.Shown in accompanying drawing 4a,, twine bunchy mutually though that beta-silicon nitride nanowire pattern and size and transmission electron microscope observing arrive is consistent.This be because transmission electron microscope observing to be the nano wire that ultra-sonic dispersion is crossed in ethanol, and electron scanning micrograph directly shows its powdered sample.The EDX spectrogram has provided stronger Si and n-signal among the accompanying drawing 4b, and by calculating, the molar ratio of Si and N content is 0.812: 1, and is approaching than theoretical value 0.75: 1, but has Si difference on the high side.This may since material surface because of oxidation or/and hydrolysis causes losing N causes.The EDX spectrum analysis is also found the signal of heterogeneous elements such as gold, a small amount of oxygen, be because metal spraying during sample preparation, sample surfaces oxidation or/and hydrolysis, and sample preparation causes with double sticky tape.
More than analyze and characterize explanation and prepared beta-silicon nitride nanowire under the described conditions.But for different preparation conditions, the beta-silicon nitride nanowire that is obtained but has different patterns.Fig. 5 has showed several different situations, is respectively (a) n=4,400 ℃ 1 hour, (b) n=4,500 ℃ 5 hours, (c) n=3,500 ℃ 1 hour, (d) n=3,500 ℃ 5 hours.As seen from the figure, factors such as proportioning, temperature and reaction times all can influence product nano wire shape characteristic.
The characterization results of the silicon nitride nano band that reaction obtained in 5 hours under 450 ℃ when accompanying drawing 6-8 had showed n=2.Wherein Fig. 6 is the X-ray diffraction style of product powder.The diffraction peak of indexing is corresponding to β-Si
3N
4Diffracted ray, be consistent with JCPDS card# 82-0710 by (thick line); All the other more weak diffraction peaks are all corresponding to α-Si
3N
4(fine rule, JCPDS card# 83-0700).According to another the difference of relative intensity, illustrate that prepared product mainly is β-Si
3N
4Estimate to obtain α-Si
3N
4/ β-Si
3N
4Mass ratio equals 0.0713, and β-Si in the product is described
3N
4Account for 93.3%, α-Si
3N
4Account for transmission electron microscope photo and EDX analysis of spectra that 6.7%. Fig. 7 has provided this sample.Shown in accompanying drawing 7a, silicon nitride nano bandwidth 40-80nm, on average about 60nm, length surpasses 500nm, and thickness estimation is no more than 20nm.The EDX spectrogram has provided stronger Si and n-signal among the accompanying drawing 7b, the molar ratio of Si and N content is 0.792: 1, relatively more approaching near theoretical value 0.75: 1, the EDX spectrum analysis is also found the signal of heterogeneous elements such as copper, a small amount of oxygen, copper comes from the TEM copper mesh, and oxygen comes from the sample surfaces oxidation or/and hydrolysis.Fig. 8 has provided the FTIR spectrogram of this sample.Its characteristic infrared absorption is similar to nano wire, illustrates that product is a silicon nitride.Also can see one corresponding to the more weak absorption peak of N-H key with corresponding to the absorption peak of O-H key.
Fig. 9 has showed the characterization result of the X-ray energy spectrum of beta-silicon nitride nanowire (reacting 5 hours at 450 ℃ during n=4) and nano belt (reacting 5 hours at 450 ℃ during n=2) powder.As seen from the figure, the X-ray energy spectrum of nano wire (a), nano belt (b) sample all has stronger signal at bound energy 101.8,152.8 and 397.3eV place, corresponds respectively to Si2p, Si2s and N1s bound energy, consistent with bibliographical information, and N: the Si atomic ratio is respectively 1.147 and 1.355, with Si
3N
4Theoretical value 1.333 more approaching, illustrate that product is a silicon nitride.At the peak of 285.5eV is the C1s signal of interior mark carbon, and corresponding to the O1s of oxygen, the existence of oxygen may be to come from the material surface oxidation or/and hydrolysis is because surface adsorption on the other hand on the one hand at the peak of 532.5eV.
Embodiment:
Embodiment 1: the preparation beta-silicon nitride nanowire
Get 3.8 gram NaN
3Add volume with 2.69 gram metal Na and be approximately the 60ml stainless steel cauldron, add 5 milliliters of liquid SiCl again
4SiCl
4Be analytical reagent, white crystalline solid NaN
3With metal Na be chemically pure reagent.Metal Na is taken out from kerosene, blots with filter paper, is cut into small pieces.Operate in the glove box that charges into dry argon gas at ambient temperature and carry out.Reactor is built, and sealing, put into well formula crucible oven then, in 450 ℃ of isothermal reactions 5 hours, drive still and take out reaction product after naturally cooling to room temperature.Product is removed by product sodium-chlor through washing, absolute ethanol washing and centrifugation, in 80 ℃ times dry 24 hours, obtains 1.895 gram white powder products in vacuum drying oven.Through structure, composition and morphology analysis, prove that product is purified silicon nitride, wherein β-Si
3N
4Account for 86.2%, α-Si
3N
4Account for 13.8%, with respect to SiCl
4Overall yield is 92.5%, and product nano wire pattern is even, its mean diameter 30nm, and length on average is about 500nm.
Embodiment 2: the preparation beta-silicon nitride nanowire
Get 3.25 gram NaN
3Add volume with 3.0 gram metal Na and be approximately the 60ml stainless steel cauldron, add 5 milliliters of liquid SiCl again
4In 450 ℃ of isothermal reactions 2 hours, drive still and take out reaction product after naturally cooling to room temperature.All the other operations are the same with above-mentioned example 1, obtain 1.947 and restrain the white powder products.Through structure, composition and morphology analysis, prove that product is purified silicon nitride, wherein β-Si
3N
4Account for 90.3%, α-Si
3N
4Account for 9.7%, with respect to SiCl
4Overall yield is 94.4%, and the product pattern is based on nano wire, and it is even to contain a small amount of nano belt.
Embodiment 3: preparation silicon nitride nano band
Get 2.70 gram NaN
3Add volume with 3.15 gram metal Na and be approximately the 60ml stainless steel cauldron, add 5 milliliters of liquid SiCl again
4In 500 ℃ of isothermal reactions 3.5 hours, drive still and take out reaction product after naturally cooling to room temperature.All the other operations are the same with above-mentioned example 1, obtain 1.863 and restrain the white powder products.Through structure, composition and morphology analysis, prove that product is purified silicon nitride, wherein β-Si
3N
4Account for 89.7%, α-Si
3N
4Account for 10.3%, with respect to SiCl
4Overall yield is 90.6%, and product also contains more nanometer rod and nano belt based on nano wire.
Embodiment 4: preparation silicon nitride nano band
Get 3.8 gram NaN
3Add volume with 6.8 gram metal Na and be approximately the 60ml stainless steel cauldron, add 10 milliliters of liquid SiCl again
4SiCl
4Be analytical reagent, white crystalline solid NaN
3With metal Na be chemically pure reagent.All the other operations are the same with above-mentioned example 1, obtain 3.733 and restrain the white powder products.Through structure, composition and morphology analysis, prove that product is purified silicon nitride, wherein β-Si
3N
4Account for 93.3%, α-Si
3N
4Account for 6.7%, with respect to SiCl
4Overall yield is 91.1%, the even wide 40-80nm of nano belt, and length is about 500nm, and thickness estimation is no more than 20nm.
Claims (10)
1, the preparation method of a kind of beta-silicon nitride nanowire or nano belt powder body material is with SiCl
4For the silicon source, with NaN
3Be nitrogenous source, in reactor, react that product is characterized in that: also add metal Na in reactor through washing, separation and the dry white powder product that gets; Be reflected at 400-600 ℃ of temperature, system autogenous pressure and be under the condition of 5-40MPa and carried out 0.5-6 hour, obtain beta-silicon nitride nanowire or nano belt; The chemical equation of its reaction is expressed as:
3SiCl
4+n?NaN
3+(12-n)Na＝Si
3N
4+12NaCl+(1.5n-2)N
2
Wherein n satisfies 1.334≤n≤11.998.
2, preparation method according to claim 1 is characterized in that: wherein n satisfies 2≤n≤4.
3, preparation method according to claim 1 is characterized in that: the SiCl that is added
4, NaN
3, Na mass ratio be 1: 0.4～0.5: 0.36～0.4, the preparation beta-silicon nitride nanowire.
4, preparation method according to claim 1 is characterized in that: the SiCl that is added
4, NaN
3, Na mass ratio be 1: 0.25-0.38: 0.40-0.45, preparation silicon nitride nano band.
5, preparation method according to claim 1 is characterized in that: carry out reacting by heating again feed rare gas element and sealing in described reactor after.
6, preparation method according to claim 5 is characterized in that: described rare gas element is nitrogen or argon gas.
7, preparation method according to claim 1 is characterized in that: described temperature of reaction is 450～500 ℃.
8, preparation method according to claim 1 is characterized in that: described reaction system autogenous pressure is 15～25MPa.
9, preparation method according to claim 1 is characterized in that: the described reaction times is 0.5～5 hour.
10, preparation method according to claim 1 is characterized in that: the centrifugation behind washing and absolute ethanol washing of described product, 80 ℃ of following dryings 24 hours in vacuum drying oven then.
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| CN100560485C (en) * | 2007-07-26 | 2009-11-18 | 山东大学 | Utilize the method for solvent thermal reaction low temperature synthesizing silicon nitride nano material |
| CN101648697B (en) * | 2009-07-17 | 2013-12-18 | 宁波工程学院 | Method for preparing nanobelt |
| CN104891455A (en) * | 2015-05-15 | 2015-09-09 | 蔡奕茗 | Preparation method for silicon nitride nano-material |
| CN106747640B (en) * | 2017-01-13 | 2019-10-25 | 武汉科技大学 | A kind of beta-silicon nitride nanowire enhancing porous silicon carbide silicon materials and preparation method thereof |
| CN112047742B (en) * | 2020-09-03 | 2022-03-15 | 中钢南京环境工程技术研究院有限公司 | Low-cost preparation method of large-size silicon nitride nanobelt aerogel |
| CN117431525A (en) * | 2022-04-01 | 2024-01-23 | 杭州芯傲光电有限公司 | Preparation method of silicon nitride film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562735A (en) * | 2004-03-19 | 2005-01-12 | 山东大学 | Method for preparing powder material of silicon nitride under low temperature |
| CN1799993A (en) * | 2005-12-14 | 2006-07-12 | 山东大学 | One-step low temperature reaction method for preparing beta-silicon nitride powder material |
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|---|---|---|---|---|
| CN1562735A (en) * | 2004-03-19 | 2005-01-12 | 山东大学 | Method for preparing powder material of silicon nitride under low temperature |
| CN1799993A (en) * | 2005-12-14 | 2006-07-12 | 山东大学 | One-step low temperature reaction method for preparing beta-silicon nitride powder material |
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