CN103754878B - The method of the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ - Google Patents
The method of the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ Download PDFInfo
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Abstract
The invention provides a kind of micron order silicon carbide powder surface in situ growth multi-walled carbon nano-tubes method, first silicon carbide powder is oxidized, pickling, alkali cleaning surface treatment, remove surface silicon oxide and other impurity; Then adopt the method for chemical codeposition to wrap up the equally distributed nano-catalyst particles of one deck at silicon carbide, more above-mentioned powder is put into quartz tube furnace, utilize the method for chemical vapour deposition to prepare carbon nanotube at silicon carbide In-stiu catalysis.The present invention can realize carbon nanotube being uniformly distributed at micron order silicon carbide, solves the difficulty that carbon nanotube is easily reunited, for the multiple dimensioned matrix material of preparation high-performance provides the foundation.Method of the present invention is simple, and feasibility is high; Obtained carbon nanotube is uniformly dispersed at silicon carbide and measures controlled.
Description
Technical field
The present invention relates to matrix material and preparing technical field thereof, particularly matrix material situ prepares the field of homodisperse carbon nanotube as wild phase from generation method.
Background technology
Since carbon nanotube in 1991 is found by Iijima, due to the structure of its novelty and distinctive mechanics, electricity and physicochemical property and potential purposes thereof, cause the very big concern of domestic and international chemistry, physics, material, electronics educational circles.Especially the mechanical property of carbon nanotube and excellence thereof: its average Young's modulus reaches 1.8TPa, be about 100 times of steel, flexural strength can reach 14.2GPa, strain energy of depositing reaches 100keV, demonstrate superpower mechanical property, and its density is low, the density about 1.2 ~ 1.3g/cm3 of Single Walled Carbon Nanotube, multi-walled carbon nano-tubes density is also only 1.7g/cm3, is only 1/6 of steel, is almost the material that current specific tenacity and specific rigidity are the highest.If therefore it is made Reinforcements for Metal Matrix Composites and not only can improve intensity, also density of material can be reduced further.
But due to the nanoscale effect of carbon nanotube, easily reuniting as during wild phase, disperseing inequality in the base, not having the effect of wild phase; The method of present stage many employings is high-energy ball milling method is that carbon nanotube scatter in the base uniformly, but this method is because the high energy of ball milling is inevitably according to the damage becoming carbon nanotube structure, last performance is impacted, and the volume fraction that even carbon nanotube can be made to disperse is very limited.And searching document finds, in the production method of carbon nanotube, chemical gaseous phase depositing process is simple, and operability is large, but needs to be separated the carrier of last Formed nanotube, obtains pure carbon nanotube.
Silicon carbide also has excellent over-all properties due to it, is widely used now, as the wild phase of metal-base composites; And if application silicon carbide is as the carrier of chemical vapor deposition for carbon nanotubes, not only can save the step that carrier is separated, and silicon carbide and carbon nanotube can be made simultaneously as the wild phase of metallic matrix, strengthening effect may be better.
Existing document and invention retrieval are found also do not have the report of this respect in document; And Chinese patent (CN102504760A) " preparation method of a kind of silicon carbide and carbon nano tube composite wave-absorbing material ", metal-carbon silicon compound is prepared at silicon carbide mainly through pickling process, then evaporate to dryness is directly put into silica tube and is passed into methane, and heating and heat preservation obtains silicon carbide and carbon nano tube composite wave-absorbing material; Chinese patent (CN102962087A) " a kind of carbon nanotube/silicon carbide foam catalytic composite material and preparation method thereof " mainly uses foam silicon carbon as carrier, Fe-Mg-Al, as composite catalyst, adopts the method for chemical vapor deposition for carbon nanotubes.These two patents have all prepared carbon nanotube, but main in these two patents what utilize is suction ripple and the catalytic performance of carbon nanotube, and have many deficiencies: the metal-carbon silicon compound that (1) adopts pickling process to prepare, metallic particles size and distribution all uneven, catalytic performance can not be played well; (2) do not adopt carrier gas to be easy to produce indefiniteness carbon in chemical vapour deposition deposition, impact is shone on the performance of material; (3) Fe-Mg-Al composite catalyst is adopted may to have bad impact to the last performance of matrix material.
Summary of the invention
The object of this invention is to provide the method for the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ.The method technique even carbon nanotube that is simple, workable, preparation is controlled.
The present invention is achieved by the following technical solutions: first being oxidized silicon carbide, pickling, alkali cleaning surface treatment, remove silicon oxide and the impurity thereof on surface; Then the method for chemical codeposition is adopted to prepare the equally distributed nano-catalyst particles of one deck at silicon carbide, quartz tube furnace will be put into containing granules of catalyst silicon carbide again, and utilize the method for chemical vapour deposition to prepare carbon nanotube in silicon carbide situ catalytic.
The present invention includes following steps:
1) surface treatment of silicon-carbide particle: take silicon-carbide particle, be placed in chamber type electric resistance furnace, be heated to 800-1200 DEG C, insulation, furnace cooling is to room temperature; Then, silicon carbide is added in the HF aqueous solution, rear washed with de-ionized water, suction filtration; Join the saturated NaOH aqueous solution again and roughening treatment is carried out to silicon carbide, then deionized water suction filtration, cleaning.Finally put into loft drier to be incubated at 100-200 DEG C.
2) preparation of silicon-carbide particle surface catalyst: be dissolved in deionized water by acetate and be made into the aqueous solution, stir to clarify, then adds the silicon-carbide particle of step 1) process, supersound process in solution; Add NH
3h
2o solution, until required pH value, magnetic agitation, room temperature leaves standstill deposition, washed with de-ionized water, and after suction filtration, 80-150 DEG C of dry 10-20 hour, then 300-600 DEG C of calcining in air, obtained the oxide particle of nano level catalyzer at catalyst surface.
3) silicon-carbide particle surface chemistry deposition of carbon nanotubes: by step 2) in the silicon-carbide particle handled well be layered in quartz boat, be placed in quartz tube furnace; Be raised to 300-550 DEG C under argon gas atmosphere protection, close argon gas, pass into hydrogen 1-5 hour; Then be warmed up to 600-900 DEG C, pass into methane and argon gas, insulation reaction 10-120 minute, stop ventilating methane, cool to room temperature under argon shield, obtains silicon carbide and carbon nano tube compound material.
In the present invention, described HF aqueous solution massfraction is 40%.
In the present invention, NH
3h
2o strength of solution is 0.5mol/L.
In the present invention, required pH value is between 6-9.
In the present invention, silicon-carbide particle size used is 10-100 μm.
In the present invention, the acetate of metal used and the mol ratio of silicon carbide are between 1:10 to 1:90.Metal used can be nickel or iron or cobalt etc.
In the present invention, described mixed solution room temperature time of repose is between 1-48 hour.
In the present invention, that tells passes into methane and argon gas, and the volume ratio of two kinds of gases is between 1:3 to 1:10.
In the present invention, the oxide particle of catalyzer that prepared by silicon carbide is between 1-200nm.
In the method for the invention, first be that the 40%HF aqueous solution and saturated sodium hydroxide process to micron order silicon carbide massfraction, the impurity on surface can not only be eliminated, and make silicon carbide alligatoring and activation, add the adsorptive power of nanoparticle at silicon carbide.Adopt acetate as the raw material preparing nanoparticle, and adopt the method for chemical codeposition that nickel acetate and weakly alkaline solution are reacted, form the particle of nm sized hydroxide at silicon carbide, this is compared with traditional pickling process, reduce calcining and reduction temperature, save the energy.Adopt the method for chemical vapour deposition to prepare carbon nanotube, this method simple and feasible, does not need the severe condition such as the High Temperature High Pressure in additive method, can realize large-scale production; Select wild phase micron order silicon carbide powder conventional in metal matrix as carrier, the silicon carbide prepared and carbon nano tube compound material directly can be used as the wild phase of matrix material, save the process that will be separated with carrier when carbon nanotube is applied;
Compared with prior art, beneficial effect of the present invention is:
1, present invention achieves in-situ growing carbon nano tube, overcome the nanoscale effect of carbon nanotube, obtain the composite strengthening phase of uniform loading on micron order silicon-carbide particle.
2, present invention eliminates the purge process of removal carrier when preparing carbon nanotube, no matter and carrier used and catalyzer finally can play strengthening effect in the composite.
3, the technological process simple and feasible of the present invention's employing, avoids the High Temperature High Pressure prepared and need in carbon nanotube process, can realize large-scale production.
Accompanying drawing explanation
Fig. 1: the process flow sheet of carbon nanotube is prepared in catalytic pyrolysis chemical vapour deposition;
Fig. 2: the granules of catalyst of silicon-carbide particle surface preparation and the scanning electron microscope (SEM) photograph of carbon nanotube;
Fig. 3: the material phase analysis figure of silicon-carbide particle area load carbon nanotube.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.It should be pointed out that following embodiment just further illustrates of the present invention, but protection scope of the present invention is not limited to following examples.
Silicon carbide described in following examples is Powdered α-SiC, all have passed through the process of oxidation, pickling, alkali cleaning before Kaolinite Preparation of Catalyst.The catalyzer of preparation and the detection of carbon nanotube mainly use scanning electronic microscope (SEM) to complete, and the thing of final product has detected X-ray diffractometer mutually and completed.Embodiment is implemented according to flow process shown in Fig. 1.
The surface treatment flow process of silicon-carbide particle: take silicon-carbide particle, be placed in chamber type electric resistance furnace, be heated to 800-1200 DEG C, insulation, furnace cooling is to room temperature; Then, silicon carbide being added massfraction is in the 40%HF aqueous solution, rear washed with de-ionized water, suction filtration; Join the saturated NaOH aqueous solution again and roughening treatment is carried out to silicon carbide, then deionized water suction filtration, cleaning.Finally put into loft drier to be incubated at 100-200 DEG C.
Embodiment 1
By four water acetic acid nickel as in the beaker of 150ml, add 80ml deionized water, stir to clarify, by surface-treated silicon carbide, join in beaker by the mol ratio 20:1 with four water acetic acid nickel, put into ultrasonic apparatus ultrasonic cleaning 0.5 hour, take out, be placed on magnetic stirring apparatus, add the NH of 0.5mol/L while stirring
3h
2the O aqueous solution, until pH value is 7, continues magnetic agitation after 1 hour, at room temperature leaves standstill 48 hours, then use deionized water rinsing, suction filtration; Take out the powder in funnel, put into 100 DEG C, loft drier, dry 10 hours, then put into the chamber type electric resistance furnace of 450 DEG C, calcine 2 hours under air atmosphere.The oxide particle of nano level catalyzer is obtained at catalyst surface.
Get the powder of the process of 500 milligrams; put into quartz boat; be placed in quartz tube furnace; under the argon atmosphere of 500ml/min; be warmed up to 500 DEG C; close argon gas; pass into the hydrogen reducing 2 hours of 300ml/min, continue to be heated to 700 DEG C, pass into argon gas and methane gas that volume ratio is 1:1; react 1 hour; close methane, cool to room temperature under argon atmosphere, take out; weigh the weight of final powder, obtaining is the silicon carbide compound powder of the carbon nanotube of 2% containing massfraction.
Embodiment 2
By four water acetic acid nickel as in the beaker of 150ml, add 50ml deionized water, stir to clarify, again by surface-treated silicon carbide, join in beaker by the mol ratio 10:1 with four water acetic acid nickel, put into ultrasonic apparatus ultrasonic cleaning 0.5 hour, take out, be placed on magnetic stirring apparatus, add the NH3H2O aqueous solution 8 of 0.5mol/L while stirring, continue stirring after 1 hour, at room temperature leave standstill 48 hours, then be neutral with deionized water rinsing to PH, suction filtration; Take out the powder in funnel, put into 150 DEG C, loft drier, dry 10 hours, then put into the chamber type electric resistance furnace of 500 DEG C, calcine 2 hours under air atmosphere.
Get the powder of the process of 500 milligrams; put into quartz boat; be placed in quartz tube furnace; under the argon atmosphere of 500ml/min; be warmed up to 550 DEG C; close argon gas; pass into the hydrogen reducing 1 hour of 300ml/min, continue to be heated to 700 DEG C, pass into argon gas and methane gas that volume ratio is 1:2; react 1.5 hours; close methane, cool to room temperature under argon atmosphere, take out; weigh the weight of final powder, obtaining is the silicon carbide compound powder of the carbon nanotube of 5% containing massfraction.
Embodiment 3
By four water acetic acid nickel as in the beaker of 150ml, add 50ml deionized water, stir to clarify, again by surface-treated silicon carbide, join in beaker by the mol ratio 20:1 with four water acetic acid nickel, put into ultrasonic apparatus ultrasonic cleaning 0.5 hour, take out, be placed on magnetic stirring apparatus, add the ammonia soln of 0.5mol/L while stirring, until pH value is 9, continue stirring after 1 hour, at room temperature leave standstill 24 hours, then use deionized water rinsing, suction filtration; Take out the powder in funnel, put into 120 DEG C, loft drier, dry 10 hours, then put into the chamber type electric resistance furnace of 500 DEG C, calcine 2 hours under air atmosphere.
Get the powder of the process of 500 milligrams; put into quartz boat; be placed in quartz tube furnace; under the argon atmosphere of 500ml/min; be warmed up to 500 DEG C; close argon gas; pass into the hydrogen reducing 2 hours of 300ml/min, continue to be heated to 800 DEG C, pass into argon gas and methane gas that volume ratio is 2:1; react 1 hour; close methane, cool to room temperature under argon atmosphere, take out; weigh the weight of final powder, obtaining is the silicon carbide compound powder of the carbon nanotube of 10% containing massfraction.
Embodiment 4
By four water acetic acid nickel as in the beaker of 150ml, add 80ml deionized water, stir to clarify, by surface-treated silicon carbide, join in beaker by the mol ratio 40:1 with four water acetic acid nickel, put into ultrasonic apparatus ultrasonic cleaning 0.5 hour, take out, be placed on magnetic stirring apparatus, add the ammonia soln of 0.5mol/L while stirring, until pH value is 8, continue stirring after 1 hour, at room temperature leave standstill 48 hours, then use deionized water rinsing, suction filtration; Take out the powder in funnel, put into 100 DEG C, loft drier, dry 10 hours, then put into the chamber type electric resistance furnace of 500 DEG C, calcine 2 hours under air atmosphere.
Get the powder of the process of 500 milligrams; put into quartz boat; be placed in quartz tube furnace; under the argon atmosphere of 500ml/min; be warmed up to 500 DEG C; close argon gas; pass into the hydrogen reducing 2 hours of 300ml/min, continue to be heated to 800 DEG C, pass into argon gas and methane gas that volume ratio is 1:3; react 2 hours; close methane, cool to room temperature under argon atmosphere, take out; weigh the weight of final powder, obtaining is the silicon carbide compound powder of the carbon nanotube of 20% containing massfraction.
Figure 2 shows that the middle silicon carbide of embodiment 3 is through H
2the stereoscan photograph of the carbon nanotube obtained after the catalyst n i particle obtained after reduction and chemical vapour deposition, as we can see from the figure, the granules of catalyst of preparation is evenly distributed, size is tiny, between a few nanometer and tens nanometers, illustrate that the catalyzer prepared by this method can well play katalysis at the preparatory phase of carbon nanotube.The stereoscan photograph of carbon nanotube as can be seen from figure, the carbon nanotube of preparation is even in silicon-carbide particle surface arrangement, does not substantially have the generation of indefiniteness carbon.Fig. 3 is the XRD figure spectrum of last composite powder, learns have the Ni simple substance of its katalysis and the existence of carbon nanotube in final powder from spectrogram.In the present invention, other embodiment effects are also fine, and therefore, the present invention can prepare the controlled carbon nanotube of one deck amount at carbon powder SiClx surface uniform.
Be more than part preferred embodiment of the present invention, should be understood that, the present invention also has other embodiment, and such as change material mixture ratio in above-described embodiment and parameter value etc., this is easy to realize to one skilled in the art.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (10)
1. a method for the spontaneous carbon nanotube of silicon-carbide particle surface in situ, is characterized in that, comprise the following steps:
1) surface treatment of silicon-carbide particle: silicon-carbide particle is placed in chamber type electric resistance furnace, is heated to 800-1200 DEG C, insulation, furnace cooling is to room temperature; Then, silicon carbide is added in the HF aqueous solution, rear washed with de-ionized water, suction filtration; Join the saturated NaOH aqueous solution again and roughening treatment is carried out to silicon carbide, then washed with de-ionized water, suction filtration; Finally put into loft drier to be incubated at 100-200 DEG C;
2) preparation of silicon-carbide particle surface catalyst: be dissolved in deionized water by metal acetate salt and be made into the aqueous solution, stir to clarify, then adds the silicon-carbide particle after step 1) process, supersound process in solution; Add NH
3h
2o solution, until required pH value, magnetic agitation, room temperature leaves standstill deposition, cleaning, and after suction filtration, 80-150 DEG C of dry 10-20 hour, then 300-600 DEG C of calcining in air, obtained the oxide particle of nano level catalyzer at catalyst surface;
3) silicon-carbide particle surface chemistry deposition of carbon nanotubes: by step 2) in the silicon-carbide particle handled well be layered in quartz boat, be placed in quartz tube furnace; Be raised to 300-550 DEG C under argon gas atmosphere protection, close argon gas, pass into hydrogen 1-5 hour; Then be warmed up to 600-900 DEG C, pass into methane and argon gas, insulation reaction 10-120 minute, stop ventilating methane atmosphere, cool to room temperature under argon shield, obtains silicon carbide and carbon nano tube compound material.
2. the method for the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ according to claim 1, is characterized in that, in step 1), be placed in chamber type electric resistance furnace, soaking time is 2 hours; Putting into loft drier soaking time is 10 hours; HF aqueous solution massfraction is 40%.
3. the method for the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ according to claim 1, is characterized in that, step 2) in, the mol ratio of metal acetate salt used and silicon carbide is between 1:10 to 1:90.
4. the method for the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ according to claim 3, is characterized in that, step 2) in, metal acetate salt is dissolved in deionized water, and strength of solution is between 0.1mol/L ~ 1mol/L; NH
3h
2o strength of solution is 0.5mol/L.
5. the method for the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ according to claim 4, is characterized in that, described metal acetate salt, and its metal is nickel or iron or cobalt.
6. the method for the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ according to any one of claim 1-5, is characterized in that, step 2) in, sonication treatment time is 30 minutes; The magnetic agitation time is 1 hour; Required pH value is between 6-9.
7. the method for the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ according to any one of claim 1-5, is characterized in that, step 2) in, it is between 1-48 hour that described room temperature leaves standstill depositing time.
8. the method for the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ according to any one of claim 1-5, is characterized in that, in step 3), the described volume ratio passing into methane and argon gas is between 1:3 to 1:10.
9. the method for the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ according to any one of claim 1-5, it is characterized in that, silicon-carbide particle size used is 10-100 μm.
10. the method for the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ according to any one of claim 1-5, is characterized in that, the oxide particle of catalyzer prepared by described silicon carbide is between 1-200nm.
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| CN105568027A (en) * | 2015-12-04 | 2016-05-11 | 上海交通大学 | Micronano particle hybrid reinforced aluminum-based composite material and preparation method thereof |
| CN105836730B (en) * | 2016-04-20 | 2019-04-19 | 上海交通大学 | A kind of method of the spontaneous carbon nanotube of graphite material surface in situ |
| CN107915217B (en) * | 2016-10-10 | 2020-10-16 | 中国科学院金属研究所 | Method for preparing semiconductor single-walled carbon nanotube by using non-metallic catalyst SiC |
| CN106565263B (en) * | 2016-11-05 | 2019-07-30 | 天津大学 | A kind of preparation method of carbon nanotube/silicon carbide heat-conductive composite material |
| CN108217629B (en) * | 2017-12-29 | 2019-07-23 | 西安理工大学 | A kind of preparation method of the compound CNTs of surface in situ generation nano SiC |
| CN109913851B (en) * | 2019-03-13 | 2021-02-23 | 肇庆市华师大光电产业研究院 | Method for preparing MWCNT @ XY by adopting co-sputtering of post-annealing treatment and MWCNT @ XY |
| CN111040729B (en) * | 2019-11-15 | 2022-07-26 | 中国人民解放军陆军工程大学 | Preparation method and application of silicon carbide-based nano composite wave-absorbing material |
| CN112607739A (en) * | 2020-11-26 | 2021-04-06 | 安徽盈锐优材科技有限公司 | Preparation method of modified silicon carbide for thermal spraying |
| CN112898101A (en) * | 2021-02-01 | 2021-06-04 | 常州大学 | Preparation method of carbon nano tube doped octogen composite flexible explosive |
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Effective date of registration: 20221121 Address after: Room 703, No. 1, Lane 406, Yishan Road, Xuhui District, Shanghai, 200000 Patentee after: OuYang Qiubao Address before: 200240 No. 800, Dongchuan Road, Shanghai, Minhang District Patentee before: SHANGHAI JIAO TONG University Effective date of registration: 20221121 Address after: 102B, Plant 1, Shangrong Science and Technology Industrial Park, No. 2, Baolong Fifth Road, Baolong Community, Longgang District, Shenzhen, Guangdong 518000 Patentee after: Shenzhen superior technology new material Co.,Ltd. Address before: Room 703, No. 1, Lane 406, Yishan Road, Xuhui District, Shanghai, 200000 Patentee before: OuYang Qiubao |