CN101260595A - Single-layer carbon nano-tube non-woven fabrics and preparation method thereof - Google Patents
Single-layer carbon nano-tube non-woven fabrics and preparation method thereof Download PDFInfo
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Abstract
The invention provides a non-woven fabric with monolayer carbon nanotubes and a preparation method thereof. The non-woven fabric is formed through mutual tangling of a plurality of monolayer carbon nanotube bundles; the area of the non-woven fabric is between 10-100cm <2> and the thickness of the non-woven fabric is 100nm-20mu m; the diameters of the monolayer carbon nanotube bundles are 100-300GPa. After simply purification, all catalyst particles in the non-woven fabric with the monolayer carbon nanotubes can be almost eliminated, and the figuration of the non-woven fabric still keeps complete. The non-woven fabric with monolayer carbon nanotubes has higher mechanical strength and macroscopical area. The preparation method has the advantages of simplicity, flexibility, environmental protection, non-pollution chemistry and low energy consumption, and the obtained non-woven fabric with the monolayer carbon nanotubes has the advantages of high productivity, stable structure and strong operability..
Description
Technical field
The present invention relates to a kind of nonwoven fabric, relate in particular to a kind of single-layer carbon nano-tube non-woven fabrics and preparation method thereof, this method is by the design consersion unit and optimize the controlled preparation that growth technique has been realized the high-intensity single-layer carbon nano-tube non-woven fabrics of large tracts of land.
Background technology
Single-layer carbon nano-tube is the seamless column structure that is only curled and formed by one deck graphite linings, has unique electronics, mechanical performance, has potential application prospect in fields such as nano-device, nano composite materials.The method that is used to prepare single-layer carbon nano-tube at present mainly contains laser ablation method and arc discharge method, so but owing to need extreme preparation condition cost higher.In addition, by pyrolysis carbon compound molecule such as CO on the nano level metal particle, CH
4Or C
2H
4Deng chemical vapour deposition technique also can produce single-layer carbon nano-tube, and chemical vapour deposition technique is considered to most possible mass and prepares one of method of mono-layer tube.In the former bibliographical information, employing floating catalytic chemical vapour deposition technique as growth promoter, is a catalyst precursor with the ferrocene with thiophene, can produce the monolayer carbon nanometer of diameter at 1～3nm by pyrolysis benzene under 1100～1200 ℃.Subsequently, the researcher adopts similar floating catalytic technology, in 800～1200 ℃ range of reaction temperature, by other hydrocarbon gas (C of pyrolysis
2H
2, CH
4) also produced single-layer carbon nano-tube.In these researchs, with hydrocarbon as single-layer carbon nano-tube growth carbon source the time, hydrocarbon is easy under reaction temperature fast from pyrolysis (on-catalytic pyrolysis), thereby forms impurity such as graphitic carbon deposit or amorphous carbon.Therefore, the more amorphous carbon of the normal covering in the surface of the single-layer carbon nano-tube that the employing hydrocarbon is produced need carry out post-processed, purifying.On the other hand, bibliographical information utilizes the disproportionated reaction of CO, can the synthesis of high purity single-layer carbon nano-tube.CO is considered to a kind of carbon source preferably because adopt it as carbon source produce single-layer carbon nano-tube cleaner, less amorphous carbon covers.Yet, because under given reaction temperature and pressure, the decomposition rate of CO is than slow many of the decomposition rate of hydrocarbon, and produces the CO that single-layer carbon nano-tube generally will adopt big flow, the conversion ratio of carbon is corresponding lower like this, therefore is unsuitable for the large-scale production of single-layer carbon nano-tube.And, above these preparation methods all can't obtain having the single-layer carbon nano-tube structure of macro-size.
In addition, because the restriction of size, the application of single-layer carbon nano-tube pipe can't be carried out always on a large scale.Though bibliographical information in the past, obtain larger area carbon nano-tube film (" backpaper ") by processing methods such as back ultrasound filtrations, but the mechanical strength of the carbon nano-tube film that obtains is very low, has limited excellent properties the giving full play in application process of CNT.In sum as can be seen, how controllably preparing large-area single-layer carbon nano-tube in batches is one of key issue of being badly in need of solution for its large-scale application.
Summary of the invention:
The purpose of this invention is to provide the high-intensity single-layer carbon nano-tube non-woven fabrics of a kind of large tracts of land.
Another object of the present invention provides a kind of method for preparing above-mentioned single-layer carbon nano-tube non-woven fabrics.
Technical scheme of the present invention is as follows:
Single-layer carbon nano-tube non-woven fabrics provided by the invention is to be tangled mutually and formed by many single-layer carbon nano-tube tube banks; Its area is 10～100cm
2, thickness is 100nm～20 μ m; The diameter of described single-layer carbon nano-tube tube bank is 10～50nm, and length is 10 μ m～1mm; Single-layer carbon nano-tube diameter in the tube bank is 1～3nm; The Young's modulus of described single-layer carbon nano-tube non-woven fabrics is 100～300GPa.
In one embodiment, the invention provides a kind of single-layer carbon nano-tube non-woven fabrics the preparation method, its step comprises:
1) be that 16: 1～4: 1 ferrocene and sublimed sulfur mix and grind and evenly make catalyst with mol ratio;
2) catalyst is placed the quartz boat in the low temperature oven of two furnace systems distil, temperature is controlled at 60～90 ℃;
3) the feeding flow is that protection gas argon gas and the flow of 800～1200sccm are the hydrocarbon gas of 1～10sccm as carbon source, and makes the catalyst that distils in low temperature oven flow into high temperature furnace;
4) mist is that 1/5～1/3 thin quartz ampoule of low temperature oven diameter enters high temperature furnace by a diameter;
5) the catalytic cracking of hydrocarbon gas and the single-layer carbon nano-tube of growing in the high temperature furnace of two furnace systems, temperature is controlled at 800 ℃～1200 ℃, pressure in the quartz tube reactor maintains 1～1.1 atmospheric pressure, and the carbon nano tube products of generation is deposited on the quartz ampoule inwall by air-flow, form original single-layer carbon nano-tube non-woven fabrics.
In another embodiment, single-layer carbon nano-tube non-woven fabrics of the present invention the preparation method further comprise purification step.Wherein, preferably purification step comprises: with the oxidation 12～48 hours under 350 ℃～450 ℃ temperature, in air atmosphere of the single-layer carbon nano-tube non-woven fabrics that obtains; The single-layer carbon nano-tube non-woven fabrics that to handle is put into concentrated hydrochloric acid 2 days～one week of immersion that concentration is 37wt.% then, and again the product after soaking being carried out washed with de-ionized water is 7 up to pH value, and drying forms again.
In the said method, described hydrocarbon is methane or acetylene.
In the said method, the reative cell of described two furnace systems is made of quartz ampoule, and it comprises the thin quartz ampoule of outer big quartz ampoule and interior insertion.
The advantage of single-layer carbon nano-tube non-woven fabrics of the present invention and preparation method thereof is:
1, the single-layer carbon nano-tube non-woven fabrics of method preparation of the present invention is compared with common carbon nanotube powder, and it is to restrain the nonwoven membrane structure that tangles mutually and form by many single-layer carbon nano-tubes.Its area is bigger, can be to any substrate according to the random tiling of different needs, for the rerum natura measurement of CNT provides the excellent research object; In addition, in preparation process, large-area sample can be taken off from the quartz ampoule inwall easily, has extraordinary operability, therefore is a research system that good CNT is used.
2, the single-layer carbon nano-tube non-woven fabrics of method preparation of the present invention has excellent mechanical property, can be used for increasing the mechanical performance of polymer composite as packing material.And the single-layer carbon nano-tube non-woven fabrics of preparation
3, the single-layer carbon nano-tube non-woven fabrics of method preparation of the present invention has unique three-dimensional structure: the weave in that the tube bank of many single-layer carbon nano-tubes is unordered has formed a kind of very peculiar three-dimensional dense mess lattice structure.And this network all is made up of carbon, and wherein carbon nano-tube bundle is as the bone train of thought of grid, and can form and have tens mesh to the hundreds of nano-scale.This can organize application study that a very desirable growth templates is provided for biomedicine substitutes, and can study absorption, growth and the propagation behavior of different albumen on single-layer carbon nano-tube non-woven fabrics.
4, the single-layer carbon nano-tube non-woven fabrics of method of the present invention preparation has very high electrical conductivity, and this comes from excellent contact between the single-layer carbon nano-tube bundle (bundle) of higher purity and formation at high temperature.Typical electrical conductivity is 2500Scm
-1, performance can be compared with at present best organic conductive material.
5, the single-layer carbon nano-tube non-woven fabrics of method of the present invention preparation has during less than 400nm at thickness and can well see through visible light, and appearance is translucent membranaceous.When thickness during near 100nm, the transmitance of visible light wave range can reach 75%, in conjunction with its high electrical conductivity and good mechanical performance, ultra-thin single-layer carbon nano-tube film can be used as bent transparent conductive material, it can be compared with the electrically conducting transparent ito thin film that extensively is used at present in performance of visible light wave range, the performance of infrared band even be better than ito thin film.
Description of drawings
Used floating catalytic experimental facilities device schematic diagram among Fig. 1 the present invention.
The optical photograph of the single-layer carbon nano-tube non-woven fabrics of Fig. 2 the present invention preparation.
The scanning electron microscope image of the original single-layer carbon nano-tube non-woven fabrics of Fig. 3 a the present invention preparation, the scale of scanning electron microscope image is 1 μ m.
The scanning electron microscope image of the original single-layer carbon nano-tube non-woven fabrics fracture of Fig. 3 b the present invention preparation, the scale of scanning electron microscope image is 10 μ m.
The scanning electron microscope image of the single-layer carbon nano-tube non-woven fabrics behind Fig. 4 a purifying of the present invention, the scale of scanning electron microscope image are 1 μ m.
The scanning electron microscope image of the single-layer carbon nano-tube non-woven fabrics fracture behind Fig. 4 b purifying of the present invention, the scale of scanning electron microscope image are 2 μ m.
The low power images of transmissive electron microscope of Fig. 5 a single-layer carbon nano-tube non-woven fabrics of the present invention, the scale of images of transmissive electron microscope are 50nm.
Fig. 5 b is the high-resolution-ration transmission electric-lens image of single-layer carbon nano-tube in the single-layer carbon nano-tube non-woven fabrics, and scale is 10nm; Wherein the images of transmissive electron microscope of Cha Ruing is the high-resolution-ration transmission electric-lens image of a small amount of double-deck CNT in the nonwoven fabric, and scale is 2nm.
The low power atomic force microscope images of Fig. 6 a single-layer carbon nano-tube non-woven fabrics of the present invention, the scale of atomic force microscope images are 5 μ m.
Fig. 6 b is the high power atomic force microscope images of single-layer carbon nano-tube in the single-layer carbon nano-tube non-woven fabrics, and scale is 500nm.
Fig. 7 a is the Raman spectrogram of original single-layer carbon nano-tube non-woven fabrics of the present invention;
Fig. 7 b is the Raman spectrogram of the single-layer carbon nano-tube non-woven fabrics behind the purifying of the present invention; Wherein, interior illustration is the Raman breathing mould (RBM) of single-layer carbon nano-tube in the nonwoven fabric.
The mechanics stretching measurement result of the single-layer carbon nano-tube non-woven fabrics of Fig. 8 the present invention preparation.
Fig. 8 a is the stress and strain curve (σ-ε) of the single-layer carbon nano-tube non-woven fabrics of original preparation;
Fig. 8 b is through the stress and strain curve of the single-layer carbon nano-tube non-woven fabrics behind the purifying (σ-ε); Wherein, interior illustration is the elastic deformation district in the single-layer carbon nano-tube non-woven fabrics drawing process, and linear A-B zone can be used for calculating the elastic modelling quantity of nonwoven fabric.
The specific embodiment
The present invention will be further explained and explanation below in conjunction with specific embodiment.
Embodiment 1: the growth of original single-layer carbon nano-tube non-woven fabrics
At first the following floating catalytic legal system of design is equipped with the experimental provision of single-layer carbon nano-tube non-woven fabrics:
Apparatus sketch as shown in Figure 1, experimental provision is made up of two resistance furnaces, rated temperature is respectively 1250 ℃ and 300 ℃.Used reative cell is the quartz ampoule with special construction in the experiment, and its structure comprises: the internal diameter of outer big quartz ampoule is 30～40mm, and length is 1～1.4m; The internal diameter of the inner little quartz ampoule that inserts is 6～10mm, and length is 30～60cm.The port of interpolation tubule is positioned at the whole reactor middle part.
Then dispose following catalyst mixture:
Take by weighing chemical pure ferrocene and sublimed sulfur and, utilize mortar to grind half an hour with mol ratio evenly mixing in 16: 1.
Prepare the high-intensity single-layer carbon nano-tube non-woven fabrics of large tracts of land then as follows:
During the growth single-layer carbon nano-tube non-woven fabrics, catalyst distils in first stove, and sublimation temperature is controlled at 60～90 ℃; Catalyst after the distillation by argon gas (flow be 800～1200sccm) and as the methane of carbon source (flow is that 1～10sccm) mist is brought into reaction growth single-layer carbon nano-tube in second stove; The growth temperature of single-layer carbon nano-tube (temperature of second stove) is controlled at 1000～1200 ℃; Pressure in the quartz tube reactor maintains 1～1.1 atmospheric pressure; The single-layer carbon nano-tube that generates in the experiment is taken to the quartz ampoule rear end by air-flow and attached on the quartzy tube wall; The single-layer carbon nano-tube non-woven fabrics product of preparation can be taken off from quartzy wall with the form of large stretch of film easily, and has good toughness and intensity.
The optical photograph of the single-layer carbon nano-tube non-woven fabrics that Fig. 2 obtains for the present invention.Sample generally is black, and is transparence when thin.In the preparation process, large-area sample can be taken off from the quartz ampoule inwall at an easy rate, has good operability.Utilize ruler to measure as can be seen, the sample for preparing in the experiment has the area of macroscopic view, can reach tens square centimeters.And, in to the sample operation process, can experience sample and have good intensity and toughness, be not easy to break.This large-area sample can be according to the random tiling of different needs to any substrate, for example silicon chip, wave carrier piece, little grid etc.
Fig. 3 a-Fig. 3 b is the scanning electron microscope image of the single-layer carbon nano-tube non-woven fabrics of the present invention's preparation.Wherein Fig. 3 a is the scanning electron microscope image on original single-layer carbon nano-tube non-woven fabrics plane.Observation shows that containing many CNTs that tangle mutually in the carbon nano-tube non-woven fabrics of producing restrains from figure, and some little particles wherein also are dotted with.
The scanning electron microscope image of the original single-layer carbon nano-tube non-woven fabrics fracture of Fig. 3 b the present invention preparation, the scale of scanning electron microscope image is 10 μ m.From the electromicroscopic photograph of nonwoven fabric fracture as can be seen, these CNTs tube bank diameters are about tens nanometers, and length is very long, from tens microns to the hundreds of micron.
Embodiment 2: the purifying of original single-layer carbon nano-tube non-woven fabrics
The original single-layer carbon nano-tube non-woven fabrics that the method purification the present invention who utilizes vapour phase oxidation process to cooperate concentrated hydrochloric acid to soak prepares.
At first, it is to carry out oxidation in 350 ℃ of resistance furnaces that the single-layer carbon nano-tube non-woven fabrics sample of original growth is placed into temperature, keeps 48 hours in air atmosphere; Then sample is put into concentrated hydrochloric acid (concentration is 37%wt) and soak a week; At last, sample being taken out the back from hydrochloric acid, to wash up to pH value with deionized water be 7.
Fig. 4 a-Fig. 4 b is the single-layer carbon nano-tube non-woven fabrics plane behind the purifying of the present invention and the scanning electron microscope image of fracture.As can be seen from the figure, through after the purification process, catalyst granules nearly all in the single-layer carbon nano-tube non-woven fabrics product all is removed, and the profile of nonwoven fabric still remains intact, and does not have destroyed.
Below aspects such as the structure and morphology of single-layer carbon nano-tube non-woven fabrics, performance are characterized:
1, the structure and morphology of single-layer carbon nano-tube non-woven fabrics
Fig. 5 a-Fig. 5 b is the images of transmissive electron microscope of the single-layer carbon nano-tube non-woven fabrics of the present invention's preparation.The single-layer carbon nano-tube non-woven fabrics that Fig. 5 a demonstrates the present invention's preparation is to be entwined mutually by many CNT tube banks of tangling mutually.From high resolution electron microscopy photo Fig. 5 b, can see that these CNT that tangles mutually tube bank overwhelming majority are single-layer carbon nano-tube tube banks, a small amount of double-deck CNT (shown in illustration in Fig. 5 b) is wherein arranged.And these particles mainly are catalyst iron particle and minority pure carbon particle which floor amorphous carbon layer some surfaces coat.In the CNT tube bank, the diameter majority of single-layer carbon nano-tube forms the single-layer carbon nano-tube that tangles the mutually tube bank of the about 10～30nm of diameter by tight arrangement between 1～3nm.
Fig. 6 a-Fig. 6 b is the atomic force microscope images of the single-layer carbon nano-tube non-woven fabrics of the present invention's preparation.From the shape appearance figure of Fig. 6 a, the three-dimensional structure of single-layer carbon nano-tube non-woven fabrics as can be seen: the weave in that the tube bank of many single-layer carbon nano-tubes is unordered has formed a kind of very peculiar three-dimensional dense mess lattice structure.This network all is made up of carbon, and wherein carbon nano-tube bundle is as the bone train of thought of grid, and can form and have tens mesh to the hundreds of nano-scale.
2, the Raman optical characterisation of single-layer carbon nano-tube non-woven fabrics
Among the present invention, respectively the single-layer carbon nano-tube non-woven fabrics before and after the purifying is carried out microcell Raman collection of illustrative plates and characterize, the optical maser wavelength of employing is 514.5nm (2.41eV).The Raman spectrum of the original single-layer carbon nano-tube non-woven fabrics of Fig. 7 a has shown and document (A.M.Rao, E.Richter, S.Bandow, B.Chase, P.C.Eklund, K.A.Williams, S.Fang, K.R.Subbaswamy, M.Menon, A.Thess, R.E.Smalley, G.Dresselhaus, M.S.Dresselhaus, Science, 1997, the characteristic peak of two groups of single-layer carbon nano-tubes that 275,187) conform to shows that the product that we produce is a single-layer carbon nano-tube.Illustration in Fig. 7 a can see that the first group of peak that is positioned at low frequency range comprises 165cm
-1, 182cm
-1, 207cm
-1, 229cm
-1, be the breathing mould (RBM) of single-layer carbon nano-tube, its frequency displacement relevant with the diameter of single-layer carbon nano-tube (ω=223.75/d, the ω Raman is breathed the frequency displacement of mould, the diameter of d single-layer carbon nano-tube).According to the relation of single-layer carbon nano-tube diameter and Raman frequency shift, the caliber scope that can obtain the single-layer carbon nano-tube that the present invention produces is at 1～1.5nm, and this result with our transmission electron microscope observing conforms to.Wherein be positioned at 207cm
-1The RBM peak higher be because the result of single-layer carbon nano-tube resonance raman.The second stack features peak position of Fig. 7 a is in 1568cm
-1And 1590cm
-1, be the tangential flexible mould of single-layer carbon nano-tube, promptly be equivalent to the G mould of graphite material Raman spectrum.Because it is folding that the small-size effect of single-layer carbon nano-tube makes that the Brillouin zone of its phonon mould takes place, produce a plurality of peaks thereby cause the G mould that division takes place.Be positioned at 1346cm
-1The peak at place is the D peak of single-layer carbon nano-tube, corresponding to amorphous carbon, nanocarbon particle and defective etc. in the single-layer carbon nano-tube sample.With 1590cm
-1G compares at the peak, and the D peak of single-layer carbon nano-tube is lower among Fig. 7 a, and the amount of amorphous carbon is lost seldom in the interpret sample, and this conforms to our electron microscopic observation.
Fig. 7 b is the Raman spectrum of the single-layer carbon nano-tube non-woven fabrics behind the purifying.As can be seen, breathe mould except on original position, going out the peak, be positioned at low frequency 143cm through the Raman of the later single-layer carbon nano-tube of purifying
-1The position has also shown characteristic peak, the corresponding about 1.6nm of caliber (shown in illustration in Fig. 7 b).This is because in the air oxidation process, single-layer carbon nano-tube with big caliber is more stable than little caliber, be not easy oxidizedly to fall, so thereby the relative quantity of the single-layer carbon nano-tube of big caliber increases its raman characteristic peak is showed in the breathing mould of Raman spectrum behind the purifying.While is for the high-frequency characteristic peak of Fig. 7 b, can see through the D peak of the single-layer carbon nano-tube behind the purifying and the ratio at G peak and reducing greatly, behind this explanation purifying in the single-layer carbon nano-tube non-woven fabrics of the present invention impurity obviously reduce, be very effective thereby the air oxidation of further adopting in the proof experiment cooperates the purification process of strong acid treatment.
3, the mechanical property of single-layer carbon nano-tube non-woven fabrics is measured
Among the present invention, the single-layer carbon nano-tube non-woven fabrics of producing has the yardstick of macroscopic view, utilizes a small-sized stretching device directly to measure the mechanical performance of single-layer carbon nano-tube non-woven fabrics, as shown in Figure 8.Fig. 8 a has shown the mechanical meaurement result of original single-layer carbon nano-tube non-woven fabrics.By calculating, the apparent Young's modulus that can obtain original single-layer carbon nano-tube non-woven fabrics is about 188GPa, and its fracture strength is 144Mpa.In addition, show (shown in Fig. 8 b) for the single-layer carbon nano-tube non-woven fabrics stretching measurement result behind the purifying, the Young's modulus of single-layer carbon nano-tube non-woven fabrics is about 139GPa behind the purifying, and its fracture strength is about 107MPa.
Report before the contrast, the mechanical moduli of the film (backpaper) of the CNT that obtains than common overlength single-layer carbon nano-tube bundle or post processing of the Young's modulus of single-layer carbon nano-tube non-woven fabrics is all wanted high many (A.B.Dalton, S.Collins as can be seen, E.Mounoz, J.M.Razal, V.H.Ebron, J.P.Ferraris, J.N.Coleman, B.G.Kim and R.H.Baughman, Nature, 2003,423,703; R.H.Baughman, C.X.Cui, A.A.Zakhidov, Z.Iqbal, J.N.Barisci, G.M.Spinks, G.G.Wallace, A.Mazzoldi, D.D Rossi, A.G.Rinzler, O.Jaschinski, S.Roth, and M.Kertesz, Science, 1999,284,1340).Take all factors into consideration among the present invention the effective cross-section of CNT in the tube bank of the voidage in the single-layer carbon nano-tube non-woven fabrics and carbon pipe, can obtain the effective cross-section that single-layer carbon nano-tube non-woven fabrics stretches and account for 26% ± 10% of total cross section greatly.Consider the influence of effective cross-section, further can calculate that the true Young's modulus of not purified single-layer carbon nano-tube non-woven fabrics can reach 700GPa.Sample to different size among the present invention is tested, and the result shows that the Young's modulus for not purified single-layer carbon nano-tube non-woven fabrics is about 700 ± 270GPa, and fracture strength is about 600 ± 231MPa.And the nonwoven fabric behind the purifying, its Young's modulus is about 500 ± 190GPa, the about 400 ± 154MPa of fracture strength.
The single-layer carbon nano-tube non-woven fabrics for preparing among the present invention can have extraordinary mechanical performance, is mainly derived from its particular structure.On the one hand, the single-layer carbon nano-tube non-woven fabrics of producing is tangled mutually and is formed by many single-layer carbon nano-tube bundles.These carbon nano-tube bundles have the length that reaches the hundreds of micron, and weave in closely.This compact structure and firm interweaving make that stress can be good at transmitting in carbon nano-tube non-woven fabrics, therefore the elasticity linear zone in the stretching experiment can just really react the elastic stretching characteristic of single-layer carbon nano-tube, thereby the Young's modulus that obtains is relatively near the elastic modelling quantity (1TPa) of single-layer carbon nano-tube.In addition, the single-layer carbon nano-tube among the present invention is to grow down in higher relatively temperature (1100 ℃) to form, and the degree of graphitization of the CNT that it comprises is very high, and defective seldom.Theoretical research shows that defective single-layer carbon nano-tube seldom has the very high elastic modelling quantity that gets.
4, the high temperature furnace growth temperature is to the influence of single-layer carbon nano-tube non-woven fabrics preparation
Among the present invention, adopt methane as carbon source, single-layer carbon nano-tube can be synthesized in wider temperature range (800～1200 ℃).Simultaneously, different reaction temperature is influential to the output of single-layer carbon nano-tube.Shown in the table 1 Relationship with Yield of reaction temperature to single-layer carbon nano-tube non-woven fabrics.Be lower than under 800 ℃ the temperature, we find to have only a spot of product attached on the quartz ampoule gatherer.Be higher than 1100 ℃ and work as reaction temperature, the primary product that obtains is the amorphous carbon of grey, and can not collect with the form of film.Among the present invention, relatively the temperature of the growth single-layer carbon nano-tube of You Huaing is 1100 ℃, the reaction temperature high more (to 1200 ℃) that this and other people report, and the output of single-layer carbon nano-tube is different more.This mainly is owing under higher temperature, owing to methane speeds up from pyrolysis, thereby changed the feed speed of carbon source to catalyst granules.Therefore produce more amorphous carbon, and generate less single-layer carbon nano-tube.
The relation of table 1 single-layer carbon nano-tube non-woven fabrics productive rate and high temperature road growth temperature
5, low temperature oven catalyst sublimation temperature is to the influence of single-layer carbon nano-tube non-woven fabrics preparation
Among the present invention,, can regulate and control the productive rate and the quality of single-layer carbon nano-tube non-woven fabrics by the sublimation temperature of control catalyst.Table 2 has shown the Relationship with Yield of low temperature oven catalyst sublimation temperature to single-layer carbon nano-tube non-woven fabrics.
The relation of table 2 single-layer carbon nano-tube non-woven fabrics productive rate and ferrocene consumption
As can be seen, with the raising of the sublimation temperature of catalyst, the amount of the catalyst that is introduced into is many more, and the output of product is big more.Certainly, a part is owing to the amount that coats the iron particle in the single-layer carbon nano-tube non-woven fabrics of original preparation has increased greatly in the output of increase.And under lower catalyst sublimation temperature, can produce purer single-layer carbon nano-tube non-woven fabrics.
The above embodiments only are used for illustrating this explanation, and it should not be construed is that protection domain to this explanation carries out any restriction.And, it will be apparent to those skilled in the art that do not breaking away under the present invention spirit and the principle, to various equivalent variation that the present invention carried out, modification and in the text not the various improvement of description all within the protection domain of this patent.
Claims (8)
1, a kind of single-layer carbon nano-tube non-woven fabrics is to be tangled mutually and formed by the single-layer carbon nano-tube tube bank; Its area is 10～100cm
2, thickness is 100nm～20 μ m; The diameter of described single-layer carbon nano-tube tube bank is 10～50nm, and length is 10 μ m～1mm; Single-layer carbon nano-tube diameter in the tube bank is 1～3nm.
2, single-layer carbon nano-tube non-woven fabrics as claimed in claim 1 is characterized in that, described thickness is 100nm-20 μ m.
3, single-layer carbon nano-tube non-woven fabrics as claimed in claim 1 or 2 is characterized in that, the Young's modulus of described single-layer carbon nano-tube non-woven fabrics is 100～300GPa.
4, a kind of single-layer carbon nano-tube non-woven fabrics the preparation method, its step comprises:
With mol ratio is that 16: 1 ferrocene and sublimed sulfur mix and grind and evenly make catalyst;
Catalyst is placed the quartz boat in the low temperature oven of two furnace systems distil, temperature is controlled at 60～90 ℃;
The feeding flow is that protection gas argon gas and the flow of 800～1200sccm is the hydrocarbon gas of 1～10sccm as carbon source, and makes the catalyst that distils in low temperature oven flow into high temperature furnace;
Mist is that the thin quartz ampoule of low temperature oven caliber 1/5～1/3 enters high temperature furnace by a diameter;
The catalytic cracking of hydrocarbon gas and the single-layer carbon nano-tube of growing in the high temperature furnace of two furnace systems, temperature is controlled at 800～1200 ℃, pressure in the quartz tube reactor maintains 1～1.1 atmospheric pressure, and the carbon nano tube products of generation is deposited on the quartz ampoule inwall by air-flow, form original single-layer carbon nano-tube non-woven fabrics.
5, preparation method as claimed in claim 4 also comprises follow-up purification step.
6, preparation method as claimed in claim 5, wherein, described purification step comprises: with the oxidation 12～48 hours under 350～450 ℃ of temperature, in air atmosphere of the single-layer carbon nano-tube non-woven fabrics that obtains; The single-layer carbon nano-tube non-woven fabrics that to handle is put into concentrated hydrochloric acid 2 days～one week of immersion that concentration is 37wt.% then, and again the product after soaking being carried out washed with de-ionized water is 7 up to pH value, and drying forms again.
7, preparation method as claimed in claim 4, wherein, the reative cell of described two furnace systems is made of quartz ampoule, and it comprises the thin quartz ampoule of outer big quartz ampoule and interior insertion.
8, as each described preparation method of claim 4-7, wherein, described hydrocarbon is methane or acetylene.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101929037A (en) * | 2010-08-13 | 2010-12-29 | 中国人民解放军国防科学技术大学 | Large-size chemical crosslinking carbon nanofiber felt and preparation method thereof |
| CN102351165A (en) * | 2011-06-23 | 2012-02-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Large-area freestanding carbon nanotube paper and preparation method thereof |
| CN102704351A (en) * | 2012-05-18 | 2012-10-03 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of carbon nano tube non-woven fabrics |
| WO2014180249A1 (en) * | 2013-05-07 | 2014-11-13 | 中国科学院物理研究所 | Ultrathin carbon nano tube film and preparation method and apparatus thereof |
| CN107338642A (en) * | 2017-06-16 | 2017-11-10 | 江南大学 | A kind of functionalization non-woven cloth desalinization material and its preparation method and application |
| WO2019167831A1 (en) * | 2018-03-02 | 2019-09-06 | 国立大学法人 奈良先端科学技術大学院大学 | Nonwoven fabric structure and producing method therefor |
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2008
- 2008-04-01 CN CNA2008101031798A patent/CN101260595A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101929037A (en) * | 2010-08-13 | 2010-12-29 | 中国人民解放军国防科学技术大学 | Large-size chemical crosslinking carbon nanofiber felt and preparation method thereof |
| CN101929037B (en) * | 2010-08-13 | 2012-07-25 | 中国人民解放军国防科学技术大学 | Large-size chemical crosslinking carbon nanofiber felt and preparation method thereof |
| CN102351165A (en) * | 2011-06-23 | 2012-02-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Large-area freestanding carbon nanotube paper and preparation method thereof |
| CN102704351A (en) * | 2012-05-18 | 2012-10-03 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of carbon nano tube non-woven fabrics |
| CN102704351B (en) * | 2012-05-18 | 2014-10-22 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of carbon nano tube non-woven fabrics |
| WO2014180249A1 (en) * | 2013-05-07 | 2014-11-13 | 中国科学院物理研究所 | Ultrathin carbon nano tube film and preparation method and apparatus thereof |
| US10144647B2 (en) | 2013-05-07 | 2018-12-04 | Institute Of Physics, Chinese Academy Of Sciences | Ultrathin carbon nanotube film and preparation method and apparatus thereof |
| CN107338642A (en) * | 2017-06-16 | 2017-11-10 | 江南大学 | A kind of functionalization non-woven cloth desalinization material and its preparation method and application |
| WO2019167831A1 (en) * | 2018-03-02 | 2019-09-06 | 国立大学法人 奈良先端科学技術大学院大学 | Nonwoven fabric structure and producing method therefor |
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