CN108623846A - Silicon-carbon composite nano tube and its preparation method and application - Google Patents
Silicon-carbon composite nano tube and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses silicon-carbon composite nano tube and its preparation method and application, it is dispersed in carbon nano tube surface with ethyl orthosilicate, it is heat-treated in an inert atmosphere, it can be in carbon nano tube surface in-stiu coating nano-tube, form silicon-carbon composite nano tube structure, to control the pattern of outer layer nano-tube in silicon-carbon composite nano tube structure, and then internal layer carbon nanotube and extraneous function and effect can be regulated and controled by adjusting the dosage of ethyl orthosilicate and carbon nanotube in preparation process.The silicon-carbon composite nano tube structure of the present invention can give full play to and adjust the respective advantage of two kinds of nanotubes, and have good application prospect in material modification field.
Description
Technical field
The invention belongs to technical field of nano material, more particularly, are related to silicon-carbon composite nano tube structure, that is, pass through
The dosage of carbon nanotube and silicon source is adjusted to realize the preparation and adjustment of silicon-carbon composite nano tube structure.
Background technology
Since carbon nanotube is found since 1991, with its excellent electricity, mechanics, thermal property, the world has been rapidly become
Research hotspot in range.However, although carbon nanotube self performance is superior, when practical application, is urgently to be resolved hurrily there are two
The problem of：On the one hand, carbon nanotube has high draw ratio and larger surface energy, while the Van der Waals between Guan Yuguan
Under the action of power, easily reunite, can not be realized in solution and macromolecule matrix evenly dispersed；On the other hand, carbon nanometer
Pipe surface is very smooth, and almost without any dangling bonds, surface inertness is presented, thus very with the interfacial interaction of matrix
Difference.These two issues lead to the property that untreated carbon nanotube is directly added into the composite material obtained in polymeric matrix
Expected requirement can be often unable to reach.In this case, the surface-functionalized modification of carbon nanotube just embodies apparent advantage.
Organic molecule is modified in carbon nano tube surface by chemical bond and various Physical interactions, on the one hand can drop low-carbon nano
Van der Waals force between pipe inhibits the reunion of carbon nanotube, improves dispersibility；On the other hand, the presence of organic molecule chain can
Effectively to improve the interfacial interaction between carbon nanotube and matrix, be conducive to the performance of carbon nanotube humidification.One
As for, the surface-functionalized modification of carbon nanotube is divided into non-covalent modification and covalent modification, and covalent modification is with its trim
The advantage that interacts that strong, trim designability is good between carbon nanotube etc. and as current widest functionalization side
Method.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of silicon-carbon composite nano tube structures, i.e., in carbon
Nanometer tube outer surface in-situ preparation silicon layer, to realize the composite construction of silicone tube enveloped carbon nanometer tube, and can be by adjusting carbon nanometer
The dosage of pipe and silicon source realizes the adjustment for carbon nanotube outer layer silicone tube.
The technical purpose of the present invention is achieved by following technical proposals：
Silicon dioxide layer is arranged on the outer wall of carbon nanotube using carbon nanotube as inner tube in silicon-carbon composite nano tube, with
Silica Nanotube is formed on the outside of carbon nanotube.
In the structure of silicon-carbon composite nano tube, carbon nanotube and Silica Nanotube form coaxial sleeve structure,
Inner tube is carbon nanotube, and outer tube is Silica Nanotube.
The preparation method of silicon-carbon composite nano tube by the evenly dispersed formation suspension of carboxylic carbon nano-tube and adjusts pH value
For alkalinity, then ethyl orthosilicate is added in the suspension of carboxylic carbon nano-tube, is sufficiently mixed and evenly dispersed；Separation is solid
State substance is heated to 550-650 degrees Celsius from room temperature in an inert atmosphere and is heat-treated, then cooled to room temperature.
When being prepared, carboxylic carbon nano-tube is dispersed in absolute ethyl alcohol and forms suspension, uses ammonium hydroxide
It is 8-10 to adjust pH value, specifically, weighs carboxylic carbon nano-tube (CNTs-COOH) and is put into beaker, anhydrous second is added
Alcohol, stirring keep CNTs dispersions abundant.Dispersion liquid is put into ultrasonic cell disrupte machine, ice-bath ultrasonic process 1h, power 500W, work
It is 3s, intermittent time 2s to make the time, weighs ammonium hydroxide, is added rapidly to adjust pH value in suspension obtained above to be alkalinity
8-10, strong stirring 0.5h obtain the suspension of carboxylic carbon nano-tube.
When being prepared, ethyl orthosilicate (TEOS) is dispersed in absolute ethyl alcohol, is forming stable homogeneous just
Ethyl silicate solution, then teos solution is added in the suspension of carboxylic carbon nano-tube, specifically, weigh just
Silester (TEOS), is put into the absolute ethyl alcohol of 300ml, and stirring fully obtains the solution of stable homogeneous.Solution is quickly added
Enter in suspension, strong stirring 2h obtains mixed liquor, this mixed liquor is put into ultrasonic cell disrupte machine again, ice-bath ultrasonic process
30min (power 500W, working time 3s, intermittent time 2s) takes out after the completion of processing, and sealing and standing is for 24 hours.
When being prepared, inert atmosphere is nitrogen, helium or argon gas；From 20-25 degrees Celsius of room temperature with 5-10 DEG C/
Min speed is warming up to 550-650 degrees Celsius and is heat-treated at least 2 hours, and preferably 600-650 degrees Celsius heat treatments 2-5 are small
When, it specifically, is filtered after standing, filters product and be placed in vacuum drying oven, dried at 60-80 DEG C, after dry, used
Mortar grinds solid sample to obtain powder, and powder is placed in Muffle furnace and is heat-treated.
It is as shown in Fig. 1, bonded using carboxyl and the ethyl orthosilicate realization of carbon nano tube surface when being prepared,
It heats up and is heat-treated again, so that ethyl orthosilicate is in carbon nano tube surface in-situ preparation silica.Pass through carbon nanotube table
The carboxyl-content in face, the dosage of ethyl orthosilicate adjust the appearance structure of silicon-carbon composite nano tube, i.e., to silicone tube thickness, silicone tube
Continuity degree etc. is regulated and controled.If carboxylic carbon nano-tube usage amount is 1 parts by weight (i.e. each parts by weight are 1g), positive silicic acid second
Ester usage amount is respectively 2.5 parts by weight, 5 parts by weight and 7.5 parts by weight, and silicone tube thickness is 5-15nm；And in carbon nanotube outer wall
Form the preferable silicone tube of continuity degree (sectional silicone tube, the content because of carbon nano tube surface carboxyl and distribution).
Compared with prior art, technical scheme of the present invention is realized in carbon nanotube outer wall in-situ preparation silicone tube, CNTs's
Caliber is small, surface energy is big, and since the effect of Van der Waals force is also easy to produce reunion between Guan Yuguan, this will make manufactured composite material
Load transference reduces, and is unfavorable for the performance of its excellent properties.And after SNTs (silicone tube) cladding CNTs (carbon pipe), isolation
Interaction force between CNTs pipes significantly improves the dispersibility of CNTs, improves the dispersibilities of CNTs in the polymer.
Description of the drawings
Fig. 1 is the structure of silicon-carbon composite nano tube of the present invention and prepares schematic diagram.
Fig. 2 is the infrared spectrogram of several substances in the present invention, wherein (a) is CNTs, CNTs-COOH；Be (b) CNTs,
SNTs and SNTs@CNTs.
Fig. 3 is the X-ray diffraction spectrogram of several substances in the present invention, wherein (a) CNTs, (b) SNTs, (c) SNTs-1
CNTs, (d) SNTs-2@CNTs and (e) SNTs-3@CNTs.
Fig. 4 is the TEM (1) of silicon-carbon composite nano tube of the present invention.
Fig. 5 is the TEM (2) of silicon-carbon composite nano tube of the present invention, wherein (a) CNTs；(b)SNTs-1@CNTs；(c)SNTs-
2@CNTs；(d)SNTs-3@CNTs.
Fig. 6 is the EDS energy spectrum analysis figures of SNTs@CNTs in the present invention, wherein (a) SNTs-1@CNTs；(b)SNTs-2@
CNTs；(c)SNTs-3@CNTs.
Fig. 7 is the transmission electron microscope photo of SNTs in the present invention, wherein (a) SNTs-1；(b)SNTs-2；(c)SNTs-3.
Fig. 8 is the thermogravimetric curve of several substances in the present invention, thermogravimetric curve under (a) CNTs, CNTs-COOH argon gas；
(b) thermogravimetric curve under CNTs, SNTs and SNTs@CNTs air.
Fig. 9 is the Fracture scan figure of the composite material of several substances and silicon rubber in the present invention, wherein (a) CNTs/SR；
(b)SNTs-1@CNTs/SR；(c)SNTs-2@CNTs/SR；(d)SNTs-3@CNTs/SR；(e)SNTs/SR.
Specific implementation mode
The technical solution further illustrated the present invention with reference to specific embodiment.The basic drug and instrument that embodiment uses
Device, as shown in the table：
Primary raw material
Key instrument equipment
By the way of collosol and gel, make nano-tube (SNTs) with the CNTs (CNTs-COOH) after acidification for mould
Plate grows up on its surface.
First, acidification is carried out to original CNTs.2.0g graphitized carbon nano pipes are weighed to be placed in there-necked flask.It weighs
The 180ml concentrated sulfuric acids and 60ml concentrated nitric acids are placed in graduated cylinder, and the concentrated sulfuric acid is added in there-necked flask first, are opened and are stirred, heating water bath,
Heating temperature is set as 60 DEG C.After to be heated to 60 DEG C, concentrated nitric acid is added in there-necked flask, makes system in sealed condensating reflux condition
4h is reacted under part.After reaction, all drugs in there-necked flask are poured into the large beaker for having filled appropriate distilled water, it is heavy to stand
Drop.It waits for that upper layer spent acid is poured out recycling after particle precipitation, then the carbon after appropriate distilled water washing acidification is added into beaker
Nanotube continues standing sedimentation, then so cycle is filtered, is first washed with distilled water up to the close neutrality of supernatant liquor,
It is washed with ethanol in proper amount when pH is close to 7.Filtered product is placed in baking oven and is dried for 24 hours.Product after drying is placed in
It grinds in mortar, until being in powdered, product is preserved mounted in labeling in sample sack
Then, SNTs is coated to by the surfaces CNTs by sol-gal process.Specifically, first, weigh CNTs-COOH powder
End, ultrasonic disperse obtain the uniform suspension of CNTs-COOH in ethanol solution；Second, ammonium hydroxide is weighed, is added rapidly to above-mentioned
In suspension obtained, strong stirring 0.5h, it is 10 to obtain the mixed liquor of stable homogeneous and adjust pH；Third weighs 2.5 respectively
Again, the TEOS of 5 times, 7.5 times CNTs-COOH mass is put into ethanol solution and is uniformly mixed；4th, third is walked into acquired solution
It is added in mixing suspension obtained by second step, strong stirring 2h obtains the evenly dispersed suspension of SNTs claddings CNTs；5th, it will
SNTs@CNTs suspensions settle 2 days at room temperature, filter, ultrasonic disperse；6th, repeat filter and ultrasound 3-4 times, will most
Gained suspension filters eventually, and is dried at 60 DEG C；7th, the product after drying is heat-treated under 600 DEG C of nitrogen atmosphere
5h obtains three kinds of SNTs@CNTs powder.Three kinds of SNTs@CNTs powder of gained are respectively designated as the dosage of TEOS from less to more
SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@CNTs.
Simultaneously by SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@CNTs powder in air atmosphere at 600 DEG C at heat
Corresponding SNTs powder is made in reason 5h.
As shown in Fig. 2, (a) is the FTIR spectrograms of CNTs and CNTs-COOH.Hydroxyl, carboxyl and carbon nanotube absorb
Water O-H keys stretching vibration characteristic peak, correspond in CNTs and CNTs-COOH infrared lines, in 3407cm-1With
1643cm-1Locate the larger absorption peak of intensity；1565cm-1The absorption peak at place belongs to the vibration peak of the C=C keys of carbon material, and
This peak is considered as the property and concentration for being strongly depend on oxide on surface.It can be seen that original carbon pipe is in 1565cm-1Place
Peak is not occurred, and there is apparent new peak in the position in the carbon pipe after being acidified.In addition, acidification carbon pipe is in 1713cm-1Wavelength
Place shows that a weaker absorption peak, this peak correspond to the C=O vibration peaks of carboxyl functional group, and intensity is by the surfaces CNTs
The carboxyl functional group concentration connect influences very big.It is acidified carbon pipe C=C stretching vibration peaks (1565cm-1) and C=O stretching vibration peaks
(1713cm-1) enhancing, this can be attributed to the effect of oxygen-containing group (- COOH ,-OH etc.).This result confirms that acidification carbon is received
The surface of mitron produces oxygen-containing functional group, this is conducive to generations of the subsequent SNTs on the surfaces CNTs.(b) it is CNTs, SNTs
With the infrared spectrogram of SNTs@CNTs.In SNTs spectrograms, 1109cm-1, 798cm-1And 476cm-1The absorption peak at place is SNTs
Upper Si-O-Si keys stretching vibration peak；1627cm-1, 957cm-1And 3460cm-1Nearby width absorption peak represents silicone hydroxyl and silicon is received
The stretching vibration characteristic peak of the O-H keys for the water that mitron absorbs.On the infrared spectrum of SNTs@CNTs, it not only observed and come from
The distinctive absorption peaks of SNTs, also in 1380-1410cm-1Occurs a new characteristic peak in range, this peak is in original CNTs
With do not occur on SNTs, it is considered to be covalently bound on CNTs and be formed by as SNTs -- caused by Si-O-C- key chatterings.
In addition, the absorption peak and-OH structures of SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@CNTs at-Si-O-Si- structures
Stretching vibration peak intensity is incremented by successively.This may be due in SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@CNTs
SNTs contents gradually increase.According to infrared spectrum comparative analysis, it can further assert that SNTs is successfully coated to CNTs tables
Face, and the covering amount different from of three kinds of SNTs@CNTs.
Such as the XRD spectra that attached drawing 3 is CNTs, SNTs and SNTs@CNTs.In CNTs spectrograms, two characteristic peaks go out respectively
At present 2 θ=26 ° and 43 °, it is belonging respectively to the diffraction maximum of carbon nanotube (002) and (100) face.Amorphous state is presented in SNTs,
In SNTs spectrograms, there is no apparent characteristic crystalline peaks to occur, and only shows as occurring one in 15 ° to 30 ° diffraction angular regions
A wide and weak amorphous peak, the diffraction maximum of SNTs is consistent with document description in figure.And the XRD spectra of SNTs@CNTs, it is in simultaneously
Show and has come from CNTs and SNTs characteristic peaks.It is worth noting that, the wide and weak amorphous diffraction maximum of SNTs is brilliant with CNTs (002)
The diffraction overlap of peaks in face, and the peak blurring on each crystal faces of CNTs, become wide and weak.By taking SNTs-2@CNTs as an example, spectral line
On show at 2 θ=43 ° diffraction maximum broaden and die down.In one wide and strong diffraction maximum of appearance of 15-30 ° of range, wherein
Nearby there are one the diffraction maximums of the crystal face of CNTs outstanding (100) for 2 θ=26 °, and this diffraction maximum does not have compared to original CNTs
It is so clear.In addition, the intensity of amorphous diffraction maximum is gradual in SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@CNTs
Enhancing, each crystallographic plane diffraction peaks of CNTs gradually weaken.This may be due to SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@
SNTs contents in CNTs gradually increase.
TEM as shown in the picture, the surfaces CNTs being not decorated are smooth；And the surfaces SNTs@CNTs after coating become coarse
And particle diameter becomes larger.Energy spectrum analysis has been carried out to SNTs@CNTs series particles.By EDS pictures, it can be found that three's is common
Feature is that observed C, O, Si and Cu element.Wherein Cu elements are interference elements caused by back end copper mesh, with nanoparticle
Son itself is unrelated.As it can be seen that SNTs has been coated on CNTs really.The different characteristic of three is the peak intensity of tri- kinds of elements of C, O, Si
Different degrees of variation has occurred in degree.In SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@tri- kinds of particles of CNTs, Si, O member
Element is gradually increased relative to the intensity at C element peak, shows that SNTs covering amounts are continuously increased.In order to further analyze SNTs clads
Specific pattern carries out SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@CNTs under air atmosphere at heat in experiment respectively
Reason obtains the TEM image of corresponding SNTs particles, SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@CNTs particles SNTs
The pipe thickness of clad is continuously increased, respectively 4-5nm, 8-10nm and 13-15nm.
Thermogravimetric curve figure as shown in drawings, (a) are thermal weight loss of the front and back CNTs particles of acidification under ar gas environment
Curve.100 DEG C to 500 DEG C of CNTs particle thermal weight losses are typically that the thermal decomposition of the oxygen-containing functional groups such as carbon pipe surface carboxyl causes
's[83].In other words, particle directly reflects CNTs acidification success or not and its surface in 100 DEG C to 500 DEG C of thermal weight loss
How much is carboxyl-content.Fig. 2-7 (a) curves show that minimum quality thermal degradation only has occurred in original CNTs, and residual qualities are up to
97.8%, and CNTs thermal degradations quality greatly improves after acidification, residual qualities drop to 91.9%.As it can be seen that CNTs by
Work(is acidified, and the oxygen-containing functional groups such as surface carboxyl groups content 5.9%.Fig. 2-7 (b) is CNTs, SNTs and three kinds of SNTs@CNTs air
Lower thermogravimetric curve.As seen from the figure, SNTs do not have substantially occur weightlessness, CNTs, SNTs-1@CNTs, SNTs-2@CNTs,
Different degrees of thermal weight loss has occurred in SNTs-3@CNTs successives, and CNTs there is no residual qualities (mf), almost all drop
Solution.Based in thermal weight loss test temperature section, nano-tube quality keeps stablizing, and carbon nanotube is almost thoroughly weightless, because
This, it is believed that in thermal weight loss test, the difference of the residual qualities between SNTs CNTs and CNTs is coated nano-tube
Mass percent.
Significant data in air atmosphere on CNTs, SNTs and SNTs@CNTs thermogravimetric curves
Upper table is the significant data on CNTs, SNTs and SNTs@CNTs thermogravimetric curves in air atmosphere.In TG curves
In, incipient degradation temperature (Ti, indicate thermal degradation temperature corresponding when particle thermal weight loss mass fraction is 5%) and it is to weigh material
One important indicator of thermal stability.By table 2-3 as it can be seen that the cladding of nano-tube particle, is greatly improved carbon nanotube
Thermal oxidation stability performance, and with the increase T of nano-tube covering amountiIt is continuously improved, is increased to by SNTs-1 in covering amount
When SNTs-2, TiIncrease by 33.71 DEG C, increasing degree is maximum.Pass through mfIt can be calculated that being coated to carbon nanometer in SNTs@CNTs
Nano-tube content on pipe is respectively：42.47wt% (SNTs-1@CNTs), 53.11wt% (SNTs-2@CNTs) and
69.74wt% (SNTs-3@CNTs).
The preparation of silicon rubber is carried out using the SNTs@CNTs of above-mentioned preparation, each parts by weight are 1g
Step 1：The accurate methyl vinyl silicon kautschuk for weighing 100 parts by weight, is added in ethyl acetate, 60 DEG C of water
Bath heats and continues stirring to obtain raw rubber solution.
Step 2：It weighs 1 parts by weight SNTs-1@CNTs nano-particles to be placed in ethyl acetate solution, is ultrasonically treated and obtains
Even dispersion liquid.It is added in raw rubber solution made from step 1, stirs evenly, 90 DEG C are evaporated while stirring, 60 DEG C of vacuum drying
48h removes solvent, obtains SNTs-1@CNTs/ raw-silastic continuouslies.
Step 3：By raw rubber made from 100 parts by weight steps 2 in the double roller of 40-50 DEG C of temperature, it is kneaded 6min, makes it
Even roll banding.
Step 4：2,5- dimethyl -2,5- di-t-butyl hexane peroxides of 0.6 parts by weight are added, continue to be kneaded 11min,
It is kneaded and uniformly obtains rubber compound.
Step 5：Rubber compound prepared by step 4 is fitted into mold, temperature is 180 ± 1 DEG C, heat under conditions of pressure 9MPa
11min sulfidization moldings are pressed, sulfide film is obtained after cooling.
Replacement SNTs-1@CNTs nano-particles are SNTs-2@CNTs, SNTs-3@CNTs, CNTs and S NTs, are respectively obtained
The composite material of each nano-particle and silicon rubber SR.
As shown in the picture, the Fracture scan figure of CNTs/SR, SNTs/SR and SNTs@CNTs/SR composite materials, clearly shows
Deployment conditions and fracture apperance of the nano-particle in silicone rubber matrix are shown.(a) disconnected for the stretching of CNTs/SR composite materials
Mouth scanned photograph.According to picture it can be found that agglomeration occurs in fracture surface, uncoated CNTs is reflected in the base
Bad dispersion feature；Incision position CNTs is largely pulled out, and the partial-length for being pulled out matrix is very long, the boundary between matrix
Limit is clear, reflects the Interface Adhesion force difference between particle and SR matrixes.The priming factors of this phenomenon are mainly by two, and
Strong interaction, makes it easily reunite between one, CNTs pipe；Second, CNTs are made of a large amount of C-C keys, are with Si-O-Si
Van der Waals interaction is fainter between the SR molecules of main chain.The two causes CNTs and reunites and interact with matrix jointly
Difference.Fig. 3-1 (e) is the stretching fracture scanned photograph of SNTs/SR systems, and as seen from the figure, SNTs is well dispersed in SR matrixes, and
Substantially it is not drawn out matrix, only can see that some circular hole spots in matrix surface, the boundary between matrix is fuzzy, reflection
SNTs it is well dispersed and its with SR matrixes good interface compatibilities.This can be attributed to the fact that three aspects, and first, SNTs is by a large amount of
Si-O keys form, and affinity is strong between the SR molecules of main chain using Si-O-Si, and Van der Waals interaction power is strong；Second, SNTs
There are Si-OH on surface, and hydrogen bond, interaction force enhancing are easily formed between SR strands；Third, the Si-OH on the surfaces SNTs are caused
Make to be not easy to reunite between SNTs pipes.Three's collective effect facilitates the fine dispersion of SNTs and the excellent compatibility with SR matrixes.
(b-d) be respectively SNTs-1@CNTs/SR, SNTs-2@CNTs/SR and SNTs-3@CNTs/SR composite materials Fracture scan shine
Piece.As seen from the figure, dispersed, the fracture nano-particle quilt more good relative to CNTs/SR of SNTs@CNTs/SR composite materials
It extracts part to be also obviously shortened, and the boundary between matrix is relatively fuzzy, reflect good between SNTs@CNTs and SR matrixes
Interface compatibility.Also, with the increase of SNTs covering amounts, dispersion of the composite nanoparticle in SR is further good, and in base
Part is pulled out in body to successively decrease.This phenomenon shows that the increase with SNTs covering amounts, CNTs dispersibilities improve further, with SR
Between interface compatibility and interaction constantly enhancing, i.e. CNTs presents well dispersed and can tightly " be embedded to " SR matrixes
In.
The above-mentioned composite material print prepared is hung on into aging in convection oven, aging condition：300 DEG C of constant temperature, puts
Set 12h.Using punching experimental machine, print (before and after aging) cutting makes it be similar to dumbbell shaped (with reference to GB/T 528-2009).It is trying
Two parallel lines easy to identify for not influencing sample physical property are spread in the relatively narrow parallel place of sample, painting, and line and center it is equidistant (25.0 ±
0.5mm).According to GB/T528-2009 and GB/T529-2008 requirements, surveyed with TestometricM350-20KN electronic tensile machines
Try the mechanical property of vulcanizate.Sample is placed in the center of clamper, is machined, with the speed tensile batten of 500mm/min
And the label of pointers track sample working portion is stretched by surveying.Load data value when each sample is pulled apart is recorded, and is sought average
Value.
Silicon rubber based composites mechanical property
| Title | Tensile strength (MPa) | Elongation at break (%) |
| Blank | 0.30±0.027 | 167.54±14.17 |
| CNTs-COOH/SR | 0.36±0.031 | 234.12±21.31 |
| SNTs-1@CNTs/SR | 0.47±0.037 | 299.43±28.50 |
| SNTs-2@CNTs/SR | 0.61±0.041 | 317.71±29.64 |
| SNTs-3@CNTs/SR | 0.50±0.035 | 306.68±26.94 |
Compared to blank sample, the tensile strength of CNTs-COOH/SR composite materials slightly improves, and improves 20%, and
The tensile strength of SNTs@CNTs/SR composite materials is then significantly improved.Three kinds of SNTs@CNTs nano-particles make the drawing of silicon rubber
It stretches intensity and has been respectively increased 56.7%, 103.3% and 66.7%.The tensile strength of wherein SNTs-2@CNTs/SR composite materials is
More than 2 times of blank sample.In addition, the elongation at break of silicon rubber composite material SNTs@CNTs particles addition after, compared to
CNTs-COOH/SR has further promotion, is 1.78,1.90 and 1.83 times of blank sample respectively.Therefore, nano-tube
Enveloped carbon nanometer tube improves the tensile strength and elongation at break of silicon rubber composite material, improves the mechanical property of silicon rubber
Energy.I.e. silicon-carbon composite nano tube is improving application of the carbon nanotube in silicon rubber in dispersibility, is improving silicon rubber mechanical property
Application in energy.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1. silicon-carbon composite nano tube, which is characterized in that using carbon nanotube as inner tube, titanium dioxide is arranged on the outer wall of carbon nanotube
Silicon layer, to form Silica Nanotube on the outside of carbon nanotube.
2. silicon-carbon composite nano tube according to claim 1, which is characterized in that in the structure of silicon-carbon composite nano tube,
Carbon nanotube and Silica Nanotube form coaxial sleeve structure, and inner tube is carbon nanotube, and outer tube is silica nanometer
Pipe.
3. silicon-carbon composite nano tube according to claim 1, which is characterized in that silicone tube thickness is 5-15nm.
4. the preparation method of silicon-carbon composite nano tube, which is characterized in that by the evenly dispersed formation suspension of carboxylic carbon nano-tube
And it is alkalinity to adjust pH value, then ethyl orthosilicate is added in the suspension of carboxylic carbon nano-tube, it is sufficiently mixed and uniform
Dispersion；Solid matter is detached, 550-650 degrees Celsius is heated to from room temperature in an inert atmosphere and is heat-treated, then natural cooling
To room temperature.
5. the preparation method of silicon-carbon composite nano tube according to claim 4, which is characterized in that, will when being prepared
Carboxylic carbon nano-tube, which is dispersed in absolute ethyl alcohol, forms suspension, and it is 8-10 to adjust pH value using ammonium hydroxide.
6. the preparation method of silicon-carbon composite nano tube according to claim 4, which is characterized in that, will when being prepared
Ethyl orthosilicate (TEOS) is dispersed in absolute ethyl alcohol, forms the teos solution of stable homogeneous, then by positive silicic acid
Ethyl ester solution is added in the suspension of carboxylic carbon nano-tube.
7. the preparation method of silicon-carbon composite nano tube according to claim 4, which is characterized in that lazy when being prepared
Property atmosphere be nitrogen, helium or argon gas；550-650 are warming up to from 20-25 degrees Celsius of room temperature with 5-10 DEG C/min speed to take the photograph
Family name's degree is heat-treated at least 2 hours, and preferably 600-650 degrees Celsius are heat-treated 2-5 hours.
8. the preparation method of silicon-carbon composite nano tube according to claim 4, which is characterized in that utilize carbon nano tube surface
Carboxyl and ethyl orthosilicate realize bonded, then heat up and be heat-treated, so that ethyl orthosilicate is in carbon nano tube surface original position
Generate silica；Silicon-carbon composite nano tube is adjusted by the dosage of the carboxyl-content of carbon nano tube surface, ethyl orthosilicate
Appearance structure.
9. the silicon-carbon composite nano tube as described in one of claim 1-3 or the preparation side according to one of claim 4-8
The silicon-carbon composite nano tube that method obtains is improving application of the carbon nanotube in silicon rubber in dispersibility.
10. the silicon-carbon composite nano tube as described in one of claim 1-3 or the preparation side according to one of claim 4-8
Application of the silicon-carbon composite nano tube that method obtains in improving Mechanical Properties of Silicone Rubber.
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