CN1884188A - Carbon nanotube/nano clay nano composite materials and method for preparing same - Google Patents
Carbon nanotube/nano clay nano composite materials and method for preparing same Download PDFInfo
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- CN1884188A CN1884188A CN 200510079598 CN200510079598A CN1884188A CN 1884188 A CN1884188 A CN 1884188A CN 200510079598 CN200510079598 CN 200510079598 CN 200510079598 A CN200510079598 A CN 200510079598A CN 1884188 A CN1884188 A CN 1884188A
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Abstract
The invention discloses a carbon nanometer pipe/ nanometer composite material of nanometer clay and preparing method, which comprises the following steps: blending metal salt solution and nanometer clay; intercalating metal salt in the nanometer clay; adopting metal as catalyst of carbon nanometer pipe; transmitting metal ion into corresponding metal hydroxide through ionic sedimenting method of weak base at 7.5-11.5 pH value; sedimenting metal hydroxide in the nanometer clay layer to obtain the product. The invention utilizes chemical gas-phase sedimenting method to grow carbon nanometer pipe on the nanometer clay, which can be good reinforcer without separating carriers.
Description
Technical field
The present invention relates to a kind of nano composite material, a kind of carbon nanotube/nano clay nano composite materials and preparation method thereof particularly, this carbon nanotube/nano clay nano composite materials can be used as the toughener of other matrix materials of preparation, improves the mechanical property of prepared matrix material effectively.
Background technology
Because nano composite material has the many excellent properties that are different from macroscopical matrix material, so the research of nano composite material and prepare extremely countries in the world and pay attention to.As everyone knows, carbon nanotube found by S.Iijima that its diameter was littler thousands of times than carbon fiber in 1991.Because carbon nanotube has excellent comprehensive mechanical properties (high elastic coefficient, high Young's modulus, low density), excellent absorption property, good thermomechanical property, so compound with carbon nanotube (single wall or multi-walled carbon nano-tubes) and certain body material, can significantly improve the mechanical property of prepared matrix material.In addition, nanoclay also is good polymkeric substance toughener, just can significantly improve physics, chemistry and the mechanical property of matrix material with lower addition.For example, with the polymkeric substance is the nano composite material (that is: polymer nanocomposites) of matrix, find after deliberation: than traditional toughener, a spot of carbon nanotube of adding and nanoclay just can significantly improve physics, chemistry and the mechanical property of polymkeric substance in polymkeric substance, so carbon nanotube and nanoclay are the present known good tougheners that is used for polymer nanocomposites.
For example, U.S. Patent application US20030143350, US20050025696 have disclosed and can directly use carbon nanotube or nanoclay to make nano composite material as toughener, and wherein: US20030143350 has disclosed use carbon nanotube, nanoclay or nano ceramics and prepared balloon catheter (balloon catheter); US20050025696 has disclosed a kind of method of making carbon nanotube, utilize this method on granules of catalyst, to deposit Single Walled Carbon Nanotube, contain for example solid support material of silicon-dioxide (support material) in this granules of catalyst, when the carbon nanotube with this method preparation is used for nano composite material, not only need to remove granules of catalyst, and remove these carriers in addition.Obviously, when directly adopting the prepared carbon nanotube of traditional solid support materials such as application molecular sieve, silicon-dioxide, aluminium sesquioxide and magnesium oxide as toughener, must remove carrier just can be applied in the matrix material enhancing field, moreover some carrier generally all can't thoroughly separate, thereby can not effectively give play to the good characteristic of carbon nanotube.
Therefore, directly still there is following technical problem during as toughener: 1) owing to need carry out the step of carrier of separating before usually carbon nanotube being added matrix (for example the matrix in the polymer composites is a polymkeric substance) with carbon nanotube and nanoclay, could will add matrix (promptly then with the isolating carbon nanotube of carrier, polymkeric substance) in, so cause the preparation process complexity; 2) carbon nanotube and the nanoclay that directly adds reunited in matrix under the effect of Van der Waals force easily, the difficult dispersion, thereby weakened between carbon nanotube and the matrix and the interface binding power between nanoclay and the matrix, the performance of carbon nanotube and nanoclay self excellence can not fully be displayed in matrix material.Therefore, need to solve how to make full use of carbon nanotube and the two technical problem of nanoclay, with the performance of further raising nano composite material as the advantage of toughener.
Summary of the invention
Goal of the invention of the present invention is to provide a kind of carbon nanotube/nano clay nano composite materials and preparation method thereof for the above-mentioned technical problem that overcomes the prior art existence, so that this carbon nanotube/nano clay nano composite materials as the preparation other matrix materials toughener the time, do not need to carry out again the step of traditional carrier of separating, and be difficult in matrix, reuniting, easily disperse, thereby further improve the performance of composites of desire preparation.
For achieving the above object, the invention provides a kind of preparation method of carbon nanotube/nano clay nano composite materials, comprise the steps:
Step a: metal salt solution and nanoclay are mixed, so that this metal-salt carries out intercalation at the sheet interlayer of nanoclay, wherein this metal is the catalyzer as carbon nano tube growth;
Step b: with the ion precipitation method of weak base by the control of pH value, metal ion in the described metal-salt is converted into corresponding metal oxyhydroxide, this metal hydroxide particle is deposited in the sheet interlayer of nanoclay, thereby obtain metal hydroxide particle/nano clay composition, wherein this pH value is the mixed potential of hydrogen of mixture behind weak base and the intercalation, and this pH value is between 7.5-11.5;
Step c: with metal hydroxides/nano clay composition as catalyst source/carrier system, utilize the excessive gas that contains carbon source that metal hydroxides is reduced to metal nanoparticle as catalyzer, and utilize chemical Vapor deposition process, the carbon that the decomposing gas that contains carbon source is obtained grows carbon nanotube on the nanoclay as carrier, thereby forms carbon nanotube/nano clay nano composite materials.
According to the above-mentioned method for preparing carbon nanotube/nano clay nano composite materials, this metal-salt is cobalt salt, molysite or nickel salt.
According to the above-mentioned method for preparing carbon nanotube/nano clay nano composite materials, this cobalt salt is a Cobaltous diacetate.
According to the above-mentioned method for preparing carbon nanotube/nano clay nano composite materials, the concentration of cobalt acetate solution is 40-60mmol/l.
According to the above-mentioned method for preparing carbon nanotube/nano clay nano composite materials, the weight ratio of this metal-salt and nanoclay is 1: (1～3).
According to the above-mentioned method for preparing carbon nanotube/nano clay nano composite materials, this nanoclay is the nanoclay of hydrated cation base.
According to the above-mentioned method for preparing carbon nanotube/nano clay nano composite materials, the average wafer thickness of the nanoclay of this hydrated cation base is less than 25nm, the about 100nm of particle diameter, and cation exchange capacity (CEC) is 110～120mequiv/100g.
According to the above-mentioned method for preparing carbon nanotube/nano clay nano composite materials, this nanoclay is sodium-based montmorillonite, calcium-base montmorillonite, Sodium base montmorillonite, magnesium base montmorillonite.
According to the above-mentioned method for preparing carbon nanotube/nano clay nano composite materials, described weak base is ammoniacal liquor.
According to the above-mentioned method for preparing carbon nanotube/nano clay nano composite materials, the described gas that contains carbon source is methane, ethene or acetylene.
According to the above-mentioned method for preparing carbon nanotube/nano clay nano composite materials, the described gas that contains carbon source is acetylene.
According to the above-mentioned method for preparing carbon nanotube/nano clay nano composite materials, describedly contain the gas of carbon source and the molar ratio range of described metal-salt is 5～20.
According to the above-mentioned method for preparing carbon nanotube/nano clay nano composite materials, describedly contain the gas of carbon source and the mol ratio of described metal-salt is 10.
According to the above-mentioned method for preparing carbon nanotube/nano clay nano composite materials, described pH value is 8.5～10.5.
According to the above-mentioned method for preparing carbon nanotube/nano clay nano composite materials, described pH value is 9.5.
According to the method for above-mentioned each carbon nanotube/nano clay nano composite materials of system, in step a and step b process, also apply ultrasonicly, disperse.
According to the above-mentioned method for preparing carbon nanotube/nano clay nano composite materials, the temperature that adopts in chemical vapor deposition processes is 720 ℃, and pressure is 250Pa, and the flow of carbonaceous gas is 20sccm, and depositing time is 0.5 hour.
The present invention also provides a kind of carbon nanotube/nano clay nano composite materials according to method for preparing, and this nano composite material comprises nanoclay part, carbon nanotubes grown and as the metallic particles of this appropriate carbon nanotube growth catalysts on the lamella of this nanoclay part.
According to above-mentioned carbon nanotube/nano clay nano composite materials, this nanoclay part and this carbon nanotube form network-like microstructure.
According to above-mentioned carbon nanotube/nano clay nano composite materials, this metal is cobalt, iron or nickel.
According to above-mentioned carbon nanotube/nano clay nano composite materials, this metal is a cobalt.
According to above-mentioned carbon nanotube/nano clay nano composite materials, this nanoclay partly is to be formed by hydrated cation base nanoclay.
According to above-mentioned carbon nanotube/nano clay nano composite materials, the average wafer thickness of this hydrated cation base nanoclay is less than 25nm, the about 100nm of particle diameter, and cation exchange capacity (CEC) is 110～120mequiv/100g.
According to above-mentioned carbon nanotube/nano clay nano composite materials, this hydrated cation base nanoclay is sodium-based montmorillonite, calcium-base montmorillonite, Sodium base montmorillonite, magnesium base montmorillonite.
It is the toughener of the nano composite material of matrix that the above-mentioned carbon nanotube/nano clay nano composite materials of method preparation of the present invention not only can be used as with the polymkeric substance, and can be used for the toughener of metal and ceramic matrix.
Carbon nanotube/nano clay nano composite materials of the present invention and preparation method thereof has following beneficial effect than prior art:
1) grows as carrier with nanoclay owing to carbon nanotube of the present invention, and nanoclay also is good polymkeric substance toughener, just can significantly improve physics, chemistry and the mechanical property of polymkeric substance with lower addition, so adopt the carbon nanotube of preparation of the present invention not need to carry out again the step of traditional carrier of separating, can directly this special carbon nanotube/nano clay nano composite materials be added in the middle of the matrix;
2) because can linking to each other with the nanoclay lamella, carbon nanotube forms reticulated structure, promptly form mechanical caging (mechanical locking) to each other, thereby not only can solve reunion and the difficult scattering problem of common carbon nanotube in polymeric matrix, and the matrix material that makes preparation combines carbon nanotube and the nanoclay double dominant as toughener, thereby can more effectively increase the performance of matrix;
3) carbon nanotube that adopts method of the present invention the to grow formation reticulated structure that links to each other with nanoclay, the nanoclay interlayer also increases the oikocryst surface layer spacing of nanoclay because of the carbon nanotube of having grown simultaneously, the laminate structure of having upset the high-sequential of nanoclay, this also is useful for preparation forms stripped shape during nano composite material in matrix nanoclay (exfoliated nanolcay), thereby can play the effect of reinforced composite effectively.
Description of drawings
Fig. 1 a is for preparing the schema of the method for carbon nanotube/nano clay nano composite materials according to an embodiment of the invention;
Fig. 1 b is a preparation method's shown in Figure 1 principle schematic;
Fig. 2 is the synoptic diagram of the CVD reaction unit that uses among the preparation method of carbon nanotube/nano clay nano composite materials of the present invention;
Fig. 3 a is low power FE-SEM (an emission scan formula electron microscope) photo of the carbon nanotube that grows from nanoclay;
Fig. 3 b is the high power FE-SEM photo of the carbon nanotube that grows from nanoclay;
Fig. 4 a is the TEM photo that shows several nanoclay lamellas and carbon nanotube coexistence;
Fig. 4 b is the Photomicrograph that shows the hollow pattern of the carbon nanotube that is generated;
Fig. 4 c is HRTEM (high-resolution electron microscope) photo of the carbon nanotube that generates;
Fig. 5 is pure nanoclay, Co (OH)
2The XRD figure of-nano clay composition, carbon nanotube/nano clay nano composite materials.
Fig. 6 is the Co (OH) that pure nanoclay, different pH value obtain
2The XRD figure of-nano clay composition;
Fig. 7 is the XRD figure of the carbon nanotube/nano clay nano composite materials of pure nanoclay, the acquisition of different pH value;
Fig. 8 has shown different the pH carbon nanotube/nano clay nano composite materials and the nanoclay XRD result of preparation down.
Embodiment
According to the method for preparing carbon nanotube/nano clay nano composite materials of the present invention, the design of its major technology is to utilize nanoclay, can be used as the gas of the salt of metal of appropriate carbon nanotube growth catalysts and carbonaceous sources as main raw material, its reaction mechanism is with the carrier of nanoclay as carbon nanotube, as catalyzer, make the carbon of the decomposing gas generation of carbonaceous sources on the nanoclay carrier, grow carbon nanotube with metal.Thereby, adopt carbon nanotube in the carbon nanotube/nano clay nano composite materials of this method preparation to link to each other and form reticulated structure, thereby do not need to carry out again the step of traditional carrier of separating, and be difficult in matrix, reuniting easily dispersion with nanoclay.
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
At first, see also Fig. 1 a and Fig. 1 b, it is respectively schema and the schematic diagram for preparing the method for carbon nanotube/nano clay nano composite materials according to an embodiment of the invention.As shown in the figure, the method key step for preparing carbon nanotube/nano clay nano composite materials of the present invention comprises: at first utilize the macroion exchange capacity of nanoclay, the salt (for example cobalt salt) that can be used as the metal of appropriate carbon nanotube growth catalysts is carried out intercalation (step a) at the sheet interlayer of nanoclay 1; The intercalation process here mainly is to utilize the macroion exchange capacity of nanoclay, and the cobalt metal ion in the metal-salt is realized with the original cationic exchange of nanoclay interlayer; Then, with the ion precipitation method of weak base, with (the Co for example of the metal ion in the above-mentioned metal-salt by pH value control
2+) be converted into corresponding metal oxyhydroxide (Co (OH) for example
2), thereby this metal hydroxide particle just is deposited in the sheet interlayer of nanoclay 1, thus obtain metal hydroxide particle/nanoclay (Co (OH) for example
2Particle/nanoclay) mixture (step b); Then, with metal hydroxides-nanoclay (for example, Co (OH)
2-nanoclay), at high temperature, under the protection of rare gas element, feeds the gas that contains carbon source, with Co (OH) as catalyst source-carrier system
2Be reduced to Co nano particle 3 (being granules of catalyst), and the carbon that obtains of the decomposing gas of utilizing catalytic chemical vapor deposition technique (CCVD) to make to contain carbon source on the lamella of nanoclay, grow carbon nanotube 2 (step c), thus form the nano composite material of carbon nanotube/nano clay.Below among Fig. 1 b has shown the microstructural synoptic diagram of nano composite material of the carbon nanotube/nano clay of final acquisition, comprising nanoclay 1 that forms network structure each other and carbon nanotube 2, and the position distribution that grows carbon nanotube on nanoclay has Co nano particle 3.
The following describes employed main raw material and preferred example thereof among the preparation method of carbon nanotube/nano clay nano composite materials of the present invention.The main raw material that relates among the preparation method of carbon nanotube/nano clay nano composite materials of the present invention comprises: nanoclay, as the salt of the metal of appropriate carbon nanotube growth catalysts and the gas of carbonaceous sources.
1) nanoclay
The employing nanoclay is the carrier as carbon nano-tube among the present invention, its reason is: compare with the micron-sized clay of tradition, fully decentralized nanoclay lamellar spacing is in nano level, they have ion-exchange capacity and unique intercalation character of bigger specific surface area, length-to-diameter ratio, excellence, make it can be used as the active main body material and produce metal hydroxides particle with uniform-dimension, thereby the generation catalyst metal particles is beneficial to carbon nano-tube.
Particularly, the nanoclay 1 that the present invention adopts is the nanoclay of hydrated cation base, for example: sodium-based montmorillonite, calcium-base montmorillonite, Sodium base montmorillonite, magnesium base montmorillonite.Because the performance perameter of the nanoclay of these different hydrated cation bases is all identical, as average wafer thickness less than 25nm, the about 100nm of particle diameter, cation exchange capacity (CEC) (CEC) is 110～120mequiv/100g, thereby adopts different nanoclays not have what influence for the growth of carbon nanotube among the present invention.Above-mentioned nanoclay 1 can be that to purchase in the product grade of Zhejiang Feng Hong clay chemical industry company limited be the nanoclay of the sodium ion exchange of NANOLIN DK1.
2) as the salt of the metal of appropriate carbon nanotube growth catalysts
Adopt salt among the present invention as the metal of appropriate carbon nanotube growth catalysts.This metal-salt for example is cobalt salt, molysite, nickel salt etc.Because the catalytic efficiency of cobalt is best, so preferred cobalt salt.In cobalt salt, preferred Cobaltous diacetate (Co (CH
3COO)
24H
2O).Preferred Cobaltous diacetate mainly be because: can on carrier (nanoclay) surface, decomposite pure CoO during the Cobaltous diacetate heating, can not bring other impurity; Secondly, the pH value that it can come control catalyst solution by weak base (hereinafter will describe) titration, and the solvability of cobalt salt depends on the pH value of solution strongly, and the size of granules of catalyst, shape all can be because of the difference of pH value be different, thereby the further growth of controlling carbon nanotube.
3) carbon-source gas
In principle, can select the carbon source of multiple carbonaceous gas among the present invention for use as carbon nano-tube.For example, methane, ethene, acetylene etc.The preferred acetylene of the present invention, its decomposition temperature is lower, very easily self decomposes under the high temperature, and the multi-walled carbon nano-tubes that suitable growth is a large amount of helps large-scale industrial production.
4) as for the present invention's employed weak base in step 2, preferred in one embodiment ammoniacal liquor.Select for use ammoniacal liquor to be because the cobalt ammino that generates in the titrating balanced reaction of step 2 closes ion at high temperature decompose after, can generate ammonia, thereby can not bring impurity, so ammoniacal liquor is optimal selection as weak base for the carbon nano-tube system to product.
To describe the embodiment of the method that adopts above-mentioned preferred raw material (Cobaltous diacetate, sodium base nanoclay and acetylene) and weak base (ammoniacal liquor) to prepare carbon nanotube/nano clay nano composite materials below and obtain carbon nanotube/nano clay nano composite materials by this preparation method.
Embodiment 1:
1) preparation process
The 1.2g Cobaltous diacetate is dissolved in the redistilled water of 100ml, adds the 2g sodium-based montmorillonite then, carry out intercalation, and apply ultra-sonic dispersion; Simultaneously, in applying ultransonic process, to pH=9.5, make Co (OH) with this mixed solution of the slow titration of ammoniacal liquor
2Precipitation; After ultrasonic 4 hours, in air in 110 ℃ dry 12 hours down, thereby obtain exsiccant Co (OH)
2Particle/nano clay composition, its FE-SEM photo is referring to Fig. 6 c.Here, need set forth related problems: the concentration of cobalt salt solution is generally elected about 40-60mmol/l as.Above-mentioned metal salt concentrations, the weight ratio of metal-salt/nanoclay can be along with the required carbon nanotube of the kind of selected metal-salt and carbon nanotube/nano clay nano composite materials and the ratio requirement between the nanoclay and are changed.Above-mentioned intercalation process mainly is to utilize the macroion exchange capacity of nanoclay, cobalt ion in the cobalt salt is realized with the exchange of the original sodium ion of nanoclay interlayer, volume owing to the cobalt ion in the present embodiment after the exchange is big than sodium ion, thereby can increase the interlamellar spacing of clay.
Then, obtaining exsiccant Co (OH)
2After particle/nano clay composition, with exsiccant Co (OH)
2Particle/nano clay composition is layered in the quartz boat after grinding evenly, (this device is known technology at CVD device shown in Figure 2 to make it, its description of Therefore, omited) reacts in the quartz pinch telescoping process furnace in, feed argon gas, with mechanical pump the vacuum in the silica tube is evacuated to 100Pa, open heating power supply, setting temperature controller is certain equilibrium temperature, and beginning is with the heat-up rate heating of about 50 ℃/min.After treating that temperature rises to 720 ℃ in the stove, with the flow feeding acetylene gas of 20sccm (standard ml/min), total pressure remains on 250Pa in the silica tube, carries out chemical vapour deposition about 0.5 hour, feeds argon gas in the entire reaction course always.Here, the flow (20sccm) of the temperature (720 ℃) in the silica tube, pressure (250Pa), carbonaceous gas and depositing time conditions such as (0.5 hours) are through testing institute's optimization in the CVD reaction; Too high or too low temperature, reaction pressure, gas flow and depositing time all can influence the output of carbon pipe, the degree of graphitization of carbon pipe, the content of decolorizing carbon, the security of production cost and experiment and the feature of environmental protection etc.In addition, because carbon-source gas is in the entire CVD reaction process, at first metal hydroxides is reduced to metal catalyst particles as reductive agent, carbon-source gas grows carbon nanotube under the katalysis of metallic particles then, so the dual function of carbon-source gas makes the consumption of carbon-source gas be generally excessive, preferred amount ranges is: carbon-source gas: metal-salt=5～20 (mol ratio), wherein preferred this mol ratio is 10, promptly the mole number of carbon-source gas is 10 times of metal-salt.
At last, the stop supplies acetylene gas stops heating simultaneously, makes silica tube naturally cool to room temperature in argon atmosphere, thereby the black powder that obtains loose shape is carbon nanotube/nano clay nano composite materials.
The carbon nanotube/nano clay nano composite materials that adopts method for preparing is when practice is in polymer composites, do not need to remove carrier nanoclay (because nanoclay also is a kind of toughener), only need remove the catalyst metal cobalt granule with concentrated hydrochloric acid, concrete steps are as follows: add 30%HNO in carbon nanotube/nano clay nano composite materials
3Solution with solution left standstill 4h, is used the redistilled water filtering and washing behind the ultrasonic 0.5h then.
2) sample characterization
Adopt JEOL-2010 microscope and JSM 6335F NT to carry out transmission electron microscope (TEM) and field emission scanning electron microscope (FE-SEM) observation sample pattern, wherein the acceleration voltage of TEM is 200kV; Adopt powder x-ray diffraction (XRD) on Philips X ' Pert System sample to be carried out crystal structure analysis, select the Ka ray (1=1.5406 ) of Cu for use, exciting voltage and electric current are respectively 40kV and 35mA.
A) microstructure of carbon nanotube/nano clay nano composite materials characterizes
Fig. 3 a and Fig. 3 b are the low power and the high power FE-SEM photos of the carbon nanotube that grows from nano clay composition.From Fig. 3 a as can be seen, the carbon nanotube 2 and the nanoclay 1 that are generated are intertwined mutually, can also see several spiral carbon nano pipes in addition with different pitches, this may be since in the CVD growth Unstable Growth of graphite six-membered carbon ring structure cause.Can clearly be seen that then that from Fig. 3 b carbon nanotube stretches out from the surface of nanoclay, show to have deposited Co (OH)
2The nanoclay lamella played the effect of carrier medium really, make carbon nanotube on the nanoclay lamella, to grow.
Fig. 4 a has provided the TEM photo of several nanoclay lamellas coexistences in the microscopic field of view, and this sample is prepared under the condition of pH=9.5.As can be seen, each clay layer can make carbon nano tube growth as organic centre, and these carbon nanotubes are intertwined again mutually, and the final sum clay layer forms network structure jointly.Fig. 4 b has confirmed that further method thus can grow the carbon nanotube of hollow structure really, and its mean outside diameter is about 15nm.Wherein the HR-TEM photo of one section tube wall (referring to Fig. 4 c) has proved the existence of orderly crystal structure of graphite, and the spacing of adjacent graphite linings is about 0.334nm, and thickness of pipe is about 4nm, shows that the multi-walled carbon nano-tubes of being grown approximately is made of 12 graphite linings.
B) XRD analysis of carbon nanotube/nano clay nano composite materials
The structural changes of nanoclay before and after carbon nano-tube can detect with XRD.Fig. 5 is pure nanoclay, Co (OH)
2The XRD of-nano clay composition, carbon nanotube/nano clay nano composite materials (X-ray diffraction) figure, wherein: A is the XRD figure spectrum of pure nanoclay, and B is Co (OH)
2The XRD figure spectrum of-nano clay composition; C is the XRD figure spectrum of carbon nanotube/nano clay nano composite materials.As seen from Figure 5, through after the high temperature of carbon nano-tube, the laminate structure of nanoclay has produced caves in, make the oikocryst face diffracting layer spacing of clay move on to the place of 1.16nm from 2.01nm, the intensity of diffraction peak obviously weakens, this is because the laminate structure of nanoclay high-sequential has been destroyed by carbon nanotube, caves in thereby produced.Can see from the diffracting spectrum C in high 2 θ intervals, the non-first-order diffraction peak 0.31nm and the 0.45nm of nanoclay still appear in the carbon nanotube/nano clay nano composite materials sample, but its relative intensity weakens to some extent, and the structure of nanoclay after this explanation carbon nano-tube is because grown carbon nanotube and deterioration.The diffraction peak of 2 θ=26.5 ° is represented the feature diffraction of graphite (002) aspect among the figure, corresponding to the graphite linings that carbon nanotube parallel sleeve structure forms, can be calculated the average layer spacing d of (002) aspect by Bragg equation
002Be 0.336nm, this result is consistent with the result's (being about 0.334nm) who estimates in the TEM photo by Fig. 4 c.
Embodiment 2:
The 1.2g Cobaltous diacetate is dissolved in the redistilled water of 100ml, adds the 2g sodium-based montmorillonite then, carry out intercalation, and apply ultra-sonic dispersion; Simultaneously, in applying ultransonic process, to pH=8.5, make Co (OH) with this mixed solution of the slow titration of ammoniacal liquor
2Precipitation; After ultrasonic 4 hours, in air in 110 ℃ dry 12 hours down, thereby obtain exsiccant Co (OH)
2Particle/nano clay composition, its FE-SEM photo is referring to Fig. 6 b.Then, obtaining exsiccant Co (OH)
2After particle/nano clay composition, with exsiccant Co (OH)
2Particle/nano clay composition is layered in the quartz boat after grinding evenly, make in its quartz pinch telescoping stove in CVD device shown in Figure 2 and react, feed argon gas, with mechanical pump the vacuum in the silica tube is evacuated to 100Pa, open heating power supply, setting temperature controller is certain equilibrium temperature, and beginning is with the heat-up rate heating of about 50 ℃/min.After treating that temperature rises to 720 ℃ in the stove, with the flow feeding acetylene gas of 20sccm (standard ml/min), total pressure remains on 250Pa in the silica tube, carries out chemical vapour deposition about 0.5 hour, feeds argon gas in the entire reaction course always.At last, the stop supplies acetylene gas stops heating simultaneously, makes silica tube naturally cool to room temperature in argon atmosphere, thereby the black powder that obtains loose shape is carbon nanotube/nano clay nano composite materials.C among Fig. 7 has shown the XRD figure spectrum of the carbon nanotube/nano clay nano composite materials for preparing under the pH=8.5 condition.Finding thus, is that the amount of the carbon nanotube that contains of 8.5 sample is less than the amount that the pH value is the carbon nanotube in 9.5 the sample in the pH value.This be because: high relatively pH value can make more Co (OH)
2Particle deposition is on the nanoclay surface, and then also can produce more Co nano particle when high temperature reduction, and the active site that therefore is used for carbon nano-tube on the nanoclay surface also can be more, thereby the amount of carbon nanotube is more.
Embodiment 3:
Except being the pH=7.5 being titrated to this mixed solution, all the other preparation process and embodiment 1 are identical, in this omission, no longer are repeated in this description.The exsiccant Co (OH) that Fig. 6 a has shown in preparation process to be obtained
2The FE-SEM photo of particle/nano clay composition.B among Fig. 7 has shown the XRD figure spectrum of the carbon nanotube/nano clay nano composite materials for preparing under the pH=7.5 condition.Find thus, when the pH value is 7.5, almost do not find carbon nanotube.In addition, in SEM observes, find the carbon nanotube that low pH value grows down, major part does not link to each other with nanoclay.
Embodiment 4 and 5:
Except being respectively pH=10.5 and the pH=11.5 being titrated to this mixed solution, all the other preparation process and embodiment 1 are identical, in this omission, no longer are repeated in this description.According to found that of embodiment 4 and 5: along with the pH value constantly increases since 9.5, then the output of carbon nanotube sharply reduces on the contrary, and caliber also increases simultaneously.This be because: the deposition Co (OH)
2Balance in, the too high meeting of pH causes too much Co (OH)
2Be deposited on established Co (OH)
2Particulate surface and form bigger particle, and large-sized catalysed particulate specific surface is less relatively, thereby the effective active point that can be used for carbon nano-tube also can correspondingly reduce, so the output of carbon nanotube will reduce.
Below by the result of the foregoing description, set forth of the influence of pH value to granules of catalyst, carbon nano tube growth and nanoclay structure.
Please relatively consult Fig. 6 a to Fig. 6 b, it is respectively the Co (OH) of preparation under different pH values
2The FE-SEM microstructure of-nano clay composition, wherein the pH value is 7.5,8.5 and 9.5 successively.The place that circle marks among the figure has shown Co (OH)
2Particles dispersed is on the nanoclay lamella.Under SEM observes, because nanoclay and Co (OH)
2Contrast gradient is too little, so can't see Co (OH) clearly
2Clear pattern.Further observe and find around the nanoclay some independently particles are arranged, they are to be deposited on the nanoclay surface by physical adsorption, the particle of peeling off out from surface of clay again in the ultrasonic procedure of SEM specimen preparation (as shown in illustration).As can be seen, along with the increase of pH value, particle size increases gradually, and it is more asymmetric that shape also gradually becomes trilateral by tetragon.According to the balanced reaction formula as can be known Co after reaction, mainly contain three kinds of forms, Co
2+, Co (OH)
2Precipitation and cobalt ammonia complex ion.By the pH value of reality, the known equilibrium constant and Co (OH)
2Solubleness (2.5 * 10
-6), can calculate Co
2+Mainly with Co (OH)
2Irregular shape is deposited on the surface of nanoclay lamella.In the balance along with OH
-The increase of concentration (higher pH), Co
2+Further be deposited on the Co (OH) of initial generation
2Particle surface is grown up particle, and at this moment, forming irregularly shaped sedimental possibility also can be bigger.Therefore, can observe the bigger large size granules of catalyst of more degree of irregularity in the sample of high pH.
The pH value has material impact to the ordered lamellar structure of nanoclay, and the variation of nanoclay structure can detect with XRD after the carbon nano-tube.Fig. 8 has shown different the pH carbon nanotube/nano clay nano composite materials and the nanoclay XRD result of preparation down, wherein A, B, the corresponding pure nanoclay of C, D difference, pH=7.5, pH=8.5, pH=9.5.Pass through as seen from the figure after the high temperature of carbon nano-tube, the laminate structure of nanoclay has produced caves in, and makes the oikocryst face diffracting layer spacing of clay move on to the place of 1.16nm, and the pH value is high more, and this first-order diffraction intensity is low more.For example, for the sample of pH=9.5, first-order diffraction disappears from diffractogram D substantially as can be seen.Grown what of carbon nanotube of this phenomenon and nanoclay interlayer are relevant.Carbon nanotube meeting and nanoclay twine the formation network structure mutually under the high pH value that TEM result is verified, therefore nanoclay will certainly be subjected to coming from the pulling force of carbon nanotube all directions, make clay layer misplace from its primary crystal position, the laminate structure of nanoclay high-sequential has just been destroyed by the carbon nanotube that grows under the high pH like this, more cave in thereby produce, so first-order diffraction disappears substantially in the D spectral line.
Please consult Fig. 7 again, it is the interval different pH of the high 2 θ carbon nanotube/nano clay nano composite materials of preparation and the XRD figure of pure nanoclay, wherein A, B, the corresponding pure nanoclay of C, D difference, pH=7.5, pH=8.5, pH=9.5 down.Can see that the non-first-order diffraction peak 0.31nm and the 0.45nm of nanoclay still appear in the XRD spectra of three composite sample, but along with the increase of the pH value relative intensity between them weakens to some extent.After this explanation carbon nano-tube the structure of nanoclay can be along with the increase of pH value deterioration more.The diffraction peak of 2 θ=26.5 ° is represented the feature diffraction of graphite (002) among spectrogram C and the D, the graphite linings that forms corresponding to carbon nanotube parallel sleeve structure, this diffraction peak will be higher than spectrogram C with respect to the intensity of the diffraction peak of the 0.45nm of clay among the spectrogram D, shows that the content of carbon nanotube in the sample of high pH is higher relatively.Can calculate the average layer spacing d of (002) aspect by Bragg equation
002Be 0.336nm, this result is consistent with the result who estimates in the TEM photo.In addition, (111) and (200) diffraction peak that it is further noted that metal Co among the spectrogram D all is better than respective peaks among the spectrogram C with respect to the intensity of the diffraction peak of the 0.45nm of clay, and does not observe the diffraction peak of Co simple substance clearly among the spectrogram B substantially.Therefore, proved again under the low pH value by XRD here and can only grow very a spot of Co (OH)
2Nano particle, thereby in next step CVD growth, can not restore a lot of Co catalysed particulates for carbon nano tube growth yet.But the pH value is not high more good more, and is unfavorable on the contrary when the pH value is higher than 9.5.So aforesaid " high pH value " refers to the higher pH value below 9.5.
Carbon nanotube/nano clay nano composite materials of the present invention and preparation method thereof has following beneficial effect than prior art:
1) CNT of the present invention is grown as carrier with nanoclay. Because nanoclay also Be good polymer intensifier, just can significantly improve physics, the change of polymer with lower addition Learn and mechanical property, so adopt the CNT of preparation of the present invention not need to carry out again traditional separation The step of carrier can directly be added this special carbon nanotube/nano clay nano composite materials to In the middle of the matrix.
2) because the CNT in the carbon nanotube/nano clay nano composite materials of the present invention's preparation Can link to each other with the nanoclay lamella forms network structure, namely forms to each other mechanical caging (mechanical locking), thus common CNT not only can be solved in polymeric matrix Reunite and difficult scattering problem, and make the composite of preparation combine CNT and nanoclay work Be the double dominant of reinforcing agent, thereby can more effectively increase the performance of matrix;
3) CNT that adopts method of the present invention to grow links to each other with nanoclay and forms network structure, While nanoclay interlayer also increases the oikocryst surface layer spacing of nanoclay because of the CNT of having grown, The layer structure of having upset the high-sequential of nanoclay, this for preparation during nano composite material at matrix The middle nanoclay (exfoliated nanolcay) that forms stripped shape also is useful, thereby can effectively rise Effect to reinforced composite.
Claims (24)
1, a kind of method for preparing carbon nanotube/nano clay nano composite materials is characterized in that, this method comprises the steps:
Step a: metal salt solution and nanoclay are mixed, so that this metal-salt carries out intercalation at the sheet interlayer of nanoclay, wherein this metal is the catalyzer as carbon nano tube growth;
Step b: with the ion precipitation method of weak base by the control of pH value, metal ion in the described metal-salt is converted into corresponding metal oxyhydroxide, this metal hydroxide particle is deposited in the sheet interlayer of nanoclay, thereby obtain metal hydroxide particle/nano clay composition, wherein this pH value is the mixed potential of hydrogen of mixture behind weak base and the intercalation, and this pH value is between 7.5-11.5;
Step c: with metal hydroxides/nano clay composition as catalyst source/carrier system, utilize the excessive gas that contains carbon source that metal hydroxides is reduced to metal nanoparticle as catalyzer, and utilize chemical Vapor deposition process, the carbon that the decomposing gas that contains carbon source is obtained grows carbon nanotube on the nanoclay as carrier, thereby forms carbon nanotube/nano clay nano composite materials.
2, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 1 is characterized in that, this metal-salt is cobalt salt, molysite or nickel salt.
3, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 2 is characterized in that, this cobalt salt is a Cobaltous diacetate.
4, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 3 is characterized in that, the concentration of cobalt acetate solution is 40-60mmol/l.
5, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 1 is characterized in that, the weight ratio of this metal-salt and nanoclay is 1: (1～3).
6, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 1 is characterized in that, this nanoclay is the nanoclay of hydrated cation base.
7, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 6, it is characterized in that, the average wafer thickness of the nanoclay of this hydrated cation base is less than 25nm, the about 100nm of particle diameter, and cation exchange capacity (CEC) is 110～120mequiv/100g.
8, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 6 is characterized in that, this nanoclay is sodium-based montmorillonite, calcium-base montmorillonite, Sodium base montmorillonite, magnesium base montmorillonite.
9, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 1 is characterized in that, described weak base is ammoniacal liquor.
10, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 1 is characterized in that, the described gas that contains carbon source is methane, ethene or acetylene.
11, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 10 is characterized in that, the described gas that contains carbon source is acetylene.
12, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 1 is characterized in that, describedly contains the gas of carbon source and the molar ratio range of described metal-salt is 5～20.
13, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 12 is characterized in that, describedly contains the gas of carbon source and the mol ratio of described metal-salt is 10.
14, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 1 is characterized in that, described pH value is 8.5～10.5.
15, the method for stating as claim 14 for preparing carbon nanotube/nano clay nano composite materials is characterized in that, described pH value is 9.5.
16, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 1 is characterized in that, also applies ultrasonicly in step a and step b process, disperses.
17, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 1, it is characterized in that the temperature that adopts in chemical vapor deposition processes is 720 ℃, pressure is 250Pa, the flow of carbonaceous gas is 20sccm, and depositing time is 0.5 hour.
18, a kind of carbon nanotube/nano clay nano composite materials of method preparation according to claim 1, it is characterized in that this nano composite material comprises nanoclay part, carbon nanotubes grown and as the metallic particles of this appropriate carbon nanotube growth catalysts on the lamella of this nanoclay part.
19, carbon nanotube/nano clay nano composite materials as claimed in claim 18 is characterized in that, this nanoclay part and this carbon nanotube form network-like microstructure.
20, carbon nanotube/nano clay nano composite materials as claimed in claim 18 is characterized in that, this metal is cobalt, iron or nickel.
21, carbon nanotube/nano clay nano composite materials as claimed in claim 20 is characterized in that, this metal is a cobalt.
22, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 1 is characterized in that, this nanoclay partly is to be formed by hydrated cation base nanoclay.
23, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 22, it is characterized in that, the average wafer thickness of this hydrated cation base nanoclay is less than 25nm, the about 100nm of particle diameter, and cation exchange capacity (CEC) is 110～120mequiv/100g.
24, the method for preparing carbon nanotube/nano clay nano composite materials as claimed in claim 22 is characterized in that, this hydrated cation base nanoclay is sodium-based montmorillonite, calcium-base montmorillonite, Sodium base montmorillonite, magnesium base montmorillonite.
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