Articles made of pure carbon nanotubes, made from superacid solutions and methods for production thereof. RU patent 2504604.

FIELD: chemistry.

SUBSTANCE: articles and methods involve extruding a solution of carbon nanotubes in a superacid, followed by removing the superacid solvent. The articles can be treated with extrusion methods of wet spinning based on a wet injection technique, wet spinning based on a dry injection technique and combined flow of the coagulant.

EFFECT: improved method.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the priority of the provisional patent application in the United States 60/983,495, filed on October 29, 2007, which is incorporated by reference as if it was presented here in its entirety.

STATEMENT ON FEDERAL FUNDING FOR RESEARCH

This work was funded Controlled scientific studies of naval forces of grant N00014-01-1-0789, and Management of scientific research, air force on theme « quantum wire on the grant FA9550-06-1-0207.

THE LEVEL OF TECHNOLOGY

Carbon nanotubes have some properties that make them candidates for the next generation of lightweight materials. Carbon nanotubes have mechanical, electrical and thermal properties superior to those for steel, copper and diamond, respectively, but at a much lower density. Although it outlined many applications using carbon nanotubes, the difficulties associated with their processing, hindered efforts to translate these objects from nano in . Macroscale objects based on carbon nanotubes can be generated from net carbon nanotubes or carbon nanotubes dispersed in a suitable matrix, such as polymer composites based on carbon nanotubes. Macroscale objects generated from net carbon nanotubes, may take such sample form as fiber, tapes, films and sheets. Processed carbon nanotubes can also be in molds. To date macroscale objects generated from carbon nanotubes, still demonstrate its features observed in the nanoscale. In many of the presented versions of the application of carbon nanotubes used oriented carbon nanotubes for use benefits directed in space, in the nature of their properties.

Two basic methods of processing materials include ways spinning in liquid and solid state. Spinning in the solid state is typically performed with the use of natural materials, where the individual fibers spun with the formation of a material such as yarn. On the contrary, most of synthetic fibers, such as fiber obtained from polymer, the form of the concentrated, of a viscous fluid. Viscous fluid may be a melt or solution fiber material flow process by means of extrusion and convert the fiber cooling or removal of solvent. These two methods were adapted for spinning carbon nanotube fiber, taking into account the intrinsic properties of carbon nanotubes. In particular, spun carbon nanotubes in a liquid state prevented the high melting carbon nanotubes and lack of solubility in common organic solvents. To date fiber of pure carbon nanotubes with the best properties receive spinning in the solid state, although fiber show no events of coalescence and of the seal, so that the most beneficial use of the advantages of the personal properties of carbon nanotubes. Spinning in the liquid state is promising in terms of getting much more dense fiber of carbon nanotubes.

To increase the solubility of carbon nanotubes for processing in the liquid state have been tried numerous ways, including functionalization of carbon nanotubes introduction of organic groups, increase the solubility, and the dispersion of carbon nanotubes in the presence of surface-active substances. These methods improve machinability of carbon nanotubes, but the applicability of such limited. Functionalization changes the structure of carbon nanotubes so that their attractive mechanical, electrical and thermal properties deteriorate. Surfactants allow to get the mortars of individual carbon nanotubes, but the concentrations are relatively low, and a surfactant to delete, during the processing of carbon nanotubes in macroscale objects. For translation of carbon nanotubes in a liquid state and the processing thereof used .

In the light of the foregoing, very useful are the ways to obtain high-concentrated solutions of carbon nanotubes that simplify processing in the liquid state in the macroscale objects. In particular, the especially beneficial would be ways of handling carbon nanotubes using traditional methods of processing in the liquid state fibres, tapes, sheets, films and castings. Next, not less useful is the application of these different methods to get the macro-scale objects that have oriented carbon nanotubes.

THE ESSENCE OF THE INVENTION

A variety of options for carrying out the invention describes how to get the products, including clean oriented carbon nanotubes. Methods include stages: 1) preparation of a solution of carbon nanotubes in solvent; 2) extrusion solution to obtain the extrudate; and 3) removal solvent of the extrudate. The concentration of carbon nanotubes in solvent chosen so that the solution was in the liquid-crystalline state. In certain embodiments of implementation methods include the application of tensile load during at least one stage.

In other various options for implementing disclosed articles that include clean oriented carbon nanotubes. Products receive treatment, which includes: 1) preparation of a solution of carbon nanotubes in solvent; 2) extrusion solution to obtain the extrudate; and 3) coagulation extruded articles for deletion solvent. The concentration of carbon nanotubes in solvent chosen so that the solution was in the liquid-crystalline state. In some cases, the implementation of the solution is extruded at least one coagulant without access of air. In some cases, the implementation of the solution is extruded at least one coagulant after passing through the air gap. In some cases, the implementation of at least one coagulant is a current flowing together with .

Another group of other different variants of implementation of the disclosed articles that include clean oriented carbon nanotubes. Products receive ways, including: 1) preparation of a solution of carbon nanotubes in solvent; 2) extrusion solution to obtain the extrudate; and 3) evaporation solvent. The concentration of carbon nanotubes in solvent chosen so that the solution was in the liquid-crystalline state.

In a variety of options for implementing presents methods of sealing of products made of carbon nanotubes. Methods include processing of products pyrotechnic acid, and then deleting the pyrotechnic acid. The existing articles of carbon nanotubes choose from the group consisting of fibres, matrices and carbon herrings».

The above outlined, in rather General terms, the signs of the present invention for a better understanding of the following detailed description. The following steps explain the supplementary features and advantages of the invention that are the subject of the claims.

BRIEF DESCRIPTION OF DRAWINGS

For a more complete understanding of the present invention and the benefits thereof will now be involved following descriptions in conjunction with the accompanying drawings describing specific embodiments of the invention, including:

FIGURE 1 shows a sample obtained using a polarizing microscopy images of the LCD solution of single-walled carbon nanotubes in pyrotechnic acid in the concentration range from 10 to 17 per cent by weight.

FIGURE 2 shows the approximate image of the phase diagram of carbon nanotubes.

FIGURE 3 shows examples of using polarizing microscopy and scanning electron microscopy (SEM) images of LCD solutions of carbon nanotubes in a pyrotechnic acid and sulfuric acid.

FIGURE 4 shows an example of the obtained using polarizing microscopy image of the LCD solution of single-walled carbon nanotubes in pyrotechnic acid, in which the single-walled carbon nanotubes have a length of about 30 microns.

FIGURE 5 shows an example of the obtained using polarizing microscopy image of the LCD solution of single-walled carbon nanotubes in pyrotechnic acid, in which carbon nanotubes have a length of about 500 microns.

FIGURE 6 shows an example of the obtained using polarizing microscopy image of the LCD solution of double-walled carbon nanotubes in pyrotechnic acid, in which the double-walled carbon nanotubes have a length of about 30 microns.

FIGURE 7 shows an example of the obtained using polarizing microscopy image of the LCD 10% (by weight) of a solution short of single-walled carbon nanotubes in pyrotechnic acid.

FIGURE 8 shows the sample obtained using a polarizing microscopy images solutions of 10% by weight of shortened single-walled carbon nanotubes in dimethylformamide (DMF) and 120%sulfuric acid.

FIGURE 9 shows an example of the obtained using scanning electron microscopy (SEM) image of the approximate fiber grown from 10% (by weight) of a solution short of single-walled carbon nanotubes in pyrotechnic acid.

FIGURE 10 illustrates a typical schematic options fibers of carbon nanotubes grown carbon nanotubes with a variety of lengths.

FIGURE 12 illustrates a typical experimental variant of the method of wet spun technology “dry-jet” («dry injection») for extrudates carbon nanotubes.

FIGURE 13 shows examples of SEM images fibers of carbon nanotubes obtained ways wet spun technology “wet injection” and «dry injection».

FIGURE 14 shows the version of condensation extrudate carbon nanotubes, held in the air gap.

FIGURE 15 shows the hardware version to obtain the extrudates carbon nanotubes in the presence jointly current coagulant.

FIGURE 16 shows an example of SEM images of extruded articles of carbon nanotubes obtained from 7% (by weight) of a solution of single-walled carbon nanotubes in pyrotechnic acid together with the current 96%sulfuric acid as a coagulant.

FIGURE 17 shows an example of SEM images of extruded articles of carbon nanotubes obtained from 17% (by weight) of a solution of single-walled carbon nanotubes in pyrotechnic acid together with the current glycol (PEG-200) as a coagulant.

FIGURE 18 shows the version of the model of the device for dry spinning extrudates carbon nanotubes using microwave heating for evaporation of the solvent.

FIGURE 19 shows the version of the film of single-walled carbon nanotubes obtained from 12% (by weight) of a solution of single-walled carbon nanotubes in pyrotechnic acid using diethyl simple ether as a coagulant.

FIGURE 20 shows the version of the film shortened from single-walled carbon nanotubes obtained from 10% (by weight) of a solution of single-walled carbon nanotubes in pyrotechnic acid.

FIGURE 21 shows the version of the mixer/extruder used for processing of carbon nanotubes.

FIGURE 22 shows the version of the mixer/extruder used for processing of carbon nanotubes, acting in his mode of extrusion.

DETAILED DESCRIPTION OF THE INVENTION

In the following description explains some of the details, such as specific quantities, sizes, etc. to ensure a full understanding of these options for implementation, disclosed here. However, the qualified experts in this area of technology is obvious that the present invention can be implemented without such specific details. In many cases, details of such matters and the like, were omitted because such details are not necessary to achieve a full understanding of this invention and are within the competence of the specialists of ordinary skill in the relevant field of technology.

With reference to the drawings in General, it is clear that the illustrations are for the purpose of describing a particular variants of the invention and do not involve restrictions such. Drawings made optional in scale.

While many of the used terms are easily recognizable for the qualified experts in this area of technology, however, are the following definitions, to promote understanding of the present invention. However, it should be clear that, not being defined explicitly, the terms should be interpreted as officially adopted with the value of the currently accepted by the qualified experts in this area of technology.

«Coagulation», as defined here, is related to the process of solvent removal of carbon extrudate nanotubes by applying coagulant.

«Essentially contains no defects», as defined herein, means a condition where less than about 5% of the centres in the lattices of the lateral walls of carbon nanotubes are defective centers.

«A stretching or pulling», as defined here, is related to the process of application of stretching or drawing efforts to the object. «Tractive force or pull forces» refers to the or force annexed to the object.

A variety of options for implementation, presented below, refer to the carbon nanotubes. These different options for implementing carbon nanotubes can be formed by any known method and can be in various forms, such as soot, powder, cords, beams, individual carbon nanotubes, the fibers of carbon nanotubes, surface-associated matrix, carbon herring» (, named so for the characteristic form), heavy-duty paper (“bucky paper”), uncleaned carbon nanotubes and purified carbon nanotubes. Carbon herring» are described in a Patent Application in the United States No. 10/189,129, belonging to the authors of the present invention, which is incorporated here by reference. Carbon nanotubes can have any length, diameter or chirality. In a variety of options for implementing carbon nanotubes are free of defects. Carbon nanotubes can have any number of concentric walls, including, but not limited to, the single-walled carbon nanotubes, double-walled carbon nanotubes and multi-walled carbon nanotubes. Carbon nanotubes can also be shortened carbon nanotubes or carbon nanotubes, introduction of functionalized organic functional groups. Shortened carbon nanotubes can be obtained by oxidative cleavage of the carbon nanotubes with a full-length. A non-limiting example of how to shortening of carbon nanotubes involves the oxidation of carbon nanotubes in a mixture of nitric acid and steaming sulfuric acid (oleum). Although a variety of options for the implementation described here, using a specific type of carbon nanotubes, such as single-walled carbon nanotubes, a qualified specialist in this area of technology, with the features and benefits described here invention, it will be clear that any of a variety of options for the implementation might be equivalent implemented in practice within nature and volume of the invention with any type of carbon nanotubes.

The different variants of implementation of the described methods of manufacturing of products, including clean oriented carbon nanotubes. Methods include stages: 1) preparation of a solution of carbon nanotubes in solvent; 2) extrusion solution to obtain the extrudate; and 3) removal solvent of the extrudate. The concentration of carbon nanotubes in solvent chosen so that the solution was in the liquid-crystalline state. In a variety of options for implementing methods include the application of tensile load during at least one stage. In a variety of options for implementing articles may take the form of, selected from the group consisting of, but not limited to, those of fiber tape, sheet or film. In certain embodiments of the implementation phase extrusion includes casting into a mold.

In various versions in the ways of carbon nanotubes choose from the group consisting of single-walled carbon nanotubes, double-walled carbon nanotubes, multiwall carbon nanotubes and shorter-single-walled carbon nanotubes. In various versions in the ways of carbon nanotubes have a length of up to about 10 mm In various other options for implementing ways to carbon nanotubes have a length of up to about 5 mm In various other versions ways carbon nanotubes have a length of up to about 1 mm In other various options for implementing ways to carbon nanotubes have a length of up to about 500 microns. In a variety of options for implementing carbon nanotubes essentially free from defects. The relative share of defect centers of carbon nanotubes can be traced by using the ratio of bands G the D produced according to Raman spectroscopy.

Chlorosulphonic acid especially preferable for the dissolution of carbon nanotubes in the techniques and processes described here below, as it can dissolve carbon nanotubes of the most diverse types and lengths of up to very high concentrations. For example, the length of the carbon nanotubes is not a limiting factor for pyrotechnic acid, as in the case with other , such as oleum, which dissolves only single-walled carbon nanotube length of about 1 micron. Next, chlorosulphonic acid easily dissolves double-walled and multi-walled carbon nanotubes, unlike other , such as oleum, which provides only limited solubility for the types of carbon nanotubes having more than one wall. Carbon nanotubes with a length of up to mm or more, each of which has any number of concentric nanotubes can be easily dissolved in pyrotechnic acid. Chlorosulphonic acid can easily dissolve long (mm and longer) carbon nanotubes grown in the form of a matrix, while others , such as oleum, do not have such dilution capacity. Other existing articles of carbon nanotubes, such as fibers and carbon herring», also can be dissolved.

Comparatively with other , such as oleum, pyrotechnic acid can be obtained much higher concentration of carbon nanotubes. For example, solutions of carbon nanotubes in a pyrotechnic acid up to a concentration of around 17 percent by weight were received and processed in products from pure carbon nanotubes. This concentration is modern limit opportunities for the processing in the laboratory scale due to viscosity solutions of carbon nanotubes in a pyrotechnic acid. However, this concentration should not be considered as limiting as a qualified specialist in this area of technology is understandable for the usefulness of the highest possible concentration of carbon nanotubes in the following ways. Next, a qualified specialist in this area of technology, it will be clear that using technological installations of industrial scale can be processed much more viscous solutions. The pyrotechnic acid were obtained solutions of carbon nanotubes with concentrations up to about 2 400 parts per million (ppm), though still not been set upper limit of solubility. The various options for implementing the pyrotechnic preferably acid dissolved carbon nanotubes, which essentially free from defects. For example, sludge is separated from the solution of carbon nanotubes in a pyrotechnic acid, demonstrates a significantly lower ratio of the bands G/D in Raman spectra compared with the initial material of carbon nanotubes. Lower ratio of the bands G/D is the characteristic of the increased number of defects in the side wall carbon nanotubes in material.

Although viscosity solution of carbon nanotubes in a pyrotechnic acid causes some problems in terms of technology, it creates advantageous features in other respects. For example, the viscosity of extruded articles of carbon nanotubes is that can be done stretching of the extrudate. As discussed further below, stretching extrudate contributes to the orientation of carbon nanotubes in extruded products. Stretching can also provide a seal of oriented carbon nanotubes. In a variety of options for implementing to perform stretching extrudate wound on the receiving roller. In other words, tension is pulling extrudate. In other various options for implementing stretching provides at least one coagulant, where coagulant flows together with . Coagulants and advantages of the combined flow in more detail below.

Spinning-up ratio is defined as the ratio of the linear velocity of the extrusion speed pick roller extraction. High spinning-up ratio shows the relative elongation of the extrudate during extrusion. In certain embodiments of the implementation of the high spinning-up attitude can contribute to the orientation and coalescence of processed fibers of carbon nanotubes.

Without the intention to go into theory or mechanism, modern understanding is that implemented between individual carbon nanotubes formed in cords or beams of nanotubes. In the filaments or beams of individual carbon nanotubes are strongly linked to each other by the van der Waals equation. which have an exceptionally high ability, reversible individual carbon nanotubes. Resulting electrostatic repulsion compels nanotubes to the release of beams, separating carbon nanotubes from each other. Competition between the electrostatic repulsion and attraction by the forces of van der Waals forces carbon nanotubes behave as dispersed Б rods in solutions. For a given concentration begin to occur interaction between terminals, ultimately leading to an LCD behaviour. As you can see in FIGURE 1, single-walled carbon nanotubes form a liquid crystalline solutions in pyrotechnic acid within a non-limiting concentration range from 10% to 17%, which is confirmed by polarizing microscopy. Isotropic solutions are obtained at low concentrations of carbon nanotubes in environment. Increases concentration is formed of two-phase solution, including the isotropic and liquid-crystal field. In the future, the greater the concentration of the solution is a liquid crystal. The approximate phase diagram of carbon nanotubes is shown in FIGURE 2. Benchmarks for phase is a function of parameters such as the length of the carbon nanotubes, and solvent nature. In a variety of options for implementing described here are ways concentration of carbon nanotubes to obtain a liquid-crystal state is up to about 17 per cent by weight. In other various options for implementing presented here, the concentration of carbon nanotubes to obtain the LCD status varies from about 10% by weight of up to about 17 per cent by weight. In certain embodiments of the implementation of the liquid-crystalline state is in equilibrium with the isotropic phase.

Liquid-crystalline behavior is beneficial to obtain dense homogeneous extrudates with oriented net carbon nanotubes. As previously illustrated in FIGURE 1, the degree of in solution of carbon nanotubes can be installed using microscopy in polarized light before extrusion. Establishing the degree of before extrusion is preferred because of the high degree of before extrusion correlates well with the best orientation of carbon nanotubes, which is achievable under extruded. Chlorosulphonic acid especially favored in this regard before more weak acids, because it creates a large domains LCD areas within a wide range of concentrations. For example, FIGURE 3 shows obtained through a polarizing microscopy image of solutions of carbon nanotubes as a pyrotechnic acid ( 301 )and sulfuric acid ( 302 ). As evident from the obtained using polarizing microscopy images, solution in pyrotechnic acid creates larger LCD domains and is more suitable for the extrusion of oriented carbon nanotubes than the solution in the steaming sulfuric acid. The corresponding image on FIGURE 3, received the scanning electron microscope (SEM), fibers, extruded from pyrotechnic acid ( 303 ) and sulfuric acid ( 304 ), reflect a higher degree of orientation in the solution pyrotechnic acid. As evident from FIGURE 3, chlorosulphonic acid forms a fiber with a smooth, well surface, in contrast to the rough surface and the inability to coalescence of fibers formed smaller LCD domains in sulfuric acid. In a variety of options for implementing sizes of liquid crystal domains in solutions of carbon nanotubes in a pyrotechnic acid influenced by the length of dissolved carbon nanotubes. In a variety of options for implementing sizes of liquid crystal domains in solutions of carbon nanotubes in a pyrotechnic acid influenced by the type of dissolved carbon nanotubes. In a variety of options for implementing sizes of liquid crystal domains in solutions of carbon nanotubes in a pyrotechnic acid influenced by the way in which the solution process during the confusion.

Chlorosulphonic acid also is imperative for transfer in a liquid state and orientation shortened single-walled carbon nanotubes, such as pipes, received oxidative splitting of single-walled carbon nanotubes with a full-length. Although shortened single-walled carbon nanotubes significantly more soluble in organic solvents than insoluble, carbon nanotubes, cropped single-walled carbon nanotubes form a liquid crystalline domains in the normal organic solvents. However, pyrotechnic acid shortened single-walled carbon nanotubes form a liquid-crystal phase at a concentration of about 10% by weight, that is confirmed by using polarizing microscopy images in FIGURE 7. Comparative image, obtained with the use of polarizing microscopy for shortened single-walled carbon nanotubes in dimethylformamide (DMF) ( 801 ) and 120%sulfuric acid ( 802 ), do not exhibit the characteristics of double refraction of the liquid crystal regions, as shown in FIGURE 8. Further, the concentration of shortened single-walled carbon nanotubes in pyrotechnic acid is much higher than can be obtained even with the best of organic solvents such as dimethyl formamide (DMF). LCD solutions in pyrotechnic acid can be used to obtain extrudates of oriented shortened carbon nanotubes. Received the scanning electron microscope (SEM) image of the model fibers of carbon nanotubes grown from 10% (by weight) of a solution short of single-walled carbon nanotubes in pyrotechnic acid, are shown in FIGURE 9. In certain embodiments of application oriented shortened carbon nanotubes may be preferred.

Ability pyrotechnic acid to dissolve very long carbon nanotubes is imperative for processing of carbon nanotubes in the products having directional characteristics, the most typical of individual carbon nanotubes. Orientation of carbon nanotubes provides preferential use them aimed in the space of physical properties. In the processed products made of carbon nanotubes obtained presented here of ways, carbon nanotubes are sealed in large bundles of oriented carbon nanotubes, held together by van der Waals forces. You can see the similarities of these beams with those found in raw carbon nanotubes, except for the macroscopic scale. As illustrated in FIGURE 10, where the length of individual carbon nanotubes are shortened ( 1001 ), there is a greater number of disconnections between individual carbon nanotubes in product, which breaks potentially become points of mechanical destruction. FIGURE 10 asterisk are unrelated separation between the ends of the individual carbon nanotubes. On the contrary, with long carbon nanotubes ( 1002 ) there is a smaller number of disconnections between individual carbon nanotubes that facilitates the transfer of the macroscopic beams mechanical properties, more typical single nanotubes. In other words, when the carbon nanotubes are long, mechanical properties of the products became independent from the ratio of geometrical dimensions of carbon nanotubes. At shorter wavelengths mechanical properties of products made of carbon nanotubes can be directly proportional to the ratio of the geometric dimensions of carbon nanotubes.

The application of carbon nanotubes, including the electrical conductivity, the most commonly used single-walled carbon nanotubes, although in certain applications can also be used to double-walled and multi-walled carbon nanotubes. Depending on their chirality, single-walled carbon nanotubes may have metal, or semiconducting properties. Like discussed above mechanical options to apply, long carbon nanotubes provide advantageous features in products made of carbon nanotubes having electrical conductivity. In metal single-walled carbon nanotube conductivity is manifested after a few micrometers without scattering along essentially one-dimensional electronic structure of individual nanotubes. In fiber, which includes net single-walled carbon nanotubes, an electric current flows through a metal single walled carbon nanotubes through the points of overlap. Thus, the longer single-walled carbon nanotubes are prior in the creation of the increased number of points of overlap between individual carbon nanotubes and a smaller number of disconnections at the ends of carbon nanotubes.

In a variety of options for implementing a solution of carbon nanotubes in solvent is extruded through the hole. Hole choose from the group consisting of the nozzle needle, glass capillary and crevice dies for the film. Qualified specialists in this field of technology may have in mind the other holes, known in the technology of liquid-phase extrusion. The length of the hole has no special significance for the described here. Thus, the length of extrusion holes can vary in a wide range of values. The embodiment extrusion hole is conical. A solution of carbon nanotubes in subjected to a shear load when it reaches through extrusion hole, whether it is a cone-shaped or not a cone-shaped. Shear strain stimulates the orientation of carbon nanotubes in the extrudate. For this extruding speed shear load varies proportional to the diameter of the holes in the third degree. Thus, to the extent of reducing the diameter of the hole is an intense orientation nanotubes. In a variety of options for implementing hole has a diameter of about 50 microns to about 500 microns. With smaller diameter of holes can be an issue clogging extrusion holes, although this circumstance, you can circumvent the deletion of pyrotechnic acid through a strainer before stage of extrusion.

In a variety of options for implementing methods of obtaining goods, including net carbon nanotubes, stage of removal includes the handling of extrudate at least one coagulant. Remove solvent from the extrudate carbon nanotubes creates the solid product incorporating net carbon nanotubes. Solid product may have an unrestricted form, such as fibres, films, tapes and sheets. Depending on how perform stage coagulation, can drastically change the microstructure and properties of products made of carbon nanotubes. For example, the speed of diffusion of solvent from the articles of carbon nanotubes or speed of diffusion of the coagulant in product carbon nanotubes may influence the characteristics of the product that determine the phase transition from liquid to solid, which occurs during the coagulation process. Diffusion coagulant in the product may be particularly a problem because the inside of the product are created cavity on drying, when diffusion inside the volume.

In a variety of options for implementing described here are ways to at least one coagulant choose from group consisting of hexane, (simple) ether diethyl simple ether, polyethylene glycol, dimethylsulfoxide, polyvinyl alcohol, sulfuric acid, water, dichloromethane, chloroform, , Triton-X capable of polymerization of monomers and combinations thereof. The different variants of implementation of at least one coagulant choose from the group consisting of water, aqueous sulfuric acid, dichloromethane, chloroform, ether, and combinations thereof. The concentration of aqueous sulfuric acid can vary from about 5% H 2 SO 4 in the water up to about 95% H 2 SO 4 in the water. In certain embodiments of the implementation of at least one coagulant includes polymer, soluble in organic solvents such as chloroform or dichloromethane. Approximate which can be polymerized monomer, which may be applicable to the implementation of the ways include, but are not limited to, those of vinylpyrrolidone and vinyl alcohol.

In a variety of options for implementing disclosed here removal stage includes evaporation solvent. In certain versions of ways evaporation spend the microwave heating. In other variants of implementation of the ways stage evaporation carried out in a vacuum. A variety of considerations relating to the evaporative removal are described in detail below.

The best of the morphology of the products in certain embodiments of the implementation preferably slow destruction of solvent. The slow destruction of solvent can be done decrease in the concentration gradient between coagulant and extruded carbon nanotubes. If solvent removed too quickly, it can often be observed skin effect (education crusts), where the product is covered by a dense layer of oriented carbon nanotubes, covering a porous core of poorly oriented carbon nanotubes. Such skin-effects give the product, which has a poor mechanical properties.

In a variety of options for implementing phase extrusion method includes selected from the group consisting of wet spun technology “wet injection”, wet spun technology «dry injection» and the combined flow of coagulant. Each of these extrusion methods discussed in greater detail below.

Fiber of pure carbon nanotubes can be spun from using the method of wet spun technology «wet injection», similar to that previously described in a Patent Application in the United States No. 10/189,129, belonging to the authors of the present invention. However, the processes of wet spun technology «wet injection and methods described here provide increased opportunities orientation thanks to the use of liquid crystal solution that can be stretched after extrusion. In the process of wet spun technology «wet injection» extrudate extruded holes directly immersed in the coagulant. In a variety of options for implementing phase extrusion perform with the introduction of at least one coagulant without contact with the atmosphere. Sample diagrams process wet spun technology «wet injection» are shown in FIGURES 11a and 11b. FIGURE 11a extruder 1101 feeds the material into the bath 1103 with coagulant with the formation of fiber 1102 . Stretching provide pulling fiber 1102 on the receiving roller 1104 continuous process. A slightly different method is illustrated in FIGURE 11b. Syringe 1110 containing a solution of carbon nanotubes in a pyrotechnic acid, feeds the material into the bath 1111 with coagulant with the formation of fiber 1112 . Stage stretching to FIGURE 11b not shown. Fiber from single-walled carbon nanotubes obtained disclosed here ways wet spun technology «wet injection»have demonstrated the electrical resistivity of 1.2 MK Ohm-m, modulus of 16.7 HPa, and tensile strength of 40 MPa. Effective coagulants include, but are not limited to, those of chloroform, dichloromethane, tetrachloroethane and ether.

Can also be used for other ways of processing of a solution of carbon nanotubes in a pyrotechnic acid. In a variety of options for implementing phase extrusion spend in the air gap. Instead of direct extrusion in the coagulant, as in the wet spinning technology «wet injection», extrudate can pass through the air gap before entering the coagulant. This process is called wet spinning technology «dry injection», and approximate the experimental variant of the method is illustrated in FIGURE 12. FIGURE 12 shows the fiber 1201 , deducible from the extrusion needle 1200 and passing through the air gap 1202 before entering the bath 1203 with coagulant. Production of products from pure carbon nanotubes using the method of wet spun technology «dry injection may be preferred before wet spinning technology «wet injection». For example, fiber, technology «dry injection», showed an increased density and the enhanced coalescence of being subjected to air in the air gap, compared with the same fibres obtained wet spinning technology «wet injection». Fiber, in the air gap, prone to withstand higher levels of tension load compared with the fibers, in solution, which is preferred for the orientation of carbon. Approximate fiber, both ways, are shown in FIGURE 13. As you can see in FIGURE 13, wet spinning ( 1301), the technology of dry injection provides a more dense and more linked fiber than wet spinning ( 1302), the technology of wet injection». In a variety of options for implementing an air gap is about 4 inches (101.6 mm) for extrudates carbon nanotubes in pyrotechnic acid. Air gap width 4-inch (101.6 mm) is a non-optimized value, and a variety of lengths air gaps can be identified by a simple experimentally within nature and volume of the invention. In certain embodiments of the implementation of the mechanical properties of the products obtained by wet spinning technology «dry injection», can be increased tenfold as compared with the wet spinning technology “wet injection”.

Instead of direct extrusion into the tub with coagulant or extruded through the air interval in a bath with coagulant can be applied to other methods of coagulation extrudate carbon nanotubes. For example, coagulant can proceed together with carbon nanotubes. A non-limiting version extrusion device, providing for joint coagulant, is shown in FIGURE 15. As shown in FIGURE 15, extruded solution of carbon nanotubes in the tank 1501 , and at the same time flows coagulant from the reservoir 1502 . A mixture of carbon nanotubes with coagulant occurs in conjunction 1503 , where coagulant 1504 first comes into contact with 1505 carbon nanotubes. As shown in FIGURE 15, coagulant 1504 proceeds in the same direction. When coagulant 1504 flows in the same direction as the extrudate 1505 carbon nanotubes, coagulant 1504 provides extraction and application of tensile load, which contributes to the orientation of carbon nanotubes. Collectively, flowing coagulant 1504 gradient is created to facilitate the slow destruction of solvent, thereby promoting a better morphology of the extrudate. In certain embodiments of the implementation of the coagulant 1504 flows together with higher average speed than the extrudate 1505 , to create more high-tensile load. The joint allows for that do not create a good morphology extrudate in direct wet spinning technology «wet injection or wet spinning technology «dry injection», act as an acceptable coagulants. For example, direct extrusion 7% (by weight) of a solution of single-walled carbon nanotubes in pyrotechnic acid, 96%sulphuric acid gives extrudate, having a poor morphology. However, if 96%sulphuric acid, is a joint course with the same solution of carbon nanotubes, it turns out extrudate without irregularities, with a very smooth surface, as shown in FIGURE 16. Since 96%sulphuric acid is similar to a solvent for carbon (solubility of carbon nanotubes provides & GE 100%sulphuric acid), coagulation process is slow, what explains the good morphology fiber. Joint during may be also conducted a 17% (by weight) of a solution of single-walled carbon nanotubes in pyrotechnic acid with the use of polyethylene glycol (PEG-200) as a coagulant with the formation of the extrudate, with a good morphology, as shown in FIGURE 17.

Another removal tool solvent from the extrudate carbon nanotubes do not include any coagulant. Instead, perform a simple evaporative remove solvent. This method is called “dry spinning”. In a variety of options for implementing solvent can be removed by evaporation at room temperature or heated. In a variety of options for implementing evaporation may be conducted at atmospheric pressure or vacuum. It was found that the samples fibers of carbon nanotubes formed slow evaporation, have the electrical resistivity of 2.1 MK Ohm-m, modulus of 16.7 HPa, and tensile strength of 40 MPa.

Extrudate can be processed further after removal solvent to improve the properties of the end products made of carbon nanotubes. In a variety of options for implementing disclosed here ways to further involve the processing stage of the product after removal. In a variety of options for implementing stage treatment involves processing, selected from the group consisting of heating, heat in vacuum, heating the air and the heating in the hydrogen (H 2 ). Annealing by heat in vacuum or air can provide a means of sealing and alignment of the generated products. In certain embodiments of the implementation of the annealing can create links between individual carbon nanotubes that can lead to hardening of the formed products for a variety of applications. When heated in hydrogen any oxidized carbon nanotubes are restored back to its state. The subsequent stages of processing can also have the effect of twisting extruded fibers of carbon nanotubes with the formation of yarn.

Autonomous film of carbon nanotubes can be obtained on surfaces such as glass and Teflon, using solutions of carbon nanotubes in . The solution is deposited on the surface and then rolled for reception of a film. After that the film is coagulated using either vacuum removal of solvent or application of liquid coagulant. The film thickness of about 1 micron, obtained from 12% (by weight) of a solution of single-walled carbon nanotubes using diethyl simple ether as a coagulant, is shown in FIGURE 19. Morphology of the surface film ( 1901 ) from the side of the glass substrate is slightly different from that on the surface ( 1902 ) by air. As shown in FIGURE 20, 10%by weight solution shortened single-walled carbon nanotubes in pyrotechnic acid can also be used to produce film on the glass, which has more smooth morphology, than during the formation of carbon nanotubes with a full-length.

In a variety of options for implementing here disclosed articles that include clean oriented carbon nanotubes. Products obtained in a variety of ways, as described below.

In a variety of options for implementing articles that include clean oriented carbon nanotubes, are obtained by including stages: 1) preparation of a solution of carbon nanotubes in solvent; 2) extrusion solution to obtain the extrudate; and 3) coagulation extruded articles for deletion solvent. The concentration of carbon nanotubes in solvent chosen so that the solution was in the liquid-crystalline state. Phase extrusion of conduct so that the solution at least one coagulant without contact with the atmosphere. These methods include the processes of wet spun technology «wet injection» for products made of carbon nanotubes.

In a variety of options for implementing articles that include clean oriented carbon nanotubes, are obtained by including stages: 1) preparation of a solution of carbon nanotubes in solvent; 2) extrusion solution to obtain the extrudate; and 3) coagulation extruded articles for deletion solvent. The concentration of carbon nanotubes in solvent chosen so that the solution was in the liquid-crystalline state. Phase extrusion of conduct so that the solution at least one coagulant after passing through the air gap. These methods include the processes of wet spun technology «dry injection» for products made of carbon nanotubes.

In a variety of options for implementing articles that include clean oriented carbon nanotubes, are obtained by including stages: 1) preparation of a solution of carbon nanotubes in solvent; 2) extrusion solution to obtain the extrudate; and 3) coagulation extruded articles for deletion solvent. The concentration of carbon nanotubes in solvent chosen so that the solution was in the liquid-crystalline state. Phase extrusion of conduct so that at least one coagulant proceeded together with . These methods include methods for the combined flow of coagulant for spinning products made of carbon nanotubes.

In a variety of options for implementing articles that include clean oriented carbon nanotubes, are obtained by including stages: 1) preparation of a solution of carbon nanotubes in solvent; 2) extrusion solution to obtain the extrudate; and 3) evaporation solvent. The concentration of carbon nanotubes in solvent chosen so that the solution was in the liquid-crystalline state.

In various versions of products ways to further include the application of tensile load during at least one stage. In various versions of the products chosen from the group consisting of fibres, tapes, sheets and film. In various versions of products carbon nanotubes choose from the group consisting of single-walled carbon nanotubes, double-walled carbon nanotubes, multiwall carbon nanotubes and shorter-single-walled carbon nanotubes. In some versions of products carbon nanotubes have a length of up to 10 mm In a variety of versions of products carbon nanotubes essentially free from defects. In various versions of products solvent includes acid.

In any of the various variants of the products by using at least one of the coagulant in the process of formation of a product, at least one coagulant can be selected from the group consisting of hexane, a simple ether diethyl simple ether, polyethylene glycol, dimethylsulfoxide, polyvinyl alcohol, water, sulfuric acid, dichloromethane, chloroform, , Triton-X capable of polymerization of monomers and combinations thereof.

In any of the different variants of implementation using the stage of evaporation in the process of formation of the product stage evaporation can be done using microwave heating. In any of the different variants of implementation using the stage of evaporation in the process of formation of the product stage evaporation can be done in a vacuum. In any of the various options for the implementation of methods for the formation of products made of carbon nanotubes extrudate can be passed through a tube filled with inert gas flow. In certain embodiments of the implementation of the ways tube filled with flowing inert gas is used in the process, which includes microwave heating of the extrudate.

In a variety of options for implementing presents methods of sealing of products made of carbon nanotubes. Methods include processing pyrotechnic acid and destruction of pyrotechnic acid. The existing articles of carbon nanotubes choose from the group consisting of fibres, matrices and carbon herrings».

Experimental Examples

The following experimental examples are given to demonstrate the concrete aspects of the present invention. Qualified specialists in the field of technology should be clear that described in the following examples, the methods are only indicative options for carrying out the invention. After the reading of the present invention qualified specialists in this field of technology should be clear that many of the changes can be done in specific described options for implementing and still receive similar or similar result without going beyond the nature and volume of the present invention.

Example 1: to Obtain solutions of carbon nanotubes in a pyrotechnic acid

Carbon nanotubes mixed with pyrotechnic acid in the glove box without access of air moisture and left to stand in for the night for the formation of a viscous solution of carbon nanotubes for processing. Solutions of carbon nanotubes were processed in a variety of ways depending on the concentration. For concentrations up to 0.5% (by weight) mixing was performed using magnetic mixing all-over anchor pattern with Teflon coating. For intermediate concentrations up to 7% (by weight) of viscosity solution incurs more complex processing to complete mixing. For a range of intermediate concentrations used small glass reactor using a mechanical stirrer with Teflon blades. For even higher concentrations of up to 17% (by weight) of a solution of carbon nanotubes placed in pressurized mixer/extruder, which used the alternating movement of the two plungers 2101 for extrusion of a solution of carbon nanotubes through the winding channel 2102 to ensure complete mixing. Photo and a schematic image of execution options mixer/extruder are shown in FIGURE 21. Spiral winding channel provided mixture with high shear load with the formation of well dispersed solutions of carbon nanotubes under high concentrations in pyrotechnic acid. Mixer/extruder was made of stainless steel SS316, since the material is resistant to pyrotechnic acid. Working pressure of up to 2000 psi (13,8 MPa). Mixer/extruder was built so that it can be easy to load in inert controlled environment, such as a glove.

Example 2: Extrusion solutions of carbon nanotubes

After mixing of viscous solution directly from the mixer/extruder. Work mixer/extruder mode extrusion shown on pictures and in the diagram in FIGURE 22. Design of the extruder is such that it can be used for any of the various extrusion processes described above.

From the above description is qualified specialist in this area of technology can easily understand the essential features of the present invention, and without going beyond the meaning and the region itself may produce a variety of changes and modifications to fit the invention to a variety of options and terms of use. The options of implementation are intended only to illustrate and should not be interpreted as limiting the amount of invention, which is defined in the following paragraphs of the claims.

1. A method of obtaining a product, including clean oriented multi-walled carbon nanotubes, this method includes: 1) preparation of the solution of multiwalled carbon nanotubes in solvent; in which the concentration of multiwalled carbon nanotubes in solvent chosen so that the solution was in the liquid-crystalline state; 2) extrusion solution to obtain the extrudate; and 3) destruction of solvent of the extrudate.

2. The method according to claim 1, wherein during at least one stage of making a tension load.

3. The method according to claim 1, wherein the product is chosen from the group consisting of fibres, tapes, sheets and film.

4. The method according to claim 1, wherein extrusion solution includes a way, selected from the group consisting of wet spun technology «wet injection», wet spun technology «dry injection» and the combined flow of coagulant.

5. The method according to claim 1, wherein extrusion solution includes casting into a mold.

6. The method according to claim 1, wherein multi-walled carbon nanotubes include double-walled carbon nanotubes.

7. The method according to claim 6, in which multi-walled carbon nanotubes have a length of up to about 10 mm

8. The method according to claim 7, in which multi-walled carbon nanotubes have a length of up to about 500 microns.

9. The method according to claim 6, in which multi-walled carbon nanotubes essentially free from defects.

10. The method according to claim 1, wherein solvent includes acid.

11. The method according to claim 1 in which the concentration of multiwalled carbon nanotubes to obtain a liquid-crystal state is up to about 17 per cent by weight.

12. The method according to claim 11, in which the concentration of multiwalled carbon nanotubes to obtain a liquid-crystal state is about 10 weight percent to about 17 per cent by weight.

13. The method according to claim 1 in which the liquid-crystalline state is in equilibrium with the isotropic phase.

14. The method according to claim 1, wherein extrusion solution is carried out through the hole, selected from the group consisting of the nozzle needle, glass capillary and crevice dies for the film.

15. The method according to paragraph 14, in which the hole has a diameter of about 50 microns to about 500 microns.

16. The method according to claim 1, wherein the removal of solvent includes evaporation solvent.

17. The method according to article 16, in which the evaporation of conduct by means of microwave heating.

18. The method according to article 16, in which evaporation is carried out in a vacuum.

19. The method according to claim 1, wherein the removal of solvent includes the handling of extrudate at least one coagulant.

20. The method according to .19, in which at least one coagulant choose from the group consisting of hexane, a simple ether diethyl (simple) ether, polyethylene glycol, dimethylsulfoxide, polyvinyl alcohol, water, sulfuric acid, dichloromethane, chloroform, , Triton-X capable of polymerization of monomers and their combinations.

21. The method according to .19, in which at least one coagulant choose from the group consisting of water, aqueous sulfuric acid, dichloromethane, chloroform, and (simple) ether and their combinations.

22. The method according to .19, in which at least one coagulant includes polymer, soluble in organic solvents.

23. The method of claim 2, in which at least one coagulant creates a tension load, and where at least one coagulant flows together with .

24. The method of claim 2, in which the extrudate wound on the receiving roller application tensile load.

25. The method according to claim 1, wherein extrusion solution spend in the air gap.

26. The method according to claim 1, wherein extrusion solution conduct a tube filled with inert gas flow.

27. The method according to claim 1, wherein extrusion solution conduct at least one coagulant without contact with the atmosphere.

28. The method according to claim 1, further comprising: processing after the removal of solvent; in which processing of the product includes processing, selected from the group consisting of heating, heat in vacuum, heating the air and heating in hydrogen.

29. Product incorporating clean oriented multi-walled carbon nanotubes, received in the way, including: 1) preparation of the solution of multiwalled carbon nanotubes in solvent; in which the concentration of multiwalled carbon nanotubes in solvent chosen so that the solution was in the liquid-crystalline state; 2) extrusion solution to obtain the extrudate; and 3) coagulation extruded articles for deletion solvent.

32. Product incorporating clean oriented multi-walled carbon nanotubes, received in the way, including: 1) preparation of the solution of multiwalled carbon nanotubes in solvent; in which the concentration of carbon nanotubes in solvent chosen so that the solution was in the liquid-crystalline state; 2) extrusion solution to obtain the extrudate; 3) evaporation solvent.

33. The product according to the clause 29, where during at least one stage of the exercise, the application of tensile load.

34. The product according to the clause 29, where the product is chosen from the group consisting of fibres, tapes, sheets and film.

35. The product according to the clause 29, in which multi-walled carbon nanotubes include double-walled carbon nanotubes.

36. The product according to .35, in which multi-walled carbon nanotubes have a length of up to about 10 mm

37. The product according to .35, in which multi-walled carbon nanotubes essentially free from defects.

38. The product according to paragraph 29, which solvent includes acid.

39. The product according to the clause 29, in which at least one coagulant choose from the group consisting of hexane, a simple ether diethyl (simple) ether, polyethylene glycol, dimethylsulfoxide, polyvinyl alcohol, water, sulfuric acid, dichloromethane, chloroform, , Triton-X capable of polymerization of monomers and their combinations.

40. The product according to .32, where evaporation of the solvent conduct by means of microwave heating.

41. The product according to .32, where evaporation of the solvent carried out in a vacuum.

42. The product according to .32 in which the extrudate passed through a tube filled with inert gas flow.

43. Way to seal the existing articles of carbon nanotubes, this method includes: processing pyrotechnic acid; and destruction of pyrotechnic acid; where an existing product of carbon nanotubes choose from the group consisting of fibres, matrices and carbon herrings».

44. The product according to the clause 29, in which the solution is extruded at least one coagulant without contact with the atmosphere.