Thermoelectric nanomaterials

FIELD: chemistry.

SUBSTANCE: melt or solution is prepared first, where said melt or solution contains at least one substrate material or corresponding precursor compounds of substrate material and at least one thermoelectrically active material or a precursor compound of thermoelectrically active material. Further, the melt or solution undergoes electroformation. Fibre which contains at least one substrate material and at least one thermoelectrically active material and a precursor compound of thermoelectrically active material is obtained. If necessary, the precursor compound of the thermoelectrically active material is converted to active form. The thermoelectrically active material contains at least one compound which contains at least one element selected from a group consisting of tellurium and boron, or the thermoelectrically active material is selected from a group consisting of antimonides, silicides, germanides, skutterudites, clathrates, bismuth, NaCo2O4, Bi2-xPbxSr2Co2Oy, where x=0-0.6 and y=8+σ, rod-like monocrystals based on Cu-Co-O or Bi-Sr-Co-O, mixtures of oxides of formula SrTiOmSn (I), where 0≤n≤0.2 and 2≤m≤2.99, Ca2Co2O5, NaCo2O4, Ca2Co4O9 and their mixtures. Disclosed also is a method of producing nanotubes, nanowire and nanotubes, as well as use of nanowire and nanotubes in thermoelectric temperature control, for generating current, in sensors and for controlling temperature.

EFFECT: production of nanowire and nanotubes of sufficient length and constant quality, which enables high-precision temperature control.

12 cl, 3 ex

 

The present invention relates to a method of manufacturing nanowires or nanotubes by electrotorture melts or solutions of suitable substrate materials, which contain the respective thermoelectric materials, nanowires and nanotubes, as well as the use of these nanowires and nanotubes for thermoelectric temperature control, for generating current in the sensors or to control.

In the field of thermoelectric energy conversion is of great importance to the search for new active materials with high efficiency. Properties of thermoelectric materials represent the so-called coefficient of q Z, often as a dimensionless quantity ZT. This dimensionless quantity is brought to maximum to get the highest possible efficiency.

ZT=S2σT/λS: Seebeck coefficient, µv/K
σ: electric conductivity, s/Cm
T: temperature in K
X: thermal conductivity, W/(m·K)

Since opening In12The3as material is particularly favorable for use in cooling, the maximum ZT value, which received more than 50 years ago, has not changed and amounts to about 1. Since ZT-value >2, thermoelectric system could compete with the conventional technique, for example for air conditioning. Areas and areas of use of thermoelectricity directly dependent on the value of ZT.

In nanostructured materials, quantum effects appear, which allow to separate the scattering of electrons and phonons, and thus reduce thermal conductivity and wide receiving electrical conductivity. Thus, this area is truly a classic ratio, based on the law of Wiedemann-Franz law which electrical conductivity is directly proportional to the conductivity, but with the restriction:

λ/σ=aTσ: electric conductivity, s/Cm
T: temperature, K
λ: thermal conductivity, In/(m·K)
a: the coefficient of proportionality

In theoretical observations debate about the one-dimensional structures, for example, of bismuth, the so-called nanowires, ZT-value with the value of ZT equal to 6. While we are talking about the wires with a diameter from about 10 nm.

Experimental work is this range of values is difficult in nature. Little is known of the methods of production of nanowires.

In "Physical Review Letters" (Review on physics, volume 88, No. 21, page from 216801-1 to 216801-4 describes a method for the production of bismuth nanowires. To do this, make rasplavlennyi bismuth under high pressure into the pores of the respective templates of Al2O3or silica gel. The thickness of the bismuth wires that can be produced this way, technologically limited quantities more than 40-50 nm. Next describe the method of production of nanowires with a diameter of 7 nm by steam separation on appropriate forms of silica. In this way the wires are also limited.

In "Thermoelectric Material 2003, Research and Applications" (Thermoelectric material. Research and application), page 3-14 describes a method for the production of nanowires with a diameter of 4-200 nm. These wires produce, precipitating in the form of nonconductive materials, such as Al2O3or SiO2such metals as bismuth, antimony and zinc. The division performed so that the metal is evaporated in a vacuum chamber, and corresponding pairs of metal deposited in the tubular channels forms.

In "Eur. J. Inorg. Chem., 2003", 3699-3702 describes a method for the production of gratings, in which the parallel is a certain amount of bismuth nanowires. To restore an aqueous solution BiCl3the powder is Inka. After removal of excess powder zinc remains black powder, which are parallel to each other are nanotubes of bismuth.

Overview today known methods of producing nanowires is presented in the "Adv. Mater. 2003", 15, No. 5, pages 353-389. In the described ways precipitated metals from the vapor phase to form the corresponding sizes of the porous material, contribute solutions or melts corresponding compounds optionally, under high pressure in these forms, or camaraderie nanoparticle nanowires or nanotubes.

In "Angew. Chem. 2004", 116, 1356-1367 describes a method for the production of nanotubes by wetting of templates appropriate form of solutions or materials which consist of nanotubes.

The disadvantage of these methods is that the alignment of the nanowires should remain forming the matrix. Therefore, it is impossible to get by known methods available nanowires experimentally useful length. The presence of the shaping matrix has a negative effect on thermal conductivity. Absolute attainable length of the nanowires is short, for example to 100 μm. Further deposition of material from the gas phase into very narrow channels can lead to blockage of the channels formed thereby nanowires will be impassable. Difficult communication to otka and arranged in a matrix of wires in order to test and use. In addition, it is difficult to monitor the number of really prokontaktirovat wires, and thereby the desired measurement results.

Polymer fibers with diameters in the nanometer range can be produced by electrotorture.

In Adv. Mater. 2004, 16, No. 14, pages 1151-1169 describes a method for the production of nanofibers by electrotorture a large number of appropriate materials, such as various polymers and copolymers, Al2O3, CuO, NiO, TiO2-SiO2V2O5, ZnO, Co3O4, Nb2O5Moo3and MgTiO3. For this metallizer spraying the melt or solution of the respective materials through small electrically charged jets, such as the tip of the syringe in the direction of the oppositely charged or grounded plate. In the electrostatic attraction of the charged molten or liquid stream is accelerated so strongly that narrows to the diameter of the nano-range. By that time, as the material gets to the opposite pole, the obtained solvent is evaporated or the melt is cooled so that hardens again. Thus, it is possible to obtain theoretically infinite thread diameter in the nano-range.

In DE 10116232 A1 describes the production process of the hollow fiber with an inner surface, the inner diameter is the Tr cavity or hollow fiber ranges from 100 to 500 nm. The length of the fiber produced in this way, ranges from 50 μm to several mm or see When using the method of electrotorture from a solution or melt of a first material selected from capable of splitting inorganic or organic materials, in particular polymers in the mixture with a second material selected from the catalytically active materials of groups Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb; Vb, VIb, VIIb and/or VIIIb of the Periodic table, produce a fiber with a diameter in the nanometer range. This fiber cover third is not capable of splitting the material. After elimination of the first capable of splitting the material in the appropriate manner to receive the hollow fiber of the third is not capable of splitting material, the inner surface of which is covered with the second catalytically active material.

The objective of the invention is to provide a method with which you can produce nanowires and nanotubes, which would contain at least one termoelektricheskii active material of sufficient length so that it was possible to eliminate the above disadvantages relative inconvenience in the use and communication. Another objective of this invention is to provide a simple and inexpensive way by which you can produce nanowires and nanotubes, which is held to be at least one termoelektricheskii active material in sufficient quantity and uniform quality.

The task is solved by means of the method of manufacturing nanowires by treating fibers containing at least one substrate material and at least one termoelektricheskii active material or compound, the precursor of one termoelektricheskii active material, including:

(A) preparing a melt or solution containing at least one substrate material or a suitable compound, the precursor to the substrate material and at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material

(B) electropermanent melt or solution of step (A), and receive fiber containing at least one substrate material and at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material

(C) optionally, coating the obtained fiber electrical insulator, and get electrically isolated fiber,

(D) optionally, converting the compound predecessor termoelektricheskii active material in the active form,

(E) optionally, removing the substrate material, and the steps (C)-(E) can be performed which, in any order.

The task is solved by method of production of nanotubes by treating fibers containing at least one substrate material and at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material, including:

(F) preparing a melt or solution containing at least one substrate material or a suitable connection, a predecessor of the substrate material,

(G) electropermanent melt or solution from step (F), and receive at least one fiber from the same substrate material,

(H) coating the fiber obtained in step (G)at least one termoelektricheskii active material or a compound predecessor termoelektricheskii active material, and get at least one substrate material and at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material

(I) optionally, coating the obtained fiber electrical insulator, and get electrically isolated fiber,

(J) optionally, converting the compound predecessor termoelektricheskii active material in the active form,

(K) optionally, removing the substrate material, the steps (I)to(K) can be performed in any sequence.

And method for the production of nanowires and method for the production of nanotubes include processing of fibers containing at least one substrate material and at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material.

Further more describes the individual steps.

Step (A).

Step (A) of the method of manufacturing nanowires of the present invention involves the preparation of a melt or solution containing at least one substrate material or suitable connections precursor material of the substrate and at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material.

In one preferred form of the substrate material is a polymer or a material obtained by Sol-gel method. In one particularly preferred form of the substrate material is a polymer. If the substrate material was produced using the Sol-gel method, the step (A) use the solution of the corresponding connection predecessor.

Suitable polymers in the production of nanofibres in this invention it is possible to use all known homopolymers and copolymers consisting of at least two different monomers, which can the be molded by way of electrotorture.

While preference is given to polymers selected from the group consisting of esters, polyamides, polyimides, ethers, polyolefins, polycarbonates, polyurethanes, natural polymers, polylactide, polyglycolide, poly-α-methylstyrene, polymethacrylates, polyacrylonitriles, latex, polyalkyleneglycol from ethylene oxide and/or propylenoxide and mixtures thereof. Particularly preferred among the polymers give polyactide or polyamide.

The polymer used in this invention can be obtained by a method known in the art, it is also present in the market.

If at step (A) production of nanofibres in accordance with this invention using the solution of the above polymers, the solution may contain any solvents or mixture of solvents, evaporating preferably at a temperature below 160°C., particularly preferably below 110°C under normal atmospheric pressure, which at least partially dissolve termoelektricheskii active materials or compounds predecessors.

In General, use a solvent from the group of chlorinated solvents, for example dichloromethane or chloroform, acetone, ethers, such as diethyl simple ether, methyl-tert.-butyl-simple ether, hydrocarbons having less than 10 carbon atoms, for example n-pentane, n-hexa is, cyclohexane, heptane, octane, dimethylsulfoxide (DMSO), N-methylpyrrolidinone (NMP), dimethylformamide (DMF), formic acid, water, liquid sulfur dioxide, liquid ammonia and mixtures thereof. As a solvent, it is preferable to use one of the group, which includes dichloromethane, acetone, formic acid and mixtures thereof.

The substrate material in this invention can be obtained and the Sol-gel method. For this phase (A) use a solution of candidate compounds, the precursors of the substrate material.

In the Sol-gel method, the production or the Department of materials begins with a liquid Sol state in which the Sol-gel transformation transforms into a solid gel state. As salts presents the dispersion of solid particles in the range between 1 nm and 100 nm, which are in water or an organic solvent in a finely dispersed state. Sol-gel methods, in General, begin with ash-based systems ORGANOMETALLIC polymers. The transition from liquid Zola to ceramic material is optionally through a gel state. During the Sol-gel transformation is 3-dimensional formation of the reticulated structure of the nanoparticles in the solvent, the resulting gel has the properties of a rigid body. The transformation of the gel into the ceramic material is in the control of the dummy processing on the air. This processing in this way is conducted during formation of the fiber. Suitable Sol-gel systems are called, for example, in "Sol-gel method, Gschmidt, Chemistry in our time, 35, 2001, No. 3, str-184".

At stage (A) of the method of manufacturing nanofibers in accordance with this invention are mixed above the substrate material with termoelektricheskii active material or compound precursor termoelektricheskii active material.

In one preferred form of termoelektricheskii active material contains at least one compound containing at least one element from the group consisting of tellurium, antimony, silicon, boron and germanium, and/or termoelektricheskii active material from the group consisting of oxides, skutterudites, clathrates and bismuth.

Examples of suitable oxides are the oxides of cobalt with a layered lattice NaCo2O4or Bi2-xPbxSr2Co2Oywith x= 0 to 0.6 and y=8+σ "Chemistry, Physics and materials Science of Thermoelectric Materials : Beyond Bismuth Tellurides" (Chemistry, physics and materials science of thermoelectric materials in addition to bismuth tellurides), Kluwer Academic/Plenum publishing, new York, 2003, pages 71-87. In addition, suitable filamentary crystals based on Cu-Co-O or Bi-Sr-With-O. In addition, as termoelektricheskii active materials on the OS is ove oxides are particularly suitable mixture of oxides of the General ormula (I)

with

- 0≤n≤0.2 and

- 2≤m≤2,99, in particular 2≤m≤2,5.

Suitable oxides are known from "R.Funahashi et al., Jpn. J.Appl. Phys.volume 39 (2000), for example Ca2Co2O5, NaCo2O4Ca2Co4O9.

Examples of suitable tellurides, tellurides are on the basis of bismuth telluride and lead, for example Bi2Te3or PbTe. Termoelektricheskii active materials on the basis of bismuth telluride or lead can be further legitamate. For suitable alloying elements from the 3rd or 5th main group of the Periodic system of elements in amounts known to the specialist. The process of doping the above mentioned compounds known to the expert.

An example of a suitable antimonide is Zn4Sb3. Preferably the antimonides use the average temperature range, i.e. at temperatures from 100 to 400°C.

Examples of suitable silicides are FeSi2and their modifications. On the basis of its special stability of the silicide is preferably used in the space program.

Examples of suitable borides are In4And SAV6or SrB6and their modifications. Suitable borides can be legitemate the corresponding elements. For suitable alloying elements selected from the 3rd or 5th main group of the Periodic system ELEH the clients in quantities well-known specialist.

The borides are characterized by low density. Therefore they are preferably used where low density termoelektricheskii active materials.

An example of a suitable germanica are molten silicon/germanium. These melts are particularly preferably used in the field of high temperatures, i.e. temperatures above 500°C.

Examples of suitable skutterudites disclosed in "Chemistry, Physics and materials Science of Thermoelectric Materials (Chemistry, physics and materials science of thermoelectric materials), Kluwer Academic/Plenum publishing, new York, pages 121-146, for example, CoSb3, FeO, 5NiO, 5Sb3.

Examples of suitable clathrates are disclosed in "the Chemistry, Physics and materials Science of Thermoelectric Materials (Chemistry, physics and materials science of thermoelectric materials), Kluwer Academic/ Plenum publishing, new York, pages 107-121, for example, type I: X2E46for example Sr8Ga16Ge30or type II: X8Y16E136for example Cs8Na16Si136Cs8Na16Ge136.

In the preferred form of the present termoelektricheskii active material selected from the group of bismuth, Bi2Te3, PbTe, and mixtures thereof.

Termoelektricheskii active materials used in this invention, produce a well-known specialist methods and are commercially available.

On stage (And method of the present invention in the melt or solution termoelektricheskii active materials can be made as such or in the form of suitable compounds predecessors. As compounds, the precursors are all considered compounds, complexes or mixtures, which can be converted by chemical and/or physical methods in termoelektricheskii active materials.

In a preferred form of execution of the connection predecessor termoelektricheskii active material is a salt or complex termoelektricheskii active materials.

At stage (A) can be prepared, at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material, at least one substrate material or the corresponding connection-the precursor of the substrate material in solution or in the form of a melt.

To obtain a solution, at least one termoelektricheskii active material or compounds of the predecessor termoelektricheskii active material and at least one of the substrate material or the appropriate connection, a predecessor of the substrate material, preferably at least one polymer, it is possible to use all known specialist methods. You can mix a solution of at least one substrate material with a solution termoelektricheskii active material or compounds of the predecessor, and you can use one or various solvents, wybran the e already formerly known as the group of solvents or mixtures. Mixing can be carried out with stirring, under the influence of ultrasound or heat. Suitable reactors are known to the specialist. The concentration of the at least one polymer in the solution is, in General, at least 0.1 wt.%, preferably 1-30 wt.%, particularly preferably 2-20 wt.%. The ratio of the mass termoelektricheskii active substances or compounds predecessor termoelektricheskii active substance to the weight of the polymer is, in General, up to 10:1, preferably from 1:1 to 3:1.

If at step (A) use the melts, you can get all the well-known specialist of ways. For example, by heating to a temperature above the melting temperature or the glass transition temperature of the polymer or polymer mixture, preferably at least 10°C., particularly preferably at least 30°C., most preferably at least 50°C above the melting temperature. Rapevine in a preferred form of execution carried out under reduced pressure or in a protective gas atmosphere, predpochtitelno in the atmosphere containing nitrogen and/or inert gas, such as argon.

If the substrate material in step (A) of the method of this invention uses the polymer, termoelektricheskii active substance or compound, the precursor termoelektricheskii actively what about the agent may be covalently attached to the polymer chain. Polymers that detect covalently linked termoelektricheskii active substances or their compounds predecessor, can be obtained by polymerization of monomers with which the substances are linked covalently. The advantage of this method is that termoelektricheskii active substance or compound, the precursor is particularly uniformly distributed along the polymer, and thereby the fiber. Suitable methods are described, for example, in J. Am. Chem. Soc. 1992, 114, 7295-7296, Chem. Mater. 1992, 4, 24-27 and Chem. Mater. 1992, 4, 894-899.

Step (B).

The step () method of production of nanowires of the present invention includes electropermanent melt or solution of step (A), and receive fiber containing at least one substrate material, preferably at least one polymer, and at least one termoelektricheskii active material or a single connection-predecessor termoelektricheskii active material.

The process of electrotorture known to the expert, for example, from Adv. Mater. 2004, 16, No. 14, pages 1151-1169. For this, in General, the solution or the melt obtained in step (A) of the method of the present invention, is pumped through a thin nozzle with an electric charge, so the result is a thin beam from a solution or melt. Instead of nozzles can be used and the specification of the sheet, geometric shapes. The apparatus used for molding, in addition to the nozzle, includes manifold with the opposite charge or ground, depending on the nozzle, so that the beam is compressed through the nozzle is drawn by the collector. In General, the voltage is 5 kV to 100 kV, preferably from 10 kV to 50 kV. A suitable distance between nozzle and collector known to the specialist. Through the resulting electric field of the dispersed particles in the beam from a solution or melt, so that the beam is reduced in diameter, as a result of this acceleration, so much that its diameter is in the nanometer range. The collector, in General, are designed in such a way that the nanowires, the liquid in the evaporation of the solvent or cooling to a temperature below the melting temperature, it is possible to walk or take the appropriate method.

If at step (A) use raplab polymer, the temperature of the melt is in front of the exit from the die, at least 10°C., preferably at least 30°C., particularly preferably at least 50°C above the melting temperature or, respectively, TGused Homo - or copolymer.

In the result of electrotorture receive fiber containing at least one substrate material, preferably, at least one polymer, and at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material.

For electrophoretogram can follow the stages of washing or cleaning accordingly. In General, the purification of the obtained fiber is not necessary.

In the result of electrotorture obtained in step (A) solution or melt containing at least one substrate material or a suitable compound, the precursor and at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material, the step (C) of the method of the present invention receive a fiber containing at least one substrate material, preferably a polymer and at least termoelektricheskii active material or compound, the precursor termoelektricheskii active material.

The length of the fiber obtained in step (C), not fundamentally limited. The continuous process allows to obtain the fiber of any length.

In a preferred form of execution received nanovolume wound on the drum. If the drum across the full width covered at least once by nanowalker completely, the molding process can be interrupted, and nanovolume can be cut vertically relative to the fiber and along the drum so that the floor is moved parallel arrangement of multiple nanofibers, the length of which corresponds to the circumference of the drum.

In another preferred form of execution instead of a drum, you can use a metal frame on which is wound the obtained fiber. In this form of execution is automatically derived a parallel arrangement of fibers. Such behavior is described, for example, in "R.Dersch et al., J. polim. Sei. Part A: Pol. Chem.", volume 41, 545-553, 2003.

The thickness of the individual fibers obtained in step (B)is less than 200 nm, more frequently less than 50 nm, most often less than 20 nm.

Step (C).

An optional step (C) of the method of manufacturing nanowires of the present invention includes the coating of the fibers obtained in step (B), an electric insulator, and get electrically isolated fiber.

To cover nanofibres containing at least one substrate material, preferably a polymer, and at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material, it is possible to use any known specialist methods.

For example, deposition from the gas phase, ion sputtering, coating by centrifugation, coating by dipping, spraying or the separation of plasma. It is preferable to apply a non-conductive material by impregnation or spraying nanofibres from step (C) with a solution of the sludge is respectively in a solution of an electrically non-conductive material and subsequent removal of solvent, for example, by heating, if necessary, under reduced pressure. As a suitable solvent, any solvent that dissolves electrically non-conductive material, but which is poorly soluble, at least one substrate material prepared in step (A).

At the stage (C) of the method of the present invention can be used with all electric insulators known to the expert.

In one preferred form of the electrical insulator is selected from aromatic and aliphatic Homo - and copolymers and mixtures thereof.

If the electrical insulator is used Homo - or copolymer, the material can be applied to nanovolume from step (C) also so that the corresponding monomers were polymerizability in the presence of the fibers so that the fiber was separated polymer or copolymer, obrazovavshijsya in the right place.

Particular preferred are polymers or copolymers of the group, which includes poly(p-xylylene), polyacrylamide, polyimides, polymers of esters, polyolefins, polycarbonates, polyamides, polyethers, polyfamily, polysilane, polysiloxane, polybenzimidazole, polybenzimidazole, polyoxazole, polysulfides, polyetherimide, polyacrilonitrile, polylactide, polyetherketone, polyurethanes, polysulfones, moceri, the polyacrylates, silicones, fully aromatic sobolifera, poly-N-vinyl pyrrolidone, polyhydroxyethylmethacrylate, polymethylmethacrylate, polyethylene terephthalate, polybutyleneterephthalate, polymethacrylates, polyacrylnitril, polyvinyl acetate, neoprene, Buna N, polybutadiene, polyterephthalate, modified or unmodified cellulose, alginates or collagen, their Homo - or copolymerizate and mixtures thereof.

These polymers can be obtained by methods known to the expert, or commercially available.

Especially preferred electric insulator poly(p-xylylene) or polyterephthalate.

The electrical insulator is applied to the fiber preferably by deposition from the gas phase.

In the framework of this invention, the coating indicates that the fiber obtained in step (B), concluded, at least 70%, preferably at least 80%, especially preferably at least 90% in electric insulator.

If optional step (C) of the method of the present invention is not carried out, the result of the method of the present invention receive nanowires electrically isolated from the external side.

Step (D).

An optional step (D) of the method of this invention involves the conversion of compounds predecessor termoelektricheskii active material in the active form is.

Step (D) of the method of this invention should be in the if stage (A) use a connection-predecessor termoelektricheskii active material in the mixture, at least one polymer.

The conversion of compounds of the predecessor in termoelektricheskii active form can be made in all well-known specialist of ways.

If the complex termoelektricheskii active material is in oxidation state 0, it can convert any popular specialist way into a free, complexional termoelektricheskii active material. An example is the transformation of these complexes of other metals or metal cations, forming a complex ligands termoelektricheskii active material of a stable complex as the corresponding complex termoelektricheskii active material.

If the compounds predecessors termoelektricheskii active material used salts or complexes, in which termoelektricheskii active material is in a higher oxidation state, connections precursor can be converted to termoelektricheskii active material with the help of recovery. Recovery may be electrochemical or liquid-chemical way. Suitable reducing agents ablauts the hydrides, base metals such as zinc and hydrogen, and restoration of connections predecessors termoelektricheskii active compounds with gaseous hydrogen is way preferable in the method of this invention.

In one of the most preferred forms of execution of the method of manufacturing nanowires of the present invention in step (A) as a connection predecessor termoelektricheskii active compounds using salt of bismuth, particularly preferably of trichloride bismuth. These bismuth compounds can be converted by restoring with hydrogen in termoelektricheskii active material bismuth.

Recovery, in General, carried out by a method known to the expert, preferably in pure hydrogen at a temperature of at least 250°C, and for long, taking at least 20 minutes

Step (E).

An optional step (E) includes removing the substrate material, preferably a polymer, which is used in step (A).

Methods appropriate for removal of the substrate material, preferably a polymer known to the specialist. Called, for example, thermal, chemical, radiation, biological, photochemical methods, and methods using plasma, ultrasound, hydrolysis or extraction with a solvent. Preferred are solvent extraction, or heat treatment of the mechanical decomposition. The decomposition takes place depending on the material under conditions of 10-500°C and 0.001 mbar to -1 bar. The removal can be performed fully or partially, at least 70%, preferably at least 80%, especially preferably at least 90%.

Removing the substrate material get nanowires composed exclusively or in part (as indicated above) from termoelektricheskii active material.

According to this invention it is possible not to remove the substrate material added in step (A), so it nanowires, which, along at least one termoelektricheskii active material contains at least one substrate material, preferably at least one polymer.

Steps (C), (D) and (E) are optional, i.e. of the three phases may be one, two, or all three.

In addition, the sequence of steps (C), (D) and (E) can be any. This means that, for example, after step (C) can be performed step (C), (D) and/or (E).

Different sequence of steps (C), (D) and (E) may be based on the fact that a variety of substrate materials and/or termoelektricheskii active materials require different sequences of these stages of the process. For example, it may be desirable to remove the substrate material according to the phase of the (E) before coating electrical insulator (step (C)) fiber, obtained in step (B). In addition, it is possible to convert compounds of the predecessor termoelektricheskii active material (step (D)) after removal of the substrate material (step (E)).

In a preferred form of execution of the steps of the method of manufacturing nanowires of the present invention is carried out in sequence (A), (B), (C), (D), (E).

The invention also concerns the method of production of nanotubes by processing fiber containing at least one substrate material and at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material including:

(F) preparing a melt or solution containing at least one substrate material or the corresponding connection-the predecessor of the substrate material,

(G) electropermanent melt or solution of step (F), and fiber receive at least one substrate material,

(H) coating the fiber obtained in step (G)at least one termoelektricheskii active material or a precursor termoelektricheskii active material, and receive fiber containing at least one substrate material and at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material is,

(I) optionally, coating the obtained fiber electrical insulator, and get electrically isolated fiber,

(J) optionally, converting the compound predecessor termoelektricheskii active material in the active form,

(K) optionally, removing the substrate material, the steps (I)to(K) can be performed in any order.

Steps (F)through(K) of the method of production of nanotubes of the present invention described in more details below.

Step (F).

Step (F) method of production of nanotubes of the present invention includes the preparation of a melt or solution containing at least one substrate material or the corresponding connection-the predecessor of the substrate material.

In a preferred form of execution the substrate material is a polymer material obtained by the Sol-gel method. In a particularly preferred form of execution the substrate material is a polymer. If the material of the substrate produced using the Sol-gel method, the step (F) using the solution of the corresponding connection predecessor.

On the stage (F) method of production of nanotubes of the present invention can use the same substrate materials, preferably polymers, and solvents, as in stage (A) of the method of manufacturing nanowires of this image is the shadow. Especially preferred Homo - and copolymers. The most preferred polymer, such as polylactic or polyamide.

The solution or melt containing at least one substrate material or relevant relationship, the predecessor of the substrate material, can be obtained by any means known to the expert.

To obtain a solution or melt containing at least one substrate material, really said relative phase (a) proposal production of nanowires of the present invention. When using the polymer, the concentration of at least one polymer in the solution is, in General, at least 0.1 wt.%, preferably 1-30 wt.%, particularly preferably 2-20 wt.%.

Step (G).

Step (G) of the method of production of nanotubes of the present invention includes electropermanent melt or solution from step (F), and the fiber is at least one of the substrate material.

The process of electrotorture known to the expert, for example from Adv. Mate." 2004, 16, No. 14. str-1169.

Regarding electrotorture has the force of what has been said with regard to stage (b) a method of production of nanowires of the present invention, with the difference that in step (G) is molded fiber containing at least one substrate material.

For electrophoretogram in step (G)can follow if necessary, the steps of washing and cleaning. In General, the purification of the obtained fiber is not necessary.

The length of the fiber obtained in step (G), not fundamentally limited. Using the continuous method, you can get the fiber of any length.

In one preferred form of the obtained nanovolume is wound on the drum. If the total width of the drum, at least once covered by nanowalker, the molding process can be interrupted, and nanovolume can be divided vertically relative to the fiber and along the drum, so it's a parallel arrangement of multiple nanofibers, the length of which corresponds to the circumference of the drum.

In another preferred form of execution instead of a drum can also be used a metal frame on which is wound made fiber. In this method of manufacturing a parallel arrangement of fibers occurs automatically. Such method steps are described, for example, in R.Dersch et al., J. of Polym. Sci. Part A: Pol. Chem., volume 41, 545-553, 2003.

The thickness of the individual fibers obtained in step (G)is less than 200 nm, preferably less than 50 nm, particularly preferably less than 20 nm.

Step (H).

Step (H) of the method of production of nanotubes of the present invention includes the coating of the fiber obtained in step (G)at least one tervalent the automatic active material or a precursor termoelektricheskii active material, and receive fiber containing at least one substrate material and at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material.

The coating of the fiber obtained in step (G)at least one termoelektricheskii active material or a precursor termoelektricheskii active material can be any well-known specialist way.

The coating of the fiber obtained in step (G), can be produced, for example, by vapor deposition, sputtering, coating by centrifugation, coating by dipping, spraying or separation of plasma. Preference is given to coating by deposition from the gas phase.

About appropriate termoelektricheskii active materials or compounds, the precursors of termoelektricheskii active material has the force of what was said for stage (A) of the method of manufacturing nanowires of the present invention.

In the method of manufacturing nanotubes as termoelektricheskii active material with special preference to use bismuth.

In the framework of this invention, the coating indicates that the fiber obtained in step (H), make at least 50%, preferably at least 80%, especially preferably, at the very the least, 90%, at least one termoelektricheskii active material or the connection predecessor termoelektricheskii active material.

Step (H) of the method of production of nanotubes in General may also include the steps of washing and cleaning coated fiber. In one preferred form of flushing and cleaning is not performed.

The thickness of the layer applied to the fiber in step (H)comprising at least one termoelektricheskii active material or compounds predecessor, in General, ranges from 1 nm to 100 nm, preferably from 5 nm to 30 nm.

At the step (H) of the method of production of nanotubes of the present invention receive a fiber containing at least one substrate material coated with one layer termoelektricheskii active material or compounds predecessor termoelektricheskii active material.

Step (I).

An optional step (I) of the method of production of nanotubes of the present invention includes coating the obtained fiber electrical insulator, and the result is electrically isolated fiber.

Regarding the coverage of the electrical insulator has the force of what was said on stage (C) the production process of the nanowires of the present invention.

To cover nanofibres obtained in step (H), containing at least the Dean of the substrate material, preferably, at least one polymer, and at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material, and termoelektricheskii active material or compound, the predecessor of the covers as the outer layer of nanovolume at least one polymer, it is possible to use any known specialist methods.

It is preferable to apply an electric insulator on the fiber by deposition from the gas phase.

Particularly preferable to use poly(p-xylylene) or polytetrafluoroethylene as an electrical insulator.

If optional step (I) does not hold, the result is the nanotube is electrically isolated from the external side.

Step (J).

An optional step (J) of the method of production of nanotubes involves the conversion of compounds of the predecessor termoelektricheskii active material in the active form.

Regarding the conversion of compounds of the predecessor termoelektricheskii active material in termoelektricheskii active material force has already said step (D) the production process of the nanowires of the present invention.

An optional step (J) should only be considered if at step (H) on the fiber of step (G) caused connection-previous what nick termoelektricheskii active compounds. If at step (H) on the fiber caused termoelektricheskii active material, step (J) can be omitted.

If at step (H) on the fiber caused salt termoelektricheskii active material, in the form of the production stage (J) hold.

Step (K).

An optional step () method of production of nanotubes of the present invention includes removing the substrate material, preferably a polymer. If step (K) does not hold, the result of the method of the invention, receive nanotubes filled with substrate material.

Regarding the removal of substrate material in step (K) the method of production of nanotubes of the present invention has the force of what has been said step (E) of the production process of the nanowires of the present invention.

In General, the substrate material preferably is removed in step (C) at least 30%, preferably at least 50%, especially preferably at least 70%.

In one preferred form of substrate material removed by solvent extraction. In General, you can use any solvents or solvent mixtures, well-dissolving material of the substrate used in step (F), but which do not dissolve electric insulator, which deal, respectively, at stage (I).

The nanotube has a diameter of less than 200nm, preferably less than 50 nm, particularly preferably 20 nm, with wall thickness less than 20 nm, preferably less than 10 nm and a length of at least 1 mm, preferably at least 10 mm, particularly preferably at least 100 mm tube Length is not limited by reason of the continuity of the process.

Stages (I), (J) and (K) can be performed in any sequence. In one preferred form of execution of the steps (I), (J) and (K) is carried out in sequence (I), (J), (K).

The present invention relates to nanowires containing at least one termoelektricheskii active material, with a diameter of less than 200 nm, preferably less than 50 nm, particularly preferably less than 20 nm, and a length of at least 1 nm, preferably at least 10 mm, particularly preferably at least 100 mm

The invention also concerns nanotubes containing at least one termoelektricheskii active material with a diameter less than 200 nm, preferably less than 50 nm, particularly preferably 20 nm, a wall thickness of less than 20 nm, preferably less than 10 nm, and a length of at least 1 mm, preferably at least 10 mm, particularly preferably at least 100 mm

The invention also concerns the use of nanowires or nanotubes of the present invention for thermoelectric termostatico the tion, for the current generation, sensors, remote communication or for temperature control.

Examples of sensors are CCD sensors, gas sensors, sensors based on semiconductor modules or the CPU.

Examples of thermoelectric temperature control system are heating, additional heating systems, installation of air-conditioning.

The advantage of using the temperature control using nanowires and/or nanotubes of the present invention is that they allow high-precision temperature regulation. In addition, this temperature regulation is very fast and accurate.

Examples of use in generating power are heated by burning fossil fuels, such as coal, oil, natural gas or wood, and the catalytic debinding, using waste heat or the sun. While heating the nanowires or nanotubes in the ways specified above using termoelektricheskii active material in the nanowires or nanotubes produced electric current.

Measurement of nanowires or nanotubes to test or use can be made in all well-known specialist ways or methods.

Examples.

Example 1.

Production of n is Notebok.

As a template for bismuth tubes are electrogalvanize RA fiber.

The receiving fiber.

Is formed into a solution of m/m 15% RE in formic acid (R.A. 98-100%). The molding is produced from polyethylene syringe with a metal cannula (⌀ 0.6 mm) aluminum roller with a diameter of 155 mm, rotating at a speed of 3500 rpm/min Applied voltage is +22 kV on the cannula against -2 kV on the platen (in each case relative to the earth) at a distance of cannula/roller approximately 60 mm (electric field strength E=400 kV/m). Pull syringe is provided so that the cannula of the syringe in there was always a solution.

For best receive fibers on the roller, on which is wound fiber, or put aluminum film or PE film. To get a good separation of the fiber from the film, it is necessary to separate multiple layers. For this, the duration of molding must be at least 15 to 30 minutes Deposited film with fiber are separated in a direction transverse to the roller. Thus, the receive fiber length of about 487 mm

Gaseous deposition of bismuth layer.

Fiber is a thin layer is removed from the film and put in a brass holder approximately 25×25 mm2.

Thermal spraying occurs in the resistive napylitel, and the sample is applied to approximately 150 mm above the molybdenum boat with itlal is authorized bismuth Wren. Molybdenum boat rotates during deposition speed of about 20 rpm around an axis in the direction of the fiber, the coating is controlled thickness using a quartz resonator. To obtain a uniform coating, spraying, produce very small batches of about 1-2 nm in minutes

Example 2.

The production of nanowires by Platania Bi-salts.

Production of poly-D,L-lactide/BiCl3nanofibers.

These include the solution of m/m 11% PDLLA/16,5% BiCl3in acetone. The molding is produced from polyethylene syringe with a metal cannula (⌀ 0.45 mm) on a rotating aluminum platen (⌀ 155 mm, 3500 rpm). The applied voltage is +13 kV on the cannula of the syringe against -2 kV on the platen (in each case relative to the earth) at a distance of cannula/roller approximately 60 mm (electric field strength E=250 kV/m). Craving to pick up the syringe so that the tip of the cannula was always the solution.

For best receive fibers on the roller causing PE film, which separates the fibers. To get a good separation of the fiber from the film, it is necessary to distinguish several layers of threads. For this, the duration of molding must be at least 10 to 20 minutes Deposited film with fiber are separated in a direction transverse to the roller. Thus, the receive fiber length of about 487 mm

alpraxolam floor.

The coating is carried out by vapor deposition on Gorgea, and use the device firm "Speciality Coating Systems" SCS (Labcoater®1, Parylene Deposition Unit Model PDS 2010), which presents on the market. As the source material is [2,2]-paracyclophane. The monomer is evaporated at temperatures up to 175°C and subjected to pyrolysis at 650°C in quinodimethane. Then at a maximum pressure of 55 mbar and a temperature of less than 30°C separates / polymerization film on the fiber.

To cover the fiber is wound on a metal frame so that they are on all sides remained open and accessible. In this way, to obtain a layer thickness of approximately 250 nm, 500 mg of monomer.

PTFE coating.

The floor is the technology of ion sputtering. From the camera ion sputtering pump gas, to obtain a pressure of 10-6mbar, and then go to start the plasma (pressure rises to approximately 10-3mbar). PTFE target (approximately ⌀ 50 mm) is a distance of about 50-60 mm from the sample fiber. Fiber pull in a brass holder approximately 25×25 mm2and rotate with the frequency of the cleaning units can 15 rpm around an axis in the direction of the fiber. The separation step is carried out with about 5 nm/min (measured with a quartz crystal).

Restore to metal is one bismuth.

The recovery is carried out in a tubular furnace using device management can start temperature apparel device. The program includes three segments: heating (30 min up to 260°C), heat treatment (20 min at 260°C), cooling (approximately 30 min until the temperature), the cooling is slower than the running of the furnace and depends on environmental conditions. Before starting the recovery sample vacuum in a tube furnace (about 0.1 mbar), and then pour hydrogen, during the recovery process through the sample continuously pass a small amount of hydrogen (about 5 ml/min).

Recovery of the metal bismuth with the subsequent removal PDLLA fibers having across-section of the structure of the nucleus.

For this there are 5 segments: heating (30 min up to 260°C), heat treatment (20 min at 260°C), heating (10 min to 270°C), heat treatment (5 h at 270°C), cooling (30 min to room temperature), the cooling is slower than that provided by the control system of the furnace and depends on environmental conditions.

Before you restore the sample vacuum in a tube furnace (about 0.1 mbar) and then pour hydrogen during recovery through the sample continuously spend a small amount of hydrogen (about 5 ml/min).

While under the roar of up to 270°C switch on protective gas (argon), carry out the washing and then vaccum, so that during the subsequent tempering process applied pressure of approximately ≤0.5 mbar.

Example 3.

The production of nanowires by Platania Bi-particles.

Production of Bi nanoparticles.

The production takes place in an argon atmosphere.

In the vessel for mixing lay 25 mmol of sodium hydride NaH, Tegaserod and washed twice with absolute tetrahydrofuran THF, then add 20 ml of THF and heated to 65°C. Add 10 mmol tert-butanol in 5 ml of THF and some time the suspension is stirred. With vigorous stirring (immediately) add 5 mmol melkopomolotogo BiCl3and the solution for half an hour left at 65°C. Immediately after addition of the solution begins to change color to black. After that, the solution is cooled to room temperature and add 20 ml of absolute THF, are left to mix overnight and rotate. Remains black powder that, when viewed under the microscope represents the particle size is about 5 nm.

Production of poly-D,L-lactide/Bi anovulatory

Is formed into a solution of m/m 4% PDLLA/4% Bi particles in dichloromethane. Molding comes from RE syringe with a metal cannula (⌀ 0.45 mm) on a rotating aluminum platen (⌀ 155 mm, 3500 rpm). The applied voltage is +13 kV on the cannula of the syringe against -2 kV on the platen (in each SL is tea in relation to the earth) at a distance of cannula/roller approximately 60 mm (electric field strength E=250 kV/m). Craving to pick up the syringe, respectively, so that the cannula of the syringe was always the solution.

For best receive fibers on the roller causing PE film, which separates the fibers. To ensure a good separation of fibres from the film, it is necessary to divide some of the provisions. This occurs at least during one molding 10 to 20 minutes Deposited film with a fiber cut transversely of the platen. Thereby obtain a fiber length of about 487 mm

Remove PDLLA fibers having across-section of the structure of the nucleus.

There are 3 segments: heating (30 min to 270°C), heat treatment (5 h at 270°C), cooling (30 min to room temperature), the cooling is slower than that provided by the control system of the furnace and depends on environmental conditions.

Before the beginning of the program vaccum tube furnace, so that during the whole program the applied pressure is approximately ≤0.5 mbar.

1. Method for the production of nanowires by treating fibers containing at least one substrate material and at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material including:
(A) preparing a melt or solution containing at least one substrate material or relevant relationship-preaches the cursors of the substrate material and, at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material,
(B) electropermanent melt or solution of step (A), and receive fiber containing at least one substrate material and at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material, (D) optionally, converting the compound predecessor termoelektricheskii active material in the active form,
and termoelektricheskii active material contains at least one compound containing at least one element selected from the group consisting of tellurium and boron, or termoelektricheskii active material selected from the group consisting of antimonides, silicides, germanides, skutterudites, clathrates, bismuth, NaCo2O4Bi2-xPbxSr2Co2Oywhere x=0-0,6 and y=8+σ, single crystal rod forms based on Cu-Co-O or Bi-Sr-Co-O, mixtures of the oxides of the formula (I)

where
0≤n≤0.2 and 2≤m≤2,99,
Ca2Co2O5, NaCo2O4Ca2Co4O9and mixtures thereof.

2. Method for the production of nanotubes by treating fibers containing at least one substrate material and at least one termoelektricheskii the active material or compound, the precursor termoelektricheskii active material, including:
(F) preparing a melt or solution containing at least one substrate material or the corresponding connection-the predecessor of the substrate material,
(G) electropermanent melt or solution from step (F), and receive fiber containing at least one substrate material,
(H) coating the fiber obtained in step (G)at least one termoelektricheskii active material or a precursor termoelektricheskii active material, and receive fiber containing at least one substrate material and at least one termoelektricheskii active material or compound, the precursor termoelektricheskii active material,
(J) optionally, converting the compound predecessor termoelektricheskii active material in the active form, and termoelektricheskii active material contains at least one compound containing at least one element selected from the group consisting of tellurium, antimony, silicon and germanium and/or termoelektricheskii active material selected from the group consisting of cobalt oxides with a layered lattice, the single crystal rod forms based on Cu-Co-O and Bi-Sr-Co-O, mixtures of the oxides of the formula (I)

where
0≤n≤0.2 and 2≤m≤2,99,
Ca2Co2O5, NaCo2O4Ca 2Co4O9, borides, skutterudites, clathrates and bismuth.

3. The method according to claim 1 or 2, characterized in that the substrate material is a polymer or a material obtained by Sol-gel method.

4. The method according to claim 3, characterized in that the polymer is polylactide or polyamide.

5. The method according to one of claims 1 or 2, characterized in that the connection predecessor termoelektricheskii active material is a salt or complex termoelektricheskii active material.

6. The method according to one of claims 1 or 2, characterized in that termoelektricheskii active material selected from the group consisting of bismuth, Bi2Te3, PbTe, and mixtures thereof.

7. The method according to one of claims 1 or 2, characterized in that the electrical insulator selected from the group consisting of aromatic and aliphatic Homo - and copolymers and mixtures thereof.

8. The method according to claim 7, characterized in that the electrical insulator are poly-para-xylylene or polytetrafluorethylene.

9. Nanowires containing at least one termoelektricheskii active material, with a diameter of less than 200 nm and a length of at least 10 mm, and termoelektricheskii active material contains at least one compound containing at least one element selected from the group consisting of tellurium and boron, or termoelektricheskii active mA is Arial selected from the group consisting of antimonides, silicides, germanides, skutterudites, clathrates, bismuth, NaCo2O4Bi2-xPbxSr2Co2Oywhere x=0-0,6 and y=8+σ, single crystal rod forms based on Cu-Co-O and Bi-Sr-Co-O, mixtures of the oxides of the formula (I)

where
0≤n≤0.2 and 2≤m≤2,99,
Ca2Co2O5, NaCo2O4Ca2Co4O9and mixtures thereof.

10. Nanotubes containing at least one termoelektricheskii active material, with a diameter of less than 200 nm, with wall thickness less than 30 nm and a length of at least 1 mm, and termoelektricheskii active material contains at least one compound containing at least one element selected from the group consisting of tellurium, antimony, silicon and germanium and/or termoelektricheskii active material selected from the group consisting of cobalt oxides with a layered lattice of the single crystal rod forms based on Cu-Co-O and Bi-Sr-Co-O, mixtures of the oxides of the formula (I)

where
0≤n≤0.2 and 2≤m≤2,99,
Ca2Co2O5, NaCo2O4Ca2Co4O9, borides, skutterudites, clathrates and bismuth.

11. The use of nanowires according to claim 9 for thermoelectric temperature control, for generating current in the sensors or to control the temperature.

12. The use of nanotubes is about 10 for thermoelectric temperature control, to generate current in the sensors or to control the temperature.



 

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3 cl, 3 dwg

FIELD: production of complex chemical filaments.

SUBSTANCE: method involves producing by known method of filament with linear density of 0.05-0.17 tex by wet or dry-wet forming and winding onto winder with winding being combined with twisting operation; after forming and twisting processes, unwinding filaments from winder and joining into yarn with following stretching, finishing, drying and winding onto bobbin. Yarn may include from 5 to 30 filaments with linear density of 5-200 tex. Each of filaments from which yarn is composed is preliminarily stretched during forming procedure. Method allows complex chemical filaments with lower linear density to be produced.

EFFECT: stabilized process for manufacture of thin chemical filaments with reduced linear density and improved quality of filaments.

4 cl, 2 dwg, 5 ex

FIELD: production of complex chemical filaments.

SUBSTANCE: method involves producing by known method of filament with linear density of 0.05-0.17 tex by wet or dry-wet forming and winding onto winder with winding being combined with twisting operation; after forming and twisting processes, unwinding filaments from winder and joining into yarn with following stretching, finishing, drying and winding onto bobbin. Yarn may include from 5 to 30 filaments with linear density of 5-200 tex. Each of filaments from which yarn is composed is preliminarily stretched during forming procedure. Method allows complex chemical filaments with lower linear density to be produced.

EFFECT: stabilized process for manufacture of thin chemical filaments with reduced linear density and improved quality of filaments.

4 cl, 2 dwg, 5 ex

FIELD: production of complex chemical filaments.

SUBSTANCE: method involves producing by known method of filament with linear density of 0.05-0.17 tex by wet or dry-wet forming and winding onto winder with winding being combined with twisting operation; after forming and twisting processes, unwinding filaments from winder and joining into yarn with following stretching, finishing, drying and winding onto bobbin. Yarn may include from 5 to 30 filaments with linear density of 5-200 tex. Each of filaments from which yarn is composed is preliminarily stretched during forming procedure. Method allows complex chemical filaments with lower linear density to be produced.

EFFECT: stabilized process for manufacture of thin chemical filaments with reduced linear density and improved quality of filaments.

4 cl, 2 dwg, 5 ex

FIELD: production of synthetic materials from thermoplastic substances and mixtures thereof, including high-quality commercial raw material and various kinds of municipal and industrial wastes of thermoplastic materials.

SUBSTANCE: apparatus has rotating hollow reactor made in the form of hollow toroid with outer and inner shells having spherical upper parts. Such construction provides reduced heating of reactor. Spinneret is mounted inside reactor on its shaft. Fibrous materials produced by means of apparatus may be used for manufacture of sorbents for catching of oil or oil products from water.

EFFECT: simplified construction, enhanced reliability in operation, reduced heat losses and improved quality of filaments.

16 cl, 4 dwg

FIELD: chemical industry; method of production of extruded cellulose continuously molded bodies.

SUBSTANCE: the invention presents a method of production of extruded cellulose continuously molded bodies from a spinning solution consisting of cellulose, water and tertiary aminoxide. To improve textile properties of extruded continuous molded bodies, as compared with existing level of engineering, the invention provides, that between an extrusion aperture of the die and the product removal device the continuous molded body is transported by a conveyor practically without stretching. At that it is preferable, that the speed of the intermediate conveyor motion should be less than the speed of extrusion and the speed of the product removal device. Due to these measures it is possible to improve considerably such textile properties as strength in a loop and a tendency to fibrillation.

EFFECT: the invention ensures improvement of textile property of extruded continuously molded bodies such as strength in a loop and a tendency to fibrillation.

34 cl, 5 dwg

FIELD: production of synthetic materials from thermoplastic substances and mixtures thereof, including high-quality industrial wastes, and also various kinds of domestic and industrial thermoplastic material wastes, in particular, may be used for producing of sorbents for catching of petroleum and petroleum products from water.

SUBSTANCE: apparatus has plate with detachable cover equipped with central opening where slider bearing for reactor shaft is mounted, inlet branch pipes adapted for feeding of melt into reactor and mounted within detachable cover, and rotating hollow reactor provided with spinneret and made in the form of truncated cone whose open part, that is, diverging cone and truncated cone of reactor are continuously joined to one another. Cylindrical rods having diameter D are serving as spinneret and spaced apart by equal gap L from each other to thereby allow separation of melt film into equal filaments of substantially equal cross-section Di. Heater is made in the form of truncated cone and arranged coaxially to reactor in spaced relation thereto. Also, rear side of heater is protected by heat-insulating sleeve of refractory ceramics to facilitate maintaining of working temperature mode within reactor, provide predetermined temperature of melt film and substantially eliminate destruction thereof to thereby increase quality of resultant filament.

EFFECT: simplified construction, enhanced reliability in operation, improved quality of filaments and increased efficiency of reactor.

9 cl, 5 dwg

FIELD: production of fibers from thermoplastic material, such as fiberglass.

SUBSTANCE: system comprises at least one spinneret cooperating with at least one stapling machine, fiber and/or filament smoothing device for smoothing of fibers and/or filaments exiting from spinneret, at least one discharge device, supporting platform, device for displacement and positioning of stapling machine to at least two positions: above supporting machine and under supporting machine, and first opening provided in supporting machine and adapted for passage of stapling machine therethrough. Said devices and supporting platform are arranged as continuation of each other. System is further provided with device for separating fibers before they are fed into stapling machine and member for closing of first opening, in particular, in case stapling machine is under supporting platform. Displacement device has horizontal axis around which stapling machine may be moved between first and second positions.

EFFECT: increased efficiency, prolonged service life of each stapling cylinder, improved quality of end product and decreased manufacture costs.

10 cl, 2 dwg

FIELD: manufacture of substantially endless thin threads from polymer solutions, in particular, lyocellulose textile masses.

SUBSTANCE: method involves forming textile mass flowing from at least one forming aperture or forming slot; drawing formed thread or film by means of gas flow accelerated to high speed by means of Laval nozzle, whose narrowest section is arranged downstream of textile mass exit end; delivering threads onto tape formed as non-woven material or gripped in the form of yarn and separated from solvents in settling tanks.

EFFECT: improved method and apparatus for manufacture of endless thin threads and film, which are not damaged by thermal action of gas flows used for drawing thereof.

31 cl, 4 dwg, 2 tbl, 3 ex

FIELD: paper-and-pulp industry.

SUBSTANCE: pulp for manufacturing lyocell fiber comprises processed alkali cellulose paste containing hemicellulose in amount at least 7% and cellulose having median degree of polymerization between about 200 and about 1100, copper number about 2.0,w herein more than 4% of pulp fibers have length-weighted average fiber length below 2.0 mm. Lyocell fiber comprises above-defined hemicellulose. Process for preparing composition to be converted into Lyocell fiber comprises boiling in boiler to produce alkali pulp wherein feed contains sawdust in amount between 0 and 100% and contacting alkali pulp containing cellulose and at least about 7% of hemicellulose, under alkaline conditions, with oxidant in amounts high enough to lower average cellulose polymerization degree from about 200 to about 1100 without decrease in content of hemicellulose in pulp to below about 50% or significant increase of copper number to above about 100%.

EFFECT: enabled preparation of rapidly dissolving compositions.

80 cl, 6 dwg, 2 tbl, 3 ex

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