Device for production of 2d or 3d fibre materials from microfibres and nanofibres

FIELD: technological processes.

SUBSTANCE: device for production of 2D or 3D fibre materials from microfibres or nanofibres comprises a set of metal spinning nozzles (3), connected with the first potential, a set of electrodes (6) of a collector facing the set of nozzles (3), arranged at regular intervals and connected with the second potential, and a collecting plate (7) or a collecting cylinder (14) for collection of microfibres or nanofibres laid between pairs of adjacent electrodes (6) of the collector. The substance of the invention consists in the following: a set of collector electrodes (6) comprises at least two electrodes (6) of the collector, arranged in one plane, and the collecting plate (7) on the line of its crossing or along the tangent to the collected cylinder (14), which is perpendicular to the line of contact with the plane of the collector electrodes (6), forming with the plane of the collector electrodes (6) an angle α in the range between 0° and 90°, at the same time the collecting plate (7) or the collecting cylinder (14) may move relative to the electrodes (6) of the collector in the direction in the plane that is perpendicular to the plane of collector electrodes (6), and where the axis of the electrode (6) lies in direction of movement of the collecting plate (7) or the collecting cylinder (14), forming with the axis of this electrode (6) the angle β, the value of which lies between 0° and 90°.

EFFECT: device makes it possible to create large flat and volume objects from ordered nanofibres.

9 cl, 14 dwg

 

AREA of TECHNOLOGY

The present invention relates to a device for producing two-dimensional and three-dimensional fibrous materials of microfibers and nanofibers containing a set of spinning nozzles connected to the first potential, the first set of electrodes facing to the set of nozzles arranged at regular spacing and connected to the second potential, and a collecting plate for collecting the microfibers or nanofibers, pending between pairs of adjacent electrodes.

Background of the INVENTION

To date in known devices for the production of microfibers and nanofibers, working on the principle of an electrostatic field of high intensity, which is formed by a melt or solution of the polymers in the form of a fibrous structure, the most frequently used plate collecting electrodes. The first few ways of spinning polymers were patented in the early 20th century - US 0705671 (1900), US 0692631 (1902), US 2048651 (1934) [1]. The individual fibers laid on this plate electrode, distributed randomly, i.e. they are not arranged in any preferred direction. This is due to the unstable phase of the moving polymer jet, the trajectory of which is very complex and spatially randomly directed to fall on the collecting electrode.

p> If produced material consists of regularly spaced microfibers or nanofibers, such materials can find limitless applications in many modern fields and directions. Their promising potential is real improvement in their morphological properties and, hence, mechanical, physiological, biological, physical, optical and chemical properties due to their internal regularly oriented structure.

Several publications describe the principles of maintenance arrangement of fibers, thus laid. There are two main ways. The first uses a mechanical principle and includes the winding of fibers on the cylinder block or disc rotating at a high speed. The second principle, which is also referred to in the present invention is to use a static collector Assembly, divided into two or more conductive parts separated by non-conductive gap of a certain size. The collector forms the lines of force of the current of the electrostatic field. The polymer trajectory of the jet is determined by these forces of the electrostatic field, the fibers falling on collecting the collector is placed in parallel with one another in the preferred direction in the non-conductive areas of a divided manifold. Structure�tour of conductive and non-conductive areas of the collector determines the forces of the electrostatic field, affecting random flight polymer jet and, thus, controlling his movement. The mechanism for an orderly arrangement of fibers on the collector can be deduced from systematic experimental studies or numerical simulation of the physical model. In principle, these methods work successfully. In 2003-2005 Dan Lee and others published the principle discussed above in professional journals [2-4].

Production of flat (2D) or three-dimensional (3D) materials, using such devices is quite limited and it is impossible to fabricate large-area 2D and thick 3D materials with a regular structure. Thus, this production is limited to only manufacturing oriented individual fibers. Ordered micro - or nanofibers are placed in non-conductive region divided manifold, where they form a thin regular layer. The split collector usually consists of a conductive metal elements separated by non-conductive rear wall having a high resistivity (higher than 1016 Ω·cm). Fiber superimposed on this manifold Assembly is mechanically connected to it, so that their further independent practical application is limited. The location of the substrate in a split manifold, or rather between the emitter and the collector causes a breakdown structures�aligned forces of the electrostatic field, which participate in the formation of the fiber orientation. For use of materials produced by this method, the resulting layer must first be removed from the collector and transferred to the next stage of processing.

Rouhollaha Jalili and others [5] describe a simple collector for collecting several of oriented fibers in the overall package. The result is not a flat structure, and the package with the fibers. This fiber sample was prepared solely for the purpose of subsequent x-ray and mechanical analysis of the properties of the package. The practical application of these multiple bundles of fibers in [5] is not mentioned, and achieved dimensions (length 30 mm and a diameter of approximately 0.08 mm), we can assume that it was insignificant.

Patent application US 2005-0104258 A1 and PPVCZ 2007-0727A3 discuss the structure of the collector electrode, forming a single level, but they don't have to deal with any orderly formation and fiber orientation. The split collector mentioned in the patent US 4689186, but it is used for various purposes and is not included directly in the formation of oriented fibers. Patent application EP 2045375 A1 describes a device for the production of 2D or 3D materials composed of micro - or nanofibers with a regular structure, using electrically separated by a cylindrical collector fo�we during the rotation of which the collection of oriented fibers. Using the described solution it is possible to obtain materials of small size, which is partially limited by the diameter of the rotating collector. In addition, the implementation of the device for production of material of this type larger area (i.e., multiple repetition of the proposed solution) is actually a complicated linear constraint and therefore ineffective.

Micro - or nanofibres low strength, especially fibers made from biopolymers are broken under the influence of their own gravity between the collector electrodes, when it is necessary to form thicker layers (2D or 3D), and thus, the entire structure is weakened. This is a limitation for any manufacturing technology and to obtain materials with desirable characteristics.

When laying the fibers in thicker layers is offset from the level orientation, and the arrangement of fibres is again random. This is due to the progressive increase of electrical kit formed in the layers of fibers, i.e. in those parts of the header that must remain non-conductive and no electric charge, to ensure correct functioning of the principle of orientation of the fibers. This negative effect results in placement oriented in�Windows only in the lower layers of the material that is, in those layers which were laid in the beginning of the process; on the other hand fiber with random location predominate in the higher layers. For this reason, design gathering collector and automatic mechanism in which the automatic mechanism retrieves thin superimposed layers of micro - or nanofibers and their layers in thicker layers (2D or 3D) simultaneously with the spinning process.

Summary of the INVENTION

The object of the present invention is the provision of management and other morphological properties stemming from these micro - or nanofiber materials, and, thus, get the best anisotropic properties of these new materials. The obtained properties of the produced fibrous materials, especially the degree of orientation of fibrous structures, morphology, density, porosity, and mechanical, physical, biological and chemical properties influenced by process parameters. New materials have large macroscopic dimensions in the form of a flat (2D) or three-dimensional (3D) objects. Various source materials, preferably polymers, namely synthetic or natural polymers that can be used in the spinning process, leading to the production of micro - or nanofibers.

This object is achieved in a device for PR�produce two-dimensional or three-dimensional fibrous materials of microfibers or nanofibers, containing a set of spinning nozzles connected to the first potential, a set of electrodes facing to the set of nozzles arranged at regular intervals and connected with a second potential, the team plate for collecting the microfibers or nanofibers, stacked between pairs of adjacent electrodes, wherein the essence of the invention consists in the following: a set of electrodes includes at least two electrodes located in a plane while collecting plate and the plane of the electrodes form an angle α, the value of which lies between 0° and 90°, while collecting plate supported movably relative to the electrodes in the direction lying in the plane perpendicular to the plane of the electrodes, in which the axis of the electrode lies in the direction of movement of the collecting plates forming with the axis of the electrode angle β, the value of which lies between 0° and 90°.

In a preferred embodiment, the apparatus for manufacturing a two-dimensional or three-dimensional fibrous materials of micro - or nanofibers according to the present invention a collecting plate rests on the electrodes with an edge, is provided with a knife.

In another preferred embodiment of this device collecting plate has parallel gaps, each of which is addressed to one of the electrodes, whereas parts of the collecting plates �between two adjacent gaps inserted in the space between two adjacent electrodes.

In an additional preferred embodiment of this device, the set of electrodes arranged at regular intervals, contains at least three parallel electrodes.

In yet another preferred embodiment of this device collects the plate is covered with a removable substrate on its surface facing away from the electrodes, to provide a layer of nanofibers loaded this substrate.

Finally, in yet another preferred embodiment of this device collects the plate has a recess on its surface facing away from the electrodes to accommodate layers of nanofibers collected by the collecting plate.

BRIEF description of the DRAWINGS

The present invention will now be explained in more detail with reference to the accompanying drawings, in which:

Figure 1 - schematic drawing of the first exemplary variant embodiment of the device for producing two-dimensional or three-dimensional fibrous materials of microfibers or nanofibers according to the present invention with the collector electrodes in the form of parallel linear guide rods;

Figure 2 - schematic drawing of the second exemplary variant embodiment of the device for producing two-dimensional or three-dimensional fibrous materials of microfibers or nanow�curl according to the present invention with the collector electrodes in the form of concentric circular guide rods, located in one plane;

Figure 3 - schematic side view of a collecting mechanism with a planar collecting plate;

Figure 4 is a schematic side view of a collecting mechanism to the collecting cylinder;

Figure 5 is a schematic side view of a collecting mechanism with direct dial fibres from the surface of the conductive studs with inclined knife;

Figure 6 - photograph of fibers, arranged in an orderly manner between the rod electrodes separated by an air gap, before removing them from the device collecting plate according to the present invention;

Figure 7 is a photograph of fibers laid in a random order on the collector plates;

Figure 8 - photograph of partially oriented fibers laid on the electrically separated header;

Figure 9 - photograph of oriented fibers, sequentially extracted from a divided manifold in accordance with the present invention;

Figure 10 - angular spectrum representing the orientation of the fibers corresponding to figures 7, 8 and 9;

Figures 11 is an example of a material made of polyvinylstyrene fibers, using a device according to the present invention, the photos with the increase of the ' 70s, h and h respectively.

Referring now to figure 1, which schematically shows a first exemplary variation�t of an embodiment of an apparatus for producing a two-dimensional or three-dimensional fibrous materials of microfibers or nanofibers. Nozzle emitter 2 is filled with a solution of polymer 1, and one pole of a source of DC voltage 4 is connected to its metal nozzle 3, in which the other pole of the source 4 is connected to the conductive rod electrodes 6 of the collector. The conductive bars of the electrodes 6 of the collector pass through the gaps provided in the collecting plate 7, which is inclined to the x-axis at a right angle α. The conductive bars of the electrodes 6 of the collector are located in the x-y plane, linear and parallel to each other.

In operation a solution of polymer 1 is extruded mechanical piston through a metal nozzle 3. High voltage direct current from the source 4 is fed between the nozzle 3 and the electrodes 6 of the collector (the electrodes are presented in the form of conductive rods), directed polymer stream from the fiber 5, which is moved from the nozzle 3 in the direction towards the collector (i.e., in the z axis direction) on a random path. This fiber 5 solidifies in the form of micro - or nanofibers prior to its collision with the collector. The strength of the electrostatic field acting on the fiber 5, will affect its imposition in the preferred direction 8, which in this case is the y axis direction, where the y - axis direction perpendicular to the conductive bars of the electrodes 6 of the collector, located in the x-y plane. Collecting PLA�Tina 7, inclined at an angle α relative to the x axis, performs translational movement in the direction of ν(t), at given time intervals, and the direction ν(t) forms an angle β with the axis X. During the movement of the collecting plate 7 fiber spontaneously 5 is superimposed on the region 9 having a size of S1=liwi. Oriented fibers 5 form a flat (2D) or three-dimensional (3D) material 10.

Referring now to figure 2, which shows a second exemplary variant embodiment of the device for producing two-dimensional or three-dimensional fibrous materials of microfibers or nanofibers according to the present invention, where schematically shows the collector electrodes 6 in the form of concentric circular guide rods arranged in the same plane. Nozzle emitter 2 is filled with a solution of polymer 1, and one pole of a source of DC voltage 4 is connected to its metal nozzle 3. The other pole of the source 4 is connected to the electrodes 6 of the collector. The conductive terminals of the collector electrode 6 are passed through the gaps in the collecting plate 7, which is inclined at an angle α to the axis X. the Conductive bars of the electrodes 6 of the collector are located in the x-y plane, and they are concentric circles.

In operation a solution of polymer 1 is extruded mechanical piston emitter nozzle 2 via� metal nozzle 3. High DC voltage between the nozzle 3 and the electrodes 6 of the collector directs the polymer jet fiber 5, which comes out from the nozzle 3 in the direction towards the collector (i.e., in the z axis direction) on a random path. This jet of polymer fibers 5 solidifies in the form of micro - or nanofibres before hitting the collector. The strength of the electrostatic field acting on the fiber 5, affect its imposition in the preferred direction 8, which is radial relative to the circular conductive bars of the electrodes 6 of the collector, located in the x-y plane. Collecting plate 7, which is inclined at an angle α relative to the x axis, is moved at predetermined time intervals, rotating around its vertical axis 11 in the direction of ω(t), whereas the center of mass collecting plates describes a circle 12 which is inclined at an angle β relative to the axis X. During this movement of the collecting plates fiber spontaneously stacked on the portion 9. Oriented fibers 5 form a flat (2D) or three-dimensional (3D) material 10. Schematic side view of a collecting mechanism with a flat collecting plate 7 is shown in figure 3. The fibers 5 are stacked on the conductive bars of the electrodes 6 of the collector by the process of electrostatic spinning. Then the fibers are placed on the surface of the collecting plate 7, pricemix orientation is maintained. In this exemplary embodiment, the collecting plate 7 is flat, and it is inclined at an angle α to the terminals of the electrodes 6 of the collector, performing a translational movement in a direction that forms an angle β to the x-axis.

A side view of a collecting mechanism to the collecting cylinder 14 is shown schematically in figure 4. The fibers 5 are stacked on the conductive bars of the electrodes 6 of the collector by the process of electrostatic spinning. Then the fibers 5 are stacked on the surface of the collecting cylinder 14, with preservation of orientation of the fibers. Collecting cylinder 14 rotates around its axis, and at the same time he performs translational motion along the x-axis.

Figure 5 shows a schematic side view of a collecting mechanism with direct collection of the fibers 5 from the surface of the conductive bars of the electrodes 6 of the collector by means of an inclined knife. The fibers 5 are stacked on the conductive bars of the electrodes 6 of the collector in the process of electrostatic spinning. Then the fibers 5 are placed on the surface of the collecting plate 7, preserving their orientation. In this exemplary embodiment, the fiber 5 is collected directly from the surface of the conductive bars of the electrodes 6 of the collector by means of an inclined knife 13. The knife 13 is tilted at an angle α relative to conductive bars of the electrodes 6 of the collector, and he makes forward d�iunie along the x-axis.

Figure 6 - photograph of fibers, arranged in an orderly manner between the conductive bars of the electrodes 6 of the collector, separated by an air gap to remove them with the help of the collecting plates. From figure 6 it follows that the nanofibers are arranged in parallel.

Figures 7, 8 and 9 are photographs illustrating the importance of collecting collector design and the method of sequential arrangement of nanofibers from polyvinyldene. The pictures were taken with an electronic microscope with magnification of approximately 5000 × lenses]. Figure 7 fiber 5, superimposed on the collector plate, stacked bespovorotno; figure 8 fiber 5 is laid on a collector electrically separated, partially oriented, and figure figure 9 - photograph of oriented fibers 5, which were sequentially removed with a divided manifold according to the present invention.

Figure 10 is a diagram of the angular spectrum, representing the orientation of the fibers 5 of the samples, are shown in figure 7 (sample A), figure 8 (sample B) and figure 9 (sample C). The spectrum was obtained on the basis of image analysis using Fourier transform. The peak in the spectrum of sample corresponds With the most important angles of placement of the fibers 5, in this case the angle of 90°, in the vertical direction. Applied analysis is commonly used in professional practice d�I automatic evaluation and comparison of fiber orientation 5 even though the image analysis is based on the use of points, i.e., image pixels, rather than individual fibers 5.

Photos are indicative of the material produced using the device of the present invention, represented in figure 11. Figure 11 presents three different magnify portions of the material from polyvinylstyrene fibers 5, namely the increase of the ' 70s in figure 11a, the increase h figure 11b and increase h in figure 11C.

Micro - or nanofibers are formed by the method of electrostatic spinning. Single or composite nozzle emitter 2 generates a stream of polymer fibers 5 in the form of jets, which move in the direction to the second electrode 6 of a header and evenly cover the entire area of the collector. Micro - or nanofibers are transferred forces of the electrostatic field and are stacked parallel to each other, because during their travel from the emitter nozzle 2 to the electrodes 6 on their trajectory is influenced by the lines of force of the electrostatic field near the collector, which to this end is divided into two or more conductive and non-conductive areas. On the basis of numerous experiments was developed and tested collecting the collector, in which the electrodes 6 of the collector consists of two or more thin conductive rods, for example, in the form of wires or strings that from�Elena from each other by an air gap. Neither their number nor their length is not limited. It was further found that the most appropriate cross-section of the bar is not round, but angular cross-section, i.e. square or rectangular, with a width of from 0.1 mm to 10 mm, preferably 1-5 mm.

Individual rods are spaced relative to each other and separated by an air gap of a given width, namely from 0.1 mm to 200 mm, most preferably from 1 mm to 100 mm. the Effect of air gap on the formation of ordered fibers 5 have been systematically studied and it was found that in the case of short distances, the degree of orientation decreases. On the contrary, in the case of long distance fiber 5 are stacked directly on conductive electrodes, and the number of oriented fibers 5 that are located between the conducting rods below, or fiber break its own gravity. Therefore, the most appropriate size of the air gap must be found experimentally for each type of polymer, to ensure the successful formation of oriented fibers 5. It was also found that the width of conductive terminals does not have to be large, on the contrary, from the project and the point of view of functionality, the use of thin rods of square cross section is favorable in contrast to the wider plates, and this is proved in the cited literature. Time�trollers air gaps were optimized for several varieties of synthetic and natural polymers, depending on their mechanical properties.

The space between the conductive bars of the electrodes 6 of the collector, where the fibers 5 are arranged along the length in one direction, or rather perpendicular to the conductive bars of the electrodes 6 of the collector of the nonconducting region, is gradually filled during the laying of the fibers. The laying of the fibers 5, oriented in thicker layers, it is impossible for reasons mentioned above, for example due to the decrease of the degree of orientation, etc., and therefore proposed a process in which thin stacked layer is removed at regular intervals and is transmitted to the rear plate preferably simultaneously with the stacking.

For the collection of oriented fibers 5, transmission and layering is used collecting plate 7 with elongated holes, which allow to impose the plate 7 on the conductive bars of the electrodes 6 of the collector and to provide a translational motion in the longitudinal direction along the conductive rods. The shape of the collecting plate 7 repeatedly experimentally tested and changed. The resulting optimal design described in this disclosure. During specified time intervals from 1 second to 1 hour collecting plate 7 is displaced in the longitudinal direction along the conductive rods, when she picks up the ordered micro - or nanofibres on swappernet. It was found that due to the inclination of the collecting plate 7 at a certain angle relative to the bars of the electrodes 6 of the collector, namely 0°<α<90°, the fibers 5, extracted around the edges of the conductive bars of the electrodes 6 of the collector, subject to the mechanical stress to a lesser extent, and also that the inclination of the collecting plate 7 helps regular stacking of individual fibers 5 on the collecting plate 7 along their entire length. The inclination of the collecting plates additionally provides simultaneous extraction of the fibers 5, are installed directly on the conductive bars of the electrodes 6 of the collector. The fibers 5 are stacked in these places more as a result of stronger electrostatic field and thus they increase the mechanical strength of the obtained material. In addition, solved the problem of collecting oriented fibers 5 in a larger area S=ΣSi=Σ (li. wi) (where l is the length and wi is the width of the region (i), namely thanks to the newly developed and experimentally proven process. Collecting plate performs translational motion with a velocity of 0.001 m/s to 10 m/s) along the conductive bars of the electrodes 6 of the collector, and the direction of this movement forms an angle β (in the range 0°<β<90°) with the conductive bars of the electrodes 6 of the collector. During this movement of micro - or nanofibres, Hulot�military orderly manner, stacked in thick layers of flat (2D) or three-dimensional (3D) objects with support for regular ordered structure of the material 10. The angle β defines the surface density of the fibers in layer 5, which is formed from a new material 10, and a length of 1 collecting the pieces of a plate that has been coated with fibers. Flat or three-dimensional material 10 is generated sequentially, depending on the total time of the process and the total area of the resulting material 10. The developed process allows you to put the micro - or nanofibres in thicker layers, while maintaining the desired direction of orientation even in the higher layers. Placing the fiber 5 to advance the back wall, you can reduce the level of mechanical stress to the minimum value, and therefore their structure is not violated.

The fibers 5 are made of different compounds, for example, synthetic or natural polymers, typically have different mechanical properties, and materials 10 produced by electrostatic spinning, also have different morphology. On the basis of the studied characteristics was chosen as one of the processes of collection and stacking of ordered fibers 5. It was found that the use of the collecting plate 7, which is inserted between the conductive bars of the electrodes 6 of the collector, suitable for fibers 5 � lower mechanical strength derived from natural polymers. Fiber 5 may be so thin that it may break under the effect of their own weight when they are suspended between the conductive bars of the electrodes 6 of the collector. In this case, there is no other way to remove the fibers 5 of the device in accordance with the present invention. In contrast, the collecting plate 7 to the collecting blade 13, which performs translational motion along the surface of the conductive rods is used with more resistant materials 10, such as synthetic polymers. The advantage of this process is that the resulting material becomes thinner in the abs 10 is not in any place and even enhanced in the areas of conductive bars of the electrodes 6 of the collector, which basically increases its resistance to subsequent mechanical stress, for example, in a particular scope.

The translational movement of the collecting plate 7 along the conductive bars of the electrodes 6 of the collector becomes reverse during specific time intervals to form a single layer of material 10. New material 10 is created on the arbitrary back wall, and back wall can be designed as a packing material. A practical solution enables the production of ordered materials that will be about�simultaneously placed in sterile containers in the cell storing the "on the spot" and, thus, it will be ready for direct application and use. The Device solves the technical problem of the mechanical requirements of the transfer material 10 made of thin fibers with another substrate, and eliminates possible causes of interference with the process, damage, contamination and wear of the material 10 during processing. The developed device allows to perform the production process in a single environment, camera placement, and therefore the necessary sterilization of material 10 intended for medical purposes, can be easily achieved.

In another case, the collecting plate 7 always moves in one direction only after the expiration of the time interval. She remains in the end position for the same time interval and then moves back. Separated by a translational motion leads to the confinement of micro - or nanofibres on both sides collecting plates 7 which form adapted to adhere to the core material. This principle allows you to create fiber layers on both sides only defensive backs.

Additionally solves the problem of the discrete movement of the collecting plate 7, which is more important - from the point of view of the design. In the Central-symmetrical design uses a circular conductive rods collective�ora as the electrodes 6 of the collector. In this case, the collecting plate 7 rotates around its Central axis. In this case, the collecting plate is moving with angular velocity ω(t) in the range of 0.001 to 10 rad/s. Fibers 5 are stacked and laminated in the same manner as in the previous embodiment. Here a continuous rotational movement of the collecting plate 7 has an advantage compared to discrete steps in the previous solution.

Constructive modification of the collecting plate 7 to allow the rotation of the individual elements collecting plates 7 at the angle γ in the range 0<γ<90°. After the expiration of the defined time interval (from 1 second to 1 hour) layering of the fiber material 10 elements collecting plates 7 having a region Si=liwiand additional layers of material 10, are stacked again. The internal structure of the material 10, thus formed, consists of a single layer of micro - or nanofibres, in which the layers are slightly rotated relative to each other to adjust the angle γ. This principle allows us to produce materials 10 with two or more orderly directions of the anisotropic material 10 and also to form an ordered 3D structure. Regular structure occurs not only flat, but also in the three-dimensional object by rotating the elements of the collecting plate 7 or a multiple �of overenie collection fibers 5 in the above-described process.

Superimposed fiber 5 fill the area between the gaps in the collecting plate 7. The size of the area 9, which are oriented micro - or nanofibres, the size is not limited. The transverse width of the conductive bars of the electrodes 6 (and the width of the gaps in the collecting plate 7 emanating from it) are the only important parameter. In these places, the fibers 5 in the resulting material 10 is not stacked in an orderly manner or some places remain unfilled. There is a maximum of 20% of these areas in the resulting material 10.

Multiple metal nozzle 3 of the radiator are used to cover a larger area of the collector fiber 5 and to increase the economic efficiency of production. Separate metal nozzle 3 of the radiator are also used for laying fibers 5 of the various polymer mixtures. When the metal of the emitter nozzle 3 are arranged in a line along the conductive bars of the electrodes 6 of the collector, the fibers 5 are laminated one after another, with separate layers of fibers are created from 5 different polymers. The fiber structure of the material obtained has the form of a composite material.

The replacement of the collecting plate 7 collecting cylinder 14 of a certain diameter R, on the side surface of which has separate cutouts for conducting rod� electrodes 6 of the collector, allows hollow tube, the walls of which are composed of fibers 5, arranged regularly in the longitudinal direction. Collecting cylinder 14 performs two independent motions: a rotary motion around its longitudinal axis and translational motion in the direction along the conductive bars of the electrodes 6 of the collector (along the X-axis). These movements of the cylinder allow you to collect micro - or nanofibres on the surface. The surface of the collecting cylinder 14 has projections, where the fibers 5 are stacked in flat (2D) material 10, or remain in the form of a pipe or spread out to create surface material 10 is large in size.

The above described construction of the reservoir and the mechanism of orientation of micro - or nanofibers and their placement provide efficient production of new materials, which can be a flat material of a large area or in bulk form (3D) with support for thin and regular fiber structure.

INDUSTRIAL APPLICABILITY

The proposed invention can be used for the production of flat (2D) or three-dimensional (3D) materials, which have their own internal fiber structure consisting of oriented micro - or nano-fibers, located along one or more directions.

Sources of information

1. S. R. N. Sangamesh G. Kumbar, Rosha James, MaCalus V. Hogan and Cato T. Laurencin, Recent Patents on Biomedical Engineering 1, 68-78 (2008).

2. D. Li, Y. Wang and Y. Xia, Nano Letters 3 (8), 1167-1171 (2003).

3. Y. W. D. Li, Y. Xia," Advanced Materials 16 (4), 361-366 (2004).

4. D. Li, G. Ouyang, J. T. McCann and Y. Xia, Nano Letters 5 (5), 913-916 (2005).

5. R. Jalili, M. Morshed, S. dolkarim and H. Ravandi, Journal of Applied Polymer Science 101 (6), 4350-4357 (2006).

1. Apparatus for producing two-dimensional or three-dimensional fibrous materials of microfibers or nanofibers containing at least one metal of the spinning nozzle (3) connected to the first potential, a set of electrodes (6) of the collector, which contains at least two electrodes (6) of the collector facing the set of nozzles (3) arranged with a constant spacing relative to each other and connected with a second potential, wherein the device further comprises a collecting plate (7) or the collecting cylinder (14) for collecting the microfibers or nanofibers, stacked between pairs of adjacent electrodes (6) of the collector and the collecting plate (7) is provided with gaps through which the electrodes (6) of the collector, the collecting plate (7) on the line of intersection or tangent to the collecting cylinder (14) which is perpendicular to the line of contact with the plane of the electrodes (6) of the collector, forming with the plane of the electrodes (6) collector angle α, the size of which lies in the range from 0° to 90°, wherein the collecting plate (7) and�and collecting cylinder (14) is movable relative to the electrodes (6) of the collector in the direction lying in a plane that is perpendicular to the plane of the electrodes (6) of the collector and in which the axis of the electrode (6), and the direction of movement of the collecting plate (7) or collecting cylinder (14) forms with the specified electrode (6) axis at angle β, the size of which lies in the range from 0° to 90°.

2. Apparatus for producing two-dimensional or three-dimensional fibrous materials of microfibers or nanofibers according to claim 1, characterized in that the collecting plate (7) provided with open parallel gaps, each of which is addressed to one of the electrodes (6) of the collector, whereas the tabs of the collecting plate (7) between two adjacent gaps are the space between two adjacent electrodes (6) of the collector.

3. Apparatus for producing two-dimensional or three-dimensional fibrous materials of microfibers or nanofibers according to any one of claims. 1-2, characterized in that the set of electrodes (6) of the manifold has a constant spacing relative to each other and has at least three parallel electrodes (6) of the collector.

4. Apparatus for producing two-dimensional or three-dimensional fibrous materials of microfibers or nanofibers according to claim 1, characterized in that the collecting plate (7) has a surface which is inclined from electrodes (6) of the collector, wherein said surface is covered with a removable substrate to provide a download of the layer of microfibers or nanofibers of the specified substrate.

5. Apparatus for producing two-dimensional or three-dimensional fibrous materials of microfibers or nanofibers according to claim 1, characterized in that the collecting plate (7) comprises a surface, which is inclined from electrodes (6) of the collector and which has a slot to accommodate layers of microfibers or nanofibers collected by the collecting plate (7).

6. Apparatus for producing two-dimensional or three-dimensional fibrous materials of microfibers or nanofibers according to claim 1, characterized in that the shape of the cross section of the electrodes (6) of the collector is square or rectangular with a width of from 0.1 mm to 10 mm.

7. Apparatus for producing two-dimensional or three-dimensional fibrous materials of microfibers or nanofibers according to claim 6, characterized in that the shape of the cross section of the electrodes (6) of the collector is square or rectangular with a width of 1-5 mm.

8. Apparatus for producing two-dimensional or three-dimensional fibrous materials of microfibers or nanofibers according to claim 1, characterized in that the electrodes (6) of the collector are separated from each other by an air gap laterally offset relative to each other at a distance of from 0.1 mm to 200 mm.

9. Apparatus for producing two-dimensional or three-dimensional fibrous materials of microfibers or nanofibers according to claim 8, characterized in that the electrodes (6) to�of lectora are separated from each other by a distance of from 1 mm to 100 mm.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to method of spinning fibre, containing polypeptide polymer, as well as to products, including said polymer fibre. Method of fibre spinning includes draft of fibre from dope solution, containing polymer, preferably silk polypeptide which can be introduced into water solution with concentration constituting at least 0.15 mg/ml, polyacrylamide (PAA), which increases longitudinal viscosity of dope solution, and solvent. Invention makes it possible to obtain fibres, including living and non-living biological material, which could perform function of framework material for fabric engineering and growing artificial organs.

EFFECT: application of PAA in dope solution results in obtaining smooth and homogeneous fibres, non-biodegradable and long-lasting, in addition, application of very low concentrations of polymers and/or very low concentrations of improvers of PAA longitudinal viscosity facilitates spinning of fibres from dope solution.

24 cl, 4 dwg, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to technology of obtaining ultrathin polymer fibres by method of electrospinning and can be used for spinning non-woven porous fibrous materials, applied as separating partitions, for instance, for filtration of gases and liquids, for manufacturing diffusion partitions, separators of chemical sources of current, etc. Solution for spinning contains 2.5-4 wt.p. of phenolformaldehyde resin, 2.5-4 wt.p. of polyvinyl butyral, 92-95 wt.p. of ethyl alcohol and as modifying additives 0.02-0.2 wt.p. of tetrabutylammonium iodide or 0.01-0.1 wt.p. of lithium chloride.

EFFECT: invention provides increase of solution electroconductivity, increased output of ultrathin fibres with diameter less than 0,1 mcm.

1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: method and apparatus for producing fine fibres via fibre electrospinning by applying an electric field between a primary electrode and a counter electrode lying at a distance from the primary electrode and often parallel thereto. The working surface of the primary electrode is coated with a polymer solution. An electric field is created between the primary electrode and the counter electrode having sufficient strength to cause formation of fine fibres in the space between the electrodes. The working surface of the primary electrode coated with a polymer solution consists of corresponding parts of surfaces of a plurality of elements that are semi-submerged in the working state and are freely lying (not connected to anything), said elements resting at the bottom of a bath or tray or some other supporting structure(s). A tool is used, which enables to apply the polymer solution on the surface of the freely lying elements protruding from the solution via rotation thereof in the polymer solution, such that their surface is coated with a thin layer of the polymer solution.

EFFECT: method and apparatus according to the present invention enable to perform spinning with high efficiency while eliminating problems encountered in the previous technological level.

12 cl, 8 dwg

FIELD: medicine.

SUBSTANCE: invention relates to chemical-pharmaceutical industry and represents artificial dura mater, produced from electrospinning layers by technology of electorspinning, with electrospinning layer, consisting of, at least, hydrophobic electrospining layer, which is produced from one or several hydrophobic polymers, selected from polylatic acid and polycaprolactone.

EFFECT: invention ensures creation of artificial dura mater, which has good tissue compatibility, anti-adhesiveness and possibility of introducing medications, preventing cerebrospinal fluid outflow during regeneration of person's own dura mater.

30 cl, 7 ex, 11 dwg

FIELD: chemistry.

SUBSTANCE: electrostatic field is formed in fibre-forming space between the fibre-forming element of a fibre-forming electrode, which is connected to one terminal of a high-voltage source and is located in a fibre-forming position, and a precipitation electrode connected to the second terminal of the high-voltage source to which a polymer matrix is fed from a reservoir with the matrix in an electrostatic field for forming fibre on the surface of the fibre-forming element of the fibre-forming electrode, wherein temperature of the fibre-forming elements of the fibre-forming electrode is raised higher than ambient temperature by direct contact heating of the fibre-forming elements.

EFFECT: more technologically effective method, and simple and efficient design of the apparatus.

8 cl, 2 dwg

FIELD: electricity.

SUBSTANCE: method includes spinning of electroconductive solution of organic and non-organic polymers and predecessor of organic polymer in presence of electric field between tip and earthing source till composite fiver is received. At that organic and non-organic phases of composite fibres are mixed and react with each other with production of -Si-O-M- links, where M is selected from the group consisting of Si, Ti, Al and Zr. The author offers composite fibre received by the above method and composite product including polymer matrix and composite fibres introduced to it.

EFFECT: improvement of method.

28 cl, 2 dwg, 1 tbl, 5 ex

FIELD: electricity.

SUBSTANCE: fibre electrospinning is carried out from an electroconductive solution of polymer in presence of electric field between a nozzle and a source of earthing. In the method realisation the polymer before and after electrospinning process is exposed to linking reaction. At the same time the polymer contains linked silane groups along the length of the main chain of polymer, and the linked groups react with water, including water contained in air. The fibre made according to the method of electrospinning contains links -Si-O-Si-.

EFFECT: using linking reaction before and during the process of electrospinning results in increased viscosity of polymer solution, making it possible to form the fibre and to reduce usage of thickeners to the minimum.

14 cl, 2 dwg, 1 tbl, 3 ex

FIELD: electricity.

SUBSTANCE: spinning solution for electrical formation of polymer precursor of fibres of siliconecarbide contains 50 - 70 % solution of polycarbosilane with average molecular weight of 800 - 1500 astronomical units of weight, cross-linking agent and photoinitiator at the following molar ration of components: polycarbosilane/cross-linking agent/photoinitiator = 1/(0.5-1.5)/(0.5-2). Method for obtaining silicone carbide fibres involves preparation of spinning solution, electrical forming of fibres of precursor of silicone carbide from spinning solution with simultaneous cross-link of precursor fibres by light irradiation in visible or UV radiation range and heat treatment of precursor fibres for their conversion to silicone carbide fibres. Silicone carbide fibres made in compliance with the above method have average diameter of 50 nm to 2 mcm and porosity of less than 10 m2/g.

EFFECT: invention provides high capacity and low cost of production of high-quality silicone carbide fibres characterised with high mechanical strength and low porosity.

6 cl, 1 tbl

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

FIELD: textile, paper.

SUBSTANCE: this invention refers to method and device for manufacture of polymeric fibres and textile products in a closed system. System for manufacture of non-woven cloth from fibres includes a spinning beam unit configured for processing and supply of many flows of polymers for extrusion through the spinning nozzle holes. At that, spinning beam unit includes many supply passages interconnected as to fluid medium with the spinning nozzle holes where at least two supply passages are configured so that they can supply separate flows of polymers with various polymeric components to the spinning nozzle holes. Besides spinning beam unit includes many collectors for separation and independent keeping of various temperatures for various flows of polymers with various polymeric components. Each collector provides homogeneous heating of polymer flow flowing inside discharge pipe of polymer inside each collector, each discharge pipe is enveloped with heat exchange pipe in fact at homogeneous temperature, quick cooling chamber for receiving and quick cooling of extruded fibres from spinning nozzle holes. At that, quick cooling chamber includes gas supply source for direction of gas flow to extruded fibres. Also the system includes an exhaust chamber interconnected with quick cooling chamber and configured for receipt and release of quick cooled fibres, and a forming surface for receipt of extruded fibres leaving the exhaust chamber and forming of non-woven fibrous cloth on the forming surface. At that, system supports extruded fibres in closed space between the spinning nozzle holes and exhaust chamber so that contact of fibres to uncontrolled gas flows can be prevented.

EFFECT: simplifying the fabrication of wide range of fibres from variety of polymeric components and textile products having the required linear density of fibre (denier) and degree of homogeneity.

8 cl, 9 dwg

FIELD: chemistry.

SUBSTANCE: inventions relate to method of producing nanofibres from polymer solution by method of electrostatic fibre formation in electric field, created due to difference of potentials between charged electrode and opposite electrode and device for its realisation. According to method polymer solution is supplied into electric field for electrostatic fibre formation by surface of rotating charged electrode, part of whose surface is submerged into polymer solution. Simultaneously formed nanofibres under impact of electric field are displaced from rotating charged electrode to opposite electrode and then are laid on means for their laying. Nanofibres are formed on cylindrical or quadrangular, or polygonal prismatic surface of charged electrode, and opposite electrode is placed opposite free part of charged electrode, air being sucked from space between charged electrode and opposite electrode. Device for method realisation contains rotating charged electrode and opposite electrode. Charged electrode represents cylinder or quadrangular or polygonal prism, and opposite electrode is placed opposite free part of charged electrode. Polymer solution for electrostatic fibre formation by surface of rotating charged electrode is supplied into created by electrodes electric field, simultaneously formed nanofibres under impact of electric field are displaced from rotating charged electrode to opposite electrode and then are directed to means of their laying, which represents air-permeable transporter. Means for laying nanofibres can be formed by flat carrying material of nanofibres.

EFFECT: increase of productivity of nanofibres production.

14 cl, 9 dwg

FIELD: textile, paper.

SUBSTANCE: this invention refers to method and device for manufacture of polymeric fibres and textile products in a closed system. System for manufacture of non-woven cloth from fibres includes a spinning beam unit configured for processing and supply of many flows of polymers for extrusion through the spinning nozzle holes. At that, spinning beam unit includes many supply passages interconnected as to fluid medium with the spinning nozzle holes where at least two supply passages are configured so that they can supply separate flows of polymers with various polymeric components to the spinning nozzle holes. Besides spinning beam unit includes many collectors for separation and independent keeping of various temperatures for various flows of polymers with various polymeric components. Each collector provides homogeneous heating of polymer flow flowing inside discharge pipe of polymer inside each collector, each discharge pipe is enveloped with heat exchange pipe in fact at homogeneous temperature, quick cooling chamber for receiving and quick cooling of extruded fibres from spinning nozzle holes. At that, quick cooling chamber includes gas supply source for direction of gas flow to extruded fibres. Also the system includes an exhaust chamber interconnected with quick cooling chamber and configured for receipt and release of quick cooled fibres, and a forming surface for receipt of extruded fibres leaving the exhaust chamber and forming of non-woven fibrous cloth on the forming surface. At that, system supports extruded fibres in closed space between the spinning nozzle holes and exhaust chamber so that contact of fibres to uncontrolled gas flows can be prevented.

EFFECT: simplifying the fabrication of wide range of fibres from variety of polymeric components and textile products having the required linear density of fibre (denier) and degree of homogeneity.

8 cl, 9 dwg

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

FIELD: electricity.

SUBSTANCE: spinning solution for electrical formation of polymer precursor of fibres of siliconecarbide contains 50 - 70 % solution of polycarbosilane with average molecular weight of 800 - 1500 astronomical units of weight, cross-linking agent and photoinitiator at the following molar ration of components: polycarbosilane/cross-linking agent/photoinitiator = 1/(0.5-1.5)/(0.5-2). Method for obtaining silicone carbide fibres involves preparation of spinning solution, electrical forming of fibres of precursor of silicone carbide from spinning solution with simultaneous cross-link of precursor fibres by light irradiation in visible or UV radiation range and heat treatment of precursor fibres for their conversion to silicone carbide fibres. Silicone carbide fibres made in compliance with the above method have average diameter of 50 nm to 2 mcm and porosity of less than 10 m2/g.

EFFECT: invention provides high capacity and low cost of production of high-quality silicone carbide fibres characterised with high mechanical strength and low porosity.

6 cl, 1 tbl

FIELD: electricity.

SUBSTANCE: fibre electrospinning is carried out from an electroconductive solution of polymer in presence of electric field between a nozzle and a source of earthing. In the method realisation the polymer before and after electrospinning process is exposed to linking reaction. At the same time the polymer contains linked silane groups along the length of the main chain of polymer, and the linked groups react with water, including water contained in air. The fibre made according to the method of electrospinning contains links -Si-O-Si-.

EFFECT: using linking reaction before and during the process of electrospinning results in increased viscosity of polymer solution, making it possible to form the fibre and to reduce usage of thickeners to the minimum.

14 cl, 2 dwg, 1 tbl, 3 ex

FIELD: electricity.

SUBSTANCE: method includes spinning of electroconductive solution of organic and non-organic polymers and predecessor of organic polymer in presence of electric field between tip and earthing source till composite fiver is received. At that organic and non-organic phases of composite fibres are mixed and react with each other with production of -Si-O-M- links, where M is selected from the group consisting of Si, Ti, Al and Zr. The author offers composite fibre received by the above method and composite product including polymer matrix and composite fibres introduced to it.

EFFECT: improvement of method.

28 cl, 2 dwg, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: electrostatic field is formed in fibre-forming space between the fibre-forming element of a fibre-forming electrode, which is connected to one terminal of a high-voltage source and is located in a fibre-forming position, and a precipitation electrode connected to the second terminal of the high-voltage source to which a polymer matrix is fed from a reservoir with the matrix in an electrostatic field for forming fibre on the surface of the fibre-forming element of the fibre-forming electrode, wherein temperature of the fibre-forming elements of the fibre-forming electrode is raised higher than ambient temperature by direct contact heating of the fibre-forming elements.

EFFECT: more technologically effective method, and simple and efficient design of the apparatus.

8 cl, 2 dwg

FIELD: medicine.

SUBSTANCE: invention relates to chemical-pharmaceutical industry and represents artificial dura mater, produced from electrospinning layers by technology of electorspinning, with electrospinning layer, consisting of, at least, hydrophobic electrospining layer, which is produced from one or several hydrophobic polymers, selected from polylatic acid and polycaprolactone.

EFFECT: invention ensures creation of artificial dura mater, which has good tissue compatibility, anti-adhesiveness and possibility of introducing medications, preventing cerebrospinal fluid outflow during regeneration of person's own dura mater.

30 cl, 7 ex, 11 dwg

FIELD: chemistry.

SUBSTANCE: method and apparatus for producing fine fibres via fibre electrospinning by applying an electric field between a primary electrode and a counter electrode lying at a distance from the primary electrode and often parallel thereto. The working surface of the primary electrode is coated with a polymer solution. An electric field is created between the primary electrode and the counter electrode having sufficient strength to cause formation of fine fibres in the space between the electrodes. The working surface of the primary electrode coated with a polymer solution consists of corresponding parts of surfaces of a plurality of elements that are semi-submerged in the working state and are freely lying (not connected to anything), said elements resting at the bottom of a bath or tray or some other supporting structure(s). A tool is used, which enables to apply the polymer solution on the surface of the freely lying elements protruding from the solution via rotation thereof in the polymer solution, such that their surface is coated with a thin layer of the polymer solution.

EFFECT: method and apparatus according to the present invention enable to perform spinning with high efficiency while eliminating problems encountered in the previous technological level.

12 cl, 8 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to technology of obtaining ultrathin polymer fibres by method of electrospinning and can be used for spinning non-woven porous fibrous materials, applied as separating partitions, for instance, for filtration of gases and liquids, for manufacturing diffusion partitions, separators of chemical sources of current, etc. Solution for spinning contains 2.5-4 wt.p. of phenolformaldehyde resin, 2.5-4 wt.p. of polyvinyl butyral, 92-95 wt.p. of ethyl alcohol and as modifying additives 0.02-0.2 wt.p. of tetrabutylammonium iodide or 0.01-0.1 wt.p. of lithium chloride.

EFFECT: invention provides increase of solution electroconductivity, increased output of ultrathin fibres with diameter less than 0,1 mcm.

1 tbl, 7 ex

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