WO2019158135A1 - Électrode destinée au traitement de surface de matériaux polymères - Google Patents

Électrode destinée au traitement de surface de matériaux polymères Download PDF

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Publication number
WO2019158135A1
WO2019158135A1 PCT/CZ2019/000010 CZ2019000010W WO2019158135A1 WO 2019158135 A1 WO2019158135 A1 WO 2019158135A1 CZ 2019000010 W CZ2019000010 W CZ 2019000010W WO 2019158135 A1 WO2019158135 A1 WO 2019158135A1
Authority
WO
WIPO (PCT)
Prior art keywords
spinning
electrode
strip
solution
coating element
Prior art date
Application number
PCT/CZ2019/000010
Other languages
English (en)
Inventor
Matej Buzgo
Miroslav DOUPNIK
Martin DOUPNIK
Original Assignee
Inocure S.R.O.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Inocure S.R.O. filed Critical Inocure S.R.O.
Publication of WO2019158135A1 publication Critical patent/WO2019158135A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0046—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by coagulation, i.e. wet electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning

Definitions

  • Methods of electrostatic spinning and spraying represent a recognised technique for preparing nanosystems in the form of nano fibres or nano particles.
  • the technical solution is based on the use of surface spinning by means of a new electrode for electrostatic spinning and spraying that increases the production capacity, utility value, and efficiency of the existing solutions.
  • the technical solution includes a description of the potential technological application of the presented electrode.
  • Electrostatic techniques are used to create functional nanosystems. Their practical applicability is substantially limited by the production capacity of the current methods.
  • the presented solution changes this status quo and enables the industrial production of both nano fibres and nano particles by means of electrostatic methods.
  • the majority of electrostatic processes are based on needle spinning systems that produce fibre from liquid or melt delivered by a capillary (needle) and subject to strong electrical field.
  • the drawbacks of the current solutions include especially the low production capacity eliminating commercial applicability of the products.
  • An example is a solution described in EP 1709218, EP2045375, EP2447396, JP2008248422, US67535454, US7575707, US8088324, and US2014353882.
  • the solution is based on the creation on so-called surface electrodes leading to the production of nano fibres and nano particles by means of self-organization from the surface of a thin polymer layer.
  • Surface electrodes demonstrate a variety of construction solutions in terms of their electrical field homogeneity design, the method of the liquid coating, elimination of the dead volume of polymer solutions, and removal of excess solutions.
  • the simplest surface design is the application of rod electrodes that allow for spinning from a drop of polymer liquid brought to the rod element.
  • An example is an electrode described in patent CZ304097. This solution is suitable mainly for the production of small volumes of polymer particles or fibres.
  • linear electrodes are limited in terms of their adaptation for particle generation and so it is necessary to integrate them in reactor systems if used for industrial production. In terms of air flow and spatial efficiency it is necessary to use circular or ellipsoidal systems. This makes linear electrodes suitable only for producing nano fibre layers.
  • the simplest example of linear electrodes represents slotted electrodes consisting of two strips with polymer fluid flowing between them. The slots deliver the polymer fluid to the active spinning zone (so-called slotted electrodes).
  • Patent US9034240 develops the slotted electrode technology by adding further shapes, from linear, concave, to convex.
  • the design described in patent application EP2173930, WO2012139533, CN 103603065 and CZ20110212 presents a technique of nano fibre production by means of applying polymer solution on a string.
  • the design describes a wire-form electrode with a stationary or mobile spinning zone onto which the polymer is applied.
  • the principle of our presented technical solution differs from the above stated designs and eliminates the shortcomings of designs presented in applications EP2173930, WO2012139533, CN103603065 and CZ20110212.
  • the presented design issues from the use of a spinning strip as the most suitable application element.
  • the main advantage of the strip for spinning is the possibility to create linear, ellipsoidal, or circular electrode shapes and to adjust its shape and dimensions to the needs of the fibre or particle deposition.
  • For an industrial production of particles through electrostatic spraying it is necessary to adjust the shape of the electrode into a circular or ellipsoidal shape to achieve an optimal function in reactor systems.
  • the reason for the elimination is the aberrant deposition caused by turbulent air flow and according to numeric simulations the most optimal shape of the reactor is circular or ellipsoidal.
  • Designs in applications EP2173930, WO2012139533, CN103603065, and CZ20110212 do not allow for a similar arrangement and are therefore useless for a practical production of nano particles in industrial conditions.
  • the geometric shape of the string leads to the concentration of the field in the highest point of the string and to production of nano systems limited to this area only.
  • Our presented solution based on the strip generates more maximums of the electrical field concentrations thanks to the shape of the spinning strip and leads to the production increase of electrostatic spinning and electrostatic spraying processes.
  • Our presented solution also eliminates the risk of mechanical damage of the electrode during the process, where a string electrode may be interrupted and therefore lose function.
  • Strip electrode on the other hand, is mechanically rigid and set in the structure of the device to eliminate damage.
  • the polymer solution is not applied on the electrode from all sides such as in document CZ20110212 and WO20122139533, but is applied to the top side of the spinning strip only.
  • DE10136255 describes an equipment for producing fibres by means of electrode consisting of parallel wires set on two endless bands around two guiding rollers; in the lower part the polymer is applied to the wires and the spinning effect occurs once the wires enter the electric field.
  • the drawback of the design solution described in document DE10136255 is the open stock container causing evaporation of solvents that affect and alter the polymer solutions. This changes the properties of the solution during the spinning process and causes nonhomogeneity of the produced layer. Similar drawbacks are characteristics also solutions described in documents CZ20032421, EP1673493, CZ2006545, US20140302245,
  • KR1020110078016, and W02007111477 which focus on surface spinning from a cylindrical electrode rotating in the polymer solution stock container.
  • the drawback of this solution is the low focus of the electric field and the shortcomings of the polymer stock containers.
  • solvents evaporate from volatile solutions even before entering the active spinning zone. In terms of construction there is more dead volume than in the presented solution, which reduces the utility value of the design.
  • a similar solution, involving an electrode that contains rotating rings or discs instead or rotating cylinders, is described in document CN102828259 and CN103484953.
  • Document CZ305037 describes a cylindrical spinning electrode made of non-conductive materials.
  • Document JP2015132028 describes spinning from two mutually moving rollers where one roller is dipped in the spinning fluid and its rotation delivers the fluid onto the second roller that brings it into the spinning zone.
  • Document US8545207 describes a spherical or polygonal electrode that rotates in the polymer fluid.
  • Document CZ2010648 focuses on spatial optimisation of the placement of long electrodes.
  • the equipment consists of long electrodes placed underneath each other so that each of them has a collecting electrode on both sides and in the same direction. Due to this, spinning occurs between the spinning electrode and at least two of its collecting electrodes. This makes the process more efficient, where both electrodes spin at the same time.
  • the technical solution claimed by this application allows for a combination with one collector of cylindrical, plate, punched plate, or string shape.
  • the principle of the presented design solution is a new design of electrode for electrostatic spinning and spraying that increases the production capacity and efficiency of the existing solutions.
  • the electrode allows for industrial production of nano fibres and nano particles with the possibility to change the shape of the electrode upon the specific requirements of the individual types of nano systems.
  • the electrode consists of two main parts - the spinning strip onto which the polymer is applied and from which the spinning or spraying process occurs, and an application device for the delivery of the polymer to the spinning strip.
  • the electrode contains one or more conductivised spinning strips onto which the polymer is delivered by means of a moving supply mechanism.
  • the spinning strip is made of conductive (mainly compounds of Fe, Ni, Zn, Sn, Cr, Al or Cu) or non-conductive materials (mainly glass, plastics - polyoxymethylene (POM), polyethylene (PE), polyetherketone (PEEK)).
  • POM polyoxymethylene
  • PE polyethylene
  • PEEK polyetherketone
  • the spinning strip provides a benefit compared to the existing solutions - it increases the effective surface of the active spinning zones, improves the mechanical stability of the electrode, and minimizes wear in a long-term operation.
  • the spinning strip may have the spinning zone arranged in a linear, ellipsoidal, or circular shape. Thanks to this it allows for choosing the optimal shape by the type of the nano system produced.
  • linear shape of the spinning strip is ideal, which makes a spinning zone allowing for large-area deposition of the fibre into non- woven textile.
  • nano particles it is best to use an ellipsoidal or circular shape of the spinning strip and therefore also of the spinning zone.
  • a circular or ellipsoidal element is produced, with the diameter or 20 - 1,000 mm.
  • the element may be also shaped as an unclosed curved shape in the form of one or more panels.
  • the purpose of the radially curved electrodes is the production of nano systems in circular chambers where the radial shape of the electrode allows for optimal production of nano systems and eliminates aberrant effects such as sticking to the walls of the chamber. In this arrangement, the inventory serves mainly for industrial production of nano particles.
  • the spinning strip may come in an unclosed linear shape with the length of 10 - 1,000 mm without curvature for linear layers deposition.
  • the structure of the electrode created homogenous or non-homogeneous electrical field on the spinning strip, which is achieved by the side curvature at the ends of the spinning strip leading to the adjustment of distribution for achieving maximum production in the active spinning zone.
  • the spinning strip thus allows for increasing the homogeneity of production and production capacity.
  • the cross-section shape of the spinning strip may consist of a combination of shapes:
  • Rectangle or square defined by its width and ranging between 0.1 mm and 1,000 mm.
  • the height of the shape may range between 1 mm and 10,000 mm;
  • the polymer is applied onto the spinning strip from the top, by means of a mechanical element connected with the polymer fluid stock container. Unlike the existing solutions it allows for an accurate application of the spun fluid on the upper part of the active spinning element only.
  • the application of the polymer onto the surface of the spinning strip is ensured by the movement of the strip and the application element.
  • the application element is made of polymer materials (e.g. POM, PE, PEEK), glass, ceramics, or metals (mainly compounds of Fe, Ni, Zn, Sn, Cr, Al, or Cu).
  • the application element is connected to the source of the polymer and allows, especially in configuration with the dosage pump, for an accurate regulation of the polymer volume delivered onto the electrode.
  • the system is characterised by allowing to apply a defined polymer coating onto the spinning strip by means of direct dosing and thus to affect the thickness of the applied polymer layer.
  • the dosage system may work on the principle of gravity flow of the fluid or mechanical forces (e.g. injection, peristaltic, piezoelectric, centrifugal, or pressure forces). Thanks to the periodical motion along the electrode it also cleans it from excess polymer and extends spinning times compared to the method of coating sans moving parts (e.g. needle electrode technique).
  • the electrode is integrated into the device for electrostatic spinning or spraying.
  • the conductivisation of the electrode is achieved by connecting to a source of direct or alternating current capable of generating 0 - 250 kV.
  • a charged electrode, onto which the polymer solution is applied, allows for atomisation of the solution or melt in the form of particles or fibres.
  • the movement of the mechanical parts is provided by a shielded moving apparatus that typically consists of a motor.
  • the moving apparatus drives the rotating mechanical parts with the speed of 0 - 20,000 rpm and the linear parts with 0 - 100 Hz frequency.
  • the moving mechanical part is the moving spinning strip and/or the application element.
  • the electrode allows for processing polymer (mainly lipids, polyesters, polyurethanes, polyalcohols, polyvinyl derivates, fluoridised polymers, polyamides, polyacrylates, biopolymers) of organic (mainly solutions of drugs, vitamins, cosmetic additives) or inorganic (mainly salts, oxides, sulphides, carbides, phosphates, carbonates, or silicates) solutions or melts.
  • the electrode is designated for processing mixtures of these solutions or melts.
  • the electrode can process colloid solutions in the form of emulsion (e.g. water/oil, oil/water, oil/water/oil types of emulsions) and dispersions (e.g. nano and micro particle dispersions).
  • the technique allows for transforming the components from the form of solutions into solid or semi-fluid state of matter.
  • the electrode is designated for encapsulation of live systems such as cells, bacteria, yeast, thrombocytes, or their parts (organelles, lyzates, secreted parts).
  • An enclosed circular or ellipsoidal spinning strip A design in which the electrode is represented by an enclosed or ellipsoidal spinning strip.
  • the spinning strip is fixed in the device of allow for the flow of air through the equipment.
  • the spinning strip is connected to high voltage sources and induces high voltage.
  • a collecting electrode with the opposite charge is typically placed opposite the electrode.
  • the solution is applied to the electrode by means of a moving application element.
  • the application element delivers the solution from the reservoir represented e.g. by a pressure pump. During the application of the solution the material flows from the strip electrode to the collecting electrode due to the effect of electrostatic forces.
  • the system of the electrodes is placed in a chamber with the Faraday cage.
  • the equipment contains a series of parallel or radially arranged electrodes to increase the system’s productivity.
  • the produced fibres and particles may be applied in a wide range of various fields.
  • the most important ones are medical applications, such as micro or nano carriers for controlled delivery of drugs, proteins, and nucleic acids.
  • Other areas include the food and pharmaceutical industry.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

La présente invention concerne une électrode destinée au traitement électrostatique de surface d'un matériau polymère. L'électrode est constituée d'une bande de filature et d'un élément de revêtement qui fournit et étale une solution filée pour produire des nanosystèmes fibreux ou particulaires au moyen d'un champ électromagnétique produit par une source de tension ayant une plage de différence de potentiel allant de 0 à 250 kV. L'invention concerne également la bande de filature et un dispositif fonctionnant sur une base d'électrode.
PCT/CZ2019/000010 2018-02-15 2019-02-13 Électrode destinée au traitement de surface de matériaux polymères WO2019158135A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CZ2018-74A CZ201874A3 (cs) 2018-02-15 2018-02-15 Elektroda pro hladinové elektrostatické zpracovávání polymerních materiálů
CZPV2018-74 2018-02-15

Publications (1)

Publication Number Publication Date
WO2019158135A1 true WO2019158135A1 (fr) 2019-08-22

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Application Number Title Priority Date Filing Date
PCT/CZ2019/000010 WO2019158135A1 (fr) 2018-02-15 2019-02-13 Électrode destinée au traitement de surface de matériaux polymères

Country Status (2)

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CZ (1) CZ201874A3 (fr)
WO (1) WO2019158135A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ294274B6 (cs) * 2003-09-08 2004-11-10 Technická univerzita v Liberci Způsob výroby nanovláken z polymerního roztoku elektrostatickým zvlákňováním a zařízení k provádění způsobu
WO2008106904A1 (fr) * 2007-03-08 2008-09-12 Elmarco S.R.O. Formation fibreuse linéaire comprenant des nanofibres de polymère, procédé et dispositif pour produire cette formation
CZ303024B6 (cs) * 2010-03-05 2012-02-29 Šafár@Václav Zpusob výroby nanovláken elektrostatickým zvláknováním polymerního roztoku a zarízení k provádení zpusobu
CZ306438B6 (cs) * 2011-04-12 2017-01-25 Elmarco S.R.O. Způsob a zařízení pro nanášení kapalné polymerní matrice na zvlákňovací struny

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ294274B6 (cs) * 2003-09-08 2004-11-10 Technická univerzita v Liberci Způsob výroby nanovláken z polymerního roztoku elektrostatickým zvlákňováním a zařízení k provádění způsobu
WO2008106904A1 (fr) * 2007-03-08 2008-09-12 Elmarco S.R.O. Formation fibreuse linéaire comprenant des nanofibres de polymère, procédé et dispositif pour produire cette formation
CZ303024B6 (cs) * 2010-03-05 2012-02-29 Šafár@Václav Zpusob výroby nanovláken elektrostatickým zvláknováním polymerního roztoku a zarízení k provádení zpusobu
CZ306438B6 (cs) * 2011-04-12 2017-01-25 Elmarco S.R.O. Způsob a zařízení pro nanášení kapalné polymerní matrice na zvlákňovací struny

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