EP1024222A2 - Process for the treatment of textile materials - Google Patents

Process for the treatment of textile materials Download PDF

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Publication number
EP1024222A2
EP1024222A2 EP00101395A EP00101395A EP1024222A2 EP 1024222 A2 EP1024222 A2 EP 1024222A2 EP 00101395 A EP00101395 A EP 00101395A EP 00101395 A EP00101395 A EP 00101395A EP 1024222 A2 EP1024222 A2 EP 1024222A2
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European Patent Office
Prior art keywords
voltage
substrate
pulses
fibers
reactor
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EP00101395A
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German (de)
French (fr)
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EP1024222A3 (en
Inventor
Werner Ing. Schmitz
Gottfried Ing. Holzer
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eybl International AG
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eybl International AG
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Priority claimed from DE10000805A external-priority patent/DE10000805A1/en
Application filed by eybl International AG filed Critical eybl International AG
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D06M10/025Corona discharge or low temperature plasma
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04Physical treatment combined with treatment with chemical compounds or elements

Definitions

  • the invention relates to a method for finishing textile substrates in low temperature plasma reactors.
  • the invention has therefore set itself the task of finishing organic to create textile substrates at low temperatures, taking the substrate evenly encased by the matrix, not just coated and that regardless of what form the substrate is in, whether it is made of fibers, monofilaments, Fabric braiding, thread rolls or other types of linkage exists.
  • the Equipment should also be independent of whether the substrate is natural or synthetic materials. A prerequisite should also be that there is no chemical conversion of the substrate, but only one Improvement of the function of the substrate for certain areas of use.
  • the object is achieved by the in the characterizing part of claim 1 contained features solved.
  • the procedure described therein enables a space-filling plasma in the reactor, surprisingly has shown that the individual particles in different directions on the Impact the substrate and thus form a matrix around each fiber of the substrate, it does not matter what form the substrate is in. This is what it is about is not a one-sided coating, but actually an all-round coating Sheathing, as amazing as this fact is. It can be natural or synthetic textile fibers or monofilaments or textile materials made up of them his. With the method according to the invention, textiles become new functions grafted on by sheathing each fiber of the substrate.
  • the frequency of the voltage pulses is in the ultrasound range, since then the Turbulence and the kinetic energy of the particles is greatest.
  • the treatment process is carried out so that all pulses of electrical Voltage have the same polarity.
  • the particles of the matrix become so highly kinetic Energy hurled at the substrate that the particles hit the fibers of the substrate sheath and also penetrate into the individual fibrils of the substrate and thus be embedded in the lattice structure of the fibrils, even with one multilayer substrate without chemical changes in the Substrate can be made.
  • Particles with a comparatively low kinetic Energy is stored on the surface of the fibers due to the resistance to penetration from and encase them, whereby the direction of movement of the particles also plays a role can play.
  • the higher-energy particles implant themselves in the fiber or penetrate the fiber or fibers to settle on the neighboring fibers to deposit or also to store in it or to penetrate it, etc.
  • Thermoplastics such as polypropylene and polyethylene treated substrates become.
  • What is new according to the invention is the sheathing of the fibers within the textile surface or within a yarn or a monofilament as well as a multifilament, and the incorporation of the matrix particles into the substrate.
  • Activation i.e. a change the surface tension in a gas plasma, e.g. an oxygen plasma without Target to form a matrix
  • the substrate special function e.g. to convey an improvement in the dyeability.
  • a cleaning process is taking place at the same time, since in the oxygen plasma organic contaminants on the substrate, e.g. Fat in its non-toxic Basic building blocks are disassembled.
  • the textile substrate can be in the form of a fabric, braid, fleece, non-woven or a thread, thread bundle and in the form of fibers of a fiber mass.
  • the matrix is also implanted, but remain anyway - be it again emphasizes - preserve the characteristic properties of the textile substrate, such as. Flexibility, tear and tensile strength or gas and liquid permeability.
  • the look of the textile is not affected either. It deals is not a fabric coating that affects porosity would, but really every fiber, whether short or long, is covered.
  • the Sheathing takes place without noticeable space, because the sheathing layer is in the nano range. No gluing was observed either.
  • the matrix particles penetrate due to the kinetic energy between the molecules of the substrate, so that a heterogeneous mixture is created and the treating textile substrates are wash, boil and cleaning resistant.
  • the pulses superimposed on the base voltage have approximately one evenly steep increase in voltage and an uneven decrease with a peak voltage in the range of KeV, preferably between 2-5 KeV.
  • the frequency of the voltage is in the ultrasound range and is preferably 100-300 MHz.
  • the pressure in the reactor is below 10 mbar, preferably between 1-2 mbar.
  • the process can be carried out in various gas plasmas, e.g. Nitrogen, oxygen, Carbon dioxide or possibly also monomer gases are carried out.
  • gas plasmas e.g. Nitrogen, oxygen, Carbon dioxide or possibly also monomer gases are carried out.
  • Matrix come organic and inorganic materials and their compounds and also synthetic materials in use as a target in the Reactor are inserted. Examples include metals, metal alloys, Metal carbides and oxides, silicates, borates and organic molecules.
  • the substrates can be made from all fibers and continuous fibers (monofilaments) Links exist. It is also possible to mix in the flake Treat spun or mixed threads from both natural and made of synthetic, organic or inorganic fibers, including surfaces as well Threads and flakes as bulk goods can be treated.
  • the functions applied by the substrates can e.g. following demands fulfill.
  • An antistatic can be achieved, the electrical conductivity can be improved shielding against electromagnetic Waves can be obtained, as well as an abrasion resistance, an improved one Sliding behavior, low creasing, a water and stain resistant function. UV protection and IR protection are also possible. All differentiations can not listed here.
  • Turbulence in the plasma reactor generated the matrix particles be removed from the target from all directions with such a high kinetic Impact energy on the substrate that they surprisingly encase are implanted and penetrate the fibers, so that without rewinding e.g. B. spools of thread and rolled-up textile webs can be equipped.
  • bulk material can be encased without circulation of the substrate material and there are crosshairs, overlaps and undercuts no light-shadow effect.
  • the essence of the present invention is that Changes in the technical properties of every fine fibril in every modification of a textile material is made possible. It is the invention around the sheathing and penetration of fibers in porous surfaces. In which The method according to the invention therefore does not seal the textile; so it remains breathable.
  • Fig. 1 illustrates a preferred course of successive Pulses of the same electrical voltage as a function of time.
  • this Drawing is the voltage of the pulses in KeV (kiloelectron volts) on the The ordinate plots the time on the abscissa.
  • the Periods of the pulses about twice as long as the voltage-free periods between two consecutive pulses, i.e. the tension-free periods in about 50% of the time between two successive pulses.
  • FIG. 2 shows a scanning electron micrograph of a carbon fiber, the has been treated with titanium carbide according to the inventive method.
  • the embedded matrix particles are closed as small white spots on the image see.
  • the casing is the white outer ring.
  • Fig. 3 is a recording of several fibers from a thread, the fibers are individually encased by the method according to the invention.
  • An example of the method according to the invention is based on an endless one Described carbon filaments with fiber diameters of 5, the carbon filaments are processed into a fabric and the fabric in a low pressure chamber while maintaining a pressure of 2 mbar in a nitrogen atmosphere or treated in an argon atmosphere using the low-temperature plasma process.
  • Coating was applied to the inside of the wall of the treatment chamber e.g. B. Titanium carbite and polytetrafluoroethylene applied to the formation of Support room plasma from all sides.
  • the pulses of the electrical voltage have a repetition frequency of 150 MHz, the peak voltage of the pulses was 3 KeV.
  • the pulses had the voltage time dependence shown in FIG. 1.
  • the current flow depends on the volume and the conductivity of the substrate. in the In the present case, it was 0.1 to 0.2 watts per liter volume of the substrate.
  • the treatment was carried out for a few minutes.
  • tensile strength and abrasion resistance of the carbon fiber fabrics treated in this way before and after the treatment are listed in the following tables: tensile strenght Fabric without cover Covered fabric Chain 36887 cN 39585 cN Shot 37855 cN 38915 cN Abrasion resistance hole formation at Fabric without cover Covered fabric Chain 3000 tours 6500 tours shot 4000 tours 8000 tours
  • the abrasion resistance was checked on a Martingdale device.

Abstract

The finishing process for textile substrates, using a matrix material in the voltage field of a low temp. plasma reactor, gives a pulsed voltage at the voltage field with a plasma within a sealed chamber. The frequency of the separate voltage pulses is in the ultrasonic range and the peak voltages are in the kilo electron volt (KeV) range.

Description

Die Erfindung bezieht sich auf ein Verfahren zur Ausrüstung von textilen Substraten in Niedertemperaturplasmareaktoren.The invention relates to a method for finishing textile substrates in low temperature plasma reactors.

Oft ist es wünschenswert, textile Substrate zusätzlich auszurüsten und ihnen nicht vorhandene Funktionen zu geben, um zum Beispiel eine bessere Färbbarkeit, eine bessere Flexibilität leicht brüchiger Materialien, eine Verbesserung der Scheuerfestigkeit, eine schwere Entflammbarkeit in Art eines Selbstlöscheffektes und/ oder eine UV-Beständigkeit zu erreichen.It is often desirable to add textile substrates to them to give functions that are not available, for example to improve dyeability, better flexibility of slightly brittle materials, an improvement in abrasion resistance, flame retardancy in the form of a self-extinguishing effect and / or to achieve UV resistance.

Es ist bereits zum Ausrüsten von Textilbahnen das sogenannte Umrollverfahren bekannt geworden. Dabei wird die Gewebebahn auf eine leere Rolle gerollt und während des Umrollvorganges mittels einer Plasmaquelle mit Matrixmaterial bestrahlt. Abgesehen davon, daß nur Bahnenmaterial, Garne bzw. Garnrollen und Vliese an der Plasmaquelle vorbeigeführt werden können und dadurch behandelbar sind, hat der Auftrag noch den Nachteil, daß die dabei entstehende Beschichtung nur auf die Oberfläche aufgebracht wird, da die Plasmapartikel nur in einer Richtung auf das Substrat strahlen. Es tritt dabei eine Ungleichheit der Beschichtung auf, die zu einem sogenannten Licht-Schatten-Effekt führt. Außerdem ist die Strahlungsbreite einer Plasmaquelle geringer als die Breite normaler Textilbahnen, so daß mehrere Plasmaquellen bei bahnenformigem Substrat nebeneinander eingesetzt werden müssen, was ebenfalls zu Ungleichmäßigkeiten in der Beschichtung führt.It is already the so-called rewinding process for finishing textile webs known. The fabric web is rolled onto an empty roll and irradiated with matrix material during the rewinding process by means of a plasma source. Apart from the fact that only web material, yarns or spools of thread and Nonwovens can be guided past the plasma source and can thus be treated are, the order still has the disadvantage that the resulting coating is only applied to the surface since the plasma particles are only in one direction radiate onto the substrate. This causes the coating to be unequal which leads to a so-called light-shadow effect. Besides, that is Radiation width of a plasma source is less than the width of normal textile webs, so that several plasma sources are used side by side with a web-shaped substrate must be, which also leads to unevenness in the coating leads.

Die Erfindung hat sich deshalb zur Aufgabe gemacht, eine Ausrüstung von organischen textilen Substraten bei niederen Temperaturen zu schaffen, wobei das Substrat gleichmäßig von der Matrix ummantelt, nicht nur beschichtet wird und zwar unabhängig davon, in welcher Form das Substrat vorliegt, ob es aus Fasern, Monofilen, Gewebegeflechten, Fadenrollen oder anderen Verknüpfungsarten besteht. Die Ausrüstung soll ferner davon unabhängig sein, ob das Substrat aus natürlichen oder synthetischen Materialien aufgebaut ist. Voraussetzung soll dabei auch sein, daß keine chemischen Umwandlung des Substrates erfolgt, sondern nur eine Verbesserung der Funktion des Substrates für bestimmte Verwendungsbereiche.The invention has therefore set itself the task of finishing organic to create textile substrates at low temperatures, taking the substrate evenly encased by the matrix, not just coated and that regardless of what form the substrate is in, whether it is made of fibers, monofilaments, Fabric braiding, thread rolls or other types of linkage exists. The Equipment should also be independent of whether the substrate is natural or synthetic materials. A prerequisite should also be that there is no chemical conversion of the substrate, but only one Improvement of the function of the substrate for certain areas of use.

Die gestellte Aufgabe wird erfindungsgemäß durch die im kennzeichnenden Teil des Anspruches 1 enthaltenen Merkmale gelöst. Das darin beschriebene Verfahren ermöglicht ein raumfüllendes Plasma im Reaktor, wobei sich überraschenderweise gezeigt hat, daß die einzelnen Partikel in unterschiedlichen Richtungen auf das Substrat auftreffen und somit eine Matrix um jede Faser des Substrates bilden, wobei es gleichgültig ist, in welcher Form das Substrat vorliegt. Dabei handelt es sich nicht um einseitige Beschichtung, sondern tatsächlich um eine allseitige Ummantelung, so erstaunlich diese Tatsache auch ist. Es können natürliche oder synthetische Textilfasern oder Monofile oder daraus aufgebaute textile Materialien sein. Mit dem erfindungsgemäßen Verfahren werden Textilien neue Funktionen aufgepropft, indem jede Faser des Substrats ummantelt wird.The object is achieved by the in the characterizing part of claim 1 contained features solved. The procedure described therein enables a space-filling plasma in the reactor, surprisingly has shown that the individual particles in different directions on the Impact the substrate and thus form a matrix around each fiber of the substrate, it does not matter what form the substrate is in. This is what it is about is not a one-sided coating, but actually an all-round coating Sheathing, as amazing as this fact is. It can be natural or synthetic textile fibers or monofilaments or textile materials made up of them his. With the method according to the invention, textiles become new functions grafted on by sheathing each fiber of the substrate.

Die Frequenz der Pulse der Spannung liegt dabei im Ultraschallbereich, da dann die Turbulenz und die kinetische Energie der Partikel am größten ist. Vorzugsweise wird das Behandlungsverfahren so durchgeführt, daß alle Pulse der elektrischen Spannung gleiche Polarität haben.The frequency of the voltage pulses is in the ultrasound range, since then the Turbulence and the kinetic energy of the particles is greatest. Preferably the treatment process is carried out so that all pulses of electrical Voltage have the same polarity.

Bei diesem Verfahren werden die Partikel der Matrix mit so hoher kinetischer Energie auf das Substrat geschleudert, daß die Partikel die Fasern des Substrats ummanteln und auch in die einzelnen Fibrillen des Substrates eindringen und somit in die Gitterstruktur der Fibrillen eingelagert werden und das auch bei einem mehrschichtigen Substrat, ohne daß dabei chemische Veränderungen in dem Substrat vorgenommen werden. Partikel mit vergleichsweise geringer kinetischer Energie lagern sich wegen des Eindringwiderstandes auf der Oberfläche der Fasern ab und ummanteln diese, wobei auch die Bewegungsrichtung der Partikel eine Rolle spielen kann. Die energiereicheren Partikel implantieren sich in der Faser oder durchdringen die Faser bzw. Fasern, um sich auf den benachbarten Fasern abzulagern oder auch sich in dieser einzulagern oder sie zu durchdringen usw.. Infolge der Verwendung eines Niedertemperaturplasmas können sogar aus Thermoplasten, wie Polypropylen und Polyethylen hergestellte Substrate behandelt werden.With this method, the particles of the matrix become so highly kinetic Energy hurled at the substrate that the particles hit the fibers of the substrate sheath and also penetrate into the individual fibrils of the substrate and thus be embedded in the lattice structure of the fibrils, even with one multilayer substrate without chemical changes in the Substrate can be made. Particles with a comparatively low kinetic Energy is stored on the surface of the fibers due to the resistance to penetration from and encase them, whereby the direction of movement of the particles also plays a role can play. The higher-energy particles implant themselves in the fiber or penetrate the fiber or fibers to settle on the neighboring fibers to deposit or also to store in it or to penetrate it, etc. As a result of using a low temperature plasma you can even get out Thermoplastics such as polypropylene and polyethylene treated substrates become.

Es hat sich gezeigt, daß bei Auskleidung des Reaktorraumes mit einem Wirrfaservlies aus keramischen Materialien besonders gute Ergebnisse erzielt werden.It has been shown that when the reactor space is lined with a random fiber fleece particularly good results can be achieved from ceramic materials.

Das erfindungsgemäß Neue ist die Ummantelung der Fasern innerhalb der Textilfläche oder innerhalb eines Garns oder eines Monofils ebenso wie eines Multifils, sowie die Einlagerung der Matrixpartikel in das Substrat. What is new according to the invention is the sheathing of the fibers within the textile surface or within a yarn or a monofilament as well as a multifilament, and the incorporation of the matrix particles into the substrate.

Dem erfindungsgemäßen Verfahren kann eine Aktivierung, d.h. eine Veränderung der Oberflächenspannung in einem Gasplasma, z.B. einem Sauerstoffplasma ohne Target zur Bildung einer Matrix vorgeschaltet werden, um dem Substrat eine besondere Funktion, z.B. eine Verbesserung der Anfärbbarkeit zu vermitteln. Außerdem geht dabei gleichzeitig ein Reinigungsprozeß vor sich, da im Sauerstoffplasma organische Verunreinigungen auf dem Substrat, z.B. Fett in seine ungiftigen Grundbausteine zerlegt werden.Activation, i.e. a change the surface tension in a gas plasma, e.g. an oxygen plasma without Target to form a matrix can be connected to the substrate special function, e.g. to convey an improvement in the dyeability. In addition, a cleaning process is taking place at the same time, since in the oxygen plasma organic contaminants on the substrate, e.g. Fat in its non-toxic Basic building blocks are disassembled.

Das textile Substrat kann in Form eines Gewebes, Geflechts, Vlieses, Non-wovens oder eines Fadens, Fadenbündels und in Form von Fasern einer Fasermasse vorliegen. Die Matrix wird dabei auch implantiert, jedoch bleiben trotzdem - es sei nochmals betont - die charakteristischen Eigenschaften des textilen Substrates erhalten, wie z.B. Flexibilität, Reiß- und Zugfestigkeit oder die Gas- und Flüssigkeitsdurchlässigkeit. Auch die Optik des Textils wird dabei nicht beeinträchtigt. Es handelt sich also nicht um eine Gewebebeschichtung, die die Porigkeit beeinträchtigen würde, sondern es wird wirklich jede Faser ob kurz oder lang ummantelt. Die Ummantelung erfolgt ohne spürbare Raumeinnahme, da die Ummantelungsschicht im Nanobereich liegt. Auch wurde keine Verklebung beobachtet. Die Matrixpartikel dringen infolge der kinetischen Energie zwischen die Moleküle des Subtrates, so daß eine heterogene Mischung entsteht und die behandelnden textilen Substrate wasch-, koch- und reinigungsbeständig sind.The textile substrate can be in the form of a fabric, braid, fleece, non-woven or a thread, thread bundle and in the form of fibers of a fiber mass. The matrix is also implanted, but remain anyway - be it again emphasizes - preserve the characteristic properties of the textile substrate, such as. Flexibility, tear and tensile strength or gas and liquid permeability. The look of the textile is not affected either. It deals is not a fabric coating that affects porosity would, but really every fiber, whether short or long, is covered. The Sheathing takes place without noticeable space, because the sheathing layer is in the nano range. No gluing was observed either. The matrix particles penetrate due to the kinetic energy between the molecules of the substrate, so that a heterogeneous mixture is created and the treating textile substrates are wash, boil and cleaning resistant.

Infolge der Umhüllung der einzelnen Fasern durch die Matrix erfolgt eine schattenfreie Aufbringung des Behandlungsmaterials in ein mehrschichtiges Gebilde bzw. in eine Fasermasse. Es zeigt sich, daß in denjenigen Fasern des textilen Substrates, welches an der Außenseite des mehrschichtigen textilen Gebildes bzw. der Fasermasse befanden und in diejenigen Fasern, welche sich im Kernbereich des mehrschichtigen textilen Gebildes bzw. Substrates befanden in etwa gleichen Mengen des Matrixmaterials eingebracht und von diesem ummantelt wurden. As a result of the covering of the individual fibers by the matrix, there is a shadow-free one Application of the treatment material in a multilayer structure or into a mass of fibers. It turns out that in those fibers of the textile substrate, which on the outside of the multilayer textile structure or the fiber mass and in those fibers that are in the core area of the multilayer Textile structure or substrate were in roughly equal amounts of the matrix material were introduced and encased by this.

Die der Basisspannung überlagerten Pulse weisen erfindungsgemäß einen etwa gleichmäßig steilen Anstieg der Spannung auf und einen ungleichmäßigen Abfall mit einer Spitzenspannung im Bereich von KeV vorzugsweise zwischen 2 - 5 KeV. Zwischen den Pulsen der elektrischen Spannung liegen spannungsfreie Zeiträume, deren Dauer etwa 50 - 60 % der Anlagezeit der Pulse ausmacht. Die Frequenz der Spannung ist im Ultraschallbereich angesiedelt und beträgt vorzugsweise 100 - 300 MHz. Der Druck in dem Reaktor liegt unterhalb von 10 mbar, vorzugsweise zwischen 1-2 mbar.According to the invention, the pulses superimposed on the base voltage have approximately one evenly steep increase in voltage and an uneven decrease with a peak voltage in the range of KeV, preferably between 2-5 KeV. There are no voltage between the pulses of the electrical voltage Periods of time that make up around 50 - 60% of the pulse's investment time. The The frequency of the voltage is in the ultrasound range and is preferably 100-300 MHz. The pressure in the reactor is below 10 mbar, preferably between 1-2 mbar.

Das Verfahren kann in verschiedenen Gasplasmen, wie z.B. Stickstoff, Sauerstoff, Kohlendioxyd oder gegebenenfalls auch Monomergase durchgeführt werden. Als Matrix kommen organische und anorganische Materialien sowie deren Verbindungen und auch synthetische Materialien in Anwendung, die als Target in dem Reaktor eingelegt sind. Beispielhaft zu nennen sind Metalle, Metallegierungen, Metallcarbide und oxyde, Silikate, Borate und organische Moleküle.The process can be carried out in various gas plasmas, e.g. Nitrogen, oxygen, Carbon dioxide or possibly also monomer gases are carried out. As Matrix come organic and inorganic materials and their compounds and also synthetic materials in use as a target in the Reactor are inserted. Examples include metals, metal alloys, Metal carbides and oxides, silicates, borates and organic molecules.

Die Substrate können aus allen aus Fasern und Endlosfasern (Monofilen) hergestellten Verknüpfungen bestehen. Auch ist es möglich, in der Flocke gemischte Gespinste oder gemischte Zwirne zu behandeln sowohl aus natürlichen als auch aus synthetischen, organischen oder anorganischen Fasern, auch Flächen sowie Fäden und auch Flocken als Schüttgut können behandelt werden.The substrates can be made from all fibers and continuous fibers (monofilaments) Links exist. It is also possible to mix in the flake Treat spun or mixed threads from both natural and made of synthetic, organic or inorganic fibers, including surfaces as well Threads and flakes as bulk goods can be treated.

Die durch die Substrate aufgetragenen Funktionen können z.B. folgende Forderungen erfüllen. Es kann eine Antistatik erreicht werden, die elektrische Leifähigkeit kann verbessert werden, eine Abschirmung gegen elektromagnetische Wellen kann erhalten werden, sowie eine Scheuerbeständigkeit, ein verbessertes Gleitverhalten, eine Knitterarmut, eine wasser- und fleckabweisende Funktion. Auch ist ein UV-Schutz und IR-Schutz möglich. Alle Differenzierungen können hier nicht aufgeführt werden. The functions applied by the substrates can e.g. following demands fulfill. An antistatic can be achieved, the electrical conductivity can be improved shielding against electromagnetic Waves can be obtained, as well as an abrasion resistance, an improved one Sliding behavior, low creasing, a water and stain resistant function. UV protection and IR protection are also possible. All differentiations can not listed here.

Zusammenfassend ist zu sagen, daß die durch das erfindungsgemäß vorgeschlagene Verfahren erzeugten Turbulenzen im Plasmareaktor die Matrixpartikel, die von dem Target abgetragen werden, aus allen Richtungen mit einer so hohen kinetischen Energie auf das Substrat aufprallen, daß sie überraschenderweise ummanteln, implantiert werden sowie die Fasern durchdringen, so daß ohne Umrollprozeß z. B. Garnspulen und aufgerollte Textilbahnen ausgerüstet werden können. In gleicher Weise kann Schüttgut ohne Umwälzung des Substratmaterials ummantelt werden und es gibt an Fadenkreuzungen, Überlagerungen und Hinterschneidungen kein Licht-Schatten-Effekt. Das Wesentliche vorliegender Erfindung liegt darin, daß Änderungen technischer Eigenschaften jeder noch so feinen Fibrillen in jeder Modifikation eines textilen Materials ermöglicht wird. Es handelt sich bei der Erfindung um die Ummantelung und Durchdringung von Fasern in porösen Flächen. Bei dem erfindungsgemäßen Verfahren wird somit das Textil nicht zugesiegelt; es bleibt also atmungsaktiv.In summary it can be said that the one proposed by the invention Turbulence in the plasma reactor generated the matrix particles be removed from the target from all directions with such a high kinetic Impact energy on the substrate that they surprisingly encase are implanted and penetrate the fibers, so that without rewinding e.g. B. spools of thread and rolled-up textile webs can be equipped. In in the same way, bulk material can be encased without circulation of the substrate material and there are crosshairs, overlaps and undercuts no light-shadow effect. The essence of the present invention is that Changes in the technical properties of every fine fibril in every modification of a textile material is made possible. It is the invention around the sheathing and penetration of fibers in porous surfaces. In which The method according to the invention therefore does not seal the textile; so it remains breathable.

Die Fig. 1 veranschaulicht einen bevorzugten Verlauf aufeinanderfolgender Pulse gleicher elektrischer Spannung in Abhängigkeit von der Zeit. In dieser Zeichnung ist die Spannung der Pulse in KeV (Kiloelektronenvolt) auf der Ordinate aufgetragen die Zeit auf der Abzisse. In der dargestellten Figur sind die Zeiträume der Pulse etwa doppelt so lang wie die spannungsfreien Zeiträume zwischen zwei sich folgenden Pulse, also die spannungsfreien Zeiträume betragen in etwa 50 % der Zeit zwischen zwei sich folgenden Pulsen.Fig. 1 illustrates a preferred course of successive Pulses of the same electrical voltage as a function of time. In this Drawing is the voltage of the pulses in KeV (kiloelectron volts) on the The ordinate plots the time on the abscissa. In the figure shown are the Periods of the pulses about twice as long as the voltage-free periods between two consecutive pulses, i.e. the tension-free periods in about 50% of the time between two successive pulses.

Die Fig. 2 zeigt eine Rasterelektronenmikroskopaufnahme einer Kohlefaser, die gemäß dem erfindungsgemäßen Verfahren mit Titancarbid behandelt worden ist. Die eingelagerten Matrixpartikel sind auf der Aufnahme als kleine weißen Stellen zu sehen. Die Ummantelung ist der weiße Außenring. 2 shows a scanning electron micrograph of a carbon fiber, the has been treated with titanium carbide according to the inventive method. The embedded matrix particles are closed as small white spots on the image see. The casing is the white outer ring.

In Fig. 3 ist eine Aufnahme von mehreren Fasern aus einem Faden, deren Fasern einzeln nach dem erfindungsgemäßen Verfahren ummantelt sind.In Fig. 3 is a recording of several fibers from a thread, the fibers are individually encased by the method according to the invention.

Ein Beispiel des erfindungsgemäßen Verfahrens ist nachfolgend an Hand eines endlosen Kohlefilaments mit Faserdurchmessern von 5 beschrieben, wobei die Kohlefilamente zu einem Gewebe verarbeitet sind und das Gewebe in einer Niederdruckkammer unter Einhaltung eines Druckes von 2 mbar in einer Stickstoffatmosphäre oder in einer Argonatmonsphäre nach dem Niedertemperaturplasmaverfahren behandelt. Auf die Innenseite der Wand der Behandlungskammer wurde Beschichtung z. B. Titancarbit und Polytetrafluorethylen aufgebracht, um die Bildung von Raumplasma von allen Seiten zu stützen. Die Pulse der elektrischen Spannung haben eine Wiederholfrequenz von 150 MHz, die Spitzenspannung der Pulse betrug 3 KeV. Die Pulse hatten die in Fig. 1 gezeigte Zeitabhängigkeit der Spannung.An example of the method according to the invention is based on an endless one Described carbon filaments with fiber diameters of 5, the carbon filaments are processed into a fabric and the fabric in a low pressure chamber while maintaining a pressure of 2 mbar in a nitrogen atmosphere or treated in an argon atmosphere using the low-temperature plasma process. Coating was applied to the inside of the wall of the treatment chamber e.g. B. Titanium carbite and polytetrafluoroethylene applied to the formation of Support room plasma from all sides. The pulses of the electrical voltage have a repetition frequency of 150 MHz, the peak voltage of the pulses was 3 KeV. The pulses had the voltage time dependence shown in FIG. 1.

Der Stromfluß ist vom Volumen und der Leitfähigkeit des Substrates abhängig. Im vorliegenden Fall betrug er 0,1 bis 0,2 Watt pro Liter Volumen des Substrates.The current flow depends on the volume and the conductivity of the substrate. in the In the present case, it was 0.1 to 0.2 watts per liter volume of the substrate.

Die Behandlung erfolgte während weniger Minuten.The treatment was carried out for a few minutes.

In den nachfolgenden Tabellen sind die Zugfestigkeit und die Scheuerfestigkeit der so behandelten Kohlefasergewebe vor der Behandlung und nach der Behandlung angeführt: Zugfestigkeit Gewebe ohne Ummantelung Gewebe mit Ummantelung Kette 36887 cN 39585 cN Schuß 37855 cN 38915 cN Scheuerfestigkeit Lochbildung bei Gewebe ohne Ummantelung Gewebe mit Ummantelung Kette 3000 Touren 6500 Touren Schuss 4000 Touren 8000 Touren The tensile strength and abrasion resistance of the carbon fiber fabrics treated in this way before and after the treatment are listed in the following tables: tensile strenght Fabric without cover Covered fabric Chain 36887 cN 39585 cN Shot 37855 cN 38915 cN Abrasion resistance hole formation at Fabric without cover Covered fabric Chain 3000 tours 6500 tours shot 4000 tours 8000 tours

Die Scheuerbeständigkeit wurde an einem Martingdale-Gerät überprüft.The abrasion resistance was checked on a Martingdale device.

Aus den obigen Ergebnissen sieht man, daß durch das Behandlungsverfahren die hohen Zugfestigkeitswerte der Kohlefasern sogar noch erhöht wurden. Die Scheuerfestigkeit wurde jedoch, wie aus den Untersuchungen am Martingdale-Gerät ersichtlich, in hervorragender Weise verbessert. Es zeigt sich dabei, daß auch Dünnstschichten, die ressourcenschonend sind, auch als Funktionsschicht eine große Wirksamkeit besitzen. Infolge des schon erwähnten Implantiereffektes durch den eine heterogene Molekülmischung ohne eine chemische Reaktion erfolgt, wird ein Abrieb oder ein Abblättern der Schicht vermieden und die guten Werte hinsichtlich der Scheuerbeständigkeit erreicht.From the results above, it can be seen that the treatment process high tensile strength values of the carbon fibers were even increased. The abrasion resistance However, as can be seen from the tests on the Martingdale device, improved in an excellent way. It shows that also Thin layers that conserve resources, also as a functional layer have great effectiveness. As a result of the implantation effect already mentioned which is a heterogeneous mixture of molecules without a chemical reaction abrasion or peeling of the layer avoided and the good values regarding the abrasion resistance achieved.

Claims (13)

Verfahren zur Ausrüstung textiler Substrate aller Art durch Behandlung mit Matrixmaterialien in dem Spannungsfeld eines Niedertemperaturplasmareaktors,
gekennzeichnet durch
Anlegen einer gepulsten Spannung an das Spannungsfeld eines Niedertemperaturplasmareaktors mit in einer gasdichten Kammer erzeugten Plasma, wobei die Frequenz der einzelnen Pulse der elektrischen Spannung im Ultraschallbereich liegt und die Spitzenspannung im KeV-Bereich.
Process for finishing textile substrates of all kinds by treatment with matrix materials in the stress field of a low-temperature plasma reactor,
marked by
Applying a pulsed voltage to the voltage field of a low-temperature plasma reactor with plasma generated in a gas-tight chamber, the frequency of the individual pulses of the electrical voltage being in the ultrasound range and the peak voltage in the KeV range.
Verfahren nach Anspruch 1,
dadurch gekennzeichnet,
daß alle Pulse der elektrischen Spannung gleiche Polarität aufweisen.
Method according to claim 1,
characterized,
that all pulses of the electrical voltage have the same polarity.
Verfahren nach Anspruch 1,
dadurch gekennzeichnet,
daß die Kammer des Reaktors mit einem Wirrfaservlies ausgelegt ist.
Method according to claim 1,
characterized,
that the chamber of the reactor is designed with a random fiber fleece.
Verfahren nach Anspruch 3,
dadurch gekennzeichnet,
daß das Wirrfaservlies aus keramischen Materialien besteht.
Method according to claim 3,
characterized by
that the random fiber fleece consists of ceramic materials.
Verfahren nach Anspruch 1,
dadurch gekennzeichnet,
daß das Substrat aus natürlichen oder synthetischen Textilfasern oder -faden sowie darauf aufgebauten Verknüpfungen und Formen besteht.
Method according to claim 1,
characterized by
that the substrate consists of natural or synthetic textile fibers or threads as well as links and shapes based thereon.
Verfahren nach Ansprüchen 1 und 3,
dadurch gekennzeichnet,
daß das Matrixmaterial aus organischen, anorganischen und synthetischen Stoffen einschließlich deren Verbindungen besteht, die als Target in den Reaktor eingelegt sind.
Method according to claims 1 and 3,
characterized by
that the matrix material consists of organic, inorganic and synthetic substances including their compounds, which are inserted as a target in the reactor.
Verfahren nach Anspruch 1,
dadurch gekennzeichnet,
daß das Substrat zunächst aktiviert und dann behandelt wird.
Method according to claim 1,
characterized by
that the substrate is first activated and then treated.
Verfahren nach den Ansprüchen 1 oder 3,
66 dadurch gekennzeichnet,
daß die Partikel der Matrix mit so hoher kinetischer Energie auf die Fasern des Substrats auftreffen, daß die Partikel die Fasern ummanteln, in die einzelnen Fibrillen des Substrats eindringen und in die Gitterstruktur der Fibrillen auch bei einem mehrschichtigen Substrat eingelagert werden, ohne daß Verklebungen und/oder eine meßbare Raumvergrößerung des Substrats erfolgen.
Method according to claims 1 or 3,
66 characterized
that the particles of the matrix hit the fibers of the substrate with such high kinetic energy that the particles coat the fibers, penetrate into the individual fibrils of the substrate and are embedded in the lattice structure of the fibrils even in the case of a multilayer substrate, without adhesions and / or a measurable enlargement of the substrate.
Verfahren nach den Anspruch 2,
dadurch gekennzeichnet,
daß zwischen den Pulsen der elektrischen Spannung spannungsfreie Zeiträume liegen, wobei die Dauer der spannungsfreien Zeiträume etwa 40 - 60 % der Pulsdauer betragen.
Method according to claim 2,
characterized by
that there are voltage-free periods between the pulses of the electrical voltage, the duration of the voltage-free periods being approximately 40-60% of the pulse duration.
Verfahren nach einem oder mehreren der vorhergehenden Ansprüche,
dadurch gekennzeichnet,
daß dieses in einer Gasatmosphäre erfolgt und der Druck, unter welchem die Plasmabehandlung stattfindet, unterhalb von 10 mbar liegt.
Method according to one or more of the preceding claims,
characterized by
that this takes place in a gas atmosphere and the pressure at which the plasma treatment takes place is below 10 mbar.
Verfahren nach Anspruch 1,
dadurch gekennzeichnet,
daß die der Basisspannung überlagerten Pulse einen gleichmäßig steilen Anstieg der Spannung und einen ungleichmäßigen Abfall aufweisen.
Method according to claim 1,
characterized by
that the pulses superimposed on the base voltage have a uniformly steep increase in voltage and an uneven decrease.
Verfahren nach Ansprüchen 1 oder 10,
dadurch gekennzeichnet,
daß die Spitzenspannung im Bereich von 2 - 5 KeV liegt.
Method according to claims 1 or 10,
characterized by
that the peak voltage is in the range of 2-5 KeV.
Nach dem Verfahren gemäß einem oder mehreren der vorhergehenden Ansprüche ausgerüsteten textilen Substrates.According to the method according to one or more of the preceding Equipped substrate.
EP00101395A 1999-01-27 2000-01-25 Process for the treatment of textile materials Withdrawn EP1024222A3 (en)

Applications Claiming Priority (4)

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DE19903080 1999-01-27
DE19903080 1999-01-27
DE10000805 2000-01-11
DE10000805A DE10000805A1 (en) 1999-01-27 2000-01-11 Process for finishing textile substrates

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EP1024222A3 EP1024222A3 (en) 2000-09-13

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Publication number Priority date Publication date Assignee Title
WO2013014211A2 (en) 2011-07-25 2013-01-31 Eckart Gmbh Use of specially coated powdered coating materials and coating methods using such coating materials
WO2013014214A2 (en) 2011-07-25 2013-01-31 Eckart Gmbh Coating method using special powdered coating materials and use of such coating materials
WO2013014213A2 (en) 2011-07-25 2013-01-31 Eckart Gmbh Methods for substrate coating and use of additive-containing powdered coating materials in such methods
DE102011052119A1 (en) 2011-07-25 2013-01-31 Eckart Gmbh Coating method of particle-containing powdery coating material used for automobile component, involves performing flame spraying, high-speed flame spraying, thermal plasma spraying and/or non-thermal plasma spraying method
EP2959992A1 (en) 2014-06-26 2015-12-30 Eckart GmbH Method for producing a particulate-containing aerosol

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US4840636A (en) * 1983-10-18 1989-06-20 Fraunhofer Geselschaft E.V. Modifying the surface of the interior pore walls of objects such as membranes with gas activated by partial brush discharge
EP0571953A1 (en) * 1992-05-26 1993-12-01 Nitto Denko Corporation Hydrophilic fiber sheet and process for producing the same
EP0803342A1 (en) * 1996-04-25 1997-10-29 Japan Vilene Company, Ltd. A process for treating outer/inner surfaces of a porous non-conductor and the modified porous non-conductor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4840636A (en) * 1983-10-18 1989-06-20 Fraunhofer Geselschaft E.V. Modifying the surface of the interior pore walls of objects such as membranes with gas activated by partial brush discharge
EP0571953A1 (en) * 1992-05-26 1993-12-01 Nitto Denko Corporation Hydrophilic fiber sheet and process for producing the same
EP0803342A1 (en) * 1996-04-25 1997-10-29 Japan Vilene Company, Ltd. A process for treating outer/inner surfaces of a porous non-conductor and the modified porous non-conductor

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013014211A2 (en) 2011-07-25 2013-01-31 Eckart Gmbh Use of specially coated powdered coating materials and coating methods using such coating materials
WO2013014214A2 (en) 2011-07-25 2013-01-31 Eckart Gmbh Coating method using special powdered coating materials and use of such coating materials
WO2013014213A2 (en) 2011-07-25 2013-01-31 Eckart Gmbh Methods for substrate coating and use of additive-containing powdered coating materials in such methods
DE102011052121A1 (en) 2011-07-25 2013-01-31 Eckart Gmbh Coating process using special powder coating materials and use of such coating materials
DE102011052120A1 (en) 2011-07-25 2013-01-31 Eckart Gmbh Use of specially coated, powdery coating materials and coating methods using such coating materials
DE102011052119A1 (en) 2011-07-25 2013-01-31 Eckart Gmbh Coating method of particle-containing powdery coating material used for automobile component, involves performing flame spraying, high-speed flame spraying, thermal plasma spraying and/or non-thermal plasma spraying method
US9580787B2 (en) 2011-07-25 2017-02-28 Eckart Gmbh Coating method using special powdered coating materials and use of such coating materials
EP2959992A1 (en) 2014-06-26 2015-12-30 Eckart GmbH Method for producing a particulate-containing aerosol

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