EP0442405A2 - Process and apparatus for the preparation of moulded articles - Google Patents
Process and apparatus for the preparation of moulded articles Download PDFInfo
- Publication number
- EP0442405A2 EP0442405A2 EP91101843A EP91101843A EP0442405A2 EP 0442405 A2 EP0442405 A2 EP 0442405A2 EP 91101843 A EP91101843 A EP 91101843A EP 91101843 A EP91101843 A EP 91101843A EP 0442405 A2 EP0442405 A2 EP 0442405A2
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- European Patent Office
- Prior art keywords
- liquid
- channel system
- thread
- nozzle
- channel
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- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 55
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000007493 shaping process Methods 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 11
- 239000011888 foil Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 238000002166 wet spinning Methods 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 2
- 229920001007 Nylon 4 Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 229960005215 dichloroacetic acid Drugs 0.000 description 2
- 238000001891 gel spinning Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
Images
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
- D01D5/06—Wet spinning methods
-
- 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
- D01D5/12—Stretch-spinning methods
- D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
Definitions
- the invention relates to a method for shaping threads, hollow threads, flat foils or tubular foils and the like (tubes, plates) from thread-forming substances, from a homogeneous isotropic or anisotropic, single-phase or multi-phase liquid multi-material system and a device for carrying out the method.
- a pressure of 2.5-250 bar is set in the liquid below the nozzle and this is reduced in the course of the channel system.
- the pressure in the course of the channel system is preferably reduced to atmospheric pressure.
- a wavy deposit of the threads can be achieved in a simple manner in the method according to the invention by arranging a diffuser at the end of the channel system to reduce the flow velocity.
- the thread-forming substances are cellulose, polyamides, polyesters, polypropylene, polyethylene, PVA, and similar polymers and / or copolymers, and silicate, aluminate or similar inorganic thread-forming substances, individually or in mixtures.
- Solutions of the polymers for wet spinning come into question as single-phase systems. Suitable multi-phase systems are gels as used in gel spinning. Transitions between single-phase solutions and gels can also occur The inventive method are taken into account, which is particularly important if membrane images are sought.
- Suitable solvents for cellulose are, for example, cuoxam, xanthate, organic solvents such as N-methyl-morpholine oxide or dimethylacetamide, N-methylpyrrolidone etc., optionally with the addition of alkali and / or alkaline earth metal salts.
- formic acid is preferred for polyamides.
- Dichloroacetic acid or m-cresol are suitable for polyesters.
- the liquid moving through the channel system should not loosen the thread-forming substances and should only slowly convert the multi-substance system into the solid phase. It is preferred to work with optionally cooled and / or heated water, which fulfills these requirements by selecting the temperature, possibly differently in the course of the channel system.
- the liquid can contain a limited amount of the respective solvent or, in the case of gels, the swelling agent.
- the setting of the flow conditions in the channel system can now be carried out in such a way that the forces to be applied to narrow the cross-section of the shaped bodies are applied gently and uniformly.
- the cross-sectional tapering can be continued immediately after leaving the duct system or in subsequent process stages.
- the method according to the invention enables the deformation of thread-forming substances for which such a hitherto was not possible in an economical manner, or the product properties of deformed thread-forming substances are influenced in a particularly favorable manner.
- nylon 4 cannot be melt spun due to a lack of thermal stability. Known wet spinning processes are uneconomical because of the slow working speed. With the method according to the invention, nylon 4 can be economically formed into textile threads, formic acid being preferred as the solvent. Both acetone and water are suitable as liquids in the sewer system.
- the polyamide threads obtained have a moisture absorption comparable to that of cotton at 20 ° C. For example, it is 6% at 65% relative humidity and 11% at 90% relative humidity.
- Polyamide 6T (polyhexamethylene terephthalate) can be mentioned as a further polyamide, for which the process according to the invention can be used with advantage. This is deformed, for example, from a 16% solution in concentrated sulfuric acid in water or dilute sulfuric acid as a liquid in the sewer system.
- the process according to the invention produces properties which have an advantageous effect during use.
- the products obtained have a certain surface porosity, which results in a matt appearance.
- the thread produced according to the invention corresponds to a conventional thread without the addition of TiO2, to which 0.4% TiO2 was added.
- the handle is fuller and drier than conventional ones and no longer has the soapy handle familiar from polyamide 6.
- gel spinning processes have been carried out in two stages.
- the extrusion of the gel into a liquid is followed by a stretching process in hot gas.
- the process according to the invention has made it possible to deform gels in a liquid, that is to say a wet spinning process.
- a liquid which is miscible with the swelling component of the gel and which can also contain a limited amount of the swelling component to delay the solidification is selected as the liquid in the channel system.
- the temperature of the liquid is kept above the swelling temperature of the gel.
- polyamide 6,6 can also be formed from gels with dimethyl sulfoxide at temperatures of the liquid in the channel system of 150-190 ° C. into threads with good properties.
- water can optionally be used with small additions of DMSO2.
- the new process advantageously also deforms anisotropic liquid-crystalline solutions.
- Polyaramides such as poly-para-phenylene terephthalamide are usually spun from anisotropic liquid crystalline solutions through an air gap into a precipitation bath. Due to the premature crystallization, this technology considerably hinders orientation in the direction of the thread. If this anisotropic polyaramide solution is deformed in the process according to the invention at temperatures of the liquid in the channel system of more than 130 ° C., this premature crystallization is suppressed and the mechanical properties of the aramid thread are significantly increased by improving the transverse strength.
- Cellulose can be shaped in warm water according to the xyanthate process, so that instead of an acid bath with approx. 15% sulfuric acid, only very dilute acids are required for washing out, which reduces the environmental pollution from viscose factories.
- Deformation of polymer mixtures from liquid multi-component systems is also possible without restriction, provided the polymer mixtures form stable solutions or gels.
- An example of this is a mixture of 70% polyamide-6 and 30% cellulose-2-acetate in DMAC / LiCl solution.
- membranes or porous bodies are produced by the process according to the invention, then skin formation occurs excluded and the products obtained have open surfaces. This applies in particular to porous molded articles which are produced by thermally induced phase separation of polymer solutions which separate in a liquid manner.
- a cellulose-Cuoxam solution of the usual composition (approx. 10% cellulose, 7% NH3 3% Cu) was fed via a spinning pump after venting and filtration to a spinneret which was arranged in a channel system filled with water. In the area of the spinneret, the water was under pressure and had a temperature of 45 ° C. The water flowed through the canal system with the thread structure that formed. The overpressure reduced to atmospheric pressure.
- the dimensions of the duct system are given in detail together with the process parameters.
- the channel system ended at the drum circumference of a centrifuge in which the thread formed was deposited. The thread was then washed out for decoupling and any customary aftertreatments were then carried out in the centrifuge.
- Figure 1 and Figure 2 show a simplified schematic representation of a section of embodiments of the device according to the invention.
- the direction of flow of the thread-forming liquid multi-material system and the liquid is indicated by arrows.
- the devices for conveying, treating and pressing the thread-forming liquid multi-material system through the nozzle openings such as pumps, vents, filters, etc., the devices for supplying and discharging the liquid to and from the channel system and for generating the desired liquid overpressure in the channel system and the devices for Storage or reception of the shaped body, for example a winding device or a centrifuge for storing thread-shaped shaped bodies, are generally known to the person skilled in the art and are not shown in the figures.
- FIG. 1 shows the area in which a nozzle 1 with the nozzle channel 2 tapering at the end and the nozzle opening 3 opens into the channel system 4, that is to say in the liquid.
- the channel system 4 is ring-shaped and funnel-shaped above the nozzle opening 3 and tubular below the nozzle opening 3. The fact that the channel system 4 begins above the spinneret opening 3 and the liquid above the nozzle opening 3 is fed to the channel system 4 ensures that the thread-forming substance is pressed out of the nozzle opening 3 into the liquid with a fully pronounced liquid flow.
- the channel system 4 is designed so that any desired overpressure can be set in the area of the nozzle opening 3, ie it is closed except for the liquid supply (not shown) in the upper area and at the (not shown) outlet end for the liquid and the shaped body open. If desired, the nozzle 1 can also be surrounded by one or more heating and / or cooling jackets. The same also applies to the channel system 4. This makes it possible to run at different temperatures in the liquid in the course of the channel system. As shown in FIG. 1, the channel system 4 already has a cross section which tapers slightly in the flow direction immediately below the nozzle opening 3, which means that the flow velocity of the liquid increases accordingly and the static liquid pressure decreases accordingly.
- FIG. 2 shows two of a plurality of nozzles 1 arranged uniformly distributed on a circle, each with a stepwise tapering nozzle channel 2 and a nozzle opening 3.
- the channel system 4 is designed in a ring shape below the nozzle openings 3, which is achieved in that a floating, self-centering core 5 is arranged in the tube 6.
- the core 5 extends over the entire length of the channel system 4. It may end before the end of the channel system 4, so that the section of the channel system 4 which is not filled by the core 5 is thus tubular.
- the channel system 4 consists of sections with a constant and / or slightly tapering cross section. This can be achieved by appropriate design of the tube 6 and / or the core 5. Otherwise, what has been said for the embodiment shown in FIG. 1 applies accordingly.
- the nozzle 1 is preferably formed as a hollow needle in the area of the nozzle opening 3.
- hollow threads these can otherwise be configured essentially as is customary for this purpose and arranged as shown in FIGS. 1 and 2.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Artificial Filaments (AREA)
Abstract
Description
Die Erfindung betrifft ein verfahren zur Formgebung von Fäden, Hohlfäden, Flachfolien oder Schlauchfolien und dergleichen (Rohre, Platten) aus fadenbildenden Stoffen, aus einem homogenen isotropen oder anisotropen, ein- oder mehrphasigen flüssigen Mehrstoffsystem sowie eine Vorrichtung zum Durchführen des Verfahrens.The invention relates to a method for shaping threads, hollow threads, flat foils or tubular foils and the like (tubes, plates) from thread-forming substances, from a homogeneous isotropic or anisotropic, single-phase or multi-phase liquid multi-material system and a device for carrying out the method.
Ein solches Verfahren ist aus der JP-OS 61-19 805 bekannt. Diese bekannte Schrift lehrt zwar eine Erhöhung der Spinngeschwindigkeit bei Naßspinnverfahren auf etwa höchstens 1500 m/min, die Qualitätsanforderungen, die an textile Fäden gestellt werden müssen, werden dabei jedoch kaum erfüllt. So beträgt die Trockendehnung bei einer Spinngeschwindigkeit von 1500 m/min nur 10%.Such a method is known from JP-OS 61-19 805. Although this known document teaches an increase in the spinning speed in wet spinning processes to a maximum of about 1500 m / min, the quality requirements that must be placed on textile threads are hardly met. The dry elongation at a spinning speed of 1500 m / min is only 10%.
Aufgabe der vorliegenden Erfindung war es, die Arbeitsgeschwindigkeiten gegenüber den bisher üblichen signifikant zu erhöhen und die Qualität der Produkte wesentlich zu verbessern.It was an object of the present invention to significantly increase the working speeds compared to the hitherto usual and to significantly improve the quality of the products.
Gelöst wird diese Aufgabe durch ein Verfahren der eingangs beschriebenen Art, bei welchem erfindungsgemäß das flüssige Mehrstoffsystem durch eine oder mehrere Düsenöffnungen in eine unter Überdruck stehende und gegebenenfalls erhitzte und/oder gekühlte Flüssigkeit gepreßt wird, die Flüssigkeit in Laufrichtung in einem Kanalsystem bewegt wird, das aus Abschnitten mit konstantem und/oder sich leicht verjüngendem Querschnitt gebildet ist, und die Strömungsgeschwindigkeit der Flüssigkeit entsprechend erhöht wird.This object is achieved by a method of the type described at the outset, in which, according to the invention, the liquid multicomponent system is pressed through one or more nozzle openings into a pressurized and possibly heated and / or cooled liquid, the liquid being moved in the running direction in a channel system which is formed from sections with a constant and / or slightly tapering cross-section, and the flow rate of the liquid is increased accordingly.
Bei einer bevorzugten Ausgestaltung des Verfahrens wird in der Flüssigkeit unterhalb der Düse ein Druck von 2,5 - 250 bar eingestellt und dieser wird im Verlaufe des Kanalsystems verringert.In a preferred embodiment of the method, a pressure of 2.5-250 bar is set in the liquid below the nozzle and this is reduced in the course of the channel system.
Vorzugsweise wird der Druck im Verlaufe des Kanalsystems auf den Atmosphärendruck verringert.The pressure in the course of the channel system is preferably reduced to atmospheric pressure.
Eine wellige Ablage der Fäden kann beim erfindungsgemäßen Verfahren auf einfache Weise dadurch erreicht werden, daß am Ende des Kanalsystems ein Diffusor zur Verringerung der Strömungsgeschwindigkeit angeordnet wird.A wavy deposit of the threads can be achieved in a simple manner in the method according to the invention by arranging a diffuser at the end of the channel system to reduce the flow velocity.
Als fadenbildende Stoffe kommen Cellulose, Polyamide, Polyester, Polypropylen, Polyethylen, PVA, und ähnliche Polymere und/oder Copolymere sowie Silikat-, Aluminat oder ähnliche anorganische fadenbildende Stoffe einzeln oder in Mischungen in Frage.The thread-forming substances are cellulose, polyamides, polyesters, polypropylene, polyethylene, PVA, and similar polymers and / or copolymers, and silicate, aluminate or similar inorganic thread-forming substances, individually or in mixtures.
Als einphasige Systeme kommen Lösungen der Polymeren für das Naßspinnen in Frage. Mehrphasige geeignete Systeme sind Gele, wie sie beim Gelspinnen eingesetzt werden. Auch Übergänge zwischen einphasigen Lösungen und Gelen können beim erfindungsgemäßen Verfahren berücksichtigt werden, was insbesondere dann von Bedeutung ist, wenn Membrangebilde angestrebt werden.Solutions of the polymers for wet spinning come into question as single-phase systems. Suitable multi-phase systems are gels as used in gel spinning. Transitions between single-phase solutions and gels can also occur The inventive method are taken into account, which is particularly important if membrane images are sought.
Als Lösungsmittel für Cellulose sind beispielsweise Cuoxam, Xanthogenat, organische Lösungsmittel wie N-Methyl-Morpholin-Oxid oder Dimethylacetamid, N-Methylpyrrolidon etc., gegebenenfalls unter Zusatz von Alkali- und/oder Erdalkalisalzen geeignet. Für Polyamide ist beispielsweise Ameisensäure bevorzugt. Für Polyester sind Dichloressigsäure oder m-Kresol geeignet.Suitable solvents for cellulose are, for example, cuoxam, xanthate, organic solvents such as N-methyl-morpholine oxide or dimethylacetamide, N-methylpyrrolidone etc., optionally with the addition of alkali and / or alkaline earth metal salts. For example, formic acid is preferred for polyamides. Dichloroacetic acid or m-cresol are suitable for polyesters.
Die durch das Kanalsystem bewegte Flüssigkeit soll die fadenbildenden Stoffe nicht lösen und das Mehrstoffsystem nur langsam in die feste Phase überführen. Bevorzugt wird mit gegebenenfalls gekühltem und/oder erhitztem Wasser gearbeitet, welches diese Voraussetzungen durch Auswahl der Temperatur, gegebenenfalls unterschiedlich im Verlaufe des Kanalsystems, hervorragend erfüllt. Die Flüssigkeit kann eine begrenzte Menge des jeweiligen Lösungsmittels, oder bei Gelen des Quellungsmittels, enthalten.The liquid moving through the channel system should not loosen the thread-forming substances and should only slowly convert the multi-substance system into the solid phase. It is preferred to work with optionally cooled and / or heated water, which fulfills these requirements by selecting the temperature, possibly differently in the course of the channel system. The liquid can contain a limited amount of the respective solvent or, in the case of gels, the swelling agent.
Die Einstellung der Strömungsverhältnisse im Kanalsystem kann nunmehr so erfolgen, daß die zur Querschnittsverjüngung der Formkörper aufzubringenden Kräfte schonend und gleichmäßig aufgebracht werden.The setting of the flow conditions in the channel system can now be carried out in such a way that the forces to be applied to narrow the cross-section of the shaped bodies are applied gently and uniformly.
Die Arbeitsgeschwindigkeiten für Naßverformungen waren bisher auf wenige hundert m/min begrenzt und können durch das erfindungsgemäße Verfahren auf mehrere tausend m/min gesteigert werden.The working speeds for wet deformations were previously limited to a few hundred m / min and can be increased to several thousand m / min using the method according to the invention.
Die Querschnittsverjüngung kann auch nach Verlassen des Kanalsystems unmittelbar oder in nachfolgenden Prozeßstufen fortgesetzt werden.The cross-sectional tapering can be continued immediately after leaving the duct system or in subsequent process stages.
Das erfindungsgemäße Verfahren ermöglicht die Verformung von fadenbildenden Stoffen, für die eine solche bisher auf wirtschaftliche Weise nicht möglich war, oder es werden die Produkteigenschaften von verformten fadenbildenden Stoffen in besonderer Weise günstig beeinflußt.The method according to the invention enables the deformation of thread-forming substances for which such a hitherto was not possible in an economical manner, or the product properties of deformed thread-forming substances are influenced in a particularly favorable manner.
So ist beispielsweise Nylon 4 wegen fehlender Thermostabilität nicht schmelzspinnbar. Bekannte Naßspinnverfahren sind wegen der geringen Arbeitsgeschwindigkeit unwirtschaftlich. Mit dem erfindungsgemäßen Verfahren läßt sich Nylon 4 wirtschaftlich zu textilen Fäden verformen, wobei als Lösungsmittel Ameisensäure bevorzugt wird. Als Flüssigkeit im Kanalsystem eignen sich dabei sowohl Aceton als auch Wasser. Die erhaltenen Polyamidfäden haben eine mit Baumwolle vergleichbare Feuchtigkeitsaufnahme bei 20°C. Sie beträgt beispielsweise bei 65% relativer Feuchte 6% und bei 90% relativer Feuchte 11%.For example,
Als weiteres Polyamid, für das sich das erfindungsgemäße Verfahren mit Vorteil einsetzen läßt, ist Polyamid 6 T (Polyhexamethylenterephthalat) zu nennen. Dieses wird beispielsweise aus einer 16%igen Lösung in konzentrierter Schwefelsäure in Wasser oder verdünnter Schwefelsäure als Flüssigkeit im Kanalsystem verformt.Polyamide 6T (polyhexamethylene terephthalate) can be mentioned as a further polyamide, for which the process according to the invention can be used with advantage. This is deformed, for example, from a 16% solution in concentrated sulfuric acid in water or dilute sulfuric acid as a liquid in the sewer system.
Bei üblicherweise schmelzgesponnenen Fäden werden durch das erfindungsgemäße Verfahren Eigenschaften erzeugt, die sich vorteilhaft beim Gebrauch auswirken. So läßt sich Polyamid 6, gelöst in Ameisensäure, und Polyethylenterephthalat, gelöst in Dichloressigsäure, nach dem erfindungsgemäßen Verfahren verformen, wobei als Flüssigkeit im Kanalsystem beispielsweise Wasser verwendet wird.In the case of usually melt-spun threads, the process according to the invention produces properties which have an advantageous effect during use. For example,
Die erhaltenen Produkte weisen eine gewisse Oberflächenporosität auf, die ein mattes Aussehen bedingt. Der erfindungsgemäß hergestellte Faden entspricht ohne Zugabe von TiO₂ einem herkömmlichen Faden, dem 0,4% TiO₂ zugesetzt waren. Der Griff ist voller und trockener als bei herkömmlichen und hat auch den von Polyamid 6 bekannten seifigen Griff nicht mehr.The products obtained have a certain surface porosity, which results in a matt appearance. The thread produced according to the invention corresponds to a conventional thread without the addition of TiO₂, to which 0.4% TiO₂ was added. The handle is fuller and drier than conventional ones and no longer has the soapy handle familiar from
Da erfindungsgemäß keine Schmelzen, sondern flüssige Mehrstoffsysteme eingesetzt werden, können Flammschutzmittel und ähnliche Zusatzstoffe leichter in das flüssige Mehrstoffsystem zugemischt werden, als es bei Schmelzen möglich ist.Since, according to the invention, no melts, but rather liquid multi-material systems are used, flame retardants and similar additives can be mixed into the liquid multi-material system more easily than is possible with melts.
Gelspinnverfahren werden bisher zweistufig durchgeführt. So schließt sich an die Extrusion des Gels in eine Flüssigkeit ein Dehnprozeß in heißem Gas an. Durch das erfindungsgemäße Verfahren ist die Verformung von Gelen in einer Flüssigkeit, also ein Naßspinnverfahren möglich geworden. Als Flüssigkeit im Kanalsystem wird eine mit der quellenden Komponente des Geles mischbare Flüssigkeit ausgewählt, die auch eine begrenzte Menge der quellenden Komponente zur Verzögerung der Verfestigung enthalten kann. Die Temperatur der Flüssigkeit wird dabei über der Quellungstemperatur des Gels gehalten.So far, gel spinning processes have been carried out in two stages. The extrusion of the gel into a liquid is followed by a stretching process in hot gas. The process according to the invention has made it possible to deform gels in a liquid, that is to say a wet spinning process. A liquid which is miscible with the swelling component of the gel and which can also contain a limited amount of the swelling component to delay the solidification is selected as the liquid in the channel system. The temperature of the liquid is kept above the swelling temperature of the gel.
Da erfindungsgemäß Überdrucke von beispielsweise bis zu 250 bar vorgesehen sind, läßt sich beispielsweise auch Polyamid 6,6 aus Gelen mit Dimethylsulfoxid bei Temperaturen der Flüssigkeit im Kanalsystem von 150 - 190°C zu Fäden mit guten Eigenschaften verformen. Als Flüssigkeit im Kanalsystem kann Wasser ggf. mit geringen DMSO₂-Zusätzen verwendet werden.Since overpressures of, for example, up to 250 bar are provided according to the invention,
Mit dem neuen Verfahren werden vorteilhaft auch anisotrope flüssigkristalline Lösungen verformt.The new process advantageously also deforms anisotropic liquid-crystalline solutions.
Polyaramide wie beispielsweise Poly-para-phenylenterephthalamid werden üblicherweise aus anisotropen flüssigkristallinen Lösungen durch einen Luftspalt in ein Fällbad versponnen. Diese Technologie behindert durch die vorzeitige Kristallisation in erheblichem Maße die Orientierung in Fadenlaufrichtung. Erfolgt die Verformung dieser anisotropen Polyaramidlösung im erfindungsgemäßen Verfahren bei Temperaturen der Flüssigkeit im Kanalsystem von mehr als 130°C, wird diese vorzeitige Kristallisation unterdrückt und die mechanischen Eigenschaften des Aramidfadens werden durch Verbesserung der Querfestigkeit deutlich erhöht.Polyaramides such as poly-para-phenylene terephthalamide are usually spun from anisotropic liquid crystalline solutions through an air gap into a precipitation bath. Due to the premature crystallization, this technology considerably hinders orientation in the direction of the thread. If this anisotropic polyaramide solution is deformed in the process according to the invention at temperatures of the liquid in the channel system of more than 130 ° C., this premature crystallization is suppressed and the mechanical properties of the aramid thread are significantly increased by improving the transverse strength.
Cellulose kann nach dem Xyanthogenatverfahren in warmem Wasser verformt werden, so daß statt einem Säurebad mit ca. 15%iger Schwefelsäure nur sehr verdünnte Säuren zum Auswaschen benötigt werden, was die von Viskosefabriken ausgehenden Umweltbelastungen verringert.Cellulose can be shaped in warm water according to the xyanthate process, so that instead of an acid bath with approx. 15% sulfuric acid, only very dilute acids are required for washing out, which reduces the environmental pollution from viscose factories.
Die bei der Regeneration von Cellulose aus Lösungen in N-Alkyl-tert. Aminoxiden, wie z.B. N-Methylmorpholinoxid, zu beobachtende Fibrillierung der Fäden wird beim erfindungsgemäßen Verfahren durch die Verzögerung der Kristallisation vermieden.The regeneration of cellulose from solutions in N-alkyl tert. Amine oxides, e.g. N-methylmorpholine oxide, fibrillation of the threads which can be observed is avoided in the method according to the invention by delaying the crystallization.
Auch die Verformung von Polymergemischen aus flüssigen Mehrstoffsystemen ist ohne Einschränkung möglich, sofern die Polymergemische stabile Lösungen oder Gele bilden. Ein Beispiel hierfür ist ein Gemisch aus 70% Polyamid-6 und 30% Cellulose-2-acetat in DMAC/LiCl-Lösung.Deformation of polymer mixtures from liquid multi-component systems is also possible without restriction, provided the polymer mixtures form stable solutions or gels. An example of this is a mixture of 70% polyamide-6 and 30% cellulose-2-acetate in DMAC / LiCl solution.
Werden nach dem erfindungsgemäßen Verfahren Membranen oder poröse Körper hergestellt, dann ist eine Hautbildung ausgeschlossen und die erhaltenen Produkte haben offene Oberflächen. In besonderem Maße gilt dieses auch für poröse Formkörper, die durch thermisch induzierte Phasentrennung von sich flüssig entmischenden Polymerlösungen erzeugt werden.If membranes or porous bodies are produced by the process according to the invention, then skin formation occurs excluded and the products obtained have open surfaces. This applies in particular to porous molded articles which are produced by thermally induced phase separation of polymer solutions which separate in a liquid manner.
Die Erfindung wird anhand nachfolgender Beispiele näher erläutert.The invention is illustrated by the following examples.
Eine Cellulose-Cuoxamlösung üblicher Zusammensetzung (ca. 10% Cellulose, 7% NH₃ 3% Cu) wurde über eine Spinnpumpe nach Entlüften und Filtration einer Spinndüse zugeführt, die in einem mit Wasser gefüllten Kanalsystem angeordnet war. Im Bereich der Spinndüse stand das Wasser unter Überdruck und hatte eine Temperatur von 45°C. Das Wasser strömte mit dem sich bildenden Fadengebilde durch das Kanalsystem. Dabei verringerte sich der Überdruck auf den Atmosphärendruck.A cellulose-Cuoxam solution of the usual composition (approx. 10% cellulose, 7%
Die Abmessungen des Kanalsystems sind im einzelnen zusammen mit den Verfahrensparametern tabellarisch angegeben. Das Kanalsystem endete am Trommelumfang einer Zentrifuge, in der der gebildete Faden abgelegt wurde. Das Auswaschen des Fadens zur Entkupferung und gegebenenfalls übliche Nachbehandlungen wurden anschließend in der Zentrifuge vorgenommen.The dimensions of the duct system are given in detail together with the process parameters. The channel system ended at the drum circumference of a centrifuge in which the thread formed was deposited. The thread was then washed out for decoupling and any customary aftertreatments were then carried out in the centrifuge.
Weitere Angaben über die Versuchsparameter und die erzielten Produktdaten gehen aus den Tabellen 1 bis 3 hervor.
Die Erfindung wird nun anhand der Zeichnung näher erläutert.The invention will now be explained in more detail with reference to the drawing.
Figur 1 und Figur 2 zeigen in vereinfachter schematischer Darstellungsweise einen Ausschnitt aus Ausführungsformen der erfindungsgemäßen Vorrichtung.Figure 1 and Figure 2 show a simplified schematic representation of a section of embodiments of the device according to the invention.
In den Figuren ist die Strömungsrichtung des fadenbildenden flüssigen Mehrstoffsystems und der Flüssigkeit durch Pfeile angegeben. Die Einrichtungen zum Fördern, Behandeln und Pressen des fadenbildenden flüssigen Mehrstoffsystems durch die Düsenöffnungen wie Pumpen, Entlüftungen, Filter usw., die Einrichtungen zum Zuführen und Abführen der Flüssigkeit zu bzw. von dem Kanalsystem und zum Erzeugen des gewünschten Flüssigkeitsüberdruckes im Kanalsystem sowie die Einrichtungen zur Ablage oder Aufnahme des Formkörpers beispielsweise eine Aufwickeleinrichtung oder eine Zentrifuge zum Ablegen von fadenförmigen Formkörpern sind dem Fachmann allgemein bekannt und in den Figuren nicht dargestellt.In the figures, the direction of flow of the thread-forming liquid multi-material system and the liquid is indicated by arrows. The devices for conveying, treating and pressing the thread-forming liquid multi-material system through the nozzle openings such as pumps, vents, filters, etc., the devices for supplying and discharging the liquid to and from the channel system and for generating the desired liquid overpressure in the channel system and the devices for Storage or reception of the shaped body, for example a winding device or a centrifuge for storing thread-shaped shaped bodies, are generally known to the person skilled in the art and are not shown in the figures.
In Figur 1 ist der Bereich dargestellt, in dem eine Düse 1 mit dem sich am Ende verjüngenden Düsenkanal 2 und der Düsenöffnung 3 in das Kanalsystem 4 also in der Flüssigkeit mündet. Das Kanalsystem 4 ist oberhalb der Düsenöffnung 3 ring- und trichterförmig und unterhalb der Düsenöffnung 3 rohrförmig ausgebildet. Dadurch, daß das Kanalsystem 4 oberhalb der Spinndüsenöffnung 3 beginnt und auch die Flüssigkeit oberhalb der Düsenöffnung 3 dem Kanalsystem 4 zugeführt wird, wird erreicht, daß das Auspressen des fadenbildenden Stoffes aus der Düsenöffnung 3 in die Flüssigkeit bei voll ausgeprägter Flüssigkeitsströmung erfolgt. Das Kanalsystem 4 ist so ausgebildet, daß im Bereich der Düsenöffnung 3 jeder gewünschte Überdruck eingestellt werden kann, d.h. es ist bis auf die (nicht dargestellte) Flüssigkeitszuführung im oberen Bereich geschlossen und am (nicht dargestellten) Austrittsende für die Flüssigkeit und den Formkörper geöffnet. Falls gewünscht, kann die Düse 1 auch von einem oder mehreren Heiz- und/oder Kühlmänteln umgeben sein. Das gleiche gilt auch für das Kanalsystem 4. Hierdurch ist es möglich, im Verlaufe des Kanalsystems auch mit unterschiedlichen Temperaturen in der Flüssigkeit zu fahren. Wie in Figur 1 darstellt, weist das Kanalsystem 4 bereits unmittelbar unterhalb der Düsenöffnung 3 einen in Strömungsrichtung sich leicht verjüngenden Querschnitt auf, wodurch erreicht wird, daß die Strömungsgeschwindigkeit der Flüssigkeit entsprechend zunimmt und der statische Flüssigkeitsdruck entsprechend abnimmt.FIG. 1 shows the area in which a
In Figur 2 sind zwei von mehreren auf einem Kreis gleichmäßig verteilt angeordneten Düsen 1 mit je einem sich stufenweise verjüngenden Düsenkanal 2 und einer Düsenöffnung 3 dargestellt. Das Kanalsystem 4 ist bei dieser Ausführungsform unterhalb der Düsenöffnungen 3 ringförmig ausgebildet, was dadurch erreicht wird, daß in dem Rohr 6 ein fliegend aufgehängter, sich selbst zentrierender Kern 5 angeordnet ist. Der Kern 5 erstreckt sich über die gesamte Länge des Kanalsystems 4. Er kann ggf. bereits vor dem Ende des Kanalsystems 4 enden, so daß der nicht durch den Kern 5 ausgefüllte Abschnitt des Kanalsystems 4 somit rohrförmig ausgebildet ist. Auch bei dieser Ausführungsform besteht das Kanalsystem 4 aus Abschnitten mit konstantem und/oder sich leicht verjüngendem Querschnitt. Dies kann durch entsprechende Ausgestaltung des Rohres 6 und/oder des Kernes 5 erreicht werden. Im übrigen gilt das für die in Figur 1 dargestellte Ausführungsform Gesagte entsprechend.FIG. 2 shows two of a plurality of
Vorteilhaft für das Verfahren ist es, wenn die Querschnittsänderung des Kanalsystems stetig, also nicht plötzlich (unstetig), erfolgt, derart, daß das Verhältnis der Durchmesserdifferenz auf einer Kanallänge L zur Kanallänge L möglichst 1 : 50 (= 0,02) oder kleiner ist. Die Düse 1 ist im Bereich der Düsenöffnung 3 vorzugsweise als Hohlnadel ausgebildet. Zum Herstellen von Hohlfäden können diese ansonsten im wesentlichen wie hierfür üblich ausgebildet und wie in den Figuren 1 und 2 dargestellt angeordnet sein.It is advantageous for the method if the cross-sectional change in the channel system takes place continuously, i.e. not suddenly (discontinuously), in such a way that the ratio of the diameter difference over a channel length L to the channel length L is as small as 1:50 (= 0.02) or less . The
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4004798 | 1990-02-16 | ||
| DE4004798A DE4004798A1 (en) | 1990-02-16 | 1990-02-16 | METHOD AND DEVICE FOR PRODUCING MOLDED BODIES |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0442405A2 true EP0442405A2 (en) | 1991-08-21 |
| EP0442405A3 EP0442405A3 (en) | 1992-10-21 |
| EP0442405B1 EP0442405B1 (en) | 1995-12-13 |
Family
ID=6400271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91101843A Expired - Lifetime EP0442405B1 (en) | 1990-02-16 | 1991-02-09 | Process and apparatus for the preparation of moulded articles |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0442405B1 (en) |
| JP (1) | JPH059803A (en) |
| AT (1) | ATE131547T1 (en) |
| DE (2) | DE4004798A1 (en) |
| ES (1) | ES2080173T3 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19515137A1 (en) * | 1995-04-25 | 1996-10-31 | Thueringisches Inst Textil | Process for the production of flat cellulose films |
| US5589125A (en) * | 1992-03-17 | 1996-12-31 | Lenzing Aktiengesellschaft | Process of and apparatus for making cellulose mouldings |
| US5698151A (en) * | 1993-07-01 | 1997-12-16 | Lenzing Aktiengesellschaft | Process of making cellulose fibres |
| WO1998001606A1 (en) * | 1996-07-04 | 1998-01-15 | Barmag Ag | Wet spinning method and device |
| US5939000A (en) * | 1993-05-24 | 1999-08-17 | Acordis Fibres (Holdings) Limited | Process of making cellulose filaments |
| WO2002055769A1 (en) * | 2000-11-03 | 2002-07-18 | Honeywell International Inc. | Spinning, processing, and applications of carbon nanotube filaments, ribbons, and yarns |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170151835A1 (en) * | 2014-06-06 | 2017-06-01 | Bridgestone Corporation | Tire |
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| DE509294C (en) * | 1930-10-06 | Fr Kuettner Akt Ges | Spinning funnel for the production of rayon using the draw spinning process | |
| US2510135A (en) * | 1947-08-25 | 1950-06-06 | American Viscose Corp | Method for spinning artificial filaments |
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| DE1660144B1 (en) * | 1964-03-25 | 1972-06-29 | Asahi Chemical Ind | Spinning funnel for wet draw spinning of copper ammonia silk at high speed |
| GB1130497A (en) * | 1966-10-21 | 1968-10-16 | Asahi Chemical Ind | Process for the high-speed funnel spinning of viscose filaments |
| GB1193314A (en) * | 1966-10-24 | 1970-05-28 | Asahi Chemical Ind | Funnel Spinning of Viscose Rayon Filaments |
| DE2056872A1 (en) * | 1969-11-15 | 1971-05-27 | Asahi Kasei Kogyo K K , Osaka (Ja pan) | High speed wet spinning of synthetic fibres - or filaments from melts |
| US3798297A (en) * | 1970-09-22 | 1974-03-19 | Bemberg Spa | Method for spinning filaments which have been regenerated from a solution of cuprammonium cellulose and filaments produced thereby |
| JP2603971B2 (en) * | 1987-11-09 | 1997-04-23 | 旭化成工業株式会社 | Flow tube wet spinning method |
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- 1990-02-16 DE DE4004798A patent/DE4004798A1/en not_active Withdrawn
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- 1991-02-09 ES ES91101843T patent/ES2080173T3/en not_active Expired - Lifetime
- 1991-02-09 EP EP91101843A patent/EP0442405B1/en not_active Expired - Lifetime
- 1991-02-09 DE DE59107049T patent/DE59107049D1/en not_active Expired - Fee Related
- 1991-02-09 AT AT91101843T patent/ATE131547T1/en not_active IP Right Cessation
- 1991-02-14 JP JP3020873A patent/JPH059803A/en active Pending
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|---|---|---|---|---|
| DE509294C (en) * | 1930-10-06 | Fr Kuettner Akt Ges | Spinning funnel for the production of rayon using the draw spinning process | |
| US2510135A (en) * | 1947-08-25 | 1950-06-06 | American Viscose Corp | Method for spinning artificial filaments |
| US3049755A (en) * | 1959-08-03 | 1962-08-21 | Asahi Chemical Ind | Process and apparatus for stretch spinning cuprammonium rayon |
| JPS59228013A (en) * | 1983-06-09 | 1984-12-21 | Asahi Chem Ind Co Ltd | Flowing bath spinning of viscose rayon |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5589125A (en) * | 1992-03-17 | 1996-12-31 | Lenzing Aktiengesellschaft | Process of and apparatus for making cellulose mouldings |
| US5798125A (en) * | 1992-03-17 | 1998-08-25 | Lenzing Aktiengesellschaft | Device for the preparation of cellulose mouldings |
| US5968434A (en) * | 1992-03-17 | 1999-10-19 | Lenzing Aktiengesellschaft | Process of making cellulose moldings and fibers |
| US5939000A (en) * | 1993-05-24 | 1999-08-17 | Acordis Fibres (Holdings) Limited | Process of making cellulose filaments |
| US5951932A (en) * | 1993-05-24 | 1999-09-14 | Acordis Fibres (Holdings) Limited | Process of making cellulose filaments |
| US5698151A (en) * | 1993-07-01 | 1997-12-16 | Lenzing Aktiengesellschaft | Process of making cellulose fibres |
| DE19515137A1 (en) * | 1995-04-25 | 1996-10-31 | Thueringisches Inst Textil | Process for the production of flat cellulose films |
| WO1998001606A1 (en) * | 1996-07-04 | 1998-01-15 | Barmag Ag | Wet spinning method and device |
| WO2002055769A1 (en) * | 2000-11-03 | 2002-07-18 | Honeywell International Inc. | Spinning, processing, and applications of carbon nanotube filaments, ribbons, and yarns |
| US6682677B2 (en) | 2000-11-03 | 2004-01-27 | Honeywell International Inc. | Spinning, processing, and applications of carbon nanotube filaments, ribbons, and yarns |
| US7247290B2 (en) | 2000-11-03 | 2007-07-24 | Honeywell International Inc. | Spinning, processing, and applications of carbon nanotube filaments, ribbons, and yarns |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0442405B1 (en) | 1995-12-13 |
| DE4004798A1 (en) | 1991-08-22 |
| EP0442405A3 (en) | 1992-10-21 |
| ES2080173T3 (en) | 1996-02-01 |
| JPH059803A (en) | 1993-01-19 |
| DE59107049D1 (en) | 1996-01-25 |
| ATE131547T1 (en) | 1995-12-15 |
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