EP0743381A2 - Procédé pour stabiliser thermiquement des produits multicouches à base de fibres de polyacrylonitrile - Google Patents
Procédé pour stabiliser thermiquement des produits multicouches à base de fibres de polyacrylonitrile Download PDFInfo
- Publication number
- EP0743381A2 EP0743381A2 EP96106044A EP96106044A EP0743381A2 EP 0743381 A2 EP0743381 A2 EP 0743381A2 EP 96106044 A EP96106044 A EP 96106044A EP 96106044 A EP96106044 A EP 96106044A EP 0743381 A2 EP0743381 A2 EP 0743381A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- gas
- fibers
- dimensional sheet
- temperatures
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 66
- 230000008569 process Effects 0.000 title claims abstract description 23
- 230000003019 stabilising effect Effects 0.000 title 1
- 239000000835 fiber Substances 0.000 claims abstract description 89
- 239000007789 gas Substances 0.000 claims abstract description 78
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 41
- 230000006641 stabilisation Effects 0.000 claims abstract description 40
- 238000011105 stabilization Methods 0.000 claims abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 230000001105 regulatory effect Effects 0.000 claims abstract description 12
- 239000004744 fabric Substances 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000004753 textile Substances 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 229920000620 organic polymer Polymers 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000007669 thermal treatment Methods 0.000 claims description 4
- 238000009940 knitting Methods 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 238000013021 overheating Methods 0.000 claims description 2
- 238000009941 weaving Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 18
- 239000000203 mixture Substances 0.000 abstract description 16
- 239000004745 nonwoven fabric Substances 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 8
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001272 nitrous oxide Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000005293 duran Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 235000013842 nitrous oxide Nutrition 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000005475 siliconizing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011318 synthetic pitch Substances 0.000 description 1
- 238000010003 thermal finishing Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- -1 wool Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
- D01F9/225—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles from stabilised polyacrylonitriles
Definitions
- the invention relates firstly to a method for producing a multi-dimensional sheet-like structure composed of carbon or predominantly composed of carbon from a starting material consisting of polyacrylonitrile or essentially polyacrylonitrile, secondly a plant for carrying out the method and a felt produced by this method.
- the thermally stabilized fibers first have to be crimped, then cut into staple fibers and then a felt has to be made from the staple fibers in a last step.
- Such a process is cumbersome and time-consuming because the PAN fibers lose part of their textile properties during thermal stabilization and are then more difficult to process into the various textile structures.
- the application of the method is necessary, however, because during thermal stabilization, strongly exothermic reactions take place in the fiber and because of the hindrance of the heat transfer when stabilizing entire textile layers or webs, the fibers adiabatically overheat and as a result the fibers melt or burn off .
- the invention was therefore based on the object of a method for the direct transfer of polyacrylonitrile or essentially polyacrylonitrile, multi-dimensional sheet-like structures composed of fibers, such as, for example, woven, knitted, knitted, laid, felted, nonwoven, into the infusible, non-carbonized form to provide in one process step.
- the task was, in particular, to provide a continuously operating method of this type, which offers the possibility of precisely regulating the reaction temperatures in the flat structures as a function of time.
- Another object was to provide a device or system by means of which the method according to the invention can be carried out.
- non-meltable, non-carbonized form of fibers or of multi-dimensional sheet-like structures made of fibers used in the claims and in the description is synonymous with the term “thermally stabilized” or “stabilized” fibers or fiber-made multi-dimensional sheet-like structures and was used to clearly differentiate this thermal treatment stage of the fibers or flat structures from those stages which are reached at temperatures above 320 ° C. and which are either designated with “partially carbonized”, “carbonized” or with “graphitized”.
- multi-dimensional sheet-like structure constructed from fibers the term “fabric web” is also used in the following due to the shorter spelling.
- the filaments in the fabric must be supplied with sufficient heat to start the reactions taking place during stabilization. From the time of the start, the total of the enthalpies of reaction is strongly exothermic and the reactions would go off with the consequence of the melting or burning of the material web, if this did not prevent the use of control measures.
- the essential feature of the method according to the invention is that the multi-dimensional sheet-like structures or fabric webs made up of PAN fibers are characterized by a gas or gas mixture which is tempered in an appropriately adapted manner during the entire thermal stabilization phase characterized by the initial heat requirement and the subsequent exothermic area is flowed through. In the start-up phase, such an amount of heat is applied to the fibers transferred that the stabilization reactions begin to take place.
- Those parameters determined according to the method described above, which can be easily measured and controlled even in a continuously operating system and which are used to set and maintain the desired temperature profile in the fabric, are then transferred to the production system.
- the monitoring and fine control of the temperature of the fabric in this system can then, if necessary, be done, for example, by measuring the temperature difference between gas flowing in and out of the fabric or, in the case of thin fabrics, by measuring the surface temperature of the fabric.
- the temperature profile during the stabilization can be controlled isothermally after the start of the reactions involved in the stabilization, decreasing starting from a certain temperature level or increasing starting from such a temperature level. Where necessary, combinations of the three types of temperature profiles mentioned can also be used.
- a fabric web for example a felt, in which the fibers are arranged very close to one another, has a high energy density in the reactions taking place during the stabilization, its thermal insulation capacity is very good and it is comparatively difficult to flow through. Driving too fast at too high temperatures would damage the fabric until the reaction went through. At first glance, it seems that it is loose but made of very thick fibers or bundles of fibers, e.g.
- a fabric, scrim or knitted fabric also has to be stabilized relatively slowly and at temperatures that are not too high, because here, despite good possibilities for heat transfer and removal, flowing gas overheating of the interior of the fibers or fiber bundles must be avoided and the stabilization reactions take a certain time because of their diffusion-controlled process.
- a thin fabric web of loose fiber structure made of thin threads which can be stabilized in a relatively short time at a comparatively high temperature, is relatively unproblematic. Given the above, it is difficult to specify a preferred driving style. Because of the importance of the invention for high mass throughputs on fabric webs, however, the preferred method is that which has the shortest time for thermal stabilization if certain quality criteria are met for the fabric web.
- stabilization can also be carried out with gas mixtures are carried out, the composition of which changes during the stabilization reaction or an inert gas, for example nitrogen or argon, is used for part of the reaction and the gas containing an oxidizing agent is used for the other part.
- an inert gas for example nitrogen or argon
- the fibers can first be pre-oxidized and loaded with oxygen under oxidizing conditions and the reactions can then be completed under inert gas in the manner envisaged.
- the temperature range within which the stabilization is generally carried out is between 180 and 320, preferably between 220 and 260 ° C., these temperatures being defined as the temperatures which the gas flowing through the fabric web has on the upstream side.
- the temperatures of the individual fibers in the fabric web can be up to a maximum of 10 K above the temperatures of the inflowing gas when the specified gas temperatures and proper reaction sequence are used.
- the stabilization is carried out within a period in the range from 0.5 to 10 hours, preferably from 0.5 to 6 hours.
- the stabilization can also be carried out with considerably longer times, however, the process then becomes increasingly uneconomical and the flat structure or its fibers can suffer, for example due to excessive oxygen absorption, quality losses.
- oxygen donors are all oxygen-releasing substances which can be converted into gas or vapor form, but especially molecular oxygen, ozone, sulfur trioxide, nitrogen dioxide or nitrous oxide, nitrous oxide or laughing gas and nitrogen monoxide. These substances are generally used in cases where this is possible, not in pure form, but in a mixture with an inert carrier gas.
- the proportion of substances consisting of or containing oxygen is preferably 20 percent by volume, based on the gas mixture, equal to 100%.
- the particularly preferred gas mixture used is air.
- Partial carbonization, carbonization and graphitization can follow the stabilization process for further processing of the multi-dimensional flat structures as additional, subsequent process steps.
- one or more of these additional process steps can be carried out in plants which are coupled to the oxidation plant or which are part of this plant.
- the partial carbonization is carried out in a manner known per se in the temperature range from 320 to 800 ° C., preferably from 500 to 700 ° C., in an inert atmosphere.
- this process step which can also be carried out continuously, the carbon content of the material webs is further increased by releasing hydrogen, oxygen and heteroatoms, in particular nitrogen, and the degree of crosslinking of the carbon skeleton in the filaments is increased.
- Partially carbonized panels can be used, for example, for flame-retardant textiles, insulating linings, as filter material or for the production of composite materials.
- Partial carbonization can be followed by carbonization, which is carried out in an inert atmosphere in the temperature range from 800 to 1800 ° C., preferably from 800 to 1400 ° C.
- carbonization which is carried out in an inert atmosphere in the temperature range from 800 to 1800 ° C., preferably from 800 to 1400 ° C.
- the fibers forming the multidimensional flat structure are completely converted into carbon.
- Such multi-dimensional flat structures can be used under protective gas up to the highest temperatures. They are extremely corrosion-resistant and have a comparatively high electrical resistance. Therefore, they can be used, for example, as filter material or as substrate material for catalytic or electrochemical applications. Felts so produced can e.g. can also be used as a high-temperature insulating material in a non-oxidizing atmosphere due to their heat-insulating properties.
- the main area of application for carbonized material webs is the production of composite materials, in particular composite materials with a synthetic resin or carbon matrix.
- the last thermal finishing stage to which the multi-dimensional sheet-like structures produced by the process according to the invention can be subjected is graphitizing, which is carried out in an inert atmosphere in the temperature range from 1800 to approximately 3000 ° C., preferably in the range above 2000 ° C.
- This process step can also be carried out continuously, for example with a system according to DE utility model 72 31 623.
- Each of the multi-dimensional sheet-like structures produced by one of the methods described is suitable for the production of a wide variety of composite materials.
- suitable materials for a variety of applications can be produced in conjunction with appropriate further processing and / or finishing steps such as carbonizing, graphitizing, impregnating, coating, siliconizing or activating.
- the apparatus for determining the parameters with which the method is controlled in a continuous mode of operation and then the system for the continuous thermal stabilization of multidimensional flat structures based on PAN fibers are first described as examples.
- a speed-controllable fan 17 ' At the end of the outflow area of the apparatus, after a gas cooling section (not shown), there is a speed-controllable fan 17 ', by means of which a differential pressure to the pressure in the inflow area can be regulated in order to improve the flow through the fabric web in the outflow area.
- a fabric web 18 is unwound from a web roll 20 located on an unwinding unit 19, on a grating 21, preferably a wire grating made of thin wires and with large open meshes, through an oven 23 consisting of at least one spatial section 22, in which the conditions for the thermal stabilization is maintained, transported and wound up on a winding device 24 after leaving the furnace 23.
- the grating 21 is expediently moved through the oven 23 in synchronism with the fabric web 18. For this purpose, it runs as an endless belt with the aid of driven rollers 25, 25 '. Another known method can also be used here.
- the fabric web 18 When passing through the furnace 23, which takes place during a certain predetermined time, the fabric web 18 is flowed through by a certain amount of gas, which has a predetermined composition and temperature and is coordinated with the respective stabilization task.
- a certain amount of gas which has a predetermined composition and temperature and is coordinated with the respective stabilization task.
- measuring points for the are in the inflow area above the fabric web 18 and in the outflow area below the fabric web Temperature (T), for the gas pressure (p) and for the flow velocity (v) installed.
- the heaters 26 for temperature control of the inflowing gas, the fans 27 in the inflow area for generating the desired gas flow and the fans 28 in the outflow area for the removal of the gases from the outflow area and for the maintenance are used by means of the values measured at these points of the differential pressure required for an effective flow through the fabric web 18.
- Grids or perforated plates 32 are provided for generating a gas flow which is uniform over the cross section of the respective department 22, 22 ', 22'',22''' of the furnace 23.
- the fans 28 in the outflow area can also be omitted.
- the measurement of the gas temperatures in the inflow and outflow areas serves to control the temperature conditions in the fabric and allows important conclusions to be drawn about the correct course of the reaction and the quality of the fabric.
- the subdivision of the furnace 23 into sections 22, 22 ', 22'',22''' can be omitted.
- the furnace must be divided into sections 22 in which the process parameters can be regulated independently of those of other sections 22.
- the number of four departments 22, 22 ', 22'',22''' has only been given here as an example. Depending on the procedural requirements, the system may also contain fewer or more departments 22.
- test results show that webs of different qualities based on PAN can be thermally stabilized using different process conditions according to the process described above. It can further be seen from the test results that the properties of the stabilized fabric produced can be influenced by the choice of process conditions for thermal stabilization. This proves that with the method according to the invention, after carrying out simple preliminary tests, it is possible to produce multi-dimensional sheet-like structures with predetermined properties in a targeted manner from thermally treated PAN fibers.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Fibers (AREA)
- Nonwoven Fabrics (AREA)
- Woven Fabrics (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19517911A DE19517911A1 (de) | 1995-05-16 | 1995-05-16 | Verfahren zum Umwandeln von aus Polyacrylnitrilfasern bestehenden mehrdimensionalen flächigen Gebilden in den thermisch stabilisierten Zustand |
| DE19517911 | 1995-05-16 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0743381A2 true EP0743381A2 (fr) | 1996-11-20 |
| EP0743381A3 EP0743381A3 (fr) | 1998-05-20 |
| EP0743381B1 EP0743381B1 (fr) | 2003-07-02 |
Family
ID=7762031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96106044A Expired - Lifetime EP0743381B1 (fr) | 1995-05-16 | 1996-04-18 | Procédé pour stabiliser thermiquement des produits multicouches à base de fibres de polyacrylonitrile |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US5967770A (fr) |
| EP (1) | EP0743381B1 (fr) |
| JP (1) | JPH08311722A (fr) |
| DE (2) | DE19517911A1 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3030705A1 (fr) * | 2014-12-17 | 2016-06-24 | Andritz Perfojet Sas | Installation de sechage d'un voile de non-tisse humide |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19548421B4 (de) | 1995-12-22 | 2004-06-03 | Celanese Ventures Gmbh | Verfahren zur kontinuierlichen Herstellung von Membranelektrodeneinheiten |
| DE19731797C2 (de) * | 1997-07-24 | 2001-05-31 | Trw Automotive Safety Sys Gmbh | Hitzebeständiges Airbaggewebe |
| JP4161473B2 (ja) * | 1999-07-01 | 2008-10-08 | 豊田合成株式会社 | インサートをもつ押出成形品及びその製造方法 |
| DE20022262U1 (de) | 1999-07-07 | 2001-08-09 | SGL CARBON AG, 65203 Wiesbaden | Elektrodensubstrat für elektrochemische Zellen |
| US6537654B1 (en) | 1999-11-04 | 2003-03-25 | Sgl Technik Gmbh | Protection products and armored products made of fiber-reinforced composite material with ceramic matrix |
| DE19953259C2 (de) | 1999-11-04 | 2003-05-28 | Sgl Carbon Ag | Verbunde aus einem mit Fasern verstärkten Verbundwerkstoff mit keramischer Matrix und einem Backing und Verwendung der Verbunde |
| DE10050512A1 (de) * | 2000-10-11 | 2002-05-23 | Freudenberg Carl Kg | Leitfähiger Vliesstoff |
| US6514072B1 (en) * | 2001-05-23 | 2003-02-04 | Harper International Corp. | Method of processing carbon fibers |
| ATE368763T1 (de) * | 2001-05-24 | 2007-08-15 | Mitsubishi Chem Functional Pro | Verfahren zur herstellung einer warenbahn aus aluminiumoxidfasern |
| US20030075579A1 (en) * | 2001-07-31 | 2003-04-24 | Bruce Dover | Array of processing drums and method of processing carbon fibers |
| US20050080449A1 (en) * | 2002-10-31 | 2005-04-14 | Mulder Rudolf T. | Safety cartridge for retrievable medical filter |
| SE524779C2 (sv) * | 2002-12-20 | 2004-10-05 | Andritz Fiber Drying Ab | Anordning vid torkning eller värmebehandling av ett banformigt material |
| WO2005003661A1 (fr) * | 2003-07-01 | 2005-01-13 | Strahm Textile Systems Ag | Four a circulation d'air |
| US20060130357A1 (en) * | 2004-12-17 | 2006-06-22 | Cemen Tech Inc. | Continuous horizontal grain drying system |
| DE102007002594B4 (de) | 2007-01-12 | 2012-08-30 | Bayerisches Zentrum für Angewandte Energieforschung e.V. | Formkörper aus hochporösem kohlenstoffhaltigen Aerogel und Verfahren zu deren Herstellung |
| EP2494296B1 (fr) * | 2009-10-28 | 2016-11-23 | Dow Technology Investments LLC | Dispositif de sechage pour convoyeur a bande de four catalyseur et procédé d'utilisation de celui-ci |
| US20110143262A1 (en) * | 2009-12-10 | 2011-06-16 | Gm Global Technology Operations, Inc. | Gas diffusion media made from electrically conductive coatings on non-conductive fibers |
| US20110204611A1 (en) * | 2010-02-18 | 2011-08-25 | Daimler Trucks North America Llc | Fiber reinforced polymer frame rail |
| CN102839448B (zh) * | 2012-09-28 | 2014-06-18 | 山东大学 | 一种防静电碳基纤维及其制备方法与应用 |
| DE102014009243B3 (de) * | 2014-06-20 | 2015-11-19 | Eisenmann Ag | Oxidationsofen |
| RU2648316C2 (ru) * | 2016-07-28 | 2018-03-23 | Общество с ограниченной ответственностью Научно-производственный центр "УВИКОМ" (ООО НПЦ "УВИКОМ") | Печь окисления полиакрилонитрильных волокон для изготовления углеродных волокон |
| KR102147418B1 (ko) | 2018-04-27 | 2020-08-24 | 주식회사 엘지화학 | 탄소섬유 제조용 전구체 섬유의 안정화 방법 및 이를 이용한 탄소섬유의 제조방법 |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE7231623U (de) * | 1972-12-21 | Sigri Elektrographit Gmbh | Widerstandsofen zum Graphitleren von Kohlenstoffilz | |
| US2319300A (en) * | 1939-09-08 | 1943-05-18 | Associated Spring Corp | Contact strip annealing furnace |
| US2319302A (en) * | 1942-08-17 | 1943-05-18 | Associated Spring Corp | Contact strip annealing furnace |
| GB1110791A (en) * | 1964-04-24 | 1968-04-24 | Nat Res Dev | The production of carbon fibres |
| US3961888A (en) * | 1968-09-18 | 1976-06-08 | Celanese Corporation | Acrylic fiber conversion utilizing a stabilization treatment conducted initially in an essentially inert atmosphere |
| DE1959984A1 (de) * | 1969-11-29 | 1971-06-09 | John Heathcoat & Company Ltd | Verfahren und Vorrichtung zur Herstellung von Kohlefaeden |
| GB1405891A (en) * | 1971-06-28 | 1975-09-10 | Quimco Gmbh | Apparatus for producing carbon fibres |
| US4452601A (en) * | 1982-03-19 | 1984-06-05 | Celanese Corporation | Process for the thermal stabilization of acrylic fibers and films |
| US4507272A (en) * | 1983-05-09 | 1985-03-26 | Hitco | Method of purifying partially carbonized pan material prior to carbonization |
| JPS60167928A (ja) * | 1984-02-10 | 1985-08-31 | Nippon Soken Inc | ピツチ系炭素繊維の不融化処理方法並びに装置 |
| US4591517A (en) * | 1984-06-08 | 1986-05-27 | Overly, Inc. | Web dryer with variable ventilation rate |
| US4789332A (en) * | 1986-06-26 | 1988-12-06 | Aluminum Company Of America | Apparatus for removing volatiles from metal |
| IT1205512B (it) * | 1986-12-30 | 1989-03-23 | Mauro Poppi | Forno per la cottura di materiali ceramici quali piastrelle e simili |
| JPH0737690B2 (ja) * | 1988-12-19 | 1995-04-26 | 大阪瓦斯株式会社 | ピッチ繊維の不融化炉 |
| CA2009546C (fr) * | 1989-02-23 | 1996-05-28 | Warren C. Schimpf | Polymeres de polyacrylonitrile stabilises par la chaleur pour la fabrication de fibres de carbone |
| JP2648073B2 (ja) * | 1992-09-14 | 1997-08-27 | 新日本製鐵株式会社 | ピッチ系炭素繊維不融化炉の炉内ガス組成の調整法 |
| EP0626548A1 (fr) * | 1993-05-28 | 1994-11-30 | Akzo Nobel N.V. | Procédé et appareil pour l'oxydation à grande vitesse de fibres organiques |
-
1995
- 1995-05-16 DE DE19517911A patent/DE19517911A1/de not_active Ceased
-
1996
- 1996-04-18 EP EP96106044A patent/EP0743381B1/fr not_active Expired - Lifetime
- 1996-04-18 DE DE59610563T patent/DE59610563D1/de not_active Expired - Fee Related
- 1996-05-15 JP JP8145194A patent/JPH08311722A/ja active Pending
-
1997
- 1997-07-11 US US08/893,396 patent/US5967770A/en not_active Expired - Fee Related
- 1997-07-11 US US08/893,737 patent/US5853429A/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3030705A1 (fr) * | 2014-12-17 | 2016-06-24 | Andritz Perfojet Sas | Installation de sechage d'un voile de non-tisse humide |
| EP3034976A3 (fr) * | 2014-12-17 | 2016-08-17 | ANDRITZ Perfojet SAS | Installation de sechage d'un voile de non-tisse humide |
| EP3141853A1 (fr) * | 2014-12-17 | 2017-03-15 | ANDRITZ Perfojet SAS | Installation de sechage d'un voile de non-tisse humide |
| US9765480B2 (en) | 2014-12-17 | 2017-09-19 | Andritz Perfojet Sas | Installation for drying a damp non-woven web |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08311722A (ja) | 1996-11-26 |
| EP0743381B1 (fr) | 2003-07-02 |
| US5967770A (en) | 1999-10-19 |
| DE19517911A1 (de) | 1996-11-21 |
| DE59610563D1 (de) | 2003-08-07 |
| US5853429A (en) | 1998-12-29 |
| EP0743381A3 (fr) | 1998-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0743381B1 (fr) | Procédé pour stabiliser thermiquement des produits multicouches à base de fibres de polyacrylonitrile | |
| DE69319621T2 (de) | Verfahren und vorrichtung zur pyrolitischen zersetzung von kohlenwasserstoffen | |
| DE2614415B2 (de) | Verfahren zur herstellung von kohlenstoff-fasern | |
| DE1181671B (de) | Durchlaessiges im wesentlichen kompaktes Metallmaterial fuer Filterzwecke | |
| DE69223449T2 (de) | Verfahren zur kontinuierlichen Herstellung von Kohlenstoffasern mittels Kalzinierofen | |
| EP3735564B1 (fr) | Four | |
| EP3382080B1 (fr) | Procédé et dispositif de fabrication d'un non-tissé à partir de fibres | |
| DE2307300A1 (de) | Verfahren zur verminderung einer bildung von koks an waenden von reaktoren fuer die thermische spaltung von kohlenwasserstoffen | |
| DE2128907A1 (de) | Verfahren zum Graphitisieren von Fasermaterial | |
| DE69408336T2 (de) | Verfahren zur chemischen gasphaseninfiltration eines materials in das innere eines fasersubtrats durch einen temperaturgradienten im substrat | |
| DE2231731A1 (de) | Verfahren und vorrichtung zur herstellung von kohlefasern | |
| DE2012284A1 (de) | Verfahren zur Herstellung von Faser-Produkten mit dünnen Kohlenstoffasern | |
| DE2148978A1 (de) | Verfahren und Vorrichtung fuer das Inberuehrungsbringen von Fluiden und den Stoff- und Waermeaustausch zwischen diesen | |
| DE2925950C3 (de) | Verfahren und Vorrichtung zur Unschmelzbarmachung von Pechfasern | |
| DE2034907C3 (de) | Verfahren und Vorrichtung zur Herstellung von Reduktionsgasen | |
| DE2823426C3 (de) | Verfahren zur Herstellung von oxidierten, carbonisierbaren Fasern und die Verwendung der danach hergestellten Fasern | |
| DE3138893C2 (fr) | ||
| DE69227490T2 (de) | Verfahren zur Herstellung aktiver Kohlenstoffasern | |
| DE2049182A1 (de) | Verfahren zur Stabilisierung einer Vielzahl von Faden oder Strängen eines polymeren Fasermaterials | |
| DE3602330A1 (de) | Verfahren und vorrichtung zur herstellung von graphitfasern | |
| EP3864202A1 (fr) | Procédé et dispositif de stabilisation de fibres ou de films précurseurs pour la fabrication de fibres ou de films de carbone | |
| DE2023918B2 (de) | Verfahren zur Herstellung von Kohlenstoff-Endlosfasern | |
| DE1959984A1 (de) | Verfahren und Vorrichtung zur Herstellung von Kohlefaeden | |
| DE2428665A1 (de) | Verfahren zur herstellung von kohlenstoffasern und anlage zur durchfuehrung des verfahrens | |
| DE1939388A1 (de) | Stabilisierte endlose,stark orientierte Acrylfasern und Verfahren zu ihrer Herstellung |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): BE DE ES FR GB IT NL |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): BE DE ES FR GB IT NL |
|
| 17P | Request for examination filed |
Effective date: 19980430 |
|
| 17Q | First examination report despatched |
Effective date: 19990205 |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: SGL CARBON AG |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Designated state(s): BE DE ES FR GB IT NL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030702 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT Effective date: 20030702 |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
| REF | Corresponds to: |
Ref document number: 59610563 Country of ref document: DE Date of ref document: 20030807 Kind code of ref document: P |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20031013 |
|
| NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040418 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040430 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| ET | Fr: translation filed | ||
| 26N | No opposition filed |
Effective date: 20040405 |
|
| BERE | Be: lapsed |
Owner name: *SGL CARBON A.G. Effective date: 20040430 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20040418 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20060313 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20060430 Year of fee payment: 11 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20071101 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070430 |