EP1994198A1 - Procede et dispositif d'enduction d'une surface interne de geometrie creuse et continue, notamment un tuyau - Google Patents

Procede et dispositif d'enduction d'une surface interne de geometrie creuse et continue, notamment un tuyau

Info

Publication number
EP1994198A1
EP1994198A1 EP07726866A EP07726866A EP1994198A1 EP 1994198 A1 EP1994198 A1 EP 1994198A1 EP 07726866 A EP07726866 A EP 07726866A EP 07726866 A EP07726866 A EP 07726866A EP 1994198 A1 EP1994198 A1 EP 1994198A1
Authority
EP
European Patent Office
Prior art keywords
gas mixture
endless geometry
geometry
endless
precursor
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.)
Withdrawn
Application number
EP07726866A
Other languages
German (de)
English (en)
Inventor
Nils Hoffmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Viega GmbH and Co KG
Original Assignee
Viega GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Viega GmbH and Co KG filed Critical Viega GmbH and Co KG
Publication of EP1994198A1 publication Critical patent/EP1994198A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/54—Apparatus specially adapted for continuous coating
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates

Definitions

  • the invention relates to a method and a device for coating an inner surface of a hollow endless geometry, in particular of a tube.
  • endless hollow sections are also generally hoses, sealing profiles, food-carrying lines, medical products-carrying lines, catheters, industrial tubes, fuel lines, lubricant lines, pure-gas and -fluid lines and hydraulic lines. This list is not exhaustive, but to be understood as an example.
  • plastic tubes which are used as drinking water pipes, it must be ensured that no additives or additives of the plastic such as plasticizers or stabilizers are washed out and thus can get into the drinking water. It must also be prevented that the plastic itself is washed out in its components and these get into the drinking water.
  • a tube having a stainless steel liner For the production of the tube so a thin-walled tube made of stainless steel is first required, which is coated with the actual pipe material, in particular consisting of a plastic.
  • Such a pipe construction has the disadvantage that the stainless steel inliner bends very easily and thus the entire pipe has unsatisfactory properties in its application.
  • the stainless steel layer is too thick to have sufficient elasticity to withstand even smaller bending radii.
  • the invention is therefore based on the technical problem of specifying a method and a device for coating an inner surface of a hollow endless geometry, in particular of a tube, which can be used for a greater variety of cross sections.
  • Another technical problem is to be able to produce very thin coatings of the inner surface, which also allow small bending radii of the tube thus produced.
  • a gas mixture having at least one precursor is introduced into the endless geometry, in which the endless geometry is passed through at least one electrode unit in which an alternating electrical voltage is applied the electrode unit is applied, in which, in the region of the electrode unit, the gas mixture within the endless geometry is at least partially converted into a plasma state in which the plasma generates a reaction product in the gas mixture from the precursor and in which the reaction product is deposited on the inner surface of the endless geometry ,
  • the atmosphere is set in the endless geometry before introducing the gas mixture by rinsing with a precursor-free or low-precursor gas mixture.
  • a pre-rinsing process with a precursor-free gas or gas mixture for displacing the existing atmosphere is thus realized.
  • the inner wall of the endless geometry is cleaned or activated by ignition of a plasma in the precursor-free or low-precursor gas mixture. This creates the opportunity to prevent or reduce unwanted side reactions.
  • a particularly effective embodiment consists in introducing the precursor-free or low-precursor gas mixture as carrier gas mixture first without precursor for setting the desired atmosphere within the endless geometry and subsequently introducing the gas mixture with admixed precursor or precursor mixture.
  • the precursor-free or low-precursor gas mixture need not be exchanged for the gas mixture containing the precursor or the precursors.
  • this approach is limited to short lengths of endless geometries, because too long geometries can not first be filled with the precursor-free gas mixture and then filled only with the enriched gas mixture.
  • plasma is understood to mean a gas state in which a significant proportion of free charge carriers, such as ions and electrons, are present.
  • the charged particles become accelerated and excited in the electric field and thus generate more charge carriers, so that the plasma is continuously maintained or constantly re-developed.
  • a special feature of the method is that the plasma is generated under normal pressure in a limited space. On the one hand, this does not result in harmful mixing with undesirable gases, for example with ambient air, as in other atmospheric plasma applications. On the other hand, it is not necessary to evacuate the volume to produce a low pressure plasma. With endless geometries such an evacuation would be technically feasible only with great effort. Because hollow endless geometries can be produced, for example, in a length of several thousand meters, which should be provided in total with an inert or additive migration-preventing coating.
  • a microwave discharge can be ignited, wherein a microwave radiation in the frequency range of the order of 1 MHz to several GHz is generated.
  • the microwave radiation By coupled by the microwave radiation into the cavity energy, the charged or polar gas particles (atoms, molecules, ions, electrons) are excited to strong vibrations, which leads to a lead to extensive ionization and excitation of the gas mixture.
  • no discharge sparks or streamer are created because the frequencies are too high to result in such streamer formation.
  • the coupled-in excitation energy is then used to convert the precursors into the reaction products, which in turn deposit or ablate on the inner surface of the tube as a coating, such as grafting and polymerizing.
  • a dielectrically impeded discharge or barrier discharge which is also referred to as corona discharge
  • the material of the plastic pipe itself serves as a dielectric or as a barrier for this purpose.
  • the time-dependent voltage is coupled within the cavity at a frequency which may be, for example, 50 to 60 Hz (mains voltage frequency) or even up to 100 kHz or more. In individual cases, it will depend on the geometry and other boundary conditions to adjust the voltage values in a suitable manner.
  • a barrier discharge is used in the void volume, discharge sparks or streamer are generated individually or in tufts which at least partially displace the gas mixture into the plasma state.
  • the conversion of the precursor or of the precursors into the reaction product to be deposited on the inner surface or the reactive species which form the reaction product during the addition reaction then takes place on account of the interaction of the gas mixture with the streamers themselves and / or with the highly excited, present in large numbers Gas particles (atoms, molecules and molecular fragments, ions and electrons) take place. It is it is preferable to adjust the plasma so that the energy of the atoms, molecules and ions is less than that of the electrons.
  • the electrical alternating voltages or alternating electric fields described above are time-dependent and can be designed as alternating voltage, that is to say with alternating sign of the voltage values, or as time-varying direct voltage, ie with voltage values with the same sign.
  • the shape of the temporal change is also variable, so sinusoidal voltage waveforms, pulsed voltage waveforms or combinations thereof can be applied.
  • the electrode unit has been generally described. Depending on the application, this can have a plurality of voltage-carrying electrodes. However, it is preferred that the at least one electrode unit has two electrodes which surround the endless geometry from two sides. The endless geometry is thus passed between the two electrodes, whereby the electric field penetrates through the wall of the endless geometry into the cavity extends and there can generate the plasma discharge. Alternatively, the electrode unit may have more than two electrodes to create a more complex electric field. For example, with four electrodes rotating electric fields can be generated, which improve the efficiency of plasma generation.
  • a plurality of electrode units are provided, and the endless geometry is successively passed through the electrode units.
  • a plurality of plasmas are generated in succession, so that the deposition is not accompanied by a thermal damage to the material of the endless geometry and still the required layer thicknesses can be achieved.
  • the plurality of plasmas are then to a considerable extent independent or separated from each other, so that a cooling can take place in each case between two continuous sections with plasma.
  • cascading-like the endless geometry can be applied to electric fields, which may differ in their orientation and in the voltage parameters frequency, amplitude and phase.
  • at least the electrode unit, which is the first to pass through the endless geometry can be used for the ignition of the plasma, and the at least one subsequent electrode unit can be used to deposit the desired layer thickness in several steps.
  • thermal damage to the endless geometry is likewise excluded or minimized, while simultaneously achieving an integrally increased deposition rate and thus applied layer thickness.
  • the number of electrode units and Their operating parameters can therefore be adapted to any application.
  • the layer need only be sufficiently dense to reliably cover the material of the pipe. An independent stability does not need to have this layer. Therefore, the layer may also be significantly thinner than a stainless steel inliner used in the prior art.
  • the thin deposited coating can then be at least so elastic due to the small thickness that an improved buckling stability and thus smaller bending radii are achieved in the tube.
  • reaction product is therefore preferably deposited as a closed surface.
  • This layer is then completely inertizing, ie sealing, so that a direct contact of the material of the tube wall is avoided with the conducted medium.
  • reaction product can be deposited on at least a predetermined proportion of the inner surface of the endless geometry.
  • This proportion can amount to at least 95% of the area or at least 90% of the area. Even smaller areas are possible.
  • This embodiment of the invention is applicable when it does not depend on the tube to a complete inerting of the tube, if so still remaining portions of the inner surface of the tube can get a direct contact with the conducted medium.
  • the gas mixture is introduced from one side into the endless geometry, that is, for example, into the tube, flows through the section of the plasma discharge and then flows out again at the other open end of the endless geometry.
  • the reaction products of the gas mixture which have not been separated and waste products are carried away with the same gas stream.
  • a further variant of the method described is that the transport speed of the endless geometry through the at least one electrode unit is smaller than that
  • Flow rate of the gas mixture is adjusted. This ensures that in the region of the at least one electrode unit continuously a fresh, so unused gas mixture is present and the plasma discharge can in any case proceed predominantly with a continuous flow of unconsumed precursor.
  • a further preferred embodiment of the method is that the endless geometry, so for example, the tube is stored on a drum and in which the gas mixture is supplied to the endless geometry within the drum hub.
  • a gas mixture storing the gas under pressure bottle is arranged within the drum hub and connected by means of a suitable connection with the endless geometry.
  • Another embodiment of the method relates to the time of inerting the inner surface of the endless geometry.
  • an endless geometry which is produced in an extrusion process, can be carried out directly after the extrusion through the at least one electrode unit.
  • the inner surface is rendered inert, so that the finished product is present immediately after the extrusion process.
  • the gas mixture of the extruded endless geometry is supplied through the extrusion channel.
  • the gas mixture is then let out after the plasma treatment at the other open end of the finished endless structure.
  • a hollow calibration mandrel can be used within the extrusion device, through which the gas mixture is introduced into the extruded endless geometry.
  • the connection with an extrusion of the tube is particularly advantageous for a direct assembly for shorter lengths of the endless geometry to be produced, for example with a length of about 50 to 150 meters.
  • the pressure of the introduced gas mixture is not too great, so that the extruded mass of the endless geometry is not inflated and thus the manufacturing process is disturbed.
  • the inerting process is carried out at a time in which the plastic has already assumed its final state and only a few changes to the inner surface of the endless geometry can arise. This leads to stable inerting layers.
  • HMDSO hexamethyldisiloxane
  • HDSN hexamethyldisilazane
  • This gas mixture enables the deposition of glassy or glass-like layers, which, due to their structure, provide an effective barrier for a wide range of media, compounds and gases. Hardness or flexibility can, inter alia, by the oxygen content in the gas mixture be set.
  • HMDSO and HMDSN a wide variety of other silicon-containing compounds are available for depositing glassy or glassy layers.
  • tetraalkoxysilanes eg tetramethoxysilane, TMOS, tetraethoxysilane, TEOS
  • trialkoxyalkylsilanes dialkoxydialkylsilanes
  • cyclic dimethylsiloxane oligomers eg D 3 , D 4
  • bis (trialkoxysilyl) -alkylenes eg D 3 , D 4
  • a mixture of acetylene or ethylene and air inert gas is indicated, from which, using the plasma, a highly crosslinked carbon layer is formed, which constitutes a diffusion barrier between the endless geometry material and the medium.
  • a fluorine-containing gas mixture is specified that represents an effective barrier layer for organic molecules of most different form by fluorination of the inner wall of the continuous geometry inner wall.
  • a fluorocarbon-containing fluorohydrocarbon gas mixture As a fourth embodiment of a gas mixture is given in which a fluorocarbon-containing fluorohydrocarbon gas mixture.
  • the result is a so-called fluorocarbon coating consisting of a highly crosslinked carbon layer whose remaining valences are saturated by fluorine substituents and which is thus hydrophobic and lipophobic.
  • the device for Coating an inner surface of a hollow endless geometry, in particular a tube, with the features of claim 1 solved.
  • the device has a gas supply device for feeding a gas mixture into the endless geometry and at least one electrode unit for generating an electric field in the endless geometry.
  • At least one transport device for feeding in an endless geometry and optionally at least one transport device for discharging the endless geometry is preferably provided in order to ensure smooth delivery and removal of the endless geometry to and from the electrode unit.
  • the transport device can be replaced by a centering or calibrating device, since then it is not a question of feeding the endless geometry, but merely of guiding and centering it.
  • the apparatus is capable of performing a method as described above.
  • the endless geometry is supplied to the at least one electrode unit, while the
  • Gas supply device supplies the gas mixture from one side of the endless geometry. In the region of the electrode unit, the gas mixture is at least partially transferred into the plasma state and the deposition of the reaction product resulting from the precursor on the inner surface can take place.
  • FIG. 1 shows a first embodiment of a device according to the invention for coating an inner surface of a pipe in a schematic representation
  • FIG. 2 shows a second embodiment of a device according to the invention for coating an inner surface of a pipe in a schematic representation
  • Fig. 3 shows a first embodiment of a
  • Electrode unit with two electrodes in cross section
  • Fig. 4 shows a second embodiment of a
  • Electrode unit with four electrodes in cross-section
  • FIG. 5 shows a tube rolled up on a drum with a gas feed arranged in the drum hub in cross section
  • Fig. 6 shows a second embodiment of a
  • Electrode unit with two electrodes in cross section wherein the electrodes enclose the endless geometry in each case and the plasma is formed between the two electrodes in a finite tube increment
  • Fig. 7 shows an embodiment of a gas supply within an extruder for producing a plastic pipe.
  • Fig. 1 shows a first embodiment of a device according to the invention for coating an inner surface of a hollow endless geometry, in this case a tube 2.
  • the tube 2 is provided with a
  • Gas supply 4 for supplying a gas mixture in the tube 2, wherein the gas supply device is formed by way of example as a gas cylinder. Furthermore, an electrode unit 6 for generating an electric field in the tube 2 is provided.
  • a varying electric field is generated in the interior of the tube 2, which at least partially displaces the gas mixture in the interior of the tube 2 into a plasma state.
  • the precursor contained in the gas mixture is chemically reacted and the reaction product is deposited on the inner surface of the tube 2 as a coating or preferably reacts there to the desired inerting from.
  • both a transport device 12 for supplying the tube and a transport device 14 for discharging the tube 2 is provided, while the gas supply device 4 is stationary, so that the tube 2 is shown interrupted.
  • the section of the tube 2 between the gas supply device 4 and the electrode unit 6 and behind it can be stored or stored in a suitable manner.
  • the transport devices 12 and 14 each have two cooperating rollers 13 and 15, which promote the tube 2. Instead of the rollers and conveyor belts or other known conveyors can be used.
  • FIG. 2 shows a second exemplary embodiment of a device according to FIG. 1, in which, in contrast to the first exemplary embodiment, three electrode units 6 are provided. In principle, even more electrode units 6 can be provided, this being dependent on the specific application and can be selected accordingly.
  • FIG. 3 shows an electrode unit 6 with two electrodes 8 and 10, each of which has a curved shape adapted to the round shape of the tube 2.
  • both electrodes 8 and 10 have a uniform distance to the tube outside the tube and the electric field is largely uniformly coupled into the interior of the tube 2.
  • Fig. 4 shows a further embodiment of
  • Electrode unit 6 with four electrodes 8, 10, 16 and 18. This can be another geometry of the electric field in the interior of the tube 2 generate.
  • FIG. 5 shows that the tube 2 is wound on a drum 20 and that the end of the tube 2 connected to the drum hub 24 is connected to the gas cylinder 4 via a connection 22.
  • the gas cylinder 4 rotates during the unwinding of the tube 2 with the drum 20 and can continuously ensure the gas supply into the tube 2 into it.
  • Fig. 6 shows a further variant of a
  • Electrode arrangement 6 in which the electrodes 26 and 28 are not distributed over certain angle sections, but are arranged axially distributed. Thus, a discharge in the axial direction is generated by an alternating electric field applied to the electrodes 26 and 28 and thus a larger area of the tube 2 is detected than is the case for the configuration of the electrode unit shown in FIGS. 3 and 4.
  • FIG. 7 shows the filling of a tube 2 extruded in an extruder 30 with a gas / precursor mixture.
  • an elongated hollow Kalibrierdorn 32 is provided in the extruder 30, which is connected to a Gaszu 1500voriques 4 in the form of one or more coupled together via a Mischvorrichting gas cylinders.
  • the hollow calibration mandrel introduces the gas mixture into the continuously extruded tube 4.
  • the extruded tube 2 then passes through a cooling device 34 to stabilize the shape of the tube 2.
  • One of the electrode arrangements 6 described above then adjoins to the right in FIG. 7 in order to generate a plasma in the cavity of the cooled tube 2.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un procédé et un dispositif d'enduction d'une surface interne d'une géométrie creuse et continue, notamment un tuyau (2), utilisables pour un large éventail de sections transversales, selon lequel un mélange gazeux contenant au moins un précurseur est introduit dans la géométrie continue, la géométrie continue est passée dans au moins une unité d'électrode (6), une tension électrique changeante est introduite dans l'unité d'électrode (6), le mélange gazeux au sein de la géométrie continue est, dans la zone de l'unité d'électrode (6), au moins en partie transféré dans un état plasma, un produit de réaction est produit par le plasma à partir du précurseur et le produit de réaction est isolé sur la surface intérieure de la géométrie continue.
EP07726866A 2006-03-14 2007-03-13 Procede et dispositif d'enduction d'une surface interne de geometrie creuse et continue, notamment un tuyau Withdrawn EP1994198A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006012021A DE102006012021A1 (de) 2006-03-14 2006-03-14 Verfahren und Vorrichtung zum Beschichten einer Innenfläche einer hohlen Endlosgeometrie, insbesondere eines Rohres
PCT/EP2007/052365 WO2007104765A1 (fr) 2006-03-14 2007-03-13 Procede et dispositif d'enduction d'une surface interne de geometrie creuse et continue, notamment un tuyau

Publications (1)

Publication Number Publication Date
EP1994198A1 true EP1994198A1 (fr) 2008-11-26

Family

ID=38042855

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07726866A Withdrawn EP1994198A1 (fr) 2006-03-14 2007-03-13 Procede et dispositif d'enduction d'une surface interne de geometrie creuse et continue, notamment un tuyau

Country Status (6)

Country Link
US (1) US20090092763A1 (fr)
EP (1) EP1994198A1 (fr)
CA (1) CA2645621A1 (fr)
DE (1) DE102006012021A1 (fr)
MX (1) MX2008011215A (fr)
WO (1) WO2007104765A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007025858A1 (de) * 2007-06-01 2008-12-04 Grünenthal GmbH Verfahren zur Herstellung einer Arzneimitteldarreichungsform
DE102008033941A1 (de) * 2008-07-18 2010-01-28 Innovent E.V. Verfahren zum Beschichten
DE102008033939A1 (de) 2008-07-18 2010-01-21 Innovent E.V. Verfahren zur Beschichtung
DE102008037159A1 (de) 2008-08-08 2010-02-11 Krones Ag Vorrichtung und Verfahren zur Plasmabehandlung von Hohlkörpern
IT1402301B1 (it) * 2010-09-16 2013-08-28 Gomma Tubi Metodo ed apparecchiatura per il trattamento superficiale di sottostrati tubolari collassabili destinati alla realizzazione di tubi multistrato

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CA1080562A (fr) * 1977-02-10 1980-07-01 Frederick D. King Methode et appareil de fabrication de fibres optiques par depot active par plasma dans un tube
JPS5598232A (en) * 1979-01-22 1980-07-26 Agency Of Ind Science & Technol Internal treatment of plastic tube member
DE4125941A1 (de) * 1991-08-05 1993-02-11 Kirchner Fraenk Rohr Rohr oder schlauch aus kunststoff und vorrichtung zur herstellung derselben
US6022602A (en) * 1994-01-26 2000-02-08 Neomecs Incorporated Plasma modification of lumen surface of tubing
DE10035177C2 (de) * 2000-07-19 2002-06-20 Fraunhofer Ges Forschung Verfahren zur plasmagestützten Behandlung der Innenfläche eines Hohlkörpers und Verwendung desselben
US7011134B2 (en) * 2000-10-13 2006-03-14 Chien-Min Sung Casting method for producing surface acoustic wave devices
AU2003267378A1 (en) * 2002-09-28 2004-04-23 Ludwig Hiss Internally coated hollow body, coating method and device
DE10323453B4 (de) * 2003-05-21 2005-08-04 Rehau Ag + Co. Verfahren zur Erzeugung von Gradientenschichten im Inneren von polymeren Rohren und Vorrichtung zu dessen Durchführung
DE102004054662B4 (de) * 2004-11-12 2009-05-07 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren und Vorrichtung zur Innenbehandlung von Hohlprofilen

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Also Published As

Publication number Publication date
US20090092763A1 (en) 2009-04-09
CA2645621A1 (fr) 2008-09-11
MX2008011215A (es) 2008-09-11
DE102006012021A1 (de) 2007-09-20
WO2007104765A1 (fr) 2007-09-20

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