EP1625244B1 - Method for removing layers from a component - Google Patents
Method for removing layers from a component Download PDFInfo
- Publication number
- EP1625244B1 EP1625244B1 EP04726500A EP04726500A EP1625244B1 EP 1625244 B1 EP1625244 B1 EP 1625244B1 EP 04726500 A EP04726500 A EP 04726500A EP 04726500 A EP04726500 A EP 04726500A EP 1625244 B1 EP1625244 B1 EP 1625244B1
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- European Patent Office
- Prior art keywords
- component
- agent
- current
- process according
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000010306 acid treatment Methods 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000002123 temporal effect Effects 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F5/00—Electrolytic stripping of metallic layers or coatings
Definitions
- the invention relates to a method for stripping a component according to the preamble of claim 1.
- Operationally stressed components such as e.g. Turbine blades of gas turbines are subjected to an acid treatment, so that the component can be reused.
- the operationally stressed MCrAlY layers on the component are removed by immersing them in approximately 50 ° -80 ° C warm 20% hydrochloric acid. After a period of time derived from empirical values, the blades are removed from the acid bath, rinsed with water and then blasted abrasive. The process sequence acid bath and blasting is repeated several times until the entire MCrAlY layer is dissolved or dissolved. The repetition of the individual process steps is usually necessary because the acid dissolves only near-surface aluminum-containing phases of the MCrAlY layer. Deeper areas of the MCrAlY layer can therefore not be resolved in one step. On the surface remains a porous layer matrix back, which is subsequently removed by means of irradiation, for example. Mechanically.
- the period of time that the blades remain in the acid does not reflect the actual time required for the individual blade to stop the dissolution process, but is defaults to a certain amount of time.
- the residence time in the acid bath is determined based on general empirical values.
- each component is claimed individually differently strong, so that a fixed specification leads to different or incomplete dissolution behavior of the claimed surface. In many cases remain Components without further progress of stripping until the expiration of the predetermined period of time in the acid bath.
- the object is achieved by a method for stripping a component according to claim 1.
- a voltage is temporarily applied to the component and another pole, during which the component is in a de-coating, in particular in an acid bath, whereby a current flows.
- the time course of the current determined from individual measuring points, has characteristic features which reflect the current state of de-coating of the component and enable the determination of an end point of the stripping process. By means of the current flow, it can thus be recognized whether the stripping proceeds at all even further. Thus, this information can be used to decide on the processing or interruption of the residence of the component in the means.
- the stripping is not dominated by a voltage-initiated electrolysis process, but only by the attack of the agent (6).
- FIG. 1 shows a device 1 with which the method according to the invention can be carried out.
- the device 1 consists of a container 3, for example, metallic or ceramic, in which a means 6, an acid 6 or an electrolyte 6 is arranged, which serve at least partially for stripping a component 9.
- the component 9 is arranged, whose surface area is to be dissolved. This happens, for example, by the acid attack or attack of the agent 6 on the example. Operated surface of the component. 9
- a voltage / current source 18 is present, which is electrically connected to the component 9 via connecting means 15.
- a circuit may be closed by connecting the connection means 15 to a pole, i. an electrode 12, which is arranged in the acid 6 or connected to the container 3, so that a current between the component 9 and the pole 3, 12 can flow, which can also be measured.
- the current flows through the interior of the component 9 through the stressed surface of the component 9 and through the means 6 toward the electrode 12 or the container 3.
- the current flows discontinuously.
- a voltage pulse can be applied at regular and irregular intervals and the current can be measured.
- FIG. 2 Such a temporal course of the current is in FIG. 2 shown.
- the current I increases at the beginning with the time t and is initially substantially constant after a certain time.
- the stripping has not yet been completed, ie the stripping rate is still high.
- the current I decreases.
- the decrease (range or point 27 in the curve I (t)) of the current I points on that only a little layer material is dissolved.
- the dissolution process can therefore be stopped if, for example, a predetermined comparison value for the current intensity is reached.
- the dissolution process is not dominated by a voltage-initiated electrolysis process, but solely by the acid attack.
- the time course of the current I (t) 24 is determined from individual measuring points 21, which are determined at regular or irregular intervals.
- the total measuring time (application of a voltage) to determine measuring points 21 in relation to the stripping time, ie the time in which the layer is removed, 1: 100, 1: 1000 or 1: 10000, since the voltage is applied only very briefly becomes.
- the magnitude of the current or voltage pulse is adjusted so that there is no effect on the process.
- an electrolyte may be present in the container 3, e.g. a dissolved salt, which also gives an acid, but since no current or voltage permanently or largely applied, no electrolytic process and thus no electrolytic stripping process takes place.
- a container 3 and several components 9 can be arranged for stripping, wherein for each component individually a current curve I (t) is determined, so that the components may be different lengths in the one container 3.
- Another component 9 can also serve as a pole 12.
- the method can also be carried out in substeps.
- an abrasive stripping is carried out in each case in an intermediate process step, which removes residues of acid products and / or leads to the acceleration of stripping, since after a certain period of time of the component 9 in the means 6, for example, a brittle layer has formed, which is abrasive better remove.
- a watering of the component 9 can be carried out in a process intermediate step.
- the method steps treatment of the component 9 in the middle 6, abrasive irradiation can be repeated as desired.
- the stripping of the component or components 9 is carried out without the presence of a voltage, i. There is no electrolytic stripping process.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Entschichtung eines Bauteils nach dem Oberbegriff des Anspruchs 1.The invention relates to a method for stripping a component according to the preamble of claim 1.
Betriebsbeanspruchte Bauteile, wie z.B. Turbinenschaufeln von Gasturbinen werden einer Säurebehandlung unterzogen, so dass das Bauteil wieder verwendet werden kann.Operationally stressed components, such as e.g. Turbine blades of gas turbines are subjected to an acid treatment, so that the component can be reused.
Im Falle von Gasturbinenschaufeln werden die betriebsbeanspruchten MCrAlY-Schichten auf dem Bauteil abgelöst, indem sie in ca. 50° - 80°C warme 20%-tige Salzsäure getaucht werden. Nach einer aus Erfahrungswerten abgeleiteten Zeitdauer werden die Schaufeln aus dem Säurebad genommen, mit Wasser gespült und anschließend abrasiv gestrahlt. Die Prozessfolge Säurebad und Strahlen wird dabei mehrfach wiederholt, bis die gesamte MCrAlY-Schicht ab- bzw. aufgelöst ist. Die Wiederholung der einzelnen Prozessschritte ist in der Regel notwendig, da durch die Säure ausschließlich oberflächennahe aluminiumhaltige Phasen der MCrAlY-Schicht aufgelöst werden. Tieferliegende Bereiche der MCrAlY-Schicht können daher nicht in einem Schritt aufgelöst werden. An der Oberfläche bleibt eine poröse Schichtmatrix zurück, welche nachfolgend mittels Bestrahlen bspw. mechanisch entfernt wird.In the case of gas turbine blades, the operationally stressed MCrAlY layers on the component are removed by immersing them in approximately 50 ° -80 ° C warm 20% hydrochloric acid. After a period of time derived from empirical values, the blades are removed from the acid bath, rinsed with water and then blasted abrasive. The process sequence acid bath and blasting is repeated several times until the entire MCrAlY layer is dissolved or dissolved. The repetition of the individual process steps is usually necessary because the acid dissolves only near-surface aluminum-containing phases of the MCrAlY layer. Deeper areas of the MCrAlY layer can therefore not be resolved in one step. On the surface remains a porous layer matrix back, which is subsequently removed by means of irradiation, for example. Mechanically.
Die Zeitdauer, in der die Schaufeln in der Säure verbleiben, spiegelt dabei nicht die tatsächliche für die individuelle Schaufel benötigte Zeit bis zum Stopp des Auflösungsprozesses wieder, sondern wird standardmäßig auf eine bestimmte Zeit festgelegt. Die Verweildauer im Säurebad wird dabei aufgrund von allgemeinen Erfahrungswerten festgelegt.The period of time that the blades remain in the acid does not reflect the actual time required for the individual blade to stop the dissolution process, but is defaults to a certain amount of time. The residence time in the acid bath is determined based on general empirical values.
Jedoch ist jedes Bauteil individuell verschieden stark beansprucht, so dass eine feste Vorgabe zu unterschiedlichen oder nicht vollständigen Auflösungsverhalten der beanspruchten Oberfläche führt. Vielfach verbleiben die Bauteile auch ohne weiteren Fortschritt der Entschichtung bis zum Ablauf der vorgegebenen Zeitspanne in dem Säurebad.However, each component is claimed individually differently strong, so that a fixed specification leads to different or incomplete dissolution behavior of the claimed surface. In many cases remain Components without further progress of stripping until the expiration of the predetermined period of time in the acid bath.
Es ist daher Aufgabe der Erfindung eine individuelle Festlegung der minimal notwendigen Auflösungsdauer pro individueller Schaufel (Typ Beschichtungsdicke, Zustand nach Betriebsbeanspruchung, usw.) zu ermöglichen.It is therefore an object of the invention to allow an individual definition of the minimum necessary dissolution time per individual blade (type coating thickness, state after service stress, etc.).
Die Aufgabe wird gelöst durch ein Verfahren zur Entschichtung eines Bauteils gemäß Anspruch 1.The object is achieved by a method for stripping a component according to claim 1.
Dabei wird eine Spannung zeitweise an das Bauteil und einem weiteren Pol angelegt, währenddessen sich das Bauteil in einem Entschichtungsmittel, insbesondere in einem Säurebad befindet, wodurch ein Strom fließt. Der zeitliche Verlauf des Stroms, bestimmt aus einzelnen Messpunkten, weist charakteristische Merkmale auf, die den aktuellen Entschichtungszustand des Bauteils widerspiegeln und die Bestimmung eines Endpunktes des Entschichtungsverfahrens ermöglichen. Über den Stromfluss kann also erkannt werden, ob die Entschichtung überhaupt noch weiter voranschreitet. Somit kann diese Information zur Entscheidung über die Bearbeitung oder Unterbrechung des Aufenthalts des Bauteils in dem Mittel herangezogen werden. Die Entschichtung wird nicht durch einen spannungsinitiierten Elektrolyseprozess, sondern allein durch den Angriff des Mittels (6) dominiert.In this case, a voltage is temporarily applied to the component and another pole, during which the component is in a de-coating, in particular in an acid bath, whereby a current flows. The time course of the current, determined from individual measuring points, has characteristic features which reflect the current state of de-coating of the component and enable the determination of an end point of the stripping process. By means of the current flow, it can thus be recognized whether the stripping proceeds at all even further. Thus, this information can be used to decide on the processing or interruption of the residence of the component in the means. The stripping is not dominated by a voltage-initiated electrolysis process, but only by the attack of the agent (6).
In den Unteransprüchen sind weitere vorteilhafte Verfahrensschritte aufgelistet, die in vorteilhafter Weise miteinander kombiniert werden können.In the dependent claims further advantageous process steps are listed, which can be combined with each other in an advantageous manner.
Es zeigen
-
Figur 1 eine Vorrichtung um das erfindungsgemäße Verfahren durchzuführen und -
Figur 2 einen zeitlichen Stromverlauf, der sich bei der Durchführung des erfindungsgemäßen Verfahrens ergibt.
-
FIG. 1 a device to perform the inventive method and -
FIG. 2 a temporal current profile, resulting in the implementation of the method according to the invention.
Die Vorrichtung 1 besteht aus einem Behälter 3, beispielsweise metallisch oder keramisch, in dem ein Mittel 6, eine Säure 6 oder ein Elektrolyt 6 angeordnet ist, die zumindest teilweise zur Entschichtung eines Bauteils 9 dienen.The device 1 consists of a container 3, for example, metallic or ceramic, in which a
In dem Mittel 6 oder in einer Säure 6 ist das Bauteil 9 angeordnet, dessen Oberflächenbereich aufgelöst werden soll. Dies geschieht beispielsweise durch den Säureangriff oder Angriff des Mittels 6 auf die bspw. betriebsbeanspruchte Oberfläche des Bauteils 9.In the
Erfindungsgemäß ist eine Spannungs/Stromquelle 18 vorhanden, die elektrisch über Verbindungsmittel 15 mit dem Bauteil 9 verbunden ist. Ein Stromkreis kann dadurch geschlossen werden, dass die Verbindungsmittel 15 mit einem Pol, d.h. einer Elektrode 12, die in der Säure 6 angeordnet ist oder mit dem Behälter 3 verbunden werden, so dass ein Strom zwischen Bauteil 9 und dem Pol 3, 12 fließen kann, der auch gemessen werden kann.According to the invention, a voltage /
Der Strom fließt über das Innere des Bauteils 9 durch die beanspruchte Oberfläche des Bauteils 9 und durch das Mittel 6 hin zu der Elektrode 12 oder den Behälter 3. Der Strom fließt diskontinuierlich. So kann daher in regelmäßigen und unregelmäßigen Abständen ein Spannungspuls angelegt werden und der Strom gemessen werden.The current flows through the interior of the component 9 through the stressed surface of the component 9 and through the
Ein solcher zeitlicher Verlauf des Stroms ist in
Nach einer gewissen Zeit t sinkt der Strom I. Das Absinken (Bereich oder Punkt 27 in der Kurve I(t)) des Stroms I zeigt an, dass nur noch wenig Schichtmaterial aufgelöst wird. Der Auflöseprozess kann daher gestoppt werden, wenn bspw. ein vorgegebener Vergleichswert für die Stromstärke erreicht ist.After a certain time t, the current I decreases. The decrease (range or
Da die Messspannung nur für sehr kurze Zeit angelegt wird, wird der Auflösungsprozess nicht durch einen spannungsinitiierten Elektrolyseprozess, sondern allein durch den Säureangriff dominiert.Since the measurement voltage is applied only for a very short time, the dissolution process is not dominated by a voltage-initiated electrolysis process, but solely by the acid attack.
Der zeitliche Verlauf des Stroms I(t) 24 wird aus einzelnen Messpunkten 21 ermittelt, die in regelmäßigen oder unregelmäßigen Abständen bestimmt werden.The time course of the current I (t) 24 is determined from
Die gesamte Messzeit (Anlegen einer Spannung) um Messpunkte 21 zu ermitteln beträgt im Verhältnis zur Entschichtungszeit, also der Zeit, in der die Schicht entfernt wird, 1:100, 1:1000 oder 1:10000, da die Spannung immer nur sehr kurz angelegt wird.The total measuring time (application of a voltage) to determine
Die Höhe des Strom oder Spannungspulses wird so eingestellt, dass sich kein Einfluss auf das Verfahren ergibt.The magnitude of the current or voltage pulse is adjusted so that there is no effect on the process.
Zwar kann in dem Behälter 3 ein Elektrolyt vorhanden sein, z.B. ein gelöstes Salz, das auch eine Säure ergibt, aber da kein Strom oder Spannung permanent oder größtenteils anliegt, findet kein elektrolytischer Prozess und damit auch kein elektrolytischer Entschichtungsprozess statt.Although an electrolyte may be present in the container 3, e.g. a dissolved salt, which also gives an acid, but since no current or voltage permanently or largely applied, no electrolytic process and thus no electrolytic stripping process takes place.
In einem Behälter 3 können auch mehrere Bauteile 9 zur Entschichtung angeordnet werden, wobei für jedes Bauteil individuell eine Stromkurve I(t) ermittelt wird, so dass die Bauteile ggf. unterschiedlich lang in dem einen Behälter 3 sind.In a container 3 and several components 9 can be arranged for stripping, wherein for each component individually a current curve I (t) is determined, so that the components may be different lengths in the one container 3.
Ein weiteres Bauteil 9 kann auch als Pol 12 dienen.Another component 9 can also serve as a
Das Verfahren kann auch in Teilschritten durchgeführt werden.The method can also be carried out in substeps.
Dabei wird jeweils in einem Verfahrenszwischenschritt eine abrasive Entschichtung durchgeführt, die Rückstände von Säureprodukten entfernt und/oder zur Beschleunigung der Entschichtung führt, da sich nach einem gewissen zeitlichen Aufenthalt des Bauteils 9 in dem Mittel 6 bspw. eine spröde Schicht gebildet hat, die sich abrasiv besser entfernen lässt.In this case, an abrasive stripping is carried out in each case in an intermediate process step, which removes residues of acid products and / or leads to the acceleration of stripping, since after a certain period of time of the component 9 in the
Ebenso kann eine Wässerung des Bauteils 9 in einem Verfahrenszwischenschritt durchgeführt werden.Likewise, a watering of the component 9 can be carried out in a process intermediate step.
Danach wird das Bauteil 9 erneut in dem Mittel (6) angeordnet wird.Thereafter, the component 9 is again placed in the means (6).
Die Verfahrensschritte Behandlung des Bauteils 9 im Mittel 6, abrasive Bestrahlung können beliebig wiederholt werden.The method steps treatment of the component 9 in the
Die Entschichtung des oder der Bauteile 9 läuft ohne das Vorhandensein einer Spannung, d.h. es liegt kein elektrolytischer Entschichtungsprozess vor.The stripping of the component or components 9 is carried out without the presence of a voltage, i. There is no electrolytic stripping process.
Claims (9)
- Process for removing the coating from a component (9), in which the component (9) is arranged in an agent (6) which at least partially attacks the surface of the component (9), characterized in that just from time to time a voltage is applied to the component (9) and a further pole (3, 12), so that a current (I) flows at least through the agent (6), the time profile (I(t)) of which current represents the state of the coating removal process and is used to decide whether to terminate or interrupt the residence of the component (9) in the agent (6), the removal of the coating being dominated not by a voltage-initiated electrolytic process, but only by attacks from the agent (6).
- Process according to Claim 1, characterized in that the further pole used is an electrode (12) in the agent (6).
- Process according to Claim 1 or 2, characterized in that the agent (6) used is an acid.
- Process according to Claim 1, characterized in that the current (I) rises with time (t) at the start of the coating removal process and then remains relatively constant.
- Process according to Claim 1, characterized in that a drop in the current (I(t)) in the time profile, in particular to a predetermined comparison value, marks an end point for the coating removal process.
- Process according to Claim 1, characterized in that the process is carried out in substeps, with abrasive coating removal in each case taking place in a process intermediate step and the component (9) then being put back in the agent (6).
- Process according to Claim 1, characterized in that the component (9) is rinsed in a process intermediate step.
- Process according to Claim 1, characterized in that the voltage is pulsed.
- Process according to Claim 1, characterized in that a vessel (3) is used for the agent (6), and in that a plurality of components (9), for each of which (9) an individual time profile (I(t)) is determined, are present in one vessel (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04726500A EP1625244B1 (en) | 2003-05-02 | 2004-04-08 | Method for removing layers from a component |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03010059A EP1473387A1 (en) | 2003-05-02 | 2003-05-02 | Method for stripping a coating from a part |
| PCT/EP2004/003818 WO2004097070A1 (en) | 2003-05-02 | 2004-04-08 | Method for removing layers from a component |
| EP04726500A EP1625244B1 (en) | 2003-05-02 | 2004-04-08 | Method for removing layers from a component |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1625244A1 EP1625244A1 (en) | 2006-02-15 |
| EP1625244B1 true EP1625244B1 (en) | 2009-06-03 |
Family
ID=32981802
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03010059A Withdrawn EP1473387A1 (en) | 2003-05-02 | 2003-05-02 | Method for stripping a coating from a part |
| EP04726500A Expired - Lifetime EP1625244B1 (en) | 2003-05-02 | 2004-04-08 | Method for removing layers from a component |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03010059A Withdrawn EP1473387A1 (en) | 2003-05-02 | 2003-05-02 | Method for stripping a coating from a part |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20070080072A1 (en) |
| EP (2) | EP1473387A1 (en) |
| CN (1) | CN100545311C (en) |
| DE (1) | DE502004009570D1 (en) |
| WO (1) | WO2004097070A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004002763A1 (en) * | 2004-01-20 | 2005-08-04 | Mtu Aero Engines Gmbh | Method for electrochemical removal of layers from components with prior determination of a working point for their removal useful for stripping coated gas turbine blades |
| DE502004006578D1 (en) | 2004-06-30 | 2008-04-30 | Siemens Ag | Method and device for surface treatment of a component |
| EP2053145A1 (en) * | 2007-10-19 | 2009-04-29 | Siemens Aktiengesellschaft | Method for removing a metal layer using FIC in an intermediate stage |
| CN103088399B (en) * | 2011-10-31 | 2016-01-06 | 通用电气公司 | Multi-step electrochemical metal coat removal method |
| CN113106532B (en) * | 2021-04-07 | 2023-04-11 | 江苏源清动力技术有限公司 | Process for removing thermal barrier coating of thermal component of aero-engine and gas turbine |
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| US6599416B2 (en) * | 2001-09-28 | 2003-07-29 | General Electric Company | Method and apparatus for selectively removing coatings from substrates |
| JP3807295B2 (en) * | 2001-11-30 | 2006-08-09 | ソニー株式会社 | Polishing method |
| US7029567B2 (en) * | 2001-12-21 | 2006-04-18 | Asm Nutool, Inc. | Electrochemical edge and bevel cleaning process and system |
| DE10259365A1 (en) * | 2002-04-08 | 2003-10-30 | Siemens Ag | Device and method for removing surface areas of a component |
| US7033466B2 (en) * | 2002-09-27 | 2006-04-25 | United Technologies Corporation | Electrochemical stripping using single loop control |
| DE502004006578D1 (en) * | 2004-06-30 | 2008-04-30 | Siemens Ag | Method and device for surface treatment of a component |
-
2003
- 2003-05-02 EP EP03010059A patent/EP1473387A1/en not_active Withdrawn
-
2004
- 2004-04-08 CN CNB2004800118915A patent/CN100545311C/en not_active Expired - Fee Related
- 2004-04-08 DE DE502004009570T patent/DE502004009570D1/en not_active Expired - Lifetime
- 2004-04-08 WO PCT/EP2004/003818 patent/WO2004097070A1/en active Application Filing
- 2004-04-08 US US10/555,137 patent/US20070080072A1/en not_active Abandoned
- 2004-04-08 EP EP04726500A patent/EP1625244B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1784509A (en) | 2006-06-07 |
| US20070080072A1 (en) | 2007-04-12 |
| EP1473387A1 (en) | 2004-11-03 |
| DE502004009570D1 (en) | 2009-07-16 |
| WO2004097070A1 (en) | 2004-11-11 |
| EP1625244A1 (en) | 2006-02-15 |
| CN100545311C (en) | 2009-09-30 |
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