EP1590111B1 - Fire-resistant ceramic gas sink - Google Patents

Fire-resistant ceramic gas sink Download PDF

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Publication number
EP1590111B1
EP1590111B1 EP03815339A EP03815339A EP1590111B1 EP 1590111 B1 EP1590111 B1 EP 1590111B1 EP 03815339 A EP03815339 A EP 03815339A EP 03815339 A EP03815339 A EP 03815339A EP 1590111 B1 EP1590111 B1 EP 1590111B1
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EP
European Patent Office
Prior art keywords
gas
gas flushing
channel
flushing brick
brick according
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.)
Expired - Lifetime
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EP03815339A
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German (de)
French (fr)
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EP1590111A1 (en
Inventor
Andreas Drescher
Johannes Taferner
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Refractory Intellectual Property GmbH and Co KG
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Refractory Intellectual Property GmbH and Co KG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D1/00—Treatment of fused masses in the ladle or the supply runners before casting
    • B22D1/002—Treatment with gases
    • B22D1/005—Injection assemblies therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D1/00—Treatment of fused masses in the ladle or the supply runners before casting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/05—Refining by treating with gases, e.g. gas flushing also refining by means of a material generating gas in situ
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24273—Structurally defined web or sheet [e.g., overall dimension, etc.] including aperture

Definitions

  • the invention relates to a refractory ceramic gas purging plug for installation in a wall or a bottom of a vessel for receiving a molten metal, wherein the gas purging plug has at least one channel extending from the cold side of the gas purging plug to a hot side of the gas purging plug, and the channel is fluidically connected to the cold side of the gas purging plug is connected to a gas supply, via which a treatment gas can be passed through the channel into the molten metal.
  • Such a gas purging plug is referred to as a gas purging plug "with directed porosity" due to the arrangement of a gas purging channel.
  • the further nomenclature can be found in the summary in "Radex-Rundschau", 1987, 288.
  • gas purging elements with "undirected porosity” are known in which the gas from the cold to the hot side of the gas purging plug by an "open pore framework" within of the refractory matrix material moves.
  • the term “cold side” or “hot side” is concerned, this obviously refers to the installation state of the gas purging plug in a vessel for receiving (including treatment) a molten metal.
  • the hot side is thus the side which is immediately adjacent to the molten metal, wherein the molten metal is usually applied against the hot side.
  • the cold side is correspondingly the side of the Gas Whyriis, which is adjacent to the outer vessel shell.
  • a gas purging element of the generic type shows the DE 38 10 098 C1.
  • a gas purging plug to a plurality of purge channels, which extend substantially in the axial direction of the gas purging plug (that is, in the flow direction of the gas).
  • a length of the gas purging plug between 30 and 120 cm, it is clear that the formation of Spülkanäle within the ceramic base material is extremely difficult, especially since the channels have a diameter ⁇ 5 mm, in part ⁇ 2 mm in the rule. This is not important in the state of the art but also because it is all about the gas from the Cold side to the hot side and then to promote the molten metal.
  • the Gas Hugheskanäle fulfill their function accordingly, if they are curved, crooked or in any way discontinuous between the cold and hot side.
  • the aim of gas purging, for example, in a steel ladle are, in particular, rapid temperature and concentration equalization of the steel bath and its cleaning.
  • non-metallic inclusions are to be transported faster by means of the gas flow in the floating slag on the molten bath.
  • EP 0082078 A1 discloses a gas purging plug in which two electrical conductors which are insulated from one another run. The conductors extend from the cold to the hot side of the rinse and end at different distances to the hot side. As soon as the melt has eroded the purging plug to the free end of both conductors, an electrical circuit is closed and the current flow is indicated by a signal. This signal gives the information about the state of wear of the purging plug.
  • the invention has the object of reshaping a gas purging plug of the type mentioned so that it can take on further tasks.
  • These further tasks include, in particular, the observation (control) of the operating state of the molten metal to be treated, for example the temperature and composition of the melt.
  • the channel in which the measuring head is inserted is suitable for conducting electromagnetic signals from the melt to the measuring head.
  • the gas distribution chamber may be subdivided into sub-chambers. Individual groups of channels can then be switched on or off. Likewise, various purge gases can be supplied.
  • the channel initially does not differ from a conventional purging channel; he is free of internals. Only in the "back" third (on the cold side) is the measuring head, which can be flowed around by purge gas. This part of the channel may have a larger cross-section than the section seen from the hot side. The transition can be gradual or fluent.
  • the "measuring channel” should run in a straight line.
  • “Straight line” is defined according to the invention so that the measuring head can detect at least 50% of the cross-sectional area of the channel on the hot side of the gas purging plug. Ideally, the value will be 100%.
  • the channel can run at right angles to the hot-side end face of the gas purging plug, that is to say parallel to the central longitudinal axis of the gas purging plug, provided the gas purging plug is, for example, cylindrical or truncated cone-shaped.
  • the channel can also run at an angle not equal to 90 ° to the end face, if the gas is to be directed, for example purposefully in the middle of the molten metal.
  • the channel may be formed with different inner cross-section.
  • the cross section may extend continuously or discontinuously from the cold side to the hot side of the gas purging plug - or vice versa; Of course it can also be constant.
  • the cross-sectional area of the channel is usually between 0.5 and 20 mm 2 , especially on the hot side.
  • the cross-sectional shape of the channel is basically arbitrary. It may, for example, be circular, triangular, rectangular or have the shape of a polygon, oval or a star shape.
  • Corresponding cross-sectional shapes also apply to the measuring device, with the measuring device and channel preferably having different cross-sectional shapes in order to ensure the necessary flow around the measuring head with flushing gas.
  • an embodiment proposes that at least the projecting into the channel part of the measuring device has a cross-sectional shape that differs from the cross-sectional shape of the corresponding channel portion.
  • the channels can be drilled.
  • the individual channels can be formed by prefabricated tubes that are integrated into the gas purging plug. These tubes may for example consist of ceramic or metal and inside have a surface that reflects electromagnetic radiation.
  • the channels can also be created by burning out mold elements during the production of the rinsing device.
  • This channel formation is particularly advantageous when the measuring device is designed to receive and transmit electromagnetic waves that are emitted by the molten metal in the channel.
  • the measuring device then comprises parts for receiving and transmitting electromagnetic waves, in particular in the visible light range and / or in the infrared spectral range and / or in the UV range.
  • electromagnetic waves are emitted by the molten metal and can be converted in an associated evaluation unit into temperature values and / or values for determining a chemical analysis.
  • Such devices are known, for example from WO-A-97/22859 and WO-A-02/48661.
  • the gas purging plug can also be designed with a residual strength indicator.
  • the residual strength indicator is then activated when the gas purging plug has worn out so far that subsequently the functionality of the measuring device would be impaired.
  • a residual intensity indicator can be formed, for example, by a gas channel which extends from the gas distribution chamber, but ends at a certain distance to the hot side of the purging plug. Only when the gas purging plug is worn down to this area, the channel is virtually “opened” and gas flows through the channel into the molten metal. At the same time, the gas pressure inside the associated gas distribution chamber drops, which can be displayed accordingly.
  • the measuring device can be arranged particularly advantageously in the region of the gas distribution chamber. It can be inserted through an opening in the outer wall of the gas distribution chamber and extend through the gas distribution chamber into the described channel.
  • a stuffing box seal can guide the metering device and seal against the gas distribution chamber.
  • the gas distribution chamber may be releasably secured to a flange attached to the cold side of the purifier for interchangeability and reuse, for example.
  • a gas distribution chamber 22 connects, which is constructed as follows:
  • the gas distribution chamber 22 is delimited by a lower end face 26 of the ceramic body 10.
  • a metal shell 24 which is shrunk onto the cold end 12 of the body 10 and projects beyond the end face 26 downwards.
  • a floor panel 28 closes the jacket 24 in parallel and at a distance from the end face 26.
  • a first opening 30 serves to connect a gas supply pipe 32, which is part of a gas supply device 34, which, inter alia, comprises a gas reservoir (not shown).
  • a measuring device 38 Through a further opening 36 extends a measuring device 38.
  • the measuring device 38 is on the outside by a gland seal 41 gas-tight relative to the bottom plate 28 and extends the rest through the Gasverteilhunt 22 in the channel 16, with a measuring head 40.
  • the measuring head 40 ends at a distance in front of an upper edge 42 of the metal shell 24, ie with a large distance in front of the front side 20 at the hot end 14 of the Spülstein stressess 10th
  • the flushing channel 16 has an inner diameter which is 1.5 mm larger than the outer diameter of the measuring head 40, so that a 0.75 mm wide annular gap runs around the measuring head 40 on all sides. Accordingly, gas can flow from the gas distribution chamber 22 around the measuring head 40 and subsequently through the channel 16 to the hot side 20. Of course, this applies analogously to the channel 18 and further (not shown) flushing channels.
  • the measuring head 40 is designed such that it receives the electromagnetic waves emitted by a molten metal into the channel 16 and passes them on to an evaluation unit 44, which calculates the temperature of the molten metal on the basis of the intensity of the received electromagnetic waves.
  • Further measuring devices can be arranged in further flushing channels in an analogous manner, for example in order to determine the chemical composition of the molten metal.
  • FIG. 2 shows a second embodiment of a gas purging device according to the invention. In the following, only the essential differences from the embodiment according to FIG. 1 will be described further.
  • a metal flange 50 is fastened on the outside, which has a radially projecting leg 52.
  • the circumferential metal shell 24 of the gas distribution chamber 22 is bent at its upper end corresponding radially outwardly (leg 25).
  • the gas distribution chamber 22 can be releasably secured by screws 54 on the flange 52.
  • the gas distribution chamber 22 can be removed and attached analogously to a new ceramic body 10. In this way, especially the measuring device 38 can be easily reused.
  • the flushing channel 18 has a smaller cross-sectional area than in the exemplary embodiment according to FIG. For the flushing channel 16, this only applies with respect to the section above the measuring head 40, so that the channel 16 is formed in the transition region with a step 17.
  • the upper portion of the channel 16 is formed by a ceramic tube 60 embedded in the body 10.
  • the measuring head 40 is sealed off from the interior of the gas distribution chamber 22 by a ring seal 23. Purging gas is passed into the channel 16 only behind the measuring head 40 (in FIG. 2: above the measuring head 40) via a further flushing channel 19, which has the function of a bypass.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
  • Carbon Steel Or Casting Steel Manufacturing (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Valve Housings (AREA)

Abstract

The invention relates to a fire-resistant ceramic gas sink which can be fitted into a wall or the base of a vessel for receiving a metal melt. The gas sink comprises at least one channel extending from the cold side of the gas sink to a hot side thereof. The channel is fluidically connected on the cold side thereof to a gas supply device enabling a treatment gas to be introduced via said canal into the metal melt.

Description

Die Erfindung betrifft einen feuerfesten keramischen Gasspülstein zum Einbau in eine Wand oder einen Boden eines Gefäßes zur Aufnahme einer Metallschmelze, wobei der Gasspülstein mindestens einen, von der Kaltseite des Gasspülsteins zu einer Heißseite des Gasspülsteins verlaufenden Kanal aufweist und der Kanal an der Kaltseite des Gasspülsteins strömungstechnisch an eine Gaszuführeinrichtung angeschlossen ist, über die ein Behandlungsgas durch den Kanal in die Metallschmelze geführt werden kann.The invention relates to a refractory ceramic gas purging plug for installation in a wall or a bottom of a vessel for receiving a molten metal, wherein the gas purging plug has at least one channel extending from the cold side of the gas purging plug to a hot side of the gas purging plug, and the channel is fluidically connected to the cold side of the gas purging plug is connected to a gas supply, via which a treatment gas can be passed through the channel into the molten metal.

Ein solcher Gasspülstein wird aufgrund der Anordnung eines Gasspülkanals als Gasspülstein "mit gerichteter Porosität" bezeichnet. Die weitergehende Nomenklatur ist der zusammenfassenden Darstellung in "Radex-Rundschau", 1987, 288 zu entnehmen.Such a gas purging plug is referred to as a gas purging plug "with directed porosity" due to the arrangement of a gas purging channel. The further nomenclature can be found in the summary in "Radex-Rundschau", 1987, 288.

Neben Gasspülsteinen mit "gerichteter Porosität", zu denen als Untergruppe sogenannte "Fugenspüler" gezählt werden können, sind insbesondere Gasspülelemente mit "ungerichteter Porosität" bekannt, bei denen sich das Gas von der Kalt- zur Heißseite des Gasspülsteins durch ein "offenes Porengerüst" innerhalb des feuerfesten Matrixmaterials bewegt.In addition to gas purging with "directed porosity", which can be counted as a subgroup so-called "Fugenspüler", especially gas purging elements with "undirected porosity" are known in which the gas from the cold to the hot side of the gas purging plug by an "open pore framework" within of the refractory matrix material moves.

Soweit von "Kaltseite" beziehungsweise "Heißseite" gesprochen wird, bezieht sich dies ersichtlich auf den Einbauzustand des Gasspülsteins in ein Gefäß zur Aufnahme (einschließlich Behandlung) einer Metallschmelze. Die Heißseite ist also die Seite, die der Metallschmelze unmittelbar benachbart ist, wobei die Metallschmelze in der Regel gegen die Heißseite anliegt. Die Kaltseite ist entsprechend die Seite des Gasspülelementes, die dem äußeren Gefäßmantel benachbart ist.As far as the term "cold side" or "hot side" is concerned, this obviously refers to the installation state of the gas purging plug in a vessel for receiving (including treatment) a molten metal. The hot side is thus the side which is immediately adjacent to the molten metal, wherein the molten metal is usually applied against the hot side. The cold side is correspondingly the side of the Gasspülelementes, which is adjacent to the outer vessel shell.

Ein Gasspülelement der gattungsgemäßen Art zeigt die DE 38 10 098 C1. Üblicherweise weist ein solcher Gasspülstein eine Vielzahl von Spülkanälen auf, die sich im Wesentlichen in Axialrichtung des Gasspülsteins (das heißt in Strömungsrichtung des Gases) erstrecken. Geht man von einer Baulänge des Gasspülsteins zwischen 30 und 120 cm aus, so wird deutlich, dass die Ausbildung der Spülkanäle innerhalb des keramischen Grundmaterials außerordentlich schwierig ist, zumal die Kanäle in der Regel einen Durchmesser < 5 mm, zum Teil < 2 mm aufweisen. Hierauf kommt es im Stand der Technik aber auch nicht an, weil es nur darum geht, das Gas von der Kaltseite zur Heißseite und anschließend in die Metallschmelze zu fördern. Die Gasspülkanäle erfüllen entsprechend auch dann ihre Funktion, wenn sie gekrümmt, schief oder in irgendeiner Weise unstetig zwischen der Kalt- und Heißseite verlaufen.A gas purging element of the generic type shows the DE 38 10 098 C1. Typically, such a gas purging plug to a plurality of purge channels, which extend substantially in the axial direction of the gas purging plug (that is, in the flow direction of the gas). Assuming a length of the gas purging plug between 30 and 120 cm, it is clear that the formation of Spülkanäle within the ceramic base material is extremely difficult, especially since the channels have a diameter <5 mm, in part <2 mm in the rule. This is not important in the state of the art but also because it is all about the gas from the Cold side to the hot side and then to promote the molten metal. The Gasspülkanäle fulfill their function accordingly, if they are curved, crooked or in any way discontinuous between the cold and hot side.

Aus der EP 1 101 825 A1 ist ein Gasspülelement mit gerichteter Porosität bekannt, bei dem die Spülkanäle zwischen benachbarten keramischen Körpern ausgebildet werden.From EP 1 101 825 A1 a gas purging element with directed porosity is known in which the purging channels are formed between adjacent ceramic bodies.

Ziel des Gasspülens zum Beispiel in einer Stahlgießpfanne sind insbesondere ein schneller Temperatur- und Konzentrationsausgleich des Stahlbades und dessen Reinigung. Insbesondere nichtmetallische Einschlüsse sollen mit Hilfe des Gasstromes schneller in die auf dem Schmelzbad schwimmende Schlacke befördert werden.The aim of gas purging, for example, in a steel ladle are, in particular, rapid temperature and concentration equalization of the steel bath and its cleaning. In particular, non-metallic inclusions are to be transported faster by means of the gas flow in the floating slag on the molten bath.

Die EP 0082078 A1 offenbart einen Gasspülstein, in dem zwei elektrische Leiter, die gegeneinander isoliert sind, verlaufen. Die Leiter erstrecken sich von der Kalt- zur Heißseite des Spülers und enden mit unterschiedlichem Abstand zur Heißseite. Sobald die Schmelze den Spülstein bis zum freien Ende beider Leiter erodiert hat wird ein elektrischer Stromkreis geschlossen und der Stromfluss wird durch ein Signal angezeigt. Dieses Signal gibt die Information über den Verschleißzustand des Spülsteins.EP 0082078 A1 discloses a gas purging plug in which two electrical conductors which are insulated from one another run. The conductors extend from the cold to the hot side of the rinse and end at different distances to the hot side. As soon as the melt has eroded the purging plug to the free end of both conductors, an electrical circuit is closed and the current flow is indicated by a signal. This signal gives the information about the state of wear of the purging plug.

Es ist auch bekannt, pulverförmige Behandlungsstoffe mit dem Gasstrom in die Metallschmelze zu führen. Die bereits genannte DE 38 10 098 C1 bietet außerdem die Möglichkeit, einen Legierungsdraht entlang eines rohrförmigen Durchlasskanals im Gasspülstein in die Schmelze zu führen. Dabei wird der Legierungsdraht von außen zugeführt und läuft durch eine Gasverteilkammer, die am kaltseitigen Ende des Gasspülsteins ausgebildet ist und die weiteren Spülkanäle mit Spülgas versorgt.It is also known to pass powdered treatment substances with the gas stream into the molten metal. The already mentioned DE 38 10 098 C1 also offers the possibility of guiding an alloy wire along a tubular passage in the gas purging plug into the melt. In this case, the alloy wire is supplied from the outside and passes through a gas distribution chamber, which is formed at the cold end of the gas purging plug and supplies the further purge channels with purge gas.

Bekannte Gasspüleinrichtungen sind insoweit Teile zur sekundärmetallurgischen Behandlung von Metallschmelzen.Known gas purging devices are insofar parts of the secondary metallurgical treatment of molten metals.

Der Erfindung liegt die Aufgabe zugrunde, einen Gasspülstein der genannten Art so umzugestalten, dass er weitere Aufgaben übernehmen kann.The invention has the object of reshaping a gas purging plug of the type mentioned so that it can take on further tasks.

Zu diesen weiteren Aufgaben gehört insbesondere die Beobachtung (Kontrolle) des Betriebs-Zustandes der zu behandelnden Metallschmelze, beispielsweise von Temperatur und Zusammensetzung der Schmelze.These further tasks include, in particular, the observation (control) of the operating state of the molten metal to be treated, for example the temperature and composition of the melt.

Dazu schlägt die Erfindung einen Gasspülstein der eingangs genannten Art vor, der folgende zusätzliche Merkmale aufweist:

  • mindestens eine Messeinrichtung zur Bestimmung physikalischer und/oder chemischer Daten der Metallschmelze, die nach dem Einbau des Gasspülsteins in das Gefäß der Heißseite des Gasspülsteins benachbart ist, wobei
  • die Messeinrichtung mit einem Messkopf in einen Kanal des Gasspülsteins hineinragt.
For this purpose, the invention proposes a gas purging plug of the type mentioned, which has the following additional features:
  • at least one measuring device for determining physical and / or chemical data of the molten metal, which is adjacent to the installation of the gas purging plug into the vessel of the hot side of the gas purging plug, wherein
  • the measuring device projects with a measuring head into a channel of the gas purging plug.

Mindestens einer der Gasspülkanäle des Gasspülsteins wird genutzt, um eine Messeinrichtung aufzunehmen. Die Messeinrichtung soll an der Kaltseite des Spülsteins in den Kanal geführt werden. Die Messeinrichtung soll so angeordnet und befestigt werden, dass sie lösbar ist. Auf diese Weise kann die Messeinrichtung beim Wechsel des Spülers (nach dessen Verschleiß) entnommen und für einen neuen Spüler wiederverwendet werden. Die Befestigung kann am Außenmantel des metallurgischen Gefäßes oder am kaltseitigen Ende des Gasspülsteins erfolgen. Eine Befestigungsmöglichkeit bietet auch eine Gasverteilkammer, die an der Kaltseite des Gasspülsteins befestigt werden kann. Die Gasverteilkammer kann lösbar am kalten Ende des Gasspülsteins befestigt werden. Ebenso können auch Teile der Gasverteilkammer hier lösbar fixiert werden. Die Gasverteilkammer dient dazu, das Gas von der Gaszuführeinrichtung auf mehrere Spülkanäle zu verteilen. Bei einem erfindungsgemäßen Gasspülstein kann auch der Kanal gespült werden, in den der Messkopf der Messeinrichtung gesteckt wird. Nach einer Ausführungsform ist dazu vorgesehen, dass zwischen Messkopf und Kanal eine Durchgangsöffnung für das Behandlungsgas frei bleibt. Die Durchgangsöffnung kann ein Ringkanal zwischen Messkopf und Spülkanal sein. Der Spüler kann aber auch so gestaltet werden, dass das Spülgas erst "hinter" dem Messkopf in den in Verlängerung des Kanals zur Aufnahme des Messkopfes verlaufenden Kanalabschnitt eingeleitet wird (nach Art eines Bypasses). Folgende Vorteile können mit den verschiedenen Varianten erreicht werden:

  • Der Messkopf kann gekühlt werden.
  • Von einer einzigen Gasverteilkammer aus können unterschiedliche Funktionskanäle mit Gas beaufschlagt werden.
  • Die Gasströmung beziehungsweise Gasbeaufschlagung verhindert ein Eindringen (eine Infiltration) von Metallschmelze in den Kanal, in dem der Messkopf liegt.
  • Bei gerader Ausbildung des Kanals kann der Messkopf unmittelbar Signale der Metallschmelze empfangen.
At least one of the gas purging passages of the gas purging plug is used to receive a measuring device. The measuring device should be guided into the channel on the cold side of the purging plug. The measuring device should be arranged and fixed so that it is detachable. In this way, the measuring device can be removed when changing the purifier (after its wear) and reused for a new dishwasher. The attachment can be done on the outer surface of the metallurgical vessel or at the cold end of the gas purging plug. A mounting option also provides a Gasverteilkammer that can be attached to the cold side of the gas purging plug. The Gasverteilkammer can be releasably attached to the cold end of the gas purging plug. Likewise, parts of the gas distribution chamber can be releasably fixed here. The gas distribution chamber serves to distribute the gas from the gas supply to a plurality of purge channels. In a gas purging plug according to the invention, it is also possible to rinse the duct into which the measuring head of the measuring device is inserted. According to one embodiment, provision is made for a passage opening for the treatment gas to remain free between the measuring head and the channel. The passage opening may be an annular channel between the measuring head and the flushing channel. However, the flusher can also be designed such that the flushing gas is introduced only "behind" the measuring head into the channel section extending in the extension of the channel for receiving the measuring head (in the manner of a bypass). The following advantages can be achieved with the different variants:
  • The measuring head can be cooled.
  • From a single gas distribution chamber from different functional channels can be acted upon with gas.
  • The gas flow or gas supply prevents penetration (infiltration) of molten metal in the channel in which the measuring head is located.
  • If the channel is straight, the probe can directly receive signals from the molten metal.

Wichtig ist, dass der Kanal, in dem der Messkopf steckt, geeignet ist, elektromagnetische Signale von der Schmelze zum Messkopf zu leiten.It is important that the channel in which the measuring head is inserted is suitable for conducting electromagnetic signals from the melt to the measuring head.

Die Gasverteilkammer kann in Teilkammern untergliedert sein. Einzelne Gruppen von Kanälen können dann zu- oder abgeschaltet werden. Ebenso können verschiedene Spülgase zugeführt werden.The gas distribution chamber may be subdivided into sub-chambers. Individual groups of channels can then be switched on or off. Likewise, various purge gases can be supplied.

In der Regel wird es genügen, den Messkopf der Messeinrichtung maximal bis zum Ende des ersten Drittels der Gesamtlänge des Kanals in den Kanal hineinragen zu lassen. Mit anderen Worten: ausgehend von der Heißseite des Gasspülsteins unterscheidet sich der Kanal zunächst nicht von einem üblichen Spülkanal; er ist frei von Einbauten. Erst im "hinteren" Drittel (an der Kaltseite) liegt der Messkopf, der von Spülgas umströmt werden kann. Dieser Teil des Kanals kann einen größeren Querschnitt aufweisen als der von der Heißseite gesehen davor liegende Abschnitt. Der Übergang kann stufig oder fließend sein.As a rule, it will suffice to allow the measuring head of the measuring device to protrude into the channel at most until the end of the first third of the total length of the channel. In other words, starting from the hot side of the gas purging plug, the channel initially does not differ from a conventional purging channel; he is free of internals. Only in the "back" third (on the cold side) is the measuring head, which can be flowed around by purge gas. This part of the channel may have a larger cross-section than the section seen from the hot side. The transition can be gradual or fluent.

Damit der Messkopf Messsignale möglichst optimal empfangen kann, soll der "Messkanal" geradlinig verlaufen. "Geradlinig" wird dabei erfindungsgemäß so definiert, dass der Messkopf mindestens 50 % der Querschnittsfläche des Kanals an der Heißseite des Gasspülsteins detektieren kann. Im Idealfall wird der Wert 100 % betragen.So that the measuring head can receive measuring signals as optimally as possible, the "measuring channel" should run in a straight line. "Straight line" is defined according to the invention so that the measuring head can detect at least 50% of the cross-sectional area of the channel on the hot side of the gas purging plug. Ideally, the value will be 100%.

Der Kanal kann im rechten Winkel zur heißseitigen Stirnfläche des Gasspülsteins verlaufen, das heißt parallel zur Mittenlängsachse des Gasspülsteins, sofern der Gasspülstein beispielsweise zylindrisch oder kegelstumpfartig gestaltet ist.The channel can run at right angles to the hot-side end face of the gas purging plug, that is to say parallel to the central longitudinal axis of the gas purging plug, provided the gas purging plug is, for example, cylindrical or truncated cone-shaped.

Der Kanal kann aber auch in einem Winkel ungleich 90 ° zur Stirnfläche verlaufen, sofern das Gas beispielsweise gezielt in die Mitte der Metallschmelze geführt werden soll.However, the channel can also run at an angle not equal to 90 ° to the end face, if the gas is to be directed, for example purposefully in the middle of the molten metal.

Der Kanal kann mit unterschiedlichem Innenquerschnitt ausgebildet sein. Der Querschnitt kann sich von der Kaltseite zur Heißseite des Gasspülsteins kontinuierlich oder diskontinuierlich erweitern - oder umgekehrt; er kann selbstverständlich auch konstant sein. Die Querschnittsfläche des Kanals liegt vor allem an der Heißseite üblicherweise zwischen 0,5 und 20 mm2. Die Querschnittsform des Kanals ist grundsätzlich beliebig. Sie kann beispielsweise kreisförmig, dreieckförmig, rechteckförmig sein oder die Form eines Polygon, Ovals oder eine Sternform besitzen.The channel may be formed with different inner cross-section. The cross section may extend continuously or discontinuously from the cold side to the hot side of the gas purging plug - or vice versa; Of course it can also be constant. The cross-sectional area of the channel is usually between 0.5 and 20 mm 2 , especially on the hot side. The cross-sectional shape of the channel is basically arbitrary. It may, for example, be circular, triangular, rectangular or have the shape of a polygon, oval or a star shape.

Entsprechende Querschnittsformen gelten auch für die Messeinrichtung, wobei Messeinrichtung und Kanal vorzugsweise unterschiedliche Querschnittsformen aufweisen, um die notwendige Umströmung des Messkopfes mit Spülgas sicherzustellen.Corresponding cross-sectional shapes also apply to the measuring device, with the measuring device and channel preferably having different cross-sectional shapes in order to ensure the necessary flow around the measuring head with flushing gas.

In diesem Sinne schlägt eine Ausführungsform vor, dass mindestens der in den Kanal ragende Teil der Messeinrichtung eine Querschnittsform aufweist, die von der Querschnittsform des korrespondierenden Kanalabschnitts abweicht.In this sense, an embodiment proposes that at least the projecting into the channel part of the measuring device has a cross-sectional shape that differs from the cross-sectional shape of the corresponding channel portion.

Die Kanäle können gebohrt sein. Alternativ können die einzelnen Kanäle von vorkonfektionierten Röhrchen gebildet werden, die in den Gasspülstein integriert sind. Diese Röhrchen können beispielsweise aus Keramik oder Metall bestehen und innenseitig eine Fläche aufweisen, die elektromagnetische Strahlung reflektiert. Die Kanäle können auch durch Ausbrennen von Formelementen bei der Herstellung der Spüleinrichtung erstellt werden.The channels can be drilled. Alternatively, the individual channels can be formed by prefabricated tubes that are integrated into the gas purging plug. These tubes may for example consist of ceramic or metal and inside have a surface that reflects electromagnetic radiation. The channels can also be created by burning out mold elements during the production of the rinsing device.

Diese Kanalausbildung ist vor allem dann vorteilhaft, wenn die Messeinrichtung zur Aufnahme und Weiterleitung elektromagnetischer Wellen ausgebildet ist, die von der Metallschmelze in den Kanal emittiert werden. Die Messeinrichtung umfasst dann Teile zur Aufnahme und Weiterleitung elektromagnetischer Wellen insbesondere im sichtbaren Lichtbereich und/oder im Infrarot-Spektralbereich und/oder im UV-Bereich. Solche elektromagnetischen Wellen werden von der Metallschmelze ausgesendet und lassen sich in einer zugehörigen Auswerteeinheit in Temperaturwerte und/oder Werte zur Bestimmung einer chemischen Analyse umrechnen. Solche Einrichtungen sind bekannt, beispielsweise aus der WO-A-97/22859 und WO-A-02/48661.This channel formation is particularly advantageous when the measuring device is designed to receive and transmit electromagnetic waves that are emitted by the molten metal in the channel. The measuring device then comprises parts for receiving and transmitting electromagnetic waves, in particular in the visible light range and / or in the infrared spectral range and / or in the UV range. Such electromagnetic waves are emitted by the molten metal and can be converted in an associated evaluation unit into temperature values and / or values for determining a chemical analysis. Such devices are known, for example from WO-A-97/22859 and WO-A-02/48661.

Der Gasspülstein kann auch mit einer Reststärkenanzeige ausgebildet sein. Die Reststärkenanzeige wird dann aktiviert, wenn der Gasspülstein soweit verschlissen ist, dass in weiterer Folge die Funktionstüchtigkeit der Messeinrichtung beeinträchtigt würde. Eine solche Reststärkenanzeige kann beispielsweise von einem Gaskanal gebildet werden, der von der Gasverteilkammer aus verläuft, jedoch in einer bestimmten Entfernung zur Heißseite des Spülsteins endet. Erst wenn der Gasspülstein bis zu diesem Bereich verschlissen ist, wird der Kanal quasi "geöffnet" und Gas strömt durch den Kanal in die Metallschmelze. Gleichzeitig sinkt der Gasdruck innerhalb der zugehörigen Gasverteilkammer, was entsprechend angezeigt werden kann.The gas purging plug can also be designed with a residual strength indicator. The residual strength indicator is then activated when the gas purging plug has worn out so far that subsequently the functionality of the measuring device would be impaired. Such a residual intensity indicator can be formed, for example, by a gas channel which extends from the gas distribution chamber, but ends at a certain distance to the hot side of the purging plug. Only when the gas purging plug is worn down to this area, the channel is virtually "opened" and gas flows through the channel into the molten metal. At the same time, the gas pressure inside the associated gas distribution chamber drops, which can be displayed accordingly.

Wie bereits erwähnt, lässt sich die Messeinrichtung besonders vorteilhaft im Bereich der Gasverteilkammer anordnen. Sie kann durch eine Öffnung in der Außenwand der Gasverteilkammer eingesetzt werden und sich durch die Gasverteilkammer in den beschriebenen Kanal hinein erstrecken. Eine Stopfbuchsendichtung kann die Messeinrichtung führen und gegenüber der Gasverteilkammer abdichten. Die Gasverteilkammer kann zur Wechselbarkeit und Wiederverwendung beispielsweise an einem Flansch lösbar befestigt werden, der an der Kaltseite des Spülers befestigt ist.As already mentioned, the measuring device can be arranged particularly advantageously in the region of the gas distribution chamber. It can be inserted through an opening in the outer wall of the gas distribution chamber and extend through the gas distribution chamber into the described channel. A stuffing box seal can guide the metering device and seal against the gas distribution chamber. The gas distribution chamber may be releasably secured to a flange attached to the cold side of the purifier for interchangeability and reuse, for example.

Weitere Merkmale der Erfindung ergeben sich aus den Merkmalen der Unteransprüche sowie den sonstigen Anmeldungsunterlagen. Hierzu gehört die Möglichkeit, mehrere Kanäle einer Messeinrichtung zuzuordnen. So lassen sich die Querschnitte der Kanäle an der Heißseite klein halten, gleichwohl aber die gewünschte Menge an (elektromagnetischer) Strahlung auf die Messzelle leiten. Alternativ überdeckt die Messeinrichtung mehrere Kanäle.Other features of the invention will become apparent from the features of the claims and the other application documents. This includes the possibility of assigning several channels to a measuring device. This makes it possible to keep the cross-sections of the channels on the hot side small, but nevertheless to conduct the desired amount of (electromagnetic) radiation to the measuring cell. Alternatively, the measuring device covers several channels.

Die Erfindung wird nachstehend anhand von zwei Ausführungsbeispielen näher erläutert. Die Figuren zeigen in schematisierter Darstellung jeweils einen Schnitt durch eine Ausführungsform eines erfindungsgemäßen Gasspülsteins.The invention will be explained in more detail below with reference to two exemplary embodiments. The figures show in schematic representation in each case a section through an embodiment of a gas purging plug according to the invention.

Dieser besteht gemäß Figur 1 in konventioneller Weise aus einem feuerfesten keramischen Körper 10 mit einer "Kaltseite" 12 und einer "Heißseite" 14. Von der Kaltseite 12 zur Heißseite 14 erstrecken sich Spülkanäle 16, 18. Die Mittenlängsachsen M16, M18 der Spülkanäle 16, 18 verlaufen exakt parallel zur Mittenlängsachse M des Gasspülsteins und im rechten Winkel zur Stirnfläche 20 der Heißseite 14 des Körpers 10.This consists according to Figure 1 in a conventional manner of a refractory ceramic body 10 with a "cold side" 12 and a "hot side" 14. From the cold side 12 to the hot side 14 extend Spülkanäle 16, 18. The central longitudinal axes M16, M18 of the flushing channels 16, 18 run exactly parallel to the central longitudinal axis M of the gas purging plug and at right angles to the end face 20 of the hot side 14 of the body 10th

An die Kaltseite 12 des Körpers 10 schließt sich eine Gasverteilkammer 22 an, die wie folgt aufgebaut ist:On the cold side 12 of the body 10, a gas distribution chamber 22 connects, which is constructed as follows:

Oberseitig wird die Gasverteilkammer 22 von einer unteren Stirnfläche 26 des keramischen Körpers 10 begrenzt. Umfangsseitig verläuft ein Metallmantel 24, der auf das kaltseitige Ende 12 des Körpers 10 aufgeschrumpft ist und über die Stirnfläche 26 nach unten vorsteht. Ein Bodenblech 28 schließt den Mantel 24 parallel und im Abstand zur Stirnfläche 26 ab. Im Bodenblech 28 sind zwei Öffnungen vorgesehen. Eine erste Öffnung 30 dient dem Anschluss eines Gaszuführrohres 32, welches Bestandteil einer Gaszuführeinrichtung 34 ist, die unter anderem ein Gasreservoir (nicht dargestellt) umfasst.On the upper side, the gas distribution chamber 22 is delimited by a lower end face 26 of the ceramic body 10. On the circumference extends a metal shell 24, which is shrunk onto the cold end 12 of the body 10 and projects beyond the end face 26 downwards. A floor panel 28 closes the jacket 24 in parallel and at a distance from the end face 26. In the bottom plate 28 two openings are provided. A first opening 30 serves to connect a gas supply pipe 32, which is part of a gas supply device 34, which, inter alia, comprises a gas reservoir (not shown).

Durch eine weitere Öffnung 36 erstreckt sich eine Messeinrichtung 38. Die Messeinrichtung 38 ist außenseitig über eine Stopfbuchsendichtung 41 gasdicht gegenüber dem Bodenblech 28 befestigt und erstreckt sich im übrigen durch die Gasverteilkammer 22 in den Kanal 16, und zwar mit einem Messkopf 40. Der Messkopf 40 endet mit Abstand vor einem oberen Rand 42 des Metallmantels 24, also mit großem Abstand vor der Stirnseite 20 am heißen Ende 14 des Spülsteinkörpers 10.Through a further opening 36 extends a measuring device 38. The measuring device 38 is on the outside by a gland seal 41 gas-tight relative to the bottom plate 28 and extends the rest through the Gasverteilkammer 22 in the channel 16, with a measuring head 40. The measuring head 40 ends at a distance in front of an upper edge 42 of the metal shell 24, ie with a large distance in front of the front side 20 at the hot end 14 of the Spülsteinkörpers 10th

Der Spülkanal 16 weist einen Innendurchmesser auf, der 1,5 mm größer ist als der Außendurchmesser des Messkopfes 40, so dass allseitig ein 0,75 mm breiter Ringspalt um den Messkopf 40 verläuft. Entsprechend kann Gas aus der Gasverteilkammer 22 um den Messkopf 40 und im Weiteren durch den Kanal 16 zur Heißseite 20 strömen. Selbstverständlich gilt dies analog für den Kanal 18 und weitere (nicht dargestellte) Spülkanäle.The flushing channel 16 has an inner diameter which is 1.5 mm larger than the outer diameter of the measuring head 40, so that a 0.75 mm wide annular gap runs around the measuring head 40 on all sides. Accordingly, gas can flow from the gas distribution chamber 22 around the measuring head 40 and subsequently through the channel 16 to the hot side 20. Of course, this applies analogously to the channel 18 and further (not shown) flushing channels.

Der Messkopf 40 ist so ausgebildet, dass er die von einer Metallschmelze in den Kanal 16 emittierten elektromagnetischen Wellen aufnimmt und an eine Auswerteeinheit 44 weitergibt, die aufgrund der Intensität der empfangenenelektromagnetischen Wellen die Temperatur der Metallschmelze berechnet.The measuring head 40 is designed such that it receives the electromagnetic waves emitted by a molten metal into the channel 16 and passes them on to an evaluation unit 44, which calculates the temperature of the molten metal on the basis of the intensity of the received electromagnetic waves.

Weitere Messeinrichtungen können in weiteren Spülkanälen auf analoge Art und Weise angeordnet werden, beispielsweise um die chemische Zusammensetzung der Metallschmelze zu bestimmen.Further measuring devices can be arranged in further flushing channels in an analogous manner, for example in order to determine the chemical composition of the molten metal.

In Figur 2 ist eine zweite Ausführungsform einer erfindungsgemäßen Gasspüleinrichtung dargestellt. Nachstehend werden lediglich die wesentlichen Unterschiede zur Ausführungsform gemäß Figur 1 weiter beschrieben.FIG. 2 shows a second embodiment of a gas purging device according to the invention. In the following, only the essential differences from the embodiment according to FIG. 1 will be described further.

An der Kaltseite des keramischen Körpers 10 ist ein Metallflansch 50 außenseitig befestigt, der einen radial abstehenden Schenkel 52 aufweist. Der umfangsseitige Metallmantel 24 der Gasverteilkammer 22 ist an seinem oberen Ende korrespondierend radial nach außen abgekröpft (Schenkel 25). Die Gasverteilkammer 22 kann so über Schrauben 54 am Flansch 52 lösbar befestigt werden.On the cold side of the ceramic body 10, a metal flange 50 is fastened on the outside, which has a radially projecting leg 52. The circumferential metal shell 24 of the gas distribution chamber 22 is bent at its upper end corresponding radially outwardly (leg 25). The gas distribution chamber 22 can be releasably secured by screws 54 on the flange 52.

Ist der Gasspülstein beziehungsweise sein keramischer Körper 10 verschlissen, kann die Gasverteilkammer 22 abgenommen und an einem neuen keramischen Körper 10 analog befestigt werden. Auf diese Weise kann vor allem auch die Messeinrichtung 38 problemlos wiederverwendet werden.If the gas purging plug or its ceramic body 10 is worn, the gas distribution chamber 22 can be removed and attached analogously to a new ceramic body 10. In this way, especially the measuring device 38 can be easily reused.

Ein weiterer Unterschied besteht in der Ausbildung der Spülkanäle 16, 18. Der Spülkanal 18 weist eine geringere Querschnittsfläche als beim Ausführungsbeispiel nach Figur 1 auf. Für den Spülkanal 16 gilt dies nur in Bezug auf den Abschnitt oberhalb des Messkopfes 40, so dass der Kanal 16 im Übergangsbereich mit einer Stufe 17 ausgebildet ist. Der obere Abschnitt des Kanals 16 wird von einem keramischen Röhrchen 60 gebildet, das im Körper 10 eingebettet ist. Der Messkopf 40 ist gegenüber dem Innenraum der Gasverteilkammer 22 durch eine Ringdichtung 23 abgedichtet. Spülgas wird erst hinter dem Messkopf 40 (in Figur 2: oberhalb des Messkopfes 40) über einen weiteren Spülkanal 19, der die Funktion eines Bypasses hat, in den Kanal 16 geleitet.Another difference is the design of the flushing channels 16, 18. The flushing channel 18 has a smaller cross-sectional area than in the exemplary embodiment according to FIG. For the flushing channel 16, this only applies with respect to the section above the measuring head 40, so that the channel 16 is formed in the transition region with a step 17. The upper portion of the channel 16 is formed by a ceramic tube 60 embedded in the body 10. The measuring head 40 is sealed off from the interior of the gas distribution chamber 22 by a ring seal 23. Purging gas is passed into the channel 16 only behind the measuring head 40 (in FIG. 2: above the measuring head 40) via a further flushing channel 19, which has the function of a bypass.

Claims (27)

  1. A refractory ceramic gas flushing brick for installation in a wall or a bottom of a vessel for receiving a molten metal, having the following features:
    a) at least one channel (16, 18) running from a cold side (12) to a hot side (14) of the gas flushing brick,
    b) the channel (16, 18) is fluidically connected to a gas supply device (34) on the cold side (12) of the gas flushing brick, via which a treatment gas may be conducted through the channel (16, 18) into the molten metal,
    c) at least one measuring device (38) for determining physical and/or chemical data of the molten metal, which' neighbors the hot side (14) of the gas flushing brick after the gas flushing brick is installed in the vessel,
    d) a measuring head (40) of the measuring device (38) projects into the channel (16).
  2. The gas flushing brick according to Claim 1,
    wherein a passage opening for the treatment gas remains free between measuring head (40) and channel
  3. The gas flushing brick according to Claim 1,
    wherein the gas supply device (34) comprises at least one gas distributor chamber (22).
  4. The gas flushing brick according to Claim 3,
    wherein the gas distributor chamber (22) or a part of the gas distributor chamber (22) is removably attachable to the cold-side end of the gas flushing brick.
  5. The gas flushing brick according to Claim 3,
    wherein the gas distributor chamber (22) is removably' attached to a flange (52) positioned on the cold side (12) of the gas flushing brick.
  6. The gas flushing brick according to Claim 3 having multiple channels (16, 18),
    wherein all channels (16, 18) or groups of channels are connected to the gas distributor chamber (22).
  7. The gas flushing brick according to Claim 1,
    wherein the measuring head (40) of the measuring device (38) projects into the channel (16) at most up to the end of the first third of the total length of the channel (16).
  8. The gas flushing brick according to Claim 1,
    wherein the channel (16, 18) runs linearly.
  9. The gas flushing brick according to Claim 1,
    wherein the channel (16, 18) is implemented so that the measuring head (40) detects at least 50% of the cross-sectional area of the channel (16) at the hot side (14) of the gas flushing brick.
  10. The gas flushing brick according to Claim 1,
    wherein the channel (16, 18) runs at a right angle to the front face (20) of the gas flushing brick at the hot side (14).
  11. The gas flushing brick according to Claim 1,
    wherein the internal cross-section of the channel (16) is smaller at the , cold side (14) than at the hot side (12) of the gas flushing brick.
  12. The gas flushing brick according to Claim 1,
    wherein the channel (16, 18) has a cross-sectional area between 0.5,and 20 mm2.
  13. The gas flushing brick according to Claim 1,
    wherein the channel (16, 18) has one of the following cross-sectional shapes: circle, triangle, rectangle, polygon, oval, star shape.
  14. The gas flushing brick according to Claim 1,
    wherein the channel (16, 18) is formed by a drilled hole implemented in the gas flushing brick.
  15. The gas flushing brick according to Claim 1,
    wherein the channel (16, 18) is formed by a tube (60) integrated into the gas flushing brick.
  16. The gas flushing brick according to Claim 15,
    wherein the tube (60) has an inner surface which reflects electromagnetic radiation.
  17. The gas flushing brick according to Claim 15,
    wherein the tube (60) comprises metal or ceramic.
  18. The gas flushing brick according to Claim 1,
    wherein at least the part (40) of the measuring device (38) projecting into the channel (16) has one of the following cross-sectional shapes: circle, triangle, rectangle, polygon, oval, star shape.
  19. The gas flushing brick according to Claim 1,
    wherein at least the part of the measuring device (38) projecting into,the channel (16) has a cross-sectional shape, which is different from the cross-sectional shape of the corresponding channel section (16).
  20. The gas flushing brick according to Claim 3,
    wherein the measuring device (38) is attached to the gas distributor chamber (22).
  21. The gas flushing brick according to Claim 3,
    wherein the measuring device (38) extends partially through an interior of the gas distributor chamber (22).
  22. The gas flushing brick according to Claim 1,
    wherein the measuring device (38) is a temperature measuring device.
  23. The gas flushing brick according to Claim 1,
    wherein the measuring device (38) is a measuring device for determining a chemical analysis of the molten metal.
  24. The gas flushing brick according to Claim 1,
    wherein the measuring device (38) is implemented for receiving and relaying electromagnetic waves which are emitted by the molten metal in the channel.
  25. The gas flushing brick according to Claim 1 having a residual thickness detector.
  26. The gas flushing brick according to Claim 1,
    wherein the residual thickness detector is implemented so that it is activated before the gas flushing brick is worn up that the functional reliability of the measuring device is impaired.
  27. The gas flushing brick according to Claim 1,
    wherein the measuring device (38) is removably attached to the cold side (12) of the gas flushing brick.
EP03815339A 2003-02-08 2003-12-24 Fire-resistant ceramic gas sink Expired - Lifetime EP1590111B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10305232 2003-02-08
DE10305232A DE10305232B3 (en) 2003-02-08 2003-02-08 Refractory ceramic gas purging plug
PCT/EP2003/014904 WO2004069450A1 (en) 2003-02-08 2003-12-24 Fire-resistant ceramic gas sink

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EP1590111A1 EP1590111A1 (en) 2005-11-02
EP1590111B1 true EP1590111B1 (en) 2006-09-20

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EP (1) EP1590111B1 (en)
KR (1) KR20050105998A (en)
CN (1) CN100360259C (en)
AT (1) ATE340041T1 (en)
AU (1) AU2003303859A1 (en)
BR (1) BR0318094A (en)
CA (1) CA2514888A1 (en)
DE (2) DE10305232B3 (en)
ES (1) ES2273093T3 (en)
WO (1) WO2004069450A1 (en)
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EP1590111A1 (en) 2005-11-02
US20060188692A1 (en) 2006-08-24
DE10305232B3 (en) 2004-08-05
ES2273093T3 (en) 2007-05-01
ATE340041T1 (en) 2006-10-15
DE50305145D1 (en) 2006-11-02
CA2514888A1 (en) 2004-08-19
WO2004069450A1 (en) 2004-08-19
KR20050105998A (en) 2005-11-08
CN100360259C (en) 2008-01-09
AU2003303859A1 (en) 2004-08-30
ZA200506281B (en) 2006-04-26
BR0318094A (en) 2005-12-20
CN1764511A (en) 2006-04-26

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