EP1513632A1 - Core material - Google Patents

Core material

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Publication number
EP1513632A1
EP1513632A1 EP03718779A EP03718779A EP1513632A1 EP 1513632 A1 EP1513632 A1 EP 1513632A1 EP 03718779 A EP03718779 A EP 03718779A EP 03718779 A EP03718779 A EP 03718779A EP 1513632 A1 EP1513632 A1 EP 1513632A1
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EP
European Patent Office
Prior art keywords
pore
casting
binder
core
added
Prior art date
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Granted
Application number
EP03718779A
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German (de)
French (fr)
Other versions
EP1513632B1 (en
Inventor
Alexander Schrey
Gotthard Wolf
Rolf Rietzscher
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.)
Georg Fischer AG
Original Assignee
Georg Fischer GmbH
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Filing date
Publication date
Application filed by Georg Fischer GmbH filed Critical Georg Fischer GmbH
Priority to SI200330536T priority Critical patent/SI1513632T1/en
Publication of EP1513632A1 publication Critical patent/EP1513632A1/en
Application granted granted Critical
Publication of EP1513632B1 publication Critical patent/EP1513632B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives

Abstract

A method for the production of cores and molds for casting molds, based on a base molding material and an organic or inorganic binding agent and an additive. According to the method, pre-forming substances are used in order to dispense with the use of sizing substances and to prevent the formation of ribs.

Description

Giesskernmasse Giesskernmasse
Die Erfindung betrifft ein Verfahren zur Herstellung von Giesskernen oder Formen für Giessformen aus einem Formgrundstoff und einem Bindemittel und Giesskerne oder Formen nach Herstellung des Verfahrens.The invention relates to a method for producing casting cores or molds for casting molds from a mold base and a binder, and casting cores or molds after the method has been produced.
Giesskerne haben die Aufgabe, Hohlräume im Gussstück oder unterschnittene Aussenkonturen zu bilden. Diese Art von Giesskernen werden auf bekannte Weise in Kernkästen mittels Kernschiessanlagen hergestellt, wobei der mit Binder und gegebenenfalls mit Additiven versehene Formsand mittels Druckluft in die Hohlräume der Kernformkästen eingeleitet wird. Als Bindemittel werden im allgemeinen flüssige Kunstharze oder anorganische Binder verwendet.Casting cores have the task of forming cavities in the casting or undercut external contours. This type of casting cores is produced in a known manner in core boxes by means of core shooting systems, the molding sand provided with binder and optionally with additives being introduced into the cavities of the core box using compressed air. Liquid synthetic resins or inorganic binders are generally used as binders.
Die Erfindung bezieht sich auf alle organischen und anorganischen Formund Kernherstellungsverfahren, vorzugsweise auf das Urethan-Cold-Box- Verfahren und/oder das Resol-C02-Verfahren. Ebenso denkbar sind physikalische Verfahren, beispielsweise Ultraschallverfahren.The invention relates to all organic and inorganic mold and core production processes, preferably to the urethane cold box process and / or the resol C0 2 process. Physical methods, for example ultrasound methods, are also conceivable.
Die Kernherstellung nach dem Urethan-Cold-Box erfolgt in kalten Kernkästen unter Verwendung organischer Bindersysteme, die unmittelbar im Kernkasten beispielsweise durch tertiäre Amine gasgehärtet werden. Die Verfestigung des Formstoffgemisches (z. B. Quarzsand, organisches Bindesystem, Härter) erfolgt nach dem Füllen des Formstoffes in den kalten Kernkästen durch einen gasförmigen Katalysator oder durch ein gasförmiges tertiäres Amin. Das Vermischen der einzelnen Komponenten erfolgt zuvor in Spezialeinrichtungen. Ein Vorteil dieses Urethan-Cold-Box-Verfahrens besteht unter anderem in der Erreichung hoher Festigkeiten der Kerne oder Formen. Andere, z. B. sogenannte Resol-CO2-Verfahren, sind Kernherstellungsverfahren mit alkalisch kondensiertem Phenolharz als Binder, der zur Härtung mit Kohlendioxid begast wird. Der Formstoff basiert wie beim Urethan-Cold- Box-Verfahren im Allgemeinen auf dem Formgrundstoff Quarzsand. Dieses Verfahren zeichnet sich durch die Verhinderung von "Blattrippen" im Giess- prozess aus. Nachteilig an diesem Begasungsverfahren sind geringere Festigkeiten, die durch erhöhte Erosion und unzureichende Thermostabilität begründet sind.The core production after the urethane cold box takes place in cold core boxes using organic binder systems that are gas-hardened directly in the core box, for example by tertiary amines. The molding material mixture (e.g. quartz sand, organic binding system, hardener) is solidified after the molding material has been filled in the cold core boxes by a gaseous catalyst or by a gaseous tertiary amine. The individual components are mixed beforehand in special facilities. One advantage of this urethane cold box process is that the cores or molds have high strength. Others, e.g. B. so-called resol-CO 2 processes are core manufacturing processes with alkaline condensed phenolic resin as a binder which is gassed with carbon dioxide for curing. As with the urethane cold box process, the molding material is generally based on the molding material quartz sand. This process is characterized by the prevention of "leaf ribs" in the casting process. A disadvantage of this gassing process are lower strengths, which are due to increased erosion and insufficient thermal stability.
Die fertiggeformten Kerne können mittels einer Schlichte überzogen werden. Das sind feuerfeste Stoffe in pulvriger, flüssiger oder pastöser Form zur Herstellung eines dünnen Überzuges auf den Giesskernen. Die Schlichte hat mehrere Aufgaben. Unter anderen dient die Schlichte der Wärmeisolierung, der Glättung, der Verhinderung von Ankleben von Metall an der Formwand, der Blattrippenbildung und somit zur Gewährleistung einer sicheren Trennung des Gussstückes von der Formwand beim Ausleeren der Form.The finished cores can be coated with a size. These are refractory substances in powder, liquid or pasty form for the production of a thin coating on the casting cores. The sizing has several tasks. Among other things, the size is used for heat insulation, smoothing, preventing metal from sticking to the mold wall, forming ribs and thus ensuring a safe separation of the casting from the mold wall when the mold is emptied.
Nach dem Giessvorgang des fertigen Gussteiles erfolgt die Entfernung der Giesskerne aus dem Gussteil. Die Giesskerne werden beispielsweise durch Strahlen, Vibrationen, Ausblasen, Klopfen oder Auswaschen entfernt.After the casting of the finished casting, the casting cores are removed from the casting. The casting cores are removed, for example, by blasting, vibrating, blowing out, tapping or washing out.
Aus der DE 195 25 307 A1 ist ein Giesskern für Giessformen bekannt geworden. Es wird ein Giesskern für Giessformen aus einem mittels eines Bindemittels verfestigten Trockenstoffs vorgeschlagen, der durch Wassereinwirkung seine Form verliert.A casting core for casting molds has become known from DE 195 25 307 A1. A casting core for casting molds is proposed from a dry substance solidified by means of a binder, which loses its shape due to the action of water.
Die DE 195 49 469 A1 beschreibt einen Giesskern zum Giessformen aus mittels eines wasserlöslichen Bindemittels auf der Basis von Polyphosphaten verfestigtem Formsand, wobei das Bindemittel instantiertes Natriumpoly- phosphat ist und dass ein Mischungsverhältnis von 3 bis 7 Gewichtsteilen Bindemittel und 0,5 bis 2 Gewichtsteilen Wasser auf 100 Gewichtsteile teile Formsand gegeben ist. Die DE 199 14 586 A1 offenbart ein Bindemittel auf Harzbasis zur Herstellung von Giessereisanden zur Verwendung im Giessereiwesen. Das Bindemittelgemisch zur Kernsandherstellung besteht aus einer Einzelkomponente (Einzelharz) oder einem Gemisch aus einem oder mehreren Einzelkomponenten (Harzgemisch) mit Additiven.DE 195 49 469 A1 describes a casting core for casting molding from molding sand consolidated by means of a water-soluble binder based on polyphosphates, the binder being instant sodium polyphosphate and that a mixing ratio of 3 to 7 parts by weight of binder and 0.5 to 2 parts by weight of water for 100 parts by weight of molding sand. DE 199 14 586 A1 discloses a resin-based binder for the production of foundry sands for use in foundries. The binder mixture for core sand production consists of a single component (single resin) or a mixture of one or more individual components (resin mixture) with additives.
Der Erfindung liegt die Aufgabe zugrunde, einen Giesskern oder eine Form der eingangs genannten Art zu schaffen, die unter Vermeidung der vorgenannten Nachteile eine Porenstruktur aufweisen. Insbesondere soll die Verwendung einer Schlichte nicht mehr erforderlich sein. Ferner sollte die nachteilige Blattrippenbildung im Giessprozess vermieden werden.The invention has for its object to provide a casting core or a shape of the type mentioned, which have a pore structure while avoiding the aforementioned disadvantages. In particular, the use of a size should no longer be necessary. Furthermore, the disadvantageous formation of leaf ribs in the casting process should be avoided.
Erfindungsgemäss wird diese Aufgabe dadurch gelöst, dass dem Formstoff und/oder dem Bindemittel ein porenbildender Stoff zugegeben wird.According to the invention, this object is achieved in that a pore-forming substance is added to the molding material and / or the binder.
Nach dem bekannten Resol-Kohlendioxid-Verfahren hergestelltefr Kerne zeigen bei rasterelektronenmikroskopischen Untersuchungen eine typische Porenstruktur. Es hat sich erwiesen, dass diese Porenstruktur die o.g. Ausdehnungsfehler ("Blattrippen") verhindert.For cores manufactured according to the known resol-carbon dioxide process, a typical pore structure is shown in scanning electron microscopic examinations. It has been shown that this pore structure has the above-mentioned Expansion errors ("leaf ribs") prevented.
Poren bildende Stoffe geben bei ihrer Zersetzung durch Säurebildner oder Wärmeeinwirkung beispielsweise Kohlendioxid ab, welches in der Formstoffmischung die gewünschte feinporige Struktur erzeugt. Ebenso können zur Bildung feinporiger Strukturen die Anwendung von physikalischen Methoden, z.B. Ultraschallverfahren, beitragen.Pore-forming substances give off, for example, carbon dioxide when they are decomposed by acid formers or the action of heat, which produces the desired fine-pored structure in the molding material mixture. Likewise, the use of physical methods, e.g. Ultrasound, contribute.
Der porenbildende Stoff ist nicht auf die Entstehung von Kohlendioxid beschränkt. Es ist jeder porenbildende Zusatz denkbar, der die gewünschten Poren im Giesskern oder der Gießform erzeugt, beispielsweise wären auch Stickstoff erzeugende Stoffe denkbar. Das Vorhandensein der Porenstruktur ermöglicht es, dass eine anschliessende Schlichtebehandlung des Giesskemes nicht mehr notwendig ist, um Ausdehnungsfehler zu vermeiden.The pore-forming substance is not limited to the generation of carbon dioxide. Any pore-forming additive is conceivable which creates the desired pores in the casting core or the casting mold, for example nitrogen-generating substances would also be conceivable. The presence of the pore structure means that a subsequent size treatment of the casting core is no longer necessary in order to avoid expansion errors.
Vorzugsweise werden als porenbildende Stoffe Stoffe verwendet, die Kohlendioxid erzeugen, wie z. B. Ammoniumkarbonat, Ammoniumhydrogenkarbonat, Natriumkarbonat und/oder Natriumhydrogenkarbonat. Es hat sich gezeigt, dass sich Natriumhydrogenkarbonat als besonders geeignet erweist.Preferably substances are used as pore-forming substances that generate carbon dioxide, such as. B. ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate and / or sodium hydrogen carbonate. It has been shown that sodium hydrogen carbonate proves to be particularly suitable.
Vorteilhafterweise wird dem Kohlendioxid bildenden Stoff ein Säuerungsmittel zugegeben und/oder Wärme zugeführt. Das Kohlendioxid wird insbesondere durch eine saure Umgebung oder durch Energiezuführung in Form von Wärme freigegeben. Um die frei werdende Kohlendioxidmenge quantitativ zu steuern und/oder auch den Zeitpunkt der Kohlendioxidabgabe festzulegen, wird dem Kohlendioxid bildenden Stoff ein Säuerungsmittel zugegeben, beispielsweise Weinstein.An acidifying agent and / or heat is advantageously added to the carbon dioxide-forming substance. The carbon dioxide is released in particular by an acidic environment or by supplying energy in the form of heat. In order to quantitatively control the amount of carbon dioxide released and / or also to determine the time at which carbon dioxide is released, an acidifying agent, for example tartar, is added to the carbon dioxide-forming substance.
Gemäss einer besonders bevorzugten Verfahrensgestaltung ist das Bindemittel im Verhältnis 1 :1 aus einer Phenolharz- und einer Isocyanatkompo- nente zusammengesetzt, wobei beide Bindemittelkomponenten gleichzeitig oder nacheinander in den Formstoff gegeben und anschliessend vermischt werden.According to a particularly preferred process design, the binder is composed of a phenolic resin and an isocyanate component in a ratio of 1: 1, the two binder components being added to the molding material at the same time or in succession and then mixed.
Vorteilhaft kann auch der porenbildende Stoff gleichzeitig oder anschliessend mit dem Bindemittel der Kernformstoffmischung zugegeben werden.The pore-forming substance can also advantageously be added to the core molding material mixture simultaneously or subsequently with the binder.
Ebenso ist denkbar, dass der Kohlendioxid bildende Stoff zusammen mit einer Komponente des Bindemittels zugegeben wird.It is also conceivable that the carbon dioxide-forming substance is added together with a component of the binder.
Aufgrund des oben ausgeführten Herstellungsverfahren für Giesskerne weisen diese eine Materialstruktur auf, die porenförmig ist. Zumindest entstehen im Giesskern porenförmige Bereiche, die die gewünschten Vorteile beim Giessvorgang und beim Entfernen der Giesskerne im Metallgussstück aufweisen.Due to the manufacturing process for casting cores described above, they have a material structure that is pore-shaped. At least pore-shaped areas arise in the casting core, which have the desired advantages during the casting process and when removing the casting cores in the metal casting.
Die wesentlichen technischen Vorteile sind ein vereinfachtes, weniger aufwendiges Giessverfahren gegenüber dem Stand der Technik. Denn die Schlichtebehandlung entfällt durch die feinporige Porenstruktur und die geeignete Festigkeit der Giesskerne.The main technical advantages are a simplified, less complex casting process compared to the prior art. Because the size treatment is eliminated due to the fine-pored pore structure and the suitable strength of the casting cores.
Nachstehend ist ein besonders vorteilhaftes Ausführungsbeispiel für die Zusammensetzung der Mischung aus Quarzsand und Bindemittel für das erfindungsgemässe Herstellungsverfahren angegeben.A particularly advantageous exemplary embodiment for the composition of the mixture of quartz sand and binder for the production process according to the invention is specified below.
100 Gewichtsteile Quarzsand100 parts by weight of quartz sand
0,6 Gewichtsteile Harz (beispielsweise Phenolharz) 0,6 Gewichtsteile Isocyanat0.6 parts by weight of resin (e.g. phenolic resin) 0.6 parts by weight of isocyanate
0,75 Gewichtsanteile porenbildender Stoff, z.B. Natriumhydrogenkarbonat0.75 parts by weight of pore-forming material, e.g. sodium bicarbonate
Die Gewichtsanteile von Harz und Isocyanat können zwischen 0,5 und 1 liegen, je nach gewünschter Festigkeit der Giesskerne. In der Regel werden Harz und Isocyanat in gleichen Mengen, d. h. im Verhältnis1 :1 zugegeben.The proportions by weight of resin and isocyanate can be between 0.5 and 1, depending on the desired strength of the casting cores. As a rule, resin and isocyanate are mixed in equal amounts, i.e. H. in a 1: 1 ratio.
Der porenbildende Stoff wird in der Regel in der Menge von 0,5 bis 1 Gewichtsanteilen zugegeben.The pore-forming substance is usually added in an amount of 0.5 to 1 parts by weight.
Optional können der Mischung zur Steuerung der Kohlendioxidabgabe 0,2 bis 0,7 Gewichtsanteile eines Säurebildners, beispielsweise Weinstein zugegeben werden.Optionally, 0.2 to 0.7 parts by weight of an acid generator, for example tartar, can be added to the mixture to control the release of carbon dioxide.
Im folgenden wird ein beispielhafter typischer Verfahrensablauf einer Giess- kernherstellung beschrieben. Die Verfahrensschritte sind im einzelnen im Urethan-Cold-Box-Verfahren • Abwiegen des Quarzsandes bzw. volumetrische DosierungAn exemplary typical process sequence of a casting core production is described below. The process steps are in detail in the urethane cold box process • Weighing the quartz sand or volumetric dosing
• Einlauf des Quarzsandes in einen Chargenmischer• The quartz sand is fed into a batch mixer
• Dosierung der Harz - und Isocyantkomponente über Dosierpumpen. Die Dosierung kann parallel oder sequenziell erfolgen• Dosing of the resin and isocyanate components via dosing pumps. The dosing can take place in parallel or sequentially
• Die Zugabe des porenbildenden Stoffes erfolgt sequenziell, parallel mit beiden Binderkomponenten oder parallel mit einer Binderkomponente, wobei gegebenenfalls der Säurebildner hinzugefügt wird• The pore-forming substance is added sequentially, in parallel with both binder components or in parallel with one binder component, the acid generator being added if necessary
• Die Mischzeit beträgt 10 bis 120 Sekunden, je nach gewünschten Anforderungen und Mischertyp• The mixing time is 10 to 120 seconds, depending on the desired requirements and mixer type
• Verarbeiten der feuchten Mischung auf der Giessschiessmaschine• Processing the moist mixture on the casting machine
• Entnahme der Kerne• Removal of the cores
• Wärmebehandlung bei beispielsweise 200°C, wobei die Wärmebehandlung unterschiedlich, abhängig von der Anwendung, sein kann• Heat treatment at 200 ° C, for example, whereby the heat treatment can be different, depending on the application
• Einlegen der fertigen Kerne in die Sandform für den eigentlichen Giessvorgang• Place the finished cores in the sand mold for the actual casting process
Weiterhin zeigt die einzige Figur die porenförmige Struktur eines Giesskern- materials, wobei die mittlere Porengrösse 100 nm bis 500 nm beträgt. Furthermore, the only figure shows the pore-shaped structure of a casting core material, the mean pore size being 100 nm to 500 nm.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Giesskernen oder Formen aus einem Formstoff, basierend auf Formgrundstoff und organischen oder anorganischen Binder, dadurch gekennzeichnet, dass dem Formstoff und/oder dem Bindemittel ein porenbildender Stoff zugegeben wird.1. A process for the production of casting cores or molds from a molding material, based on the basic molding material and organic or inorganic binder, characterized in that a pore-forming substance is added to the molding material and / or the binder.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass als porenbil- dende Stoffe Ammoniumkarbonat, Ammoniumhydrogenkarbonat,2. The method according to claim 1, characterized in that as pore-forming substances ammonium carbonate, ammonium hydrogen carbonate,
Natriumkarbonat und/oder Natriumhydrogenkarbonat oder andere geeignete Karbonatsalze verwendet werden.Sodium carbonate and / or sodium hydrogen carbonate or other suitable carbonate salts can be used.
3. Verfahren nach mindestens einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass dem porenbildenden Stoff zur Steuerung der abzugebenden Menge und/oder zur Steuerung des Abgabezeitpunktes von Kohlendioxid ein Säuerungsmittel zugegeben wird.3. The method according to at least one of claims 1 or 2, characterized in that an acidifying agent is added to the pore-forming substance to control the amount to be dispensed and / or to control the time of release of carbon dioxide.
4. Verfahren nach mindestens einem der Ansprüche 1 , 2 oder 3, dadurch gekennzeichnet, dass der geformte Kern oder die Form einer Wärmebehandlung unterzogen werden.4. The method according to at least one of claims 1, 2 or 3, characterized in that the shaped core or the shape are subjected to a heat treatment.
5. Verfahren nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Bindemittel im Verhältnis 1 :1 aus einer Phenolharz- und einer Isocyanatkomponente zusammengesetzt ist, wobei beide Bindemittelkomponenten gleichzeitig in den Quarzsand gegeben und anschliessend vermischt werden.5. The method according to at least one of the preceding claims, characterized in that the binder is composed in a ratio of 1: 1 from a phenolic resin and an isocyanate component, both binder components being added simultaneously to the quartz sand and then mixed.
6. Verfahren nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der porenbildende Stoff gleichzeitig oder anschliessend mit dem Bindemittel der Kernformstoffmischung zugegeben wird. 6. The method according to at least one of claims 1 to 5, characterized in that the pore-forming substance is added to the core molding material mixture simultaneously or subsequently with the binder.
7. Verfahren nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der porenbildende Stoff zusammen mit einer Komponente oder mehreren Komponenten des Bindemittels zugegeben wird.7. The method according to at least one of claims 1 to 5, characterized in that the pore-forming substance is added together with one or more components of the binder.
8. Giesskern oder Giessform nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Materialstruktur des Giesskerns oder der Giessform porenförmig ist und/oder porenförmige Bereiche aufweist. 8. casting core or casting mold according to at least one of the preceding claims, characterized in that the material structure of the casting core or the casting mold is pore-shaped and / or has pore-shaped areas.
EP03718779A 2002-06-19 2003-04-19 Method for manufacturing of a foundry core or mould Expired - Lifetime EP1513632B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI200330536T SI1513632T1 (en) 2002-06-19 2003-04-19 Method for manufacturing of a foundry core or mould

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10227512A DE10227512B4 (en) 2002-06-19 2002-06-19 Process for the production of foundry cores or molds, and foundry cores or molds produced by this process
DE10227512 2002-06-19
PCT/EP2003/004107 WO2004000484A1 (en) 2002-06-19 2003-04-19 Core material

Publications (2)

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EP1513632A1 true EP1513632A1 (en) 2005-03-16
EP1513632B1 EP1513632B1 (en) 2006-09-06

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US (1) US7645814B2 (en)
EP (1) EP1513632B1 (en)
JP (1) JP4397040B2 (en)
CN (1) CN1305599C (en)
AT (1) ATE338598T1 (en)
AU (1) AU2003222830B2 (en)
BR (1) BR0308414B1 (en)
CA (1) CA2484263C (en)
DE (2) DE10227512B4 (en)
DK (1) DK1513632T3 (en)
ES (1) ES2268348T3 (en)
MX (1) MXPA04009502A (en)
PT (1) PT1513632E (en)
RU (1) RU2309813C2 (en)
WO (1) WO2004000484A1 (en)
ZA (1) ZA200409842B (en)

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ZA200409842B (en) 2005-07-18
ATE338598T1 (en) 2006-09-15
RU2309813C2 (en) 2007-11-10
AU2003222830A1 (en) 2004-01-06
RU2005101334A (en) 2005-07-20
EP1513632B1 (en) 2006-09-06
ES2268348T3 (en) 2007-03-16
PT1513632E (en) 2007-01-31
WO2004000484A1 (en) 2003-12-31
CA2484263C (en) 2010-07-13
CA2484263A1 (en) 2003-12-31
US20050176845A1 (en) 2005-08-11
DK1513632T3 (en) 2007-01-08
BR0308414B1 (en) 2011-06-28
DE10227512A1 (en) 2004-01-15
DE50304963D1 (en) 2006-10-19
JP4397040B2 (en) 2010-01-13
AU2003222830B2 (en) 2008-10-09
BR0308414A (en) 2005-01-18
CN1662319A (en) 2005-08-31
US7645814B2 (en) 2010-01-12
CN1305599C (en) 2007-03-21
JP2005533656A (en) 2005-11-10
DE10227512B4 (en) 2004-07-08
MXPA04009502A (en) 2005-12-12

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