EP2082819B1 - Pressure-resistant core with improved adhesive - Google Patents
Pressure-resistant core with improved adhesive Download PDFInfo
- Publication number
- EP2082819B1 EP2082819B1 EP08018459A EP08018459A EP2082819B1 EP 2082819 B1 EP2082819 B1 EP 2082819B1 EP 08018459 A EP08018459 A EP 08018459A EP 08018459 A EP08018459 A EP 08018459A EP 2082819 B1 EP2082819 B1 EP 2082819B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- mixture
- salt core
- soluble salt
- binding agent
- 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.)
- Revoked
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/10—Cores; Manufacture or installation of cores
- B22C9/105—Salt cores
Definitions
- the present invention relates to water-soluble salt cores for foundry purposes, which consist of a mixture of water-soluble salts and a binder.
- One application in which moldings are used for casting are pistons of internal combustion engines. Especially when charged Engines and highly loaded diesel and gasoline engines, the resulting heat in the piston during the firing process is so high that an intensive piston cooling is necessary.
- the piston can be specially equipped by a cooling channel arranged in the piston bottom, so that the necessary heat dissipation is ensured.
- the prefabricated salt cores are inserted into the casting mold during casting, which have the geometry of the later cooling channel and which are rinsed out after the solidification of the metal with water and compressed air.
- salt cores for casting are only suitable for gravity casting, as they are less resistant to pressure and at the same time tend to penetrate, so that in the finished cooling channel bumps or even small partitions arise that hinder the cooling oil flow.
- various methods have become known.
- a method for producing a generic salt core is known in which the salt core 0.5% to 5% of a phosphate-containing binder is added. This ensures that the binder polymerized under a high pressure of about 800 bar and an elevated temperature of about 350 ° C, which can also lead to a melting of the binder, so that a pressure-resistant, against the liquid metal resistant salt core is formed ,
- the object of the invention is to develop an improved salt core and a method for producing a water-soluble salt core, with which a salt core can be prepared, which can be easily removed, has a good resistance to the infiltrating metal and at the same time a low penetration of the liquid Metal allows.
- the procedure should inexpensive and be integrated into the existing procedure.
- the mixture of water-soluble salts and a binder additionally contains a protein combination with inorganic constituents.
- a protein combination with inorganic constituents which may be present for example in the form of a gelatin, the loading capacity, in particular resistance to breakage, of the salt cores according to the invention can be increased.
- the mixture contains from 0.5 to 5% by weight and in particular about 2% of the protein combination with inorganic constituents.
- the binder used is preferably an inorganic phosphate or a mixture of inorganic phosphates.
- the use of such phosphate-containing binders ensures that the salt core faces the liquid metal increased resistance and also characterized by an excellent surface smoothness, so that a penetration of the liquid metal is prevented.
- the salt core is extremely inexpensive to produce and can also be integrated without additional process steps in the production process of the casting process.
- the proportion of the binder is preferably 0.5 to 10 wt.% Of the mixture.
- Phosphate-containing binders which can be used here are, for example, phosphates in the form of sodium hexametaphosphate, which is also marketed under the trade name Budit 6, boron phosphate monohydrate, which is sold under the commercial name FFB 761, monoaluminum hydrogen orthophosphate, sold under the trade name FFB 716 is sold or a combination of inorganic borates and phosphates, which are sold under the trade name FFB 102 and which include, for example, the mono zinc phosphates are used.
- the salt core To prepare the salt core, first the protein combination with inorganic components, for example in the form of a gelatin, is mixed with the phosphate-based binder. The mixture is carried out until a homogeneous mixture is present. Subsequently, the mixture of protein combination and binder is homogeneously mixed with, for example, table salt to prepare the finished salt core mixture. The constituents are weighed in such a way that the proportion of the protein combination is 0.5 to 5% and in particular 2% of the salt core mixture and the proportion of the binding agent is 0.5 to 10% and in particular about 0.5 to 5% by weight.
- the salt mixture thus prepared is filled in a mold to form the salt core.
- the mold is a permanent mold, which may, for example, constitute a cooling channel for a piston or a cylinder crankcase.
- the salt mixture is compressed for up to one minute under a pressure of about 800 bar and pressed at an elevated temperature of about 200 ° C to bond the salt core.
- the binder polymerizes to form a pressure resistant, liquid metal resistant salt core.
- the polymerization or the melting of the binder produces a very smooth surface on the salt core, which prevents penetration of the liquid metal into the salt core.
- salt cores with low masses such as salt cores for cooling channels in pistons
- the salt core is easy to dissolve and can easily be rinsed out of the cast component by means of water.
- the phosphate binder and salt are water-soluble in the present form, but at the same time offer the advantage of a pressure-resistant salt core and a resistant surface. It can thus be produced castings that have undercut contours and are free from the surface of the finished casting roughening penetrations or even partitions by breaks in the salt cores.
- a further advantage results from the fact that during the transfusion of the salt cores produced according to the invention with, for example, liquid aluminum temperature ranges of about 700 ° C, which again lead to a surface polymerization and thus counteract penetration of the liquid aluminum in the salt core.
Abstract
Description
Die vorliegende Erfindung betrifft wasserlösliche Salzkerne für Gießereizwecke, welche aus einem Gemisch aus wasserlöslichen Salzen und einem Bindemittel bestehen.The present invention relates to water-soluble salt cores for foundry purposes, which consist of a mixture of water-soluble salts and a binder.
Bei verschiedenen Gütern, die mittels eines Gießverfahrens hergestellt werden, ist es erforderlich, Formhohlräume im Inneren dieser Güter zu erzeugen. Insbesondere beim Metallgießen, wobei hier insbesondere die Leichtmetalle und deren Legierungen angesprochen sind, gibt es verschiedene Möglichkeiten, die Güter zu gießen. Eine Möglichkeit, die Gießverfahren zu unterscheiden ist die Einteilung in drucklose und druckbeaufschlagte Gießverfahren. Bei den drucklosen Verfahren, wie beispielsweise das Schwerkraftgießen, wird ein Formkern aus verfestigtem Sand oder Salz innerhalb der Gießform angeordnet und mit Metallschmelze umgössen, wobei die Gießform gefüllt und der Formkern umschlossen wird. Bei den druckbeaufschlagten Gießverfahren besteht ein Hauptproblem darin, einen druckfesten Formkern zu erzeugen. Der Formkern muss einerseits druckfest, er muss andererseits aber nach dem Erkalten des Gussteils auch leicht zu entfernen sein. Darüber hinaus muss der Formkern eine Penetration des ihn umgebenden flüssigen Gießmetalls verhindern. Das flüssige Metall wird zumeist unter hohem Druck in die Gießform eingefüllt, so dass der Formkern neben der hohen Druckfestigkeit auch eine hohe Resistenz gegen das flüssige Metall besitzen sollte.In various goods made by a casting process, it is necessary to produce mold cavities inside these goods. In particular, in metal casting, which in particular the light metals and their alloys are addressed, there are various ways to pour the goods. One way of distinguishing the casting processes is the classification into pressureless and pressurized casting processes. In non-pressurized processes, such as gravity casting, a mold core of solidified sand or salt is placed within the mold and molten with molten metal, filling the mold and enclosing the mold core. In the pressurized casting process, a major problem is to produce a pressure-resistant mandrel. On the one hand, the mandrel must be pressure-resistant, but on the other hand, it must also be easy to remove after the casting has cooled down. In addition, the mandrel must prevent penetration of the surrounding liquid casting metal. The liquid metal is usually filled under high pressure in the mold, so that the mold core in addition to the high pressure resistance should also have a high resistance to the liquid metal.
Ein Einsatzgebiet bei dem Formkörper zum Gießen verwendet werden sind Kolben von Verbrennungsmotoren. Besonders bei aufgeladenen Motoren und bei hochbelasteten Diesel- und auch Ottomotoren ist die im Kolben entstehende Wärme beim Brennvorgang so hoch, dass eine intensive Kolbenkühlung notwendig wird. In diesem Fall kann der Kolben durch einen im Kolbenboden angeordneten Kühlkanal besonders ausgerüstet werden, damit die notwendige Wärmeabfuhr gesichert ist.One application in which moldings are used for casting are pistons of internal combustion engines. Especially when charged Engines and highly loaded diesel and gasoline engines, the resulting heat in the piston during the firing process is so high that an intensive piston cooling is necessary. In this case, the piston can be specially equipped by a cooling channel arranged in the piston bottom, so that the necessary heat dissipation is ensured.
Dazu werden beim Gießen die vorgefertigten Salzkerne in die Gießform eingelegt, die die Geometrie des späteren Kühlkanals besitzen und die nach dem Erstarren des Metalls mit Wasser und Druckluft wieder ausgespült werden. Salzkerne zum Gießen sind aber nur zum Schwerkraftgießen geeignet, da sie wenig druckbeständig und gleichzeitig zur Penetration neigen, so dass im fertigen Kühlkanal Unebenheiten oder sogar kleine Trennwände entstehen, die den Kühlöldurchfluss behindern. Um das Eindringen von Metallschmelze in den Salzkern zu verhindern und den Salzkern gleichzeitig druckfest zu gestalten, sind verschiedene Verfahren bekannt geworden.For this purpose, the prefabricated salt cores are inserted into the casting mold during casting, which have the geometry of the later cooling channel and which are rinsed out after the solidification of the metal with water and compressed air. However, salt cores for casting are only suitable for gravity casting, as they are less resistant to pressure and at the same time tend to penetrate, so that in the finished cooling channel bumps or even small partitions arise that hinder the cooling oil flow. In order to prevent the penetration of molten metal into the salt core and to make the salt core pressure resistant at the same time, various methods have become known.
Aus der
Aufgabe der Erfindung ist es, einen verbesserten Salzkern sowie ein Verfahren zur Herstellung eines wasserlöslichen Salzkerns zu entwickeln, mit dem ein Salzkern hergestellt werden kann, der sich leicht entfernen lässt, eine gute Beständigkeit gegen das umgießende Metall aufweist und der gleichzeitig eine geringe Penetration des flüssigen Metalls zulässt. Darüber hinaus soll das Verfahren kostengünstig und in den vorhandenen Verfahrensablauf integrierbar sein.The object of the invention is to develop an improved salt core and a method for producing a water-soluble salt core, with which a salt core can be prepared, which can be easily removed, has a good resistance to the infiltrating metal and at the same time a low penetration of the liquid Metal allows. In addition, the procedure should inexpensive and be integrated into the existing procedure.
Diese Aufgabe ist erfindungsgemäß dadurch gelöst, dass das Gemisch aus wasserlöslichen Salzen und einem Bindemittel zusätzlich eine Protein-Kombination mit anorganischen Bestandteilen enthält. Versuche haben gezeigt, dass durch die Zugabe einer solchen Protein-Kombination mit anorganischen Bestandteilen, die beispielsweise in der Form einer Gelatine vorliegen kann, die Belastbarkeit, insbesondere Bruchsicherheit, der erfindungsgemäßen Salzkerne erhöht werden kann.This object is inventively achieved in that the mixture of water-soluble salts and a binder additionally contains a protein combination with inorganic constituents. Experiments have shown that by adding such a protein combination with inorganic constituents, which may be present for example in the form of a gelatin, the loading capacity, in particular resistance to breakage, of the salt cores according to the invention can be increased.
Es hat sich herausgestellt, dass gute Ergebnisse erzielt werden, wenn das Gemisch 0,5 bis 5 Gew.% und insbesondere etwa 2% der Protein-Kombination mit anorganischen Bestandteilen enthält.It has been found that good results are obtained when the mixture contains from 0.5 to 5% by weight and in particular about 2% of the protein combination with inorganic constituents.
Als Bindemittel wird vorzugsweise ein anorganisches Phosphat oder einer Mischung anorganischer Phosphate gewählt. Durch Einsatz solcher phosphathaltiger Bindemittel wird erreicht, dass der Salzkern dem flüssigen Metall einen erhöhten Widerstand gegenüberstellt und sich darüber hinaus durch eine ausgezeichnete Oberflächenglätte auszeichnet, so dass eine Penetration des flüssigen Metalls verhindert wird. Durch die Zumischung eines handelsüblichen Binders auf Phosphatbasis ist der Salzkern äußerst günstig herzustellen und kann ebenfalls ohne zusätzliche Verfahrensschritte in den Fertigungsablauf des Gießverfahrens integriert werden.The binder used is preferably an inorganic phosphate or a mixture of inorganic phosphates. The use of such phosphate-containing binders ensures that the salt core faces the liquid metal increased resistance and also characterized by an excellent surface smoothness, so that a penetration of the liquid metal is prevented. By adding a commercial binder based on phosphate, the salt core is extremely inexpensive to produce and can also be integrated without additional process steps in the production process of the casting process.
Der Anteil des Bindemittels beträgt vorzugsweise 0,5 bis 10 Gew.% des Gemischs. Als phosphathaltige Binder können dabei zum Beispiel Phosphate in der Form von Natriumhexametaphosphat, das auch unter dem Handelsnamen Budit 6 vertrieben wird, Borphosphatmonohydrat, das unter dem handelsüblichen Namen FFB 761 vertrieben wird, Monoaluminiumhydrogenorthophosphat, das unter dem Handelsnamen FFB 716 vertrieben wird oder eine Kombination aus anorganischen Boraten und Phosphaten, die unter dem Handelsnamen FFB 102 vertrieben werden und zu denen z.B. die Monozink-Phosphate gehören, eingesetzt werden.The proportion of the binder is preferably 0.5 to 10 wt.% Of the mixture. Phosphate-containing binders which can be used here are, for example, phosphates in the form of sodium hexametaphosphate, which is also marketed under the trade name Budit 6, boron phosphate monohydrate, which is sold under the commercial name FFB 761, monoaluminum hydrogen orthophosphate, sold under the trade name FFB 716 is sold or a combination of inorganic borates and phosphates, which are sold under the trade name FFB 102 and which include, for example, the mono zinc phosphates are used.
Zur Herstellung des Salzkerns wird zunächst die Protein-Kombination mit anorganischen Bestandteilen beispielsweise in der Form einer Gelatine mit dem Bindemittel auf Phosphatbasis vermischt. Die Mischung erfolgt so lange, bis ein homogenes Gemisch vorliegt. Anschließend wird das Gemisch aus Proteinkombination und Bindemittel homogen mit zum Beispiel Speisesalz vermischt, um das fertige Salzkerngemisch herzustellen. Die Bestandteile sind dabei so abgewogen, dass der Anteil der Protein-Kombination 0,5 bis 5% und insbesondere 2% des Salzkerngemischs und der Anteil des Bindesmittels 0,5 bis 10% und insbesondere etwa 0,5 bis 5 Gew.% beträgt.To prepare the salt core, first the protein combination with inorganic components, for example in the form of a gelatin, is mixed with the phosphate-based binder. The mixture is carried out until a homogeneous mixture is present. Subsequently, the mixture of protein combination and binder is homogeneously mixed with, for example, table salt to prepare the finished salt core mixture. The constituents are weighed in such a way that the proportion of the protein combination is 0.5 to 5% and in particular 2% of the salt core mixture and the proportion of the binding agent is 0.5 to 10% and in particular about 0.5 to 5% by weight.
Das so hergestellte Salzgemisch wird in ein Formwerkzeug zur Bildung des Salzkerns gefüllt. Das Formwerkzeug ist eine Dauerform, die zum Beispiel einen Kühlkanal für einen Kolben oder ein Zylinderkurbelgehäuse darstellen kann. Im Formwerkzeug wird das Salzgemisch bis zu eine Minute lang unter einem Druck von ca. 800bar verdichtet und bei einer erhöhten Temperatur von ca. 200°C zur Bindung des Salzkernes verpresst. Unter dem hohen Druck und dem Einfluss der erhöhten Temperatur polymerisiert der Binder, so dass ein druckbeständiger, gegen das flüssige Metall widerstandsfähiger Salzkern gebildet wird. Durch die Polymerisation oder das Anschmelzen des Binders wird eine sehr glatte Oberfläche am Salzkern erzeugt, die ein Penetrieren des flüssigen Metalls in den Salzkern verhindert. Bei Salzkernen mit geringen Massen, wie beispielsweise Salzkerne für Kühlkanäle in Kolben, ergeben sich Herstellungs- oder Formzeiten für die Salzkerne von kleiner oder gleich einer Minute. Bei größeren Massen wie beispielsweise Salzkernen zum Gießen für Zylinderkurbelgehäuse erhöhen sich die Formzeiten bis zu etwa 5 Minuten.The salt mixture thus prepared is filled in a mold to form the salt core. The mold is a permanent mold, which may, for example, constitute a cooling channel for a piston or a cylinder crankcase. In the mold, the salt mixture is compressed for up to one minute under a pressure of about 800 bar and pressed at an elevated temperature of about 200 ° C to bond the salt core. Under the high pressure and the influence of the elevated temperature, the binder polymerizes to form a pressure resistant, liquid metal resistant salt core. The polymerization or the melting of the binder produces a very smooth surface on the salt core, which prevents penetration of the liquid metal into the salt core. In salt cores with low masses, such as salt cores for cooling channels in pistons, resulting in manufacturing or molding times for the salt cores of less than or equal to one minute. at larger masses such as salt cores for casting for cylinder crankcases, the molding times increase up to about 5 minutes.
Durch den Einsatz des phosphathaltigen Binders ist der Salzkern leicht aufzulösen und kann mittels Wasser aus dem gegossenen Bauteil sehr leicht herausgespült werden. Der Phosphatbinder und das Salz sind in der vorliegenden Form wasserlöslich, bieten aber gleichzeitig den Vorteil eines druckbeständigen Salzkerns und einer resistenten Oberfläche. Es können somit Gussteile hergestellt werden, die Hinterschnittkonturen aufweisen und die frei von der Oberfläche des fertigen Gussteils aufrauhenden Penetrationen oder sogar Trennwänden durch Brüche in den Salzkernen sind.By using the phosphate-containing binder, the salt core is easy to dissolve and can easily be rinsed out of the cast component by means of water. The phosphate binder and salt are water-soluble in the present form, but at the same time offer the advantage of a pressure-resistant salt core and a resistant surface. It can thus be produced castings that have undercut contours and are free from the surface of the finished casting roughening penetrations or even partitions by breaks in the salt cores.
Ein weiterer Vorteil ergibt sich dadurch, dass während des Umgießens der erfindungsgemäß hergestellten Salzkerne mit zum Beispiel flüssigem Aluminium Temperaturbereiche von etwa 700°C einstellen, die wieder zu einer Oberflächenpolymerisation führen und somit einer Penetration des flüssigen Aluminiums in dem Salzkern entgegenwirken.A further advantage results from the fact that during the transfusion of the salt cores produced according to the invention with, for example, liquid aluminum temperature ranges of about 700 ° C, which again lead to a surface polymerization and thus counteract penetration of the liquid aluminum in the salt core.
Claims (17)
- A water-soluble salt core for foundry purposes, made from a mixture of water-soluble salts and a binding agent, characterized in that the mixture further includes a protein combination with inorganic components.
- The water-soluble salt core of claim 1, characterized in that the mixture contains 0.5 to 5% by weight of the protein combination with inorganic components.
- The water-soluble salt core of claim 2, characterized in that that the mixture contains 2% of the protein combination with inorganic components.
- The water-soluble salt core of one of the preceding claims, characterized in that the protein combination with inorganic components is a gelatin.
- The water-soluble salt core of one of the preceding claims, characterized in that the binding agent contains an inorganic phosphate or a mixture of inorganic phosphates.
- The water-soluble salt core of claim 5, characterized in that the proportion of binding agent is 0.5 to 10% by weight.
- The water-soluble salt core of claim 5, characterized in that the proportion of binding agent is 0.5 to 5% by weight.
- The water-soluble salt core of claim 5 or 7, characterized in that the inorganic phosphate contains a monoaluminum hydrogenorthophosphate.
- The water-soluble salt core of one of claims 5 to 8, characterized in that the inorganic phosphate contains a borophosphate monohydrate.
- The water-soluble salt core of one of claims 5 to 9, characterized in that the inorganic phosphate contains a sodium polyphosphate.
- The water-soluble salt core of one of claims 5 to 9, characterized in that the inorganic phosphate contains a sodium hexametaphosphate.
- A method for manufacturing a water-soluble salt core, wherein water-soluble salts are mixed with a binding agent, the mixture is filled into a molding tool to form a salt core, and the mold core is compacted under pressure and/or at high temperatures, characterized in that 0.5 to 5% of a protein combination with inorganic components is added to the mixture.
- The method of claim 12, characterized in that the protein combination with the inorganic components is mixed homogeneously with the binding agent and the mixture is then mixed with the salts.
- The method of claim 12 or 13, characterized in that the mixture of the protein combination with inorganic components and the binding agent is homogeneously mixed with table salt.
- The method of one of claims 12 to 14, characterized in that a monoaluminum phosphate is used as the binding agent.
- The method of one of claims 12 to 15, characterized in that the mixture is compacted in the molding tool and is heated to up to 200°C.
- The method of one of claims 12 to 16, characterized in that the salts used in the mixture are chlorides, sulfates, and borates of alkaline or alkaline earth metals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL08018459T PL2082819T3 (en) | 2008-01-18 | 2008-10-22 | Pressure-resistant core with improved adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102008004929A DE102008004929A1 (en) | 2008-01-18 | 2008-01-18 | Pressure-resistant core with improved binder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2082819A1 EP2082819A1 (en) | 2009-07-29 |
| EP2082819B1 true EP2082819B1 (en) | 2011-12-14 |
Family
ID=40475056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP08018459A Revoked EP2082819B1 (en) | 2008-01-18 | 2008-10-22 | Pressure-resistant core with improved adhesive |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2082819B1 (en) |
| AT (1) | ATE536950T1 (en) |
| DE (1) | DE102008004929A1 (en) |
| ES (1) | ES2380071T3 (en) |
| PL (1) | PL2082819T3 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102012217939A1 (en) | 2012-10-01 | 2014-04-03 | Mahle International Gmbh | Process for the production of cores for the casting production of workpieces |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5320157A (en) * | 1993-01-28 | 1994-06-14 | General Motors Corporation | Expendable core for casting processes |
| US6467525B2 (en) * | 2000-07-24 | 2002-10-22 | Hormel Foods, Llc | Gelatin coated sand core and method of making same |
| DE102004006600B4 (en) | 2004-02-11 | 2006-03-23 | Ks Aluminium-Technologie Ag | Removable metal casting core and method of making a core |
| DE102006031531A1 (en) * | 2006-07-07 | 2008-01-10 | Emil Müller GmbH | Salt cores for plastic (injection) casting |
| DE102006031532B3 (en) * | 2006-07-07 | 2008-04-17 | Emil Müller GmbH | Water-soluble salt core with functional component |
-
2008
- 2008-01-18 DE DE102008004929A patent/DE102008004929A1/en not_active Withdrawn
- 2008-10-22 AT AT08018459T patent/ATE536950T1/en active
- 2008-10-22 ES ES08018459T patent/ES2380071T3/en active Active
- 2008-10-22 PL PL08018459T patent/PL2082819T3/en unknown
- 2008-10-22 EP EP08018459A patent/EP2082819B1/en not_active Revoked
Non-Patent Citations (1)
| Title |
|---|
| ULLMANN: "Ullmann's ecyclopedia of industrial chemistry: "Milk and Diary Products"", 2007, WEINHEIM: WILEY-VCH VERLAGSGESELLSCHAFT, ISBN: 9783527306732, pages: 1, 6, 41 - 43 * |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE536950T1 (en) | 2011-12-15 |
| EP2082819A1 (en) | 2009-07-29 |
| PL2082819T3 (en) | 2012-07-31 |
| DE102008004929A1 (en) | 2009-07-23 |
| ES2380071T3 (en) | 2012-05-08 |
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