EP2643114B1 - Method for producing high-temperature resistant jet engine component - Google Patents

Method for producing high-temperature resistant jet engine component Download PDF

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Publication number
EP2643114B1
EP2643114B1 EP11793368.9A EP11793368A EP2643114B1 EP 2643114 B1 EP2643114 B1 EP 2643114B1 EP 11793368 A EP11793368 A EP 11793368A EP 2643114 B1 EP2643114 B1 EP 2643114B1
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Prior art keywords
melting
phase
metal powder
low
point
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EP11793368.9A
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German (de)
French (fr)
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EP2643114A1 (en
Inventor
Dan Roth-Fagaraseanu
Alexander Schult
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Rolls Royce Deutschland Ltd and Co KG
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Rolls Royce Deutschland Ltd and Co KG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F3/26—Impregnating
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0475—Impregnated alloys

Definitions

  • the invention relates to a method for near-net-shape production of geometrically complex designed, consisting of an intermetallic phase engine components.
  • metal injection molding also known as MIM (Metal Injection Molding)
  • a metal powder is first mixed with a binder consisting of thermoplastic material and waxes to form a flowable material (feedstock).
  • feedstock a flowable material
  • the granular material is injected into a mold using an extruder in a conventional injection molding process.
  • a so-called green part is initially available, from which the binder is then dissolved out chemically, thermally or catalytically.
  • the open-pored brown part resulting as a result of the binder removal is compacted down to its final shape in a subsequent sintering process and, due to the remaining low residual porosity, has mechanical properties which essentially correspond to the properties of the solid material.
  • the invention has for its object to develop a method for cost-effective, near net shape production of existing from an intermetallic phase, high temperature resistant engine components with geometrically complex structure.
  • the basic idea of the invention lies in the use of metal powder spraying for the production of engine components made of an intermetallic phase, but where the binder is a low-melting metallic phase in molten or near-molten state and the metal powder is made from a higher-melting metallic phase and the present as a result of an injection molding process, substantially corresponding to the final contour molding is not debinded, but is subjected to a heat treatment to produce an intermetallic phase.
  • the binder is a low-melting metallic phase in molten or near-molten state and the metal powder is made from a higher-melting metallic phase and the present as a result of an injection molding process, substantially corresponding to the final contour molding is not debinded, but is subjected to a heat treatment to produce an intermetallic phase.
  • three or more metallic phases may also be used to produce high temperature intermetallic phase engine components.
  • the mixing of the molten or near-molten state low-melting phase with the metal powder consisting of the high-melting phase is carried out under the action of kneading and shearing forces generated by an extruder screw in an extruder.
  • good mixing and temperature increase and a reduction in viscosity of the metal powder-melt mixture for carrying out the injection molding process are ensured.
  • the metal powder-melt mixture can be additionally heated in the extruder by means of heating means.
  • the engine component which has been demolded after solidification can be subjected to a machining finish before the heat treatment.
  • the first low-melting point metallic phase may also be present in a not completely molten state - in the case of the aluminum used here in a below the melting point temperature range between 400 ° C and 600 ° C -.
  • the metal powder produced from a metallic phase in this case iron
  • the two metallic phases are intensively mixed with one another. Due to the shearing and kneading forces exerted by the extruder screw 4 on the mixture, the viscosity of the mixture continues to decrease. Due to the mechanical force and optionally an extruder heating, the mixture is also heated.
  • the binder required for the injection molding process does not consist of thermoplastics and waxes, but is formed by the molten, low-melting metallic phase acting as a binder.
  • the metal powder binder mixture can either be injected directly from the extruder 4 in the mold 5 or, as the drawing shows, are first introduced into a cylinder 6 and then pressed by means of a pressure piston 7 in the cavity 8 of the mold 5.
  • a molded part corresponding to the final shape or substantially the final shape of the engine component is removed from the mold after cooling and solidification, which can be machined in a further step VI with little machining effort.
  • the low-melting metallic phase serving as a binder in the metal powder injection molding process in step IV remains in the molding, that is, unlike the conventional metal injection molding, the molding produced in the injection molding process is not debinded.
  • the molded part is subjected to a specific heat treatment tailored to the two metallic phases, in this case iron and aluminum, to produce a high-temperature-resistant intermetallic phase. Since, in contrast to the known metal powder injection molding using a thermoplastic binder after demolding a compact (non-porous) molded part is present, it is not difficult to control shrinkage of the component during the intended to produce the intermetallic compound heat treatment.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Description

Die Erfindung betrifft ein Verfahren zur endkonturnahen Herstellung von geometrisch komplex gestalteten, aus einer intermetallischen Phase bestehenden Triebwerksbauteilen.The invention relates to a method for near-net-shape production of geometrically complex designed, consisting of an intermetallic phase engine components.

Es ist allgemein bekannt, Bauteile mit geometrisch komplizierter Gestalt in wenigen Arbeitsschritten endkonturnah durch Metallpulverspritzgießen herzustellen. Bei dem auch als MIM-Verfahren (Metal Injection Moulding) bezeichneten Metallpulverspritzguss wird zunächst ein Metallpulver mit einem aus thermoplastischem Kunststoff und Wachsen bestehenden Binder zu einem fließfähigen Werkstoff (Feedstock) vermischt. Das in Form eines Granulats vorliegende Material wird in einem herkömmlichen Spritzgießprozess mithilfe eines Extruders in eine Form gespritzt. Nach dem Abkühlen, Erstarren und Entformen steht zunächst ein sogenanntes Grünteil zur Verfügung, aus dem anschließend der Binder chemisch, thermisch oder katalytisch herausgelöst wird. Das im Ergebnis der Entbinderung entstehende offenporige Braunteil wird in einem darauffolgenden Sinterprozess bis auf seine endgültige Form verdichtet und weist aufgrund der verbleibenden geringen Restporosität mechanische Eigenschaften auf, die mit den Eigenschaften des Vollmaterials im Wesentlichen übereinstimmen.It is well known to produce components with geometrically complicated shape in a few steps near net shape by metal powder injection molding. In the metal injection molding process, also known as MIM (Metal Injection Molding), a metal powder is first mixed with a binder consisting of thermoplastic material and waxes to form a flowable material (feedstock). The granular material is injected into a mold using an extruder in a conventional injection molding process. After cooling, solidification and demolding, a so-called green part is initially available, from which the binder is then dissolved out chemically, thermally or catalytically. The open-pored brown part resulting as a result of the binder removal is compacted down to its final shape in a subsequent sintering process and, due to the remaining low residual porosity, has mechanical properties which essentially correspond to the properties of the solid material.

Zur endkonturnahen Fertigung hochtemperaturbeständiger Bauteile werden bekanntermaßen in Pulverform vorliegende Superlegierungen im MIM-Verfahren verarbeitet. Darüber hinaus wurde bereits vorgeschlagen, ein aus einer intermetallischen Phase bestehendes Metallpulver zu erzeugen und daraus auf der Grundlage des Metallpulverspritzgießens hochtemperaturbeständige Triebwerksbauteile endabmessungsnah und mit gegenüber herkömmlichen Herstellungsverfahren vermindertem Zerspanungsaufwand herzustellen. Die herkömmliche Herstellung intermetallischer Phasen und eines daraus gefertigten Metallpulvers für das Metallpulverspritzgießen ist mit einem hohen Arbeits- und Kostenaufwand verbunden. Zudem bereitet die endkonturnahe maßgenaue Fertigung des Bauteils aufgrund der Schrumpfung des Braunteils im Ergebnis des sich an die Entbinderung anschließenden Sinterprozesses Schwierigkeiten.For near-net-shape production of high-temperature resistant components are known to be present in powder form superalloys processed in the MIM process. Moreover, it has already been proposed to produce a metal powder consisting of an intermetallic phase and to produce on the basis of the metal powder injection molding high-temperature resistant engine components close to the final dimensions and with respect to conventional manufacturing processes reduced machining costs. The conventional production of intermetallic phases and a metal powder produced therefrom for metal powder injection molding involves a great deal of work and expense. In addition, due to the shrinkage of the brown part as a result of the sintering process subsequent to the debindering process, the close-to-net shape dimensional production of the component causes difficulties.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur kostengünstigen, endkonturnahen Herstellung von aus einer intermetallischen Phase bestehenden, hochtemperaturbeständigen Triebwerksbauteilen mit geometrisch komplexer Struktur zu entwickeln.The invention has for its object to develop a method for cost-effective, near net shape production of existing from an intermetallic phase, high temperature resistant engine components with geometrically complex structure.

Erfindungsgemäß wird die Aufgabe mit einem Verfahren gemäß den Merkmalen des Patentanspruchs 1 gelöst.According to the invention the object is achieved by a method according to the features of patent claim 1.

Vorteilhafte Weiterbildungen der Erfindung sind Gegenstand der Unteransprüche.Advantageous developments of the invention are the subject of the dependent claims.

Der Grundgedanke der Erfindung liegt in de Anwendung des Metallpulverspritzens zur Herstellung von aus einer intermetallischen Phase bestehenden Triebwerksbauteilen, wobei jedoch als Binder eine in schmelzflüssigem oder nahe dem schmelzflüssigen Zustand befindliche niedrig schmelzende metallische Phase dient und das Metallpulver aus einer höher schmelzenden metallischen Phase hergestellt ist und das im Ergebnis eines Spritzgießprozesses vorliegende, im Wesentlichen der Endkontur entsprechende Formteil nicht entbindert wird, sondern einer Wärmebehandlung zur Erzeugung einer intermetallischen Phase unterzogen wird. Somit können mit geringem Fertigungs- und Kostenaufwand aus einer intermetallischen Phase bestehende, hochtemperaturbeständige Triebwerksbauteile mit geometrisch komplexer Struktur endkonturnah hergestellt werden. In dem gleichen Verfahren können auch drei oder mehr metallische Phasen zur Herstellung von hochtemperaturbeständigen, aus einer intermetallischen Phase bestehenden Triebwerksbauteilen eingesetzt werden.The basic idea of the invention lies in the use of metal powder spraying for the production of engine components made of an intermetallic phase, but where the binder is a low-melting metallic phase in molten or near-molten state and the metal powder is made from a higher-melting metallic phase and the present as a result of an injection molding process, substantially corresponding to the final contour molding is not debinded, but is subjected to a heat treatment to produce an intermetallic phase. Thus, with little manufacturing and Cost incurred from an intermetallic phase, high-temperature resistant engine components with geometrically complex structure near net shape produced. In the same process, three or more metallic phases may also be used to produce high temperature intermetallic phase engine components.

Das Vermischen der schmelzflüssigen oder nahe dem schmelzflüssigen Zustand befindlichen niedrig schmelzenden Phase mit dem aus der hoch schmelzenden Phase bestehenden Metallpulver erfolgt unter der Wirkung von mittels einer Extruderschnecke erzeugten Knet- und Scherkräften in einem Extruder. Dadurch sind eine gute Durchmischung und Temperaturerhöhung sowie eine Viskositätsverringerung des Metallpulver-Schmelze-Gemisches zur Durchführung des Spritzgießprozesses gewährleistet.The mixing of the molten or near-molten state low-melting phase with the metal powder consisting of the high-melting phase is carried out under the action of kneading and shearing forces generated by an extruder screw in an extruder. As a result, good mixing and temperature increase and a reduction in viscosity of the metal powder-melt mixture for carrying out the injection molding process are ensured.

In weiterer Ausgestaltung der Erfindung kann das Metallpulver-Schmelze-Gemisch im Extruder mittels Heizmitteln zusätzlich erwärmt werden.In a further embodiment of the invention, the metal powder-melt mixture can be additionally heated in the extruder by means of heating means.

Das nach dem Erstarren entformte Triebwerksbauteil kann vor der Wärmebehandlung einer spanenden Fertigbearbeitung unterworfen werden.The engine component which has been demolded after solidification can be subjected to a machining finish before the heat treatment.

Ein Ausführungsbeispiel der Erfindung wird anhand der Zeichnung, in deren einziger Figur schematisch eine Metallpulverspritzgießvorrichtung dargestellt ist, und eines Verfahrensablaufschemas näher erläutert.An embodiment of the invention will be explained in more detail with reference to the drawing, in whose sole figure schematically a metal powder injection molding is shown, and a process flow diagram.

In Schritt I des Verfahrens zur endkonturnahen Herstellung eines geometrisch komplex gestalteten, aus einer intermetallischen Phase bestehenden, hochtemperaturbeständigen Triebwerksbauteils, beispielsweise einer Turbinenschaufel, werden eine erste niedrig schmelzende Phase, zum Beispiel Aluminium, in geschmolzenem Zustand und eine zweite hoch schmelzende metallische Phase, zum Beispiel Eisen, als Metallpulver bereitgestellt. Die erste niedrig schmelzende metallische Phase kann auch in einem nicht vollständig geschmolzenen Zustand - im Falle des hier eingesetzten Aluminiums in einem unterhalb des Schmelzpunkts Temperaturbereich zwischen 400°C und 600°C - vorliegen. Gegenüber einem aus einer intermetallischen Verbindung bestehenden Metallpulver kann das aus einer metallischen Phase (hier Eisen) gefertigte Metallpulver mit geringem Aufwand hergestellt werden.In step I of the method for near-net-shape production of a geometrically complex designed, consisting of an intermetallic phase, high-temperature resistant engine component, such as a turbine blade, a first low-melting phase, For example, aluminum, in the molten state, and a second refractory metallic phase, for example, iron, are provided as metal powder. The first low-melting point metallic phase may also be present in a not completely molten state - in the case of the aluminum used here in a below the melting point temperature range between 400 ° C and 600 ° C -. Compared with a metal powder consisting of an intermetallic compound, the metal powder produced from a metallic phase (in this case iron) can be produced with little effort.

In dem nachfolgenden Schritt II werden die geschmolzene niedrig schmelzende metallische Phase (Aluminium) und die als Metallpulver vorliegende hoch schmelzende metallische Phase (Eisen) jeweils über einen ersten und einen zweiten Trichter 1, 2 in einen Extruder 3 eingetragen. In dem im Extruder 3 stattfindenden Schritt III werden die beiden metallischen Phasen intensiv miteinander vermischt. Durch die von der Extruderschnecke 4 auf das Gemisch ausgeübten Scher- und Knetkräfte nimmt die Viskosität des Gemisches weiter ab. Aufgrund der mechanischen Kraftwirkung und gegebenenfalls einer Extruderheizung wird das Gemisch zudem erwärmt.In the subsequent step II, the molten low-melting point metallic phase (aluminum) and present as metal powder high-melting metallic phase (iron) in each case via a first and a second funnel 1, 2 entered into an extruder 3. In the step III taking place in the extruder 3, the two metallic phases are intensively mixed with one another. Due to the shearing and kneading forces exerted by the extruder screw 4 on the mixture, the viscosity of the mixture continues to decrease. Due to the mechanical force and optionally an extruder heating, the mixture is also heated.

Das zuvor in einen niedrig viskosen, spritzgießfähigen Zustand gebrachte Gemisch aus einer pulverförmigen hoch schmelzenden metallischen Phase und einer niedrig schmelzenden, geschmolzenen metallischen Phase (Fe, A1) wird nun in Schritt IV durch Spritzgießen in ein Formwerkzeug 5 eingetragen. Im Unterschied zu einem herkömmlichen Metallpulverspritzgießverfahren besteht der für den Spritzgussprozess erforderliche Binder nicht aus thermoplastischen Kunststoffen und Wachsen, sondern wird durch die als Binder fungierende schmelzflüssige, niedrig schmelzende metallische Phase gebildet. Das Metallpulver-Binder-Gemisch kann entweder direkt aus dem Extruder 4 in das Formwerkzeug 5 eingespritzt werden oder, wie die Zeichnung zeigt, erst in einen Zylinder 6 eingebracht werden und dann mithilfe eines Druckkolbens 7 in den Hohlraum 8 des Formwerkzeugs 5 gepresst werden.The previously brought into a low-viscosity, injection-moldable state mixture of a powdery high-melting metallic phase and a low-melting molten metallic phase (Fe, A1) is now introduced in step IV by injection molding in a mold 5. In contrast to a conventional metal powder injection molding process, the binder required for the injection molding process does not consist of thermoplastics and waxes, but is formed by the molten, low-melting metallic phase acting as a binder. The metal powder binder mixture can either be injected directly from the extruder 4 in the mold 5 or, as the drawing shows, are first introduced into a cylinder 6 and then pressed by means of a pressure piston 7 in the cavity 8 of the mold 5.

Im nachfolgenden Schritt V wird nach dem Erkalten und Erstarren ein der Endform oder im Wesentlichen der Endform des Triebwerkbauteils entsprechendes Formteil entformt, das in einem weiteren Schritt VI mit geringem Zerspanungsaufwand spanend bearbeitet werden kann. Die beim Metallpulverspritzgussprozess in Schritt IV als Binder dienende niedrig schmelzende metallische Phase bleibt in dem Formteil, das heißt, anders als bei dem herkömmlichen Metallpulverspritzguss wird das im Spritzgießprozess erzeugte Formteil nicht entbindert.In the subsequent step V, a molded part corresponding to the final shape or substantially the final shape of the engine component is removed from the mold after cooling and solidification, which can be machined in a further step VI with little machining effort. The low-melting metallic phase serving as a binder in the metal powder injection molding process in step IV remains in the molding, that is, unlike the conventional metal injection molding, the molding produced in the injection molding process is not debinded.

In einem sich anschließenden Schritt VII wird das Formteil einer auf die beiden metallischen Phasen - hier Eisen und Aluminium - abgestimmten spezifischen Wärmebehandlung zur Erzeugung einer hochtemperaturbeständigen intermetallischen Phase unterzogen. Da im Gegensatz zu dem bekannten Metallpulverspritzgießen unter Verwendung eines thermoplastischen Binders bereits nach der Entformung ein kompaktes (nicht poröses) Formteil vorliegt, kommt es auch nicht zu einer nur schwer beherrschbaren Schrumpfung des Bauteils während der zur Erzeugung der intermetallischen Verbindung vorgesehenen Wärmebehandlung.In a subsequent step VII, the molded part is subjected to a specific heat treatment tailored to the two metallic phases, in this case iron and aluminum, to produce a high-temperature-resistant intermetallic phase. Since, in contrast to the known metal powder injection molding using a thermoplastic binder after demolding a compact (non-porous) molded part is present, it is not difficult to control shrinkage of the component during the intended to produce the intermetallic compound heat treatment.

Im Ergebnis der zuvor beschriebenen Verfahrensschritte I bis VII steht ein aus einer intermetallischen Verbindung bestehendes, hochtemperaturbeständiges und durch den Einsatz von Leichtbaukomponenten zudem leichtes Triebwerksbauteil zur Verfügung, das in einer nahezu beliebigen komplexen Struktur mit vergleichsweise geringem Fertigungsaufwand kostengünstig hergestellt werden kann. Neben der oben beispielhaft erwähnten Materialkombination aus Eisen und Aluminium kann eine Vielzahl weiterer hoch und niedrig schmelzender metallischer Phasen, beispielsweise Titan und Aluminium, verwendet werden.As a result of the method steps I to VII described above, there is an existing high-temperature resistant from an intermetallic compound, and by the use of lightweight components also lightweight engine component available in a virtually arbitrary complex structure with relatively little manufacturing effort can be produced inexpensively. In addition to the above-exemplified material combination of iron and aluminum, a variety of other high and low melting metallic phases, such as titanium and aluminum, can be used.

BezugszeichenlisteLIST OF REFERENCE NUMBERS

11
erster Trichter von 3 (Fe-Pulver)first funnel of 3 (Fe powder)
22
zweiter Trichter von 3 (Al-Schmelze)second funnel of 3 (Al melt)
33
Extruderextruder
44
Extruderschneckeextruder screw
55
Formwerkzeugmold
66
Zylindercylinder
77
Druckkolbenpressure piston
88th
Hohlraum von 5Cavity of 5

Claims (4)

  1. Method for the near-net-shape fabrication of high-temperature-resistant engine parts that have a geometrically complex design and consist of an intermetallic phase, characterized in that at least one low-melting-point metallic phase, in a molten state or in a temperature range close to the molten state, is mixed with at least one high-melting-point metallic phase which takes the form of a metal powder, with the mixture being machined and heated up and its viscosity being decreased in the process, and in that the engine part, which substantially corresponds to the final contour, is subsequently formed in an injection moulding process, with the engine part then being subjected to a heat treatment for the production of an intermetallic phase.
  2. Method according to claim 1, characterized in that the intermixture of the low-melting-point and the high-melting-point phase is performed in an extruder where it is subjected to the effects of kneading and shearing forces.
  3. Method according to claim 1, characterized in that the mixture of metal powder and molten mass is additionally heated by using a heating medium.
  4. Method according to claim 1, characterized in that the engine part which is demoulded after solidification is submitted to mechanical finish-machining prior to the heat treatment.
EP11793368.9A 2010-11-25 2011-11-18 Method for producing high-temperature resistant jet engine component Not-in-force EP2643114B1 (en)

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Application Number Priority Date Filing Date Title
DE102010061959A DE102010061959A1 (en) 2010-11-25 2010-11-25 Method of making high temperature engine components
PCT/EP2011/070438 WO2012069373A1 (en) 2010-11-25 2011-11-18 Method for producing high-temperature resistant jet engine component

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EP2643114A1 EP2643114A1 (en) 2013-10-02
EP2643114B1 true EP2643114B1 (en) 2014-10-01

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EP (1) EP2643114B1 (en)
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WO (1) WO2012069373A1 (en)

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US10597761B2 (en) 2014-06-12 2020-03-24 University Of Florida Research Foundation, Inc. Self-repairing metal alloy matrix composites, methods of manufacture and use thereof and articles comprising the same

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US20130266470A1 (en) 2013-10-10

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