EP2552630A1 - Method for producing shaped bodies from aluminium alloys - Google Patents

Method for producing shaped bodies from aluminium alloys

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Publication number
EP2552630A1
EP2552630A1 EP11720714A EP11720714A EP2552630A1 EP 2552630 A1 EP2552630 A1 EP 2552630A1 EP 11720714 A EP11720714 A EP 11720714A EP 11720714 A EP11720714 A EP 11720714A EP 2552630 A1 EP2552630 A1 EP 2552630A1
Authority
EP
European Patent Office
Prior art keywords
binder
debinding
remove
aluminum
thermal debinding
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.)
Granted
Application number
EP11720714A
Other languages
German (de)
French (fr)
Other versions
EP2552630B1 (en
Inventor
Herbert Danninger
Christian Gierl
Branislav Zlatkov
Johan Ter Maat
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.)
Technische Universitaet Wien
Rupert Fertinger GmbH
BASF SE
Original Assignee
Technische Universitaet Wien
Rupert Fertinger GmbH
BASF SE
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Filing date
Publication date
Application filed by Technische Universitaet Wien, Rupert Fertinger GmbH, BASF SE filed Critical Technische Universitaet Wien
Priority to PL11720714T priority Critical patent/PL2552630T3/en
Publication of EP2552630A1 publication Critical patent/EP2552630A1/en
Application granted granted Critical
Publication of EP2552630B1 publication Critical patent/EP2552630B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/20Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22Manufacture 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12Both compacting and sintering
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/1017Multiple heating or additional steps
    • B22F3/1021Removal of binder or filler
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22Manufacture 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
    • B22F3/225Manufacture 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24After-treatment of workpieces or articles
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/0408Light metal alloys
    • C22C1/0416Aluminium-based alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/06Alloys based on aluminium with magnesium as the next major constituent

Definitions

  • the manufacturing process consists essentially of the process steps described below.
  • a feedstock is prepared in the form of a sprayable granulate of metal powder and a plastic component comprising at least two intensively mixed polymer components.
  • This feedstock is then sprayed into molded parts in plastic injection molding machines.
  • This so-called "green body” or “green body” usually contains about 40% by volume of plastic binder, which is removed in the subsequent step, the so-called debindering, for the most part.
  • a particular difficulty in the processing of aluminum in the manner described above is also the relatively low melting point of aluminum (660 ° C), which is enhanced by the addition of alloying elements, such as aluminum. Tin, still lowered.
  • the resulting problem is that the debindering of the plastic component must be completed at very low temperatures, which often makes the available process window too small to ensure complete removal.
  • undesirable reactions of residual organic constituents with the metallic components can occur, hindering sintering and thus impairing the mechanical properties that can be achieved.
  • Liu et al. in Powder Metallurgy 51, 78-83 (2008) discloses a method of adding tin as an alloying metal as well as magnesium blocks, wherein the magnesium is referred to as a "sacrificial metal", i.
  • the object of the invention was the development of a metal powder injection molding process by means of which molded articles made of aluminum materials with good mechanical properties can be produced in a simpler and reproducible manner.
  • step c) the binder is completely removed, wherein, optionally after performing one or more preceding debindering stages, a thermal Entbin- tion takes place to remove the (residual) binder in at least one , 5 vol .-% oxygen-containing atmosphere is carried out, after which the resulting completely unbonded Braunling is sintered.
  • the aluminum alloy contains, besides aluminum, one or more other metals which are not specifically limited.
  • the alloying partners are selected from the group consisting of magnesium, copper, silicon and manganese, and more preferably are contained in a respective proportion of 0.5 to 25% by weight to obtain moldings having desirable properties.
  • the other metals are used as alloys with aluminum, ie as master alloy or so-called master alloy powder.
  • binders which are known to be removable at low temperatures, more preferably polyacetal-based binders, for example polyoxymethylene (POM) binders, for example those described by BASF in EP 413,231, WO 94/25205 and WO 92/25205 especially EP 446708 disclosed and also sold under the brand name Catamold ®.
  • POM polyoxymethylene
  • binder systems can be used which are based on wax polymer-based and in which the main component wax by previous Wegsentbindtation, ie prior to the inventive implementation of the thermal debinding in the presence of oxygen, is removed.
  • Debinding in step c) of the process of the invention may involve a single step of thermal debinding in the presence of oxygen, in which the entire binder is removed.
  • one or more preceding debinding steps may be performed to remove the bulk of the binder, followed by the thermal debinding step of the present invention to remove the residual binder in the presence of oxygen.
  • a previous debinding step may also be a thermal debindering - in the absence or also in the presence of oxygen. This means that debranking can also involve multi-stage thermal debindering at different process parameters, for example different temperature or atmospheric pressure. re, eg with and without oxygen or with air and pure oxygen etc.
  • a catalytic debinding and / or a solution debinding is carried out in step c) before the thermal debindering in order to remove the residual binder in the presence of oxygen.
  • the bulk of the binder is already removed from the composition, so that in the subsequent thermal debinding preferably only the "backbone" component needs to be removed.
  • the catalytic debinding is carried out preferably in the presence of at least one acid selected from nitric acid, oxalic acid, formic acid and acetic acid, since these acids accelerate the complete removal of the preferred polyacetal binder by acidolysis, without leading to undesirable side reactions with the alloying partners.
  • the bulk of the binder is obtained by extraction with a suitable solvent or solvent mixture, e.g. Acetone, n-heptane, water etc., removed.
  • a catalytic debindering with sublimed oxalic acid is particularly preferred according to the present invention.
  • the thermal debinding to remove the residual binder in step c) is carried out at a relatively low temperature in order to suppress oxidation reactions, especially of the aluminum in the powder mixture.
  • a relatively low temperature herein is meant a temperature well below the melting point of aluminum, preferably below 500 ° C, more preferably between 100 and 420 ° C.
  • an empirically optimized temperature profile for the respective powder mixture is set, which preferably provides a heating rate of not more than 5 K / min, more preferably not more than 1 to 2 K / min.
  • the sintering step d) of the process of the present invention is not specifically limited except for the requirement that the binder must be completely removed beforehand. Preferably, however, is sintered to form a liquid phase, as will be explained in more detail below.
  • This liquid phase which according to the inventors - without wishing to be bound by any particular theory - is present partly intermediate, but predominantly stationary, ie in thermodynamic equilibrium with the solid Al phase, via microcracks, pores or similar "openings" in the oxide skins of the metal powder particles and infiltration of the oxide skins the required contact between the metals in the powder mixture ago and thus supports the formation of a high-density sintered body from the completely unbonded Bönling.
  • the sintering in step d) is carried out at a temperature between the solidus and the liquidus temperature of the respective aluminum alloy, so that at any time during the sintering process only a controllable by the choice of a corresponding temperature profile proportion of alloying metals in liquid ger phase, which effectively prevents loss of dimensional and dimensional stability.
  • the composition of the particular atmosphere in the individual steps of the process according to the invention is not particularly limited, except for the presence of the oxygen in the thermal debindering in step c), and the person skilled in the art can select the most suitable for each powder mixture in each individual step Choose atmosphere, whereby also vacuum is possible.
  • the sintering step d) is preferably carried out in an extremely dry nitrogen-containing atmosphere, i. in pure nitrogen, under normal pressure or reduced pressure ("partial pressure sintering"), or in a mixture of nitrogen and pure inert gas (helium, argon), preferably with a dew point ⁇ -40 ° C, since the presence of nitrogen with the wettability of the powder the resulting molten metal significantly supported.
  • sintering may be followed by a suitable after-treatment, by means of which the finished molded parts are obtained in the desired shape.
  • a suitable after-treatment for example, the known method of hot isostatic pressing (HIP) can be used to bring the moldings to the desired final density.
  • HIP hot isostatic pressing
  • residual pores remaining after sintering are pressed by the simultaneous action of external gas pressure and temperature, and the pore walls are welded together.
  • Fig. 1 is a photograph of the green compact (above) and the sintered body (bottom) obtained therefrom of Example 9.
  • Fig. 2 is a photograph of the green compact (left) and the sintered body (right) thereof obtained in Example 10.
  • feedstocks prepared in the examples below were homogenized in a heated kneader at 190 ° C. From these feedstocks, tensile test bars or hollow cylinders were molded by means of injection molding in accordance with ISO 2740, the method according to the invention being used as follows. To produce the green parts, a hydraulic injection molding machine (Battenfeld HM 600/130) with PIM equipment was used.
  • the feedstock was first filled into a hopper of the injection molding machine.
  • the powder injection molding for the production of the green parts was carried out in the following steps:
  • the prepared feed material was plasticized and pre-dosed by means of a heated injection cylinder in which a screw rotates according to preset setting parameters (such as, for example, rotational speed, metering volume, dynamic pressure, etc.).
  • preset setting parameters such as, for example, rotational speed, metering volume, dynamic pressure, etc.
  • the pre-metered quantity was injected into a correspondingly tempered tool.
  • the plasticizing temperature in the injection cylinder was between 120 and 220 ° C, while in the tool between 25 and 140 ° C prevailed.
  • the injection mold was opened and the green part was ejected from the mold and removed with a handling.
  • Example 1 Ingredients: Solution Disinfectant / Thermal Debinder
  • a commercially available metal powder mixture (Alumix ® 231 of Ecka) consisting of aluminum, with 14 wt .-% of silicon, 2.5 wt .-% copper and 0.6 wt .-% magnesium, was with a group consisting of wax / thermoplastic Solvent binder is carefully mixed into a feedstock.
  • Solvent binder wax content 14.8
  • This feedstock was first debinded by solvent extraction in a 60 L oven with acetone at a temperature of 45 ° C within 12 h.
  • the Bhoffnling thus obtained contained a residual binder content of about 14.5 wt .-%, which then by thermal debinding according to the invention by means of a temperature profile of 150 ° C to 320 ° C for 1 h and then from 320 to 420 ° C for 1, 5 h was removed at a heating rate of 3 K / min under a pure oxygen-containing atmosphere.
  • the thus completely unbonded B syndromenling was then sintered at 560 ° C within 1 h in pure nitrogen (dew point: -50 ° C).
  • Feedstock component proportion (% by weight)
  • Weight loss after thermal debinding was 24.2%.
  • the sintering was carried out at a furnace setting temperature of 665 ° C, which corresponds to a temperature within the furnace of about 630 ° C, during 1 h in pure nitrogen.
  • Feedstock component proportion (% by weight)
  • Example 4 Supplies: catalytic / thermal debinding
  • Feedstock component proportion (% by weight)
  • Example 3 a thermal debindering to 420 ° C under pure oxygen within 1 h, after which it was again sintered at a Ofeneinstelltemperatur of 665 ° C for 1 h under nitrogen.
  • Example 5 Supplies: catalytic / thermal debinding
  • Feedstock component proportion (% by weight)
  • Example 4 a catalytic debinding was carried out analogously to Example 4, but using 80 g of anhydrous oxalic acid on a Sublimierschale instead of HNO 3 at 140 ° C for 24 h. Weight loss: 23.0%. Due to the use of oxalic acid, no outgrowths appeared on the surface. Subsequently, thermal debinding and sintering were also carried out analogously to Example 4.
  • Feedstock component proportion (% by weight)
  • Example 5 a catalytic debinding was carried out analogously to Example 5. Weight loss: 25.2%. Subsequently, thermal debinding and sintering were carried out analogously to Example 4, but at a Ofeneinstelltemperatur of 560 ° C.
  • Example 7 Ingredients: Catalytic / Thermal Debinding
  • Feedstock component proportion (% by weight)
  • Example 5 a catalytic debinding was carried out analogously to Example 5. Weight loss: 23.2%. Subsequently, thermal debinding and sintering were carried out analogously to Example 4.
  • Example 8 Hollow Cylinder: Catalytic / Thermal Debinding
  • Feedstock component proportion (% by weight)
  • Example 5 a catalytic debinding was carried out analogously to Example 5. Weight loss: 23.7%. Subsequently, thermal debinding and sintering were carried out analogously to Example 4.
  • Example 9 Tension rods: catalytic / thermal debinding
  • Feedstock component proportion (% by weight)
  • Example 5 a catalytic debinding was carried out analogously to Example 5. Weight loss: 25.7%. Subsequently, thermal debinding and sintering were carried out analogously to Example 4.
  • Example 10 Hollow Cylinder: Catalytic / Thermal Debinding
  • Feedstock component proportion (% by weight)
  • Example 5 a catalytic debinding was carried out analogously to Example 5. Weight loss: 25.6%. Subsequently, thermal debinding and sintering were carried out analogously to Example 4.
  • sintered bodies of aluminum alloys can be provided by means of injection molding, which are suitable for practical use in many fields, e.g. in the transport sector, construction, mechanical engineering, packaging, iron and steel, electrical engineering, household appliances, etc., for example for heat dissipation in electronic devices ("heat sinks") or as components of air conditioning systems.

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

Abstract

The invention relates to a method for producing shaped bodies based on aluminium alloys by metal powder injection moulding, comprising the following steps: a) preparing a feedstock by blending the metals contained in the desired alloy in the form of metal powders and/or one or more metal alloy powders with a binder; b) preparing a green compact by injection moulding the feedstock; c) preparing a brown compact by at least partially removing the binder from the green compact by catalytic and/or solvent and/or thermal debinding; d) sintering the at least partially de-bindered brown compact to obtain the desired shaped body. The invention is characterised in that in step c) the binder is removed completely, wherein, optionally after carrying out one or more preceding de-binding stages, a thermal debinding in order to remove the (residual) binder is effected and is carried out in an atmosphere containing at least 0.5% by volume of oxygen, after which the resulting completely de-bindered brown compact is sintered.

Description

Verfahren zur Herstellung von Formkörpern aus Aluminiumlegierungen  Process for the production of moldings from aluminum alloys
Die Technologie des Metallpulverspritzgusses hat in den letzten Jahren einen enormen Aufschwung genommen und ist zur Herstellung vor! kompliziert geformten Klein- teilen eine eingeführte Technologie mit einem weltweiten Jahresumsatz von etwa 1 Mrd.€. Die Möglichkeit, die Formgebungstechnologie des Kunststoffspritzgusses mit der Werkstoffvielfalt der Pulvertechnologie zu verbinden, hat für viele Werkstoffe interessante Märkte erschlossen. Das Herstellungsverfahren besteht im Wesentlichen aus den nachstehend beschriebenen Prozessschritten. Zunächst wird ein Feedstock in Form eines spritzbaren Granulats aus Metallpulver und einer Kunststoffkomponente, die zumindest zwei intensiv vermischte Polymerkomponenten umfasst, hergestellt. Dieser Feedstock wird anschließend in Kunststoffspritzgussmaschinen zu Formteilen verspritzt. Dieser sog. "Grünkörper" oder "Grünling" enthält üblicherweise ca. 40 Vol.-% Kunststoffbinder, der im nachfolgenden Schritt, der sog. Entbinderung, zum überwiegenden Teil entfernt wird. Es verbleibt nur eine Restkomponente des Binders, das sog. "Backbone", das die Restfestigkeit des entbinderten Körpers gewährleistet. Die Entbinderung kann auf vielfältige Weise geschehen, z.B. thermisch, durch Lösungsmittel, kataly- tisch usw., wobei sie sehr gut auf den eingesetzten Kunststoffbinder abgestimmt sein muss. Der entbinderte Körper, der sog. "Braunteil" oder "Bräunling", wird nun einem Sinterprozess unterzogen, in dessen erster Stufe normalerweise der "Backbone"- Restbinder thermisch entfernt und der Körper dann unter entsprechender Schrumpfung zu einem annähernd dichten metallischen Bauteil gesintert wird. Die Technolo- gie wird derzeit für hoch- und niedrig legierte Stähle, Edelmetalle, Hartmetalle, aber auch für Keramiken eingesetzt. The technology of metal powder injection molding has taken a tremendous boost in recent years and is ready for production! intricately shaped small parts have introduced a technology with a worldwide annual turnover of about € 1 billion. The possibility of combining the molding technology of plastic injection molding with the material diversity of powder technology has opened up interesting markets for many materials. The manufacturing process consists essentially of the process steps described below. First, a feedstock is prepared in the form of a sprayable granulate of metal powder and a plastic component comprising at least two intensively mixed polymer components. This feedstock is then sprayed into molded parts in plastic injection molding machines. This so-called "green body" or "green body" usually contains about 40% by volume of plastic binder, which is removed in the subsequent step, the so-called debindering, for the most part. There remains only a residual component of the binder, the so-called. "Backbone", which ensures the residual strength of the unbent body. Debinding can be done in a variety of ways, e.g. thermally, by solvents, catalytically, etc., whereby it must be very well matched to the plastic binder used. The debinded body, the so-called "brown part" or "browning", is now subjected to a sintering process, in the first stage of which the "backbone" residual binder is normally removed thermally and the body is then sintered with appropriate shrinkage to form an approximately dense metallic component. The technology is currently used for high and low alloy steels, precious metals, hard metals, but also for ceramics.
Obwohl mehrere diesbezügliche Patente existieren, wurde Metallpulverspritzguss für Aluminiumwerkstoffe bisher noch nicht erfolgreich industriell eingeführt, da sich die Mechanismen des Sinterns von Aluminiumlegierungen sehr stark von dem der oben erwähnten Werkstoffe unterscheiden. Die Anwesenheit von nicht reduzierbaren Oxiden auf der Oberfläche von Aluminiumpulvern behindert nämlich massiv die Sinte- rung. Aus diesem Grund wird in der Fachliteratur auch durchwegs eine sauerstofffreie Atmosphäre beschrieben. Although several related patents exist, metal powder injection molding for aluminum materials has not been successfully introduced industrially since the mechanisms of sintering aluminum alloys are very different from those of the above-mentioned materials. The presence of non-reducible oxides on the surface of aluminum powders hampers massively the sintering tion. For this reason, the literature also consistently describes an oxygen-free atmosphere.
Eine besondere Schwierigkeit bei der Verarbeitung von Aluminium auf die oben be- schriebene Weise ist auch der relativ niedrige Schmelzpunkt von Aluminium (660 °C), der durch den Zusatz von Legierungselementen, wie z.B. Zinn, noch gesenkt wird. Das daraus resultierende Problem besteht darin, dass die Entbinderung der Kunststoffkomponente bei sehr niedrigen Temperaturen abgeschlossen sein muss, wodurch das zur Verfügung stehende Prozessfenster oftmals zu klein wird, um eine vollständige Entfernung zu gewährleisten. Falls dies jedoch nicht gelingt, kann es zu unerwünschten Reaktionen von organischen Restbestandteilen mit den metallischen Komponenten kommen, die die Sinterung behindern und damit die erzielbaren mechanischen Eigenschaften verschlechtern. Beispielsweise beschreiben Liu et al. in Powder Metallurgy 51 , 78-83 (2008) ein Verfahren unter Zusatz von Zinn als Legierungsmetall sowie von Magnesiumblöcken, wobei das Magnesium als "Opfermetall", d.h. als Sauerstoff- und Feuchtigkeitsfänger, dient. Ziel der Erfindung war vor diesem Hintergrund die Entwicklung eines Metallpulver- spritzgussverfahrens, durch das Formkörper aus Aluminiumwerkstoffen mit guten mechanischen Eigenschaften auf einfachere Weise und reproduzierbar hergestellt werden können. OFFENBARUNG DER ERFINDUNG A particular difficulty in the processing of aluminum in the manner described above is also the relatively low melting point of aluminum (660 ° C), which is enhanced by the addition of alloying elements, such as aluminum. Tin, still lowered. The resulting problem is that the debindering of the plastic component must be completed at very low temperatures, which often makes the available process window too small to ensure complete removal. However, if this fails, undesirable reactions of residual organic constituents with the metallic components can occur, hindering sintering and thus impairing the mechanical properties that can be achieved. For example, Liu et al. in Powder Metallurgy 51, 78-83 (2008) discloses a method of adding tin as an alloying metal as well as magnesium blocks, wherein the magnesium is referred to as a "sacrificial metal", i. as an oxygen and moisture scavenger. Against this background, the object of the invention was the development of a metal powder injection molding process by means of which molded articles made of aluminum materials with good mechanical properties can be produced in a simpler and reproducible manner. DISCLOSURE OF THE INVENTION
Dieses Ziel haben die Erfinder durch Bereitstellung eines Verfahrens zur Herstellung von Formkörpern auf Basis von Aluminiumlegierungen durch Metallpulverspritzguss erreicht, das die folgenden Schritte umfasst:  This object has been achieved by the inventors by providing a process for the production of moldings based on aluminum alloys by metal injection molding, comprising the following steps:
a) Herstellung eines Feedstocks durch Vermischen der in der gewünschten Legierung enthaltenen Metalle in Form von Metallpulvern und/oder einem oder mehreren Metalllegierungspulvern mit einem Binder;  a) production of a feedstock by mixing the metals contained in the desired alloy in the form of metal powders and / or one or more metal alloy powders with a binder;
b) Herstellung eines Grünlings durch Spritzgießen des Feedstocks; c) Herstellung eines Bräunlings durch zumindest teilweises Entfernen des Binders aus dem Grünling durch katalytisches und/oder Lösungsmittel- und/oder thermisches Entbindern; b) production of a green compact by injection molding of the feedstock; c) preparation of a browning by at least partial removal of the binder from the green compact by catalytic and / or solvent and / or thermal debinding;
d) Sintern des zumindest teilweise entbinderten Bräunlings zum Erhalt des ge- wünschten Formkörpers;  d) sintering the at least partially debinded browning to obtain the desired shaped article;
wobei das erfindungsgemäße Verfahren dadurch gekennzeichnet ist, dass in Schritt c) der Binder vollständig entfernt wird, wobei, gegebenenfalls nach Durchführung eines oder mehrerer vorhergehender Entbinderungsstufen, eine thermische Entbin- derung zur Entfernung des (Rest-)Binders erfolgt, die in einer zumindest 0,5 Vol.-% Sauerstoff enthaltenden Atmosphäre durchgeführt wird, wonach der so erhaltene, vollständig entbinderte Bräunling gesintert wird. wherein the inventive method is characterized in that in step c) the binder is completely removed, wherein, optionally after performing one or more preceding debindering stages, a thermal Entbin- tion takes place to remove the (residual) binder in at least one , 5 vol .-% oxygen-containing atmosphere is carried out, after which the resulting completely unbonded Braunling is sintered.
Durch dieses Verfahren werden hochreine Formkörper aus Aluminiumlegierungen erhalten, da es aufgrund der vollständigen Entfernung des Binders in Schritt c) zu kei- nen unerwünschten Reaktionen des Kunststoffs mit den Legierungsmetallen kommt. Diese restlose Entfernung des Binders gelingt - sogar bei relativ niedrigen Temperaturen - aufgrund der Gegenwart von Sauerstoff in der Atmosphäre. Entgegen der herrschenden Lehre, wonach Sauerstoff unbedingt zu vermeiden ist, haben die Erfinder herausgefunden, dass ein geringer Anteil von zumindest 0,5 Vol.-%, die Oxida- tion des Aluminiums nicht nennenswert fördert, aber zu einer raschen und vollständigen Entbinderung beiträgt. In Abhängigkeit von Zusammensetzung des Pulverge- mischs und den Temperaturbedingungen wird beispielsweise ein Sauerstoffanteil zwischen 20 und 100 Vol.-% eingesetzt, d.h. es kann sogar reines (VGas eingesetzt werden. As a result of the complete removal of the binder in step c), no undesired reactions of the plastic with the alloying metals occur due to this process. This complete removal of the binder succeeds - even at relatively low temperatures - due to the presence of oxygen in the atmosphere. Contrary to the prevailing theory that oxygen must be avoided at all costs, the inventors have found that a small proportion of at least 0.5% by volume does not appreciably promote the oxidation of the aluminum, but contributes to rapid and complete debindering. Depending on the composition of the powder mixture and the temperature conditions, an oxygen content of between 20 and 100% by volume is used, for example. it can even be used pure (VGas.
Die Aluminiumlegierung enthält neben Aluminium ein oder mehrere andere Metalle, die nicht speziell eingeschränkt sind. Vorzugsweise sind die Legierungspartner aus der aus Magnesium, Kupfer, Silicium und Mangan bestehenden Gruppe ausgewählt und sind besonders bevorzugt in einem jeweiligen Anteil von 0,5 bis 25 Gew.-% ent- halten, um Formkörper mit wünschenswerten Eigenschaften zu erhalten. Deutlich niedriger schmelzende Metalle, wie z.B. Bismut, Zinn, Blei, Indium oder auch Zink, oder Legierungen wie etwa Woodsches Metall, die mitunter als Sinterhilfen zur Ernie- drigung der Temperatur des Schmelzbeginns dienen, sind gemäß vorliegender Erfindung nicht erforderlich, können jedoch auf Wunsch dennoch als Legierungspartner zugesetzt werden, um Sinterkörper aus den entsprechenden Legierungen zu erhalten. In besonders vorteilhafter Weise werden die weiteren Metalle als Legierungen mit Aluminium, d.h. als Vorlegierungs- oder so genannte Masteralloy-Pulver, eingesetzt. The aluminum alloy contains, besides aluminum, one or more other metals which are not specifically limited. Preferably, the alloying partners are selected from the group consisting of magnesium, copper, silicon and manganese, and more preferably are contained in a respective proportion of 0.5 to 25% by weight to obtain moldings having desirable properties. Significantly lower melting metals, such as bismuth, tin, lead, indium or even zinc, or alloys such as Wood's metal, sometimes as sintering aids for the Ernie- Tempering serve the temperature of the onset of melting, are not required according to the present invention, but can still be added as an alloying partner, if desired, to obtain sintered bodies of the corresponding alloys. In a particularly advantageous manner, the other metals are used as alloys with aluminum, ie as master alloy or so-called master alloy powder.
Gemäß vorliegender Erfindung werden vorzugsweise Binder eingesetzt, die bekanntermaßen bei niedrigen Temperaturen entfernbar sind, besonders bevorzugt Poly- acetal-basierte Binder, z.B. Polyoxymethylen- (POM-) Binder, beispielsweise solche, wie sie von BASF in EP 413.231 , WO 94/25205 und vor allem EP 446.708 offenbart und auch unter dem Markennamen Catamold® vertrieben werden. Um die rasche und vollständige Entfernbarkeit bei niedrigen Temperaturen und in Gegenwart von Sauerstoff zu fördern, ist im Binder ein hoher Polyacetal-Anteil wünschenswert, wes- wegen der Binder vorzugsweise zu 50 bis 95 %, noch bevorzugter zu 80 bis 90 %, aus Polyacetal besteht. Alternativ können auch Bindersysteme zum Einsatz kommen, die auf Wachs-Polymer-Basis aufgebaut sind und bei denen die Hauptkomponente Wachs durch vorhergehende Lösungsentbinderung, d.h. vor der erfindungsgemäßen Durchführung der thermischen Entbinderung in Gegenwart von Sauerstoff, entfernt wird. According to the present invention, preference is given to using binders which are known to be removable at low temperatures, more preferably polyacetal-based binders, for example polyoxymethylene (POM) binders, for example those described by BASF in EP 413,231, WO 94/25205 and WO 92/25205 especially EP 446708 disclosed and also sold under the brand name Catamold ®. In order to promote rapid and complete removability at low temperatures and in the presence of oxygen, a high polyacetal content is desirable in the binder, for which reason the binder is preferably 50 to 95%, more preferably 80 to 90% polyacetal , Alternatively, binder systems can be used which are based on wax polymer-based and in which the main component wax by previous Lösungsentbinderung, ie prior to the inventive implementation of the thermal debinding in the presence of oxygen, is removed.
Die Entbinderung in Schritt c) des erfindungsgemäßen Verfahrens kann einen einzigen Schritt der thermischen Entbinderung in Gegenwart von Sauerstoff umfassen, in dem der gesamte Binder entfernt wird. Alternativ dazu können ein oder mehrere vor- hergehende Entbinderungsschritte durchgeführt werden, um die Hauptmenge des Binders zu entfernen, worauf der erfindungsgemäße thermische Entbinderungsschritt zur Entfernung des Restbinders in Gegenwart von Sauerstoff folgt. So kann ein vorhergehender Entbinderungsschritt ebenfalls eine thermische Entbinderung - in Abwesenheit oder ebenfalls in Gegenwart von Sauerstoff - sein. Das heißt, als Entbin- derung kann auch eine mehrstufige thermische Entbinderung bei unterschiedlichen Verfahrensparametern, beispielsweise unterschiedlicher Temperatur oder Atmosphä- re, z.B. ohne und mit Sauerstoff oder mit Luft und reinem Sauerstoff usw., durchgeführt werden. Debinding in step c) of the process of the invention may involve a single step of thermal debinding in the presence of oxygen, in which the entire binder is removed. Alternatively, one or more preceding debinding steps may be performed to remove the bulk of the binder, followed by the thermal debinding step of the present invention to remove the residual binder in the presence of oxygen. Thus, a previous debinding step may also be a thermal debindering - in the absence or also in the presence of oxygen. This means that debranking can also involve multi-stage thermal debindering at different process parameters, for example different temperature or atmospheric pressure. re, eg with and without oxygen or with air and pure oxygen etc.
In bevorzugten Ausführungsformen der Erfindung wird in Schritt c) vor der thermi- sehen Entbinderung zur Entfernung des Restbinders in Gegenwart von Sauerstoff zunächst eine katalytische Entbinderung und/oder eine Lösungsentbinderung durchgeführt. Dabei wird bereits die Hauptmenge des Binders aus der Zusammensetzung entfernt, so dass bei der anschließenden thermischen Entbinderung vorzugsweise nur noch die "Backbone"-Komponente entfernt zu werden braucht. In preferred embodiments of the invention, a catalytic debinding and / or a solution debinding is carried out in step c) before the thermal debindering in order to remove the residual binder in the presence of oxygen. In this case, the bulk of the binder is already removed from the composition, so that in the subsequent thermal debinding preferably only the "backbone" component needs to be removed.
Die katalytische Entbinderung erfolgt dabei vorzugsweise in Gegenwart zumindest einer Säure, ausgewählt aus Salpetersäure, Oxalsäure, Ameisensäure und Essigsäure, da diese Säuren durch Acidolyse die vollständige Entfernung der bevorzugten Polyacetal-Binder beschleunigen, ohne zu unerwünschten Nebenreaktionen mit den Legierungspartnern zu führen. Im Falle der Lösungsentbinderung wird hingegen die Hauptmenge des Binders durch Extraktion mit einem geeigneten Lösungsmittel oder Lösungsmittelgemisch, wie z.B. Aceton, n-Heptan, Wasser etc., entfernt. Besonders bevorzugt ist gemäß vorliegender Erfindung eine katalytische Entbinderung mit subli- mierter Oxalsäure. The catalytic debinding is carried out preferably in the presence of at least one acid selected from nitric acid, oxalic acid, formic acid and acetic acid, since these acids accelerate the complete removal of the preferred polyacetal binder by acidolysis, without leading to undesirable side reactions with the alloying partners. In the case of solution debonding, on the other hand, the bulk of the binder is obtained by extraction with a suitable solvent or solvent mixture, e.g. Acetone, n-heptane, water etc., removed. Particularly preferred according to the present invention is a catalytic debindering with sublimed oxalic acid.
Wie bereits erwähnt wird die thermische Entbinderung zur Entfernung des Restbinders in Schritt c) bei einer relativ niedrigen Temperatur durchgeführt, um Oxida- tionsreaktionen, vor allem des Aluminiums im Pulvergemisch, zu unterdrücken. Unter einer relativ niedrigen Temperatur ist hierin eine Temperatur deutlich unterhalb des Schmelzpunkts von Aluminium, vorzugsweise unterhalb von 500 °C, noch bevorzugter zwischen 100 und 420 °C, zu verstehen. Insbesondere wird ein für das jeweilige Pulvergemisch empirisch optimiertes Temperaturprofil eingestellt, das vorzugsweise eine Heizrate von nicht mehr als 5 K/min, noch bevorzugter von nicht mehr als 1 bis 2 K/min, vorsieht. Dadurch wird das zu entbindemde Gemisch auf schonende, gleichmäßige Weise erhitzt. Der Sinterschritt d) des erfindungsgemäßen Verfahrens ist abgesehen von der Anforderung, dass der Binder zuvor vollständig entfernt worden sein muss, nicht speziell eingeschränkt. Vorzugsweise wird jedoch unter Ausbildung einer flüssigen Phase gesintert, wie dies nachstehend näher ausgeführt wird. As already mentioned, the thermal debinding to remove the residual binder in step c) is carried out at a relatively low temperature in order to suppress oxidation reactions, especially of the aluminum in the powder mixture. By a relatively low temperature herein is meant a temperature well below the melting point of aluminum, preferably below 500 ° C, more preferably between 100 and 420 ° C. In particular, an empirically optimized temperature profile for the respective powder mixture is set, which preferably provides a heating rate of not more than 5 K / min, more preferably not more than 1 to 2 K / min. As a result, the mixture to be debindered is heated in a gentle, uniform manner. The sintering step d) of the process of the present invention is not specifically limited except for the requirement that the binder must be completely removed beforehand. Preferably, however, is sintered to form a liquid phase, as will be explained in more detail below.
Die bisher bekannte Technologie der pulvermetallurgischen Formteilherstellung von Aluminiumlegierungen mittels Formpressen beruht auf dem theoretischen Ansatz, dass durch den Pressvorgang in der Matrize die Oberfläche der mit einer Aluminiumoxidschicht überzogenen Aluminiumpartikel mechanisch verletzt wird, wodurch eine metallurgische Reaktion überhaupt erst ermöglicht wird. Bei einem (vollständig) entbinderten Braunkörper aus dem Pulverspritzguss handelt es sich aber de facto um eine Metallpulverschüttung, wobei die Oxidhäute der Metalle keinerlei mechanischer Belastung ausgesetzt waren und deshalb diesem bekannten Mechanismus nicht unterliegen. Das heißt, es gibt hier keine direkten Metall-Metall-Kontakte zwischen den Pulverpartikeln. Trotzdem gelingt es im erfindungsgemäßen Verfahren, durch geeignete Wahl der Sinterbedingungen die erforderliche Schrumpfung zu erzielen, anhand derer sich die Verdichtung des Sinterkörpers manifestiert, und somit weitestgehend dichte Bauteile zu erhalten. Erfindungsgemäß bevorzugt werden daher Ausführungsformen, bei denen der vollständig entbinderte Bräunling in Schritt d) unter Ausbildung einer flüssigen Phase gesintert wird. Diese flüssige Phase, die nach Ansicht der Erfinder - ohne sich auf eine spezielle Theorie festegen zu wollen - zu einem Teil intermediär, aber vorwiegend stationär, d.h. im thermodynamischen Gleichgewicht mit der festen AI-Phase, vor- liegt, stellt über Mikrorisse, -poren oder ähnliche "Öffnungen" in den Oxidhäuten der Metallpulverpartikel und Unterwanderung der Oxidhäute den erforderlichen Kontakt zwischen den Metallen im Pulvergemisch her und unterstützt so die Ausbildung eines hochdichten Sinterkörpers aus dem vollständig entbinderten Bräunling. Besonders bevorzugt wird das Sintern in Schritt d) bei einer Temperatur zwischen der Solidus- und der Liquidus-Temperatur der jeweiligen Aluminiumlegierung durchgeführt, so dass zu jedem Zeitpunkt während des Sintervorgangs nur ein durch die Wahl eines entsprechenden Temperaturprofils steuerbarer Anteil der Legierungsmetalle in flüssi- ger Phase vorliegt, was einen Verlust der Maß- und Formstabilität wirksam verhindert. The hitherto known technology of powder metallurgical molding of aluminum alloys by means of compression molding is based on the theoretical approach that the surface of the aluminum particles coated with an aluminum oxide layer is mechanically damaged by the pressing process in the matrix, whereby a metallurgical reaction is made possible in the first place. In the case of a (completely) bindered brown body from powder injection molding, however, it is de facto a metal powder spill, with the oxide skins of the metals not being exposed to any mechanical stress and therefore not subject to this known mechanism. That is, there are no direct metal-to-metal contacts between the powder particles. Nevertheless, it is possible in the process according to the invention, by suitable choice of the sintering conditions to achieve the required shrinkage, by means of which manifests the compression of the sintered body, and thus to obtain largely dense components. Embodiments according to the invention are therefore preferred in which the completely debinded browning material is sintered in step d) to form a liquid phase. This liquid phase, which according to the inventors - without wishing to be bound by any particular theory - is present partly intermediate, but predominantly stationary, ie in thermodynamic equilibrium with the solid Al phase, via microcracks, pores or similar "openings" in the oxide skins of the metal powder particles and infiltration of the oxide skins the required contact between the metals in the powder mixture ago and thus supports the formation of a high-density sintered body from the completely unbonded Bräunling. Particularly preferably, the sintering in step d) is carried out at a temperature between the solidus and the liquidus temperature of the respective aluminum alloy, so that at any time during the sintering process only a controllable by the choice of a corresponding temperature profile proportion of alloying metals in liquid ger phase, which effectively prevents loss of dimensional and dimensional stability.
Die Zusammensetzung der jeweiligen Atmosphäre in deh einzelnen Schritten des er- findungsgemäßen Verfahrens ist abgesehen von der Gegenwart des Sauerstoffs bei der thermischen Entbinderung in Schritt c) nicht speziell eingeschränkt, und der einschlägige Fachmann kann in jedem einzelnen Schritt die für das jeweilige Pulvergemisch am besten geeignete Atmosphäre wählen, wobei auch Vakuum möglich ist. Der Sinterschritt d) wird jedoch vorzugsweise in extrem trockener stickstoffhaltiger Atmosphäre durchgeführt, d.h. in reinem Stickstoff, unter Normaldruck oder reduziertem Druck ("Teildrucksintern"), oder in einem Gemisch aus Stickstoff und reinem Edelgas (Helium, Argon), vorzugsweise mit einem Taupunkt < -40 °C, da die Gegenwart von Stickstoff die Benetzbarkeit der Pulverteilchen mit der entstehenden Metallschmelze maßgeblich unterstützt. The composition of the particular atmosphere in the individual steps of the process according to the invention is not particularly limited, except for the presence of the oxygen in the thermal debindering in step c), and the person skilled in the art can select the most suitable for each powder mixture in each individual step Choose atmosphere, whereby also vacuum is possible. However, the sintering step d) is preferably carried out in an extremely dry nitrogen-containing atmosphere, i. in pure nitrogen, under normal pressure or reduced pressure ("partial pressure sintering"), or in a mixture of nitrogen and pure inert gas (helium, argon), preferably with a dew point <-40 ° C, since the presence of nitrogen with the wettability of the powder the resulting molten metal significantly supported.
Auf das Sintern kann gegebenenfalls eine geeignete Nachbehandlung folgen, mittels derer die fertigen Formteile in der gewünschten Form erhalten werden. Beispielsweise kann das bekannte Verfahren des heißisostatischen Pressens (HIP) angewandt werden, um die Formteile auf die gewünschte endgültige Dichte zu bringen. Dabei werden nach dem Sintern verbliebene Restporen durch die gleichzeitige Einwirkung von äußerem Gasdruck und Temperatur zugedrückt und die Porenwände miteinander verschweißt. If appropriate, sintering may be followed by a suitable after-treatment, by means of which the finished molded parts are obtained in the desired shape. For example, the known method of hot isostatic pressing (HIP) can be used to bring the moldings to the desired final density. In this case, residual pores remaining after sintering are pressed by the simultaneous action of external gas pressure and temperature, and the pore walls are welded together.
KURZBESCHREIBUNG DER ZEICHNUNGEN BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 ist eine Fotografie des Grünlings (oben) und des daraus erhaltenen Sinterkörpers (unten) aus Beispiel 9. Fig. 1 is a photograph of the green compact (above) and the sintered body (bottom) obtained therefrom of Example 9.
Fig. 2 ist eine Fotografie des Grünlings (links) und des daraus erhaltenen Sinterkörpers (rechts) aus Beispiel 10. Fig. 2 is a photograph of the green compact (left) and the sintered body (right) thereof obtained in Example 10.
Die Erfindung wird nachstehend anhand von nichteinschränkenden konkreten Ausführungsbeispielen näher beschrieben. BEISPIELE The invention will be described below with reference to non-limiting specific embodiments. EXAMPLES
Sämtliche in den nachstehenden Beispielen hergestellten Feedstocks wurden in einem beheizten Messkneter bei 190 °C homogenisiert. Aus diesen Feedstocks wurden mittels Spritzguss gemäß ISO 2740 Zugprobestäbe bzw. Hohlzylinder geformt, wobei das erfindungsgemäße Verfahren wie folgt zum Einsatz kam. Zur Herstellung der Grünteile wurde eine hydraulische Spritzgießmaschine (Battenfeld HM 600/130) mit PIM-Ausstattung herangezogen.  All feedstocks prepared in the examples below were homogenized in a heated kneader at 190 ° C. From these feedstocks, tensile test bars or hollow cylinders were molded by means of injection molding in accordance with ISO 2740, the method according to the invention being used as follows. To produce the green parts, a hydraulic injection molding machine (Battenfeld HM 600/130) with PIM equipment was used.
In einem ersten Schritt wurde zunächst der Feedstock in einen Trichter der Spritz- gießmaschine eingefüllt. Das Pulverspritzgießen zur Herstellung der Grünteile erfolgte in folgenden Schritten: Das aufbereitete Einsatzmaterial wurde mittels eines beheizten Spritzzylinders, in dem sich eine Schnecke dreht, nach voreingestellten Einstellungsparameten (wie z.B. Umdrehungsgeschwindigkeit, Dosiervolumen, Staudruck usw.) plastifiziert und vordosiert. Anschließend wurde in ein entsprechend tem- periertes Werkzeug die vordosierte Menge eingespritzt. In Abhängigkeit vom Feedstock bzw. eingesetzten Binder betrug die Plastifizierungstemperatur im Spritzzylinder zwischen 120 und 220 °C, während im Werkzeug zwischen 25 bis 140 °C herrschten. Nach ausreichender Kühlzeit wurde das Spritzgießwerkzeug geöffnet und der Grünteil aus dem Werkzeug ausgeworfen und mit einem Handling entnom- men. In a first step, the feedstock was first filled into a hopper of the injection molding machine. The powder injection molding for the production of the green parts was carried out in the following steps: The prepared feed material was plasticized and pre-dosed by means of a heated injection cylinder in which a screw rotates according to preset setting parameters (such as, for example, rotational speed, metering volume, dynamic pressure, etc.). Subsequently, the pre-metered quantity was injected into a correspondingly tempered tool. Depending on the feedstock or binder used, the plasticizing temperature in the injection cylinder was between 120 and 220 ° C, while in the tool between 25 and 140 ° C prevailed. After sufficient cooling time, the injection mold was opened and the green part was ejected from the mold and removed with a handling.
Beispiel 1 - Zuqstäbe: Lösunqsentbinderunq/thermische Entbinderung Example 1 - Ingredients: Solution Disinfectant / Thermal Debinder
Ein im Handel erhältliches Metallpulvergemisch (Alumix® 231 von Ecka), bestehend aus Aluminium mit 14 Gew.-% Silicium, 2,5 Gew.-% Kupfer und 0,6 Gew.-% Magnesium, wurde mit einem aus Wachs/Thermoplast bestehenden Solventbinder sorgfäl- tig zu einem Feedstock vermischt. A commercially available metal powder mixture (Alumix ® 231 of Ecka) consisting of aluminum, with 14 wt .-% of silicon, 2.5 wt .-% copper and 0.6 wt .-% magnesium, was with a group consisting of wax / thermoplastic Solvent binder is carefully mixed into a feedstock.
Feedstock-Komponente Anteil (Gew Feedstock component proportion (wt
Alumix 231 -Pulver* 74,8  Alumix 231 powder * 74.8
Solventbinder: Wachsanteil 14,8 Solvent binder: wax content 14.8
Solventbinder: Thermoplastanteil 8,2 Solvent binder: thermoplastic content 8.2
Stearinsäure 2,2 Stearic acid 2,2
100,0  100.0
* Im Handel erhältliches Metallpulvergemisch aus Aluminium mit 14 Gew.-% Silicium, 2,5 Gew.-% Kupfer und 0,6 Gew.-% Magnesium (von Ecka) * Commercially available metal powder mixture of aluminum with 14% by weight of silicon, 2.5% by weight of copper and 0.6% by weight of magnesium (from Ecka)
Entbinderung und Sintern der Zugstäbe Debinding and sintering of the tension rods
Dieser Feedstock wurde zunächst mittels Solventextraktion in einem 60-l-Ofen mit Aceton bei einer Temperatur von 45 °C innerhalb von 12 h entbindert.  This feedstock was first debinded by solvent extraction in a 60 L oven with acetone at a temperature of 45 ° C within 12 h.
Der so erhaltene Bräunling enthielt einen Restbinderanteil von rund 14,5 Gew.-%, der anschließend durch erfindungsgemäße thermische Entbinderung mittels eines Temperaturprofils von 150 °C bis 320 °C für 1 h und danach von 320 bis 420 °C für 1 ,5 h mit einer Heizrate von 3 K/min unter einer reinen Sauerstoff enthaltenden At- mosphäre entfernt wurde. Der somit vollständig entbinderte Bräunling wurde danach bei 560 °C innerhalb 1 h in reinem Stickstoff (Taupunkt: -50 °C) gesintert. The Bräunling thus obtained contained a residual binder content of about 14.5 wt .-%, which then by thermal debinding according to the invention by means of a temperature profile of 150 ° C to 320 ° C for 1 h and then from 320 to 420 ° C for 1, 5 h was removed at a heating rate of 3 K / min under a pure oxygen-containing atmosphere. The thus completely unbonded Bräunling was then sintered at 560 ° C within 1 h in pure nitrogen (dew point: -50 ° C).
Ergebnisse Results
Längenschwindung: 11 ,6 %  Length shrinkage: 11, 6%
Schwindung des Stabdurchmessers: 12,25 % Shrinkage of the bar diameter: 12.25%
Sinterdichte: 2,36 g/cm3 Beispiel 2 - Zuqstäbe: thermische Entbinderung in einem Schritt Sintered density: 2.36 g / cm 3 Example 2 - Zuqstäbe: thermal debindering in one step
Feedstock-Komponente Anteil (Gew.-%) Feedstock component proportion (% by weight)
Aluminiumpulver 67,1 Aluminum powder 67.1
Masteralloy-Pulver* 4,3 Masteralloy powder * 4.3
POM-Binder 25,8  POM binder 25.8
Lucryl G55 **  Lucryl G55 **
100,0 * Vorlegierung aus Aluminium und Magnesium im Verhältnis 50:50 100.0 * Aluminum and magnesium master alloy in the ratio 50:50
** Im Handel erhältliches Polymethylmethacrylat (PMMA; von BASF) ** Commercially available polymethylmethacrylate (PMMA, from BASF)
Entbinderung und Sintern der Zugstäbe Debinding and sintering of the tension rods
Hier wurde eine vollständige thermische Entbinderung in einem 40-l-Ofen mit 200 l/h reinem Sauerstoff nach folgendem Entbinderungsprofil durchgeführt:  Here, a complete thermal debinding was carried out in a 40-liter oven with 200 l / h of pure oxygen according to the following debindering profile:
- Aufheizen auf 130 °C mit einer Heizrate von 2 K/min  - Heating to 130 ° C with a heating rate of 2 K / min
- 4 h Haltezeit bei 130 °C - 4 h hold time at 130 ° C
- Aufheizen auf 200 °C mit einer Heizrate von 2 K/min  - Heating to 200 ° C with a heating rate of 2 K / min
- 5 h Haltezeit bei 200 °C  - 5 h hold time at 200 ° C
- Aufheizen auf 420 °C mit einer Heizrate von 2 K/min - Heating to 420 ° C with a heating rate of 2 K / min
- 4 h Haltezeit bei 420 °C  - 4 hours hold at 420 ° C
Der Gewichtsverlust nach der thermischen Entbinderung betrug 24,2 %.  Weight loss after thermal debinding was 24.2%.
Anschließend erfolgte das Sintern bei einer Ofeneinstelltemperatur von 665 °C, die einer Temperatur innerhalb des Ofens von etwa 630 °C entspricht, während 1 h in reinem Stickstoff. Subsequently, the sintering was carried out at a furnace setting temperature of 665 ° C, which corresponds to a temperature within the furnace of about 630 ° C, during 1 h in pure nitrogen.
Ergebnisse Results
Längenschwindung: 12,27 %  Length shrinkage: 12.27%
Schwindung des Stabdurchmessers: 14,52 % Shrinkage of the bar diameter: 14.52%
Sinterdichte: 2,46 g/cm3 Beispiel 3 - Zugstäbe: zweifache thermische Entbinderung Sintered density: 2.46 g / cm 3 Example 3 - Tension rods: double thermal debinding
Feedstock-Komponente Anteil (Gew.-%) Feedstock component proportion (% by weight)
Aluminiumpulver 70,1  Aluminum powder 70.1
Magnesiumpulver 2,2  Magnesium powder 2.2
POM-Binder 24,0  POM binder 24.0
Tensid* 3,7 Surfactant * 3.7
100,0 * Ethoxylierter C 3-C 5-Oxoalkohol mit 7 EO-Einheiten Entbinderung und Sintern der Zugstäbe 100.0 * Ethoxylated C 3 -C 5 -oxoalcohol with 7 EO units debinding and sintering of the tensile bars
Zunächst erfolgte eine erste thermische Entbinderung in einem 50-l-Ofen in 500 l/h Luft bei 80 °C während 14 h. Gewichtsverlust: 27,0 %.  First, a first thermal debinding was carried out in a 50-liter oven in 500 l / h of air at 80 ° C for 14 h. Weight loss: 27.0%.
Anschließend erfolgte eine zweite thermische Entbinderung bis 420 °C unter reinem Sauerstoff innerhalb 1 h, wonach wiederum bei einer Ofeneinstelltemperatur von 665 °C 1 h lang unter Stickstoff gesintert wurde. Ergebnisse This was followed by a second thermal debindering to 420 ° C under pure oxygen within 1 h, which in turn was sintered under nitrogen at a Ofeneinstelltemperatur of 665 ° C for 1 h. Results
Längenschwindung: 9,5 %  Length shrinkage: 9.5%
Schwindung des Stabdurchmessers: 11 ,4 %  Shrinkage of the bar diameter: 11, 4%
Sinterdichte: 2,13 g/cm3 Sintered density: 2.13 g / cm 3
Beispiel 4 - Zuqstäbe: katalvtische/thermische Entbinderung Example 4 - Supplies: catalytic / thermal debinding
Feedstock-Komponente Anteil (Gew.-%) Feedstock component proportion (% by weight)
Aluminiumpulver 70,1  Aluminum powder 70.1
Magnesiumpulver 2,2  Magnesium powder 2.2
POM-Binder 24,0  POM binder 24.0
Tensid* __3 Surfactant * __3
100,0 * Ethoxylierter Ci3-Ci5-Oxoalkohol mit 7 EO-Einheiten Entbinderung und Sintern der Zugstäbe 100.0 * Ethoxylated Ci 3 -Ci 5 -Oxoalkohol with 7 EO units debinding and sintering of the tensile bars
Zunächst erfolgte eine katalytische Entbinderung in einem 50-l-Ofen mit 2 Vol-% HNO3 in 500 l/h Stickstoff (technisch rein) bei 140 °C während 10 h. Gewichtsverlust: 22,1 %. Dabei zeigten sich perlenähnliche Auswüchse auf der Oberfläche, die sich vermutlich durch Reaktion des Mg mit HNO3 gebildet hatten. First, a catalytic debinding in a 50-liter oven with 2% by volume of HNO 3 in 500 l / h of nitrogen (technically pure) at 140 ° C for 10 h. Weight loss: 22.1%. There were pearl-like outgrowths on the surface, which had probably been formed by reaction of Mg with HNO3.
Anschließend erfolgte wie in Beispiel 3 eine thermische Entbinderung bis 420 °C unter reinem Sauerstoff innerhalb 1 h, wonach erneut bei einer Ofeneinstelltemperatur von 665 °C 1 h lang unter Stickstoff gesintert wurde. Subsequently, as in Example 3, a thermal debindering to 420 ° C under pure oxygen within 1 h, after which it was again sintered at a Ofeneinstelltemperatur of 665 ° C for 1 h under nitrogen.
Ergebnisse Results
Längenschwindung: 10,7 %  Length shrinkage: 10.7%
Schwindung des Stabdurchmessers: 14,65 % Shrinkage of the bar diameter: 14.65%
Sinterdichte: 2,36 g/cm3 Sintered density: 2.36 g / cm 3
Beispiel 5 - Zuqstäbe: katalvtische/thermische Entbinderung Example 5 - Supplies: catalytic / thermal debinding
Feedstock-Komponente Anteil (Gew.-%) Feedstock component proportion (% by weight)
Aluminiumpulver 70,1 Aluminum powder 70.1
Magnesiumpulver 2,2 Magnesium powder 2.2
POM-Binder 24,0  POM binder 24.0
Tensid* _3 Surfactant * _3
100,0 * Ethoxylierter Ci3-Ci5-Oxoalkohol mit 7 EO-Einheiten Entbinderung und Sintern der Zugstäbe 100.0 * Ethoxylated Ci 3 -Ci 5 -Oxoalkohol with 7 EO units debinding and sintering of the tensile bars
Zunächst erfolgte eine katalytische Entbinderung analog zu Beispiel 4, jedoch unter Einsatz von 80 g wasserfreier Oxalsäure auf einer Sublimierschale anstelle der HNO3 bei 140 °C während 24 h. Gewichtsverlust: 23,0 %. Aufgrund der Verwendung von Oxalsäure zeigten sich keine Auswüchse auf der Oberfläche. Anschließend erfolgten thermische Entbinderung und Sintern ebenfalls analog zu Beispiel 4. First, a catalytic debinding was carried out analogously to Example 4, but using 80 g of anhydrous oxalic acid on a Sublimierschale instead of HNO 3 at 140 ° C for 24 h. Weight loss: 23.0%. Due to the use of oxalic acid, no outgrowths appeared on the surface. Subsequently, thermal debinding and sintering were also carried out analogously to Example 4.
Ergebnisse Results
Längenschwindung: 14,28 % Length shrinkage: 14.28%
Schwindung des Stabdurchmessers: 15,68 %  Shrinkage of the bar diameter: 15.68%
Sinterdichte: 2,42 g/cm3 Sintered density: 2.42 g / cm 3
Beispiel 6 - Zuqstäbe: katalytische/thermische Entbinderung Example 6 - Supplies: Catalytic / Thermal Debinding
Feedstock-Komponente Anteil (Gew.-%) Feedstock component proportion (% by weight)
Alumix 231 -Pulver* 70,8  Alumix 231 powder * 70.8
POM-Binder 25,6  POM binder 25.6
Tensid ** Surfactant * *
100,0  100.0
* Im Handel erhältliches Metallpulvergemisch aus Aluminium mit 14 Gew.-% Silicium, 2,5 Gew.-% Kupfer und 0,6 Gew.-% Magnesium (von Ecka) * Commercially available metal powder mixture of aluminum with 14% by weight of silicon, 2.5% by weight of copper and 0.6% by weight of magnesium (from Ecka)
** Ethoxylierter C13-C15-Oxoalkohol mit 7 EO-Einheiten ** Ethoxylated C 13 -C 15 oxo alcohol with 7 EO units
Entbinderung und Sintern der Zugstäbe Debinding and sintering of the tension rods
Zunächst erfolgte eine katalytische Entbinderung analog zu Beispiel 5. Gewichtsver- lust: 25,2 %. Anschließend erfolgten thermische Entbinderung und Sintern analog zu Beispiel 4, allerdings bei einer Ofeneinstelltemperatur von 560 °C.  First, a catalytic debinding was carried out analogously to Example 5. Weight loss: 25.2%. Subsequently, thermal debinding and sintering were carried out analogously to Example 4, but at a Ofeneinstelltemperatur of 560 ° C.
Ergebnisse Results
Längenschwindung: 11 ,2 %  Length shrinkage: 11, 2%
Schwindung des Stabdurchmessers: 13,2 % Shrinkage of the bar diameter: 13.2%
Sinterdichte: 2,45 g/cm3 Sintered density: 2.45 g / cm 3
Beispiel 7 - Zuqstäbe: katalytische/thermische Entbinderung Example 7 - Ingredients: Catalytic / Thermal Debinding
Feedstock-Komponente Anteil (Gew.-%) Feedstock component proportion (% by weight)
Aluminiumpulver 68,0 Aluminum powder 68.0
Masteralloy-Pulver* 4,3 Masteralloy powder * 4.3
POM-Binder 24,0  POM binder 24.0
Tensid ** 3,7  Surfactant ** 3,7
100,0 * Vorlegierung aus Aluminium und Magnesium im Verhältnis 50:50  100.0 * Aluminum and magnesium master alloy in the ratio 50:50
** Ethoxylierter Ci3-Ci5-Oxoalkohol mit 7 EO-Einheiten ** Ethoxylated Ci 3 -Ci 5 -Oxoalkohol with 7 EO units
Entbinderung und Sintern der Zuqstäbe Debinding and sintering of the Zuqstäbe
Zunächst erfolgte eine katalytische Entbinderung analog zu Beispiel 5. Gewichtsver- lust: 23,2 %. Anschließend erfolgten thermische Entbinderung und Sintern analog zu Beispiel 4.  First, a catalytic debinding was carried out analogously to Example 5. Weight loss: 23.2%. Subsequently, thermal debinding and sintering were carried out analogously to Example 4.
Ergebnisse Results
Längenschwindung: 12,6 %  Length shrinkage: 12.6%
Schwindung des Stabdurchmessers: 13,25 % Shrinkage of the rod diameter: 13.25%
Sinterdichte: 2,56 g/cm3 Sintered density: 2.56 g / cm 3
Beispiel 8 - Hohlzylinder: katalytische/thermische Entbinderung Example 8 - Hollow Cylinder: Catalytic / Thermal Debinding
Feedstock-Komponente Anteil (Gew.-%) Feedstock component proportion (% by weight)
Aluminiumpulver 68,0  Aluminum powder 68.0
Masteralloy-Pulver* 4,3 Masteralloy powder * 4.3
POM-Binder 24,0  POM binder 24.0
Tensid **  Surfactant **
100,0 * Vorlegierung aus Aluminium und Magnesium im Verhältnis 50:50  100.0 * Aluminum and magnesium master alloy in the ratio 50:50
** Ethoxylierter C13-Ci5-Oxoalkohol mit 7 EO-Einheiten ** Ethoxylated C 13 -C 5 -oxoalcohol with 7 EO units
Entbinderung und Sintern der Hohlzylinder Debinding and sintering of the hollow cylinder
Zunächst erfolgte eine katalytische Entbinderung analog zu Beispiel 5. Gewichtsver- lust: 23,7 %. Anschließend erfolgten thermische Entbinderung und Sintern analog zu Beispiel 4.  First, a catalytic debinding was carried out analogously to Example 5. Weight loss: 23.7%. Subsequently, thermal debinding and sintering were carried out analogously to Example 4.
Ergebnisse Results
Höhenschwindung: 17,24 %  Height shrinkage: 17.24%
Schwindung des Durchmessers: 14,48 % Shrinkage of the diameter: 14.48%
Sinterdichte: 2,59 g/cm3 Sintered density: 2.59 g / cm 3
Beispiel 9 - Zugstäbe: katalvtische/thermische Entbinderung Example 9 - Tension rods: catalytic / thermal debinding
Feedstock-Komponente Anteil (Gew.-%) Feedstock component proportion (% by weight)
Aluminiumpulver 67,1 Aluminum powder 67.1
Masteralloy-Pulver* 4,3 Masteralloy powder * 4.3
POM-Binder* 25,8  POM binder * 25,8
Lucryl G55 ** 2,8  Lucryl G55 ** 2,8
100,0 * Vorlegierung aus Aluminium und Magnesium im Verhältnis 50:50  100.0 * Aluminum and magnesium master alloy in the ratio 50:50
** Im Handel erhältliches Polymethylmethacrylat (PMMA; von BASF) ** Commercially available polymethylmethacrylate (PMMA, from BASF)
Entbinderung und Sintern der Zugstäbe Debinding and sintering of the tension rods
Zunächst erfolgte eine katalytische Entbinderung analog zu Beispiel 5. Gewichtsver- lust: 25,7 %. Anschließend erfolgten thermische Entbinderung und Sintern analog zu Beispiel 4.  First, a catalytic debinding was carried out analogously to Example 5. Weight loss: 25.7%. Subsequently, thermal debinding and sintering were carried out analogously to Example 4.
Ergebnisse Results
Längenschwindung: 13,57 %  Length shrinkage: 13.57%
Schwindung des Stabdurchmessers: 19,55 % Shrinkage of the bar diameter: 19.55%
Sinterdichte: 2,59 g/cm3 Sintered density: 2.59 g / cm 3
Beispiel 10 - Hohlzylinder: katalytische/thermische Entbinderung Example 10 - Hollow Cylinder: Catalytic / Thermal Debinding
Feedstock-Komponente Anteil (Gew.-%) Feedstock component proportion (% by weight)
Aluminiumpulver 67,1 Aluminum powder 67.1
Masteralloy-Pulver* 4,3 Masteralloy powder * 4.3
POM-Binder 25,8  POM binder 25.8
Lucryl G55 ** Α  Lucryl G55 ** Α
100,0 * Vorlegierung aus Aluminium und Magnesium im Verhältnis 50:50  100.0 * Aluminum and magnesium master alloy in the ratio 50:50
** Im Handel erhältliches Polymethylmethacrylat (PMMA; von BASF) ** Commercially available polymethylmethacrylate (PMMA, from BASF)
Entbinderung und Sintern der Hohlzylinder Debinding and sintering of the hollow cylinder
Zunächst erfolgte eine katalytische Entbinderung analog zu Beispiel 5. Gewichtsver- lust: 25,6 %. Anschließend erfolgten thermische Entbinderung und Sintern analog zu Beispiel 4.  First, a catalytic debinding was carried out analogously to Example 5. Weight loss: 25.6%. Subsequently, thermal debinding and sintering were carried out analogously to Example 4.
Ergebnisse Results
Höhenschwindung: 16,52 %  Height shrinkage: 16.52%
Schwindung des Durchmessers: 14,48 % Shrinkage of the diameter: 14.48%
Sinterdichte: 2,56 g/cm3 Sintered density: 2.56 g / cm 3
Somit können durch das erfindungsgemäße Verfahren Sinterkörper aus Aluminiumlegierungen mittels Spritzguss bereitgestellt werden, die für den praktischen Einsatz auf vielerlei Gebieten, z.B. auf dem Verkehrssektor, im Bauwesen, im Maschinenbau, in der Verpackungsindustrie, Eisen- und Stahlindustrie, Elektrotechnik, in Haushaltsgeräten usw., beispielsweise zur Wärmeableitung in elektronischen Geräten ("heat sinks") oder als Komponenten von Klimaanlagen, bestens geeignet sind. Thus, by the method according to the invention sintered bodies of aluminum alloys can be provided by means of injection molding, which are suitable for practical use in many fields, e.g. in the transport sector, construction, mechanical engineering, packaging, iron and steel, electrical engineering, household appliances, etc., for example for heat dissipation in electronic devices ("heat sinks") or as components of air conditioning systems.

Claims

PATENTANSPRÜCHE
1. Verfahren zur Herstellung von Formkörpern auf Basis von Aluminiumlegierungen durch Metallpulverspritzguss, umfassend die folgenden Schritte: 1. A process for the production of moldings based on aluminum alloys by metal injection molding, comprising the following steps:
a) Herstellung eines Feedstocks durch Vermischen der in der gewünschten a) Production of a feedstock by mixing in the desired
Legierung enthaltenen Metalle in Form von Metallpulvern und/oder einem oder mehreren Metalllegierungspulvern mit einem Binder; Alloy-containing metals in the form of metal powders and / or one or more metal alloy powders with a binder;
b) Herstellung eines Grünlings durch Spritzgießen des Feedstocks;  b) production of a green compact by injection molding of the feedstock;
c) Herstellung eines Bräunlings durch zumindest teilweises Entfernen des Bin- ders aus dem Grünling durch katalytisches und/oder Lösungsmittel- und/oder thermisches Entbindern;  c) preparation of a browning by at least partial removal of the binder from the green product by catalytic and / or solvent and / or thermal binder removal;
d) Sintern des zumindest teilweise entbinderten Bräunlings zum Erhalt des gewünschten Formkörpers;  d) sintering the at least partially debinded browning to obtain the desired shaped article;
dadurch gekennzeichnet, dass in Schritt c) der Binder vollständig entfernt wird, wo- bei, gegebenenfalls nach Durchführung eines oder mehrerer vorhergehender Entbin- derungsstufen, eine thermische Entbinderung zur Entfernung des (Rest-)Binders erfolgt, die in einer zumindest 0,5 Vol.-% Sauerstoff enthaltenden Atmosphäre durchgeführt wird, wonach der so erhaltene, vollständig entbinderte Bräunling gesintert wird. characterized in that in step c) the binder is completely removed, whereby, optionally after carrying out one or more preceding Entbin- mentation stages, a thermal debinding to remove the (residual) binder is carried out in at least 0.5 vol % Oxygen-containing atmosphere is carried out, after which the resulting completely unbonded Braunling is sintered.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass die Aluminiumlegierung neben Aluminium ein oder mehrere Metalle, ausgewählt aus Magnesium, Kupfer, Silicium und Mangan, enthält. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Aluminiumlegierung neben Aluminium ein oder mehrere Metalle in einem jeweiligen Anteil von 0,5 bis 25 Gew.-% enthält. 2. The method according to claim 1, characterized in that the aluminum alloy in addition to aluminum one or more metals selected from magnesium, copper, silicon and manganese. 3. The method according to claim 1 or 2, characterized in that the aluminum alloy in addition to aluminum contains one or more metals in a respective proportion of 0.5 to 25 wt .-%.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das oder die Metall(e) als Vorlegierungs- ("Master Alloy"-) Pulver eingesetzt wird bzw. werden. 4. The method according to any one of claims 1 to 3, characterized in that the or the metal (s) is used as a master alloy ("master alloy") powder or are.
5. Verfahren nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass als Binder ein Polyacetal-basierter Binder, z.B. Polyoxymethylen- (POM-) Binder, eingesetzt wird. 6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass der Binder zu 50 bis 95 % aus Polyacetal besteht. Process according to any one of the preceding claims, characterized in that a polyacetal-based binder, e.g. Polyoxymethylene (POM) binder is used. 6. The method according to claim 5, characterized in that the binder consists of 50 to 95% of polyacetal.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass der Binder zu 80 bis 90 % aus Polyacetal besteht. 7. The method according to claim 6, characterized in that the binder consists of 80 to 90% of polyacetal.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass in Schritt c) ausschließlich thermische Entbinderung in Gegenwart von Sauerstoff, in ein oder mehreren Schritten, durchgeführt wird, bei der der gesamte Binder entfernt wird. 8. The method according to any one of claims 1 to 7, characterized in that in step c) only thermal debinding in the presence of oxygen, in one or more steps, is performed, in which the entire binder is removed.
9. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass in Schritt c) eine Lösungsentbinderung zur Entfernung der Hauptmenge des Binders, gefolgt von der thermischen Entbinderung zur Entfernung des Restbinders durchgeführt werden. 9. The method according to any one of claims 1 to 7, characterized in that in step c) a Lösungsentbinderung to remove the main amount of the binder, followed by the thermal debinding to remove the residual binder are performed.
10. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass in Schritt c) eine katalytische Entbinderung zur Entfernung der Hauptmenge des Binders, gefolgt von der thermischen Entbinderung zur Entfernung des Restbinders durchgeführt werden. 10. The method according to any one of claims 1 to 7, characterized in that in step c) a catalytic debinding to remove the main amount of the binder, followed by the thermal debinding to remove the residual binder are performed.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass die katalytische Entbinderung in Gegenwart zumindest einer Säure, ausgewählt aus Salpetersäure, Oxalsäure, Ameisensäure und Essigsäure, durchgeführt wird. 12. Verfahren nach Anspruch 11 , dadurch gekennzeichnet, dass als Säure subli- mierte Oxalsäure eingesetzt wird. 11. The method according to claim 10, characterized in that the catalytic debinding in the presence of at least one acid selected from nitric acid, oxalic acid, formic acid and acetic acid, is performed. 12. The method according to claim 11, characterized in that as acid sublimed oxalic acid is used.
13. Verfahren nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass die thermische Entbinderung zur Entfernung des Restbinders bei einer Temperatur unterhalb von 500 °C durchgeführt wird. 14. Verfahren nach Anspruch 13, dadurch gekennzeichnet, dass die thermische Entbinderung zur Entfernung des Restbinders bei einem bestimmten Temperaturprofil zwischen 100 und 420 °C durchgeführt wird. 5. Verfahren nach Anspruch 13 oder 14, dadurch gekennzeichnet, dass während der thermischen Entbinderung zur Entfernung des Restbinders die Heizrate nicht mehr als 5 K/min beträgt. 13. The method according to any one of the preceding claims, characterized in that the thermal debinding to remove the residual binder is carried out at a temperature below 500 ° C. 14. The method according to claim 13, characterized in that the thermal debinding to remove the residual binder at a certain temperature profile between 100 and 420 ° C is performed. 5. The method according to claim 13 or 14, characterized in that during the thermal debinding to remove the residual binder, the heating rate is not more than 5 K / min.
16. Verfahren nach Anspruch 15, dadurch gekennzeichnet, dass die Heizrate nicht mehr als 1 bis 2 K/min beträgt. 16. The method according to claim 15, characterized in that the heating rate is not more than 1 to 2 K / min.
17. Verfahren nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass der vollständig entbinderte Bräunling in Schritt d) unter Ausbildung einer flüssigen Phase gesintert wird. 18. Verfahren nach Anspruch 17, dadurch gekennzeichnet, dass das Sintern bei einer Temperatur zwischen der Solidus- und der Liquidus-Temperatur der jeweiligen Aluminiumlegierung erfolgt. 17. The method according to any one of the preceding claims, characterized in that the completely unbonded Bräunling is sintered in step d) to form a liquid phase. 18. The method according to claim 17, characterized in that the sintering takes place at a temperature between the solidus and the liquidus temperature of the respective aluminum alloy.
19. Verfahren nach einem der vorangegangenen Ansprüche, dadurch gekenn- zeichnet, dass nach der thermischen Entbinderung zur Entfernung des Restbinders die Heizrate auf die Sintertemperatur 4 bis 20 K/min beträgt. 19. The method according to any one of the preceding claims, characterized in that after the thermal debinding to remove the residual binder, the heating rate to the sintering temperature 4 to 20 K / min.
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CN103038006A (en) 2013-04-10
ES2639134T3 (en) 2017-10-25
AT509613A1 (en) 2011-10-15
AT509613B1 (en) 2017-05-15
EP2552630B1 (en) 2017-05-31
JP2013524006A (en) 2013-06-17
KR20130079373A (en) 2013-07-10
DK2552630T3 (en) 2017-09-25
SG184423A1 (en) 2012-10-30
PL2552630T3 (en) 2018-05-30
US20130101456A1 (en) 2013-04-25

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