EP1264903B1 - Refining of aluminium casting alloys by boron addition - Google Patents
Refining of aluminium casting alloys by boron addition Download PDFInfo
- Publication number
- EP1264903B1 EP1264903B1 EP20020009964 EP02009964A EP1264903B1 EP 1264903 B1 EP1264903 B1 EP 1264903B1 EP 20020009964 EP20020009964 EP 20020009964 EP 02009964 A EP02009964 A EP 02009964A EP 1264903 B1 EP1264903 B1 EP 1264903B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- boron
- melt
- alloy
- reaction time
- aluminium casting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
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- 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
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/06—Obtaining aluminium refining
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/06—Obtaining aluminium refining
- C22B21/062—Obtaining aluminium refining using salt or fluxing agents
-
- 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
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
Definitions
- the invention relates to a method for removing interfering alloy constituents from an aluminum casting alloy.
- the boron combines in the course of a reaction time of at least one hour at the expense of grain coarsening with the interfering alloy constituents of the molten aluminum and precipitates together with these as slag (scabies), which removed from the melt before or during their casting or is held back.
- the boron addition required for cleaning purposes is such that, after the end of the reaction time, by far the predominant part, namely about 90% or more, is eliminated from the melt and only a boron content of not more than 0.005% by weight remains.
- the aluminum casting alloy can then be subjected to a further, known melt treatment for the purpose of grain refining;
- aluminum master alloys are used, such as Al Ti5 B1.
- this melt was admixed with 0.012% by weight of boron in the form of an aluminum-boron master alloy. After a reaction time of more than three hours, the respective proportion of the above-mentioned interfering elements was then measured. The proportion of vanadium and zirconium in the melt decreased on average by 30% and that of titanium by an average of 35%, while the proportion of chromium remained unchanged remained. The boron content in the melt had fallen to 0.0031% by weight.
- the proportion of vanadium in the melt reduced by an average of 50% and that of zirconium and chromium by 33%.
- the share of titanium had decreased by about 60%.
- the boron content in the melt had degraded to 0.0005 wt .-%.
- the proportion of vanadium was reduced by a total of 90% compared to the initial value and that of zirconium and chromium by 60%.
- the titanium content had decreased by more than 90% after the second purification procedure.
- the boron content remained low.
- the melt showed a significantly improved filling and flow behavior and on the finished castings could be a significantly increased casting quality and in particular a significantly lower casting porosity can be detected.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Beseitigung von störenden Legierungsbestandteilen aus einer Aluminium-Gusslegierung.The invention relates to a method for removing interfering alloy constituents from an aluminum casting alloy.
Für die Herstellung von Leichtmetallkomponenten aus Aluminium-Gusslegierungen kommt insbesondere im Kraftfahrzeugbau zunehmend Recyclingmaterial zur Anwendung, welches zusätzlich zu den gewünschten Legierungsbestandteilen, wie zum Beispiel Silizium, Kupfer, Mangan, Magnesium oder Nickel, auch Vanadium, Zirkonium oder andere unerwünschte Bestandteile aufweist, die als Störelemente vor allem das Fließ- und Füllungsverhalten der Schmelze negativ beeinflussen sowie zu einer erhöhten Porosität des Gussteils führen. Auch an sich erwünschte Legierungsbestandteile können sich bei zu hohen Konzentrationen in gleicher Weise negativ auswirken. Erschwerend kommt hinzu, dass die Anteile der oben erwähnten Legierungsbestandteile im Recyclingmaterial erheblich schwanken können.For the production of light metal components from cast aluminum alloys, recycling material is increasingly being used, especially in motor vehicle construction, which, in addition to the desired alloy constituents, such as silicon, copper, manganese, magnesium or nickel, also comprises vanadium, zirconium or other undesirable constituents, which Disturbing elements, in particular, adversely affect the flow and filling behavior of the melt and lead to an increased porosity of the casting. Even desired alloy constituents can have the same negative effect if the concentrations are too high. To make matters worse, that the proportions of the above-mentioned alloying components in the recycling material can vary considerably.
Es ist daher Aufgabe der vorliegenden Erfindung, ein Verfahren zur Beseitigung von störenden Legierungsbestandteilen aus einer Aluminium-Gusslegierung zu schaffen, welches sowohl in der Lage ist, Störelemente weitgehend zu entfernen als auch zu hohe Konzentrationen von an sich erwünschten Bestandteilen zu reduzieren.It is therefore an object of the present invention to provide a method for the removal of interfering alloy constituents from an aluminum casting alloy, which is both able to largely remove interfering elements and to reduce too high concentrations of desired per se components.
Diese Aufgabe wird erfindungsgemäß durch ein Verfahren mit den Merkmalen des Patentanspruchs 1 gelöst.This object is achieved by a method having the features of claim 1.
Es hat sich gezeigt, dass durch eine Zugabe von Bor in die aufgeschmolzene Aluminium-Gusslegierung eine Art Reinigungsprozess eingeleitet wird, welcher relativ langsam über eine längere Reaktionszeit abläuft und in dessen Verlauf sich der Borgehalt in der Schmelze bis auf einen geringen Restgehalt abbaut. Die Zugabe von Bor zu Aluminium-Gusslegierungen ist zwar an sich bekannt, jedoch zu einem anderen Zweck und mit deutlich höher in der Schmelze verbleibenden Konzentrationen sowie ohne Einhaltung von Reaktions-Mindestzeiten. So wird in der DE 3739187 C 1 ein Verfahren zur Herstellung von hochschmelzende Elemente enthaltenden Aluminiumvorlegierungen beschrieben, bei welchem zur Herstellung von beispielsweise 100 kg einer Al Ti5 B1-Vorlegierung unter anderem 11,6kg Kaliumborfluorid zugegeben wird. Die daraus angefertigten Gussstücke zeichnen sich besonders durch Feinkörnigkeit und Homogenität aus. Weiterhin ist aus der DE 3632609 C 2 die Verwendung einer Aluminiumlegierung bekannt, welche 0,05 bis 0,3 Gew.-% Bor enthält. Hiermit soll insbesondere die Zugfestigkeit und Dehnung von Formteilen verbessert werden.It has been shown that a type of cleaning process is initiated by adding boron into the molten aluminum casting alloy, which proceeds relatively slowly over a longer reaction time and in the course of which the boron content in the melt degrades to a low residual content. Although the addition of boron to cast aluminum alloys is known per se, but for a different purpose and with significantly higher concentrations remaining in the melt and without observing minimum reaction times. For example, DE 3739187 C1 describes a process for producing aluminum master alloys containing high-melting elements, in which, for example, 11.6 kg of potassium borofluoride are added for the preparation of, for example, 100 kg of an Al Ti5 B1 master alloy. The resulting castings are characterized by fine grain and homogeneity. Furthermore, DE 3632609 C2 discloses the use of an aluminum alloy which contains 0.05 to 0.3% by weight of boron. This is intended in particular to improve the tensile strength and elongation of molded parts.
Ähnliche Verfahren zur Reinigung von Al- und Al-Legierungsschmelzen durch Zugabe von Bor oder Al-B sind aus den Patentschriften US-A-4507150 und RU-A-2084548 bekannt.Similar methods for purifying Al and Al alloy melts by adding boron or Al-B are known from the patents US-A-4507150 and RU-A-2084548.
Bei dem erfindungsgemäßen Verfahren verbindet sich das Bor im Laufe einer Reaktionszeit von mindestens einer Stunde unter Inkaufnahme einer Kornvergröberung mit den störenden Legierungsbestandteilen der Aluminiumschmelze und fällt gemeinsam mit diesen als Schlacke (Krätze) aus, welche aus der Schmelze vor oder während ihres Vergießens entfernt bzw. zurückgehalten wird. Dabei wird die zu Reinigungszwecken erforderliche Borzugabe so bemessen, dass sie nach Ablauf der Reaktionszeit zum weitaus überwiegenden Teil, nämlich zu etwa 90% oder mehr, aus der Schmelze ausgeschieden und in dieser nur noch ein Borgehalt von maximal 0,005 Gew.-% verblieben ist.In the process of the invention, the boron combines in the course of a reaction time of at least one hour at the expense of grain coarsening with the interfering alloy constituents of the molten aluminum and precipitates together with these as slag (scabies), which removed from the melt before or during their casting or is held back. In this case, the boron addition required for cleaning purposes is such that, after the end of the reaction time, by far the predominant part, namely about 90% or more, is eliminated from the melt and only a boron content of not more than 0.005% by weight remains.
Als besonders vorteilhaft hat es sich erwiesen, die für die Zwecke dieser Behandlung vorgesehene Menge an Bor der Schmelze in mehreren Teilmengen zuzumischen, wobei nach jeder Zugabe einer Teilmenge die Reaktions-Mindestzeit von einer Stunde eingehalten wird.It has proved to be particularly advantageous to mix the amount of boron intended for the purpose of this treatment into the melt in several sub-quantities, the minimum reaction time of one hour being maintained after each addition of a subset.
Da sich Bor in Aluminium nur schlecht löst, ist es von Vorteil, die für die Zwecke dieser Behandlung notwendige Menge an Bor in Form einer Aluminium-Bor-Vorlegierung zuzugeben, welche, wie zum Beispiel die Al B2-Phase, bereits bei 660 Grad Celsius schmilzt und sich daher in der Aluminiumschmelze leicht auflöst.Since boron dissolves only poorly in aluminum, it is advantageous to add the amount of boron required for the purposes of this treatment in the form of an aluminum boron master alloy, which, for example, the Al B2 phase, already at 660 degrees Celsius melts and therefore dissolves easily in the molten aluminum.
Nach Ablauf des obengenannten Reinigungsprozesses kann dann die Aluminium-Gusslegierung einer weiteren, an sich bekannten Schmelzebehandlung zum Zwecke der Kornfeinung unterzogen werden; hierbei kommen ebenfalls Aluminium-Vorlegierungen zur Anwendung, wie zum Beispiel Al Ti5 B1.After the abovementioned cleaning process, the aluminum casting alloy can then be subjected to a further, known melt treatment for the purpose of grain refining; In this case also aluminum master alloys are used, such as Al Ti5 B1.
Im folgenden wird die Erfindung anhand eines Ausführungsbeispieles näher beschrieben:In the following the invention will be described in more detail with reference to an embodiment:
Zugrundegelegt wurde eine Aluminium-Sekundärlegierung 226 nach DIN, welche bei etwa 760 Grad Celsius aufgeschmolzen wurde und als Störelemente vor allem Vanadium, Zirkonium und Chrom, aber auch einen zu hohen Anteil an Titan aufwies.Based on an aluminum secondary alloy 226 according to DIN, which was melted at about 760 degrees Celsius and had as disruptive elements, especially vanadium, zirconium and chromium, but also a high proportion of titanium.
In einer ersten Versuchsreihe wurden dieser Schmelze 0,012 Gew.-% Bor in Form einer Aluminium-Bor-Vorlegierung zugemischt. Nach einer Reaktionszeit von mehr als drei Stunden wurde dann der jeweilige Anteil der oben genannten Störelemente gemessen. Dabei war der Anteil an Vanadium und Zirkonium in der Schmelze um durchschnittlich jeweils 30 % und derjenige von Titan um durchschnittlich 35 % zurückgegangen, während der Anteil an Chrom unverändert blieb. Der Borgehalt in der Schmelze war auf 0,0031 Gew,-% zurückgegangen.In a first series of experiments, this melt was admixed with 0.012% by weight of boron in the form of an aluminum-boron master alloy. After a reaction time of more than three hours, the respective proportion of the above-mentioned interfering elements was then measured. The proportion of vanadium and zirconium in the melt decreased on average by 30% and that of titanium by an average of 35%, while the proportion of chromium remained unchanged remained. The boron content in the melt had fallen to 0.0031% by weight.
In einer zweiten Versuchsreihe wurden der gleichen Ausgangsschmelze nacheinander zwei Teilmengen von jeweils 0,025 Gew.-% Bor, ebenfalls in Form einer Aluminium-Bor-Vorlegierung, beigemischt, wobei jeweils nach Zugabe einer Teilmenge eine Reaktionszeit von mehr als 20 Stunden abgewartet und dann der jeweilige Anteil der oben genannten Störelemente gemessen wurde.In a second series of experiments, two subsets of 0.025 wt .-% boron, also in the form of an aluminum-boron master alloy, admixed successively to the same starting melt, in each case after addition of a subset a reaction time of more than 20 hours and then the respective Proportion of the above interfering elements has been measured.
Nach Zugabe der ersten Teilmenge und einer Reaktionszeit von 24 Stunden reduzierte sich der Anteil an Vanadium in der Schmelze um durchschnittlich 50 % und derjenige von Zirkonium sowie Chrom um jeweils 33 %. Der Anteil an Titan war um etwa 60 % zurückgegangen. Der Borgehalt in der Schmelze hatte sich dabei auf 0,0005 Gew.-% abgebaut. Nach Zugabe der zweiten Teilmenge an Bor und einer nochmaligen Wartezeit von 24 Stunden reduzierte sich der Anteil an Vanadium um insgesamt 90 % gegenüber dem Ausgangswert und derjenige von Zirkonium sowie Chrom um jeweils 60 %. Der Titananteil hatte sich nach der zweiten Reinigungsprozedur um mehr als 90 % verringert. Der Boranteil war weiterhin gering.After addition of the first portion and a reaction time of 24 hours, the proportion of vanadium in the melt reduced by an average of 50% and that of zirconium and chromium by 33%. The share of titanium had decreased by about 60%. The boron content in the melt had degraded to 0.0005 wt .-%. After addition of the second portion of boron and a further waiting time of 24 hours, the proportion of vanadium was reduced by a total of 90% compared to the initial value and that of zirconium and chromium by 60%. The titanium content had decreased by more than 90% after the second purification procedure. The boron content remained low.
Beim Vergießen zeigte die Schmelze ein deutlich verbessertes Füll- und Fließverhalten und an den fertigen Gussteilen konnte eine merklich erhöhte Gussqualität und insbesondere eine wesentlich geringere Gussporosität nachgewiesen werden.When casting, the melt showed a significantly improved filling and flow behavior and on the finished castings could be a significantly increased casting quality and in particular a significantly lower casting porosity can be detected.
Claims (5)
- A method of eliminating unwanted constituents from an aluminium casting alloy in the following steps:- complete melting of the aluminium casting alloy,- addition of boron up to a maximum boron content of 0.005 wt.% remaining in the melt for the purpose of purification as follows: the boron is repeatedly added in individual portions after each of which the melt is held for the minimum time required for reacting the respective boron portion with the unwanted alloy constituents, and- removal or retention of resulting solids from the melt before or during casting.
- A method according to claim 1, characterised in that the boron added to the melt is in the form of an aluminium-boron intermediate alloy.
- A method according to claim 1 or 2, characterised in that a reaction time of at least 1 hour is kept to.
- A method according to any of claims 1 to 3, characterised in that at the end of the reaction time, the aluminium casting alloy is subjected to further melting treatment in known manner in order to refine the grains.
- A method according to claim 4, characterised in that in order to refine the grains, a titanium-boron intermediate alloy is mixed with the melt at the end of the reaction time.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10127753 | 2001-06-07 | ||
| DE10127753A DE10127753A1 (en) | 2001-06-07 | 2001-06-07 | Removing impurity alloying components from an aluminum cast alloy comprises completely melting the cast alloy, mixing with boron, casting the melt, and removing or retaining solids produced from the melt before or during casting |
| DE2001157722 DE10157722A1 (en) | 2001-11-24 | 2001-11-24 | Removing impurity alloying components from an aluminum cast alloy comprises completely melting the cast alloy, mixing with boron, casting the melt, and removing or retaining solids produced from the melt before or during casting |
| DE10157722 | 2001-11-24 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP1264903A2 EP1264903A2 (en) | 2002-12-11 |
| EP1264903A3 EP1264903A3 (en) | 2003-08-27 |
| EP1264903B1 true EP1264903B1 (en) | 2006-09-20 |
Family
ID=26009486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP20020009964 Expired - Lifetime EP1264903B1 (en) | 2001-06-07 | 2002-05-03 | Refining of aluminium casting alloys by boron addition |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1264903B1 (en) |
| DE (1) | DE50208178D1 (en) |
| ES (1) | ES2271139T3 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010060670A1 (en) * | 2010-11-19 | 2012-05-24 | Martinrea Honsel Germany Gmbh | Cylinder head for combustion engines made of aluminum alloy |
| CN103572081A (en) * | 2013-11-20 | 2014-02-12 | 江苏江旭铸造集团有限公司 | Casting process of 7475 aluminium alloy slab ingot |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0099948B1 (en) * | 1982-07-28 | 1986-11-20 | Showa Aluminum Corporation | Process for producing high-purity aluminum |
| EP0112024B1 (en) * | 1982-11-16 | 1986-10-22 | Alcan International Limited | Removal of impurities from molten aluminium |
| NL8600394A (en) * | 1985-03-25 | 1986-10-16 | Cabot Corp | MOTHER-ALLOY FOR GRANULATING SILICON CONTAINING ALUMINUM ALLOYS. |
| GB9114586D0 (en) * | 1991-07-05 | 1991-08-21 | Shell Int Research | Process for the preparation of a grain refiner |
| JPH0885832A (en) * | 1994-09-19 | 1996-04-02 | Kobe Steel Ltd | Method for melting aluminum or aluminum alloy |
| RU2084548C1 (en) * | 1994-10-12 | 1997-07-20 | Акционерное общество "Красноярский металлургический завод" | Method of cleaning of aluminium and its alloys of heavy metal impurities |
-
2002
- 2002-05-03 DE DE50208178T patent/DE50208178D1/en not_active Expired - Lifetime
- 2002-05-03 EP EP20020009964 patent/EP1264903B1/en not_active Expired - Lifetime
- 2002-05-03 ES ES02009964T patent/ES2271139T3/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP1264903A3 (en) | 2003-08-27 |
| DE50208178D1 (en) | 2006-11-02 |
| EP1264903A2 (en) | 2002-12-11 |
| ES2271139T3 (en) | 2007-04-16 |
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