EP2705171B1 - Method for the refining and structure modification of al-mg-si alloys - Google Patents
Method for the refining and structure modification of al-mg-si alloys Download PDFInfo
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- EP2705171B1 EP2705171B1 EP12722272.7A EP12722272A EP2705171B1 EP 2705171 B1 EP2705171 B1 EP 2705171B1 EP 12722272 A EP12722272 A EP 12722272A EP 2705171 B1 EP2705171 B1 EP 2705171B1
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- 238000000034 method Methods 0.000 title claims description 13
- 238000007670 refining Methods 0.000 title claims description 6
- 230000004048 modification Effects 0.000 title claims description 3
- 238000012986 modification Methods 0.000 title claims description 3
- 229910021365 Al-Mg-Si alloy Inorganic materials 0.000 title claims 4
- 229910045601 alloy Inorganic materials 0.000 claims description 36
- 239000000956 alloy Substances 0.000 claims description 36
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 238000007528 sand casting Methods 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011833 salt mixture Substances 0.000 claims description 2
- 238000010120 permanent mold casting Methods 0.000 claims 1
- 239000011777 magnesium Substances 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 238000004512 die casting Methods 0.000 description 9
- 239000011575 calcium Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 230000005496 eutectics Effects 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910019018 Mg 2 Si Inorganic materials 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910018125 Al-Si Inorganic materials 0.000 description 2
- 229910018520 Al—Si Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- -1 MgCl 2 Chemical class 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
- C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon
Definitions
- the present invention relates to a process for refining and microbial modification of AlMgSi alloys.
- Alloys of the AlMgSi type are preferably used in die-casting processes, and they are particularly advantageous for producing thin-walled components.
- a significant deterioration of the elongation at break with increasing wall thickness recorded.
- AlMgSi-type AlMgSi-type workpieces produced in mold or sand casting have poor mechanical properties, in particular with regard to breaking elongation.
- the elongation at break [A5] is 3% for a workpiece with 20 mm wall thickness made by sand casting, and also 3% for a workpiece with 16 mm wall thickness made with chill casting. This results in comparable poor elongation at break values as in the die casting process.
- grain refining treatment is not required in die casting and may even be detrimental.
- microstructure of AlMgSi alloys can be controlled by adding alloying elements such as Mn, Cr, Zr, please refer ASM Specialty Handbook: Aluminum and Aluminum Alloys, 1993, ASM International, p. 44 ,
- AlSiMg in contrast to AlMgSi, means that such an alloy contains a higher proportion of Si than of Mg.
- Hypereutectic AlSiMg alloys are those having a Si content of slightly or considerably more than 12% Si. At a content of 12% Si is exclusively a eutectic in the form of a fine-grained Al-Si mixed crystal.
- the present invention provides a process for refining AlMgSi alloys for mold or sand casting, which AlMgSi alloys have the general composition 5.0-10.0 wt .-% Mg; 1.0-5.0 wt% Si; 0.001-1.0 wt% Mn, 0.01-0.2 wt% Ti, less than 0.001 wt% Ca, less than 0.001 wt% Na, and less than 0.001 wt% Sr and the remainder Al, and wherein the alloy melt is added to phosphorus in an amount ranging from 0.01 to 0.06 wt .-%, based on the total mass of the alloy.
- -% Sr and the balance Al have, more preferably.
- the phosphorus addition causes the eutectic to grow decoupled.
- the morphology of the eutectic Mg 2 Si phase changes from lamellar and coarse to globular and fine.
- the phosphorus binds the calcium and thereby suppresses the formation of the intermetallic phases CaMg 2 , Al 2 Ca, Al 4 Ca, and so on.
- These phases are nucleation sites for the eutectic Mg 2 Si; if they are absent, the nucleation sites are absent at the host level and the Mg 2 Si phase is formed by supercooling. Since nucleation is necessary for each particle, growth is extremely slow compared to unmodified alloys. The nucleation is self-sufficient or on the aluminum, which is also a poor nucleating agent and thereby minimizes the growth rate.
- the peak of the ternary eutectic disappears or decreases with increasing phosphorus content.
- the addition of the phosphorus can be in the form of a phosphor master alloy or phosphorus salt mixtures.
- Preferred phosphor master alloys which can be used in the present invention include CuP8, AlCuP, AlFeP, and FeP master alloys.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Continuous Casting (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
- Mold Materials And Core Materials (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Raffination und Gefügemodifikation von AlMgSi-Legierungen.The present invention relates to a process for refining and microbial modification of AlMgSi alloys.
Legierungen vom Typ AlMgSi finden bevorzugt in Druckgussverfahren Verwendung, wobei sie insbesondere zur Herstellung von dünnwandigen Bauteilen vorteilhaft sind.Alloys of the AlMgSi type are preferably used in die-casting processes, and they are particularly advantageous for producing thin-walled components.
Beispielsweise beträgt die Bruchdehnung [A5] für eine AlMgSi-Legierung der allgemeinen Zusammensetzung: 5,0-6,0 Gew.-% Mg, 1,8-2,6 Gew.-% Si, 0,5-0,8 Gew.-% Mn und A1 als restlichem Bestandteil für Bauteile mit einer Wanddicke von 4 mm 16%, einer Wanddicke von 18 mm 7% und einer Wanddicke von 24 mm nur 4%. Somit ist bei Werkstücken, die mittels Druckguss hergestellt werden, eine deutliche Verschlechterung der Bruchdehnung mit zunehmender Wanddicke zu verzeichnen.For example, the elongation at break [A5] for an AlMgSi alloy of the general composition: 5.0-6.0 wt.% Mg, 1.8-2.6 wt.% Si, 0.5-0.8 wt % Of Mn and A1 as the remaining component for components with a wall thickness of 4 mm 16%, a wall thickness of 18 mm 7% and a wall thickness of 24 mm only 4%. Thus, for workpieces that are produced by die casting, a significant deterioration of the elongation at break with increasing wall thickness recorded.
Ferner ist bekannt, dass Werkstücke aus Legierungen vom AlMgSi-Typ, die im Kokillen- bzw. Sandguss hergestellt wurden, schlechte mechanische Eigenschaften, insbesondere hinsichtlich der Bruchdehnung, aufweisen.It is also known that AlMgSi-type AlMgSi-type workpieces produced in mold or sand casting have poor mechanical properties, in particular with regard to breaking elongation.
Wird beispielsweise eine Legierung mit der allgemeinen Zusammensetzung: 4,5-6,5 Gew.-% Mg, 1,5 Gew.-% Si, 0,45 Gew.-% Mn und A1 als restlichem Bestandteil im Kokillen- oder Sandguss verwendet, liegt die Bruchdehnung [A5] beispielsweise bei 3% für ein Werkstück mit 20 mm Wanddicke, hergestellt mittels Sandguss, und ebenfalls bei 3% für ein Werkstück mit 16 mm Wanddicke, hergestellt mit Kokillenguss. Damit werden vergleichbar schlechte Bruchdehnungswerte wie beim Druckgussverfahren erhalten.For example, when an alloy having the general composition: 4.5-6.5 wt% of Mg, 1.5 wt% of Si, 0.45 wt% of Mn and Al is used as a residual ingredient in mold or sand casting For example, the elongation at break [A5] is 3% for a workpiece with 20 mm wall thickness made by sand casting, and also 3% for a workpiece with 16 mm wall thickness made with chill casting. This results in comparable poor elongation at break values as in the die casting process.
Zur Verbesserung der mechanischen Eigenschaften von Bauteilen können u.a. Kornfeinungsbehandlungen vorgenommen werden.To improve the mechanical properties of components, i.a. Grain refining treatments are made.
Im Allgemeinen ist eine Kornfeinungsbehandlung beim Druckguss nicht erforderlich und sie kann sich sogar negativ auswirken. Die Erstarrungsbedingungen beim Druckguss, insbesondere die hohe Kühlrate, wirken bereits einem Kornwachstum ausreichend entgegen. Allerdings ist im Stand der Technik eine Behandlung mit halogenhaltigen Schmelzbehandlungssalzen, wie MgCl2, oder sogenannten Aktivgasen, wie Chlorgas mit Stickstoff oder Argon, in verschiedenen Konzentrationen zur Erzielung eines feinen Gefüges und damit guten mechanischen Eigenschaften bekannt.Generally, grain refining treatment is not required in die casting and may even be detrimental. The solidification conditions during die casting, in particular the high cooling rate, already sufficiently counteract grain growth. However, in the prior art, a treatment with halogen-containing melting treatment salts, such as MgCl 2 , or so-called active gases, such as chlorine gas with nitrogen or argon, in various concentrations to achieve a fine microstructure and thus good mechanical properties known.
Außerdem ist bekannt, dass die Gefügestruktur von AlMgSi-Legierungen, insbesondere für den Druckguss, durch Zugabe von Legierungselementen, wie Mn, Cr, Zr gesteuert werden kann, siehe
Allen Datenblättern der entsprechenden Legierungen und der Literatur ist zu entnehmen, dass jedwede absichtliche oder unbeabsichtliche Phosphorzugabe zu vermeiden ist, da sie einer vorteilhaften Gefügeausbildung entgegenwirkt und damit die mechanischen Eigenschaften der Werkstücke aus diesen Legierungen verschlechtert.It is evident from all the data sheets of the corresponding alloys and the literature that any intentional or unintentional addition of phosphorus is to be avoided, since it counteracts advantageous microstructural formation and thus worsens the mechanical properties of the workpieces made from these alloys.
Im Stand der Technik bekannt ist hingegen eine Phosphorzugabe zu AlSiMg-Legierungen, siehe beispielsweise ASM Speciality
Die Phosphorzugabe erfolgt dabei insbesondere bei naheutektischen und übereutektischen AlSiMg-Legierungen. Übereutektische AlSiMg-Legierungen sind solche mit einem Si-Gehalt von geringfügig oder beträchtlich mehr als 12% Si. Bei einem Gehalt von 12% Si liegt ausschließlich ein Eutektikum in Form eines feinkörnigen Al-Si-Mischkristalls vor.The addition of phosphorus takes place in particular in near-eutectic and hypereutectic AlSiMg alloys. Hypereutectic AlSiMg alloys are those having a Si content of slightly or considerably more than 12% Si. At a content of 12% Si is exclusively a eutectic in the form of a fine-grained Al-Si mixed crystal.
Bei übereutektischen AlSiMg-Legierungen bilden sich beim Abkühlen der Legierungsschmelze zuerst grobkörnige Si-Kristalle aus, die in der Folge im feinkörnigen Mischkristallgefüge eingebettet sind. Durch die groben Si-Kristalle verschlechtern sich die mechanischen Eigenschaften. Eine Zugabe von AlP bewirkt eine Feinung dieser Si-Kristalle, weil AlP als Keimbildner für Si-Kristalle wirkt und diese daher mit deutlich verkleinerter Dimension im erhaltenen Gefüge vorliegen, was eine Verbesserung der mechanischen Eigenschaften mit sich bringt.In hypereutectic AlSiMg alloys, coarse-grained Si crystals first form on cooling of the alloy melt, which are subsequently embedded in the fine-grained solid-solution structure. Worsen by the coarse Si crystals the mechanical properties. Addition of AlP causes these Si crystals to be refined because AlP acts as a nucleating agent for Si crystals and therefore has a significantly reduced dimension in the resulting structure, resulting in an improvement in mechanical properties.
Eine solche Phosphorzugabe zu untereutektischen AlSiMg-Legierungen ist hingegen wirkungslos, da beim Abkühlen dieser Legierungen zuerst α-Al-Kristalle, und keine Si-Kristalle, und anschließend das Al-Si-Eutektikum ausgebildet werden.On the other hand, such phosphorus addition to hypoeutectic AlSiMg alloys is ineffective because upon cooling of these alloys, α-Al crystals, not Si crystals, and then the Al-Si eutectic are formed first.
Überaschenderweise wurde nun festgestellt, dass eine Phosphorzugabe zu einer AlMgSi-Legierung, wie sie im Druckguss eingesetzt werden kann, die mechanischen Eigenschaften, insbesondere die Bruchdehnung, bei Werkstücken mit stärkeren Wanddicken verbessern kann, wenn diese aus den Phosphor-enthaltenden Legierungen in Kokillen- oder Sandgussverfahren hergestellt werden.Surprisingly, it has now been found that a phosphorus addition to an AlMgSi alloy, as can be used in die casting, the mechanical properties, in particular the elongation at break, can improve for workpieces with thicker wall thickness, if these from the phosphorus-containing alloys in mold or Sand casting process are produced.
Demgemäß stellt die vorliegende Erfindung ein Verfahren zur Raffination von AlMgSi-Legierungen für den Kokillen- oder Sandguss bereit, welche AlMgSi-Legierungen die allgemeine Zusammensetzung 5,0-10,0 Gew.-% Mg; 1,0-5,0 Gew.-% Si; 0,001-1,0 Gew.-% Mn, 0,01-0,2 Gew.-% Ti, weniger als 0,001 Gew.-% Ca, weniger als 0,001 Gew.-% Na, und weniger als 0,001 Gew.-% Sr sowie als Rest Al besitzen, und wobei der Legierungsschmelze Phosphor in einem Mengenbereich von 0,01 bis 0,06 Gew.-%, bezogen auf die Gesamtmasse der Legierung, zugefügt wird.Accordingly, the present invention provides a process for refining AlMgSi alloys for mold or sand casting, which AlMgSi alloys have the general composition 5.0-10.0 wt .-% Mg; 1.0-5.0 wt% Si; 0.001-1.0 wt% Mn, 0.01-0.2 wt% Ti, less than 0.001 wt% Ca, less than 0.001 wt% Na, and less than 0.001 wt% Sr and the remainder Al, and wherein the alloy melt is added to phosphorus in an amount ranging from 0.01 to 0.06 wt .-%, based on the total mass of the alloy.
Zur Verwendung mit dem erfindungsgemäßen Verfahren sind AlMgSi-Legierungen, welche die allgemeine Zusammensetzung 6-9 Gew.-% Mg; 2,5-4,5 Gew.-% Si; 0,02-0,5 Gew.-% Mn, 0,01-0,2 Gew.-% Ti, weniger als 0,001 Gew.-% Ca, weniger als 0,001 Gew.-% Na, und weniger als 0,001 Gew.-% Sr und als Rest Al besitzen, besonders bevorzugt.For use with the process of the invention, AlMgSi alloys containing the general composition 6-9 wt.% Mg; 2.5-4.5% by weight of Si; 0.02-0.5 wt% Mn, 0.01-0.2 wt% Ti, less than 0.001 wt% Ca, less than 0.001 wt% Na, and less than 0.001 wt%. -% Sr and the balance Al have, more preferably.
So werden für eine Legierung mit der Zusammensetzung 7,88-7,96 Gew.-% Mg, 4,53-4,60 Gew.-% Si, 0,017-0,018 Gew.-% Mn, 0,0003-0,0007 Gew.-% Ca und jeweils weniger als 0,0001 Gew.-% Na und Sr, sowie als Rest Al für ein Werkstück mit einer Wanddicke von 25 mm, hergestellt mittels Kokillenguss, die nachfolgenden Bruchdehnungswerte gemessen:
Aus der vorstehenden Tabelle ist ersichtlich, dass Werkstücke mit der erfindungsgemäßen Phosphorzugabe (Probe 3) eine Verbesserung der Bruchdehnung um mehr als das Siebenfache gegenüber dem Stand der Technik (Probe 1) aufweisen.From the above table it can be seen that workpieces with the addition of phosphorus according to the invention (sample 3) have an improvement in elongation at break of more than seven times that of the prior art (sample 1).
Ohne an die Theorie gebunden zu sein, wird angenommen, dass die Phosphorzugabe dafür sorgt, dass das Eutektikum entkoppelt wächst. Dadurch ändert sich die Morphologie der eutektischen Mg2Si-Phase von lamellar und grob auf globular und fein. Es wird angenommen, dass der Phosphor das Calcium bindet und dadurch die Ausbildung der intermetallischen Phasen CaMg2, Al2Ca, Al4Ca, usw. unterdrückt. Diese Phasen sind Keimstellen für das eutektische Mg2Si, sind sie nicht vorhanden fehlen die Keimstellen auf der Wirtebene und die Mg2Si-Phase entsteht durch Unterkühlung. Da für jedes einzelne Partikel eine Keimbildung notwendig ist, erfolgt das Wachstum extrem langsam gegenüber den unmodifizierten Legierungen. Die Keimbildung erfolgt autark oder auf dem Aluminium, das jedoch auch ein schlechter Keimbildner ist und dadurch die Wachstumsgeschwindigkeit minimiert. In der thermischen Analyse verschwindet bzw. verringert sich der Peak des ternären Eutektikums mit zunehmendem Phosphorgehalt.Without being bound by theory, it is believed that the phosphorus addition causes the eutectic to grow decoupled. As a result, the morphology of the eutectic Mg 2 Si phase changes from lamellar and coarse to globular and fine. It is believed that the phosphorus binds the calcium and thereby suppresses the formation of the intermetallic phases CaMg 2 , Al 2 Ca, Al 4 Ca, and so on. These phases are nucleation sites for the eutectic Mg 2 Si; if they are absent, the nucleation sites are absent at the host level and the Mg 2 Si phase is formed by supercooling. Since nucleation is necessary for each particle, growth is extremely slow compared to unmodified alloys. The nucleation is self-sufficient or on the aluminum, which is also a poor nucleating agent and thereby minimizes the growth rate. In thermal analysis, the peak of the ternary eutectic disappears or decreases with increasing phosphorus content.
Die Zugabe des Phosphors kann in Form einer Phosphorvorlegierung oder phosphorabgebenden Salzgemischen erfolgen. Bevorzugte Phosphorvorlegierungen, die erfindungsgemäß verwendet werden können, umfassen CuP8-, AlCuP-, AlFeP-, und FeP-Vorlegierungen.The addition of the phosphorus can be in the form of a phosphor master alloy or phosphorus salt mixtures. Preferred phosphor master alloys which can be used in the present invention include CuP8, AlCuP, AlFeP, and FeP master alloys.
Die erfindungsgemäße Herstellung einer Legierung mit verbesserten mechanischen Eigenschaften für den Kokillen- oder Sandguss erfolgt nach folgendem Schema:
- Aufschmelzen von Reinaluminium oder geeignetem Sekundäraluminium in ausreichender Qualität (z.B. von AlMg-Blechen)
- Auflegieren von Silizium, Magnesium, Titan durch Zugabe von Reinmetallen (Silizium, Magnesium, Titan) oder sogenannten Vorlegierungen aus z.B. 90% Aluminium und 10% Titan
- Bestimmung der Schmelzezusammensetzung (z.B. durch Funkenemissionsspektrometrie)
- Reinigung der Schmelze durch Zugabe von Reinigungssalzen (z.B. MgCl2), durch Spülen mit Aktivgasgemischen (z.B. Ar:Cl2 98:2) oder Inertgasen (z.B. N2 oder Ar). Ziel der Metallreinigung ist die Entfernung von Oxiden, Wasserstoff und Spurenverunreinigungen, wie Natrium und Calcium
- Einstellen der Schmelzetemperatur auf 730 - 780°C
- Auflegieren des Phosphors auf 0,01 - 0,06% durch Zugabe von CuP8-, AlCuP-, AlFeP- oder FeP-Vorlegierungen
- Kontrolle der chemischen Zusammensetzung und gegebenenfalls Korrektur durch erneute Zugabe von Legierungselementen
- Einstellen der Gießtemperatur
- Abguss der Schmelze im horizontalen Strangguss oder anderen geeigneten Verfahren wie z.B. Vergießen in Kokillen (sog. Masselgießband) oder im Properziverfahren.
- Melting of pure aluminum or suitable secondary aluminum in sufficient quality (eg of AlMg sheets)
- Alloying of silicon, magnesium, titanium by adding pure metals (silicon, magnesium, titanium) or so-called master alloys of eg 90% aluminum and 10% titanium
- Determination of the melt composition (eg by spark emission spectrometry)
- Cleaning the melt by adding cleaning salts (eg MgCl 2 ), by rinsing with active gas mixtures (eg Ar: Cl 2 98: 2) or inert gases (eg N 2 or Ar). The aim of metal cleaning is the removal of oxides, hydrogen and trace impurities, such as sodium and calcium
- Set the melt temperature to 730 - 780 ° C
- Alloy the phosphor to 0.01-0.06% by adding CuP8, AlCuP, AlFeP or FeP master alloys
- Control of the chemical composition and, if necessary, correction by adding alloying elements again
- Setting the pouring temperature
- Casting of the melt in horizontal continuous casting or other suitable processes such as casting in molds (so-called pig casting line) or in the propylene oxide process.
Claims (4)
- A method for the refining and structural modification of Al-Mg-Si alloys for permanent-mold casting or sandcasting, which Al-Mg-Si alloys have the general composition of 5.0-10.0 weight % Mg; 1.0-5.0 weight % Si; 0.001-1.0 weight % Mn, 0.01-0.2 weight % Ti, less than 0.001 weight % Ca, less than 0.001 weight % Na, and less than 0.001 weight % Sr, and as the remainder, Al, and wherein phosphorus is added to the alloy melt in a quantitative range of from 0.01 to 0.06 weight %, referred to the total mass of the alloy.
- The method of claim 1, wherein the phosphorus is added in the form of phosphorus master alloys or phosphorus-yielding salt mixtures.
- The method of claim 2, wherein the phosphorus master alloys include CuP8, AlcuP, AlFeP and FeP master alloys.
- The method of one of claims 1-3, wherein the Al-Mg-Si alloys have the general composition of 6-9 weight % Mg; 2.5-4.5 weight % Si; 0.02-0.5 weight % Mn, 0.01-0.2 weight % Ti, less than 0.001 weight % Ca, less than 0.001 weight % Na, and less than 0.001 weight % Sr, and as the remainder, Al.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ATA615/2011A AT511397B1 (en) | 2011-05-03 | 2011-05-03 | METHOD OF REFINING AND PERMITTING MODIFICATION OF AIMGSI ALLOYS |
| PCT/AT2012/000124 WO2012149589A1 (en) | 2011-05-03 | 2012-05-03 | Method for the refining and structure modification of al-mg-si alloys |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2705171A1 EP2705171A1 (en) | 2014-03-12 |
| EP2705171B1 true EP2705171B1 (en) | 2015-08-26 |
Family
ID=46146481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP12722272.7A Revoked EP2705171B1 (en) | 2011-05-03 | 2012-05-03 | Method for the refining and structure modification of al-mg-si alloys |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US9279170B2 (en) |
| EP (1) | EP2705171B1 (en) |
| AT (1) | AT511397B1 (en) |
| CA (1) | CA2866094A1 (en) |
| MX (1) | MX2013012681A (en) |
| WO (1) | WO2012149589A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101565025B1 (en) * | 2013-11-27 | 2015-11-02 | 현대자동차주식회사 | Aluminum alloy for low density, high heat resistance |
| ES2724953T3 (en) | 2015-03-10 | 2019-09-18 | Cms Jant Ve Makine Sanayi Anonim Sirketi | Grain refining method for aluminum alloys |
| CN104988346B (en) * | 2015-07-08 | 2017-03-29 | 龙口市丛林铝材有限公司 | A kind of preparation method of vehicle body of railway vehicle aluminium alloy |
| JP2017210653A (en) * | 2016-05-26 | 2017-11-30 | 日本軽金属株式会社 | Aluminum alloy and casting |
| EP4234123A3 (en) * | 2018-05-07 | 2023-09-27 | Alcoa USA Corp. | Al-mg-si-mn-fe casting alloys |
| CN115323228A (en) * | 2022-08-19 | 2022-11-11 | 光智科技股份有限公司 | Manufacturing method of novel aluminum alloy for scribing cutter aluminum flying disc |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0457380A1 (en) | 1990-05-16 | 1991-11-21 | METALLGESELLSCHAFT Aktiengesellschaft | Process for manufacturing of alloys containing magnesium disilicide |
| WO1996015281A1 (en) | 1994-11-15 | 1996-05-23 | Aluminium Rheinfelden Gmbh | Cast aluminium alloy |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1608165C2 (en) * | 1967-12-01 | 1981-10-22 | Honsel-Werke Ag, 5778 Meschede | Use of AlMgSi cast alloys for cylinder heads subject to alternating thermal loads |
| JPH05500831A (en) * | 1989-08-09 | 1993-02-18 | コマルコ アルミニウム リミテッド | Casting of improved Al-based Si-Cu-Ni-Mn-Zr hypereutectic alloy |
| US6669792B2 (en) * | 1998-09-08 | 2003-12-30 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Process for producing a cast article from a hypereutectic aluminum-silicon alloy |
| ES2330332T3 (en) * | 2003-01-23 | 2009-12-09 | Aluminium Rheinfelden Gmbh | ALUMINUM ALLOY FUSED TO PRESSURE. |
| PT1612286E (en) * | 2004-06-29 | 2011-09-19 | Rheinfelden Aluminium Gmbh | Aluminium alloy for pressure die casting |
| AT501867B1 (en) * | 2005-05-19 | 2009-07-15 | Aluminium Lend Gmbh & Co Kg | ALUMINUM ALLOY |
| EP1757709B1 (en) * | 2005-08-22 | 2007-10-17 | ALUMINIUM RHEINFELDEN GmbH | Heat resistant aluminium alloy |
| KR101534864B1 (en) * | 2009-06-30 | 2015-07-08 | 현대자동차주식회사 | Manufacturing method of cylinder liners for vehicles |
-
2011
- 2011-05-03 AT ATA615/2011A patent/AT511397B1/en not_active IP Right Cessation
-
2012
- 2012-05-03 EP EP12722272.7A patent/EP2705171B1/en not_active Revoked
- 2012-05-03 US US14/114,989 patent/US9279170B2/en not_active Expired - Fee Related
- 2012-05-03 MX MX2013012681A patent/MX2013012681A/en not_active Application Discontinuation
- 2012-05-03 WO PCT/AT2012/000124 patent/WO2012149589A1/en active Application Filing
- 2012-05-03 CA CA2866094A patent/CA2866094A1/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0457380A1 (en) | 1990-05-16 | 1991-11-21 | METALLGESELLSCHAFT Aktiengesellschaft | Process for manufacturing of alloys containing magnesium disilicide |
| WO1996015281A1 (en) | 1994-11-15 | 1996-05-23 | Aluminium Rheinfelden Gmbh | Cast aluminium alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2705171A1 (en) | 2014-03-12 |
| MX2013012681A (en) | 2014-10-17 |
| WO2012149589A1 (en) | 2012-11-08 |
| AT511397B1 (en) | 2013-02-15 |
| US9279170B2 (en) | 2016-03-08 |
| AT511397A1 (en) | 2012-11-15 |
| US20140290437A1 (en) | 2014-10-02 |
| CA2866094A1 (en) | 2012-11-08 |
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