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EP 2 758 557 B1 |
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EUROPEAN PATENT SPECIFICATION |
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Mention of the grant of the patent: |
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04.11.2015 Bulletin 2015/45 |
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Date of filing: 19.09.2012 |
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International Patent Classification (IPC):
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International application number: |
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PCT/EP2012/068465 |
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International publication number: |
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WO 2013/041584 (28.03.2013 Gazette 2013/13) |
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IMPROVED ALUMINUM CASTING ALLOYS CONTAINING VANADIUM
VERBESSERTE ALUMINIUMGUSSLEGIERUNGEN MIT VANADIUM
ALLIAGES DE MOULAGE D'ALUMINIUM AMÉLIORÉS CONTENANT DU VANADIUM
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Designated Contracting States: |
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AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL
NO PL PT RO RS SE SI SK SM TR |
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Priority: |
19.09.2011 US 201161536451 P
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Date of publication of application: |
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30.07.2014 Bulletin 2014/31 |
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Proprietor: Alcoa GmbH |
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72636 Frickenhausen (DE) |
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Inventors: |
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- MÜLLER, Claus, Michael
35423 Lich (DE)
- SCHEID, Ralf
52078 Aachen (DE)
- VOS, Martijn
8113 Boppelsen (CH)
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Representative: Lenzing Gerber Stute |
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Partnerschaft von Patentanwälten mbB
Bahnstraße 9 40212 Düsseldorf 40212 Düsseldorf (DE) |
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References cited: :
EP-A2- 1 524 324
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US-A1- 2006 133 949
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| Note: Within nine months from the publication of the mention of the grant of the European
patent, any person may give notice to the European Patent Office of opposition to
the European patent
granted. Notice of opposition shall be filed in a written reasoned statement. It shall
not be deemed to
have been filed until the opposition fee has been paid. (Art. 99(1) European Patent
Convention).
|
BACKGROUND
[0001] Aluminum casting alloys are useful in a variety of applications. However, improving
one property of an aluminum casting alloy without degrading another property is elusive.
For example, it is difficult to increase the strength of an alloy without decreasing
the ductility of an alloy.
[0002] EP 1 524 324 A2 discloses aluminum alloys having 4 - 12 mass % of Si, less than 0.2 mass % of Cu,
0.1 - 0.5 mass % of Mg, 0.2 - 3.0 mass % of Ni, 0.1 - 0.7 mass % of Fe, 0.15 - 0.3
mass % of Ti and the remainder of AC and inevitable impurities.
SUMMARY OF THE DISCLOSURE
[0003] Broadly, the present patent application relates to improved aluminum casting alloys
(also known as foundry alloys), and methods for producing the same. Specifically,
the present patent application relates to aluminum casting alloys having silicon vanadium
and, optionally, iron. Generally, the new aluminum casting alloys including vanadium,
and optionally iron, achieve an improved combination of properties.
[0004] The new aluminum casting alloys generally include from about 0.01 to 0.15 wt. % vanadium
(V). In one embodiment, the new aluminum casting alloy may include from about 0.03
to 0.12 wt. % vanadium. In another embodiment, the new aluminum casting alloy may
include from about 0.05 to 0.10 wt. % vanadium. By maintaining vanadium within the
aluminum casting alloy in the above-described amounts, optionally with iron, an improved
combination of properties may be realized. For example, the aluminum casting alloy
may realize an improved combination of strength and elongation, among other properties.
[0005] In one embodiment, the aluminum casting alloy includes not greater than 0.08 wt.
% iron. In another embodiment, the aluminum casting alloy includes not greater than
0.05 wt. % iron. In some embodiments, iron is included in the alloy. In one embodiment,
the aluminum casting alloy includes 0.01 - 0.08 wt. % iron.
[0006] In one approach, the aluminum casting alloy is a silicon-based casting alloy including
the above-described amounts of vanadium, optionally with iron. The silicon-based casting
alloys may be any of the 3xx series of casting alloys known to those skilled in the
art. In this approach, the silicon-based casting alloy includes from 4.0 to 10.0 wt.
% silicon, and silicon is the predominate alloying element of the casting alloy, except
for aluminum. The silicon-based casting alloys may optionally include secondary element,
tertiary elements, and other elements, defined below. In one embodiment, the silicon-based
casting alloy includes from about 6.0 to 9.0 wt. % silicon. In one embodiment, the
silicon-based casting alloy includes from about 6.5 to 8.5 wt. % silicon.
[0007] The silicon-based aluminum alloy may include one or more secondary elements. These
secondary elements are selected from the group consisting of magnesium, copper, zinc,
nickel, and combinations thereof. The secondary elements may be included in the alloy
for various purposes, such as for strengthening (e.g., solid solution, precipitate
and constituent strengthening). In one approach, the silicon-based casting alloy includes
magnesium. In one embodiment, the silicon-based casting alloy includes magnesium,
and in the range of from about 0.05 to 1.5 wt. % magnesium. In other embodiments,
the silicon-based casting alloy includes magnesium as an impurity, i.e., not greater
than 0.04 wt. % magnesium.
[0008] In one approach, the silicon-based casting alloy includes copper. In one embodiment,
the silicon-based casting alloy includes copper, and in the range of from about 0.40
to 5.0 wt. % copper. In other embodiments, the silicon-based casting alloy includes
copper as an impurity, i.e., not greater than 0.39 wt. % copper.
[0009] In one approach, the silicon-based casting alloy includes zinc. In one embodiment,
the silicon-based casting alloy includes zinc, and in the range of from about 0.25
to 5.0 wt. % zinc. In other embodiments, the silicon-based casting alloy includes
zinc as an impurity, i.e., not greater than 0.24 wt. % zinc.
[0010] In one approach, the silicon-based casting alloy includes nickel. In one embodiment,
the silicon-based casting alloy includes nickel, and in the range of from about 0.50
to 3.0 wt. % nickel. In other embodiments, the silicon-based casting alloy includes
nickel as an impurity, i.e., not greater than 0.49 wt. % nickel.
[0011] The silicon-based aluminum alloy may include tertiary elements, such as manganese,
chromium, titanium, strontium, sodium, antimony, and combinations thereof. One or
more of these tertiary elements may be added to the alloy for various purposes. For
example, manganese and/or chromium may be included in the silicon-based aluminum alloy
to prevent die soldering for high pressure die casting. Titanium may be included in
the silicon-based aluminum alloy for grain refining. Strontium, sodium and/or antimony
may be added for silicon particle modification. In these embodiments, the silicon-based
aluminum alloy generally includes not greater than about 1.0 wt. % each of the tertiary
elements. When a tertiary element is included, the alloy generally includes at least
about 0.01 wt. % of that tertiary element (e.g., 0.01 - 1.0 wt. % Mn). In one embodiment,
the silicon-based aluminum alloy includes 0.01 to 0.8 wt. % manganese. In one embodiment,
the silicon-based aluminum alloy includes 0.01 to 0.5 wt. % chromium. In one embodiment,
the silicon-based aluminum alloy includes 0.01 to 0.25 wt. % titanium. In one embodiment,
the silicon-based aluminum alloy includes 0.001 to 0.1 wt. % strontium. In one embodiment,
the silicon-based aluminum alloy includes 0.001 to 0.1 wt. % sodium. In one embodiment,
the silicon-based aluminum alloy includes 0.001 to 0.1 wt. % antimony.
[0012] In addition or as an alternative to titanium grain refining, the silicon-based aluminum
alloy may include TiB
2 and/or TiC as a grain refiner. In one embodiment, the silicon-based aluminum alloy
includes 0.001 to 0.03 wt. % boron. In one embodiment, the silicon-based aluminum
alloy includes 0.001 to 0.03 wt. % carbon.
[0013] The silicon-based aluminum alloy may be substantially free of other elements (e.g.,
deoxidizers, impurities). Other elements means any other element of the periodic table
that may be included in the silicon-based aluminum alloy, except for aluminum, the
silicon, the vanadium, the iron, the secondary elements, and the tertiary elements,
described above. In the context of this paragraph the phrase "substantially free"
means that the aluminum alloy body contains not more than 0.25 wt. % each of any element
of the other elements, with the total combined amount of these other elements not
exceeding 0.50 wt. %. In one embodiment, each one of these other elements, individually,
does not exceed about 0.10 wt. % in the silicon-based aluminum alloy, and the total
combined amount of these other elements does not exceed about 0.35 wt. %, in the silicon-based
aluminum alloy. In another embodiment, each one of these other elements, individually,
does not exceed about 0.05 wt. % in the silicon-based aluminum alloy, and the total
combined amount of these other elements does not exceed about 0.15 wt. % in the silicon-based
aluminum alloy. In another embodiment, each one of these other elements, individually,
does not exceed about 0.03 wt. % in the silicon-based aluminum alloy, and the total
combined amount of these other elements does not exceed about 0.10 wt. % in the silicon-based
aluminum alloy.
[0014] The silicon-based aluminum alloy may be used in various types of foundry casting
processes, such as sand mold casting, investment casting (ceramic shell mold), lost
foam casting, permanent mold casting, high pressure die casting, squeeze casting,
and semi-solid casting, to name a few. The Secondary Dendrite Arm Spacing (SDAS) of
the silicon-based aluminum alloy produced by various casting methods may range from
1 micrometer (e.g., with a fast solidification rate) to 100 micrometers (e.g., with
a slow solidification rate). SDAS may be determined, for instance, using standard
metallographic techniques and the "intercept method". The intercept method involves
(1) drawing a straight line parallel to the primary dendrite,(2) counting the number
of dendrite arm intercepted, (3) using the following equation to calculate a specific
SDAS: SDAS= line length / number of arms / magnification; and (4) repeating several
times (at least 5) and averaging the results to obtain an overall SDAS.
[0015] These and other aspects, advantages, and novel features of this new technology are
set forth in part in the description that follows and will become apparent to those
skilled in the art upon examination of the following description and figures, or may
be learned by practicing one or more embodiments of the technology provided for by
the patent application.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016]
FIG. 1 is a graph illustrating the performance of various silicon-based aluminum casting
alloys.
FIG. 2 is a graph illustrating the performance of various silicon-based aluminum casting
alloys.
FIGS. 3a-3b are pictures illustrating the microstructure of various silicon-based
aluminum casting alloys.
DETAILED DESCRIPTION
Example 1
[0017] Several silicon-based aluminum casting alloys having the compositions listed in Table
1, below, are cast via sand mold casting.
Table 1 - Composition of Silicon-based casting alloy (all values in weight percent)
| Alloy (Variante) |
Si |
Mg |
Fe |
V |
Ti |
Na |
Other, Each |
Others, Total |
Bal. |
| 1 |
6.92 |
0.318 |
0.074 |
0.083 |
0.113 |
0.0078 |
≤ 0.05 |
≤ 0.15 |
Al |
| 2 |
7.06 |
0.332 |
0.077 |
<0.001 |
0.108 |
0.0046 |
≤ 0.05 |
≤ 0.15 |
Al |
| 3 |
7.08 |
0.319 |
0.141 |
0.079 |
0.113 |
0.0039 |
≤ 0.05 |
≤ 0.15 |
Al |
[0018] After casting, the properties of the alloys have been measured (i.e., in the F temper)
for each alloy in the same way. The results are illustrated in FIG. 1. The given average
of the measured data include tensile yield strength data (ØR
p0.2) and ultimate tensile strength data (ØR
m) given in MPa and Brinell scale hardness data HBW5/250 (ØHärte). Moreover, average
elongation data are given, where ØA (lower graph) refers to average elongation based
on machine measured data, and where ØAI (upper graph) refers to average elongation
based on manually measured data. Alloy 1 with 0.08 wt. % V and 0.08 wt. % Fe has both
better strength and elongation than Alloys 2-3 achieving an ultimate tensile strength
of about 143 MPa, and an elongation of about 4.2-4.4%. By comparison, Alloys 2-3 achieve
only about 123-130 MPa in ultimate tensile strength, and with much lower elongation
(2.6-2.8 %).
[0019] These alloys (Variante 1 - 3) are also aged to a T6 temper. The same mechanical characteristics
(ØR
p0.2, ØR
m, ØHärte, ØA, ØAI) as that depicted in Fig. 1 have been determined. The results of
the measurements are illustrated in FIG. 2 (one with water quench after a 5h solution
heat treatment at 540 °C, followed by a two step artificial ageing for 3h at 140°
and 6h at 160°C, and one with air cooling after a 3.5h solution heat treatment at
540 °C, followed by a one step artificial ageing for 5h at 185°C).
[0020] Again, Alloy 1 with 0.08 wt. % vanadium and 0.08 wt. % iron outperforms Alloys 2-3
in terms of strength and elongation, achieving both higher strength and elongation
than Alloys 2-3.
[0021] The microstructures of Alloys 1-3 are illustrated in FIGS. 3a-3b, below.
[0022] Alloy 1 contains smaller β-AlFeSi particles and less/smaller π-AlFeMgSi particles.
The porosity of Alloys 1-3 is also measured (by image analysis), the results of which
are provided in Table 2, below. Alloys 1 and 3 with 0.08 wt. % V have reduced porosity.
It is believed that both factors, i.e., less/smaller particles and less porosity,
may contribute to the higher strength and elongation properties.
Table 2 - Porosity of Silicon-based casting alloy (all porosity values in percent)
| Measurement |
Alloy 1 |
Alloy 2 |
Alloy 3 |
| 1 |
0.88 |
5.03 |
1.57 |
| 2 |
2.04 |
3.96 |
1.63 |
| 3 |
1.91 |
6.32 |
1.31 |
| 4 |
1.36 |
5.9 |
1.44 |
| 5 |
1.87 |
4.84 |
1.17 |
| 6 |
1.13 |
7.19 |
1.19 |
| 7 |
0.84 |
2.92 |
1.37 |
| 8 |
1.28 |
3.48 |
1.07 |
| 9 |
1.26 |
4.05 |
2.18 |
| 10 |
0.96 |
4.83 |
1.59 |
| 11 |
0.67 |
3.71 |
0.57 |
| 12 |
|
5.93 |
1.37 |
| 13 |
|
3.08 |
1.91 |
| 14 |
|
1.94 |
1.31 |
| 15 |
|
1.86 |
0.93 |
| 16 |
|
1.49 |
0.92 |
| 17 |
|
1.09 |
|
| 18 |
|
2.11 |
|
| Average |
1.291 |
3.874 |
1.346 |
| STDEV |
0.467 |
1.792 |
0.392 |
1. An aluminum casting alloy comprising:
from 4.0 to 10.0 wt. % silicon (Si);
from 0.01 to 0.15 wt. % vanadium (V);
up to 0.08 wt. % iron (Fe);
optionally one or more of the following secondary elements:
from 0.05 to 1.5 wt. % magnesium (Mg);
from 0.40 to 5.0 wt. % copper (Cu);
from 0.25 to 5.0 wt. % zinc (Zn); and
from 0.50 to 3.0 wt. % nickel (Ni);
optionally 0.01 - 1.0 wt. % each of one or more of the following tertiary elements:
manganese (Mn), chromium (Cr), titanium (Ti), strontium (Sr), sodium (Na), and antimony
(Sb);
optionally from 0.001 to 0.03 wt. % boron (B);
optionally from 0.001 to 0.03 wt. % carbon (C);
not more than 0.25 wt. % each of any other element, with the total combined amount
of these other elements not exceeding 0.50 wt. %;
the balance being aluminum and impurities.
2. The aluminum casting alloy of claim 1, comprising from 0.03 to 0.12 wt. % V.
3. The aluminum casting alloy of claim 1, comprising from 0.05 to 0.10 wt. % V.
4. The aluminum casting alloy of any of claims 1-3, comprising not greater than 0.05
wt. % iron.
5. The aluminum casting alloy of any of claims 1-4, comprising at least 0.01 wt. % iron.
6. The aluminum casting alloy of any of claims 1-5, comprising from 6.0 to 9.0 wt. %
silicon.
7. The aluminum casting alloy of any of claims 1-5, comprising from 6.5 to 8.5 wt. %
silicon.
8. The aluminum casting alloy of any of claims 1-7, comprising from 0.01 to 0.8 wt. %
manganese.
9. The aluminum casting alloy of any of claims 1-8, comprising from 0.01 to 0.5 wt. %
chromium.
10. The aluminum casting alloy of any of claims 1-9, comprising from 0.01 to 0.25 wt.
% titanium.
11. The aluminum casting alloy of any of claims 1-10, comprising from 0.001 to 0.1 wt.
% strontium.
12. The aluminum casting alloy of any of claims 1-11, comprising from 0.001 to 0.1 wt.
% sodium.
13. The aluminum casting alloy of any of claims 1-12, comprising from 0.001 to 0.1 wt.
% antimony.
14. The aluminum casting alloy of any of claims 1-13, wherein the alloy comprises not
more than 0.10 wt. % each of the other elements, with the total combined amount of
these other elements not exceeding 0.35 wt. %.
15. The aluminum casting alloy of any of claims 1-14, wherein the alloy realizes a Secondary
Dendrite Arm Spacing (SDAS) of from 1 micrometer to 100 micrometers.
1. Eine Aluminiumgusslegierung aufweisend:
von 4,0 bis 10,0 Gew.% Silizium (Si);
von 0,01 bis 0,15 Gew.% Vanadium (V);
bis zu 0,08 Gew.% Eisen (Fe);
optional ein oder mehrere der folgenden Sekundärelemente:
von 0,05 bis 1,5 Gew.% Magnesium (Mg);
von 0,40 bis 5,0 Gew.% Kupfer (Cu);
von 0,25 bis 5,0 Gew.% Zink (Zn);
von 0,50 bis 3,0 Gew.% Nickel (Ni);
optional jeweils 0,01 bis 1,0 Gew.% von einem oder mehreren der folgenden Tertiärelemente:
Mangan (Mn), Chrom (Cr), Titan (Ti), Strontium (Sr), Natrium (Na), und Antimon (Sb);
optional von 0,001 bis 0,03 Gew.% Bor (B);
optional von 0,001 bis 0,03 Gew.% Kohlenstoff (C);
nicht mehr als 0,25 Gew.% jeweils von einem anderen Element, die gesamte Menge dieser
anderen Elemente 0,50 Gew.% nicht übersteigend;
der Rest Aluminium und Verunreinigungen.
2. Die Aluminiumgusslegierung nach Anspruch 1, enthaltend von 0,03 bis 0,12 Gew.% V.
3. Die Aluminiumgusslegierung nach Anspruch 1, enthaltend von 0,05 bis 0,10 Gew.% V.
4. Die Aluminiumgusslegierung gemäß einem der Ansprüche 1 - 3, enthaltend nicht mehr
als 0,05 Gew.% Eisen.
5. Die Aluminiumgusslegierung gemäß einem der Ansprüche 1- 4, enthaltend mindestens 0,01
Gew.% Eisen.
6. Die Aluminiumgusslegierung gemäß einem der Ansprüche 1- 5, enthaltend von 6,0 bis
9,0 Gew.% Silizium.
7. Die Aluminiumgusslegierung gemäß einem der Ansprüche 1- 5, enthaltend von 6,5 bis
8,5 Gew.% Silizium.
8. Die Aluminiumgusslegierung gemäß einem der Ansprüche 1- 7, enthaltend von 0,01 bis
0,8 Gew.% Mangan.
9. Die Aluminiumgusslegierung gemäß einem der Ansprüche 1-8, enthaltend von 0,01 bis
0,5 Gew.% Chrom.
10. Die Aluminiumgusslegierung gemäß einem der Ansprüche 1- 9, enthaltend von 0,01 bis
0,25 Gew.% Titan.
11. Die Aluminiumgusslegierung gemäß einem der Ansprüche 1 - 10, enthaltend von 0,001
bis 0,1 Gew.% Strontium.
12. Die Aluminiumgusslegierung gemäß einem der Ansprüche 1-11, enthaltend von 0,001 bis
0,1 Gew.% Natrium.
13. Die Aluminiumgusslegierung gemäß einem der Ansprüche 1 - 12, enthaltend von 0,001
bis 0,1 Gew.% Antimon.
14. Die Aluminiumgusslegierung gemäß einem der Ansprüche 1 - 13, wobei die Legierung nicht
mehr als 0,10 Gew.% eines der anderen Elemente enthält, wobei die Gesamtmenge der
anderen Elemente 0,35 Gew.% nicht überschreitet.
15. Die Aluminiumgusslegierung gemäß einem der Ansprüche 1 - 14, wobei die Legierung einen
sekundären Dendritenarmabstand (SDAS) von 1 Mikrometer bis 100 Mikrometer erreicht.
1. Alliage de fonderie d'aluminium comprenant :
de 4,0 à 10,0 % en poids de silicium (Si) ;
de 0,01 à 0,15 % en poids de vanadium (V) ;
jusqu'à 0,08 % en poids de fer (Fe) ;
éventuellement un ou plusieurs des éléments secondaires suivants :
de 0,05 à 1,5 % en poids de magnésium (Mg) ;
de 0,40 à 5,0 % en poids de cuivre (Cu) ;
de 0,25 à 5,0 % en poids de zinc (Zn) ; et
de 0,50 à 3,0 % en poids de nickel (Ni) ;
éventuellement 0,01 - 1,0 % en poids de chacun d'un ou plusieurs des éléments tertiaires
suivants : manganèse (Mn), chrome (Cr), titane (Ti), strontium (Sr), sodium (Na),
et antimoine (Sb) ;
éventuellement de 0,001 à 0,03 % en poids de bore (B) ;
éventuellement de 0,001 à 0,03 % en poids de carbone (C) ;
au plus 0,25 % en poids de chacun d'un autre élément, avec la quantité combinée totale
de ces autres éléments n'excédant pas 0,50 % en poids ;
le reste étant de l'aluminium et des impuretés.
2. Alliage de fonderie d'aluminium selon la revendication 1, comprenant de 0,03 à 0,12
% en poids de V.
3. Alliage de fonderie d'aluminium selon la revendication 1, comprenant de 0,05 à 0,10
% en poids de V.
4. Alliage de fonderie d'aluminium selon l'une quelconque des revendications 1-3, comprenant
au plus 0,05 % en poids de fer.
5. Alliage de fonderie d'aluminium selon l'une quelconque des revendications 1-4, comprenant
au moins 0,01 % en poids de fer.
6. Alliage de fonderie d'aluminium selon l'une quelconque des revendications 1-5, comprenant
de 6,0 à 9,0 % en poids de silicium.
7. Alliage de fonderie d'aluminium selon l'une quelconque des revendications 1-5, comprenant
de 6,5 à 8,5 % en poids de silicium.
8. Alliage de fonderie d'aluminium selon l'une quelconque des revendications 1-7, comprenant
de 0,01 à 0,8 % en poids de manganèse.
9. Alliage de fonderie d'aluminium selon l'une quelconque des revendications 1-8, comprenant
de 0,01 à 0,5 % en poids de chrome.
10. Alliage de fonderie d'aluminium selon l'une quelconque des revendications 1-9, comprenant
de 0,01 à 0,25 % en poids de titane.
11. Alliage de fonderie d'aluminium selon l'une quelconque des revendications 1-10, comprenant
de 0,001 à 0,1 % en poids de strontium.
12. Alliage de fonderie d'aluminium selon l'une quelconque des revendications 1-11, comprenant
de 0,001 à 0,1 % en poids de sodium.
13. Alliage de fonderie d'aluminium selon l'une quelconque des revendications 1-12, comprenant
de 0,001 à 0,1 % en poids d'antimoine.
14. Alliage de fonderie d'aluminium selon l'une quelconque des revendications 1-13, dans
lequel l'alliage comprend au plus 0,10 % en poids de chacun des autres éléments, avec
la quantité combinée totale de ces autres éléments n'excédant pas 0,35 % en poids.
15. Alliage de fonderie d'aluminium selon l'une quelconque des revendications 1-14, dans
lequel l'alliage réalise un espacement de bras dendritique secondaire (SDAS) de 1
micromètre à 100 micromètres.
REFERENCES CITED IN THE DESCRIPTION
This list of references cited by the applicant is for the reader's convenience only.
It does not form part of the European patent document. Even though great care has
been taken in compiling the references, errors or omissions cannot be excluded and
the EPO disclaims all liability in this regard.
Patent documents cited in the description