CA2871260C - Diecasting alloy based on al-si, comprising particularly secondary aluminium - Google Patents
Diecasting alloy based on al-si, comprising particularly secondary aluminium Download PDFInfo
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- CA2871260C CA2871260C CA2871260A CA2871260A CA2871260C CA 2871260 C CA2871260 C CA 2871260C CA 2871260 A CA2871260 A CA 2871260A CA 2871260 A CA2871260 A CA 2871260A CA 2871260 C CA2871260 C CA 2871260C
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 99
- 239000000956 alloy Substances 0.000 title claims abstract description 99
- 238000004512 die casting Methods 0.000 title claims abstract description 81
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 22
- 239000004411 aluminium Substances 0.000 title abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011572 manganese Substances 0.000 claims abstract description 44
- 239000010949 copper Substances 0.000 claims abstract description 37
- 239000011777 magnesium Substances 0.000 claims abstract description 37
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 32
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910018125 Al-Si Inorganic materials 0.000 claims abstract description 8
- 229910018520 Al—Si Inorganic materials 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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 claims abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 239000000356 contaminant Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 9
- 239000000470 constituent Substances 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 15
- 229910052725 zinc Inorganic materials 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- 229910019752 Mg2Si Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910018191 Al—Fe—Si Inorganic materials 0.000 description 1
- 229910015136 FeMn Inorganic materials 0.000 description 1
- 229910019089 Mg-Fe Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 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
- 238000009864 tensile test Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/002—Castings of light metals
- B22D21/007—Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
-
- 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
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
- C22C21/04—Modified aluminium-silicon alloys
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mounting, Exchange, And Manufacturing Of Dies (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Extrusion Of Metal (AREA)
- Conductive Materials (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
A diecasting alloy based on Al-Si, comprising especially secondary aluminium, is disclosed. In order to be able to meet high demands on strength, ductility and corrosion resistance, it is proposed that the diecasting alloy comprise 6 to 12% by weight of silicon (Si), at least 0.3% by weight of iron (Fe), at least 0.25% by weight of manganese (Mn), at least 0.1% by weight of copper (Cu), 0.24 to 0.8% by weight of magnesium (Mg) and 0.40 to 1.5% by weight of zinc (Zn), and that the diecasting alloy comprise 50 to 300 ppm of strontium (Sr) and/or 20 to 250 ppm of sodium (Na) and/or 20 to 350 ppm of antimony (Sb), and at least one of the following constituents: titanium (Ti) to an extent of not more than 0.2% by weight; not more than 0.3% by weight of zirconium; not more than 0.3% by weight of vanadium (V); and as the remainder aluminium and unavoidable impurities resulting from the production, where the total content of Fe and Mn in the diecasting alloy together is not more than 1.5% by weight, the quotient of the percentages by weight of Fe and Mn is 0.35 to 1.5, and the quotient of the percentages by weight of Cu and Mg is 0.2 to 0.8.
Description
, CA 02871260 2014-10-21 , , Diecasting Alloy Based on Al-Si, Comprising Particularly Secondary Aluminium Technical Field The invention relates to a die-casting alloy on the basis of Al-Si, particularly having secondary aluminum.
State of the Art Inexpensive die-casting alloys can be obtained from scrap aluminum, for example, but generally contain undesirably high levels of contaminants in the form of iron, copper, and zinc alloy components, in disadvantageous manner (EP1111077A1). This not only leads to reduced ductility potential, but rather can also have negative influences on strength as well as quenching sensitivity of the die-casting alloy. The most varied measures for reciprocal weighting of the alloy elements, as well as diverse suggestions for additives are known from the state of the art - particularly in order to thereby compensate for the negative influences of the contaminants.
. CA 02871260 2014-10-21
State of the Art Inexpensive die-casting alloys can be obtained from scrap aluminum, for example, but generally contain undesirably high levels of contaminants in the form of iron, copper, and zinc alloy components, in disadvantageous manner (EP1111077A1). This not only leads to reduced ductility potential, but rather can also have negative influences on strength as well as quenching sensitivity of the die-casting alloy. The most varied measures for reciprocal weighting of the alloy elements, as well as diverse suggestions for additives are known from the state of the art - particularly in order to thereby compensate for the negative influences of the contaminants.
. CA 02871260 2014-10-21
2 For example, a die-casting alloy having 5 to 13 wt.-% Si, having maximally 0.5 wt.-% Mg, having 0.1 to 1.0 wt.-% Mn, and having 0.1 to 2.0 wt.-% Fe is known from JP9-003610. In this connection, Mn is supposed to suppress the formation of Al-Fe-Si needle crystals, for example, in order to prevent a reduction in strength. Furthermore, in order to obtain the casting properties, Mg is supposed to be kept to a content as low as possible, maximally 0.5 wt.-%. Cu and Zn contaminants, as these usually occur in significant amounts in the case of secondary aluminum, are not taken into consideration by the die-casting alloy in JP9-003610.
DE102004013777B4 proposes a die-casting alloy having 5 to 18 wt.-% Si, having 0.15 to 0.45 wt.-% Mn, having 0.2 to 0.6 wt.-%
Fe, having 0.3 to 0.5 wt.-% Mg, possibly having 0.1 to 0.5 wt.-%
Cu, and having 4 to 5 wt.-% Zn. The content of maximally 0.5 wt.-% magnesium is supposed to prevent the formation of Mg-Fe "pi" phases, in order to thereby obtain stretchability. Cu is supposed to improve the heat strength of the alloy, whereby the content of zinc is supposed to be restricted to 4 to 5 wt.-%, in order to thereby adjust the strength and quenching sensitivity of the alloy. However, it is disadvantageous that such a composition of alloy elements can demonstrate low corrosion
DE102004013777B4 proposes a die-casting alloy having 5 to 18 wt.-% Si, having 0.15 to 0.45 wt.-% Mn, having 0.2 to 0.6 wt.-%
Fe, having 0.3 to 0.5 wt.-% Mg, possibly having 0.1 to 0.5 wt.-%
Cu, and having 4 to 5 wt.-% Zn. The content of maximally 0.5 wt.-% magnesium is supposed to prevent the formation of Mg-Fe "pi" phases, in order to thereby obtain stretchability. Cu is supposed to improve the heat strength of the alloy, whereby the content of zinc is supposed to be restricted to 4 to 5 wt.-%, in order to thereby adjust the strength and quenching sensitivity of the alloy. However, it is disadvantageous that such a composition of alloy elements can demonstrate low corrosion
3 resistance, particularly because of the comparatively high zinc content, and this can lead to restrictions of the die-cast parts produced from it, in terms of safety technology.
Furthermore, a die-casting alloy having 9 to 11 wt.-% Si, having maximally 0.6 wt.-% Fe, having 0.2 to 0.6 wt.-% Mn, having 0.05 to 0.4 wt.-% Cu, having 0.2 to 0.35 wt.-% Mg, and having maximally 0.35 wt.-% Zn, is known from DE102009012073A1. It is true that DE102009012073A1 concerns itself with secondary aluminum - because of the lower limits of permissible Cu and Zn contents, which are set to be comparatively low, the bandwidth of secondary aluminum that can be used is comparatively restricted. Furthermore, such a composition cannot allow comparatively great strength, ductility, and castability, particularly since Zn as a contaminant is supposed to be limited to a small value. Something similar is also known from 13E102005061668A1, according to which the Zn content in the die-casting alloy is to be kept to below 0.05 wt.-%.
Presentation of the Invention It is therefore the task of the invention to create a die-casting alloy on the basis of Al-Si, proceeding from the state
Furthermore, a die-casting alloy having 9 to 11 wt.-% Si, having maximally 0.6 wt.-% Fe, having 0.2 to 0.6 wt.-% Mn, having 0.05 to 0.4 wt.-% Cu, having 0.2 to 0.35 wt.-% Mg, and having maximally 0.35 wt.-% Zn, is known from DE102009012073A1. It is true that DE102009012073A1 concerns itself with secondary aluminum - because of the lower limits of permissible Cu and Zn contents, which are set to be comparatively low, the bandwidth of secondary aluminum that can be used is comparatively restricted. Furthermore, such a composition cannot allow comparatively great strength, ductility, and castability, particularly since Zn as a contaminant is supposed to be limited to a small value. Something similar is also known from 13E102005061668A1, according to which the Zn content in the die-casting alloy is to be kept to below 0.05 wt.-%.
Presentation of the Invention It is therefore the task of the invention to create a die-casting alloy on the basis of Al-Si, proceeding from the state
4 of the art described initially, which alloy can allow die-cast parts that meet great demands with regard to strength, ductility, and chemical reaction resistance, particularly corrosion resistance, despite the use of secondary aluminum.
Furthermore, this die-casting alloy is supposed to be able to ensure not only complex forming, in terms of die-casting technology, but also excellent demoldability, and offer excellent processability for the components produced from it.
The invention accomplishes the stated task in that the die-casting alloy contains 6 to 12 wt.-% silicon (Si), at least 0.3 wt.-% iron (Fe), at least 0.25 wt.-% manganese (Mn), at least 0.1 wt.-% copper (Cu), 0.24 to 0.8 wt.-% magnesium (Mg) and 0.40 to 1.5 wt.-% zinc (Zn), and that the die-casting alloy contains 50 to 300 ppm strontium (Sr) and/or 20 to 250 ppm sodium (Na) and/or 20 to 350 ppm antimony (Sb), as well as at least one of the following components, at maximally 0.2 wt.-% titanium (Ti);
=
maximally 0.3 wt.-% zirconium;
maximally 0.3 wt.-% vanadium (V);
and aluminum as the remainder, as well as production-related unavoidable contaminants, wherein the total proportion of Fe and Mn in the die-casting alloy, together, amounts to maximally 1.5 wt.-%, the quotient of the weight percents of Fe and Mn amounts to 0.35 to 1.5, and the quotient of the weight percents of Cu and Mg amounts to 0.2 to 0.8.
By means of permitting comparatively high wt.-% contaminants, as is also proposed, according to the invention, for iron, copper, and zinc, a cost-advantageous die-casting alloy on the basis of Al-Si can be made available, because essentially, the proportion of primary aluminum is reduced or actually dispensed with, and thereby secondary aluminum can be used to a greater extent for the production of cast parts. However, this only becomes possible in that the alloy components of the casting alloy are forced to remain within certain content limits, according to the invention, in order to thereby approach the parameters known for primary aluminum (for example strength values, ductility values, chemical reaction resistance, processability and/or castability).
, CA 02871260 2014-13-21 Fe, Mn:
For example, a quotient of weight percents of Fe and Mn of 0.35 to 1.5 can lead to the result that despite a comparatively high iron content, the formation of the p phase (for example A15FeS1/A18.9Fe2Si2) in the structure, which precipitates in the form of fine needles, can be clearly reduced. An increasing occurrence of the a phase can be expected, which can be present due to the manganese content, according to the invention, of at least 0.25 wt.-%, as A115(FeMn)3Si2. This a phase crystallizes in globulite form, and because of its compact structure can have a clearly more advantageous influence on the ductility than is known for the needle-shaped p phases. A die-casting alloy having comparatively great ductility can be ensured in this way.
In general, however, it should still be mentioned that because of this ratio of Fe/Mn, in combination with great cooling speeds (for example by means of accelerated cooling), its phases and thereby its influence on the structure can be kept comparatively low. If, in addition, the total proportion of Fe and Mn in the die-casting alloy is restricted to maximally 1.5 wt.-%, the formation of coarse a phases can also be further reduced, even if the high cooling speeds that are usually carried out in die-casting methods are applied. The concentration provisions ' CA 02871260 2014-10-21 ..
regarding Fe and Mn can therefore be beneficial for the ductility of the die-casting alloy, in particular.
Cu, Mg:
By means of introduction and/or adjustment of a magnesium excess, in that the quotient of the weight percents of Cu and Mg amounts to 0.2 and 0.8, and taking into consideration that at least 0.1 wt.-% Cu and 0.24 to 0.8 wt.-% Mg are provided, the copper present can essentially be bound in the Q phase (Al5Cu2Mg8Si6) that preferentially forms. This concentration provision can therefore prevent the formation of phases susceptible to corrosion, such as, for example, the tao phase (A15Cu4Zn) or the theta phase (Al2Cu) in the structure, so that despite comparatively high weight percents of Cu, which fact is utilized, according to the invention, for improving the heat hardening of the die-casting alloy, great corrosion resistance can also be maintained. Furthermore, because of this magnesium excess, the hardening mechanism of the alloy can be improved, because part of the Mg is bound in the Q phase (A15Cu2Mg8Si6), and thereby limits known in this regard, which occur as the result of excessive precipitation of Mg2Si pre-phases, can be overcome.
The concentration provisions concerning Cu and Mg can therefore satisfy particularly great demands of the die-casting alloy with regard to strength and chemical reaction resistance.
Furthermore, improved processability, for example with regard to the weldability and rivetability of components composed of this die-casting alloy, can be achieved by means of the proposed concentration ratio of Cu and Mg.
Mg, Fe, Mn:
Furthermore, it was possible to determine that the introduction and/or adjustment of the aforementioned magnesium excess with regard to Cu can also be utilized to bind the increased Fe content of the die-casting alloy in a pi phase (A18FeMg3Si6). In this way, on the one hand it was possible to reduce the phase (for example A15FeSi/A18.9Fe2Si2), which impairs ductility, because less Fe is available for formation of this p phase, but in particular, on the other hand, it was also possible to reduce the Mn content in the die-casting alloy, because the pi phase (for example A18FeMg3Si6) can be used for absorption of Fe. Die-casting problems, which generally have to be accepted as the result of a increased Mn content for compensation of Fe effects, can thereby be reduced. Complex forming and also excellent demoldability can be ensured by means of the particular content limits of Mg, Fe, Mn, in combination with their concentration provisions.
. CA 02871260 2014-13-21 Zn:
The strength of the alloy, determined, for example, by means of an interaction of the pre-phases Mg2Si and the Q phase (A15Cu2Mg8Si6), can be further improved by means of mixed crystal hardening, using embedded zinc. For this purpose, zinc must be adjusted within the content limits of 0.40 to 1.5 wt.-%.
Furthermore, this can be beneficial for the ductility of the die-casting alloy. In this way, a possible negative influence of a comparatively high Mg content on the ductility of the die-casting alloy can be reduced. Furthermore, the content limits of Zn, according to the invention, can distinguish themselves in the improvement in castability of the die-casting alloy, thereby making it possible to compensate impairments, in this regard, to a great extent, on the basis of the proposed content limits of Mn in the die-casting alloy.
The die-casting alloy on the basis of Al-Si, which is balanced in terms of the alloy components Fe, Mn, Cu, Mg, and Zn, can therefore combine comparatively great ductility, corrosion resistance, strength, castability, and processability with one another, and thereby overcome parameter limits known from the state of the art, even if the die-casting alloy contains ' CA 02871260 2014-10-21 secondary aluminum and/or the latter is added to it, or comparatively high contents of contaminants are brought about thereby.
For purposes of permanent modification, the die-casting alloy can contain 50 to 300 ppm strontium (Sr) and/or 20 to 250 ppm sodium (Na) and/or 20 to 350 ppm antimony (Sb). Optionally, maximally 0.2 wt.-% titanium (Ti) and/or maximally 0.3 wt.-%
zirconium and/or maximally 0.3 wt.-% vanadium (V) can prove to be advantageous for grain refinement of the die-casting alloy.
The die-casting alloy can be supplemented to 100 wt.-%, in each instance, with Al, whereby this die-casting alloy can also contain process-related unavoidable contaminants. In general, it should be mentioned that the die-casting alloy can contain contaminants at maximally 0.1 wt.-% per contaminant, and at most 1 wt.-% in total.
For the sake of completeness, it should be mentioned that secondary aluminum is understood to be aluminum or an aluminum alloy obtained from scrap aluminum. Furthermore, for the same reason, it should be mentioned that the measurement unit ppm is understood to mean weight ppm.
Strength, ductility, processability, and chemical reaction resistance of the die-casting alloy can be further improved if this alloy contains 0.3 to 1.0 wt.-% iron (Fe), 0.25 to 1.0 wt.-% manganese (Mn), and 0.1 to 0.6 wt.-% copper (Cu).
If the die-casting alloy fulfills the order relation wt.-% Mg > 0.2 + 0.12 x (wt.-% Fe / wt.-% Mn) in terms of its composition, a simple method provision for increasing the proportion of the pi phase (for example A18FeMg3Si6) in the structure of the die-casting alloy can be present. Increased Fe components can be compensated in this way, thereby making it possible to maintain excellent castability of the die-casting alloy at a reduced Mn component.
Furthermore, this pi phase can be converted into an a phase, which is harmless for the required properties of the die-casting alloy, by means of solution annealing.
The die-casting alloy can be further improved with regard to the ductility, strength, and corrosion resistance that can be achieved for it if the total proportion of Fe and Mn in the die-casting alloy, together, amounts to maximally 1.2 wt.-%, the quotient of the weight percents of Fe and Mn amount to 0.5 to ' CA 02871260 2014-10-21 1.25, and the quotient of the weight percents of Cu and Mg amounts to 0.2 to 0.5.
If the die-casting alloy contains 9.5 to 11.5 wt.-% silicon (Si) and/or 0.35 to 0.6 wt.-% iron (Fe) and/or 0.3 to 0.75 wt.-%
manganese (Mn) and/or 0.1 to 0.4 wt.-% copper (Cu) and/or 0.24 to 0.5 wt.-% magnesium (Mg) and/or 0.40 to 1.0 wt.-% zinc (Zn), narrower limit ranges for a die-casting alloy on the basis of Al-Si, which is improved in terms of its mechanical strength and/or chemical resistance, occur. In general, it should be mentioned that by means of the proposed content of Si, the flow properties of the melt can be improved, and brittle primary silicon phases can be avoided. In this way, it can also be made possible to die-cast even comparatively thin-walled components.
For this purpose, 9.5 to 11.5 wt.-% silicon (Si) can prove to be particularly advantageous.
Way to Implement the Invention In the following, the invention will be explained in greater detail, using exemplary embodiments:
=
For proof of the effects achieved, thin-walled cast components were produced from different die-casting alloys, using the die-casting method. The compositions of the alloys investigated are listed in Table 1.
Alloy No. Composition Fe/Mn Cu/Mg 1 AlSil0Mn0.5Fe0.1Mg0.4 0.2 0 2 A1Si10Mn0.5Fe0.5Mg0.4Cu0.25Zn0.75 1 0.63 Table 1: Overview of alloys investigated The alloy 1 is a die-casting alloy composed of primary aluminum with a low degree of contamination. Alloy 2, in contrast, demonstrates a significant degree of contaminants of iron and copper alloy components, which can be introduced by secondary aluminum, for example.
The alloys or the die-cast parts or test bodies produced from them were subjected to T7 heat treatment with one hour at 460 C, solution annealing, quenching with water, and two hours of hot aging at 220 C. The finished test bodies were finally investigated with regard to their mechanical properties. For this purpose, the tensile strength Rm, the yield strength R0.2, and the elongation to rupture A5 were determined in a tensile test. The measurement values obtained are summarized in Table 2.
Alloy No. R0.2 [MPa] Rm [MPa] A5 [96]
1 155 230 14.3 2 160 240 13.8 Table 2: Mechanical characteristic values of the alloys investigated Studies of the die-casting alloy No. 2 showed that the formation of an undesirable beta phase during solidification can be avoided by means of the adjusted iron component and manganese content. The copper component can also be completely bound in the Q phase by means of a magnesium component, thereby achieving comparatively great corrosion resistance. On the basis of this combination of elements, increased strength and elongation to rupture of 13.8% can be achieved, despite the iron content of 0.5 wt.-%. The comparatively high zinc content leads to an increase in strength, without any negative influence on the mechanical properties.
. CA 02871260 2014-10-21 As can now be seen in a comparison of the two die-casting alloys 1 and 2 according to Table 2, these two alloys demonstrate similar mechanical properties, although alloy 2 has a clearly higher iron and copper content as compared with alloy 1.
It has therefore been shown that the concentration conditions proposed for a die-casting alloy according to the invention make it possible to ensure comparatively great ductility, corrosion resistance, strength, castability, and processability.
Furthermore, this die-casting alloy is supposed to be able to ensure not only complex forming, in terms of die-casting technology, but also excellent demoldability, and offer excellent processability for the components produced from it.
The invention accomplishes the stated task in that the die-casting alloy contains 6 to 12 wt.-% silicon (Si), at least 0.3 wt.-% iron (Fe), at least 0.25 wt.-% manganese (Mn), at least 0.1 wt.-% copper (Cu), 0.24 to 0.8 wt.-% magnesium (Mg) and 0.40 to 1.5 wt.-% zinc (Zn), and that the die-casting alloy contains 50 to 300 ppm strontium (Sr) and/or 20 to 250 ppm sodium (Na) and/or 20 to 350 ppm antimony (Sb), as well as at least one of the following components, at maximally 0.2 wt.-% titanium (Ti);
=
maximally 0.3 wt.-% zirconium;
maximally 0.3 wt.-% vanadium (V);
and aluminum as the remainder, as well as production-related unavoidable contaminants, wherein the total proportion of Fe and Mn in the die-casting alloy, together, amounts to maximally 1.5 wt.-%, the quotient of the weight percents of Fe and Mn amounts to 0.35 to 1.5, and the quotient of the weight percents of Cu and Mg amounts to 0.2 to 0.8.
By means of permitting comparatively high wt.-% contaminants, as is also proposed, according to the invention, for iron, copper, and zinc, a cost-advantageous die-casting alloy on the basis of Al-Si can be made available, because essentially, the proportion of primary aluminum is reduced or actually dispensed with, and thereby secondary aluminum can be used to a greater extent for the production of cast parts. However, this only becomes possible in that the alloy components of the casting alloy are forced to remain within certain content limits, according to the invention, in order to thereby approach the parameters known for primary aluminum (for example strength values, ductility values, chemical reaction resistance, processability and/or castability).
, CA 02871260 2014-13-21 Fe, Mn:
For example, a quotient of weight percents of Fe and Mn of 0.35 to 1.5 can lead to the result that despite a comparatively high iron content, the formation of the p phase (for example A15FeS1/A18.9Fe2Si2) in the structure, which precipitates in the form of fine needles, can be clearly reduced. An increasing occurrence of the a phase can be expected, which can be present due to the manganese content, according to the invention, of at least 0.25 wt.-%, as A115(FeMn)3Si2. This a phase crystallizes in globulite form, and because of its compact structure can have a clearly more advantageous influence on the ductility than is known for the needle-shaped p phases. A die-casting alloy having comparatively great ductility can be ensured in this way.
In general, however, it should still be mentioned that because of this ratio of Fe/Mn, in combination with great cooling speeds (for example by means of accelerated cooling), its phases and thereby its influence on the structure can be kept comparatively low. If, in addition, the total proportion of Fe and Mn in the die-casting alloy is restricted to maximally 1.5 wt.-%, the formation of coarse a phases can also be further reduced, even if the high cooling speeds that are usually carried out in die-casting methods are applied. The concentration provisions ' CA 02871260 2014-10-21 ..
regarding Fe and Mn can therefore be beneficial for the ductility of the die-casting alloy, in particular.
Cu, Mg:
By means of introduction and/or adjustment of a magnesium excess, in that the quotient of the weight percents of Cu and Mg amounts to 0.2 and 0.8, and taking into consideration that at least 0.1 wt.-% Cu and 0.24 to 0.8 wt.-% Mg are provided, the copper present can essentially be bound in the Q phase (Al5Cu2Mg8Si6) that preferentially forms. This concentration provision can therefore prevent the formation of phases susceptible to corrosion, such as, for example, the tao phase (A15Cu4Zn) or the theta phase (Al2Cu) in the structure, so that despite comparatively high weight percents of Cu, which fact is utilized, according to the invention, for improving the heat hardening of the die-casting alloy, great corrosion resistance can also be maintained. Furthermore, because of this magnesium excess, the hardening mechanism of the alloy can be improved, because part of the Mg is bound in the Q phase (A15Cu2Mg8Si6), and thereby limits known in this regard, which occur as the result of excessive precipitation of Mg2Si pre-phases, can be overcome.
The concentration provisions concerning Cu and Mg can therefore satisfy particularly great demands of the die-casting alloy with regard to strength and chemical reaction resistance.
Furthermore, improved processability, for example with regard to the weldability and rivetability of components composed of this die-casting alloy, can be achieved by means of the proposed concentration ratio of Cu and Mg.
Mg, Fe, Mn:
Furthermore, it was possible to determine that the introduction and/or adjustment of the aforementioned magnesium excess with regard to Cu can also be utilized to bind the increased Fe content of the die-casting alloy in a pi phase (A18FeMg3Si6). In this way, on the one hand it was possible to reduce the phase (for example A15FeSi/A18.9Fe2Si2), which impairs ductility, because less Fe is available for formation of this p phase, but in particular, on the other hand, it was also possible to reduce the Mn content in the die-casting alloy, because the pi phase (for example A18FeMg3Si6) can be used for absorption of Fe. Die-casting problems, which generally have to be accepted as the result of a increased Mn content for compensation of Fe effects, can thereby be reduced. Complex forming and also excellent demoldability can be ensured by means of the particular content limits of Mg, Fe, Mn, in combination with their concentration provisions.
. CA 02871260 2014-13-21 Zn:
The strength of the alloy, determined, for example, by means of an interaction of the pre-phases Mg2Si and the Q phase (A15Cu2Mg8Si6), can be further improved by means of mixed crystal hardening, using embedded zinc. For this purpose, zinc must be adjusted within the content limits of 0.40 to 1.5 wt.-%.
Furthermore, this can be beneficial for the ductility of the die-casting alloy. In this way, a possible negative influence of a comparatively high Mg content on the ductility of the die-casting alloy can be reduced. Furthermore, the content limits of Zn, according to the invention, can distinguish themselves in the improvement in castability of the die-casting alloy, thereby making it possible to compensate impairments, in this regard, to a great extent, on the basis of the proposed content limits of Mn in the die-casting alloy.
The die-casting alloy on the basis of Al-Si, which is balanced in terms of the alloy components Fe, Mn, Cu, Mg, and Zn, can therefore combine comparatively great ductility, corrosion resistance, strength, castability, and processability with one another, and thereby overcome parameter limits known from the state of the art, even if the die-casting alloy contains ' CA 02871260 2014-10-21 secondary aluminum and/or the latter is added to it, or comparatively high contents of contaminants are brought about thereby.
For purposes of permanent modification, the die-casting alloy can contain 50 to 300 ppm strontium (Sr) and/or 20 to 250 ppm sodium (Na) and/or 20 to 350 ppm antimony (Sb). Optionally, maximally 0.2 wt.-% titanium (Ti) and/or maximally 0.3 wt.-%
zirconium and/or maximally 0.3 wt.-% vanadium (V) can prove to be advantageous for grain refinement of the die-casting alloy.
The die-casting alloy can be supplemented to 100 wt.-%, in each instance, with Al, whereby this die-casting alloy can also contain process-related unavoidable contaminants. In general, it should be mentioned that the die-casting alloy can contain contaminants at maximally 0.1 wt.-% per contaminant, and at most 1 wt.-% in total.
For the sake of completeness, it should be mentioned that secondary aluminum is understood to be aluminum or an aluminum alloy obtained from scrap aluminum. Furthermore, for the same reason, it should be mentioned that the measurement unit ppm is understood to mean weight ppm.
Strength, ductility, processability, and chemical reaction resistance of the die-casting alloy can be further improved if this alloy contains 0.3 to 1.0 wt.-% iron (Fe), 0.25 to 1.0 wt.-% manganese (Mn), and 0.1 to 0.6 wt.-% copper (Cu).
If the die-casting alloy fulfills the order relation wt.-% Mg > 0.2 + 0.12 x (wt.-% Fe / wt.-% Mn) in terms of its composition, a simple method provision for increasing the proportion of the pi phase (for example A18FeMg3Si6) in the structure of the die-casting alloy can be present. Increased Fe components can be compensated in this way, thereby making it possible to maintain excellent castability of the die-casting alloy at a reduced Mn component.
Furthermore, this pi phase can be converted into an a phase, which is harmless for the required properties of the die-casting alloy, by means of solution annealing.
The die-casting alloy can be further improved with regard to the ductility, strength, and corrosion resistance that can be achieved for it if the total proportion of Fe and Mn in the die-casting alloy, together, amounts to maximally 1.2 wt.-%, the quotient of the weight percents of Fe and Mn amount to 0.5 to ' CA 02871260 2014-10-21 1.25, and the quotient of the weight percents of Cu and Mg amounts to 0.2 to 0.5.
If the die-casting alloy contains 9.5 to 11.5 wt.-% silicon (Si) and/or 0.35 to 0.6 wt.-% iron (Fe) and/or 0.3 to 0.75 wt.-%
manganese (Mn) and/or 0.1 to 0.4 wt.-% copper (Cu) and/or 0.24 to 0.5 wt.-% magnesium (Mg) and/or 0.40 to 1.0 wt.-% zinc (Zn), narrower limit ranges for a die-casting alloy on the basis of Al-Si, which is improved in terms of its mechanical strength and/or chemical resistance, occur. In general, it should be mentioned that by means of the proposed content of Si, the flow properties of the melt can be improved, and brittle primary silicon phases can be avoided. In this way, it can also be made possible to die-cast even comparatively thin-walled components.
For this purpose, 9.5 to 11.5 wt.-% silicon (Si) can prove to be particularly advantageous.
Way to Implement the Invention In the following, the invention will be explained in greater detail, using exemplary embodiments:
=
For proof of the effects achieved, thin-walled cast components were produced from different die-casting alloys, using the die-casting method. The compositions of the alloys investigated are listed in Table 1.
Alloy No. Composition Fe/Mn Cu/Mg 1 AlSil0Mn0.5Fe0.1Mg0.4 0.2 0 2 A1Si10Mn0.5Fe0.5Mg0.4Cu0.25Zn0.75 1 0.63 Table 1: Overview of alloys investigated The alloy 1 is a die-casting alloy composed of primary aluminum with a low degree of contamination. Alloy 2, in contrast, demonstrates a significant degree of contaminants of iron and copper alloy components, which can be introduced by secondary aluminum, for example.
The alloys or the die-cast parts or test bodies produced from them were subjected to T7 heat treatment with one hour at 460 C, solution annealing, quenching with water, and two hours of hot aging at 220 C. The finished test bodies were finally investigated with regard to their mechanical properties. For this purpose, the tensile strength Rm, the yield strength R0.2, and the elongation to rupture A5 were determined in a tensile test. The measurement values obtained are summarized in Table 2.
Alloy No. R0.2 [MPa] Rm [MPa] A5 [96]
1 155 230 14.3 2 160 240 13.8 Table 2: Mechanical characteristic values of the alloys investigated Studies of the die-casting alloy No. 2 showed that the formation of an undesirable beta phase during solidification can be avoided by means of the adjusted iron component and manganese content. The copper component can also be completely bound in the Q phase by means of a magnesium component, thereby achieving comparatively great corrosion resistance. On the basis of this combination of elements, increased strength and elongation to rupture of 13.8% can be achieved, despite the iron content of 0.5 wt.-%. The comparatively high zinc content leads to an increase in strength, without any negative influence on the mechanical properties.
. CA 02871260 2014-10-21 As can now be seen in a comparison of the two die-casting alloys 1 and 2 according to Table 2, these two alloys demonstrate similar mechanical properties, although alloy 2 has a clearly higher iron and copper content as compared with alloy 1.
It has therefore been shown that the concentration conditions proposed for a die-casting alloy according to the invention make it possible to ensure comparatively great ductility, corrosion resistance, strength, castability, and processability.
Claims (11)
1. Die-casting alloy on the basis of Al-Si, wherein the die-casting alloy contains 6 to 12 wt.-% silicon (Si), at least 0.3 wt.-% iron (Fe), at least 0.25 wt.-% manganese (Mn), at least 0.1 wt.-% copper (Cu), 0.24 to 0.8 wt.-% magnesium (Mg) and 0.40 to 1.5 wt.-% zinc (Zn), and that the die-casting alloy contains 50 to 300 ppm strontium (Sr) and/or 20 to 250 ppm sodium (Na) and/or 20 to 350 ppm antimony (Sb), as well as at least one of the following components, at maximally 0.2 wt.-% titanium (Ti);
maximally 0.3 wt.-% zirconium;
maximally 0.3 wt.-% vanadium (V);
and aluminum as the remainder, as well as production-related unavoidable contaminants, wherein the total proportion of Fe and Mn in the die-casting alloy, together, amounts to maximally 1.5 wt.-%, the quotient of the weight percents of Fe and Mn amount to 0.35 to 1.5, and the quotient of the weight percents of Cu and Mg amounts to 0.2 to 0.8.
maximally 0.3 wt.-% zirconium;
maximally 0.3 wt.-% vanadium (V);
and aluminum as the remainder, as well as production-related unavoidable contaminants, wherein the total proportion of Fe and Mn in the die-casting alloy, together, amounts to maximally 1.5 wt.-%, the quotient of the weight percents of Fe and Mn amount to 0.35 to 1.5, and the quotient of the weight percents of Cu and Mg amounts to 0.2 to 0.8.
2. Die-casting alloy according to claim 1, wherein the die-casting alloy contains secondary aluminum.
3. Die-casting alloy according to claim 1 or claim 2, characterized in that the die-casting alloy contains 0.3 to 1.0 wt.-% iron (Fe), 0.25 to 1.0 wt.-% manganese (Mn) and 0.1 to 0.6 wt.-% copper (Cu).
4. Die-casting alloy according to any one of claims 1 to 3, characterized in that the die-casting alloy fulfills the order relation wt.-% Mg > 0.2 + 0.12 x (wt.-% Fe / wt.-% Mn) in terms of its composition.
5. Die-casting alloy according to any one of claims 1 to 4, characterized in that the total proportion of Fe and Mn in the die-casting alloy, together, amounts to maximally 1.2 wt.-%, the quotient of the weight percents of Fe and Mn amounts to 0.5 to 1.25, and the quotient of the weight percents of Cu and Mg amounts to 0.2 to 0.5.
6. Die-casting alloy according to any one of claims 1 to 5, characterized in that the die-casting alloy contains 9.5 to 11.5 wt.-% silicon (Si).
7. Die-casting alloy according to any one of claims 1 to 6, characterized in that the die-casting alloy contains 0.35 to 0.6 wt.-% iron (Fe).
8. Die-casting alloy according to any one of claims 1 to 7, characterized in that the die-casting alloy contains 0.3 to 0.75 wt.-% manganese (Mn).
9. Die-casting alloy according to any one of claims 1 to 8, characterized in that the die-casting alloy contains 0.1 to 0.4 wt.-% copper (Cu).
10. Die-casting alloy according to any one of claims 1 to 9, characterized in that the die-casting alloy contains 0.24 to 0.5 wt.-% magnesium (Mg).
11. Die-casting alloy according to any one of claims 1 to 10, characterized in that the die-casting alloy contains 0.40 to 1.0 wt.-% zinc (Zn).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12165829.8A EP2657360B1 (en) | 2012-04-26 | 2012-04-26 | Pressure cast alloy on an Al-Si basis, comprising secondary aluminium |
| EP12165829.8 | 2012-04-26 | ||
| PCT/EP2013/057521 WO2013160108A2 (en) | 2012-04-26 | 2013-04-10 | Diecasting alloy based on al-si, comprising particularly secondary aluminium |
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| Publication Number | Publication Date |
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| CA2871260A1 CA2871260A1 (en) | 2013-10-31 |
| CA2871260C true CA2871260C (en) | 2020-09-22 |
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| CA2871260A Active CA2871260C (en) | 2012-04-26 | 2013-04-10 | Diecasting alloy based on al-si, comprising particularly secondary aluminium |
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| Country | Link |
|---|---|
| US (1) | US20150098859A1 (en) |
| EP (1) | EP2657360B1 (en) |
| CN (1) | CN104350165B (en) |
| CA (1) | CA2871260C (en) |
| ES (1) | ES2466345T3 (en) |
| PL (1) | PL2657360T3 (en) |
| SI (1) | SI2657360T1 (en) |
| WO (1) | WO2013160108A2 (en) |
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| CN105624479B (en) * | 2015-11-26 | 2017-10-03 | 新疆众和股份有限公司 | One kind welding Alar bar and its production method |
| EP3235916B1 (en) | 2016-04-19 | 2018-08-15 | Rheinfelden Alloys GmbH & Co. KG | Cast alloy |
| EP3235917B1 (en) | 2016-04-19 | 2018-08-15 | Rheinfelden Alloys GmbH & Co. KG | Alloy for pressure die casting |
| US20180010214A1 (en) * | 2016-07-05 | 2018-01-11 | GM Global Technology Operations LLC | High strength high creep-resistant cast aluminum alloys and hpdc engine blocks |
| ES2753168T3 (en) | 2016-12-28 | 2020-04-07 | Befesa Aluminio S L | Aluminum alloy for casting |
| ES2753167T3 (en) | 2016-12-28 | 2020-04-07 | Befesa Aluminio S L | Aluminum alloy for casting |
| EP3342889B1 (en) | 2016-12-28 | 2019-05-29 | Befesa Aluminio, S.L. | Aluminium casting alloy |
| EP3607103B1 (en) * | 2017-04-05 | 2021-06-02 | AMAG casting GmbH | Additive production method, and starting material for same |
| CN107858565A (en) * | 2017-12-13 | 2018-03-30 | 浙江诺达信汽车配件有限公司 | A kind of aluminium diecasting alloy material of high-strength and high-ductility |
| CN111139371A (en) * | 2018-11-06 | 2020-05-12 | 临沂利信铝业有限公司 | Preparation method and equipment of green low-cost regenerated aluminum alloy |
| CN110106458B (en) * | 2019-04-30 | 2020-06-19 | 中国科学院合肥物质科学研究院 | Heat treatment method of forged manganese-copper vibration damping alloy |
| CN110541094A (en) * | 2019-09-30 | 2019-12-06 | 中信戴卡股份有限公司 | Die-casting aluminum alloy and automobile part |
| US20220341005A1 (en) * | 2019-10-01 | 2022-10-27 | Ahresty Corporation | Aluminum alloy diecast, diecast unit and method for producing same |
| CN111004947B (en) * | 2019-11-25 | 2020-12-22 | 连云港星耀材料科技有限公司 | Preparation method of aluminum alloy hub |
| EP3825428B1 (en) * | 2019-11-25 | 2022-11-16 | AMAG casting GmbH | Die cast component and method for producing a die cast component |
| DE102020100688A1 (en) * | 2020-01-14 | 2021-07-15 | Audi Aktiengesellschaft | Method for producing a motor vehicle rim from an aluminum alloy for a wheel of a motor vehicle and corresponding motor vehicle rim |
| US20230002863A1 (en) * | 2021-07-02 | 2023-01-05 | Magna International Inc. | Low cost high ductility cast aluminum alloy |
| CN115161521B (en) * | 2022-07-14 | 2023-09-08 | 山西瑞格金属新材料有限公司 | Heat treatment-free die-casting aluminum-silicon-zinc alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH093610A (en) | 1995-06-15 | 1997-01-07 | Nippon Light Metal Co Ltd | Thin aluminum diecast product excellent in dimensional accuracy and ductility and its production |
| EP1111077A1 (en) | 1999-12-24 | 2001-06-27 | ALUMINIUM RHEINFELDEN GmbH | Aluminium alloy produced from scrap metal and casting alloy so produced |
| CN1555423A (en) * | 2001-07-25 | 2004-12-15 | �Ѻ͵繤��ʽ���� | Aluminum alloy excellent in machinability, and aluminum alloy material and method for production thereof |
| DE102004013777B4 (en) | 2004-03-20 | 2005-12-29 | Hydro Aluminium Deutschland Gmbh | Method for producing a cast part from an AL / Si casting alloy |
| JP2006183122A (en) | 2004-12-28 | 2006-07-13 | Denso Corp | Aluminum alloy for die casting and method for producing aluminum alloy casting |
| US9353429B2 (en) * | 2007-02-27 | 2016-05-31 | Nippon Light Metal Company, Ltd. | Aluminum alloy material for use in thermal conduction application |
| CN101363091B (en) * | 2008-09-08 | 2010-06-02 | 营口华润有色金属制造有限公司 | High-silicon aluminum alloy and method for preparing same |
| DE102009012073B4 (en) | 2009-03-06 | 2019-08-14 | Andreas Barth | Use of an aluminum casting alloy |
| JP2011208253A (en) * | 2010-03-30 | 2011-10-20 | Honda Motor Co Ltd | Aluminum die-cast alloy for vehicle material |
| US20120027639A1 (en) * | 2010-07-29 | 2012-02-02 | Gibbs Die Casting Corporation | Aluminum alloy for die casting |
-
2012
- 2012-04-26 PL PL12165829T patent/PL2657360T3/en unknown
- 2012-04-26 SI SI201230032T patent/SI2657360T1/en unknown
- 2012-04-26 ES ES12165829.8T patent/ES2466345T3/en active Active
- 2012-04-26 EP EP12165829.8A patent/EP2657360B1/en active Active
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2013
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- 2013-04-10 CN CN201380022231.6A patent/CN104350165B/en active Active
- 2013-04-10 WO PCT/EP2013/057521 patent/WO2013160108A2/en active Application Filing
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| CN104350165B (en) | 2017-06-16 |
| WO2013160108A2 (en) | 2013-10-31 |
| PL2657360T3 (en) | 2014-09-30 |
| EP2657360B1 (en) | 2014-02-26 |
| SI2657360T1 (en) | 2014-07-31 |
| WO2013160108A3 (en) | 2013-12-19 |
| EP2657360A1 (en) | 2013-10-30 |
| CA2871260A1 (en) | 2013-10-31 |
| CN104350165A (en) | 2015-02-11 |
| US20150098859A1 (en) | 2015-04-09 |
| ES2466345T3 (en) | 2014-06-10 |
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