EP1902150B1 - Alliages d'aluminium à résistance élevée et procédé de fabrication correspondant - Google Patents
Alliages d'aluminium à résistance élevée et procédé de fabrication correspondant Download PDFInfo
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- EP1902150B1 EP1902150B1 EP06849740.3A EP06849740A EP1902150B1 EP 1902150 B1 EP1902150 B1 EP 1902150B1 EP 06849740 A EP06849740 A EP 06849740A EP 1902150 B1 EP1902150 B1 EP 1902150B1
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- 238000000034 method Methods 0.000 title claims description 16
- 229910000838 Al alloy Inorganic materials 0.000 title claims description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 87
- 239000000956 alloy Substances 0.000 claims description 87
- 229910052706 scandium Inorganic materials 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 229910052726 zirconium Inorganic materials 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000005496 eutectics Effects 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 241000288673 Chiroptera Species 0.000 claims description 2
- 238000005242 forging Methods 0.000 claims description 2
- 239000010949 copper Substances 0.000 description 25
- 239000011777 magnesium Substances 0.000 description 17
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 13
- 239000011701 zinc Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910018569 Al—Zn—Mg—Cu Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000005275 alloying Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 238000003483 aging Methods 0.000 description 2
- -1 aluminum-zinc-magnesium-copper Chemical compound 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910017539 Cu-Li Inorganic materials 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
Images
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
- C22C21/10—Alloys based on aluminium with zinc as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/053—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with zinc as the next major constituent
Definitions
- the present invention relates, in general, to a high strength aluminum alloy based on the Al-Zn-Mg-Cu alloy system and a process for forming the same.
- the alloys are particularly suited for use in sporting goods and aerospace applications.
- the highest strength aluminum alloys known at this time are based on the aluminum-zinc-magnesium-copper system. Such alloys are disclosed for instance in US 2005/0056353 A1
- Commercial high-strength alloys currently being produced include AA7055 (nominally 8% Zn-2% Mg-2.2% Cu-0.10% Zr), AA7068 (nominally 7.8% Zn-2.5% Mg-2.0% Cu-0.10% Zr) and a Kaiser Aluminum alloy designated K749 (nominally 8% Zn-2.2% Mg-1.8% Cu-0.14% Zr). From the published phase relationships at 860°F for an alloy containing 8% Zn, one can note that K749 is near a phase boundary, while the other two alloys are in multiple phase fields.
- the present invention addresses the foregoing need in a number of ways. More particularly, there are three distinct avenues for increasing an alloy's strength while maintaining its toughness: rich alloy chemistries; processing to maximize alloying effectiveness; and preventing recrystallization. Rich alloys provide more solute, which is potentially available for age hardening to higher strength levels; effective processing ensures that the solute is available for strengthening and not out of solution as second phases, which detract from fracture toughness; and maintaining an unrecrystallized microstructure optimizes both strength and toughness.
- the present invention comprises aluminum alloys based on the Al-Zn-Mg-Cu alloy system that preferably include high levels of zinc and copper, but modest levels of magnesium. As an option, small amounts of scandium can also be employed to prevent recrystallization.
- Each of the alloys preferably includes at least 8.5% Zn and 2.25% Cu by weight. Higher levels of each of these elements up to about 10.5% Zn and 3.0% Cu can be used. However, modestly lower amounts of Mg (max 1.85%) are preferably used to allow higher levels of the Cu.
- the ranges of all elements in the alloys include by weight, 8.5-10.5% Zn, 1.4-1.85 % Mg, 2.25-3.0% Cu, and at least one element from the group Zr, V, or Hf not exceeding about 0.5%, the balance substantially aluminum and incidental impurities.
- 0., optionally 0.03-0.10% Si and 0.03-0.12% Fe is also included in the alloys to prevent recrystallization.
- toughness decreases as the total weight percentage of magnesium and copper increases. Experiments have established that the ideal range of these two elements be between 4.1 and 4.5% combined. Still further, the total weight percent of Zn, Cu and Mg is ideally between 13.0 and 14.5%.
- a homogenization process is preferably employed after alloy ingot casting in which a slow rate of temperature increase is employed as the alloy is heated as near as possible to its melting temperature.
- the rate of increase is limited to 20°F/hr. or less to minimize the amount of low melting point eutectic phases and thereby further enhance fracture toughness of the alloy.
- the product is exposed to a temperature range of 175-310 degrees F for 3 to 30 hours.
- the first step is followed by heating at 310 to 360 degrees F for 2 to 24 hours.
- the product is heated at 175 to 300 degrees F for 1 to 30 hours.
- the second and third aging steps can be used without the first aging step.
- the foregoing alloys and processing operations enhance the properties of the Al-Zn-Mg-Cu alloy system, such that they can be more effectively employed in numerous applications.
- Specific products or items in which the subject alloys can be employed include, among others, sporting goods including baseball and soft ball bats, golf shafts, lacrosse sticks, tennis rackets, and arrows; and aerospace application including aerospace components such as wing plates, bulkheads, fuselage stringers, and structural extrusions and forgings; and ordnance parts such as sabots and missile launchers.
- a heretofore unexplored region of the Al-Zn-Mg-Cu alloy system consists of compositions comprising about 9% to 10% zinc, 2.2% to 2.8% copper, and 1.6% to 2.0% magnesium.
- the alloy compositions listed in Table 1 were cast as 9-in. diameter billets: note that all these alloys contain about 0.05% scandium, an element which in combination with zirconium is effective in preventing recrystallization. Table 1.
- the billets were homogenized at 880F (F means degrees Fahrenheit) and extruded to seamless 4-in. diameter tubes with a 0.305 in. wall thickness.
- the extrusions were solution heat treated at 880F, quenched in cold water and "peak” aged to the T6 temper (24-hr soak at 250F). They were tested for tensile properties in the longitudinal direction and sections from all of the extrusions were cut and flattened to pieces about 12" square, which were also solution heat treated at 880F, quenched in cold water and peak aged. These flattened sections were tested for fracture toughness (ASTM B645) in the T-L orientation. The tensile and fracture toughness properties are listed in Table 2. Table 2.
- FIG. 1 shows how the compositions listed in Table 1 relate to the magnesium and copper solubility limits at 885F for alloys containing a nominal zinc level of 9%.
- compositions lying below the demarcation line between the solid solution and the Al + S phase regions are single phase alloys, which have superior fracture toughness values for a given strength level, compared to those in the 2-phase region.
- the best combinations of strength and toughness are associated with alloys near the solvus line, which is why the 2.7% Cu/1.9% Mg composition has a relatively low toughness level.
- the preferred compositions therefore lie within the dashed lines that run approximately parallel to the solvus. These relationships are defined by controlling the total copper plus magnesium concentrations between 4.1% and 4.5%.
- a tube from composition #213 when drawn to a tube 2.625" in diameter with a 0.110" wall thickness and aged by a 2-step practice of 8 hr at 250F plus 4 hr at 305F had yield and tensile strengths of 100.9 ksi and 102.6 ksi, respectively.
- the subject alloy can be over aged beyond peak strength in a second step at temperatures in the 310-360F temperature range for 2 to 24 hours to provide a desirable combination of strength and corrosion resistance.
- Another preferred embodiment includes a final aging treatment in a third step at a lower temperature in the range 175-300F for 1 to 30 hours, which provides an additional strength benefit with no loss in corrosion properties.
- the alloy can be subjected only to the aforementioned second and third aging steps by skipping the first step.
- FIG. 4 compares the toughness levels of these alloys on the basis of Mg/Cu ratio with the invention alloys, using those compositions that have similar strength levels (93-95 ksi) and total Mg + Cu contents (4.0-4.2%).
- Alloys of the compositions listed in the following table were prepared as 5" diameter billets, which were processed as described below. Although the sample alloys contained more Mg and less Cu than the preferred alloys discussed previously, it is believed that the effect of Sc addition to the alloys would be essentially the same for the preferred alloys. % by wt. Alloy No. Si Fe Cu Mg Zn Zr Sc A 0.03 0.04 1.95 2.20 8.07 0.11 0.00 B 0.03 0.05 1.86 2.17 8.05 0.00 0.22 C 0.03 0.05 1.89 2.18 8.09 0.11 0.06 D 0.03 0.04 1.84 2.12 8.11 0.12 0.11 E 0.03 0.05 1.95 2.18 8.08 0.11 0.22
- the ingots were homogenized at 875F using a 50F/hr heating rate and air cool, and then reheated to 800F and extruded to a 0.25" by 3" flat bar. Sections of each extrusion were annealed at 775F for 3 hr, cooled 50F/hr to 450F, held 4 hr and cooled 50F/hr to room temperature. The sections were then cold rolled to 0.040" sheet using five pass reductions (84% total reduction). The sheets were solution heat treated at 885F for 30 min, quenched in cold water, and then aged to the peak strength condition (10 hr at 305F).
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Extrusion Of Metal (AREA)
- Forging (AREA)
- Golf Clubs (AREA)
- Contacts (AREA)
- Conductive Materials (AREA)
Claims (18)
- Produit en alliage d'aluminium ayant une résistance élevée et une bonne dureté, contenant en poids, de 8,5 à 10,5 % de Zn, de 1,4 à 1,85 % de Mg, de 2,25 à 3,0 % de Cu, et au moins un élément du groupe Zr, V, ou Hf n'excédant pas 0,5 %, éventuellement de 0,05 à 0,30 % de Sc, éventuellement de 0,03 à 0,10 % de Si et de 0,03 à 0,12 % de Fe, le reste étant de l'aluminium et des impuretés incidentes.
- Produit en alliage selon la revendication 1, dans lequel ledit alliage contient de 0,05 à 0,2 % de Zr.
- Produit en alliage selon la revendication 1, dans lequel ledit alliage contient de 0,05 à 0,30 % de Sc.
- Produit en alliage selon la revendication 3, dans lequel ledit alliage contient de 0,05 à 0,20 % de Zr.
- Produit en alliage selon la revendication 1, dans lequel ledit alliage contient de 0,03 à 0,10 % de Si et de 0,03 à 0,12 % de Fe.
- Produit en alliage selon la revendication 1, dans lequel les pourcentages en poids combinés de Mg et Cu sont dans la plage de 4,1 à 4,5 %.
- Produit en alliage selon la revendication 6, dans lequel les pourcentages en poids combinés de Zn, Mg et Cu sont dans la plage de 13,0 à 14,5 %.
- Produit en alliage d'aluminium selon la revendication 1, dans lequel ledit produit est choisi dans le groupe comprenant les articles de sport tels que les battes de baseball et de softball, les clubs de golf, les bâtons de jeu de crosse, les raquettes de tennis, et les flèches ; les composants pour l'industrie aérospatiale tels que les plaques d'ailes, les cloisons étanches, les raidisseurs de fuselage, et les extrusions et les pièces forgées structurales ; et les pièces d'artillerie telles que les sabots et les lanceurs de missiles.
- Procédé de fabrication d'un produit en alliage d'aluminium contenant de 8,5 à 10,5 % de Zn, de 1,4 à 1,85 % de Mg, de 2,25 à 3,0 % de Cu, et au moins un élément du groupe Zr, V, ou Hf n'excédant pas 0,5 %, éventuellement de 0,05 à 0,30 % de Sc, le reste étant de l'aluminium et des impuretés incidentes, ledit procédé comprenant les étapes de :coulage dudit produit en alliage pour former un lingot en alliage ; ethomogénéisation dudit lingot en alliage pour réduire au minimum la quantité de phases eutectiques à bas points de fusion par chauffage dudit lingot à une vitesse de chauffage inférieure ou égale à 11,11 °K/h (20 °F/h) depuis une première température au moins 11,11 °K (20 °F) au-dessous de la température de fusion dudit lingot jusqu'à une seconde température environ 2,78 °K (5 °F) au-dessous de ladite température de fusion.
- Procédé selon la revendication 9, dans lequel ladite première température est 272,04 °K (30 °F) au-dessous de ladite température de fusion.
- Procédé selon la revendication 9, dans lequel ladite première température est choisie pour être de 738,71 °K (870 °F) et ladite seconde température est choisie pour être dans la plage de 747,04 à 749,82 °K (885 à 890 °F).
- Procédé selon la revendication 9 dans lequel le lingot en alliage est maintenu à ladite première température pendant au moins 8 heures.
- Procédé selon la revendication 9, dans lequel ledit alliage contient de 0,05 à 0,30 % de Sc.
- Procédé selon la revendication 9, dans lequel ledit lingot en alliage est formé en fonction de la forme du produit fini, soumis à un traitement thermique de mise en solution de 738,71 à 755,37 degrés K (870 à 900 degrés F) puis artificiellement vieilli dans une première étape de vieillissement par chauffage de 352,59 à 427,59 degrés K (175 à 310 degrés F) pendant 3 à 30 heures.
- Procédé selon la revendication 14, dans lequel ledit produit est exposé à une deuxième étape de vieillissement par chauffage de 427,59 à 455,37 degrés K (310 à 360 degrés F) pendant 2 à 24 heures.
- Procédé selon la revendication 15, dans lequel ledit produit en alliage est exposé à une troisième étape de vieillissement par chauffage de 352,59 à 422,39 degrés K (175 à 300 degrés F) pendant 1 à 30 heures.
- Procédé selon la revendication 9, dans lequel ledit lingot en alliage est formé en fonction de la forme du produit fini, soumis à un traitement thermique de mise en solution puis artificiellement vieilli dans une première étape de vieillissement par chauffage de 427,59-455,37 degrés K (310 à 360 degrés F) pendant 2 à 24 heures.
- Procédé selon la revendication 17, dans lequel ledit produit en alliage est exposé à une seconde étape de vieillissement par chauffage de 352,59 à 422,39 degrés K (175 à 300 degrés F) pendant 1 à 30 heures.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SI200632270T SI1902150T1 (en) | 2005-03-24 | 2006-03-22 | Aluminum alloys of high strength and process for their manufacture |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/087,733 US20060213591A1 (en) | 2005-03-24 | 2005-03-24 | High strength aluminum alloys and process for making the same |
PCT/US2006/010684 WO2007102831A1 (fr) | 2005-03-24 | 2006-03-22 | Alliages d'aluminium à résistance élevée et procédé de fabrication correspondant |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1902150A1 EP1902150A1 (fr) | 2008-03-26 |
EP1902150A4 EP1902150A4 (fr) | 2016-09-07 |
EP1902150B1 true EP1902150B1 (fr) | 2018-06-20 |
Family
ID=37033998
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06849740.3A Revoked EP1902150B1 (fr) | 2005-03-24 | 2006-03-22 | Alliages d'aluminium à résistance élevée et procédé de fabrication correspondant |
Country Status (5)
Country | Link |
---|---|
US (2) | US20060213591A1 (fr) |
EP (1) | EP1902150B1 (fr) |
CN (1) | CN101193839B (fr) |
SI (1) | SI1902150T1 (fr) |
WO (1) | WO2007102831A1 (fr) |
Families Citing this family (18)
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US9068252B2 (en) * | 2009-03-05 | 2015-06-30 | GM Global Technology Operations LLC | Methods for strengthening slowly-quenched/cooled cast aluminum components |
US8636855B2 (en) | 2009-03-05 | 2014-01-28 | GM Global Technology Operations LLC | Methods of enhancing mechanical properties of aluminum alloy high pressure die castings |
US9163304B2 (en) | 2010-04-20 | 2015-10-20 | Alcoa Inc. | High strength forged aluminum alloy products |
WO2012120434A1 (fr) * | 2011-03-07 | 2012-09-13 | Koninklijke Philips Electronics N.V. | Module émetteur de lumière, lampe, luminaire et dispositif d'affichage |
US20120247623A1 (en) * | 2011-04-04 | 2012-10-04 | Matuska Robert A | Optimization and Control of Metallurgical Properties During Homogenization of an Alloy |
CN103572127A (zh) * | 2013-11-05 | 2014-02-12 | 吴高峰 | 一种高尔夫球杆用铝合金 |
CN103572128A (zh) * | 2013-11-05 | 2014-02-12 | 吴高峰 | 一种高尔夫球杆用铝合金及制备方法 |
CN103572129A (zh) * | 2013-11-05 | 2014-02-12 | 吴高峰 | 一种高尔夫球杆用铝合金制备方法 |
CN103898382B (zh) * | 2014-03-27 | 2017-01-04 | 北京科技大学 | 超强高韧耐蚀Al‐Zn‐Mg‐Cu铝合金材料及其制备方法 |
CN104152761A (zh) * | 2014-07-31 | 2014-11-19 | 天津大学 | 含钪的Al-Zn-Mg-Cu-Zr合金及制备方法 |
CN104862551B (zh) * | 2015-05-21 | 2017-09-29 | 北京科技大学 | Al‑Mg‑Cu‑Zn系铝合金及铝合金板材制备方法 |
JP6661870B2 (ja) * | 2016-05-13 | 2020-03-11 | 日本軽金属株式会社 | アルミニウム合金製バット用素管及びバット並びにその製造方法 |
CN106422240A (zh) * | 2016-11-11 | 2017-02-22 | 佛山市南海区卓航五金厂 | 一种兵乓球网架 |
CN107099706A (zh) * | 2017-05-02 | 2017-08-29 | 嘉禾福顺机械实业有限公司 | 一种高硬度泵用合金及其制备方法 |
CN109266879A (zh) * | 2018-11-20 | 2019-01-25 | 天津百恩威新材料科技有限公司 | 一种布拉磨头及高强度铝合金在制备布拉磨头中的应用 |
CN111519057B (zh) * | 2020-05-22 | 2021-11-23 | 佛山市三水凤铝铝业有限公司 | 一种提高制备铝合金的模具寿命的方法 |
CN114346217B (zh) * | 2021-12-22 | 2024-06-04 | 中山市奥博精密科技有限公司 | 一种金属铸件及其制备方法和应用 |
CN114457266A (zh) * | 2021-12-27 | 2022-05-10 | 有研金属复材技术有限公司 | 超高强韧铸造铝合金及其成型方法 |
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US6462120B2 (en) * | 1999-06-07 | 2002-10-08 | Eastman Chemical Company | Agricultural mulch films with triggered degradation |
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FR2820438B1 (fr) * | 2001-02-07 | 2003-03-07 | Pechiney Rhenalu | Procede de fabrication d'un produit corroye a haute resistance en alliage alznmagcu |
US20040099352A1 (en) * | 2002-09-21 | 2004-05-27 | Iulian Gheorghe | Aluminum-zinc-magnesium-copper alloy extrusion |
US7214281B2 (en) * | 2002-09-21 | 2007-05-08 | Universal Alloy Corporation | Aluminum-zinc-magnesium-copper alloy extrusion |
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2005
- 2005-03-24 US US11/087,733 patent/US20060213591A1/en not_active Abandoned
-
2006
- 2006-03-22 CN CN2006800173184A patent/CN101193839B/zh active Active
- 2006-03-22 WO PCT/US2006/010684 patent/WO2007102831A1/fr active Application Filing
- 2006-03-22 EP EP06849740.3A patent/EP1902150B1/fr not_active Revoked
- 2006-03-22 SI SI200632270T patent/SI1902150T1/en unknown
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2009
- 2009-12-04 US US12/591,956 patent/US20100180988A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
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WO2007102831A1 (fr) | 2007-09-13 |
WO2007102831A8 (fr) | 2007-11-29 |
EP1902150A4 (fr) | 2016-09-07 |
EP1902150A1 (fr) | 2008-03-26 |
CN101193839A (zh) | 2008-06-04 |
US20100180988A1 (en) | 2010-07-22 |
CN101193839B (zh) | 2010-07-14 |
US20060213591A1 (en) | 2006-09-28 |
SI1902150T1 (en) | 2018-08-31 |
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