EP1439239B1 - An aluminium based alloy - Google Patents
An aluminium based alloy Download PDFInfo
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- EP1439239B1 EP1439239B1 EP04250180A EP04250180A EP1439239B1 EP 1439239 B1 EP1439239 B1 EP 1439239B1 EP 04250180 A EP04250180 A EP 04250180A EP 04250180 A EP04250180 A EP 04250180A EP 1439239 B1 EP1439239 B1 EP 1439239B1
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- Prior art keywords
- alloy
- aluminum
- precipitate
- aluminum alloy
- alloy according
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 46
- 239000000956 alloy Substances 0.000 title claims abstract description 46
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000004411 aluminium Substances 0.000 title 1
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 30
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 22
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 19
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 14
- 239000006104 solid solution Substances 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 17
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 238000000889 atomisation Methods 0.000 claims description 8
- 238000007712 rapid solidification Methods 0.000 claims description 8
- 238000009646 cryomilling Methods 0.000 claims description 6
- 238000005551 mechanical alloying Methods 0.000 claims description 5
- 238000002074 melt spinning Methods 0.000 claims description 4
- 238000009718 spray deposition Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 abstract description 30
- 238000007792 addition Methods 0.000 abstract description 12
- 238000005728 strengthening Methods 0.000 abstract description 10
- 238000005275 alloying Methods 0.000 abstract description 9
- 239000000843 powder Substances 0.000 description 16
- 239000011777 magnesium Substances 0.000 description 14
- 238000001816 cooling Methods 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000005056 compaction Methods 0.000 description 6
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000007731 hot pressing Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- 238000009849 vacuum degassing Methods 0.000 description 3
- 229910018134 Al-Mg Inorganic materials 0.000 description 2
- 229910018467 Al—Mg Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000001427 coherent effect Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910018575 Al—Ti Inorganic materials 0.000 description 1
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- 229910034327 TiC Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010120 permanent mold casting Methods 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 238000007783 splat quenching Methods 0.000 description 1
- 238000009716 squeeze casting Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/08—Amorphous alloys with aluminium as the major constituent
Definitions
- the present invention relates to an aluminum based alloy having excellent mechanical properties and suitable for applications in temperature ranges between -420°F to 573°F (-215°C-300°C).
- Aluminum alloys have been used in aerospace and space applications owing to their good combination of strength, ductility and density. Aluminum alloys are, however, limited in their use in temperature above 300°F (150°C) as most aluminum alloys at these elevated temperatures lose their strength due to rapid coarsening of strengthening precipitates.
- None of the prior approaches provides an aluminum alloy having excellent mechanical properties in the temperature range of -420°F and 573°F (-215°C and 300°C).
- an aluminum alloy comprising 0.1 to 2.9 wt.% Sc, 0.1 to 20 wt.% Gd, 0.1 to 1.9 wt.% Zr, 1 to 7 wt.% Mg and balance A1.
- the aluminum alloy preferably comprises an aluminum solid solution matrix and a dispersion of Al 3 x having an L1 2 structure where X comprises Sc, and at least one of Gd and Zr.
- the alloy of the present invention can be produced by any rapid solidification technique that includes melt spinning, atomization, spray deposition, mechanical alloying and cryomilling.
- Gd and/or Zr are excellent alloying elements in addition to Sc to produce thermally stable microstructures based on their low diffusivities and solid solubilities in aluminum.
- the additions of Gd and Zr also help in controlling strengthening and coarsening kinetics through control in lattice constant of Al 3 Sc precipitate by substitution of Gd and Zr as Al 3 (Sc,Gd,Zr).
- Gd and Zr have considerable solubilities in Al 3 Sc L1 2 precipitate.
- Magnesium is added to increase the lattice constant of aluminum and also provides considerable solid solution strengthening in aluminum. It has been found that when lattice constants of aluminum solid solution and Al 3 Sc based precipitates are matched closely, then the precipitate particles are thermally stable at elevated temperatures. The foregoing results in an aluminum alloy with high strength at elevated temperatures.
- the present invention is drawn to an aluminum based alloy having excellent mechanical properties and suitable for applications in temperature ranges between -420°F to 573°F (-215° to 300°C).
- the aluminum alloy comprises aluminum (Al), scandium (Sc), gadolinium (Gd) zirconium (Zr) and magnesium (Mg).
- a desired microstructure of the material should have uniform distribution of fine coherent precipitates having lower diffusivity and lower interfacial energy in the aluminum matrix.
- the matrix should be solid solution strengthened. Solid solution alloying is beneficial to provide additional strengthening and greater work hardening capability. A material with a larger work hardening exponent would strain at higher level without causing any damage resulting in the improved failure strain and toughness.
- the Al 3 Sc is a potent strengthener in aluminum alloys and forms an Al 3 Sc precipitate with aluminum in the equilibrium condition.
- the Al 3 Sc has L1 2 structure that is an ordered face centered cubic (FCC) structure with Sc atoms located in corners and aluminum atoms on the cubic faces.
- FCC ordered face centered cubic
- the purpose of this invention is to produce thermally stable microstructure by making Al 3 Sc precipitate more resistant to coarsening at elevated temperatures through suitable alloying additions.
- gadolinium and/or zirconium both are excellent alloy elements for this purpose. If only one of the elements are to be added in combination with scandium, gadolinium is preferred; however, ideally both gadolinium and zirconium are added as alloying elements with or without magnesium, preferably with magnesium.
- an aluminum alloy having the following composition is particularly useful in the desired temperature range applications: 0.1 to 2.9 wt.% Sc, 0.1 to 20 wt.% Gd, 0.1 to 1.9 wt.% Zr and 1 to 7 wt.% Mg.
- Gadolinium forms Al 3 Gd precipitate with Al that is stable up to very high temperature 842°F (450°C) due to its low diffusion coefficient in aluminum.
- Al 3 Gd precipitate has DO 19 structure in the equilibrium condition. It has been found that Gd substitutes with Al 3 Sc precipitate forming L1 2 ordered phase of Al 3 (Sc x , Gd 1-x ) precipitate resulting in improved thermal and structural stability. Despite large atomic size, Gd has fairly high solubility in Al 3 (Sc x , Gd 1-x ) precipitates.
- Al 3 Zr precipitate that has L1 2 structure in the metastable condition and DO 23 structure in the equilibrium condition.
- the Al 3 Zr precipitate is highly resistant to coarsening. Similarity in the nature of Al 3 Zr and Al 3 Sc precipitates would allow complete or partial intersolubility of these phases resulting in the Ll 2 ordered Al 3 (Sc x Zr 1-x ) phase.
- the Al-Sc-Gd-Zr alloy would form Ll 2 ordered precipitate of Al 3 (Sc, Gd, Zr) with improved thermal and structural stability which is believed to be due to reduced lattice mismatch between the aluminum matrix and the precipitate. Additionally, this modified Al 3 (Sc, Gd, Zr) precipitate is more resistant to dislocation shearing compared to Al 3 Sc precipitate, thereby improving mechanical properties of the alloy at room temperature.
- Magnesium is a preferred alloying element because the magnesium (1) increases the lattice parameters of aluminum, (2) provides substantial solid solution strengthening, and (3) decreases density of the resulting aluminum alloy.
- the scandium addition can vary from 0.1 to 2.9 wt.% depending on the processing technique used for producing the material.
- the phase diagram of Al-Sc indicates an eutectic reaction at 0.5 wt.% of Sc and 1219°F (660°C) resulting in a mixture of aluminum solid solution and Al 3 Sc phase.
- the phase diagram also shows a steep liquidus for hypereutectic compositions. This suggests that casting techniques can be used for Sc composition only up to 0.5 wt.%.
- rapid solidification techniques such as melt spinning, atomization or spray deposition utilizing higher cooling rates to process the material.
- the amount of Sc that can be taken in supersaturation also depends on the cooling rate. Ideally one would like to keep all the Sc in solution to avoid formation of primary particles. Primary particles are usually large in size and therefore, not considered to be beneficial for mechanical properties.
- the higher limit of 2.9 wt.% Sc has been selected because atomization, that is the most common processing technique, can provide complete supersaturation of Sc up to 3 wt.%.
- Gadolinium addition is from 0.1 to 20 wt.% in the present invention.
- Gd can be added as high as 20 wt.%, the amount of Gd addition should depend on the solubility of Gd in Al 3 Sc precipitate.
- the preferred composition of Gd would be equivalent to Sc level in terms of atomic percent so that Gd can substitute up to 50% in Al 3 (Sc x , Gd 1-x ) precipitate.
- Al-Gd forms eutectic at 23 wt.% Gd composition, slower cooling rate process such as casting may be used for processing of the present alloy.
- rapid solidification technique will be preferred due to the presence of other elements and especially when they are present with hypereutectic compositions.
- Zirconium is present from 0.1 to 1.9 wt.% in the preferred alloy.
- the role of Zr is that Al 3 Zr precipitate is substituted in Al 3 Sc precipitate to control the coarsening kinetics of the alloy.
- Zr it has been found, has good solubility in Al 3 Sc precipitate. While casting may be used with small Zr additions, rapid solidification will be preferred for larger Zr additions.
- Mg can vary from 1 to 7 wt.% in the present alloy, it will be preferred to use 4-6 wt.% of Mg to impart sufficient solid solution strengthening and increase in lattice constant to match with Al 3 Sc precipitate. If the amount of Mg is higher, it may form Mg 5 Al 8 particle that is deleterious to the mechanical properties of alloy. Lower Mg content may not provide sufficient solid solution strengthening.
- Binary Al-Mg alloy is not a heat treatable alloy. However, it responds to heat treatment in the presence of Sc, Gd and Zr additions especially for cast alloys. Aging temperatures for the cast Al-Sc based alloys are usually very high 400-550°F (205-290°C) that is also indicative of the superior thermal stability of Al 3 Sc based precipitate.
- the alloy of the present invention can be processed by any rapid solidification technique utilizing cooling rates in excess of 10 3 °C/s.
- the rapid solidification process includes melt spinning, splat quenching, atomization, spray deposition and laser melting.
- the particular processing technique is not important. The most important aspect is the cooling rate of the process. Higher cooling rate is required for the alloy with larger amount of solute additions. These processes produce different forms of the product such as ribbon, flake or powder.
- Atomization is the most commonly used rapid solidification technique to produce large volume of powder. The cooling rate experienced during atomization depends on the powder size and usually varies from 10 3 -10 5 °C/s.
- Finer size (-325 mesh (0.044 mm openings)) of powder is preferred to have maximum supersaturation of alloying elements that can precipitate out during compaction and extrusion of powder.
- the powder of invented alloy was produced using helium gas atomization. Helium gas provides higher heat transfer coefficient leading to higher cooling rate in the powder.
- the ribbon or powder of alloy can be compacted using vacuum hot pressing, hot isostatic pressure or blind die compaction after suitable vacuum degassing. Compaction takes place by shear deformation in vacuum hot pressing and blind die compaction, whereas diffusional creep is key for compaction in hot isostatic pressing. Vacuum hot pressing was used for compaction of the present alloy. The alloy is further extruded, forged or rolled to impart deformation.
- This step is important to achieve highest mechanical properties. Although lower extrusion ratio may be useful, it is preferred to use around 20:0 ratio.
- the present alloy was extruded using 22:1 ratio.
- the temperature for vacuum degassing, vacuum hot pressing and extrusion can be in the range of 572-842°F (300-450°C).
- the alloy powder of the present invention can also be produced using mechanical alloying ( U.S. Patent 3,816,080 ) or cryomilling ( U.S. Patents 4,599,214 and 4,601,650 ) where powder is milled using high energy ball milling at room temperature or at cryogenic temperature in liquid nitrogen environment. While both mechanical alloying and cryomilling processes can provide supersaturation of alloying elements, cryomilling is preferred because it has less oxygen content. Cryomilling introduces oxynitride particles in the grains that can provide additional strengthening to the alloy at high temperature by increasing threshold stress for dislocation climb. In addition, the nitride particles when located on grain boundaries can reduce the grain boundary sliding in the alloy by pinning the dislocation resulting in reduced dislocation mobility in the grain boundary.
- the alloy powder can also be used for making components using vacuum plasma spray or cold spray processes.
- vacuum plasma spray the powder particle is melted and deposited onto the substrate resulting in a highly dense product.
- cold spray process the powder is ejected from nozzle at very high velocity and deposited onto the substrate without melting the powder. While either of these processes can be used for the invented alloy, cold spray is preferred because it does not melt the powder thereby, retaining the original microstructure of the powder.
- the alloy may also be produced using casting processes such as squeeze casting, die casting or permanent mold casting provided the alloy contains small amount of Sc, Gd and Zr additions.
- the following alloy compositions have been produced using a powder metallurgy process: Al-6Mg-2Sc-1Gd-1Zr, Al-6Mg-1Sc-1Gd-1Zr, Al-6Mg-lSc-1.5Gd-0.5Zr and Al-6Mg-1Sc-1Gd-0.5Zr (wt.%).
- the powder metallurgy process used for these alloys consisted of atomization, vacuum degassing, vacuum hot pressing and extrusion. These alloys showed a good combination of strength and ductility at ambient temperature. The above alloy compositions provide good strength at elevated temperatures.
- Additional alloy compositions for improvement in elevated temperature capability (a) Al-6Mg-2.8Sc-6Gd-1.8Zr, (b) Al-6Mg-2.8Sc-12Gd-1.8Zr, and (c) Al-6Mg-2.8Sc-18Gd-1.8Zr (wt.%). These alloys were produced using the powder metallurgy technique as described above.
- the alloy of the present invention can be used in monolithic form or can contain continuous or discontinuous reinforcement second phase to produce metal-matrix composite.
- Suitable reinforcement materials include oxides, carbides, nitrides, oxynitrides, oxycarbonitrides, silicides, borides, boron, graphite, ferrous alloys, tungsten, titanium and mixtures thereof.
- Specific reinforcing materials include SiC, Si 3 N 4 , Boron, Graphite, Al 2 O 3 , B 4 C, Y 2 O 3 , MgAl 2 O 4 , TiC, TiB 2 and mixtures thereof. These reinforcing materials may be present in volume fractions of up to about 50 vol.% and preferably 0.5-50 vol.% and more preferably 0.5-20 vol.%.
- the present invention can be seen to provide an aluminum alloy having excellent mechanical properties and suitable for applications in temperature ranges of - 420°F to 573°F (-215°C to 300°C).
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Abstract
Description
- The present invention relates to an aluminum based alloy having excellent mechanical properties and suitable for applications in temperature ranges between -420°F to 573°F (-215°C-300°C).
- Aluminum alloys have been used in aerospace and space applications owing to their good combination of strength, ductility and density. Aluminum alloys are, however, limited in their use in temperature above 300°F (150°C) as most aluminum alloys at these elevated temperatures lose their strength due to rapid coarsening of strengthening precipitates.
- There has been considerable effort in the prior art to improve the high temperature strength of aluminum alloys up to and exceeding 500°F (260°C). Prior attempts to improve the high temperature mechanical properties of aluminum alloys have included (a) aluminum-iron and aluminum-chromium based alloys that contain incoherent dispersoids and (b) mechanically alloyed pure aluminum and aluminum alloys strengthened by incoherent oxide particles. The strength of the aluminum alloys provided from approach (a) above tended to degrade at high temperatures due to coarsening of incoherent dispersoids. In addition, these aluminum alloys exhibited lower ductility and fracture toughness due to large volume fraction of incoherent particles. Accordingly, these alloy systems have not found widespread applications particularly with respect to high temperature environments. Some of the alloys considered for approach (b) included commercially pure aluminum, Al-Mg and Al-Ti produced using mechanical alloying process. While these aluminum alloys showed promising strengths at high temperature, these alloys did not find widespread applications in high temperature environments possibly due to lower ductility and fracture toughness. See also
U.S. Patent 3,816,080 .U.S. Patent 6,248,453 discloses Al-Sc based alloys which contain high volume fractions of strengthening coherent dispersoids. While these alloys are useful at high temperatures, we would prefer a material with higher ductility and fracture toughness. Furthermore, the problem vis-à-vis low ductility and fracture toughness will be increased at cryogenic temperatures. - None of the prior approaches provides an aluminum alloy having excellent mechanical properties in the temperature range of -420°F and 573°F (-215°C and 300°C).
- According to the present invention there is provided an aluminum alloy comprising 0.1 to 2.9 wt.% Sc, 0.1 to 20 wt.% Gd, 0.1 to 1.9 wt.% Zr, 1 to 7 wt.% Mg and balance A1.
- The aluminum alloy preferably comprises an aluminum solid solution matrix and a dispersion of Al3x having an L12 structure where X comprises Sc, and at least one of Gd and Zr. The alloy of the present invention can be produced by any rapid solidification technique that includes melt spinning, atomization, spray deposition, mechanical alloying and cryomilling.
- In accordance with the present invention, it has been found that Gd and/or Zr are excellent alloying elements in addition to Sc to produce thermally stable microstructures based on their low diffusivities and solid solubilities in aluminum. The additions of Gd and Zr also help in controlling strengthening and coarsening kinetics through control in lattice constant of Al3Sc precipitate by substitution of Gd and Zr as Al3(Sc,Gd,Zr). Gd and Zr have considerable solubilities in Al3Sc L12 precipitate. Magnesium is added to increase the lattice constant of aluminum and also provides considerable solid solution strengthening in aluminum. It has been found that when lattice constants of aluminum solid solution and Al3Sc based precipitates are matched closely, then the precipitate particles are thermally stable at elevated temperatures. The foregoing results in an aluminum alloy with high strength at elevated temperatures.
- Preferred embodiments of the present invention will now be described in greater detail by way of example only.
- The present invention is drawn to an aluminum based alloy having excellent mechanical properties and suitable for applications in temperature ranges between -420°F to 573°F (-215° to 300°C).
- The aluminum alloy comprises aluminum (Al), scandium (Sc), gadolinium (Gd) zirconium (Zr) and magnesium (Mg). In order to achieve higher strength and toughness for a wide temperature range from cryogenic to elevated temperatures, a desired microstructure of the material should have uniform distribution of fine coherent precipitates having lower diffusivity and lower interfacial energy in the aluminum matrix. The matrix should be solid solution strengthened. Solid solution alloying is beneficial to provide additional strengthening and greater work hardening capability. A material with a larger work hardening exponent would strain at higher level without causing any damage resulting in the improved failure strain and toughness.
- Scandium is a potent strengthener in aluminum alloys and forms an Al3Sc precipitate with aluminum in the equilibrium condition. The Al3Sc has L12 structure that is an ordered face centered cubic (FCC) structure with Sc atoms located in corners and aluminum atoms on the cubic faces. The purpose of this invention is to produce thermally stable microstructure by making Al3Sc precipitate more resistant to coarsening at elevated temperatures through suitable alloying additions. In accordance with the present invention it has been found that gadolinium and/or zirconium both are excellent alloy elements for this purpose. If only one of the elements are to be added in combination with scandium, gadolinium is preferred; however, ideally both gadolinium and zirconium are added as alloying elements with or without magnesium, preferably with magnesium.
- It has been found that an aluminum alloy having the following composition is particularly useful in the desired temperature range applications: 0.1 to 2.9 wt.% Sc, 0.1 to 20 wt.% Gd, 0.1 to 1.9 wt.% Zr and 1 to 7 wt.% Mg.
- Gadolinium forms Al3Gd precipitate with Al that is stable up to very high temperature 842°F (450°C) due to its low diffusion coefficient in aluminum. Al3Gd precipitate has DO19 structure in the equilibrium condition. It has been found that Gd substitutes with Al3Sc precipitate forming L12 ordered phase of Al3 (Scx, Gd1-x) precipitate resulting in improved thermal and structural stability. Despite large atomic size, Gd has fairly high solubility in Al3 (Scx, Gd1-x) precipitates.
- It has been found that Zr forms Al3Zr precipitate that has L12 structure in the metastable condition and DO23 structure in the equilibrium condition. The Al3Zr precipitate is highly resistant to coarsening. Similarity in the nature of Al3Zr and Al3Sc precipitates would allow complete or partial intersolubility of these phases resulting in the Ll2 ordered Al3(ScxZr1-x) phase. The Al-Sc-Gd-Zr alloy would form Ll2 ordered precipitate of Al3(Sc, Gd, Zr) with improved thermal and structural stability which is believed to be due to reduced lattice mismatch between the aluminum matrix and the precipitate. Additionally, this modified Al3(Sc, Gd, Zr) precipitate is more resistant to dislocation shearing compared to Al3Sc precipitate, thereby improving mechanical properties of the alloy at room temperature.
- Magnesium is a preferred alloying element because the magnesium (1) increases the lattice parameters of aluminum, (2) provides substantial solid solution strengthening, and (3) decreases density of the resulting aluminum alloy.
- In the present invention, the scandium addition can vary from 0.1 to 2.9 wt.% depending on the processing technique used for producing the material. The phase diagram of Al-Sc indicates an eutectic reaction at 0.5 wt.% of Sc and 1219°F (660°C) resulting in a mixture of aluminum solid solution and Al3Sc phase. The phase diagram also shows a steep liquidus for hypereutectic compositions. This suggests that casting techniques can be used for Sc composition only up to 0.5 wt.%. For hypereutectic compositions, i.e. Sc greater than 0.5 wt.%, rapid solidification techniques such as melt spinning, atomization or spray deposition utilizing higher cooling rates to process the material. The amount of Sc that can be taken in supersaturation also depends on the cooling rate. Ideally one would like to keep all the Sc in solution to avoid formation of primary particles. Primary particles are usually large in size and therefore, not considered to be beneficial for mechanical properties. The higher limit of 2.9 wt.% Sc has been selected because atomization, that is the most common processing technique, can provide complete supersaturation of Sc up to 3 wt.%.
- Gadolinium addition is from 0.1 to 20 wt.% in the present invention. Although, Gd can be added as high as 20 wt.%, the amount of Gd addition should depend on the solubility of Gd in Al3Sc precipitate. The preferred composition of Gd would be equivalent to Sc level in terms of atomic percent so that Gd can substitute up to 50% in Al3 (Scx, Gd1-x) precipitate. Since Al-Gd forms eutectic at 23 wt.% Gd composition, slower cooling rate process such as casting may be used for processing of the present alloy. However, rapid solidification technique will be preferred due to the presence of other elements and especially when they are present with hypereutectic compositions.
- Zirconium is present from 0.1 to 1.9 wt.% in the preferred alloy. In the present alloy, the role of Zr is that Al3Zr precipitate is substituted in Al3Sc precipitate to control the coarsening kinetics of the alloy. Zr, it has been found, has good solubility in Al3Sc precipitate. While casting may be used with small Zr additions, rapid solidification will be preferred for larger Zr additions.
- While Mg can vary from 1 to 7 wt.% in the present alloy, it will be preferred to use 4-6 wt.% of Mg to impart sufficient solid solution strengthening and increase in lattice constant to match with Al3Sc precipitate. If the amount of Mg is higher, it may form Mg5Al8 particle that is deleterious to the mechanical properties of alloy. Lower Mg content may not provide sufficient solid solution strengthening. Binary Al-Mg alloy is not a heat treatable alloy. However, it responds to heat treatment in the presence of Sc, Gd and Zr additions especially for cast alloys. Aging temperatures for the cast Al-Sc based alloys are usually very high 400-550°F (205-290°C) that is also indicative of the superior thermal stability of Al3Sc based precipitate.
- The alloy of the present invention can be processed by any rapid solidification technique utilizing cooling rates in excess of 103 °C/s. The rapid solidification process includes melt spinning, splat quenching, atomization, spray deposition and laser melting. The particular processing technique is not important. The most important aspect is the cooling rate of the process. Higher cooling rate is required for the alloy with larger amount of solute additions. These processes produce different forms of the product such as ribbon, flake or powder. Atomization is the most commonly used rapid solidification technique to produce large volume of powder. The cooling rate experienced during atomization depends on the powder size and usually varies from 103-105 °C/s. Finer size (-325 mesh (0.044 mm openings)) of powder is preferred to have maximum supersaturation of alloying elements that can precipitate out during compaction and extrusion of powder. The powder of invented alloy was produced using helium gas atomization. Helium gas provides higher heat transfer coefficient leading to higher cooling rate in the powder. The ribbon or powder of alloy can be compacted using vacuum hot pressing, hot isostatic pressure or blind die compaction after suitable vacuum degassing. Compaction takes place by shear deformation in vacuum hot pressing and blind die compaction, whereas diffusional creep is key for compaction in hot isostatic pressing. Vacuum hot pressing was used for compaction of the present alloy. The alloy is further extruded, forged or rolled to impart deformation. This step is important to achieve highest mechanical properties. Although lower extrusion ratio may be useful, it is preferred to use around 20:0 ratio. The present alloy was extruded using 22:1 ratio. The temperature for vacuum degassing, vacuum hot pressing and extrusion can be in the range of 572-842°F (300-450°C).
- The alloy powder of the present invention can also be produced using mechanical alloying (
U.S. Patent 3,816,080 ) or cryomilling (U.S. Patents 4,599,214 and4,601,650 ) where powder is milled using high energy ball milling at room temperature or at cryogenic temperature in liquid nitrogen environment. While both mechanical alloying and cryomilling processes can provide supersaturation of alloying elements, cryomilling is preferred because it has less oxygen content. Cryomilling introduces oxynitride particles in the grains that can provide additional strengthening to the alloy at high temperature by increasing threshold stress for dislocation climb. In addition, the nitride particles when located on grain boundaries can reduce the grain boundary sliding in the alloy by pinning the dislocation resulting in reduced dislocation mobility in the grain boundary. - The alloy powder can also be used for making components using vacuum plasma spray or cold spray processes. In vacuum plasma spray (VPS), the powder particle is melted and deposited onto the substrate resulting in a highly dense product. In cold spray process, the powder is ejected from nozzle at very high velocity and deposited onto the substrate without melting the powder. While either of these processes can be used for the invented alloy, cold spray is preferred because it does not melt the powder thereby, retaining the original microstructure of the powder.
- The alloy may also be produced using casting processes such as squeeze casting, die casting or permanent mold casting provided the alloy contains small amount of Sc, Gd and Zr additions.
- The following alloy compositions have been produced using a powder metallurgy process: Al-6Mg-2Sc-1Gd-1Zr, Al-6Mg-1Sc-1Gd-1Zr, Al-6Mg-lSc-1.5Gd-0.5Zr and Al-6Mg-1Sc-1Gd-0.5Zr (wt.%). The powder metallurgy process used for these alloys consisted of atomization, vacuum degassing, vacuum hot pressing and extrusion. These alloys showed a good combination of strength and ductility at ambient temperature. The above alloy compositions provide good strength at elevated temperatures. Additional alloy compositions for improvement in elevated temperature capability: (a) Al-6Mg-2.8Sc-6Gd-1.8Zr, (b) Al-6Mg-2.8Sc-12Gd-1.8Zr, and (c) Al-6Mg-2.8Sc-18Gd-1.8Zr (wt.%). These alloys were produced using the powder metallurgy technique as described above.
- The alloy of the present invention can be used in monolithic form or can contain continuous or discontinuous reinforcement second phase to produce metal-matrix composite. Suitable reinforcement materials include oxides, carbides, nitrides, oxynitrides, oxycarbonitrides, silicides, borides, boron, graphite, ferrous alloys, tungsten, titanium and mixtures thereof. Specific reinforcing materials include SiC, Si3N4, Boron, Graphite, Al2O3, B4C, Y2O3, MgAl2O4, TiC, TiB2 and mixtures thereof. These reinforcing materials may be present in volume fractions of up to about 50 vol.% and preferably 0.5-50 vol.% and more preferably 0.5-20 vol.%.
- Thus, at least in the illustrated embodiments, the present invention can be seen to provide an aluminum alloy having excellent mechanical properties and suitable for applications in temperature ranges of - 420°F to 573°F (-215°C to 300°C).
- This invention may be embodied in other forms or carried out in other ways without departing from the essential characteristics thereof. The present embodiment is therefore to be considered as in all respects illustrative and not restrictive, the scope of the invention being indicated by the appended claims.
Claims (10)
- An aluminum alloy comprising 0.1 to 2.9 wt.% Sc, 0.1 to 20 wt.% Gd, 0.1 to 1.9 wt.% Zr, 1 to 7 wt.% Mg and balance Al.
- An aluminum alloy according to claim 1 further comprising an aluminum solid solution matrix and a dispersion of Al3X having an L12 structure where X comprises Sc, and at least one of Gd and Zr.
- An aluminum alloy according to claim 2 wherein X comprises Sc and Zr.
- An aluminum alloy according to claim 2 wherein X comprises Sc and Gd.
- An aluminum alloy according to claim 2 wherein the X comprises Sc, Gd and Zr.
- An aluminum alloy according to any preceding claim wherein the alloy is produced by a rapid solidification technique selected from the group of melt spinning, atomization, spray deposition, mechanical alloying and cryomilling.
- An aluminum alloy according to any preceding claim having the composition Al-6Mg-2Sc-1Gd-1Zr (wt.%).
- An aluminum alloy according to any of claims 1 to 6 having the composition Al-6Mg-2.8Sc-6Gd-1.8Zr (wt.%).
- An aluminum alloy according to any of claims 1 to 6 having the composition Al-6Mg-2.8Sc-12Gd-1.8Zr (wt.%).
- An aluminum alloy according to any of claims 1 to 6 having the composition Al-6Mg-2.8Sc-18Gd-1.8Zr(wt.%).
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US34283903A | 2003-01-15 | 2003-01-15 | |
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JP2008248279A (en) * | 2007-03-29 | 2008-10-16 | Honda Motor Co Ltd | Method for producing alloy laminate material containing dispersed quasicrystal grains, method for producing alloy bulk material containing dispersed quasicrystal grains, alloy laminate material containing dispersed quasicrystal grains, and alloy bulk material containing dispersed quasicrystal grains |
DE102007018123B4 (en) * | 2007-04-16 | 2009-03-26 | Eads Deutschland Gmbh | Method for producing a structural component from an aluminum-based alloy |
US8409373B2 (en) * | 2008-04-18 | 2013-04-02 | United Technologies Corporation | L12 aluminum alloys with bimodal and trimodal distribution |
US20090263273A1 (en) * | 2008-04-18 | 2009-10-22 | United Technologies Corporation | High strength L12 aluminum alloys |
US7871477B2 (en) * | 2008-04-18 | 2011-01-18 | United Technologies Corporation | High strength L12 aluminum alloys |
US8002912B2 (en) | 2008-04-18 | 2011-08-23 | United Technologies Corporation | High strength L12 aluminum alloys |
US20090260724A1 (en) * | 2008-04-18 | 2009-10-22 | United Technologies Corporation | Heat treatable L12 aluminum alloys |
US8017072B2 (en) | 2008-04-18 | 2011-09-13 | United Technologies Corporation | Dispersion strengthened L12 aluminum alloys |
US7879162B2 (en) | 2008-04-18 | 2011-02-01 | United Technologies Corporation | High strength aluminum alloys with L12 precipitates |
US7811395B2 (en) * | 2008-04-18 | 2010-10-12 | United Technologies Corporation | High strength L12 aluminum alloys |
US7875133B2 (en) | 2008-04-18 | 2011-01-25 | United Technologies Corporation | Heat treatable L12 aluminum alloys |
US8778098B2 (en) | 2008-12-09 | 2014-07-15 | United Technologies Corporation | Method for producing high strength aluminum alloy powder containing L12 intermetallic dispersoids |
US8778099B2 (en) | 2008-12-09 | 2014-07-15 | United Technologies Corporation | Conversion process for heat treatable L12 aluminum alloys |
US8020509B2 (en) | 2009-01-08 | 2011-09-20 | General Electric Company | Apparatus, systems, and methods involving cold spray coating |
US20100226817A1 (en) * | 2009-03-05 | 2010-09-09 | United Technologies Corporation | High strength l12 aluminum alloys produced by cryomilling |
US20100252148A1 (en) * | 2009-04-07 | 2010-10-07 | United Technologies Corporation | Heat treatable l12 aluminum alloys |
US9611522B2 (en) | 2009-05-06 | 2017-04-04 | United Technologies Corporation | Spray deposition of L12 aluminum alloys |
US9127334B2 (en) | 2009-05-07 | 2015-09-08 | United Technologies Corporation | Direct forging and rolling of L12 aluminum alloys for armor applications |
US8728389B2 (en) | 2009-09-01 | 2014-05-20 | United Technologies Corporation | Fabrication of L12 aluminum alloy tanks and other vessels by roll forming, spin forming, and friction stir welding |
US8409496B2 (en) | 2009-09-14 | 2013-04-02 | United Technologies Corporation | Superplastic forming high strength L12 aluminum alloys |
US20110064599A1 (en) * | 2009-09-15 | 2011-03-17 | United Technologies Corporation | Direct extrusion of shapes with l12 aluminum alloys |
US9194027B2 (en) | 2009-10-14 | 2015-11-24 | United Technologies Corporation | Method of forming high strength aluminum alloy parts containing L12 intermetallic dispersoids by ring rolling |
US20110091345A1 (en) * | 2009-10-16 | 2011-04-21 | United Technologies Corporation | Method for fabrication of tubes using rolling and extrusion |
US8409497B2 (en) | 2009-10-16 | 2013-04-02 | United Technologies Corporation | Hot and cold rolling high strength L12 aluminum alloys |
KR102422213B1 (en) * | 2018-05-21 | 2022-07-18 | 오브쉬체스트보 에스 오그라니첸노이 오트벳스트베노스트유 “오베디넨나야 꼼파니야 루살 인제네르노-테크놀로지체스키 첸트르” | Aluminum alloys for additive manufacturing technology |
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JP4098917B2 (en) * | 1999-04-19 | 2008-06-11 | 昭和電工株式会社 | High strength aluminum alloy |
US6139653A (en) * | 1999-08-12 | 2000-10-31 | Kaiser Aluminum & Chemical Corporation | Aluminum-magnesium-scandium alloys with zinc and copper |
AU7571000A (en) * | 1999-08-12 | 2001-03-13 | Kaiser Aluminum & Chemical Corporation | Aluminum-magnesium-scandium alloys with hafnium |
JP2001131719A (en) * | 1999-10-29 | 2001-05-15 | Hitachi Cable Ltd | HEAT RESISTANT Al ALLOY WIRE ROD FOR ELECTRICAL CONDUCTION AND PRODUCING METHOD THEREFOR |
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JP2001348637A (en) * | 2000-06-05 | 2001-12-18 | Hitachi Cable Ltd | Aluminum alloy material and method for producing wiring rod using the same |
WO2003052154A1 (en) * | 2001-12-14 | 2003-06-26 | Eads Deutschland Gmbh | Method for the production of a highly fracture-resistant aluminium sheet material alloyed with scandium (sc) and/or zirconium (zr) |
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