# Patent

## Title
Heat treatable L12 aluminum alloys

## Abstract

A method of forming high temperature heat treatable aluminum alloys that can be used at temperatures from about −420° F. (−251° C.) up to about 650° F. (343° C.) are described. The alloys are strengthened by dispersion of particles based on the L12 intermetallic compound Al3X. These alloys comprise aluminum, copper, magnesium, at least one of scandium, erbium, thulium, ytterbium, and lutetium; and at least one of gadolinium, yttrium, zirconium, titanium, hafnium, and niobium. Lithium is an optional alloying element.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a divisional application of U.S. application Ser. No. 12/148,396, filed Apr. 18, 2008 for HEAT TREATABLE L12 ALUMINUM ALLOYS.


BACKGROUND
The present invention relates generally to aluminum alloys and more specifically to heat treatable aluminum alloys produced by melt processing and strengthened by L12 phase dispersions.
The combination of high strength, ductility, and fracture toughness, as well as low density, make aluminum alloys natural candidates for aerospace and space applications. However, their use is typically limited to temperatures below about 300° F. (149° C.) since most aluminum alloys start to lose strength in that temperature range as a result of coarsening of strengthening precipitates.
The development of aluminum alloys with improved elevated temperature mechanical properties is a continuing process. Some attempts have included aluminum-iron and aluminum-chromium based alloys such as Al—Fe—Ce, Al—Fe—V—Si, Al—Fe—Ce—W, and Al—Cr—Zr—Mn that contain incoherent dispersoids. These alloys, however, also lose strength at elevated temperatures due to particle coarsening. In addition, these alloys exhibit ductility and fracture toughness values lower than other commercially available aluminum alloys.
Other attempts have included the development of mechanically alloyed Al—Mg and Al—Ti alloys containing ceramic dispersoids. These alloys exhibit improved high temperature strength due to the particle dispersion, but the ductility and fracture toughness are not improved.
U.S. Pat. No. 6,248,453 discloses aluminum alloys strengthened by dispersed Al3X L12 intermetallic phases where X is selected from the group consisting of Sc, Er, Lu, Yb, Tm, and U. The Al3X particles are coherent with the aluminum alloy matrix and are resistant to coarsening at elevated temperatures. The improved mechanical properties of the disclosed dispersion strengthened L12 aluminum alloys are stable up to 572° F. (300° C.). In order to create aluminum alloys containing fine dispersions of Al3X L12 particles, the alloys need to be manufactured by expensive rapid solidification processes with cooling rates in excess of 1.8×103 F/sec (103° C./sec). U.S. Patent Application Publication No. 2006/0269437 A1 discloses an aluminum alloy that contains scandium and other elements. While the alloy is effective at high temperatures, it is not capable of being heat treated using a conventional age hardening mechanism.
Heat treatable aluminum alloys strengthened by coherent L12 intermetallic phases produced by standard, inexpensive melt processing techniques would be useful.
SUMMARY
The present invention is heat treatable aluminum alloys that can be cast, wrought, or formed by rapid solidification, and thereafter heat treated. The alloys can achieve high temperature performance and can be used at temperatures up to about 650° F. (343° C.).
These alloys comprise copper, magnesium, lithium and an Al3X L12 dispersoid where X is at least one first element selected from scandium, erbium, thulium, ytterbium, and lutetium, and at least one second element selected from gadolinium, yttrium, zirconium, titanium, hafnium, and niobium. The balance is substantially aluminum.
The alloys have less than about 1.0 weight percent total impurities.
The alloys are formed by a process selected from casting, deformation processing and rapid solidification. The alloys are then heat treated at a temperature of from about 900° F. (482° C.) to about 1100° F. (593° C.) for between about 30 minutes and four hours, followed by quenching in water, and thereafter aged at a temperature from about 200° F. (93° C.) to about 600° F. (315° C.) for about two to about forty-eight hours.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an aluminum copper phase diagram.
FIG. 2 is an aluminum magnesium phase diagram.
FIG. 3 is an aluminum lithium phase diagram.
FIG. 4 is an aluminum scandium phase diagram.
FIG. 5 is an aluminum erbium phase diagram.
FIG. 6 is an aluminum thulium phase diagram.
FIG. 7 is an aluminum ytterbium phase diagram.
FIG. 8 is an aluminum lutetium phase diagram.



DETAILED DESCRIPTION
The alloys of this invention are based on the aluminum, copper, magnesium, lithium system. The amount of copper in these alloys ranges from about 1.0 to about 8.0 weight percent, more preferably about 2.0 to about 7.0 weight percent, and even more preferably about 3.5 to about 6.5 weight percent. The amount of magnesium in these alloys ranges from about 0.2 to about 4.0 weight percent, more preferably about 0.4 to about 3.0 weight percent, and even more preferably about 0.5 to about 2.0 weight percent. The amount of lithium in these alloys ranges from about 0.5 to about 3.0 weight percent, more preferably about 1.0 to about 2.5 weight percent, and even more preferably about 1.0 to about 2.0 weight percent.
Copper, magnesium and lithium are completely soluble in the composition of the inventive alloys discussed herein. Aluminum magnesium lithium alloys are heat treatable with L12 Al3Li (δ′), Al2LiMg, Al2CuMg (S′) and Al2CuLi precipitating following a solution heat treatment, quench and age process. These phases precipitate as coherent second phases in the aluminum magnesium lithium solid solution matrix. Also, in the solid solutions are dispersions of Al3X having an L12 structure where X is at least one first element selected from scandium, erbium, thulium, ytterbium, and lutetium and at least one second element selected from gadolinium, yttrium, zirconium, titanium, hafnium, and niobium.
The aluminum copper phase diagram is shown in FIG. 1. The aluminum copper binary system is a eutectic alloy system with a eutectic reaction at 31.2 weight percent magnesium and 1018° F. (548.2° C.). Copper has maximum solid solubility of 6 weight percent in aluminum at 1018° F. (548.2° C.) which can be extended further by rapid solidification processing. Copper provides a considerable amount of precipitation strengthening in aluminum by precipitation of fine second phases. The present invention is focused on hypoeutectic alloy composition ranges.
The aluminum magnesium phase diagram is shown in FIG. 2. The binary system is a eutectic alloy system with a eutectic reaction at 36 weight percent magnesium and 842° F. (450° C.). Magnesium has maximum solid solubility of 16 weight percent in aluminum at 842° F. (450° C.) which can be extended further by rapid solidification processing. Magnesium provides substantial solid solution strengthening in aluminum. In addition, magnesium provides precipitation strengthening through precipitation of Al2CuMg (S′) phase in the presence of copper.
The aluminum lithium phase diagram is shown in FIG. 3. The binary system is a eutectic alloy system with a eutectic reaction at 8 weight percent magnesium and 1104° F. (596° C.). Lithium has maximum solid solubility of about 4.5 weight percent in aluminum at 1104° F. (596° C.). Lithium has lesser solubility in aluminum in the presence of magnesium compared to when magnesium is absent. Therefore, lithium provides significant precipitation strengthening through precipitation of Al3Li (δ′) phase. Lithium in addition provides reduced density and increased modulus in aluminum. In the presence of magnesium and copper, lithium forms ternary precipitates based on Al2CuLi and Al2MgLi.
The alloys of this invention contain phases consisting of primary aluminum, aluminum copper solid solutions, aluminum magnesium solid solutions, and aluminum lithium solid solutions. In the solid solutions are dispersions of Al3X having an L12 structure where X is at least one element selected from scandium, erbium, thulium, ytterbium, and lutetium. Also present is at least one element selected from gadolinium, yttrium, zirconium, titanium, hafnium, and niobium.
Exemplary aluminum alloys of this invention include, but are not limited to (in weight percent):
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-0.5)Sc-(0.1-4.0)Gd;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-6)Er-(0.1-4.0)Gd;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-10)Tm-(0.1-4.0)Gd;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-15)Yb-(0.1-4.0)Gd;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-12)Lu-(0.1-4.0)Gd;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-0.5)Sc-(0.1-4.0)Y;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-6)Er-(0.1-4.0)Y;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-10)Tm-(0.1-4.0)Y;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-15)Yb-(0.1-4.0)Y;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-12)Lu-(0.1-4.0)Y;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-0.5)Sc-(0.05-1.0)Zr;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-6)Er-(0.05-1.0)Zr;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-10)Tm-(0.05-1.0)Zr;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-15)Yb-(0.05-1.0)Zr;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-12)Lu-(0.05-1.0)Zr;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-0.5)Sc-(0.05-2.0)Ti;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-0.5)Er-(0.05-2.0)Ti;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-10)Tm-(0.05-2.0)Ti;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-15)Yb-(0.05-2.0)Ti;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-4)-Lu-(0.05-2.0)Ti;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-0.5)Sc-(0.05-2.0)Hf;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-6)Er-(0.05-2.0)Hf;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-10)Tm-(0.05-2.0)Hf;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-15)Yb-(0.05-2.0)Hf;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-12)Lu-(0.05-2.0)Hf;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-0.5)Sc-(0.05-1.0)Nb;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-6)Er-(0.05-1.0)Nb;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-10)Tm-(0.05-1.0)Nb;
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-15)Yb-(0.05-1.0)Nb; and
Al-(1-8)Cu-(0.2-4)Mg-(0.5-3.0)Li-(0.1-12)Lu-(0.05-1.0)Nb.
Preferred examples of similar alloys to these are alloys with about 2.0 to about 7.0 weight percent copper, alloys with about 0.4 to about 3.0 weight percent magnesium, and alloys with about 1.0 to about 2.5 weight percent lithium.
In the inventive aluminum based alloys disclosed herein, scandium, erbium, thulium, ytterbium, and lutetium are potent strengtheners that have low diffusivity and low solubility in aluminum. All these element form equilibrium Al3X intermetallic dispersoids where X is at least one of scandium, erbium, ytterbium, lutetium, that have an L12 structure that is an ordered face centered cubic structure with the X atoms located at the corners and aluminum atoms located on the cube faces of the unit cell.
Scandium forms Al3Sc dispersoids that are fine and coherent with the aluminum matrix. Lattice parameters of aluminum and Al3Sc are very close (0.405 nm and 0.410 nm respectively), indicating that there is minimal or no driving force for causing growth of the Al3Sc dispersoids. This low interfacial energy makes the Al3Sc dispersoids thermally stable and resistant to coarsening up to temperatures as high as about 842° F. (450° C.). In the alloys of this invention these Al3Sc dispersoids are made stronger and more resistant to coarsening at elevated temperatures by adding suitable alloying elements such as gadolinium, yttrium, zirconium, titanium, hafnium, niobium, or combinations thereof, that enter Al3Sc in solution.
Erbium forms Al3Er dispersoids in the aluminum matrix that are fine and coherent with the aluminum matrix. The lattice parameters of aluminum and Al3Er are close (0.405 nm and 0.417 nm respectively), indicating there is minimal driving force for causing growth of the Al3Er dispersoids. This low interfacial energy makes the Al3Er dispersoids thermally stable and resistant to coarsening up to temperatures as high as about 842° F. (450° C.). Additions of magnesium in solid solution in aluminum increase the lattice parameter of the aluminum matrix, and decrease the lattice parameter mismatch further increasing the resistance of the Al3Er to coarsening. Additions of copper increase the strength of alloys through precipitation of Al2Cu (θ′) and Al2CuMg (S′) phases. In the alloys of this invention, these Al3Er dispersoids are made stronger and more resistant to coarsening at elevated temperatures by adding suitable alloying elements such as gadolinium, yttrium, zirconium, titanium, hafnium, niobium, or combinations thereof that enter Al3Er in solution.
Thulium forms metastable Al3TM dispersoids in the aluminum matrix that are fine and coherent with the aluminum matrix. The lattice parameters of aluminum and Al3TM are close (0.405 nm and 0.420 nm respectively), indicating there is minimal driving force for causing growth of the Al3TM dispersoids. This low interfacial energy makes the Al3TM dispersoids thermally stable and resistant to coarsening up to temperatures as high as about 842° F. (450° C.). Additions of magnesium in solid solution in aluminum increase the lattice parameter of the aluminum matrix, and decrease the lattice parameter mismatch further increasing the resistance of the Al3TM to coarsening. Additions of copper increase the strength of alloys through precipitation of Al2Cu (θ′) and Al2CuMg (S′) phases. In the alloys of this invention these Al3Tm dispersoids are made stronger and more resistant to coarsening at elevated temperatures by adding suitable alloying elements such as gadolinium, yttrium, zirconium, titanium, hafnium, niobium, or combinations thereof that enter Al3Tm in solution.
Ytterbium forms Al3Yb dispersoids in the aluminum matrix that are fine and coherent with the aluminum matrix. The lattice parameters of Al and Al3Yb are close (0.405 nm and 0.420 nm respectively), indicating there is minimal driving force for causing growth of the Al3Yb dispersoids. This low interfacial energy makes the Al3Yb dispersoids thermally stable and resistant to coarsening up to temperatures as high as about 842° F. (450° C.). Additions of magnesium in solid solution in aluminum increase the lattice parameter of the aluminum matrix, and decrease the lattice parameter mismatch further increasing the resistance of the Al3Yb to coarsening. Additions of copper increase the strength of alloys through precipitation of Al2Cu (θ′) and Al2CuMg (S′) phases. In the alloys of this invention, these Al3Yb dispersoids are made stronger and more resistant to coarsening at elevated temperatures by adding suitable alloying elements such as gadolinium, yttrium, zirconium, titanium, hafnium, niobium, or combinations thereof that enter Al3Yb in solution.
Lutetium forms Al3Lu dispersoids in the aluminum matrix that are fine and coherent with the aluminum matrix. The lattice parameters of Al and Al3Lu are close (0.405 nm and 0.419 nm respectively), indicating there is minimal driving force for causing growth of the Al3Lu dispersoids. This low interfacial energy makes the Al3Lu dispersoids thermally stable and reistant to coarsening up to temperatures as high as about 842° F. (450° C.). Additions of magnesium in solid solution in aluminum increase the lattice parameter of the aluminum matrix, and decrease the lattice parameter mismatch further increasing the resistance of the Al3Lu to coarsening Additions of copper increase the strength of alloys through precipitation of Al2Cu (θ′) and Al2CuMg (S′) phases. In the alloys of this invention, these Al3Lu dispersoids are made stronger and more resistant to coarsening at elevated temperatures by adding suitable alloying elements such as gadolinium, yttrium, zirconium, titanium, hafnium, niobium, or mixtures thereof that enter Al3Lu in solution.
Gadolinium forms metastable Al3Gd dispersoids in the aluminum matrix that are stable up to temperatures as high as about 842° F. (450° C.) due to their low diffusivity in aluminum. The Al3Gd dispersoids have a D019 structure in the equilibrium condition. Despite its large atomic size, gadolinium has fairly high solubility in the Al3X intermetallic dispersoids (where X is scandium, erbium, thulium, ytterbium or lutetium). Gadolinium can substitute for the X atoms in Al3X intermetallic, thereby forming an ordered L12 phase which results in improved thermal and structural stability.
Yttrium forms metastable Al3Y dispersoids in the aluminum matrix that have an L12 structure in the metastable condition and a D019 structure in the equilibrium condition. The metastable Al3Y dispersoids have a low diffusion coefficient which makes them thermally stable and highly resistant to coarsening. Yttrium has a high solubility in the Al3X intermetallic dispersoids allowing large amounts of yttrium to substitute for X in the Al3X L12 dispersoids which results in improved thermal and structural stability.
Zirconium forms Al3Zr dispersoids in the aluminum matrix that have an L12 structure in the metastable condition and D023 structure in the equilibrium condition. The metastable Al3Zr dispersoids have a low diffusion coefficient which makes them thermally stable and highly resistant to coarsening. Zirconium has a high solubility in the Al3X dispersoids allowing large amounts of zirconium to substitute for X in the Al3X dispersoids, which results in improved thermal and structural stability.
Titanium forms Al3Ti dispersoids in the aluminum matrix that have an L12 structure in the metastable condition and D022 structure in the equilibrium condition. The metastable Al3Ti despersoids have a low diffusion coefficient which makes them thermally stable and highly resistant to coarsening. Titanium has a high solubility in the Al3X dispersoids allowing large amounts of titanium to substitute for X in the Al3X dispersoids, which result in improved thermal and structural stability.
Hafnium forms metastable Al3Hf dispersoids in the aluminum matrix that have an L12 structure in the metastable condition and a D023 structure in the equilibrium condition. The Al3Hf dispersoids have a low diffusion coefficient, which makes them thermally stable and highly resistant to coarsening. Hafnium has a high solubility in the Al3X dispersoids allowing large amounts of hafnium to substitute for scandium, erbium, thulium, ytterbium, and lutetium in the above mentioned Al3X dispersoides, which results in stronger and more thermally stable dispersoids.
Niobium forms metastable Al3Nb dispersoids in the aluminum matrix that have an L12 structure in the metastable condition and a D022 structure in the equilibrium condition. Niobium has a lower solubility in the Al3X dispersoids than hafnium or yttrium, allowing relatively lower amounts of niobium than hafnium or yttrium to substitute for X in the Al3X dispersoids. Nonetheless, niobium can be very effective in slowing down the coarsening kinetics of the Al3X dispersoids because the Al3Nb dispersoids are thermally stable. The substitution of niobium for X in the above mentioned Al3X dispersoids results in stronger and more thermally stable dispersoids.
Al3X L12 precipitates improve elevated temperature mechanical properties in aluminum alloys for two reasons. First, the precipitates are ordered intermetallic compounds. As a result, when the particles are sheared by glide dislocations during deformation, the dislocations separate into two partial dislocations separated by an anti-phase boundary on the glide plane. The energy to create the anti-phase boundary is the origin of the strengthening. Second, the cubic L12 crystal structure and lattice parameter of the precipitates are closely matched to the aluminum solid solution matrix. This results in a lattice coherency at the precipitate/matrix boundary that resists coarsening. The lack of an interphase boundary results in a low driving force for particle growth and resulting elevated temperature stability. Alloying elements in solid solution in the dispersed strengthening particles and in the aluminum matrix that tend to decrease the lattice mismatch between the matrix and particles will tend to increase the strengthening and elevated temperature stability of the alloy.
Copper has considerable solubility in aluminum at 1018° F. (548.2° C.), which decreases with a decrease in temperature. The aluminum copper alloy system provides considerable precipitation hardening response through precipitation of Al2Cu (θ′) second phase. Magnesium has considerable solubility in aluminum at 842° F. (450° C.) which decreases with a decrease in temperature. The aluminum magnesium binary alloy system does not provide precipitation hardening, rather it provides substantial solid solution strengthening. When magnesium is added to aluminum copper alloy, it increases the precipitation hardening response of the alloy considerably through precipitation of Al2CuMg (S′) phase. When the ratio of copper to magnesium is high, precipitation hardening occurs through precipitation of GP zones through coherent metastable Al2Cu (θ′) to equilibrium Al2Cu (θ) phase. When the ratio of copper to magnesium is low, precipitation hardening occurs through precipitation of GP zones through coherent metastable Al2CuMg (S′) to equilibrium Al2CuMg (S) phase. Lithium provides considerable strengthening through precipitation of coherent Al3Li (δ′) phase. Lithium also forms Al2MgLi and Al2CuLi phases which provide additional strengthening when precipitated in desired size and shape. In addition, lithium reduces density and increases modulus of the aluminum alloys due to its lower density and higher modulus.
The amount of scandium present in the alloys of this invention if any may vary from about 0.1 to about 0.5 weight percent, more preferably from about 0.1 to about 0.35 weight percent, and even more preferably from about 0.1 to about 0.25 weight percent. The Al—Sc phase diagram shown in FIG. 4 indicates a eutectic reaction at about 0.5 weight percent scandium at about 1219° F. (659° C.) resulting in a solid solution of scandium and aluminum and Al3Sc dispersoids. Aluminum alloys with less than 0.5 weight percent scandium can be quenched from the melt to retain scandium in solid solution that may precipitate as dispersed L12 intermetallic Al3Sc following an aging treatment. Alloys with scandium in excess of the eutectic composition (hypereutectic alloys) can only retain scandium in solid solution by rapid solidification processing (RSP) where cooling rates are in excess of about 103° C./second. Alloys with scandium in excess of the eutectic composition cooled normally will have a microstructure consisting of relatively large Al3Sc dispersoids in a finally divided aluminum-Al3Sc eutectic phase matrix.
The amount of erbium present in the alloys of this invention, if any, may vary from about 0.1 to about 6.0 weight percent, more preferably from about 0.1 to about 4.0 weight percent, and even more preferably from about 0.2 to about 2.0 weight percent. The Al—Er phase diagram shown in FIG. 5 indicates a eutectic reaction at about 6 weight percent erbium at about 1211° F. (655° C.). Aluminum alloys with less than about 6 weight percent erbium can be quenched from the melt to retain erbium in solid solutions that may precipitate as dispersed L12 intermetallic Al3Er following an aging treatment. Alloys with erbium in excess of the eutectic composition can only retain erbium in solid solution by rapid solidification processing (RSP) where cooling rates are in excess of about 103° C./second. Alloys with erbium in excess of the eutectic composition (hypereutectic alloys) cooled normally will have a microstructure consisting of relatively large Al3Er dispersoids in a finely divided aluminum-Al3Er eutectic phase matrix.
The amount of thulium present in the alloys of this invention, if any, may vary from about 0.1 to about 10.0 weight percent, more preferably from about 0.2 to about 6.0 weight percent, and even more preferably from about 0.2 to about 4.0 weight percent. The Al—Tm phase diagram shown in FIG. 6 indicates a eutectic reaction at about 10 weight percent thulium at about 1193° F. (645° C.). Thulium forms Al3TM dispersoids in the aluminum matrix that have an L12 structure in the equilibrium condition. The Al3TM dispersoids have a low diffusion coefficient which makes them thermally stable and highly resistant to coarsening. Aluminum alloys with less than 10 weight percent thulium can be quenched from the melt to retain thulium in solid solution that may precipitate as dispersed metastable L12 intermetallic Al3TM following an aging treatment. Alloys with thulium in excess of the eutectic composition can only retain Tm in solid solution by rapid solidification processing (RSP) where cooling rates are in excess of about 103° C./second.
The amount of ytterbium present in the alloys of this invention, if any, may vary from about 0.1 to about 15.0 weight percent, more preferably from about 0.2 to about 8.0 weight percent, and even more preferably from about 0.2 to about 4.0 weight percent. The Al—Yb phase diagram shown in FIG. 7 indicates a eutectic reaction at about 21 weight percent ytterbium at about 1157° F. (625° C.). Aluminum alloys with less than about 21 weight percent ytterbium can be quenched from the melt to retain ytterbium in solid solution that may precipitate as dispersed L12 intermetallic Al3Yb following an aging treatment. Alloys with ytterbium in excess of the eutectic composition can only retain ytterbium in solid solution by rapid solidification processing (RSP) where cooling rates are in excess of about 103° C. per second. Alloys with ytterbium in excess of the eutectic composition cooled normally will have a microstructure consisting of relatively large Al3Yb dispersoids in a finally divided aluminum-Al3Yb eutectic phase matrix.
The amount of lutetium present in the alloys of this invention, if any, may vary from about 0.1 to about 12.0 weight percent, more preferably from about 0.2 to about 8.0 weight percent, and even more preferably from about 0.2 to about 4.0 weight percent. The Al-Lu phase diagram shown in FIG. 8 indicates a eutectic reaction at about 11.7 weight percent Lu at about 1202° F. (650° C.). Aluminum alloys with less than about 11.7 weight percent lutetium can be quenched from the melt to retain Lu in solid solution that may precipitate as dispersed L12 intermetallic Al3Lu following an aging treatment. Alloys with Lu in excess of the eutectic composition can only retain Lu in solid solution by rapid solidification processing (RSP) where cooling rates are in excess of about 103° C./second. Alloys with lutetium in excess of the eutectic composition cooled normally will have a microstructure consisting of relatively large Al3Lu dispersoids in a finely divided aluminum-Al3Lu eutectic phase matrix.
The amount of gadolinium present in the alloys of this invention, if any, may vary from about 0.1 to about 4 weight percent, more preferably from 0.2 to about 2 weight percent, and even more preferably from about 0.5 to about 2 weight percent.
The amount of yttrium present in the alloys of this invention, if any, may vary from about 0.1 to about 4 weight percent, more preferably from 0.2 to about 2 weight percent, and even more preferably from about 0.5 to about 2 weight percent.
The amount of zirconium present in the alloys of this invention, if any, may vary from about 0.05 to about 1 weight percent, more preferably from 0.1 to about 0.75 weight percent, and even more preferably from about 0.1 to about 0.5 weight percent.
The amount of titanium present in the alloys of this invention, if any, may vary from about 0.05 to about 2 weight percent, more preferably from 0.1 to about 1 weight percent, and even more preferably from about 0.1 to about 0.5 weight percent.
The amount of hafnium present in the alloys of this invention, if any, may vary from about 0.05 to about 2 weight percent, more preferably from about 0.1 to about 1 weight percent, and even more preferably from about 0.1 to about 0.5 weight percent.
The amount of niobium present in the alloys of this invention, if any, may vary from about 0.05 to about 1 weight percent, more preferably from about 0.1 to about 0.75 weight percent, and even more preferably from about 0.1 to about 0.5 weight percent.
In order to have the best properties for the alloys of this invention, it is desirable to limit the amount of other elements. Specific elements that should be reduced or eliminated include no more than about 0.1 weight percent iron, about 0.1 weight percent chromium, about 0.1 weight percent manganese, about 0.1 weight percent vanadium, about 0.1 weight percent cobalt, and about 0.1 weight percent nickel. The total quantity of additional elements should not exceed about 1% by weight, including the above listed impurities and other elements.
Other additions in the alloys of this invention include at least one of about 0.001 weight percent to about 0.10 weight percent sodium, about 0.001 weight percent to about 0.10 weight calcium, about 0.001 weight percent to about 0.10 weight percent strontium, about 0.001 weight percent to about 0.10 weight percent antimony, about 0.001 weight percent to about 0.10 weight percent barium and about 0.001 weight percent to about 0.10 weight percent phosphorus. These are added to refine the microstructure of the eutectic phase and the primary magnesium or lithium morphology and size.
These aluminum alloys may be made by any and all consolidation and fabrication processes known to those in the art such as casting (without further deformation), deformation processing (wrought processing), rapid solidification processing, forging, extrusion, rolling, die forging, powder metallurgy and others. The rapid solidification process should have a cooling rate greater that about 103° C./second including but not limited to powder processing, atomization, melt spinning, splat quenching, spray deposition, cold spray, plasma spray, laser melting and deposition, ball milling and cryomilling.
Additional exemplary aluminum alloys of this invention include, but are not limited to (in weight percent):
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.1-0.35)Sc-(0.2-2.0)Gd;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.1-4)Er-(0.2-2.0)Gd;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.2-6)Tm-(0.2-2.0)Gd;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.2-8)Yb-(0.2-2.0)Gd;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.2-8)Lu-(0.2-2.0)Gd;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.1-0.35)Sc-(0.2-2.0)Y;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.1-4)Er-(0.2-2.0)Y;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.2-6)Tm-(0.2-2.0)Y;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.2-8)Yb-(0.2-2.0)Y;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.2-8)Lu-(0.2-2.0)Y;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.1-0.35)Sc-(0.1-0.75)Zr;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.1-4)Er-(0.1-0.75)Zr;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.2-6)Tm-(0.1-0.75)Zr;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.2-8)Yb-(0.1-0.75)Zr;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.2-8)Lu-(0.1-0.75)Zr;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.1-0.35)Sc-(0.1-1.0)Ti;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.1-0.5)Er-(0.1-1.0)Ti;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.2-6)Tm-(0.1-1.0)Ti;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.2-8)Yb-(0.1-1.0)Ti;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.1-4)-Lu-(0.1-1.0)Ti;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.1-0.35)Sc-(0.1-1.0)Hf;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.1-4)Er-(0.1-1.0)Hf;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.2-6)Tm-(0.1-1.0)Hf;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.2-8)Yb-(0.1-1.0)Hf;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.2-8)Lu-(0.1-1.0)Hf;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.1-0.35)Sc-(0.1-0.75)Nb;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.1-4)Er-(0.1-0.75)Nb;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.2-6)Tm-(0.1-0.75)Nb;
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.2-8)Yb-(0.1-0.75)Nb; and
about Al-(2-7)Cu-(0.4-3)Mg-(1-2.5)Li-(0.2-8)Lu-(0.1-0.75)Nb.
Preferred examples of similar alloys to these are alloys with about 3.5 to about 6.5 weight percent copper, alloys with about 0.5 to about 2.0 weight percent magnesium, and alloys with about 1.0 to about 2.0 weight percent lithium.
Even more preferred exemplary aluminum alloys of this invention include, but are not limited to (in weight percent):
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.1-0.25)Sc-(0.2-2.0)Gd;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-2)Er-(0.2-2.0)Gd;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-4)Tm-(0.2-2.0)Gd;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-4)Yb-(0.2-2.0)Gd;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-4)Lu-(0.2-2.0)Gd;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.1-0.25)Sc-(0.5-2.0)Y;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-2)Er-(0.5-2.0)Y;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-4)Tm-(0.5-2.0)Y;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-4)Yb-(0.5-2.0)Y;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-4)Lu-(0.5-2.0)Y;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.1-0.25)Sc-(0.1-0.5)Zr;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-2)Er-(0.1-0.5)Zr;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-4)Tm-(0.1-0.5)Zr;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-4)Yb-(0.1-0.5)Zr;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-4)Lu-(0.1-0.5)Zr;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.1-0.25)Sc-(0.1-0.5)Ti;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.1-0.5)Er-(0.1-0.5)Ti;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-4)Tm-(0.1-0.5)Ti;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-4)Yb-(0.1-0.5)Ti;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.1-4)-Lu-(0.1-0.5)Ti;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.1-0.25)Sc-(0.1-0.5)Hf;
about Al-(-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-2)Er-(0.1-0.5)Hf;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-4)Tm-(0.1-0.5)Hf;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-4)Yb-(0.1-0.5)Hf;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-4)Lu-(0.1-0.5)Hf;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.1-0.25)Sc-(0.1-0.5)Nb;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-2)Er-(0.1-0.5)Nb;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-4)Tm-(0.1-0.5)Nb;
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-4)Yb-(0.1-0.5)Nb; and
about Al-(3.5-6.5)Cu-(0.5-2)Mg-(1-2)Li-(0.2-4)Lu-(0.1-0.5)Nb.
Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention.

## Claims

1. A method of forming a heat treatable aluminum alloy, the method comprising:
(a) forming a melt consisting of:
about 1.0 to about 8.0 weight percent copper;
about 0.2 to about 4.0 weight percent magnesium;
about 0.5 to about 3.0 weight percent lithium;
at least one first element selected from the group consisting of about 0.1 to about 0.5 weight percent scandium, about 0.1 to about 6.0 weight percent erbium, about 0.1 to about 10.0 weight percent thulium, about 0.1 to about 15.0 weight percent ytterbium, and about 0.1 to about 12.0 weight percent lutetium;
at least one second element selected from the group consisting of about 0.1 to about 4.0 weight percent gadolinium, about 0.1 to about 4.0 weight percent yttrium, about 0.05 to about 1.0 weight percent zirconium, about 0.05 to about 2.0 weight percent titanium, about 0.05 to about 2.0 weight percent hafnium, and about 0.05 to about 1.0 weight percent niobium;
and the balance substantially aluminum;

(b) solidifying the melt to form a solid body; and
(c) heat treating the solid body.

2. The method of claim 1, further comprising:
refining the structure of the solid body by deformation processing comprising at least one of: extrusion, forging and rolling.

3. The method of claim 1, wherein solidifying comprises a casting process.

4. The method of claim 1, wherein solidifying comprises a rapid solidification process in which the cooling rate is greater than about 103° C./second and comprising at least one of: powder processing, atomization, melt spinning, splat quenching, spray deposition, cold spray, plasma spray, laser melting, laser deposition, ball milling, and cryomilling.

5. The method of claim 1, wherein the heat treating comprises:
solution heat treatment at about 800° F. (426° C.) to about 1100° F. (593° C.) for about thirty minutes to four hours;
quenching; and
aging at about 200° F. (93° C.) to about 600° F. (316° C.) for about two to forty-eight hours.

6. A method of forming a heat treatable aluminum alloy, the method comprising:
(a) forming a melt consisting of:
about 1.0 to about 8.0 weight percent copper;
about 0.2 to about 4.0 weight percent magnesium;
about 0.5 to about 3.0 weight percent lithium;
at least one first element selected from the group consisting of about 0.1 to about 0.5 weight percent scandium, about 0.1 to about 6.0 weight percent erbium, about 0.1 to about 10.0 weight percent thulium, about 0.1 to about 15.0 weight percent ytterbium, and about 0.1 to about 12.0 weight percent lutetium;
at least one second element selected from the group consisting of about 0.1 to about 4.0 weight percent gadolinium, about 0.1 to about 4.0 weight percent yttrium, about 0.05 to about 1.0 weight percent zirconium, about 0.05 to about 2.0 weight percent titanium, about 0.05 to about 2.0 weight percent hafnium, and about 0.05 to about 1.0 weight percent niobium;
consisting of no more than about 0.1 weight percent iron, about 0.1 weight percent chromium, about 0.1 weight percent manganese, about 0.1 weight percent vanadium, about 0.1 weight percent cobalt, and about 0.1 weight percent nickel;
no more than about 1.0 weight percent total other additional elements not listed therein including impurities;
and the balance substantially aluminum;

(b) solidifying the melt to form a solid body; and
(c) heat treating the solid body.

7. The method of claim 6, further comprising:
refining the structure of the solid body by deformation processing comprising at least one of: extrusion, forging and rolling.

8. The method of claim 6, wherein solidifying comprises a casting process.

9. The method of claim 6, wherein solidifying comprises a rapid solidification process in which the cooling rate is greater than about 103° C./second and comprising at least one of: powder processing, atomization, melt spinning, splat quenching, spray deposition, cold spray, plasma spray, laser melting, laser deposition, ball milling, and cryomilling.

10. The method of claim 6, wherein the heat treating comprises:
solution heat treatment at about 800° F. (426° C.) to about 1100° F. (593° C.) for about thirty minutes to four hours;
quenching; and
aging at about 200° F. (93° C.) to about 600° F. (316° C.) for about two to forty-eight hours.

11. A method of forming a heat treatable aluminum alloy, the method comprising:
(a) forming a melt consisting of:
about 1.0 to about 8.0 weight percent copper;
about 0.2 to about 4.0 weight percent magnesium;
about 0.5 to about 3.0 weight percent lithium;
at least one first element selected from the group consisting of about 0.1 to about 0.5 weight percent scandium, about 0.1 to about 6.0 weight percent erbium, about 0.1 to about 10.0 weight percent thulium, about 0.1 to about 15.0 weight percent ytterbium, and about 0.1 to about 12.0 weight percent lutetium;
at least one second element selected from the group consisting of about 0.1 to about 4.0 weight percent gadolinium, about 0.1 to about 4.0 weight percent yttrium, about 0.05 to about 1.0 weight percent zirconium, about 0.05 to about 2.0 weight percent titanium, about 0.05 to about 2.0 weight percent hafnium, and about 0.05 to about 1.0 weight percent niobium;
no more than about 1.0 weight percent total other additional elements not listed therein including impurities;
and the balance substantially aluminum;

(b) solidifying the melt to form a solid body; and
(c) heat treating the solid body.

12. The method of claim 11, further comprising:
refining the structure of the solid body by deformation processing comprising at least one of: extrusion, forging and rolling.

13. The method of claim 11, wherein solidifying comprises a casting process.

14. The method of claim 11, wherein solidifying comprises a rapid solidification process in which the cooling rate is greater than about 103° C./second and comprising at least one of: powder processing, atomization, melt spinning, splat quenching, spray deposition, cold spray, plasma spray, laser melting, laser deposition, ball milling, and cryomilling.

15. The method of claim 11 wherein the heat treating comprises:
solution heat treatment at about 800° F. (426° C.) to about 1100° F. (593° C.) for about thirty minutes to four hours;
quenching; and
aging at about 200° F. (93° C.) to about 600° F. (316° C.) for about two to forty-eight hours.