WO2018009359A1

WO2018009359A1 - Ribbons and powders from high strength corrosion resistant aluminum alloys

Info

Publication number: WO2018009359A1
Application number: PCT/US2017/039211
Authority: WO
Inventors: Nhon Q. VO; Joseph R. CROTEAU; Davaadorj BAYANSAN; Amirreza Sanaty-Zadeh; Evander RAMOS
Original assignee: NanoAL LLC
Priority date: 2016-07-05
Filing date: 2017-06-26
Publication date: 2018-01-11
Also published as: JP7049312B2; EP3481971A4; CN109844150A; JP2019527299A; EP3481971A1

Abstract

Aluminum alloys, fabricated by a rapid solidification process, with high strength, high ductility, high corrosion resistance, high creep resistance, and good weldability.

Description

RIBBONS AND POWDERS FROM HIGH STRENGTH

CORROSION RESISTANT ALUMINUM ALLOYS

[ 0001 ] The present application claims the benefit of the filing dates of US Ser. No. 62/358,400, filed 5 July 2016, and

US Ser. No. 62/477,838, filed 28 March 2017. This invention was made with government support under PTE Federal Award No. W911NF-

15-2-0026, Subaward No. 504062-78050, awarded by DOD/US Army through PTE Northeastern University. The Government has certain rights in the invention.

FIELD

[ 0002 ] This application relates to a family of aluminum alloys with high strength and ductility, excellent corrosion resistance and weldability. The disclosed alloys are especially advantageous for improving performance of aerospace, automotive, and recently developed additive manufacturing or so-called "3D- printing" components, and for forming a protective coating for magnesium or aluminum components.

BACKGROUND

[ 0003 ] Aluminum alloys have a wide range of applications in light weight structures in aerospace, automotive, marine, wire and cable, electronics, nuclear, and consumer products

industries. Typically, aluminum alloys are produced by a

traditional casting process, in which they are melted then poured into molds. The cast article can be near net-shape or in slab or billet forms, which are subsequently rolled to form sheet and plate products or extruded to produce profiles.

Properties of the final products, thus, depend on the aluminum alloys' chemistry, casting solidification rate, and subsequent thermo-mechanical processes. The solidification rate of the aluminum alloys during traditional casting process is relatively low (<50 °C/s). Thus, only certain casting microstructures in aluminum alloys can be obtained by a traditional casting process .

[ 0004 ] Rapid solidification processes (RSP) developed in the past decades can achieve refined grain size and extended solid solubility of alloying elements, and form non- equilibrium metastable phases. These enhance the properties of the alloys as compared to the ones manufactured by the traditional casting methods. RSP requires the solidification rate to be higher than 1,000 °C/s. The time of contact between the molten aluminum and quenching medium is limited to a few thousandths of a second. The quenching medium, such as copper, water, or liquid nitrogen, significantly lowers the temperature of the molten aluminum to below its solidus temperature in a short amount of time, hence, rapid solidification is achieved by a very fast cooling rate. See U.S. Pat. No. 4,347,076.

[ 0005 ] A number of different RSP have been developed

including gas atomization, spray deposition, melt spinning, melt extraction and beam glazing. Fabricated products can be in the form of ribbons, fibers, flakes, splats, granules, and powders. These small individual fragments are typically processed (cold isostatic compaction, hot pressing and extrusion) to fabricate the final products. Applications of aluminum alloys that are fabricated by RSP are in racing, automotive, aerospace,

sporting, medical component, electronics, and optical

industries .

[ 0006 ] Recent efforts in the prior art have been made to produce aluminum-magnesium- scandium alloys by RSP. These alloys typically contain high concentration of magnesium (3 to 5 wt.%) and scandium (0.7-1.4 wt.%) . The alloys are strengthened by a combination of Al₃Sc Ll₂-structured nano-precipitates and

aluminum matrix solid solution containing magnesium. The Al₃Sc nano-precipitates form during solidification and subsequent aging in the temperature range from 250 to 350 °C. The nano- precipitates are also responsible for the good weldability. See U.S. Pat. No. 5,624,632.

[ 0007 ] However, there are several drawbacks with Al-Mg-Sc alloys produced by RSP. Scandium is very expensive (ten- fold as expensive as silver) . Thus, the cost of the Al-Mg-Sc alloy is very high, which severely limits its commercial application. This alloy also has a limited thermal working window (<375 °C) . Beyond this temperature, the beneficial strengthening of the Al₃Sc nano-precipitates is permanently lost because they rapidly coarsen and become ineffective. This limits the extrusion temperature to be less than 375 °C, which is undesirable to obtain fully dense extruded components.

[ 0008 ] Accordingly, it is desirable to improve upon the drawbacks of the Al-Mg-Sc alloys, produced by RSP, while maintaining the same combination of other properties. These include high strength at room and at elevated temperatures, high creep resistance, good weldability, and high corrosion

resistance .

SUMMARY

[ 0009 ] The embodiments described herein relate to aluminum alloys, fabricated by any rapid solidification process, and can be heat-treated (aged) to achieve precipitation and dispersion hardening. They have high strength and ductility, high creep resistance, excellent corrosion resistance, and weldability. In some embodiments, the alloys are heat and creep resistant at temperatures as high as 400 °C. These alloys comprise 1 to 10% by weight magnesium, 0.3-3% by weight zirconium and preferably 0.45-3% by weight zirconium, optional 0.3-1.5% by weight

vanadium, with aluminum as the remainder. The aluminum alloys contain a simultaneous dispersion of Al₃Zr primary precipitates, having an average diameter ranging from 0.05 to 1.5 μτη, and a dispersion of nano-precipitates of Al₃Zr having Ll₂ crystal structure in the aluminum matrix, having an average diameter ranging from 3 to 50 nm.

[00010] It has been found that thermally stable Al₃Zr primary precipitates are formed during RSP and thermally stable Al₃Zr nano-precipitates are formed during a subsequent aging process in the Al-Mg-Zr alloys. Both Al₃Zr primary precipitates and nano- precipitates are stable and coarsening-resistant up to the operating temperature of 425 °C, due to the low diffusivity of zirconium in aluminum. It results in an aluminum alloy with high strength at both room- and elevated- temperatures , for extended period of times. The alloys are completely free of scandium, or at least no scandium is added intentionally and any scandium present as an impurity does not exceed 0.05 wt%. This results in the low material cost . Due to the very high thermal

stability, the disclosed materials can be extruded at a higher thermal working window (up to 450 °C) compared to Al-Mg-Sc alloys (only up to 350 °C) . The foregoing results in lower extrusion forces, thus lowering the extrusion cost. It also results in denser (less porous) extruded materials, thus, higher quality extruded parts utilizing the disclosed alloys.

[00011] In some embodiments, the aluminum alloys comprise magnesium and at least one element selected from Group 4B

elements Ti , Zr and Hf, Group 5B elements V, Nb and Ta, and

Group 6B elements Cr, Mo and W. These alloys possess high strength at room and at elevated temperatures, high creep

resistance, high corrosion resistance and good weldability.

[00012] A component fabricated from a rapidly solidified powder or ribbon utilizing a method such as additive

manufacturing, spray deposition, or compaction, has a

significant concentration of alloying elements trapped in solid- solution. When the manufactured component is subjected to a single-step heat treatment as discussed below, nano-scale aluminum- transition metal precipitates are formed. This differs from conventional alloys which often require a two-step heat treatment consisting of a " solutionizing" or "homogenizing" heat treatment at temperatures above about 450 °C, followed by a precipitation heat treatment at temperatures between about 100 and 200 °C.

BRIEF DESCRIPTION OF THE DRAWINGS

[00013] Figure 1 is Knoop microhardness evolution, as a function of the highest aging temperature, of baseline Al-4.5Mg, Al-4.5Mg-0.5Sc and disclosed embodiment Al -4.5Mg- 0.5Zr at . % alloy (Al-4Mg, Al-4Mg-0.8Sc and Al-4Mg- 1.7Zr wt.%, respectively) in the form of ribbons, produced by melt spinning. Heat

treatment is performed in the form of isochronal aging with 25 °C/2 h increments.

[00014] Figure 2 is Knoop microhardness evolution, as a function of the highest aging temperature, of baseline Al-4.5Mg and disclosed embodiment Al-4.5Mg-0.5Zr at . % alloy (Al-4Mg and Al-4Mg-1.7Zr wt.%, respectively) , produced by melt spinning at different wheel speeds 12 m/s and 40 m/s. Heat treatment is performed in the form of isochronal aging with 25 °C/2 h

increments .

[00015] Figure 3 shows a scanning electron microscope images of the microstructure of an example alloy Al-4Mg-1.7Zr wt.% alloy, fabricated by a melt spinning process.

[00016] Figure 4 shows peak microhardness of disclosed

embodiments Al - 4.5Mg- 0.5TM at . % alloys, where TM is the

indicated transition metal (Group 4B elements Ti, Zr and Hf, Group 5B elements V, Nb and Ta, and Group 6B elements Cr and Mo) , produced by melt spinning at 12 m/s, during isochronal aging with 25 °C/2hr increments. [ 00017 ] Figure 5 shows peak microhardness of disclosed embodiments Al-4Mg-0.5Zr-0.1TM at . % alloys, where TM is the indicated transition metal (Group 4B elements Ti and Hf, and Group 5B elements V, Nb and Ta) , produced by melt spinning at 12 m/s, during isochronal aging with 25 °C/lhr increments.

[ 00018 ] Figure 6 shows a plot of Vickers Microhardness for several 3D-printed components, in both as-printed and peak-aged condition, from Al-3.6Mg-l.2Zr wt . % powder having the same alloy composition but being 3D-printed using different parameters.

[ 00019 ] Figure 7 shows a scanning electron micrograph of the microstructure of a 3D-printed component in the as -printed condition from Al-3.6Mg-l.2Zr wt . % powder.

[ 00020 ] Figure 8 shows a scanning electron micrograph of the microstructure of a 3D-printed component in the as-printed condition from Al-3.6Mg-l.2Zr wt . % powder after it has been aged at 400°C for 8 hours.

[ 00021 ] Figure 9 shows a scanning electron micrograph of the microstructure of a 3D-printed component in the as-printed condition from Al - 3.6Mg- 1.2Zr wt . % powder after it has been aged at 400°C for 144 hours.

[ 00022 ] Figure 10 shows a large-view scanning electron

micrograph of the microstructure of a 3D-printed component in the as-printed condition from Al - 3.6Mg- 1.2Zr wt . % powder after it has been aged at 400°C for 144 hours.

[ 00023 ] Figure 11 shows a scanning electron micrograph of the boundary between the coarse and fine grain region of a 3D- printed component in the as -printed condition from Al-3.6Mg- 1.2Zr wt . % powder.

[ 00024 ] Figure 12 shows a high-magnification scanning electron micrograph of the fine-grain region of a 3D-printed component in the as-printed condition of a 3D-printed component from Al- 3.6Mg-1.2Zr wt . % powder. [ 00 025 ] Figure 13 shows a scanning electron micrograph of the microstructure of a 3D-printed component in the as-printed condition from Al-3.6Mg-l.2Zr wt . % powder after it has been aged at 400 °C for 8 hours followed by an extended exposure at 300°C for 144 hours.

[ 00 026 ] Figure 14 compares the tensile yield strength, ultimate tensile strength (UTS) , and elongation of a disclosed alloy (3D-printed component in the peak-aged condition from Al- 3.6Mg-1.2Zr wt . % powder) compared to that of commercially 3D- printed aluminum alloys.

DETAILED DESCRIPTION

[ 0 0 027 ] The embodiments described herein relate to aluminum alloys, fabricated by a rapid solidification process, with high strength and ductility, high creep resistance, and excellent corrosion resistance and weldability. The alloys are heat- and creep-resistant at temperatures as high as 400°C.

[ 0 0 02 8 ] In some embodiments, these alloys comprise 1 to 10% by weight magnesium, 0.3-3% by weight zirconium and preferably 0.45-3% by weight zirconium, optional 0.3-1.5% by weight

vanadium, and aluminum as the remainder. The aluminum alloys contain a simultaneous dispersion of Al₃Zr primary precipitates, having an average diameter ranging from 0.05 to 1.5 μχη, and a dispersion of nano-precipi tates of Al₃Zr having Ll₂ crystal structure in the aluminum matrix, having an average diameter ranging from 3 to 50 nm. The alloys of disclosed embodiments can be produced by any rapid solidification process including gas atomization (e.g. to produce aluminum powders) , spray

deposition, melt spinning (e.g. to produce aluminum ribbons) , melt extraction, beam glazing. Additionally, these alloys can be fabricated by other non-equilibrium processes such as mechanical alloying. The alloys can be heat-treated (aged) to achieve precipitation hardening. [00029] Al-Sc alloys form nanometer- scale , coherent, reordered Al₃Sc precipitates (structurally and chemically analogous to the Ni₃Al γ' -phase in nickel-based superalloys) resulting in significant precipitation hardening (U.S. Pat. No. 5,597,529) . Scandium, however, is very expensive and rare. Moreover, Al₃Sc precipitates are only coarsening resistant to 325 °C because of the moderate diffusivity of Sc in aluminum matrix. Improved coarsening resistance, to -400 °C, can be achieved by alloying Al-Sc alloys with the neighboring Group VI_A transition metal (Ti, Zr, Hf ) , which are much slower diffusers in Al than Sc. Among the three transition metals, Zr provides the best coarsening resistance characteristics, due to favorable thermodynamic and kinetic properties in the aluminum matrix. Magnesium is commonly added to Al-Sc alloys to provide solid solution strengthening. It also improves corrosion resistance for the alloys.

[00030] In disclosed embodiments, it is shown that Zr can replace Sc completely in the Al-Mg-Sc alloys that are produced by RSP. The following alloy compositions have been produced utilizing a melt spinner, an RSP: Al -4.5Mg- 0.2Zr and Al-4.5Mg- 0.5Zr at. % or Al-4Mg-0.7Zr and Al-4Mg-1.7Zr wt . % . The strength of these two alloys are comparable to that of Al-4.5Mg-0.2Sc and Al-4.5Mg-0.5Sc (at.%) alloys, produced by a melt spinner. It is demonstrated in Figure 1. Peak strength of Al -4.5Mg- 0.5Zr at.%, obtained at 425 °C, is comparable to that of Al-4.5Mg-0.5Sc at.%, obtained at 325 °C, during isochronal aging. The discovery is important because the cost of Zr is about a thousand times lower than Sc, thus the material cost of Al-Mg-Zr alloys is low. Moreover, due to the very high thermal stability, the Al-Mg-Zr alloys can be extruded at a higher thermal working window (up to 450 °C) compared to Al-Mg-Sc alloys (only up to 350 °C) . It results in lower extrusion forces, thus lowering the extrusion cost. It also results in denser material, thus, higher quality extruded parts utilizing the Al-Mg-Zr alloys.

[ 00031] Vanadium is known to be able to substitute Zr in the Ll₂-structured Al₃Zr phase. Thus, V co-precipitates with Zr during heat aging. Co-precipitation of V and Zr will increase the volume fraction of Al₃(Zr,V) nano-precipitates , thus

increasing strength of the Al-Mg-Zr-V alloys. Vanadium is also known to decrease the melting point of Al-Zr alloys, which makes the powder fabricating process easier. Moreover, elements in the Group 4B, such as Ti and Hf, and Group 5B, such as Nb and Ta, are also known to form Ll₂-structured Al₃(Zr,X) nano- precipitates, where X can be Ti, Hf , Nb, or Ta.

[ 00032 ] Zirconium has a low liquid solubility (~0.11 wt.%) at the melting temperature of aluminum (-660 °C) and a low solid solubility (<0.01 wt.%) at room temperature in aluminum. Thus, it tends to precipitate and form Al₃Zr primary phase during cooling in the liquid phase and during solidification in the traditional casting process. Therefore, the maximum Zr

concentration that is utilized to strengthen aluminum matrix by precipitation strengthening and/or to act as a grain refiner is limited to about 0.3 wt.% for conventional methods. Beyond this concentration, the cast material contains large Al₃Zr primary phases, which do not contribute to the strengthening. However, during RSP, the solidification rate can be higher than 1,000 °C/s. It takes much less than a second to solidify the molten aluminum from the casting to room temperature. Thus Zr solute atoms in the Al matrix do not have enough time to precipitate and form large primary precipitates. It was found that during a melt spinning process with the casting temperature above 1,100 °C, Zr forms a dispersion of fine Al₃Zr primary precipitates, having an average diameter ranging from 0.05 to 1.5 /m, along with a high concentration of Zr solute atoms in the aluminum matrix. The fine Al₃Zr primary precipitates act as reinforcement strengthener , whereas Zr solute atoms form Al₃Zr nano-precipitate during subsequent heat treatment, acting as a precipitation strengthener. Both strengthening mechanisms are responsible for the observed high strength in Al-4Mg-1.7Zr wt . % alloy.

Dispersion of fine primary precipitates during RSP is also anticipated in aluminum alloys containing Group 4B elements (Ti or Hf ) besides Zr, Group 5B elements (V, Nb or Ta) , and Group 6B elements (Cr, Mo or W) . Additionally, the fine Al₃Zr primary precipitates also act as grain refiner, producing small grain size in the Al matrix, which also contributes to the

strengthening .

[ 00033 ] In disclosed embodiments, it is shown that reducing the casting wheel speed from 40 to 12 m/s during melt spinning only slightly reduces the maximum strength of Al-4Mg-1.7Zr wt . % alloy. Reducing the casting wheel speed is equivalent to

reducing the solidification rate. However, the solidification rate is anticipated to still be higher than 1,000 °C/s for the lower casting wheel speed of 12 m/s. It is shown that in this high solidification rate regime, the maximum strength of Al-4Mg- 1.7Zr wt . % alloy is insensitive to the actual cooling rate. This is demonstrated in Figure 2.

[ 00034 ] Magnesium in the disclosed alloys acts as a solid solution strengthener. Magnesium has high solid solubility in aluminum at all temperatures. Thus 4 wt . % Mg remains in solid solution during RSP and subsequent heat treatments. It is also the case during arc welding, where the aluminum alloys are melted and re-solidified, or during friction- stir welding, where the aluminum alloys are heated and cooled down to room

temperature. Thus, Al-Mg-based alloys are typically considered to have good weldability. Magnesium is also known for improving corrosion resistance of aluminum alloys. Therefore, Al-Mg-based alloys are commonly utilized in marine applications.

[ 00035 ] Comparing to the Al -4.5Mg- 0.5Sc alloy, the Al-4.5Mg- 0.5Zr at . % alloy also has a higher operating temperature range. During subsequent heat treatment, precipitation of Ll₂- structured Al₃Sc nano-precipitates occurs at the temperature range of 250- 350 °C, whereas precipitation of Ll₂-structured Al₃Zr nano- precipitates occurs at the temperature range of 350-450 °C. This is demonstrated in Figure 1. It means that after aging, the operating temperature of Al-4.5Mg-0.5Sc and Al-4.5Mg-0.5Zr at . % alloys need to be less than 350 and 450 °C, respectively, as exceeding these temperatures would lead to rapid coarsening and loss of strength. This is important for a hot extrusion process, in which the higher thermal working window results in denser and higher quality extruded parts. It also results in lower

extrusion forces, thus low-capacity extruders can be utilized. Currently the extrusion temperature for the Al-4.5Mg-0.5Sc alloy is limited to about 350 °C. For the disclosed Al-Mg-Zr alloys, the compacted powders or ribbons can be extruded at temperatures up to 450 °C, a large improvement in terms of thermal working window .

[ 00036 ] Figure 3 shows scanning electron microscope images of the microstructure of an example alloy Al-4Mg-1.7Zr wt . % alloy, fabricated by a melt spinning process. The microstructure is homogenous with a fine uniform distribution of primary Al₃Zr precipitates .

[ 00037 ] Figure 4 shows peak microhardness of disclosed

embodiments Al-4.5Mg-0.5TM at . % alloys, where TM is the

indicated transition metal (Group 4B elements Ti, Zr and Hf, Group 5B elements V, Nb and Ta, and Group 6B elements Cr and Mo) , produced by melt spinning at 12 m/s, during isochronal aging with 25 °C/2hr increments. It shows that additions of transition elements in the base Al-4.5Mg at . % alloy drastically increase the alloy's strength. Zirconium appears to be to the most effective, compared to other investigated transition elements .

[00038] Figure 5 shows peak microhardness of disclosed embodiments Al-4Mg-0.5Zr-0.1TM at . % alloys, where TM is the indicated transition metal (Group 4B elements Ti and Hf, and Group 5B elements V, Nb and Ta) , produced by melt spinning at 12 m/s, during isochronal aging with 25 °C/lhr increments. It shows that additions of Zirconium, combined with other

transition metals, in the base Al-4Mg at . % alloy drastically increase the alloy's strength.

[00039] Figure 6 shows a plot of Vickers microhardness for several 3D-printed components from Al-3.6Mg-l .2Zr wt . % powder having the same alloy composition but being 3D-printed using different parameters. Trials 1 - 5 used powder with an average size of 37 μπι, and trials 7 - 9 used powder with an average size of 13 μπι. Both the as -printed hardness and the maximum

achievable hardness after heat treating are statistically equivalent per a sample t-test, showing that the alloy chemistry and age-hardening potential are unaffected by the printing parameter. Error bars represent one standard deviation of 10 measurements taken on the same sample.

[00040] Figure 7 shows a scanning electron micrograph of the microstructure of a 3D-printed component in the as-printed condition from Al - 3.6Mg- 1.2Zr wt . % powder. A mixture of coarse, columnar and fine grains is evident, and primary precipitates are evident in the fine grain regions.

[00041] Figure 8 shows a scanning electron micrograph of the microstructure of a 3D-printed component in the as-printed condition from Al-3.6Mg-l .2Zr wt . % powder after it has been aged at 400 °C for 8 hours. It is evident that the coarse, columnar grains have recrystallized so that they are now equiaxed.

Precipitates are evident in the fine grain regions and prohibit grain growth during aging.

[ 00042 ] Figure 9 shows a scanning electron micrograph of the microstructure of a 3D-printed component in the as -printed condition from Al-3.6Mg-l.2Zr wt . % powder after it has been aged at 400°C for 144 hours. It is evident that precipitates have coarsened, which is followed by grain growth in the fine grain region .

[ 00043 ] Figure 10 shows a large-view scanning electron

micrograph of the microstructure of a 3D-printed component in the as-printed condition from Al - 3.6Mg- 1.2Zr wt . % powder after it has been aged at 400°C for 144 hours. It is evident that both precipitate and grain coarsening have resulted in an essentially homogenous microstructure, which promotes isotropic mechanical properties .

[ 00044 ] Figure 11 shows a scanning electron micrograph of the boundary between the coarse and fine grain regions. Cubic Ll₂ precipitates act as seed crystals to promote formation of nano- grains in the 3D-printed component from Al-3.6Mg-l.2Zr wt . % powder .

[ 00045 ] Figure 12 shows a high-magnification scanning electron micrograph of the fine-grain region of a 3D-printed component in the as-printed condition. A cubic Ll₂ precipitate is centered in a grain, acting as a seed crystal to promote nano-grains in the 3D-printed component from Al-3.6Mg-l.2Zr wt . % powder.

[ 00046 ] Figure 13 shows a scanning electron micrograph of the microstructure of a 3D-printed component in the as-printed condition from Al-3.6Mg-l.2Zr wt . % powder after it has been aged at 400 °C for 8 hours followed by an extended exposure at 300°C for 144 hours. Thermally stable microstructure consisting of a mixture of coarse grains and fine, equiaxed grains about 1 micrometer, is pinned by cubic Ll₂ Al₃Zr precipitates.

[ 00047 ] Figure 14 compares the tensile yield strength, ultimate tensile strength (UTS) , and elongation of a disclosed alloy (3D-printed component in the peak-aged condition from Al- 3.6Mg-1.2Zr wt . % powder) compared to that of commercial 3D- printed aluminum alloys. Disclosed alloys achieve the highest yield strength and the best combination of yield strength and ductility, compared to that of commercial 3D-printed aluminum alloys .

[ 00048 ] Some embodiments of the disclosed aluminum alloys comprise about 1 to 10% by weight magnesium, and about 0.3 to about 3% by weight zirconium and preferably about 0.45 to about 3% by weight zirconium, with aluminum as the remainder, wherein the alloy possesses high strength and ductility at room and at elevated temperatures, high creep resistance, high corrosion resistance, and good weldability. Some embodiments further comprise about 0.3 to about 1.5% by weight of at least one of titanium, hafnium, vanadium, niobium and tantalum. In some embodiments, the alloy comprises a dispersion of Al₃Zr primary precipitates, having an average diameter ranging from about 0.05 to about 1.5 μτ . In some embodiments, the alloy comprises a dispersion of nano-precipitates of Al₃Zr with Ll₂ crystal structure in the aluminum matrix, having an average diameter ranging from about 3 to about 50 nm. In some of the

embodiments, the alloy comprises an aluminum solid solution matrix and a simultaneous dispersion of Al₃Zr primary

precipitates, having an average diameter ranging from about 0.05 to about 1.5 μτη, and a dispersion of nano-precipitates of Al₃Zr with hi2 crystal structure in the aluminum matrix, having an average diameter ranging from about 3 to about 50 nm. Some embodiments further comprise unavoidable impurities including at least one of zinc, copper, manganese, chromium, silicon and iron. Some embodiments are completely free of scandium. At least no scandium is added intentionally, though some

embodiments further comprise scandium as an impurity not exceeding about 0.05 wt . % . Some embodiments are completely free of erbium, thulium, ytterbium, and lutetium. At least none of those elements is added intentionally, though some embodiments further comprise any one of erbium, thulium, ytterbium, or lutetium as an impurity not exceeding about 0.05 wt . % .

[00049] Some embodiments of the disclosed aluminum alloys comprise magnesium; and at least one element selected from Group 4B elements Ti, Zr, and Hf, Group 5B elements V, Nb and Ta, and Group 6B elements Cr, Mo and W; with aluminum as the remainder, wherein the alloy possesses high strength and ductility at room and at elevated temperatures, high creep resistance, high corrosion resistance and good weldability. In some embodiments, the alloy is completely free of an intentionally added scandium, erbium, thulium, ytterbium, or lutetium. In some embodiments, the alloy comprises a dispersion of nano-scale aluminum- transition metal precipitates in the aluminum matrix, having an average diameter ranging from about 3 nm to about 50 nm, and where the transition metals are selected from the group

consisting of Ti , Zr, Hf, V, Nb, Ta, Cr, Mo, and W.

[00050] Some embodiments of the disclosed aluminum alloys are thermally stable up to an operating temperature of about 425 °C. For some embodiments, the alloy can be extruded at a thermal working window up to about 450 °C.

[00051] Some embodiments of the disclosed aluminum alloys are produced by a rapid solidification process. In some

embodiments, the rapidly solidified alloy has a fine grain structure with average grain diameters between about 200 nm and about 2 μπι. The average grain diameter is influenced by the alloy chemistry and can be controlled by the concentration of alloying components.

[ 00052 ] The disclosed aluminum alloys may be fabricated in various forms, such as powder, chips, ribbons, wires, sheets, plates, or foils. Powder fabricated from the disclosed alloys can, for example, be compacted by hot isostatic pressing, uniaxial hot pressing or any other pressure-assisted methods, and finally, optionally, extruded to a component. Ribbons fabricated from the disclosed alloys can, for example, be cut into chips, then compacted by hot isostatic pressing, uniaxial hot pressing or any other pressure-assisted methods, and finally, optionally, extruded to a component.

[ 00053 ] There are many applications for extruded components formed of the disclosed aluminum alloys, such as aerospace, automotive, and marine applications, for example.

[ 00054 ] The disclosed alloys can, for example, be fabricated as a powder and used by a cold spray process to form a

protective coating for magnesium or aluminum components. The cold spray process can also be used to restore the worn surface of a component by depositing a new layer of material.

[ 00055 ] Powder fabricated from the disclosed alloys can, for example, can be utilized in an additive manufacturing method. Characteristics of the disclosed aluminum alloys, including high strength and weldability, are specifically important for additive manufacturing processes, or so-called 3D-printing, such as powder bed methods, selective laser melting, direct metal laser sintering, laser engineering net shaping, and especially powder- fed directed energy deposition. During the powder- fed directed energy deposition process, aluminum powders are fully or partially melted by laser energy and welded together to form bigger parts. Upon re- solidification, the solidification rate is very fast due to surrounding cold powders and underlying solid material acting as quenching medium. Thus, the additive manufacturing process is generally considered an RSP. Good weldability of the powders is important to create porosity- free welded or 3D-printed parts.

[ 00056 ] The additively manufactured component made of gas- atomized powders of the disclosed alloys can be heat-treated after production at temperatures between about 350 to about 450 °C for times between about 0.5 to about 24 hours to achieve precipitation and dispersion strengthening. The microstructure of such peak-aged, additively manufactured components is thermally stable and is unchanged by exposure to elevated temperatures for extended times. Such a peak-aged, additively manufactured component is strengthened by the following

mechanisms: solid solution strengthening, Al₃Zr primary

precipitates, having an average diameter ranging from about 0.05 to about 1.5 μτα , a dispersion of nano-precipitates of Al₃Zr having Ll₂ crystal structure in the aluminum matrix, having an average diameter ranging from about 3 to about 50 nm, and grain boundary strengthening resulting from fine grains.

[ 00057 ] The properties of the additively manufactured

component, including high- strength and low-density (i.e., high specific strength) make it suitable for applications which require high- strength at or below room temperature. Such

applications include, but are not limited to, structural

components of vehicle chasses and suspensions for land- , air- and sea-craft, structural components of satellites and

spacecraft, weaponry and defense systems, prosthetics,

recreational and leisure equipment, artistic and novelty items.

[ 00058 ] The properties of the additively manufactured

component, including high-strength and low-density (i.e., high specific strength) combined with good corrosion resistance, make it suitable for applications which require high- strength at or below room temperature in harsh environments. Such applications include, but are not limited to, structural components of sea- craft, recreational and leisure equipment, artistic and novelty items .

[ 00059 ] The properties of the additively manufactured

component, including high- strength, thermal stability, and creep resistance, make it suitable for applications which require high-strength at elevated temperatures. Such applications include, but are not limited to, structural components in or near combustion-, jet-, and rocket -engines or electric motors, structural components near rotating parts which generate heat such as wheels and brake rotors, air-to-air heat exchangers and thermal management components in transportation and electronics applications .

[ 00060 ] The properties of the additively manufactured

component, including high- strength, thermal stability, creep resistance, and corrosion resistance, make it suitable for applications which require high- strength at elevated

temperatures in harsh environments. Such applications include, but are not limited to, liquid- to-air heat exchangers in

automotive, aerospace, and marine applications, and heat

exchangers in electronic components.

[ 00061 ] The additively manufactured component made of gas- atomized dislcosed powders also has a fine grain structure with average grain diameters between about 200 nm and about 2 μπι.

Additionally, the microstructure of the additively manufactured component has a bimodal distribution of grain sizes, with a continuous network of sub-micrometer grains, and regions of elongated grains about 1 μπι in width and about 2 μπι to

about 10 μπι in length. The average grain diameter is influenced by the alloy chemistry and can be controlled by the

concentration of alloying components. [ 00062 ] In its peak-aged condition, the additively

manufactured component made of gas-atomized powders of the disclosed alloys has retained its microstructure so that the component has a continuous network of fine grains ranging from about 0.5 to about 1.5 μπι and regions of coarser grains ranging from about 2 μιτι to about 10 μπι. The average grain diameter in the peak-aged, additively manufactured component is influenced by the alloy chemistry and can be controlled by adjusting the concentration of alloying components.

[ 00063 ] In its over-aged condition, the additively

manufactured component made of gas-atomized powders of the disclosed alloys has undergone precipitate and grain coarsening so that the microstructure is characterized by an essentially homogenous microstructure. The average grain diameter in the over-aged, additively manufactured component is influenced by the alloy chemistry and can be controlled by the adjusting the concentration of alloying components. Additionally, some of the cubic Ll₂ structured precipitates have transformed to platelet D0₂₃ structured precipitates and are located at grain boundaries in the over-aged material.

[ 00064 ] A method of producing a disclosed aluminum alloy can, for example, comprise producing the aluminum alloy by a rapid solidification process. The rapid solidification process can, for example, be selected from a group such as gas atomization, spray deposition, melt spinning, melt extraction, or beam glazing .

[ 00065 ] A method of producing a disclosed aluminum alloy can, for example, comprise producing the aluminum alloy by any non- equilibrium process. The non-equilibrium process can, for example, be mechanical alloying.

[ 00066 ] A method of performing additive manufacturing can, for example, comprise fabricating a powder form of a disclosed aluminum alloy, and utilizing the powder form in executing an additive manufacturing process. The additive manufacturing process can, for example, be selected from a group such as powder bed methods, powder fed directed energy deposition, selective laser melting, selective laser sintering, direct metal laser sintering, or laser engineering net shaping.

[00067] A method for manufacturing a component can, for example, comprise fabricating a ribbon from a disclosed aluminum alloy, cutting the ribbon into chips, compacting the chips by hot isostatic pressing, uniaxial hot pressing or any other pressure-assisted methods, and extruding the compacted chips to manufacture the component.

[00068] A method of manufacturing a component can, for

example, comprise fabricating a powder from a disclosed aluminum alloy, compacting the powder by hot isostatic pressing, uniaxial hot pressing or any other pressure-assisted methods, and

extruding the compacted powder to manufacture the component.

[00069] A method of manufacturing a component can, for

example, comprise fabricating a powder from a disclosed aluminum alloy, compacting the powder to near-net- shape by hot isostatic pressing, uniaxial hot pressing or any other pressure-assisted methods, and machining the compact to its final shape.

[00070] A method of forming a protective coating for magnesium or aluminum components can, for example, comprise fabricating a powder from a disclosed aluminum alloy, and coating the

magnesium or aluminum components by a cold spray process using the powder.

[00071] From the foregoing, it will be understood that

numerous modifications and variations can be effectuated without departing from the true spirit and scope of the novel concepts of the present invention. It is to be understood that no limitation with respect to the specific embodiments illustrated and described is intended or should be inferred.

Claims

Claims :

1. An aluminum alloy comprising:

about 1 to about 10% by weight magnesium;

about 0.45 to about 3% by weight zirconium;

aluminum as the remainder; and

wherein the alloy is completely free of any intentionally added scandium, erbium, thulium, ytterbium, or lutetium.

2. The aluminum alloy of claim 1, wherein the alloy comprises a dispersion of nano-precipitates of Al₃Zr with Ll₂ crystal structure in the aluminum matrix, having an average diameter ranging from about 3 nm to about 50 nra.

3. The aluminum alloy of claim 1, further comprising about 0.3 to about 1.5% by weight of at least one of titanium, hafnium, vanadium, niobium and tantalum.

4. The aluminum alloy of claim 1, wherein the alloy comprises a dispersion of Al₃Zr primary precipitates, having an average diameter ranging from about 0.05 μιτι to about 1.5 μιη.

5. The aluminum alloy of claim 1, wherein the alloy is

produced by a rapid solidification process.

6. The aluminum alloy of claim 1, wherein the alloy comprises as an impurity no more than about 0.05 wt . % of any one of scandium, erbium, thulium, ytterbium, or lutetium.

7. The aluminum alloy of claim 1, wherein the alloy is

thermally stable up to an operating temperature of about 425 °C.

8. The aluminum alloy of claim 1, wherein the alloy can be extruded at a thermal working window up to about 450 °C.

9. The aluminum alloy of claim 1, wherein the alloy is fabricated to a powder form that can be utilized in an additive manufacturing method.

10. The aluminum alloy of claim 1, wherein the alloy has a fine grain structure with average grain diameters between about

200 nra and about 2 μτα .

11. An extruded component formed of the aluminum alloy of claim 1.

12. The extruded component of claim 11, wherein the extruded component is adapted for use in at least one application

selected from a group consisting of aerospace, automotive and marine applications.

13. A ribbon fabricated from the aluminum alloy of claim 1.

14. The ribbon of claim 13, wherein the ribbon is adapted to be cut into chips, then compacted by hot isostatic pressing, uniaxial hot pressing or any other pressure-assisted methods, and finally extruded to a component.

15. A powder fabricated from the aluminum alloy of claim 1.

IS. The powder of claim 15, wherein the powder is adapted to be compacted by hot isostatic pressing, uniaxial hot pressing or any other pressure-assisted methods, and finally extruded to a component .

17. The powder of claim 15, wherein the powder is adapted to be used by a cold spray process to form a protective coating for magnesium or aluminum components.

18. A fabricated form of the aluminum alloy of claim 1, the fabricated form selected from a group consisting of powder, chips, ribbons, wires, sheets, plates and foils.

19. An additively manufactured component made of gas-atomized powders of the alloy in claim 1.

20. The additively manufactured component of claim 19, the component having a thermally stable microstrueture that remains unchanged by exposure to elevated temperatures for extended times .

21. A method of producing the aluminum alloy of claim 1, the method comprising: producing the aluminum alloy by a rapid solidification process.

22. The method of claim 21, wherein the rapid solidification process is selected from a group consisting of gas atomization, spray deposition, melt spinning, melt extraction and beam glazing .

23. A method of producing the aluminum alloy of claim 1; the method comprising: producing the aluminum alloy by any non- equilibrium process.

24. The method of claim 23, wherein the non-equilibrium process is mechanical alloying.

25. A method for manufacturing a component, the method comprising :

fabricating a powder form of the aluminum alloy of claim 1 ; and

utilizing the powder form in executing an additive

manufacturing process to manufacture the component.

26. The method of claim 25, wherein the additive manufacturing process is selected from a group consisting of powder bed methods, powder fed directed energy deposition, selective laser melting, selective laser sintering, direct metal laser sintering and laser engineering net shaping.

27. The method of claim 25, further comprising:

heat-treating the component at temperatures of about 350 °C to about 450°C for a duration of about 0.5 hours to about 24 hours .

28. A method for manufacturing a component, the method

comprising :

fabricating a ribbon from the aluminum alloy of claim 1 ; cutting the ribbon into chips;

compacting the chips by hot isostatic pressing, uniaxial hot pressing or any other pressure-assisted methods; and

extruding the compacted chips to manufacture the component .

29. A method of manufacturing a component, the method

comprising :

fabricating a powder from the aluminum alloy of claim 1; compacting the powder by hot isostatic pressing, uniaxial ot pressing or any other pressure-assisted methods; and extruding the compacted powder to manufacture the component .

30. A method of manufacturing a component, the method

comprising :

fabricating a powder from the aluminum alloy of claim 1 ; compacting the powder to near-net-shape by hot isostatic pressing, uniaxial hot pressing or any other pressure-assisted methods; and

machining the compact to its final shape.

31. A method of forming a protective coating for magnesium or aluminum components, the method comprising:

fabricating a powder from the aluminum alloy of claim 1 · and

coating the magnesium or aluminum components by a cold spray process using the powder.

32. An aluminum alloy comprising:

magnesium;

at least one element selected from Group 4B elements Ti , Zr, and Hf, Group 5B elements V, Nb and Ta, and Group 6B elements Cr, Mo and W;

aluminum as the remainder;

wherein the alloy is completely free of any intentionally added scandium, erbium, thulium, ytterbium, or lutetium; and wherein the alloy comprises a dispersion of nano-scale aluminum-transition metal precipitates in the aluminum matrix, having an average diameter ranging from about 3 nm to about 50 nm, and where the transition metals are selected from the group consisting of Ti, Zr, Hf , V, Nb, Ta, Cr, Mo, and W.

33. The aluminum alloy of claim 32, wherein the alloy is produced by a rapid solidification process.

34. A method of producing an aluminum alloy; the method comprising: producing the aluminum alloy of claim 32 by a rapid solidification process.