The present application relates to certain aluminum alloys. More particularly, aluminum alloys are described that exhibit improved properties at elevated temperatures.
Aluminum alloys as a class are some of the most versatile engineering and construction materials available. For example, aluminum alloys are light in comparison to steel or copper and have high strength to weight ratios. Additionally, aluminum alloys resist corrosion, are up to three times more thermally conductive than steel, and can be easily fabricated into various forms. However, current commercial light-weight age-hardenable aluminum alloys are not useable above about 220° C. (428° F.) because the strengthening precipitates they contain dissolve, coarsen or transform to undesirable phases. Although aluminum-scandium alloys have been developed that can withstand higher temperatures, they are typically very expensive due to the costs associated with the use of scandium. Thus, there is a need for commercially viable uncladded aluminum alloys that have good processability characteristics and can be used in applications that are exposed to higher temperatures (e.g. 300-450° C. or 572-842° F.), such as automotive brake rotors or engine components. Cast iron, which is about three times heavier than aluminum, or titanium alloys, which are much more expensive than aluminum alloys, are commonly used for these high temperature, high stress applications.
Other potential applications for such aluminum superalloys include engine components such as pistons, where car manufacturers presently are limited to aluminum components that operate at a maximum temperature of about 220° C., therefore reducing engine efficiency, increasing emissions, and inflating the cost and mass of the cooling system. Another application is for aircraft engine structural components, such as the auxiliary power unit (APU) located in the tails of airplanes. APU frames, mounting brackets, and exhaust ducting currently use expensive titanium alloys due to the high-temperature environment of about 300° C. (572° F.), which could be replaced by lighter, much less expensive high-temperature aluminum alloys that are disclosed herein.
An inventive alloy, described herein in various embodiments, comprises aluminum, zirconium, and at least one inoculant, such as a Group 3A, 4A, and 5A metal or metalloid, and include one or more types of nanoscale Al3Zr precipitates. An alloy also can include aluminum, zirconium, a lanthanide series metal such as erbium and at least one inoculant, such as Group 3A, 4A, and 5A metals and metalloids. Such an alloy can have one or more nanoscale high number density precipitates such as Al3Zr, Al3Er, and Al3(Zr,Er) precipitates. The inventive alloy exhibits good strength, hardness, creep resistance and aging resistance at elevated temperatures and excellent electrical and thermal conductivity at all temperatures, while being less expensive than Sc-bearing aluminum alloys.
This application is directed to, inter alia, aluminum-zirconium and aluminum-zirconium-lanthanide superalloys that can be used in high temperature, high stress and a variety of other applications. The lanthanide is preferably holmium, erbium, thulium or ytterbium, most preferably erbium. Also, methods of making the aforementioned alloys are disclosed. The superalloys, which have commercially-suitable hardness at temperatures above about 220° C., include nanoscale Al3Zr precipitates and optionally nanoscale Al3Er precipitates and nanoscale Al3(Zr,Er) precipitates that create a high-strength alloy capable of withstanding intense heat conditions. These nanoscale precipitates have a L12-structure in α-Al(f.c.c.) matrix, an average diameter of less than about 20 nanometers (“nm”), preferably less than about 10 nm, and more preferably about 4-6 nm and a high number density, which for example is larger than about 1021 m−3, of the nanoscale precipitates. Additionally, methods for increasing the diffusivity of Zr in Al are disclosed.
A first embodiment of the invention is directed to an alloy of aluminum (including any unavoidable impurities) alloyed with zirconium, and one or more of the following elements: tin, indium, antimony, and magnesium, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A second embodiment of the invention is directed to an alloy of aluminum (including any unavoidable impurities) alloyed with zirconium, erbium and one or more of the following elements: silicon, tin, indium, antimony, and magnesium, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A third embodiment of the invention is directed to an alloy of aluminum (including any unavoidable impurities) alloyed with zirconium and a combination of any two, three, four, or all five of the following elements: silicon, tin, indium, antimony and magnesium, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A fourth embodiment of the invention is directed to an alloy of aluminum (including any unavoidable impurities) alloyed with zirconium, a lanthanide series metal preferably holmium, erbium, thulium or ytterbium, most preferably erbium, and a combination of any two, three, four, or all five of the following elements: silicon, tin, indium, antimony and magnesium, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3X precipitates and nanoscale Al3(Zr,X) precipitates having a L12-structure, where X is a lanthanide series metal.
A fifth embodiment is directed to an alloy of about 0.3 atomic percent (“at. %”) Zr (all concentrations herein are given in atomic percent unless otherwise indicated), about 1.5 at. % Si, about 0.1 at. % Sn, about 0.1 at. % In, about 0.1 at. % Sb, the balance being aluminum and any unavoidable impurities, the alloy further including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A sixth embodiment is directed to an alloy of about 0.1 at. % Zr, about 0.01 at. % Sn, and the balance being aluminum and any unavoidable impurities, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A seventh embodiment is directed to an alloy of about 0.1 at. % Zr, about 0.02 at. % Sn, and the balance being aluminum and any unavoidable impurities, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
An eighth embodiment is directed to an alloy of about 0.06 at. % Zr, about 0.02 at. % In, and the balance being aluminum and any unavoidable impurities, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A ninth embodiment is directed to an alloy of about 0.3 at. % Zr, about 0.05 at. % Er, about 1.5 at. % Si, about 0.1 at. % Sn, about 0.1 at. % In, about 0.1 at. % Sb, and the balance being aluminum and any unavoidable impurities, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A tenth embodiment is directed to an alloy of about 0.1 at. % Zr, about 0.04 at. % Er, about 0.01 at. % Sn, and the balance being aluminum and any unavoidable impurities, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
An eleventh embodiment is directed to an alloy of about 0.1 at. % Zr, about 0.04 at. % Er, about 0.02 at. % Sn, and the balance being aluminum and any unavoidable impurities, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A twelfth embodiment comprises an alloy of about 0.1 at. % Zr, about 0.04 at. % Er, about 0.2 at. % Si, and the balance being aluminum and any unavoidable impurities, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A thirteenth embodiment is directed to an alloy of about 0.1 at. % Zr, about 0.04 at. % Er, about 0.02 at. % In, and the balance being aluminum and any unavoidable impurities, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A fourteenth embodiment is directed to an alloy of about 0.1 at. % Zr, about 0.04 at. % Er, about 0.02 at. % antimony, and the balance being aluminum and any unavoidable impurities, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A fifteenth embodiment is directed to an alloy of Al—Zr—X—Si—Mg, wherein Si and Mg are alloying elements and X can be a Group 3A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure. Alloying elements are understood to be elements typically present in commercial aluminum alloys such as 1000 to 8000 series alloys, for example.
A sixteenth embodiment is directed to an alloy of Al—Zr—X—Si—Mg, wherein Si and Mg are alloying elements and X is a Group 4A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A seventeenth embodiment is directed to an alloy of Al—Zr—X—Si—Mg, wherein Si and Mg are alloying elements and X can be a Group 5A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
An eighteenth embodiment is directed to an alloy of Al—Zr—Er—X—Si—Mg, wherein Si and Mg are alloying elements and X is a Group 3A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A nineteenth embodiment is directed to an alloy of Al—Zr—Er—X—Si—Mg, wherein Si and Mg are alloying elements and X is a Group 4A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A twentieth embodiment is directed to an alloy of Al—Zr—Er—X—Si—Mg, wherein Si and Mg are alloying elements and X is a Group 5A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A twenty-first embodiment is directed to an alloy of Al—Zr—X—Fe, wherein Fe is an alloying element and X can be a Group 3A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A twenty-second embodiment is directed to an alloy of Al—Zr—X—Fe, wherein Fe is an alloying element and X is a Group 4A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A twenty-third embodiment is directed to an alloy of Al—Zr—X—Fe, wherein Fe is an alloying element and X can be a Group 5A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A twenty-fourth embodiment is directed to an alloy of Al—Zr—Er—X—Fe, wherein Fe is an alloying element and X is a Group 3A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A twenty-fifth embodiment is directed to an alloy of Al—Zr—Er—X—Fe, wherein Fe is an alloying element and X is a Group 4A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A twenty-sixth embodiment is directed to an alloy of Al—Zr—Er—X—Fe, wherein Fe is an alloying element and X is a Group 5A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A twenty-seventh embodiment is directed to an alloy of Al—Zr—X—Mg, wherein Mg is an alloying element and X can be a Group 3A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A twenty-eighth embodiment is directed to an alloy of Al—Zr—X—Mg, wherein Mg is an alloying element and X is a Group 4A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A twenty-nineth embodiment is directed to an alloy of Al—Zr—X—Mg, wherein Mg is an alloying element and X can be a Group 5A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A thirtieth embodiment is directed to an alloy of Al—Zr—Er—X—Mg, wherein Mg is an alloying element and X is a Group 3A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A thirty-first embodiment is directed to an alloy of Al—Zr—Er—X—Mg, wherein Mg is an alloying element and X is a Group 4A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A thirty-second embodiment is directed to an alloy of Al—Zr—Er—X—Mg, wherein Mg is an alloying element and X is a Group 5A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A thirty-third embodiment is directed to an alloy of Al—Zr—X—Cu, wherein Cu is an alloying element and X can be a Group 3A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A thirty-fourth embodiment is directed to an alloy of Al—Zr—X—Cu, wherein Cu is an alloying element and X is a Group 4A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A thirty-fifth embodiment is directed to an alloy of Al—Zr—X—Cu, wherein Cu is an alloying element and X can be a Group 5A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A thirty-sixth embodiment is directed to an alloy of Al—Zr—Er—X—Cu, wherein Cu is an alloying element and X is a Group 3A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A thirty-seventh embodiment is directed to an alloy of Al—Zr—Er—X—Cu, wherein Cu is an alloying element and X is a Group 4A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A thirty-eighth embodiment is directed to an alloy of Al—Zr—Er—X—Cu, wherein Cu is an alloying element and X is a Group 5A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A twenty-ninth embodiment is directed to an alloy of Al—Zr—X—Si, wherein Si is an alloying element and X can be a Group 3A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A fortieth embodiment is directed to an alloy of Al—Zr—X—Si, wherein Si is an alloying element and X is a Group 4A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A forty-first embodiment is directed to an alloy of Al—Zr—X—Si, wherein Si is an alloying element and X can be a Group 5A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A forty-second embodiment is directed to an alloy of Al—Zr—Er—X—Si, wherein Si is an alloying element and X is a Group 3A metal or metalloid, the alloy including a plurality of nano scale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A forty-third embodiment is directed to an alloy of Al—Zr—Er—X—Si, wherein Si is an alloying element and X is a Group 4A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A forty-fourth embodiment is directed to an alloy of Al—Zr—Er—X—Si, wherein Si is an alloying element and X is a Group 5A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A forty-fifth embodiment is directed to an alloy of Al—Zr—X—Zn—Mg, wherein Zn and Mg are alloying elements and X can be a Group 3A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A forty-sixth embodiment is directed to an alloy of Al—Zr—X—Zn—Mg, wherein Zn and Mg are alloying elements and X is a Group 4A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A forty-seventh embodiment is directed to an alloy of Al—Zr—X—Zn—Mg, wherein Zn and Mg are alloying elements and X can be a Group 5A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
An forty-eighth embodiment is directed to an alloy of Al—Zr—Er—X—Zn—Mg, wherein Zn and Mg are alloying elements and X is a Group 3A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A forty-nineth embodiment is directed to an alloy of Al—Zr—Er—X—Zn—Mg, wherein Zn and Mg are alloying elements and X is a Group 4A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A fiftieth embodiment is directed to an alloy of Al—Zr—Er—X—Zn—Mg, wherein Zn and Mg are alloying elements and X is a Group 5A metal or metalloid, the alloy including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
A fifty-first embodiment of the invention is directed to an alloy of aluminum, zirconium, and one or more of the following elements: tin, indium and antimony, the alloy being essentially scandium free and including a plurality of nanoscale Al3Zr precipitates having a L12-structure.
A fifty-second embodiment of the invention is directed to an alloy of aluminum, zirconium, erbium and one or more of the following elements: silicon, tin, indium and antimony, the alloy being essentially scandium-free and including a plurality of nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure.
In another aspect of the invention, the Al3Zr precipitates and/or nanoscale Al3Er precipitates and/or nanoscale Al3(Zr,Er) precipitates are less than about 10 nm in average diameter. In another aspect of the invention, the Al3Zr precipitates and/or nanoscale Al3Er precipitates are about 4-6 nm in average diameter.
In another aspect of the invention, disclosed is a method of forming an essentially scandium-free aluminum alloy having a plurality of nanoscale precipitates having a L12-structure that are selected from the group consisting of Al3Zr, Al3Er and Al3(Zr,Er)L12. The method may include the following steps: (a) making a melt of aluminum and an addition of zirconium, and one or more of erbium, silicon, tin, indium, antimony, and magnesium; (b) solidifying the melt and cooling the resulting solid piece to a temperature of about 0° C. (32° F.) to about 300° C. (572° F.); (c) optionally homogenizing the solid piece at a temperature of about 600° C. (1112° F.) to about 660° C. (1220° F.) (e.g., 640° C. or 1184° F.) for about 0.3 hour to about 72 hours; (d) optionally performing a first heat-treating step to precipitate some of the alloying elements, which includes maintaining a temperature of about 100° C. (212° F.) to about 375° C. (707° F.) for about 1 to about 12 hours; and (e) after the first optional heat-treating step, performing a main heat treating step that comprises heating and maintaining a temperature of about 375° C. (707° F.) to about 550° C. (1022° F.) for about 1 hour to 48 hours.
In another aspect of the invention, disclosed is a method of forming an essentially scandium-free aluminum alloy having a plurality of nanoscale Al3Zr precipitates or nanoscale Al3Zr precipitates, nanoscale Al3Er precipitates, and nanoscale Al3(Zr,Er) precipitates having a L12-structure. The method may include the following steps: (a) making a melt of aluminum and an addition of zirconium, and one or more of erbium, silicon, tin, indium, antimony, and magnesium; (b) solidifying the melt and cooling the resulting solid piece to a temperature of about 0° C. (32° F.) to about 300° C. (572° F.); (c) optionally homogenizing the solid piece at a temperature of about 600° C. (1112° F.) to about 660° C. (1220° F.) (e.g., 640° C. or 1184° F.) for about 0.3 hour to about 72 hours; (d) performing a first heat-treating step by maintaining a temperature of about 100° C. (212° F.) to about 375° C. (707° F.) for about 1 hour to about 12 hours; and (e) performing a second heat-treating step maintaining a temperature of about 375° C. (707° F.) to about 550° C. (1022° F.) for about 1 hour to 48 hours.
Additional details and aspects of the disclosed aluminum alloys and methods of making will be described in the following description, including drawings.
It should be understood that the present disclosure is to be considered as an exemplification of the present invention, which has multiple embodiments, and is not intended to limit the invention to the specific embodiments illustrated. It should be further understood that the title of this section of this application (“Detailed Description of the Invention”) relates to a requirement of the United States Patent Office, and should not be found to limit the subject matter disclosed herein.
Novel aluminum based superalloys are disclosed. The alloys comprise aluminum, zirconium and at least one inoculant, and include nanoscale Al3Zr precipitates. Also disclosed are alloys that comprise aluminum, zirconium, a lanthanide preferably holmium, erbium, thulium or ytterbium, most preferably erbium, and at least one inoculant, and include nanoscale Al3Zr precipitates, nanoscale Al3 lanthanide precipitates, and Al3(Zr,lanthanide) precipitates. These superalloys are readily processable and have high heat resistance, especially at about 300-450° C. (572-842° F.). Further, a method for increasing the diffusivity of zirconium in aluminum by using a Group 3A, Group 4A or Group 5A metal or metalloid as an inoculant is disclosed. Also, a method for decreasing the precipitate diameter of Al3Zr(L12) precipitates by the use of an inoculant is described. Inoculants such as Group 3A, 4A, and 5A metals or metalloids are provided in sufficient amounts to provide for the formation of the high number density of nanoscale precipitates, and includes the amounts described in the Examples and Figures.
A contemplated aluminum alloy also can be essentially scandium-free (meaning that scandium (Sc) is present in a range of less than about 0.04 at. % to about 0.00 at. % of the alloy), while displaying the same or improved mechanical properties at ambient and elevated temperatures when compared to scandium-containing aluminum alloys. The conventional wisdom is that the elimination of Sc in the alloy is unlikely to succeed, because, for example, no other elements possess the same thermodynamic and kinetic properties as Sc in the α-Al matrix, including eutectic (rather than peritectic) solidification, relatively high solubility in solid aluminum near the melting point, said solubility decreasing to near zero values at about 200° C. (392° F.), ability to create coherent and semi-coherent Al3X precipitates, wherein X is a metal, having (L12 structure) with high resistance to shearing, with low coarsening rate tendency and with a small lattice parameter mismatch with Al, diffusivities small enough to prevent coarsening, but fast enough to permit homogenization, high corrosion and oxidation resistance after dissolution, low density, sufficiently low melting point to allow for rapid dissolution in liquid aluminum. For example, as illustrated in
It is thus desirable to add an inoculant that shifts the temperature of precipitation to lower temperatures by increasing the diffusivity of Zr in Al, thus increasing the supersaturation of Zr in Al. In such alloys, aging at a temperature of about 200° C. (392° F.) to about 400° C. (752° F.) creates smaller precipitates with higher volume fractions, which are thus more effective strengtheners. Zirconium, however, diffuses very slowly in that range of temperature, and thus does not nucleate small precipitates, with diameters smaller than 20 nm, in aluminum. During artificial aging at a higher temperatures of about 400° C. (752° F.) to about 600° C. (1112° F.), or during cooling to a solid mass from a melt, Al3Zr precipitates can be formed, but with relatively large diameters of about 20 nm to about 200 nm Therefore, an aluminum alloy, containing only zirconium typically is unsatisfactory in forming a high-strength alloy.
It has been discovered that the presence of one or more of the following elements: tin, indium, and antimony, in an aluminum-zirconium alloy can create a high-strength alloy. Silicon also can be used in conjunction with one or more of these elements. It is believed that atoms of tin, indium, and antimony bind with zirconium atoms to provide for faster diffusion of zirconium in aluminum. Thereafter, smaller Al3Zr precipitates can be created during artificial aging at lower temperatures, of about 300° C. (572° F.) to about 400° C. (752° F.), as compared to Al—Zr alloys free of an inoculant. These nanoscale precipitates form and have average diameters that are less than about 20 nm and preferably less than about 10 nm, and more preferably about 4-6 nm. An example is shown in
Therefore, an aluminum alloy comprising zirconium with one or more of the following inoculants, tin, indium and antimony, and optionally also including silicon, which will create a higher-strength alloy than without inoculants is disclosed.
It also has been discovered that the addition of erbium in an aluminum-zirconium alloy, further comprising one or more of the following elements, tin, indium and antimony, and optionally also including silicon, can create a high number density of Al3Er precipitates during artificial aging at a lower temperature of about 200° C. (572° F.) to about 350° C. (662° F.). These alloys also precipitate Al3Zr precipitates at temperatures of about 350° C. (662° F.) to about 550° C. (1022° F.), like those alloys without Er, as well as Al3(Zr,Er) precipitates. The nanoscale Al3Er precipitates, nanoscale Al3Zr precipitates, and nanoscale Al3(Zr,Er) precipitates create a combined matrix that displays an improvement in strength compared to an Al3Zr alloy with no addition of erbium.
The following examples are set forth to aid in the understanding of the invention, and should not be construed to limit in any way the invention as defined in the claims that follow thereafter.
Alloys 1-4
Alloy Composition, Processing and Analytical Techniques
One binary control alloy and three ternary inoculated alloys were cast with a nominal composition, in atomic percent, at. %, of Al-0.1 Zr, Al-0.1 Zr-0.01 Sn, Al-0.1 Zr-0.02 Sn, Al-0.06 Zr-0.02 In. Master alloys, including 99.99 wt. % pure Al, Al-5.0 Zr wt. %, 99.99 wt. % pure Sn, and 99.99 wt. % pure In, were melted in alumina crucibles in air. The melt was held for 60 minutes at 800° C., stirred vigorously, and then cast into a graphite mold, which was optionally preheated to 200° C. The mold was placed on an ice-cooled copper platen during solidification to enhance directional solidification and decrease formation of shrinkage cavities. The alloy's chemical composition was measured by direct-current plasma atomic-emission spectroscopy (DCP-AES).
The cast alloys were homogenized in air at about 640° C. for 24 hours (“h”), then water quenched to ambient temperature. Isochronal aging in 3 hour steps of 25° C. for temperatures of about 150° C. to about 550° C. was conducted. All heat treatments were conducted in air and terminated by water quenching to ambient temperature.
Vickers microhardness measurements were performed with a Duramin-5 microhardness tester (Struers) using a 200 g load applied for 5 seconds(s) on samples polished to a 1 μm surface finish. At least ten indentations across different grains were made per specimen. Electrical conductivity measurements were performed at room temperature using a Sigmatest 2.069 eddy current instrument. Five measurements at 120, 240, 480, and 960 kHz were performed per specimen.
Isochronal Aging Heat Treatment
Microhardness and electrical conductivity temporal evolutions of Alloys 1-3 during isochronal aging treatment in stages of 25° C./3 hours, following homogenization at 640° C. for 24 hours, are shown in
In the Al-0.1 Zr-0.01 Sn alloy, microhardness commences to increase at 150° C., peaking at about 225° C. for the first time with a microhardness of 287±6 MPa. It then decreases at higher temperatures, but increases again at 375° C., peaking at about 475° C. for the second time with a microhardness of 451±17 MPa. The microhardness continuously decreases beyond an aging temperature of 475° C. Al-0.1 Zr-0.02 Sn behaves similarly to the Al-0.1 Zr-0.01 Sn alloy, except that its first microhardness peak is at a lower temperature of 200° C. with a higher value of 357±9 MPa, and its second microhardness peak is at a lower temperature of 425° C. and a higher value of 493±22 MPa. It is noted that the first peak-microhardness value of Al-0.1 Zr-0.02 Sn, occurring at 200° C. is the same as the peak-microhardness value of Al-0.1 Zr alloy, occurring at 500° C. It is also noted that the addition of 0.01-0.02 at. % of Sn improves peak-microhardness of Al-0.1 Zr from 367 to 451 and 493 MPa, respectively, while decreasing peak temperature. The larger obtained peak-microhardness values in Sn-containing alloys are believed to be due to the formation of smaller nanoscale precipitates with diameters smaller than 10 nm With the same precipitate volume fraction, a distribution of smaller precipitates proved more effective in strengthening the alloy as compared to an alloy composed of coarser precipitates.
The temporal evolution of the electrical conductivity of Alloys 1-3 are shown in
In alloy 3, Al-0.1 Zr-0.02 Sn,
The data show that the addition of 0.01-0.02 at. % Sn as an inoculant provides improved microhardness, thus mechanical strength, electrical conductivity, and possibly thermal conductivity, in the Al-0.1 Zr alloy. An addition of 200 ppm In as an inoculant improves microhardness, thus mechanical strength, and slightly decreases electrical conductivity. The inoculants facilitate formation of nanosized precipitates at lower temperatures and create high-strength alloys with precipitates that are less than 20 nm in diameter and are usually less than about 10 nm in diameter.
Alloys 5-10
Alloy Composition, Processing and Analytical Techniques
One ternary and five quaternary alloys were cast with a nominal composition, in atomic percent, at. %, of Al-0.1 Zr-0.04 Er, Al-0.1 Zr-0.04 Er-0.17 Si, Al-0.1 Zr-0.04 Er-0.01 Sn, Al-0.1 Zr-0.04 Er-0.02 Sn, Al-0.1 Zr-0.04 Er-0.02 In, Al-0.1 Zr-0.04 Er-0.02 Sb. Master alloys, including 99.99 wt. % pure Al, Al-5.0 Zr wt. %, Al-5.0 Er wt. %, Al-12 Si wt. %, 99.99 wt. % pure Sn, and 99.99 wt. % pure In and 99.99 wt. % pure Sb were melted in alumina crucibles in air. The melt was held for 60 minutes at 800° C., stirred vigorously, and then cast into a graphite mold, which was optionally preheated to 200° C. The mold was placed on an ice-cooled copper platen during solidification to enhance directional solidification and decrease formation of shrinkage cavities. The alloy's chemical composition was measured by direct-current plasma atomic-emission spectroscopy (DCP-AES).
Isochronal Aging Heat Treatment
The temporal evolutions of microhardness and electrical conductivity were measured for Alloys 5-7 during isochronal aging treatments in stages of 25° C./3 hours, following homogenization at 640° C. for 24 hours, and are shown in
The temporal evolution of the electrical conductivity of Al-0.01 Zr-0.04 Er, Al-0.01 Zr-0.04 Er-0.01 Sn, and Al-0.01 Zr-0.04 Er-0.02 Sn, following homogenization at 640° C. for 24 hours, are similar. With a relatively high degree of fluctuation, the electrical conductivity values of the homogenized states are in the range from 32.2 to 32.5 MS/m. They commence to increase at 350° C. to 400° C. then peak at 475° C. with a value of 34.33±0.23 (59.2% IACS) for Al-0.01 Zr-0.04 Er, at 500° C. with a value of 34.27±0.06 (59.1% IACS) for Al-0.01 Zr-0.04 Er-0.01 Sn, and at 450° C. with a value of 34.20±0.06 (59.0% IACS) for Al-0.01 Zr-0.04 Er-0.02 Sn.
The temporal evolution of the microhardness and electrical conductivity values of Alloys 5 (the control alloy) and 8-10 during isochronal aging treatment in stages of 25° C./3 hours, following homogenization at 640° C. for 24 hours, are shown in
For the Al-0.01 Zr-0.04 Er-0.02 In alloy,
The temporal evolution of the microhardness and electrical conductivity values of Alloys 9-10 during isochronal aging treatment in stages of 25° C./3 hours, without homogenization, and Alloy 5 (the control alloy), following homogenization at 640° C. for 24 hours, are shown in
For the Al-0.01 Zr-0.04 Er-0.02 In alloy,
The addition of any of 0.17 Si, 0.01 Sn, 0.02 Sn, 0.02 In, or 0.02 Sb as inoculants to a Al-0.1 Zr-0.04 Er alloy provides a means for improving microhardness, thus mechanical strength, while maintaining the same relatively high electrical conductivity at peak microhardness. The inoculant facilitates the early formation of precipitates at low temperatures. The precipitates are nanosized and are less than about 20 nm in diameter and are believed to be less than about 10 nm.
Electrical and thermal conductivities are known to be correlated with one another, so that an improvement in electrical conductivity described herein likely results in a corresponding improvement in thermal conductivity.
The foregoing description and-examples are intended as illustrative and are not to be taken as limiting what can be accomplished. Still other variations within the spirit and scope of this invention are possible and will present themselves to those skilled in the art and science of preparing alloys with specific goals for the electrical and thermal conductivities.
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