Patent Grant
10851447
The present disclosure relates to high-strength aluminum alloys which may be used, for example, in devices requiring high yield strength. More particularly, the present disclosure relates to high-strength aluminum alloys that have high yield strength and which may be used to form cases or enclosures for electronic devices. Methods of forming high-strength aluminum alloys and high-strength aluminum cases or enclosures for portable electronic devices are also described.
There is a general trend toward decreasing the size of certain portable electronic devices, such as laptop computers, cellular phones, and portable music devices. There is a corresponding desire to decrease the size of the outer case or enclosure that holds the device. As an example, certain cellular phone manufacturers have decreased the thickness of their phone cases, for example, from about 8 mm to about 6 mm. Decreasing the size, such as the thickness, of the device case may expose the device to an increased risk of structural damage, both during normal use and during storage between uses, specifically due to device case deflection. Users handle portable electronic devices in ways that put mechanical stresses on the device during normal use and during storage between uses. For example, a user putting a cellular phone in a back pocket of his pants and sitting down puts mechanical stress on the phone which may cause the device to crack or bend. There is thus a need to increase the strength of the materials used to form device cases in order to minimize elastic or plastic deflection, dents, and any other types of damage.
Disclosed herein is a method of forming a high strength aluminum alloy. The method comprises heating an aluminum material containing magnesium and zinc to a solutionizing temperature for a solutionizing time such that the magnesium and zinc are dispersed throughout the extruded aluminum material to form a solutionized aluminum material. The method includes quenching the solutionized aluminum material to below about room temperature such that the magnesium and zinc remain dispersed throughout the solutionized aluminum material to form a quenched aluminum material. The method further includes aging the quenched aluminum material to form an aluminum alloy. The method also includes subjecting the aluminum alloy to an ECAE process while maintaining the aluminum alloy at a temperature to produce a high strength aluminum alloy.
Also disclosed herein is a method forming a high strength aluminum alloy comprising subjecting an aluminum material containing magnesium and zinc to a first equal channel angular extrusion (ECAE) process while maintaining the aluminum material at a temperature between about 100° C. to about 400° C. to produce an extruded aluminum material. The method also includes heating the extruded aluminum material to a solutionizing temperature for a solutionizing time such that the magnesium and zinc are dispersed throughout the extruded aluminum material to form a solutionized aluminum material. The method includes quenching the solutionized aluminum material to below about room temperature such that the magnesium and zinc remain dispersed throughout the solutionized aluminum material to form a quenched aluminum material. The method includes subjecting the quenched aluminum material to a second ECAE process while maintaining the aluminum alloy at a temperature between about 20° C. and 150° C. to form a high strength aluminum alloy.
Also disclosed herein is a high strength aluminum alloy material comprising an aluminum material containing aluminum as a primary component. The aluminum material contains from about 0.5 wt. % to about 4.0 wt. % magnesium and from about 2.0 wt. % to about 7.5 wt. % zinc by weight. The aluminum material has an average grain size from about 0.2 μm to about 0.8 μm and an average yield strength greater than about 300 MPa.
While multiple embodiments are disclosed, still other embodiments of the present invention will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments of the invention. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not restrictive.
Disclosed herein is a method of forming an aluminum (Al) alloy that has high yield strength. More particularly, described herein is a method of forming an aluminum alloy that has a yield strength from about 400 MPa to about 650 MPa. In some embodiments, the aluminum alloy contains aluminum as a primary component and magnesium (Mg) and/or zinc (Zn) as secondary components. For example, aluminum may be present in an amount greater than an amount of magnesium and/or zinc. In other examples, aluminum may be present at a weight percentage of greater than about 70 wt. %, greater than about 80 wt. %, or greater than about 90 wt. %. Methods of forming a high strength aluminum alloy including by equal channel angular extrusion (ECAE) are also disclosed. Methods of forming a high strength aluminum alloy having a yield strength from about 400 MPa to about 650 MPa, including by equal channel angular extrusion (ECAE) in combination with certain heat treatment processes, are also disclosed. In some embodiments, the aluminum alloy may be cosmetically appealing. For example, the aluminum alloy may be free of a yellow or yellowish color.
In some embodiments, the methods disclosed herein may be carried out on an aluminum alloy having a composition containing Zinc in the range from 2.0 wt. % to 7.5 wt. %, from about 3.0 wt. % to about 6.0 wt. %, or from about 4.0 wt. % to about 5.0 wt. %; and Magnesium in the range from 0.5 wt. % to about 4.0 wt. %, from about 1.0 wt. % to 3.0 wt %, from about 1.3 wt. % to about 2.0 wt. %. In some embodiments, the methods disclosed herein may be carried out with an aluminum alloy having a Zinc/Magnesium weight ratio from about 3:1 to about 7:1, from about 4:1 to about 6:1, or about 5:1. In some embodiments, the methods disclosed herein may be carried out on an aluminum alloy having Magnesium and Zinc and having copper (Cu) in limited concentrations, for example, Copper at a concentration of less than 1.0 wt. %, less than 0.5 wt. %, less than 0.2 wt. %, less than 0.1 wt. %, or less than 0.05 wt. %.
In some embodiments, the methods disclosed herein may be carried out with an aluminum-zinc alloy. In some embodiments, the methods disclosed herein may be carried out with an aluminum alloy in the A17000 series and form an aluminum alloy having a yield strength from about 400 MPa to about 650 MPa, from about 420 MPa to about 600 MPa, or from about 440 MPa to about 580 MPa. In some embodiments, the methods disclosed herein may be carried out with an aluminum alloy in the A17000 series and form an aluminum alloy having a submicron grain size less than 1 micron in diameter.
A method 100 of forming a high strength aluminum alloy having Magnesium and Zinc is shown in
After formation, the aluminum material billet may optionally be subjected to a homogenizing heat treatment in step 112. The homogenizing heat treatment may be applied by holding the aluminum material billet at a suitable temperature above room temperature for a suitable time to improve the aluminum's hot workability in following steps. The temperature and time of the homogenizing heat treatment may be specifically tailored to a particular alloy. The temperature and time may be sufficient such that the magnesium and zinc are dispersed throughout the aluminum material to form a solutionized aluminum material. For example, the magnesium and zinc may be dispersed throughout the aluminum material such that the solutionized aluminum material is substantially homogenous. In some embodiments, a suitable temperature for the homogenizing heat treatment may be from about 300° C. to about 500° C. The homogenizing heat treatment may improve the size and homogeneity of the as-cast microstructure that is usually dendritic with micro and macro segregations. Certain homogenizing heat treatments may be performed to improve structural uniformity and subsequent workability of billets. In some embodiments, a homogenizing heat treatment may lead to the precipitation occurring homogenously, which may contribute to a higher attainable strength and better stability of precipitates during subsequent processing.
After the homogenizing heat treatment, the aluminum material billet may be subjected to solutionizing in step 114. The goal of solutionizing is to dissolve the additive elements, such as Zinc, Magnesium, and Copper, into the aluminum material to form an aluminum alloy. A suitable solutionizing temperature may be from about 400° C. to about 550° C., from about 420° C. to about 500° C., or from about 450° C. to about 480° C. Solutionizing may be carried out for a suitable duration based on the size, such as the cross sectional area, of the billet. For example, the solutionizing may be carried out for from about 30 minutes to about 8 hours, from 1 hour to about 6 hours, or from about 2 hours to about 4 hours, depending on the cross section of the billet. As an example, the solutionizing may be carried out at 450° C. to about 480° C. for up to 8 hours.
The solutionizing may be followed by quenching, as shown in step 116. For standard metal casting, heat treatment of a cast piece is often carried out near the solidus temperature (i.e. solutionizing) of the cast piece, followed by rapidly cooling the cast piece by quenching the cast piece to about room temperature or lower. This rapid cooling retains any elements dissolved into the cast piece at a higher concentration than the equilibrium concentration of that element in the aluminum alloy at room temperature.
In some embodiments, after the aluminum alloy billet is quenched, artificial aging may be carried out, as shown in step 118. Artificial aging may be carried out using a two-step heat treatment. In some embodiments, a first heat treatment step may be carried out at temperatures from about 80° C. to about 100° C., from about 85° C. to about 95° C., or from about 88° C. to about 92° C., for a duration of from 1 hour to about 50 hours, from about 8 hours to about 40 hours, or from about 10 hours to about 20 hours. In some embodiments, a second heat treatment step may be carried out at temperatures from about 100° C. to about 170° C., from about 100° C. to about 160° C., or from about 110° C. to about 160° C. for a duration of from 20 hours to about 100 hours, from about 35 hours to about 60 hours, or from about 40 hours to about 45 hours. For example, the first step may be carried out at about 90° C. for about 8 hours and the second step may be carried out at about 115° C. for about 40 hours or less. Generally, a first artificial aging heat treatment step may be carried out at a lower temperature and for less time than the temperature and duration that the second artificial aging heat treatment step is carried out at. In some embodiments, the second artificial aging heat treatment step may include temperatures and time that are less than or equal to conditions suitable for artificially aging an aluminum alloy having Magnesium and Zinc to peak hardness, i.e. peak aging.
After artificial aging, the aluminum alloy billet may be subjected to severe plastic deformation such as equal channel angular extrusion (ECAE), as shown in step 120. For example, the aluminum alloy billet may be passed through an ECAE device to extrude the aluminum alloy as a billet having a square or circular cross section. The ECAE process may be carried out at relatively low temperatures compared to the solutionizing temperature of the particular aluminum alloy being extruded. For example, ECAE of an aluminum alloy having Magnesium and Zinc may be carried out at a temperature of from about 0° C. to about 160° C., or from about 20° C. to about 125° C., or about room temperature, for example, from about 20° C. to about 35° C. In some embodiments, during the extrusion, the aluminum alloy material being extruded and the extrusion die may be maintained at the temperature that the extrusion process is being carried out at to ensure a consistent temperature throughout the aluminum alloy material. That is, the extrusion die may be heated to prevent the aluminum alloy material from cooling during the extrusion process. In some embodiments, the ECAE process may include one pass, two or more passes, or four or more extrusion passes through the ECAE device.
Following severe plastic deformation by ECAE, the aluminum alloy may optionally undergo further plastic deformation, such as rolling in step 122, to further tailor the aluminum alloy properties and/or change the shape or size of the aluminum alloy. Cold working (such as stretching) may be used to provide a specific shape or to stress relief or straighten the aluminum alloy billet. For plate applications where the aluminum alloy is to be a plate, rolling may be used to shape the aluminum alloy.
The starting material may be optionally subjected to a homogenizing heat treatment in step 212. This homogenizing heat treatment may be applied by holding the aluminum material billet at a suitable temperature above room temperature to improve the aluminum's hot workability. Homogenizing heat treatment temperatures may be in the range of 300° C. to about 500° C. and may be specifically tailored to particular aluminum alloys.
After the homogenzing heat treatment, the aluminum material billet may be subjected to a first solutionizing in step 214. The goal of solutionizing is to dissolve the additive elements, such as Zinc, Magnesium, and Copper, to form an aluminum alloy. A suitable first solutionizing temperature may be from about 400° C. to about 550° C., from about 420° C. to about 500° C., or from about 450° C. to about 480° C. Solutionizing may be carried out for a suitable duration based on the size, such as the cross sectional area, of the billet. For example, the first solutionizing may be carried out for from about 30 minutes to about 8 hours, from 1 hour to about 6 hours, or from about 2 hours to about 4 hours, depending on the cross section of the billet. As an example, the first solutionizing may be carried out at 450° C. to about 480° C. for up to 8 hours.
The first solutionizing may be followed by quenching, as shown in step 216. This rapid cooling retains any elements dissolved into the cast piece at a higher concentration than the equilibrium concentration of that element in the aluminum alloy at room temperature.
In some embodiments, after the aluminum alloy billet is quenched, artificial aging may optionally be carried out in step 218. Artificial aging may be carried out using a two-step heat treatment. In some embodiments, a first heat treatment step may be carried out at temperatures from about 80° C. to about 100° C., from about 85° C. to about 95° C., or from about 88° C. to about 92° C., for a duration of from 1 hour to about 50 hours, from about 8 hours to about 40 hours, or from about 8 hours to about 20 hours. In some embodiments, a second heat treatment step may be carried out at temperatures from about 100° C. to about 170° C., from about 100° C. to about 160° C., or from about 110° C. to about 160° C. for a duration of from 20 hours to about 100 hours, from about 35 hours to about 60 hours, or from about 40 hours to about 45 hours. For example, the first step may be carried out at about 90° C. for about 8 hours and the second step may be carried out at about 115° C. for about 40 hours or less. Generally, a first artificial aging heat treatment step may be carried out at a lower temperature and for less time than the temperature and duration that the second artificial aging heat treatment step is carried out at. In some embodiments, the second artificial aging heat treatment step may include temperatures and time that are less than or equal to conditions suitable for artificially aging an aluminum alloy having Magnesium and Zinc to peak hardness, i.e. peak aging.
As shown in
In some embodiments, after a first severe plastic deformation, the aluminum alloy may be subjected to a second solutionizing in step 222. The second solutionizing may be carried out on the aluminum alloy at similar temperature and time conditions as the first solutionizing. In some embodiments, the second solutionizing may be carried out at a temperature and/or duration that are different than the first solutionizing. In some embodiments, a suitable second solutionizing temperature may be from about 400° C. to about 550° C., from about 420° C. to about 500° C., or from about 450° C. to about 480° C. A second solutionizing may be carried out for a suitable duration based on the size, such as the cross sectional area, of the billet. For example, the second solutionizing may be carried out for from about 30 minutes to about 8 hours, from 1 hour to about 6 hours, or from about 2 hours to about 4 hours, depending on the cross section of the billet. In some embodiments, the second solutionizing may be from about 450° C. to about 480° C. for up to 8 hours. The second solutionizing may be followed by quenching.
In some embodiments, after the second solutionizing, the aluminum alloy may be subjected to a second severe plastic deformation step, such as an ECAE process, in step 226. In some embodiments, the second ECAE process may be carried out at lower temperatures than that used in the first ECAE process of step 220. For example, the second ECAE process may be carried out at temperatures greater than 0° C. and less than 160° C., or from about 20° C. to about 125° C., or from about 20° C. to about 100° C., or about room temperature, for example from about 20° C. to about 35° C. In some embodiments, during the extrusion, the aluminum alloy material being extruded and the extrusion die may be maintained at the temperature that the extrusion process is being carried out at to ensure a consistent temperature throughout the aluminum alloy material. That is, the extrusion die may be heated to prevent the aluminum alloy material from cooling during the extrusion process. In some embodiments, the second ECAE process may include one pass, two or more passes, or four or more extrusion passes through the ECAE device.
In some embodiments, after the aluminum alloy is submitted to a second severe plastic deformation step such as ECAE, a second artificial aging process may be carried out in step 228. In some embodiments, artificial aging may be carried out in a single heat treatment step, or be carried out using a two-step heat treatment. In some embodiments, a first heat treatment step may be carried out at temperatures from about 80° C. to about 100° C., from about 85° C. to about 95° C., or from about 88° C. to about 92° C., for a duration of from 1 hour to about 50 hours, from about 8 hours to about 40 hours, or from about 8 hours to about 20 hours. In some embodiments, a second heat treatment step may be carried out at temperatures from about 100° C. to about 170° C., from about 100° C. to about 160° C., or from about 110° C. to about 160° C. for a duration of from 20 hours to about 100 hours, from about 35 hours to about 60 hours, or from about 40 hours to about 45 hours. For example, the first aging step may be carried out at about 90° C. for about 8 hours and the second aging may be carried out at about 115° C. for about 40 hours or less. In some embodiments, the second step may include temperatures and time that are less than or equal to conditions suitable for artificially aging an aluminum alloy having Magnesium and Zinc to peak hardness, i.e. peak hardness.
Following method 200, the aluminum alloy may optionally undergo further plastic deformation, such as rolling to change the shape or size of the aluminum alloy.
A method 300 of forming a high strength aluminum alloy is shown in
After formation, the aluminum material billet may be subjected to an optional homogenizing heat treatment in step 312. The homogenizing heat treatment may be applied by holding the aluminum material billet at a suitable temperature above room temperature to improve the aluminum's hot workability in following steps. The homogenizing heat treatment may be specifically tailored to a specific aluminum alloy having Magnesium and Zinc, such as an aluminum-zinc alloy. In some embodiments, a suitable temperature for the homogenizing heat treatment may be from about 300° C. to about 500° C.
After the homogenizing heat treatment, the aluminum material billet may be subjected to an optional first solutionizing in step 314 to form an aluminum alloy. The first solutionizing may be similar to that described herein with respect to steps 114 and 214. A suitable first solutionizing temperature may be from about 400° C. to about 550° C., from about 420° C. to about 500° C., or from about 450° C. to about 480° C. A first solutionizing may be carried out for a suitable duration based on the size, such as the cross sectional area, of the billet. For example, the first solutionizing may be carried out for from about 30 minutes to about 8 hours, from 1 hour to about 6 hours, or from about 2 hours to about 4 hours, depending on the cross section of the billet. As an example, the solutionizing may be carried out at 450° C. to about 480° C. for up to 8 hours. The solutionizing may be followed by quenching. During quenching, the aluminum alloy billet is rapidly cooled by quenching the aluminum alloy billet is cooled to about room temperature or lower. This rapid cooling retains any elements dissolved into the aluminum alloy at a higher concentration than the equilibrium concentration of that element in the aluminum alloy at room temperature.
In some embodiments, after the aluminum alloy is quenched, artificial aging may optionally be carried out in step 316. In some embodiments, artificial aging may be carried out with two heat treatment steps that form the artificial aging step. In some embodiments, a first heat treatment step may be carried out at temperatures from about 80° C. to about 100° C., from about 85° C. to about 95° C., or from about 88° C. to about 92° C., for a duration of from 1 hour to about 50 hours, from about 8 hours to about 40 hours, or from about 8 hours to about 20 hours. In some embodiments, a second heat treatment step may be carried out at temperatures from about 100° C. to about 170° C., from about 100° C. to about 160° C., or from about 110° C. to about 160° C. for a duration of from 20 hours to about 100 hours, from about 35 hours to about 60 hours, or from about 40 hours to about 45 hours. For example, the first step may be carried out at about 90° C. for about 8 hours and the second step may be carried out at about 115° C. for about 40 hours or less. Generally, a first artificial aging heat treatment step may be carried out at a lower temperature and for less time than the temperature and duration that the second artificial aging heat treatment step is carried out at. In some embodiments, the second artificial aging heat treatment step may include temperatures and time that are less than or equal to conditions suitable for artificially aging an aluminum alloy having Magnesium and Zinc to peak hardness, i.e. peak aging.
After artificial aging, the aluminum alloy billet may be subjected to severe plastic deformation, such as a first ECAE process, in step 318. For example, the aluminum alloy billet may be passed through an ECAE device to extrude the aluminum alloy as a billet having a square or circular cross section. In some embodiments, a first ECAE process may be carried out at elevated temperatures, for example, temperatures below the homogenizing heat treatment but above the artificial aging temperature of a particular aluminum-zinc alloy. In some embodiments, the first ECAE process may be carried out with the aluminum alloy maintained at temperatures from about 100° C. to about 400° C., or from about 200° C. to about 300° C. In some embodiments, the first ECAE process may be carried out with the aluminum alloy maintained at temperatures higher than 300° C. Temperatures at this level may provide certain advantages, such as healing of cast defects and redistribution of precipitates, but may also lead to coarser grain sizes and may be more difficult to implement in processing conditions. In some embodiments, during the extrusion, the aluminum alloy material being extruded and the extrusion die may be maintained at the temperature that the extrusion process is being carried out at to ensure a consistent temperature throughout the aluminum alloy material. That is, the extrusion die may be heated to prevent the aluminum alloy material from cooling during the extrusion process. In some embodiments, the first ECAE process may include one pass, two or more passes, or four or more extrusion passes through the ECAE device.
In some embodiments, after severe plastic deformation, the aluminum alloy may be subjected to a second solutionizing in step 320. A suitable second solutionizing temperature may be from about 400° C. to about 550° C., from about 420° C. to about 500° C., or from about 450° C. to about 480° C. A second solutionizing may be carried out for a suitable duration based on the size, such as the cross sectional area, of the billet. For example, the second solutionizing may be carried out for from about 30 minutes to about 8 hours, from 1 hour to about 6 hours, or from about 2 hours to about 4 hours, depending on the cross section of the billet. In some embodiments, the second solutionizing may be from about 450° C. to about 480° C. for up to 8 hours. The second solutionizing may be followed by quenching.
In some embodiments, after the aluminum alloy is quenched after the second solutionizing, a second artificial aging process may be carried out in step 322. In some embodiments, artificial aging may be carried out in a single heat treatment step, or be carried out using a two-step heat treatment. In some embodiments, a first heat treatment step may be carried out at temperatures from about 80° C. to about 100° C., from about 85° C. to about 95° C., or from about 88° C. to about 92° C., for a duration of from 1 hour to about 50 hours, from about 8 hours to about 40 hours, or from about 8 hours to about 20 hours. In some embodiments, a second heat treatment step may be carried out at temperatures from about 100° C. to about 170° C., from about 100° C. to about 160° C., or from about 110° C. to about 160° C. for a duration of from 20 hours to about 100 hours, from about 35 hours to about 60 hours, or from about 40 hours to about 45 hours. For example, the first aging step may be carried out at about 90° C. for about 8 hours and the second aging may be carried out at about 115° C. for about 40 hours or less. In some embodiments, the second step may include temperatures and time that are less than or equal to conditions suitable for artificially aging an aluminum alloy having Magnesium and Zinc to peak hardness, i.e. peak hardness.
In some embodiments, after the second artificial aging process, the aluminum alloy may be subjected to a second severe plastic deformation process, such as a second ECAE process, in step 324. In some embodiments, the second ECAE process may be carried out at lower temperatures than that used in the first ECAE process. For example, the second ECAE process may be carried out at temperatures greater than 0° C. and less than 160° C., or from about 20° C. to about 125° C., or about room temperature, for example from about 20° C. to about 35° C. In some embodiments, during the extrusion, the aluminum alloy material being extruded and the extrusion die may be maintained at the temperature that the extrusion process is being carried out at to ensure a consistent temperature throughout the aluminum alloy material. That is, the extrusion die may be heated to prevent the aluminum alloy material from cooling during the extrusion process. In some embodiments, the second ECAE process may include one pass, two or more passes, or four or more extrusion passes through the ECAE device.
Following severe plastic deformation, the aluminum alloy may optionally undergo further plastic deformation in step 326, such as rolling, to change the shape or size of the aluminum alloy.
A method of forming a high strength aluminum alloy is shown in
After the homogenizing heat treatment, the aluminum material may be subjected to a first solutionizing in step 414, to form an aluminum alloy. A suitable first solutionizing temperature may be from about 400° C. to about 550° C., from about 420° C. to about 500° C., or from about 450° C. to about 480° C. A first solutionizing may be carried out for a suitable duration based on the size, such as the cross sectional area, of the billet. For example, the first solutionizing may be carried out for from about 30 minutes to about 8 hours, from 1 hour to about 6 hours, or from about 2 hours to about 4 hours, depending on the cross section of the billet. As an example, the solutionizing may be carried out at 450° C. to about 480° C. for up to 8 hours. The solutionizing may be followed by quenching, as shown in step 416.
In some embodiments, after the solutionizing and quenching, the aluminum alloy billet may be subjected to a severe plastic deformation process in step 418. In some embodiments, the severe plastic deformation process may be ECAE. For example, the aluminum alloy billet may be passed through an ECAE device having a square or circular cross section. For example, an ECAE process may include one or more ECAE passes. In some embodiments, the ECAE process may be carried out with the aluminum alloy billet at temperatures greater than 0° C. and less than 160° C., or from about 20° C. to about 125° C., or about room temperature, for example from about 20° C. to about 35° C. In some embodiments, during the ECAE, the aluminum alloy billet being extruded and the extrusion die may be maintained at the temperature that the extrusion process is being carried out at to ensure a consistent temperature throughout the aluminum alloy billet. That is, the extrusion die may be heated to prevent the aluminum alloy from cooling during the extrusion process. In some embodiments, the ECAE process may include one pass, two or more passes, or four or more extrusion passes through the ECAE device.
In some embodiments, after the aluminum alloy is subjected to severe plastic deformation in step 418, artificial aging may be carried out in step 420. In some embodiments, artificial aging may be carried out in a single heat treatment step, or be carried out using a two-step heat treatment. In some embodiments, a first heat treatment step may be carried out at temperatures from about 80° C. to about 100° C., from about 85° C. to about 95° C., or from about 88° C. to about 92° C., for a duration of from 1 hour to about 50 hours, from about 8 hours to about 40 hours, or from about 8 hours to about 20 hours. In some embodiments, a second heat treatment step may be carried out at temperatures from about 100° C. to about 170° C., from about 100° C. to about 160° C., or from about 110° C. to about 160° C. for a duration of from 20 hours to about 100 hours, from about 35 hours to about 60 hours, or from about 40 hours to about 45 hours. For example, the first aging step may be carried out at about 90° C. for about 8 hours and the second aging may be carried out at about 115° C. for about 40 hours or less. In some embodiments, the second step may include temperatures and time that are less than or equal to conditions suitable for artificially aging an aluminum alloy having Magnesium and Zinc to peak hardness, i.e. peak hardness.
Following artificial aging, the aluminum alloy may optionally undergo further plastic deformation in step 422, such as rolling, to change the shape or size of the aluminum alloy billet.
The methods shown in
In addition to the mechanical strength requirements there may also be a desire for the aluminum alloy to meet particular cosmetic appearance requirements, such as a color or shade. For example, in the portable electronics area, there may be a desire for an outer alloy case to have a specific color or shade without the use of paint or other coatings.
It has been found that copper-containing aluminum alloys often display a yellowish color after being anodized. In certain applications, this coloring is undesirable for various reasons such as marketing or cosmetic design. Certain aluminum-zinc alloys may thus make better candidates for certain applications because they contain zinc (Zinc) and magnesium (Magnesium) as the main elements, with Copper present in lower concentrations. To facilitate the desired coloring characteristics, the Copper level must be kept relatively low, preferably less than about 0.5 wt. %. The weight percentages and weight ratio of Zinc and Magnesium in the aluminum alloy may also be carefully controlled. For example, Zinc and Magnesium are responsible for the increase in strength by forming (ZnMg) precipitates such as MgZn2 that increase the strength of the aluminum alloy by precipitation hardening. However having too much Zinc and Magnesium present decreases the resistance to stress corrosion during specific manufacturing steps such as anodizing. Therefore, a suitable aluminum alloy has a balanced composition with a specific weight ratio of Zinc to Magnesium, such as from about 3:1 to about 7:1. Additionally, the overall weight percentage of Magnesium and Zinc may be controlled. In most examples, Zinc may be present from about 4.25 wt. % to about 6.25 wt. % and Magnesium may be present from about 0.5 wt. % to about 2.0 wt. %.
As-cast yield strengths for aluminum alloys having the Zinc and Magnesium weight percentages listed above have been found to be around 350-380 MPa. Using the methods disclosed herein, it has been found possible to further increase the strength of aluminum alloys having Zinc and Magnesium and low concentrations of Copper, thus making the resulting alloy attractive for use in electronic device cases. For example, using the methods described with reference to
As described herein the mechanical properties of aluminum-zinc alloys can be improved by subjecting the alloy to severe plastic deformation (SPD). As used herein, severe plastic deformation includes extreme deformation of bulk pieces of material. In some embodiments, ECAE provides suitable levels of desired mechanical properties when applied to the materials described herein.
ECAE is an extrusion technique which consists of two channels of roughly equal cross-sections meeting at a certain angle comprised practically between 90° and 140°, preferably 90°. An example ECAE schematic of an ECAE device 500 is shown in
ECAE provides high deformation per pass, and multiple passes of ECAE can be used in combination to reach extreme levels of deformation without changing the shape and volume of the billet after each pass. Rotating or flipping the billet between passes allows various strain paths to be achieved. This allows control over the formation of the crystallographic texture of the alloy grains and the shape of various structural features such as grains, particles, phases, cast defects or precipitates. Grain refinement is enabled with ECAE by controlling three main factors: (i) simple shear, (ii) intense deformation and (iii) taking advantage of the various strain paths that are possible using multiple passes of ECAE. ECAE provides a scalable method, a uniform final product, and the ability to form a monolithic piece of material as a final product.
Because ECAE is a scalable process, large billet sections and sizes can be processed via ECAE. ECAE also provides uniform deformation throughout the entire billet cross-section because the cross-section of the billet can be controlled during processing to prevent changes in the shape or size of the cross-section. Also, simple shear is active at the intersecting plane between the two channels.
ECAE involves no intermediate bonding or cutting of the material being deformed. Therefore, the billet does not have a bonded interface within the body of the material. That is, the produced material is a monolithic piece of material with no bonding lines or interfaces where two or more pieces of previously separate material have been joined together. Interfaces can be detrimental because they are a preferred location for oxidation, which is often detrimental. For example, bonding lines can be a source for cracking or delamination. Furthermore, bonding lines or interfaces are responsible for non-homogeneous grain size and precipitation and result in anisotropy of properties.
In some instances, the aluminum alloy billet may crack during ECAE. In certain aluminum alloys having Magnesium and Zinc, the high diffusion rate of Zinc in the aluminum alloy may affect processing results. In some embodiments, carrying out ECAE at increased temperatures may avoid cracking of the aluminum alloy billet during ECAE. For example, increasing the temperature that the aluminum alloy billet is held at during extrusion may improve the workability of the aluminum alloy and make the aluminum alloy billet easier to extrude. However, increasing the temperature of the aluminum alloy generally leads to undesirable grain growth, and in heat treatable aluminum alloys, higher temperatures may affect the size and distribution of precipitates. The altered precipitate size and distribution may have a deleterious effect on the strength of the aluminum alloy after processing. This may be the result when the temperature and time used during ECAE are above the temperature and time that correspond to peak hardness for the aluminum alloy being processed, i.e. above the temperature and time conditions that correspond to peak aging. Carrying out ECAE on an aluminum alloy with the alloy at a temperature too close to the peak aging temperature of the aluminum alloy may thus not be a suitable technique for increasing the final strength of certain aluminum alloys even though it may improve the billet surface conditions (i.e. reduce the number of defects produced).
Processing an aluminum alloy having Magnesium and Zinc via ECAE with the aluminum alloy held at about room temperature after an initial solutionizing and quenching may provide a suitable process for increasing the strength of the aluminum alloy. This technique may be fairly successful when a single ECAE pass is conducted almost immediately (i.e, within one hour) after the initial solutionizing and quenching treatments. However, this technique is not generally successful when multiple passes of ECAE are used, especially for aluminum alloys having Zinc and Magnesium in weight concentrations close to the upper level for the A17000 series (i.e., Zinc and Magnesium values of about 6.0 wt. % and 4.0 wt. % respectively). It has been found that for most aluminum alloys having Magnesium and Zinc, such as aluminum-zinc alloys, a single pass ECAE may not adequately increase the alloy strength or provide a sufficiently fine submicron structure.
In some embodiments, it may be beneficial to perform artificial aging on an aluminum-zinc alloy, such as an aluminum alloy having Magnesium and Zinc and a low concentration of Copper, before cold working the aluminum-zinc alloy if the aluminum-zinc alloy has been subjected to an initial solutionizing and quenching. This is because the effects of cold working an aluminum alloy having Magnesium and Zinc after solutionizing are the opposite of some other heat treatable aluminum alloys such as A12000 alloys. Cold work reduces the maximum attainable strength and toughness in overaged tempers of an aluminum alloy having Magnesium and Zinc, for example. The negative effect of cold work before artificial aging aluminum-zinc alloys is attributed to the nucleation of coarse precipitates on dislocations. The approach of using ECAE directly after solutionizing and quenching and before aging may therefore require particular parameters. This effect is shown further in the examples below.
Keeping the above considerations in mind, it has been found that particular processing parameters may improve the outcome of ECAE processes for aluminum alloys having Magnesium and Zinc, such as A17000 series alloys. These parameters are outlined further below.
Process Parameters for ECAE
Pre-ECAE Heat Treatment
It has been discovered that producing stable Guinier Preston (GP) zones and establishing thermally stable precipitates in an aluminum alloy before performing ECAE may improve workability which, for example, may lead to reduced billet cracking during ECAE. In some embodiments, this is accomplished by performing heat treatment such as artificial aging before carrying out ECAE. In some embodiments, artificial aging incorporates a two-step heat treatment which limits the effects of unstable precipitation at room temperature (also referred to as natural aging). Controlling precipitation is important for ECAE processing of aluminum alloys having Magnesium and Zinc alloys because these alloys have a fairly unstable sequence of precipitation, and high deformation during ECAE makes the alloy even more unstable unless the processing conditions and order of heat treatment are carefully controlled.
The effects of heat and time on precipitation in an aluminum alloy having Magnesium and Zinc have been evaluated. The sequence of precipitation in an aluminum alloy having Magnesium and Zinc is complex and dependent on temperature and time. First, using high temperature heat treatment such as solutionizing, solutes such as Magnesium and/or Zinc are put in solution by distributing throughout the aluminum alloy. The high temperature heat treatment is often followed by rapid cooling in water or oil, also known as quenching, to hold the solutes in solution. At relatively low temperatures for long time periods and during initial periods of artificial aging at moderately elevated temperatures, the principal change is a redistribution of solute atoms within the solid solution lattice to form clusters termed Guinier Preston (GP) zones that are considerably enriched in solute. This local segregation of solute atoms produces a distortion of the alloy lattice. The strengthening effect of the zones is a result of the additional interference with the motion of dislocations when they cut the GP zones. The progressive strength increase with aging time at room temperature (defined as natural aging) has been attributed to an increase in the size of the GP zones.
In most systems as aging time or temperature are increased, the GP zones are either converted into or replaced by particles having a crystal structure distinct from that of the solid solution and also different from the structure of the equilibrium phase. Those are referred as “transition” precipitates. In many alloys, these precipitates have a specific crystallographic orientation relationship with the solid solution, such that the two phases remain coherent on certain planes by adaptation of the matrix through local elastic strain. Strength continues to increase as the size and number of these “transition” precipitates increase, as long as the dislocations continue to cut the precipitates. Further progress of the precipitation reaction produces growth of “transition” phase particles, with an accompanying increase in coherency strains until the strength of interfacial bond is exceeded and coherency disappears. This usually coincides with the change in the structure of the precipitate from “transition” to “equilibrium” form and corresponds to peak aging, which is the optimum condition to obtain maximum strength. With loss of coherency, strengthening effects are caused by the stress required to cause dislocations to loop around rather than to cut precipitates. Strength progressively decreases with growth of equilibrium phase particles and an increase in inter-particle spacing. This last phase corresponds to overaging and in some embodiments is not suitable when the main goal is to achieve maximum strength.
In an aluminum alloy having Magnesium and Zinc, the GP zones are very small in size (i.e. less than 10 nm) and quite unstable at room temperature. As shown in the examples provided herein, a high level of hardening occurs after the alloy has been held at room temperature for a few hours after quenching, a phenomenon called natural aging. One reason for this hardening in an aluminum alloy having Magnesium and Zinc is the fast diffusion rate of Zinc, which is the element with the highest diffusion rate in aluminum. Another factor is the presence of Magnesium which strongly influences the retention of a high concentration of non-equilibrium vacancies after quenching. Magnesium has a large atomic diameter that makes the formation of magnesium-vacancy complexes and their retention during quenching easier. These vacancies are available for Zinc to diffuse into and form GP zones around the Magnesium atoms. Extended aging time and temperatures above room temperature (i.e. artificial aging) transform the GP zones into the transition precipitate called II′ or M′, the precursor of the equilibrium MgZn2 phases termed η or M. For aluminum alloys having a higher Magnesium content (e.g. greater than 2.0 wt. %), the precipitation sequence includes the GP zone transforming into a transition precipitate called T′ that becomes the equilibrium Mg3Zn3Al2 precipitate called T at extended aging time and temperature. The precipitation sequence in A17000 can be summarized in the flow schematic shown in
As shown in the flow schematic in
First, ECAE introduces a high level of subgrain, grain boundaries and dislocations that may enhance heterogeneous nucleation and precipitation and therefore lead to a non-homogenous distribution of precipitates. Second, GP zones or precipitates may decorate dislocations and inhibit their movement which leads to a reduction in local ductility. Third, even at room temperature processing, there is some level of adiabatic heating occurring during ECAE that provides energy for faster nucleation and precipitation. These interactions may happen dynamically during each ECAE pass. This leads to potentially detrimental consequences for the processing of a solutionized and quenched aluminum alloy having Magnesium and Zinc during ECAE.
Some of the potentially detrimental consequences are as follows. A propensity for surface cracking of the billet due to a loss in local ductility and heterogeneous precipitate distribution. This effect is most severe at the top billet surface. Limitation of the number of ECAE passes that can be used. As the number of passes increases the effects become more severe and cracking becomes more likely. A decrease in the maximum achievable strength during ECAE, partly due to heterogeneous nucleation effects and partly due to limitation of the number of ECAE passes, which affects the ultimate level of grain size refinement. An additional complication arises with the processing of solutionized and quenched aluminum-zinc alloys, such as A17000 series alloys, due to the fast kinetics of precipitation even at room temperature (i.e. during natural aging). It has been found that the time between the solutionizing and quenching steps and ECAE may be important to control. In some embodiments, ECAE may be conducted relatively soon after the quenching step, for example, within one hour.
Stable precipitates may be defined as precipitates that are thermally stable in an aluminum alloy even when the aluminum alloy is at a temperature and time that is substantially close to artificial peak aging for its given composition. In particular, stable precipitates are precipitates that will not change during natural aging at room temperature. Note that these precipitates are not GP zones but instead include transition and/or equilibrium precipitates (e.g. η′ or M′ or T′ for aluminum-zinc alloys). The goal of heating (i.e. artificial aging) is to eliminate most of the unstable GP zones, which may lead to billet cracking during ECAE, and replace these with stable precipitates, which may be stable transition and equilibrium precipitates. It may also be suitable to avoid heating the aluminum alloy to conditions that are above peak aging (i.e. overaging conditions), which may produce mostly equilibrium precipitates that have grown and become too large, which may decrease the aluminum alloy final strength.
These limitations may be avoided by transforming most of the unstable GP zones into stable transition and/or equilibrium precipitates before performing the first ECAE pass. This may be accomplished, for example, by conducting a low temperature heat treatment (artificial aging) after or immediately after the solutionizing and quenching step, but before the ECAE process. In some embodiments, this may lead to most of the precipitation sequence occurring homogenously, contributing to a higher attainable strength and better stability of precipitates for ECAE processing. Furthermore, the heat treatment may consist of a two-step procedure that includes a first step that includes holding the material at a low temperature of 80° C. to 100° C. for less than or about 40 hours, and a second step that includes holding the material at a temperature and time that are less or equal than the peak aging conditions for the given an aluminum alloy having Magnesium and Zinc, for example holding the material between 100° C. and 150° C. for about 80 hours or less. The first low temperature heat treatment step provides a distribution of GP zones that is stable when the temperature is raised during the second heat treatment step. The second heat treatment step achieved the desired final distribution of stable transition and equilibrium precipitates.
In some embodiments, it may be advantageous to increase the uniformity and achieve a predetermined grain size of the alloy microstructure before conducting the final ECAE process at low temperature. In some embodiments, this may improve the mechanical properties and workability of the alloy material during ECAE as demonstrated by a reduced amount of cracking.
Aluminum alloys having Magnesium and Zinc are characterized by heterogeneous microstructures with large grain sizes and a large amount of macro and micro segregations. For example, the initial cast microstructure may have a dendritic structure with solute content increasing progressively from center to edge with an interdendritic distribution of second phase particles or eutectic phases. Certain homogenizing heat treatments may be performed before the solutionizing and quenching steps in order to improve structural uniformity and subsequent workability of billets. Cold working (such as stretching) or hot working is also often used to provide a specific billet shape or to stress relief or straighten the product. For plate applications such as forming a phone case, rolling may be used and may lead to anisotropy of the microstructure and properties in the final product even after heat treatments such as solutionizing, quenching and peak aging. Typically, grains are elongated along the rolling direction but are flattened along the thickness as well as the direction transverse to the rolling direction. This anisotropy is also reflected in the precipitate distribution, particularly along the grain boundaries.
In some embodiments, the microstructure of an aluminum alloy having Magnesium and Zinc with any temper, such as for example T651 may be broken down, refined, and made more uniform by applying a processing sequence that includes at least a single ECAE pass at elevated temperatures, such as below 450° C. This step is may be followed by solutionizing and quenching. In another embodiment, a billet made of the aluminum alloy having Magnesium and Zinc may be subjected to a first solutionizing and quenching step, followed by a single pass or multi-pass ECAE at moderately elevated temperatures between 150° C. and 250° C., followed by a second solutionizing and quenching step. After either of the above mentioned thermo-mechanical routes, the aluminum alloy can be further subjected to ECAE at a low temperature, either before or after artificial aging. In particular, it has been discovered that the initial ECAE process at elevated temperatures helps reduce cracking during a subsequent ECAE process at low temperatures of a solutionized and quenched aluminum alloy having Magnesium and Zinc. This result is described further in the examples below.
In some embodiments, ECAE may be used to impart severe plastic deformation and increase the strength of aluminum-zinc alloys. In some embodiments, ECAE may be performed after solutionizing, quenching and artificial aging is carried out. As described above, an initial ECAE process carried out while the material is at an elevated temperature may create a finer, more uniform and more isotropic initial microstructure before the second or final ECAE process at low temperature.
There are two main mechanisms for strengthening with ECAE. The first is refinement of structural units, such as the material cells, sub-grains and grains at the submicron or nanograined levels. This is also referred as grain size or Hall Petch strengthening and can be quantified using Equation 1.
Where σy is the yield stress, σo is a material constant for the starting stress or dislocation movement (or the resistance of the lattice to dislocation motion), ky is the strengthening coefficient (a constant that is specific to each material), and d is the average grain diameter. Based on this equation, strengthening becomes particularly effective when d is less than 1 micron. The second mechanism for strengthening with ECAE is dislocation hardening, which is the multiplication of dislocations within the cells, subgrains, or grains of the material due to high straining during the ECAE process. These two strengthening mechanisms are activated by ECAE and it has been discovered that certain ECAE parameters can be controlled to produce particular final strengths in the aluminum alloy, particularly when extruding aluminum-zinc alloys that have previously been subjected to solutionizing and quenching.
First, the temperatures and time used for ECAE may be less than those corresponding to the conditions of peak aging for the given aluminum alloy having Magnesium and Zinc. This involves controlling both the die temperature during ECAE and potentially employing an intermediate heat treatment in between each ECAE pass, when an ECAE process including multiple passes is performed, to maintain the material being extruded at a desired temperature. For example, the material being extruded may be kept maintained at a temperature of about 160° C. for about 2 hours between each extrusion pass. In some embodiments, the material being extruded may be kept maintained at temperature of about 120° C. for about 2 hours in between each extrusion pass.
Second, in some embodiments, it may be advantageous to maintain the temperature of the material being extruded at as low a temperature as possible during ECAE to get the highest strength. For example, the material being extruded may be maintained at about room temperature. This may result in an increased number of dislocations formed and produce a more efficient grain refinement.
Third, it may be advantageous to perform multiple ECAE passes. For example, in some embodiments, two or more passes may be used during an ECAE process. In some embodiments, three or more, or four or more passes may be used. In some embodiments, a high number of ECAE passes provides a more uniform and refined microstructure with more equiaxed high angle boundaries and dislocations that result in superior strength and ductility of the extruded material.
In some embodiments, ECAE affects the grain refinement and precipitation in at least the following ways. In some embodiments, ECAE has been found to produce faster precipitation during extrusion, due to the increased volume of grain boundaries and higher mechanical energy stored in sub-micron ECAE processed materials. Additionally, diffusion processes associated with precipitate nucleation and growth are enhanced. This means that some of the remaining GP zones or transition precipitates can be transformed dynamically into equilibrium precipitates during ECAE. In some embodiments, ECAE has been found to produce more uniform and finer precipitates. For example, a more uniform distribution of very fine precipitates can be achieved in ECAE submicron structures because of the high angle boundaries. Precipitates can contribute to the final strength of the aluminum alloy by decorating and pinning dislocations and grain boundaries. Finer and more uniform precipitates may lead to an overall increase in the extruded aluminum alloy final strength.
There are additional parameters of the ECAE process that may be controlled to further increase success. For example, the extrusion speed may be controlled to avoid forming cracks in the material being extruded. Second, suitable die designs and billet shapes can also assist in reducing crack formation in the material.
In some embodiments, additional rolling and/or forging may be used after the aluminum alloy has undergone ECAE to get the aluminum alloy closer to the final billet shape before machining the aluminum alloy into its final production shape. In some embodiments, the additional rolling or forging steps can add further strength by introducing more dislocations in the micro-structure of the alloy material.
In the examples described below, Brinell hardness was used as an initial test to evaluate the mechanical properties of aluminum alloys. For the examples included below, a Brinell hardness tester (available from Instron®, located in Norwood, Mass.) was used. The tester applies a predetermined load (500 kgf) to a carbide ball of fixed diameter (10 mm), which is held for a predetermined period of time (10-15 seconds) per procedure, as described in ASTM E10 standard. Measuring Brinell hardness is a relatively straightforward testing method and is faster than tensile testing. It can be used to form an initial evaluation for identifying suitable materials that can then be separated for further testing. The hardness of a material is its resistance to surface indentation under standard test conditions. It is a measure of the material's resistance to localized plastic deformation. Pressing a hardness indentor into the material involves plastic deformation (movement) of the material at the location where the indentor is impressed. The plastic deformation of the material is a result of the amount of force applied to the indentor exceeding the strength of the material being tested. Therefore, the less the material is plastically deformed under the hardness test indentor, the higher the strength of the material. At the same time, less plastic deformation results in a shallower hardness impression; so the resultant hardness number is higher. This provides an overall relationship, where the higher a material's hardness, the higher the expected strength. That is, both hardness and yield strength are indicators of a metal's resistance to plastic deformation. Consequently, they are roughly proportional.
Tensile strength is usually characterized by two parameters: yield strength (YS) and ultimate tensile strength (UTS). Ultimate tensile strength is the maximum measured strength during a tensile test and it occurs at a well-defined point. Yield strength is the amount of stress at which plastic deformation becomes noticeable and significant under tensile testing. Because there is usually no definite point on an engineering stress-strain curve where elastic strain ends and plastic strain begins, the yield strength is chosen to be that strength where a definite amount of plastic strain has occurred. For general engineering structural design, the yield strength is chosen when 0.2% plastic strain has taken place. The 0.2% yield strength or the 0.2% offset yield strength is calculated at 0.2% offset from the original cross-sectional area of the sample. The equation that may be used is s=P/A, where s is the yield stress or yield strength, P is the load and A is the area over which the load is applied.
Note that yield strength is more sensitive than ultimate tensile strength due to other microstructural factors such as grain and phase size and distribution. However, it is possible to measure and empirically chart the relationship between yield strength and Brinell hardness for specific materials, and then use the resulting chart to provide an initial evaluation of the results of a method. Such a relationship was evaluated for the materials and examples below. The data was graphed and the results are shown in
The following non-limiting examples illustrate various features and characteristics of the present invention, which is not to be construed as limited thereto.
The effect of natural aging was evaluated in an aluminum alloy having aluminum as a primary component and Magnesium and Zinc as secondary components. For this initial assay, A17020 was chosen because of its low Copper weight percentage and the Zinc to Magnesium ratio from about 3:1 to 4:1. As discussed above, these factors affect the cosmetic appearance for applications such as device casings. The composition of the sample alloy is displayed in Table 1 with a balance of aluminum. It should be noted that Zinc (at 4.8 wt. %) and Magnesium (at 1.3 wt. %) are the two alloying elements present in the highest concentrations and the Copper content is low (at 0.13 wt. %).
The as-received A17020 material was subjected to a solutionizing heat treatment by holding the material at 450° C. for two hours and then was quenched in cold water. The sample material was then kept at room temperature (25° C.) for several days. The Brinell hardness was used to evaluate the stability of the mechanical properties of the sample material after being stored at room temperature for a number of days (so called natural aging). The hardness data is presented in
The aluminum alloy formed in Example 1 was subjected to hot rolling to form the alloy material into a billet followed by thermo-mechanical processing to the T651 temper that includes solutionizing, quenching, stress relief by stretching to an increase of 2.2% greater than the starting length and artificial peak aging. The measured mechanical properties of the resulting material are listed in Table 2. The yield strength, ultimate tensile strength and Brinell hardness of the A17020 material are 347.8 MPa, 396.5 MPa and 108 HB respectively. The tensile testing was conducted with the example material at room temperature using round tension bars with threaded ends. The diameter of the tension bars were 0.250 inch and the gage was length 1.000 inch. The geometry of round tension test specimens is described in ASTM Standard E8.
As shown in
A billet of A17020 material with the same composition and T651 temper as in Example 2 was subjected to solutionizing at a temperature of 450° C. for 2 hours and immediately quenched in cold water. This process was carried out to retain the maximum number of elements added as solutes, such as Zinc and Magnesium, in solid solution in the aluminum material matrix. It is believed that this step also dissolved the (ZnMg) precipitates present in the aluminum material back into the solid solution. The resulting microstructure of the A17020 material was very similar to the one described in Example 2 for aluminum material that had the temper T651, and consisted of large elongated grains parallel to the initial rolling direction. The only difference is the absence of fine soluble precipitates. The soluble precipitates are not visible by optical microscopy because they are below the resolution limit of 1 micron; only the large (i.e. greater than 1 micron in diameter) non soluble precipitates are visible. Thus, the results of Example 3 illustrate that the after solutionizing and quenching steps the grain size and anisotropy of the initial T651 microstructure remained unchanged.
The A17020 material was then shaped into three billets, i.e. bars, with a square cross-section and a length that is greater than the cross-section, and ECAE was then performed on the billets. The first pass was performed within 30 minutes after the solutionizing and quenching to minimize the effect of natural aging. Furthermore, ECAE was conducted at room temperature to limit the temperature effects on precipitation.
The three sample billets were further submitted to a two-step peak aging treatment consisting of a first heat treatment step with the samples held at 90° C. for 8 hours followed by a second heat treatment step with the samples held at 115° C. for 40 hours. Table 3 displays Brinell hardness data as well as tensile data for the first billet 620. The second billet 622 and the third billet 624 had too deep of cracking and the machine tensile test could not be conducted for these samples. All measurements were conducted with the sample material at room temperature.
As shown in Table 3, a steady increase in hardness from about 127 to 138 was recorded with increasing number of ECAE passes. This increase is higher than the hardness value for material having only the T651 temper condition, as shown in Example 2. Yield strength data for the first sample after one pass also shows increased hardness when compared to material having only the T651 temper. That is, the yield strength increased to 382 MPa from 347.8 MPa.
This example demonstrates the ability of ECAE to improve strength in aluminum-zinc alloys as well as certain limitations due to billet cracking during ECAE processing. The next examples illustrate techniques to improve the overall processing during ECAE at a low temperature and, as a result, enhance the material strength without cracking the material.
To evaluate the potential effect of the initial microstructure on the processing results, A17020 material with the T651 temper of Examples 1 and 2 was submitted to a more complex thermo-mechanical processing route than in Example 3. In this Example, ECAE was performed in two steps, one before and one after a solutionizing and quenching step with each step including an ECAE cycle having multiple passes. The first ECAE cycle was aimed at refining and homogenizing the microstructure before and after the solutionizing and quenching step, whereas the second ECAE cycle was conducted at a low temperature to improve the final strength as in Example 3.
The following process parameters were used for the first ECAE cycle. Four ECAE passes were used, with a 90 degree rotation of the billet between each pass to improve the uniformity of deformation and as a result the uniformity of microstructure. This is accomplished by activating simple shear along a three dimensional network of active shear planes during multi-pass ECAE. The A17020 material that formed the billet was maintained at a processing temperature of 175° C. throughout the ECAE. This temperature was chosen because it is low enough to give submicron grains after ECAE, but is above the peak aging temperature and therefore provides an overall lower strength and higher ductility, which is favorable for the ECAE process. The A17020 material billets did not suffer any cracking during this first ECAE cycle.
After the first ECAE process, solutionizing and quenching was carried out using the same conditions as described in Example 3 (i.e. the billet was held at 450° C. for 2 hours followed by immediate quenching in cold water). The microstructure of the resulting A17020 material was analyzed by optical microscopy and is shown in
After the solutionizing and quenching, the samples were again deformed via another process of ECAE, this time at a lower temperature than used in the first ECAE process. For comparison, the same process parameters used in Example 3 were used in this second ECAE process. The second ECAE process was performed at room temperature with two passes as soon as possible after the quench step (i.e. within 30 minutes of quenching). The overall ECAE processing was discovered to have improved results using the second ECAE process as the lower temperature ECAE process. In particular, unlike in Example 3, the billet in Example 4 did not crack after two ECAE passes conducted with the billet material at lower temperature. Table 4 shows tensile data collected after the sample material had been subjected to two ECAE passes.
As shown in Table 4, the resulting material also had a substantial improvement over material that has only had a T651 temper condition. That is, the A17020 material that underwent the two step ECAE process had a yield strength of 416 MPa and an ultimate tensile strength of 440 MPa.
Example 4 demonstrates that the grain size and isotropy of the material before ECAE can affect the processing results and ultimate attainable strength. ECAE at relatively moderate temperatures (around 175° C.) may be an effective method to break, refine and uniformize the structure of A17000 alloy material and make the material better for further processing. Other important factors for processing A17000 with ECAE are the stabilization of GP zone and precipitates prior to ECAE processing. This is described further in the following examples.
In this Example, the A17020 alloy material of Example 1 was submitted to an initial processing that included solutionizing, quenching, stress relief by stretching to 2.2% greater than the starting length, and artificial peak aging. Artificial peak aging of this A17020 material consisted of a two-step procedure that included a first heat treatment at 90° C. for 8 hours followed by a second heat treatment at 115° C. for 40 hours, which is similar to a T651 temper for this material. Peak aging was started within a few hours after the quenching step. The Brinell hardness of the resulting material was measured at 108 HB and the yield strength was 347 MPa (i.e. similar to the material in Example 2). The first heat treatment step is used to stabilize the distribution of GP zones before the second heat treatment and to inhibit the influence of natural aging. This procedure was found to encourage homogeneous precipitation and optimize strengthening from precipitation.
Low temperature ECAE was then conducted after the artificial peak aging. Two ECAE process parameters were evaluated. First, the number of ECAE passes was varied. One, two, three, and four passes were tested. For all ECAE cycles, the material billets were rotated by 90 degrees between each pass. Second, the effect of material temperature during ECAE was varied. The ECAE die and billet temperatures evaluated were 25° C., 110° C., 130° C., 150° C., 175° C., 200° C., and 250° C. Both Brinell hardness and tensile data were taken with the sample material at room temperature after certain processing conditions in order to evaluate the effects on strengthening. Optical microscopy was used to create images of samples of the resulting material and is shown in
As an initial observation, no cracking was observed in the material of any of the sample billets, even for billets that underwent ECAE processing at room temperature. This example contrasts with Example 3, where ECAE was conducted right after the unstable solutionized and quenched state and cracking occurred in the second and third samples. This result shows the effect of stabilization of GP zones and precipitates on the processing of A17000 alloy material. This phenomenon is very specific to A17000 alloys due to the nature and fast diffusion of the two main constitutive elements, Zinc and Magnesium.
Table 5 contains the measured results of Brinnell hardness and tensile strength as a result of varying the temperature of the A17020 alloy material during ECAE.
Holding the A17020 alloy material at temperatures from about 115° C. to 150° C. for a few hours corresponds to an overaging treatment in A17000 alloys when precipitates have grown larger than during conditions of peak aging, which gives peak strength. At temperatures of about 115° C. to about 150° C., the ECAE extruded material is still stronger than material having only undergone the T651 temper because the strength loss due to overaging is compensated by grain size hardening due to ECAE. The strength loss due to overaging is rapid, which explains the lowered final strength when the material is held at temperatures increasing from 110° C. to about 150° C., as shown in
Temperatures around 110° C. to about 115° C. are near the conditions for peak aging of A17000 (i.e. the T651 temper) and the increased strength above the strength of material having only a T651 temper is due mainly to grain size and dislocation hardening by ECAE. When the A17020 alloy material is at temperatures below about 110° C. to about 115° C., precipitates are stable and in the peak aged condition. As the material is lowered to temperatures near room temperature, ECAE hardening becomes more effective because more dislocations and finer submicron grain sizes are created. The rate of strength increase when the material is processed around room temperature is more gradual compared to temperatures between about 110° C. and 150° C.
The samples used to create the data in the graphs of
As shown in Example 5, improvements in strength were achieved without cracking the material by performing ECAE after artificial aging that used a two-step aging procedure to stabilize GP zones and precipitates. Avoiding cracking of the billet enables a lower ECAE processing temperature and allows for a higher number of ECAE passes to be used. As a consequence, higher strengths can be formed in the A17020 alloy material.
Table 7 and
As shown in
The procedure described in Example 5 was applied to material formed into plates rather than bars, as shown in
Workability of the plate 650 was good with no severe cracking at all temperatures, including at room temperature. The results of hardness and strength testing of the plate 650 are contained in Table 8. As shown in Table 8, hardness and strength tests were taken after applying one, two, and four ECAE passes and tensile data after two and four ECAE passes. Table 8 shows that the results of applying ECAE to plates were similar to those for ECAE bars. In particular, yield strength (YS) in the material that was extruded as a plate was well above 400 MPa.
Various modifications and additions can be made to the exemplary embodiments discussed without departing from the scope of the present invention. For example, while the embodiments described above refer to particular features, the scope of this invention also includes embodiments having different combinations of features and embodiments that do not include all of the above described features.
This application claims priority to Provisional Application No. 62/429,201, filed Dec. 2, 2016 and also claims priority to Provisional Application No. 62/503,111, filed May 8, 2017, both of which are herein incorporated by reference in their entireties.
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