Patent Application
20220170139
This application relates to magnesium alloys and, more particularly, to calcium-bearing magnesium and rare earth element alloys and, even more particularly, to calcium-bearing magnesium and rare earth element alloy sheets with superior room temperature formability.
Magnesium alloys have a series of advantages, such as high specific strength, high specific stiffness, good damping performance and good magnetic-shielding performance. Furthermore, magnesium alloys are readily recyclable and are commonly referred to as the green engineering material in the 21st century. Therefore, magnesium alloys may find particular utility in the aerospace, automobile and electronic industries.
However, since magnesium alloys have a hexagonal close packed structure and, therefore, less slip plane, the room temperature formability of magnesium alloy sheets is poor, and to a certain extent limits the application of magnesium alloy sheets. The formability of a sheet is mainly characterized by its Erichsen index (IE value). The Erichsen cupping test of a metallic sheet, which combines the process features of tension and bulging, is an important testing method for measuring the sheet formability and, therefore, has become a standard test for measuring the formability of a material. The higher the IE value of a metallic sheet, the better the formability.
To a certain extent, some advanced preparation or processing methods, such as equal channel angular pressing (ECAP), cross rolling (CR), accumulative roll bonding (ARB), differential speed rolling (DSR) and the like, could create a weak texture and improve the formability of magnesium alloys. However, these methods have low efficiencies in production compared with the conventional rolling method.
Accordingly, those skilled in the art continue with research and development efforts in the field of magnesium alloys.
Disclosed are calcium-bearing magnesium and rare earth element alloys with high formability and method for manufacturing the same. The disclosed calcium-bearing magnesium and rare earth element alloys may exhibit higher room temperature formability, as well as excellent mechanical properties, better anti-flammability and better corrosion resistance performance.
In one embodiment, the disclosed calcium-bearing magnesium and rare earth element alloy consists essentially of, in mass percent:
In another embodiment, the disclosed calcium-bearing magnesium and rare earth element alloy consists essentially of, in mass percent:
In yet another embodiment, the disclosed calcium-bearing magnesium and rare earth element alloy consists essentially of, in mass percent:
Also disclosed are methods for manufacturing the disclosed calcium-bearing magnesium and rare earth element alloys. In one embodiment, the disclosed manufacturing method includes the following steps:
Step 1: burdening: weighting raw materials according to the designed composition, wherein the raw materials are magnesium ingot of no less than 99.99 mass percent, aluminum ingot of no less than 99.9 mass percent, zinc ingot of no less than 99.99 mass percent, master alloy of magnesium and calcium, master alloy of magnesium and gadolinium, master alloy of magnesium and yttrium, and master alloy of magnesium and manganese;
Step 2: melting and casting: charging the raw materials into a vacuum induction melting furnace, and heating up to 750° C. for 10 to 15 minutes; then magnesium alloy ingot is produced via semi continuous direct-chill casting or permanent mold casting;
Step 3: solid solution treatment: keeping the magnesium alloy ingot obtained in Step 2 at the temperature of 300 to 450° C. for 12 to 24 hours, and then air-cooling to room temperature;
Step 4: preparation of sheet: subjecting the magnesium alloy ingot after the solid solution treatment to hot rolling, or extrusion followed by hot rolling, or isothermal forging followed by hot rolling, or the like processes, and then cutting the defects at the head, tail and edge to obtain a hot rolled magnesium alloy sheet;
Step 5: annealing: subjecting the hot rolled sheet obtained in Step 4 to annealing treatment at 300 to 350° C. for 30 to 60 minutes.
Further, after the raw materials are completely melted during melting and casting in Step 2, an electromagnetic, mechanical or gas stirring is performed for about 5 to 10 minutes.
Further, the hot rolling process in the Step 4 is: the magnesium alloy slab is hot rolled at 400 to 450° C. in multiple passes, wherein the total reduction in thickness by the hot rolling is 90 percent, and the thickness reductions are within 15 percent for the first two passes, within 10 to 30 percent for the other passes, and within 8 to 18 percent for the last two passes. Between each pass, the slab is kept at required temperature for 5 to 8 minutes.
Further, the extrusion followed by hot rolling process in the Step 4 is: magnesium alloy billet is extruded into a magnesium alloy plates (5 to 20 mm in thickness) or rod (Φ20 to 25 mm) at 250 to 350° C., wherein the extrusion ratio is (16-23):1, and the extrusion rate is 0.5 to 3 mm/s; Further, the extruded magnesium alloy rod or sheet is hot rolled into a thin sheet with a thickness of 1 mm at 400 to 450° C., wherein the thickness reductions are controlled within 20 percent for the first two passes, within 15 to 35 percent for other passes, and within 10 to 25 percent for the last two passes. Between each pass, the work piece is kept at required temperature for 5 to 8 minutes.
Further, the isothermal forging followed by hot rolling process in the Step 4 is: magnesium alloy billet is isothermally forged into thin round billet of a certain size at 300 to 350° C., wherein the total reduction in thickness by forging is about 75 to 85 percent, and the forging rate is 1 to 3 mm/s; Further, the magnesium alloy billet after isothermal forging is hot rolled into a thin plate with a thickness of 1 mm at 400 to 450° C., wherein the thickness reductions are controlled within 20 percent for the first two passes, within 15 to 35 percent for the other passes, and within 10 to 25 percent for the last two passes. Between each pass, the work piece is kept at required temperature for 5 to 8 minutes.
The addition of Al and Zn may effectively improve the mechanical properties of the magnesium alloy. The addition of Ca, Gd and Y may not only improve the mechanical properties of the magnesium alloy, but may also greatly improve the room temperature formability of the magnesium alloy. The addition of an appropriate amount of Mn may eliminate the impurity element Fe, which may effectively purify the magnesium alloy melt, and improve the corrosion-resistance of the magnesium alloy. At the same time, the addition of Ca, Gd and Y may effectively increase the ignition point of the magnesium alloy and improve the flame resistance thereof. Finally, the disclosed preparation process, such as rolling, extrusion followed by rolling, isothermal forging followed by rolling, and the like, may further improve performance and reduce costs.
It has now been discovered that optimizing a magnesium alloy composition by adding alkaline earth and rare earth elements that can weaken the basal plane texture of magnesium alloys, in combination with conventional rolling, is an economical and effective way to improve the room temperature formability of magnesium alloys.
Furthermore, since magnesium is very reactive with a standard electrode potential of −2.37V, which is the lowest in all the structural metals, it acts as an anode relative to other structural metals and easily reacts with a second phase or impurity elements to cause galvanic corrosion. The oxidative films naturally formed on the surfaces of magnesium alloys are porous, which could not provide sufficient protection for the metal matrix and, therefore, magnesium alloys are not suitable for most of the corrosive environments. This poor corrosion resistance seriously restricts the application of magnesium alloys. However, without being limited to any particular theory, it is believed that addition of rare earth elements to magnesium alloys, as disclosed herein, can effectively improve the corrosion resistance of magnesium alloys.
Still furthermore, magnesium alloys can be easy to ignite, which leads to poor anti-flammability. However, without being limited to any particular theory, it is believed that addition of rare earth elements, as disclosed herein, can improve the anti-flammability of magnesium alloys due to their affinity for oxygen and the formed REO film could effectively prevent the continuous burning of magnesium alloys. Additionally, rare earth elements and alkaline earth metal elements have significant effect on increasing the ignition point of magnesium alloys.
Thus, the optimization of alloy composition by the addition of alkaline earth and rare earth metal elements, further in combination with the optimized extrusion, rolling, isothermal forging process, etc., may not only improve the mechanical properties, the room temperature formability, flame resistance, corrosion resistance and like properties of magnesium alloys, but may also have a lower cost compared to equal channel angular pressing, differential speed rolling and like preparation processes.
In one embodiment, the disclosed calcium-bearing magnesium and rare earth element alloy has the composition shown in Table 1.
While magnesium forms the balance (essentially) of the calcium-bearing magnesium and rare earth element alloy of Table 1, those skilled in the art will appreciate that impurities may be present.
The calcium-bearing magnesium and rare earth element alloy of Table 1, in sheet form, has a tensile strength of 245.0 to 280.0 MPa, an elongation to failure of 18.0 to 32.0 percent, and an IE value of 4.5 to 7.0.
In another embodiment, the disclosed calcium-bearing magnesium and rare earth element alloy has the composition shown in Table 2.
While magnesium forms the balance (essentially) of the calcium-bearing magnesium and rare earth element alloy of Table 2, those skilled in the art will appreciate that impurities may be present.
Aluminum at 1 to 2 mass percent may effectively strengthen the magnesium alloy, improve the rollability and improve the corrosion resistance. Zinc at 1 to 2 mass percent may have a function of solid solution strengthening, and may form a second phase particle with elements Mg, Gd, etc., and may play a role of precipitation strengthening. Calcium at 0.1 to 0.2 mass percent not only could refine grain and strengthen the magnesium alloy, but also may improve the annealed texture of the alloy. Gadolinium at 0.1 to 0.2 mass percent may enhance the strength and ductility of the magnesium alloy, weaken the basal plane texture, and improve the formability of the magnesium alloy sheet. Yttrium at 0 to 0.2 mass percent may effectively enhance the strength of the magnesium alloy sheet. Manganese at 0 to 0.2 mass percent may improve the corrosion resistance of the magnesium alloy. A low content of alloy elements, in particular the low content of rare earth elements, in combination with the conventional preparation process, greatly reduces the preparation cost of the disclosed magnesium alloy.
In one embodiment, the disclosed calcium-bearing magnesium and rare earth element alloys may be manufactured as follows.
Step 1: burdening: weighting raw materials according to the designed composition, wherein the raw materials are magnesium ingot of no less than 99.99 mass percent, aluminum ingot of no less than 99.9 mass percent, zinc ingot of no less than 99.99 mass percent, master alloy of magnesium and calcium, master alloy of magnesium and gadolinium, master alloy of magnesium and yttrium, and master alloy of magnesium and manganese.
Step 2: melting and casting: charging the raw materials into a vacuum induction melting furnace, and heating up to 750° C. for 10 to 15 minutes; then the magnesium alloy ingot is produced via semi-continuous direct-chill casting or permanent mold casting.
Step 3: solid solution treatment: keeping the magnesium alloy ingot obtained in Step 2 at a temperature of 300 to 450° C. for 12 to 24 hours, and then air-cooling to room temperature.
Step 4: preparation of sheet: subjecting the magnesium alloy ingot after the solid solution treatment to hot rolling, or extrusion followed by hot rolling, or isothermal forging followed by hot rolling, or like processes, and then cutting the defects at the head, tail and edge to obtain a hot rolled magnesium alloy sheet with good shape.
Step 5: annealing: subjecting the hot rolled sheet obtained in Step 4 to annealing treatment at 350° C. for 30 to 60 minutes.
Mg96.6Al2Zn1Ca0.2Gd0.2 magnesium alloy sheet (1 mm in thickness): weighting raw materials according to the designed composition, wherein the raw materials were: magnesium ingot of 99.99 mass percent, aluminum ingot of 99.9 mass percent, zinc ingot of 99.99 mass percent, master alloy of magnesium and calcium of 30 mass percent, and master alloy of magnesium and gadolinium of 30 mass percent. The burdening was carried out, according to the nominal composition of the magnesium alloy, and also in consideration of the thermal loss of elements.
Melting and casting of Mg96.6Al2Zn1Ca0.2Gd0.2. The raw materials were charged into a crucible in a vacuum induction melting furnace and the melting furnace was vacuumed and heated under inert atmosphere. The temperature was increased to 750° C. and maintained for 15 minutes. After the raw materials were completely melted, the melts were electromagnetically stirred for about 8 minutes. Finally, the melts were poured into the graphite crucible and placed in the air to cool, giving an ingot.
Solid solution treatment of Mg96.6Al2Zn1Ca0.2Gd0.2. The magnesium alloy ingot was placed in a resistance furnace and kept at 450° C. for 12 hours, and then air-cooled to room temperature.
Hot rolling of Mg96.6Al2Zn1Ca0.2Gd0.2. The magnesium alloy ingot after the solid solution treatment was wire-cut into a slab having a thickness of 10 mm, and then the surface of the slab was polished for hot rolling. The specific hot rolling process was as follows: the slab was kept at 450° C. for about 30 minutes and then was hot rolled. The total reduction in thickness by hot rolling was 90 percent, that is, the final thickness of sheet was 1 mm. The thickness reductions of the first two passes was 8 percent and 10 percent, respectively, and the thickness reductions of other passes were controlled within 10 to 30 percent, wherein the thickness reductions of the last two passes were 15 percent and 10 percent, respectively. Due to the fast heat dissipation of the magnesium alloy, in order to stabilize the temperature during the rolling, the sample was kept at 450° C. for 5 minutes in the resistance furnace after each rolling pass. After the hot rolling, the defects at head, tail and edge of the hot rolled sheet were cut to obtain a hot rolled magnesium alloy sheet.
Annealing of the hot rolled Mg96.6Al2Zn1Ca0.2Gd0.2 sheet. The finally rolled sheet was placed into a resistance furnace and kept at 350° C. for 60 minutes.
The Mg96.6Al2Zn1Ca0.2Gd0.2 sheet has a yield strength of 231 MPa, a tensile strength of 260 MPa, an elongation to failure of 21 percent and an IE value of 5.87, and has an average corrosion rate of 0.2987 mg/cm2/d after 5 days salt spray test with 3.5 percent NaCl neutral solution (pH=7) at 25° C. The microstructure photograph of this sheet after rolling and annealing is shown in
Mg96.6Al2Zn1Ca0.2Gd0.2 magnesium alloy sheet (5 mm in thickness): the same burdening, melting and casting, and solid solution treatment processes of Mg96.6Al2Zn1Ca0.2Gd0.2 as in Example 1 was carried out.
Hot rolling of Mg96.6Al2Zn1Ca0.2Gd0.2. The magnesium alloy ingot after the solid solution treatment was wire-cut into a slab having a thickness of 30 mm, and then the surface of the slab was polished for hot rolling. The specific hot rolling process was as follows: the slab was kept at 450° C. for about 50 minutes and then was hot rolled. The total thickness reduction by hot rolling was 83.3 percent, that is, the final thickness of the sheet was 5 mm. The thickness reductions of the first two passes were 8 percent and 10 percent, respectively, and the thickness reductions of other passes were controlled within 10 to 30 percent, wherein the thickness reductions of the last two passes were 15 percent and 10 percent, respectively. Due to the fast heat dissipation of the magnesium alloy, in order to stabilize the temperature during the rolling, the sample was kept at 450° C. for 5 to 8 minutes in the resistance furnace after each rolling pass. After the hot rolling, the defects at head, tail and edges of the hot rolled sheet were cut to obtain a hot rolled magnesium alloy sheet with good shape.
Annealing of the hot rolled Mg96.6Al2Zn1Ca0.2Gd0.2 sheet. The finally rolled sheet was placed into a resistance furnace and kept at 350° C. for 60 minutes.
The Mg96.6Al2Zn1Ca0.2Gd0.2 sheet has a yield strength of 167 MPa, a tensile strength of 245 MPa, and an elongation to failure of 18 percent. The microstructure photograph of this sheet after rolling and annealing is shown in
Mg96.6Al2Zn1Ca0.2Gd0.2 magnesium alloy sheet (1 mm in thickness): the same burdening, melting and casting, and solid solution treatment processes of Mg96.6Al2Zn1Ca0.2Gd0.2 as in Example 1 was carried out.
Isothermal forging of Mg96.6Al2Zn1Ca0.2Gd0.2. The magnesium ingot after the solid solution treatment was cut into a cylindrical billet (Φ 140 mm×110 mm), and then the billet was isothermally forged into a round billet having a thickness of 20 mm at 350° C., wherein the forging rate was 1 mm/s, and the total reduction by forging was about 80 percent.
Hot rolling of Mg96.6Al2Zn1Ca0.2Gd0.2. The round billet obtained by isothermal forging was wire-cut into a slab having a thickness of 10 mm, and then the surface of the slab was polished for hot rolling. The specific hot rolling process was as follows: the slab was kept at 400° C. for about 30 minutes and then was hot rolled. The total reduction in thickness by hot rolling was 95 percent, that is, the final thickness of sheet was 1 mm. The thickness reductions of the first two passes were 10 percent and 15 percent, respectively, and thickness reductions of other passes were controlled within 15 to 35 percent, wherein the thickness reductions of the last two passes were 20 percent and 15 percent, respectively. Due to the fast heat dissipation of the magnesium alloy, in order to stabilize the temperature during the rolling, the sample was kept at 450° C. for 5 minutes in the resistance furnace after each rolling pass. After the hot rolling, the defects at head, tail and edges of the hot rolled sheet were cut in order to obtain a hot rolled magnesium alloy sheet.
Annealing of the hot rolled Mg96.6Al2Zn1Ca0.2Gd0.2 sheet. Finally, the rolled sheet was placed into a resistance furnace and kept at 350° C. for 60 minutes.
Mg96.6Al2Zn1Ca0.2Gd0.2 sheet has a yield strength of 231 MPa, a tensile strength of 249 MPa, an elongation to failure of 23 percent and an IE value of 5.51. The microstructure photograph of this sheet after rolling and annealing is shown in
Mg96.6Zn2Al1Ca0.2Gd0.2 sheet (1 mm in thickness): weighting raw materials according to the designed composition, wherein the raw materials were: magnesium ingot of 99.99 mass percent, aluminum ingot of 99.9 mass percent, zinc ingot of 99.99 mass percent, master alloy of magnesium and calcium of 30 mass percent, and master alloy of magnesium and gadolinium of 30 mass percent. The burdening was carried out, according to the nominal composition of the magnesium alloy, and also in consideration of the thermal loss of each of elements.
Melting and casting of Mg96.6Zn2Al1Ca0.2Gd0.2. The raw materials were charged into a crucible in a vacuum induction melting furnace and the melting furnace was vacuumed and heated under inert atmosphere. The temperature was increased to 750° C. and maintained for 15 minutes. After the raw materials were completely melted, the melts were electromagnetically stirred for about 8 minutes. Finally, the melts were poured into the graphite crucible and placed in the air to cool, giving an ingot.
Solid solution treatment of Mg96.6Zn2Al1Ca0.2Gd0.2. The magnesium alloy ingot was placed in a resistance furnace and kept at 300° C. for 20 hours, and then air-cooled to room temperature.
Hot rolling of Mg96.6Zn2Al1Ca0.2Gd0.2. The magnesium alloy ingot after the solid solution treatment was wire-cut into a slab having a thickness of 10 mm, and then the surface of the slab was polished for hot rolling. The specific hot rolling process was as follows: the slab was kept at 400° C. for about 30 minutes and then was hot rolled. The total thickness reduction by hot rolling was 90 percent, that is, the final thickness of sheet was 1 mm. The thickness reductions of the first two passes were 8 percent and 10 percent, respectively, and the thickness reductions of the other passes were controlled within about 10 to 30 percent, wherein the thickness reductions of the last two passes were 15 percent and 10 percent, respectively. Due to the fast heat dissipation of the magnesium alloy, in order to stabilize the rolling temperature, the sample was kept at 400° C. for 5 minutes in the resistance furnace after each rolling pass. After the hot rolling, the defects at head, tail and edges of the hot rolled sheet were cut to obtain a hot rolled magnesium alloy sheet with good shape.
Annealing of the hot rolled Mg96.6Zn2Al1Ca0.2Gd0.2 sheet. The finally rolled sheet was placed into a resistance furnace and kept at 350° C. for 45 minutes.
The Mg96.6Zn2Al1Ca0.2Gd0.2 sheet has a yield strength of 145 MPa, a tensile strength of 245 MPa, an elongation to failure of 26 percent and an IE value of 6.38. The microstructure photograph of this sheet after rolling and annealing is shown in
Mg96.6Zn2Al1Ca0.2Gd0.2 sheet (5 mm in thickness): the same burdening, melting and casting, and solid solution treatment processes of Mg96.6Zn2Al1Ca0.2Gd0.2 as in Example 4 was carried out.
Hot rolling of Mg96.6Zn2Al1Ca0.2Gd0.2. The magnesium alloy ingot after the solid solution treatment was wire-cut into a slab having a thickness of 30 mm, and then the surface of the slab was polished for hot rolling. The specific hot rolling process was as follows: the slab was kept at 400° C. for about 30 minutes and then was hot rolled. The total thickness reduction by hot rolling was 83.3 percent, that is, the final thickness of sheet was 5 mm. The thickness reductions of the first two passes were 8 percent and 10 percent, respectively, and the thickness reductions of the other passes were controlled within about 10 to 30 percent, wherein the thickness reductions of the last two passes were 15 percent and 10 percent, respectively. Due to the fast heat dissipation of the magnesium alloy, in order to stabilize the temperature during the rolling, the sample was kept at 400° C. for 5 to 8 minutes in the resistance furnace after each rolling pass was complete. After the hot rolling was complete, the defects at head, tail and edges of the hot rolled sheet were cut to obtain a hot rolled magnesium alloy sheet with good shape.
Annealing of the hot rolled Mg96.6Zn2Al1Ca0.2Gd0.2 sheet. The finally rolled sheet was placed into a resistance furnace and kept at 350° C. for 45 minutes.
The Mg96.6Zn2Al1Ca0.2Gd0.2 sheet has a yield strength of 227 MPa, a tensile strength of 250 MPa, and an elongation to failure of 23 percent. The microstructure photograph of this sheet after rolling and annealing is shown in
Mg96.6Zn2Al1Ca0.2Gd0.2 sheet (1 mm in thickness): the same burdening, melting and casting, and solid solution treatment processes of Mg96.6Zn2Al1Ca0.2Gd0.2 as in Example 4 was carried out.
Extrusion of Mg96.6Zn2Al1Ca0.2Gd0.2. The magnesium alloy ingot after the solid solution treatment was wire-cut into a cylindrical billet (Φ 120 mm×110 mm), and then the billet was extruded into a magnesium alloy sheet (90×6 mm) at 250° C., wherein the extrusion ratio was about 20:1, and the extrusion rate was 1 mm/s.
Hot rolling of Mg96.6Zn2Al1Ca0.2Gd0.2. The magnesium alloy slab after the extrusion was polished for hot rolling. The specific hot rolling process was as follows: the slab was kept at 400° C. for about 30 minutes and then was hot rolled. The total thickness reduction by hot rolling was 83 percent, that is, the final thickness of sheet was 1 mm. The thickness reductions of the first two passes were 10 percent and 15 percent, respectively, and the thickness reductions of other passes were controlled within about 15 to 30 percent, wherein the thickness reductions of the last two passes were 20 percent and 15 percent, respectively. Due to the fast heat dissipation of the magnesium alloy, in order to stabilize the temperature during the rolling, the sample was kept at 400° C. for 5 minutes in the resistance furnace after each rolling pass was complete. After the hot rolling was complete, the defects at head, tail and edges of the hot rolled sheet were cut to obtain a hot rolled magnesium alloy sheet with good shape.
Annealing of the hot rolled Mg96.6Zn2Al1Ca0.2Gd0.2 sheet. The finally rolled sheet was placed into a resistance furnace and kept at 350° C. for 60 minutes.
The Mg96.6Zn2Al1Ca0.2Gd0.2 sheet has a yield strength of 184.8 MPa, a tensile strength of 252.6 MPa, an elongation to failure of 31.4 percent. The microstructure photograph of this sheet after rolling and annealing is shown in
Mg96.6Zn2Al1Ca0.2Gd0.2 sheet (1 mm in thickness): the same burdening, melting and casting, and solid solution treatment processes of Mg96.6Zn2Al1Ca0.2Gd0.2 as in Example 4 was carried out.
Isothermal forging of Mg96.6Zn2Al1Ca0.2Gd0.2. The magnesium ingot after the solid solution treatment was cut into a cylindrical billet (Φ 140 mm×110 mm), and then the billet was isothermally forged into a round billet having a thickness of 20 mm at 350° C., wherein the forging rate was 1 mm/s, and the total reduction by forging was about 80 percent.
Hot rolling of Mg96.6Zn2Al1Ca0.2Gd0.2. The round billet obtained by isothermal forging was wire-cut into a slab having a thickness of 10 mm, and then the surface of the slab was polished for hot rolling. The specific hot rolling process was as follows: the slab was kept at 400° C. for about 30 minutes and then was hot rolled. The total thickness reduction by hot rolling was 95 percent, that is, the final thickness of sheet was 1 mm. The thickness reductions of the first two passes were 15 percent and 20 percent, respectively, and the thickness reductions of other passes were controlled within 15%-35%, wherein the thickness reductions of the last two passes were 20 percent and 15 percent, respectively. Due to the fast heat dissipation of the magnesium alloy, in order to stabilize the temperature during the rolling, the sample was kept at 400° C. for 5 minutes in the resistance furnace after each rolling pass. After the hot rolling, the defects at head, tail and edges of the hot rolled sheet were cut to obtain a hot rolled magnesium alloy sheet with good shape.
Annealing of the hot rolled Mg96.6Zn2Al1Ca0.2Gd0.2 sheet. The finally rolled sheet was placed into a resistance furnace and kept at 350° C. for 60 minutes.
The Mg96.6Zn2Al1Ca0.2Gd0.2 sheet has a yield strength of 170 MPa, a tensile strength of 255 MPa, an elongation to failure of 24 percent and an IE value of 5.62. The microstructure photograph of this sheet after rolling and annealing is shown in
Mg96.4Zn2Al1Ca0.2Gd0.1Y0.1Mn0.2 magnesium alloy sheet (1 mm in thickness): weighting raw materials according to the mass percent of composition, wherein the raw materials were: magnesium ingot of 99.99 mass percent, aluminum ingot of 99.9 mass percent, zinc ingot of 99.99 mass percent, master alloy of magnesium and calcium of 30 mass percent, and master alloy of magnesium and gadolinium of 30 mass percent, master alloy of magnesium and manganese of 30 mass percent. The burdening was carried out, according to the nominal composition of the magnesium alloy, and also in consideration of the thermal loss of each of elements.
Melting and casting of Mg96.4Zn2Al1Ca0.2Gd0.1Y0.1Mn0.2. The raw materials were charged into a crucible in a vacuum induction melting furnace and the melting furnace was vacuumed and heated under inert atmosphere. The temperature was increased to 750° C. and maintained for 15 minutes. After the raw materials were completely melted, the melts were electromagnetically stirred for about 8 minutes. Finally, the melts were poured into the graphite crucible and placed in the air to cool, giving an ingot.
Solid solution treatment of Mg96.4Zn2Al1Ca0.2Gd0.1Y0.1Mn0.2. The magnesium alloy ingot was placed in a resistance furnace and kept at 300° C. for 12 hours, and then air-cooled to room temperature.
Hot rolling of Mg96.4Zn2Al1Ca0.2Gd0.1Y0.1Mn0.2. The magnesium alloy ingot after the solid solution treatment was wire-cut into a slab having a thickness of 10 mm, and then the surface of the slab was polished for hot rolling. The specific hot rolling process was as follows: the slab was kept at 400° C. for about 30 minutes and then was hot rolled. The total thickness reduction by hot rolling was 90 percent, that is, the final thickness of sheet was 1 mm. The thickness reductions of the first two passes were 8 percent and 10 percent, respectively, and the thickness reductions of other passes were controlled within 10 to 30 percent, wherein the thickness reductions of the last two passes were 15 percent and 10 percent, respectively. Due to the fast heat dissipation of the magnesium alloy, in order to stabilize the temperature during the rolling, the sample was kept at 400° C. for 5 minutes in the resistance further after each rolling pass. After the hot rolling, the defects at head, tail and edges of the hot rolled sheet were cut to obtain a hot rolled magnesium alloy sheet with good shape.
Annealing of the hot rolled Mg96.4Zn2Al1Ca0.2Gd0.1Y0.1Mn0.2 sheet. The finally rolled sheet was placed into a resistance furnace and kept at 350° C. for 60 minutes.
The Mg96.4Zn2Al1Ca0.2Gd0.1Y0.1Mn0.2 has a yield strength of 202.8 MPa, a tensile strength of 265.6 MPa, an elongation to failure of 26.6 percent and an IE value of 5.10. The microstructure photograph of this sheet after rolling and annealing is shown in
Mg95Al3Zn1Ca0.4Gd0.4Mn0.2 magnesium alloy sheet (1 mm in thickness): weighting raw materials according to the mass percent of composition, wherein the raw materials were: magnesium ingot of 99.99 mass percent, aluminum ingot of 99.9 mass percent, zinc ingot of 99.99 mass percent, master alloy of magnesium and calcium of 30 mass percent, master alloy of magnesium and gadolinium of 30 mass percent, and master alloy of magnesium and manganese of 30 mass percent. The burdening was carried out, according to the nominal composition of the magnesium alloy, and also in consideration of the thermal loss of each of elements.
Melting and casting of Mg95Al3Zn1Ca0.4Gd0.4Mn0.2. The raw materials were charged into a crucible in a vacuum induction melting furnace and the melting furnace was vacuumed and heated under inert atmosphere. The temperature was increased to 750° C. and maintained for 15 minutes. After the raw materials were completely melted, the melts were electromagnetically stirred for about 10 minutes. Finally, the melts were poured into the graphite crucible and placed in the air to cool, giving an ingot.
Solid solution treatment of Mg95Al3Zn1Ca0.4Gd0.4Mn0.2. The magnesium alloy ingot was placed in a resistance furnace and kept at 450° C. for 12 hours, and then air-cooled to room temperature.
Hot rolling of Mg95Al3Zn1Ca0.4Gd0.4Mn0.2. The magnesium alloy ingot after the solid solution treatment was wire-cut into a slab having a thickness of 10 mm, and then the surface of the slab was polished for hot rolling. The specific hot rolling process was as follows: the slab was kept at 400° C. for about 30 minutes and then was hot rolled. The total thickness reduction by hot rolling was 90 percent, that is, the final thickness of sheet was 1 mm. The thickness reductions of the first two passes were 8 percent and 10 percent, respectively, and the thickness reductions of other passes were controlled within 10 to 30 percent, wherein thickness reductions of the last two passes were 15 percent and 10 percent, respectively. Due to the fast heat dissipation of the magnesium alloy, in order to stabilize the temperature during the rolling, the sample was kept at 400° C. for 8 minutes in the resistance further after each rolling pass. After the hot rolling, the defects at head, tail and edges of the hot rolled sheet were cut to obtain a hot rolled magnesium alloy sheet with good shape.
Annealing of the hot rolled Mg95Al3Zn1Ca0.4Gd0.4Mn0.2 sheet. The finally rolled sheet was placed into a resistance furnace and kept at 350° C. for 60 minutes.
The Mg95Al3Zn1Ca0.4Gd0.4Mn0.2 sheet has a yield strength of 200 MPa, a tensile strength of 275 MPa, an elongation to failure of 20 percent and an IE value of 5.0. The microstructure photograph of this sheet after rolling and annealing is shown in
Mg95Al3Zn1Ca0.4Y0.4Mn0.2 magnesium alloy sheet (1 mm in thickness): weighting raw materials according to the mass percent of composition, wherein the raw materials were: magnesium ingot of 99.99 mass percent, aluminum ingot of 99.9 mass percent, zinc ingot of 99.99 mass percent, master alloy of magnesium and calcium of 30 mass percent, master alloy of magnesium and yttrium of 30 mass percent, and master alloy of magnesium and manganese of 30 mass percent. The burdening was carried out, according to the nominal composition of the magnesium alloy, and also in consideration of the thermal loss of each of elements.
Melting and casting of Mg95Al3Zn1Ca0.4Y0.4Mn0.2. The raw materials were charged into a crucible in a vacuum induction melting furnace and the melting furnace was vacuumed and heated under inert atmosphere. The temperature was increased to 750° C. and maintained for 15 minutes. After the raw materials were completely melted, the melts were electromagnetically stirred for about 10 minutes. Finally, the melts were poured into the graphite crucible and placed in the air to cool, giving an ingot.
Solid solution treatment of Mg95Al3Zn1Ca0.4Y0.4Mn0.2. The magnesium alloy ingot was placed in a resistance furnace and kept at 450° C. for 15 hours, and then air-cooled to room temperature.
Hot rolling of Mg95Al3Zn1Ca0.4Y0.4Mn0.2. The magnesium alloy ingot after the solid solution treatment was wire-cut into a slab having a thickness of 10 mm, and then the surface of the slab was polished for hot rolling. The specific hot rolling process was as follows: the slab was kept at 400° C. for about 30 minutes and then was hot rolled. The total thickness reduction by hot rolling was 90 percent, that is, the final thickness of sheet was 1 mm. The thickness reductions of the first two passes were 8 percent and 10 percent, respectively, and the thickness reductions of the other passes were controlled within 10 to 30 percent, wherein the thickness reductions of the last two passes were 15 percent and 10 percent, respectively. Due to the fast heat dissipation of the magnesium alloy, in order to stabilize the rolling temperature, the sample was kept at 400° C. for 8 minutes in the resistance further after each rolling pass. After the hot rolling, the defects at head, tail and edges of the hot rolled sheet were cut to obtain a hot rolled magnesium alloy sheet with good shape.
Annealing of the hot rolled Mg95Al3Zn1Ca0.4Y0.4Mn0.2 sheet. The finally rolled sheet was placed into a resistance furnace and kept at 350° C. for 60 minutes.
The Mg95Al3Zn1Ca0.4Y0.4Mn0.2 sheet has a yield strength of 205 MPa, a tensile strength of 280 MPa, an elongation to failure of 18 percent and an IE value of 4.5. The microstructure photograph of this sheet after rolling and annealing is shown in
Mg95.2Zn3Al1Ca0.3Gd0.3Mn0.2 magnesium alloy sheet (1 mm in thickness): weighting raw materials according to the mass percent of composition, wherein the raw materials were: magnesium ingot of 99.99 mass percent, aluminum ingot of 99.9 mass percent, zinc ingot of 99.99 mass percent, master alloy of magnesium and calcium of 30 mass percent, master alloy of magnesium and gadolinium of 30 mass percent, and master alloy of magnesium and manganese of 30 mass percent. The burdening was carried out, according to the nominal composition of the magnesium alloy, and also in consideration of the thermal loss of each of elements.
Melting and casting of Mg95.2Zn3Al1Ca0.3Gd0.3Mn0.2. The raw materials were charged into a crucible in a vacuum induction melting furnace and the melting furnace was vacuumed and heated under inert atmosphere. The temperature was increased to 750° C. and maintained for 15 minutes. After the raw materials were completely melted, the melts were electromagnetically stirred for about 10 minutes. Finally, the melts were poured into the graphite crucible and placed in the air to cool, giving an ingot.
Solid solution treatment of Mg95.2Zn3Al1Ca0.3Gd0.3Mn0.2. The magnesium alloy ingot was placed in a resistance furnace and kept at 300° C. for 20 hours, and then air-cooled to room temperature.
Hot rolling of Mg95.2Zn3Al1Ca0.3Gd0.3Mn0.2. The magnesium alloy ingot after the solid solution treatment was wire-cut into a slab having a thickness of 10 mm, and then the surface of the slab was polished for hot rolling. The specific hot rolling process was as follows: the slab was kept at 400° C. for about 30 minutes and then was hot rolled. The total thickness reduction by hot rolling was 90 percent, that is, the final thickness of sheet was 1 mm. The thickness reductions of the first two passes were 8 percent and 10 percent, respectively, and the thickness reductions of other passes were controlled within 10 to 30 percent, wherein the thickness reductions of the last two passes were 15 percent and 10 percent, respectively. Due to the fast heat dissipation of the magnesium alloy, in order to stabilize the temperature during the rolling, the sample was kept at 400° C. for 8 minutes in the resistance furnace after each rolling pass. After the hot rolling, the defects at head, tail and edges of the hot rolled sheet were cut to obtain a hot rolled magnesium alloy sheet with good shape.
Annealing of the hot rolled Mg95.2Zn3Al1Ca0.3Gd0.3Mn0.2 sheet. The finally rolled sheet was placed into a resistance furnace and kept at 350° C. for 60 minutes.
The Mg95.2Zn3Al1Ca0.3Gd0.3Mn0.2 sheet has a yield strength of 210 MPa, a tensile strength of 275 MPa, an elongation to failure of 22 percent and an IE value of 5. The microstructure photograph of this sheet after rolling and annealing is shown in
Compared with the prior art, the tensile strength, the ductility and IE value of the present invention are significantly improved. As shown in Table 3, the commonly rolled AZ31 (NR) only has an IE value of 3.45 (prior art 1), and even using differential speed rolling (DSR), its IE value is only increased to 3.73 (prior art 2). As disclosed herein, the chemical composition has been modified and adds 0.2 wt % Ca and 0.2 wt % Gd on the basis of AZ21, and the tensile strength thereof is increased to 260 MPa, the elongation to failure to 21 percent, and the IE value to 5.87 (Example 1). Further, the content of Al is reduced and the strengthening element Zn is added so as to obtain Mg96.6Zn2Al1Ca0.2Gd0.2, the IE value of which is increased to 6.67 (Example 4). Further, on the basis of Mg96.6Zn2Al1Ca0.2Gd0.2, 0.1 wt % Gd is reduced and 0.1 wt % Y is added, so as to obtain Mg96.4Zn2Al1Ca0.2Gd0.1Y0.1Mn0.2, the tensile-strength of which is increased to 265.6 MPa. On the other hand, in order to further increase mechanical properties, more Al/Zn, Ca, Gd/Y and Mn elements were added based on Mg96.6Al2Zn1Ca0.2Gd0.2 (Example 1) and Mg96.6Zn2Al1Ca0.2Gd0.2 (Example 4) to obtain Mg95Al3Zn1Ca0.4Gd0.4Mn0.2 (Example 9), Mg95Al3Zn1Ca0.4Y0.4Mn0.2 (Example 10) and Mg95.2Zn3Al1Ca0.3Gd0.3Mn0.2 (Example 11). In addition, the disclosed magnesium alloys contain a lower content of rare earth elements, have a better processability, and have a higher yield during the whole preparation process including melting, extruding, rolling, etc. Therefore, the disclosed magnesium alloy not only has a high room temperature formability, better mechanical properties, and anti-flammability and corrosion-resistance performance, but also has a low cost in preparation, and may be an ideal material for forming non-structural parts in the aerospace field and the like.
Table 1 shows the mechanical properties and IE values for alloys AZ31 (NR) (prior art 1), AZ31 (DSR) (prior art 2), Mg96.6Al2Zn1Ca0.2Gd0.2 (Examples 1-3), Mg96.6Zn2Al1Ca0.2Gd0.2 (Examples 4-7), Mg96.4Zn2Al1Ca0.2Gd0.1Y0.1Mn0.2 (Example 8), Mg95Al3Zn1Ca0.4Y0.4Mn0.2 (Example 9), Mg95Al3Zn1Ca0.4Y0.4Mn0.2 (Example 10) and Mg95Zn3Al1Ca0.3Gd0.3Mn0.2 (Example 11).
Although various embodiments of the disclosed calcium-bearing magnesium and rare earth element alloys and methods have been shown and described, modifications may occur to those skilled in the art upon reading the specification. The present application includes such modifications and is limited only by the scope of the claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201710020396X | Jan 2017 | CN | national |
This application is a divisional of U.S. Ser. No. 16/471,168 filed on Jun. 19, 2019, which is the U.S. national phase entry of Intl. Pat. App. No. PCT/US2017/050913 filed on Sep. 11, 2017, which claims priority from Chinese Pat. App. No. 201710020396X filed on Jan. 11, 2017. The entire contents of U.S. Ser. No. 16/471,168, Intl. Pat. App. No. PCT/US2017/050913, and Chinese Pat. App. No. 201710020396X are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16471168 | Jun 2019 | US |
| Child | 17672950 | US |
