CN108342628B - Aluminum-copper-magnesium high-strength heat-resistant cast aluminum alloy and preparation method thereof - Google Patents
Aluminum-copper-magnesium high-strength heat-resistant cast aluminum alloy and preparation method thereof Download PDFInfo
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Abstract
Aiming at the outstanding problem that the tensile strength of the existing high-strength heat-resistant cast aluminum alloy is sharply reduced at high temperature, the invention provides an aluminum-copper-magnesium series high-strength heat-resistant cast aluminum alloy and a preparation method thereof, wherein the alloy comprises the following components in percentage by weight: 3.5-7.5 wt.% Cu; 0.5-1.5 wt.% Mg; 0.2-1.0 wt.% of Ag; 0.2-1.0 wt.% Mn; RE 0.05-0.85 wt.%; 0.05-1.25 wt.% of Ti; 0.1-0.8 wt.% Zr; 0-0.2 wt.%; the balance being aluminum. The invention obviously improves the elongation of the high-strength heat-resistant cast aluminum alloy at normal temperature, improves the high-temperature mechanical property of the alloy, and ensures that the cast aluminum alloy still has higher mechanical property at the high temperature of 300 ℃.
Description
Technical Field
The invention belongs to the technical field of high-strength heat-resistant light-structure cast metal materials, and particularly provides an aluminum-copper-magnesium series high-strength heat-resistant cast aluminum alloy and a preparation method thereof.
Background
The aluminum alloy has the outstanding characteristics of low specific gravity, corrosion resistance, easy forming and the like, and is an important light structural material. In recent years, with the rapid development of aerospace industry, the flight speed of aviation and spacecraft is continuously improved, and the aircraft generates a large amount of heat by friction with the atmosphere, so that the external temperature of the aircraft is continuously increased, and higher requirements on the heat resistance of structural materials of the aviation and spacecraft are provided. However, the conventional aluminum alloy for casting is difficult to satisfy the demand, and the industry is eagerly eager to obtain a new aluminum alloy material for high-strength heat-resistant casting.
At present, the high-strength heat-resistant cast aluminum alloys mainly applied at home comprise ZL206, ZL207, ZL208 and ZL205A, and the alloy at foreign countries mainly comprise American 201 and A201 alloy and Russian BA pi 10 alloy. The performance of ZL205A in China and A201 alloy in the United states is the most remarkable in the above alloys. The main chemical components of ZL205A are Cu 4.6-5.3%, Mg 1.5%, Mn 0.3-0.5%, Zr 0.05-0.2%, Ti 0.15-0.35%, Cd 0.15-0.35%, and Al in balance. The tensile strength at room temperature is 440-510MPa, the tensile strength at 300 ℃ is 170MPa, and the elongation is 3.5. The A201 alloy mainly comprises Cu 4.0-5.0%, Mg0.15-0.35%, Ag 0.4-1.0%, Mn 0.2-0.4%, Zr 0.05-0.2%, Ti 0.15-0.35%, and Al in balance. The elongation of the material is 9.0% at room temperature tensile strength of 460MPa, 140MPa at 300 deg.C and 12%. The materials are difficult to meet the requirements on the mechanical properties of the materials under the current high-temperature condition.
Disclosure of Invention
The invention provides an aluminum-copper-magnesium series high-strength heat-resistant cast aluminum alloy and a preparation method thereof, aiming at the outstanding problem that the tensile strength of the existing high-strength heat-resistant cast aluminum alloy is sharply reduced at high temperature. The invention obviously improves the elongation of the high-strength heat-resistant cast aluminum alloy at normal temperature, improves the high-temperature mechanical property of the alloy, and ensures that the cast aluminum alloy still has higher mechanical property (tensile strength sigma) at the high temperature of 300 DEG Cb210MPa or more and the elongation delta is 7 or more).
The technical scheme of the invention is as follows:
the aluminum alloy for aluminum-copper-magnesium high-strength heat-resistant casting is characterized by comprising the following components in percentage by weight: 3.5-7.5 wt.% Cu; 0.5-1.5 wt.% Mg; 0.2-1.0 wt.% of Ag; 0.2-1.0 wt.% Mn; RE 0.05-0.85 wt.%; 0.05-1.25 wt.% of Ti; 0.1-0.8 wt.% Zr; 0-0.2 wt.%; the balance being aluminum.
As a preferred technical scheme:
the rare earth element RE is a single rare earth element or more than one mixed rare earth element, preferably one or more of La, Ce, Pr, Nd, Er, Y and Sc.
The aluminum alloy also contains one or more of the following elements in each group to further improve the performance of the alloy, and the aluminum alloy comprises the following components in percentage by weight: cr: 0-0.7 wt.%, V: 0-0.2 wt.%.
The aluminum alloy for aluminum-copper-magnesium high-strength heat-resistant casting is characterized in that the mass ratio of Mg to Ag elements is that Mg/Ag is 0.8-2.5, the Ag elements are subjected to segregation in the stacking faults of alloy α phase interfaces after being added into an alloy matrix, Ag and Mg are subjected to strong interaction to form Ag-Mg atomic groups, the atomic groups can obviously influence the composition of a heat-resistant strengthening phase in the aging heat treatment process of the alloy, and the strengthening phase in the alloy consists of a large amount of theta ' phases and a small amount of omega phases along with the increase of the content of the Ag elements, and is gradually converted into a large amount of omega phases and a small amount of theta ' phases (the omega phases are far better than the theta ' phases in heat resistance), so that the heat resistance of the alloy is improved, but when the ratio of the Mg/Ag elements is too small, enough Ag-Mg atomic groups cannot be formed, the precipitation of heat-resistant precipitation phases of the alloy is not facilitated, the heat resistance of the alloy is reduced, but when the ratio of the Mg/Ag elements is too large, the surplus Mg element can form a low-melting point S phase, and the heat resistance of the alloy is also reduced, and the heat resistance of the alloy is limited to 0.8-5.
In the alloy of the present invention, the mass ratio of Cu to Mg is preferably 5 to 15 (more preferably 8 to 13) to improve the high-temperature mechanical properties of the alloy of the present invention.
The aluminum alloy for aluminum-copper-magnesium high-strength heat-resistant casting is characterized by comprising the following typical components in percentage by weight: 5.5 wt.% Cu; 0.5 wt.% Mg; 0.6 wt.% Ag; 0.5 wt.% Mn; RE:0.6 wt.%; 0.85 wt.% Ti; 0.7 wt.% Zr; 0.05 wt.% B; 0.2 wt.% Cr; the balance being aluminum.
The invention also provides a preparation method of the aluminum alloy for the aluminum-copper-magnesium high-strength heat-resistant casting, which is characterized by comprising the following steps of:
1) calculating the mass of each simple substance metal or the mass of the intermediate alloy within the proportion range of each element;
2) when the smelting starts, adding pure aluminum ingot and Al-Mn intermediate alloy into a resistance furnace, and preserving heat at 700-800 ℃;
3) after the alloy is cleaned, adding Al-Cu intermediate alloy and Al-Zr intermediate alloy (when the alloy contains Cr and/or V elements, Al-Cr intermediate alloy and/or Al-V intermediate alloy are also needed to be added);
4) adding Ag into the solution when the temperature is raised to 700-760 ℃;
5) when the temperature is reduced to 620-710 ℃, pressing the pure magnesium block by using a pressing spoon, and adding a rare earth intermediate alloy;
6) adding Al-Ti and KBF when the temperature rises to 700-750 DEG C4(fluoride salt) or Al-Ti-B master alloy;
7) after each alloy element is added, refining and degassing are carried out when the temperature is reduced to 700-730 ℃; standing for 2-30min, removing slag, and waiting for pouring; the gas used for refining and degassing is preferably inert gas such as nitrogen or argon;
8) casting;
9) and (3) heat treatment: the multi-stage solid solution treatment is carried out at the temperature of 450-550 ℃ for 35 hours or less, and the aging treatment is carried out at the temperature of 150-200 ℃ for 12 hours or less.
In order to dissolve uneven alloy precipitated phases precipitated in the cooling process into α (Al) solid solution matrix, eliminate element segregation generated in the solidification process of the alloy and prevent over-burning, the invention adopts multi-stage solution treatment, and the multi-stage solution treatment is secondary solution treatment or tertiary solution treatment:
secondary solution treatment: keeping the temperature at 440-510 ℃ for 0.5-15 h, and then keeping the temperature at 510-550 ℃ for 0.5-20 h; third-stage solution treatment: keeping the temperature at 480 ℃ of 440-.
As a preferred technical scheme:
secondary solution treatment: preserving heat for 3-6 h at 470-500 ℃, and then preserving heat for 6-15 h at 510-540 ℃;
third-stage solution treatment: keeping the temperature at 440-470 ℃ for 5-8 h, then heating to 480-510 ℃ for 6-15 h, and finally heating to 510-540 ℃ for 8-15 h.
The invention adopts a multi-stage solution treatment process, can effectively prevent the over-burning phenomenon, and can improve the quenching temperature of the alloy, so that the precipitated phase generated in the casting process of the alloy can be dissolved in the alloy solid solution as much as possible.
The invention mainly regulates and controls the alloy strengthening phase from the following two aspects:
1) controlling the precipitation of a strengthening phase by adjusting the alloy components;
2) the precipitation of the strengthening phase is controlled by the aging heat treatment process.
Through the regulation and control of the precipitation of the alloy strengthening phase, the invention obtains a fine dispersed precipitation strengthening phase, and the size of the precipitation strengthening phase is below 0.8 mu m, as shown in figure 1. The alloy of the invention has extremely high tensile strength at normal temperature and high temperature, and shows excellent mechanical properties.
Compared with the existing alloy:
1) the result of comparing the mechanical property of the alloy of the invention with the existing alloy grades at home and abroad is shown in table 1, and as can be seen from table 1, the mechanical property of the alloy of the invention with high temperature strength is obviously superior to that of the existing aluminum alloys with all grades.
2) The invention realizes the precipitation control of the alloy strengthening phase by controlling the alloy components, forms the main alloy strengthening phase omega phase under the combined action of magnesium and silver atomic groups, and effectively improves the high-temperature strength of the alloy.
3) The invention adopts a multi-stage solution treatment process, can effectively prevent the over-burning phenomenon, and can improve the quenching temperature of the alloy, so that the precipitated phase generated in the casting process of the alloy can be dissolved in the alloy solid solution as much as possible. In the aging treatment process, the precipitation process of the alloy strengthening phase is regulated and controlled by optimizing the aging temperature and time, and finally the high-temperature resistant strengthening phase with fine dispersion is obtained, so that the high-temperature strength of the alloy is effectively improved.
TABLE 1 comparison of alloy Properties
The advantages of the invention are as follows:
1. according to the invention, through optimization of alloy components and a heat treatment process, a large amount of fine and dispersed high-temperature strengthening phases are obtained, the size of a precipitated phase is only about 0.8 mu m, and the high-temperature strengthening alloy has excellent high-temperature mechanical properties.
2. Compared with the existing similar alloy, the alloy has the outstanding characteristics of being capable of resisting the high temperature of 300 ℃, has the outstanding advantages of impact resistance and high temperature resistance, and is a novel high-strength heat-resistant aluminum alloy with high competitiveness at present.
3. The old material has good reusability, and the alloy still has good mechanical properties after being remelted for many times (please refer to figure 2 for the relationship between the remelting times of the alloy and the strength of the alloy).
4. The alloy of the invention does not contain cadmium which is harmful to human body. Chronic poisoning can be caused by long-term inhalation of cadmium, and can cause kidney damage, and anemia can be caused by chronic cadmium poisoning.
Drawings
FIG. 1 is a phase diagram of the alloy after heat treatment of the alloy of the present invention.
FIG. 2 shows the relationship between the number of times of remelting the alloy and the strength of the alloy.
Detailed Description
Example 1:
1) preparing 30Kg of alloy according to the element proportion in the following table;
TABLE 2 alloy content (% by weight)
| Element(s) | Cu | Mg | Ag | Mn | Zr | Ti | RE | Al |
| Content/% | 4 | 0.45 | 0.46 | 0.25 | 0.2 | 0.15 | 0.08 | Surplus |
2) When the smelting starts, adding pure aluminum ingots and Al-Mn intermediate alloy into a resistance furnace, and preserving heat at 700-800 ℃;
3) after the mixture is cleaned, adding Al-Cu intermediate alloy and Al-Zr intermediate alloy;
4) adding Ag when the temperature rises to 700-760 ℃;
5) when the temperature is reduced to 620-710 ℃, pressing the pure magnesium blocks by a pressing spoon, and adding the dilute intermediate alloy;
6) adding Al-Ti intermediate alloy and KBF when the temperature rises to 700-750 DEG C4(fluoride salts);
7) after each alloy element is added, refining and degassing are carried out when the temperature is reduced to 700-730 ℃; standing for 2-30min, removing slag, and waiting for pouring;
8) casting;
9) multi-stage solution treatment: preserving heat at 470-500 ℃ for 6h, and then preserving heat at 510-540 ℃ for 9 h;
aging treatment: the aging treatment is carried out at the temperature of 150 ℃ and 200 ℃ for 12 hours or less.
10) The sample indexes are as follows: the normal-temperature tensile strength is 464MPa, and the elongation is 6%; the tensile strength is 216MPa at 300 ℃, and the elongation is 9%.
Example 2:
1) preparing 30Kg of alloy according to the element proportion in the following table;
TABLE 3 alloy content (% by weight)
2) When the smelting starts, adding pure aluminum ingots and Al-Mn intermediate alloy into a resistance furnace, and preserving heat at 700-800 ℃;
3) after the mixture is cleaned, adding Al-Cu intermediate alloy, Al-Zr intermediate alloy and Al-Cr intermediate alloy;
4) when the temperature rises to 700-760 ℃, adding simple substance Ag;
5) when the temperature is reduced to 620-710 ℃, pressing the pure magnesium blocks by a pressing spoon, and adding the rare earth intermediate alloy;
6) adding Al-Ti intermediate alloy and KBF when the temperature rises to 700-750 DEG C4；
7) After each alloy element is added, refining and degassing are carried out when the temperature is reduced to 700-730 ℃; standing for 2-30min, removing slag, and waiting for pouring;
8) casting;
9) multi-stage solution treatment: preserving heat for 5h at 470-500 ℃ and then preserving heat for 11h at 510-540 ℃;
aging treatment: the aging treatment is carried out at the temperature of 150 ℃ and 200 ℃ for 12 hours or less.
10) The sample indexes are as follows: tensile strength is 501MPa, and elongation is 5%; the tensile strength is 232Mpa at 300 ℃, and the elongation is 8%.
Example 3:
1) preparing 30Kg of alloy according to the element proportion in the following table;
TABLE 4 alloy content (% by weight)
| Element(s) | Cu | Mg | Ag | Mn | Zr | Ti | RE | Cr | B | Al |
| Content/% | 5.5 | 1.0 | 0.5 | 0.8 | 0.5 | 0.5 | 0.3 | 0.1 | 0.03 | Surplus |
2) When the smelting starts, adding pure aluminum ingots and Al-Mn intermediate alloy into a resistance furnace, and preserving heat at 700-800 ℃;
3) after the mixture is cleaned, adding Al-Cu intermediate alloy, Al-Zr intermediate alloy and Al-Cr intermediate alloy;
4) when the temperature rises to 700-760 ℃, adding simple substance Ag;
5) when the temperature is reduced to 620-710 ℃, pressing the pure magnesium blocks by a pressing spoon, and adding the rare earth intermediate alloy;
6) adding Al-Ti intermediate alloy and KBF when the temperature rises to 700-750 DEG C4；
7) After each alloy element is added, refining and degassing are carried out when the temperature is reduced to 700-730 ℃; standing for 2-30min, removing slag, and waiting for pouring;
8) casting;
9) multi-stage solution treatment: preserving heat for 6h at the temperature of 440-;
aging treatment: the aging treatment is carried out at the temperature of 150 ℃ and 200 ℃ for 12 hours or less.
10) The sample indexes are as follows: tensile strength is 501MPa, and elongation is 5%; tensile strength of 252MPa at 300 ℃ and elongation of 7.5 percent
Example 4:
1) preparing 30Kg of alloy according to the element proportion in the following table;
TABLE 5 alloy content (% by weight)
| Element(s) | Cu | Mg | Ag | Mn | Zr | Ti | RE | Al |
| Content/% | 6 | 1.2 | 0.7 | 0.55 | 0.6 | 0.15 | 0.2 | Surplus |
2) When the smelting starts, adding pure aluminum ingots and Al-Mn intermediate alloy into a resistance furnace, and preserving heat at 700-800 ℃;
3) after the mixture is cleaned, adding Al-Cu intermediate alloy and Al-Zr intermediate alloy;
4) adding Ag when the temperature rises to 700-760 ℃;
5) when the temperature is reduced to 620-710 ℃, pressing the pure magnesium blocks by a pressing spoon, and adding the dilute intermediate alloy;
6) adding Al-Ti intermediate alloy and KBF when the temperature rises to 700-750 DEG C4(fluoride salts);
7) after each alloy element is added, refining and degassing are carried out when the temperature is reduced to 700-730 ℃; standing for 2-30min, removing slag, and waiting for pouring;
8) casting;
9) multi-stage solution treatment: preserving heat for 4h at the temperature of 440-;
aging treatment: the aging treatment is carried out at the temperature of 150 ℃ and 200 ℃ for 12 hours or less.
10) The sample indexes are as follows: tensile strength is 524MPa, and elongation is 4%; tensile strength of 280MPa at 300 ℃ and elongation of 7 percent
Example 5:
1) preparing 30Kg of alloy according to the element proportion in the following table;
TABLE 6 alloy content (% by weight)
| Element(s) | Cu | Mg | Ag | Mn | Zr | Ti | RE | V | Al |
| Content/% | 6.5 | 0.8 | 0.9 | 0.55 | 0.6 | 0.25 | 0.2 | 0.1 | Surplus |
2) When the smelting starts, adding pure aluminum ingots and Al-Mn intermediate alloy into a resistance furnace, and preserving heat at 700-800 ℃;
3) after the mixture is cleaned, adding Al-Cu intermediate alloy and Al-Zr intermediate alloy;
4) adding Ag when the temperature rises to 700-760 ℃;
5) when the temperature is reduced to 620-710 ℃, pressing the pure magnesium blocks by a pressing spoon, and adding the dilute intermediate alloy;
6) adding Al-Ti intermediate alloy and KBF when the temperature rises to 700-750 DEG C4(fluoride salts);
7) after each alloy element is added, refining and degassing are carried out when the temperature is reduced to 700-730 ℃; standing for 2-30min, removing slag, and waiting for pouring;
8) casting;
9) multi-stage solution treatment: keeping the temperature at 440-;
aging treatment: the aging treatment is carried out at the temperature of 150 ℃ and 200 ℃ for 12 hours or less.
10) The sample indexes are as follows: tensile strength is 524MPa, and elongation is 4%; tensile strength 285Mpa and elongation 7% at 300 deg.C.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (7)
1. The aluminum alloy for aluminum-copper-magnesium high-strength heat-resistant casting is characterized by comprising the following components in percentage by weight:
Cu:5.0～6.0wt.％
Mg:0.5～0.8wt.％
Ag:0.5～0.7wt.％
Mn:0.3～0.8wt.％
RE:0.4～0.8wt.％
Ti:0.3～0.9wt.％
Zr:0.3～0.8wt.％
B:0.05～0.2wt.％
Cr：0～0.7wt.％
V：0～0.2wt.％
the balance being aluminum;
the mass ratio of Mg to Ag element is Mg/Ag 0.8-1.1.
2. The aluminum alloy for aluminum-copper-magnesium high-strength heat-resistant casting according to claim 1, characterized in that: the rare earth element RE is a single rare earth element or more than one mixed rare earth element.
3. The aluminum alloy for aluminum-copper-magnesium high-strength heat-resistant casting according to claim 1, characterized in that: the rare earth element RE is one or more of La, Ce, Pr, Nd, Er, Y and Sc.
4. A preparation method of the aluminum alloy for aluminum-copper-magnesium high-strength heat-resistant casting according to claim 1 is characterized by comprising the following steps:
1) calculating the mass of each simple substance metal or the mass of the intermediate alloy within the proportion range of each element;
2) when the smelting starts, adding pure aluminum ingot and Al-Mn intermediate alloy into a resistance furnace, and preserving heat at 700-800 ℃;
3) after the aluminum alloy is dissolved and cleaned, adding an Al-Cu intermediate alloy and an Al-Zr intermediate alloy;
4) adding Ag into the solution when the temperature is raised to 700-760 ℃;
5) pressing the pure magnesium block when the temperature is reduced to 620-710 ℃, and adding rare earth intermediate alloy;
6) adding Al-Ti and KBF when the temperature rises to 700-750 DEG C4Or an Al-Ti-B master alloy;
7) after each alloy element is added, refining and degassing are carried out when the temperature is reduced to 700-730 ℃; standing for 2-30min, removing slag, and waiting for pouring;
8) casting;
9) and (3) heat treatment: performing multi-stage solid solution treatment at 450-550 ℃ for less than 35 hours, and performing aging treatment at 150-200 ℃ for less than 12 hours;
the multistage solution treatment is a secondary solution treatment, namely: keeping the temperature at 440-510 ℃ for 0.5-15 h, and then keeping the temperature at 510-550 ℃ for 0.5-20 h; or three-stage solution treatment, namely: keeping the temperature at 480 ℃ of 440-.
5. The method according to claim 4, wherein: when the alloy contains Cr and/or V elements, Al-Cr master alloy and/or Al-V master alloy are added in the step 3).
6. The method according to claim 4, wherein: the gas adopted for refining and degassing in the step 7) is nitrogen or argon.
7. The production method according to claim 4, wherein the multistage solution treatment is:
secondary solution treatment: preserving heat for 3-6 h at 470-500 ℃, and then preserving heat for 6-15 h at 510-540 ℃;
or carrying out three-stage solution treatment: keeping the temperature at 440-470 ℃ for 5-8 h, then heating to 480-510 ℃ for 6-15 h, and finally heating to 510-540 ℃ for 8-15 h.
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