CN112501482B - Si microalloyed AlZnMgCu alloy and preparation method thereof - Google Patents
Si microalloyed AlZnMgCu alloy and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 91
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 38
- 238000005098 hot rolling Methods 0.000 claims abstract description 8
- 229910018569 Al—Zn—Mg—Cu Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 239000011777 magnesium Substances 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052710 silicon Inorganic materials 0.000 claims abstract 2
- 239000010703 silicon Substances 0.000 claims abstract 2
- 238000000137 annealing Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 6
- 238000000265 homogenisation Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims 2
- -1 aluminum-zinc-magnesium-copper Chemical compound 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 22
- 230000007797 corrosion Effects 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005728 strengthening Methods 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005275 alloying Methods 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 238000003483 aging Methods 0.000 description 6
- 229910000838 Al alloy Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004299 exfoliation Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017758 Cu-Si Inorganic materials 0.000 description 1
- 229910017931 Cu—Si Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/10—Alloys based on aluminium with zinc as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/053—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with zinc as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B2003/001—Aluminium or its alloys
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Abstract
A Si microalloyed AlZnMgCu alloy and a preparation method thereof belong to the field of high-strength Al-Zn-Mg-Cu alloys, and comprise the following alloy components: 4.0 to 5.0 weight percent of zinc, 1.0 to 2.0 weight percent of magnesium, 0.5 to 1.5 weight percent of copper, 0.15 to 0.5 weight percent of silicon, and inevitable impurities with the weight not more than 0.2 weight percent, and the balance of aluminum. The invention adopts Si micro-alloying and aging treatment (single-stage aging treatment or double-stage aging treatment), has obvious aging strengthening effect, improves the corrosion resistance of the alloy, and further improves the alloy strength after hot rolling. The purpose of the patent is to improve the strength and corrosion resistance of the Al-Zn-Mg-Cu alloy.
Description
Technical Field
The invention belongs to the technical field of metal alloy, and relates to a microalloyed aluminum alloy material and a preparation process thereof.
Technical Field
The Al-Zn-Mg-Cu alloy (7xxx series) high-strength aluminum alloy is a heat-treatable strengthened aluminum alloy, has the advantages of low density, high strength, good processability and the like, and is widely used in the aviation and civil industries. But the balance of strength and corrosion performance has not been well solved. The present invention therefore addresses this problem by optimizing the alloy composition to produce a new high strength aluminum alloy that combines high strength with good corrosion resistance.
The strength and the corrosion resistance of the Al-Zn-Mg-Cu alloy are mainly influenced by three organization structures of a matrix precipitated phase, a grain boundary precipitated phase and a non-precipitated zone near the grain boundary. Small, dense matrix precipitates (MPt) in the alloy can significantly strengthen the alloy, but at the same time the continuous grain boundary phase formed leads to a high corrosion susceptibility. In order to improve the strength and corrosion resistance of the alloy, it is necessary to make the matrix precipitate phase (MPt) of the alloy fine and dispersed, while making the grain boundary precipitate phase (GBP) coarse and discontinuous. The present invention attempts to add Si to a 7xxx aluminum alloy, where Si is desired to stabilize the intergranular precipitates under high temperature or long heat treatment conditions, to maintain higher strength of the alloy, and to discontinue the intergranular precipitates (GBP) to improve the corrosion resistance of the alloy.
Based on the consideration, the invention designs the Al-Zn-Mg-Cu-Si alloy, and determines the proper component range and the corresponding preparation process of the alloy.
Disclosure of Invention
The invention aims to invent a Si microalloyed AlZnMgCu alloy and a preparation method thereof. The preparation method of the alloy is to add an Si element with low price into the AlZnMgCu alloy, and enable an intra-grain precipitated phase of the alloy to be stable under the condition of high-temperature or long-time heat treatment through a special aging process, so as to keep higher strength of the alloy and simultaneously enable the grain boundary precipitated phase to be discontinuous, thereby improving the corrosion resistance of the alloy.
In the alloy of the invention, the mass percentages of Zn, Mg and Cu in the alloy are preferably as follows: zn: 4.0wt% -5.0 wt%; mg: 1.0wt% -2.0 wt%; cu: 0.5wt% -1.5 wt%; si: 0.15wt% -0.5wt%, and the balance of Al.
The invention is realized by the following technical scheme: a preparation method of Si microalloyed AlZnMgCu alloy comprises the following steps: (1) preparing an AlZnMgCuSi alloy ingot by adopting graphite crucible smelting and iron mold casting; (2) carrying out homogenization annealing treatment on the alloy at 450-500 ℃ for 13-15 h; (3) hot rolling the alloy after the homogenizing annealing; (4) the alloy after hot rolling is subjected to solution treatment at 500-550 ℃ for 0.5-1.5 h, and then is subjected to artificial aging. The first process is to age the alloy at 125 ℃ for 12-48 h, and then carry out secondary aging at 175 ℃ for 3-12 h; the second one is to age the alloy in single stage at 125-225 deg.c for 0.5-120 hr.
And (1) placing the raw materials into a smelting furnace, keeping the smelting temperature at 770-790 ℃, keeping the temperature and standing after the temperature is reached, so that all element components in the melt are uniformly distributed, and then casting to obtain the required alloy ingot.
The hot rolling process parameters in the step (3) are as follows: the alloy after the homogenizing annealing is firstly subjected to heat preservation at 450 +/-10 ℃ and then is rolled, and the deformation is 75% -95%.
The single-stage aging of the artificial aging is as follows: single-stage aging treatment is carried out for 1 to 10 hours at the temperature of 175 to 225 ℃.
According to the invention, Si element is added in the AlZnMgCu alloy in a compounding manner, so that an intra-grain precipitated phase of the alloy is stable under the condition of high-temperature or long-time heat treatment under a special aging process, the higher strength of the alloy is maintained, and meanwhile, the grain boundary precipitated phase is discontinuous, thereby improving the corrosion resistance of the alloy. The problem of unbalanced strength and corrosion resistance of the AlZnMgCu alloy is solved.
In the method, the Si element has relatively low price, and the adopted aging process is simple and is suitable for industrial production.
Description of the drawings:
FIG. 1: the microhardness curve of the alloy obtained by artificial aging at 125 ℃.
FIG. 2: the microhardness curve obtained by artificially aging the alloy at 175 ℃.
FIG. 3: the microhardness curve obtained by artificially aging the alloy at 225 ℃.
FIG. 4: and (3) artificially aging the alloy at 125 ℃ for 24h, and then artificially aging at 175 ℃ to obtain a microhardness curve.
FIG. 5 a: 540 solid solution of Al-4.5Zn-1.5Mg-1.0Cu alloy after hot rolling for 1h, 125 ℃ aging for 24h, 175 ℃ aging for 24h, intercrystalline corrosion photo.
FIG. 5 b: and after Al-4.5Zn-1.5Mg-1.0Cu-0.35Si alloy is hot rolled, 540 is subjected to solid solution for 1h, 125 ℃ and 24h, 175 ℃ and 24h, and intercrystalline corrosion photos are obtained.
The specific implementation mode is as follows:
the following examples are set forth to further illustrate the present invention, but the present invention is not limited to the following examples.
Example 1 (i.e., comparative):
the alloy ingot is prepared by adopting graphite crucible melting and iron mold casting, the used raw materials are pure aluminum, pure zinc, pure magnesium and Al-50Cu and Al-24Si intermediate alloy, and the melting temperature is 780 +/-10 ℃. After reaching the smelting temperature, the temperature is kept for 30 minutes, and then the casting is carried out by using an iron mold. Alloy-forming metals al4.5zn1.5mg1.0cu and al4.5zn1.5mg1.0cu0.35si were prepared, and actual components thereof were passed through XRF (refer to table 1). The two alloys are subjected to homogenization annealing at 500 ℃/15h, then water quenched to room temperature, and then heated to 450 ℃ for rolling (deformation amount is 90%). After a solution treatment at 540 ℃ for 1 hour, water quenching to room temperature and then single stage ageing at 125 ℃ the aged hardness curves (refer to figure 1) of the two alloys are obtained, and it can be seen from figure 1 that the addition of Si has no significant strengthening effect on the age hardening of the alloys at low temperature of 125 ℃.
Table 1: XRF measured composition table of alloy
Example 2: alloys al4.5zn1.5mg1.0cu, al4.5zn1.5mg1.0cu0.15si, and al4.5zn1.5mg1.0cu0.35si were prepared in the same manner as in example 1 (actual components are shown in table 1), and these three alloys were subjected to homogenization annealing at 500 ℃/15 hours, water-quenched to room temperature, and then heated to 450 ℃ to be rolled (deformation amount 90%). After the alloy is subjected to solid solution at 540 ℃ for 1 hour, water quenching is carried out to room temperature, and then single-stage aging is carried out at 175 ℃, the aging hardness curves of the three alloys (refer to figure 2) are obtained, and as the Si content is increased, the aging hardening peak value of the alloy is higher and lower, the peak value is also slower and slower (the hardness peak values of the alloy containing no Si, 0.15Si and 0.35Si are respectively 117.7HV, 129.6HV and 148.9HV), and the hardness is reduced more and more rapidly after the peak value is reached. Indicating that the strengthening effect of the Si element begins to become obvious after aging at the medium temperature of 175 ℃.
Example 3: alloys al4.5zn1.5mg1.0cu and al4.5zn1.5mg1.0cu0.35si were prepared in the same manner as in example 1 (actual components are shown in table 1), and the two alloys were subjected to homogenization annealing at 500 ℃/15 hours, water-quenched to room temperature, and then heated to 450 ℃ for rolling (deformation 90%). After a solution treatment at 540 c for 1 hour, water quenching to room temperature and then a single stage ageing at 225 c, the age hardness curves (see figure 3) for the two alloys are obtained, and it can be seen from figure 3 that the age hardening effect of Si on the alloys is more pronounced. And with the increase of the Si content, the age hardening peak value of the alloy is improved, and the hardness reduction speed becomes slow after the peak value is reached. The intergranular corrosion and spalling corrosion performance tests are carried out on two alloys of Al4.5Zn1.5Mg1.0Cu and Al4.5Zn1.5Mg1.0Cu0.35Si at the single-stage aging hardness peak state (1 h and 3h respectively) at 225 ℃, and the intergranular corrosion performance of the Si-containing alloy is found to be superior to that of the Si-free alloy. It is shown that the strengthening effect of Si can make the hardness and corrosion resistance of Al4.5Zn1.5Mg1.0Cu alloy reach better balance only under high-temperature single-stage aging.
Example 4: alloys al4.5zn1.5mg1.0cu and al4.5zn1.5mg1.0cu0.35si were prepared in the same manner as in example 1 (actual components are shown in table 1), and the two alloys were subjected to homogenization annealing at 500 ℃/15 hours, water-quenched to room temperature, and then heated to 450 ℃ for rolling (deformation 90%). Carrying out solid solution at 540 ℃ for 1 hour, carrying out water quenching to room temperature, then carrying out aging at 125 ℃ to obtain aged hardness curves of the two alloys, and selecting the two alloys at 125 ℃/24h state to carry out secondary aging at 175 ℃ to obtain an aged hardness curve (refer to figure 4). It can be seen that the hardness of the alloy without Si is in a descending trend during the second stage aging, while the hardness of the alloy with Si is in a descending trend after the alloy with Si is firstly increased, which shows that the addition of Si can further improve the hardness of the alloy after the two-stage aging. The two alloys were chosen for intercrystalline corrosion and exfoliation corrosion performance testing in the 24h aged state of the secondary ageing, and it was found that the intercrystalline corrosion performance (cf. fig. 5a and 5b) and exfoliation corrosion performance of the Si-containing alloy was better than the Si-free alloy. It is stated that Si can well balance the hardness and corrosion resistance of Al4.5Zn1.5Mg1.0Cu alloy under the two-stage aging.
Claims (3)
1. An Si microalloyed aluminum-zinc-magnesium-copper alloy is characterized by comprising the following alloy components: 4.0-5.0 wt% of zinc, 1.0-2.0 wt% of magnesium, 0.5-1.5 wt% of copper, 0.15-0.5 wt% of silicon and the balance of Al;
the preparation method comprises the following steps: (1) preparing an AlZnMgCuSi alloy ingot by adopting graphite crucible smelting and iron mold casting; (2) carrying out homogenization annealing treatment on the alloy at 450-500 ℃ for 13-15 h; (3) hot rolling the alloy after the homogenizing annealing; (4) carrying out solution treatment on the alloy after hot rolling at 500-550 ℃ for 0.5-1.5 h, and then carrying out artificial aging; the first process is to age the alloy at 125 ℃ for 12-48 h, and then carry out secondary aging at 175 ℃ for 3-12 h; secondly, single-stage aging is carried out on the alloy at the temperature of 125-225 ℃ for 0.5-120 h;
the hot rolling process parameters in the step (3) are as follows: and (3) performing heat preservation on the alloy subjected to the homogenizing annealing at 450 +/-10 ℃, and then rolling, wherein the deformation is 75-95%.
2. The Si microalloyed al-zn-mg-cu alloy as claimed in claim 1, wherein (1) the ingot is prepared by: placing the raw materials in a smelting furnace, wherein the smelting temperature is 770-790 ℃, preserving heat and standing after reaching the temperature, so that all element components in the melt are uniformly distributed, and then casting to obtain the required alloy ingot.
3. The Si microalloyed Al-Zn-Mg-Cu alloy as claimed in claim 1, wherein the single stage ageing temperature is in the range of 175 to 225 ℃ and the ageing time is in the range of 1 to 10 hours.
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| CN115369294B (en) * | 2022-08-28 | 2023-09-12 | 北京工业大学 | Heat-resistant Al-Mg-Cu-Zn alloy and heat treatment process |
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| CN108823472A (en) * | 2018-07-25 | 2018-11-16 | 江苏大学 | A kind of High Strength and Tenacity Al-Zn-Mg-Cu Aluminum Alloy and its heat treatment method |
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