CN101838763B - High-zinc aluminum alloy 2099 microalloyed with strontium and preparation method thereof - Google Patents
High-zinc aluminum alloy 2099 microalloyed with strontium and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-zinc aluminum alloy 2099 microalloyed with strontium and a preparation method thereof. The aluminum alloy is formed by microalloying aluminum alloy 2099 with a small amount of strontium and appropriately increasing the content of zinc, and mainly comprises Al, Cu, Li, Zn, Mg, Mn, Zr and Sr. The preparation process flow of the alloy is as follows: melting pure Al, sequentially adding Al-Cu intermediate alloy, Al-Sr intermediate alloy, Al-Mn intermediate alloy, Al-Zr intermediate alloy, pure Zn and pure Mg until being molten, adding hexachloroethane for refining, standing and maintaining the temperature for 5-10 minutes, adding LiF covering agent, then adding pure Li, adding hexachloroethane again for refining and degassing, standing and maintaining the temperature for 3-5 minutes, and then casting into ingots; and carrying out post treatments of annealing, stamping and T6 treatment on the alloy ingots formed by casting. The alloy has the characteristics of low density, high rigidity, good corrosion resistance and the like, and can meet the requirements for high-performance aluminum alloy in the fields of aerospace, weaponry and the like in China.
Description
Technical field
The present invention relates to a kind of non-ferrous metal and preparation method thereof, relate in particular to a kind of Al-Cu-Li-Zn-Mg-Zr type aluminium alloy that contains strontium and preparation method thereof.Specifically, be a kind of high-zinc aluminum alloy 2099 and preparation method thereof of microalloyed with strontium.
Background technology
Lithium (Li) is the lightest metallic element of occurring in nature, and its density has only 0.535g/cm
3, the Li of every adding 1～2wt% (mass percent) in aluminium can make alloy density descend 3～10%, and Young's modulus improves 5～20%.Because Al-Li alloy has low density, high specific strength, high specific stiffness, good resistance to low temperature, excellent corrosion resisting performance, remarkable superplastic forming performance and can weld etc., is considered to ideal structured material in the Aeronautics and Astronautics industry.Wherein, 2099 aluminium alloys (a kind of Al-Cu-Li-Zn-Mg-Zr alloy) with its loss of weight significantly (substitute 2024 aluminium alloy losss of weight 7～17%), characteristics such as erosion resistance is good, the plastic making performance is good, can weld, less anisotropy, on the big aircraft A380 of Air Passenger a new generation, widely apply.
As everyone knows, alloying and microalloying are the effective means that improves aluminum alloy organization and performance.The basal component of 2099 aluminium alloys is copper (Cu) 2.4～3.0, lithium (Li) 1.6～2.0, and zinc (Zn) 0.4～1.0, magnesium (Mg) 0.1～0.5, manganese (Mn) 0.1～0.5, zirconium (Zr) 0.05～0.12, surplus is aluminium and small amount of impurities element.From microalloying, this alloy has only adopted transition element Zr to carry out microalloying.Strontium (Sr) is a kind of high reactivity element, is a kind of long-acting alterant in aluminium alloy, can purify melt effectively, alleviate harm, the thinning microstructure of impurity, hinders recrystallize and grain growth, improves the thermostability of alloy.From main alloying element, this alloy has adopted Zn to carry out alloying, has reduced the stacking fault energy of alloy, has promoted Tl (Al
2CuLi) separate out mutually, reduced the anisotropy of alloy, improved the stress corrosion resistance of alloy, visible Zn is the beneficial element of 2099 aluminium alloys.Therefore, in 2099 aluminium alloys,, suitably improve the content of Zn simultaneously, can further improve the performance of 2099 aluminium alloys by adding the Sr of trace.
But up to the present, China does not have a kind of 2099 type aluminium alloys with independent intellectual property right available as yet, and this has restricted industrial expansions such as China's aerospace, weaponry to a certain extent.
Summary of the invention
The objective of the invention is on the basis of 2099 aluminium alloys, add the Sr element, invent a kind of high performance 2099 type aluminium alloys and preparation method thereof, satisfy the demand in fields such as aerospace, weaponry by composition and the trace of adjusting master alloying element Zn.
One of technical scheme of the present invention is:
A kind of high-zinc aluminum alloy 2099 of microalloyed with strontium is characterized in that it is mainly elementary composition by aluminium (Al), copper (Cu), lithium (Li), zinc (Zn), magnesium (Mg), manganese (Mn), zirconium (Zr) and strontium (Sr); Wherein, the mass percent of copper (Cu) is 2.36～2.52%, the mass percent of lithium (Li) is 1.87～1.98%, the mass percent of zinc (Zn) is 1.19～1.27%, the mass percent of magnesium (Mg) is 0.451～0.497%, and the mass percent of manganese (Mn) is 0.309～0.313%, and the mass percent of zirconium (Zr) is 0.0791～0.0825%, the mass percent of strontium (Sr) is 0.0605～0.80%, and surplus is aluminium and small amount of impurities element.
The mass percent of described Zn is high by 0.19～0.27% than the higher limit of Zn content in 2099 aluminium alloys.
Two of technical scheme of the present invention is:
A kind of preparation method of high-zinc aluminum alloy 2099 of microalloyed with strontium is characterized in that:
At first, with pure Al fusing;
Secondly, add successively with ordinary method preparation or direct commercial Al-Cu master alloy, Al-Sr master alloy, Al-Mn master alloy, Al-Zr master alloy and pure Zn, pure Mg, behind the centre or melting of metal to be added, add the hexachloroethane refining again until there not being gas evolution, add lithium fluoride (LiF) insulating covering agent after leaving standstill insulation 5～10min, add pure Li then, add the hexachloroethane refining once more, leave standstill insulation and remove slag behind 3～5min and be cast into ingot until there not being gas evolution.
At last, the alloy that is cast into ingot is carried out aftertreatment; Can obtain the high-zinc aluminum alloy 2099 of microalloyed with strontium.
The mass percent of Cu is about 50.12% in the described Al-Cu master alloy, the mass percent of Sr is about 9.89% in the Al-Sr master alloy, the mass percent of Mn is about 10.02% in the Al-Mn master alloy, and the mass percent of Zr is about 4.11% in the Al-Zr master alloy.
Described its optimised process of aftertreatment that is cast into the aluminium alloy of ingot be forging and pressing processing, the T6 after 470～490 ℃ * 24h annealing, 470～490 ℃ of preheatings handle (121 ℃ of 540 ℃ * 2h+ of solution treatment ageing treatment * 14h-151 ℃ * 48h).
The invention has the beneficial effects as follows:
(1) alloy of the present invention has characteristics such as density is little, hardness is high, erosion resistance is good.Such as, alloy of the present invention through T6 handle (121 ℃ of 540 ℃ * 2h+ of solution treatment ageing treatment * 14h-151 ℃ * 48h) after, its hardness is 162.7～174.1HV, (191 ℃ of 500 ℃ * 2h+ of solution treatment ageing treatment * 12h) hardness of aluminium alloy is high by 14.7～22.7%, and corrosion resistance is similar to the 2024-T6 aluminium alloy than 2024-T6.
(2) the invention discloses a kind of preparation method of high-zinc aluminum alloy 2099 of microalloyed with strontium, broken to a certain extent abroad, can satisfy the demand in fields such as China's aerospace, weaponry the blockade on new techniques of high-performance aluminium alloy.
(3) the present invention has obtained the ideal preparation method by a large amount of tests, especially by adopting the method that adds each master alloy and pure metal successively to control each component content, could finally obtain satisfactory aluminum alloy materials by process sequence of the present invention.
Description of drawings
Fig. 1 is cross section metallographic structure after the high-zinc aluminum alloy 2099 Huey test of microalloyed with strontium of the present invention;
Fig. 2 is cross section metallographic structure behind the commercial standard 2024-T6 intergranular corrosion test for aluminium alloy.
Embodiment
The present invention is further described below in conjunction with accompanying drawing.
Embodiment one
As shown in Figure 1
A kind of high-zinc aluminum alloy 2099 of microalloyed with strontium, adopt following method manufacturing and get:
Be formulated as example by 28kg.
Earlier with the pure Al of 23.44kg A00 grade (composition: 99.79Al, 0.14Fe, 0.04Si, the numeral of element before meeting all represented mass percent among all embodiment) add 1.50kgAl-Cu (49.62Al successively after the fusing, 50.12Cu, 0.15Fe, 0.11Si) master alloy (can directly purchase from market according to proportioning by the Al-Cu master alloy, also can adopt the ordinary method preparation, the rate of loss of Cu is about 6.25%), 0.29kgAl-Sr (89.86Al, 9.89Sr, 0.15Fe, 0.10Si) master alloy (can directly purchase from market according to proportioning by the Al-Sr master alloy, also can adopt the ordinary method preparation, the rate of loss of Sr is about 40%), 0.96kgAl-Mn master alloy (89.73Al, 10.02Mn, 0.19Fe, 0.06Si) (the Al-Mn master alloy can directly be purchased from market according to proportioning, also can adopt the ordinary method preparation, the rate of loss of Mn is about 10%), 0.61kg Al-Zr master alloy (95.69Al, 4.11Zr, 0.20Fe, 0.10Si) (the Al-Zr master alloy can directly be purchased from market according to proportioning, also can adopt the ordinary method preparation, the rate of loss of Zr is about 8%), 0.36kg pure Zn (rate of loss of Zn is about 8%), 0.17kg pure Mg (rate of loss of Mg is about 20%), treat that its fusing back adds hexachloroethane refining (add-on is 56g) degasification, (lithium wherein occurs with the form of impurity adding LiF insulating covering agent after leaving standstill insulation 5～10min, therefore can not influence the total content of lithium, down together), add the pure Li of 0.67kg (rate of loss of Li is about 22%) then, add hexachloroethane refining (add-on is 28g) degasification once more, leave standstill insulation and be cast into ingot behind 3～5min; To the alloy that is cast into ingot carry out 470～490 ℃ * 24h annealing, the forging and pressing processing after 470～490 ℃ of preheatings, T6 handle (121 ℃ of 540 ℃ * 2h+ of solution treatment ageing treatment * 14h-151 ℃ * 48h); Promptly obtain the high-zinc aluminum alloy 2099 of microalloyed with strontium.
The measured hardness of the aluminium alloy of present embodiment is 162.7HV, and (191 ℃ of 500 ℃ * 2h+ of solution treatment ageing treatment * 12h) aluminium alloy is high by 14.7% than 2024-T6; Corrode by GB/T 7998-2005 (aluminium alloy intergranular corrosion testing method), its intergranular corrosion full depth only is 122.78 μ m (accompanying drawings 1), and the intergranular maximum corrosion depth of 2024-T6 aluminium alloy is 202 μ m (accompanying drawings 2).
The aluminium alloy of present embodiment through spectrum actual measurement composition is: 2.52 (mass percent, down together) Cu, and 1.87Li, 1.19Zn, 0.497Mg, 0.309Mn, 0.0825Zr, 0.0605Sr, surplus is aluminium and impurity element.
Embodiment two
A kind of high-zinc aluminum alloy 2099 of microalloyed with strontium, its manufacture method is:
Be formulated as example by 28kg.
Earlier with the pure Al of 23.39kgA00 grade (composition: 99.79Al, 0.14Fe, 0.04Si) fusing after add 1.41kg Al-Cu (49.62Al successively, 50.12Cu, 0.15Fe, 0.11Si) (the Al-Cu master alloy is standby can directly purchase or adopt ordinary method to prepare from market after for master alloy, wherein the rate of loss of Cu is about 6.25%), 0.38kg Al-Sr (89.86Al, 9.89Sr, 0.15Fe, 0.10Si) (the Al-Sr master alloy is standby can directly purchase or adopt ordinary method to prepare from market after for master alloy, the rate of loss of Sr is about 40%), 0.97kg Al-Mn master alloy (89.73Al, 10.02Mn, 0.19Fe, 0.06Si) (the Al-Mn master alloy is standby can directly purchase or adopt ordinary method to prepare from market after, the rate of loss of Mn is about 10%), 0.59kg Al-Zr master alloy (95.69Al, 4.11Zr, 0.20Fe, 0.10Si) (the Al-Zr master alloy is standby can directly purchase or adopt ordinary method to prepare from market after, the rate of loss of Zr is about 8%), 0.39kg pure Zn (rate of loss of Zn is about 8%), 0.16kg pure Mg (rate of loss of Mg is about 20%), treat that its fusing back adds hexachloroethane refining (add-on is 56g) degasification, add the slag making of LiF insulating covering agent after leaving standstill insulation 5～10min, add the pure Li of 0.71kg (rate of loss of Li is about 22%) then, add hexachloroethane refining (add-on is 28g) degasification once more, leave standstill insulation and be cast into ingot behind 3～5min; To the alloy that is cast into ingot carry out 470～490 ℃ * 24h annealing, the forging and pressing processing after 470～490 ℃ of preheatings, T6 handle (121 ℃ of 540 ℃ * 2h+ of solution treatment ageing treatment * 14h-151 ℃ * 48h); Promptly obtain the high-zinc aluminum alloy 2099 of microalloyed with strontium.
The measured hardness of the aluminium alloy of present embodiment is 174.1HV, and (191 ℃ of 500 ℃ * 2h+ of solution treatment ageing treatment * 12h) aluminium alloy is high by 22.7% than 2024-T6; By GB/T 7998-2005 aluminium alloy intergranular corrosion testing method) corrode, its intergranular maximum corrosion depth is 245.65 μ m.
The aluminium alloy of present embodiment gained through spectrum actual measurement composition is: 2.36 (mass percent, down together) Cu, and 1.98Li, 1.27Zn, 0.451Mg, 0.313Mn, 0.0791Zr, 0.080Sr, surplus is aluminium and impurity element).
Embodiment three
A kind of high-zinc aluminum alloy 2099 of microalloyed with strontium, adopt following method manufacturing and get:
Be formulated as example by 28kg.
Earlier with the pure Al of 23.39kg A00 grade (composition: 99.79Al, 0.14Fe, 0.04Si, the numeral of element before meeting all represented mass percent among all embodiment) add 1.44kgAl-Cu (49.62Al successively after the fusing, 50.12Cu, 0.15Fe, 0.11Si) master alloy (can directly purchase from market according to proportioning by the Al-Cu master alloy, also can adopt the ordinary method preparation, the rate of loss of Cu is about 6.25%), 0.34kgAl-Sr (89.86Al, 9.89Sr, 0.15Fe, 0.10Si) master alloy (can directly purchase from market according to proportioning by the Al-Sr master alloy, also can adopt the ordinary method preparation, the rate of loss of Sr is about 40%), 1.01kgAl-Mn master alloy (89.73Al, 10.02Mn, 0.19Fe, 0.06Si) (the Al-Mn master alloy can directly be purchased from market according to proportioning, also can adopt the ordinary method preparation, the rate of loss of Mn is about 10%), 0.60kgAl-Zr master alloy (95.69Al, 4.11Zr, 0.20Fe, 0.10Si) (the Al-Zr master alloy can directly be purchased from market according to proportioning, also can adopt the ordinary method preparation, the rate of loss of Zr is about 8%), 0.37kg pure Zn (rate of loss of Zn is about 8%), 0.17kg pure Mg (rate of loss of Mg is about 20%) treats that its fusing back adds hexachloroethane refining (add-on is 56g) degasification, adds the LiF insulating covering agent after leaving standstill insulation 5～10min, add the pure Li of 0.68kg (rate of loss of Li is about 22%) then, add hexachloroethane refining (add-on is 28g) degasification once more, leave standstill insulation and be cast into ingot behind 3～5min; To the alloy that is cast into ingot carry out 470～490 ℃ * 24h annealing, the forging and pressing processing after 470～490 ℃ of preheatings, T6 handle (121 ℃ of 540 ℃ * 2h+ of solution treatment ageing treatment * 14h-151 ℃ * 48h); Promptly obtain the high-zinc aluminum alloy 2099 of microalloyed with strontium.
The actual measurement of the hardness of the aluminium alloy of present embodiment is 171.8HV, and (191 ℃ of 500 ℃ * 2h+ of solution treatment ageing treatment * 12h) aluminium alloy is high by 21.2% than 2024-T6; Corrode by GB/T 7998-2005 (aluminium alloy intergranular corrosion testing method), its intergranular corrosion full depth only is 263.40 μ m.
The aluminium alloy of present embodiment through spectrum actual measurement composition is: 2.41 (mass percent, down together) Cu, and 1.90Li, 1.23Zn, 0.474Mg, 0.325Mn, 0.0813Zr, 0.0715Sr, surplus is aluminium and impurity element.
Embodiment four
A kind of high-zinc aluminum alloy 2099 of microalloyed with strontium, its manufacture method is:
Be formulated as example by 28kg.
Earlier with the pure Al of 23.43kgA00 grade (composition: 99.79Al, 0.14Fe, 0.04Si) fusing after add 1.45kg Al-Cu (49.62Al successively, 50.12Cu, 0.15Fe, 0.11Si) (the Al-Cu master alloy is standby can directly purchase or adopt ordinary method to prepare from market after for master alloy, wherein the rate of loss of Cu is about 6.25%), 0.33kg Al-Sr (89.86Al, 9.89Sr, 0.15Fe, 0.10Si) (the Al-Sr master alloy is standby can directly purchase or adopt ordinary method to prepare from market after for master alloy, the rate of loss of Sr is about 40%), 0.98kgAl-Mn master alloy (89.73Al, 10.02Mn, 0.19Fe, 0.06Si) (the Al-Mn master alloy is standby can directly purchase or adopt ordinary method to prepare from market after, the rate of loss of Mn is about 10%), 0.59kgAl-Zr master alloy (95.69Al, 4.11Zr, 0.20Fe, 0.10Si) (the Al-Zr master alloy is standby can directly purchase or adopt ordinary method to prepare from market after, the rate of loss of Zr is about 8%), 0.38kg pure Zn (rate of loss of Zn is about 8%), 0.17kg pure Mg (rate of loss of Mg is about 20%), treat that its fusing back adds hexachloroethane refining (add-on is 56g) degasification, add the LiF insulating covering agent after leaving standstill insulation 5～10min, add the pure Li of 0.67kg (rate of loss of Li is about 22%) then, add hexachloroethane refining (add-on is 28g) degasification once more, be cast into ingot after leaving standstill insulation 3～5min; To the alloy that is cast into ingot carry out 470～490 ℃ * 24h annealing, the forging and pressing processing after 470～490 ℃ of preheatings, T6 handle (121 ℃ of 540 ℃ * 2h+ of solution treatment ageing treatment * 14h-151 ℃ * 48h); Promptly obtain the high-zinc aluminum alloy 2099 of microalloyed with strontium.
The actual measurement of the hardness of the aluminium alloy of present embodiment is 169.2HV, and (191 ℃ of 500 ℃ * 2h+ of solution treatment ageing treatment * 12h) aluminium alloy is high by 19.3% than 2024-T6; By GB/T 7998-2005 aluminium alloy intergranular corrosion testing method) corrode, its intergranular maximum corrosion depth only is 251.60 μ m.
The aluminium alloy of present embodiment gained through spectrum actual measurement composition is: 2.43 (mass percent, down together) Cu, and 1.88Li, 1.24Zn, 0.467Mg, 0.317Mn, 0.0803Zr, 0.0708Sr, surplus is aluminium and impurity element).
Below only listed the proportioning and the manufacture method of the aluminium alloy of several common proportionings, those skilled in the art can suitably adjust the proportioning of each component and strict can obtain ideal hardness height, 2099 type Al-Li alloys that etch resistant properties is good by above-mentioned steps manufacturing according to above-mentioned example.
The part that the present invention does not relate to prior art that maybe can adopt all same as the prior art is realized.
Claims (4)
1. the high-zinc aluminum alloy 2099 of a microalloyed with strontium is characterized in that it mainly is made up of aluminium (Al), copper (Cu), lithium (Li), zinc (Zn), magnesium (Mg), manganese (Mn), zirconium (Zr) and strontium (Sr); Wherein, the mass percent of copper (Cu) is 2.36～2.52%, the mass percent of lithium (Li) is 1.87～1.98%, the mass percent of zinc (Zn) is 1.19～1.27%, the mass percent of magnesium (Mg) is 0.451～0.497%, and the mass percent of manganese (Mn) is 0.309～0.325%, and the mass percent of zirconium (Zr) is 0.0791～0.0825%, the mass percent of strontium (Sr) is 0.0605～0.80%, and surplus is aluminium (Al) and small amount of impurities.
2. the preparation method of the high-zinc aluminum alloy 2099 of the described microalloyed with strontium of claim 1 is characterized in that:
At first, with pure Al fusing;
Secondly, add Al-Cu master alloy, Al-Sr master alloy, Al-Mn master alloy, Al-Zr master alloy, pure Zn and pure Mg successively, in the interpolation process, must add by listed order, promptly must etc. add back one master alloy or metal again behind last master alloy or the melting of metal, and then add the hexachloroethane refining until there not being gas evolution, add lithium fluoride (LiF) insulating covering agent after leaving standstill insulation 5～10min, add pure Li then, add the hexachloroethane refining once more until there not being gas evolution, leave standstill insulation and be cast into ingot behind 3～5min;
At last, the aluminium alloy that is cast into ingot is carried out aftertreatment; Promptly obtain the high-zinc aluminum alloy 2099 of microalloyed with strontium.
3. the preparation method of the high-zinc aluminum alloy 2099 of microalloyed with strontium according to claim 2, it is characterized in that: the mass percent of Cu is 50.12% in the described Al-Cu master alloy, the mass percent of Sr is 9.89% in the Al-Sr master alloy, the mass percent of Al-Mn master alloy Mn is 10.02%, and the mass percent of Zr is 4.11% in the Al-Zr master alloy.
4. the preparation method of the high-zinc aluminum alloy 2099 of microalloyed with strontium according to claim 2 is characterized in that: the described post-treating method that is cast into the aluminium alloy of ingot comprises that it is 121 ℃ * 14h of 540 ℃ * 2h+ of solution treatment ageing treatment and 151 ℃ * 48h that forging and pressing processing, the T6 after 470～490 ℃ * 24h annealing, 470～490 ℃ of preheatings handles.
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| CN107385287A (en) * | 2017-07-31 | 2017-11-24 | 江苏大学 | Zirconium is strontium compound microalloyed and the high tough Al-Si-Cu-based cast aluminium alloy gold and preparation method of MnZn alloying |
| CN109666830B (en) * | 2019-01-30 | 2021-05-04 | 中南大学 | Wrought aluminum-lithium-copper-zinc alloy and preparation method thereof |
| CN110423926B (en) * | 2019-07-29 | 2020-12-29 | 中国航发北京航空材料研究院 | Heat-resistant aluminum-lithium alloy and preparation method thereof |
| CN110592448B (en) * | 2019-08-27 | 2021-06-22 | 江苏大学 | Heat-resistant corrosion-resistant 2219 type aluminum alloy and preparation method thereof |
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| EP0512056B1 (en) * | 1990-01-26 | 1996-02-28 | Martin Marietta Corporation | Ultra high strength aluminum-base alloys |
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| EP0512056B1 (en) * | 1990-01-26 | 1996-02-28 | Martin Marietta Corporation | Ultra high strength aluminum-base alloys |
| CN1444665A (en) * | 2000-08-01 | 2003-09-24 | Eads德国有限公司 | ALuminium-based alloy and method of fabrication of semiproducts thereof |
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