CN101838764A - Scandium and strontium compound microalloyed high zinc 2099 type aluminium alloy and preparation method thereof - Google Patents

Scandium and strontium compound microalloyed high zinc 2099 type aluminium alloy and preparation method thereof Download PDF

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CN101838764A
CN101838764A CN 201010134381 CN201010134381A CN101838764A CN 101838764 A CN101838764 A CN 101838764A CN 201010134381 CN201010134381 CN 201010134381 CN 201010134381 A CN201010134381 A CN 201010134381A CN 101838764 A CN101838764 A CN 101838764A
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CN101838764B (en
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许晓静
王彬
罗勇
王宏宇
吴桂潮
潘励
赵梓皓
成城
宋涛
程晓农
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Jiangsu University
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Abstract

The invention discloses a scandium and strontium compound microalloyed high zinc 2099 type aluminium alloy and preparation method thereof. The aluminium alloy is mainly composed of the following elements by mass percent: 2.3-2.57% of copper (Cu), 1.86-1.96% of lithium (Li), 1.14-1.31% of zinc (Zn), 0.269-0.420% of magnesium (Mg), 0.219-0.321% of manganese (Mn), 0.0733-0.08% of zirconium (Zr), 0.0643-0.0943% of strontium (Sr) and 0.0433-0.079% of scandium (Sc), the balance is aluminium (Al) and less impurity elements. The preparation method of the alloy adopts the manufacturing method of intermediate alloy. The invention has simple method, the prepared alloy has low density, high rigidity and good corrosion resistance, and the invention can meet the requirement of the national aviation and weaponry fields to high performance aluminium alloy.

Description

Scandium and strontium compound microalloyed high-zinc aluminum alloy 2099 and preparation method thereof
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 scandium and strontium and preparation method thereof.Specifically, be a kind of scandium and strontium compound microalloyed high-zinc aluminum alloy 2099 and preparation method thereof.
Background technology
Al-Li alloy has that density is low, specific tenacity and specific rigidity height, weldability, corrosion resistance nature and superplastic forming performance that resistance to low temperature is good, good, replace conventional aluminium alloy with it, can make component quality alleviate 15%, rigidity improves 15~20%, is considered to the ideal structure material in the Aeronautics and Astronautics industry.Wherein 2099 Al-Li alloys with its loss of weight significantly (substitute 2024 aluminium alloy losss of weight 7~17%), erosion resistance is good, the plastic making performance is good, can weld, less anisotropy or the like characteristic, 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 main alloying element, this alloy has adopted Zn to carry out alloying, has reduced the stacking fault energy of alloy, has promoted T1 (Al 2CuLi) separate out mutually, reduced the anisotropy of alloy, improved the corrosion resistance of alloy, visible Zn is the beneficial element of 2099 aluminium alloys.From microalloying, this alloy has only adopted transition element Zr to carry out microalloying.Scandium (Sc) is the 3d transition element, is again rare earth element, and aluminium alloy is had magical alloying action.And when itself and transition element Zr carry out combined microalloying, then can form and compare Al 3The Sc size is littler, with the better ternary coherence of the coherency of matrix Al mutually 3(Sc 1-x, Zr x), make the microalloying effect multiplication of Sc.Strontium (Sr) element is the very high long-acting alterant of a kind of activity, adds to purify melt, thinning microstructure, raising alloying elements distribution homogeneity, obstruction recrystallize and grain growth in the aluminium effectively, and can the scaling loss of Sc, Zr be played a protective role.Therefore, in 2099 aluminium alloys,, suitably improve the content of Zn simultaneously, can further improve the over-all properties of 2099 aluminium alloys by adding the Sc and 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 alloying constituents, master alloying element by adjusting alloy also adds micro-Sc and the Sr element, invent 2099 aluminium alloys of a kind of high performance Sc and Sr combined microalloying and preparation method thereof, with its over-all properties of further raising, satisfy the demand in fields such as aerospace, weaponry.
One of technical scheme of the present invention is:
A kind of scandium and strontium compound microalloyed high-zinc aluminum alloy 2099 is characterized in that it mainly is made up of aluminium (Al), copper (Cu), lithium (Li), zinc (Zn), magnesium (Mg), manganese (Mn), zirconium (Zr), strontium (Sr) and scandium (Sc); Wherein, the mass percent of copper (Cu) is 2.33~2.57%, the mass percent of lithium (Li) is 1.86~1.96%, the mass percent of zinc (Zn) is 1.14~1.31%, the mass percent of magnesium (Mg) is 0.269~0.420%, the mass percent of manganese (Mn) is 0.219~0.321%, the mass percent of zirconium (Zr) is 0.0733~0.08%, the mass percent of strontium (Sr) is 0.0643~0.0943%, the mass percent of scandium (Sc) is 0.0433~0.079%, surplus is aluminium (Al) and small amount of impurities, and the mass percent sum of each component is 100%.
The quality percentage of described Zn is 1.14~1.31%, than the last limit for height 0.14~0.31% of 2099 alloy Zn content, so that make alloy have lower anisotropy, higher intensity and the erosion resistance of Geng Gao.
Two of technical scheme of the present invention is:
The preparation method of a kind of scandium and strontium compound microalloyed high-zinc aluminum alloy 2099 is characterized in that:
At first, with pure Al fusing, add the Al-Cu master alloy then successively, the Al-Sr master alloy, the Al-Mn master alloy, the Al-Zr master alloy, the Al-Sc master alloy, pure Zn and pure Mg, in the interpolation process, must add by listed order, promptly must etc. add back one master alloy or metal to be added again behind last master alloy or the melting of metal to be added, 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 remove slag behind 3~5min and be cast into ingot;
Secondly, the alloy that is cast into ingot is carried out aftertreatment; Can obtain scandium and strontium compound microalloyed high-zinc aluminum alloy 2099.
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 Al-Mn master alloy Mn is about 10.02%, the mass percent of Zr is about 4.11% in the Al-Zr master alloy, and the mass percent of Sc is about 2.0% in the Al-Sc master alloy.
Described its optimised process of aftertreatment that is cast into the ingot alloy is that forging and pressing processing, the T6 after 470~490 ℃ * 24h annealing, 470~490 ℃ of preheatings handles that (promptly carry out twice ageing treatment of the solution treatment of 540 ℃~550 ℃ * 2~4.6h and 121 ℃ * 14h+151 ℃ * 48h, twice ageing treatment should be carried out continuously.
The invention has the beneficial effects as follows:
(1) the present invention has added Sc and Sr in alloy, original Zr carries out combined microalloying to alloy in alloy, bring into play the effect of each micro alloying element efficiently, significantly improved the over-all properties of alloy, had characteristics such as density is little, hardness is high, erosion resistance is good.
(2) preparation method of scandium of the present invention and strontium compound microalloyed high-zinc aluminum alloy 2099 has broken abroad to a certain extent to the blockade on new techniques of high-performance aluminium alloy, can satisfy the demand in fields such as China's aerospace, weaponry.
(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.
(4) aluminum alloy materials of the present invention the experiment proved that when continue keeping loss of weight (substituting 2024 aluminium alloy losss of weight 7~17%), can improve erosion resistance more than 10%, plastic making performance, weldability and anisotropy and remain unchanged.
Description of drawings
Fig. 1 is cross section metallographic structure after scandium of the present invention and the strontium compound microalloyed high-zinc aluminum alloy 2099 Huey test;
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, 2
A kind of scandium and strontium compound microalloyed high-zinc aluminum alloy 2099, adopt following method manufacturing and get:
Be formulated as example by 28kg.
Earlier with the pure Al of 22.884kg A00 grade (composition: 99.79Al, 0.14Fe, 0.04Si, numeral among all embodiment before the symbol of element is all represented mass percent) add 1.39kg Al-Cu master alloy (49.62Al successively after the fusing, 50.12Cu, 0.15Fe, 0.11Si) (the Al-Cu master alloy can directly be purchased from market according to proportioning, also can adopt the ordinary method preparation, the rate of loss of Cu is about 6.25%), 0.303kgAl-Sr master alloy (89.86Al, 9.89Sr, 0.15Fe 0.10Si) (the Al-Sr master alloy can directly be purchased from market according to proportioning, also can adopt the ordinary method preparation, the rate of loss of Sr is about 40%), 0.99kg Al-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%), 0.543kg
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%), 0.68kg Al-Sc master alloy (98%Al, 2%Sc) (rate of loss of Sc is about 8%), 0.38kg pure Zn (rate of loss of Zn is about 8%), 0.13kg 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 0.70kg (rate of loss of Li is about 22%) then, add hexachloroethane refining (add-on is 28g) degasification once more, leave standstill insulation and remove slag behind 3~5min and be cast into ingot; 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 (comprise 121 ℃ of 540 ℃ of solution treatment~550 ℃ * 2~4.6h, ageing treatment * 14h+151 ℃ * 48h); Promptly obtain scandium and strontium compound microalloyed high-zinc aluminum alloy 2099.
The performance that adopts different T6 to handle material to the alloy after the forging and pressing during concrete enforcement also has certain difference, as after the solution treatment of 540 ℃ * 2h and 121 ℃ * 14h+151 ℃ * twice ageing treatment of 48h, the hardness of actual measurement is 169.3HV, and (191 ℃ of 500 ℃ * 2h of solution treatment, ageing treatment * 12h) hardness of aluminium alloy is high by 19.3% than 2024-T6; Corrode by GB/T 7998-2005 (aluminium alloy intergranular corrosion testing method), its intergranular corrosion full depth is 111.5 μ m (accompanying drawings 1), and the intergranular maximum corrosion depth of 2024-T6 aluminium alloy is 202 μ m (accompanying drawings 2), can improve erosion resistance about 50%.
For another example after twice ageing treatment of twice solution treatment of 540 ℃ * 2h+550 ℃ * 2.6h and 121 ℃ * 14h+151 ℃ * 48h, the hardness of actual measurement is 156.0HV, and (191 ℃ of 500 ℃ * 2h of solution treatment, ageing treatment * 12h) aluminium alloy is high by 10.0% than 2024-T6; Corrode by GB/T 7998-2005 (aluminium alloy intergranular corrosion testing method), its intergranular corrosion full depth is 141.52 μ m.Corrosion resistance nature improves about 30%.
The aluminium alloy of present embodiment through spectrum actual measurement composition is: 2.33 (mass percent, down together) Cu, and 1.96Li, 1.249Zn, 0.371Mg, 0.319Mn, 0.0733Zr, 0.0643Sr, 0.0447Sc, surplus is aluminium and impurity element.
Embodiment two
A kind of scandium and strontium compound microalloyed high-zinc aluminum alloy 2099, adopt following method manufacturing and get:
Be formulated as example by 28kg.
Earlier with the pure Al of 22.611kgA00 grade (composition: 99.79Al, 0.14Fe, 0.04Si) fusing after add 1.53kg Al-Cu master alloy (49.62Al successively, 50.12Cu, 0.15Fe, 0.11Si) (the Al-Cu master alloy can directly be purchased from market according to proportioning, also can adopt the ordinary method preparation, the rate of loss of Cu is about 6.25%), 0.445kg Al-Sr master alloy (89.86Al, 9.89Sr, 0.15Fe, 0.10Si) (the Al-Sr master alloy can directly be purchased from market according to proportioning, also can adopt the ordinary method preparation, the rate of loss of Sr is about 40%), 0.997kg Al-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%), 0.544kg 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%), 0.659kg Al-Sc master alloy (98%Al, 2%Sc) (rate of loss of Sc is about 8%), 0.399kg pure Zn (rate of loss of Zn is about 8%), 0.147kg 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 0.668kg (rate of loss of Li is about 22%) then, add hexachloroethane refining (add-on is 28g) degasification once more, leave standstill insulation and remove slag behind 3~5min and be cast into ingot; 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 ℃~550 ℃ * 2~4.6h of solution treatment, ageing treatment * 14h+151 ℃ * 48h); Promptly obtain scandium and strontium compound microalloyed high-zinc aluminum alloy 2099.
Adopt different T6 to handle to the alloy after the above-mentioned forging and pressing final performance is also had certain influence, as behind 121 ℃ of 540 ℃ * 2h of solution treatment, ageing treatment * 14h+151 ℃ * 48h, actual hardness is 176.4HV, and (191 ℃ of 500 ℃ * 2h of solution treatment, ageing treatment * 12h) aluminium alloy is high by 24.2% than 2024-T6; Corrode by GB/T 7998-2005 (aluminium alloy intergranular corrosion testing method), its intergranular corrosion full depth is 198.3 μ m.
For another example behind 121 ℃ of 540 ℃ of twice solution treatment * 2h+550 ℃ * 2.6h and twice ageing treatment * 14h-151 ℃ * 48h, actual hardness is 161.4HV, and (191 ℃ of 500 ℃ * 2h of solution treatment, ageing treatment * 12h) aluminium alloy is high by 13.8% than 2024-T6; Corrode by GB/T 7998-2005 (aluminium alloy intergranular corrosion testing method), its intergranular corrosion full depth is 173.47 μ m.
The aluminium alloy of present embodiment through spectrum actual measurement composition is: 2.57 (mass percent, down together) Cu, and 1.86Li, 1.31Zn, 0.42Mg, 0.321Mn, 0.0733Zr, 0.0943S r, 0.0433Sc, surplus is aluminium and impurity element.
Embodiment three
A kind of scandium and strontium compound microalloyed high-zinc aluminum alloy 2099, adopt following method manufacturing and get:
Be formulated as example by 28kg.
Earlier with the pure Al of 22.552kgA00 grade (composition: 99.79Al, 0.14Fe, 0.04Si) fusing after add 1.466kg Al-Cu (49.62Al successively, 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%), 0.382kgAl-Sr master alloy (89.86Al, 9.89Sr, 0.15Fe, 0.10Si) (the Al-Sr master alloy can directly be purchased from market according to proportioning, also can adopt the ordinary method preparation, the rate of loss of Sr is about 40%), 0.68kg Al-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%), 0.592kg 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%), 1.202kgAl-Sc master alloy (98%Al, 2%Sc) (rate of loss of Sc is about 8%), 0.35kg pure Zn (rate of loss of Zn is about 8%), 0.094kg 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 0.682kg (rate of loss of Li is about 22%) then, add hexachloroethane refining (add-on is 28g) degasification once more, leave standstill insulation and remove slag behind 3~5min and be cast into ingot; 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 ℃~550 ℃ * 2~4.6h of solution treatment, ageing treatment * 14h+151 ℃ * 48h); Promptly obtain scandium and strontium compound microalloyed high-zinc aluminum alloy 2099.
Adopt different T6 to handle to the alloy after the above-mentioned forging and pressing final performance is also had certain influence, as behind 121 ℃ of 540 ℃ * 2h of solution treatment, ageing treatment * 14h+151 ℃ * 48h, actual hardness is 173.2HV, and (191 ℃ of 500 ℃ * 2h of solution treatment, ageing treatment * 12h) aluminium alloy is high by 22% than 2024-T6; Corrode by GB/T 7998-2005 (aluminium alloy intergranular corrosion testing method), its intergranular corrosion full depth is 193.34 μ m.
The present embodiment alloy is behind 121 ℃ of 540 ℃ of solution treatment * 2h+550 ℃ * 2.6h, ageing treatment * 14h+151 ℃ * 48h, actual hardness is 157.4HV, and (191 ℃ of 500 ℃ * 2h of solution treatment, ageing treatment * 12h) aluminium alloy is high by 10.8% than 2024-T6; Corrode by GB/T 7998-2005 (aluminium alloy intergranular corrosion testing method), its intergranular corrosion full depth is 168.56 μ m.
The aluminium alloy of present embodiment through spectrum actual measurement composition is: 2.46 (mass percent, down together) Cu, and 1.96Li, 1.14Zn, 0.269Mg, 0.219Mn, 0.08Zr, 0.081S r, 0.079Sc, 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 good scandium of ideal hardness height, etch resistant properties and 2099 strontium compound microalloyed type Al-Li alloys 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. a scandium and strontium compound microalloyed high-zinc aluminum alloy 2099 is characterized in that it mainly is made up of aluminium (Al), copper (Cu), lithium (Li), zinc (Zn), magnesium (Mg), manganese (Mn), zirconium (Zr), strontium (Sr) and scandium (Sc); Wherein, the mass percent of copper (Cu) is 2.33~2.57%, the mass percent of lithium (Li) is 1.86~1.96%, the mass percent of zinc (Zn) is 1.14~1.31%, the mass percent of magnesium (Mg) is 0.269~0.420%, the mass percent of manganese (Mn) is 0.219~0.321%, the mass percent of zirconium (Zr) is 0.0733~0.08%, the mass percent of strontium (Sr) is 0.0643~0.0943%, the mass percent of scandium (Sc) is 0.0433~0.079%, surplus is aluminium (Al) and small amount of impurities, and the mass percent sum of each component is 100%.
2. the preparation method of described scandium of claim 1 and strontium compound microalloyed high-zinc aluminum alloy 2099 is characterized in that:
At first, with pure Al fusing, add the Al-Cu master alloy then successively, the Al-Sr master alloy, the Al-Mn master alloy, the Al-Zr master alloy, the Al-Sc master alloy, pure Zn and pure Mg, in the interpolation process, must add by listed order, promptly must etc. add back one master alloy or metal to be added again behind last master alloy or the melting of metal to be added, 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 remove slag behind 3~5min and be cast into ingot;
Secondly, the alloy that is cast into ingot is carried out aftertreatment; Can obtain scandium and strontium compound microalloyed high-zinc aluminum alloy 2099.
3. the preparation method of scandium according to claim 2 and strontium compound microalloyed high-zinc aluminum alloy 2099, it is characterized in that: 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 Al-Mn master alloy Mn is about 10.02%, the mass percent of Zr is about 4.11% in the Al-Zr master alloy, and the mass percent of Sc is about 2.0% in the Al-Sc master alloy.
4. the preparation method of scandium according to claim 2 and strontium compound microalloyed high-zinc aluminum alloy 2099, it is characterized in that: the described aftertreatment that is cast into the ingot alloy comprises that forging and pressing processing and the T6 after 470~490 ℃ * 24h annealing, 470~490 ℃ of preheatings handles, and described T6 handles the ageing treatment of 121 ℃ of the solution treatment of the 540 ℃~550 ℃ * 2~4.6h that comprises at least one time and twice * 14h+151 ℃ * 48h.
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CN104451272A (en) * 2014-11-21 2015-03-25 上海交通大学 Light-weight and high-strength cast aluminum lithium alloy and preparation method thereof
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