WO2010031255A1 - 一种适于大截面主承力结构件制造的铝合金材料 - Google Patents

一种适于大截面主承力结构件制造的铝合金材料 Download PDF

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WO2010031255A1
WO2010031255A1 PCT/CN2009/070735 CN2009070735W WO2010031255A1 WO 2010031255 A1 WO2010031255 A1 WO 2010031255A1 CN 2009070735 W CN2009070735 W CN 2009070735W WO 2010031255 A1 WO2010031255 A1 WO 2010031255A1
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alloy
pure
aluminum
casting
ingot
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PCT/CN2009/070735
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French (fr)
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熊柏青
张永安
李志辉
朱宝宏
王�锋
刘红伟
李锡武
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北京有色金属研究总院
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/053Changing 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
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/03Making non-ferrous alloys by melting using master alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/10Alloys based on aluminium with zinc as the next major constituent

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  • the present invention relates to an aluminum alloy, particularly an aluminum alloy material suitable for use in the manufacture of large cross-section products and a process for the preparation thereof.
  • aluminum alloy As the most typical lightweight material in metal materials, aluminum alloy has the advantages of low specific gravity, easy processing and low cost, and has always been an indispensable key material in the aerospace industry.
  • the 7xxx series aluminum alloy is a general term for Al-Zn-Mg-Cu-based aluminum alloys. It is also the most strong type of various deformed aluminum alloys that have been successfully commercialized.
  • the 7xxx series aluminum alloy pre-stretched sheets are each A key intermediate for the manufacture of large monolithic structural components used in aircraft, ground and marine transportation. With the development of the whole machine, the comprehensive performance requirements of large-scale integral structural parts are continuously improved, the internal structure complexity of large-scale monolithic structural parts is increased, the overall height and partial wall thickness are increased, etc.
  • the comprehensive performance of aluminum alloy materials (including mechanical properties, physical properties, corrosion resistance, etc.), as well as processing properties (including machining performance, welding properties, etc.) put forward higher and higher requirements, and more importantly, The thickness of the semi-finished product is increased, and the material is required to have good heat treatment hardenability.
  • the existing 7050, 7150, 7055 alloys already have good strength and other comprehensive properties, especially represented by 7050- ⁇ 74 alloy, and are one of the most widely used alloys in the aviation field.
  • these alloys have the problem of medium or even poor heat treatment hardenability, and the hardening thickness is generally not more than 150 mm. It is not suitable for the manufacture of large-scale aviation main bearing structural parts, which limits the further application of this series of alloys in the aviation field.
  • the main reason for the above problems is that the composition of the chemical composition of the above alloys and the ratio of the main elements are not reasonable.
  • the object of the present invention is to provide a high-strength, high-toughness, low-quenching and sensitive aluminum alloy material with high strength, fracture toughness, corrosion resistance, electrical conductivity, etc., and excellent heat treatment hardenability, without using Special heat treatment process, the material is equivalent to the strength and fracture toughness of the traditional commercial 7050-T74 alloy, the stress corrosion resistance (conductivity) is significantly improved, and the heat treatment hardening depth is doubled.
  • the present invention adopts the following technical solutions:
  • a new high-strength, high-toughness, low-tempering-sensitive aluminum alloy material for the manufacture of large-section aeronautical components whose chemical composition and content (by weight percentage) are: Zn7.4 - 8.4wt%, Mgl .4 - 2.2 wt%, Cu l. l - 1.7 wt%, Zr 0. 15-0. 3 wt%, Fe is less than 0.10 wt%, Si is less than 0.08 wt%, and the balance is Al.
  • the invention mainly selects the chemical composition window of the alloy according to the requirements of the alloy in terms of hardenability and comprehensive performance, and the total amount of alloying elements in the alloy is selected from 10.05 to 12.6 wt.
  • the content of Mg element is lowered, and the Zn/Mg value is selected within the range of 3.5 to 6.
  • Cu element can improve the corrosion resistance of the alloy, but too high content will significantly deteriorate the heat treatment and hardenability of the alloy's large-size semi-finished products. Therefore, under the premise of ensuring that the alloy meets the corrosion resistance requirements, the Cu element is selected to be moderately low. That is l. l ⁇ 1.7 wt%.
  • the addition of Mn and Cr elements significantly increases the tendency of the ingot to crack and deteriorates the hardenability of the semi-finished product, which is not conducive to the manufacture of large-section members and should be strictly controlled.
  • the Zr element is the best alternative to the Cr element. It can solve the problem that the Cr element can significantly reduce the hardenability of the semi-finished product while refining the grain and hindering the recrystallization. Moreover, the Zr element content is increased to 0.15 ⁇ 0.3 wt. %, can play a complementary and strengthening role. In addition, impurity elements such as Fe and Si can significantly deteriorate the fracture, fatigue and corrosion resistance of the alloy, and the content should be strictly controlled to the lowest level.
  • the invention discloses a preparation method of a novel high-strength and high-toughness aluminum alloy material suitable for the manufacture of large-section aeronautical products, comprising the following steps:
  • the composition of the aluminum alloy is Zn7.4-8.4wt%, Mg 1.4-2.2 wt%, Cu 1.1-1.7 wt%, Zr O. 15-0. 3 wt%, and the balance is Al,
  • the raw material is selected, wherein pure zinc is used as the raw material of the component Zn, pure magnesium is used as the raw material of the component Mg, aluminum-copper intermediate alloy or pure copper is used as the raw material of the component Cu, and the magnesium-zirconium intermediate alloy is used as the raw material of the component Zr. Pure aluminum ingot as the raw material of component A1;
  • the semi-finished product is subjected to quenching treatment and aging heat treatment to obtain a novel high-strength and high-toughness aluminum alloy material of the present invention.
  • the ingot to be used is sued, that is, a turning process can be employed to coat the outer surface of the ingot.
  • the pure aluminum ingot is high purity A1 (purity greater than 99.99%), pure zinc is industrial pure Zn (purity greater than 99.95%), and pure magnesium is industrial pure Mg (purity greater than 99.95%).
  • the melt temperature is generally controlled at 720 to 780 °C.
  • the casting temperature is 690 to 720 ° C
  • the casting speed is
  • the homogenization heat treatment may be performed by a single-stage homogenization treatment at 450 to 470 ° C for 18 to 32 h, or 420 to 450 ° C / 8 ⁇ .
  • Two-stage homogenization heat treatment process of 16 h+460 ⁇ 475 °C/ 16-28 h.
  • the two-stage homogenization heat treatment process is a two-stage homogenization heat treatment at 420-450 ° C for 8-16 h, and then at 460-475 ° C for 16-28 h.
  • the ingot after the suede is first kept at 380 to 420 ° C for 6 to 18 hours, and then subjected to forging, rolling or extrusion hot deformation processing to obtain a semi-finished material.
  • the semi-finished material is subjected to a quenching heat treatment process by a single-stage solution treatment, and is kept at 465 to 475 ° C for 30 to 300 min, and rapidly transferred to 15 to 40. °C Rapid quenching in water.
  • the semi-finished aging heat treatment process is a single-stage, two-stage or three-stage aging treatment.
  • An aluminum alloy material obtained by the invention has superior fracture toughness, corrosion resistance and electrical conductivity while maintaining a high level of strength
  • the aluminum alloy material itself has superior heat treatment and hardenability, and the common quenching heat treatment method is adopted, and the heat treatment hardening thickness of the semi-finished material can reach 300 mm or more, which is a special It is suitable for high-performance aluminum alloy materials for the manufacture of large-section aviation main bearing structural parts.
  • Figure 1 is a schematic diagram of the end quenching test.
  • Figure 2 is a graph showing the solid solution conductivity of three different alloy end quenched samples as a function of water-cooled end distance.
  • Figure 3 is a graph showing the relationship between the age hardness of the 7B04 alloy end-quenched sample and the distance from the water-cooled end.
  • Al-7.4Zn-l.7Mg-l .4Cu-0.2Zr (wt%) alloy was prepared by ingot metallurgy.
  • the raw materials used are high purity aluminum, industrial pure magnesium, industrial pure zinc, aluminum copper intermediate alloy and magnesium zirconium intermediate alloy.
  • the melting furnace is a resistance heating furnace, and the casting machine is a vertical semi-continuous casting machine.
  • the casting process used is as follows: furnace (first high-purity aluminum furnace) ⁇ melting (addition of industrial pure zinc, aluminum-copper intermediate alloy and magnesium-zirconium intermediate alloy for melting) ⁇ slag ⁇ processing industry pure magnesium ( Add industrial pure magnesium to the furnace for melting) ⁇ Stirring ⁇ Sampling for component analysis ⁇ Adjusting the ingredients ⁇ Stirring ⁇ Refining (refining temperature is 730 ° C) ⁇ Slag slag ⁇ standing (staying time is 10 minutes) ⁇ Casting, The casting temperature was 700 ° C and the casting speed was 50 mm/min.
  • the ingot is subjected to a homogenization heat treatment at 470 ° C / 24 h, and the ingot is kneaded, and the temperature is kept at 410 ° C for 6 h.
  • Hot extrusion processing extrusion of extruded strips with a cross-section of 25x l02mm. Sampling was carried out at 475 °C / 45min and quenched in room temperature water.
  • the aging system can be used for single-stage aging at 120 °C / 24 h, tensile strength is 580-600 MPa, elongation is about 15%, and fracture toughness (LT direction). Up to 36 MPa'm 1/2 , good electrical conductivity and corrosion resistance.
  • the heat treatment hardenability of the commercial 7050 alloy, the 7B04 alloy and the alloy of the present invention was evaluated by a terminal quenching test.
  • the chemical composition of the three alloys is shown in Table 1.
  • the so-called hardenability refers to the ability of the alloy to achieve a certain depth for the quenching effect, which is closely related to the performance of the central region of the semi-finished alloy.
  • the End Quenching Test is a commonly used test method for studying the hardenability of materials.
  • the schematic diagram of the test device is shown in Figure 1.
  • the high level tank 1 is used, and the high level tank 1 is filled with 20 °C tap water 2, at the high level.
  • the lower part of the tank 1 is connected to the water pipe 3, the outlet of the water pipe 3 is quenched at the bottom of the sample 4, and the end quenching sample 4 is a round bar having a length of 150 mm, and the circumferential surface of the round bar is wrapped with a heat insulating material 5 for heat preservation.
  • the end quenching sample 4 is a round bar having a length of 150 mm, and the circumferential surface of the round bar is wrapped with a heat insulating material 5 for heat preservation.
  • a heat insulating material 5 for heat preservation.
  • the - country-curve curve shows the value of the conductivity of the 7B04 alloy after end quenching and the change of the aging hardness with the distance from the water-cooled end; - the curve of the 7050 alloy after end quenching The conductivity value and the change of the hardness of the aging state with the distance from the water-cooled end; the curve shows the conductivity value after the end quenching of the alloy of Example 1 and the change of the aging hardness with the distance from the water-cooled end.
  • Fig. 2 shows the change of the conductivity value of the three alloy materials after the end quenching with the distance from the water-cooled end. It can be seen that the solid solution conductivity of the alloy of the present invention changes little with the distance, and commercial use The electrical conductivity of 7050 alloy and 7B04 alloy increases with the distance from the water-cooled end, especially the change of 7B04 alloy. The conductivity is closely related to the supersaturated solid solution obtained during the quenching process. The better the solid solution effect of the alloying elements, the larger the lattice distortion of the aluminum matrix and the greater the hindrance to the scattering of free electrons. Large, low conductivity. It can be seen from Fig.
  • the conductivity of the 7B04 alloy and the 7050 alloy quenched sample has a large difference between the head and the tail, indicating that the alloy itself has higher heat treatment quenching sensitivity.
  • the electrical conductivity of the alloy of the present invention is extremely stable, indicating that the quenching effect of the sample at different distances from the water-cooled end is almost the same, and the quenching sensitivity is extremely low.
  • FIG. 3 shows a comparison of the hardness of the alloy of the present invention and the 7B04 and 7050 alloys after end-hardening and hardening by aging treatment.
  • the hardness value is an important index to evaluate the quenching effect of the alloy. It can be seen from Fig. 3 that the hardness of the 7B04 aluminum alloy decreases sharply from the water-cooled end, and the hardness of the commercial 7050 alloy decreases significantly, but the decrease is less than that of the 7B04 alloy. In comparison, the end quenched samples of the present invention have almost the same hardness values at different depths and have excellent uniformity.
  • the free end quenching depth of the 7B04 alloy and 7050 alloy is about 30mm and 60mm, respectively, and the free end quenching sample of the alloy of the present invention is in the range of 150mm depth.
  • the heat-treating thickness of 7B04 and 7050 alloy products is about 60-80mm and 120-150mm respectively; and the heat-treating thickness of the alloy products of the invention can reach more than 300mm, and the quenching sensitivity is extremely low, especially suitable for large-section plates and forgings. Manufacturing.
  • Al-8.0Zn-l.7Mg-l.4Cu-0.22Zr (wt%) alloy was prepared by ingot metallurgy.
  • the raw materials used are high purity aluminum, industrial pure magnesium, industrial pure zinc, aluminum copper intermediate alloy and magnesium zirconium intermediate alloy.
  • the melting furnace is a resistance heating furnace, and the casting machine is a vertical semi-continuous casting machine.
  • the casting process used is: furnace (first high-purity aluminum furnace) ⁇ melting (addition of industrial pure zinc, aluminum-copper intermediate alloy and magnesium-zirconium intermediate alloy in the furnace) ⁇ slag ⁇ processing industry pure magnesium (in the furnace Add industrial pure magnesium for melting) ⁇ Stirring ⁇ Sampling for component analysis ⁇ Adjusting ingredients ⁇ Stirring ⁇ Refining (refining temperature is 725 °C) ⁇ Slag slag ⁇ Resting (resting time is 10 minutes) ⁇ Casting, casting temperature is The casting speed is 40 mm/min at 695 °C.
  • the ingot was subjected to two-stage homogenization heat treatment at 440 °C / 12 h + 470 °C / 18 h, and the ingot was mined, and heat-extruded at 400 ° C for 6 h, and the cross-sectional size was 25 x. 102mm extruded strip plate. Sampling was carried out at 470 ° C / 60 min and quenched in room temperature water for a three-stage aging treatment.
  • Al-7.8Zn-l.4Mg-l.6Cu-0.3Zr (wt%) alloy was prepared by ingot metallurgy.
  • the raw materials used are high purity aluminum, industrial pure magnesium, industrial pure zinc, aluminum copper intermediate alloy and magnesium zirconium intermediate alloy.
  • the melting furnace is a resistance heating furnace, and the casting machine is a vertical semi-continuous casting machine.
  • the casting process used is as follows: furnace (first high-purity aluminum furnace) ⁇ melting (addition of industrial pure zinc, aluminum-copper intermediate alloy and magnesium-zirconium intermediate alloy for melting) ⁇ slag ⁇ processing industry pure magnesium ( Add industrial pure magnesium to the furnace for melting) ⁇ Stirring ⁇ Sampling for component analysis ⁇ Adjusting ingredients ⁇ Stirring ⁇ Refining (refining temperature is 725 °C) ⁇ Slag ⁇ Static
  • Al-8.4Zn-2.2Mg-1.2Cu-0.18Zr (wt%) alloy was prepared by ingot metallurgy.
  • the raw materials used are high purity aluminum, industrial pure magnesium, industrial pure zinc, aluminum copper intermediate alloy and magnesium zirconium intermediate alloy.
  • the melting furnace is a resistance heating furnace, and the casting machine is a vertical semi-continuous casting machine.
  • the casting process used is as follows: furnace (first high-purity aluminum furnace) ⁇ melting (addition of industrial pure zinc, aluminum-copper intermediate alloy and magnesium-zirconium intermediate alloy for melting) ⁇ slag ⁇ processing industry pure magnesium ( Add industrial pure magnesium to the furnace for melting) ⁇ Stirring ⁇ Sampling for component analysis ⁇ adjustment of ingredients ⁇ stirring ⁇ refining (refining temperature of 720 ° C) ⁇ slag slag ⁇ standing (resting time of 10 minutes) ⁇ casting, casting temperature of 690 ° C, casting speed of 35 mm / min.
  • the ingot was subjected to a homogenization heat treatment at 468 ° C / 28 h, and the ingot was subjected to kneading, and after heat-sealing at 410 ° C for 6 hours, hot extrusion processing was performed to extrude a extruded strip having a cross-sectional size of 25 x 102 mm.
  • the samples were incubated at 470 ° C / 90 min and quenched in room temperature water for two-stage T74 aging treatment.
  • An Al-7.8Zn-l.6Mg-l.45Cu-0.17Zr (wt%) alloy was prepared by ingot metallurgy.
  • the raw materials used are high purity aluminum, industrial pure magnesium, industrial pure zinc, aluminum copper intermediate alloy and magnesium zirconium intermediate alloy.
  • the melting furnace is a resistance heating furnace, and the casting machine is a vertical semi-continuous casting machine.
  • the casting process used is as follows: furnace (first high-purity aluminum furnace) ⁇ melting (addition of industrial pure zinc, aluminum-copper intermediate alloy and magnesium-zirconium intermediate alloy for melting) ⁇ slag ⁇ processing industry pure magnesium ( Add industrial pure magnesium to the furnace for melting) ⁇ Stirring ⁇ Sampling for component analysis ⁇ Adjusting ingredients ⁇ Stirring ⁇ Refining (refining temperature is 720 ° C) ⁇ Slag slag ⁇ Resting (resting time is 10 minutes) ⁇ Casting, Casting The temperature was 710 ° C and the casting speed was 20 mm/min.
  • the ingot was subjected to two-stage homogenization heat treatment at 440 °C/12h+467 °C/24h, and the ingot was kneaded. After fortification at 410 ° C for 12 h, free forging deformation was performed, and the forged size was 400 mm (T direction) x 200 mm. (S-direction) Free forging of xl500mm (L-direction). The sample was quenched in 490 ° C for 240 min and then quenched in room temperature water. The workpiece was subjected to 1.8-3.0% pre-compression plastic deformation and then subjected to two-stage T74 aging treatment.
  • Example 6 Example 6:
  • An Al-7.75Zn-2.0Mg-l.3Cu-0.18Zr (wt%) alloy was prepared by ingot metallurgy.
  • the raw materials used are high purity aluminum, industrial pure magnesium, industrial pure zinc, aluminum copper intermediate alloy and magnesium zirconium intermediate alloy.
  • the melting furnace is a resistance heating furnace, and the casting machine is a vertical semi-continuous casting machine.
  • the casting process used is as follows: furnace (first high-purity aluminum furnace) ⁇ melting (addition of industrial pure zinc, aluminum-copper intermediate alloy, magnesium-zirconium intermediate alloy for melting) ⁇ slag ⁇ processing industry pure magnesium ( Add industrial pure magnesium to the furnace for melting) ⁇ Stirring ⁇ Sampling for component analysis ⁇ Adjusting ingredients ⁇ Stirring ⁇ Refining (refining temperature is 720 ° C) ⁇ Slag slag ⁇ Resting (resting time is 10 minutes) ⁇ Casting, Casting The temperature was 700 ° C and the casting speed was 20 mm/min.
  • the ingot was subjected to two-stage homogenization heat treatment at 440 °C/12h+467 °C/24h, and the ingot was subjected to kneading. After being kept at 410 ° C for 12 h, the rolling was subjected to hot deformation, and the rolling size was 1000 mm (T direction). ) xl20mm (S-direction) x3000mm (L-direction) hot-rolled slab. Sampling was carried out at 470 ° C for 150 min and then quenched in room temperature water. The workpiece was subjected to 1.8 to 3.0% pre-stretch plastic deformation and then subjected to two-stage T76 aging treatment.
  • Table 2 shows the alloy performance data for each of the comparative examples and their comparison with other alloys. Table 2 Comparison of performance of examples with other alloys
  • the aluminum alloy material obtained by the present invention has excellent fracture toughness, corrosion resistance and electrical conductivity while maintaining a high level of strength, and is excellent in hardenability, and is particularly suitable for use. High-performance aluminum alloy material manufactured by large-section aviation main bearing structural parts.

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Description

一种适于大截面主承力结构件制造的铝合金材料 技术领域
本发明涉及一种铝合金, 特别是适合用于大截面产品制造的铝合金材料及 其制备方法。
背景技术
铝合金作为金属材料中最典型的轻质材料, 具有比重低、 易加工、 成本低 等优点, 一直是航空航天领域不可缺少的关键材料。
7xxx系铝合金是 Al-Zn-Mg-Cu系铝合金的总称, 也是目前已成功地实现 商业化应用的各种变形铝合金中强度最高的一类,7xxx系铝合金预拉伸板是各 种飞机、地面和海上交通运输工具中所使用的大型整体式结构件制造用的关键 中间产品。 随着整机发展对大型整体式结构件综合性能要求的不断提高, 大型 整体式结构件内部结构复杂程度的上升、 总体高度和部分壁厚的增大等等, 对 大型结构件制造用 7χχχ系铝合金材料的综合使用性能 (包括力学性能、 物理 性能、 抗腐蚀性能等) 、 以及加工工艺性能(包括切削加工性能、 焊接性能等) 提出了越来越高的要求, 更为重要的是随着半成品的厚度增加, 需要材料具有 良好的热处理淬透性能。
现有的 7050、 7150、 7055合金已经具有良好的强度和其他综合性能, 尤 其以 7050-Τ74合金为代表, 是当前航空领域使用的最为广泛的合金之一。 但 这些合金都存在热处理淬透性能中等甚至较差的问题, 其淬透厚度一般不超过 150mm, 不适于大型航空主承力结构件的制造, 限制了该系列合金在航空领域 的进一步应用。造成上述问题的主要原因在于以上合金的化学成分组成窗口及 主元素的配比不尽合理。
发明的公开
本发明的目的是提供一种强度保持在较高水平, 断裂韧性、 耐蚀性能、 电 导率等明显提高, 同时具有优越热处理淬透性能的高强度高韧性低淬火敏感性 铝合金材料, 无需采用特殊的热处理工艺, 该材料与传统商用 7050-T74合金 强度和断裂韧性相当, 抗应力腐蚀性能 (电导率) 明显提高, 热处理淬透深度 提高一倍。
为实现上述目的, 本发明采取以下技术方案:
一种用于大截面航空构件制造的新型高强度、 高韧性、 低淬火敏感性铝合 金材料,其化学成分及含量(按重量百分比计)为: Zn7.4— 8.4wt%, Mgl .4— 2.2 wt% , Cu l. l— 1.7 wt%, Zr 0. 15—0. 3 wt% , Fe小于 0.10 wt %, Si小于 0.08 wt %, 余量为 Al。 本发明主要依据合金在淬透性和综合性能方面的要求对合 金的化学成分组成窗口进行选择, 合金内合金元素总量选择为 10.05~12.6 wt %, 保证了合金具有较高的强度水平。 考虑到提高可铸造成型性和断裂韧性的 因素, 降低了 Mg元素的含量, Zn/Mg值选择 3.5~6范围之内。 Cu元素可提高 合金的耐腐蚀性能, 但含量过高会明显恶化合金大尺寸半成品的热处理淬透性 能, 因而在保证合金满足耐蚀性要求的前提下, Cu 元素选择为中等偏低的水 平, 即 l . l~1.7 wt %。 Mn和 Cr元素的加入明显增加铸锭开裂倾向且恶化半成 品的淬透性, 不利于大截面构件的制造, 应严格控制。 Zr元素是替代 Cr元素 的最佳选择, 在起到细化晶粒、 阻碍再结晶作用的同时, 可解决 Cr元素明显 降低半成品淬透性的问题, 而且将 Zr元素含量提高到 0.15~0.3 wt %, 可起到 补充强化的作用。 另外, Fe和 Si等杂质元素会显著恶化合金的断裂、 疲劳、 耐蚀性能, 应该严格控制其含量在最低水平。
本发明的一种适用于大截面航空制品制造的新型高强度高韧性铝合金材 料的制备方法, 包括下述步骤:
( 1 ) 以重量百分比计, 该铝合金成分为 Zn7.4— 8.4wt%, Mg 1.4— 2.2 wt % , Cu 1.1—1.7 wt% , Zr O. 15—0. 3 wt%, 其余为 Al, 按照上述铝合金成分 进行配料; 其中, 选取纯锌作为成分 Zn的原料, 纯镁作为成分 Mg的原料, 铝铜中间合金或纯铜作为成分 Cu的原料, 镁锆中间合金作为成分 Zr的原料, 纯铝锭作为成分 A1的原料;
( 2 ) 将配置好的纯铝锭装入熔化炉中, 待纯铝锭熔化后, 陆续加入铝铜 中间合金或纯铜, 纯锌和镁锆中间合金; 扒渣后, 加入纯镁, 对熔体进行搅拌, 取样分析化学成分, 看是否满足成分控制要求, 如有必要进行成分调整; 加入 精炼剂对熔体进行精炼, 以消除熔体内的气体、 氧化膜及非金属夹杂物, 使熔 体净化; 扒渣后进行静置, 完成整个熔炼过程, 等待铸造;
( 3 ) 采用立式半连续铸造机进行铸造, 制备出表面质量合格和无铸造裂 纹的铸锭;
( 4) 对铸锭进行均匀化热处理;
( 5 ) 铸锭扒皮后, 进行锻造、 轧制或挤压热变形加工, 加工成相应的半 成品;
( 6 ) 将该半成品进行淬火处理和时效热处理, 即得到本发明的一种新型 高强度高韧性铝合金材料。
在所述的第 (5 ) 步骤中, 对所采用的铸锭进行扒皮, 即可以采用车削工 艺, 车铸锭的外表面。
所述的纯铝锭为高纯 A1 (纯度大于 99.99%) , 纯锌为工业纯 Zn (纯度 大于 99.95%) , 纯镁为工业纯 Mg (纯度大于 99.95%) 。
在本发明的方法的步骤 (2) 中, 熔体温度一般控制在 720〜780°C。
在本发明的方法的步骤 (3 ) 中, 铸造温度为 690~720°C, 铸造速度为
15~50mm/min。 在本发明的方法的步骤(4)中,所述的均匀化热处理可采用在 450~470°C 下保温 18~32 h 的单级均匀化处理, 亦可采用 420~450 °C/8~16 h+460~475 °C/ 16-28 h 的双级均匀化热处理工艺。 所述的双级均匀化热处理工艺是在 420-450 °C下保温 8~16 h, 然后再在 460~475 °C下保温 16~28 h的双级均匀化 热处理。
在本发明的方法的步骤(5 ) 中, 先将扒皮后的铸锭在 380〜420°C下保温 6~18小时, 随后再进行锻造、 轧制或挤压热变形加工, 获得半成品料。
在本发明的方法的步骤 (6) 中, 所述的将半成品料进行淬火热处理的过 程是进行单级固溶处理,在 465~475°C下保温 30~300 min,快速转移至 15~40°C 水中快速淬冷。
在本发明的方法的步骤(6 )中, 所述的半成品时效热处理过程是在单级、 双级或三级时效处理。
本发明的优点是:
( 1 ) 本发明获得的一种铝合金材料, 在保持较高的强度水平的前提下, 具有优越断裂韧性、 耐蚀性能和电导率;
( 2) 由于本发明对主元素进行优化设计, 因而该铝合金材料本身具有优 越的热处理淬透性能, 采用常用的淬火热处理方法, 半成品料的热处理淬透厚 度可达 300mm 以上, 是一种特别适合用于大截面航空主承力结构件制造的高 性能铝合金材料。
附图说明
图 1为末端淬火试验示意图。
图 2 为三种不同合金端淬试样的固溶态电导率随至水冷端距离的变化曲线 图。
图 3 为国产 7B04 合金端淬试样的时效态硬度随至水冷端距离的变化曲线 图。
实施发明的方式
实施例 1 :
采用铸锭冶金的方法制备 Al-7.4Zn-l .7Mg-l .4Cu-0.2Zr (wt%) 合金。 所用 原料为高纯铝、 工业纯镁、 工业纯锌、 铝铜中间合金和镁锆中间合金。 熔化炉 为电阻加热炉, 铸造机为立式半连续铸造机。 采用的熔铸工序为: 装炉 (先将 高纯铝装炉) →熔化 (再在炉中加入工业纯锌、 铝铜中间合金和镁锆中间合金 进行熔化) →扒渣→加工业纯镁 (在炉中加入工业纯镁进行熔化) →搅拌→取 样进行成分分析→调整成分→搅拌→精炼 (精炼的温度为 730°C ) →扒渣→静 置(静置时间为 10分钟)→铸造, 铸造温度为 700°C, 铸造速度为 50mm/min。 将铸锭进行 470°C/24h均匀化热处理, 将铸锭进行扒皮, 在 410°C保温 6h后进 行热挤压加工, 挤压出截面大小为 25x l02mm的挤压带板。 取样进行 475 °C / 45min保温并在室温水中进行淬火, 时效制度可采用单级时效 120°C/ 24h, 抗 拉强度为 580~600MPa,延伸率约为 15%,断裂韧度(L-T方向)达 36 MPa'm1/2, 电导率和耐蚀性能良好。
采用末端淬火试验对商业化 7050合金、 7B04合金和本发明合金的热处理 淬透性能进行评价, 三种合金的化学成分组成对比如表 1所示。 所谓淬透性是 指合金对淬火效应能达到一定深度的能力, 它与合金半成品中心区的性能紧密 相关。 末端淬火试验(End Quenching Test)是用来研究材料淬透性的常用试验 方法, 其试验装置示意图如图 1所示, 采用高位槽 1, 高位槽 1中装有 20°C自 来水 2, 在高位槽 1的下部接通水管 3, 水管 3的出口正对端淬试样 4的底部, 端淬试样 4是长度为 150mm的圆棒, 圆棒的圆周面采用隔热保温材料 5包裹 进行保温, 以减少外界因素干扰。 利用高位槽 1 自来水 2到水管 3的出口的高 度 H对端淬试样 4的一个端面进行自由喷水淬火,自由端淬的时间约为 10min, 图 1中 (H-H ) 表示高位槽中储水高度。
在图 2、 图 3中, -國 -的曲线表示 7B04合金的端淬后的电导率数值以及 时效态硬度随至水冷端距离的变化图;- · -的曲线表示 7050合金的端淬后的电 导率数值以及时效态硬度随至水冷端距离的变化图; 的曲线表示实施例 1 合金的端淬后的电导率数值以及时效态硬度随至水冷端距离的变化图。
如图 2所示, 图 2表示三种合金材料端淬后的电导率数值随至水冷端距离 的变化情况, 可以看出, 本发明合金固溶态电导率随距离的变化较小, 而商用 7050合金和 7B04合金的电导率随至水冷端距离的不断增加, 尤其是 7B04合 金的变化更为显著。 电导率的大小与合金在淬火过程中所获得过饱和固溶体息 息相关, 合金元素的固溶效果越好, 铝基体的晶格畸变越大, 对自由电子散射 起较大阻碍作用, 因而合金电阻率较大, 电导率较小。 从图 2可以发现, 在相 同的外界淬火条件下,7B04合金和 7050合金端淬试样的电导率头尾相差较大, 说明合金本身的热处理淬火敏感性较高。 相比而言, 本发明合金的电导率变化 极为平稳, 说明试样在至水冷端不同距离处的淬火效果相差无几, 淬火敏感性 极低。
如图 3所示, 图 3表示比较了本发明合金与 7B04、 7050合金端淬并经时 效处理硬化后硬度随至水冷端距离的变化情况。硬度值是评价合金淬火效应的 一个重要指标, 从图 3 中可以看出, 7B04铝合金的硬度从水冷端开始就急剧 下降, 商业化 7050合金的硬度下降也较为明显, 但下降幅度小于 7B04合金, 相比较而言, 本发明合金端淬试样在不同深度的硬度值几乎相同, 具有极好的 均匀性。 若将最大硬度的 85~90%处定义为淬透深度, 7B04合金、 7050合金的 自由端淬淬透深度分别约为 30mm和 60mm, 而本发明合金的自由端淬试样在 150mm深度的范围内完全淬透。 因此, 实际工业生产中采用双面喷淋淬火时, 7B04、 7050合金制品的热处理淬透厚度分别约为 60~80mm和 120~150mm; 而 本发明合金制品的热处理淬透厚度可达 300mm 以上, 淬火敏感性极低, 尤为 适合大截面板材、 锻件的制造。
表 1 三种合金的主要合金元素含量对比
Alloy Zn Mg Cu Mn Zr Cr Al
7B04 6.23 2.88 1.58 0.31 - 0.16 Bal
7050 6.43 2.30 2.19 <0.01 0.1 1 - Bal 实施例 1 7.4 1.7 1.4 0.20 Bal 实施例 2 :
采用铸锭冶金的方法制备 Al-8.0Zn-l .7Mg- l .4Cu-0.22Zr ( wt% ) 合金。 所 用原料为高纯铝、 工业纯镁、 工业纯锌、 铝铜中间合金和镁锆中间合金。 熔化 炉为电阻加热炉, 铸造机为立式半连续铸造机。 采用的熔铸工序为: 装炉 (先 将高纯铝装炉) →熔化 (再在炉中加入工业纯锌、 铝铜中间合金和镁锆中间合 金) →扒渣→加工业纯镁 (在炉中加入工业纯镁进行熔化) →搅拌→取样进行 成分分析→调整成分→搅拌→精炼 (精炼温度为 725 °C ) →扒渣→静置 (静置 时间为 10分钟) →铸造, 铸造温度为 695 °C, 铸造速度为 40mm/min。 将铸锭 进行 440 °C/12 h+470 °C/18 h双级均匀化热处理, 将铸锭进行扒皮, 在 400°C 保温 6h后进行热挤压加工, 挤压出截面大小为 25 x 102mm的挤压带板。 取样 进行 470°C / 60min保温并在室温水中进行淬火, 进行三级时效处理。
实施例 3 :
采用铸锭冶金的方法制备 Al-7.8Zn-l .4Mg-l .6Cu-0.3Zr ( wt% ) 合金。 所用 原料为高纯铝、 工业纯镁、 工业纯锌、 铝铜中间合金和镁锆中间合金。 熔化炉 为电阻加热炉, 铸造机为立式半连续铸造机。 采用的熔铸工序为: 装炉 (先将 高纯铝装炉) →熔化 (再在炉中加入工业纯锌、 铝铜中间合金和镁锆中间合金 进行熔化) →扒渣→加工业纯镁 (在炉中加入工业纯镁进行熔化) →搅拌→取 样进行成分分析→调整成分→搅拌→精炼 (精炼温度为 725 °C ) →扒渣→静置
(静置时间为 10分钟) →铸造, 铸造温度为 710°C, 铸造速度为 50mm/min。 将铸锭进行 470°C/24h均匀化热处理, 将铸锭进行扒皮, 在 400°C保温 8h后进 行热挤压加工, 挤压出截面大小为 25x 102mm的挤压带板。 取样进行 475 °C / 45min保温并在室温水中进行淬火, 进行双级 T76时效处理。
实施例 4:
采用铸锭冶金的方法制备 Al-8.4Zn-2.2Mg- l .2Cu-0.18Zr ( wt% ) 合金。 所 用原料为高纯铝、 工业纯镁、 工业纯锌、 铝铜中间合金和镁锆中间合金。 熔化 炉为电阻加热炉, 铸造机为立式半连续铸造机。 采用的熔铸工序为: 装炉 (先 将高纯铝装炉) →熔化 (再在炉中加入工业纯锌、 铝铜中间合金和镁锆中间合 金进行熔化) →扒渣→加工业纯镁 (在炉中加入工业纯镁进行熔化) →搅拌→ 取样进行成分分析→调整成分→搅拌→精炼 (精炼温度为 720°C) →扒渣→静 置(静置时间为 10分钟)→铸造, 铸造温度为 690°C, 铸造速度为 35mm/min。 将铸锭进行 468°C/28h均匀化热处理, 将铸锭进行扒皮, 在 410°C保温 6h后进 行热挤压加工, 挤压出截面大小为 25x102mm的挤压带板。 取样进行 470°C / 90min保温并在室温水中进行淬火, 进行双级 T74时效处理。
实施例 5:
采用铸锭冶金的方法制备 Al-7.8Zn-l.6Mg-l.45Cu-0.17Zr (wt%) 合金。 所 用原料为高纯铝、 工业纯镁、 工业纯锌、 铝铜中间合金和镁锆中间合金。 熔化 炉为电阻加热炉, 铸造机为立式半连续铸造机。 采用的熔铸工序为: 装炉 (先 将高纯铝装炉) →熔化 (再在炉中加入工业纯锌、 铝铜中间合金和镁锆中间合 金进行熔化) →扒渣→加工业纯镁 (在炉中加入工业纯镁进行熔化) →搅拌→ 取样进行成分分析→调整成分→搅拌→精炼 (精炼温度为 720°C) →扒渣→静 置(静置时间为 10分钟)→铸造, 铸造温度为 710°C, 铸造速度为 20mm/min。 将铸锭进行 440 °C/12h+467 °C/24h双级均匀化热处理, 将铸锭进行扒皮, 在 410°C保温 12h后进行自由锻造变形,锻造出尺寸大小为 400mm(T向) x200mm(S 向) xl500mm(L向)的自由锻件。 取样进行在 470°C保温 240min后在室温水中 进行淬火, 对工件进行 1.8~3.0%的预压缩塑性变形后进行双级 T74时效处理。 实施例 6:
采用铸锭冶金的方法制备 Al-7.75Zn-2.0Mg-l.3Cu-0.18Zr (wt%) 合金。 所 用原料为高纯铝、 工业纯镁、 工业纯锌、 铝铜中间合金和镁锆中间合金。 熔化 炉为电阻加热炉, 铸造机为立式半连续铸造机。 采用的熔铸工序为: 装炉 (先 将高纯铝装炉) →熔化 (再在炉中加入工业纯锌、 铝铜中间合金、 镁锆中间合 金进行熔化) →扒渣→加工业纯镁 (在炉中加入工业纯镁进行熔化) →搅拌→ 取样进行成分分析→调整成分→搅拌→精炼 (精炼温度为 720°C) →扒渣→静 置(静置时间为 10分钟)→铸造, 铸造温度为 700°C, 铸造速度为 20mm/min。 将铸锭进行 440 °C/12h+467 °C/24h双级均匀化热处理, 将铸锭进行扒皮, 在 410°C保温 12h后进行轧制热变形,轧制出尺寸大小为 1000mm(T向) xl20mm(S 向) x3000mm(L向)的热轧厚板。 取样进行在 470°C保温 150min后在室温水中 进行淬火, 对工件进行 1.8~3.0%的预拉伸塑性变形后进行双级 T76时效处理。
表 2为各对比例中合金性能数据及其与其他合金对比情况。 表 2 实施例与其他合金的性能对比
抗拉强度 屈服强度 延伸率 Kic 剥落腐蚀 电导率 抗 SCC 淬透性 / MPa /MPa /% / MPa-m1/2 等级 / MS-m"1
7B04T74 510 530 440 470 7 9 29 32 中 EA 21 22 差
7050T74 520 550 470 490 8 10 34 38 良 EB 22 23 良 实施例 1 580 600 545 555 13 15 36 良 P 20 21 优 实施例 2 570 580 555 565 12 14 36.5 优 EA 23.5 24.5 优 实施例 3 540 550 515 525 12 15 37 良 EA 21.5 22 优 实施例 4 520 540 475 495 12 14 40 优 EB 23 23.5 优 实施例 5 500 530 445 485 7 12 35 优 EA 22.5 24 优 实施例 6 510 545 465 505 8 12 34 良 EA 22 24 优 注: 常规力学性能拉伸方向为 L向; Klc测试时裂紋扩展方向为垂直热变形方向 (L-T) 表 2中充分显示出本发明所获得的铝合金材料, 在保持较高的强度水平的 前提下, 具有优越断裂韧性、 耐蚀性能和电导率, 并且淬透性优越, 是一种特 别适合用于大截面航空主承力结构件制造的高性能铝合金材料。
工业上的应用性 本发明所获得的铝合金材料, 在保持较高的强度水平的前提下, 具有优越 断裂韧性、 耐蚀性能和电导率, 并且淬透性优越, 是一种特别适合用于大截面 航空主承力结构件制造的高性能铝合金材料。

Claims

权 利 要 求 书
1、 一种适合用于大截面航空结构件制造的铝合金材料, 其特征在于: 按 重量百分比计,该铝合金成分为 Zn7.4— 8.4wt%, Mg 1.4— 2.2 wt% , Cu 1.1— 1.7 wt% , Zr 0. 15—0. 3 wt% , Fe小于 0.10 wt %, Si小于 0.08 wt %, 其余为
Al。
2、根据权利要求 1所述的适合用于大截面航空结构件制造的铝合金材料, 其特征在于: 在所述的铝合金成分中, Zn/Mg值为 3.5~6。
3、 一种制备适合用于大截面航空结构件制造的铝合金材料的方法, 其特 征在于: 该方法包括下述步骤:
( 1 ) 以重量百分比计, 该铝合金成分为 Zn7.4— 8.4wt%, Mg 1.4— 2.2 wt % , Cu 1.1— 1.7 wt% , Zr O. 15—0. 3 wt%, 其余为 Al, 按照上述铝合金成分 进行配料; 其中, 选取纯锌作为成分 Zn的原料, 纯镁作为成分 Mg的原料, 铝铜中间合金或纯铜作为成分 Cu的原料, 镁锆中间合金作为成分 Zr的原料, 纯铝锭作为成分 A1的原料;
( 2 ) 将配置好的纯铝锭装入熔化炉中, 待纯铝锭熔化后, 陆续加入铝铜 中间合金或纯铜, 纯锌和镁锆中间合金; 扒渣后, 加入纯镁, 对熔体进行搅拌, 取样分析化学成分, 看是否满足成分控制要求, 如有必要进行成分调整; 加入 精炼剂对熔体进行精炼, 以消除熔体内的气体、 氧化膜及非金属夹杂物, 使熔 体净化; 扒渣后进行静置, 完成整个熔炼过程, 等待铸造;
( 3 ) 采用立式半连续铸造机进行铸造, 制备出表面质量合格和无铸造裂 纹的铸锭;
( 4 ) 对铸锭进行均匀化热处理;
( 5 ) 铸锭扒皮后, 进行热挤压、 热轧制或锻造变形加工, 加工成相应的 半成品;
( 6 ) 将该半成品进行淬火处理和时效热处理, 即得到本发明的一种适合 用于大截面航空结构件制造的铝合金材料。
4、 根据权利要求 3 所述的方法, 所述的纯铝锭为纯度大于 99.99%的高 纯 Al, 纯锌为工业纯 Zn, 纯镁为工业纯 Mg。
5、 根据权利要求 3 所述的方法, 其特征在于: 所述的步骤 (2 ) 中, 熔 体温度控制在 720〜780°C。
6、 根据权利要求 3 所述的方法, 其特征在于: 所述的步骤 (3 ) 中, 铸 造温度为 690~720°C, 铸造速度为 15~50mm/min。
7、 根据权利要求 3 所述的方法, 其特征在于: 所述的步骤 (4 ) 中, 所 述的均匀化热处理为采用在 450~470°C下保温 18~32 h的单级均匀化处理, 或 是采用 420~450 °C/8~16 h+460~475 °C/16~28 h的双级均匀化热处理工艺。
8、 根据权利要求 3 所述的方法, 其特征在于: 所述的步骤 (5 ) 中, 先 将扒皮后的铸锭在 380〜420°C下保温 6~18小时, 随后再进行热挤压、 热轧制 或锻造变形加工。
9、 根据权利要求 3所述的方法, 其特征在于: 所述的步骤步骤 (6 ) 中, 所述的将半成品料进行淬火热处理的过程是进行固溶处理, 在 465~475 °C下保 温 30~300 min, 快速转移至 15~40°C水中快速淬冷。
10、 根据权利要求 3所述的方法, 其特征在于: 所述的步骤 (6 ) 中, 所 述的半成品时效热处理过程是单级、 双级或三级时效处理。
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