CN115961193A - Strontium-zirconium-titanium-erbium-lanthanum five-element composite microalloyed 790MPa ultrahigh-strength super intergranular corrosion-resistant aluminum alloy and preparation method thereof - Google Patents

Strontium-zirconium-titanium-erbium-lanthanum five-element composite microalloyed 790MPa ultrahigh-strength super intergranular corrosion-resistant aluminum alloy and preparation method thereof Download PDF

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CN115961193A
CN115961193A CN202210438920.6A CN202210438920A CN115961193A CN 115961193 A CN115961193 A CN 115961193A CN 202210438920 A CN202210438920 A CN 202210438920A CN 115961193 A CN115961193 A CN 115961193A
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aluminum alloy
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许晓静
罗耘天
李建伟
沙少辉
韩梦楠
韦韬
包国宁
王昊
孙智伟
洪志恒
刘乐乐
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Jiangsu University
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Abstract

A strontium zirconium titanium erbium lanthanum quinary composite micro-alloyed 790MPa ultrahigh strength super intergranular corrosion resistant aluminum alloy and a preparation method thereof are characterized in that: the alloy mainly comprises aluminum (Al), zinc (Zn), magnesium (Mg), copper (Cu), strontium (Sr), zirconium (Zr), titanium (Ti), erbium (Er) and lanthanum (La). The preparation of the alloy sequentially comprises the following steps: (1) fusion casting; (2) Homogenizing (keeping the temperature at 450 ℃ for 24h and then cooling along with the furnace); (3) hot extrusion (temperature 400 ℃, extrusion ratio 10; (4) Solution treatment (450 ℃ is multiplied by 2h +460 ℃ is multiplied by 2h +470 ℃ is multiplied by 2h, room temperature water quenching); and (5) aging treatment. The alloy of the invention has the highest strength of 791.5MPa, the elongation after fracture is 5.2%, and no obvious intergranular corrosion (the maximum corrosion depth is 15.75 mu m) is found according to the national standard GB/T7998-2005.

Description

Strontium-zirconium-titanium-erbium-lanthanum five-element composite microalloyed 790MPa ultrahigh-strength super intergranular corrosion-resistant aluminum alloy and preparation method thereof
Technical Field
The invention relates to an aluminum alloy material, in particular to a novel 7000 series aluminum alloy and a preparation method thereof, and specifically relates to a 790MPa ultrahigh strength ultra-intergranular corrosion resistant aluminum alloy obtained by five-element composite microalloying of Sr, zr, ti, er and La and a preparation method thereof.
Background
The leap-type improvement of a certain important single performance or comprehensive performance of the high-strength aluminum alloy plays an important role in influencing and supporting the development of advanced lightweight equipment in different periods. So far, the research on 750-800MPa strength grade aluminum alloy for casting and forming blank is very rare both at home and abroad. At present, with the continuous improvement of various weaponry such as warplanes, missiles, heavy rockets, military satellites and the like on the requirements of service performance indexes, 750-800MPa strength-level ultrahigh-strength high-comprehensive-performance aluminum alloy is urgently needed as a support.
The research and development of the novel high-strength high-toughness aluminum alloy and the improvement of the performance of the existing alloy are closely related to the component design of the alloy. Microalloying has been widely used in industrial aluminum alloy systems as an important means for improving the performance of aluminum alloys. Although it is well known that rare earth elements may have a great effect on the structural properties of aluminum alloys, there are many problems that are not solved, such as: (1) Which rare earth element is most effective for aluminum alloys of different aluminum alloy systems and different strength levels? Is it most effective for which performance? What is its best quality? (ii) a (2) Is the composite microalloying of two or more rare earth elements, the composite action of which is additive or mutually offset? How well the effects of the additive effects? .
The Sr, zr, ti, Y and La quinary composite micro-alloying can improve the performance of the 800MPa strength-level ultrahigh-strength aluminum alloy. Strontium (Sr) is an alkaline earth element, is a long-acting modifier in aluminum alloy, and has the functions of purifying aluminum alloy melt and refining coarse intermetallic compounds. Zirconium (Zr) and titanium (Ti) are 3d transition group elements, erbium (Er) and lanthanum (La) are two rare earth group elements with large electronegativity difference (Er electronegativity 1.2 and La electronegativity 1.1), zr, ti, er and La are compositely microalloyed, and Al can be formed in the alloy homogenization treatment process 3 The (Zr, ti, Y, la) dispersed phase inhibits recrystallization and improves the alloy performance.
It is well known that there is generally an inverse relationship between strength and corrosion resistance of aluminum alloys. Intergranular corrosion is a common corrosion form of the high-strength aluminum alloy and is also a basic corrosion form, and great damage is brought to the service life and the use safety of the high-strength aluminum alloy. Generally, the higher the strength of a high strength aluminum alloy, the lower the intergranular corrosion performance. The maximum depth of intergranular corrosion of the prior 7000 series high-strength aluminum alloy is generally far higher than 100 mu m.
Until now, no ingredient design and preparation method of 790MPa ultrahigh strength super intergranular corrosion resistant aluminum alloy which is formed by quinary composite microalloying of Sr, zr, ti, er and La and has independent intellectual property rights can be used, and the development of industries such as aerospace, weaponry and the like in China is restricted to a certain extent.
Disclosure of Invention
The invention aims to solve the problem that the strength and the corrosion resistance of the existing 800MPa strength-level aluminum alloy are difficult to take into account, and invents a 790MPa ultrahigh-strength super intergranular corrosion-resistant aluminum alloy obtained by five-element composite microalloying of Sr, zr, ti, er and La and a preparation method thereof through component design and preparation processing technology design.
One of the technical schemes of the invention is as follows:
the 790MPa ultrahigh-strength super intercrystalline corrosion resistant aluminum alloy compounded and microalloyed by the five elements of Sr, zr, ti, er and La is characterized in that: the alloy mainly comprises aluminum (Al), zinc (Zn), magnesium (Mg), copper (Cu), strontium (Sr), zirconium (Zr), titanium (Ti), erbium (Er) and lanthanum (La), wherein the mass percent of zinc (Zn) is 11.2-11.7%, the mass percent of magnesium (Mg) is 3.02-3.1%, the mass percent of copper (Cu) is 1.17-1.21%, the mass percent of strontium (Sr) is 0.0087-0.0093%, the mass percent of zirconium (Zr) is 0.229-0.237%, the mass percent of titanium (Ti) is 0.0816-0.0844%, the mass percent of erbium (Er) is 0.15% (nominal), the mass percent of lanthanum (La) is 0.15% (nominal), and the balance is aluminum and a small amount of impurity elements; the sum of all the components is 100 percent.
The second technical scheme of the invention is as follows:
a preparation method of 790MPa ultrahigh-strength super-intergranular corrosion-resistant aluminum alloy compositely microalloyed by Sr, zr, ti, er and La quinary is characterized by sequentially comprising the following steps: (1) fusion casting; (2) homogenizing; (3) hot extrusion; (4) solution treatment; (5) aging treatment;
and (3) casting: heating a smelting furnace to 900 ℃, putting pure Al, al-Cu intermediate alloy, al-Sr intermediate alloy, al-Zr intermediate alloy and Al-Ti-B intermediate alloy into a crucible of the smelting furnace to be melted for 45 minutes, preserving heat for 60 minutes, then cooling to 750 ℃, adding pure Zn and pure Mg, stirring the melt, standing for 15 minutes, adding a hexachloroethane refining agent to refine until no gas escapes, standing and preserving heat for 15 minutes, adding Al-Er intermediate alloy and Al-La intermediate alloy, stirring the melt, preserving heat for 15 minutes, slagging off, casting into a cast iron mold preheated to 400 ℃, and casting into ingots;
the homogenization treatment comprises the following steps: the process is that the temperature is maintained at 450 ℃ for 24 hours and then the product is cooled along with the furnace;
the hot extrusion: the process comprises the steps of heating the alloy to 400 ℃, keeping the temperature for more than or equal to 1h, and then carrying out extrusion with an extrusion ratio of 10;
the solution treatment comprises the following steps: the process is room temperature water quenching after heat preservation at 450 ℃ multiplied by 2h +460 ℃ multiplied by 2h +470 ℃ multiplied by 2 h;
the aging treatment comprises the following steps: the process is T6I4 (water cooling at 121 ℃ C. Times.4 h (room temperature) +65 ℃ C. Times.120 h).
Thus obtaining the 790MPa ultrahigh strength super intergranular corrosion resistant aluminum alloy which is compositely microalloyed by Sr, zr, ti, er and La quinary and the preparation method thereof.
The mass percent of Cu in the Al-Cu intermediate alloy is 50.12%, the mass percent of Sr in the Al-Sr intermediate alloy is 9.89%, the mass percent of Zr in the Al-Zr intermediate alloy is 4.11%, the mass percent of Ti in the Al-Ti-B intermediate alloy is 5.11%, the mass percent of Er in the Al-Er intermediate alloy is 20%, and the mass percent of La in the Al-La intermediate alloy is 10%.
The beneficial effects of the invention are:
(1) The invention obtains the components of a 790MPa ultrahigh strength super intergranular corrosion resistant aluminum alloy obtained by compositely microalloying five elements of Sr, zr, ti, er and La and the preparation method thereof.
(2) The invention adopts two rare earth elements with larger electronegativity difference, namely erbium (Er) and lanthanum (La), to carry out composite micro-alloying, thereby obtaining the effect of super intergranular corrosion resistance.
(3) The alloy of the invention has the highest strength of 791.5MPa, the elongation after fracture is 5.2%, and no obvious intergranular corrosion (the maximum corrosion depth is 15.75 mu m) is found according to the national standard GB/T7998-2005 (aluminum alloy intergranular corrosion determination method).
(4) The invention discloses a composition and a preparation method of a 790MPa ultrahigh-strength super-intergranular corrosion-resistant aluminum alloy obtained by compositely microalloying five elements of Sr, zr, ti, er and La, which break through the technical blockade of foreign high-performance aluminum alloys to a certain extent and can meet the requirements of the fields of aerospace, weaponry and the like in China.
(5) The invention obtains an ideal preparation method through a large number of tests, particularly controls the content of each component by adopting a method of adding each intermediate alloy and pure metal in sequence, and can easily obtain the aluminum alloy material meeting the requirements according to the process of the invention.
Drawings
FIG. 1 is an optical microscopic photograph of a solid-solution metallographic structure according to an embodiment of the present invention.
FIG. 2 is a cross-sectional gold phase diagram after a T6I4 aged intergranular corrosion test in accordance with an embodiment of the present invention.
Detailed Description
Example one
A790 MPa ultrahigh-strength super-intergranular corrosion-resistant aluminum alloy formed by Sr, zr, ti, er and La quinary composite microalloying is prepared by the following method:
firstly, casting, wherein a smelting furnace is heated to 900 ℃, pure Al, al-Cu intermediate alloy, al-Sr intermediate alloy, al-Zr intermediate alloy and Al-Ti-B intermediate alloy are placed into a crucible of the smelting furnace to be melted for 45 minutes and insulated for 60 minutes, then the temperature is reduced to 750 ℃, pure Zn and pure Mg are added and the melt is stirred, the mixture is kept stand for 15 minutes, hexachloroethane refining agent is added for refining until no gas escapes, the mixture is kept stand and insulated for 15 minutes, al-Er intermediate alloy and Al-La intermediate alloy are added and the melt is stirred, the temperature is kept for 15 minutes, slag is removed, and the mixture is cast into a cast iron die preheated to 400 ℃ to be cast into ingots; the addition amount of each component can be determined by routine calculation according to the content of the target formula, and the loss amount and the volatilization amount of the easily-lost and easily-volatilized components are properly added and supplemented when necessary.
Secondly, homogenizing the aluminum alloy cast ingot, wherein the process comprises the following steps: keeping the temperature at 450 ℃ for 24h and then cooling the mixture along with the furnace;
thirdly, performing hot extrusion, wherein the process comprises the steps of heating the alloy to 400 ℃, keeping the temperature for more than or equal to 1h, and then performing extrusion with an extrusion ratio of 10;
fourthly, carrying out solution treatment, wherein the process is carried out at the temperature of 450 ℃ multiplied by 2h +460 ℃ multiplied by 2h +470 ℃ multiplied by 2h, and then carrying out room temperature water quenching;
finally, aging treatment is carried out, and the process is T6I4 (121 ℃ multiplied by 4h (water cooling at room temperature) +65 ℃ multiplied by 120 h).
Thus obtaining the 790MPa ultrahigh strength super intergranular corrosion resistant aluminum alloy which is compositely microalloyed by Sr, zr, ti, er and La quinary.
The aluminum alloy of the present example has the following components by spectral measurement: 11.7% Zn,3.08% Mg,1.17% Cu,0.009% Sr,0.237% Zr,0.084% Ti,0.15% Er (nominal), 0.15% La (nominal), the balance aluminum and unavoidable impurity elements.
The aluminum alloy of the embodiment has larger crystal grains and low recrystallization degree (figure 1), the tensile strength of T6I4 (121 ℃ multiplied by 4-8h (room temperature water cooling) +65 ℃ multiplied by 120 h) is 791.527MPa, the elongation after fracture is 5.2%, and no obvious intergranular corrosion (figure 2) (the maximum corrosion depth is 15.75 mu m) is found according to the national standard GB/T7998-2005 (aluminum alloy intergranular corrosion determination method); the tensile strength of T6 (121 ℃ multiplied by 24 h) in the aging state is 792.363MPa, and the elongation after fracture is 6%.
Example two
The preparation method is the same as the first embodiment.
The aluminum alloy of the present example has the following components by spectral measurement: 11.2% Zn,3.1% Mg,1.21% Cu,0.0087% Sr,0.229% Zr,0.0816% Ti,0.15% Er (nominal), the balance being aluminum and unavoidable impurity elements.
Aluminum alloy of the present example: the tensile strength of T6I4 (121 ℃ multiplied by 4h (room temperature water cooling) +65 ℃ multiplied by 120 h) state is 786.267MPa, the elongation after fracture is 6.0%, and no obvious intergranular corrosion is found according to the national standard GB/T7998-2005 (aluminum alloy intergranular corrosion determination method); the tensile strength of the T6 (121 ℃ multiplied by 24 h) state is 786.793MPa, and the elongation after fracture is 7.4%.
EXAMPLE III
The preparation method is the same as in the first embodiment.
The aluminum alloy of the present example has the following components by spectral measurement: 11.5% Zn,3.02% Mg,1.18% Cu,0.0093% Sr,0.231% Zr,0.0844% Ti,0.15% Er (nominal), 0.15% La (nominal), the balance being aluminum and unavoidable impurity elements.
Aluminum alloy of the present example: the tensile strength of the T6I4 (121 ℃ multiplied by 4h (room temperature water cooling) +65 ℃ multiplied by 120 h) state is 781.225MPa, the elongation after fracture is 6.8%, and no obvious intergranular corrosion is found according to the national standard GB/T7998-2005 (aluminum alloy intergranular corrosion determination method); the tensile strength of the T6 (121 ℃ multiplied by 24 h) state is 789.875MPa, and the elongation after fracture is 6.5%.
The proportion and the manufacturing method of the aluminum alloy with only a few common proportions are listed above, and the technical personnel in the field can properly adjust the proportion of each component according to the above examples and strictly manufacture the aluminum alloy according to the steps to obtain the ideal Sr, zr, ti, er and La quinary composite microalloyed 790MPa ultrahigh-strength ultra-high intercrystalline corrosion resistant aluminum alloy and the preparation method thereof.
The parts not involved in the present invention are the same as or can be implemented using the prior art.

Claims (3)

1. A790 MPa ultrahigh-strength super-intergranular corrosion-resistant aluminum alloy compositely microalloyed by Sr, zr, ti, er and La quinary is characterized in that: the alloy mainly comprises aluminum (Al), zinc (Zn), magnesium (Mg), copper (Cu), strontium (Sr), zirconium (Zr), titanium (Ti), erbium (Er) and lanthanum (La), wherein the mass percent of zinc (Zn) is 11.2-11.7%, the mass percent of magnesium (Mg) is 3.02-3.1%, the mass percent of copper (Cu) is 1.17-1.21%, the mass percent of strontium (Sr) is 0.0087-0.0093%, the mass percent of zirconium (Zr) is 0.229-0.237%, the mass percent of titanium (Ti) is 0.0816-0.0844%, the mass percent of erbium (Er) is 0.15% (nominal), the mass percent of lanthanum (La) is 0.15% (nominal), and the balance is aluminum and a small amount of impurity elements; the sum of all the components is 100 percent.
2. The preparation method of the 790MPa ultrahigh-strength super-intergranular corrosion resistant aluminum alloy which is compositely microalloyed by quinary elements of Sr, zr, ti, er and La and is described in claim 1 is characterized by sequentially comprising the following steps of: (1) fusion casting; (2) homogenizing; (3) hot extrusion; (4) solution treatment; (5) aging treatment;
the casting comprises the following steps: heating a smelting furnace to 900 ℃, putting pure Al, al-Cu intermediate alloy, al-Sr intermediate alloy, al-Zr intermediate alloy and Al-Ti-B intermediate alloy into a crucible of the smelting furnace to be melted for 45 minutes, preserving heat for 60 minutes, then cooling to 750 ℃, adding pure Zn and pure Mg, stirring the melt, standing for 15 minutes, adding a hexachloroethane refining agent to refine until no gas escapes, standing and preserving heat for 15 minutes, adding Al-Er intermediate alloy and Al-La intermediate alloy, stirring the melt, preserving heat for 15 minutes, slagging off, casting into a cast iron mould preheated to 400 ℃ and casting into ingots;
the homogenization treatment comprises the following steps: the process is that the temperature is maintained at 450 ℃ for 24 hours and then the product is cooled along with the furnace;
the hot extrusion: the process comprises the steps of heating the alloy to 400 ℃, keeping the temperature for more than or equal to 1h, and then carrying out extrusion with an extrusion ratio of 10;
the solid solution treatment comprises the following steps: the process is that water quenching is carried out at room temperature after heat preservation is carried out at 450 ℃ multiplied by 2h +460 ℃ multiplied by 2h +470 ℃ multiplied by 2 h;
the aging treatment comprises the following steps: the process comprises the following step of aging T6I4 (water cooling at 121 ℃ for 4h (room temperature) + water cooling at 65 ℃ for 120 h) to obtain the 790MPa ultrahigh-strength ultra-corrosion-resistant aluminum alloy obtained by performing five-element composite microalloying on Sr, zr, ti, er and La and the preparation method thereof.
3. The method of claim 2, wherein the mass percent of Cu in the Al-Cu master alloy is 50.12%, the mass percent of Sr in the Al-Sr master alloy is 9.89%, the mass percent of Zr in the Al-Zr master alloy is 4.11%, the mass percent of Ti in the Al-Ti-B master alloy is 5.11%, the mass percent of Er in the Al-Er master alloy is 20%, and the mass percent of La in the Al-La master alloy is 10%.
CN202210438920.6A 2022-04-25 2022-04-25 Strontium-zirconium-titanium-erbium-lanthanum five-element composite microalloyed 790MPa ultrahigh-strength super intergranular corrosion-resistant aluminum alloy and preparation method thereof Pending CN115961193A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4995920A (en) * 1988-12-19 1991-02-26 Pechiney Recherche Groupement D'interet Economique Process for the production of aluminum alloys by spray deposition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4995920A (en) * 1988-12-19 1991-02-26 Pechiney Recherche Groupement D'interet Economique Process for the production of aluminum alloys by spray deposition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘懿芳等: "Al-Zn-Mg-Cu系铝合金微合金化的研究进展", 《有色金属材料与工程》, vol. 39, no. 1, 15 February 2018 (2018-02-15), pages 38 - 41 *

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