CN113957303A - Low-density high-toughness aluminum alloy plate and preparation method thereof - Google Patents

Low-density high-toughness aluminum alloy plate and preparation method thereof Download PDF

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CN113957303A
CN113957303A CN202111092740.9A CN202111092740A CN113957303A CN 113957303 A CN113957303 A CN 113957303A CN 202111092740 A CN202111092740 A CN 202111092740A CN 113957303 A CN113957303 A CN 113957303A
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aluminum
percent
alloy
lithium
rare earth
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袁婷
孙文兵
朱志超
耿飞
王玉丰
江静华
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Changshu Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/026—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon

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  • Engineering & Computer Science (AREA)
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Abstract

The invention discloses a low-density high-toughness aluminum alloy plate and a preparation method thereof. The alloy comprises the following components in percentage by weight: less than 0.10 percent of silicon, less than 0.10 percent of iron, 3.0 to 4.5 percent of magnesium, 1.0 to 2.5 percent of lithium, 0.05 to 0.25 percent of rare earth and the balance of aluminum. The method comprises the following steps: selecting and matching aluminum ingots, smelting, refining, casting into ingots, and rolling into aluminum alloy plates with the thickness of 0.5-2.0 mm, wherein the alloy density is less than 2.6g/cm3Tensile strength of the steel sheet>400MPa, elongation>10 percent. Compared with the traditional aluminum alloy material, the aluminum alloy plate provided by the invention has high mechanical property and low density, and has a good aerospace application prospect.

Description

Low-density high-toughness aluminum alloy plate and preparation method thereof
Technical Field
The invention relates to a low-density high-toughness aluminum alloy plate suitable for aerospace and a manufacturing method thereof, belonging to the technical field of aluminum alloy material preparation.
Background
With the requirements of the world energy crisis and energy conservation and emission reduction, higher requirements are put forward on the density and performance of materials used in various fields such as ship transportation, aerospace and the like. Aluminum lithium alloys are particularly emphasized because they have the characteristics of lower density and higher strength than conventional aluminum alloys. However, addition of lithium also tends to form a delta' that is not resistant to cutting (Al)3Li) phase, which is very easy to cause coplanar slippage of dislocation, thereby causing the reduction of ductility and toughness and the deterioration of processing performance of the aluminum alloy; meanwhile, active lithium element makes the smelting of the aluminum alloy difficult, and as-cast defects are increased, which seriously affects the application prospect of the aluminum-lithium alloy.
Disclosure of Invention
The invention provides an aluminum alloy plate for aerospace use with low density and excellent obdurability and a manufacturing method thereof, aiming at solving the problems of low plastic toughness and poor processability of the existing aluminum lithium alloy.
The purpose of the invention is realized by the following technical scheme: a low-density high-toughness aluminum alloy plate comprises the following components in percentage by mass: less than 0.10 percent of silicon, less than 0.10 percent of iron, 3.0 to 4.5 percent of magnesium, 1.0 to 2.5 percent of lithium, 0.05 to 0.25 percent of rare earth and the balance of aluminum.
Preferably, the aluminum alloy plate has the thickness of 0.5-2.0 mm, low density and high strength and toughness, and the density of the aluminum alloy plate is less than 2.7g/cm3Tensile strength of the steel sheet>400MPa, elongation>10％。
Preferably, the rare earth is one or more of Er, Sc, Ce and the like.
The invention also provides a preparation method of the low-density high-toughness aluminum alloy plate, which comprises the following steps:
firstly, weighing a pure aluminum ingot, a pure magnesium ingot and an aluminum rare earth intermediate alloy according to a proportion, smelting, stirring and standing after all raw materials are melted;
adding an aluminum lithium intermediate alloy and a covering agent, and standing;
thirdly, adding a refining agent, stirring, cleaning surface slag, introducing argon for refining, and standing to obtain alloy liquid;
and fourthly, casting the alloy liquid into ingots, cooling to room temperature, and rolling into the aluminum plate by adopting a rolling mill.
Preferably, in the step I, the content of the rare earth in the aluminum rare earth intermediate alloy is 5-10 wt%.
Preferably, in the second step, the lithium content in the aluminum lithium intermediate alloy is 10 to 20 wt%.
Preferably, in the step II, the covering agent is a mixture of lithium chloride and lithium fluoride, wherein the mass ratio of the lithium chloride to the lithium fluoride is 3/2-2/3.
Preferably, in the third step, the refining agent is hexachloroethane, and the addition amount of the hexachloroethane is 0.4-0.8% of the total alloy ingredient mass.
Preferably, in the third step, the temperature is kept between 720 ℃ and 760 ℃ in the smelting and refining process.
Preferably, in the step (c), the surface of the melt is continuously purged by adopting argon in the feeding and casting processes.
Preferably, in the third step, in the refining process by introducing argon, an argon pipe is introduced into the aluminum melt for refining for 10-25 minutes.
Preferably, in the step (iv), the temperature of the alloy liquid at the beginning of casting is more than 730 ℃.
Preferably, in the step (iv), when the alloy liquid is cast into an ingot, an iron mold preheated to 200 ℃ is used to cast the alloy liquid into a square ingot with a thickness of 20 mm.
Preferably, in the fourth step, the aluminum plate is rolled by a rolling mill, the thickness of the aluminum plate is 0.5 mm-2.0 mm, and the rolling rate of each pass is 10-30%.
Compared with the prior art, the invention has the following remarkable advantages:
(1) the invention strictly controls the contents of Mg and Li in the aluminum alloy material, combines the process of the invention, adopts the mixture of lithium chloride and lithium fluoride as a covering agent, uses argon gas for protection in the casting process to reduce the burning loss of alloy liquid, and leads the aluminum alloy plate to have fine grain structure and uniformly dispersed fine precipitated phase through argon gas and hexachloroethane refining and rare earth micro-alloying, thereby keeping the tensile strength of more than 400Mpa and the elongation of more than 10 percent while keeping the low density.
(2) The invention promotes the precipitation of impurity elements by adding a certain amount of rare earth elements and utilizing the extremely low solid solubility of the rare earth elements in aluminum to form phases with the impurity elements, and the impurities are mixed with delta' (Al)3The Li) phase forms a shearing-resistant uniform dispersion Al3(Li, RE) composite phase, and the coplanar slippage phenomenon of dislocation is effectively reduced. Therefore, the damage of lithium and impurities to the performance of the aluminum alloy is reduced, the precipitation strengthening effect is achieved, and the toughness of the alloy is improved.
Drawings
Fig. 1 is a TEM photograph of the aluminum alloy sheet prepared in example 1.
Detailed Description
The following detailed description of the embodiments of the present invention will be given in conjunction with examples to better understand the aspects of the present invention and the advantages of its various aspects. However, the specific embodiments and examples described below are for illustrative purposes only and are not limiting of the invention.
The invention utilizes rare earth elements to react with delta' (Al) in an aluminum matrix3Li) phase, and the super strong capability of separating out the phase with impurity elements, reduces the damage of lithium to the organization and performance, and adopts covering agent, argon and refining agent to protect and refine the melt, so as to meet the performance requirement of low density, high strength and toughness of the aluminum alloy material.
Example 1:
a low-density high-toughness aluminum alloy plate comprises the following components in percentage by weight: less than 0.1 percent of silicon, less than 0.1 percent of iron, 4.2 percent of magnesium, 2.0 percent of lithium, 0.11 percent of rare earth Er0, and the balance of aluminum. The preparation method comprises the following steps:
(1) 1635.2 g of pure aluminum ingot, 93.3 g of pure magnesium ingot and 30.5 g of aluminum rare earth alloy (commercial Al-Er intermediate alloy, the content of rare earth Er is 8 wt%) are weighed and smelted in a silicon carbide graphite crucible in a well furnace (the burning loss rate is calculated by 10%), stirred for 2min and kept stand for 10min, 241 g of aluminum lithium alloy (the content of lithium is 19.5 wt%, the burning loss rate is calculated by 15%) and a covering agent are added, the covering agent is a mixture of lithium chloride and lithium fluoride in a mass ratio of 1:1 after mechanical mixing, the covering agent is covered on the surface of the aluminum liquid, the burning loss can be reduced, and the mixture is kept stand for 15 min. The smelting temperature is 730 ℃, and argon is blown in during the smelting process. Adding 12 g of refining agent, blowing argon gas for refining for 10min, standing for 8min, and cleaning aluminum slag on the surface to obtain alloy liquid;
(2) maintaining the temperature of the alloy liquid at about 730 ℃, casting the alloy liquid into ingots, and cooling to room temperature. And casting the aluminum liquid into a square aluminum ingot with the thickness of 20mm by adopting an iron mold preheated to 200 ℃. And continuously purging the surface of the melt by adopting argon in the casting process.
(3) The compression ratio of each pass of the rolling mill is 20 percent, and the aluminum plate with the thickness of 0.5mm is rolled.
The microstructure (figure 1), density and mechanical property of the aluminum alloy plate are detected, and the density is 2.51g/cm3The tensile strength was 412MPa, the elongation was 11%, and the rare earth elements Er and delta' (Al) are shown in FIG. 13The Li) phase forms a shearing-resistant uniform dispersion Al3(Li, Er) composite phase, and the coplanar slippage phenomenon of dislocation is effectively reduced.
Example 2:
a low-density high-toughness aluminum alloy plate comprises the following components in percentage by weight: less than 0.1 percent of silicon, less than 0.1 percent of iron, 4.5 percent of magnesium, 1.5 percent of lithium, 0.15 percent of rare earth Sc0.15 percent, and the balance of aluminum. The preparation method comprises the following steps:
(1) 1223.5 g of pure aluminum ingot, 75 g of pure magnesium ingot and 25 g of aluminum rare earth alloy (commercial Al-Sc master alloy, the content of the rare earth Sc is 10 wt%) are weighed and put into a silicon carbide graphite crucible to be melted in a well furnace (the burning loss rate is calculated as 10%), stirred for 2min and kept stand for 10min, 176.5 g of aluminum lithium alloy (containing 15 wt% of lithium and the burning loss rate is calculated as 15%) and a covering agent (the mass ratio of lithium chloride to lithium fluoride is 2: 3) are added, and then kept stand for 15 min. The smelting temperature is 750 ℃, and argon is blown in during the smelting process. Adding 7.5 g of refining agent, blowing argon gas for refining for 15min, standing for 10min, and cleaning aluminum slag on the surface to obtain alloy liquid;
(2) and casting the alloy liquid into ingots, and cooling to room temperature. And casting the alloy liquid into a square aluminum ingot with the thickness of 20mm by adopting an iron die preheated to 200 ℃. And continuously purging the surface of the melt by adopting argon in the casting process.
(3) The compression ratio of each pass of the rolling mill is 15 percent, and the aluminum plate with the thickness of 1.0mm is rolled.
The density and the mechanical property of the aluminum alloy plate are detected, and the density is 2.55g/cm3The tensile strength was 423MPa, and the elongation was 15%.
Example 3:
a low-density high-toughness aluminum alloy plate comprises the following components in percentage by weight: less than 0.1 percent of silicon, less than 0.1 percent of iron, 3.5 percent of magnesium, 2.2 percent of lithium, 0.20 percent of rare earth Ce0.20 percent, and the balance of aluminum. The preparation method comprises the following steps:
(1) 1968.2 g of pure aluminum ingot, 97.2 g of pure magnesium ingot and 111.1 g of aluminum rare earth alloy (commercial Al-Ce intermediate alloy, the content of rare earth Ce is 5 wt%) are weighed and melted in a silicon carbide graphite crucible in a well furnace (the burning loss rate is calculated as 10%), stirred for 2min and kept stand for 10min, 323.5 g of aluminum lithium alloy (containing 20wt% of lithium and having the burning loss rate of 15%) and a covering agent (the mass ratio of lithium chloride to lithium fluoride is 3: 2) are added, and the mixture is kept stand for 15 min. The smelting temperature is 740 ℃, and argon is blown in during the smelting process. Adding 10 g of refining agent, blowing argon gas for refining for 20min, standing for 10min, and cleaning aluminum slag on the surface to obtain alloy liquid;
(2) and casting the alloy liquid into ingots, and cooling to room temperature. And casting the aluminum liquid into a square aluminum ingot with the thickness of 20mm by adopting an iron mold preheated to 200 ℃. And continuously purging the surface of the melt by adopting argon in the casting process.
(3) The compression ratio of each pass of the rolling mill is 25 percent, and the aluminum plate with the thickness of 1.5mm is rolled. .
The density and the mechanical property of the aluminum alloy plate are detected, and the density is 2.48g/cm3The tensile strength was 415MPa, and the elongation was 13%.
Comparative example 1:
a low-density high-toughness aluminum alloy plate comprises the following components in percentage by weight: less than 0.1 percent of silicon, less than 0.1 percent of iron, 4.2 percent of magnesium, 1.5 percent of lithium, 0.11 percent of rare earth Er0, and the balance of aluminum. The preparation method comprises the following steps:
(1) 1635.2 g of pure aluminum ingot, 93.3 g of pure magnesium ingot and 30.5 g of aluminum rare earth alloy (commercial Al-Er intermediate alloy, the content of rare earth Er is 8 wt%) are weighed and put into a silicon carbide graphite crucible to be smelted in a well type furnace (the burning loss rate is calculated by 10%), stirred for 2min and kept stand for 10min, then 241 g of aluminum lithium alloy (the content of lithium is 19.5 wt%) is added and kept stand for 15 min. The melting temperature is 730 ℃. Adding 12 g of refining agent, blowing argon gas for refining for 10min, standing for 8min, and cleaning aluminum slag on the surface to obtain alloy liquid;
(2) maintaining the temperature of the alloy liquid at about 730 ℃, casting the alloy liquid into ingots, and cooling to room temperature. And casting the aluminum liquid into a square aluminum ingot with the thickness of 20mm by adopting an iron mold preheated to 200 ℃.
(3) The compression ratio of each pass of the rolling mill is 20 percent, and the aluminum plate with the thickness of 0.5mm is rolled.
Because covering agent and argon protection are not adopted in the casting process, the lithium burning loss is serious, and the calculated lithium burning loss rate is up to 40 percent.
The density and the mechanical property of the aluminum alloy plate are detected, because the melt is not protected by the covering agent and the argon, the cast structure has more defects, and the density is 2.56g/cm3The tensile strength is 386Mpa, and the elongation is 6%.
Comparative example 2:
a low-density high-toughness aluminum alloy plate comprises the following components in percentage by weight: less than 0.1 percent of silicon, less than 0.1 percent of iron, 2.0 percent of magnesium, 0.5 percent of lithium, 0.15 percent of rare earth Sc0.15 percent, and the balance of aluminum. The preparation method comprises the following steps:
(1) 1382.9 g of pure aluminum ingot, 33.3 g of pure magnesium ingot and 25 g of aluminum rare earth alloy (commercial Al-Sc master alloy, the content of the rare earth Sc is 10 wt%) are weighed and melted in a silicon carbide graphite crucible in a well furnace (the burning loss rate is calculated as 10%), stirred for 2min and kept stand for 10min, 58.8 g of aluminum lithium alloy (containing 15 wt% of lithium and the burning loss rate is calculated as 15%) and a covering agent (the mass ratio of lithium chloride to lithium fluoride is 2: 3) are added, and the mixture is kept stand for 15 min. The smelting temperature is 750 ℃, and argon is blown in during the smelting process. Adding 7.5 g of refining agent, blowing argon gas for refining for 15min, standing for 10min, and cleaning aluminum slag on the surface to obtain alloy liquid;
(2) and casting the alloy liquid into ingots, and cooling to room temperature. And casting the aluminum liquid into a square aluminum ingot with the thickness of 20mm by adopting an iron mold preheated to 200 ℃. And continuously purging the surface of the melt by adopting argon in the casting process.
(3) The compression ratio of each pass of the rolling mill is 15 percent, and the aluminum plate with the thickness of 1.0mm is rolled.
The density and the mechanical property of the aluminum alloy plate are detected, and the density is 2.67g/cm3The tensile strength was 353MPa, and the elongation was 15%.
Comparative example 3:
a low-density high-toughness aluminum alloy plate comprises the following components in percentage by weight: less than 0.1 percent of silicon, less than 0.1 percent of iron, 3.5 percent of magnesium, 2.2 percent of lithium and the balance of aluminum. The preparation method comprises the following steps:
(1) 2079.3 g of pure aluminum ingot and 97.2 g of pure magnesium ingot are weighed and put into a silicon carbide graphite crucible to be melted in a well type furnace (the burning loss rate is calculated as 10 percent), stirred for 2min and kept stand for 10min, 323.5 g of aluminum-lithium alloy (containing 20wt percent of lithium and the burning loss rate is calculated as 15 percent) and a covering agent (the mass ratio of lithium chloride to lithium fluoride is 3: 2) are added, and the mixture is kept stand for 15 min. The smelting temperature is 740 ℃, and argon is blown in during the smelting process. Adding 10 g of refining agent, blowing argon gas for refining for 20min, standing for 10min, and cleaning aluminum slag on the surface to obtain alloy liquid;
(2) and casting the alloy liquid into ingots, and cooling to room temperature. And casting the aluminum liquid into a square aluminum ingot with the thickness of 20mm by adopting an iron mold preheated to 200 ℃. And continuously purging the surface of the melt by adopting argon in the casting process.
(3) The compression ratio of each pass of the rolling mill is 25 percent, and the aluminum plate with the thickness of 1.5mm is rolled.
The density and the mechanical property of the aluminum alloy plate are detected, and the density is 2.47g/cm3Tensile strength of 389Mpa, elongation of 9%.
In the above comparative test, the covering agent and the argon protection are not added in comparative example 1, the burning loss of lithium is serious, and the macroscopic tissue defect can be seen; comparative example 2 the Mg and Li contents are both less than those of examples 1-3 of the present invention, so the alloy has higher density and lower strength; comparative example 3 has no rare earth element added, and both tensile strength and elongation are reduced.
Finally, it should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.

Claims (10)

1. A low-density high-toughness aluminum alloy plate is characterized by comprising the following components in percentage by mass: less than 0.10 percent of silicon, less than 0.10 percent of iron, 3.0 to 4.5 percent of magnesium, 1.0 to 2.5 percent of lithium, 0.05 to 0.25 percent of rare earth and the balance of aluminum.
2. The aluminum alloy sheet according to claim 1, wherein the aluminum alloy sheet has a thickness of 0.5 to 2.0mm, a low density of < 2.7g/cm, and high toughness3Tensile strength of the steel sheet>400MPa, elongation>10％。
3. The aluminum alloy sheet according to claim 1, wherein the rare earth is one or more of Er, Sc and Ce.
4. A method for producing an aluminium alloy sheet according to any one of claims 1 to 3, comprising the steps of:
firstly, weighing a pure aluminum ingot, a pure magnesium ingot and an aluminum rare earth intermediate alloy according to a proportion, smelting, stirring and standing after all raw materials are melted;
adding an aluminum lithium intermediate alloy and a covering agent, and standing;
thirdly, adding a refining agent, stirring, cleaning surface slag, introducing argon for refining, and standing to obtain alloy liquid;
and fourthly, casting the alloy liquid into ingots, cooling to room temperature, and rolling into the aluminum plate by adopting a rolling mill.
5. The method as claimed in claim 4, wherein in step (r), the rare earth content in the aluminum rare earth master alloy is 5 to 10 wt%.
6. The method of claim 4, wherein in the second step, the lithium content in the aluminum lithium intermediate alloy is 10 to 20 wt%; the covering agent is a mixture of lithium chloride and lithium fluoride, and the mass ratio of the lithium chloride to the lithium fluoride is 3/2-2/3.
7. The method of claim 4, wherein in step (c), the refining agent is hexachloroethane, and the amount of the refining agent added is 0.4-0.8% of the total alloy batch mass.
8. The method as claimed in claim 4, wherein the temperature of the smelting and refining process is maintained at 720-760 ℃ in the third step.
9. The method of claim 4, wherein in the third step, in the refining process by introducing argon, an argon pipe is introduced into the aluminum melt for refining for 10-25 minutes.
10. The method according to claim 4, wherein in the step (iv), the aluminum plate is rolled by a rolling mill, the thickness of the aluminum plate is 0.5 mm-2.0 mm, and the rolling rate of each pass is 10-30%.
CN202111092740.9A 2021-09-17 2021-09-17 Low-density high-toughness aluminum alloy plate and preparation method thereof Withdrawn CN113957303A (en)

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Application publication date: 20220121