CN112981195A - High-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy and preparation method thereof - Google Patents
High-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy and preparation method thereof Download PDFInfo
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/047—Changing 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 magnesium as the next major constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/05—Changing 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 of the Al-Si-Mg type, i.e. containing silicon and magnesium in approximately equal proportions
Abstract
The invention discloses a high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy and a preparation method thereof. The high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy comprises, by mass, 0.59-0.9% of Mg, 0.5-0.9% of Si, 0.253-0.386% of Ca and the balance of Al, wherein the impurity content is less than or equal to 0.1%; the method takes an Al block (the purity is more than 99.8%), an Al-12Si intermediate alloy and an Mg-10Al-27Ca eutectic intermediate alloy as raw materials, and adopts a common gravity casting method to prepare an as-cast Al-Mg-Si-Ca alloy by smelting; after solid solution, water quenching and pre-aging treatment, cold rolling and hot rolling are carried out for two times by controlling the reduction, and finally aging treatment is carried out to prepare the high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy. The high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy prepared by the method realizes the great improvement of mechanical properties under the condition of higher conductivity, and expands the application of the aluminum-magnesium-silicon-calcium conductive aluminum alloy in the field of power transmission.
Description
Technical Field
The invention relates to the technical field of processing and preparation of conductive aluminum alloy, in particular to a high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy and a preparation method thereof.
Background
With the continuous development of economy in China, the demand of various industries on power utilization is increased year by year, and a wire material with the characteristics of light weight, high conductivity and high strength is urgently needed. The 6xxx aluminum-magnesium-silicon alloy is often used as an overhead power transmission conductor because of high conductivity, high specific strength, good corrosion resistance and long service life. At present, the aluminum-magnesium-silicon alloy wire is industrially prepared by adopting the traditional process, which comprises solution treatment, water quenching after solution treatment, cold drawing and artificial aging. The aluminum-magnesium-silicon alloy prepared by the method has the tensile strength of 255-325 MPa and the electric conductivity of 52.5-57.5% IACS (International annealed copper standard). Therefore, the aluminum-magnesium-silicon alloy wire used in the industry at present has the problems that the conductivity is slightly high, but the strength is low, and the two contradictory with each other, so that the application of the aluminum-magnesium-silicon alloy wire in the field of long-distance power transmission is greatly limited. How to obtain an aluminum alloy wire with high strength and high conductivity becomes a technical problem which needs to be solved urgently in the current electric power energy industry.
The existing method for improving the strength of the aluminum-magnesium-silicon alloy mainly comprises the following steps: (1) alloying, such as adding elements such as Ca, Mn, Sc, etc., but in general, the electrical conductivity of the alloy is inevitably lost while the strength is improved by alloying; (2) machining deformation, such as equal channel angular extrusion, rolling deformation and the like, wherein if the grains of the deformed aluminum alloy matrix are refined and the solute atom content is reduced due to the precipitation of a second phase, the strength and the conductivity can be simultaneously improved due to the machining deformation; (3) and heat treatment, such as solution treatment and aging treatment, improves the microstructure of the alloy and enhances the strength and the electric conductivity of the alloy.
By retrieval, the CN201810208279.0 patent introduces a 'preparation method of high-strength high-conductivity aluminum-magnesium-silicon-calcium alloy', the conductivity of the alloy prepared by vacuum melting and equal channel angular pressing methods reaches 57.2 percent IACS, and the tensile strength is 370 MPa. The CN201811445500.0 patent introduces a 'preparation method of a high-strength high-conductivity aluminum alloy wire', the conductivity of the prepared aluminum alloy wire is 55.5% -58.5% IACS, the elongation is 2.0-4.0%, and the tensile strength is 310-350 MPa. The CN201711465441.9 patent introduces a heat-resistant aluminum alloy wire with high strength and high conductivity and a preparation method thereof, the conductivity of the prepared heat-resistant aluminum wire reaches 62 percent IACS, but the tensile strength is 322MPa at most. Therefore, in order to make the aluminum-magnesium-silicon alloy more widely and effectively applied in the field of power transmission, the strength of the aluminum-magnesium-silicon alloy is urgently required to be greatly improved under the condition of high conductivity.
Disclosure of Invention
The invention aims to prepare a high-strength conductive aluminum alloy, and provides a high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
one of the technical schemes of the invention is as follows: the high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy comprises, by mass, 0.59-0.9% of Mg, 0.5-0.9% of Si, 0.253-0.386% of Ca and the balance of Al, wherein the impurity content is less than or equal to 0.1%.
Preferably, the raw materials of the high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy comprise an Al block, an Al-12Si intermediate alloy and an Mg-10Al-27Ca eutectic intermediate alloy.
More preferably, the purity of the Al block is 99.8% or more.
Preferably, the preparation method of the Mg-10Al-27Ca eutectic intermediate alloy comprises the following steps:
preparing Al block (purity over 99.8%) and Mg-30Ca intermediate alloy according to element proportion; under the protection of inert gas, firstly, keeping the temperature of an Al block at 700-720 ℃ for 20min, after the Al block is melted, removing floating slag, then adding Mg-30Ca intermediate alloy, scattering a covering agent (RJ-2 flux) on the surface of a melt, keeping the temperature at 720-740 ℃ for 20min, removing slag after the heat preservation is finished, adding the RJ-2 flux for refining, finally keeping the temperature at 690-700 ℃ for 20min to prepare a melt, and pouring the obtained melt to prepare the Mg-10Al-27Ca intermediate alloy.
Mg-10Al-27Ca is a eutectic intermediate alloy, fine and uniformly dispersed intermetallic compounds exist in the matrix structure of the eutectic intermediate alloy, and when the eutectic intermediate alloy is added into aluminum alloy as a raw material, fine and uniformly dispersed (Mg, Al) can be formed in the solidification structure of the as-cast aluminum alloy according to the tissue genetic principle2A Ca particle reinforcing phase. And high density and small (Mg, Al)2The Ca particle reinforcing phase can promote Mg in aluminum matrix2The Si particle reinforced phase is greatly separated out, so that the solid solubility of Mg atoms in an aluminum matrix is obviously reduced, and the strength and the conductivity of the aluminum-magnesium-silicon-calcium alloy are improved.
The addition of Si in the form of Al-12Si intermediate alloy can obviously reduce the melting point of Si, so that the raw materials are easier to melt, and the oxidation in the melting process can be reduced.
The second technical scheme of the invention is as follows: the preparation method of the high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy is characterized in that an Al block, an Al-12Si intermediate alloy and an Mg-10Al-27Ca eutectic intermediate alloy are used as raw materials to prepare an as-cast alloy, and the as-cast alloy is rolled twice to prepare the high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy.
Preferably, the cast alloy is subjected to solution treatment before rolling, water quenching and pre-aging treatment after solution treatment, and aging treatment after two times of rolling. The solid solution treatment can ensure that the alloy elements are fully solid-dissolved and the as-cast alloy components are uniform; the pre-aging treatment can precipitate a certain amount of nano precipitated phase in advance.
More preferably, the temperature of the solution treatment is 500-560 ℃, and the time is 3-5 h; the temperature of the pre-aging treatment is 150-180 ℃, and the time is 1-2 h; the temperature of the aging treatment is 130-150 ℃, and the time is 18-30 h.
Preferably, the two-pass rolling is specifically a first-pass cold rolling and a second-pass hot rolling. After the first cold rolling, high-density dislocation is generated in the alloy matrix, and the precipitated phase and the dislocation have interaction (the precipitated phase pins the dislocation), so that the rapid formation of a large-angle grain boundary in the high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy matrix crystal grains is promoted, the grain refinement is accelerated, the formation of cellular elongated crystal grains is inhibited, the texture is reduced, and the strength and the plastic toughness of the high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy are improved.
Preferably, the first rolling reduction of the two-pass rolling is 46%, the second rolling reduction is 37.8%, and the total reduction of the two-pass rolling is 66.6%. The high strength and toughness of the aluminum-magnesium-silicon-calcium alloy can be realized only by carrying out two times of conventional rolling, wherein the total deformation is far less than the ECAP strong plastic deformation (the strain of ECAP per pass is about 100%). The process is simple to operate, the equipment is conventional, and the industrial production is easy to realize.
More preferably, after the solid solution and pre-aging alloy plate is rolled at room temperature for the first time, the solid solution and pre-aging alloy plate is placed into a vacuum tube furnace heated to 250-350 ℃ under the protection of argon, is taken out after heat preservation is carried out for 5-10 min, and is immediately rolled for the second time. The short-time heating can partially eliminate dislocation, promote recovery and reduce residual stress, and is favorable for the second pass rolling; the second pass rolling can continuously promote the precipitation of a high-density second phase and refine aluminum matrix grains.
Preferably, the method of preparing the as-cast alloy comprises: preparing Al blocks, Al-12Si intermediate alloy and Mg-10Al-27Ca eutectic intermediate alloy according to element proportion; under the protection of inert gas, firstly, preserving heat of an Al block and an Al-12Si intermediate alloy for 30-40 min at the temperature of 740-760 ℃, after the raw materials are melted, removing floating slag, then adding an Mg-10Al-27Ca eutectic intermediate alloy, scattering a covering agent on the surface of a melt, continuously preserving heat for 20-30 min at the temperature of 720-740 ℃, removing slag after heat preservation, adding a refining agent for refining, finally preserving heat for 20-30 min at the temperature of 700-720 ℃ to prepare a melt, and pouring the obtained melt to prepare the as-cast alloy.
The invention has the following beneficial technical effects:
the invention adopts the Mg-10Al-27Ca eutectic crystal which is added and designed to be prepared in 6201 alloyThe intermediate alloy combines solid solution, pre-aging treatment, rolling deformation and subsequent aging treatment to refine the crystal grains of the high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy matrix, the average crystal grain size is less than or equal to 0.2 mu m, and fine Mg is uniformly dispersed and distributed in the matrix2Si、(Mg,Al)2The Ca second phase, so that the strength of the prepared high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy is greatly improved under the condition of higher conductivity.
The high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy prepared by the invention has yield strength of 348MPa, tensile strength of 523MPa, elongation of 5.4% and conductivity of 46.77% IACS.
The preparation method of the high-strength conductive aluminum alloy provided by the invention has the advantages of simple process, conventional equipment, easiness in industrial production, low cost of the used alloy system and excellent comprehensive performance.
Drawings
FIG. 1 is a graph of as-cast OM of Mg-10Al-27Ca master alloy used in examples and comparative examples 2 to 3.
FIG. 2 is an as-cast OM diagram of the Mg-30Ca master alloy used in comparative example 1.
Fig. 3 is an OM diagram of the high strength al-mg-si-ca conductive aluminum alloy prepared in example 1.
FIG. 4 is a TEM structural image of the high-strength Al-Mg-Si-Ca conductive aluminum alloy prepared in example 1.
FIG. 5 is a tensile stress-strain curve of the high strength Al-Mg-Si-Ca conductive aluminum alloy of example 1.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the present invention, examples of which are illustrated in the accompanying drawings, and this detailed description should not be taken to be limiting of the invention, but is rather a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The preparation method of the Mg-10Al-27Ca eutectic intermediate alloy used in the embodiment and the comparative example of the invention comprises the following steps: preparing Al block (purity over 99.8%) and Mg-30Ca intermediate alloy according to element proportion; under the protection of inert gas, firstly, keeping the temperature of an Al block at 700-720 ℃ for 20min, after the Al block is melted, removing floating slag, then adding Mg-30Ca intermediate alloy, scattering a covering agent (RJ-2 flux) on the surface of a melt, keeping the temperature at 720-740 ℃ for 20min, removing slag after the heat preservation is finished, adding the RJ-2 flux for refining, finally keeping the temperature at 690-700 ℃ for 20min to prepare a melt, and pouring the obtained melt to prepare the Mg-10Al-27Ca intermediate alloy.
Example 1
The high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy comprises, by mass, 0.59% of Mg, 0.54% of Si, 0.253% of Ca and the balance of Al, wherein the content of impurities is less than or equal to 0.1%, and the preparation method comprises the following steps:
(1) melting as-cast alloys
The preparation of the alloy is completed in a crucible resistance furnace by adopting a common gravity casting method under the protection of argon gas:
472.82g of weighed and ground Al blocks (the purity is more than 99.8 percent), 22.5g of Al-12Si intermediate alloy, 4.68g of Mg-10Al-27Ca eutectic intermediate alloy, and the weighed covering agent and refining agent are put into a drying oven for drying.
Secondly, brushing materials: and (3) putting the graphite crucible into a resistance furnace for heating, starting brushing when the temperature reaches 400 ℃, and uniformly and firmly attaching the prepared coating to the inner wall of the crucible for at least three times.
Feeding: and after finishing brushing, adding the dried Al block and the Al-12Si intermediate alloy into the crucible, introducing argon for protection, keeping the temperature for 30min after the furnace temperature is raised to 760 ℃, and waiting for the raw materials to be molten.
Slagging off and feeding: after the raw materials are completely melted, the power supply is closed, the furnace door is opened, the tool is used for removing the scum on the surface, then the Mg-10Al-27Ca eutectic intermediate alloy wrapped by the aluminum foil is added, then the dried covering agent is scattered on the surface of the melt, the furnace door is closed, the power supply is opened, and the temperature is kept for 20min after the temperature is increased to 740 ℃.
And fifthly, refining: after heat preservation, the power supply is turned off, slag is removed, and then the dried refining agent is poured into the melt and fully stirred. After stirring, the furnace door is closed, the power supply is turned on, the temperature is raised to 720 ℃, and then the temperature is kept for 20 min.
Pouring: and after opening the furnace and removing slag, taking out the smelting crucible, and pouring until the steel mould pouring gate is fully poured.
(2) Wire-electrode cutting casting
And (2) taking the casting obtained in the step (1) out of the die, and cutting the casting into rectangular blocks with the size of 50mm multiplied by 20mm multiplied by 4mm by a linear cutting machine.
(3) Solid solution and pre-aging treatment
Solution treatment: coating Vaseline on the surface of the rectangular block, wrapping the rectangular block with aluminum foil, burying the rectangular block in an iron box filled with graphite powder, placing the rectangular block in a box type resistance furnace, and carrying out solution treatment for 5 hours at 550 ℃; after the solution treatment, the steel is immediately quenched by cold water at 20 ℃ for less than or equal to 10 s.
Pre-aging treatment: and putting the quenched rectangular block into a box-type resistance furnace at the temperature of 180 ℃ again for heat preservation for 2h, taking out the rectangular block, and cooling the rectangular block to room temperature in the air.
(4) Rolling of
A two-roll flat rolling mill is adopted, the roll gap is debugged by using waste materials before the experiment, and the roll gap is debugged to the expected thickness.
Before rolling, the rectangular blocks treated in the step (3) are ground by 240-mesh sand paper to remove surface defects.
Primary rolling: and rotating the switch to rotate the roller for rolling. After one-pass rolling, the rectangular block is rolled into a thin plate, the thickness of the thin plate is rolled from 3.65mm to 1.96mm, and the rolling reduction reaches 46%.
And (3) rolling for two times: before two-pass rolling, the sheet after one-pass rolling is placed into a 300 ℃ tubular heating furnace for heat preservation for 5min (argon protection), the roll gap thickness is adjusted, after 5min, the sheet is rapidly taken out of the furnace and immediately rolled, the thickness of the sheet is rolled from 1.96mm to 1.22mm, and the reduction is 37.8%. The total pressure reduction in the two passes was 66.6%.
(5) Aging treatment
And (4) wrapping the thin plate obtained in the step (4) with aluminum foil, and placing the thin plate into a tubular heating furnace for aging treatment at the temperature of 130 ℃ for 24 hours. After the aging treatment, the specimens were allowed to cool to room temperature in air.
Example 2
The high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy comprises, by mass, 0.59% of Mg, 0.50% of Si, 0.253% of Ca and the balance of Al, wherein the content of impurities is less than or equal to 0.1%, and the preparation method comprises the following steps:
(1) melting as-cast alloys
The preparation of the alloy is completed in a crucible resistance furnace by adopting a common gravity casting method under the protection of argon gas:
474.49g of weighed and ground Al blocks (the purity is more than 99.8 percent), 20.83g of Al-12Si intermediate alloy, 4.68g of Mg-10Al-27Ca eutectic intermediate alloy, and the weighed covering agent and refining agent are put into a drying oven for drying.
Secondly, brushing materials: and (3) putting the graphite crucible into a resistance furnace for heating, starting brushing when the temperature reaches 400 ℃, and uniformly and firmly attaching the prepared coating to the inner wall of the crucible for at least three times.
Feeding: and after finishing brushing, adding the dried Al block and the Al-12Si intermediate alloy into the crucible, introducing argon for protection, keeping the temperature for 40min after the furnace temperature is increased to 750 ℃, and waiting for the raw materials to be molten.
Slagging off and feeding: after the raw materials are completely melted, the power supply is closed, the furnace door is opened, the floating slag on the surface is removed by a tool, then Mg-10Al-27Ca eutectic intermediate alloy wrapped by aluminum foil is added, then the dried covering agent is scattered on the surface of the melt, the furnace door is closed, the power supply is opened, and the temperature is kept for 30min after the temperature is raised to 730 ℃.
And fifthly, refining: after heat preservation, the power supply is turned off, slag is removed, and then the dried refining agent is poured into the melt and fully stirred. After stirring, the furnace door is closed, the power supply is turned on, the temperature is raised to 710 ℃, and then the temperature is kept for 20 min.
Pouring: and after opening the furnace and removing slag, taking out the smelting crucible, and pouring until the steel mould pouring gate is fully poured.
(2) Wire-electrode cutting casting
And (2) taking the casting obtained in the step (1) out of the die, and cutting the casting into rectangular blocks with the size of 50mm multiplied by 20mm multiplied by 4mm by a linear cutting machine.
(3) Solid solution and pre-aging treatment
Solution treatment: coating Vaseline on the surface of the rectangular block, wrapping the rectangular block with aluminum foil, burying the rectangular block in an iron box filled with graphite powder, placing the rectangular block in a box type resistance furnace, and carrying out solution treatment for 3 hours at 560 ℃; after solid solution, quenching the steel plate by cold water at 20 ℃ for less than or equal to 10 s.
Pre-aging treatment: and putting the quenched rectangular block into a box-type resistance furnace at the temperature of 150 ℃ for heat preservation for 2h, taking out the rectangular block, and cooling the rectangular block to room temperature in the air.
(4) Rolling of
A two-roll flat rolling mill is adopted, the roll gap is debugged by using waste materials before the experiment, and the roll gap is debugged to the expected thickness.
Before rolling, the rectangular blocks treated in the step (3) are ground by 240-mesh sand paper to remove surface defects.
Primary rolling: and rotating the switch to rotate the roller for rolling. After one-pass rolling, the rectangular block is rolled into a thin plate, the thickness of the thin plate is rolled from 3.65mm to 1.96mm, and the rolling reduction reaches 46%.
And (3) rolling for two times: before two-pass rolling, the sheet after one-pass rolling is placed into a tube heating furnace at 250 ℃ for heat preservation for 10min (argon protection), the roll gap thickness is adjusted, after 10min, the sheet is rapidly taken out of the furnace and immediately rolled, the thickness of the sheet is rolled from 1.96mm to 1.22mm, and the reduction is 37.8%. The total pressure reduction in the two passes was 66.6%.
(5) Aging treatment
And (4) wrapping the thin plate obtained in the step (4) with aluminum foil, and placing the thin plate into a tubular heating furnace for aging treatment at the temperature of 150 ℃ for 18 hours. After the aging treatment, the specimens were allowed to cool to room temperature in air.
Example 3
The high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy comprises, by mass, 0.59% of Mg, 0.9% of Si, 0.253% of Ca and the balance of Al, wherein the content of impurities is less than or equal to 0.1%, and the preparation method comprises the following steps:
(1) melting as-cast alloys
The preparation of the alloy is completed in a crucible resistance furnace by adopting a common gravity casting method under the protection of argon gas:
457.82g of weighed and ground Al blocks (the purity is more than 99.8 percent), 37.5g of Al-12Si intermediate alloy, 4.68g of Mg-10Al-27Ca eutectic intermediate alloy, and the weighed covering agent and refining agent are put into a drying oven for drying.
Secondly, brushing materials: and (3) putting the graphite crucible into a resistance furnace for heating, starting brushing when the temperature reaches 400 ℃, and uniformly and firmly attaching the prepared coating to the inner wall of the crucible for at least three times.
Feeding: and after finishing brushing, adding the dried Al block and the Al-12Si intermediate alloy into the crucible, introducing argon for protection, keeping the temperature for 35min after the furnace temperature is raised to 760 ℃, and waiting for the raw materials to be molten.
Slagging off and feeding: after the raw materials are completely melted, closing the power supply, opening the furnace door, removing floating slag on the surface by a tool, adding Mg-10Al-27Ca eutectic intermediate alloy wrapped by aluminum foil, then scattering the dried covering agent on the surface of the melt, closing the furnace door, opening the power supply, and preserving heat for 30min after the temperature is raised to 720 ℃.
And fifthly, refining: after heat preservation, the power supply is turned off, slag is removed, and then the dried refining agent is poured into the melt and fully stirred. After stirring, the furnace door is closed, the power supply is turned on, the temperature is raised to 700 ℃, and then the temperature is kept for 30 min.
Pouring: and after opening the furnace and removing slag, taking out the smelting crucible, and pouring until the steel mould pouring gate is fully poured.
(2) Wire-electrode cutting casting
And (2) taking the casting obtained in the step (1) out of the die, and cutting the casting into rectangular blocks with the size of 50mm multiplied by 20mm multiplied by 4mm by a linear cutting machine.
(3) Solid solution and pre-aging treatment
Solution treatment: coating Vaseline on the surface of the rectangular block, wrapping the rectangular block with aluminum foil, burying the rectangular block in an iron box filled with graphite powder, placing the rectangular block in a box type resistance furnace, and carrying out solution treatment for 5 hours at 500 ℃; after solid solution, quenching the steel plate by cold water at 20 ℃ for less than or equal to 10 s.
Pre-aging treatment: and putting the quenched rectangular block into a box-type resistance furnace at the temperature of 180 ℃ again for heat preservation for 1h, taking out the rectangular block, and cooling the rectangular block to room temperature in the air.
(4) Rolling of
A two-roll flat rolling mill is adopted, the roll gap is debugged by using waste materials before the experiment, and the roll gap is debugged to the expected thickness.
Before rolling, the rectangular blocks treated in the step (3) are ground by 240-mesh sand paper to remove surface defects.
Primary rolling: and rotating the switch to rotate the roller for rolling. After one-pass rolling, the rectangular block is rolled into a thin plate, the thickness of the thin plate is rolled from 3.65mm to 1.96mm, and the rolling reduction reaches 46%.
And (3) rolling for two times: before two-pass rolling, the sheet after one-pass rolling is placed into a 350 ℃ tubular heating furnace for heat preservation for 5min (argon protection), the roll gap thickness is adjusted, after 5min, the sheet is rapidly taken out of the furnace and immediately rolled, the thickness of the sheet is rolled from 1.96mm to 1.22mm, and the reduction is 37.8%. The total pressure reduction in the two passes was 66.6%.
(5) Aging treatment
And (4) wrapping the thin plate obtained in the step (4) with aluminum foil, and placing the thin plate into a tubular heating furnace for aging treatment at the temperature of 130 ℃ for 30 hours. After the aging treatment, the specimens were allowed to cool to room temperature in air.
Comparative example 1
Compared with the example 1, the difference is that Mg-10Al-27Ca eutectic type master alloy is not used, and the added raw materials are 473.29g of Al block, 22.5g of Al-12Si master alloy and 4.21g of Mg-30Ca master alloy. The step of adding the Mg-30Ca master alloy is the same as the step of adding the Mg-10Al-27Ca eutectic type master alloy, and other steps and parameters are the same as those in the embodiment 1.
Comparative example 2
Compared with the embodiment 1, the difference is that the first cold rolling reduction is 35.2%; the hot rolling reduction of the second pass is 31.0 percent, and the total reduction of the two passes is 55.3 percent; the other steps and parameters were the same as those in example 1.
Comparative example 3
Compared with the embodiment 1, the difference is that the first cold rolling reduction is 49.2%; the second hot rolling reduction is 49.5 percent, and the total reduction of the two times of rolling is 74.3 percent; the other steps and parameters were the same as those in example 1.
FIG. 1 is a graph of as-cast OM of Mg-10Al-27Ca master alloy used in examples and comparative examples 2 to 3. As can be seen from FIG. 1, Mg-10Al-27Ca is a eutectic master alloy, except for primary (Mg, Al)2Eutectic Mg in the matrix outside the Ca phase2The Ca phase is much finer.
FIG. 2 is an as-cast OM diagram of the Mg-30Ca master alloy used in comparative example 1. From FIG. 2, Mg in the matrix can be seen2Ca is relatively coarse.
Fig. 3 is an OM diagram of the high strength al-mg-si-ca conductive aluminum alloy prepared in example 1. As can be seen from FIG. 3, Mg is uniformly dispersed and distributed in the rolled and aged high-strength Al-Mg-Si-Ca conductive aluminum alloy matrix2Si granular phase, (Mg, Al)2A particulate phase of Ca.
FIG. 4 is a TEM structural image of the high-strength Al-Mg-Si-Ca conductive aluminum alloy prepared in example 1. As can be seen from FIG. 4, the average grain size in the rolled and aged high-strength Al-Mg-Si-Ca conductive Al-Mg-Al alloy matrix is less than or equal to 0.2 μm, and a large number of dislocations exist in the matrix.
FIG. 5 is a tensile stress-strain curve of the high strength Al-Mg-Si-Ca conductive aluminum alloy of example 1. The figure shows that the yield strength reaches 348MPa, the tensile strength reaches 523MPa, and the elongation reaches 5.4%.
At room temperature, a Sigma 2008B handheld eddy current conductivity meter is adopted, five positions of the sample are selected for measurement, the average value of the conductivity is taken, and finally the conductivity of the aluminum-magnesium-calcium-silicon alloy prepared in example 1, comparative example 2 and comparative example 3 is 46.77% IACS, 52.4% IACS, 47.80% IACS and 47.45% IACS respectively.
The mechanical properties and conductivity of the aluminum alloys prepared in example 1 and comparative examples 1 to 3 were measured, and the results are shown in table 1.
TABLE 1 mechanical and conductivity properties of aluminum alloys
| Performance of | Yield strength/MPa | Tensile strength/MPa | Elongation/percent | conductivity/IACS |
| Example 1 | 348 | 523 | 5.4 | 46.77 |
| Comparative example 1 | 133 | 248 | 5.8 | 52.40 |
| Comparative example 2 | 155 | 331 | 4.3 | 47.80 |
| Comparative example 3 | 283 | 353 | 5.7 | 47.45 |
As can be seen from table 1, the strength of the al-mg-si-ca alloy prepared in comparative example 1 is lower than that of example 1 because: according to the principle of tissue inheritance, the cast solidification structure of example 1 has fine uniformly dispersed (Mg, Al)2Ca particulate phase which promotes Mg in the aluminum matrix2Since a large amount of Si reinforcing phase was precipitated, the strength was higher and the electrical conductivity was lower in example 1 at the same reduction.
The strength of the al-mg-si-ca alloy prepared in comparative example 2 is lower than that of example 1 because: example 1 because of the larger rolling reduction, the deformed matrix has finer grain size and more fine Mg2The Si particle phase is dispersed in the aluminum matrix, making it stronger.
The strength of the al-mg-si-ca alloy prepared in comparative example 3 is lower than that of example 1 because: in comparative example 3, the alloy undergoes dynamic recovery and recrystallization during rolling at a large reduction, so that compared with example 1, the size of matrix grains is increased, the dislocation density is reduced, precipitated phases are increased, the number is reduced, and the strength is reduced.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. The high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy is characterized in that the high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy comprises, by mass, 0.59-0.9% of Mg, 0.5-0.9% of Si, 0.253-0.386% of Ca and the balance of Al, and the impurity content is less than or equal to 0.1%.
2. The high-strength Al-Mg-Si-Ca conductive aluminum alloy as claimed in claim 1, wherein the raw materials of the high-strength Al-Mg-Si-Ca conductive aluminum alloy comprise Al blocks, Al-12Si intermediate alloy, and Mg-10Al-27Ca eutectic intermediate alloy.
3. The high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy as claimed in claim 2, wherein the Mg-10Al-27Ca eutectic intermediate alloy is prepared by the following steps: preparing Al blocks and Mg-30Ca intermediate alloy according to element proportion; under the protection of inert gas, firstly, keeping the temperature of an Al block at 700-720 ℃ for 20min, after the Al block is melted, removing floating slag, then adding Mg-30Ca intermediate alloy, scattering a covering agent on the surface of a melt, keeping the temperature at 720-740 ℃ for 20min, removing slag after the heat preservation is finished, adding RJ-2 flux for refining, keeping the temperature at 690-700 ℃ for 20min to prepare a melt, and pouring the obtained melt to prepare the Mg-10Al-27Ca intermediate alloy.
4. The preparation method of the high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy according to any one of claims 2 to 3, wherein an as-cast alloy is prepared by taking an Al block, an Al-12Si intermediate alloy and an Mg-10Al-27Ca eutectic intermediate alloy as raw materials, and the as-cast alloy is subjected to two-pass rolling to prepare the high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy.
5. The method for preparing a high-strength Al-Mg-Si-Ca conductive aluminum alloy as claimed in claim 4, wherein the cast alloy is subjected to solution treatment before rolling, water quenching and pre-aging treatment after solution treatment, and aging treatment after two times of rolling.
6. The method for preparing the high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy according to claim 5, wherein the temperature of the solution treatment is 500-560 ℃ and the time is 3-5 h; the temperature of the pre-aging treatment is 150-180 ℃, and the time is 1-2 h; the temperature of the aging treatment is 130-150 ℃, and the time is 18-30 h.
7. The method for preparing the high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy according to claim 4, wherein the two-pass rolling is specifically a first-pass cold rolling and a second-pass hot rolling.
8. The method for preparing the high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy according to claim 4, wherein the reduction of the first rolling of the two-pass rolling is 46%, and the reduction of the second rolling of the two-pass rolling is 37.8%.
9. The method for preparing the high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy according to claim 4, wherein the as-cast alloy is subjected to first-pass room temperature rolling, placed into a vacuum tube furnace heated to 250-350 ℃ under the protection of argon, kept warm for 5-10 min, taken out and immediately subjected to second-pass rolling.
10. The method for preparing the high-strength aluminum-magnesium-silicon-calcium conductive aluminum alloy according to claim 4, wherein the method for preparing the as-cast alloy comprises the following steps: preparing Al blocks, Al-12Si intermediate alloy and Mg-10Al-27Ca eutectic intermediate alloy according to element proportion; under the protection of inert gas, firstly, preserving heat of an Al block and an Al-12Si intermediate alloy for 30-40 min at the temperature of 740-760 ℃, after the raw materials are melted, removing floating slag, then adding an Mg-10Al-27Ca eutectic intermediate alloy, scattering a covering agent on the surface of a melt, continuously preserving heat for 20-30 min at the temperature of 720-740 ℃, removing slag after heat preservation, adding a refining agent for refining, finally preserving heat for 20-30 min at the temperature of 700-720 ℃ to prepare a melt, and pouring the obtained melt to prepare the as-cast alloy.
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