CN110564992A - sr, Zr, Ti and Ce quaternary composite microalloyed Al-Si-Cu series cast aluminum alloy and preparation method thereof - Google Patents
sr, Zr, Ti and Ce quaternary composite microalloyed Al-Si-Cu series cast aluminum alloy and preparation method thereof Download PDFInfo
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- C22C1/02—Making non-ferrous alloys by melting
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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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Abstract
A Sr, Zr, Ti and Ce quaternary composite microalloyed high-strength and high-plasticity Al-Si-Cu series cast aluminum alloy mainly comprises aluminum, silicon, copper, strontium, zirconium, titanium and cerium, and the preparation method sequentially comprises (1) casting, (2) homogenizing annealing, (3) solution treatment and (4) aging.
Description
Technical Field
The invention relates to a cast aluminum alloy, in particular to an Al-Si-Cu cast aluminum alloy, and specifically relates to a high-strength high-plasticity Al-Si-Cu cast aluminum alloy obtained by Sr, Zr, Ti and Ce quaternary composite microalloying and a preparation method thereof.
Background
The cast aluminum alloy has higher tensile strength and elongation, excellent casting performance and corrosion resistance, and is widely applied to various fields of industrial manufacturing, such as: the fields of automobiles, aerospace and the like. With the rapid increase of the number of automobiles, the continuous improvement of the automobile performance and the increasingly prominent problem of energy resources, the requirements of the automobile industry on the light weight and high strength of products are more and more strict, and the improvement of the mechanical property of the cast aluminum alloy becomes the problem which needs to be solved urgently in the current society.
Patent application No. 201710193447.9 discloses a method for preparing a high-strength cast aluminum alloy, the obtained alloy has higher strength and hardness, good wear resistance and corrosion resistance, but the alloy is centrifugally cast and has higher production cost; patent application No. 201611031488.X discloses a 2a12 aluminum alloy casting process, the resulting workpiece has a lower tensile strength; patent application No. 201010607633.0 discloses a high strength cast aluminum alloy that has a high room temperature tensile strength but a low elongation at break. Cast aluminum alloys with strength and plasticity that fully meet the service requirements have not been developed in the market to date. The performance of the aluminum alloy can be improved by adding a proper amount of trace elements into the alloy, and the invention provides a quaternary composite microalloying technology based on the design idea of microalloying 'multi-element and small-quantity'.
Sr is used as modifier and Al is mainly used in alloy liquid4Sr exists, the compound is unstable and easy to decompose, can not play a non-uniform nucleation role, and is ineffective in refining primary silicon, but free Sr is adsorbed on the surface of growing Si to prevent eutectic silicon from growing in a flaky mode. Addition of Ce can form CeO2and CeO2Can be used as a non-uniform nucleation core of eutectic silicon. Therefore, the Sr and the Ce are added simultaneously to achieve the composite modification effect, and even if the nucleation rate of the eutectic silicon is increased, the growth form of the eutectic silicon is changed to be crushed into fine points. Therefore, the Sr and the Ce are added simultaneously to better refine the structure, so that the structure is more compact, the size and the number of primary silicon phases are reduced, and the performance of the aluminum alloy is more effectively improved.
Zr element is added into the aluminum alloy, and forms A1 with Al in the process of alloy solidification3Zr and other high-melting-point phases play a role in heterogeneous nucleation on subsequent solidification of the alloy, refine the as-cast matrix structure and improve the fluidity and element distribution uniformity of the liquid alloy. Ti is also a common trace element of the aluminum alloy, and can form Al in the aluminum alloy after being added3The Ti phase forms a non-spontaneous core during crystallization, and remarkably refines the cast structure. And Al formed when Zr and Ti are added simultaneously3ZrxT1-xphase, better refined tissue, with a1 ratio than a single phase3Zr phase, Al3The Ti phase has better refining effect, so that the strengthening effect of adding Zr and Ti simultaneously is better than that of adding Zr or Ti only.
So far, cast aluminum alloys reinforced by using Sr, Zr, Ti and Ce quaternary composite micro-alloying have not appeared in the market. In order to solve the problems of low tensile strength and low plasticity of cast aluminum alloy in the prior art, the invention of a high-strength and high-plasticity Al-Si-Cu series cast aluminum alloy obtained by Sr, Zr, Ti and Ce quaternary composite microalloying and a preparation method thereof is urgently needed.
Disclosure of Invention
The invention aims to overcome the defects of the existing cast aluminum alloy and use a Sr, Zr, Ti and Ce quaternary composite microalloying technology (by utilizing Sr and Ce composite modification effect and utilizing Al formed by compounding Zr and Ti)3ZrxT1-xPhase), provides a Sr, Zr, Ti and Ce quaternary composite microalloyed high-strength high-plasticity Al-Si-Cu series cast aluminum alloy and a preparation method thereof, and solves the problems of low tensile strength and poor plasticity of the cast aluminum alloy.
One of the technical schemes of the invention is as follows:
the Sr, Zr, Ti and Ce quaternary composite microalloyed high ~ strength high ~ plasticity Al ~ Si ~ Cu series cast aluminum alloy is characterized by mainly comprising 7.5 ~ 11.16% of silicon (Si), 4.34 ~ 5.31% of copper (Cu), 0.55 ~ 0.7% of strontium (Sr), 0.42 ~ 0.59% of zirconium (Zr), 0.14 ~ 0.18% of titanium (Ti), 0.15 ~ 0.23% of cerium (Ce) and the balance of aluminum and inevitable impurity elements, wherein the sum of the components is 100%.
The second technical scheme of the invention is as follows:
A preparation method of Sr, Zr, Ti and Ce quaternary composite microalloyed high-strength and high-plasticity Al-Si-Cu series cast aluminum alloy is characterized by sequentially comprising the following steps: (1) casting, (2) homogenizing annealing, (3) solution treatment, and (4) aging;
The fusion casting is as follows: heating to 850 +/-10 ℃ after Al, Al-Si intermediate alloy and Al-Cu intermediate alloy are melted, sequentially adding Al-Sr intermediate alloy, Al-Zr intermediate alloy, Al-Ti-B intermediate alloy and Al-Ce intermediate alloy, preserving heat for 2-2.5 hours after all intermediate alloy and metal are melted, reducing the temperature to 750-780 ℃, adding a hexachloroethane refining agent for refining, standing for 10min after refining, removing slag after standing, adding the hexachloroethane refining agent again for refining, standing for 10min after refining, removing slag after standing, and casting into ingots;
the homogenizing annealing refers to the following steps: 250 plus or minus 10 ℃ multiplied by 6h +350 plus or minus 10 ℃ multiplied by 6h +450 plus or minus 10 ℃ multiplied by 6h +
480±10℃×20h；
The solid solution treatment is 480 +/-10 ℃ multiplied by 1h +490 +/-10 ℃ multiplied by 1h, and then water quenching is carried out at room temperature;
the aging refers to: 191 plus or minus 10 ℃ multiplied by 12 hours;
the Sr, Zr, Ti and Ce quaternary composite microalloying can be obtained by the four ~ step method, and the high ~ strength high ~ plasticity Al ~ Si ~ Cu series cast aluminum alloy with the Sr, Zr, Ti and Ce quaternary composite microalloying, the tensile strength of 360MPa ~ 391.58MPa and the elongation at break of 5.75 ~ 7.5 percent can be obtained.
The mass percent of Si in the Al-Si intermediate alloy is 17%, 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%, and the mass percent of Ce in the Al-Ce intermediate alloy is 10%.
The invention has the following beneficial effects:
(1) By using the quaternary composite microalloying technology, Sr and Ce are added simultaneously, so that the composite modification effect is achieved, the structure is more compact, the alloy components are more uniform, the number and the size of primary silicon phases are reduced, and the performance of the aluminum alloy is improved more effectively; al formed by simultaneous addition of Zr and Ti3ZrxT1-xphase, better refined tissue, with a1 ratio than a single phase3Zr phase, Al3The Ti phase has better refining effect, and the strength and the plasticity of the cast aluminum alloy are more effectively improved.
(2) The cast aluminum alloy prepared by the invention has higher tensile strength and elongation at break, and meets the requirements of automobile industry on light weight, high strengthening and high toughness of alloy parts.
Drawings
FIG. 1 is an SEM image of tensile fracture of a quaternary composite microalloyed Al-Si-Cu series cast aluminum alloy in example 1 of the invention.
FIG. 2 is an SEM image of the surface of a quaternary composite microalloyed Al-Si-Cu based cast aluminum alloy of example 1 of the invention.
FIG. 3 is an SEM image of tensile fracture of an Al-Si-Cu series cast aluminum alloy of example 2 of the present invention;
FIG. 4 is an SEM image of the surface of a quaternary composite microalloyed Al-Si-Cu based cast aluminum alloy of example 1 of the invention.
FIG. 5 is an SEM image of tensile fracture of a quaternary composite microalloyed Al-Si-Cu series cast aluminum alloy of comparative example 1 in accordance with the present invention.
FIG. 6 is an SEM image of the surface of a quaternary composite microalloyed Al-Si-Cu based cast aluminum alloy of example 1 of the invention.
FIG. 7 is an SEM image of tensile fracture of a quaternary composite microalloyed Al-Si-Cu series cast aluminum alloy of comparative example 2 in accordance with the present invention.
FIG. 8 is an SEM image of the surface of a quaternary composite microalloyed Al-Si-Cu based cast aluminum alloy of example 1 of the invention.
Detailed Description
The present invention will be further described with reference to the following examples.
example 1.
A Sr, Zr, Ti and Ce quaternary composite microalloyed high-strength and high-plasticity Al-Si-Cu series cast aluminum alloy is prepared by the following method:
Firstly, melting Al, Al-Si intermediate alloy and Al-Cu intermediate alloy, heating to 850 +/-10 ℃, sequentially adding Al-Sr intermediate alloy, Al-Zr intermediate alloy, Al-Ti-B intermediate alloy and Al-Ce intermediate alloy, preserving heat for 2-2.5 hours after all intermediate alloy and metal are melted, reducing the temperature to 750-780 ℃, adding a hexachloroethane refining agent for refining, standing for 10min after refining, standing for deslagging, adding the hexachloroethane refining agent again for refining, standing for 10min after refining, standing for deslagging, and casting into ingots.
Secondly, carrying out homogenizing annealing on the aluminum alloy cast ingot, wherein the homogenizing annealing process comprises the following steps:
250±10℃×6h+350±10℃×6h+450±10℃×6h+480±10℃×20h；
Thirdly, carrying out solid solution treatment, wherein the solid solution treatment process is 480 +/-10 ℃ multiplied by 1h +490 +/-10 ℃ multiplied by 1h, and carrying out water quenching at room temperature;
And finally, carrying out aging treatment at 191 +/-10 ℃ for 12h to obtain the Sr, Zr, Ti and Ce quaternary composite microalloyed high-strength high-plasticity Al-Si-Cu series cast aluminum alloy.
The aluminum alloy of the present example has the following components measured by EDS: si11.16%, Cu4.34%, Sr0.70%, Zr0.42%, Ti0.14%, Ce0.19%, and the balance of aluminum and inevitable impurity elements.
The aluminum alloy of this example had a tensile strength of 391.58MPa and an elongation at break of 5.75%. The aluminum alloy tearing edges of the embodiment are very many, the structure is very uniform and compact, and no obvious looseness (shrinkage porosity) is generated; the primary silicon phase is very small and almost completely dissolved, so the alloy has very high strength and plasticity.
Example 2.
A Sr, Zr, Ti and Ce quaternary composite microalloyed high-strength high-plasticity Al-Si-Cu series cast aluminum alloy is prepared by the same method as in example 1.
The aluminum alloy of the present example has the following components measured by EDS: 7.66% of Si, 4.84% of Cu, 0.57% of Sr, 0.59% of Zr, 0.16% of Ti, 0.15% of Ce, and the balance of aluminum and inevitable impurity elements.
The aluminum alloy of this example had a tensile strength of 368MPa and an elongation at break of 7.5%. The aluminum alloy of the embodiment has a plurality of tearing edges, compact and uniform tissues and less looseness (shrinkage porosity) by combining with the attached figure 2; the primary silicon phase is few, and the size is small, so that the alloy has high strength and good plasticity.
example 3.
A Sr, Zr, Ti and Ce quaternary composite microalloyed high-strength high-plasticity Al-Si-Cu series cast aluminum alloy is prepared by the same method as in example 1.
The aluminum alloy of the present example has the following components measured by EDS: si7.5 percent, Cu5.31 percent, Sr0.55 percent, Zr0.46 percent, Ti0.18 percent, Ce0.23 percent and the balance of aluminum and inevitable impurity elements.
The aluminum alloy of this example had a tensile strength of 360MPa and an elongation at break of 7.25%.
Comparative example 1.
An Al-Si-Cu cast aluminum alloy to which Sr and Zr were added was prepared in the same manner as in example 1.
The aluminum alloy of the present example has the following components measured by EDS: si7.39%, Cu4.9%, Sr0.54%, Zr0.36%, and the balance of aluminum and inevitable impurity elements.
The aluminum alloy of this comparative example had a tensile strength of 218.97MPa and an elongation at break of 3.25%. The aluminum alloy of the comparative example has fewer tearing edges, more looseness (shrinkage porosity) and less compact structure as can be seen by combining the attached figure 3; the primary silicon phase is more and the size is very large, so the strength is lower and the plasticity is poorer.
Comparative example 2.
An Al-Si-Cu cast aluminum alloy to which Sr and Zr were added was prepared in the same manner as in example 1.
the aluminum alloy of the present example has the following components measured by EDS: si7.21%, Cu4.98%, Sr0.51%, Zr0.33%, and the balance of aluminum and inevitable impurity elements.
The aluminum alloy of this comparative example had a tensile strength of 208.84MPa and an elongation at break of 5%. The aluminum alloy of the comparative example has few tearing edges, obvious looseness (shrinkage porosity), a large number and a non-compact structure as can be seen by combining the attached figure 3; the primary silicon has many phases and large size, and thus has low strength and plasticity.
comparative example 3.
An Al-Si-Cu cast aluminum alloy to which Sr and Zr were added was prepared in the same manner as in example 1.
the aluminum alloy of the present example has the following components measured by EDS: 6.93 percent of Si, 3.45 percent of Cu, 0.42 percent of Sr0, 0.42 percent of Zr0, and the balance of aluminum and inevitable impurity elements.
The aluminum alloy of this comparative example had a tensile strength of 300.45MPa and an elongation at break of 3.5%.
Comparative example 4.
An Al-Si-Cu cast aluminum alloy to which Sr and Zr were added was prepared in the same manner as in example 1.
The aluminum alloy of the present example has the following components measured by EDS: 6.11 percent of Si, 3.31 percent of Cu, 0.46 percent of Sr0, 0.54 percent of Zr0, and the balance of aluminum and inevitable impurity elements.
the aluminum alloy of this comparative example had a tensile strength of 299.69MPa and an elongation at break of 4%.
the high MPa ~ strength and high MPa ~ plasticity Al MPa ~ Si MPa ~ Cu series cast aluminum alloy prepared by using the quaternary microalloying technology has the tensile strength of 360MPa ~ 391.58MPa, the maximum tensile strength of 182.74MPa compared with Sr and Zr binary alloyed Al MPa ~ Si MPa ~ Cu series cast aluminum alloy, the elongation at break of 5.75 MPa ~ 7.5 percent and the maximum tensile strength of 4.25 percent compared with Sr and Zr binary alloyed Al MPa ~ Si MPa ~ Cu series cast aluminum alloy.
While particular embodiments of the present invention have been described, it will be understood that the invention is not limited to the particular embodiments described, but that variations and modifications can be effected within the scope of the claims by those skilled in the art without departing from the spirit of the invention.
The present invention is not concerned with parts which are the same as or can be implemented using prior art techniques.
Claims (3)
1. the Sr, Zr, Ti and Ce quaternary composite microalloyed high ~ strength high ~ plasticity Al ~ Si ~ Cu series cast aluminum alloy is characterized by mainly comprising 7.5 ~ 11.16% of silicon (Si), 4.34 ~ 5.31% of copper (Cu), 0.55 ~ 0.7% of strontium (Sr), 0.42 ~ 0.59% of zirconium (Zr), 0.14 ~ 0.18% of titanium (Ti), 0.15 ~ 0.23% of cerium (Ce) and the balance of aluminum and inevitable impurity elements, wherein the sum of the components is 100%.
2. the preparation method of the Sr, Zr, Ti and Ce quaternary composite microalloyed high-strength and high-plasticity Al-Si-Cu series cast aluminum alloy of claim 1 is characterized by sequentially comprising the following steps of: (1) casting, (2) homogenizing annealing, (3) solution treatment, and (4) aging;
The fusion casting is as follows: heating to 850 +/-10 ℃ after Al, Al-Si intermediate alloy and Al-Cu intermediate alloy are melted, sequentially adding Al-Sr intermediate alloy, Al-Zr intermediate alloy, Al-Ti-B intermediate alloy and Al-Ce intermediate alloy, preserving heat for 2-2.5 hours after all intermediate alloy and metal are melted, reducing the temperature to 750-780 ℃, adding a hexachloroethane refining agent for refining, standing for 10min after refining, removing slag after standing, adding the hexachloroethane refining agent again for refining, standing for 10min after refining, removing slag after standing, and casting into ingots;
The homogenizing annealing refers to the following steps: 250 plus or minus 10 ℃ multiplied by 6h +350 plus or minus 10 ℃ multiplied by 6h +450 plus or minus 10 ℃ multiplied by 6h +
480±10℃×20h；
The solid solution treatment is 480 +/-10 ℃ multiplied by 1h +490 +/-10 ℃ multiplied by 1h, and then water quenching is carried out at room temperature;
The aging refers to: 191 plus or minus 10 ℃ multiplied by 12 hours;
the high ~ strength and high ~ plasticity Al ~ Si ~ Cu series cast aluminum alloy with Sr, Zr, Ti and Ce quaternary compound microalloying, the tensile strength of 360MPa ~ 391.58MPa and the elongation at break of 5.75 ~ 7.5 percent can be obtained.
3. The method as set forth in claim 2, wherein the Al-Si master alloy contains Si 17% by mass, the Al-Cu master alloy contains Cu 50.12% by mass, the Al-Sr master alloy contains Sr 9.89% by mass, the Al-Zr master alloy contains Zr 4.11% by mass, the Al-Ti-B master alloy contains Ti 5.11% by mass, and the Al-Ce master alloy contains Ce 10% by mass.
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| CN111705245A (en) * | 2020-07-13 | 2020-09-25 | 西安工业大学 | Heat treatment method of die-casting aluminum alloy material |
| US20220258240A1 (en) * | 2021-02-12 | 2022-08-18 | Desktop Metal, Inc. | The jetting performance of molten metal alloys by controlling the concentration of key alloying elements |
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| CN106591638A (en) * | 2015-10-19 | 2017-04-26 | 通用汽车环球科技运作有限责任公司 | New high pressure die casting aluminum alloy for high temperature and corrosive applications |
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| CN111705245A (en) * | 2020-07-13 | 2020-09-25 | 西安工业大学 | Heat treatment method of die-casting aluminum alloy material |
| US20220258240A1 (en) * | 2021-02-12 | 2022-08-18 | Desktop Metal, Inc. | The jetting performance of molten metal alloys by controlling the concentration of key alloying elements |
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