CN114717455A - Heat treatment-free high-strength and high-toughness die-casting aluminum alloy and preparation method thereof - Google Patents
Heat treatment-free high-strength and high-toughness die-casting aluminum alloy and preparation method thereof Download PDFInfo
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Abstract
A heat treatment-free high-strength and high-toughness die-casting aluminum alloy and a preparation method thereof are disclosed, the alloy comprises: 7.5-9.5 wt.% of Si, 0-1.5 wt.% of Ni, 0.4-0.8 wt.% of Mn, 0-0.4 wt.% of Mg, 0.08-0.3 wt.% of Cr, 0.01-0.15 wt.% of Zr, 0.03-0.1 wt.% of Ti, 0.005-0.025 wt.% of Sr, and the balance of aluminum and unavoidable impurity elements. The die-casting aluminum alloy has good thermal stability, the mechanical property change is not more than 10% after the die-casting aluminum alloy is kept at the temperature of not more than 150 ℃ for 1000 hours, the die-casting aluminum alloy has excellent mechanical properties of die-casting yield strength of more than 120MPa and elongation of more than 14%, the performance requirements of a die-casting structural part of a vehicle body can be met without subsequent heat treatment, the qualification rate of a thin-wall die-casting structural part product can be greatly improved, and the use cost of automobile parts is reduced.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a heat-treatment-free die-casting aluminum alloy with excellent thermal stability and high toughness and a preparation method thereof.
Background
In recent years, with implementation of a light weight development strategy and rapid development of die casting equipment and process technology, an automobile stressed structural member prepared by high vacuum die casting becomes an important way for realizing light weight of a new energy automobile. At present, the aluminum alloy die-casting structural part generally adopts AlSiMnMg alloy to match with heat treatment to realize the strengthening and toughening of parts. Heat treatment typically results in deformation of the thin-walled structural member and increased cost. In order to improve the yield of the thin-wall structural member and reduce the cost, the preparation of the thin-wall structural member by adopting the heat-treatment-free high-strength and high-toughness aluminum alloy is an important development direction. This requires that the heat-treatment-free aluminum alloy not only have high yield strength, high toughness, high fatigue strength and other comprehensive mechanical properties, but also have excellent casting fluidity, dimensional stability and specific stiffness. According to the material characteristics of the aluminum alloy die-casting structural part, the heat-treatment-free aluminum alloy die-casting structural part is easy to be connected with other parts through cementation and self-piercing, compared with a steel part, the weight of the part is greatly reduced, and the mileage and the operation performance of a new energy automobile are improved. With the higher integration degree of new energy automobile structural parts, the die-casting aluminum alloy material without heat treatment becomes the only choice.
The die-casting aluminum alloy for the automobile body structural member has excellent comprehensive performance, and needs to have excellent die-casting performance, high yield strength, high toughness and excellent thermal stability. The die casting performance is generally satisfied by adding Si, solid solution strengthening elements are added for high strength in an as-cast state, and the volume fraction of the second phase is required to be reduced as much as possible for high toughness, so that lattice distortion is reduced, and the three are difficult to be considered together. In addition, the body structural member needs to be connected with other parts, and the new alloy is required to have excellent thermal stability when the size and the performance are required to be stable in the baking finish and the service process.
At present, several manufacturers and research units disclose some non-heat-treated die-casting aluminum alloys, such as CN 104471090B, CN 105316542A, CN10548365B, CN 106636787B and CN 110079712 a, which ensure high fluidity, high strength and high toughness of the alloy by adding alloying elements such as Si, Mg, Cu, V, Zr, rare earth and Sr, but do not mention the thermal stability of the alloy. The thermal stability is a main performance index of a vehicle body part, the requirement of a host factory on a structural member is that the mechanical property fluctuation is not more than 10% after the temperature is 150 ℃ for 1000 hours, particularly, the elongation and the yield strength still need to be within the performance index range, and the influencing factors mainly comprise the grain uniformity, the content of reinforcing phase elements such as Mg, Cu, Zn and the like, the type and the morphological characteristics of a second phase and the like. Therefore, in order to ensure the smooth development of the light weight of the automobile, the development of a novel heat-treatment-free die-casting aluminum alloy meeting the requirements of excellent thermal stability and high toughness and a preparation process thereof are urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the die-casting Al-Si-Mn-Mg-X aluminum alloy which has good heat treatment-free fluidity, high strength, high toughness and excellent thermal stability and the preparation method thereof.
The invention is realized by the following technical scheme.
The heat-treatment-free high-strength and high-toughness die-casting aluminum alloy is characterized by comprising the following components in percentage by mass: 7.5-9.5 wt.% of Si, 0-1.5 wt.% of Ni, 0.4-0.8 wt.% of Mn, 0-0.4 wt.% of Mg, 0.08-0.3 wt.% of Cr, 0.01-0.15 wt.% of Zr, 0.03-0.1 wt.% of Ti, 0.005-0.025 wt.% of Sr, and the balance of aluminum and unavoidable impurity elements, wherein Fe in the unavoidable impurity elements is less than or equal to 0.18 wt.%, the content of other single impurity elements is less than or equal to 0.05 wt.%, and the total amount of other impurities is less than or equal to 0.3 wt.%.
Further, the content ratio of Si/Ni is controlled to be not less than 7:1, the content ratio of Mn/Cr is controlled to be 3: 1-4: 1, and the content ratio of Cr/Zr is controlled to be 2: 1-3: 1.
Further, a second phase (elemental phase of another element other than the primary aluminum phase or a phase rich in another alloying element, e.g. eutectic silicon phase, Al-Fe-Mn-Si phase, Mg2Si equal) size < 20 μm.
Further, the unavoidable impurity elements include Cu, V, P, Ca, and Zn.
Further, the Mn content is 0.4-0.6 wt.%, the Mg content is 0.05-0.25 wt.%, the Cr content is 0.08-0.25 wt.%, the Zr content is 0.03-0.12 wt.%, and the Sr content is 0.01-0.025 wt.%.
Further, the content ratio of the Ni to the Cr is controlled to be not less than 7:1, the content ratio of the Mn to the Cr is controlled to be 3.5:1 to 4:1, the content ratio of the Cr to the Zr is controlled to be 2.5:1 to 3:1, the content of other single impurity elements in unavoidable impurity elements is not more than 0.03 wt%, and the total content of other impurities is not more than 0.2 wt%.
Further, the content of Si is 7.5-9.0 wt.%, Ni is 0-1.2 wt.%, Mn is 0.44-0.53 wt.%, Mg is 0.05-0.20 wt.%, Cr is 0.1-0.2 wt.%, Zr is 0.05-0.12 wt.%, Ti is 0.05-0.1 wt.%, Sr is 0.01-0.02 wt.%, and Fe is less than or equal to 0.12 wt.%, wherein the content ratio of Mn to Cr is 3.5: 1-4: 1, the content ratio of Cr to Zr is 2.5: 1-3: 1, the content of other single impurity elements in unavoidable impurity elements is less than or equal to 0.03 wt.%, and the total content of other impurities is less than or equal to 0.2 wt.%.
The preparation method of the aluminum alloy is characterized by comprising the following steps:
(1) preheating raw materials of aluminum, silicon, nickel, manganese, Sr, chromium, zirconium, titanium and magnesium to 150-200 ℃;
(2) according to the component ratio, firstly putting the aluminum raw material obtained by the treatment in the step (1) into an industrial smelting furnace, heating to 760-800 ℃, then adding the manganese, chromium, zirconium, nickel, titanium and silicon raw materials into the smelting furnace to be melted, controlling the temperature to 740-780 ℃, and finally adding the magnesium raw material and stirring until the magnesium raw material is completely melted to obtain an alloy melt;
(3) adding a slag removing agent into the alloy melt obtained in the step (2), wherein the weight of the slag removing agent accounts for 0.1-0.3 wt% of the total weight of the alloy melt, and the temperature of the alloy melt is controlled at 730-750 ℃;
(4) detecting the alloy melt obtained in the step (3), adding a Sr raw material after the components are qualified, controlling the temperature of the alloy melt to be 720-740 ℃, stirring, standing for 5-10min to ensure that the added raw material is fully melted, and then adding an aluminum-titanium-carbon-boron refiner, wherein the weight of the refiner accounts for 0.3-0.8 wt% of the total weight of the alloy melt, and the temperature of the alloy melt is controlled to be 720-740 ℃;
(5) adding a covering agent into the alloy melt obtained in the step (4) within 0-2min, then directly refining and degassing, wherein the adding amount is 0.05-0.1 wt.%, argon or high-purity nitrogen is introduced into the refining and degassing, the introducing pressure is 0.18-0.25 MPa, the guarantee time is 5-20 minutes, and the temperature is controlled at 720-730 ℃;
(6) and (3) carrying out component detection, density detection and slag content detection on the alloy melt obtained by refining, standing and cooling to 690-720 ℃ after the alloy melt is qualified, and thus obtaining the heat-treatment-free high-strength and high-toughness die-casting aluminum alloy.
Further, the aluminum raw material adopts pure aluminum or electrolytic aluminum, the silicon raw material adopts aluminum-silicon intermediate alloy or industrial silicon or instant silicon, the nickel raw material adopts aluminum-nickel intermediate alloy or pure nickel, the manganese raw material adopts aluminum-manganese intermediate alloy or manganese agent, the Sr raw material adopts Al-10Sr intermediate alloy, the chromium raw material adopts pure chromium or aluminum-chromium intermediate alloy, the zirconium raw material adopts pure zirconium or aluminum-zirconium intermediate alloy, the titanium raw material adopts pure titanium or titanium agent or aluminum-titanium intermediate alloy, the aluminum-titanium-carbon-boron refiner adopts aluminum-titanium-carbon-boron intermediate alloy wire rods, and the magnesium raw material adopts pure magnesium.
Further, the weight of the Sr raw material added in the step (4) accounts for 0.1-0.3 wt% of the total weight of the alloy melt, and the weight of the aluminum-titanium-carbon-boron refiner added accounts for 0.4-0.7 wt% of the total weight of the alloy melt.
Furthermore, in the aluminum-titanium-carbon-boron refiner, the mass percent of titanium element is 4-6 wt.%, the mass percent of carbon element is 0.09-0.1 wt.%, and the mass percent of boron element is 0.08-0.12 wt.%.
Further, the deslagging agent added in the step (3) is a sodium-free refining agent, and the covering agent in the step (5) is a sodium-free covering agent.
Further, the alloy melt qualification standard of the step (6) is as follows: the components are qualified, and the density value of the sample obtained by adopting a reduced pressure solidification method is not lower than 2.61g/cm3The modulus K is not higher than 1/20.
Further, the obtained aluminum alloy can be made into automobile stressed structural members or chassis members including sub-frames, shock absorber mounts, and the like, by a vacuum die-casting forming method.
The high-strength and high-toughness heat-treatment-free die-casting aluminum alloy with excellent thermal stability has the following effects of various elements:
the latent heat of crystallization of the silicon element is far greater than that of aluminum, so that the die-casting fluidity of the aluminum alloy can be obviously improved in the aluminum alloy, and the strength and the machining performance of the aluminum alloy can be improved. The higher the silicon content is, the more the eutectic structure is, the better the die-casting fluidity of the aluminum alloy is, but the larger the size of the silicon phase is, the toughness of the die-casting aluminum alloy can be reduced, and in order to ensure the fluidity and the high toughness of the die-casting aluminum alloy, the silicon element content needs to be within 7-10 wt.%.
The nickel element can not only obviously improve the flow property of the aluminum alloy, but also form a Ni-rich phase with stronger thermal stability, thereby improving the thermal stability of the aluminum alloy. However, too high a Ni content results in formation of a coarse Al3Ni phase, which results in a significant decrease in the toughness of the aluminum alloy, and the Ni content is limited to 1.5 wt.% or less in order to ensure the high toughness of the die-cast aluminum alloy.
Magnesium element is solid-dissolved in aluminum-silicon die-cast aluminum alloy to form solid-solution strengthening on one hand, and forms Mg with silicon on the other hand2Si strengthening phase, enhanced die castingThe higher the strength of the aluminum alloy, the higher the magnesium content, the higher the strength of the die-cast aluminum alloy, but the toughness will gradually decrease, and in order to ensure the strength and toughness of the die-cast aluminum alloy, the content range of the weight percentage of Mg may be limited to be within 0.6 wt.%.
The iron element obviously improves the anti-die-bonding performance of the die-casting aluminum alloy, but a small amount of iron can form coarse acicular beta-Al in the die-casting aluminum alloy5The FeSi phase seriously cracks the aluminum alloy matrix, so that the strength and toughness of the traditional die-casting aluminum alloy are low, and the content of Fe is controlled within 0.18 wt.%.
Manganese and chromium do not greatly affect the strength of die-cast aluminum alloys, but manganese and chromium will cause acicular beta-Al5Al with FeSi phase converted into block or Chinese character15(Mn,Cr,Fe)3Si2Thereby improving the toughness of the alloy. In addition, manganese and chromium elements can improve the die bonding property of the die-casting aluminum alloy. However, too high manganese and chromium elements can form large-size manganese-rich and chromium-rich phases, which affect the toughness of the alloy. Meanwhile, the addition of Cr and Mn can reduce the content of Mn, thereby ensuring the demolding performance and reducing the size of the AlFeMnCrSi phase, and further effectively improving the as-cast elongation. Typically, the manganese content is within 0.8 wt.% and the Cr content is within 0.3 wt.%.
The solid solubility of the zirconium element in an aluminum matrix is extremely low, and fine and stable Al can be preferentially precipitated during solidification3While Zr significantly improves the thermal stability of the alloy by pinning grain boundary movement at high temperatures, excessive addition of Zr results in coarse phase size and loss of the function as nucleation cores and pinning grain boundaries. The Zr content is limited to below 0.15 wt.% to ensure a thermal stabilizing effect.
The strontium element mainly plays a role in the die-casting aluminum alloy in changing a coarse and thin eutectic silicon phase into a short fiber shape, a short rod shape or a worm shape, and the strength and the toughness of the die-casting aluminum alloy are obviously improved. However, the increase of the strontium content increases the gettering ability of the alloy and increases the gas content in the alloy, so the strontium content can be limited to 0.005-0.03 wt.%, but the presence of boron causes strontium poisoning.
The solid solubility of titanium and boron elements in an aluminum matrix is extremely low, and fine and stable TiB can be preferentially precipitated during solidification2As a nucleation core of alpha-Al, the crystal grain size is refined, the uniformity of the structure is improved, but when the crystal grain size is added, boron and strontium elements are poisoned, so that the refining and modification effects disappear. When the titanium element is completely added in the form of pure titanium or titanium agent or aluminum-titanium intermediate alloy, the refining effect cannot be ensured, so that when a certain amount of titanium is added, a part of titanium and boron elements are added in the form of aluminum-titanium-carbon-boron intermediate alloy, the refining and modification effects can be ensured, and the addition amount of the aluminum-titanium-carbon-boron intermediate alloy is 0.3-0.8 wt% of the total weight of the melt.
The invention has the beneficial technical effects that: the invention provides a heat-treatment-free high-strength and high-toughness die-casting aluminum alloy and a preparation method thereof, which ensure that eutectic silicon has good modification effect while the grain size in the alloy is fine and uniform through a composite modification/refinement process, and avoid the strontium poisoning phenomenon. The die-casting aluminum alloy has good thermal stability, the mechanical property change is not more than 10% after the die-casting aluminum alloy is kept at the temperature of not more than 150 ℃ for 1000 hours, the die-casting aluminum alloy has excellent mechanical properties of die-casting yield strength of more than 120MPa and elongation of more than 14%, the performance requirements of a car body die-casting structural part can be met without subsequent heat treatment, the die-casting aluminum alloy is suitable for producing large thin-wall die-casting structural parts, the qualification rate of thin-wall die-casting structural part products can be greatly improved, and the use cost of automobile parts is reduced.
Detailed Description
The invention will be described in detail with reference to specific embodiments, illustrative embodiments and descriptions herein are provided to explain the invention, but the description is not intended to limit the invention, and any equivalent changes made according to the inventive concept, which are merely formal and insubstantial, should be considered within the scope of the invention.
Example 1
A heat treatment-free high-strength and high-toughness die-casting aluminum alloy belongs to an Al-Si-Mn-Mg-X alloy and comprises the following components in percentage by mass: 7.56 wt.% of Si, 1.5 wt.% of Ni, 0.59 wt.% of Mn, 0.05 wt.% of Mg, 0.1 wt.% of Cr, 0.05 wt.% of Zr, 0.1 wt.% of Ti, 0.011 wt.% of Sr, and the balance of aluminum and unavoidable impurities, wherein the content of Fe in the unavoidable impurities is 0.13 wt.%, the content of other individual impurity elements is less than or equal to 0.003 wt.%, and the total amount of other impurities is less than or equal to 0.01 wt.%. The second phase size is less than 20 μm.
(1) Firstly, preheating pure aluminum, aluminum-silicon intermediate alloy, aluminum-nickel intermediate alloy, manganese agent, aluminum-chromium intermediate alloy, aluminum-zirconium intermediate alloy, aluminum-titanium intermediate alloy, Al-10Sr intermediate alloy and pure magnesium to 200 ℃.
(2) Calculating the weight of each required raw material according to the expected alloy components, putting the pure aluminum processed in the step (1) into an industrial smelting furnace, heating to 760-780 ℃, adding a manganese agent, an aluminum-chromium intermediate alloy, an aluminum-zirconium intermediate alloy, an aluminum-titanium intermediate alloy, an aluminum-nickel intermediate alloy and an aluminum-silicon intermediate alloy, melting in the industrial smelting furnace, controlling the temperature to 740-750 ℃, and finally adding pure magnesium and stirring until the pure magnesium is completely melted to obtain an alloy melt;
(3) adding a deslagging agent, specifically a sodium-free refining agent, into the alloy melt obtained by the treatment in the step (2), wherein the weight of the deslagging agent accounts for 0.3 wt% of the total amount of the melt, and the temperature of the alloy melt is controlled at 730 ℃.
(4) And (3) carrying out component detection on the alloy melt obtained in the step (3), transferring the alloy melt into a slag ladle after the components are qualified, adding Al-10Sr intermediate alloy into the melt, wherein the weight of the intermediate alloy accounts for 0.13 wt% of the total amount of the melt, controlling the temperature of the alloy solution at 730-740 ℃, standing for 6min after stirring, ensuring that the intermediate alloy is fully melted, then adding an Al-Ti-C-B intermediate alloy wire rod, wherein the weight of the Al-Ti-C-B intermediate alloy wire rod accounts for 0.4 wt% of the total amount of the melt, and controlling the temperature of the alloy solution at 720-740 ℃.
(5) And (3) adding a sodium-free covering agent accounting for 0.07 wt.% of the melt into the melt obtained in the step (4) within 1min, and then directly introducing argon for refining and degassing, wherein the refining and degassing are carried out twice, the first time is 10 minutes, the second time is 5 minutes, the aeration pressure is 0.19MPa, and the temperature is controlled at 720-730 ℃.
(6) And (3) carrying out component detection, density detection and slag content detection on the melt obtained by refining, wherein the qualified standard of the melt is as follows: the density value of the components is 2.632g/cm within the design range3The modulus K is not higher than 0/20. Standing and cooling to 690 deg.C, and preparing standard tensile test bar by vacuum die casting process with vacuum degree of 30-50mbar and die casting temperature of680-700 ℃, the injection speed is 2m/s, and the casting pressure is 104 MPa.
Example 2
A heat treatment-free high-strength and high-toughness die-casting aluminum alloy belongs to an Al-Si-Mn-Mg-X alloy and comprises the following components in percentage by mass: 8.01 wt.% of Si, 1.25 wt.% of Ni, 0.63 wt.% of Mn, 0.1 wt.% of Mg, 0.12 wt.% of Cr, 0.15 wt.% of Zr, 0.07 wt.% of Ti, 0.015 wt.% of Sr, and the balance of aluminum and inevitable trace impurities, wherein the inevitable trace impurities comprise 0.11 wt.% of Fe, less than or equal to 0.003 wt.% of other single impurity elements, and less than or equal to 0.01 wt.% of other impurities. Ensuring that the second phase size is less than 20 μm.
(1) Firstly, electrolytic aluminum, instant silicon, pure nickel, aluminum-manganese intermediate alloy, pure magnesium, pure chromium, pure zirconium, pure titanium and Al-10Sr intermediate alloy are preheated to 185 ℃.
(2) Calculating the weight of each required raw material according to the expected alloy components, putting the electrolytic aluminum processed in the step (1) into an industrial smelting furnace, heating to 770-790 ℃, adding an aluminum-manganese intermediate alloy, pure chromium, pure zirconium, pure nickel, pure titanium and instant silicon, melting in the industrial smelting furnace, controlling the temperature at 750-770 ℃, adding pure magnesium, and stirring until the pure magnesium is completely melted to obtain an alloy melt.
(3) Adding a slag removing agent, specifically a sodium-free refining agent, into the melt obtained in the step (2), wherein the weight of the slag removing agent accounts for 0.2 wt% of the total weight of the melt, and the temperature of the alloy melt is controlled at 740 ℃.
(4) And (3) carrying out component detection on the melt obtained in the step (3), transferring the melt into a slag ladle after the components are qualified, adding an Al-10Sr intermediate alloy into the treated melt, wherein the weight of the intermediate alloy accounts for 0.15 wt% of the total amount of the melt, the temperature of the alloy solution is controlled to be 720-730 ℃, standing for 8min after stirring, ensuring that the intermediate alloy is fully melted, and then adding an Al-Ti-C-B intermediate alloy wire rod, the weight of the Al-Ti-C-B intermediate alloy wire rod accounts for 0.5 wt% of the total amount of the melt, and the temperature of the alloy solution is controlled to be 720-730 ℃.
(5) And (3) adding a covering agent accounting for 0.09 wt.% of the melt into the melt treated in the step (4) within 1.5min, and then directly introducing argon for refining and degassing, wherein the refining and degassing are carried out twice, the first time is 10 minutes, the second time is 5 minutes, the aeration pressure is 0.2MPa, and the temperature is controlled to be 720-730 ℃.
(6) And (3) carrying out component detection, gas content detection and slag content detection on the refined melt, wherein the qualified standard of the melt is as follows: the density value of the components is 2.643g/cm within the design range3The modulus K is not higher than 0/20. Standing and cooling to 700 ℃, and then casting into an alloy ingot to obtain the alloy expected by the embodiment. And then preparing a standard tensile test bar by a vacuum die casting process, wherein the vacuum degree is controlled to be 30-50mbar, the die casting temperature is 680-700 ℃, the injection speed is 2m/s, and the casting pressure is 104 MPa.
Example 3
A heat treatment-free high-strength and high-toughness die-casting aluminum alloy belongs to an Al-Si-Mn-Mg-X alloy and comprises the following components in percentage by mass: 8.94 wt.% of Si, 0.78 wt.% of Ni, 0.47 wt.% of Mn, 0.15 wt.% of Mg, 0.17 wt.% of Cr, 0.08 wt.% of Zr, 0.09 wt.% of Ti, 0.025 wt.% of Sr, and the balance of aluminum and inevitable trace impurities, wherein the inevitable trace impurities comprise 0.10 wt.% of Fe, less than or equal to 0.01 wt.% of other single impurity elements, and less than or equal to 0.1 wt.% of other impurities. Ensuring that the second phase size is less than 20 μm.
(1) Firstly, preheating pure aluminum, aluminum-silicon intermediate alloy, aluminum-nickel intermediate alloy, manganese agent, aluminum-chromium intermediate alloy, aluminum-zirconium intermediate alloy, aluminum-titanium intermediate alloy, pure magnesium and Al-10Sr intermediate alloy to 175 ℃.
(2) Calculating the weight of each required raw material according to the expected alloy components, putting the pure aluminum processed in the step (1) into an industrial smelting furnace, heating to 790-800 ℃, adding a manganese agent, an aluminum-nickel intermediate alloy, an aluminum-chromium intermediate alloy, an aluminum-zirconium intermediate alloy, an aluminum-titanium intermediate alloy and an aluminum-silicon intermediate alloy, melting in the industrial smelting furnace, controlling the temperature at 770-780 ℃, and then adding and stirring the pure magnesium until the pure magnesium is completely melted to obtain an alloy melt.
(3) Adding a slag removing agent, specifically a sodium-free refining agent, into the melt obtained in the step (2), wherein the weight of the slag removing agent accounts for 0.1 wt% of the total weight of the melt, and the temperature of the alloy melt is controlled at 750 ℃.
(4) And (4) detecting components of the melt obtained in the step (3), transferring the melt into a slag ladle after the components are qualified, adding Al-10Sr intermediate alloy into the treated melt, wherein the weight of the intermediate alloy accounts for 0.18 wt% of the total weight of the melt, the temperature of the alloy melt is controlled to be 730-740 ℃, stirring and standing for 7min to ensure that the intermediate alloy is fully melted, then adding an Al-Ti-C-B intermediate alloy wire rod, the weight of the Al-Ti-C-B intermediate alloy wire rod accounts for 0.6 wt% of the total weight of the melt, and the temperature of the alloy solution is controlled to be 720-740 ℃.
(5) Adding a sodium-free covering agent which accounts for 0.06 wt.% of the melt into the melt treated in the step (4) within 2min, and then directly introducing high-purity nitrogen for refining and degassing, wherein the refining and degassing are carried out twice, the first time is 10 minutes, the second time is 8 minutes, the aeration pressure is 0.18MPa, and the temperature is controlled at 720-730 ℃.
(6) And (3) carrying out component detection, gas content detection and slag content detection on the refined melt, wherein the qualified standard of the melt is as follows: the density value of the components is 2.611g/cm within the design range3The modulus K is not higher than 0/20. Standing and cooling to 710 ℃, and then preparing a standard tensile test bar by a vacuum die casting process, wherein the vacuum degree is controlled to be 30-50mbar, the die casting temperature is 680-700 ℃, the injection speed is 2m/s, and the casting pressure is 104 MPa.
Example 4
A heat treatment-free high-strength and high-toughness die-casting aluminum alloy belongs to Al-Si-Mn-Mg-X alloy and comprises the following components in percentage by mass: si 8.48 wt.%, Ni 0.05 wt.%, Mn 0.45 wt.%, Mg 0.19 wt.%, Cr 0.12 wt.%, Zr 0.07 wt.%, Ti 0.06 wt.%, Sr 0.011 wt.%, balance aluminum and unavoidable trace impurities, wherein the unavoidable trace impurities comprise Fe0.11 wt.%, the content of other individual impurity elements is less than or equal to 0.01 wt.%, and the total amount of other trace impurities is less than or equal to 0.1 wt.%. Ensuring that the second phase size is less than 20 μm.
(1) Firstly, preheating pure aluminum, aluminum-silicon intermediate alloy, manganese agent, pure chromium, pure zirconium, pure titanium, pure magnesium, aluminum-nickel intermediate alloy and Al-10Sr intermediate alloy to 190 ℃.
(2) Calculating the weight of each required raw material according to the expected alloy components, putting the pure aluminum processed in the step (1) into an industrial smelting furnace, heating to 790-800 ℃, adding a manganese agent, pure chromium, pure zirconium, pure titanium, an aluminum-nickel intermediate alloy and an aluminum-silicon intermediate alloy, melting in the industrial smelting furnace, controlling the temperature at 770-780 ℃, and then adding pure magnesium and stirring until the pure magnesium is completely melted to obtain an alloy melt.
(3) And (3) adding a deslagging agent, specifically a sodium-free refining agent, into the melt after the treatment of the step (2), wherein the weight of the deslagging agent accounts for 0.1 wt% of the total weight of the melt, and the temperature of the alloy melt is controlled at 730 ℃.
(4) And (3) detecting components of the melt processed in the step (3), transferring the melt into a slag ladle after the components are qualified, adding an Al-10Sr intermediate alloy into the processed melt, wherein the weight of the intermediate alloy accounts for 0.2 wt% of the total amount of the melt, the temperature of an alloy solution is controlled to be 730-740 ℃, stirring and standing for 10min to ensure that the intermediate alloy is fully melted, then adding an Al-Ti-C-B intermediate alloy wire rod, the weight of the Al-Ti-C-B intermediate alloy wire rod accounts for 0.6 wt% of the total amount of the melt, and the temperature of the alloy melt is controlled to be 720-740 ℃.
(5) Adding a sodium-free covering agent which accounts for 0.1 wt.% of the melt into the melt treated in the step (4) within 0.5min, directly introducing argon for refining and degassing, wherein the refining and degassing are carried out twice, the first time is 8min, the second time is 3 min, the aeration pressure is 0.25MPa, and the temperature is controlled at 720-730 ℃.
(6) And (3) carrying out component detection, gas content detection and slag content detection on the refined melt, wherein the qualified standard of the melt is as follows: the density value of the components is within the design range and is 2.619g/cm3The modulus K is not higher than 0/20. Standing and cooling to 700 ℃, and then preparing a standard tensile test bar by a vacuum die casting process, wherein the vacuum degree is controlled to be 30-50mbar, the die casting temperature is 680-700 ℃, the injection speed is 2m/s, and the casting pressure is 104 MPa.
Example 5
A heat treatment-free high-strength and high-toughness die-casting aluminum alloy belongs to an Al-Si-Mn-Mg-X alloy and comprises the following components in percentage by mass: 9.47 wt.% of Si, 0.81 wt.% of Ni, 0.53 wt.% of Mn, 0.1 wt.% of Mg, 0.11 wt.% of Cr, 0.05 wt.% of Zr, 0.07 wt.% of Ti, 0.015 wt.% of Sr, and the balance of aluminum and inevitable trace impurities, wherein the inevitable trace impurities comprise Fe0.11wt.%, the content of other single impurity elements is less than or equal to 0.003 wt.%, and the total amount of other trace impurities is less than or equal to 0.01 wt.%. Ensuring that the second phase size is less than 20 μm.
(1) Firstly, preheating pure aluminum, industrial silicon, an aluminum-nickel intermediate alloy, a manganese agent, an aluminum-chromium intermediate alloy, an aluminum-zirconium intermediate alloy, an aluminum-titanium intermediate alloy, pure magnesium and an Al-10Sr intermediate alloy to 150 ℃.
(2) Calculating the weight of each required raw material according to the expected alloy components, putting the pure aluminum processed in the step (1) into an industrial smelting furnace, heating to 770-790 ℃, adding a manganese agent, an aluminum-chromium intermediate alloy, an aluminum-zirconium intermediate alloy, an aluminum-titanium intermediate alloy, an aluminum-nickel intermediate alloy and industrial silicon, melting in the industrial smelting furnace, controlling the temperature to 750-760 ℃, and then adding pure magnesium and stirring until the pure magnesium is completely melted to obtain an alloy melt.
(3) Adding a deslagging agent, specifically a sodium-free refining agent, into the melt obtained in the step (2), wherein the weight of the deslagging agent accounts for 0.3 wt% of the total weight of the melt, and the temperature of the alloy melt is controlled at 740 ℃.
(4) And (3) detecting components of the melt processed in the step (3), transferring the melt into a slag ladle after the components are qualified, adding an Al-10Sr intermediate alloy into the processed melt, wherein the weight of the intermediate alloy accounts for 0.25 wt% of the total amount of the melt, the temperature of the alloy melt is controlled to be 730-740 ℃, stirring and standing for 8min to ensure that the intermediate alloy is fully melted, then adding an Al-Ti-C-B intermediate alloy wire rod, the weight of the Al-Ti-C-B intermediate alloy wire rod accounts for 0.7 wt% of the total amount of the melt, and the temperature of the alloy melt is controlled to be 720-740 ℃.
(5) Adding a sodium-free covering agent accounting for 0.08 wt.% of the melt into the melt treated in the step (4) within 2min, and then directly introducing high-purity nitrogen for refining and degassing, wherein the refining and degassing are carried out twice, the first time is 12 minutes, the second time is 5 minutes, the aeration pressure is 0.23MPa, and the temperature is controlled at 720-730 ℃.
(6) And (3) carrying out component detection, gas content detection and slag content detection on the refined melt, wherein the qualified standard of the melt is as follows: the density value of the components is within the design range and is 2.625g/cm3The modulus K is not higher than 0/20. Standing and cooling to 700 ℃, and then casting into an alloy ingot to obtain the alloy expected by the embodiment. And then preparing a standard tensile test bar by a vacuum die casting process, wherein the vacuum degree is controlled to be 30-50mbar, the die casting temperature is 680-700 ℃, the injection speed is 2m/s, and the casting pressure is 104 MPa.
Example 6
A heat treatment-free high-strength and high-toughness die-casting aluminum alloy belongs to an Al-Si-Mn-Mg-X alloy and comprises the following components in percentage by mass: si 8.17 wt.%, Ni 0.51 wt.%, Mn 0.43 wt.%, Mg 0.09 wt.%, Cr 0.13 wt.%, Zr 0.06 wt.%, Ti 0.07 wt.%, Sr 0.014 wt.%, balance aluminum and unavoidable trace impurities, wherein the content of fe0.1 wt.% in the trace impurities is unavoidable, the content of other individual impurity elements is 0.003 wt.% or less, and the total amount of other trace impurities is 0.01 wt.% or less. Ensuring that the second phase size is less than 20 μm.
(1) Firstly, preheating pure aluminum, aluminum-silicon intermediate alloy, aluminum-nickel intermediate alloy, manganese agent, aluminum-chromium intermediate alloy, aluminum-titanium intermediate alloy, pure zirconium, pure magnesium and Al-10Sr intermediate alloy to 190 ℃.
(2) Calculating the weight of each required raw material according to the expected alloy components, putting the pure aluminum processed in the step (1) into an industrial smelting furnace, heating to 770-780 ℃, adding a manganese agent, an aluminum-nickel intermediate alloy, an aluminum-chromium intermediate alloy, an aluminum-titanium intermediate alloy, pure zirconium and an aluminum-silicon intermediate alloy, melting in the industrial smelting furnace, controlling the temperature at 740-750 ℃, and then adding pure magnesium and stirring until the pure magnesium is completely melted to obtain an alloy melt.
(3) Adding a deslagging agent, specifically a sodium-free refining agent, into the melt processed in the step (2), wherein the weight of the deslagging agent accounts for 0.2 wt% of the total weight of the melt, and the temperature of the alloy melt is controlled at 740 ℃.
(4) And (4) detecting components of the melt processed in the step (3), transferring the melt into a slag ladle after the components are qualified, adding Al-10Sr intermediate alloy into the processed melt, wherein the weight of the Al-10Sr intermediate alloy accounts for 0.3 wt% of the total weight of the melt, the temperature of the alloy melt is controlled to be 730-740 ℃, stirring and standing for 6min to ensure that the intermediate alloy is fully melted, then adding an Al-Ti-C-B intermediate alloy wire rod, the weight of the Al-Ti-C-B intermediate alloy wire rod accounts for 0.7 wt% of the total weight of the melt, and the temperature of the alloy melt is controlled to be 720-740 ℃.
(5) Adding a sodium-free covering agent which accounts for 0.05 wt.% of the melt into the melt treated in the step (4) within 2min, and then directly introducing high-purity nitrogen for refining and degassing, wherein the refining and degassing are carried out twice, the first time is 8 minutes, the second time is 2 minutes, the aeration pressure is 0.24MPa, and the temperature is controlled at 720-730 ℃.
(6) And (3) carrying out component detection, gas content detection and slag content detection on the refined melt, wherein the qualified standard of the melt is as follows: the density value of the components is 2.623g/cm within the design range3The K modulus is not higher than 0/20. Standing and cooling to 705 ℃, and then casting into an alloy ingot to obtain the alloy expected by the embodiment. And preparing a standard tensile test bar by a vacuum die casting process, wherein the vacuum degree is controlled to be 30-50mbar, the die casting temperature is 680-700 ℃, the injection speed is 2m/s, and the casting pressure is 104 MPa.
The performance comparison ratio of the novel aluminum alloy die casting prepared by the invention and the mechanical properties of the common die casting aluminum alloy A380 and ADC12 die casting and the imported Silafant-36 aluminum alloy die casting for the current automobile structural part is shown in Table 1.
TABLE 1 mechanical properties of alloy die castings of different designations
Therefore, in the embodiment provided by the invention, the mechanical property change value of the die casting in a die casting state and after high-temperature treatment is 5-9 wt.%, the mechanical property change value can meet the requirements of a common high-strength and high-toughness structure die casting, and the thermal stability and the comprehensive mechanical property, particularly the elongation rate of the die casting are obviously higher than those of typical high-strength and high-toughness Silafant-36 aluminum alloy, Castasil-37 aluminum alloy and common die casting aluminum alloy.
In conclusion, aiming at the problems of poor strength and toughness, heat treatment requirement, poor thermal stability and the like of the existing Al-Si series alloy die casting, the invention researches a novel aluminum alloy with excellent thermal stability and high toughness, improves the mechanical property, especially the elongation rate of the casting in a die casting state on the premise of not increasing the cost, simultaneously has equivalent fluidity to that of the traditional die casting alloy, meets the requirements of the existing industrial production, can be quickly realized on the existing die casting production line, and does not need a large amount of investment.
While the present invention has been described by way of examples, and not by way of limitation, other variations of the disclosed embodiments, as would be readily apparent to one of skill in the art, are intended to be within the scope of the present invention, as defined by the claims.
Claims (14)
1. The heat-treatment-free high-strength and high-toughness die-casting aluminum alloy is characterized by comprising the following components in percentage by mass: 7.5-9.5 wt.% of Si, 0-1.5 wt.% of Ni, 0.4-0.8 wt.% of Mn, 0-0.4 wt.% of Mg, 0.08-0.3 wt.% of Cr, 0.01-0.15 wt.% of Zr, 0.03-0.1 wt.% of Ti, 0.005-0.025 wt.% of Sr, and the balance of aluminum and unavoidable impurity elements, wherein Fe in the unavoidable impurity elements is less than or equal to 0.18 wt.%, the content of other single impurity elements is less than or equal to 0.05 wt.%, and the total amount of other impurities is less than or equal to 0.3 wt.%.
2. The heat-treatment-free high-toughness die-casting aluminum alloy as claimed in claim 1, wherein the content ratio of Si/Ni is controlled to be not less than 7:1, the content ratio of Mn/Cr is 3: 1-4: 1, and the content ratio of Cr/Zr is 2: 1-3: 1.
3. The heat-treatment-free high-toughness die-cast aluminum alloy as recited in claim 1, wherein the size of the second phase is less than 20 μm.
4. The heat-treatment-free high-strength and high-toughness die-cast aluminum alloy as recited in claim 1, wherein the unavoidable impurity elements comprise Cu, V, P, Ca and Zn.
5. The heat-treatment-free high-toughness die-cast aluminum alloy as recited in claim 1, wherein the Mn is 0.4-0.6 wt.%, the Mg is 0.05-0.25 wt.%, the Cr is 0.08-0.25 wt.%, the Zr is 0.03-0.12 wt.%, and the Sr is 0.01-0.025 wt.%.
6. The heat-treatment-free high-strength and high-toughness die-cast aluminum alloy as claimed in claim 1, wherein the Ni is 0-1.2 wt.%, the Mn is 0.4-0.55 wt.%, the Mg is 0.05-0.20 wt.%, the Cr is 0.08-0.18 wt.%, the Zr is 0.03-0.12 wt.%, the Ti is 0.03-0.08 wt.%, the Sr is 0.01-0.02 wt.%, and the Fe is less than or equal to 0.15 wt.%, wherein the content ratio of Si/Ni is not less than 7:1, the content ratio of Mn/Cr is 3.5: 1-4: 1, the content ratio of Cr/Zr is 2.5: 1-3: 1, the content of other single impurity elements in unavoidable impurity elements is less than or equal to 0.03 wt.%, and the total content of other impurities is less than or equal to 0.2 wt.%.
7. The heat-treatment-free high-toughness die-cast aluminum alloy as claimed in claim 1, wherein the Si is 7.5-9.0 wt.%, the Ni is 0-1.2 wt.%, the Mn is 0.44-0.53 wt.%, the Mg is 0.05-0.20 wt.%, the Cr is 0.1-0.2 wt.%, the Zr is 0.05-0.12 wt.%, the Ti is 0.05-0.1 wt.%, the Sr is 0.01-0.02 wt.%, and the Fe is less than or equal to 0.12 wt.%, wherein the content ratio of Mn to Cr is 3.5: 1-4: 1, the content ratio of Cr to Zr is 2.5: 1-3: 1, the content of other single impurity elements in unavoidable impurity elements is less than or equal to 0.03 wt.%, and the total content of other impurities is less than or equal to 0.2 wt.%.
8. A method of making the aluminum alloy of any of claims 1-7, comprising:
(1) preheating raw materials of aluminum, silicon, nickel, manganese, Sr, chromium, zirconium, titanium and magnesium to 150-200 ℃;
(2) according to the component ratio, firstly putting the aluminum raw material obtained by the treatment in the step (1) into an industrial smelting furnace, heating to 760-800 ℃, then adding the manganese, chromium, zirconium, nickel, titanium and silicon raw materials into the smelting furnace to be melted, controlling the temperature to 740-780 ℃, and finally adding the magnesium raw material and stirring until the magnesium raw material is completely melted to obtain an alloy melt;
(3) adding a slag removing agent into the alloy melt obtained in the step (2), and controlling the temperature of the alloy melt at 730-750 ℃;
(4) detecting the alloy melt obtained in the step (3), adding a Sr raw material after the components are qualified, controlling the temperature of the alloy melt to be 720-740 ℃, stirring, standing for 5-10min, adding an aluminum-titanium-carbon-boron refiner, wherein the weight of the refiner accounts for 0.3-0.8 wt% of the total weight of the alloy melt, and controlling the temperature of the alloy melt to be 720-740 ℃;
(5) adding a covering agent into the alloy melt obtained in the step (4) within 0-2min, and then directly refining and degassing, wherein the time is ensured to be 5-20 minutes, and the temperature is controlled to be 720-730 ℃;
(6) and (3) carrying out component detection, density detection and slag content detection on the alloy melt obtained by refining, standing and cooling to 690-720 ℃ after the alloy melt is qualified, and thus obtaining the heat-treatment-free high-strength and high-toughness die-casting aluminum alloy.
9. The preparation method according to claim 8, wherein the aluminum raw material is pure aluminum or electrolytic aluminum, the silicon raw material is aluminum-silicon master alloy or industrial silicon or instant silicon, the nickel raw material is aluminum-nickel master alloy or pure nickel, the manganese raw material is aluminum-manganese master alloy or manganese agent, the Sr raw material is Al-10Sr master alloy, the chromium raw material is pure chromium or aluminum-chromium master alloy, the zirconium raw material is pure zirconium or aluminum-zirconium master alloy, the titanium raw material is pure titanium or titanium agent or aluminum-titanium master alloy, the aluminum-titanium-carbon-boron refiner is aluminum-titanium-carbon-boron master alloy wire rod, and the magnesium raw material is pure magnesium.
10. The preparation method according to claim 8, wherein the Sr raw material added in the step (4) accounts for 0.1-0.3 wt% of the total weight of the alloy melt, and the Al-Ti-C-B refiner accounts for 0.4-0.7 wt% of the total weight of the alloy melt.
11. The method according to claim 10, wherein the aluminum-titanium-carbon-boron refiner contains 4 to 6 wt.% of titanium, 0.09 to 0.1 wt.% of carbon, and 0.08 to 0.12 wt.% of boron.
12. The preparation method according to claim 8, wherein the weight of the added slag removing agent in the step (3) accounts for 0.1-0.3 wt.% of the total weight of the alloy melt, and the added slag removing agent is a sodium-free refining agent; and (3) the covering agent in the step (5) is a sodium-free covering agent, the adding amount is 0.05-0.1 wt.%, argon or high-purity nitrogen is introduced for refining and degassing, and the pressure is 0.18-0.25 MPa.
13. The preparation method according to claim 8, wherein the alloy melt qualification criteria of the step (6) is as follows: qualified components, density value not less than 2.61g/cm3The modulus K is not higher than 1/20.
14. The preparation method according to claim 8, wherein the obtained aluminum alloy can be made into a stressed structural member or chassis member for an automobile by a vacuum die-casting forming method.
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