CN113061791B - Magnesium alloy, magnesium alloy casting and manufacturing method thereof - Google Patents
Magnesium alloy, magnesium alloy casting and manufacturing method thereof Download PDFInfo
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- CN113061791B CN113061791B CN202110325593.9A CN202110325593A CN113061791B CN 113061791 B CN113061791 B CN 113061791B CN 202110325593 A CN202110325593 A CN 202110325593A CN 113061791 B CN113061791 B CN 113061791B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
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- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
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- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
Abstract
The invention belongs to the technical field of alloy casting, and provides a magnesium alloy, a magnesium alloy casting and a manufacturing method thereof, wherein the magnesium alloy comprises the following components in percentage by weight: 8 to 10 percent of Zn, 5.5 to 7 percent of Cu, 0.2 to 0.5 percent of Zr, 0.05 to 0.1 percent of Ce, and the balance of Mg and inevitable impurity elements. The invention also discloses a manufacturing method of the magnesium alloy casting, which comprises the following steps: the method comprises the following steps of alloy raw material proportioning, preheating, smelting, degassing, impurity removing and refining the raw materials to obtain a refined metal melt, pouring the metal melt into a metal die of an extruder, and obtaining a magnesium alloy casting product after extrusion molding, ultrasonic vibration, pressure maintaining, cooling and solidification. The magnesium alloy casting obtained by the manufacturing method has high thermal conductivity and lower thermal expansion coefficient, and is applied to the production of parts needing heat dissipation and low expansion.
Description
Technical Field
The invention belongs to the technical field of alloy casting, and particularly relates to a magnesium alloy, a magnesium alloy casting and a manufacturing method thereof.
Background
With the development of industries such as automobiles, aerospace, communication electronics and the like, the problem of heat dissipation of various devices and devices gradually becomes a key problem restricting the performance of products. Taking structural materials in the aerospace industry as an example, these structural materials are often magnesium alloys or aluminum alloys with high specific strength in order to meet the requirement of light weight. If these alloy components do not have good thermal conductivity to lower their temperature, they are highly susceptible to deformation under load and have a reduced service life. Therefore, there is a need to develop a new alloy material with low density, high specific strength and good thermal conductivity and a forming method thereof.
Magnesium alloy is the lightest metal structural material at present, has high specific strength and specific stiffness, high dimensional stability, good damping and shock-absorbing performance and convenient machining, and is known as a green engineering metal structural material in the 21 st century. Thermal conductivity is an important physical parameter for evaluating the heat conductivity of metal, and pure magnesium is used at room temperatureThe thermal conductivity is 158 W.m-1·K-1Second only to Al (237W · m) in common commercial metallic materials-1·K-1) And Cu (401 W.m)-1·K-1). The pure magnesium has a thermal expansion coefficient of 26X 10 at room temperature-6K-1The thermal expansion coefficient is higher than that of pure Al, but after alloying treatment, the magnesium alloy with high thermal conductivity and low expansion can be obtained.
The currently developed heat-conducting magnesium alloy is mainly Mg-Zn alloy, because the atomic radius of Zn atoms is similar to that of Mg atoms, the valence electron number is the same, and the heat-conducting capability of the matrix is minimally hindered. On the basis of the Mg-Zn binary alloy, the heat conduction capability of the magnesium alloy can be effectively improved by adding high heat conduction elements or rare earth elements, and other properties of the magnesium alloy are improved.
Chinese patent document CN102719716A discloses a heat-conducting magnesium alloy and a preparation method thereof, wherein the chemical components of the alloy are 1-7% of Zn, 0.1-3% of Ca, 0.1-3% of La, 0.1-3% of Ce and the balance of Mg. The thermal conductivity of the alloy is about 125 W.m at room temperature-1·K-1The yield strength is about 300MPa, and the tensile strength is about 340 MPa. The magnesium alloy has good heat-conducting property and strength, but the alloy has high cost due to the fact that the alloy contains a certain amount of rare earth elements, and the thermal expansion property is not considered.
Chinese patent document CN108486446A discloses a low-expansion magnesium alloy and a preparation method thereof, wherein the magnesium alloy comprises the following components: si: 3.2% -8.0%, Ce: 0.32-1.2%, Ca: 0.3% -0.8%, the rest is Mg and inevitable impurity elements, the thermal expansion coefficient of the magnesium alloy is less than 19.0 multiplied by 10-6K-1The thermal conductivity is 90 W.m-1·K-1Left and right. The magnesium alloy has low thermal expansion coefficient, is beneficial to being made into parts matched with other materials, but has low thermal conductivity and is not beneficial to heat dissipation.
In the prior disclosed heat-conducting magnesium alloy system, almost no magnesium alloy can simultaneously take heat conduction and expansion properties, processability, mechanical properties and cost into consideration.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a magnesium alloy and a magnesium alloy casting, and aims to solve the problem that the conventional magnesium alloy is difficult to combine heat conduction and expansion properties, processability, mechanical properties, cost and other aspects.
In order to achieve the purpose, the invention provides a magnesium alloy which comprises the following components in percentage by weight: 8 to 10 percent of Zn, 5.5 to 7 percent of Cu, 0.2 to 0.5 percent of Zr, 0.05 to 0.1 percent of Ce, and the balance of Mg and inevitable impurity elements.
In another aspect, the present invention provides a magnesium alloy casting comprising the above magnesium alloy.
Preferably, the magnesium alloy casting is formed by extrusion casting, and the heat conductivity at room temperature is more than 130 W.m-1·K-1Coefficient of thermal expansion of not more than 21.5X 10-6K-1。
Further preferably, the magnesium alloy casting has room temperature thermal conductivity of more than 144 W.m-1·K-1。
The invention also aims to provide a method for manufacturing the magnesium alloy casting, which aims to solve the problems of difficult forming, easy cracking and low toughness caused by the magnesium alloy casting with high mixed phase content.
In order to achieve the above object, the present invention provides a method for producing a magnesium alloy casting, comprising the steps of:
s1, preparing raw materials according to the weight percentage of the magnesium alloy components, wherein Zr and Ce are respectively added in the form of Mg-Zr and Mg-Ce intermediate alloy, Zn and Cu are added in the form of pure metal ingots, and the rest Mg is added in the form of pure metal ingots;
s2, preheating the prepared raw materials respectively;
s3, mixing and smelting the preheated raw materials into metal melt;
s4, blowing the metal melt by using inert gas, controlling the flow rate to make micro bubbles on the surface of the metal melt emerge, slagging off and standing to obtain refined metal melt;
and S5, pouring the refined metal melt into a preheated mold, closing the mold, extruding and filling the mold, maintaining the pressure, cooling, solidifying, opening the mold, ejecting the casting and demolding to obtain the magnesium alloy casting.
Preferably, in step S2, the preheating temperature is 150 ℃ to 200 ℃.
Preferably, the specific process of step S3 is: heating the preheated pure Mg ingot under the protection of protective gas until the pure Mg ingot is completely melted; continuously heating to 720-740 ℃, and adding the preheated pure Zn ingot and the Mg-Zr intermediate alloy; raising the temperature to 740-770 ℃, and adding the preheated pure Cu ingot; preserving the heat at 750-760 ℃ for 20-40 min, and adding preheated Mg-Ce intermediate alloy; stirring evenly and standing to obtain the metal melt.
Preferably, in the step S5, the casting temperature of the refined metal melt is 670-700 ℃, and the speed of the inner gate is 1.5-3 m/S.
Preferably, in step S5, the extrusion pressure is 100MPa to 220 MPa.
Preferably, in step S5, the dwell time is 1.0S/mm to 2.0S/mm of the average wall thickness of the magnesium alloy casting.
Preferably, in step S5, ultrasonic vibration processing is performed after the extrusion molding, and then pressure is maintained.
Further preferably, the ultrasonic vibration treatment process specifically includes: the ultrasonic tool head acts on a cushion block, then acts on the metal melt through the cushion block, the ultrasonic vibration frequency is 20kHz, and the ultrasonic power density is 5W/cm2～10W/cm2The ultrasonic vibration time is 10 s-20 s.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
(1) the invention provides a magnesium alloy, which is added with Zn and Cu elements, wherein the Zn element has a solid solution strengthening effect on an Mg matrix to generate MgZn2The thermal expansion coefficient of the alloy is small, so that the thermal expansion coefficient of the magnesium alloy can be reduced; cu belongs to high heat conduction elements, can effectively improve the heat conduction performance of the magnesium alloy, and can form a MgZnCu ternary phase with high heat conductivity with Mg and Zn; excessive Zn and Cu form a strengthening phase to be precipitatedAnd the mechanical property of the magnesium alloy is strengthened. Control of bimetallic phase (MgZn) by adjusting Zn/Cu ratio2Phase, MgZnCu phase) to achieve synchronous optimization of thermal conductivity and thermal expansion properties.
(2) A small amount of Zr and Ce is added into the magnesium alloy provided by the invention, so that the crystal grains of the magnesium alloy can be refined, the hot cracking tendency can be reduced, and the alloy strength can be improved.
(3) The invention also provides a manufacturing method of the magnesium alloy casting, which adopts extrusion casting technology, greatly refines the size of alloy crystal grains, and not only can improve the strength of the material, but also can improve the toughness of the material. Meanwhile, because high pressure is applied in the solidification process, the content of air holes in the material is reduced, and the mechanical property of the material is ensured by the high-density microstructure.
(4) The method for manufacturing the magnesium alloy casting provided by the invention applies ultrasonic vibration in the process of solidifying the molten metal, and can further refine crystal grains and refine intermetallic compounds by utilizing the cavitation effect and the acoustic flow effect of the ultrasonic vibration.
(5) The mixed phase (MgZn) in the metallographic structure of the part formed by extrusion casting of the magnesium alloy2Phase + MgZnCu phase) up to 20% to 25% by volume; the thermal conductivity reaches 146 W.m-1·K-1About 21.1X 10 in coefficient of thermal expansion at room temperature-6K-1Left and right; the yield strength is not less than 130MPa, the tensile strength is more than 200MPa, and the elongation after fracture is more than 8 percent. Can meet the requirements of a plurality of magnesium alloy structural parts requiring high heat conduction and low expansion coefficient.
Drawings
Fig. 1 is a sectional view of an extrusion casting mold, contents (a) being a sectional view of the mold at the time of extrusion molding and (b) being a sectional view of the mold at the time of ejection of a casting, wherein: 1-moving die, 2-metal melt, 3-fixed die, 4-ultrasonic tool head, 5-simple-shaped casting, 6-cushion block, 7-ejector rod, 8-connecting wire and 9-ultrasonic generator;
FIG. 2 is a metallographic structure of a Mg-8Zn-7Cu-0.5Zr-0.05Ce magnesium alloy casting produced in example 1 of the present invention;
FIG. 3 shows the metallographic structure of a Mg-10Zn-7Cu-0.4Zr-0.1Ce magnesium alloy casting produced by comparative example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The invention provides a magnesium alloy which comprises the following components in percentage by weight: 8 to 10 percent of Zn, 5.5 to 7 percent of Cu, 0.2 to 0.5 percent of Zr, 0.05 to 0.1 percent of Ce, and the balance of Mg and inevitable impurity elements.
The magnesium alloy provided by the invention is an Mg-Zn-Cu-Zr-Ce alloy, wherein the matrix phase is alpha-Mg, and the second phase is MgZn2And a MgZnCu dual intermetallic compound phase.
Zn in the magnesium alloy is a main strengthening element, plays a role in solid solution strengthening on an Mg matrix, and can improve the creep resistance of a casting. MgZn formed2The coefficient of thermal expansion of the alloy can be reduced because of the small coefficient of thermal expansion of the alloy. The redundant Zn and Cu form a strengthening phase to be separated out, so that the mechanical property of the alloy is strengthened. And the lattice distortion generated by Zn solid solution in Mg lattice is small, and the influence on the heat-conducting property of the magnesium alloy is small.
The magnesium alloy is added with the high-thermal-conductivity alloy element Cu so as to effectively improve the thermal conductivity of the magnesium alloy, and the Cu can form a MgZnCu ternary phase with Mg and Zn, so that the MgZnCu phase has high thermal conductivity, and simultaneously plays a role in strengthening the thermal conductivity and reducing the solid solution effect of Zn in a matrix.
A small amount of Zr and Ce is also added into the magnesium alloy. Zr is the most effective grain refiner in the magnesium alloy, Zr is added into the magnesium alloy, so that grains can be refined, the hot cracking tendency can be reduced, the strength, the plasticity and the creep resistance of the alloy are improved, and multiple experiments show that excessive Zr seriously damages the heat-conducting property of the magnesium alloy, so that the weight percentage of Zr is preferably controlled to be less than 0.5 percent. Meanwhile, Ce is used as a rare earth element and can modify the intermetallic compound phase, so that the intermetallic compound phase is distributed in a finer and more dispersed manner in the matrix, the effect of refining magnesium alloy grains is achieved, the hot cracking tendency and the micro-porosity of the magnesium alloy are reduced, and the creep resistance and the mechanical property of the magnesium alloy are improved.
The magnesium alloy provided by the invention consists of a matrix phase and a bimetal intermetallic compound phase, and the content of the bimetal intermetallic compound phase is controlled by reasonably adjusting the Zn/Cu ratio, so that the synchronous optimization of the heat conductivity and the thermal expansion performance is realized. MgZn in the alloy2The phase is C14 type Laves phase, and the thermal expansion coefficient at room temperature is less than that of pure magnesium; the MgZnCu phase is a cubic C15 type Laves phase, so that the plastic deformation capacity of the alloy is ensured, and the thermal conductivity of the alloy can be improved.
The invention also provides a magnesium alloy casting which is cast by the Mg-Zn-Cu-Zr-Ce alloy. The magnesium alloy casting has good thermal conductivity and low expansibility, is easy to process and good in forming effect, can be widely applied to the fields of automobile manufacturing, aerospace, communication, optical instruments, computer manufacturing and the like, and is particularly suitable for large, thin and near-net-shaped boxes, frames, wall plates, automobile bodies and other parts.
The magnesium alloy provided by the invention has higher content of alloy elements, so that the number of second phases is obviously increased, and practices show that the magnesium alloy with high content of mixed phases is difficult to form, easy to crack and low in toughness in the magnesium alloy casting process, so that the forming process technology of the magnesium alloy casting is optimized. The invention provides a method for manufacturing a magnesium alloy casting, which comprises the following steps:
s1, preparing raw materials according to the weight percentage of the components of the magnesium alloy provided by the invention, wherein Zr and Ce are respectively added in the form of Mg-Zr and Mg-Ce intermediate alloys, Zn and Cu are added in the form of pure metal ingots, and the rest Mg is added in the form of pure metal ingots;
s2, preheating the prepared raw materials respectively;
s3, mixing and smelting the preheated raw materials into metal melt;
s4, blowing the metal melt by using inert gas, controlling the flow rate to make micro bubbles on the surface of the metal melt emerge, slagging off and standing to obtain refined metal melt;
and S5, pouring the refined metal melt into a preheated mold, closing the mold, extruding and filling the mold, maintaining the pressure, cooling, solidifying, opening the mold, ejecting the casting and demolding to obtain the magnesium alloy casting.
The raw materials used in the method for manufacturing the magnesium alloy casting can be directly used in various pure metal ingots, but pure zirconium and pure cerium are expensive and are not easy to store, so magnesium-zirconium intermediate alloy and magnesium-cerium intermediate alloy are adopted, and other metals are pure metal ingots. The magnesium zirconium master alloy may be selected from various commercially available forms of alloys such as Mg-25Zr, Mg-30Zr, Mg-35Zr and Mg-40 Zr; the magnesium cerium alloy can also be selected from commercially available Mg-5Ce, Mg-20Ce and Mg-25 Ce.
In some embodiments, in step S2, the prepared raw materials are respectively placed into a resistance furnace to be preheated and dried, the preheating temperature is 150 ℃ to 200 ℃, so as to remove water molecules in air adsorbed on the surface of the furnace charge, prevent splashing and explosion when the furnace charge is added into the high-temperature magnesium alloy melt, and if the preheating temperature is too high, the furnace charge will be oxidized.
In some embodiments, the specific process of step S3 is: heating the preheated pure Mg ingot under the protection of protective gas until the pure Mg ingot is completely melted; continuously heating to 720-740 ℃, and adding the preheated pure Zn ingot and the Mg-Zr intermediate alloy; raising the temperature to 740-770 ℃, and adding the preheated pure Cu ingot; preserving the heat at 750-760 ℃ for 20-40 min, and adding preheated Mg-Ce intermediate alloy; stirring evenly, standing for at least 10min to obtain the metal melt.
In order to achieve a good magnesium alloy smelting effect, pure metals and intermediate alloys are not directly mixed for smelting, but are sequentially added into a smelting furnace at different temperatures according to the characteristics of different metals and intermediate alloys, so that all metal elements in a magnesium alloy melt are kept in the optimal state. The melting point, i.e. liquidus temperature, of metals and alloys is mainly considered, and the melting temperature should not be too high, so that oxidation or burning loss is easily caused.
In some embodiments, the shielding gas is N2And SF6Mixed gas of (2), wherein N2And SF6Is 99: 1. SF6Can be used as a good magnesium alloy protective gas, can generate a compact magnesium sulfide or fluoride film on the surface of magnesium liquid, and prevents the magnesium alloy from generating oxidation reaction with air.
In some embodiments, in step S4, the metal melt is blown with an inert gas at a flow rate controlled such that micro bubbles are blown out from the surface of the metal melt, and the blowing time is 10min to 20min, so as to remove dissolved gaseous impurities, such as hydrogen, in the metal melt; and then the slag removing spoon is used for removing solid impurities on the surface of the metal melt, so that the phenomenon that subsequent castings are difficult to form and easy to crack and influence the performance due to impurity components is prevented. And standing for at least 20min after slagging off to obtain refined metal melt. The inert gas is preferably high-purity argon, and other inert gases are expensive.
In some embodiments, in step S5, the refined metal melt is poured at a temperature of 670 ℃ to 700 ℃ and at an in-gate velocity of 1.5m/S to 3 m/S.
Alloy pouring temperature means the average temperature of the metal melt entering the cavity of the die from the pressure chamber. Aiming at castings with different shapes and structures, the pouring temperature of magnesium alloy during extrusion is controlled to be 670-700 ℃. For thin-wall castings, the pouring temperature can be higher so as to improve the fluidity of the metal melt and improve the extrusion forming capability; for thick-walled castings, lower temperatures can be used to reduce shrinkage cavities and porosity caused by solidification shrinkage. If the pouring temperature is too high, the oxidation of the metal melt is easily intensified, the oxidation impurities are mixed too much, the density and the plasticity of the magnesium alloy casting are reduced, and the cracking is easy; if the casting temperature is too low, the defects of cold shut, surface flow lines, insufficient casting and the like are easily generated.
The ingate velocity is the linear velocity of the metal melt entering the cavity through the ingate. The faster speed of the inner sprue enables the molten metal to quickly fill the cavity before solidification, so that a casting with clear outline and smooth surface is obtained, and the dynamic pressure of the molten metal is improved. When the casting is complicated in shape or thin-walled, the in-gate velocity should be faster. However, when the inner gate speed is too high, the gas is easily trapped to form bubbles, and the wear of the mold is easily accelerated.
In some embodiments, in step S5, the pressing pressure is 100MPa to 220 MPa.
In some embodiments, in step S5, after the metal melt fills the die cavity, the dwell time is 1.0S/mm to 2.0S/mm of the average wall thickness of the magnesium alloy casting.
The magnesium alloy casting manufacturing method provided by the invention adopts an extrusion casting process, reasonably controls the extrusion pressure and the pressure maintaining time in the magnesium alloy extrusion casting process, fully extrudes and fills the metal melt, greatly refines the alloy grain size, reduces the pore content in the melt, improves the density of the casting, ensures the stability of the forming effect, and reduces the possibility of cracking of the magnesium alloy casting.
In some embodiments, in step S5, ultrasonic vibration processing is performed after extrusion molding, and pressure is maintained after ultrasonic processing.
The invention utilizes ultrasonic waves to improve the metal solidification structure, changes the microstructure of the magnesium alloy and achieves the purpose of refining grains. Ultrasonic vibration of the metal melt produces cavitation effects, which are the primary reason for the ability to refine the metal microstructure. When ultrasonic vibration is applied to the metal melt, a sine change rule of alternating positive and negative high pressure can appear in the melt, and when the positive pressure part is adopted, liquid molecules in the melt are pressed, so that the density is increased; when the liquid molecules receive suction force in the negative pressure part, the density is reduced, so that the liquid molecules in the part are more and more sparse, and when the amplitude of ultrasonic vibration reaches a certain critical value, the liquid molecules can be broken, and a large number of fine dispersed bubbles are generated. These bubbles grow with time and continue to break into small bubbles as the pressure within the bubble reaches its critical point. The bubbles generate great pressure at the moment of bursting, so that intense impact is generated on nearby melt, namely the cavitation effect of ultrasonic waves.
At the same time, ultrasonic vibration also produces acoustic streaming effects. Ultrasonic waves are weakened more and more in the process of propagation due to factors such as scattering, diffusion and absorption, so that the pressure applied to liquid molecules is smaller and smaller from a sound source, and the pressure at the two positions is unequal to form pressure difference, so that the liquid is forced to flow at a high speed in the pressure gradient direction. When the metal melt is subjected to ultrasonic vibration treatment, when the pressure of ultrasonic reaches a certain critical value, jet flow can be generated in the melt; the jet forms an elliptical loop (from the ultrasonic horn) throughout the metal melt, which promotes phase distribution and temperature dispersion in the melt, and the phenomenon of liquid flow due to acoustic wave propagation is acoustic flow. The sound flow is a combination of the interaction of circular flow and turbulent flow, and can generate violent vibration and stirring action on the metal melt.
In some embodiments, the ultrasonic vibration treatment process is specifically: the ultrasonic tool head acts on a cushion block, then acts on the metal melt through the cushion block, the ultrasonic vibration frequency is 20kHz, and the ultrasonic power density is 5W/cm2～10W/cm2The ultrasonic vibration time is 10 s-20 s.
When the ultrasonic vibration is carried out on the metal melt, the ultrasonic tool head does not directly act on the metal melt, but indirectly acts on the metal melt through the cushion block of the steel, so that the ultrasonic tool head is prevented from being adhered to the high-temperature metal melt. The grains of the magnesium alloy are refined through ultrasonic vibration, and the second phase is changed into uniform and fine particles from an original coarse mesh.
The above technical solution is described in detail below with reference to specific examples.
Example 1
The embodiment discloses a two-phase mixed reinforced low-expansion high-heat-conductivity magnesium alloy which comprises the following chemical components in percentage by weight: 8% of Zn, 7% of Cu, 0.5% of Zr, 0.05% of Ce and the balance of Mg.
The manufacturing method of the casting comprises the following steps:
preparing the magnesium alloy according to the weight percentage of the components in the embodiment; wherein Zr and Ce are respectively added in the form of Mg-30Zr and Mg-20Ce intermediate alloys, Zn and Cu are added in the form of pure metal ingots, and the rest Mg is added in the form of pure metal ingots.
Drying and preheating the prepared metal or alloy at 150 ℃, wherein the preheating furnace is a resistance furnace.
In the smelting furnace, pure magnesium is firstly put into the smelting furnace to be N2And SF6The mixed protective gas (volume ratio is 99:1) is completely melted under the protection of the mixed protective gas. The temperature is continuously increased to 720 ℃, and Zn and Mg-30Zr alloy are added. The temperature was then raised to 740 ℃ and preheated pure copper was added.
Keeping the temperature of the melt at 760 ℃ for 20min, and adding Mg-20Ce intermediate alloy. And (3) standing the melt for 10min after uniformly stirring the melt, and then blowing Ar gas, wherein the flow rate is controlled to make micro bubbles on the surface of the melt emerge. Blowing for 10min, skimming after blowing, and standing for 20 min.
As shown in fig. 1, content (a), the metal mold is preheated to 200 c, and the molten metal 2 is poured into the preheated fixed mold 3 of the metal mold at a pouring temperature of 670 c. And starting the extruder to match the movable die 1 and the fixed die 3, extruding and filling, and controlling the speed of the magnesium alloy melt to be 1.5m/s through the inner pouring gate.
And starting the ultrasonic generator 9 to generate ultrasonic vibration after the mold filling is finished. The ultrasonic vibration wave is applied to the pad 6 through the ultrasonic tool head 4 and is applied to the metal melt 2 through the pad 6. The ultrasonic vibration frequency is 20kHz, and the ultrasonic power density is 5W/cm2And ultrasonic vibration time 10 s.
And then, removing the ultrasonic tool head 4, moving a mandril 7 of the extruder to the position below the cushion block as shown in the content (b) of the figure 1, continuously pressurizing the unset metal melt 2 by using the mandril 7, wherein the extrusion pressure is 100MPa, the pressure maintaining time is 1.0s/mm, then removing the pressure, moving the movable die 1 to open the die, and ejecting the casting 5 to obtain the high-heat-conductivity low-expansion magnesium alloy casting. FIG. 2 is a microscopic view of the metallographic structure of the magnesium alloy casting, in which the gray part is an alpha-Mg phase and the white part is a second phase (MgZn)2Mixed phase with MgZnCu), the second phase presents a fine granular or flake shape with uniform distribution.
Example 2
The embodiment discloses a two-phase mixed reinforced low-expansion high-heat-conductivity magnesium alloy which comprises the following chemical components in percentage by weight: 9% of Zn, 6% of Cu, 0.4% of Zr, 0.1% of Ce and the balance of Mg.
The manufacturing method of the casting comprises the following steps:
preparing the magnesium alloy according to the weight percentage of the components in the embodiment; wherein Zr and Ce are respectively added in the form of Mg-30Zr and Mg-20Ce intermediate alloys, Zn and Cu are added in the form of pure metal ingots, and the rest Mg is added in the form of pure metal ingots.
Drying and preheating the prepared metal or alloy at 200 ℃, wherein the preheating furnace is a resistance furnace.
In the smelting furnace, pure magnesium is firstly put into the smelting furnace to be N2And SF6The mixed protective gas (volume ratio is 99:1) is completely melted under the protection of the mixed protective gas. The temperature is continuously increased to 740 ℃, and Zn and Mg-30Zr alloy are added. The temperature is then raised to 760 ℃ and the preheated pure copper is added.
Keeping the temperature of the melt at 750 ℃ for 25min, and adding Mg-20Ce intermediate alloy. And (3) stirring the melt uniformly, standing for 20min, blowing Ar gas, and controlling the flow rate to make micro bubbles on the surface of the melt emerge. Blowing for 15min, skimming after blowing, and standing for 30 min.
Preheating the metal mold to 200 ℃, pouring the melt into the preheated metal mold, wherein the pouring temperature is 690 ℃. And (5) starting the extruder to mold, extruding and filling, and controlling the speed of the magnesium alloy melt to be 2.0m/s through the inner pouring gate.
And starting the ultrasonic generator to generate ultrasonic vibration after the mold filling is finished. The ultrasonic vibration wave acts on the cushion block through the ultrasonic tool head and acts on the metal melt through the cushion block. The ultrasonic vibration frequency is 20kHz, and the ultrasonic power density is 10W/cm2And the ultrasonic vibration time is 15 s.
And then moving the ultrasonic tool head away, moving an ejector rod of the extruder to the position below the cushion block, continuously pressurizing the unset metal melt by using the ejector rod, wherein the extrusion pressure is 150MPa, the pressure maintaining time is 1.6s/mm, then removing the pressure, moving the movable die to open the die, and ejecting the casting to obtain the high-heat-conductivity low-expansion magnesium alloy casting.
Example 3
The embodiment discloses a two-phase mixed reinforced low-expansion high-heat-conductivity magnesium alloy which comprises the following chemical components in percentage by weight: 10% of Zn, 5.5% of Cu, 0.2% of Zr, 0.07% of Ce and the balance of Mg.
The manufacturing method of the casting comprises the following steps:
preparing the magnesium alloy according to the weight percentage of the components in the embodiment; wherein Zr and Ce are respectively added in the form of Mg-30Zr and Mg-20Ce intermediate alloys, Zn and Cu are added in the form of pure metal ingots, and the rest Mg is added in the form of pure metal ingots.
Drying and preheating the prepared metal or alloy at 180 ℃, wherein the preheating furnace is a resistance furnace.
In the smelting furnace, pure magnesium is firstly put into the smelting furnace to be N2And SF6The mixed protective gas (volume ratio is 99:1) is completely melted under the protection of the mixed protective gas. The temperature is continuously increased to 730 ℃, and Zn and Mg-30Zr alloy are added. The temperature was then raised to 770 deg.C and preheated pure copper was added.
And (3) preserving the temperature of the melt at 760 ℃ for 30min, and adding Mg-20Ce intermediate alloy. And (3) stirring the melt uniformly, standing for 15min, blowing Ar gas, and controlling the flow rate to make micro bubbles on the surface of the melt emerge. Blowing for 20min, skimming after blowing, and standing for 20 min.
Preheating a metal mold to 200 ℃, pouring melt into the preheated metal mold, wherein the pouring temperature is 700 ℃. And (5) starting the extruder to mold, extruding and filling, and controlling the speed of the magnesium alloy melt to be 2.5m/s through the inner pouring gate.
And starting the ultrasonic generator to generate ultrasonic vibration after the mold filling is finished. The ultrasonic vibration wave acts on the cushion block through the ultrasonic tool head and acts on the metal melt through the cushion block. The ultrasonic vibration frequency is 20kHz, and the ultrasonic power density is 8W/cm2And ultrasonic vibration time is 20 s.
And then moving the ultrasonic tool head away, moving an ejector rod of the extruder to the position below the cushion block, continuously pressurizing the unset metal melt by using the ejector rod, wherein the extrusion pressure is 200MPa, the pressure maintaining time is 2.0s/mm, then removing the pressure, moving the movable die to open the die, and ejecting the casting to obtain the high-heat-conductivity low-expansion magnesium alloy casting.
Example 4
The embodiment discloses a two-phase mixed reinforced low-expansion high-heat-conductivity magnesium alloy which comprises the following chemical components in percentage by weight: 10% Zn, 7% Cu, 0.4% Zr, 0.1% Ce, and the balance Mg.
The manufacturing method of the casting comprises the following steps:
preparing the magnesium alloy according to the weight percentage of the components in the embodiment; wherein Zr and Ce are respectively added in the form of Mg-30Zr and Mg-20Ce intermediate alloys, Zn and Cu are added in the form of pure metal ingots, and the rest Mg is added in the form of pure metal ingots.
Drying and preheating the prepared metal or alloy at 200 ℃, wherein the preheating furnace is a resistance furnace.
In the smelting furnace, pure magnesium is firstly put into the smelting furnace to be N2And SF6The mixed protective gas (volume ratio is 99:1) is completely melted under the protection of the mixed protective gas. The temperature is continuously increased to 730 ℃, and Zn and Mg-30Zr alloy are added. The temperature is then raised to 760 ℃ and the preheated pure copper is added.
And (3) preserving the temperature of the melt at 760 ℃ for 40min, and adding Mg-20Ce intermediate alloy. And (3) standing the melt for 10min after uniformly stirring the melt, and then blowing Ar gas, wherein the flow rate is controlled to make micro bubbles on the surface of the melt emerge. Blowing for 10min, skimming after blowing, and standing for 30 min.
Preheating a metal mold to 200 ℃, pouring melt into the preheated metal mold, wherein the pouring temperature is 700 ℃. And (5) starting an extruder to mold, extruding and filling, and controlling the speed of the magnesium alloy melt to be 3.0m/s through the inner gate.
And starting the ultrasonic generator to generate ultrasonic vibration after the mold filling is finished. The ultrasonic vibration wave acts on the cushion block through the ultrasonic tool head and acts on the metal melt through the cushion block. The ultrasonic vibration frequency is 20kHz, and the ultrasonic power density is 10W/cm2And ultrasonic vibration time is 20 s.
And then moving the ultrasonic tool head away, moving an ejector rod of the extruder to the position below the cushion block, continuously pressurizing the unset metal melt by using the ejector rod, wherein the extrusion pressure is 220MPa, the pressure maintaining time is 1.6s/mm, then removing the pressure, moving the movable die to open the die, and ejecting the casting to obtain the high-heat-conductivity low-expansion magnesium alloy casting.
Example 5
The embodiment discloses a two-phase mixed reinforced low-expansion high-heat-conductivity magnesium alloy which comprises the following chemical components in percentage by weight: 10% Zn, 7% Cu, 0.4% Zr, 0.1% Ce, and the balance Mg.
The manufacturing method of the casting comprises the following steps:
preparing the magnesium alloy according to the weight percentage of the components in the embodiment; wherein Zr and Ce are respectively added in the form of Mg-30Zr and Mg-20Ce intermediate alloys, Zn and Cu are added in the form of pure metal ingots, and the rest Mg is added in the form of pure metal ingots.
Drying and preheating the prepared metal or alloy at 200 ℃, wherein the preheating furnace is a resistance furnace.
In the smelting furnace, pure magnesium is firstly put into the smelting furnace to be N2And SF6The mixed protective gas (volume ratio is 99:1) is completely melted under the protection of the mixed protective gas. The temperature is continuously increased to 730 ℃, and Zn and Mg-30Zr alloy are added. Then the temperature is raised to 760 ℃, and the preheated pure copper is added.
And (3) preserving the temperature of the melt at 760 ℃ for 40min, and adding Mg-20Ce intermediate alloy. And (3) standing the melt for 10min after uniformly stirring the melt, and then blowing Ar gas, wherein the flow rate is controlled to make micro bubbles on the surface of the melt emerge. Blowing for 10min, skimming after blowing, and standing for 30 min.
Preheating a metal mold to 200 ℃, pouring melt into the preheated metal mold, wherein the pouring temperature is 700 ℃. And (5) starting an extruder to mold, extruding and filling, and controlling the speed of the magnesium alloy melt to be 3.0m/s through the inner gate.
And continuously pressurizing the unset metal melt by using a push rod of the extruder, wherein the extrusion pressure is 220MPa, the pressure maintaining time is 1.6s/mm, then removing the pressure, moving the movable die to open the die, and ejecting the casting to obtain the high-heat-conductivity low-expansion magnesium alloy casting.
Comparative example 1
The comparative example discloses a magnesium alloy which comprises the following chemical components in percentage by weight: 10% Zn, 7% Cu, 0.4% Zr, 0.1% Ce, and the balance Mg.
The manufacturing method of the casting comprises the following steps:
preparing the magnesium alloy according to the weight percentage of the components of the magnesium alloy in the comparative example; wherein Zr and Ce are respectively added in the form of Mg-30Zr and Mg-20Ce intermediate alloys, Zn and Cu are added in the form of pure metal ingots, and the rest Mg is added in the form of pure metal ingots.
Drying and preheating the prepared metal or alloy at 200 ℃, wherein the preheating furnace is a resistance furnace.
In the smelting furnace, pure magnesium is firstly put into the smelting furnace to be N2And SF6The mixed protective gas (volume ratio is 99:1) is completely melted under the protection of the mixed protective gas. The temperature is continuously increased to 730 ℃, and Zn and Mg-30Zr alloy are added. The temperature is then raised to 760 ℃ and the preheated pure copper is added.
And (3) preserving the temperature of the melt at 760 ℃ for 40min, and adding Mg-20Ce intermediate alloy. And (3) standing the melt for 10min after uniformly stirring the melt, and then blowing Ar gas, wherein the flow rate is controlled to make micro bubbles on the surface of the melt emerge. Blowing for 10min, skimming after blowing, and standing for 30 min.
Preheating a gravity metal mold to 200 ℃, after closing the mold, pouring the melt into the preheated metal mold by gravity, wherein the pouring temperature is 700 ℃. And after the magnesium alloy melt is cooled and solidified, opening the die and ejecting out the casting to obtain the magnesium alloy casting. FIG. 3 is a microscopic view of the metallographic structure of the magnesium alloy casting, in which the gray portion is an alpha-Mg phase and the white portion is a second phase (MgZn)2Mixed phase with MgZnCu), the second phase is in a coarse network.
Comparative example 2
The comparative example discloses a magnesium alloy which comprises the following chemical components in percentage by weight: 9% of Zn, 6% of Cu, 0.4% of Zr, 0.1% of Ce and the balance of Mg.
The manufacturing method of the casting comprises the following steps:
preparing the magnesium alloy according to the weight percentage of the components of the magnesium alloy in the comparative example; wherein Zr and Ce are respectively added in the form of Mg-30Zr and Mg-20Ce intermediate alloys, Zn and Cu are added in the form of pure metal ingots, and the rest Mg is added in the form of pure metal ingots.
Drying and preheating the prepared metal or alloy at 200 ℃, wherein the preheating furnace is a resistance furnace.
In the smelting furnace, pure magnesium is firstly put into the smelting furnace to be N2And SF6The mixed protective gas (volume ratio is 99:1) is completely melted under the protection of the mixed protective gas. The temperature is continuously increased to 740 ℃, and Zn and Mg-30Zr alloy are added. The temperature is then raised to 760 ℃ and the preheated pure copper is added.
Keeping the temperature of the melt at 750 ℃ for 25min, and adding Mg-20Ce intermediate alloy. And (3) stirring the melt uniformly, standing for 20min, blowing Ar gas, and controlling the flow rate to make micro bubbles on the surface of the melt emerge. Blowing for 15min, removing slag after blowing, and standing for 30 min.
Preheating a gravity metal mold to 200 ℃, after closing the mold, pouring the melt into the preheated metal mold by gravity, wherein the pouring temperature is 690 ℃. And opening the mould after the magnesium alloy melt is cooled and solidified, and ejecting the casting to obtain the magnesium alloy casting.
The results of the room temperature property test of the magnesium alloy castings manufactured in examples 1 to 5 and comparative examples 1 to 2 are shown in table 1.
TABLE 1 test results of Room temperature Properties of magnesium alloy castings manufactured in examples 1 to 5 and comparative examples 1 to 2
As can be seen from table 1, the magnesium alloy squeeze cast parts of examples 1 to 5 of the present invention are significantly superior in each performance to the gravity cast parts of comparative examples 1 to 2, and the magnesium alloy castings of examples 1 to 4 manufactured by squeeze casting in combination with the ultrasonic vibration process are also superior in performance to magnesium alloy castings of pure squeeze casting. The heat conductivity at room temperature of the magnesium alloy casting manufactured by the invention is more than 130 W.m-1·K-1No more than 21.5X 10 Coefficient of Thermal Expansion (CTE)-6K-1The tensile strength at room temperature is not less than 180MPa, and the elongation is more than 5%. More preferably, the magnesium alloy castings have room temperature thermal conductivities of more than 144 W.m-1·K-1No more than 21.5X 10 Coefficient of Thermal Expansion (CTE)-6K-1The tensile strength at room temperature is more than 200MPa, and the elongation is more than 8%.
The magnesium alloy has high heat conductivity and good mechanical property, and can meet the requirements of industrial production. Meanwhile, the extrusion casting technology used by the invention strengthens the mechanical property of the material without damaging the heat-conducting property of the material, has good processing and forming effects and has practical application value.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (2)
1. The magnesium alloy is characterized by comprising the following components in percentage by weight: 8% -10% of Zn, 5.5% -7% of Cu, 0.2% -0.5% of Zr, 0.05% -0.1% of Ce, and the balance of Mg and inevitable impurity elements;
the manufacturing method of the magnesium alloy comprises the following steps:
s1, preparing raw materials according to the weight percentage of the magnesium alloy components, wherein Zr and Ce are respectively added in the form of Mg-Zr and Mg-Ce intermediate alloy, Zn and Cu are added in the form of pure metal ingots, and the rest Mg is added in the form of pure metal ingots;
s2, preheating various prepared raw materials respectively, wherein the preheating temperature is 150-200 ℃;
s3, heating the preheated pure Mg ingot under the protection of protective gas until the pure Mg ingot is completely melted; continuously heating to 720-740 ℃, and adding the preheated pure Zn ingot and the Mg-Zr intermediate alloy; raising the temperature to 740-770 ℃, and adding the preheated pure Cu ingot; preserving the heat at 750-760 ℃ for 20-40 min, and adding preheated Mg-Ce intermediate alloy; stirring uniformly, standing to obtain a metal melt;
s4, blowing the metal melt by using inert gas, controlling the flow rate to make micro bubbles on the surface of the metal melt emerge, slagging off and standing to obtain refined metal melt;
S5、pouring the refined metal melt into a preheated die, wherein the pouring temperature is 670-700 ℃, the speed of an inner pouring gate is 1.5-3 m/s, closing the die, extruding and filling the die, acting an ultrasonic tool head on a cushion block after the filling is finished, and then acting the refined metal melt through the cushion block to carry out ultrasonic vibration treatment on the refined metal melt, wherein the ultrasonic vibration frequency is 20kHz, and the ultrasonic power density is 5W/cm2~10W/cm2And keeping the pressure for 10-20 s of ultrasonic vibration, wherein the extrusion pressure is 100-220 MPa, the pressure keeping time is 1.0-2.0 s/mm of the average wall thickness of the magnesium alloy casting, and after cooling and solidification, opening the die, ejecting and demolding to obtain the magnesium alloy.
2. A magnesium alloy casting is characterized in that: the magnesium alloy casting comprises the magnesium alloy according to claim 1.
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