CN108500239B - Magnesium-copper composite casting material and preparation method thereof - Google Patents
Magnesium-copper composite casting material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a magnesium-copper composite casting material and a preparation method thereof, belonging to the field of alloy materials. The composite material comprises two components of magnesium alloy and copper alloy, which are metallurgically bonded together by casting, two layered structures are formed at the interface, the thickness of a sub-layer structure close to the copper side is relatively thin, is about 10-50 mu m, and is mainlyIs Mg2Cu phase, on which some MgCu dendritic phase is distributed, the sub-layer structure near to magnesium is about 100-200 μm, and is uniformly distributed in network form, and it is mainly Mg-Mg2A Cu eutectic phase. The magnesium-copper composite material is prepared by taking a copper alloy bar as a casting core and pouring a magnesium alloy as a melt into the copper core and then cooling the copper core by circulating water, maintains some excellent electric conduction and heat conduction properties and light weight and high strength properties of the copper alloy and the magnesium alloy, and simultaneously forms large potential difference between the magnesium alloy and the copper alloy to form galvanic corrosion, thereby accelerating the degradation of the magnesium alloy and the copper alloy more quickly. The magnesium-copper composite material is expected to be applied to the fields of aerospace, petroleum metallurgy and the like.
Description
Technical Field
The invention belongs to the field of alloy materials, and particularly relates to a magnesium-copper composite casting material and a preparation method thereof.
Technical Field
Magnesium alloy has received attention from many researchers because of its high degradation rate, and particularly in the field of biomedical science, magnesium alloy has emerged as a biodegradable biomaterial and has a hot research trend. Moreover, by utilizing the extremely active chemical property of the magnesium alloy, the magnesium alloy degradable material can also be applied to some specific engineering environments, such as self-decomposition fracturing balls in petroleum fracturing.
The addition of some alloy elements capable of reducing the corrosion resistance of magnesium alloys to accelerate the degradation of magnesium alloys is a major direction of current research. Research shows that when the concentration of Fe, Ni and Cu is lower than 0.2%, the corrosion of magnesium alloy is accelerated obviously, the solubility of Ni, Cu and the like in magnesium is extremely low, and Mg is formed by the Ni, Cu and the like and magnesium2Ni、Mg2Cu and other intermetallic compounds to reduce the corrosion resistance of magnesium [ Hanawalt J D, Nelson C E, Peloube J A. corosion students of magnesium and its alloys. trans. AIME,147(1942):273-]. However, the solubility of impurity elements in magnesium alloys is very limited, so that the corrosion rate of magnesium alloys is still extremely limited, although the formation of intermetallic compounds can reduce their corrosion performance. If two alloys with large potential difference are connected, the corrosion rate of the metal with low potential is greatly accelerated. The standard electrode potential of copper is+0.34V, much higher than the standard electrode potential of magnesium-2.37V. Magnesium and copper are connected together to form a composite material, galvanic corrosion is formed on the premise of ensuring light weight and high strength, and therefore the corrosion rate of the magnesium alloy is greatly improved.
For Mg/Cu composite materials, much research is not available at present, and the hydrogen storage performance is mainly researched. JianhongDai et al studied the diffusion kinetics of the Mg-Cu binary system, observed the solid-solid interface reaction at 673K, 703K and 733K for 24-72h, and found that two intermediate MgCu layers are formed between the Mg and Cu substrates2And Mg2Cu, and Mg2Cu interlayer to MgCu2Much thicker intermediate layer [ Jianhong Dai, Bin Jiang, Jianyue Zhang, Qingshan Yang, Zhongtao Jiang, Hanwu Dong, and Fusheng Pan. Diffusion Kinetics in Mg-Cu Binary System. journal of Phase Equilibria and Diffusion:36,6(2015)613-]. Koji Tanaka et al produced a Hydrogen storage material for Mg/Cu super thin sheets by 20-pass cumulative rolling [ Koji Tanaka, Daiji Nishino, Kousei Hayashi, Shuki Ikeuchi, Ryota Kondo, Hiroyuki T.Takeshita.Formation of Mg2Cu at low temperature reaction in Mg/Cu super-laminate compositions with heating reaction.International Journal of Hydrogen Energy (2017): 1-9]. However, since Cu has much better ductility than Mg, cracking is easily caused during rolling, the reduction per time must be strictly controlled, and the number of rolling passes is too many, which makes the process complicated. Therefore, the research adopts a novel solid-liquid composite casting method, copper is used as a casting core, magnesium is used as a melting matrix, and the Mg/Cu casting composite material is manufactured, so that the material can achieve light weight and high strength, and can be rapidly decomposed in the electrolyte environment. The method has important application value in the engineering field that certain structural strength is needed in the early stage and rapid degradation is needed in the later stage.
Disclosure of Invention
Aiming at the technical problems, the invention provides a magnesium-copper composite casting material which has the characteristics of high strength, good electric and heat conducting properties, rapid degradation and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the magnesium-copper composite casting material is characterized in that: the magnesium-copper composite casting alloy takes magnesium alloy and copper alloy as components, and an interface bonding layer forms two sublayer structures.
The thickness of a sublayer structure of the magnesium-copper composite casting alloy interface layer close to the copper side is relatively thin and is about 10-50 mu m, and the main component of the sublayer structure is Mg2Cu phase, which is distributed with dendritic phase, the sub-layer structure near the magnesium is about 120-180 μm and is distributed in uniform network, and the main component is Mg-Mg2A Cu eutectic phase.
The magnesium alloy comprises pure magnesium series, AZ (Mg-Al-Zn-Mn) series, AM (Mg-Al-Mn) series, AS (Mg-Al-Si) series, AE (Mg-Al-RE) series, Mg-Y-Zn, Mg-Gd-Y-Zr alloy series, binary alloy systems such AS Mg-Ca, Mg-Zn, Mg-Sr, Mg-Si, Mg-Li, Mg-Mn and Mg-RE and ternary and multicomponent alloy systems such AS Mg-Zn-Ca and Mg-Zn-Ca-X (X ═ Mn, Sn, Sr and RE).
The copper alloy comprises a pure copper series, a high copper alloy series, a brass (mainly comprising Cu-Zn, Cu-Zn-Pb, Cu-Zn-Sn, Cu-Zn-Si and the like) alloy series, a bronze (Cu-Sn-P, Cu-Sn-Pb-P, Cu-Al, Cu-Si, Cu-Sn-Pb, Cu-Sn-Ni, Cu-Al and the like) alloy series, a copper-nickel-zinc alloy series, a copper-lead alloy series and other special copper alloy series.
The hardness value of the magnesium-copper composite material is distributed in a step form from copper to magnesium, and the hardness of the intermediate layer is obviously higher than that of the matrix.
The invention determines the specific component brands of the magnesium alloy and the copper alloy and the preparation process of the composite material according to the service conditions of the magnesium-copper composite material structural member.
The method comprises the following process steps:
the first step is as follows: machining the solid copper alloy to obtain a required material pattern, polishing the surface of the copper alloy by using abrasive paper, and chemically cleaning to remove surface oxides and oil stains to obtain the copper alloy with ideal roughness and smooth surface;
the second step is that: preheating the prefabricated solid copper alloy, wherein the preheating temperature is generally 50-300 ℃;
the third step: smelting a magnesium alloy ingot in a low-carbon steel crucible by using a well-type resistance furnace, wherein sulfur hexafluoride and carbon dioxide mixed gas is required to be protected until the magnesium alloy ingot is completely molten;
the fourth step: after the temperature of the magnesium alloy melt is stable, pouring the magnesium alloy melt into a mold filled with the solid copper alloy which is well pretreated, and blowing CO in the pouring process2As protective gas, and is cooled by circulating water;
the fifth step: and after the pouring is finished, continuously introducing circulating water for cooling to a certain temperature, taking out, and carrying out air cooling to obtain the magnesium-copper composite casting material.
In the preparation process steps of the magnesium-copper composite material, the material style in the first step is different according to the required mechanical property and corrosion rate and the required volume ratio of magnesium to copper.
In the preparation process of the magnesium-copper composite material, the melting temperature of the magnesium alloy in the third step is generally 20-50 ℃ above the liquidus and is 670-700 ℃.
In the preparation process of the magnesium-copper composite material, the stable temperature of the magnesium alloy melt in the fourth step is generally between the solidus temperature and the liquidus temperature of the melt, and is 420-650 ℃.
The preparation process of the magnesium-copper composite casting material is characterized by comprising the following steps of: fifthly, circulating water is introduced for cooling until the temperature is 70-200 ℃.
According to the invention, by adopting a solid-liquid composite casting method, the magnesium alloy is used as a matrix melt, the copper alloy is used as a casting core, the magnesium-copper composite material is successfully prepared, the magnesium-copper composite material has good mechanical property and electric and heat conduction properties, and can be rapidly degraded by forming galvanic corrosion under the electrolyte condition.
Drawings
FIG. 1 is an SEM micrograph of a pure Mg/pure Cu composite prepared in example 1 of the present invention (a) and an enlarged view of the interface layer (b, c);
FIG. 2 is a hardness distribution curve of a pure Mg/pure Cu composite material prepared in example 1 of the present invention;
FIG. 3 is an SEM micrograph of AZ 31/pure Cu composite prepared according to example 2 of the present invention.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific embodiments.
Example 1
The pure magnesium-coated pure copper composite material and the preparation method thereof comprise the following steps:
the first step is as follows: machining a pure copper rod to obtain a diameter
Polishing the bar by using 100# and 240# coarse abrasive paper, primarily removing surface oxides and oil stains to enable scratches polished by the abrasive paper to be uniform, then ultrasonically cleaning the bar by using acetone, immediately drying the bar by using cold air after cleaning the bar by using alcohol, and enabling the surface of the pure copper to be smooth;
the second step is that: the prefabricated pure copper bar is directly cast at room temperature without preheating treatment;
the third step: smelting a pure magnesium ingot in a low-carbon steel crucible by using a well-type resistance furnace, wherein the melting temperature is 680 ℃, and the mixed gas of sulfur hexafluoride and carbon dioxide is required to protect the pure magnesium ingot during the melting period until the pure magnesium ingot is completely melted;
the fourth step: after the temperature of the pure magnesium melt is stabilized at 640 ℃, pouring the pure magnesium melt into a mould filled with a pretreated pure copper rod, and blowing CO in the pouring process2As protective gas, and is cooled by circulating water;
the fifth step: and after the pouring is finished, continuously introducing circulating water for cooling to 100 ℃, and taking out for air cooling to obtain the pure Mg/pure Cu composite casting material.
The microstructure morphology of the interface of the pure Mg/pure Cu composite casting material is shown in figure 1, the interface is divided into 2 sub-layers with the thicknesses of 30 mu m and 140 mu m respectively, and (b) and (c) are respectively the microstructure enlargement images of a first sub-layer and a second sub-layer, wherein Mg is mainly arranged on the first sub-layer2Cu phase with branch-shaped MgCu phase, and second sub-layer with network structure and Mg-Mg phase2A Cu eutectic phase. Fig. 2 is a plot of the pure Mg/pure Cu composite casting hardness profile, and it can be seen that the intermediate sub-layer hardness is much higher than the matrix, with the first sub-layer hardness exceeding 300Hv and the second sub-layer exceeding 150 Hv. And the hardness curve is in gradient distribution.
Example 2
The AZ31 coated pure copper composite material and the preparation method thereof comprise the following steps:
the AZ31 comprises the following components in percentage by weight: 3.4 percent of Al, 0.9 percent of Zn, and the balance of Mg and inevitable impurities of Si, Cu, Ca, Fe and Ni less than 0.2 percent.
The first step is as follows: machining a pure copper rod to obtain a diameter
Polishing the bar by using 100# and 240# coarse abrasive paper, primarily removing surface oxides and oil stains to enable scratches polished by the abrasive paper to be uniform, then ultrasonically cleaning the bar by using acetone, immediately drying the bar by using cold air after cleaning the bar by using alcohol, and enabling the surface of the pure copper to be smooth;
the second step is that: preheating a prefabricated pure copper rod in a muffle furnace at 100 ℃;
the third step: smelting AZ31 magnesium alloy in a low-carbon steel crucible by using a well-type resistance furnace, wherein the melting temperature is 670 ℃, and the mixed gas of sulfur hexafluoride and carbon dioxide is required to be protected until a magnesium alloy ingot is completely melted;
the fourth step: after the temperature of the magnesium alloy melt is stable at 620 ℃, pouring the magnesium alloy melt into a mould filled with a pretreated pure copper bar, and blowing CO in the pouring process2As protective gas, and is cooled by circulating water;
the fifth step: and after the pouring is finished, continuously introducing circulating water for cooling to 200 ℃, taking out and air-cooling to obtain the AZ 31/pure Cu composite casting material.
FIG. 3 is a microstructure of AZ 31/pure Cu composite cast material interface, which is similar in structure and some properties to the pure Mg/pure Cu composite cast material of example 1. The first sublayer had a thickness of 45 μm and a predominant phase of Mg2Cu, on which a small amount of MgCu dendritic phase is distributed. The second sublayer had a thickness of 120 μm and a major phase of Mg-Mg2A Cu eutectic phase.
Claims (7)
1. The magnesium-copper composite casting material is characterized in that: the magnesium-copper composite casting material is prepared by magnesium alloy or pure magnesium and copperGold or pure copper is used as a component, and the interface bonding layer forms two sublayer structures; the tissue thickness of a sublayer close to the copper side of the magnesium-copper composite casting material interface layer is relatively thin and is 10-50 mu m, and the main part is Mg2Cu phase, also distributing some MgCu dendritic phase, the sub-layer structure near the magnesium is 100-200 μm, and is distributed in uniform network, which is mainly Mg-Mg2A Cu eutectic phase;
the hardness value of the magnesium-copper composite casting material is distributed in a step form from copper to magnesium, and the hardness of the middle layer is obviously higher than that of the matrix;
the preparation method of the magnesium-copper composite casting material comprises the following steps:
the first step is as follows: machining the solid copper alloy or pure copper to obtain a required material pattern, then polishing the surface of the copper alloy or pure copper by using abrasive paper, carrying out chemical cleaning, and removing surface oxides and oil stains to obtain the copper alloy or pure copper with ideal roughness and smooth surface;
the second step is that: preheating the prefabricated solid copper alloy or pure copper at 50-300 deg.coC；
The third step: smelting magnesium alloy or pure magnesium ingots in a low-carbon steel crucible by using a well-type resistance furnace, wherein sulfur hexafluoride and carbon dioxide mixed gas is required to protect the magnesium alloy or pure magnesium ingots until the magnesium alloy or pure magnesium ingots are completely molten;
the fourth step: after the temperature of the magnesium alloy or pure magnesium melt is stable, pouring the magnesium alloy or pure magnesium melt into a mold filled with pretreated solid copper alloy or pure copper, and blowing CO in the pouring process2As protective gas, and is cooled by circulating water;
the fifth step: and after the pouring is finished, continuously introducing circulating water for cooling to a certain temperature, taking out, and carrying out air cooling to obtain the magnesium-copper composite casting material.
2. The magnesium copper composite cast material according to claim 1, characterized in that: the magnesium alloy comprises AZ series, AM series, A series, AE series, Mg-Y-Zn, Mg-Gd-Y-Zr alloy series, Mg-Ca, Mg-Zn, Mg-Sr, Mg-Si, Mg-Li, Mg-Mn, Mg-RE binary alloy series, Mg-Zn-Ca ternary alloy series, Mg-Zn-Ca-X multi-element alloy series, and X = Mn, Sn, Sr and RE.
3. The magnesium copper composite cast material according to claim 1, characterized in that: the copper alloy comprises brass alloy series, bronze alloy series, copper-nickel-zinc alloy series and copper-lead alloy series.
4. The magnesium copper composite cast material according to claim 1, characterized in that: the first step material has different volume ratios of Mg to Cu and different sizes and shapes according to the required mechanical property and corrosion performance.
5. The magnesium copper composite cast material according to claim 1, characterized in that: thirdly, the melting temperature of the magnesium alloy exceeds the liquidus by 20-50oC。
6. The magnesium copper composite cast material according to claim 1, characterized in that: and fourthly, the stable temperature of the magnesium alloy melt is between the solidus temperature and the liquidus temperature of the melt.
7. The magnesium copper composite cast material according to claim 1, characterized in that: fifthly, circulating water is introduced for cooling to the temperature of 70-200 DEGoAnd C, taking out.
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| GB561661A (en) * | 1942-12-09 | 1944-05-30 | William Ferrier Proctor | Improvements in or relating to the manufacture of composite metals |
| CN100506432C (en) * | 2006-02-27 | 2009-07-01 | 陈新华 | Pressure casting process for finned convection radiator with composite magnesium alloy copper-column |
| CN101104325A (en) * | 2007-08-01 | 2008-01-16 | 中国科学院金属研究所 | Magnesium-base layer-shaped composite material and its composite casting preparation method |
| CN102254634A (en) * | 2011-07-04 | 2011-11-23 | 珠海光乐电力母线槽有限公司 | Method for manufacturing metal composite material and material manufactured by same |
| CN103277765A (en) * | 2013-05-20 | 2013-09-04 | 广东工业大学 | Magnesium-copper composite metal LED radiator and precision forging forming technology thereof |
| CN103691909B (en) * | 2014-01-07 | 2016-05-11 | 北京科技大学 | A kind of aluminium/magnesium solid-liquid composite casting forming method |
| CN106825900A (en) * | 2017-04-07 | 2017-06-13 | 太原理工大学 | A kind of explosive welding forming method of magnesium copper metal composite plate |
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