CN102031433A - Magnesium-zinc-manganese-cerium magnesium alloy material with high zinc content - Google Patents
Magnesium-zinc-manganese-cerium magnesium alloy material with high zinc content Download PDFInfo
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Abstract
The invention relates to a magnesium-zinc-manganese-cerium magnesium alloy material with high zinc content. The magnesium alloy comprises the following components in percentage by mass: 5.0 to 8.0% of Zn, 0.5 to 1.25% of Mn, 0.2 to 1.0% of Ce, less than or equal to 0.15% of inevitable impurities and balance of Mg. Compared with a cerium-containing magnesium-zinc-manganese magnesium alloy, the tensile strength and shear strength of the material provided by the invention are greatly improved; compared with a Mg-Zn-Mn magnesium alloy with high zinc content, the comprehensive mechanical property of the material provided by the invention is obviously improved; compared with a Mg-Al-Zn magnesium alloy, the mechanical property of the material provided by the invention is greatly improved; and compared with a typical ZK60 Mg-Zn-Zr magnesium alloy, the mechanical property of the material provided by the invention is the same as that of the ZK60 alloy, the elongation rate is significantly improved, and the formability is higher, thus the magnesium-zinc-manganese-cerium magnesium alloy material provided by the invention can be used for replacing the ZK60 alloy in the industrial production of metal materials with high mechanical property requirements, such as aviation, war industries and the like.
Description
Technical field
The present invention relates to a kind of metallic substance, belong to non-ferrous metal magnesium alloy production field, particularly a kind of magnesium-zinc-manganese-cerium series magnesium alloy material with high zinc content of high strength and high-ductility.
Background technology
Magnesium alloy is as the structural metallic materials of density minimum in the present industrial application, compare with other structural metallic materialss, have high specific tenacity, specific rigidity, good damping property, and antimagnetic, shielding, heat radiation, easily machining, easy numerous characteristics such as recovery, having extremely important using value and wide application prospect at automobile, electronics, electrical equipment, traffic, space flight, aviation and national defense and military industrial circle, is the 3rd metalloid structured material that grows up after iron and steel and aluminium alloy.Since the nineties in 20th century, states such as the U.S., Japan, Germany and Australia put into effect magnesium research project separately in succession, with the grand strategy goods and materials of magnesium resource as 21 century, have strengthened the research and development at aspects such as resource, processing, application of magnesium and magnesium alloy.
For the widespread use of magnesium alloy, China focuses on Mg Alloy Research above the research and development high-strength-toughness magnesium alloy, and the tensile strength general requirement surpasses 300MPa.Present most of high-strength magnesium alloy material all contains zirconium, generally is meant the Mg-Zn-Zr alloy, its typical alloy designations such as ZK60.Contain the zirconium magnesium alloy and have higher room temperature and high-temperature behavior, be mainly used in fields such as space flight and aviation, military affairs, but its cost height hinders its range of application.No zirconium magnesium alloy is a metallic substance the most widely in the present magnesium alloy, but its intensity is low, extrusion performance is bad, mechanical property can not satisfy far away and expands magnesium alloy to the requirement of industrial circle widely, therefore develops novel not zirconic high-strength high-plasticity magnesium alloy and has very important significance.
Zinc content usually≤2% in the common not zirconic Mg-Zn-Mn series magnesium alloy, this is because in the process of setting of Mg-Zn-Mn series magnesium alloy after casting, along with temperature reduces, Zn solubleness descends (100 ℃ time drop to 2% below), when zinc content above 2%, excessive zinc can not be solidly soluted in the magnesium matrix, there is a large amount of Mg-Zn phases, formability and toughness are had adverse influence, be mainly ZM21 so Mg-Zn-Mn is traditional trade mark of alloy, the ZM21 alloy has medium tenacity, and plasticity is general.On ZM21 alloy basis, contriver's participation contains the development of the magnesium-zincium-manganese based magnesium alloy (patent No. 200810069375.8) of cerium, and this alloy phase has obviously improved plasticity than ZM21 alloy, and is limited but intensity improves, and does not reach the scope of high-strength magnesium alloy; The contriver also participates in the development of the magnesium-zincium-manganese based magnesium alloy (number of patent application 200710078329.X) of high zinc content, and its elongation after fracture generally is no more than 11%, and its plasticity is bad, has limited range of application.
Summary of the invention
The purpose of this invention is to provide a kind of magnesium-zinc-manganese-cerium series high strength high plastic magnesium alloy material of high zinc content, material of the present invention is compared with the magnesium-zincium-manganese based magnesium alloy that contains cerium, and tensile strength and yield strength improve greatly; Compare with the Mg-Zn-Mn series magnesium alloy of high zinc content, comprehensive mechanical property is improved significantly; Compare with the Mg-Al-Zn series magnesium alloy, mechanical property improves greatly; With the typical trade mark ZK60 alloy phase ratio of Mg-Zn-Zr series magnesium alloy, mechanical property is identical, and unit elongation obtains more significantly improving, and processability is higher, and alternative ZK60 is used for the high industrial production of mechanical property requirements of metallic substance, as aviation, military project etc.
Technical scheme of the present invention is that described magnesium alloy is made up of Mg, Zn, Mn and Ce, and its each constituent mass percentage composition is: Zn:5.0～8.0%; Mn:0.5～1.25%; Ce:0.2～1.0%; Inevitable impurity≤0.15%; All the other are magnesium.
The present invention's technical scheme preferably is that the mass percent of each component of magnesium alloy is: Zn:5.8%; Mn:0.7%; Ce:0.5%; Inevitable impurity≤0.15%; All the other are magnesium.
Unavoidable impurities of the present invention is Al, Si, Ni, Cu, Fe, its total amount≤0.15%.
Smelting process according to common magnesium alloy obtains above-mentioned magnesium alloy materials, carries out homogenizing and handles, and is squeezed into bar on extrusion machine, and cooling fast can process various magnesium-alloy materials simultaneously.
Magnesium alloy materials of the present invention has the following advantages:
1. magnesium alloy materials of the present invention and the patent No. are that the magnesium-zincium-manganese based magnesium alloy that contains cerium of 200810069375.8 low zinc content is compared, improved the content of zinc, wherein element zinc is in later stage homogenizing annealing process, can be solidly soluted in the magnesium matrix lattice, the highest solid solubility reaches 6.2%, cooling fast after hot extrusion, zinc atom and magnesium matrix form sosoloid, thereby play the solution strengthening effect, the MgZn precipitated phase and the ageing strengthening effect of sufficient amount have been guaranteed simultaneously, therefore, magnesium alloy materials of the present invention is compared with the magnesium-zincium-manganese based magnesium alloy that contains cerium of low zinc content, tensile strength and yield strength improve greatly, and the mechanical property of material is significantly improved.
2. magnesium alloy materials of the present invention is owing to added rare-earth element cerium, in process of setting, its evenly distribute COEFFICIENT K≤1, cerium mainly is enriched in the forward position of solid/liquid interfaces, as can be seen from Figure 1, cerium mainly is distributed in crystal boundary and interdendritic, and crystal boundary is had pinning effect, can suppress grain growth, gained crystal grain is tiny.
3. magnesium alloy materials of the present invention has added rare-earth element cerium, cerium and matrix element magnesium and alloying element zinc are in conjunction with having formed the Mg-Ce compound mutually, this compound has high melt point and thermostability mutually, in hot extrusion process, disperse is distributed in and contains cerium second effective pinning crystal boundary mutually on the crystal boundary, and machine-processed recrystal grain is grown up, and obtains tiny thermal distortion grain structure, so obviously improve YIELD STRENGTH and tensile strength, can effectively improve the plasticity and toughness of material.
4. magnesium alloy materials of the present invention has good thermostability, can effectively suppress the thick and grain growth of compound in the subsequent thermal mechanical treatment, simultaneously in the thermal deformation process when temperature raises, begin to occur the temperature raising of local melting, help selecting for use higher temperature to carry out thermal distortion, to improve the thermal distortion plasticity of alloy, reduce resistance to deformation, improve thermal distortion speed.
5. magnesium alloy materials of the present invention does not need to apply special deformation technique, and as waiting passage extruding etc., deformation processing on general industry extruding, texturing machine such as rolling can obtain the small grains tissue of size at 2～10 μ m.
Recrystallize can take place in magnesium alloy materials of the present invention in hot extrusion process, the high-melting-point that disperse is distributed on the crystal boundary contains the cerium second phase pinning crystal boundary, hinders growing up of new crystal grain, thereby improves mechanical property by obtaining more tiny crystal grain.Magnesium alloy materials of the present invention is compared with the magnesium-zincium-manganese based magnesium alloy that contains cerium (patent No. 200810069375.8), and tensile strength and yield strength improve greatly; Compare with the Mg-Zn-Mn series magnesium alloy of high zinc content, comprehensive mechanical property is improved significantly; Compare with the Mg-Al-Zn series magnesium alloy, mechanical property improves greatly; With the typical trade mark ZK60 alloy phase ratio of Mg-Zn-Zr series magnesium alloy, mechanical property is identical, and unit elongation obtains more significantly improving, and processability is higher, and alternative ZK60 is used for the high industrial production of mechanical property requirements of metallic substance, as aviation, military project etc.
Mechanical property of the present invention is meant tensile strength, yield strength and the unit elongation of metallic substance.
The preparation method of magnesium alloy of the present invention is similar with the preparation method of conventional magnesium alloy ingot, and therefore simple, the maneuverable advantage of technology is arranged.
Magnesium alloy of the present invention can process the various plate of size, rod, pipe, section bar and forging products.
With reference to the accompanying drawings and in conjunction with specific examples, further set forth the present invention, be understood that; these examples are to be used to illustrate the present invention; rather than limitation of the present invention, under design prerequisite of the present invention to preparation method's of the present invention simple modifications, the scope that all belongs to the present invention and protected.
Description of drawings
Fig. 1 is microstructure under the cross-sectional scans Electronic Speculum of numbering B magnesium alloy; Among the figure, spectrogram is handled: do not have uncared-for peak; Processing option: all elements (normalization method) by analysis; Multiplicity=3 standard models:
Mg MgO 1-Jun-1999?12:00?AM
Mn Mn 1-Jun-1999?12:00?AM
Zn Zn 1-Jun-1999?12:00?AM
Ce CeO2 1-Jun-1999?12:00?AM
Fig. 2, Fig. 3 are the microtexture photo of numbering B magnesium alloy cast, homogenizing attitude;
Fig. 4 is the vertical section microstructure of ZM61 alloy extruded bars;
Fig. 5 is the vertical section microstructure of the extruded bar from magnesium alloy of numbering B;
Fig. 6 is the x-ray diffraction pattern of ZM61, numbering B magnesium alloy.X-coordinate is 2 θ angles; Ordinate zou is diffracted intensity (arbitrary unit).
Embodiment
Use following prescription,, can obtain the Mg-Zn-Mn-Ce series magnesium alloy material (following is the quality percentage composition) of high-strength high-plasticity of the present invention according to the common smelting process of magnesium alloy:
This magnesium alloy materials of table 1 chemical constitution
Following example is defined as the ZME610 magnesium alloy with the magnesium alloy that is numbered A, B, C in the table 1 of the present invention.
Get prescription in the above-mentioned table 1, obtain magnesium alloy of the present invention with following method:
1. melting: according to above-mentioned table 1 recipe configuration alloy, starting material are technical pure magnesium ingot, industrial-purity zinc, Mg-20.82%Ce rare earth intermediate alloy and Mg-4.1%Mn master alloy, carry out on semicontinuous casting equipment.Heat fused pure magnesium in the resistance crucible furnace at first, temperature all melts at 700 ℃ of masterbatch; 750 ℃ of left and right sides slag hittings, add zinc ingot metal and magnesium-manganese master alloy then, stirred after off-bottom 2～5 minutes, make homogenization of composition, then refining is 4～8 minutes, static insulation 30min; Add magnesium-cerium master alloy then, stir after dissolving, add refining agent, refining 4～8 minutes, static insulation 20 minutes cools to 690～720 ℃, afterwards at CO
2And SF
6Mixed gas protected casting down.
2. machining: carry out railway carriage etc. according to the size of extrusion machine container and be machined into suitable dimension;
3. homogenizing is handled: 330 ℃ of following homogenizing annealings 24 hours;
4. extrusion processing: under 330～400 ℃, be squeezed into bar on the extrusion machine, fast cooling.The squeezing parameter of ZME610 magnesium alloy sees Table 2.
Table 2ZM61, the main squeezing parameter of ZME610 alloy material
1. microtexture characterizes
Its preparation process of the sample of structure observation is as follows: adopt No. 1000 silicon carbide silicon carbide papers to polish the surface; Adopt diamond paste mechanical polishing then; Main phase X-ray diffraction analysis is α-Mg, MgZn, MgZn in the alloy
2And Mg
12Ce, X-ray diffracting spectrum list on the accompanying drawing 6; By dispose can spectral apparatus scanning electron microscope (TESCAN VEGA II) go up the distribution that can determine alloy interalloy and element, stereoscan photograph and EDAX results are listed on the accompanying drawing 1 accordingly.
2. Mechanics Performance Testing
Standard according to GB GB228-2002, the described magnesium alloy materials of the embodiment of the invention is carried out tension test through extruding and the heat treated standard tensile sample that is processed into, the stretching sample is the pole shape, its axis direction is parallel to the vertical of material, draws the mechanical performance data (seeing Table 3) of magnesium alloy of the present invention.
Table 3 extruded bar from magnesium alloy mechanical property of the present invention
Be used as magnesium alloy such as correlated AZ61 of mechanical property and AZ31, compare with magnesium alloy of the present invention.ZME210, ZM61, ZK60, AZ31, ZM21 and ZME610 mechanical performance data see Table 4.
The room-temperature mechanical property of table 4ZME210, ZM61, ZK60, AZ31, ZM21 and ZME610 (numbering B magnesium alloy) alloy extruded bars
Annotate: the magnesium-zinc-manganese magnesium alloy (number of patent application 200810069375.8) that contains the low zinc content of cerium is defined as the ZME210 magnesium alloy.
Contrast table 3,4, magnesium alloy materials of the present invention and ZME210 alloy phase ratio, tensile strength and yield strength improve 13%, 10% respectively; With ZM61 alloy phase ratio, comprehensive mechanical property all is improved; Improve 16%, 22% with AZ31, ZM21 alloy phase respectively than tensile strength, yield strength improves 18%, 34%.Compare with present commercial high-strength magnesium alloy ZK60, tensile strength is suitable, and yield strength is improved slightly, and unit elongation improves 36%, and processability is higher, and alternative ZK60 is used for the high industrial production of mechanical property requirements of metallic substance, as aviation, military project etc.
Referring to Fig. 2, Fig. 3, in castingprocesses, because various segregations that non-equilibrium crystallization brought and be present in crystal boundary and interdendritic intermetallic compound, make that the chemical ingredients and the tissue odds of ingot casting are even, cause the weakening of thermoplastic reduction and processing characteristics, for improving the ununiformity of ingot casting chemical ingredients and tissue, improve its formability, need after casting, carry out homogenizing annealing and handle strand.After handling through homogenizing annealing, the thick dendrite of ingot casting disappears, and crystal grain obtains obvious refinement, the chemical ingredients of ingot casting and organize more evenly, and crystal boundary is inner the tangible second phase particle to occur.
Comparison diagram 4, Fig. 5 can see that the crystal grain of the ZME610 alloy that adds Ce elements obtains obvious refinement.Dynamic recrystallization can take place in numbering B magnesium alloy in hot extrusion process, disperse is distributed in high-melting-point on the crystal boundary and contains cerium second and hindered growing up of new crystal grain mutually, and as shown in Figure 6, this cerium second that contains is mainly Mg mutually
12The Ce phase, Mg
12Ce mainly is by the pinning crystal boundary mutually, hinders grain growth, and then makes it to obtain more tiny crystal grain, plays the purpose that improves mechanical property, and the mean diameter of crystal grain is at 1-6 μ m.
Conclusion: the magnesium-zinc-manganese of high zinc content-cerium series magnesium alloy, with ZME210 alloy phase ratio, mechanical property is obviously promoted; The magnesium-zincium-manganese based magnesium alloy comprehensive mechanical property of comparing high zinc content increases; Though with AZ31, ZM21 alloy phase than being that intensity or plasticity all improve greatly; Compare with commercial high-strength wrought magnesium alloys ZK60, yield strength, tensile strength are suitable with it, and have better plasticity, can partly substitute the ZK60 magnesium alloy materials.
Claims (3)
1. the magnesium-zinc-manganese of a high zinc content-cerium series magnesium alloy material, it is characterized in that: be made up of Mg, Zn, Mn and Ce, its each constituent mass percentage composition is:
Zn：5.0～8.0％；
Mn：0.5～1.25％；
Ce：0.2～1.0％；
Inevitable impurity≤0.15%;
All the other are magnesium.
2. the magnesium-zinc-manganese of high zinc content according to claim 1-cerium series magnesium alloy material, it is characterized in that: be made up of Mg, Zn, Mn and Ce, its each constituent mass percentage composition is:
Zn：5.8％；
Mn：0.7％；
Ce：0.5％；
Inevitable impurity≤0.15%;
All the other are magnesium.
3. the magnesium-zinc-manganese of high zinc content according to claim 1 and 2-cerium series magnesium alloy material, it is characterized in that: unavoidable impurities is Al, Si, Ni, Cu, Fe, its total amount≤0.15%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152769A (en) * | 2014-08-21 | 2014-11-19 | 重庆大学 | Heat conduction magnesium alloy and manufacturing method thereof |
| CN106521278A (en) * | 2016-12-29 | 2017-03-22 | 湘潭大学 | High-strength magnesium-zinc-manganese-yttrium-cerium magnesium alloy and preparation method thereof |
| CN106834850A (en) * | 2017-02-27 | 2017-06-13 | 广东省材料与加工研究所 | A kind of high-strength anticorrosion magnesium alloy and preparation method thereof |
| CN107190189A (en) * | 2017-05-19 | 2017-09-22 | 宝鸡市金得利新材料有限公司 | A kind of magnesium alloy for having mechanics and corrosion resistance concurrently and preparation method thereof |
| KR20190015066A (en) * | 2017-08-03 | 2019-02-13 | 주식회사 포스코 | Magnesium alloy sheet and method for manufacturing the same |
| CN111455246A (en) * | 2020-03-02 | 2020-07-28 | 华南理工大学 | High-thermal-conductivity magnesium alloy and preparation method thereof |
| CN113514303A (en) * | 2021-07-15 | 2021-10-19 | 东北轻合金有限责任公司 | 3A11 aluminum alloy as-cast spectrum and chemical standard sample and preparation method thereof |
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| CN101020981A (en) * | 2007-03-26 | 2007-08-22 | 重庆大学 | Mg-Zn-Mn alloy material with high Zn content |
| CN101270430A (en) * | 2008-02-19 | 2008-09-24 | 重庆大学 | Magnesium-zincium-manganese based magnesium alloy containing cerium |
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101020981A (en) * | 2007-03-26 | 2007-08-22 | 重庆大学 | Mg-Zn-Mn alloy material with high Zn content |
| CN101270430A (en) * | 2008-02-19 | 2008-09-24 | 重庆大学 | Magnesium-zincium-manganese based magnesium alloy containing cerium |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152769A (en) * | 2014-08-21 | 2014-11-19 | 重庆大学 | Heat conduction magnesium alloy and manufacturing method thereof |
| CN106521278A (en) * | 2016-12-29 | 2017-03-22 | 湘潭大学 | High-strength magnesium-zinc-manganese-yttrium-cerium magnesium alloy and preparation method thereof |
| CN106834850A (en) * | 2017-02-27 | 2017-06-13 | 广东省材料与加工研究所 | A kind of high-strength anticorrosion magnesium alloy and preparation method thereof |
| CN106834850B (en) * | 2017-02-27 | 2018-03-20 | 广东省材料与加工研究所 | A kind of high-strength anticorrosion magnesium alloy and preparation method thereof |
| CN107190189A (en) * | 2017-05-19 | 2017-09-22 | 宝鸡市金得利新材料有限公司 | A kind of magnesium alloy for having mechanics and corrosion resistance concurrently and preparation method thereof |
| KR20190015066A (en) * | 2017-08-03 | 2019-02-13 | 주식회사 포스코 | Magnesium alloy sheet and method for manufacturing the same |
| KR102045063B1 (en) | 2017-08-03 | 2019-12-02 | 주식회사 포스코 | Magnesium alloy sheet and method for manufacturing the same |
| CN111455246A (en) * | 2020-03-02 | 2020-07-28 | 华南理工大学 | High-thermal-conductivity magnesium alloy and preparation method thereof |
| CN113514303A (en) * | 2021-07-15 | 2021-10-19 | 东北轻合金有限责任公司 | 3A11 aluminum alloy as-cast spectrum and chemical standard sample and preparation method thereof |
| CN113514303B (en) * | 2021-07-15 | 2024-04-12 | 东北轻合金有限责任公司 | 3A11 aluminum alloy as-cast spectrum and chemical standard sample and preparation method thereof |
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Application publication date: 20110427 |