CN105220041A - A kind of high-strength wrought magnesium alloys and preparation method thereof - Google Patents
A kind of high-strength wrought magnesium alloys and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high-strength magnesium alloy and preparation method thereof, belong to light metal material technical field.Weight percentage, this magnesium alloy composition is: Zn2.0-6.5%, RE0.1-3.0%, Ca0.1-2.0%, and all the other are Mg and inevitable impurity; Also grain-refining agent Mn and/or Zr can be contained.Zn is main strengthening element in alloy, and it improves the room temperature strength of magnesium alloy by solution strengthening and Precipitation strengthening; Ca is for promoting precipitation, crystal grain thinning, raising alloy high-temp intensity; A small amount of RE is for suppressing recrystallize, and after refinement distortion, alloy grain and regulation and control texture, improve alloy plasticity.The present invention replaces expensive rare earth element by the common alloy element that employing is cheap, makes it to produce the strengthening effect same with rare-earth phase, replaces completely or reduces content of rare earth, while proof strength, reducing cost of alloy.
Description
Technical field
The present invention relates to light metal material technical field, be specifically related to a kind of high-strength wrought magnesium alloys and preparation method thereof.
Background technology
Magnesium alloy, as a kind of novel light metallic substance, has the series of advantages such as density is low, specific tenacity is high, shock resistance, reusable edible, has broad application prospects.Especially along with the high speed development of the military industry fields such as the traffic and transport field such as aviation, high ferro and space flight, day by day urgent to the demand of high-strength wrought magnesium alloys.
At present, the high-strength wrought magnesium alloys of business only has AZ80 (Mg-8Al-0.4Zn) and ZK60 (Mg-6Zn-0.5Zr).Their tensile strength after distortion+aging strengthening model is about 300-350MPa, room temperature elongation 8%.And be applied in the tensile strength of traffic and transport field as the aluminium alloy of structural part at present generally higher than 400MPa, therefore high-strength magnesium alloy to be made to replace part aluminium alloy and to be applied in traffic and transport field, 400MPa is greater than in the urgent need to development tensile strength, and cost and the close low-cost high-strength wrought magnesium alloys of aluminium alloy.
By adding a small amount of rare earth element (1-3%RE) to AZ80 and ZK60 alloy, utilizing ternary precipitated phase to improve intensity, thus obtaining high-strength wrought magnesium alloys.As Chinese invention patent (denomination of invention: a kind of weldable deformable rare earth magnesium alloy with high intensity and high toughness, application number: 200610172788.X) disclose a kind of Mg-(5.5wt% ~ 6.4wt%) Zn-(0.7wt.% ~ 1.7wt%) Ym-(0.45wt% ~ 0.8wt%) Zr alloy, this alloy is under As-extruded, and room temperature average tensile strength is 340MPa.Disclose a kind of high-strength deforming magnesium alloy in CN101805865A patent, its chemical composition is Al:7.8 ~ 9.2%, Zn:0.2 ~ 0.8%, Mn:0.2 ~ 0.5%, the rare earth of 0.5 ~ 2.0%, the maximum tensile strength of acquisition is 360MPa, and maximum room temperature elongation is 11.5%.Mg-(4.5wt% ~ 5.5wt%) Zn-(0.5wt.% ~ 2.5wt%) Ce-(0.01wt.% ~ 0.2wt%) Ti alloy is disclosed in the patent of " a kind of Wrought magnesium alloys in high intensity, high plasticity and preparation method thereof ", room temperature average tensile strength after extruding is 360MPa, yield strength is 245MPa, elongation after fracture 7%.Above-mentioned alloy is on the basis of ZK60 or AZ80, adds a small amount of rare earth element (1 ~ 3wt%), puies forward heavy alloyed room temperature strength, hot strength and welding property.But the content of rare earth added in these alloys is less, and precipitating reinforcing effect is undesirable, its deformation states strength of alloy, all lower than 400MPa, can not meet the requirement of traffic and transport field to light material intensity.
Subsequently, people are by reducing Zn content and increasing content of rare earth, content of rare earth is made to reach more than 10wt%, develop the Mg-RE-Zn-Zr system alloy of the low zinc of high rare earth, the intensity of alloy is further increased by techniques such as extruding or rollings, its intensity can more than 400MPa, and in high-strength and high-ductility magnesium alloy and manufacture method thereof disclosed in patent CN101705404A, the intensity of alloy part reaches 400MPa; Also has [T.Homma in document, N.Kunito, andS.Kamado, Fabricationofextraordinaryhigh-strengthmagnesiumalloybyh otextrusion.ScriptaMaterialia, 2009.61 (6): p.644-647] mention Mg-10Gd-3Y-1Zn-0.5Zr alloy, after extruding and thermal treatment, tensile strength reaches 450MPa, and elongation reaches 6%.Due to rare earth element (alloy Rare-Earth Content the is greater than 10%) element containing a large amount of costliness in the Mg-RE-Zn-Zr system alloy of the low zinc of this kind of high rare earth; cost of alloy is caused to be multiplied (20 yuan/kilogram, magnesium; rare earth 300-500 unit/kilogram), thus this kind of high strength Mg-RE-Zn-Zr alloy is difficult to industrially obtain mass-producing application.
In sum, there is the shortcomings such as intensity does not reach that requirement or intensity reach more than 400MPa but cost is too high in the distortion high-strength magnesium alloy developed now.Therefore, in the urgent need to exploring and develop the Low-cost wrought magnesium alloy that a kind of tensile strength is greater than 400MPa, in order to meet the demand of the fields such as communications and transportation to light-weight high-strength material, the industrial application process of high-strength wrought magnesium alloys is promoted.
Summary of the invention
The problem of undercapacity or high cost is there is for existing wrought magnesium alloys, the invention provides a kind of high-strength wrought magnesium alloys and preparation method thereof, expensive rare earth element is replaced by adopting cheap common alloy element, make it to produce the strengthening effect same with rare-earth phase, replace completely or reduce content of rare earth, while proof strength, reducing cost of alloy.
Technical solution of the present invention is:
A kind of high-strength wrought magnesium alloys, weight percentage, this magnesium alloy composition is: Zn2.0-6.5%, RE0.1-3.0%, Ca0.1-2.0%, and all the other are Mg and inevitable impurity; Wherein: RE is rare earth element, RE can be one or more in Gd, Y, Ce, La, Nd and Er.
Also containing grain-refining agent in this magnesium alloy, described crystalline substance material fining agent is Mn and/or Zr, and the content of described Mn is 0.2-2.0wt% (being preferably 0.3-1.5wt%), and the content of Zr is 0.01-0.8wt% (being preferably 0.3-0.7wt%).
In magnesium alloy of the present invention, Zn content is preferably 2.0-6.0wt%, and RE content is preferably 0.3-1.5wt%, and Ca content is preferably 0.2-1.5wt%.
By above-mentioned alloying constituent batch mixing also obtained alloy cast ingot, alloy cast ingot, through viscous deformation hot-work, obtains high-strength wrought magnesium alloys of the present invention; Described viscous deformation hot-work be carry out extruding, the viscous deformation processing such as rolling or forging.
Principle of design of the present invention is as follows:
The present invention is by Mg-Zn alloy, adding a small amount of rare earth element makes itself and Mg, Zn form Mg-Zn-RE ternary precipitated phase, add cheap Ca element makes itself and Mg, Zn form Mg-Zn-Ca ternary precipitated phase simultaneously, can replace part Mg-Zn-RE precipitation strength phase; Add a small amount of Mn and or Zr element, refinement as-cast grain, and in conjunction with the Grain Refinement Effect of RE and Ca element in deformation process, realize the complex intensifying of refined crystalline strengthening and precipitation strength, both the content of rare earth can have been reduced, intensity can also be improved further, obtain a kind of low-cost high-strength wrought magnesium alloys.
The present invention is selected alloying element by science, is optimized element proportioning, and regulation and control precipitated phase kind, quantity and distribution, strengthen precipitating reinforcing effect; The grain-size of refining alloy as-cast grain and the rear alloy of distortion, plays refined crystalline strengthening effect, utilizes the complex intensifying effect of precipitation strength and refined crystalline strengthening, improve magnesium alloy strength simultaneously.
The present invention, by adding specific alloy elements organization of regulation control structure to improve mechanical property, by Composition Design and the tissue modulation of alloy, and utilizes plastic working, obtains a kind of high-strength wrought magnesium alloys.With the high-strength ZK60 of business compared with the high-strength magnesium alloy prepared of AZ80 magnesium alloy, high rare earth high-strength magnesium alloy and special process, the present invention has a series of advantage:
1, high-strength wrought magnesium alloys Rare-Earth Content of the present invention is less than 3%, and its cost reduces by 2/3 than the cost of the Mg-RE-Zn-Zr alloy of high rare-earth content.
2, high-strength wrought magnesium alloys tensile strength of the present invention reaches more than 400MPa, and far above the high-strength magnesium alloy such as business ZK60 and AZ80, and cost only increases by 5%.
3, the preparation of high-strength wrought magnesium alloys of the present invention can pass through industrial conventional equipment, as common extruding or rolling can realize, can realize batch production on existing industrial equipments, and without the need to passing through special processing mode, tooling cost is low.
Accompanying drawing explanation
Fig. 1 is the tissue of low-cost high-strength wrought magnesium alloys in the embodiment of the present invention 1; Wherein: (a) as-cast structure, the tissue after (b) extruding.
Fig. 2 is the tissue of low-cost high-strength wrought magnesium alloys in the embodiment of the present invention 2; Wherein: (a) as-cast structure, the tissue after (b) extruding.
Fig. 3 is the tissue of low-cost high-strength wrought magnesium alloys in the embodiment of the present invention 3; Wherein: (a) as-cast structure, the tissue after (b) extruding.
Fig. 4 is the tissue of low-cost high-strength wrought magnesium alloys in the embodiment of the present invention 4; Wherein: (a) as-cast structure, the tissue after (b) extruding.
Embodiment
Be described in detail technical solution of the present invention below in conjunction with drawings and Examples, described example is only the present invention's part embodiment, instead of whole embodiments, is not also limitation of the invention.Based on the embodiment in invention, those skilled in the art, not making other embodiments all obtained under creative work prerequisite, belong to the scope of protection of the invention.
For low-cost high-strength wrought magnesium alloys Mg-Zn-RE-Ca-Mn-(Zr) alloy composition in embodiment of the present invention 1-5, (in table, data are chemico-analytic result to table 1; in mass percentage), the fractions be only in protection domain of filling a prescription described in table 1.Table 2 is the room temperature tensile mechanical property of embodiment 1-5 interalloy after extruding.Table 3 is the high-strength wrought magnesium alloys room-temperature mechanical property of existing business and research and development.
Embodiment 1
Adopting metal mold gravity casting to obtain the length of side is 200mm, and height is the square ingot casting of 150mm.Through chemical analysis, its chemical composition is: Mg-2.0Zn-0.8Gd-0.7Ca-0.5Mn.Its as-cast structure is as shown in Fig. 1 (a), and as-cast grain size is 50-100 micron.
Alloy cast ingot carries out Homogenization Treatments 16h at 420 DEG C; The extrusion billet that diameter is 50mm is cut into after process.Extrusion billet, 380 DEG C of insulations 2 hours, is put into container and is extruded, and obtaining diameter is the extruded rod of 12mm.The microtexture of extruded rod is as Fig. 1 (b); After extruding, grain refining is to 2-5 micron, and according to Hall-Petch relation, grain refining will put forward heavy alloyed intensity.Carry out Mechanics Performance Testing by GB GB/T228-2002, its tensile strength is 418MPa, yield strength 405MPa, and elongation 8.5% is as shown in table 2.
Embodiment 2
Adopting metal mold gravity casting to obtain the length of side is 200mm, and height is the square ingot casting of 150mm.Through chemical analysis, its chemical composition is: Mg-3.0Zn-0.2Gd-2.0Ca-0.2Mn-0.3Zr.Its as-cast structure is as shown in Fig. 2 (a), and as-cast grain size is 50-100 micron, due to the increase of Zn content, defines dendrite, and creates more second-phase.
Alloy cast ingot carries out Homogenization Treatments 12h at 400 DEG C; The extrusion billet that diameter is 50mm is cut into after process.Extrusion billet, 380 DEG C of insulations 2 hours, is put into container and is extruded, and obtaining diameter is the extruded rod of 12mm.The microtexture of extruded rod is as Fig. 2 (b); After extruding, grain refining is to 1-5 micron, and creates a lot of fine particle precipitated phase, grain refining and precipitation hardenedly further increase intensity.Carry out Mechanics Performance Testing by GB GB/T228-2002, its tensile strength is 425MPa, yield strength 409MPa, and elongation 7.3% is as shown in table 2.
Embodiment 3
Adopting metal mold gravity casting to obtain the length of side is 200mm, and height is the square ingot casting of 150mm.Through chemical analysis, its chemical composition is: Mg-4.1Zn-3Y-0.2Ca-2.0Mn.Its as-cast structure is as shown in Fig. 3 (a), and as-cast grain size is 50-100 micron, and because the continuation of Zn content increases, dentrite quantity is more, and second-phase quantity also increases.
Alloy cast ingot carries out Homogenization Treatments 12h at 380 DEG C; The extrusion billet that diameter is 50mm is cut into after process.Extrusion billet, 380 DEG C of insulations 2 hours, is put into container and is extruded, and obtaining diameter is the extruded rod of 12mm.The microtexture of extruded rod is as Fig. 3 (b); After extruding, grain refining is to 1-5 micron, and creates a lot of fine particle precipitated phase, and also there are some thick second-phases, grain refining and precipitation hardened complex intensifying improve the intensity of alloy simultaneously.Carry out Mechanics Performance Testing by GB GB/T228-2002, its tensile strength is 439MPa, yield strength 422MPa, and elongation 7.0% is as shown in table 2.
Embodiment 4
Adopting metal mold gravity casting to obtain the length of side is 200mm, and height is the square ingot casting of 150mm.Through chemical analysis, its chemical composition is: Mg-6.0Zn-1.5Y-1.0Ca-0.6Mn-0.8Zr.Its as-cast structure is as shown in Fig. 4 (a), and as-cast grain size is 50-100 micron, and because the continuation of Zn content increases, dentrite quantity is more, and second-phase quantity also increases.
Alloy cast ingot carries out Homogenization Treatments 12h at 380 DEG C; The extrusion billet that diameter is 50mm is cut into after process.Extrusion billet, 360 DEG C of insulations 2 hours, is put into container and is extruded, and obtaining diameter is the extruded rod of 12mm.The microtexture of extruded rod is as Fig. 4 (b); After extruding, grain refining is to 1-5 micron, and creates a lot of fine particle precipitated phase, and also there are some thick second-phases, grain refining and precipitation hardened complex intensifying improve the intensity of alloy simultaneously.Carry out Mechanics Performance Testing by GB GB/T228-2002, its tensile strength is 460MPa, yield strength 446MPa, and elongation 6.5% is as shown in table 2.
Embodiment 5
Adopting metal mold gravity casting to obtain the length of side is 200mm, and height is the square ingot casting of 150mm.Through chemical analysis, its chemical composition is: Mg-5.9Zn-0.9Ce-0.5Ca-0.5Zr.Its as-cast structure as-cast grain size is 50-100 micron, there is a lot of dendrite and second-phase quantity, the interpolation of Zr, as-cast grain is reduced to some extent.
Alloy cast ingot carries out Homogenization Treatments 12h at 380 DEG C; The extrusion billet that diameter is 50mm is cut into after process.Extrusion billet, 360 DEG C of insulations 2 hours, is put into container and is extruded, and obtaining diameter is the extruded rod of 12mm.The grain refining of extruded rod, to 1-5 micron, also also exists a lot of fine particle precipitated phase, and some thick second-phases, and grain refining and precipitation hardened complex intensifying are the major causes that alloy strength improves.Carry out Mechanics Performance Testing by GB GB/T228-2002, its tensile strength is 462MPa, yield strength 445MPa, and elongation 6.8% is as shown in table 2.
Embodiment 6
Adopting metal mold gravity casting to obtain the length of side is 200mm, and height is the square ingot casting of 150mm.Through chemical analysis, its chemical composition is: Mg-5.2Zn-1.1Gd-1.2Ca.Its as-cast structure as-cast grain size is 100-200 micron, there is a lot of dendrite and second-phase quantity.
Alloy cast ingot carries out Homogenization Treatments 12h at 380 DEG C; The extrusion billet that diameter is 50mm is cut into after process.Extrusion billet, 360 DEG C of insulations 2 hours, is put into container and is extruded, and obtaining diameter is the extruded rod of 12mm.The grain refining of extruded rod, to 2-5 micron, also also exists a lot of fine particle precipitated phase, and some thick second-phases.Carry out Mechanics Performance Testing by GB GB/T228-2002, its tensile strength is 443MPa, yield strength 425MPa, and elongation 6.9% is as shown in table 2.
Mg-Zn-RE-Ca-Mn-(Zr) alloy composition (wt%) in table 1 embodiment 1-6
| Numbering | Zn | RE | Ca | Mn | Zr | Mg |
| Alloy 1 | 2.0 | 0.8 | 0.7 | 0.5 | 0 | Surplus |
| Alloy 2 | 3.0 | 0.2 | 2.0 | 0.2 | 0.3 | Surplus |
| Alloy 3 | 4.1 | 3 | 0.2 | 2.0 | 0 | Surplus |
| Alloy 4 | 6.0 | 1.5 | 1.0 | 0.6 | 0.8 | Surplus |
| Alloy 5 | 5.9 | 0.9 | 0.5 | 0 | 0.5 | Surplus |
| Alloy 6 | 5.2 | 1.1 | 1.2 | 0 | 0 | Surplus |
Mechanical property after Mg-Zn-RE-Ca-Mn-(Zr) alloy extrusion in table 2 embodiment 1-6
| Numbering | Yield strength (MPa) | Tensile strength (MPa) | Stretch | Long rate |
| Alloy 1 | 405 | 418 | 8.5 |
| Alloy 2 | 409 | 425 | 7.3 |
| Alloy 3 | 422 | 439 | 7.0 |
| Alloy 4 | 446 | 460 | 6.5 |
| Alloy 5 | 445 | 462 | 6.8 |
| Alloy 6 | 425 | 443 | 6.9 |
The high-strength wrought magnesium alloys room-temperature mechanical property of table 3 business and research and development
| Alloys (wt.％) | Processing mode | Yield strength MPa | Tensile strength/MPa |
| Mg-6.0Zn-0.4Zr(ZK60) | Extruding | 275 | 380 |
| Mg-8Al-0.4Zn-0.2Mn(AZ80) | Extruding | 305 | 365 |
| Mg-6.0Zn-0.4Ag-0.2Ca-0.6Zr | Extruding | 288 | 351 |
| Mg-9.8Sn-1.2Zn-1.0Al | Extruding | 280 | 308 |
| Mg-14.0Gd-2.3Zn | Extruding | 345 | 380 |
| Mg-10.0Gd-5.7Y-1.6Zn-0.6Zr | Extruding | 419 | 461 |
| Mg-10.0Gd-3Y-1Zn-0.5Zr | Extruding | 401 | 450 |
Claims (10)
1. a high-strength wrought magnesium alloys, is characterized in that: weight percentage, and this magnesium alloy composition is: Zn2.0-6.5%, RE0.1-3.0%, Ca0.1-2.0%, and all the other are Mg and inevitable impurity; Wherein RE is rare earth element.
2. high-strength wrought magnesium alloys according to claim 1, is characterized in that: also containing grain-refining agent in this magnesium alloy, and described crystalline substance material fining agent is Mn and/or Zr.
3. high-strength wrought magnesium alloys according to claim 2, is characterized in that: the content of described Mn is the content of 0.2-2.0wt%, Zr is 0.01-0.8wt%.
4. high-strength wrought magnesium alloys according to claim 2, is characterized in that: the content of described Mn is the content of 0.3-1.5wt%, Zr is 0.3-0.7wt%.
5., according to the arbitrary described high-strength wrought magnesium alloys of claim 1-4, it is characterized in that: described Zn content is 2.0-6.0wt%.
6., according to the arbitrary described high-strength wrought magnesium alloys of claim 1-4, it is characterized in that: described RE content is 0.3-1.5wt%.
7., according to the arbitrary described high-strength wrought magnesium alloys of claim 1-4, it is characterized in that: described Ca content is 0.2-1.5wt%.
8. high-strength wrought magnesium alloys according to claim 1, is characterized in that: described RE can be one or more in Gd, Y, Ce, La, Nd and Er.
9. the preparation method of high-strength wrought magnesium alloys according to claim 1, is characterized in that: by required alloying constituent batch mixing also obtained alloy cast ingot, alloy cast ingot, through viscous deformation hot-work, obtains described high-strength wrought magnesium alloys.
10. the preparation method of high-strength wrought magnesium alloys according to claim 9, is characterized in that: described viscous deformation hot-work be carry out extruding, the viscous deformation processing such as rolling or forging.
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| CN105886866A (en) * | 2016-06-22 | 2016-08-24 | 重庆大学 | High-formability magnesium alloy |
| CN106987747A (en) * | 2017-03-23 | 2017-07-28 | 济南大学 | A kind of even corrosion resistant Biological magnesium alloy and preparation method thereof |
| CN107201471A (en) * | 2017-07-28 | 2017-09-26 | 山东省科学院新材料研究所 | A kind of wrought magnesium alloy and preparation method thereof |
| CN107475590A (en) * | 2017-08-21 | 2017-12-15 | 中北大学 | A kind of High-strength high-plasticity cast magnesium alloy and preparation method thereof |
| CN107541627A (en) * | 2016-06-24 | 2018-01-05 | 北京科技大学 | A kind of wrought magnesium alloy sheet material with good room temperature formability and preparation method thereof |
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