CN101476072A - Temperature distortion resistant magnesium alloy containing Ca and Sr - Google Patents
Temperature distortion resistant magnesium alloy containing Ca and Sr Download PDFInfo
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- CN101476072A CN101476072A CNA2009100425373A CN200910042537A CN101476072A CN 101476072 A CN101476072 A CN 101476072A CN A2009100425373 A CNA2009100425373 A CN A2009100425373A CN 200910042537 A CN200910042537 A CN 200910042537A CN 101476072 A CN101476072 A CN 101476072A
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Abstract
The invention provides an advanced heat-resisting deformation magnesium alloy comprising the following components by weight: Al of 6.0%-9.0%, Ca of 0.5%-3.0%, Sr of 0.05%-0.5%, Mn of 0.1%-0.8%, Mg and ineluctable foreign matters of the rest.The cost of the alloy which does not contain rare-earth elements is low. The formability range of the alloy is extended because the added elements can thin the alloy tissue substantially; and the distribution of heat-resisting phases is turned from bulky bocks or bones to fine and scattered state, which improves the formability of the alloy. The alloy which has a good plastic property and forming ability and has a large deformation temperature range is suitable for common processes of extrusion pressing, drawing, rolling and smithing and can bear bigger deflection and higher deformation velocity at one time. The alloy that can be used as the light high-strength heat-resistant structural metallic material will be widely used for high-temperature transportation piping and high-temperature load-carrying construction of aerospace, automobiles, track trains and the like.
Description
Technical field
The present invention relates to a kind of wrought magnesium alloys, particularly relate to the heat-resistant deforming magnesium alloy of a kind of Ca of containing and Sr.Belong to the structural metallic materials technical field.
Background technology
Magnesium alloy is as the lightest commercial structural metallic materials, with its high specific tenacity, specific rigidity, good damping property, and multifrequency natures such as antimagnetic, shielding, heat radiation have obtained to use widely in aerospace, automobile, 3C fields such as (computer, communication, consumer electronics).On automobile, motorcycle, track train, be applied as example with magnesium alloy, it obviously loss of weight, improve vehicles dynamic performance and cut down the consumption of energy, improve vehicle structure and absorbing vibration and noise but also can limit.But the existing behaviour in service of magnesium is far from giving full play to the potential advantages of magnesium alloy materials, and its major cause is: most magnesium structural part all comes from a kind of processing mode of die casting, and this has limited the kind and the type of product; Range of application is little, and 80% of magnesium die casting is used for automobile industry, and 90% be again the structural part that room temperature is used, and mainly is confined to the small volume part.
Compare with cast magnesium alloys, the wrought magnesium alloys tissue obtains refinement, casting flaw is eliminated, has higher intensity, ductility, more diversified mechanical property is more suitable in making large-sized structural parts and satisfying the diversified demand of structure, and the application of magnesium alloy on large-sized structural parts is following application trend.Development trend from world's magnesium alloy Application Areas, wrought magnesium alloys is the important structure material in fields such as future transportation, aerospace, household electrical appliances, and the needed many sheet materials in these fields, bar, section bar, tubing, forging are can't be displaced with cast article.The magnesium alloy deformation material that exploitation is used for industries such as automobile, motorcycle, aerospace, 3C has the important commercial using value.
Magnesium and magnesium alloy have the close-packed hexagonal crystalline structure, compare with titanium alloy with aluminium alloy, and its plastic deformation ability is lower, and plastic processings such as its extruding, rolling, forging are difficulty comparatively.In addition, as Mg-Al base alloy, often there is low-melting eutectic phase in most of magnesium alloy, has limited the expansion of alloy deformation temperature range to a certain extent.Therefore, when definite deformed magnesium alloy material composition, must both consider the requirement of strength of material, take into account Drawing abillity again.The wrought magnesium alloys series of having researched and developed in the world wide has Mg-Al, Mg-Zn, Mg-Re, Mg-Li, Mg-Th system etc. at present, and the important commercial magnesium alloy of wherein having used has AZ31B or AZ31C and ZK60 etc.However, the kind of wrought magnesium alloys is still less, it is all excellent inadequately to have developed alloy at room temperature and hot strength, ductility, thermotolerance that the more important thing is alloy is also all generally relatively poor, these shortcomings seriously restricting wrought magnesium alloys in the structural metallic materials field expanded application further.
Be intensity and the thermotolerance of improving magnesium alloy, the investigator adopts the alloying means more.People such as I.P.Moreno, Yi Zhen L ǔ add a certain amount of rare earth element by independent or proportioning and come alloy modification, but the cost costliness of this type of alloy.People such as A.Luo, LIY makes alloy structure form Mg by adding a certain amount of Si
2The Si phase, but this phase very easily forms thick Chinese character shape and worsens alloy property, and such alloy one-step casting molding condition harshness.In recent years, Lian Jia alkaline earth element is considered to improve the beneficial element of alloy property.People such as R.Ninomiya report, a certain amount of Ca can make the alloy structure refinement, and produces dystectic Al
2Ca and Mg
2The Ca phase significantly improves the resistance toheat of alloy.But Al
2Ca is thicker usually mutually, can have a strong impact on alloy at room temperature mechanical property and one-step casting forming property, and very unfavorable to the secondary deformation processing characteristics of alloy.The Ca element has had a strong impact on the Application and Development of this alkali earths alloy to these harm of alloy property.By literature search, also do not report at present on the basis that adds the Ca alloy by adding method, patent and the application that Sr is rotten to the alloy structure generation, repair improves Alloy Forming, intensity and resistance toheat.
Summary of the invention
The technical problem to be solved in the present invention is, the deficiency at existing wrought magnesium alloys exists proposes a kind of heat-resistant deforming magnesium alloy that contains Ca and Sr, and it is by a certain amount of Ca of compound interpolation and Sr, and effective refinement alloy structure combines the dystectic Al of generation with Al
2Ca and Al
4The heat-resisting phase of Sr reduces low melting point β-Mg
17Al
12The quantity of phase, simultaneously, Sr is also to Al
2Ca is heat-resisting to be gone bad mutually, repairs, and makes it be tending towards the small and dispersed attitude by thick bulk or bone shape and is distributed in the alloy crystal boundary, thereby improve the forming property of magnesium alloy, intensity and thermotolerance.
The technical scheme that the present invention adopts for achieving the above object is that the mass percent component of the heat-resistant deforming magnesium alloy of described Ca of containing and Sr is:
Al 6.0％～9.0％， Ca 0.5％～3.0％，
Sr 0.05％～0.5％， Mn 0.1％～0.8％，
Surplus is the inevitable impurity of Mg and trace.
Among the present invention, the total mass that can not keep away impurity (as Fe, Si, Ni, Cu etc.) of trace was less than 0.03% described in it was formed.
Do not contain rare earth element in the component of the heat-resistant deforming magnesium alloy of Ca of containing of the present invention and Sr.
The present invention adds 6-9%Al in alloy, to produce the solution strengthening effect, improve alloy at room temperature intensity.In addition, Al also can improve the one-step casting forming technology performance of alloy; In alloy, add 0.5-3.0%Ca, make its effective refinement alloy structure, generate dystectic Al simultaneously
2The heat-resisting phase of Ca reduces low-melting β-Mg
17Al
12The quantity of phase; Add 0.05-0.5%Sr, make it Al
2Ca is heat-resisting to be gone bad mutually, repairs, and make it be tiny shape disperse and be distributed in the alloy crystal boundary, and the further crystal grain thinning and combine with Al and to generate Al of Sr
4The heat-resisting phase of Sr, thus casting, the deformation technique performance of magnesium alloy improved, intensity and thermotolerance; Add 0.1-0.8%Mn, to improve corrosion resistance of alloy.Make alloy grain refinement more by deformation processing, high-melting-point two second phases small and dispersed more distribute, and interior tissue is fine and close more.
The heat-resistant deforming magnesium alloy of Ca of containing of the present invention and Sr can adopt following method to make:
Under the protective condition of flux or protective atmosphere, after pure magnesium melted fully, when 710 ℃-730 ℃ (preferred 720 ℃), add commercial-purity aluminium, technical pure manganese, Al-Ca master alloy and Al-Sr master alloy in proportion respectively; After treating that alloying element all dissolves, when 730 ℃-750 ℃ (preferred 740 ℃), stir alloy 8min-12min, then under this temperature, leave standstill 15min-25min with stirring rod; After static the finishing, under protective atmosphere, alloy liquid steadily is poured in the metal die of preheating 240 ℃-260 ℃ (preferred 250 ℃); The ingot casting of alloy homogenizing under 410 ℃-450 ℃ (preferred 430 ℃) is handled 10h-15h, promptly.Then can carry out conventional extruding or drawing or rolling or forging deformation equipressure processing.Used flux can be RJ-1 or RJ-2 solvent, and used protective atmosphere can be SF
6And CO
2Mixed gas.
The heat-resistant deforming magnesium alloy of Ca of containing of the present invention and Sr does not contain expensive rare earth element, and cost is low; Its one-step casting and secondary deformation processing performance are good, the production efficiency height; Post forming can adopt extruding or rolling or forging process, and can once bear bigger deflection and higher Deformation velocity; Extrusion ratio can reach 20～60 during as hot extrusion, and extrusion speed can reach 1mm/s-8mm/s; Room temperature strength and hot strength, unit elongation and thermotolerance all show excellence, and yield strength, tensile strength and unit elongation reach 200MPa, 330MPa and 14% respectively during as a certain embodiment alloy of the present invention room temperature (25 ℃); Yield strength, tensile strength and unit elongation during high temperature (175 ℃) reach 170MPa, 215MPa and 29% respectively; Steady state creep speed and 100h creep elongation under the 200 ℃/56MPa condition are respectively 0.3 * 10
-9%/S and 0.07%.
Description of drawings
Fig. 1 is that the alloy cast ingot of Comparative Examples 1 of the present invention, Comparative Examples 2, embodiment 1 organizes grain fineness number relatively.
Fig. 2 is the comparison of two second phase sizes in the alloy cast ingot tissue of Comparative Examples 1 of the present invention, Comparative Examples 2, embodiment 1, form, distribution.
Fig. 3 is the comparison of two second phase kinds in the alloy cast ingot tissue of Comparative Examples 2 of the present invention, embodiment 1, quantity.
Fig. 4 is the thermo compression true stress-true strain curve of the embodiment of the invention 1 alloy in the time of 450 ℃.
Fig. 5 is the surface quality contrast after the alloy hot extrusion of Comparative Examples 1 of the present invention, Comparative Examples 2, embodiment 1.
Fig. 6 is the tissue behind the embodiment of the invention 1 alloy hot extrusion deformation.
Fig. 7 is the section bar of the embodiment of the invention 1 alloy hot extrusion processing back different cross section specification.
Specific embodiments
The invention will be further described below in conjunction with Comparative Examples and embodiment.
Comparative Examples 1: a kind of Mg-Al base wrought magnesium alloys, the weight percent of each component is 8%Al in the described magnesium alloy, 0.6%Mn, surplus is Mg and micro-unavoidable impurities.
Comparative Examples 2: a kind of Mg-Al base wrought magnesium alloys that contains Ca, the weight percent of each component is 8%Al in the described magnesium alloy, 1.5%Ca, 0.6%Mn, surplus is Mg and micro-unavoidable impurities.
Embodiment 1: a kind of advanced heat-resistant deforming magnesium alloy that contains Ca and Sr, and the weight percent of each component is 8%Al in the described magnesium alloy, 1.5%Ca, 0.2%Sr, 0.6%Mn, surplus is Mg and micro-unavoidable impurities.
The alloy of Comparative Examples 1, Comparative Examples 2, embodiment 1 can adopt following step of preparation process to produce:
(1) under the protective condition of flux RJ-2, after pure magnesium melted fully, add commercial-purity aluminium, technical pure manganese in the time of 720 ℃ respectively, wherein Comparative Examples 2 alloys add the Al-Ca master alloy again, and embodiment 1 alloy adds Al-Ca master alloy and Al-Sr master alloy again;
(2) treat in the time of 740 ℃, to stir the about 10min of alloy after the whole dissolvings of alloying element, then under this temperature, leave standstill 20min with stirring rod;
(3) after static the finishing, at SO
2Under the protective atmosphere alloy liquid steadily is poured in the metal die of 250 ℃ of preheatings;
(4) ingot casting of alloy is handled 10h-15h 430 ℃ of following homogenizing, then in ingot casting temperature, container temperature and die temperature when being respectively 450 ℃, 400 ℃ and 400 ℃, extrusion ratio and extrusion speed are respectively 15 and carry out hot extrusion deformation processing during 5mm/s, and extrusion is incubated 12h-24h and carries out timeliness thermal treatment and prepare magnesium alloy profiles in the time of 200 ℃ subsequently.
The room-temperature mechanical property of Comparative Examples 1 of the present invention, Comparative Examples 2, embodiment 1 hot extrusion aging state is as shown in table 1.As can be seen from Table 1, the mechanical property rangeability of Comparative Examples 1 of the present invention, Comparative Examples 2, embodiment 1 alloy is bigger, and wherein, embodiment 1 alloy that contains Ca and Sr has optimum room temperature strength, hot strength and creep-resistant property.
The mechanical property of table 1 alloy
The grain-size of Fig. 1-a contrast of display example 1 alloy is thick.The crystal grain of Fig. 1-b contrast of display example 2 alloys obviously obtains refinement, and this mainly is owing to the thinning effect of Ca to alloy substrate.The crystal grain of the embodiment 1 that Fig. 1-c shows further obtains refinement, and this mainly is the Sr element in the Ca alloy organizing that continued refinement on to the basis of alloy structure refinement.The thinner grain fineness number that embodiment 1 alloy shows provides good basis for the follow-up plastic working of alloy.
Fig. 2-a contrast of display example 1 alloy structure, many thick bulks of one-tenth of its two second phase or bone shape are concentrated and are distributed in the crystal boundary place, also have a certain amount of secondary precipitated phase in addition.Fig. 2-b contrast of display example 2 alloy structures, the obvious refinement of its two second phase is distributed in the crystal boundary place than dispersive, and the secondary precipitated phase disappears substantially.This mainly is because the Ca element has consumed a part of Al atom, and two second phases at crystal boundary place have been produced thinning effect.Embodiment 1 alloy structure that Fig. 2-c shows, its two second phase is tiny bar-shaped or strip disperse and is distributed in the crystal boundary place.The distribution of this two second phase small and disperseds mainly has benefited from micro-Sr element to Al
2The reparation of the heat-resisting phase of Ca, metamorphism.Two second phase distributions of this alloy structure are also favourable to the follow-up plastic working of alloy.
Fig. 3-a contrast of display example 2 alloy structures, it contains a certain amount of eutectic β-Mg
17Al
12Phase and Al
2The heat-resisting phase of Ca.Embodiment 1 alloy structure that Fig. 3-b shows, its Al
2The volume fraction of the heat-resisting phase of Ca obviously increases, eutectic β-Mg
17Al
12Almost disappear mutually.This mainly is because reparation, the metamorphism of Sr, and combines with the Al atom and to have generated a certain amount of Al
4Sr high-melting-point phase, and make low melting point β-Mg
17Al
12Almost disappear mutually.Increasing of this heat-resisting phase volume fraction of embodiment 1 alloy enlarged the hot worked temperature range of alloy, and also helps the stable on heating raising of alloy.
The true stress-true strain curve display of 1 alloy embodiment illustrated in fig. 4 alloy of the present invention can under 450 ℃ high temperature, carry out strain rate up to 10s
-1Compression set, and its dependent variable has also reached 1.0 amplitude.When being respectively 450 ℃, 400 ℃ and 400 ℃, extrusion ratio and extrusion speed are respectively 15 and during 5mm/s, and Comparative Examples 1, Comparative Examples 2, embodiment 1 alloy are carried out crimp processing in ingot casting temperature, container temperature and die temperature, and extruded section is seen Fig. 5.Because the two second phase β-Mg that exist in Comparative Examples 1 alloy structure
17Al
12Fusing point lower, have only about 430 ℃, the crystal boundary of alloy then can burning and crack in the time of 450 ℃, section bar limit portion produces a large amount of crackles when therefore causing pushing.For Comparative Examples 2 alloys, high-melting-point Al in its tissue
2Ca compares thick, and it is comparatively concentrated to distribute, and easily produces stress concentration and cause the crack initiation expansion in loading process, therefore causes section bar limit portion a large amount of crackles also to occur when extruding.Compare with Comparative Examples 1, Comparative Examples 2, the extruded section bright in color of embodiment 1 alloy, clear-cut, surface quality is very good.This mainly is because on the basis of Comparative Examples 2 alloys, and a certain amount of Sr makes tiny being distributed in around the alloy crystal boundary of wherein two second phase disperses to rotten, the repair of alloy structure among the embodiment 1, and it has suppressed separating out of low melting point phase substantially.The form of this two second phases, size, distribution are most important to the raising of alloy plasticity.Fig. 5 has shown embodiment 1 alloy after crimp, and through the resulting typical fine grain structure of recovery and recrystallization, this tissue crystal grain is tiny, and two second phases are by further broken.Fig. 7 is the section bar of embodiment 1 alloy through the resulting different cross section shape in hot extrusion processing back.
Based on above-mentioned Comparative Examples 1, contrast 2 and the differentiation situation of embodiment 1 alloy organizing and performance and the mechanical property of the excellence that embodiment 1 alloy is shown, the advanced heat-resistant deforming magnesium alloy of Ca of containing of the present invention and Sr can be used as the heat-stable structural metallic materials of a kind of cheap high-strength light, to satisfy the service requirements of high temperature transport pipes such as aerospace, automobile and track train and high temperature load bearing structure spare, thereby the range of application of expansion magnesium alloy, particularly wrought magnesium alloys.
Claims (2)
1. a heat-resistant deforming magnesium alloy that contains Ca and Sr is characterized in that, its mass percent consists of:
Al?6?.0％～9.0％， Ca?0.5％～3.0％，
Sr?0.05％～0.5％， Mn?0.1％～0.8％，
Surplus is the inevitable impurity of Mg and trace.
According to the described heat-resistant deforming magnesium alloy that contains Ca and Sr of claim 1, it is characterized in that 2, the total mass that can not keep away impurity F e, Si, Ni, Cu of described trace is less than 0.03%.
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Cited By (7)
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| CN102304631A (en) * | 2011-10-17 | 2012-01-04 | 闻喜县瑞格镁业有限公司 | Preparation method of heat-resistant creep-resistant low-cost magnesium alloy |
| CN103334038A (en) * | 2013-04-29 | 2013-10-02 | 太原科技大学 | Alkaline earth magnesium alloy and plate melting-casting treatment method thereof |
| CN107858573A (en) * | 2017-12-11 | 2018-03-30 | 广西趣创想创客空间管理有限责任公司 | A kind of magnesium alloy and preparation method thereof |
| WO2019098269A1 (en) * | 2017-11-17 | 2019-05-23 | 住友電気工業株式会社 | Magnesium alloy and magnesium alloy member |
| CN110438380A (en) * | 2019-08-13 | 2019-11-12 | 中南大学 | A kind of heat-proof combustion-resistant magnesium alloy and its deformation heat treatment method |
| CN111826563A (en) * | 2020-07-23 | 2020-10-27 | 重庆大学 | Thermal cracking resistant casting material based on magnesium-calcium based alloy and preparation method thereof |
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| CN102304631B (en) * | 2011-10-17 | 2013-03-20 | 闻喜县瑞格镁业有限公司 | Preparation method of heat-resistant creep-resistant low-cost magnesium alloy |
| CN102304631A (en) * | 2011-10-17 | 2012-01-04 | 闻喜县瑞格镁业有限公司 | Preparation method of heat-resistant creep-resistant low-cost magnesium alloy |
| CN103334038A (en) * | 2013-04-29 | 2013-10-02 | 太原科技大学 | Alkaline earth magnesium alloy and plate melting-casting treatment method thereof |
| CN103334038B (en) * | 2013-04-29 | 2015-11-25 | 太原科技大学 | A kind of alkaline earth magnesium alloy plate treatment process |
| JPWO2019098269A1 (en) * | 2017-11-17 | 2020-11-26 | 住友電気工業株式会社 | Magnesium alloy and magnesium alloy members |
| WO2019098269A1 (en) * | 2017-11-17 | 2019-05-23 | 住友電気工業株式会社 | Magnesium alloy and magnesium alloy member |
| US11268173B2 (en) | 2017-11-17 | 2022-03-08 | Sumitomo Electric Industries, Ltd. | Magnesium alloy and magnesium alloy member |
| CN107858573A (en) * | 2017-12-11 | 2018-03-30 | 广西趣创想创客空间管理有限责任公司 | A kind of magnesium alloy and preparation method thereof |
| CN110438380A (en) * | 2019-08-13 | 2019-11-12 | 中南大学 | A kind of heat-proof combustion-resistant magnesium alloy and its deformation heat treatment method |
| CN110438380B (en) * | 2019-08-13 | 2021-02-26 | 中南大学 | Heat-resistant flame-retardant magnesium alloy and thermomechanical treatment method thereof |
| CN111826563B (en) * | 2020-07-23 | 2021-12-28 | 重庆大学 | Thermal cracking resistant casting material based on magnesium-calcium based alloy and preparation method thereof |
| CN111826563A (en) * | 2020-07-23 | 2020-10-27 | 重庆大学 | Thermal cracking resistant casting material based on magnesium-calcium based alloy and preparation method thereof |
| CN115449682A (en) * | 2022-09-28 | 2022-12-09 | 广东汇天航空航天科技有限公司 | Magnesium-based alloy compounded by rare earth and alkaline earth elements and preparation method thereof |
| CN115449682B (en) * | 2022-09-28 | 2024-04-26 | 广东汇天航空航天科技有限公司 | Rare earth and alkaline earth element compounded magnesium-based alloy and preparation method thereof |
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