CN100408709C - High-strength-toughness magnesium alloy and its preparing method - Google Patents

High-strength-toughness magnesium alloy and its preparing method Download PDF

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Publication number
CN100408709C
CN100408709C CNB2005800098757A CN200580009875A CN100408709C CN 100408709 C CN100408709 C CN 100408709C CN B2005800098757 A CNB2005800098757 A CN B2005800098757A CN 200580009875 A CN200580009875 A CN 200580009875A CN 100408709 C CN100408709 C CN 100408709C
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alloy
casting
temperature
crucible
magnesium
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CN1938441A (en
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马跃群
陈荣石
韩恩厚
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Institute of Metal Research of CAS
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Institute of Metal Research of CAS
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Priority to CNB2004100205671A priority patent/CN100338250C/en
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Priority to PCT/CN2005/000479 priority patent/WO2005111251A1/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • C22C23/02Alloys based on magnesium with aluminium as the next major constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/002Castings of light metals
    • B22D21/007Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making alloys
    • C22C1/02Making alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • C22C23/04Alloys based on magnesium with zinc or cadmium as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/06Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon

Abstract

The present invention relates to a high-strength, high-toughness cast magnesium alloy and the method thereof, in which the alloy consists substantially of aluminum 3-9 wt%, zinc 3.5-9 wt%, manganese 0.15-1.0 wt%, antimony 0.01-2wt%, and the balance magnesium. The alloy may further comprises an element selected from the group consisting of cerium-riched misch metals, calcium or silicon in 0-2 wt%. In the invention, after the T6 (solution + aging) heat treatment, the mechanical property of the typical alloy of the invention can reach the following requirement: the tensile strength sigma b >=270 Mpa, the yield strength sigma0.2>=140 Mpa, the elongation delta5>=6 %, the Brinell hardness >=70, the ballistic work alpha k >=12J. Some alloys of the invention not only have excellent room temperature mechanical property, but also have good elevated mechanical property. The production cost of the invention is relatively low, and it is suitable to produce in large scale. The alloy of the invention is applicable of the casting process, such as permanent mould casting, sand mould casting, press casting, extrusion casting, and the like.

Description

A kind of high-strength-toughness magnesium alloy and preparation method thereof
Technical field
The present invention relates to a kind of cast magnesium alloys and technology of preparing thereof.The objective of the invention is by adopting means such as alloying and thermal treatment to prepare a kind of low cost, high-intensity high-tenacity cast magnesium alloys.The present invention is not only applicable to the casting of metal mold permanent mould, is equally applicable to technologies such as sand mold casting, pressure die casting, extrusion casting.
Background technology
As a kind of light metal material, magnesium alloy has many advantages, such as high specific strength, and fabulous machining and castability, good damping characteristic, dimensional stability and electromagnetic shielding ability etc.Owing to have above characteristic, magnesium alloy component has been widely used in many industrial sectors, comprises automobile industry, 3C Product (computer, communication, consumer electronics) production, military project department etc.In recent years, because urgent day by day automobile loss of weight demand, the low density of magnesium alloy makes it produce extremely strong magnetism once more at traffic and transport field.A quick rise period has appearred in the demand of magnesium alloy.
Yet, relative aluminium alloy, more weak intensity and/or plasticity have seriously limited Application of Magnesium (for example, the application of aspects such as light-duty vehicle wheel hub etc. need high strength, high tenacity simultaneously).Table 1 has provided the tensile mechanical properties of some typical commercial cast magnesium alloyss.
The tensile mechanical properties of the typical cast magnesium alloys of table 1
As can be seen from Table 1, the pressure die casting AZ91 alloy of application quantity maximum has higher intensity at present, but relatively low plasticity has limited its application.In addition, though the AM60 alloy has higher plasticity, not too high intensity has also limited their extensive application.Although there is a spot of magnesium-rare earth to have high strength and high tenacity simultaneously, ZE63 for example, too high cost and complicated heat treatment technology make these alloys be difficult to large-area applications.Because improving the intensity and the plasticity of magnesium alloy is the key point that further enlarges the magnesium alloy range of application, therefore, develop a kind of low cost, high-strength-toughness magnesium alloy is very urgent task.
Although the trial of existing many raising magnesium alloy tensile mechanical properties, major part work wherein concentrate on the drawing by high temperature mechanical property aspect that improves magnesium alloy, and the raising of these alloy ambient temperature mechanical properties is limited.For example, European patent EP 0879898A1 discloses a kind of magnesium alloy with excellent high-temperature behavior and pressure die casting performance, but the disclosed alloy of this invention but has lower room temperature strength (tensile strength<230MPa) and plasticity (unit elongation<5%).United States Patent (USP) 20030084968A1 discloses a kind of high-strength creep resistant magnesium alloy, but the disclosed alloy of this invention also is to have lower temperature-room type plasticity (unit elongation<5%).United States Patent (USP) 6139651 discloses the magnesium alloy that a kind of high temperature is used, but this disclosed alloy at room temperature intensity of invention and plasticity are all undesirable.Although there is a few patents to obtain some promising high-strength-toughness magnesium alloys, such as United States Patent (USP) 20010055539A1, the development of ideal room temperature high-strength-toughness magnesium alloy also needs further expansion more.
In recent years, although more research has been carried out in trace element (rare earth element, beryllium, bismuth, strontium, antimony element etc.) effect in magnesium alloy, most of work concentrates on the modification of commercial magnesium alloy and improves on the creep-resistant property of alloy.For example, Chinese patent CN1401804 discloses a kind of heat resistanceheat resistant magnesium alloy, and this alloy contains the aluminium of 2-10wt% (weight percent, together following), the zinc of 0.2-2wt%, and the manganese of 0.1-0.6wt%, the bismuth of 0.1-2wt%, the antimony of 0.1-1.5wt%, other is a magnesium.European patent EP 1241276 discloses a kind of creep resistance Dow metal magnesium alloy, and this alloy contains the aluminium of 1.5-4.0wt%, the silicon of 0.5-1.8wt%, and the rare earth of 0.05-0.6wt%, the strontium of 0.005-1.5wt% or antimony, magnesium are the balance surplus.Chinese patent CN1341767 discloses automobile-used heat resistanceheat resistant magnesium alloy of a kind of multicomponent and casting technique thereof, and this alloy contains the aluminium of 5-7wt%, the zinc of 0.5-1.0wt%, the silicon of 0.6-1.5wt%, 0.4-0.7wt% antimony, the rare earth of 0.1-0.3wt%, the beryllium of 0.002wt%, magnesium are the balance surplus.
On the basis that lot of documents is analyzed, but we notice the magnesium-aluminum-zinc ternary pressure die casting district at medium aluminium content, medium zinc content, if adopt this property of suitable trace element, may there be the potentiality of developing low cost, high-strength-toughness magnesium alloy in proper heat treatment in addition again.As a result, we have found that some have the magnesium alloy of these characteristics, will go through below.
Summary of the invention
Main purpose of the present invention is by the choose reasonable alloy element and adopts the proper heat treatment means, a kind of cast magnesium alloys that has high strength and high tenacity concurrently is provided.
Second purpose of the present invention is that the magnesium alloy of this method preparation is not only applicable to the permanent mould casting, and is applicable to technologies such as sand mold casting, pressure die casting, extrusion casting.
The 3rd purpose of the present invention is that the magnesium alloy of this method preparation not only has excellent room-temperature mechanical property, and some alloy also can have outstanding mechanical behavior under high temperature.
The 4th purpose of the present invention is the magnesium alloy of this method preparation except having These characteristics, and the production cost of alloy is lower.
The most important discovery of the present invention is: medium aluminium content and medium zinc content have constituted the high-strength-toughness magnesium alloy foundational system; The adding and the proper heat treatment technology of trace element further make alloy reach best mechanical property.
By weight percentage, the aluminium content in the alloy of the present invention is 3~9wt%; Zinc content is 3.5~9wt%; Manganese content is 0.15~1.0wt%; Antimony content is 0.01~2wt%; Mg content is the balance surplus; Can also further contain cerium-rich mischmetal, the calcium of 0~2wt%, certain element of silicon thrin in the alloy.
1), the solution strengthening mechanism of element enhancing toughening mechanism of the present invention is as follows:.2), the precipitation hardened mechanism of secondary: along with the increase of zinc content, Mg 17Al 12Reduce gradually mutually, Mg-Al-Zn ternary phase and magnesium zinc binary increase mutually gradually simultaneously; In addition, behind the trace elements such as adding Mn, Sb, produce new particle wild phase or particle such as Al-Mn, Mg according to meeting 3Sb 2Deng.3), the adding (for example antimony) of some element also can crystal grain thinning and be distributed in continuous fragility secondary precipitated phase on the crystal boundary, thereby play the effect of the intensity, plasticity and the castability that improve alloy.4) thereby, proper heat treatment technology can be by adjusting the secondary precipitated phase quantity and the shape mechanical property that further promote alloy.
Aluminium (Al): 3~9wt%
Aluminium element is very effective for room temperature strength that improves magnesium alloy and hardness not only, and makes magnesium alloy be easier to casting by the freezing range of widening alloy.In order to obtain tangible strengthening effect, the aluminium content in the alloy is 3wt% at least; But too high aluminium content can have a negative impact to the plasticity of alloy.Therefore, the maximum of the aluminium content of interalloy of the present invention is decided to be 9wt%.
Zinc (Zn): 3.5~9wt%
In magnesium alloy, zinc element is the another kind of important alloying element except that aluminium.Zinc and aluminium are used for improving alloy at room temperature intensity and castability jointly in the present invention.Yet, well-known, in magnalium zinc alloy system,, will increase the hot cracking tendency of alloy if the coupling of zinc and aluminium is improper, worsen casting forming function.The present invention is according to the relation (referring to accompanying drawing 1) of the die casting performance and the aluminium zinc content of magnesium-aluminum-zinc ternary alloy system, by selecting suitable aluminium, zinc content, and under the effect of some trace element (for example antimony), thereby on the basis that guarantees the alloy die cast performance, obtained the magnesium alloy that low hot tearing is inclined to.Therefore, the minimum 3.5wt% that should be of the zinc content in the alloy of the present invention.In addition, because too high zinc content can reduce the plasticity of alloy, the highest zinc content should not surpass 9wt%.
Manganese (Mn): 0.15~1wt%
Manganese element adds with the form of aluminium-manganese master alloy in the alloy of the present invention.Although the effect of manganese aspect the raising strength of alloy is not obvious, it can play the effect that some improve yield strengths mutually by the aluminium-manganese particle that is present in the primary crystal crystal grain.Manganese main effect in the present invention is the corrosion resistance nature that improves alloy.Manganese can form compound with the impurity element (as iron, nickel etc.) in the alloy in the alloy melting process, be deposited to crucible bottom, removes impurity, eliminates the deleterious effect of these elements to the alloy corrosion resistance nature.The add-on of manganese is subjected to the restriction of its low solid solubility, and the add-on of manganese is 0.15~1wt% among the present invention.
Antimony (Sb): 0.01~2wt%
Antimony element among the present invention or add with the powder-form of aluminium-foil paper parcel, or add with bulk form.A spot of antimony element meeting refinement primary crystal crystal grain and secondary precipitated phase, thus play the effect that improves alloy mechanical property and alleviate hot cracking tendency.But, when antimony content surpasses 2wt%, the Mg of alligatoring 3Sb 2Particle can reduce mechanical property on the contrary.Therefore, antimony content should be controlled at 0.01%~2wt% among the present invention.
Other element: 0~2wt%
Can also further contain cerium-rich mischmetal, the calcium of 0~2wt%, certain element of silicon thrin in the alloy among the present invention.
Cerium-rich mischmetal among the present invention is the commercially available prod, and its manufacturer is Baotou HUAMEI RE products Co., Ltd..In the cerium-rich mischmetal about 50% be cerium, other main component is lanthanum and neodymium.A spot of rare earth adds the hardness and the mechanical behavior under high temperature that can improve magnesium alloy, but excessive rare earth can increase cost on the one hand, can produce the particle precipitated phase of alligatoring on the other hand and cause mechanical property and the decline of castability.Content of rare earth should be controlled at 0~2wt%, and better is to be limited in 0~1wt%.
The interpolation of calcium constituent not only can be played fire-retardant effect, and can improve the mechanical behavior under high temperature and the creep resistance of alloy.Yet, calcium add the hot cracking tendency that affiliation reduces castability and aggravates alloy.
The interpolation of element silicon also can improve the mechanical behavior under high temperature and the creep resistance of alloy, but too much element silicon can produce thick Mg 2The Si particle produces and causes the decline of mechanical property.
The smelting of interalloy of the present invention and casting technique can be divided into following a few step:
1) setting the crucible target temperature earlier is 700~750 ℃, begins heating; Then various batchings are placed on and are preheated to 140~200 ℃ in the baking oven, the insulating covering agent (can adopt magnesium alloy commonly used insulating covering agent) that will account for purpose alloy gross weight 0.6~4wt% is simultaneously put into baking oven and is toasted; In addition, casting is preheated to 200~400 ℃ with mould in other box-type furnace.
2) when crucible is warming up to 280~320 ℃, feed CO 2Gas carries out gas displacement to crucible, add 30%~50% the insulating covering agent that has toasted then in crucible bottom, again after the pure magnesium batching that preheating is good put into crucible.
3) fusing of pure magnesium batching and etc. after crucible temperature is stabilized in 700~750 ℃, add the various batchings of preheating from high to low successively according to fusing point, melt carried out stir about 8~10 minutes then; In this process, take the circumstances into consideration to add the remaining insulating covering agent that has toasted, do not fire with the surface and be as the criterion.
4) after crucible temperature was stabilized in 700~750 ℃, melt left standstill 4~6 minutes, and per-cent by volume is at 99~99.5% air (or CO 2)+0.5~1%SF 6Draw out surface scum under mixed gas protected;
5) draw slag and finish after, keep crucible temperature at 700~750 ℃, per-cent by volume is at 99~99.5% air (or CO 2)+0.5~1%SF 6Mixed gas protected cast molding down.
Thermal treatment of the present invention has influenced the mechanical property of alloy to a great extent.Alloy heat treatment mode of the present invention can be divided into three kinds of T4 (solution treatment), T5 (ageing treatment), T6 (adding timeliness after the solution treatment again handles), introduces respectively below.
The T4 solution treatment is preferably in protective atmosphere (as argon gas, 99~99.5% air (or CO 2)+0.5~1%SF 6Mixed gass etc.) carry out in, its temperature range is 340~400 ℃ and closely related with zinc content.In general, the solid solubility temperature of magnesium alloy should hang down 10~20 ℃ than the solidus temperature of alloy.The solidus temperature of magnesium-aluminum-zinc ternary alloy system can be with reference to the accompanying drawings 2.In addition, the affiliation that adds of some element (as antimony) produces minimal effect to solidus temperature, and therefore, more accurate solidus temperature can be determined by the differential thermal analysis data of alloy.Time as for the T4 solution treatment can be taken as 8~24 hours.
The temperature of T5 ageing treatment is taken as 70~200 ℃, and the time of ageing treatment can be taken as 8~24 hours.As for T6 thermal treatment, can be understood as the heat treated a kind of combination of T4 and T5.Specifically, be to carry out T4 thermal treatment earlier, and then carry out T5 thermal treatment.
Because thermal treatment has changed the distribution mode and the quantity of particle wild phase, thus remarkably influenced mechanical property.In general, the sample of T4 solution treatment dissolves in the matrix again owing to intermediate phase, so can improve plasticity and shock resistance, but yield strength can decrease.The T5 ageing treatment can be eliminated unrelieved stress and improve mechanical property to a certain extent.T6 handles owing to can redistribute the quantity and the shape of secondary precipitated phase, so can significantly promote the intensity and the hardness of alloy, but the plasticity of alloy can descend to some extent.
Exemplary alloy of the present invention is after T6 (solid solution+timeliness) thermal treatment, and its room-temperature mechanical property can reach: tensile strength sigma b〉=270MPa, yield strength σ 0.2〉=140MPa, unit elongation δ 5〉=6%, Brinell hardness 〉=70, ballistic work α k〉=12J.
The present invention has following advantage:
1) magnesium alloy of the present invention preparation has the characteristic of high-intensity high-tenacity concurrently, and what be particularly suitable for lightweight, high-strength, high-ductility uses the material demand, as automotive hub etc.
2) magnesium alloy of the present invention's preparation not only has excellent room-temperature mechanical property, and some alloy also has mechanical behavior under high temperature preferably.
3) cost performance height of the present invention.Used starting material are easy to get, and cost is low, are suitable for scale operation.
4) smelting of the present invention and casting technique simple and stable.Obvious side reaction, process stabilizing do not take place with irony sidewall of crucible or insulating covering agent in the alloy element that the present invention adopts.
5) applicable craft scope of the present invention is wide.The present invention is not only applicable to permanent mold casting, is equally applicable to technologies such as sand mold casting, pressure die casting, extrusion casting.
Description of drawings
Fig. 1 is the pressure die casting performance and the embodiment alloy position synoptic diagram of Mg-Al-Zn ternary alloy.
Fig. 2 is Mg-Al-Zn ternary alloy phase diagram (solid phase surface) and embodiment alloy position synoptic diagram.
Fig. 3 is the DTA curve of the embodiment of the invention 1 alloy.
Fig. 4 is the as cast condition microtexture of the embodiment of the invention 1 alloy.
Fig. 5 is Mg 3Sb 2Distribution schematic diagram in embodiment 1 alloy after T4 thermal treatment, the arrow mark is Mg among the figure 3Sb 2The distribution of particle in embodiment 1 alloy.
Fig. 6 is the microtexture of embodiment 1 alloy after T4 thermal treatment.
Fig. 7 is the microtexture of embodiment 1 alloy after T6 thermal treatment.
Fig. 8 is the room-temperature mechanical property contrast situation of three kinds of alloys (AM60, AZ91, embodiment 1) as cast condition.
Fig. 9 is the room-temperature mechanical property contrast situation of three kinds of alloys (AM60, AZ91, embodiment 1) T6 heat treatment state.
Figure 10 is the room-temperature mechanical property contrast situation of four kinds of alloys (embodiment 1, embodiment 2, embodiment 3, AZ91) T6 heat treatment state.
Figure 11 is 150 ℃ of mechanical behavior under high temperature contrast situations of four kinds of alloys (embodiment 1, embodiment 2, embodiment 3, AZ91) T6 heat treatment state.
Figure 12 is 150 ℃ of mechanical behavior under high temperature contrast situations of three kinds of alloys (embodiment 4, embodiment 5, AZ91) T6 heat treatment state.
Embodiment
Below in conjunction with embodiment in detail high-strength-toughness magnesium alloy of the present invention is described in detail:
Embodiment 1
I), alloy composition
Three kinds of magnesium alloy adopt commercial high pure raw materials to be prepared from the soft steel crucible.In three kinds of alloys, commercial trade mark AZ91 and tested alloys AM60 are the comparative example alloy.The chemical ingredients of three kinds of magnesium alloy adopts inductively coupled plasma-atomic emission spectrum (ICP-AES) technology to analyze.The chemical ingredients of three kinds of magnesium alloy sees Table 2.
The chemical component table of three kinds of alloys of table 2. (weight percent wt%)
II), alloy smelting and casting
The smelting of alloy is carried out in the crucible of one 15 kg capacity and resistance furnace.Crucible and mold and pattern for casting tool adopt low-carbon steel material.Be example with embodiment 1 below, elaborate the smelting and the casting technique of alloy.
1) setting the crucible target temperature is 720 ℃, begins heating; Then various batchings such as pure magnesium, fine aluminium, aluminium manganese master alloy, star antimony, pure zinc are placed on and are preheated to 160 ℃ in the baking oven, the RJ-2 insulating covering agent (RJ-2 insulating covering agent manufacturer is a Sichuan Lan Degaoke industry company limited, and its trade names are ZS-MF1) that will account for purpose alloy gross weight 2wt% is simultaneously put into baking oven and is toasted; Casting is preheated to 300 ℃ with mould in other box-type furnace.
2) when crucible is warming up to 300 ℃, feed CO 2Gas carries out gas displacement to crucible, add about 1/2 the insulating covering agent that has toasted then in crucible bottom, again after the pure magnesium batching that preheating is good put into crucible.
3) fusing of pure magnesium batching and etc. after crucible temperature is stabilized in 720 ℃, add the various batchings (fine aluminium, aluminium manganese master alloy, star antimony, pure zinc etc.) of preheating from high to low successively according to fusing point, melt carried out stir about 8~10 minutes then; In this process, take the circumstances into consideration to add the remaining insulating covering agent that has toasted, do not fire with the surface and be as the criterion.
4) after crucible temperature was stabilized in 720 ℃, melt left standstill 4~6 minutes, and per-cent by volume is at 99~99.5% air (or CO 2)+0.5~1%SF 6Draw slag under mixed gas protected;
5) draw slag and finish after, keep crucible temperature and be stabilized in 720 ℃, per-cent by volume is at 99~99.5% air (or CO 2)+0.5~1%SF 6Mixed gas protected cast molding down.
The smelting of AZ91 and AM60 alloy and casting technique and AZY641 are similar, are the add-on difference of various alloying elements.
III), heat treatment of alloy:
Three kinds of heat treatment of alloy all can be divided into three kinds of T4 (solid solution), T5 (timeliness), T6 (solid solution+timeliness):
A) T4 thermal treatment: the T4 thermal treatment temp can be deduced from differential thermal analysis (DTA) data of alloy and draw.For example (with reference to figure 3), the DTA curve of embodiment 1 alloy show in place existence two flex points (377 ℃, 354 ℃) near solidus curve.According to experiment, the T4 thermal treatment temp of embodiment 1 alloy can not be above 370 ℃.The T4 thermal treatment temp of embodiment 1 alloy is 370 ℃, and the time is 12 hours.The T4 thermal treatment temp of AZ91 and AM60 alloy is 410 ℃, and heat treatment time was controlled at 16~24 hours.The sample that T4 thermal treatment finishes all adopts air cooling to room temperature.
B) T5 thermal treatment: three kinds of alloys can adopt identical T5 thermal treatment.The heat treated temperature of T5 is controlled at 180 ℃, and the heat treated temperature of T5 is 16 hours, and the sample that thermal treatment finishes all adopts air cooling to room temperature.
C) T6 thermal treatment: T6 thermal treatment can be regarded T4 and the heat treated combination of T5 as.Every kind of alloy all successively gets final product by above-mentioned suitable separately T4 and T5 thermal treatment.
IV), microtexture characterizes
Its preparation process of the sample of microstructure observation is as follows: adopt No. 1000 silicon carbide silicon carbide papers to polish the surface; Adopt the mechanical polishing of oil base diamond paste then; Sample surfaces after the polishing adopts the nital of 2% concentration to carry out corruption and carves.Microstructure observation is being furnished with and can carrying out on the scanning electron microscope Philips XL30 ESEM-FEG/EDAX of spectral apparatus.
Than the alloy that does not add antimony element, its primary crystal crystal grain of the as-cast structure of embodiment 1 alloy and secondary precipitated phase have all obtained refinement to a certain degree (with reference to figure 4).The mechanism of this process can be understood like this: a spot of antimony element can generate the Mg that fusing point reaches 1228 ℃ with magnesium 3Sb 2Particle; These Mg 3Sb 2Particle can be in melt cools preferentially generates, and the effect of refinement primary phase is played in the heterogeneous nucleating center that some particle wherein will become primary phase; Other Mg 3Sb 2Thereby particle can appear at the liquid phase forward position of continuous growth with separating out of two second phases the secondary precipitated phase distribution that interaction causes disperse more takes place.In scanning electron microscope and power spectrum observation, Mg 3Sb 2Particle not only appears at primary crystal crystal grain inside, and appears at (with reference to figure 5) on the crystal boundary.
The microtexture that Fig. 6 and Fig. 7 have provided embodiment 1 alloy that different heat treatment modes causes develops.As can be seen from Figure 6, T4 thermal treatment causes most secondary precipitated phase to dissolve in again in the primary phase, and residual particles all is to have dystectic particle (as Mg among the figure 3Sb 2And the Al-Mn particle etc.).T6 thermal treatment makes solute element separate out again from primary grain, and is distributed in crystal boundary and crystal grain inside (with reference to figure 7) with the form of more disperse.
V), Mechanics Performance Testing
Alloy at room temperature mechanics tensile property sample prepares with reference to Chinese national standard GB 6397-86.The parallel distance of sample is of a size of 30 * 6 * 3 (mm).No. 1000 carborundum paper polishings are adopted on the surface of sample.The strain rate of tension test is 1.11 * 10 -3S -1
The parallel distance of the high temperature of alloy (150 ℃) mechanics tensile property sample is of a size of 27 * 5 * 3 (mm).No. 1000 carborundum paper polishings are adopted on the surface of sample.The strain rate of tension test is 5.55 * 10 -4S -1
The Brinell hardness specimen preparation of alloy and experimental technique are with reference to GB231-84, and specimen size is 15 * 15 * 5 (mm).
The impact property sample of alloy prepares with reference to Chinese national standard GB/T 229-1994.The parallel distance of sample is of a size of 10 * 10 * 55 (mm), and sample is the non-notch sample.
Fig. 8 has provided the room-temperature mechanical property contrast of cast alloy (AZ91-F, AM60-F, embodiment 1-F).Fig. 9 has provided the room-temperature mechanical property contrast of T6 heat treatment state alloy (AZ91-T6, AM60-T6, embodiment 1-T6).
Table 3 embodiment 1 alloy at room temperature mechanical property
As can be seen from Table 3, T4 thermal treatment has improved the plasticity of embodiment 1 alloy; T5 thermal treatment has also improved mechanical property to a certain extent.T6 thermal treatment has obtained the highest yield strength and tensile strength, but has sacrificed some plasticity with T4 thermal treatment ratio.
Embodiment 1 sees Figure 10 with AZ91 alloy room-temperature mechanical property contrast situation, and embodiment 1 sees Figure 11 with the contrast situation of the mechanical behavior under high temperature of AZ91 alloy.As can be seen, though the room temperature comprehensive mechanical property of embodiment 1 is better than AZ91, mechanical behavior under high temperature but is inferior to AZ91 a little.
Embodiment 2
I), alloy composition
The chemical ingredients of embodiment 2 alloys sees Table 4.
The chemical component table of table 4. embodiment 2 alloys (weight percent wt%)
II), alloy smelting and casting
The smelting of reference example 1 and casting.Difference is: both zinc content differences.
III), heat treatment of alloy:
The thermal treatment of reference example 1.Difference is: according to the DTA data of embodiment 2 alloys, the temperature of its solution heat treatment is 360 ℃, and the time is 12 hours; The temperature of ageing treatment is 180 ℃, and the time is 16 hours.
IV), Mechanics Performance Testing
The Mechanics Performance Testing of reference example 1.
Table 5. embodiment 2 alloy at room temperature mechanical properties
Embodiment 2 sees Figure 11 with the contrast situation of the mechanical behavior under high temperature of AZ91 alloy.As can be seen, embodiment 2 not only room temperature comprehensive mechanical property is better than AZ91, and mechanical behavior under high temperature also is better than AZ91.
Embodiment 3
I), alloy composition
The chemical ingredients of embodiment 3 alloys sees Table 6.
The chemical component table of table 6. embodiment 3 alloys (weight percent wt%)
II), alloy smelting and casting
The smelting of reference example 1 and casting.Difference is: both zinc content differences.
III), heat treatment of alloy:
The thermal treatment of reference example 1.Difference is: according to the DTA data of embodiment 3 alloys, the temperature of its solution heat treatment is 350 ℃, and the time is 12 hours; The temperature of ageing treatment is 180 ℃, and the time is 16 hours.
IV), Mechanics Performance Testing
The Mechanics Performance Testing of reference example 1.
Table 7. embodiment 3 alloy at room temperature mechanical properties
Embodiment 3 sees Figure 11 with the contrast situation of the mechanical behavior under high temperature of AZ91 alloy.As can be seen, embodiment 3 not only room temperature comprehensive mechanical property is higher than AZ91, and the intensity attribute of mechanical behavior under high temperature also is better than AZ91.
Embodiment 4
I), alloy composition
The chemical ingredients of embodiment 4 alloys sees Table 8.
The chemical component table of table 8. embodiment 4 alloys (weight percent wt%)
II), alloy smelting and casting
The smelting of reference example 1 and casting.Difference is: embodiment 4 alloys have added a small amount of cerium-rich mischmetal on the basis of embodiment 1 alloy.
Because the fusing point of mishmetal is higher, when therefore adding batching, adds cerium-rich mischmetal earlier, and be preferably in and add mishmetal when melt temperature in the crucible is 750~800 ℃.
III), heat treatment of alloy:
The thermal treatment of reference example 1.Difference is: according to the DTA data of embodiment 4 alloys, the heat treatment of alloy solid solution temperature is 370 ℃, and the time is 12 hours; The temperature of ageing treatment is 180 ℃, and the time is 16 hours.
IV), Mechanics Performance Testing
The Mechanics Performance Testing of reference example 1.
Table 9 embodiment 4 alloy at room temperature mechanical properties
Embodiment 4 sees Figure 12 with the contrast situation of the mechanical behavior under high temperature of AZ91 alloy.As can be seen, though the room temperature comprehensive mechanical property of embodiment 1 is better than AZ91, mechanical behavior under high temperature but is inferior to AZ91 a little.
Embodiment 5
I), alloy composition
The chemical ingredients of embodiment 5 alloys sees Table 10.
The chemical component table of table 10. embodiment 5 alloys (weight percent wt%)
II), alloy smelting and casting
The smelting of reference example 1 and casting.Difference is: the smelting of reference example 1 and casting.Difference is: except aluminium, zinc content are different, also added a small amount of cerium-rich mischmetal in embodiment 5 alloys.
Because the fusing point of mishmetal is higher, when therefore adding batching, adds cerium-rich mischmetal earlier, and be preferably in and add mishmetal when melt temperature in the crucible is 750~800 ℃.
III), heat treatment of alloy:
The thermal treatment of reference example 1.Difference is: according to the DTA data of embodiment 5 alloys, the heat treatment of alloy solid solution temperature is 350 ℃, and the time is 12 hours; The temperature of ageing treatment is 180 ℃, and the time is 16 hours.
IV), Mechanics Performance Testing
The Mechanics Performance Testing of reference example 1.
Table 11 embodiment 5 alloy at room temperature mechanical properties
Embodiment 5 sees Figure 12 with the contrast situation of the mechanical behavior under high temperature of AZ91 alloy.As can be seen, embodiment 5 not only room temperature comprehensive mechanical property is better than AZ91, and the intensity attribute of mechanical behavior under high temperature also is better than AZ91.

Claims (7)

1. cast magnesium alloys, it is characterized in that: by weight percentage, the principal element that is used for alloying is composed as follows: aluminium content is 3~9%; Zinc content is 3.5~9%; Manganese content is 0.15~1.0%; Antimony content is 0.01~2%; Mg content is the balance surplus.
2. according to the described cast magnesium alloys of claim 1, it is characterized in that: also further contain cerium-rich mischmetal, the calcium of 0~2wt%, the element of silicon thrin in the alloy.
3. according to the preparation method of the described cast magnesium alloys of claim 1, it is characterized in that its melting and casting process are as follows:
1) setting the crucible target temperature earlier is 700~750 ℃, begins heating; Then various batchings are placed on and are preheated to 140~200 ℃ in the baking oven, and the insulating covering agent that will account for purpose alloy gross weight 0.6~4% is put into baking oven and toasted; In addition, casting is preheated to 200~400 ℃ with mould in other box-type furnace;
2) when crucible is warming up to 280~320 ℃, feed CO 2Gas carries out gas displacement to crucible, add 30%~50% the above-mentioned insulating covering agent that has toasted then in crucible bottom, and then that preheating is good pure magnesium batching is put into crucible;
3) fusing of pure magnesium batching and etc. after crucible temperature is stabilized in 700~750 ℃, add the various batchings of preheating from high to low successively according to fusing point, melt stirred 8~10 minutes then; In this process, add the remaining insulating covering agent that has toasted, do not fire with the surface and be as the criterion;
4) after crucible temperature was stabilized in 700~750 ℃, melt left standstill 4~6 minutes, and per-cent by volume is at 99~99.5% air or CO 2+ 0.5~1%SF 6Draw out surface scum under mixed gas protected;
5) draw slag and finish after, keep crucible temperature at 700~750 ℃, per-cent by volume is at 99~99.5% air or CO 2+ 0.5~1%SF 6Mixed gas protected cast molding down.
4. according to the described cast magnesium alloys preparation method of claim 3, it is characterized in that: the thermal treatment that alloy adopts is divided into three kinds: solution treatment, artificial aging and solution treatment+artificial aging.
5. according to the preparation method of the described cast magnesium alloys of claim 4, it is characterized in that: the temperature range of described solution treatment is 340~400 ℃, and the time of solution treatment is 8~24 hours.
6. according to the preparation method of the described cast magnesium alloys of claim 4, it is characterized in that: described artificially aged temperature range is 70~200 ℃, and the time of processing is 8~24 hours.
7. according to the preparation method of the described cast magnesium alloys of claim 3, it is characterized in that: permanent mold casting is adopted in described cast molding, perhaps adopts sand mold casting, pressure die casting or Extrution casting technique.
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