CN100547100C - Contain the magnesium alloy of mishmetal, the wrought magnesium alloy of producing the method for the wrought magnesium alloy that contains mishmetal and producing thus - Google Patents
Contain the magnesium alloy of mishmetal, the wrought magnesium alloy of producing the method for the wrought magnesium alloy that contains mishmetal and producing thus Download PDFInfo
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- CN100547100C CN100547100C CNB2006800076413A CN200680007641A CN100547100C CN 100547100 C CN100547100 C CN 100547100C CN B2006800076413 A CNB2006800076413 A CN B2006800076413A CN 200680007641 A CN200680007641 A CN 200680007641A CN 100547100 C CN100547100 C CN 100547100C
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04M—TELEPHONIC COMMUNICATION
- H04M1/00—Substation equipment, e.g. for use by subscribers
- H04M1/02—Constructional features of telephone sets
- H04M1/0202—Portable telephone sets, e.g. cordless phones, mobile phones or bar type handsets
- H04M1/0206—Portable telephones comprising a plurality of mechanically joined movable body parts, e.g. hinged housings
- H04M1/0208—Portable telephones comprising a plurality of mechanically joined movable body parts, e.g. hinged housings characterized by the relative motions of the body parts
- H04M1/0235—Slidable or telescopic telephones, i.e. with a relative translation movement of the body parts; Telephones using a combination of translation and other relative motions of the body parts
- H04M1/0237—Sliding mechanism with one degree of freedom
Abstract
The invention provides a kind of magnesium alloy of mishmetal, wrought magnesium alloy of producing the method for the wrought magnesium alloy that contains mishmetal and producing thus of containing, wherein in magnesium, added the macro-mixing rare earth, make resistant to elevated temperatures eutectic phase or heterogeneously form stable reticulated structure or stable disperse phase, at high temperature be out of shape and kept high strength thereby suppressed magnesium matrix thus.The described magnesium alloy that contains mishmetal has following formula: Mg
100-x-y-zA
xB
yC
z, wherein A is zinc (Zn) or aluminium (Al); B is a mishmetal; C is at least a element that is selected from manganese (Mn), nickel (Ni), copper (Cu), tin (Sn), yttrium (Y), phosphorus (P), silver (Ag) and strontium (Sr); And x, y and z are respectively the compositions that satisfies 0 atom %≤x≤6 atom %, 0.8 atom %≤y≤7 atom % and 0 atom %≤z≤2 atom %.
Description
Technical field
The present invention relates to contain the magnesium alloy of mishmetal, wherein in magnesium, added the macro-mixing rare earth, make the described magnesium alloy that contains mishmetal have at high temperature stable reticulated structure or disperse phase thus, therefore show excellent mechanical property.In addition; the invention still further relates to the method for producing malleable (wrought) magnesium alloy; described method by hot extrusion and hot rolling with consolidated structure; i.e. second phase (secondary phase) or heterogeneous granulating; and the super-refinement blapharoplast, the invention still further relates to the wrought magnesium alloy of producing by described method.
Background technology
At present, along with environment and power saving receive much concern in worldwide, the weight that alleviates component becomes very necessary.The carbonic acid gas that generates in highway, aviation and the transportation by railroad can cause problem of environmental pollution, and is at present strong day by day to the needs that address this problem, simultaneously, also strong day by day so that save the needs of transport fuel for making lighter component or the finished product.Under this situation, magnesium alloy most possibly is used to make lighter product, because its density in commercial alloys is minimum, promptly its density is low to moderate 2/3 and 1/5 of aluminium alloy and iron alloy density respectively.In addition, magnesium alloy also has excellent specific tenacity, rigidity, absorption of vibrations, workability, dimensional stability and electromagnetic wave shielding effect, therefore is widely used as the cover material such as electronics/communication products such as mobile communication equipment and portable computers.
The magnesium alloy that is used for thermal structure is divided into two classes usually: do not heat-treat promptly the cast magnesium alloys that uses with by being deposited on the sand mold casting magnesium alloy that matrix improves high-temperature behavior mutually with second.
In cast magnesium alloys, because when the die orifice by metal die entered die cavity, melt metal can produce eddy current usually, so its product contains a large amount of pores.In thermal treatment, comprise that in the solution heat treatment process afterwards, these residual pores can cause producing bubble on the product surface, thereby described product is not heat-treated usually.Therefore, be widely used as a kind of Mg-Al alloy of cast magnesium alloys at present, i.e. the high-temperature behavior of AZ91 alloy, particularly creep resistance is very poor.Therefore, the AZ91 alloy is difficult to be applied in such as automobile gearbox etc. and is exposed in the component under the high temperature (more than or equal to 150 ℃).This is because when adding aluminium in magnesium, though intensity under the room temperature and molten metal flow are improved, can form the Mg that makes the high-temperature creep resistance deterioration
17Al
12Phase.In order to overcome this defective, can be as United States Patent (USP) 6,264,763 disclosed add rare earth element or add calcium (Ca), silicon (Si), strontium (Sr) etc. like that.Yet up to the present, still there is restriction in these ways to applicability aspect productivity, the mechanical property that comprises high-temperature creep resistance and erosion resistance and the cost.
In the sand mold casting magnesium alloy, be deposited on mutually in the matrix second by thermal treatment, improve hot strength and thermotolerance thus.Therefore can obtain fine and close relatively foundry goods.For this purpose, the solvability of the element of adding in magnesium matrix should be with variation of temperature significantly changes, and keeps its solvability commonly used under more than or equal to 200 ℃ temperature.As the main adding elements of sand mold casting magnesium alloy, can use silver (Ag), thorium (Th), yttrium (Y), neodymium (Nd), scandium (Sc) etc., they are all very expensive, perhaps contain radioactive substance.Therefore, these elements all strictly are applied in always the needs that improve performance are better than occasion to the consideration of cost.
Simultaneously, there is technical problem usually in the moulding of magnesium alloy.Mainly be that magnesium alloy has HCP structure, there is restriction in this to the required sliding system of plastic working.Based on this reason, at room temperature be difficult to form product.Therefore, need form product by hot-work.
In this way, for intermediates and the finished product of developing magnesium alloy, be starved of and improve formability.The crystalline texture that effective means is refinement (refine) magnesium alloy is to improve extensibility.In addition, the magnesium alloy of described fine grained structure should be mainly by commercial run production.Demand for magnesium alloy plate increases day by day.But, use current commercially available magnesium alloy, still can't effectively produce magnesium alloy plate with required fine grained structure.
In the situation of existing AZ31 alloy, for crystal grain thinning, thickness reduces and will aggravate in the operation of rolling.In the case, therefore reducing because of serious crackle is restricted of thickness limited the refinement of crystal grain.In other words, this solid solution alloy is subjected to the restriction that the source of recrystallization can take place in inside, and therefore the refinement for crystal grain has certain limitation.
Summary of the invention
Technical problem
An object of the present invention is to provide the magnesium alloy that contains mishmetal, wherein in magnesium, added the macro-mixing rare earth, therefore with resistant to elevated temperatures eutectic phase or heterogeneous stable reticulated structure or the stable disperse phase of forming, can suppress magnesium matrix thus at high temperature is out of shape, in addition also to wherein adding other element, precipitation/solid-solution in the basal body structure is enhanced or reticulated structure is enhanced, make it to have excellent mechanical property thus, wherein at high temperature can keep very high intensity.
Another object of the present invention provides the method for production wrought magnesium alloy; in the method, by hot extrusion and hot rolling will add mishmetal second mutually or the consolidated structure of heterogeneous magnesium alloy, promptly second mutually or heterogeneous granulating; lay equal stress on crystalline matrix, crystal grain thinning thus.
Another object of the present invention provides wrought magnesium alloy, described wrought magnesium alloy has fine grained structure, show very high mechanical property, for example in the room temperature interval that this alloy mainly uses, have high strength and high tenacity, under the temperature of mainly carrying out moulding, have favorable extensibility, can improve its formability thus.
Technical solution
For realizing these purposes, the magnesium alloy that contains mishmetal according to the present invention has by Mg
100-x-y-zA
xB
yC
zThe formula of tabular form, wherein A is zinc (Zn) or aluminium (Al); B is a mishmetal; C is at least a element that is selected from manganese (Mn), nickel (Ni), copper (Cu), tin (Sn), yttrium (Y), phosphorus (P), silver (Ag) and strontium (Sr); And x, y and z are respectively the compositions that satisfies 0 atom %≤x≤6 atom %, 0.8 atom %≤y≤7 atom % and 0 atom %≤z≤2 atom %.
In addition, described mishmetal can be didymium-based misch metal or cerium base mishmetal.
Didymium-based misch metal can be the rare earth alloy composition that comprises neodymium (Nd) and praseodymium (Pr) herein.
In addition, cerium base mishmetal can comprise 45 weight %≤Ce≤65 weight %, 20 weight %≤La≤weight %, 5 weight %≤Nd≤15 weight % and 0 weight %≤Pr≤10 weight %.
In addition, described magnesium alloy can also comprise the calcium that is less than or equal to 2 atom %.
The method that production according to the present invention contains the wrought magnesium alloy of mishmetal comprises the steps: that melt casting type is Mg
100-x-y-zA
xB
yC
zMagnesium alloy compositions, wherein A is zinc (Zn) or aluminium (Al); B is a mishmetal; C is at least a element that is selected from manganese (Mn), nickel (Ni), copper (Cu), tin (Sn), yttrium (Y), phosphorus (P), silver (Ag) and strontium (Sr); And x, y and z are respectively the compositions that satisfies 0 atom %≤x≤6 atom %, 0.8 atom %≤y≤7 atom % and 0 atom %≤z≤2 atom %; The described foundry goods of hot extrusion then, by granulating with disperse foundry goods in outside the demagging other come crystal grain thinning mutually, the crystalline matrix of laying equal stress on.
At this, described method can also comprise carries out hot rolling to form the step of sheet material to hot-extruded product.
In addition, the hot extrusion step can be carried out under following extruding condition: temperature range is 350 ℃～450 ℃, and it is 5～80: 1 that the cross section reduces ratio.
In addition, hot-rolled step can carry out under following rolling condition: temperature range is 350 ℃～500 ℃, and it is 25%～50% that the single of thickness reduces per-cent.
In addition, the wrought magnesium alloy that contains mishmetal is by following step production: melt casting type is Mg
100-x-y-zA
xB
yC
zComposition, wherein A is zinc (Zn) or aluminium (Al); B is a mishmetal; C is at least a element that is selected from manganese (Mn), nickel (Ni), copper (Cu), tin (Sn), yttrium (Y), phosphorus (P), silver (Ag) and strontium (Sr); And x, y and z are respectively the compositions that satisfies 0 atom %≤x≤6 atom %, 0.8 atom %≤y≤7 atom % and 0 atom %≤z≤2 atom %; The described foundry goods of hot extrusion, by granulating with disperse foundry goods in outside the demagging other come crystal grain thinning mutually, the recrystallization matrix; Then hot-extruded product is carried out hot rolling to form wrought product.
At this, the size of other phase outside the demagging can be less than or equal to 20 μ m.
In addition, from the sosoloid border to eutectic point or hypereutectic district comprise other phase outside the described demagging.
Advantageous effects
As previously mentioned, in the magnesium alloy that contains mishmetal according to the present invention, added mishmetal, made resistant to elevated temperatures eutectic phase or heterogeneous stable reticulated structure or the stable disperse phase of forming like this, suppressed magnesium matrix thus and at high temperature be out of shape.In addition, also add other element, precipitation/solid-solution in the basal body structure has been enhanced or reticulated structure is enhanced, had excellent mechanical property thus, wherein at high temperature can keep very high intensity.
In addition, in the method for production wrought magnesium alloy according to the present invention, by hot extrusion and hot rolling make added mishmetal second mutually or heterogeneous magnesium alloy recrystallization, and crystal grain thinning.
In addition, the wrought magnesium alloy that contains mishmetal according to the present invention has thin crystalline-granular texture, therefore shows very high mechanical property, and for example the room temperature region of mainly using at this alloy shows high strength and high tenacity.In addition, described wrought magnesium alloy has favorable extensibility under the temperature of mainly carrying out moulding, so formability also is improved.
Like this, the magnesium alloy that contains mishmetal with very good mechanical properties according to the present invention can satisfy required high strength and the stable on heating requirement of automobile power transmission component.
In addition, by in the magnesium alloy that contains mishmetal according to the present invention, adding calcium (Ca), make in air fusion and be cast as be possible, thereby help saving production cost.
In addition, the magnesium alloy that contains mishmetal according to the present invention shows than by the better hot strength of the heat resistance magnesium alloy of current treatment production, therefore can be applied to the parts of automobile and flyer.
In addition, the magnesium alloy that contains mishmetal according to the present invention shows than the better relatively erosion resistance of aforementioned commercially available heat resistance magnesium alloy, therefore can be used for tolerating the lightweight component such as severe condition such as high temperature and corrosion.
Simultaneously, in the method for production wrought magnesium alloy according to the present invention, can produce the magnesium alloy plate that contains a large amount of ultra-fine grains, the plate of being produced has close grain, and formability is very excellent.Therefore, lighter highway, aviation and transportation by railroad instrument can be made into, and cover material can be widely used as such as electronics/communication products such as mobile communication equipment and portable computers according to wrought magnesium alloy of the present invention.
Description of drawings
Fig. 1 is α magnesium structure and the Mg in the alloy 3 in the indicator gauge 1
12The cancellated electron scanning micrograph of Ce phase;
Fig. 2 is the photo of molten metal, has wherein added the calcium (Ca) of 2 weight % in the alloy in table 19, and fusion in air;
Fig. 3 shows according to embodiment 5 near the photo of the cast structure of the magnesium alloy eutectic point;
Fig. 4 shows according to embodiment 5, the microstructure photograph of the wrought product that obtains by following manner, and described mode is for to carry out hot extrusion to magnesium alloy under 450 ℃ temperature, and extrusion speed is 2mm/ second, and it is 6: 1 that the cross section reduces ratio;
Fig. 5 shows according to embodiment 5, the microstructure photograph of the wrought product that forms by following manner, and described mode is for being 100 ℃ of rolling magnesium alloy down in the roller temperature, the single of thickness is reduced to 40% when making specimen temperature be 400 ℃;
Fig. 6 is the photo that is presented among the embodiment 5 by in the wrought product of carrying out preparing under hot extrusion and the rolling condition, is 500 ℃ in temperature, and stress is 1 * 10
-3s
-1, 1 * 10
-2s
-1, 1 * 10
-1s
-1With 1 * 10
-0s
-1Condition under carry out drawing by high temperature test, also shown the unit elongation of described wrought product among the figure;
Fig. 7 shows according to embodiment 6, the microstructure photograph of the wrought product that obtains by following manner, and described mode is for to carry out hot extrusion to magnesium alloy under 450 ℃ temperature, and extrusion speed is 2mm/ second, and it is 6: 1 that the cross section reduces ratio;
Fig. 8 shows according to embodiment 6, the microstructure photograph of the wrought product that forms by following manner, and described mode is for being 100 ℃ of rolling magnesium alloy down in the roller temperature, the single of thickness is reduced to 40% when making specimen temperature be 400 ℃;
Fig. 9 shows according to embodiment 7, the microstructure photograph of the wrought product that obtains by following manner, and described mode is for to carry out hot extrusion to magnesium alloy under 450 ℃ temperature, and extrusion speed is 2mm/ second, and it is 6: 1 that the cross section reduces ratio; With
Figure 10 shows according to embodiment 7, the microstructure photograph of the wrought product that forms by following manner, and described mode is for being 100 ℃ of rolling magnesium alloy down in the roller temperature, the single of thickness is reduced to 40% when making specimen temperature be 400 ℃.
Embodiment
Describe illustrative embodiments of the present invention below with reference to the accompanying drawings in detail.
The magnesium alloy that contains mishmetal according to the present invention has by Mg
100-x-y-zA
xB
yC
zThe formula of expressing, wherein A is zinc (Zn) or aluminium (Al); B is a mishmetal; C is at least a element that is selected from manganese (Mn), nickel (Ni), copper (Cu), tin (Sn), yttrium (Y), phosphorus (P), silver (Ag) and strontium (Sr); And x, y and z are respectively the compositions that satisfies 0 atom %≤x≤6 atom %, 0.8 atom %≤y≤7 atom % and 0 atom %≤z≤2 atom %.
When solidifying according to the magnesium alloy that contains mishmetal of the present invention by casting, rich magniferous sosoloid (α magnesium) constitutes basal body structure.Second by mishmetal (element B) crystallization, forms reticulated structure or disperse phase with the compound formation of magnesium matrix.This reticulated structure is at high temperature stable, and excellent mechanical property is provided thus.In addition, A group and C group element can produce third phase (tertiaryphase), and third phase is mainly used to strengthen the solid-solution/precipitation of magnesium matrix or strengthen reticulated structure, improves mechanical property thus.
To add fashionablely above the A group element aluminium (Al) of 5 atom % with element B, in the α magnesium matrix, will form Mg
17Al
12Phase, this can make the mechanical property variation.Therefore, preferably the amount of the aluminium that adds is restricted to and is less than or equal to 5 atom %.
In addition, with respect to magnesium (Mg), zinc in the time of 340 ℃ (Zn) has 2.4% the peak value sosoloid limit.Yet, consider to be dissolved in second mutually or the amount in the third phase, preferably the adding scope of A group element is restricted to and is less than or equal to 5 atom %.
In the magnesium alloy that contains mishmetal according to the present invention, can be included in the Mg-mishmetal with A group element aluminium (Al) and the zinc (Zn) that magnesium mixes, so that can obtain heterogeneous.Is that 57～71 element constitutes at the mishmetal of this adding by ordination number, and comprises didymium-based misch metal or cerium base mishmetal.Didymium-based misch metal is the rare earth alloy composition that comprises neodymium (Nd) and praseodymium (Pr).Particularly, described cerium base mishmetal is meant a kind of commercially available mixed rare earth alloy, it mainly consists of 45 weight %≤Ce≤65 weight %, 20 weight %≤La≤30 weight %, 5 weight %≤Nd≤15 weight % and 0 weight %≤Pr≤10 weight %, in view of mishmetal crystallization property therein, wherein also there are other trace elementss more than 15 kinds.This mishmetal (element B) can be used for being formed on the reticulated structure or the disperse phase of high temperatures, and improves erosion resistance and molten metal flow.When the adding scope of described mishmetal (element B) surpasses 7 atom % is disadvantageous, because this can cause the ratio of brittle second phase with increase, thereby makes described material at room temperature lose extensibility.Therefore, in the present invention, the adding scope of mishmetal (element B) should be restricted to and be less than or equal to 7 atom %.
In the magnesium alloy that contains mishmetal according to the present invention,, added C group element (Si, P, B, Mn, Sr, Y, Ni, Cu, Sn and Ag) for promoting sosoloid or sedimentary enhancing or strengthening reticulated structure in the magnesium matrix structure.In the case, the C group element of adding has very strong affinity for magnesium (Mg) or mishmetal.When a small amount of adding C group element, the cancellated mechanical property of improving simultaneously can kept.The illustrative examples of C group element has phosphorus (P), boron (B), manganese (Mn), strontium (Sr), yttrium (Y), nickel (Ni), copper (Cu), tin (Sn) and silver (Ag).Therefore, the adding scope of C group element should be restricted to and be less than or equal to 2 atom %,, that is,, strengthen the precipitation/solid-solution in the basal body structure in the cancellated while that keeps or strengthen high-temperature stable so that can obtain the following desired result that causes.
In addition, in the magnesium alloy that contains mishmetal according to the present invention, also need to add small amount of calcium (Ca), so as can be in air fusion and the described magnesium alloy compositions of casting, and need not to use protection gas or flux (flux).In order to obtain the ideal effect of calcium (Ca), the adding scope of calcium should be restricted to and be less than or equal to 2 atom %.
Embodiment
To describe the magnesium alloy that contains mishmetal according to an exemplary embodiment of the present invention in detail below.
Be prepared as follows the molten metal of magnesium alloy compositions given in the table 1, and obtain foundry goods by casting.More specifically, in electric induction furnace, under 700 ℃ temperature, heat plumbago crucible.Molten magnesium in this plumbago crucible adds other additive then.Form molten alloy thus, it is poured in the mould that is preheated to 1200 ℃.So just formed foundry goods.
In the specified composition of table 1, B is meant with atom % to be the cerium base mishmetal of unit.By second of addition element B generation is Mg mutually
12The Ce phase.Fig. 1 is the electron scanning micrograph of alloy 3, shows α magnesium structure and Mg
12Ce has formed reticulated structure mutually.Because it at high temperature is stable forming cancellated described structure, therefore can suppress the distortion of α magnesium structure, so they have at high temperature shown high strength.Therefore, along with the increase of B amount of element, Mg
12Ce also corresponding increase mutually, yield strength under room temperature and the high temperature and tensile strength also all improve thereupon.In addition, in the situation of alloy 10, as the Mg of second phase
12Ce phase and third phase have improved mechanical property thus with the form crystallization of aluminum compound.
[table 1]
Alloy 1:Mg
97.5Zn
1B
1.5, alloy 2:Mg
97Zn
1B
2, alloy 3:Mg
96.5Zn
1B
2.5,
Alloy 4:Mg
95.5Zn
1.5B
3, alloy 5:Mg
96Zn
2B
2, alloy 6:Mg
95.5Zn
2B
2.5,
Alloy 7:Mg
95Zn
2B
3, alloy 8:Mg
94.5Zn
2B
3.5, alloy 9:Mg
94Zn
2B
4,
Alloy 10:Mg
94Zn
2B
4, alloy 11:Mg
92.5Zn
2.5B
5, alloy 12:Mg
89.5Zn
3.5B
7
Therefore, compare with existing magnesium refractory alloy, the magnesium alloy that the magnesium alloy that contains mishmetal according to the present invention can replace heat resistant type sand mold casting heat resistance magnesium alloy and form by die casting, wherein heat resistant type sand mold casting heat resistance magnesium alloy can keep high strength under more than or equal to 300 ℃ temperature, and mainly use under more than or equal to 200 ℃ temperature, the reason that can replace has been to form Strength Changes for second very little phase or the third phase reticulated structure of the dependency of temperature variation.
The E that provides in the table 1
CorrValue is measured by the open circuit potential that carried out in sodium-chlor (NaCl) solution of 3.5 weight % 3 hours and is obtained.Measurement is with respect to the relative erosion resistance of the existing refractory alloy ZA91 of object as a comparison.Found that along with the increase of B amount of element, erosion resistance also increases.
Embodiment 2
Fig. 2 be in the listed alloy 9 of table 1, add the calcium (Ca) of 2 weight % and in air the photo of fused molten metal, shown by to magnesium alloy compositions (for example alloy 9) in, add behind the calcium (Ca) can be in air fusion with cast this magnesium alloy compositions.As seen from Figure 2, in air, during fusion, find on molten metal surface, not form thick oxide compound when described magnesium alloy compositions.
Embodiment 3
[table 2]
| Form (atom %) | Hardness value (H v) | Whether crack |
| Alloy 12 | 165 | ○ |
| Alloy 12+Ni 0.3 | 169 | △ |
| Alloy 12+Cu 0.3 | 190 | × |
| Alloy 12+Sn 0.3 | 176 | × |
| Alloy 12+Al 0.3 | 185 | △ |
| Alloy 12+Mn 0.3 | 195 | × |
| Alloy 12+Si 0.3 | 191 | × |
Zero: crack
△: produce small crackle
*: do not crack
Foregoing according to the magnesium alloy that contains mishmetal of the present invention in, by in magnesium (Mg), adding the Mg that the basic mishmetal of cerium (Ce) produces
12Ce is intermetallic compound mutually and enbrittles.Therefore, work as Mg
12When Ce phase ratio was higher than magnesium matrix, magnesium alloy had the character that extensibility reduces.Therefore in the present embodiment, carried out improving the trial of performance by adding element-specific.In embodiment 3, select to contain Mg in the composition that from table 1, provides
12The alloy 12 that Ce phase ratio is the highest, the fragility of testing second phase then is to adding the degree of dependence of element.The molten metal of preparation magnesium alloy compositions as shown in table 2 obtains foundry goods by casting then, and carries out the Vickers' hardness test.At this moment, test under the condition that between the sunken load of the pressure that is applied is from 100g to 1000g, changes.Be displayed in Table 2 by in alloy 12, adding nickel (Ni), copper (Cu), tin (Sn), aluminium (Al), manganese (Mn) or silicon (Si) and can have increased hardness value.Find that in addition when carrying out hardness test, the degree that produces tiny crack around the impression on surface also decreases or disappears.In table 2, the reason that the increase of hardness value or crackle generation degree change is to add element and has strengthened reticulated structure.In the case, according to present embodiment of the present invention as can be seen, when in the magnesium alloy that contains mishmetal of the present invention, adding the element that has strong affinity for magnesium (Mg) or cerium base mishmetal, when for example the C group is added element (Si, P, B, Mn, Sr, Y, Ni, Cu, Sn and Ag), can improve physical strength.
Embodiment 4
[table 3]
Table 3 has shown and has added in the alloy composite shown in the embodiment 1 (for example alloy 2 and alloy 6) after the Al, it has been carried out the unit elongation that Elongation test obtains.As can be seen from Table 3, unit elongation increases with the trace change of Al.Yet, when the add-on of Al surpasses 4 atom %, be disadvantageous, can at high temperature keep high-intensity reticulated structure because this can't keep, and in magnesium matrix, produce Mg
17Al
12Phase.
As previously mentioned, can find that the magnesium alloy that contains mishmetal according to the present invention is the thermal structure magnesium alloy, compare that its mechanical property and erosion resistance are all improved greatly with existing heat resistance magnesium alloy.
Next the wrought magnesium alloy of being produced by the magnesium alloy that contains mishmetal according to the present invention will be described.
In the present invention, extruding and the rolling Mg alloy castings that has added the mishmetal with aforementioned component form wrought product thus.Usually, magnesium alloy can not be guaranteed the formability under the room temperature.Therefore, in order to obtain fine and close wrought product, Mg alloy castings need carry out hot-work, is set in the scope of the compactness that can guarantee Mg alloy castings by the processing temperature of test with Mg alloy castings.When extruding, preheating and extrusion magnesium alloy foundry goods in 350 ℃～500 ℃ temperature range.Adopted following extruding condition: extrusion ratio: 6.5: 1, the overflow mould angle: 180 ℃, ram speed: 2cm/ minute.
Extruding causes the dispersion and basal body structure recrystallization mutually of second phase, obtains all improved application product of intensity and unit elongation thus.In addition, at the described Mg alloy castings of repeat-rolling, making its per-cent that reduces at 400 ℃ of following thickness is 40%, when obtaining thickness thus and being the rolled products of 1mm, can obtain and pushes similar effect.
The grain refining mechanism that contains the magnesium alloy of mishmetal according to the present invention has been utilized dynamic recrystallization phenomenon, wherein will produce the nucleus of new crystal grain during the hot-work of described magnesium alloy in the structure.For wherein being distributed with a large amount of particulate magnesium alloy, recrystallization source increases, and can carry out grain refining very effectively like this.For making this characteristic maximization, need at first to form the magnesium alloy of volume ratio in 5%～50% scope of other phase except matrix magnesium by casting, then by hot extrusion or hot extrusion and hot rolling with interiorly being dispersed in the magnesium matrix effectively mutually of existing in the magnesium alloy.Like this, because described disperse phase produces dynamic recrystallization effectively, thereby make the grain refining maximization.
More specifically, the wrought magnesium alloy that contains mishmetal according to the present invention can be by chemical general formula Mg
100-x-y-zA
xB
yC
zExpression, wherein A is zinc (Zn) or aluminium (Al), B is a mishmetal, C is at least a element that is selected from manganese (Mn), nickel (Ni), copper (Cu), tin (Sn), yttrium (Y), phosphorus (P), silver (Ag) and strontium (Sr), and x, y and z are respectively the compositions of satisfied 0 atom %≤x≤6 atom %, 0.8 atom %≤y≤7 atom % and 0 atom %≤z≤2 atom %.The mishmetal of Jia Ruing is that 57～71 element constitutes by ordination number herein, and comprises didymium-based misch metal or cerium base mishmetal.Described didymium-based misch metal is the rare earth alloy composition that contains neodymium (Nd) and praseodymium (Pr), described cerium base mishmetal then is meant a kind of commercially available mixed rare earth alloy particularly, it mainly consists of 45 weight %≤Ce≤65 weight %, 20 weight %≤La≤30 weight %, 5 weight %≤Nd≤15 weight % and 0 weight %≤Pr≤10 weight %, in view of mishmetal crystallization property therein, wherein also there are other trace elementss more than 15 kinds.
In Mg, adding at least a these interpolation elements, promptly, can form the element of eutectic, when particularly being rich in the mishmetal of Al, Si, Ag, Ca, Ni, Cu, Zn, Y, Sn, La, Ce, Pr, Nd, Ce and being rich in the mishmetal of didymium, can form the magnesium alloy that contains a large amount of aforementioned phases by casting.When the described magnesium alloy of hot extrusion, its cast structure is with destroyed, and other outside the demagging is by granulating and dispersion.In view of this reason, dynamic recrystallization phenomenon can take place effectively, thereby can crystal grain thinning.With respect to the particle that forms because of the impurity element of introducing inevitably during magnesium alloy cast, this hot extrusion makes can also carry out fragmentation and dispersion effectively.Therefore can make the squeezing prod of magnesium alloy more stable.
When squeezing prod is carried out hot rolling, can be formed on and have a large amount of out of phase magnesium alloy plates in the magnesium matrix.Usually, when existing a large amount of out of phase foundry goods to carry out hot rolling in to magnesium alloy, these with destroyed, become formation of crack mutually, therefore can not rolling described foundry goods.Yet by granulating and dispersive squeezing prod, even produced crackle, its crystal grain has also obtained refinement, and the size of these crystal grain also has been limited to certain particle diameter for wherein said.Therefore, described size can not produce obviously influence to hot rolling, makes squeezing prod be easy to carry out hot rolling.In addition, even when in order effectively to carry out hot rolling during the rising hot-rolled temperature, grain growing also can be because of a large amount of particles that distribute be suppressed, so hot rolling is easy to carry out.
The exemplary embodiment of producing according to the method for the wrought magnesium alloy that contains mishmetal of the present invention will be described below.
In the following embodiments, will be described near the eutectic point or sosoloid border and the production of squeezing prod and magnesium alloy plate in hypereutectic or hypoeutectic district.
Embodiment 5
In the present embodiment, use near the Mg-Ce base mishmetal-Zn alloy of eutectic point to form squeezing prod and sheet material.
The Ce base mishmetal of Mg, the 4.25 atom % of 93.75 atom % and the Zn of 2.0 atom % are mixed and founding, form sheet material thus.Fig. 3 is the photo of the cast structure of Mg-Ce base norium-Zn alloy.For these eutectic phases that distribute effectively to obtain the compact grained magnesium matrix, under 450 ℃ temperature, carry out hot extrusion, extrusion speed is 2mm/ second, it is 6: 1 that the cross section reduces ratio.
Fig. 4 is the microstructure photograph of the hot-extruded product of present embodiment.Observations is, do not have crackle in the internal structure, and crystal grain is very tiny, and its mean sizes is less than 14 μ m.Usually, in not having the particulate magnesium alloy, can't obtain this grain-size by hot extrusion merely.
In addition, be that to reduce per-cent be under 40% the condition, by squeezing prod being rolled the formation magnesium alloy plate under 400 ℃ for 100 ℃, the single of thickness in the roller temperature.Fig. 5 is the microstructure photograph of milled sheet.Observations is, do not have crackle, and crystal grain is very tiny, and its mean sizes is less than 8 μ m.
Formed sheet material is carried out the drawing by high temperature test.The photo of the sample of sheet material to be measured as shown in Figure 6.Under 500 ℃ temperature, use 1 * 10
-3s
-1, 1 * 10
-2s
-1, 1 * 10
-1s
-1With 1 * 10
-0s
-1Stress carry out drawing by high temperature test, sample shows very high unit elongation, is respectively 580%, 370%, 340% and 250%.Therefore can find that near the magnesium alloy that has a large amount of phases eutectic point can stably carry out hot extrusion and hot rolling, and have the formability of excellence because of grain refining.
Embodiment 6
Present embodiment relates to the squeezing prod of Mg-Ce mishmetal in hypoeutectic district and the production of sheet material.
The Ce base mishmetal that mixes the Mg of 95.7 atom % and 4.3 atom % is cast under the condition identical with embodiment 5, hot extrusion and hot rolling then.Fig. 7 is the microstructure photograph of the sample of hot extrusion under this condition, does not wherein have crackle, and crystal grain is very tiny, and its mean sizes is less than 15 μ m.In addition, Fig. 8 is the microstructure photograph of carrying out the wrought magnesium alloy of hot extrusion, has wherein produced very thin crystal grain, and its mean sizes is less than 8 μ m, and does not have crackle.
Can find that in the present embodiment the magnesium alloy that has a large amount of phases until the hypoeutectic district can stably carry out hot extrusion and hot rolling, makes grain refining thus.
Embodiment 7
Present embodiment relates to the Mg-Ce mishmetal-squeezing prod of Zn alloy and the production of sheet material in hypoeutectic district.
Mix the Ce base mishmetal of Mg, 1.5 atom % of 97.0 atom % and the Zn of 1.5 atom %, under the condition identical, cast then, hot extrusion and hot rolling with embodiment 5.Fig. 9 is the microstructure photograph of the sample of hot extrusion under this condition, and wherein there is not crackle in inside, and average grain size is less than 20 μ m.In addition, Figure 10 is the microstructure photograph of carrying out the wrought magnesium alloy of hot extrusion, and wherein crystal grain is very tiny, and its mean sizes is less than 9 μ m.Can find that in the present embodiment the magnesium alloy that has a large amount of phases until the hypoeutectic district can stably carry out hot extrusion, makes grain refining thus.
Claims (12)
1. magnesium alloy that contains mishmetal, described magnesium alloy has following formula:
Mg
100-x-y-zA
xB
yC
z，
Wherein
A is zinc or aluminium;
B is a mishmetal;
C is a kind of element that is selected from manganese, nickel, copper, tin, yttrium, phosphorus, silver and strontium; And
X, y and z are respectively the compositions that satisfies 0 atom %≤x≤6 atom %, 0.8 atom %≤y≤7 atom % and 0 atom %≤z≤2 atom %.
2. magnesium alloy as claimed in claim 1, described magnesium alloy also comprises the calcium that is less than or equal to 2 atom %.
3. magnesium alloy as claimed in claim 1, wherein said mishmetal are didymium-based misch metal or cerium base mishmetal.
4. magnesium alloy as claimed in claim 3, wherein said didymium-based misch metal are the rare earth alloy compositions that comprises didymum.
5. magnesium alloy as claimed in claim 3, wherein said cerium base mishmetal comprise 45 weight %≤Ce≤65 weight %, 20 weight %≤La≤30 weight %, 5 weight %≤Nd≤15 weight % and 0 weight %≤Pr≤10 weight %.
6. a production contains the method for the wrought magnesium alloy of mishmetal, said method comprising the steps of:
Melt casting type is Mg
100-x-y-zA
xB
yC
zMagnesium alloy compositions, wherein A is zinc or aluminium; B is a mishmetal; C is a kind of element that is selected from manganese, nickel, copper, tin, yttrium, phosphorus, silver and strontium; And x, y and z are respectively the compositions that satisfies 0 atom %≤x≤6 atom %, 0.8 atom %≤y≤7 atom % and 0 atom %≤z≤2 atom %; With
The described foundry goods of hot extrusion, by granulating with disperse described foundry goods in outside the demagging other come crystal grain thinning mutually, the crystalline matrix of laying equal stress on.
7. method as claimed in claim 6, described method also comprise carries out hot rolling to form the step of sheet material to hot-extruded product.
8. method as claimed in claim 6, wherein said hot extrusion step is carried out under following extruding condition: temperature range is 350 ℃～450 ℃, and it is 5～80: 1 that the cross section reduces ratio.
9. method as claimed in claim 7, described hot-rolled step carries out under following rolling condition: temperature range is 350 ℃～500 ℃, and it is 25%～50% that the single of thickness reduces per-cent.
10. wrought magnesium alloy that contains mishmetal, described wrought magnesium alloy are by following step production:
Melt casting type is Mg
100-x-y-zA
xB
yC
zComposition, wherein A is zinc or aluminium; B is a mishmetal; C is a kind of element that is selected from manganese, nickel, copper, tin, yttrium, phosphorus, silver and strontium; And x, y and z are respectively the compositions that satisfies 0 atom %≤x≤6 atom %, 0.8 atom %≤y≤7 atom % and 0 atom %≤z≤2 atom %;
The described foundry goods of hot extrusion, by granulating with disperse described foundry goods in outside the demagging other come crystal grain thinning mutually, the crystalline matrix of laying equal stress on; With
Hot-extruded product is carried out hot rolling, to form wrought product.
11. wrought magnesium alloy as claimed in claim 10, the size of other phase outside the wherein said demagging are less than or equal to 20 μ m.
12. wrought magnesium alloy as claimed in claim 10, wherein from the sosoloid border to eutectic point or hypereutectic district comprise other phase outside the described demagging.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020050019242 | 2005-03-08 | ||
| KR1020050019242A KR100671195B1 (en) | 2005-03-08 | 2005-03-08 | High temperature structural Mg alloys containing misch metal |
| KR1020050027811 | 2005-04-02 |
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| CN101137762A CN101137762A (en) | 2008-03-05 |
| CN100547100C true CN100547100C (en) | 2009-10-07 |
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| CN102051511A (en) * | 2011-01-19 | 2011-05-11 | 重庆大学 | Magnesium-zinc-copper magnesium alloy containing cerium |
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| US8361251B2 (en) | 2007-11-06 | 2013-01-29 | GM Global Technology Operations LLC | High ductility/strength magnesium alloys |
| CN101323924B (en) * | 2008-07-24 | 2010-04-21 | 上海交通大学 | Ag-containing cast magnesium alloy and method for preparing the same |
| DE102009038449B4 (en) * | 2009-08-21 | 2017-01-05 | Techmag Ag | magnesium alloy |
| CN102251160A (en) * | 2010-05-19 | 2011-11-23 | 四川大学 | Multielement composite wirelike Mg-Sr(Ba)-mixed rare earth grain refining alterative and preparation method thereof |
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|---|---|---|---|---|
| CN102051511A (en) * | 2011-01-19 | 2011-05-11 | 重庆大学 | Magnesium-zinc-copper magnesium alloy containing cerium |
| CN102051511B (en) * | 2011-01-19 | 2012-09-05 | 重庆大学 | Magnesium-zinc-copper magnesium alloy containing cerium |
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| KR100671195B1 (en) | 2007-01-25 |
| KR20060098039A (en) | 2006-09-18 |
| CN101137762A (en) | 2008-03-05 |
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