CN1886529B - High strength and high toughness magnesium alloy and method for production thereof - Google Patents
High strength and high toughness magnesium alloy and method for production thereof Download PDFInfo
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- CN1886529B CN1886529B CN2004800346907A CN200480034690A CN1886529B CN 1886529 B CN1886529 B CN 1886529B CN 2004800346907 A CN2004800346907 A CN 2004800346907A CN 200480034690 A CN200480034690 A CN 200480034690A CN 1886529 B CN1886529 B CN 1886529B
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- 238000000034 method Methods 0.000 claims abstract description 72
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000005266 casting Methods 0.000 claims description 105
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- 238000007669 thermal treatment Methods 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 26
- 229910052746 lanthanum Inorganic materials 0.000 claims description 26
- 229910052684 Cerium Inorganic materials 0.000 claims description 25
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- 239000013078 crystal Substances 0.000 claims description 25
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- 229910052779 Neodymium Inorganic materials 0.000 claims description 24
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 24
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- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
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- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 31
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Abstract
To provide a high strength and high toughness magnesium alloy which has a strength and a toughness both being at a level sufficient for the alloy to be practically used corresponding to the expanded application of a magnesium alloy and a method for producing the alloy. A high strength and high toughness magnesium alloy, characterized in that it is a plastically worked product produced by a method comprising preparing a magnesium alloy cast product containing a atomic % of Zn, b atomic % of Y, a and b satisfying the following formulae (1) to (3), and the balance amount of Mg, subjecting the magnesium alloy cast product to a plastic working to form a preliminary plastically worked product, and subjecting the preliminary plastically worked product to a heat treatment, and it has a hcp structure magnesium phase and a long period stacking structure phase at an ordinary temperature; (1) 0.5 <= a < 5.0 (2) 0.5 < b < 5.0 (3) 2/3a - 5/6 <= b.
Description
Technical field
The present invention relates to high-strength high-toughness magnesium alloy and manufacture method thereof, more particularly, relate to by contain specific rare earth element with specified proportion and realized the high-strength high-toughness magnesium alloy and the manufacture method thereof of high-intensity high-tenacity.
Background technology
Magnesium alloy is because of its recycling, promptly begins with parts to popularize as the basket or the automobile of portable phone or subnotebook PC.
In order to can be used in these purposes, require high strength and high tenacity for magnesium alloy.In order to make the magnesium alloy of high-intensity high-tenacity, in the past from the material aspect and the method for making aspect carried out various researchs.
Aspect method for making, in order to promote the nano junction crystallization, developed quench solidification powder metallurgy (RS-P/M) method, can obtain the magnesium alloy of the intensity about about 2 times 400MPa of cast material.
As magnesium alloy, the known alloy that composition systems such as Mg-Al class, Mg-Al-Zn class, Mg-Th-Zn class, Mg-Th-Zn-Zr class, Mg-Zn-Zr class, Mg-Zn-Zr-RE (rare earth element) class are arranged.Promptly use the casting manufacturing to have the magnesium alloy of these compositions, also can't obtain enough intensity.When having the magnesium alloy of described composition with described RS-P/M manufactured, though with compare the intensity that can reach higher with the situation of casting manufacturing, yet intensity is still insufficient, even perhaps intensity is enough, toughness (ductility) is also insufficient, is difficult to the shortcoming used thereby have in the purposes that requires high strength and high tenacity.
As magnesium alloy, Mg-Zn-RE (rare earth element) class alloy (for example patent documentation 1,2 and 3) was proposed with high strength and high tenacity.
In addition, announce that in patent documentation 4 Mg-1 atom %Zn-2 atom %Y alloy, the Mg-1 atom %Zn-3 atom %Y alloy that utilizes the liquid quench method to make arranged.This alloy makes the crystal grain miniaturization realize high strength by utilizing chilling.
In addition, announce that in non-patent literature 1 castings have Mg-1 atom %Zn-2 atom %Y alloy with extrusion ratio 4,420 ℃ of extruding of temperature, has carried out the magnesium alloy of 16 ECAE processing.This magnesium alloy belongs to by utilizing chilling to make the crystal grain miniaturization realize the extension of the thought of the invention of being announced in the patent documentation 4 of high strength.For this reason, by carrying out the miniaturization that 16 times ECAE processing realizes crystal grain.
Patent documentation 1: No. 3238516 communiques of patent (Fig. 1)
Patent documentation 2: No. 2807374 communiques of patent
Patent documentation 3: the spy opens 2002-256370 communique (scope of claim, embodiment)
Patent documentation 4:WO02/066696 (PCT/JP01/00533)
Non-patent literature 1:Material Transactions, Vol.44, (2003) 463～467 pages of No.4
But, in the Mg-Zn-RE class alloy in the past, for example be with the alloy material thermal treatment of amorphous, carry out fine crystallineization, obtain high-intensity magnesium alloy.Like this, for the zinc that obtains the alloy material of described amorphous, just have to need a great deal of and the prejudice of rare earth element, use the magnesium alloy that contains zinc and rare earth element more.
Though record in patent documentation 1 and 2 and can obtain high strength and high tenacity, intensity and toughness all reach the alloy that is used for practical level yet do not have in fact basically.In addition, the purposes of magnesium alloy enlarges now, and intensity in the past and toughness are also insufficient, need have higher intensity and flexible magnesium alloy.
In addition, in the non-patent literature 1, owing to after pushing, carry out 16 times ECAE processing, therefore the shortcoming that has manufacturing cost to increase with extrusion ratio 4.In addition, even by the ECAE processing of carrying out 16 times total deformation is increased to more than 16, yield strength also stays in about 200MPa, and intensity is insufficient.
Summary of the invention
The present invention considers aforesaid situation and finishes, and its purpose is, at the expansion of magnesium alloy purposes, provide intensity and toughness all to be in to can be used in the high-strength high-toughness magnesium alloy and the manufacture method thereof of practical level.
In order to solve described problem, the feature of the magnesium alloy of high-intensity high-tenacity of the present invention is, contains the Zn of a atom %, contains the Y of b atom %, and remainder is made of Mg, and a and b satisfy following formula (1)～(3).
(1)0.5≤a＜5.0
(2)0.5＜b＜5.0
(3)2/3a-5/6≤b
In addition, best described high-strength high-toughness magnesium alloy has hcp structure magnesium phase, is the plastic working thing that the casting of magnesium alloy divine force that created the universe has been carried out plastic working.
The feature of high-strength high-toughness magnesium alloy of the present invention is, the casting of magnesium alloy divine force that created the universe that is produced as follows, promptly, the Zn that contains a atom %, the Y that contains b atom %, remainder is made of Mg, and a and b satisfy following formula (1)～(3), the described casting of magnesium alloy divine force that created the universe has been carried out the plastic working thing after the plastic working had hcp structure magnesium at normal temperatures and reach long period rhythmo structure phase mutually.
(1)0.5≤a＜5.0
(2)0.5＜b＜5.0
(3)2/3a-5/6≤b
The feature of high-strength high-toughness magnesium alloy of the present invention is, the casting of magnesium alloy divine force that created the universe that is produced as follows, promptly, the Zn that contains a atom %, contain the Y of b atom %, remainder is made of Mg, and a and b satisfy following formula (1)～(3), the described casting of magnesium alloy divine force that created the universe is carried out plastic working and makes the plastic working thing, described plastic working thing has been carried out the plastic working thing after the thermal treatment had hcp structure magnesium at normal temperatures and reach long period rhythmo structure phase mutually.
(1)0.5≤a＜5.0
(2)0.5＜b＜5.0
(3)2/3a-5/6≤b
In addition, in the high-strength high-toughness magnesium alloy of the present invention, the median size of best described hcp structure magnesium phase is more than 2 μ m.In addition, there are a plurality of random grain boundaries in the median size of best described long period rhythmo structure phase at the intragranular of described long period rhythmo structure phase more than 0.2 μ m, by the median size of the crystal grain of described random grain boundary regulation more than 0.05 μ m.
In addition, in the high-strength high-toughness magnesium alloy of the present invention, preferably compare with described hcp structure magnesium dislocation desity mutually, the dislocation desity of described long period rhythmo structure phase is a kind of order of magnitude extremely when young.
In addition, in the high-strength high-toughness magnesium alloy of the present invention, the percentage by volume of the crystal grain of best described long period rhythmo structure phase is more than 5%.
In addition, in the high-strength high-toughness magnesium alloy of the present invention, also can make described plastic working thing have at least a precipitate of from the precipitate group that the compound by the compound of compound, Zn and the rare earth element of compound, Mg and the Zn of Mg and rare earth element and Mg and Zn and rare earth element constitutes, selecting.
In addition, in the high-strength high-toughness magnesium alloy of the present invention, also can make the total percentage by volume of described at least a precipitate surpass 0% and below 40%.
In addition, in the high-strength high-toughness magnesium alloy of the present invention, best described plastic working be roll, at least one the processing in the middle of extruding, ECAE, stretch process, forging, punching press, rolling forming, bending, FSW processing and their processing repeatedly.
In addition, in the high-strength high-toughness magnesium alloy of the present invention, be preferably in total deformation when carrying out described plastic working below 15.
In addition, in the high-strength high-toughness magnesium alloy of the present invention, be preferably in total deformation when carrying out described plastic working below 10.
In addition, in the high-strength high-toughness magnesium alloy of the present invention, also can add up at least a element of selecting that contains c atom % in described Mg from be made of Yb, Tb, Sm and Nd one group, c satisfies following formula (4) and (5).
(4)0≤c≤3.0
(5)0.2≤b+c≤6.0
In addition, in the high-strength high-toughness magnesium alloy of the present invention, also can add up at least a element of selecting from be made of La, Ce, Pr, Eu, Mm and Gd a group that contains c atom % in described Mg, c satisfies following formula (4) and (5) or satisfies (5) and (6).
(4)0≤c＜2.0
(5)0.2≤b+c≤6.0
(6)c/b≤1.5
In addition, in the high-strength high-toughness magnesium alloy of the present invention, also can in described Mg, add up at least a element of from constitute by Yb, Tb, Sm and Nd a group, selecting that contains c atom %, add up at least a element of selecting from be made of La, Ce, Pr, Eu, Mm and Gd a group contain d atom %, c and d satisfy following formula (4)～(6) or satisfy (6) and (7).
(4)0≤c≤3.0
(5)0≤d＜2.0
(6)0.2≤b+c+d≤6.0
(7)d/b≤1.5
The feature of high-strength high-toughness magnesium alloy of the present invention is, contains the Zn of a atom %, contains the Y of b atom %, and remainder is made of Mg, and a and b satisfy following formula (1)～(3).
(1)0.25≤a≤5.0
(2)0.5≤b≤5.0
(3)0.5a≤b
In addition, best described high-strength high-toughness magnesium alloy has hcp structure magnesium phase, is the plastic working thing that has carried out plastic working after the casting of magnesium alloy divine force that created the universe is cut.
The feature of high-strength high-toughness magnesium alloy of the present invention is, the casting of magnesium alloy divine force that created the universe that is produced as follows, promptly, the Zn that contains a atom %, contain the Y of b atom %, remainder is made of Mg, and a and b satisfy following formula (1)～(3), make flaky castings by cutting the described casting of magnesium alloy divine force that created the universe, utilize plastic working thing that described castings has been solidified in plastic working to have hcp structure magnesium at normal temperatures and reach long period rhythmo structure phase mutually.
(1)0.25≤a≤5.0
(2)0.5≤b≤5.0
(3)0.5a≤b
The feature of high-strength high-toughness magnesium alloy of the present invention is, the casting of magnesium alloy divine force that created the universe that is produced as follows, promptly, the Zn that contains a atom %, the Y that contains b atom %, remainder is made of Mg, a and b satisfy following formula (1)～(3), make flaky castings by cutting the described casting of magnesium alloy divine force that created the universe, the plastic working thing that making utilizes plastic working that described castings has been solidified has carried out the plastic working thing after the thermal treatment to described plastic working thing and has had hcp structure magnesium at normal temperatures and reach long period rhythmo structure phase mutually.
(1)0.25≤a≤5.0
(2)0.5≤b≤5.0
(3)0.5a≤b
In addition, in the high-strength high-toughness magnesium alloy of the present invention, the median size of best described hcp structure magnesium phase is more than 0.1 μ m.The crystal particle diameter of sheet solidifying formation material is littler than cast material.
In addition, in the high-strength high-toughness magnesium alloy of the present invention, preferably compare with described hcp structure magnesium dislocation desity mutually, the dislocation desity of described long period rhythmo structure phase is a kind of order of magnitude extremely when young.
In addition, in the high-strength high-toughness magnesium alloy of the present invention, the percentage by volume of the crystal grain of best described long period rhythmo structure phase is more than 5%.
In addition, in the high-strength high-toughness magnesium alloy of the present invention, also can make described plastic working thing have at least a precipitate of from the precipitate group that the compound by the compound of compound, Zn and the rare earth element of compound, Mg and the Zn of Mg and rare earth element and Mg and Zn and rare earth element constitutes, selecting.
In addition, in the high-strength high-toughness magnesium alloy of the present invention, also can make the total percentage by volume of described at least a precipitate surpass 0% and below 40%.
In addition, in the high-strength high-toughness magnesium alloy of the present invention, best described plastic working be roll, at least one the processing in the middle of extruding, ECAE, stretch process, forging, punching press, rolling forming, bending, FSW processing and their processing repeatedly.
In addition, in the high-strength high-toughness magnesium alloy of the present invention, be preferably in total deformation when carrying out described plastic working below 15.
In addition, in the high-strength high-toughness magnesium alloy of the present invention, be preferably in total deformation when carrying out described plastic working below 10.
In addition, in the high-strength high-toughness magnesium alloy of the present invention, also can add up at least a element of selecting that contains c atom % in described Mg from be made of Yb, Tb, Sm and Nd one group, c satisfies following formula (4) and (5).
(4)0≤c≤3.0
(5)0.1≤b+c≤6.0
In addition, in the high-strength high-toughness magnesium alloy of the present invention, also can add up at least a element of selecting that contains c atom % in described Mg from be made of La, Ce, Pr, Eu, Mm and Gd one group, c satisfies following formula (4) and (5).
(4)0≤c≤3.0
(5)0.1≤b+c≤6.0
In addition, in the high-strength high-toughness magnesium alloy of the present invention, also can in described Mg, add up at least a element of from constitute by Yb, Tb, Sm and Nd a group, selecting that contains c atom %, add up at least a element of selecting from be made of La, Ce, Pr, Eu, Mm and Gd a group contain d atom %, c and d satisfy following formula (4)～(6).
(4)0≤c≤3.0
(5)0≤d≤3.0
(6)0.1≤b+c+d≤6.0
In addition, in the high-strength high-toughness magnesium alloy of the present invention, also can in described Mg, add up to contain to surpass 0 atom % and at least a element of from constitute by Al, Th, Ca, Si, Mn, Zr, Ti, Hf, Nb, Ag, Sr, Sc, B, C, Sn, Au, Ba, Ge, Bi, Ga, In, Ir, Li, Pd, Sb and V a group, selecting below 2.5 atom %.
The feature of the manufacture method of high-strength high-toughness magnesium alloy of the present invention is to possess:
The operation of the casting of magnesium alloy divine force that created the universe that is produced as follows promptly, contains the Zn of a atom %, contains the Y of b atom %, and remainder is made of Mg, and a and b satisfy following formula (1)～(3);
By described magnesium alloy is carried out the operation that the plastic working thing is made in plastic working.
(1)0.5≤a＜5.0
(2)0.5＜b＜5.0
(3)2/3a-5/6≤b
In addition, in the manufacture method of high-strength high-toughness magnesium alloy of the present invention, the best described casting of magnesium alloy divine force that created the universe has hcp structure magnesium and reaches long period rhythmo structure phase mutually.
According to the manufacture method of described high-strength high-toughness magnesium alloy of the present invention,, can make the castings before the hardness of the plastic working thing after the plastic working and yield strength and the plastic working compare raising by the casting of magnesium alloy divine force that created the universe is carried out plastic working.
In addition, in the manufacture method of high-strength high-toughness magnesium alloy of the present invention, also can and make between the operation of described plastic working thing, append the described casting of magnesium alloy divine force that created the universe is implemented to homogenize heat treated operation in the operation of making the described casting of magnesium alloy divine force that created the universe.The heat-treat condition of this moment is preferably: temperature is 400 ℃～550 ℃, and the treatment time is 1 minute～1500 minutes.
In addition, in the manufacture method of high-strength high-toughness magnesium alloy of the present invention, also can after the operation of making described plastic working thing, append described plastic working thing is implemented heat treated operation.The heat-treat condition of this moment is preferably: temperature is 150 ℃～450 ℃, and the treatment time is 1 minute～1500 minutes.
In addition, in the manufacture method of high-strength high-toughness magnesium alloy of the present invention, also can add up at least a element of selecting that contains c atom % in described Mg from be made of Yb, Tb, Sm and Nd one group, c satisfies following formula (4) and (5).
(4)0≤c≤3.0
(5)0.2≤b+c≤6.0
In addition, in the manufacture method of high-strength high-toughness magnesium alloy of the present invention, also can add up at least a element of selecting from be made of La, Ce, Pr, Eu, Mm and Gd a group that contains c atom % in described Mg, c satisfies following formula (4) and (5) or satisfies (5) and (6).
(4)0≤c＜2.0
(5)0.2≤b+c≤6.0
(6)c/b≤1.5
In addition, in the high-strength high-toughness magnesium alloy of the present invention, also can in described Mg, add up at least a element of from constitute by Yb, Tb, Sm and Nd a group, selecting that contains c atom %, add up at least a element of selecting from be made of La, Ce, Pr, Eu, Mm and Gd a group contain d atom %, c and d satisfy following formula (4)～(6) or satisfy (6) and (7).
(4)0≤c≤3.0
(5)0≤d＜2.0
(6)0.2≤b+c+d≤6.0
(7)d/b≤1.5
The feature of the manufacture method of high-strength high-toughness magnesium alloy of the present invention is to possess:
The operation of the casting of magnesium alloy divine force that created the universe that is produced as follows promptly, contains the Zn of a atom %, contains the Y of b atom %, and remainder is made of Mg, and a and b satisfy following formula (1)～(3);
Make the operation of flaky cutting object by cutting described magnesium alloy;
By utilizing the curing of plastic working to make the operation of plastic working thing to described cutting object.
(1)0.25≤a≤5.0
(2)0.5≤b≤5.0
(3)0.5a≤b
In addition, in the manufacture method of high-strength high-toughness magnesium alloy of the present invention, the best described casting of magnesium alloy divine force that created the universe has hcp structure magnesium and reaches long period rhythmo structure phase mutually.
In addition, in the manufacture method of high-strength high-toughness magnesium alloy of the present invention, also can add up at least a element of selecting that contains c atom % in described Mg from be made of Yb, Tb, Sm and Nd one group, c satisfies following formula (4) and (5).
(4)0≤c≤3.0
(5)0.1≤b+c≤6.0
In addition, in the manufacture method of high-strength high-toughness magnesium alloy of the present invention, also can add up at least a element of selecting that contains c atom % in described Mg from be made of La, Ce, Pr, Eu, Mm and Gd one group, c satisfies following formula (4) and (5).
(4)0≤c≤3.0
(5)0.1≤b+c≤6.0
In addition, in the manufacture method of high-strength high-toughness magnesium alloy of the present invention, also can in described Mg, add up at least a element of from constitute by Yb, Tb, Sm and Nd a group, selecting that contains c atom %, add up at least a element of selecting from be made of La, Ce, Pr, Eu, Mm and Gd a group contain d atom %, c and d satisfy following formula (4)～(6).
(4)0≤c≤3.0
(5)0≤d≤3.0
(6)0.1≤b+c+d≤6.0
In addition, in the manufacture method of high-strength high-toughness magnesium alloy of the present invention, also can in described Mg, add up to contain to surpass 0 atom % and at least a element of from constitute by Al, Th, Ca, Si, Mn, Zr, Ti, Hf, Nb, Ag, Sr, Sc, B, C, Sn, Au, Ba, Ge, Bi, Ga, In, Ir, Li, Pd, Sb and V a group, selecting below 2.5 atom %.
In addition, in the manufacture method of high-strength high-toughness magnesium alloy of the present invention, best described plastic working be roll, at least one the processing in the middle of extruding, ECAE, stretch process, forging, punching press, rolling forming, bending, FSW processing and their processing repeatedly.That is, no matter described plastic working is that use can or be used in combination separately in the middle of calendering, extruding, ECAE, stretch process, forging, punching press, rolling forming, bending, FSW processing.
In addition, in the manufacture method of high-strength high-toughness magnesium alloy of the present invention, be preferably in total deformation when carrying out described plastic working below 15, in addition, preferred total deformation is below 10.Deflection each time when in addition, carrying out described plastic working is preferred more than 0.002 below 4.6.
And so-called total deformation is meant, the total deformation that thermal treatment is eliminated such as is not annealed.That is, for not including in total deformation because of in the way of manufacturing process, heat-treating the distortion that is eliminated.
But the situation for the high-strength high-toughness magnesium alloy of the operation of making flaky cutting object is meant the total deformation when carrying out plastic working after having made the material that finally is used for solidifying formation.That is, for making deflection before the material that finally is used for solidifying formation not very in total deformation.The material that described what is called finally is used for solidifying formation is meant poor, the material of tensile strength below 200MPa of connectivity of flaky material.In addition, the solidifying formation of flaky material has been to use the processing of extruding, calendering, forging, punching press, ECAE etc.Also can behind solidifying formation, use calendering, extruding, ECAE, stretching, forging, punching press, rolling forming, bending, FSW etc.In addition, before final solidifying formation, also can increase flaky material is carried out ball milling, various plastic workings such as forges, stamps repeatedly.
In addition, in the manufacture method of high-strength high-toughness magnesium alloy of the present invention, after the operation of making described plastic working thing, also can also possess the operation that described plastic working thing is heat-treated.Compare further raising before like this, just can making the hardness of the plastic working thing after the thermal treatment and yield strength and thermal treatment.
In addition, in the manufacture method of high-strength high-toughness magnesium alloy of the present invention, preferably described heat treated condition is: more than 200 ℃ and less than 500 ℃, more than 10 minutes and less than 24 hours.
In addition, in the manufacture method of high-strength high-toughness magnesium alloy of the present invention, it is big a kind more than the order of magnitude that the dislocation desity of having carried out the hcp structure magnesium phase of the magnesium alloy after the described plastic working cans be compared to the dislocation desity of long period rhythmo structure phase most.
As above shown in the explanation, according to the present invention, at the expansion of magnesium alloy purposes, can provide intensity and toughness all to be in to can be used in the high-strength high-toughness magnesium alloy and the manufacture method thereof of practical level.
Description of drawings
Fig. 1 is the photo of the crystalline structure of expression embodiment 1, comparative example 1 and comparative example 2 cast material separately.
Fig. 2 is the compositing range of preferred magnesium alloy is considered in expression from the viewpoint of practicability figure.
Fig. 3 is the photo of the crystalline structure of expression embodiment 2～4 cast material separately.
Fig. 4 is the photo of the crystalline structure of expression embodiment 5 and 6 cast material separately.
Fig. 5 is the photo of the crystalline structure of expression embodiment 7～9 cast material separately.
Fig. 6 is the photo of the crystalline structure of expression comparative example 3～9 cast material separately.
Fig. 7 is the photo of crystalline structure of the cast material of expression reference example.
Fig. 8 is the figure of compositing range of the magnesium alloy of expression embodiments of the present invention 1.
Fig. 9 is the figure of compositing range of the magnesium alloy of expression embodiments of the present invention 7.
Figure 10 is the photo of crystalline structure of the cast material of expression embodiment 10.
Figure 11 is the photo of crystalline structure of the cast material of expression embodiment 26.
Figure 12 has represented that the sample of embodiment 1 has been implemented ECAE under 375 ℃ temperature add the cycle index of ECAE in man-hour and yield strength (σ y), tensile strength (σ
UTS), the chart of relation of elongation (%).
Figure 13 has represented that the sample of embodiment 1 has been implemented ECAE under 400 ℃ temperature add the cycle index of ECAE in man-hour and yield strength (σ y), tensile strength (σ
UTS), the chart of relation of elongation (%).
Embodiment
To describe embodiments of the present invention below.
The inventor returns substantially, from 2 yuan of magnesium alloy the begin one's study intensity and the toughness of alloy, expands this research to complex magnesium alloy then.It found that, it is the Mg-Zn-Y class that intensity and toughness all have high-caliber magnesium alloy, in addition unlike previous technologies, is below the 5.0 atom % at the content of zinc, the content of Y is under the following such low levels of 5.0 atom %, can obtain unexistent in the past high strength and high tenacity.
The casting alloy that is formed with long period rhythmo structure phase can obtain the magnesium alloy of high-strength high-tractility high tenacity after the plastic working or by implement thermal treatment after plastic working.In addition, find to have formed the long period rhythmo structure, after carrying out plastic working, perhaps after plastic working thermal treatment, can obtain the alloy composition of high-strength high-tractility high tenacity.
Find in addition, the casting alloy that has formed the long period rhythmo structure by cutting is made flaky castings, this castings is carried out plastic working, perhaps after plastic working, implement thermal treatment, compare with the situation of not cutting, can obtain the more more high ductibility magnesium alloy of high tenacity more of high strength to flaky operation.In addition, found to have formed the long period rhythmo structure, cut and be sheet, carry out plastic working after, perhaps after plastic working thermal treatment, can obtain the alloy composition of high-strength high-tractility high tenacity.
By having the plastic forming of metals of long period rhythmo structure phase, can make at least a portion bending or the warpage of long period rhythmo structure phase.So just can obtain the metal of high-strength high-tractility high tenacity.
In addition, bending or warpage the long period rhythmo structure contain random grain boundary in mutually.It is believed that: by high strength, the intercrystalline slip under the high temperature is suppressed by this random grain boundary magnesium alloy, thereby can at high temperature obtain high strength.
In addition, because of containing highdensity dislocation at hcp structure magnesium in mutually, thereby magnesium alloy because of the dislocation desity of long period rhythmo structure phase is low, thereby can be realized the raising and the high strength of the ductility of magnesium alloy by high strength.The dislocation desity of described long period rhythmo structure phase is preferably compared with described hcp structure magnesium dislocation desity mutually to a kind of order of magnitude when young.
(embodiment 1)
The magnesium alloy of embodiments of the present invention 1 is the above alloy of ternary that contains Mg, Zn and Y basically.
The compositing range of the Mg-Zn-Y alloy of present embodiment is the scope by the encirclement of H-I-C-D-E-H line shown in Figure 8.That is, when the content with zinc is made as a atom %, the content of Y is added up to when being made as b atom %, then a and b just satisfy following formula (1)～(3).
(1)0.5≤a＜5.0
(2)0.5＜b＜5.0
(3)2/3a-5/6≤b
In addition, the compositing range of the Mg-Zn-Y alloy of the present embodiment scope by the encirclement of F-G-C-D-E-F line preferred shown in Figure 8.That is, when the content with zinc is made as a atom %, the content of Y is added up to when being made as b atom %, then a and b just satisfy following formula (1)～(4).
(1)0.5≤a＜5.0
(2)0.5＜b＜5.0
(3)2/3a-5/6≤b
(4)0.75≤b
In addition, the compositing range of the preferred Mg-Zn-Y alloy of present embodiment is the scope by the encirclement of A-B-C-D-E-A line shown in Figure 8.That is, when the content with zinc is made as a atom %, the content of Y is added up to when being made as b atom %, then a and b just satisfy following formula (1)～(3).
(1)0.5≤a≤5.0
(2)1.0≤b≤5.0
(3)0.5a≤b，
This be because, when the content of zinc when 5 atom % are above, then particularly toughness (or ductility) just has the tendency of reduction.In addition also because when the content of Y is aggregated in 5 atom % when above, then particularly toughness (or ductility) just has the tendency of reduction.
In addition, when the content of zinc less than 0.5 atom %, or the content of Y is when adding up to less than 1.0 atom %, then at least one side of intensity and flexible just becomes insufficient.So, the lower limit of the content of zinc is made as 0.5 atom %, the lower limit of the content of Y is made as 1.0 atom %.
It is that 0.5～1.5 atom % place becomes obvious that intensity and flexible increase at zinc.Near zinc content is 0.5 atom %, when rare earth element content tails off,, yet under the situation of this scope, also demonstrate than higher in the past intensity and higher toughness though intensity has the tendency of reduction.So the scope of the content of the zinc of the magnesium alloy of present embodiment is the wideest to be below the above 5.0 atom % of 0.5 atom %.
In the Mg-Zn-Y class magnesium alloy of present embodiment, zinc and rare earth element composition in addition with content of described scope are magnesium, yet also can contain the impurity of the degree that can not impact alloy characteristic.
(embodiment 2)
The magnesium alloy of embodiments of the present invention 2 is the above alloy of quaternary that contains Mg, Zn and Y basically, and the 4th element is the element of selecting from be made of Yb, Tb, Sm and Nd a group more than a kind or 2 kinds.
The compositing range of the magnesium alloy of present embodiment is: when the content with Zn is made as a atom %, the content of Y is made as b atom %, when the total content of the 4th element more than a kind or 2 kinds was made as c atom %, then a, b and c just satisfied following formula (1)～(5).
(1)0.5≤a＜5.0
(2)0.5＜b＜5.0
(3)2/3a-5/6≤b
(4)0≤c≤3.0
(5)0.2≤b+c≤6.0
In addition, the compositing range of the preferred magnesium alloy of present embodiment is: when the content with Zn is made as a atom %, the content of Y is made as b atom %, and when the total content of the 4th element more than a kind or 2 kinds was made as c atom %, then a, b and c just satisfied following formula (1)～(6).
(1)0.5≤a＜5.0
(2)0.5＜b＜5.0
(3)2/3a-5/6≤b
(4)0.75≤b
(5)0≤c≤3.0
(6)0.2≤b+c≤6.0
In addition, the compositing range of the preferred magnesium alloy of present embodiment is: when the content with Zn is made as a atom %, the content of Y is made as b atom %, and when the total content of the 4th element more than a kind or 2 kinds was made as c atom %, then a, b and c just satisfied following formula (1)～(5).
(1)0.5≤a≤5.0
(2)1.0≤b≤5.0
(3)0.5a≤b
(4)0≤c≤3.0
(5)0.2≤b+c≤6.0
With the content of zinc be made as reason below the 5 atom %, with the content of Y be made as reason below the 5 atom %, with the content of zinc be made as reason more than the 0.5 atom %, reason that the content of Y is made as more than the 1.0 atom % is identical with embodiment 1.In addition, the reason that the upper limit of the content of the 4th element is made as 3.0 atom % is: the solid solution limit of the 4th element is low.In addition, the reason that makes it to contain the 4th element is because have the effect that makes the crystal grain miniaturization and have the effect that intermetallic compound is separated out.
In the Mg-Zn-Y class magnesium alloy of present embodiment, also can contain the impurity of the degree that alloy characteristic is not impacted.
(embodiment 3)
The magnesium alloy of embodiments of the present invention 3 is the above alloy of quaternary that contains Mg, Zn and Y basically, and the 4th element is the element of selecting from be made of La, Ce, Pr, Eu, Mm and Gd a group more than a kind or 2 kinds.And, so-called Mm (mixed rare earth alloy) is to be the mixture or the alloy of a plurality of rare earth elements of principal constituent with Ce and La, be will be as the residue after concise the removing such as the Sm of useful rare earth element or Nd from ore, its composition depends on the composition of the ore before concise.
The compositing range of the magnesium alloy of present embodiment is: when the content with Zn is made as a atom %, the content of Y is made as b atom %, the content of the 4th element more than a kind or 2 kinds is added up to when being made as c atom %, and then a, b and c just satisfy following formula (1)～(5) or satisfy (1)～(3), (5) and (6).
(1)0.5≤a＜5.0
(2)0.5＜b＜5.0
(3)2/3a-5/6≤b
(4)0≤c≤2.0
(5)0.2≤b+c≤6.0
(6)c/b≤1.5
In addition, the compositing range of the preferred magnesium alloy of present embodiment is: when the content with Zn is made as a atom %, the content of Y is made as b atom %, the content of the 4th element more than a kind or 2 kinds is added up to when being made as c atom %, and then a, b and c just satisfy following formula (1)～(6) or satisfy (1)～(4), (6) and (7).
(1)0.5≤a＜5.0
(2)0.5＜b＜5.0
(3)2/3a-5/6≤b
(4)0.75≤b
(5)0≤c＜2.0
(6)0.2≤b+c≤6.0
(7)c/b≤1.5
The compositing range of the preferred magnesium alloy of present embodiment is: when the content with Zn is made as a atom %, the content of Y is made as b atom %, the content of the 4th element more than a kind or 2 kinds is added up to when being made as c atom %, and then a, b and c just satisfy following formula (1)～(5) or satisfy (1)～(3), (5) and (6).
(1)0.5≤a≤5.0
(2)1.0≤b≤5.0
(3)0.5a≤b
(4)0≤c＜2.0
(5)0.2≤b+c≤6.0
(6)c/b≤1.5
The reason that is made as described formula (6) is because because when greater than 1.5 times, then the effect of the formation of long period rhythmo structure phase is weakened, so the weight of magnesium alloy becomes big.
The content of zinc is made as reason below the 5 atom %, the content of the rare earth element more than a kind or 2 kinds is added up to the reason that is made as below the 5 atom %, the content of zinc is made as reason more than the 0.5 atom %, adds up to the reason that is made as more than the 1.0 atom % identical with embodiment 1 content of rare earth element.In addition, the main reason that the upper limit of the content of the 4th element is made as 2.0 atom % is: the solid solution limit of the 4th element does not have basically.In addition, the reason that makes it to contain the 4th element is because have the effect that makes the crystal grain miniaturization and have the effect that intermetallic compound is separated out.
In the Mg-Zn-Y class magnesium alloy of present embodiment, also can contain the impurity of the degree that alloy characteristic is not impacted.
(embodiment 4)
The magnesium alloy of embodiments of the present invention 4 is the alloy more than five yuan that contains Mg, Zn and Y basically, the 4th element is the element of selecting from be made of Yb, Tb, Sm and Nd a group more than a kind or 2 kinds, and the 5th element is the element of selecting from be made of La, Ce, Pr, Eu, Mm and Gd a group more than a kind or 2 kinds.
The compositing range of the magnesium alloy of present embodiment is: when the content with Zn is made as a atom %, the content of Y is made as b atom %, the content total of the 4th element more than a kind or 2 kinds is made as c atom %, the content of the 5th element more than a kind or 2 kinds is added up to when being made as d atom %, and then a, b, c and d just satisfy following formula (1)～(6) or satisfy (1)～(3), (6) and (7).
(1)0.5≤a＜5.0
(2)0.5＜b＜5.0
(3)2/3a-5/6≤b
(4)0≤c≤3.0
(5)0≤d＜2.0
(6)0.2≤b+c+d≤6.0
(7)d/b≤1.5
In addition, the compositing range of the preferred magnesium alloy of present embodiment is: when the content with Zn is made as a atom %, the content of Y is made as b atom %, the content total of the 4th element more than a kind or 2 kinds is made as c atom %, the content of the 5th element more than a kind or 2 kinds is added up to when being made as d atom %, and then a, b, c and d just satisfy following formula (1)～(7) or satisfy (1)～(3), (7) and (8).
(1)0.5≤a＜5.0
(2)0.5＜b＜5.0
(3)2/3a-5/6≤b
(4)0.75≤b
(5)0≤c≤3.0
(6)0≤d＜2.0
(7)0.2≤b+c+d≤6.0
(8)d/b≤1.5
In addition, the compositing range of the preferred magnesium alloy of present embodiment is: when the content with Zn is made as a atom %, the content of Y is made as b atom %, the content total of the 4th element more than a kind or 2 kinds is made as c atom %, the content of the 5th element more than a kind or 2 kinds is added up to when being made as d atom %, and then a, b, c and d just satisfy following formula (1)～(6) or satisfy (1)～(3), (6) and (7).
(1)0.5≤a≤5.0
(2)1.0≤b≤5.0
(3)0.5a≤b
(4)0≤c≤3.0
(5)0≤d＜2.0
(6)0.2≤b+c+d≤6.0
(7)d/b≤1.5
The reason that is made as described formula (7) is because because when greater than 1.5 times, then the effect of the formation of long period rhythmo structure phase is weakened, so the weight of magnesium alloy becomes big.
The reason that the total content of Zn, Y, the 4th element and the 5th element is made as below the 6.0 atom % is: when surpassing 6%, then can become heavy, raw materials cost raises, and toughness can reduce in addition.The content of Zn is made as more than the 0.5 atom %, and the reason that the total content of Y, the 4th element and the 5th element is made as more than the 1.0 atom % is: when being made as lower concentration, then intensity just becomes insufficient.In addition, the reason that makes it to contain the 4th element, the 5th element is because have the effect that makes the crystal grain miniaturization and have the effect that intermetallic compound is separated out.
In the Mg-Zn-Y class magnesium alloy of present embodiment, also can contain the impurity of the degree that alloy characteristic is not impacted.
(embodiment 5)
As the magnesium alloy of embodiments of the present invention 5, can enumerate the magnesium alloy that in the composition of embodiment 1～4, has increased Me.Wherein, Me is at least a element of selecting from be made of Al, Th, Ca, Si, Mn, Zr, Ti, Hf, Nb, Ag, Sr, Sc, B, C, Sn, Au, Ba, Ge, Bi, Ga, In, Ir, Li, Pd, Sb and V a group.The content of this Me is made as and surpasses 0 atom % and below 2.5 atom %.When adding Me, then can when keeping high-intensity high-tenacity, improve other character.For example, has effect at aspects such as erosion resistance or crystal grain miniaturizations.
(embodiment 6)
Manufacture method to the magnesium alloy of embodiments of the present invention 6 describes.
To cast by any one forming the magnesium alloy dissolving that constitutes of embodiment 1～5, make the casting of magnesium alloy divine force that created the universe.Speed of cooling during casting is 1000K/ below second, and more preferably 100K/ is below second.As casting technique, can use various technologies, for example can use high-pressure casting, roller cast (roll cast), tilted plate casting, continuous casting, thixo casting (thixo molding), die casting etc.In addition, also can use the technology that the casting of magnesium alloy divine force that created the universe is cut out with given shape.
Then, also can implement to homogenize thermal treatment to the casting of magnesium alloy divine force that created the universe.The heat-treat condition of this moment preferably is made as: temperature is 400 ℃～550 ℃, and the treatment time is 1 minute～1500 minutes (or 24 hours).
Then, the described casting of magnesium alloy divine force that created the universe is carried out plastic working.As the method for this plastic working, for example use extruding, ECAE (equal-channel-angular-extrusion) processing method, calendering, stretch process, forging, punching press, rolling forming, bending, FSW (friction stir welding; Friction stir weld) processing, their processing repeatedly etc.
When utilizing the plastic working of extruding, preferably extrusion temperature is made as more than 250 ℃ below 500 ℃, will be made as more than 5% by the cross section decrement that extruding causes.
The ECAE processing method is the method that makes sample long side direction half-twist in order to import distortion uniformly in sample in each circulation.Specifically, it is following method, promptly, the shaping that has formed the shaped hole of L font at cross-sectional shape is used in the described shaped hole of mould, the casting of magnesium alloy divine force that created the universe as molding material is entered forcibly, particularly at 90 ° the part place of bending to of L shape shaped hole,, and obtain the molding of intensity and good-toughness to described casting of magnesium alloy divine force that created the universe stress application.As preferred 1～8 circulation of the cycle index of ECAE.More preferably 3～5 circulations.The temperature that adds man-hour of ECAE is preferred more than 250 ℃ below 500 ℃.
When utilizing the plastic working of calendering, preferably rolling temperature is made as more than 250 ℃ below 500 ℃, draft is made as more than 5%.
When utilizing the plastic working of stretch process, the temperature when preferably carrying out stretch process is more than 250 ℃ below 500 ℃, and the cross section decrement of described stretch process is more than 5%.
When utilizing forged plastic working, preferably forge the temperature that adds man-hour more than 250 ℃ below 500 ℃, the working modulus of described forging processing is more than 5%.
Preferably each time deflection is more than 0.002 below 4.6 in the plastic working that the described casting of magnesium alloy divine force that created the universe is carried out, and total deformation is below 15.In addition, more preferably each time deflection is more than 0.002 below 4.6 in described plastic working, and total deformation is below 10.Preferred deflection is made as below 15, and the reason that preferred deflection is made as below 10 is, even increase total deformation, the intensity of magnesium alloy can not increase thereupon yet, in addition, increases total deformation more, and then manufacturing cost is just high more.
And the deflection of ECAE processing is 0.95～1.15/ time, for example carries out the total deformation that 16 ECAE add man-hour and becomes 0.95 * 16=15.2, carries out the total deformation that 8 ECAE add man-hour and becomes 0.95 * 8=7.6.
In addition, the deflection of extrusion processing is: extrusion ratio be 2.5 o'clock be 0.92/ time, extrusion ratio be 4 o'clock be 1.39/ time, extrusion ratio be 10 o'clock be 2.30/ time, extrusion ratio be 20 o'clock be 2.995/ time, extrusion ratio be 50 o'clock be 3.91/ time, extrusion ratio be 100 o'clock be 4.61/ time, extrusion ratio be 1000 o'clock be 6.90/ time.
The plastic working thing that the casting of magnesium alloy divine force that created the universe has been carried out plastic working has the crystalline structure that hcp structure magnesium reaches long period rhythmo structure phase mutually at normal temperatures as described above, the percentage by volume of crystal grain with this long period rhythmo structure phase is at (more preferably more than 10%) more than 5%, the median size of described hcp structure magnesium phase is more than 2 μ m, and the median size of described long period rhythmo structure phase is more than 0.2 μ m.There are a plurality of random grain boundaries in intragranular in this long period rhythmo structure phase, by the median size of the crystal grain of this random grain boundary regulation more than 0.05 μ m.Though dislocation desity is big in random grain boundary, yet the dislocation desity of the part beyond the random grain boundary of long period rhythmo structure phase is little.So the dislocation desity of the part beyond the dislocation desity of hcp structure magnesium phase and the long period rhythmo structure random grain boundary is mutually compared big a kind more than the order of magnitude.
At least a portion bending or the warpage of described long period rhythmo structure phase.In addition, described plastic working thing also can have at least a precipitate of selecting from the precipitate group that the compound by the compound of compound, Zn and the rare earth element of compound, Mg and the Zn of Mg and rare earth element and Mg and Zn and rare earth element constitutes.The total percentage by volume of described precipitate is preferably above 0% and below 40%.In addition, for the plastic working thing that has carried out after the described plastic working, compare with the castings before carrying out plastic working, Vickers' hardness and yield strength all rise.
Also can implement thermal treatment for the described casting of magnesium alloy divine force that created the universe having been carried out the plastic working thing after the plastic working.This heat-treat condition preferably is made as: temperature is more than 200 ℃ and less than 500 ℃, heat treatment time is 10 minutes～1500 minutes (or 24 hours).Being made as thermal treatment temp less than 500 ℃ is because when more than 500 ℃ the time, then the deflection that applies because of plastic working just is eliminated.
For the plastic working thing that has carried out after this thermal treatment, to compare with the plastic working thing before heat-treating, Vickers' hardness and yield strength all rise.In addition, in the plastic working thing after thermal treatment also with thermal treatment before identical, has the crystalline structure that hcp structure magnesium reaches long period rhythmo structure phase mutually at normal temperatures, the percentage by volume of crystal grain with this long period rhythmo structure phase is at (more preferably more than 10%) more than 5%, the median size of described hcp structure magnesium phase is more than 2 μ m, and the median size of described long period rhythmo structure phase is more than 0.2 μ m.There are a plurality of random grain boundaries in intragranular in this long period rhythmo structure phase, by the median size of the crystal grain of this random grain boundary regulation more than 0.05 μ m.Though dislocation desity is big in random grain boundary, yet the dislocation desity of the part beyond the random grain boundary of long period rhythmo structure in mutually is little.So the dislocation desity of the part beyond the dislocation desity of hcp structure magnesium phase and the long period rhythmo structure random grain boundary in is mutually compared big a kind more than the order of magnitude.
At least a portion bending or the warpage of described long period rhythmo structure phase.In addition, described plastic working thing also can have at least a precipitate of selecting from the precipitate group that the compound by the compound of compound, Zn and the rare earth element of compound, Mg and the Zn of Mg and rare earth element and Mg and Zn and rare earth element constitutes.The total percentage by volume of described precipitate is preferably above 0% and below 40%.
According to described embodiment 1～6, at the expansion of magnesium alloy purposes, for example all be required the purposes of high performance hi-tech, can provide intensity and toughness all to be in to can be used in the high-strength high-toughness magnesium alloy and the manufacture method thereof of practical level with alloy as intensity and toughness.
(embodiment 7)
The magnesium alloy of embodiments of the present invention 7 is the alloys that are applicable to by the square following sheet castings of a plurality of several mm of making of cutting castings, is the above alloy of ternary that contains Mg, Zn and Y basically.
The compositing range of the Mg-Zn-Y alloy of present embodiment is the scope by the encirclement of A-B-C-D-E line shown in Figure 9.That is, when the content with zinc is made as a atom %, when the content of Y was made as b atom %, then a and b just satisfied following formula (1)～(3).
(1)0.25≤a≤5.0
(2)0.5≤b≤5.0
(3)0.5a≤b
This be because, when the content of zinc when 5 atom % are above, then particularly toughness (or ductility) just has the tendency of reduction.In addition also because, when the content of Y when 5 atom % are above, then particularly toughness (or ductility) just has the tendency of reduction.
In addition, when the content of zinc less than 0.25 atom %, or the content of Y element is during less than 0.5 atom %, then at least one side of intensity and flexible just becomes insufficient.So, the lower limit of the content of zinc is made as 0.25 atom %, the lower limit of the total content of rare earth element is made as 0.5 atom %.Can make the content lower limit separately of the content of zinc and Y compare low 1/2 reason with embodiment 1 like this is because be applicable to the sheet castings.
It is that 0.5～1.5 atom % place becomes obvious that intensity and flexible increase at zinc.Near zinc content is 0.5 atom %, when rare earth element content tails off,, yet under the situation of this scope, also demonstrate than higher in the past intensity and higher toughness though intensity has the tendency of reduction.So the scope of the content of the zinc of the magnesium alloy of present embodiment is the wideest to be below the above 5.0 atom % of 0.25 atom %.
In the Mg-Zn-RE class magnesium alloy of present embodiment, zinc and rare earth element composition in addition with content of described scope are magnesium, yet also can contain the impurity of the degree that can not impact alloy characteristic.
(embodiment 8)
The magnesium alloy of embodiments of the present invention 8 is the alloys that are applicable to by the square following sheet castings of a plurality of several mm of making of cutting castings, be the above alloy of quaternary that contains Mg, Zn and Y basically, the 4th element is the element of selecting from be made of Yb, Tb, Sm and Nd a group more than a kind or 2 kinds.
The compositing range of the magnesium alloy of present embodiment is: when the content with Zn is made as a atom %, the content of Y is made as b atom %, the content of the 4th element more than a kind or 2 kinds is added up to when being made as c atom %, then a, b and c just satisfy following formula (1)～(5).
(1)0.25≤a≤5.0
(2)0.5≤b≤5.0
(3)0.5a≤b
(4)0≤c≤3.0
(5)0.1≤b+c≤6.0
With the content of zinc be made as reason below the 5 atom %, with the content of the rare earth element more than a kind or 2 kinds add up to the reason that is made as below the 5 atom %, with the content of zinc be made as reason more than the 0.25 atom %, reason that the content of Y is made as more than the 0.5 atom % is identical with embodiment 7.In addition, the reason that the upper limit of the content of the 4th element is made as 3.0 atom % is: the solid solution limit of the 4th element is lower.In addition, the reason that makes it to contain the 4th element is because have the effect that makes the crystal grain miniaturization and have the effect that intermetallic compound is separated out.
In the Mg-Zn-RE class magnesium alloy of present embodiment, also can contain the impurity of the degree that alloy characteristic is not impacted.
(embodiment 9)
The magnesium alloy of embodiments of the present invention 9 is the alloys that are applicable to by the square following sheet castings of a plurality of several mm of making of cutting castings, basically be quaternary or the alloy more than five yuan that contains Mg, Zn and Y, the 4th element is the element of selecting from be made of La, Ce, Pr, Eu, Mm and Gd a group more than a kind or 2 kinds.
The compositing range of the magnesium alloy of present embodiment is: when the content with Zn is made as a atom %, the content of Y is made as b atom %, the content of the 4th element more than a kind or 2 kinds is added up to when being made as c atom %, then a, b and c just satisfy following formula (1)～(5).
(1)0.25≤a≤5.0
(2)0.5≤b≤5.0
(3)0.5a≤b
(4)0≤c≤3.0
(5)0.1≤b+c≤6.0
With the content of zinc be made as reason below the 5 atom %, with the content of the rare earth element more than a kind or 2 kinds add up to the reason that is made as below the 5 atom %, with the content of zinc be made as reason more than the 0.25 atom %, reason that the content of Y is made as more than the 0.5 atom % is identical with embodiment 7.In addition, the reason that the upper limit of the content of the 4th element is made as 2.0 atom % is: the solid solution limit of the 4th element does not have basically.In addition, the reason that makes it to contain the 4th element is because have the effect that makes the crystal grain miniaturization and have the effect that intermetallic compound is separated out.
In the Mg-Zn-RE class magnesium alloy of present embodiment, also can contain the impurity of the degree that alloy characteristic is not impacted.
(embodiment 10)
The magnesium alloy of embodiments of the present invention 10 is the alloys that are applicable to by the square following sheet castings of a plurality of several mm of making of cutting castings, basically be the alloy more than five yuan that contains Mg, Zn and Y, the 4th element is the element of selecting from be made of Yb, Tb, Sm, Nd and Gd a group more than a kind or 2 kinds, and the 5th element is the element of selecting from be made of La, Ce, Pr, Eu and Mm a group more than a kind or 2 kinds.
The compositing range of the magnesium alloy of present embodiment is: when the content with Zn is made as a atom %, the content of Y is made as b atom %, the content total of the 4th element more than a kind or 2 kinds is made as c atom %, the content of the 5th element more than a kind or 2 kinds is added up to when being made as d atom %, and then a, b, c and d just satisfy following formula (1)～(6).
(1)0.25≤a≤5.0
(2)0.5≤b≤5.0
(3)0.5a≤b
(4)0≤c≤3.0
(5)0≤d≤3.0
(6)0.1≤b+c+d≤6.0
With the total content of Zn, Y, the 4th element and the 5th element be made as reason less than 6.0 atom %, that the total content of Zn, Y, the 4th element and the 5th element is made as the reason that surpasses 1.0 atom % is identical with embodiment 4.
In the Mg-Zn-RE class magnesium alloy of present embodiment, also can contain the impurity of the degree that alloy characteristic is not impacted.
(embodiment 11)
As the magnesium alloy of embodiments of the present invention 11, can enumerate the magnesium alloy that in the composition of embodiment 7～10, has increased Me.Wherein, Me is at least a element of selecting from be made of Al, Th, Ca, Si, Mn, Zr, Ti, Hf, Nb, Ag, Sr, Sc, B, C, Sn, Au, Ba, Ge, Bi, Ga, In, Ir, Li, Pd, Sb and V a group.The content of this Me is made as and surpasses 0 atom % and below 2.5 atom %.When adding Me, then can when keeping high-intensity high-tenacity, improve other character.For example, has effect at aspects such as erosion resistance or crystal grain miniaturizations.
(embodiment 12)
Manufacture method to the magnesium alloy of embodiments of the present invention 12 describes.
To cast by any one forming the magnesium alloy dissolving that constitutes of embodiment 7～11, make the casting of magnesium alloy divine force that created the universe.Speed of cooling during casting is 1000K/ below second, and more preferably 100K/ is below second.As this casting of magnesium alloy divine force that created the universe, use the material that from ingot, cuts out with given shape.
Then, also can implement to homogenize thermal treatment to the casting of magnesium alloy divine force that created the universe.The heat-treat condition of this moment preferably is made as: temperature is 400 ℃～550 ℃, and the treatment time is 1 minute～1500 minutes (or 24 hours).
Then, by cutting this casting of magnesium alloy divine force that created the universe, make the square following sheet castings of a plurality of several mm.
Then, the method that also can use compression or plastic working method implements to homogenize thermal treatment with sheet castings preliminary shaping.The heat-treat condition of this moment preferably is made as: temperature is 400 ℃～550 ℃, and the treatment time is 1 minute～1500 minutes (or 24 hours).In addition, for described preformed shaping thing, also can under 150 ℃～450 ℃ temperature, implement the thermal treatment of 1 minute～1500 minutes (or 24 hours).
Flaky castings generally is used in the raw material of thixotroping mould (thixo mold) for example.
And, also can use the compression or the method for plastic working method will mix the material preliminary shaping of sheet castings and ceramic particle, implement to homogenize thermal treatment.In addition, before with sheet castings preliminary shaping, also can implement severe deformation processing in additivity ground.
Then, by described sheet castings is carried out plastic working, and with sheet castings solidifying formation.As the method for this plastic working, can make in the same manner with the situation of embodiment 6 in all sorts of ways.And, before with this sheet castings solidifying formation, also can increase processing treatment repeatedly such as the mechanical alloying that utilizes ball milling or stamp mill, high-energy ball milling etc. or body material mechanical alloying (bulk mechanicalalloying).In addition, behind solidifying formation, also can increase plastic working or shot peening again.In addition, both the described casting of magnesium alloy divine force that created the universe and intermetallic compound particles or compoundization such as ceramic particle, fiber also can be mixed described cutting object with ceramic particle, fiber etc.
The plastic working thing that has carried out plastic working like this has the crystalline structure that hcp structure magnesium reaches long period rhythmo structure phase mutually at normal temperatures.At least a portion bending or the warpage of this long period rhythmo structure phase.For the plastic working thing that has carried out after the described plastic working, to compare with the castings before carrying out plastic working, Vickers' hardness and yield strength all rise.
Total deformation when described sheet castings is carried out plastic working is preferred below 15, and in addition, preferred total deformation is below 10.Deflection when in addition, at every turn carrying out described plastic working is preferred more than 0.002 below 4.6.
And said here total deformation is meant, the total deformation that thermal treatment is eliminated such as is not annealed, and is the total deformation when carrying out plastic working behind the sheet castings preliminary shaping.That is, for not including in total deformation because of in the way of manufacturing process, heat-treating the distortion that is eliminated, in addition, for the deflection before the sheet castings preliminary shaping is not included in total deformation.
Also can implement thermal treatment for described sheet castings having been carried out the plastic working thing after the plastic working.This heat-treat condition preferably is made as: temperature is more than 200 ℃ and less than 500 ℃, heat treatment time is 10 minutes～1500 minutes (or 24 hours).Being made as thermal treatment temp less than 500 ℃ is because when more than 500 ℃ the time, then the deflection that applies because of plastic working just is eliminated.
For the plastic working thing that has carried out after this thermal treatment, to compare with the plastic working thing before heat-treating, Vickers' hardness and yield strength all rise.In addition, in the plastic working thing after thermal treatment also with thermal treatment before identical, have the crystalline structure that hcp structure magnesium reaches long period rhythmo structure phase mutually at normal temperatures.At least a portion bending or the warpage of this long period rhythmo structure phase.
Therefore in the described embodiment 12,, make and organize miniaturization, compare with embodiment 6, can make the more high ductibility plastic working thing etc. of high tenacity more of high strength more owing to make the sheet castings by the cutting castings.In addition, the magnesium alloy of present embodiment is compared with the magnesium alloy of embodiment 1～6, even zinc and rare earth element are lower concentration, also can obtain the characteristic of high strength and high tenacity.
According to described embodiment 7～12, at the expansion of magnesium alloy purposes, for example all be required the purposes of high performance hi-tech, can provide intensity and toughness all to be in to can be used in the high-strength high-toughness magnesium alloy and the manufacture method thereof of practical level with alloy as intensity and toughness.
Embodiment
Below will describe embodiment.
Among the embodiment 1, use the ternary system magnesium alloy of 97 atom %Mg-1 atom %Zn-2 atom %Y.
Among the embodiment 2, use the quaternary system magnesium alloy of 96.5 atom %Mg-1 atom %Zn-1 atom %Y-1.5 atom %Gd.The magnesium alloy of embodiment 2 is the compound alloy that forms the rare earth element of long period rhythmo structure and do not form the rare earth element of long period rhythmo structure that added.
Among the embodiment 3, use the quaternary system magnesium alloy of 97.5 atom %Mg-1 atom %Zn-2 atom %Y-0.5 atom %La.
Among the embodiment 4, use the quaternary system magnesium alloy of 97.5 atom %Mg-0.5 atom %Zn-1.5 atom %Y-0.5 atom %Yb.
Among the embodiment 5, use the quaternary system magnesium alloy of 96.5 atom %Mg-1 atom %Zn-1.5 atom %Y-1 atom %Gd.
Among the embodiment 6, use the ternary system magnesium alloy of 96 atom %Mg-1 atom %Zn-3 atom %Y.
In the comparative example 1, use the ternary system magnesium alloy of 97 atom %Mg-1 atom %Zn-2 atom %La.
In the comparative example 2, use the ternary system magnesium alloy of 97 atom %Mg-1 atom %Zn-2 atom %Yb.
In the comparative example 3, use the ternary system magnesium alloy of 97 atom %Mg-1 atom %Zn-2 atom %Ce.
In the comparative example 4, use the ternary system magnesium alloy of 97 atom %Mg-1 atom %Zn-2 atom %Pr.
In the comparative example 5, use the ternary system magnesium alloy of 97 atom %Mg-1 atom %Zn-2 atom %Nd.
In the comparative example 6, use the ternary system magnesium alloy of 97 atom %Mg-1 atom %Zn-2 atom %Sm.
In the comparative example 7, use the ternary system magnesium alloy of 97 atom %Mg-1 atom %Zn-2 atom %Eu.
In the comparative example 8, use the ternary system magnesium alloy of 97 atom %Mg-1 atom %Zn-2 atom %Tm.
In the comparative example 9, use the ternary system magnesium alloy of 97 atom %Mg-1 atom %Zn-2 atom %Lu.
As a reference example, use the binary system magnesium alloy of 98 atom %Mg-2 atom %Y.
(structure observation of cast material)
At first, in Ar gas atmosphere, utilize the high frequency dissolving to make the ingot of embodiment 1～6, comparative example 1～9 and reference example composition separately, from these ingots, cut out the shape of Φ 10 * 60mm.Utilize SEM, XRD to carry out the structure observation of this cast material that cuts out.The photo of these crystalline structures is shown among Fig. 1～Fig. 7.
Among Fig. 1, represented the photo of embodiment 1 and comparative example 1,2 crystalline structure separately.Among Fig. 3, represented the photo of the crystalline structure of embodiment 2.Among Fig. 4, represented the photo of the crystalline structure of embodiment 3,4.Among Fig. 5, represented the photo of the crystalline structure of embodiment 5.Among Fig. 6, represented the photo of the crystalline structure of comparative example 3～9.Among Fig. 7, represented the photo of the crystalline structure of reference example.Among Figure 10, represented the photo of the crystalline structure of embodiment 6.
Shown in Fig. 1, Fig. 3～5, in the magnesium alloy of embodiment 1～6, be formed with the crystalline structure of long period rhythmo structure.Different with it, as Fig. 1, Figure 6 and Figure 7, comparative example 1～9 and reference example magnesium alloy does not separately form the crystalline structure of long period rhythmo structure.
Confirmed following situation according to embodiment 1～6 and comparative example 1～9 crystalline structure separately.
In Mg-Zn-RE ternary system casting alloy, be to form the long period rhythmo structure under the situation of Y at RE, and when RE is La, Ce, Pr, Nd, Sm, Eu, Gd, Yb, then do not form the long period rhythmo structure.The character of Gd is slightly different with La, Ce, Pr, Nd, Sm, Eu, Yb, though the independent interpolation of Gd (Zn must be arranged) can not form the long period rhythmo structure, yet with as the compound interpolation of Y of the element that forms the long period rhythmo structure time, even 2.5 atom % also can form long period rhythmo structure (with reference to embodiment 2,5).
In addition, under situation about Yb, Tb, Sm, Nd and Gd being made an addition among the Mg-Zn-Y,, then can not hinder the formation of long period rhythmo structure if below the 5.0 atom %.In addition, under situation about La, Ce, Pr, Eu and Mm being made an addition among the Mg-Zn-Y,, then can not hinder the formation of long period rhythmo structure if below the 5.0 atom %.
The crystal particle diameter of the cast material of comparative example 1 is about 10～30 μ m, and the crystal particle diameter of the cast material of comparative example 2 is about 30～100 μ m, and the crystal particle diameter of the cast material of embodiment 1 is 20～60 μ m, has all observed a large amount of crystallisates on crystal boundary.In addition, in the crystalline structure of the cast material of comparative example 2, have fine precipitate at intragranular.
(the Vickers' hardness experiment of cast material)
Utilized Vickers' hardness experimental evaluation embodiment 1, comparative example 1 and comparative example 2 cast material separately.The Vickers' hardness of the cast material of comparative example 1 is 75Hv, and the Vickers' hardness of the cast material of comparative example 2 is 69Hv, and the Vickers' hardness of the cast material of embodiment 1 is 79Hv.
(ECAE processing)
Described embodiment 1 and comparative example 1,2 cast material have separately been implemented ECAE processing under 400 ℃.In order to import distortion uniformly in sample, the ECAE processing method is used in each circulation and is made the sample long side direction revolve the method that turn 90 degrees, and carries out 4 times and 8 circulations.The process velocity of this moment is the 2mm/ certain value of second.
(the Vickers' hardness experiment of ECAE work material)
Utilize the Vickers' hardness experimental evaluation and implemented the sample of ECAE processing.The Vickers' hardness of the sample after 4 ECAE processing is: the sample of comparative example 1 is 82Hv, and the sample of comparative example 2 is 76Hv, and the sample of embodiment 1 is 96Hv, compares with the cast material before the ECAE processing, observes the raising of 10～20% hardness.Carried out in the sample of 8 ECAE processing, compared, on hardness, do not changed basically with the sample that has carried out 4 ECAE processing.
(crystalline structure of ECAE work material)
Utilize SEM, XRD to carry out structure observation to the sample of having implemented ECAE processing.The crystallisate that is present in the work material of comparative example 1,2 on the crystal boundary is blocked to count μ m magnitude, disperse equably imperceptibly, and in the work material of embodiment 1, confirm that crystallisate is not blocked imperceptibly, but under the state that keeps dot matrix and matching, be cut off.Carried out in the sample of 8 ECAE processing, compared, do not changed basically organizationally with the sample that has carried out 4 ECAE processing.
(stretching experiment of ECAE work material)
Utilize stretching experiment to estimate and implemented the sample that ECAE processes.Stretching experiment be with the direction of extrusion abreast in the early stage Deformation velocity be 5 * 10
-4Carry out under the condition of/second.For the tensile properties of the sample that has carried out 4 ECAE processing, in the sample of comparative example 1,2, demonstrate following yielding stress of 200MPa and 2～3% elongation, and in the sample of embodiment 1, then demonstrated the yielding stress of 260MPa and 15% elongation.The characteristic of cast material is 0.2% endurance 100MPa, elongation 4%, and it is the characteristic that has surpassed this characteristic out and away.
Figure 12 has represented that the sample of embodiment 1 has been implemented ECAE under 375 ℃ temperature add the cycle index of ECAE in man-hour and yield strength (σ y), tensile strength (σ
UTS), the chart of relation of elongation (%).
Figure 13 has represented that the sample of embodiment 1 has been implemented ECAE under 400 ℃ temperature add the cycle index of ECAE in man-hour and yield strength (σ y), tensile strength (σ
UTS), the chart of relation of elongation (%).
Find that from Figure 12 and Figure 13 increase total deformation even increase the cycle index of ECAE, the intensity of magnesium alloy can not increase thereupon yet.
(thermal treatment of ECAE work material)
The sample of having implemented 4 times ECAE processing is kept at 225 ℃ of following isothermals, investigated the relation of hold-time and changes in hardness.In the sample of embodiment 1, by implementing 225 ℃ thermal treatment, hardness further improves, and the yielding stress of utilizing stretching experiment to obtain can be increased to 300MPa.
In addition, when making processing temperature to the ECAE of the cast material of embodiment 1 drop to 375 ℃ (, cast material to embodiment 1, not under 400 ℃, but add man-hour) at 375 ℃ of ECAE that implement 4 times down, the yielding stress of the ECAE work material of embodiment 1 is 300MPa, has shown 12% elongation.Confirm that in addition implement 225 ℃ thermal treatment by the sample of this having been implemented ECAE processing, the yielding stress of utilizing stretching experiment to obtain can be increased to 320MPa.
(extruding of the casting alloy of embodiment 6)
The casting alloy of embodiment 6 is the ternary system magnesium alloy with 96 atom %Mg-1 atom %Zn-3 atom %Y of long period rhythmo structure.To this casting alloy, be that 300 ℃, cross section decrement are 90%, extrusion speed is to have carried out extrusion processing under the 2.5mm/ condition of second in temperature.Magnesium alloy after this extruding has at room temperature demonstrated the tensile yield strength of 420MPa and 2% elongation.
(characteristic after the extruding of the casting alloy of embodiment 6～42 and comparative example 10～15)
The cast material that making has the magnesium alloy of forming shown in the table 1 has carried out extrusion processing to this cast material with extrusion temperature shown in the table 1 and extrusion ratio.To the extruded material after this extrusion processing, under the experimental temperature shown in the table 1, utilize stretching experiment to measure 0.2% endurance (yield strength), tensile strength, elongation.These measurement results are illustrated in the table 1.
[table 1]
Mg-Zn-Y class extruded alloy mechanical characteristics
| Form (at.%) | Extrusion temperature (℃) | Extrusion ratio | Experimental temperature (℃) | 0.2% endurance (MPa) | Tensile strength (MPa) | Elongation (%) | |
| Embodiment 7 | Mg-1Zn-2.5Y | 350 | 10 | Normal temperature | 339 | 403 | 8 |
| Embodiment 6 | Mg-1Zn-3Y | 350 | 10 | Normal temperature | 335 | 408 | 8 |
| Embodiment 8 | Mg-1Zn-3.5Y | 350 | 10 | Normal temperature | 356 | 430 | 7.5 |
| Embodiment 9 | Mg-1.5Zn-1.25Y | 350 | 10 | Normal temperature | 340 | 364 | 9 |
| Embodiment 10 | Mg-1.5Zn-2Y | 400 | 10 | Normal temperature | 365 | 396 | 5 |
| Embodiment 11 | Mg-2Zn-2Y | 350 | 10 | Normal temperature | 389 | 423 | 5 |
| Embodiment 12 | ↓ | 400 | 10 | Normal temperature | 326 | 361 | 4 |
| Embodiment 13 | Mg-2Zn-2Y-0.2Zr | 350 | 10 | Normal temperature | 405 | 465 | 8.5 |
| Embodiment 14 | ↓ | 400 | 10 | Normal temperature | 425 | 471 | 8.5 |
| Embodiment 15 | ↓ | 400 | 2.5 | Normal temperature | 345 | 406 | 4.87 |
| Embodiment 16 | ↓ | 450 | 2.5 | Normal temperature | 356 | 406 | 6.5 |
| Embodiment 17 | Mg-2Zn-2Y-2Al | 350 | 10 | Normal temperature | 366 | 380 | 8.5 |
| Embodiment 18 | Mg-2Zn-2Y-1.3Ca | 350 | 10 | Normal temperature | 411 | 450 | 3 |
| Form (at.%) | Extrusion temperature (℃) | Extrusion ratio | Experimental temperature (℃) | 0.2% endurance (MPa) | Tensile strength (MPa) | Elongation (%) | |
| Embodiment 19 | Mg-2Zn-2Y-0.5Ag | 350 | 10 | Normal temperature | 388 | 438 | 9 |
| Embodiment 20 | Mg-2Zn-2Y-1Si | 350 | 10 | Normal temperature | 396 | 433 | 6.5 |
| Embodiment 21 | Mg-2Zn-3.5Y | 350 | 10 | Normal temperature | 360 | 446 | 9.5 |
| Embodiment 22 | Mg-2.5Zn-1.5Y | 350 | 10 | Normal temperature | 343 | 361 | 7 |
| Embodiment 23 | Mg-2.5Zn-2Y | 350 | 10 | Normal temperature | 385 | 415 | 3.7 |
| Embodiment 24 | ↓ | 400 | 10 | Normal temperature | 345 | 369 | 6 |
| Embodiment 25 | Mg-2.5Zn-3.5Y | 450 | 10 | Normal temperature | 360 | 442 | 9 |
| Embodiment 26 | Mg-2.5Zn-4Y | 450 | 10 | Normal temperature | 370 | 450 | 6 |
| Embodiment 27 | ↓ | 450 | 10 | 200 | 286 | 385 | 18.1 |
| Embodiment 28 | Mg-3Zn-3Y | 450 | 10 | Normal temperature | 430 | 487 | 7.5 |
| Embodiment 29 | ↓ | 450 | 10 | 200 | 287 | 351 | 21.1 |
| Embodiment 30 | Mg-3Zn-3.5Y | 450 | 10 | Normal temperature | 440 | 492 | 6 |
| Embodiment 31 | Mg-3.5Zn-3Y | 350 | 10 | Normal temperature | 425 | 490 | 7.5 |
| Embodiment 32 | Mg-3.5Zn-4.5Y | 350 | 10 | Normal temperature | 404 | 491 | 3.5 |
| Embodiment 33 | Mg-4.5Zn-3Y | 450 | 10 | Normal temperature | 342 | 363 | 7.5 |
| Embodiment 34 | Mg-1Zn-2Y | 350 | 2.5 | Normal temperature | 273 | 325 | 0.5 |
| Embodiment 35 | Mg-0.5Zn-2Y | 350 | 10 | Normal temperature | 310 | 350 | 6 |
| Embodiment 36 | ↓ | 400 | 10 | Normal temperature | 270 | 300 | 2 |
| Embodiment 37 | ↓ | 400 | 10 | Normal temperature | 365 | 396 | 5 |
| Embodiment 38 | Mg-1Zn-1Y | 350 | 10 | Normal temperature | 360 | 390 | 2 |
| Embodiment 39 | ↓ | ↓ | 10 | Normal temperature | 373 | 384 | 4 |
| Embodiment 40 | Mg-1Zn-1.5Y | 350 | 10 | Normal temperature | 367 | 380 | 1.3 |
| Form (at.%) | Extrusion temperature (℃) | Extrusion ratio | Experimental temperature (℃) | 0.2% endurance (MPa) | Tensile strength (MPa) | Elongation (%) | |
| Embodiment 41 | Mg-1Zn-2Y | 350 | 10 | Normal temperature | 375 | 420 | 4 |
| Embodiment 42 | ↓ | 400 | 10 | Normal temperature | 330 | 385 | 7 |
| Comparative example 10 | Mg-2Zn-2Y | 350 | 1 | Normal temperature | 80 | 104 | 1.5 |
| Comparative example 11 | Mg-4Zn-1Y | 400 | 10 | Normal temperature | 260 | 325 | 9.8 |
| Comparative example 12 | Mg-1Zn-0.5Y | 350 | 10 | Normal temperature | 320 | 340 | 0.5 |
| Comparative example 13 | Pure Mg | 350 | 10 | Normal temperature | 45 | 35 | |
| Comparative example 14 | Mg-1Zn | 350 | 10 | Normal temperature | 67 | 50 | |
| Comparative example 15 | Mg-2Y | 350 | 10 | Normal temperature | 210 | 15 |
Table 1 has represented that the various Mg-Zn-Y alloy casting materials that the addition of Zn and Y is different with extrusion temperature shown in the table 1 and extrusion ratio, have carried out the result of the stretching experiment under the room temperature after the extrusion processing second with extrusion speed 2.5mm/.
The crystalline structure of cast material of magnesium alloy that will have the composition of embodiment 30 is shown among Figure 11.
Can find from the measurement result of embodiment 17～20,, compare, can improve intensity or elongation or intensity and elongation two aspects with ternary system by adding the 4th element.
Consider from the viewpoint of the practicability of high-strength high-toughness magnesium alloy,,,,, then also can stand practicality as long as elongation is big even intensity is lower slightly in addition as long as the intensity height then also can be stood practicality even extend for a short time.So, when yield strength (MPa) is made as S, will extend (%) when being made as d, consider from the viewpoint of practicability, preferably satisfy the magnesium alloy of following formula (1) and (2).
S＞-15d+435...(1)
S≥325...(2)
According to the determination data of table 1, satisfy described formula (1) and (2) the Mg-Zn-Y alloy compositing range as shown in Figure 2.
That is, the compositing range that satisfies the Mg-Zn-Y alloy of described formula (1) and (2) is the scope that the line by K-L-C-D-E-F-G-H-K shown in Figure 2 surrounds, and is the scope that does not comprise on the line of G-H-K-L-C-D-E-F.
In addition, the compositing range that satisfies the preferred L g-Zn-Y alloy of described formula (1) and (2) is the scope that the line by I-J-C-D-E-F-G-H-I shown in Figure 2 surrounds, and is the scope that does not comprise on the line of G-H-I-J-C-D-E-F.
In addition, the compositing range that satisfies the preferred Mg-Zn-Y alloy of described formula (1) and (2) is the scope that the line by A-B-C-D-E-F-G-H-A shown in Figure 2 surrounds, and is the scope that does not comprise on the line of G-H-A-B-C-D-E-F.
And some I shown in Figure 2 is that Zn is 1 atom %, and Y is 0.75 atom %, point K is that Zn is 1 atom %, and Y is 0.5 atom %, and some K is that Zn is 1 atom %, Y is 0.5 atom %, and some L is that Zn is 5/3 atom %, and Y is 0.5 atom %, point J is that Zn is 2 atom %, Y is 0.75 atom %, and some C is that Zn is 5 atom %, and Y is 3 atom %, point D is that Zn is 5 atom %, Y is 5 atom %, and some E is that Zn is 2.5 atom %, and Y is 5 atom %, point F is that Zn is 0.5 atom %, Y is 3.5 atom %, and some G is that Zn is 0.5 atom %, and Y is 2 atom %, point H is that Zn is 1 atom %, and Y is 2 atom %.
(characteristic after the extruding of the casting alloy of embodiment 43～62)
Use the melting in Ar gas atmosphere of high frequency dissolving stove to have the ingot of the Mg-Zn-Y alloy of forming shown in the table 2, make flaky cast material by cutting this ingot.Then, flaky material is filled in made of copper jar in after, under 150 ℃, carry out the heating, vacuum degassing and seal.To be filled in flaky material in jar, each jar respectively with extrusion temperature table 2 shown in and extrusion ratio carried out extrusion processing thereafter.To the extruded material after this extrusion processing, under the experimental temperature shown in the table 2, utilize stretching experiment to measure 0.2% endurance (yield strength), tensile strength, elongation.In addition, the hardness (Vickers' hardness) of extruded material is also measured.These measurement results are illustrated in the table 2.
The flaky material that table 2 has been represented to make by the addition different Mg-Zn-Y alloy casting material of cutting Zn and Y is with various extrusion temperatures and extrusion ratio, pushes the stretching experiment under the room temperature of the sample that has solidified and the result of experiment of hardness second with extrusion speed 2.5mm/.
Can find from the measurement result of embodiment 46～48, be higher than casting plastic working alloy until 200 ℃ hot strengths.
And the present invention is not limited to described embodiment and embodiment, in the scope that does not break away from purport of the present invention, can carry out various changes and implements.
Claims (46)
1. a high-strength high-toughness magnesium alloy is characterized in that, is by the Zn that contains a atom %, contain the Y of b atom %, remainder is made of Mg, and a and b satisfy the castings that the magnesium alloy of following formula (1)～(3) forms, wherein said castings has long period rhythmo structure phase
(1)0.5≤a＜5.0
(2)0.5＜b＜5.0
(3)2/3a-5/6≤b。
2. high-strength high-toughness magnesium alloy, it is characterized in that, the casting of magnesium alloy divine force that created the universe that is produced as follows, that is, contain the Zn of a atom %, contain the Y of b atom %, remainder is made of Mg, a and b satisfy following formula (1)～(3), the described casting of magnesium alloy divine force that created the universe has been carried out the plastic working thing after the plastic working had hcp structure magnesium at normal temperatures and reach long period rhythmo structure phase mutually
(1)0.5≤a＜5.0
(2)0.5＜b＜5.0
(3)2/3a-5/6≤b。
3. high-strength high-toughness magnesium alloy, it is characterized in that, the casting of magnesium alloy divine force that created the universe that is produced as follows promptly, contains the Zn of a atom %, the Y that contains b atom %, remainder is made of Mg, and a and b satisfy following formula (1)～(3), and the described casting of magnesium alloy divine force that created the universe is carried out plastic working and makes the plastic working thing, described plastic working thing has been carried out the plastic working thing after the thermal treatment to have hcp structure magnesium at normal temperatures and reaches long period rhythmo structure phase mutually
(1)0.5≤a＜5.0
(2)0.5＜b＜5.0
(3)2/3a-5/6≤b。
4. according to claim 2 or 3 described high-strength high-toughness magnesium alloys, it is characterized in that the median size of described hcp structure magnesium phase is more than 2 μ m.
5. according to claim 2 or 3 described high-strength high-toughness magnesium alloys, it is characterized in that, compare that the dislocation desity of described long period rhythmo structure phase is a kind of order of magnitude extremely when young with described hcp structure magnesium dislocation desity mutually.
6. according to claim 2 or 3 described high-strength high-toughness magnesium alloys, it is characterized in that the percentage by volume of the crystal grain of described long period rhythmo structure phase is more than 5%.
7. according to claim 2 or 3 described high-strength high-toughness magnesium alloys, it is characterized in that described plastic working thing has at least a precipitate of selecting from the precipitate group that the compound by the compound of compound, Zn and the rare earth element of compound, Mg and the Zn of Mg and rare earth element and Mg and Zn and rare earth element constitutes.
8. high-strength high-toughness magnesium alloy according to claim 7 is characterized in that, the total percentage by volume of described at least a precipitate surpasses 0% and below 40%.
9. according to any described high-strength high-toughness magnesium alloy in the claim 2,3,8, it is characterized in that, described plastic working be roll, at least one the processing in the middle of extruding, ECAE, stretch process, forging, punching press, rolling forming, bending, FSW processing and their processing repeatedly.
10. according to any described high-strength high-toughness magnesium alloy in the claim 2,3,8, it is characterized in that the total deformation when carrying out described plastic working is below 15.
11., it is characterized in that the total deformation when carrying out described plastic working is below 10 according to any described high-strength high-toughness magnesium alloy in the claim 2,3,8.
12. according to any described high-strength high-toughness magnesium alloy in the claim 2,3,8, it is characterized in that, add up at least a element of selecting from be made of Yb, Tb, Sm and Nd a group contain c atom % in described Mg alloy, c satisfies following formula (4) and (5)
(4)0＜c≤3.0
(5)0.2≤b+c≤6.0。
13. according to any described high-strength high-toughness magnesium alloy in the claim 2,3,8, it is characterized in that, in described Mg alloy, add up at least a element of from constitute by La, Ce, Pr, Eu, Mm and Gd a group, selecting contain c atom %, c satisfies following formula (4) and (5) or satisfied (5) and (6)
(4)0＜c＜2.0
(5)0.2≤b+c≤6.0
(6)c/b≤1.5。
14. according to any described high-strength high-toughness magnesium alloy in the claim 2,3,8, it is characterized in that, in described Mg alloy, add up at least a element of from constitute by Yb, Tb, Sm and Nd a group, selecting contain c atom %, add up at least a element of from constitute by La, Ce, Pr, Eu, Mm and Gd a group, selecting contain d atom %, c and d satisfy following formula (4)～(6) or satisfy (6) and (7)
(4)0＜c≤3.0
(5)0＜d＜2.0
(6)0.2≤b+c+d≤6.0
(7)d/b≤1.5。
15. a high-strength high-toughness magnesium alloy is characterized in that, is by the Zn that contains a atom %, contain the Y of b atom %, remainder is made of Mg, and a and b satisfy the castings that the magnesium alloy of following formula (1)～(3) constitutes, wherein said castings has long period rhythmo structure phase
(1)0.25≤a≤5.0
(2)0.5≤b≤5.0
(3)0.5a≤b。
16. high-strength high-toughness magnesium alloy, it is characterized in that, the casting of magnesium alloy divine force that created the universe that is produced as follows promptly, contains the Zn of a atom %, the Y that contains b atom %, remainder is made of Mg, and a and b satisfy following formula (1)～(3), makes flaky castings by cutting the described casting of magnesium alloy divine force that created the universe, utilize plastic working thing that described castings has been solidified in plastic working to have hcp structure magnesium at normal temperatures and reach long period rhythmo structure phase mutually
(1)0.25≤a≤5.0
(2)0.5≤b≤5.0
(3)0.5a≤b。
17. high-strength high-toughness magnesium alloy, it is characterized in that, the casting of magnesium alloy divine force that created the universe that is produced as follows, promptly, the Zn that contains a atom %, the Y that contains b atom %, remainder is made of Mg, a and b satisfy following formula (1)～(3), make flaky castings by cutting the described casting of magnesium alloy divine force that created the universe, the plastic working thing that making utilizes plastic working that described castings has been solidified has carried out the plastic working thing after the thermal treatment to described plastic working thing and has had hcp structure magnesium at normal temperatures and reach long period rhythmo structure phase mutually
(1)0.25≤a≤5.0
(2)0.5≤b≤5.0
(3)0.5a≤b。
18., it is characterized in that the median size of described hcp structure magnesium phase is more than 2 μ m according to claim 16 or 17 described high-strength high-toughness magnesium alloys.
19., it is characterized in that according to claim 16 or 17 described high-strength high-toughness magnesium alloys, to compare with described hcp structure magnesium dislocation desity mutually, the dislocation desity of described long period rhythmo structure phase is a kind of order of magnitude extremely when young.
20., it is characterized in that the percentage by volume of the crystal grain of described long period rhythmo structure phase is more than 5% according to claim 16 or 17 described high-strength high-toughness magnesium alloys.
21. according to claim 16 or 17 described high-strength high-toughness magnesium alloys, it is characterized in that described plastic working thing has at least a precipitate of selecting from the precipitate group that the compound by the compound of compound, Zn and the rare earth element of compound, Mg and the Zn of Mg and rare earth element and Mg and Zn and rare earth element constitutes.
22. high-strength high-toughness magnesium alloy according to claim 21 is characterized in that, the total percentage by volume of described at least a precipitate surpasses 0% and below 40%.
23. according to any described high-strength high-toughness magnesium alloy in the claim 16,17,22, it is characterized in that, described plastic working be roll, at least one the processing in the middle of extruding, ECAE, stretch process, forging, punching press, rolling forming, bending, FSW processing and their processing repeatedly.
24., it is characterized in that the total deformation when carrying out described plastic working is below 15 according to any described high-strength high-toughness magnesium alloy in the claim 16,17,22.
25., it is characterized in that the total deformation when carrying out described plastic working is below 10 according to any described high-strength high-toughness magnesium alloy in the claim 16,17,22.
26. according to any described high-strength high-toughness magnesium alloy in the claim 15,16,17,22, it is characterized in that, add up at least a element of selecting from be made of Yb, Tb, Sm and Nd a group contain c atom % in described Mg alloy, c satisfies following formula (4) and (5)
(4)0＜c≤3.0
(5)0.1≤b+c≤6.0。
27. according to any described high-strength high-toughness magnesium alloy in the claim 15,16,17,22, it is characterized in that, in described Mg alloy, add up at least a element of from constitute by La, Ce, Pr, Eu, Mm and Gd a group, selecting contain c atom %, c satisfies following formula (4) and (5)
(4)0＜c≤3.0
(5)0.1≤b+c≤6.0。
28. according to any described high-strength high-toughness magnesium alloy in the claim 15,16,17,22, it is characterized in that, in described Mg alloy, add up at least a element of from constitute by Yb, Tb, Sm and Nd a group, selecting contain c atom %, add up at least a element of from constitute by La, Ce, Pr, Eu, Mm and Gd a group, selecting contain d atom %, c and d satisfy following formula (4)～(6)
(4)0＜c≤3.0
(5)0＜d≤3.0
(6)0.1≤b+c+d≤6.0。
29. according to any described high-strength high-toughness magnesium alloy in the claim 1,2,3,8,15,16,17,22, it is characterized in that, in described Mg alloy, add up to contain to surpass 0 atom % and at least a element of from constitute by A1, Th, Ca, Si, Mn, Zr, Ti, Hf, Nb, Ag, Sr, Sc, B, C, Sn, Au, Ba, Ge, Bi, Ga, In, Ir, Li, Pd, Sb and V a group, selecting below 2.5 atom %.
30. the manufacture method of a high-strength high-toughness magnesium alloy is characterized in that, possesses:
The operation of the casting of magnesium alloy divine force that created the universe that is produced as follows promptly, contains the Zn of a atom %, contains the Y of b atom %, and remainder is made of Mg, and a and b satisfy following formula (1)～(3);
By the described casting of magnesium alloy divine force that created the universe is carried out the operation that the plastic working thing is made in plastic working, the wherein said casting of magnesium alloy divine force that created the universe has long period rhythmo structure phase,
(1)0.5≤a＜5.0
(2)0.5＜b＜5.0
(3)2/3a-5/6≤b。
31. the manufacture method of high-strength high-toughness magnesium alloy according to claim 30 is characterized in that, the described casting of magnesium alloy divine force that created the universe has hcp structure magnesium phase.
32. manufacture method according to claim 30 or 31 described high-strength high-toughness magnesium alloys, it is characterized in that, add up at least a element of selecting from be made of Yb, Tb, Sm and Nd a group contain c atom % in described Mg alloy, c satisfies following formula (4) and (5)
(4)0＜c≤3.0
(5)0.2≤b+c≤6.0。
33. manufacture method according to claim 30 or 31 described high-strength high-toughness magnesium alloys, it is characterized in that, in described Mg alloy, add up at least a element of from constitute by La, Ce, Pr, Eu, Mm and Gd a group, selecting contain c atom %, c satisfies following formula (4) and (5) or satisfied (5) and (6)
(4)0＜c＜2.0
(5)0.2≤b+c≤6.0
(6)c/b≤1.5。
34. manufacture method according to claim 30 or 31 described high-strength high-toughness magnesium alloys, it is characterized in that, in described Mg alloy, add up at least a element of from constitute by Yb, Tb, Sm and Nd a group, selecting contain c atom %, add up at least a element of from constitute by La, Ce, Pr, Eu, Mm and Gd a group, selecting contain d atom %, c and d satisfy following formula (4)～(6) or satisfy (6) and (7)
(4)0＜c≤3.0
(5)0＜d＜2.0
(6)0.2≤b+c+d≤6.0
(7)d/b≤1.5。
35. the manufacture method of a high-strength high-toughness magnesium alloy is characterized in that, possesses:
The operation of the casting of magnesium alloy divine force that created the universe that is produced as follows promptly, contains the Zn of a atom %, contains the Y of b atom %, and remainder is made of Mg, and a and b satisfy following formula (1)～(3);
Make the operation of flaky cutting object by cutting described magnesium alloy;
By utilizing the curing of plastic working to make the operation of plastic working thing to described cutting object, the wherein said casting of magnesium alloy divine force that created the universe has long period rhythmo structure phase,
(1)0.25≤a≤5.0
(2)0.5≤b≤5.0
(3)0.5a≤b。
36. the manufacture method of high-strength high-toughness magnesium alloy according to claim 35 is characterized in that, the described casting of magnesium alloy divine force that created the universe has hcp structure magnesium phase.
37. manufacture method according to claim 35 or 36 described high-strength high-toughness magnesium alloys, it is characterized in that, add up at least a element of selecting from be made of Yb, Tb, Sm and Nd a group contain c atom % in described Mg alloy, c satisfies following formula (4) and (5)
(4)0＜c≤3.0
(5)0.1≤b+c≤6.0。
38. manufacture method according to claim 35 or 36 described high-strength high-toughness magnesium alloys, it is characterized in that, add up at least a element of selecting from be made of La, Ce, Pr, Eu, Mm and Gd a group contain c atom % in described Mg alloy, c satisfies following formula (4) and (5)
(4)0＜c≤3.0
(5)0.1≤b+c≤6.0。
39. manufacture method according to claim 35 or 36 described high-strength high-toughness magnesium alloys, it is characterized in that, in described Mg alloy, add up at least a element of from constitute by Yb, Tb, Sm and Nd a group, selecting contain c atom %, add up at least a element of from constitute by La, Ce, Pr, Eu, Mm and Gd a group, selecting contain d atom %, c and d satisfy following formula (4)～(6)
(4)0＜c≤3.0
(5)0＜d≤3.0
(6)0.1≤b+c+d≤6.0。
40. manufacture method according to any described high-strength high-toughness magnesium alloy in the claim 30,31,35,36, it is characterized in that, in described Mg alloy, add up to contain to surpass 0 atom % and at least a element of from constitute by Al, Th, Ca, Si, Mn, Zr, Ti, Hf, Nb, Ag, Sr, Sc, B, C, Sn, Au, Ba, Ge, Bi, Ga, In, Ir, Li, Pd, Sb and V a group, selecting below 2.5 atom %.
41. manufacture method according to any described high-strength high-toughness magnesium alloy in the claim 30,31,35,36, it is characterized in that, described plastic working be roll, at least one the processing in the middle of extruding, ECAE, stretch process, forging, punching press, rolling forming, bending, FSW processing and their processing repeatedly.
42. the manufacture method according to any described high-strength high-toughness magnesium alloy in the claim 30,31,35,36 is characterized in that the total deformation when carrying out described plastic working is below 15.
43. the manufacture method according to any described high-strength high-toughness magnesium alloy in the claim 30,31,35,36 is characterized in that the total deformation when carrying out described plastic working is below 10.
44. the manufacture method according to any described high-strength high-toughness magnesium alloy in the claim 30,31,35,36 is characterized in that, after the operation of making described plastic working thing, also possesses the operation that described plastic working thing is heat-treated.
45. the manufacture method according to the described high-strength high-toughness magnesium alloy of claim 44 is characterized in that, described heat treated condition is: more than 200 ℃ and less than 500 ℃, more than 10 minutes and less than 24 hours.
46. manufacture method according to any described high-strength high-toughness magnesium alloy in the claim 30,31,35,36,45, it is characterized in that the dislocation desity of hcp structure magnesium phase of having carried out the magnesium alloy after the described plastic working is bigger a kind more than the order of magnitude than the dislocation desity of long period rhythmo structure phase.
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| JP2003395905 | 2003-11-26 | ||
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| JP096344/2004 | 2004-03-29 | ||
| JP2004287912 | 2004-09-30 | ||
| JP287912/2004 | 2004-09-30 | ||
| PCT/JP2004/017616 WO2005052203A1 (en) | 2003-11-26 | 2004-11-26 | High strength and high toughness magnesium alloy and method for production thereof |
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| CN102181763B (en) * | 2011-05-22 | 2012-07-25 | 河南科技大学 | Rare earth magnesium alloy with stable high-temperature strength |
| CN103205591B (en) * | 2012-10-24 | 2016-12-28 | 哈尔滨东安发动机（集团）有限公司 | MgYNdZr alloy method of refining |
| WO2014171550A1 (en) * | 2013-04-15 | 2014-10-23 | 国立大学法人 熊本大学 | Fire-resistant magnesium alloy and production method therefor |
| CN104004979B (en) * | 2014-06-04 | 2016-08-24 | 北京工业大学 | A kind of microstructure thinning method improving magnesium alloy temperature-room type plasticity |
| CN104152768B (en) * | 2014-09-05 | 2016-07-13 | 唐伟 | A kind of heat resisting magnesium-rare earth alloy and preparation method thereof |
| CN104372224B (en) * | 2014-10-20 | 2016-10-05 | 西南交通大学 | A kind of accurate brilliant enhancing complex magnesium alloy and preparation method thereof |
| CN105483481B (en) * | 2015-11-25 | 2017-10-27 | 山东银光钰源轻金属精密成型有限公司 | A kind of preparation method of magnesium alloy motor-car table support arm |
| CN105937005B (en) * | 2016-06-17 | 2019-12-06 | 东北大学秦皇岛分校 | Ageing strengthening magnesium alloy with uniformly distributed granular quasicrystal and rod-shaped phase and preparation method thereof |
| CN108707796A (en) * | 2018-06-04 | 2018-10-26 | 北京华北轻合金有限公司 | The manufacturing method of impact-resisting and heat resistant magnesium alloy dashboard cross member |
| CN109182810B (en) * | 2018-11-19 | 2021-03-02 | 河北工业大学 | Low-cost high-room-temperature plastic deformation magnesium alloy and preparation method thereof |
| CN110284033B (en) * | 2019-08-05 | 2020-11-24 | 深圳市爱斯特新材料科技有限公司 | High-strength Mg-Zn-Al-based microalloyed magnesium alloy and preparation method thereof |
| CN113373358B (en) * | 2021-06-23 | 2023-01-31 | 西安四方超轻材料有限公司 | High-strength easily-deformed single-phase magnesium-lithium alloy material and preparation method thereof |
| CN113528917A (en) * | 2021-07-27 | 2021-10-22 | 重庆大学 | High-strength magnesium alloy with long-period phase and preparation method thereof |
| CN115537621B (en) * | 2022-10-08 | 2023-07-14 | 重庆大学 | High-temperature-resistant high-strength Mg-Gd-Y-Zn-Mn alloy and preparation method thereof |
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Non-Patent Citations (1)
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| T. Itoi等.Long-period ordered structure in a high-Long period stackingstructures observed in Mg97Zn1Y2 alloy.Scripta Materialia51.2004,51107-111. * |
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