CN101194035A - Zn-Al alloy having excellent high-speed deformation properties and its making method - Google Patents
Zn-Al alloy having excellent high-speed deformation properties and its making method Download PDFInfo
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- CN101194035A CN101194035A CNA2005800497070A CN200580049707A CN101194035A CN 101194035 A CN101194035 A CN 101194035A CN A2005800497070 A CNA2005800497070 A CN A2005800497070A CN 200580049707 A CN200580049707 A CN 200580049707A CN 101194035 A CN101194035 A CN 101194035A
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 55
- 239000000956 alloy Substances 0.000 title claims abstract description 55
- 229910007570 Zn-Al Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 10
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- 238000001816 cooling Methods 0.000 claims description 46
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- 238000012545 processing Methods 0.000 claims description 38
- 239000013078 crystal Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 230000003068 static effect Effects 0.000 abstract description 15
- 239000011148 porous material Substances 0.000 abstract description 3
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- 238000013016 damping Methods 0.000 description 12
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/002—Castings of light metals
- B22D21/007—Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
- B22D21/027—Casting heavy metals with low melting point, i.e. less than 1000 degrees C, e.g. Zn 419 degrees C, Pb 327 degrees C, Sn 232 degrees C
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/10—Alloys based on aluminium with zinc as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/053—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with zinc as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/165—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon of zinc or cadmium or alloys based thereon
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Abstract
This invention provides a Zn-Al alloy, which is excellent in static deformability, as well as in dynamic deformability, and can be applied to a large structure, and a process useful for producing the Zn-Al alloy. The Zn-Al alloy comprises Zn: 30 to 99% (% by mass; the same shall apply hereinafter) with the balance consisting of Al and unavoidable impurities, wherein the Zn-Al alloy has a texture comprising a ss phase finely dispersed in an a phase or a' phase having an average grain diameter of not more than 5 [mu]m, the maximum diameter of Al-based inclusions is not more than 50 [mu]m, and, at the same time, pores having a equivalent circle diameter of not less than 0.5 mm are absent, and the macrosegregation of Al is less than 3.0%, and the microsegregation of Al is less than 2.0%.
Description
Technical field
The Zn-Al alloy and the manufacture method thereof of the deformation characteristic excellence when Zn-Al alloy of the present invention and manufacture method thereof, particularly rate of straining are high speed.At this, Zn-Al alloy is as following by rocking or crooked so-called effectively shock insulation damping device metal that wind and earthquake etc. causes.
Background technology
Always, as the strain that can absorb wind loading, earthquake load or follow so-called shock insulation damping device crooked and that rock, Pb system deoscillator (damper), vibration-proof rubber, oil dash-pot (oildamper) arranged and adopted the device of LYP vibration damping steel plates such as (extremely low yield point steel) etc.Yet I. is because there is the problem that degenerates with age in vibration-proof rubber, so be not suitable for the shock insulation damping device that the buildings of durable over a long time requirement is used.In addition, II. is because oil dash-pot needs regular maintenance, thus the same with vibration-proof rubber, as the shock insulation damping device of buildings with problem is arranged.On the other hand, work hardening takes place because of tension set in the vibration damping steel plate of III.LYP etc., if for repeated load the material deterioration takes place, then being not only energy absorption reduces, and if become really up to the mark, then vibration is transmitted to works, therefore is restricted with its purposes of metal as shock insulation damping device.
On the other hand, IV. Pb shown in Figure 1 system deoscillator because Pb is very soft, can be followed the rocking of frequency of 0.1～10Hz as earthquake and wind, in addition because of the flexible this problem of material deterioration that causes is also few, so general now as the shock insulation damping device of installing on the buildings.Also have, 1 is plumbous cast body among Fig. 1, the 2nd, and homogeneous (homogen) weld part, the 3rd, steel plate.
Yet,, have the such problem of constructional difficulties because this large-scale deoscillator weight is very big.In addition, because the yield-point of Pb is soft to 5MPa, thus in order to make member and the Pb damper joint that is engaged on works or the works, just need special technique, thus on the scope of application, there is limitation.In addition, because Pb is poisonous, so as the use of buildings the tendency that is restricted is arranged in recent years.
From these situations, the metal that just requires a kind of damping that the device of nontoxic, small-sized light weight can be provided to use in recent years as the damping metal that can substitute Pb, demonstrates superplastic Zn-Al alloy and is gazed at.
With above-mentioned this Zn-Al alloy associated, the Zn-22%Al alloy of nanocrystal is also confirmed by report under 373K (about 100 ℃) can follow 1 * 10
-4S
-1Rate of straining and the superplasticity (for example with reference to non-patent literature 1) of being out of shape.Yet at room temperature such superplasticity can't realize, so it can not reality be used as the shock insulation device for building that extends requirement is at room temperature arranged.
In addition, also openly the Zn-22%Al-2%Cu alloy is carried out water-cooled under soaking, carry out cold working thereafter, thereby obtain the inner mutually tissue that has β to separate out mutually, demonstrate room temperature superplasticity (with reference to non-patent literature 2) at α.The unit elongation here is 135%, and maximum demonstrates and can access 160% unit elongation.Yet in the document, be not presented at and warmly add man-hour it at room temperature has such unit elongation.In addition, even under cold worked situation, also expect to have more excellent isolation property and damping performance and be used as substituting of Pb deoscillator, considering thus needs unit elongation to improve (for example unit elongation more than 180%) further.
In addition, also experimental small test portion is used in report, is at room temperature shown the main idea (with reference to non-patent literature 3) of superplastic Zn-22%Al alloy.Specifically, disclosing by the initial stage particle diameter that makes metal structure is the columniform Zn-22%Al alloy of 1～15 μ m torsional deformation (cold deformation) by force under the such high pressure of 5GPa, thereby as the central part of fine portion, final tissue becomes 0.1～0.5 μ m.
Yet, in aforesaid method, even central part is that the micro organization that demonstrates the superplasticity possibility is arranged, but it is still thick to leave the granular structure of peripheral part of central part, thereby can not show the superplasticity phenomenon, and only can obtain at the remarkable different tissue of peripheral part and central part.In addition, can use the size of this torsional deformation by force, be restricted to about diameter 15mm, the so very little size of thickness 0.3mm, therefore in this member that bears big load of earthquake isolating equipment, being difficult to make member integral body to become above-mentioned micro organization, as a result of is can't obtain to make member integral body give play to superplastic result.
Present inventors are for above-mentioned this Zn-Al alloy, improving this viewpoint from its characteristic studies very early, as a ring of its research a kind of Zn-Al alloy of building slab level is proposed, it has the ultra-fine grain structure of stable homogeneous, even at room temperature also can show so-called superplastic unit elongation (with reference to patent documentation 1).By the exploitation of this technology, can realize at room temperature demonstrating the Zn-Al alloy of excellent superplastic practical dimensions, still, in such Zn-Al alloy, still leave over the problem that will solve.That is, in the alloy of above-mentioned exploitation, though it is 10 at rate of straining
-3S
-1About low speed under energy of deformation (hereinafter referred to as " static deformation energy ") excellence, at room temperature demonstrate good superplasticity, but rate of straining is 10
-1S
-1About than the energy of deformation under the higher speed (hereinafter referred to as " dynamic deformation energy ") unsettled situation is arranged then like this.In addition, this phenomenon can become large-scale and remarkable all the more along with ingot casting.
Patent documentation 1: the spy opens the scope of flat 11-222643 communique patent request
Non-patent literature 1:R.S.Mishra etc., The observation of tensile superplasticityin nanocrystalline materials:Nanostruct Mater.Vol.9, No.1/8p473-476 (1997)
Non-patent literature 2:G.Toress-Villasenor etc., " A reinvestigation of themechanical history on superplasticity of Zn-22Al-2Cu at room temperature " (Material.Science.Forum Vol.243/245 P553 (1997))
Non-patent literature 3:M.Furukawa etc., " Fabrication of submicrometer-grainedZn-22%Al by torsion straining " J.Mater.Res.Vol.11 No.9 P2128 (1996)
Summary of the invention
The present invention is under this situation and form, and its purpose is, provides a kind of not only model deformation can be excellent, and dynamic deformation can be also excellent, can also be applicable to Zn-Al alloy and effective manufacture method thereof on the large structure.
It is 10 that present inventors are based on improving rate of straining
-3S
-1High speed under this viewpoint of deformation characteristic, study from various angles.It found that, except control originally as the ultra-fine grain structure in the technology of patent documentation 1 proposition, if realizing thick Al is the reduction of inclusion and macrosegregation and microsegregation, then can reaches above-mentioned purpose, and propose (special be willing to 2002-328106).
And when further studying with keen determination, also found still can obtain the Zn-Al alloy and the manufacture method thereof of same effect even without the control of carrying out ultra-fine grain structure closely for above-mentioned technology.Be to find specifically, up to now, need make in order positively to make superplasticity performance α mutually or α ' mutually in the average crystal grain footpath miniaturization of dispersive β phase to " below the 0.05 μ m ", but, in the manufacturing processed of this alloy, there is not the above hole of median size 0.5mm in the alloy structure of inevitable generation if make, even when then the average crystal grain of this β phase directly surpasses 0.05 μ m, still can access excellent dynamic deformation energy, thereby arrive the present invention mutually.
Therefore, so-called Zn-Al alloy of the present invention, be to contain the Zn:30～99% (meaning of quality %, down together), the Zn-Al alloy that surplus is made of Al and unavoidable impurities, be α mutually or α ' β dispersive tissue is compactly mutually arranged in mutually, the average crystal grain of α phase or α ' phase directly is below the 5 μ m, Al is that the maximum diameter of inclusion is counted below the 50 μ m with equivalent circle diameter, and do not exist with equivalent circle diameter and count hole more than the 0.5mm, and the macrosegregation of Al is lower than 3.0%, and the microsegregation of Al is lower than 2.0%.
Foundation of the present invention is, if the hole of above-mentioned size is existed, even the average crystal grain of then above-mentioned β phase footpath is big, still can access excellent dynamic deformation energy, though it is still indeterminate about its reason, but consider it is owing to making, so the toughness of material improves as the hole miniaturization that destroys starting point.
As shown in Figure 5, β compactly be dispersed in mutually α mutually in.This compactly dispersive β generally constitute (Fig. 6) mutually by a plurality of crystal grain.If the average crystal grain of β phase footpath is big, kinetic characteristic is reduced, therefore be preferably below the 3 μ m, more preferably 0.1 μ m, particularly below the 0.05 μ m, but as described later,, still find to obtain excellent dynamic deformation energy even be more than the 3 μ m.
But if average crystal grain footpath is excessive, then therefore mutually big or small thickization of dispersive β compactly be preferably below the 5 μ m.Also has, have the β of invention can constitute by a crystal grain mutually, also can constitute, but β be a plurality of when grain formation mutually that β size mutually is preferably below the 10 μ m, when β is made of 1 crystal grain, then as above-mentioned being preferably below the 5 μ m by a plurality of crystal grain.
The present invention has also stipulated to make the method for the Zn-Al alloy of this high speed deformation characteristic excellence, and this method comprises following operation:
When the Zn-Al alloy liquation is injected the mold manufacturing, cut off the operation that injection liquation and outside atmosphere are cast simultaneously;
In the mold process of cooling after casting, cool off 425～375 ℃ temperature range, and carry out the refrigerative operation 275～250 ℃ temperature range with the average cooling rate more than 0.020 ℃/second with the average cooling rate more than 0.25 ℃/second;
Keep the reheat operation of back chilling in heating more than 350 ℃;
In the operation of carrying out breaking down processing below 275 ℃; And
In the operation of carrying out warm processing below 275 ℃.
Zn-Al alloy of the present invention not only static deformation can be excellent, and dynamic deformation can be also excellent, therefore is suitable as most the former material of damping of large structure.
Description of drawings
Fig. 1 is the diagrammatic illustration figure that represents the formation of always employed Pb system deoscillator.
To be expression carry out the graphic representation of the relation of temperature and plate temperature in the atmosphere process furnace in when heating to 150kg level ingot casting to Fig. 2.
Fig. 3 is the state graph of Zn-Al alloy.
Fig. 4 be expression ingot casting internal temperature through the time change the graphic representation of an example of (cooling curve).
Fig. 5 is an example of 5000 times SEM photo of tissue of the present invention (β disperses the α phase mutually).
Fig. 6 is an example of the enlarged photograph of the β phase part in the tissue of the present invention (β disperses the α phase mutually).
Fig. 7 is the photo at the average crystal grain mensuration place directly of the α phase in the medelling ground expression tissue of the present invention.
Nomenclature
1 plumbous cast body
2 homogeneous weld parts
3 steel plates
Embodiment
At first, the tissue with regard to Zn-Al alloy of the present invention describes.In order to make Zn-Al alloy demonstrate superplasticity, need α mutually or α ' be dispersed with the tissue (below be referred to as " β disperses the α phase ") of above-mentioned β phase in mutually.β disperses α different fully mutually with the α that does not have β to separate out mutually, can demonstrate the unit elongation more than 200% owing to the mobile viscous deformation that brings of crystal grain.
; even satisfy above-mentioned important document; but according to Zn content and metal structure can be different; under the situation of the Zn-Al alloy that constitutes by Zn:30～80%, surplus Al and unavoidable impurities; be the α single phase structure on the macroscopic view, have each α mutually or α ' compactly be dispersed with the tissue of β phase in mutually.
With respect to this, Zn is 80% when above, shows as Fig. 3, must become the mixed structure of 2 phases of alpha+beta.That is, the Zn content of the present invention regulation is 80～99%, and the thick β that can become the about 10 μ m of particle diameter mutually and β compactly dispersive α phase or α ' phase phase blended 2 phase constitutions are mutually arranged.
Under the situation of this Zn-Al alloy that constitutes by Zn:80～99%, surplus Al and unavoidable impurities, though thick β has only given play to the ductility about 65% under the normal temperature memory phenomenon, but β dispersion α has given play to the unit elongation more than 200% mutually, thereby can avoid the crystal boundary face generation stress concentration in the β phase, therefore whole demonstrating surpasses 160% unit elongation.
With respect to this, the α that separates out that does not have a β as inside is during mutually with mutually 2 phase constitutions (alpha+beta) of β, and α phase, β just show ductility separately mutually, can not show superplasticity.In addition, normal temperature memory phenomenon (recovery of dislocation) takes place in thick β mutually, though the distortion impedance stabilization, unit elongation is about 65%.Therefore, do not have the α that the separates out phase and β 2 phase constitutions (alpha+beta) mutually of β, unit elongation as a whole rests on about 68%.
The α that the preferred this β of not having separates out does not exist mutually with thick β mutually, if but have the tissue that can give play to superplastic β dispersion α phase, then in the scope of not damaging effect of the present invention, can be mixed with does not have α phase that β separates out and thick β mutually yet.Here, thick β also comprises the such lamellar structure of aftermentioned mutually.
Become and at room temperature given play to the Zn-Al alloy of the present invention that unit elongation surpasses 160% room temperature superplasticity (static deformation energy), if just α mutually or α ' compactly be dispersed with the tissue of β phase in mutually, the fine more then easy more superplasticity of having given play to, therefore, the average crystal grain of preferred α phase or α ' phase directly is below the 5 μ m, is preferably especially below the 3.5 μ m.
For the dynamic deformation that makes Zn-Al alloy can reach well, need to realize that thick Al is the reduction of inclusion and macrosegregation and microsegregation, the miniaturization of pore dimension.
(Al is the maximum diameter of inclusion: count below the 50 μ m with equivalent circle diameter)
Thick Al is that inclusion becomes the destructive starting point dynamic deformation can be reduced, and static deformation can reduce, and therefore, need do one's utmost to make such Al is that inclusion does not exist, in the present invention, be that the maximum diameter of inclusion is defined as below the 50 μ m in equivalent circle diameter with Al.This maximum diameter is preferably below the 20 μ m.Also have, Al is that inclusion mainly refers to Al
2O
3
(macrosegregation of Al is lower than 3.0%, Al microsegregation be lower than 2.0%)
Macrosegregation is the segregation of (top bottom) from top to bottom (segregation that ingot casting integral body takes place on a large scale) of ingot casting, needs the Al concentration of this part and the difference of average A l concentration to be lower than 3.0% (that is, macrosegregation is lower than 3.0%) in the present invention.Be preferably below 2%.On the other hand, though microsegregation is to count the segregation that takes place in several mu m ranges with a crystal grain quantity, need to make the Al concentration of this part and the concentration difference of average A l concentration to be lower than 2.0% in the present invention.Be preferably below 1%.
(pore size)
Thick hole becomes the destructive starting point, is that inclusion is the same with Al, and dynamic deformation can be reduced, but also static deformation can be reduced, therefore need do one's utmost to make such hole not exist, in the present invention, the maximum diameter of hole is defined as below the 0.5mm in equivalent circle diameter.This maximum diameter is preferably below the 0.3mm.When particularly the average crystal grain of β phase footpath was big, recommending the maximum diameter of hole was below the 0.3mm.
In the present invention, all satisfy above-mentioned important document as above-mentioned macrosegregation and microsegregation, again by doing one's utmost that hole is not existed, then can obtain good high speed distortion (dynamic deformation energy), shortcoming any one important document wherein all can not be reached purpose of the present invention.
Next, the chemical constitution with regard to Zn-Al alloy of the present invention describes.The composition of Zn-Al alloy of the present invention consists of, and the Zn containing ratio is 30～99% (be preferably 50～99%, more preferably 70～99%), and surplus is Al and unavoidable impurities.Wherein, preferred especially Zn-22%Al eutectoid alloy.As described above shown in the state graph of the Zn-Al alloy of Fig. 3,,, superplasticity is shown at 22% o'clock so carry out organizational controls the easiliest because the containing ratio of Al is eutectoid point to be arranged.
On the other hand, in the above range, along with the containing ratio of Zn diminishes, the β amount of separating out reduces, even by the mobile viscous deformation that brings of crystal grain the tendency that still has unit elongation to reduce takes place.And, when the containing ratio of Zn is lower than 30%,, still can not show unit elongation above 100% even handle by condition of the present invention, be not preferred therefore.Also have, in described Fig. 3, α is that principal constituent is the crystal region of the face-centered cubic lattice of Al mutually, and α ' is that principal constituent is the crystal region of the face-centered cubic lattice of Zn mutually, and β is that Zn is the crystal region of the intensive hexagonal lattice of principal constituent mutually, and L represents liquid phase.
If Zn-Al alloy of the present invention satisfies above-mentioned important document, then also can be in the scope of the stability of not damaging hysteresis (hysteresis), so that permanent stress can not contain strengthening element Cu, Si, Mn, Mg because of amount of finish, the undue mode that changes of rate of straining.In addition, for the raising of unit elongation, also can be added with the effective Zr of crystallization miniaturization, TiB.
Next, describe in detail at being used for the method that high-level efficiency obtains to satisfy the Zn-Al alloy of above-mentioned important document.
(casting operation: when Zn-Al alloy liquation injection mold is made, cut off and inject liquation and outside atmosphere)
The Zn-Al alloy liquation being injected mold and when making, inject liquation and outside atmosphere is cast simultaneously by cutting off, can suppress and the combining of oxygen, therefore, as a result of is to suppress Al
2O
3Thickization, the maximum diameter that can be inclusion with Al is suppressed at below the 50 μ m in equivalent circle diameter. as the method for cutting off, effective means has specifically, surrounding atmosphere when making casting is vacuum atmosphere and Ar gas atmosphere (Ar sealing) and makes stopper noz(zle) be impregnated with (stopper noz(zle) dipping) in the liquation.
(the mold process of cooling (I) after the casting :) with the temperature range cooling of the average cooling rate more than 0.25 ℃/second at 425～375 ℃
In the mold process of cooling after casting,, can suppress to become the generation of thick solidified structure of the reason of macrosegregation by cooling off in 425～375 ℃ the temperature range that is equivalent to solid-liquid 2 regions with the average cooling rate more than 0.25 ℃/second.That is,, can suppress thickization of crystallisate of Al, and suppress the generation of the thick solidified structure that causes thus by above-mentioned temperature range is cooled off than speed of cooling faster.Above-mentioned average cooling rate is preferably more than 0.30 ℃/second.
(the mold process of cooling (II) after the casting :) with the temperature range cooling of the average cooling rate more than 0.020 ℃/second at 275～250 ℃
In the mold process of cooling after casting, by cooling off in 275～250 ℃ temperature range of 2 regions that are equivalent to alpha+beta with the average cooling rate more than 0.020 ℃/second, the β that can suppress to separate out is thickization of size mutually, and can suppress with the interior mutually thick β of α is the microsegregation of major cause mutually.That is,, can suppress thickization of the precipitate of Zn and Al, and suppress the generation of the thick β phase (more than the 10 μ m) cause thus, thereby obtain dispersive β phase compactly by above-mentioned temperature range is cooled off than fast speeds.Above-mentioned average cooling rate is preferably more than 0.025 ℃/second.
(reheat operation: keep the back chilling) in heating more than 350 ℃
As above-mentioned, in mold internal cooling process, pass through the acceleration speed of cooling, can suppress the generation of thick solidified structure to a certain extent, but, after above-mentioned cooling, carry out reheat in order further to suppress this generation, this is effective on realization homogenizes.
Homogenize in order to realize fully, can make soaking temperature is more than 350 ℃.But if become more than 390 ℃, then ingot casting might fuse, and therefore preferably is lower than 390 ℃.
In addition, hold-time under said temperature during reheat for example is that it is just homogenized about 1 hour fully under the situation of the following small-sized ingot casting of 50kg, if but for example 150kg level or above large-sized casting ingot then need to make alloy monolithic more than 350 ℃ and keep the long period.
Fig. 2 be expression when the Zn-Al ingot casting of 150kg level is heated (atmosphere heating) the interior temperature of process furnace and the relation of plate temperature, but be more than 350 ℃ in order to make plate temperature, need 8 hours heat-up time as can be known.This be since β phase particle solid solution time caloric receptivity is excessive again in α phase matrix, ingot casting has absorbed the heat from the outside, has to carry out for a long time the atmosphere heating under the situation of large-sized casting ingot.Also consider to carry out ratio-frequency heating thus.Because ratio-frequency heating is to carry out enforceable heating, thus also can heat for a long time, but this becomes the essential factor that cost rises industrial under the situation of large-sized casting ingot.
Keep the back chilling above-mentioned the heating more than 350 ℃.When reheat by remaining on more than 350 ℃, β can be enclosed in mutually α mutually in and prevent microsegregation, in order to obtain the alloy of this tissue, need carry out chilling in (after the soaking) behind the reheat.Chilling also can be chilled to breaking down processing temperature described later except proceeding to room temperature.
By carrying out chilling, can suppress from α ' to suppress β at macroscopic scale and to diffuse to 2 degree that are separated mutually mutually to the moving of stable α phase from above-mentioned structural state.Consequently, obtain to bring into play superplastic β and disperse the α phase constitution by reaching the state that β is separated out mutually in mutually at α.
Above-mentioned so-called chilling is meant that speed of cooling is more than 10 ℃/second, preferred specifically water-cooled.This is because when stove cold (below 0.1 ℃/second) and air cooling (being lower than 10 ℃/second), β spreads mutually, spreads all over whole and become the sheet tissue.This is because if form lamellar structure whole of this stage, when then the working modulus in following processing treatment is low, make α insufficient with β miniaturization mutually mutually easily, the unit elongation under the room temperature rests on about 100～140%, surpasses 160% unit elongation and can not positively reach.
Preferably do one's utmost not make the lamellar structure utmost point to exist, but in the scope of not damaging characteristic, also can have lamellar structure in the part of tissue.In this case, the size of lamellar structure is preferably about 30 μ m, is preferably below 20% in area occupation ratio.
(breaking down manufacturing procedure: carry out breaking down processing) in the temperature below 275 ℃
After the soaking, obtain β in the chilling stage and disperse the α phase, α is about 10～2 μ m with α ' mutually mutually, and β phase crystal grain is preferably below the 5 μ m, is preferably especially about 0.05～0.1 μ m.Though such tissue can demonstrate so-called superplastic unit elongation more than 180% in about 100～150 ℃ high temperature territory, at room temperature but can not show such unit elongation.
In order at room temperature to show the such unit elongation of so-called superplasticity, need be in the external force of the after-applied physics of soaking-chilling, make α and α ' mutually crystal grain, be present in α mutually or the β phase miniaturization of α ' in mutually in addition, and eliminate hole.Therefore in the present invention, in order to eliminate hole, must be behind described reheat chilling, carry out breaking down processing (forge etc.) with the temperature below 275 ℃ after, carry out warm processing again.
Why with the breaking down processing temperature as below 275 ℃, as above-mentioned shown in Figure 3, be because if surpass 275 ℃ of then tissue inter-variables, the β of formation disperse α might become once again mutually α and α ' mutually with β 2 kinds of tissues mutually.Preferably carrying out breaking down processing below 200 ℃.On the other hand,, then there is the possibility that produces the processing crackle, therefore is recommended in and carries out breaking down processing more than 100 ℃ if processing temperature is low excessively.
Also have, in the present invention,, can realize the ultra micro refinement organized, so not need to carry out again cold working by carrying out breaking down processing and warm processing like this.
In the present invention, can after breaking down processing, not make it cooling, but make alloy temperature proceed warm processing for the pyritous state, in addition also can be after breaking down processing cool to room temperature at once, carry out warm processing afterwards again, but when being the latter, need make speed of cooling after the breaking down processing be about 3 ℃/second with on cool off.Its reason with add again after cooling same, be for the fixing β that has obtained disperses the α phase, preferably carry out water-cooled specifically.
(warm manufacturing procedure: carry out warm processing) with the temperature below 275 ℃
Warm processing need carried out below 275 ℃.Shown in Figure 3 as described, this is because if surpass 275 ℃ of then tissue inter-variables, the β of formation disperse α might become once again mutually α and α ' mutually with β 2 kinds of tissues mutually.Preferably carrying out warm processing below 200 ℃.On the other hand,, then there is the possibility that produces the processing crackle, therefore is recommended in and carries out warm processing more than 100 ℃ if warm processing temperature is low excessively.
Said temperature processing can be enumerated forging, extrusion, Wire Drawing etc. specifically so long as apply the operation of external force for the crystal grain miniaturization and get final product.
Warm processing back is cooled to room temperature more than 3 ℃/second and gets final product with about.Preferably carry out water-cooled specifically.This with add again after cooling be that if speed of cooling at this moment is slow, then β disperses the mutually thick change of α, does not find the superplasticity under the room temperature for the fixing β that has obtained disperses α mutually equally.
Zn-Al alloy of the present invention, its hardness and mild steel are equal or than softer slightly, therefore also can connect at bolt, use in the general joining technique of riveted joint etc., and can easily carry out and the engaging of building structure etc.But,, preferably be suppressed at below 100 ℃ applying heat and when engaging, Heating temperature need be suppressed at below 250 ℃ as soldering.This be because as above-mentioned, tissue might phase transformation more than 250 ℃ the time, if do not carry out chilling after being heated to more than 100 ℃ in addition, then not at all easy thickization of micro organization that obtains exists unit elongation at room temperature to be difficult to guarantee situation above 160%.
Below, illustrate in greater detail the present invention by embodiment, but following embodiment not limiting character of the present invention, the average packet that carries out design alteration according to preceding aim described later is contained in the technical scope of the present invention.
EXAMPLE l
[manufacturing of Zn-Al alloy]
Adopt iron mold or the copper mold of cross-sectional shape, under two sides' of air cooling or water-cooled condition, Zn-22%Al alloy liquation is cast for long 200mm * wide 350mm.Also have, it is that the water-cooled copper mold at 200mm angle casts continuously that its part (No.12 of aftermentioned table 1) is adopted cross-sectional shape.Like this, obtain the Zn-22%Al that macrosegregation takes place alloying constituent easily ingot casting (the ingot casting size: 180kg) of (adding up to impurity level: below 0.5%).
Also have, the cooling movement of ingot casting is in the position (kernel of section position) apart from the bottom surface 300mm of each ingot casting thermopair to be set to measure.Show among Fig. 4 the ingot casting internal temperature through the time change the example of (cooling curve).According to above-mentioned cooling curve, calculate the speed of cooling (average cooling rate 1) of solid-liquid 2 phase regions (425～375 ℃) and the speed of cooling (average cooling rate 2) that β separates out starting point temperature (275～250 ℃).In addition, ingot casting sealing (with the partition of outside atmosphere) is when dress ingot (ingot charge), and mold inside and mould (ト ユ) are carried out the Ar sealing in advance.In addition, when continuous casting,, seals stopper noz(zle) by being immersed in the liquation.
With the ingot casting of the Zn-Al alloy that obtains with atmospheric furnace reheat (soaking) to the temperature shown in the table 1, under this temperature, kept 1 hour or 8 hours.This hold-time is to make ingot casting surface patch thermocouple in atmospheric furnace, and the plate temperature reaches the temperature time afterwards of regulation.
Behind the reheat, from stove, take out behind the ingot casting at once water-cooled to the breaking down processing temperature, then with the Heating temperature shown in the table 1, use 400 tons of hydraulic pressure stamping machines, cogging (forging) is thick: 350mm * wide: 200mm * length: 450mm, carry out water-cooled (do not carry out breaking down and add man-hour, water-cooled is to room temperature behind the reheat) thereafter.Then carry out warm processing (ausrolling) and water-cooled, obtain the alloy sheets of thickness of slab 20mm.
[table 1]
| No. | Meltage (kg/ch) | Casting process | Sealing method | Average cooling rate 1 (℃/second) | Average cooling rate 2 (℃/second) | The reheat condition | Breaking down processing (casting) temperature (℃) | Temperature processing back (rolling) temperature (℃) | Speed of cooling (℃/second) after the temperature processing | |
| Temperature (℃) | Time (Hr) | |||||||||
| 1 | 180 | Air cooling cast iron casting mould | Ar | 0.160 | 0.010 | 350 | 8 | 250 | 200 | 0.1 |
| 2 | 180 | Water-cooled cast iron casting mould | Ar | 0.200 | 0.017 | 350 | 8 | 250 | 200 | 10 |
| 3 | 180 | The water-cooled copper mold | Ar | 0.300 | 0.025 | 350 | 8 | Do not have | 200 | 10 |
| 4 | 180 | The water-cooled copper mold | Ar | 0.300 | 0.025 | 300 | 8 | Do not have | 200 | 10 |
| 5 | 180 | The water-cooled copper mold | Ar | 0.300 | 0.025 | 350 | 8 | 250 | 250 | 10 |
| 6 | 180 | The water-cooled copper mold | Ar | 0.300 | 0.025 | 350 | 8 | 250 | 350 | 10 |
| 7 | 180 | The water-cooled copper copper mold | Ar | 0.300 | 0.025 | 350 | 8 | 150 | 250 | 10 |
| 8 | 180 | The water-cooled copper mold | Ar | 0.300 | 0.025 | 350 | 8 | 150 | 250 | 10 |
| 9 | 180 | The water-cooled copper mold | Ar | 0.300 | 0.025 | 350 | 8 | 350 | 250 | 10 |
| 10 | 180 | The water-cooled copper mold | Ar | 0.190 | 0.010 | 350 | 8 | 250 | 250 | 10 |
| 11 | 180 | The water-cooled copper mold | Do not have | 0.300 | 0.025 | 350 | 8 | 250 | 250 | 10 |
| 12 | 180 | The water-cooled copper mold | The wet stain of spraying | 0.500 | 0.033 | 350 | 8 | 250 | 250 | 10 |
| 13 | 180 | The water-cooled copper mold | Ar | 0.300 | 0.025 | 300 | 8 | 250 | 250 | 10 |
| 14 | 180 | The water-cooled copper mold | Nitrogen | 0.300 | 0.025 | 350 | 8 | 250 | 250 | 10 |
| 15 | 180 | The water-cooled copper mold | Ar | 0.300 | 0.025 | 350 | 1 | 250 | 250 | 10 |
| 16 | 180 | The water-cooled copper mold | Do not have | 0.300 | 0.025 | 350 | 8 | 250 | 250 | 10 |
| 17 | 180 | The water-cooled copper mold | Ar | 0.300 | 0.025 | 350 | 8 | 250 | 270 | 10 |
The characteristic of the Zn-Al alloy that so obtains according to following method evaluation.
[evaluating characteristics]
For the above-mentioned sheet material that obtains,, measure the particle diameter of α (containing α ') with its metal structure of electron microscope observation.
In detail, be to have implemented etched alloy test portion after to polishing (buffing) with 5000 times multiplying power to carry out SEM (scanning electron microscope) and observe, take 3 microphotographs.In each photo, pull out the long straight lines of 3 100 μ m arbitrarily, the length of line part that will be by each α phase is as the particle diameter of each α phase.In each photo, each bar straight line, that it is average and as the round equivalent particle diameter of α phase.Also have, according to the size of α phase, will observe multiplying power suitably 1000～10000 times of variations, making straight length is 500 μ m, 50 μ m, similarly measures the round equivalent particle diameter of α phase.(Fig. 7)
In addition, extracting thickness is the JIS5 test film of 10mm, and making gauge length is 50mm, and (rate of straining is 1.67 * 10 to pinblock speed (crosshead speed) for the 5mm/ branch
-3/ s: the quasistatic energy of deformation) and 250mm (rate of straining is 8.33 * 10
-2/ s: the dynamic deformation energy) carry out tension test.Unit elongation (tension set) when measuring tensile strength TS and fracture is estimated the static characteristics (tensile strength TS and tension set during the low speed distortion) and the kinetic characteristic (tensile strength TS and tension set when high speed is out of shape) of each alloy.
Al is that the maximum diameter of inclusion is tried to achieve as follows.Promptly, with opticmicroscope with 1000 times multiplying power to rolling former material (thickness: 18mm, above-mentioned grinded) rolling horizontal 100mm position observe, take 3 microphotographs, wherein Zui Da particle diameter (equivalent circle diameter) is judged as the maximum particle diameter that Al is an inclusion.Macrosegregation and microsegregation are according to following method evaluation.
(macrosegregation)
With the mode cutting pass material that can observe from the top of ingot casting the section of bottom arbitrarily 2, skin section from the ingot casting and 1/2t portion (t: the thickness of slab of rolled stock), the skin section of the skin section of ingot casting intermediate altitude and 1/2t portion, ingot casting bottom and 1/2t portion 6 extract test films, measure the Al concentration at each position, the maximum value that will be offset from the Al concentration (22%) of target is estimated as macrosegregation.
(microsegregation)
For any one of the 2 place's test portions that extract in the macroscopic evaluation, (beam diameter: 10 μ m), whether the change of estimating Al concentration is in 2% in this measurement range with EPMA (electron probe microanalyser) 1mm length arbitrarily to be carried out linear analysis.
(hole evaluation method)
Prepare standard test specimen (50mm angle section), carry out after 10 hours that HIP handles and after removing hole fully with 350 ℃ of reheat, make the boring of diameter 0.5mm and 0.3mm be positioned at standard test portion sheet central authorities, the UT that carries out this test portion checks (UT (Ultrasonic Testing) inspection), and investigation can detect the UT noise level (noise level) of the hole of this diameter 0.5mm and 0.3mm.
Then, the UT that carries out each test portion (rolled stock of thick 20mm) checks, has diameter 0.5mm and the above hole of 0.3mm about the noise more than the above-mentioned noise level having taken place, having confirmed as.Only have the ◎ that is of the following hole of 0.3mm, what only have the following hole of 0.5mm is zero, and is presented in the following table 2.
[table 2]
| No. | Macrosegregation (quality %) | Microsegregation (quality %) | Al is the maximum diameter (μ m) of inclusion | Metal structure | Moving characteristic | Quiet characteristic | ||||
| α phase (μ m) | β phase (μ m) | Hole | Tensile strength (MPa) | Unit elongation (%) | Tensile strength (MPa) | Unit elongation (%) | ||||
| 1 | 3.5 | 3.1 | 6 | 8.9 | 0.011 | ○ | 132.2 | 145.2 | 293 | 41.3 |
| 2 | 3.3 | 2.9 | 4 | 10 | 0.019 | × | 135.1 | 149.4 | 287.5 | 45.3 |
| 3 | 2.5 | 1.8 | 7 | 3.1 | 0.038 | × | 128.3 | 181.5 | 283.4 | 89.3 |
| 4 | 2.5 | 2.7 | 5 | 6.1 | 0.06 | × | 129.1 | 121.4 | 300.3 | 39.1 |
| 5 | 2.5 | 1.8 | 7 | 4.4 | 2.1 | ○ | 123.5 | 203.1 | 289.3 | 83.1 |
| 6 | 2.5 | 1.8 | 7 | 6.1 | 5.2 | ○ | 129.2 | 204.3 | 289.1 | 48.1 |
| 7 | 2.5 | 1.8 | 7 | 4.4 | 2.2 | ○ | 130.5 | 204.1 | 289.9 | 87.4 |
| 8 | 2 5 | 1.8 | 7 | 4.2 | 1.6 | ○ | 132.1 | 203.8 | 291.3 | 86.9 |
| 9 | 2.5 | 1.8 | 7 | 5.9 | 4.1 | ○ | 127.5 | 134.2 | 294.3 | 42.5 |
| 10 | 3.4 | 2.8 | 7 | 4.3 | 1.3 | ○ | 1 28.2 | 220.3 | 291.3 | 38.2 |
| 11 | 2.6 | 1.8 | 58 | 3.9 | 1.5 | ○ | 126.4 | 201.2 | 299 | 45.3 |
| 12 | 1.1 | 1.2 | 4 | 3.8 | 0.8 | ○ | 113.1 | 250.4 | 298.1 | 120.5 |
| 13 | 2.5 | 2.7 | 5 | 7.3 | 4.3 | ○ | 127.5 | 121.4 | 300.3 | 38.6 |
| 14 | 2.5 | 1.7 | 30 | 4.3 | 1.6 | ○ | 127.9 | 173.1 | 298.4 | 69.5 |
| 15 | 2.5 | 1.8 | 6 | 5.4 | 1.4 | ○ | 128.4 | 119.3 | 299.3 | 33.6 |
| 16 | 2.5 | 1.5 | 60 | 4.2 | 1.3 | ○ | 128.5 | 111.5 | 289.7 | 34.6 |
| 17 | 2.5 | 1.5 | 7 | 4.8 | 3.1 | ◎ | 127.0 | 201.0 | 298.8 | 72.0 |
Can carry out following investigation by table 1 and table 2.At first, No.5,7,8,12,14 is because all satisfy the important document of the present invention's regulation, so the characteristic of dynamic as can be known characteristic and static state is all excellent.Wherein, particularly No.5,14 reaches the speed of cooling of regulation by using the water-cooled copper mold as can be known, thereby macrosegregation and microsegregation are reduced, even meltage is the large-sized casting ingot of 180kg, also can access good deformation characteristic.
Also have, though No.7,8 satisfies important document of the present invention, cogging (forging) temperature is low, has the possibility that forge crack takes place.Therefore as above-mentioned, preferably carrying out breaking down processing (forging) more than 200 ℃.
Though the brilliant particle diameter ratio 3 μ m of No.17 β phase are big, the particle diameter ratio 5 μ m of α phase are little, do not have the above hole of 0.3mm, therefore can access good deformation characteristic.
With respect to this, a certain important document of No.1,2,4,6,9～11,13,15,16 shortcoming the present invention regulations, at least one deterioration in characteristics of static characteristics and kinetic characteristic, or have the danger of forge crack.
In detail, No.1,2,10 because average cooling rate 1,2 slow, so macrosegregation and microsegregation are big, the equal step-down of static characteristics and kinetic characteristic.No.6 is because warm processing (rolling) temperature is too high, so thickization of metal structure, the result is that unit elongation reduces.
No.9 is because breaking down processing (forging) temperature is too high, so thickization of metal structure becomes static characteristics and kinetic characteristic and all be not preferred result.
No.11,16 is not because carry out the partition of liquation and outside atmosphere, so the Al inclusion becomes big and the kinetic characteristic deterioration.
In addition, No.4 does not carry out breaking down processing (forging) in addition because the reheat temperature is low, so the microsegregation change is big, and the miniaturization of the tissue of being unrealized, static characteristics and kinetic characteristic inequality.No.13 is because the reheat temperature is low, so that microsegregation becomes is big, and also thickization of metal structure in addition, static characteristics and kinetic characteristic also all reduce.No.15 is because the size of α phase is big, so become the result of static characteristics and kinetic characteristic inequality.
Also have, No.3 be original propose above-mentioned β is suppressed at mutually reference example below the 0.05 μ m, even there is hole to exist as can be known, but static characteristics and kinetic characteristic are still all excellent.
Claims (3)
1. the Zn-Al alloy of a high speed deformation characteristic excellence is to contain Zn:30～99% in quality %, and surplus is characterized in that by the Zn-Al alloy that Al and unavoidable impurities constitute,
Be α mutually or α ' compactly be dispersed with the tissue of β phase in mutually,
The average crystal grain of α phase or α ' phase directly is below the 5 μ m,
Al is that the maximum diameter of inclusion is counted below the 50 μ m with equivalent circle diameter, and does not exist with equivalent circle diameter and count hole more than the 0.5mm,
And the macrosegregation of Al is lower than 3.0%, and the microsegregation of Al is lower than 2.0%.
2. the Zn-Al alloy of high speed deformation characteristic excellence according to claim 1 is characterized in that, the average crystal grain of β phase directly is below the 3 μ m, more preferably below the 0.1 μ m.
3. the manufacture method of the Zn-Al alloy of a high speed deformation characteristic excellence is characterized in that, comprising:
When Zn-Al alloy liquation injection mold is made, will inject liquation and outside atmosphere and cut off, and the operation of casting simultaneously;
In the mold process of cooling after casting, cool off 425～375 ℃ temperature range, and carry out the refrigerative operation 275～250 ℃ temperature range with the average cooling rate more than 0.020 ℃/second with the average cooling rate more than 0.25 ℃/second;
After heating keeps more than 350 ℃, carry out the reheat operation of chilling;
In the operation of carrying out breaking down processing below 275 ℃; And
In the operation of carrying out warm processing below 275 ℃.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2005/010049 WO2006129355A1 (en) | 2005-06-01 | 2005-06-01 | Zn-Al ALLOY HAVING EXCELLENT HIGH-SPEED DEFORMATION PROPERTIES AND PROCESS FOR PRODUCING THE SAME |
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| Publication Number | Publication Date |
|---|---|
| CN101194035A true CN101194035A (en) | 2008-06-04 |
| CN100557051C CN100557051C (en) | 2009-11-04 |
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| US (1) | US20080196796A1 (en) |
| CN (1) | CN100557051C (en) |
| WO (1) | WO2006129355A1 (en) |
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| CN103924179A (en) * | 2014-03-28 | 2014-07-16 | 上海龙烁焊材有限公司 | Heat treatment method of zinc-aluminum rolled strip |
| CN107058828A (en) * | 2017-06-27 | 2017-08-18 | 桂林理工大学 | With high intensity, high tenacity, the high Zn content deformation Al Zn alloys of low cost and preparation method |
| CN107058829A (en) * | 2017-06-27 | 2017-08-18 | 桂林理工大学 | High-performance with ultra-fine grained structure contains the high zinc wrought aluminium alloy of scandium and preparation method |
| CN116065010A (en) * | 2022-12-16 | 2023-05-05 | 成都先进金属材料产业技术研究院股份有限公司 | Homogenization treatment method for ultra-high strength maraging steel |
| CN116516223A (en) * | 2023-04-03 | 2023-08-01 | 北京工业大学 | Erbium-containing high-zinc Al-Zn-Cu-Si-Er-Zr alloy and preparation method thereof |
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| KR101760076B1 (en) * | 2016-06-09 | 2017-07-24 | 한국기계연구원 | Al-Zn alloy comprising precipitation with improved strength and elongation and method of manufacturing the same |
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| JP3674897B2 (en) * | 1998-02-06 | 2005-07-27 | 株式会社神戸製鋼所 | Zn-Al alloy for vibration control and manufacturing method thereof |
| JP3773893B2 (en) * | 2002-11-12 | 2006-05-10 | 株式会社神戸製鋼所 | Zn-Al alloy having excellent high-speed deformation characteristics and method for producing the same |
| JP4315797B2 (en) * | 2003-12-26 | 2009-08-19 | 株式会社神戸製鋼所 | Zn-Al alloy having excellent high-speed deformation characteristics and method for producing the same |
| JP4769065B2 (en) * | 2005-11-17 | 2011-09-07 | 株式会社神戸製鋼所 | Zn-Al alloy having excellent elongation and method for producing the same |
-
2005
- 2005-06-01 WO PCT/JP2005/010049 patent/WO2006129355A1/en active Application Filing
- 2005-06-01 CN CNB2005800497070A patent/CN100557051C/en not_active Expired - Fee Related
- 2005-06-01 US US11/916,293 patent/US20080196796A1/en not_active Abandoned
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103924179A (en) * | 2014-03-28 | 2014-07-16 | 上海龙烁焊材有限公司 | Heat treatment method of zinc-aluminum rolled strip |
| CN107058828A (en) * | 2017-06-27 | 2017-08-18 | 桂林理工大学 | With high intensity, high tenacity, the high Zn content deformation Al Zn alloys of low cost and preparation method |
| CN107058829A (en) * | 2017-06-27 | 2017-08-18 | 桂林理工大学 | High-performance with ultra-fine grained structure contains the high zinc wrought aluminium alloy of scandium and preparation method |
| CN116065010A (en) * | 2022-12-16 | 2023-05-05 | 成都先进金属材料产业技术研究院股份有限公司 | Homogenization treatment method for ultra-high strength maraging steel |
| CN116065010B (en) * | 2022-12-16 | 2024-09-03 | 成都先进金属材料产业技术研究院股份有限公司 | Homogenization treatment method for ultra-high strength maraging steel |
| CN116516223A (en) * | 2023-04-03 | 2023-08-01 | 北京工业大学 | Erbium-containing high-zinc Al-Zn-Cu-Si-Er-Zr alloy and preparation method thereof |
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|---|---|
| WO2006129355A1 (en) | 2006-12-07 |
| CN100557051C (en) | 2009-11-04 |
| US20080196796A1 (en) | 2008-08-21 |
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