CN100441717C - Wrought magnesium alloy having excellent formability and method of producing same - Google Patents
Wrought magnesium alloy having excellent formability and method of producing same Download PDFInfo
- Publication number
- CN100441717C CN100441717C CNB2005800104334A CN200580010433A CN100441717C CN 100441717 C CN100441717 C CN 100441717C CN B2005800104334 A CNB2005800104334 A CN B2005800104334A CN 200580010433 A CN200580010433 A CN 200580010433A CN 100441717 C CN100441717 C CN 100441717C
- Authority
- CN
- China
- Prior art keywords
- family element
- magnesium alloy
- atom
- magnesium
- wrought magnesium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Forging (AREA)
- Extrusion Of Metal (AREA)
- Metal Rolling (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
Disclosed is a wrought magnesium alloy having excellent strength and extrusion or rolling formability, and a method of producing the same. The wrought magnesium alloy comprises 0.1 - 1.5 at% group IIIa, 1.0 - 4.0 at% group IIIb, 0.35 at% or less of one selected from the group consisting of groups IIa, IVa, VIIa, IVb, and a mixture thereof, 1.0 at% or less of group IIb, and a balance of Mg and unavoidable impurities and thus has a second phase composite microstructure. The wrought magnesium alloy of the present invention has high strength, toughness, and formability in addition to the electromagnetic wave shield ability of magnesium. Accordingly, the wrought magnesium alloy is a material useful to portable electronic goods, such as notebook personal computers, mobile phones, digital cameras, camcorders, CD players, PDA, or MP3 players, automotive parts, such as engine room hoods, oil pans, or inner panel of door, or structural parts for airplane.
Description
Technical field
The present invention relates to a kind ofly second have outstanding intensity mutually because of containing by what intermetallic compound constituted, the wrought magnesium alloys of plasticity and erosion resistance, more specifically, the present invention relates to a kind of wrought magnesium alloys and manufacture method thereof of containing, described magnesium alloy contains the IIIA family element of 0.1-1.5 atom %, 1.0-4.0 the IIIB family element of atom %, be equal to or less than being selected from of 0.35 atom % by IIA, IVA, VIIA, at least a element in the group that IVB family element and composition thereof is formed, be equal to or less than the IIB family element of 1.0 atom %, surplus is magnesium and unavoidable impurities, thereby this wrought magnesium alloys has the complex tissue of second phase that is made of intermetallic compound.
Background technology
Magnesium alloy have about 1.74-1.95 gram/cubic centimetre than low density, proportion is 2/3 of aluminium, has outstanding specific tenacity and workability, has developed into the light structure material that is used for aircraft and automobile.But because magnesium has six side's closely packed (HCP) crystalline networks, so plasticity is lower, thereby its application limitations is using casting process to realize the field that is shaped.Particularly, owing to descend and the problems such as erosion resistance of difference such as severe oxidation, the hot strength in when fusing, its practical application is restricted.Study for overcoming above-mentioned deficiency, make it in atmospheric environment, stablize dissolving, use sulfur hexafluoride (SF simultaneously
6) gas, carbon dioxide, argon gas etc., and produce sheet material by direct chill casting operation.
In magnesium alloy, the Mg-Zn alloy shows outstanding aging hardening behavior, and its advantage is, because by the thermal treatment thinning microstructure, intensity and ductility obviously improve, and process easily and weld.On the other hand, its shortcoming is that owing to add Zn, casting process forms micropore, so the Mg-Zn alloy is difficult to be applied to casting process, for example die casting.In addition, because grow up to coarse grain, therefore be difficult to raising intensity as expection.In order to overcome the problems referred to above, after deliberation the slippage of use crystal boundary improve plasticity, wherein alloying elements is added crystal grain thinning in the Mg-Zn binary alloy.About this, J.P.Doan and G.Ansel propose a kind of method that improves alloy strength, wherein add the Zr refinement and form the crystal grain of Mg-Zn alloy (J.P.Goan and G.Ansel, Trans, AIME, the 171st volume (1947), 286-295 page or leaf).But because the fusing point height of Zr, the solubleness under the room temperature in Mg is low, therefore mainly is present in crystal boundary, thereby becomes formation of crack (fracture initiation site) when applying external stress.At this on the one hand, having developed the alloy material for example behind AZ31B or the AM20 that comprises aluminum and zinc or magnesium, utilize the ductility of single phase solid solution, carrying out plastic working operation (plastic working process) becomes possibility.But, even their tissue is single phase solid solution and has outstanding ductility thus that these alloy materials still exist owing to the strain hardening capacity difference and because of anisotropy is difficult to suppress grain growth, the shortcoming of plasticity difference.In order to address the above problem, proposed a kind ofly under differing temps, to heat different piece, realize the method for warm manufacturing procedure.But the problem of this method is that the different heating temperature of different piece has obviously increased the manufacturing cost of pressing mold.As another kind of method, a kind of thixotropic forming method (thixo-molding method) is proposed, wherein the powder of the preliminary slabbing of compacting under the high temperature between liquid phase and solid phase coexistence.But the shortcoming of this method is, the powder costliness, and because the powder compression material has vesicular structure, thereby be difficult to use electroplating work procedure.The corrosion-resistant of magnesium, therefore essential surface of handling magnesium, but unfortunately, chemistry that gas phase plating operation or electroless plating operation need and processing cost are apparently higher than electroplating work procedure.Yet, because immersing in the hole, chemicals corrode, have highly porous and low-density product, and for example die casting and thixotropic forming product are difficult to use wet plating operation.
In addition, the open 2003-0048412 of Korean Patent special permission has disclosed a kind of alloy, and this alloy contains 3.0-10.0 weight %Zn, 0.25-3.0 weight %Mn, Al, Si and Ca.But, even being equal to or greater than 2% alloy, Zn content has high strength, this alloy still exists free zinc (Zn) to form the shortcoming of low melting point eutectic phase easily.For example, if exist fusing point to be lower than 350 ℃ low melting point Mg
7Zn
3, corrosion-resistant then.And being used for the roughing operation process of broken large dendritic crystal structure, ftractures easily in the sheet material both sides, thereby because high anisotropy, drawing is poor.The open 2002-0078936 (United States Patent (USP) 6471797) of Korean Patent special permission has disclosed a kind of utilization and has contained the accurate crystalline phase raising intensity of Mg-Zn-Y eutectic ternary alloy of 1-10 atom % (at%) Zn and 0.1-3 atom %Y and the method for plasticity.But the shortcoming of this method is that Zn content is essential enough big, thereby guarantees accurate crystalline phase effect as expection.Because the proportion of zinc and magnesium is obviously different, the uneven components of cast article.The micropore of crystal boundary reduces erosion resistance, and in the hot-rolled process process, (tears) torn in formation in the sheet material side.On the other hand, in the korean patent application 10-2003-0044997 that applicant of the present invention proposes, reduce tearing that inhomogeneous composition causes in the rolling process process by reducing zinc content.But, be the low melting point eutectic phase that after matrix forms, forms mutually owing to improve second of plasticity at crystal boundary, therefore it is disperseed by the broken rolling process after solidifying.Correspondingly, this also is difficult to its homodisperse.Therefore, must depress than (reduction ratio) to repeating first rolling process several times in the scope of 5-10%, and must depress than carrying out this operation after the cast structure fragmentation, thereby obtain high quality, not have the side crackle in the scope of 15-20%.
A lot of other Patent publish a kind of method of making light magnesium alloy band of high strength or powder, wherein obtain non-crystal structure by the rapid solidification operation.The open 1990-0004953 of Korean Patent special permission, denomination of invention is " high-strength magnesium alloy (high strength magnesium alloy) ", the open 1993-846 of Korean Patent special permission, denomination of invention is " high-strength magnesium alloy (magnesium alloy having highstrength) ", the open H05-70880 of Japanese Patent Laid, denomination of invention is " high-strength magnesium alloy material and manufacture method thereof (magnesium alloy material having high strength and method ofproducing the same) ", the open H06-41701 of Japanese Patent Laid, denomination of invention is " high strength amorphous magnesium alloy and manufacture method thereof (amorphous magnesium alloy having high strengthand method of producing the same) ", Japanese Patent H07-54026, denomination of invention is " high-strength magnesium alloy and manufacture method thereof (magnesium alloy having high strength and methodof producing the same) ", United States Patent (USP) 4675157,4765954,4853035,4857109,4938809,5071474,5078806,5078807,5087304,5129960 and 5316598, European patent EP 0361136A1 and French Patent 2688233 have disclosed by the rapid solidification operation and have formed amorphous structure.Must reach 10 owing to form the rate of cooling of amorphous structure
5-10
7℃/second, so these patents are used to produce powder or strip is useful, do not produce common sheet material but be suitable for.Therefore, in order to be rolled or press forming, to use and press down the spindle that manufacture-illegal crystalline flour end obtains in recrystallization temperature.
In addition, United States Patent (USP) 637040,3391034,4116731,4194908 and 5959390 and English Patent 2095288 disclosed and use some rare earth elements to suppress grain growths, perhaps at high temperature when there is eutectic phase in crystal boundary, prevent the crystal boundary slippage, thereby improve creep resistance.But eutectic phase has and the incoherent thick tissue of matrix usually, therefore can not fully improve plasticity.In addition, the open H7-109538A of Japanese Patent Laid, United States Patent (USP) 5693158,5800640 and 6395224 has disclosed a kind of method of making the low-crackle sensitive product, wherein uses Sr, Li or B, and heat-treats the grain size of refinement cast article.But these patents are useful to cast article, but can not be directly used in texturising product.The open H10-147830A of Japanese Patent Laid has disclosed use 6-12 weight %Y and 1-6 weight %Gd, and forge hot and ageing treatment subsequently, and raising is used for the creep resistance of engine part.But, because use a large amount of expensive elements that product cost is obviously improved, and thick intermetallic compound and matrix incoherence, so this patent can not be applied to texturising product.In addition, also propose a kind of method of improving plasticity, wherein used excessive Li that the lattice structure of matrix is become body-centered cubic lattice.But in the Galvanic reaction of considering Li and owing to using excessive Li to raise the cost, this method can not be applied to wrapping material.
Summary of the invention
Therefore, the present invention proposes when being the problems referred to above that occur in considering prior art, the purpose of this invention is to provide a kind of wrought magnesium alloys, this alloy contains with the intermetallic compound of matrix coherence and has second complex tissue mutually, thereby improve elongation and anisotropy, guarantee outstanding plasticity and erosion resistance.In order to achieve the above object, use the alloy that constitutes by the element more than three kinds or three kinds to activate slip plane.In addition, in order raise to activate slip plane with temperature, IIIA and IIIB family element added together reduce stacking fault energy (stacking fault energy), and improve the erosion resistance of matrix.In addition, utilize tiny intermetallic compound particle raising strain hardening capacity of dispersive and plasticity in extruding and the rolling process process.
In order to achieve the above object, the invention provides a kind of wrought magnesium alloys with excellent formability and plating (platingproperties), this alloy contains the IIIA family element of 0.1-1.5 atom %, 1.0-4.0 the IIIB family element of atom %, be equal to or less than at least a element in the group that IIA, IVA, VIIA, IVB family element and composition thereof form of being selected from of 0.35 atom %, be equal to or less than the IIB family element of 1.0 atom %, surplus is magnesium and impurity, this alloy thereby have the second phase intermetallic compound.
Description of drawings
The box sample that Fig. 1 represents to use magnesium alloy plate according to a modification of this invention to make;
The cup-shaped sample that Fig. 2 represents to use magnesium alloy plate according to a modification of this invention to make;
Fig. 3 represents the box sample that uses the AZ31 plate to make;
Fig. 4 represents the tissue of No. 1 material in the table 1, and wherein material is cast, then 400 ℃ of diffusion annealings 5 hours;
Fig. 5 represents the tissue according to extruded material of the present invention (extruded material), is annealed state; And
Fig. 6 represents the tissue according to rolled plate of the present invention.
Embodiment
The invention is characterized in, in having outstanding ductile solid solution structure, form tiny second throw out (precipitates) mutually with the basal body structure coherence, thereby make grain refining and improve plasticity.When crystal grain attenuates hour, the intensity of most of materials increases.Its reason is that dislocation is moved along specific slip plane in metal ductility deformation process, makes dislocation directly not move to another crystal grain from a crystal grain.But because crystal boundary barrier effect (grain boundary barrier effect), dislocation direction changes its route.Therefore, owing to the potential barrier of crystal boundary as dislocation motion, dislocation is long-pending at the crystal boundary plug, thereby stops distortion.For crystal grain thinning must can form the high-temperature stable phase, and in order to guarantee solid solubility required under the high temperature with the matrix coherence.In addition, it is about 15% that the difference in size between basic metallic element and the atom is necessary for, thereby guarantee required matrix reinforcing effect.For the influence of intermetallic compound, a lot of researchs have been carried out to solid solution.Particularly, the matrix enhancement that is caused by tiny intermetallic compound particle disperse distribution is known (Mechanical Metallurgy, 2 of metallurgical engineering field
NdEd., George E.Dieter, McGraw-Hill, 1981,221-227).Intermetallic compound has high fusing point and high bond strength, thereby has high rigidity and thermostability.Because the homodisperse second phase particle, these alloy ratio single-phased alloys more can be resisted recrystallize and grain growth.But, if the tissue of intermetallic compound and matrix incoherence just become formation of crack, though improve intensity, even matrix has ductility, Zong elongation or ductility also descend.
If second of traditional magnesium alloy is not the high-melting-point phase in the matrix mutually, second is the low melting point eutectic phase of process of setting mutually, rather than throw out.Therefore, eutectic phase great majority and matrix incoherence.Matrix does not almost have the atom coupling, thereby stops grain growth or overaging effectively.This reduces the plasticity of material, perhaps as formation of crack but disadvantageously.Therefore, the alloy of these types is unsuitable for wrought magnesium alloys.Even form duplex structure (duplex microstructure),, cause undesirable anisotropy or intensity to improve if second phase can not stop dislocation motion by force effectively.
The IIIA family element that the present invention uses form easily intermetallic compound with cubic lattice and thereby have high matrix reinforced effects and ductility, this is known.Alan Russel and KarlGschneidner Jr. are the members of the Ames Laboratory of USDOE accessory Iowa State University, they have reported that the intermetallic compound that is formed by IIIA family element has the B2 cubic lattice, CsCl for example, and B27, B33 or the DO of compound between conventional metals
11Quadrature dot matrix difference.Therefore, it have outstanding ductility (Nature Materials, 2, Sep.2003,587-590).At present, reported a lot of intermetallic compounds and the magnesium matrix coherence that contain IIIA family element, and thought that the ductility of intermetallic compound is caused by fault.
In addition, Many researchers comprises A.P.Tsai, and is verified, because the accurate brilliant intermetallic compound that IIIA family element forms has high adhesion energy (adhesion energy) and Young's modulus, is a kind of have high strength and ductile material therefore.Based on the above fact,, a lot of researchs have been carried out for the brilliant intermetallic compound of standard is applied in the structured material.Particularly, in the magnesium alloy field, Japan and Korea S have obtained leading position (MaterialsScience and Engineering A300,2001,312-315 in containing the Mg-Zn-Y alloy research of quasicrystal particle; Acta Materialia 50 (2002), 2343-2356; Materials Transactions, the 42nd volume, No.10 (2001), 2144-2147; TMS2002conference, Magnesium Technology 2002,141-150; Journal ofAlloys andCompounds 342 (2002), 445-450).
Above-mentioned research is verified following true: because uneven components zinc poly-(separation) partially appears, in zinc content height (being equal to or greater than 4 atom %) in dissolution process.And free zinc forms the low melting point eutectic phase, causes the operation of rolling not wish the side crackle that occurs.But Y, IIIA family element form icosahedral quasicrystal mutually together with Mg and Zn, thereby this has strengthened matrix mutually, simultaneously and the matrix coherence, have therefore stoped the high temperature grain growth up to 400 ℃ effectively.Particularly, the A.Inoue of Japan uses high-resolution electron microscope (HREM) to confirm, producing by the RSP operation and containing in the magnesium alloy of 2 atom %Y and 1 atom %Zn, per 6 cycles form ABACAB type fault (ScriptaMaterialia 49 (2003) p417-422; Philosophical Magazine Letters the 82nd volume (2002), 543-551; Acta Materialia the 50th volume (2002), 3845-3857).
The formation of fault is because the stacking sequence of a tightly packed side changes, and is different with normal stacking sequence, and known that they mainly are because the ductility distortion forms.If the stacking fault energy height just is difficult to form fault, thereby the required strain hardening of pressed material is not high.Therefore, because fine aluminium or copper have high stacking fault energy, the energy major part of room temperature process supply changes into heat.So just be difficult to accumulate internal modification, the nucleation motivating force of recrystallization process reduces.But, in magnesium alloy of the present invention, IIIB and IIIA family element with as the magnesium alloy chemical of matrix element, thereby reduce the stacking fault energy of intermetallic compound, produce ductility.In addition, tiny second promotes the nucleation of the process that reheats mutually, makes grain refining.Intermetallic compound particle stops the grain growth under recrystallization temperature or higher temperature.
Based on above-mentioned explanation, the conclusion that the present inventor obtains is, when IIIA family element and magnesium alloy chemical form the low sosoloid of stacking fault energy, in sosoloid, add the element increase solution strengthening of IIIB family and do the time spent, and when adding IIB family element and other miniaturization element (miniaturized elements) when forming the structure of the intermetallic compound that contains coherence, can form strain hardening capacity outstanding, by refinement of thermal treatment recrystallize and the improved material of anisotropy.
To describe the element and the composition of magnesium alloy according to a modification of this invention below in detail.
IIIA family element, key element promptly of the present invention comprises Sc, Y, lanthanon and actinide elements.About this, preferably be used alone or in combination Sc, Y or lanthanon, rather than send the columbium series elements of radioactive rays.They are solid-solubilized in the magnesium, thereby reduce the c/a ratio, increase ductility and reduce stacking fault energy, thereby increase the nucleation motivating force of recrystallize.In addition, under the high temperature of process of setting with Mg
5The particle that the RE form exists forms by peritectic transformation at about 500 ℃ and to have the HCP structure promptly, DO
19Lattice structure, for example Mg
3RE or Mg
17RE
5The prism-like sheet particle of (RE is the abbreviation that belongs to the rare earth element of IIIA family).Therefore, particle have high enhancement and with the matrix coherence, the result no longer becomes formation of crack.After rolling process, particle can be pressed into rod, ball or cube.
In the present invention, eutectic phase can solid solution after diffusion heat treatments, in extruding and rolling process, disperseed well, thus the grain growth of prevention heat treatment process, and as the nucleation site of recrystallize.When IIIA family constituent content less than 0.1% the time, second quantity not sufficient that forms mutually.When content surpassed 1.5%, refining effect was saturated, so elongation descends the manufacturing cost raising.This is the reason of restriction IIIA family amount of element.
IIIB family element comprises B, Al, Ga, In and Tl.Because low-melting Ga, In form low melting point eutectic mutually with Tl, therefore preferably only use the mixture of Al or B and Al.IIIB family element forms tiny throw out, thereby helps to strengthen matrix.Use Al as main alloy element.Because B solubleness in magnesium is low, and form high melting compound, for example B
2Y, B
3Y
2Or B
5Y
3Therefore, use with Al to be equal to or less than 0.010% amount, thereby make grain refining.
In the present invention, IIIB family element al is solid-solubilized among the Mg, increases erosion resistance, and prevents the dendritic structure growth, thereby makes cast structure tiny.In addition, because Al forms tiny cubes, for example Al at process of setting
2RE or Al
3RE, and the ductility of increase matrix therefore can the high and outstanding products of ductility of production intensity.When Al content less than 1.0% the time, be difficult to guarantee required enhancement.When content surpasses 4.0%, because unsettled bar-shaped or sheet Al
2Mg
3Or Al
12Mg
17Enlarge at crystal boundary, though therefore room temperature strength height, but hot strength and erosion resistance descend.This is the reason of the amount of restriction Al.
In order to make grain refining and to help to form intermetallic compound, optionally be used singly or in combination and be equal to or less than 0.35% IIA family element, IVA family element, VIIA family element or IVB family element, and be used singly or in combination and be equal to or less than 1.0% IIB family element.
IIA family element, IVA family element and VIIA family element are as the supplement of IIIA and IIIB family element.In IIA family element, preferably use Ca and Sr.Because Be, Ba and Ra produce toxic gas, only when adopting special ventilation plant, use them.When the present invention cast diameter and is equal to or greater than 200 millimeters billet, Ca and Sr were particularly useful for forming tiny cast structure, and form discoid particle, and for example (Mg, Al)
2Ca, thus enhancement improved.
In IVA family element, that the most frequently used is Ti, Zr and Hf, and when adding Rf, because emit radioactive rays, thereby uses safety guard under unavoidable situation.IVB family element makes cast structure tiny, and because fusing point is high and processing easily, that the most frequently used is Si and Ge.The amount of every kind of element of adding is depended in the grain refining effect.That is, Zr, Si and Ca make crystal grain have the micron order fine size, corresponding to 52,19 and 15 microns inverse.
Mn in the VIIA family element is cheap alloying element, stops Al
12Mg
17And Al
2Mg
3Form mutually, and promote high temperature cube Al
2Y forms, and helps crystal grain thinning and improves erosion resistance.Therefore Tc in the VIIA family element and Re price height use under unavoidable situation.
IIA family element, IVA family element, VII family element and IVB family element solubleness in magnesium are low, if therefore too much add them, after casting process, when rate of cooling is low, high brittle big particle occurs gathering partially or forming.Therefore, the amount of above-mentioned element is limited in and is equal to or less than 0.35%.
IIB family element comprises Zn, Cd and Hg.Because poisonous to human body when Hg sucks, so the use of Hg is restricted, and uses with extra protector.When independent adding or combination adding Zn and Cd, in the magnesium matrix tissue, form the fault structure, cause strain hardening; And Zn and Cd and IIIA family element and IIIB family element solid solution are smooth, promote the formation of isometric particle, and for example (Mg, Zn)
5RE, Zn
6Mg
2RE or (Mg, Zn)
17RE
3But excessive Zn and Cd increase the gas solid solubility, thereby reduce erosion resistance or plating processibility (plating workability), and cause the appearance of the poly-partially phenomenon of hot tear crack and gravity.Therefore, the amount of IIB family element is limited in and is equal to or less than 1.0%, preferably is equal to or less than 0.65%.
To describe in detail according to a kind of method of using magnesium alloy slab to produce sheet material of the present invention by following embodiment below, these embodiment are used for explaining, do not constitute restriction of the present invention.
(a) at SF
6With Ar or CO
2Mixed-gas atmosphere perhaps prevents to melt magnesium raw material under the ingress of air condition in Ar atmosphere simultaneously, and adds alloy or mother alloy in the magnesium of fusing.Usually, make magnesium alloy plate by die casting, direct chill cast share, continuous casting or thin slice continuous casting (strip casting) method.
In this embodiment, will have thick 30 millimeters, the mould of wide 250 millimeters and high 400 millimeters cavitys and in process furnace, be preheating to about 200 ℃.The magnesium alloy of fusing is poured in the mould at 710-760 ℃, and the surface imperfection of cast article is removed in processing then.
(b) carry out diffusion annealing at 250-450 ℃, the time length is equal to or greater than 1 minute/millimeter according to slab thickness.When Heating temperature is lower than 250 ℃, or time length when being lower than 1 minute/millimeter, the inner heating of slab is insufficient, thereby forms crackle in the operation of rolling on the surface or at the edge.Preferably heat slab, thereby shorten diffusion time at 350-400 ℃.When Heating temperature surpasses 450 ℃, in the diffusion annealing process, can form free low melting point eutectic phase.In this stage, eutectic phase can refuse, and separates with slab thus.Therefore, the eutectic phase of fusing can be adhered on the roll.When alloying element content is high, increases time length and Heating temperature, thereby improve workability.
(c) carry out the first roughing of one or many (initialcoarse rolling) with each depressing than being equal to or less than 20%, thus broken thick cast structure through the diffusion annealing material, and eliminate tiny gathering partially.After rolling process finishes, carry out one or many process annealing (processannealing) down at 200-450 ℃, make the time length be equal to or greater than 1 minute/millimeter according to slab thickness.When Heating temperature less than 200 ℃ or time length during less than 1 minute/millimeter, the inner heating of slab is insufficient, thereby forms crackle in the operation of rolling on the surface or at the edge.When first roughing, when depressing, may form crackle at the crystal boundary of cast structure than greater than 20% the time.In this stage, the surface temperature of roll must remain on 50-150 ℃, thereby causes the formation of tiny surface crack because slab quenches when preventing that slab from contacting with roll.When roller temperature is higher than 150 ℃, layering appears in the operation of rolling, and wherein a part of rolling stock is adhered to layering then on the roll, thereby makes the steel slab surface roughening.If sheet material does not have undercooling after first roughing, just can be rolled operation once more, and needn't reheat.
(d) when slab casting historrhexis, carry out the reroll operation repeatedly to depress at every turn, up to obtaining desired thickness than being equal to or less than 50%.In this stage, depress the radiating state than the capacity motor that depends on milling train, contraction process, the recoverable deformation of roll and the planeness of plate.Under the preferable case, in the reroll operation, carry out the secondary process annealing repeatedly under 200-450 ℃, the time length remains on and is equal to or greater than 1 minute/millimeter simultaneously at every turn.But in the reroll operation, rolling structure attenuates little, forms crack resistance.In addition, in some cases, can carry out cold rolling.Therefore, rolling process is unnecessary at every turn anneals.
(e) after the finish to gauge operation finishes, carry out final annealing at 180-350 ℃, thickness, intensity and the elongation according to plate keeps the time length for being equal to or greater than 1 minute/millimeter simultaneously.When annealing temperature height and time were long, elongation increased but strength degradation.Particularly, when annealing temperature was higher than 350 ℃, unfortunately yield strength obviously descended.
To describe in detail below and use magnesium alloy billet according to the present invention to push.
(a) at SF
6With Ar or CO
2In the mixed-gas atmosphere, perhaps in Ar atmosphere, prevent from simultaneously to melt magnesium raw material under the condition of ingress of air, and in the magnesium of fusing, add alloy raw material or mother alloy.Subsequently, the magnesium alloy of fusing is poured in 185 millimeters of diameters, long 650 millimeters the mould at 710-760 ℃ forms billet, and then surface imperfection is removed in processing.Need not explanation, except die casting, can use continuous casting.
(b) carry out diffusion annealing at 250-450 ℃, the time length (duration time) according to the billet diameter for being equal to or greater than 1 minute/millimeter, thereby the thick cast structure of broken casting material and eliminates tiny poly-partially.When Heating temperature is lower than 250 ℃, or time length when being lower than 1 minute/millimeter, stress concentration is at crystal boundary, and be full of cracks appears in the possibility of result, and material is ftractureed in the direction of extrusion.Preferably, at 350-400 ℃ of this material of heating, thereby shorten diffusion time.When Heating temperature surpassed 450 ℃, the free low melting point eutectic mutually can refuse in the diffusion annealing process, and and material separation.When alloying element content is high, increases time length and Heating temperature, thereby improve workability.
(c) the diffusion annealing billet is reheated under 250-400 ℃ in process furnace push.The extrusion speed of extrusion machine when squeeze pressure is equal to or greater than 850 MPas is 20 meters/minute to the maximum.Carry out if be squeezed under 500 MPas, then extrusion speed obviously drop to 3-4 rice/minute.The temperature of container is 300-450 ℃.When temperature is lower than 300 ℃, form a lot of surface cracks.When temperature surpasses 450 ℃, obviously form heat cracking or distortion at extrusion process.Container is in about 350 ℃ of heating, and extrusion ratio (extrusion ratio) is generally 10-100.In addition, in the present invention, material can be wound in coil shape in extrusion process, thereby can carry out back and forth rolling.
(d) if billet is very big or cast structure is thick, then carry out first extruding, with broken casting tissue and disperse second phase, then carry out second and push.After first extruding, preferably carry out process annealing at 200-450 ℃, the time length remains on and is equal to or greater than 1 minute/millimeter simultaneously.But in first extrusion process, tissue attenuates for a short time, causes crack resistance, and carries out in container and reheat.Therefore, annealing must not carried out.
(e) after the finish to gauge operation finishes, if material is rolled into sheet material, carry out final annealing at 180-350 ℃, the time length remains on and is equal to or greater than 1 minute/millimeter simultaneously, specifically depends on thickness, intensity and the elongation of plate.When annealing temperature height and time were long, elongation increased and strength degradation.Particularly, when annealing temperature surpassed 350 ℃, unfortunately yield strength obviously descended.Need not explanation,, can use nonstorage calorifier such as well heater when sheet material and when annealing volume, the using gas nozzle, perhaps induction heater, and do not use stove to carry out thermal treatment.In this stage,, higher annealing temperature must be set because heating rate is fast.In this regard, annealing temperature can depart from above-mentioned scope, and does not depart from scope of the present invention and notion.
Shown in following table 1 and 2, with the rolling test result that obtains of wrought magnesium alloys of the present invention.They are rolled into 150 millimeters sheet materials with 1 millimeter of thickness of width tests afterwards.
Make wide 80 millimeters, long 100 millimeters, dark 45 millimeters rectangular phantom, and observe the Edge crack of mould, thereby realize forming test.The sample of 80 millimeters * 50 millimeters of areas is hung over as on the nylon wire that hangs worker's group, and immerse in 200 milliliters of 2%HCl aqueous solution of beaker.Thereby the gas that is produced by sample is dissolved in the solution.In this stage, measure weightlessness, finish the erosion resistance evaluation thus.Plasticity is estimated as follows: shaping is finished in zero expression, does not have crackle and local thickness to reduce; △ represents not crack, but local thickness's deviation occurs; * expression plasticity is very poor, because form crackle.When the wet plating processing of evaluation (wet plating process) characteristic, zero expression plated thickness and the outstanding state of coating surface sticking power; △ represents that sticking power is general, does not observe pin hole, and the uneven state of plated thickness; Pin hole is observed in * expression, perhaps the state that comes off from the surface of some position of sample of coating.
Table 1
Table 2
| 7 | Y 0.30 | Al 2.50 B 0.005 | Zr 0.10 | Zn 0.50 | Diameter 185 circle base castings | T.331 MPa MPa El.23% Y.275 | 4F.○ 5C.R.3.2 6P.○ | 10I.S. |
| 8 | Y 0.15 | Al 2.00 | Ca 0.10 Mn0.10 | Zn 0.30 | Diameter 185 circle base castings | T.245 MPa MPa El.18% Y.203 | 4F.○ 5C.R.3.8 6P.○ | 10I.S. |
| 9 | Y 0.25 | - | Zr0.80 | Zn 1.55 | The direct chill cast share of D360 * t120 (D.C.casting) | T.285 MPa MPa El.16% Y.253 | 4F.○ 5C.R.3.8 7Failure Ni | 11C.S. |
| 10 | Y 0.15 | Al 0.90 | - | Zn 0.75 | 30 * 250 * 400 die castings | T.261 MPa MPa El.18% Y.205 | 4F.○ 5C.R.5.2 8Layer is peeled off | 11C.S. |
| 11 | - | Al 2.54 | Mn 0.09 | Zn 0.30 | 30 * 250 * 400 die castings | T.265 MPa MPa El.18% Y.185 | 4F.X 5C.R.4.1 9Pin hole | 11C.S. (AZ 31) |
1T: tensile strength,
2Y: yield-point,
3El.: elongation
4F.: plasticity,
5C.R.: corrosion weight loss rate
6P: plating,
7Failure Ni: can not form Ni coating
8Layer is peeled off: coating comes off from the surface
9Pin hole: coating forms small pin hole
10I.S.: sample of the present invention,
11C.S.: comparative sample
(the 1st, 9,10, No. 11: 1.6 meters/minute of roll speeds, first roughing depress than 15% 20-45% then 2-8 number: roll speed 16-20 rice/minute, depress than 30-67% after the extruding)
When estimating erosion resistance, using permissible error is the beaker weight of per 5 minutes measurement dresses of the precision balance sample of 1/1000 gram, measures 60 minutes, and calculated weight reduces slope, finishes the erosion resistance evaluation thus.Higher slope weightlessness is many, causes corrosion-resistant.
In table 1, because No. 11 magnesium alloy are according to produced in conventional processes, its plasticity is poor, as shown in Figure 3, cracks in forming process.In wet plating operation, in liquid, carry out activation treatment earlier, implement electroplating work procedure again, for example plate cupric cyanide, plating copper sulfate or nickel plating, carry out final plating then, for example chromium plating or plating precious metal.In this stage, if formation pin hole or coating come off from the surface, then the reliability of erosion resistance obviously descends.
Industrial usability
As mentioned above, in the present invention, tiny second-phase intermetallic compound disperse distributes, thereby obviously improves formability and the corrosion resistance of the difference of traditional magnesium plate. Therefore, the magnesium plate has the excellent in performance as structural material, the result, and the magnesium plate being applied in the structural material of portable electronic products, automobile or aircraft becomes possibility.
Claims (3)
1. wrought magnesium alloys with excellent formability and plating, this wrought magnesium alloys contains the IIIA family element of 0.1-1.5 atom %, 1.0-4.0 the IIIB family element of atom %, be equal to or less than being selected from of 0.35 atom % by IIA, IVA, VIIA, at least a element in the group that IVB family element and composition thereof is formed, be equal to or less than the IIB family element of 1.0 atom %, surplus is magnesium and unavoidable impurities, thereby described wrought magnesium alloys has the second phase intermetallic compound, described IIIA family element is used alone or in combination Sc, Y and lanthanon, described IIIB family element is Al and/or B, described IIA family element is Ca and Sr, described IVA family element is Ti, Zr and Hf, described VIIA family element is Mn, and described IVB family element is Si and Ge, and described IIB family element is used alone or in combination Zn and Cd.
2. wrought magnesium alloys according to claim 1, wherein, the content of described IIB family element is equal to or less than 0.65 atom %.
3. method of making wrought magnesium alloys, this method comprises:
Preparation magnesium alloy strand, described magnesium alloy strand contains the IIIA family element of 0.1-1.5 atom %, 1.0-4.0 the IIIB family element of atom %, be equal to or less than being selected from of 0.35 atom % by IIA, IVA, VIIA, at least a element in the group that IVB family element and composition thereof is formed, be equal to or less than the IIB family element of 1.0 atom %, surplus is magnesium and unavoidable impurities, thereby described wrought magnesium alloys strand has the second phase intermetallic compound, described IIIA family element is used alone or in combination Sc, Y and lanthanon, described IIIB family element is Al and/or B, described IIA family element is Ca and Sr, described IVA family element is Ti, Zr and Hf, described VIIA family element is Mn, and described IVB family element is Si and Ge, and described IIB family element is used alone or in combination Zn and Cd;
Described magnesium alloy strand is carried out diffusion annealing at 250 ℃-450 ℃;
Magnesium alloy strand after the diffusion annealing reheated under 250-400 ℃ in process furnace push, rolling then.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020040023288 | 2004-04-06 | ||
| KR1020040023288A KR100605741B1 (en) | 2004-04-06 | 2004-04-06 | magnesium alloy wrought product with anti-corrosion and good plating characteristics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1938440A CN1938440A (en) | 2007-03-28 |
| CN100441717C true CN100441717C (en) | 2008-12-10 |
Family
ID=36677821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800104334A Expired - Fee Related CN100441717C (en) | 2004-04-06 | 2005-03-11 | Wrought magnesium alloy having excellent formability and method of producing same |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20080304997A1 (en) |
| EP (1) | EP1759029B1 (en) |
| JP (1) | JP5047778B2 (en) |
| KR (1) | KR100605741B1 (en) |
| CN (1) | CN100441717C (en) |
| AT (1) | ATE486145T1 (en) |
| AU (1) | AU2005324597B2 (en) |
| DE (1) | DE602005024392D1 (en) |
| RU (1) | RU2384639C2 (en) |
| WO (1) | WO2006075814A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020083387A1 (en) * | 2018-10-26 | 2020-04-30 | 宝山钢铁股份有限公司 | High-strength and corrosion-resistant magnesium alloy material and method for fabricating same |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5089945B2 (en) * | 2006-09-14 | 2012-12-05 | 国立大学法人 熊本大学 | High strength magnesium alloy with high corrosion resistance |
| CN101624661B (en) * | 2008-07-08 | 2011-06-08 | 山西银光华盛镁业股份有限公司 | Method for fusion casting of mercury-containing anode magnesium alloy of torpedo battery |
| KR20100023262A (en) * | 2008-08-21 | 2010-03-04 | 현대자동차주식회사 | Oil pan made from magnesium |
| JP5540780B2 (en) * | 2009-05-29 | 2014-07-02 | 住友電気工業株式会社 | Magnesium alloy wire, bolt, nut and washer |
| CN102108466B (en) * | 2009-12-23 | 2012-07-11 | 中国科学院金属研究所 | Anticorrosion magnesium alloy |
| KR101066536B1 (en) * | 2010-10-05 | 2011-09-21 | 한국기계연구원 | Ignition-proof magnesium alloy with excellent mechanical properties and method for manufacturing the ignition-proof magnesium alloy |
| EP2481825B1 (en) * | 2011-02-01 | 2013-05-08 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Magnesium alloy containing rare earth metals |
| CN102230116A (en) * | 2011-06-23 | 2011-11-02 | 江汉大学 | High-hardness cast magnesium alloy |
| CN102644040A (en) * | 2012-05-28 | 2012-08-22 | 重庆大学 | Heat treatment process for improving electromagnetic shielding performance of high-strength wrought magnesium alloy |
| CN104451304B (en) * | 2014-12-13 | 2017-02-22 | 重庆大学 | High-conductivity and high-shielding-effectiveness magnesium alloy and preparation method thereof |
| KR101685818B1 (en) * | 2015-05-26 | 2016-12-12 | 현대제철 주식회사 | Magnesium alloy material and manufacturing method thereof |
| WO2017116020A1 (en) * | 2015-12-28 | 2017-07-06 | 한국기계연구원 | Magnesium alloy having excellent mechanical properties and corrosion resistance, and method for manufacturing same |
| CN108431261A (en) * | 2015-12-28 | 2018-08-21 | 韩国机械研究院 | Magnesium alloy and its manufacturing method with excellent mechanical performance and corrosion resistance |
| CN105624501B (en) * | 2016-03-04 | 2017-09-29 | 山东省科学院新材料研究所 | A kind of high shielding properties magnesium alloy materials of high-ductility and preparation method and application |
| KR101644330B1 (en) * | 2016-06-02 | 2016-08-01 | 울산과학기술원 | Magnesium alloys and method for producing the same |
| WO2017209566A1 (en) * | 2016-06-02 | 2017-12-07 | 울산과학기술원 | Magnesium alloy and method for manufacturing same |
| WO2018117632A1 (en) * | 2016-12-23 | 2018-06-28 | 주식회사 포스코 | Magnesium alloy having excellent corrosion resistance and method for manufacturing same |
| CN108300918B (en) * | 2017-01-11 | 2020-05-12 | 北京科技大学 | Calcium-containing rare earth magnesium alloy sheet with high room temperature forming performance and preparation method thereof |
| CN106890865B (en) * | 2017-03-23 | 2018-08-21 | 中南大学 | Major diameter AQ80M magnesium alloy cake materials squeeze forging and integrate forming technology |
| CN108774723A (en) * | 2018-07-07 | 2018-11-09 | 中南大学 | A kind of powerful block nanometer magnesium alloy preparation method of superelevation |
| KR102210236B1 (en) * | 2018-12-14 | 2021-02-01 | 울산과학기술원 | Magnesium alloy materials and method for producing the same |
| SE543126C2 (en) | 2019-02-20 | 2020-10-13 | Husqvarna Ab | A magnesium alloy, a piston manufactured by said magnesium alloy and a method for manufacturing said piston |
| CN113564440A (en) * | 2021-08-02 | 2021-10-29 | 西安四方超轻材料有限公司 | High-performance easily-forged magnesium alloy material and preparation method thereof |
Family Cites Families (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US637040A (en) * | 1899-09-01 | 1899-11-14 | Cyrus E Smith | Clearer for drawing-rolls. |
| US3391034A (en) * | 1965-12-01 | 1968-07-02 | Army Usa | Magnesium yttrium alloy |
| US4194908A (en) * | 1975-12-17 | 1980-03-25 | Bradshaw Stephen L | Magnesium alloys |
| US4116731A (en) * | 1976-08-30 | 1978-09-26 | Nina Mikhailovna Tikhova | Heat treated and aged magnesium-base alloy |
| US4675157A (en) * | 1984-06-07 | 1987-06-23 | Allied Corporation | High strength rapidly solidified magnesium base metal alloys |
| US4765954A (en) * | 1985-09-30 | 1988-08-23 | Allied Corporation | Rapidly solidified high strength, corrosion resistant magnesium base metal alloys |
| US4853035A (en) * | 1985-09-30 | 1989-08-01 | Allied-Signal Inc. | Rapidly solidified high strength, corrosion resistant magnesium base metal alloys |
| US4857109A (en) * | 1985-09-30 | 1989-08-15 | Allied-Signal Inc. | Rapidly solidified high strength, corrosion resistant magnesium base metal alloys |
| US4908181A (en) * | 1988-03-07 | 1990-03-13 | Allied-Signal Inc. | Ingot cast magnesium alloys with improved corrosion resistance |
| US5078806A (en) * | 1988-05-23 | 1992-01-07 | Allied-Signal, Inc. | Method for superplastic forming of rapidly solidified magnesium base metal alloys |
| US4938809A (en) * | 1988-05-23 | 1990-07-03 | Allied-Signal Inc. | Superplastic forming consolidated rapidly solidified, magnestum base metal alloy powder |
| US5059390A (en) * | 1989-06-14 | 1991-10-22 | Aluminum Company Of America | Dual-phase, magnesium-based alloy having improved properties |
| EP0419375B1 (en) * | 1989-08-24 | 1994-04-06 | Pechiney Electrometallurgie | High strength magnesium alloys and process for manufacturing by rapid solidification |
| JP3023797B2 (en) * | 1990-01-16 | 2000-03-21 | 本田技研工業株式会社 | High corrosion resistant magnesium alloy |
| US5071474A (en) * | 1990-06-15 | 1991-12-10 | Allied-Signal Inc. | Method for forging rapidly solidified magnesium base metal alloy billet |
| US5316598A (en) * | 1990-09-21 | 1994-05-31 | Allied-Signal Inc. | Superplastically formed product from rolled magnesium base metal alloy sheet |
| US5078807A (en) * | 1990-09-21 | 1992-01-07 | Allied-Signal, Inc. | Rapidly solidified magnesium base alloy sheet |
| US5129960A (en) * | 1990-09-21 | 1992-07-14 | Allied-Signal Inc. | Method for superplastic forming of rapidly solidified magnesium base alloy sheet |
| US5087304A (en) * | 1990-09-21 | 1992-02-11 | Allied-Signal Inc. | Hot rolled sheet of rapidly solidified magnesium base alloy |
| US5693158A (en) * | 1993-02-12 | 1997-12-02 | Mazda Motor Corporation | Magnesium light alloy product and method of producing the same |
| JPH0748646A (en) * | 1993-03-15 | 1995-02-21 | Toyota Motor Corp | High strength magnesium base alloy and production thereof |
| JP2730847B2 (en) * | 1993-06-28 | 1998-03-25 | 宇部興産株式会社 | Magnesium alloy for castings with excellent high temperature creep strength |
| JPH0941065A (en) * | 1994-03-23 | 1997-02-10 | Takeshi Masumoto | High strength magnesium alloy and its production |
| JPH07331375A (en) * | 1994-06-06 | 1995-12-19 | Toyota Motor Corp | Heat resistant magnesium alloy for casting |
| JP3982780B2 (en) * | 1998-03-26 | 2007-09-26 | 日立金属株式会社 | Method for manufacturing forged thin-walled casing made of magnesium alloy |
| JP2000104136A (en) * | 1998-07-31 | 2000-04-11 | Toyota Central Res & Dev Lab Inc | Magnesium alloy having fine crystal grain and its production |
| KR100331154B1 (en) | 1999-10-22 | 2002-04-01 | 황해웅 | Non-combustible Mg-Alloy |
| JP3603706B2 (en) * | 1999-12-03 | 2004-12-22 | 株式会社日立製作所 | High-strength Mg-based alloys and Mg-based cast alloys and articles |
| JP3693583B2 (en) * | 2001-03-05 | 2005-09-07 | 独立行政法人科学技術振興機構 | High strength and high ductility Mg-based alloy |
| KR20020078936A (en) * | 2001-04-11 | 2002-10-19 | 학교법인연세대학교 | Quasicrystalline phase hardened Mg-based metallic alloy exhibiting warm and hot formability |
| KR100421102B1 (en) | 2001-08-22 | 2004-03-04 | 미츠비시 알루미늄 컴파니 리미티드 | Die casting magnesium alloy |
| JP4275899B2 (en) * | 2002-05-09 | 2009-06-10 | 財団法人鉄道総合技術研究所 | Manufacturing method of fuel cell separator |
| JP2003328065A (en) * | 2002-05-10 | 2003-11-19 | Toyo Kohan Co Ltd | Wrought magnesium thin-sheet superior in formability, and manufacturing method therefor |
| JP4064720B2 (en) * | 2002-05-10 | 2008-03-19 | 東洋鋼鈑株式会社 | Magnesium sheet for extending excellent in formability and manufacturing method thereof |
| KR100509648B1 (en) * | 2003-05-23 | 2005-08-24 | 연우인더스트리(주) | High formability the Magnesium alloy and manufacture method of the Magnesium alloy product thereof |
-
2004
- 2004-04-06 KR KR1020040023288A patent/KR100605741B1/en active IP Right Grant
-
2005
- 2005-03-11 US US11/547,298 patent/US20080304997A1/en not_active Abandoned
- 2005-03-11 EP EP05856294A patent/EP1759029B1/en not_active Not-in-force
- 2005-03-11 JP JP2007507237A patent/JP5047778B2/en not_active Expired - Fee Related
- 2005-03-11 CN CNB2005800104334A patent/CN100441717C/en not_active Expired - Fee Related
- 2005-03-11 AU AU2005324597A patent/AU2005324597B2/en not_active Ceased
- 2005-03-11 AT AT05856294T patent/ATE486145T1/en not_active IP Right Cessation
- 2005-03-11 RU RU2006134447/02A patent/RU2384639C2/en not_active IP Right Cessation
- 2005-03-11 DE DE602005024392T patent/DE602005024392D1/en active Active
- 2005-03-11 WO PCT/KR2005/000697 patent/WO2006075814A1/en active Application Filing
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020083387A1 (en) * | 2018-10-26 | 2020-04-30 | 宝山钢铁股份有限公司 | High-strength and corrosion-resistant magnesium alloy material and method for fabricating same |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2006134447A (en) | 2008-05-20 |
| AU2005324597A1 (en) | 2006-07-20 |
| WO2006075814A1 (en) | 2006-07-20 |
| KR20040035646A (en) | 2004-04-29 |
| CN1938440A (en) | 2007-03-28 |
| JP5047778B2 (en) | 2012-10-10 |
| US20080304997A1 (en) | 2008-12-11 |
| EP1759029A1 (en) | 2007-03-07 |
| KR100605741B1 (en) | 2006-08-01 |
| DE602005024392D1 (en) | 2010-12-09 |
| AU2005324597B2 (en) | 2009-01-08 |
| EP1759029A4 (en) | 2007-07-18 |
| ATE486145T1 (en) | 2010-11-15 |
| RU2384639C2 (en) | 2010-03-20 |
| JP2007538146A (en) | 2007-12-27 |
| EP1759029B1 (en) | 2010-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100441717C (en) | Wrought magnesium alloy having excellent formability and method of producing same | |
| KR100509648B1 (en) | High formability the Magnesium alloy and manufacture method of the Magnesium alloy product thereof | |
| CN113557318B (en) | Coated steel sheet | |
| CN105755340B (en) | High strength and low cost high-ductility high heat conduction wrought magnesium alloy and preparation method thereof | |
| JP4189687B2 (en) | Magnesium alloy material | |
| US20130183193A1 (en) | Non-flammable magnesium alloy with excellent mechanical properties, and preparation method thereof | |
| JP5365194B2 (en) | Steel sheet having high {222} plane integration and method for producing the same | |
| US20130280121A1 (en) | Magnesium alloy with excellent ignition resistance and mechanical properties, and method of manufacturing the same | |
| EP3276019B1 (en) | Magnesium-lithium alloy, rolled material formed from magnesium-lithium alloy, and processed article containing magnesium-lithium alloy as starting material | |
| WO2010056130A1 (en) | Magnesium based alloys and processes for preparation thereof | |
| CN103255329A (en) | Low-cost fine-grain weak-texture magnesium alloy sheet and manufacturing method thereof | |
| KR20160011136A (en) | Magnesium alloy having improved corrosion resistance and method for manufacturing magnesium alloy member using the same | |
| EP2453031A1 (en) | Magnesium alloy plate | |
| CN110295317A (en) | Flat cold-rolled bar product and its manufacturing method for deep-draw application | |
| CN105483485A (en) | High-strength cast magnesium alloy containing Zn and heavy rare-earth Gd and preparation method of high-strength cast magnesium alloy | |
| JP3996340B2 (en) | Boron and magnesium-containing Al-based alloy and method for producing the same | |
| JP3563323B2 (en) | Aluminum alloy plate excellent in thread rust resistance and method for producing the same | |
| CN100482834C (en) | Easily-workable magnesium alloy and method for preparing same | |
| WO2012113241A1 (en) | Multi-combinational degenerated low-zinc hot-dipped aluminum-galvanized alloy plating material containing mg, and preparation method therefor | |
| JP5059505B2 (en) | Aluminum alloy cold-rolled sheet that can be formed with high strength | |
| KR20150071215A (en) | Magnesium alloys plate and method for manufacturing the same | |
| KR101001893B1 (en) | Mg-based Alloy Exhibiting High Strength and Large Elongation and Method for Manufacturing thereof | |
| CN110114485A (en) | The excellent high-strength magnesium alloy of flame resistance and its manufacturing method | |
| JP3248254B2 (en) | Method for producing Al-Mg based alloy rolled sheet for cryogenic forming | |
| JP3523512B2 (en) | Forging method of magnesium alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081210 Termination date: 20190311 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |