CN100338250C - High strength and high toughness cast magnesium alloy and preparing process thereof - Google Patents
High strength and high toughness cast magnesium alloy and preparing process thereof Download PDFInfo
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- CN100338250C CN100338250C CNB2004100205671A CN200410020567A CN100338250C CN 100338250 C CN100338250 C CN 100338250C CN B2004100205671 A CNB2004100205671 A CN B2004100205671A CN 200410020567 A CN200410020567 A CN 200410020567A CN 100338250 C CN100338250 C CN 100338250C
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims description 8
- 230000008569 process Effects 0.000 title description 3
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 90
- 239000000956 alloy Substances 0.000 claims abstract description 90
- 239000011777 magnesium Substances 0.000 claims abstract description 34
- 239000011701 zinc Substances 0.000 claims abstract description 24
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 23
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 18
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 13
- 239000011572 manganese Substances 0.000 claims abstract description 12
- 239000006104 solid solution Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 239000005030 aluminium foil Substances 0.000 claims abstract description 5
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 4
- 239000002893 slag Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 24
- -1 magnesium rare earth Chemical class 0.000 claims description 18
- 238000011282 treatment Methods 0.000 claims description 18
- 239000004411 aluminium Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 238000005266 casting Methods 0.000 claims description 14
- 238000004512 die casting Methods 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 7
- 238000005275 alloying Methods 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 229910018503 SF6 Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims description 2
- 229960000909 sulfur hexafluoride Drugs 0.000 claims description 2
- 238000011284 combination treatment Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 230000001550 time effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 239000012071 phase Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 238000003723 Smelting Methods 0.000 description 8
- 239000000470 constituent Substances 0.000 description 7
- 229910002058 ternary alloy Inorganic materials 0.000 description 7
- 238000007669 thermal treatment Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000010587 phase diagram Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- 229910018137 Al-Zn Inorganic materials 0.000 description 2
- 229910016943 AlZn Inorganic materials 0.000 description 2
- 229910018573 Al—Zn Inorganic materials 0.000 description 2
- 101001108245 Cavia porcellus Neuronal pentraxin-2 Proteins 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- 229910017640 MgSb Inorganic materials 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 230000010429 evolutionary process Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- MIOQWPPQVGUZFD-UHFFFAOYSA-N magnesium yttrium Chemical compound [Mg].[Y] MIOQWPPQVGUZFD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010120 permanent mold casting Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- 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
- C22C23/04—Alloys based on magnesium with zinc or cadmium 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
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The present invention relates to a high-strength high-toughness cast magnesium alloy and a preparation method thereof. The alloy comprises 3 to 9 wt% of aluminum, 3.5 to 9 wt% of zinc, 0.15 to 1.0 wt% of manganese, 0 to 2 wt% of antimony, 0 to 2 wt% of rare earth element and balance of magnesium. The preparation method comprises the steps that firstly, various batching materials, covering agents and molds are preheated; then, after the target temperature of a crucible is set, the materials starts to be heated, the preheated pure magnesium batching material is put into the crucible, and pure aluminum, an aluminum and manganese master alloy, a magnesium and rare earth master alloy and the pure zinc batching material are orderly added into the crucible under the protection of mixed gas of CO2 and SF6; and finally, antimony powder covered by aluminium foil paper is added into the crucible, and the mixture is stirred, slag removed and cast to form the alloy. After the alloy is treated through solid solution and time effect(T6), the tensile strength (sigma b) reaches 260 to 280MPa, the yield strength (sigma 0.2) is greater than or equal to 140MPa, the elongation rate (delta 5) is greater than or equal to 6%, the impulsive work (alpha k) is greater than or equal to 14J, and the Brinell hardness (HB) is greater than or equal to 70.
Description
Technical field
The present invention relates to the cast magnesium alloys technology, specifically a kind of low cost, high-intensity high-tenacity cast magnesium alloys and by alloying and thermal treatment improve cast magnesium alloys intensity and flexible preparation method simultaneously.The present invention is not only applicable to metal mold and sand mold casting, is equally applicable to technologies such as pressure die casting, extrusion casting.
Background technology
Magnesium alloy is as a kind of new metallic material, and, specific tenacity little with its density and specific rigidity advantages of higher have obtained widespread use in aerospace, automobile, 3C fields such as (computer, communication, consumer electronics).With the automotive industry is example: on the one hand, the motor vehicle exhaust amount accounts for about 65% of global air pollution; On the other hand, problem such as energy shortage, rise of the oil price is serious day by day.The automobile loss of weight is the effective measure that address these problems.It is calculated that automotive dead weight whenever alleviates 10%, its fuel efficiency can improve about 5.5%.For another example, magnesium alloy is also with its favorable conductive thermal conductivity and be easy to advantage such as recycling, locates at the shell structure part of 3C series products etc., and substituted for plastic obtains to be extensive use of.Therefore, magnesium alloy has also obtained the good reputation of " the green engineering material of 21st century ".
At present, commercial magnesium alloy can be divided into cast magnesium alloys and wrought magnesium alloys two big classes substantially, and the ratio of its consumption approximately is 35: 1, the market share maximum of visible cast magnesium alloys.In cast magnesium alloys, AZ91 series and AM60/50 serial application are the most extensive.Wherein, though the high (tensile strength sigma of typical die casting AZ91D of AZ91 series intensity
bBe 230MPa, yield strength σ
0.2Be 160MPa), but plasticity relatively poor (the unit elongation δ 5 of typical die casting AZ91D is 3%); Though and good (the unit elongation δ of typical die casting AM60/50 of AM60/50 series plasticity
5Be 8～10%), but the intensity (tensile strength sigma of typical die casting AM60/50 on the weak side
bBe 200～220MPa, yield strength σ
0.2Be 110～130MPa).
In order to adapt to market demands, further enlarge the range of application of cast magnesium alloys, under low-cost prerequisite, improving intensity and toughness simultaneously is key point.Although many investigators have carried out work such as microalloying, grain refining based on AZ91 series and AM60/50 series, its result produce effects not quite or cost too high.Therefore, the cast magnesium alloys of developing a kind of low cost, high-strength and high ductility is present problem demanding prompt solution.
Summary of the invention
The object of the present invention is to provide a kind of low cost, high-intensity high-tenacity cast magnesium alloys, and, obtained the cast magnesium alloys preparation method of a kind of low cost, high-strength and high ductility by choose reasonable alloy element and employing proper heat treatment means.
Technical scheme of the present invention is:
The present invention has constituted the novel magnesium alloy system of the high zinc of high alumina by add high-content aluminium, high-content zinc in magnesium; On high alumina high-zinc magnesium alloy basis,, reached the toughness reinforcing purpose of enhancing of magnesium alloy by adding the microalloying effect that elements such as antimony, rare earth produce.This invention specifically composed as follows: by weight percentage, magnesium (Mg) content is the balance surplus; Aluminium (Al) content is 3.5～9%; Zinc (Zn) content is 3～9%; Manganese (Mn) content is 0.15～1.0%; Antimony (Sb) content is 0～2%; Content of rare earth is 0～2%; Other inevitable trace impurity iron (Fe)≤0.005%, nickel (Ni)≤0.002%, copper (Cu)≤0.015%.
Enhancing toughening mechanism of the present invention is as follows: in the high alumina high-zinc magnesium alloy, except there being common β (Mg in a spot of magnalium system
17Al
12) wild phase outside, main wild phase has become Mg
32(AlZn)
49Phase; In addition, behind the adding Sb element,, can produce new particle wild phase Mg according to the result of X ray and EDAX electron microscopic observation
3Sb
2And (Mg
0.43Zn
0.57)
2MgSb
2Deng.These new particle wild phases not only play the effect that improves intensity, and the continuous fragility phase in the high zinc alloy of refinement high alumina to a certain extent, thereby play the effect that improves castability and plasticity.
As everyone knows, the adding of zinc can improve the flowability of melt in the magnesium alloy, and the effect of solution strengthening is arranged, and can improve intensity; But if the add-on of zinc is improper, will increase the hot cracking tendency of alloy, worsen casting forming function (referring to accompanying drawing 1).Present common cast magnesium alloys such as AZ91, AM60, AM50 etc., over-all properties is not fine, wherein the zinc content of AZ91 is 0.45-0.9%wt (weight percent), its intensity is higher, but toughness is relatively poor, zinc content≤0.20%wt of AM60 and AM50, its toughness is better, but intensity is relatively poor.The present invention is according to the magnesium-aluminum-zinc ternary phase diagrams, by selecting suitable aluminium, zinc content, thereby guaranteed the castability of magnesium alloy, higher intensity and toughness; On this basis, by adding antimony (Sb) and rare earth element, and, alloy strength and toughness are greatly improved again by proper heat treatment.
Aluminum in Alloy of the present invention also is main strengthening element, and it forms β (Mg by solution strengthening with magnesium
17Al
12) generate Mg mutually and with magnesium, zinc element
32(AlZn)
49The precipitation strength of phase has improved alloy at room temperature intensity.In addition, the adding of aluminium also can improve the casting technique performance of alloy.
Rare earth element yttrium, neodymium or the cerium-rich mischmetal etc. that can also contain 0～2%wt in the alloy of the present invention, rare earth element can improve the alloy casting performance, reduce crystal boundary low melting point precipitate, improve comprehensive mechanical property and good solid solution strengthening effect, by the reinforcement of rare earth element to crystal boundary, and and Zn, Al to the beneficial effect of alloy mechanical property, and various elements is reasonably combined, makes the over-all properties of alloy better.
The effect of manganese is to improve corrosion resistance nature in the alloy of the present invention, and manganese can form compound with the impurity element iron in the alloy in the alloy melting process, be deposited to crucible bottom, removes impurity, eliminates the deleterious effect of iron to the alloy corrosion resistance nature.
The preparation method of high-intensity high-tenacity cast magnesium alloys of the present invention, concrete steps are as follows:
1) earlier pure magnesium, magnesium rare earth intermediate alloy, fine aluminium, aluminium manganese master alloy, pure zinc, the various batchings of antimony powder are preheated to 140～160 ℃ in baking oven, insulating covering agent is put into baking oven simultaneously dries; Mould is preheated to 300～400 ℃ in other box-type furnace; Setting the crucible target temperature then is 710～730 ℃, begins heating;
2) when crucible is warming up to 280～320 ℃, feed CO
2Gas carries out gas displacement, adds the insulating covering agent that accounts for batching gross weight 0.3～2% in crucible bottom then, and the pure magnesium batching that preheating is good is put into crucible;
3) fusing of pure magnesium batching and etc. after crucible temperature is stabilized in 710～730 ℃, add the insulating covering agent that accounts for batching gross weight 0.3～2%, add fine aluminium, aluminium manganese master alloy, magnesium rare earth intermediate alloy and pure zinc batching then successively, add the antimony powder batching of wrapping with aluminium-foil paper at last;
4) the equal constant temperature of each operation carries out under 710～730 ℃ below, and batching can stir after adding, and leaves standstill after stirring 4～6 minutes, and per-cent by volume is at 99～99.5%CO2+0.5～1%SF
6Draw out surface scum under mixed gas protected;
5) draw slag and finish after, stop heating, per-cent by volume is at 99～99.5%CO
2+ 0.5～1%SF
6Mixed gas protected cast molding down.
Heat treatment mode of the present invention can be divided into solid solution (T4), timeliness (T5), " solid solution+timeliness " (T6) three kinds, 1., the T4 solution treatment is preferably in the protective atmosphere (as argon gas, sulfur hexafluoride etc.) and carries out introduce respectively below:, its temperature and aluminium, zinc content are closely related, and actual temp can be with reference to magnesium-aluminum-zinc ternary alloy phase diagram (accompanying drawing 1); Experiment shows in addition, and the adding of a small amount of manganese, antimony is little to the solid solubility temperature influence, can determine according to aluminium, zinc content; The T4 solution time can be taken as 16～24 hours, and the time, too short solid solution effect was undesirable, and grain growth can appear in overlong time.2., the T5 ageing treatment, temperature is taken as 160～200 ℃, the time can be taken as 8～24 hours.3., T6 thermal treatment can be understood as the combination of T4 and T5 mode.
Because thermal treatment has changed the distribution mode and the quantity of particle wild phase, thus remarkably influenced mechanical property.Mode with sosoloid exists the sample of T4 solution treatment because intermediate phase dissolves in the matrix substantially, so can improve plasticity, but yield strength can decrease; The sample that T6 handles is because intermediate phase is again can be at crystal grain inner or separate out (but distribution mode and quantity significantly are different from as-cast specimen) again along crystal boundary, so can be when improving intensity, plasticity descends to some extent.
Though what triturating of the present invention adopted is permanent mold casting, but as can be known according to the die casting performance (referring to accompanying drawing 2) of magnesium-aluminum-zinc ternary alloy, but alloy component range of the present invention drops on the casting area, therefore be equally applicable to technologies such as pressure die casting, extrusion casting, and can not have hot tearing and hot-short tendency.
The present invention has following advantage:
1. the magnesium alloy of the present invention preparation has the characteristic of high-intensity high-tenacity concurrently, and what be particularly suitable for lightweight, high-strength, high-ductility uses the material demand, as automotive hub etc.; Its tensile strength sigma
bReach 260～280MPa, yield strength σ
0.2〉=140MPa, unit elongation δ
5〉=6%, ballistic work α
k〉=14J, Brinell hardness HB 〉=70.
2. cost performance height of the present invention.The used starting material of the present invention are easy to get, and cost is low.
3. smelting technology of the present invention is stable.Obvious side reaction does not take place with irony sidewall of crucible or insulating covering agent in the alloy element that the present invention adopts, and process stabilizing is easy to tissue production.
4. applicable craft scope of the present invention is wide.The present invention is not only applicable to metal mold and sand mold casting, is equally applicable to technologies such as pressure die casting, extrusion casting, does not have hot tearing and hot-short tendency.
Description of drawings
Fig. 1 is the pressure die casting performance synoptic diagram of Mg-Al-Zn ternary alloy.
Fig. 2 is Mg-Al-Zn ternary alloy phase diagram (solid phase surface).
Fig. 3 a～c is the influence of different heat treatment mode to embodiment 1 alloy microtexture, and wherein Fig. 3 a is the electromicroscopic photograph under the as cast condition (F); Fig. 3 b is the electromicroscopic photograph under the solid solution (T4); Fig. 3 c is the electromicroscopic photograph under solid solution+timeliness (T6).
Fig. 4 is the used tabular tension specimen synoptic diagram of the present invention, its thickness δ=3mm.
Fig. 5 is Fig. 4 middle plateform shape tension specimen dimensioned drawing.
Fig. 6 is that embodiment 1 alloy and comparative example alloy A Z91, AM60 contrast situation in the mechanical property of T6 heat treatment state.
Fig. 7 is that embodiment 2 alloys and comparative example alloy A Z91, AM60 contrast situation in the mechanical property of T6 heat treatment state.
Fig. 8 is that embodiment 3 alloys and comparative example alloy A Z91, AM60 contrast situation in the mechanical property of T6 heat treatment state.
Embodiment
Below in conjunction with embodiment in detail the present invention is described in detail:
Embodiment 1
Present embodiment 1 alloy (comparative example 1 alloy A Z91, comparative example 2 alloy A M60) basic operational steps is as follows:
I), alloying constituent:
| Alloy designations | Constituent content (weight percent %) | ||||
| Magnesium (Mg) | Aluminium (Al) | Zinc (Zn) | Manganese (Mn) | Antimony (Sb) | |
| Embodiment 1 | 89.2 | 6 | 4 | 0.3 | 0.5 |
| AZ91 | 89.7 | 9 | 1 | 0.3 | 0 |
| AM60 | 93.7 | 6 | 0 | 0.3 | 0 |
II), alloy smelting and casting:
The smelting work of embodiment 1 is to carry out in pit furnace, and crucible adopts carbon steel material; The cast molding of alloy is then finished in metal mold.Operation is as follows in detail:
1) earlier with various batchings preheatings in 150 ℃ of baking ovens such as pure magnesium, fine aluminium, aluminium manganese master alloy, pure zinc, antimony powders, the RJ-2 insulating covering agent can be put into baking oven simultaneously dries; Mould is preheated to 350 ℃ in other box-type furnace, setting the crucible target temperature then is 720 ℃, begins heating.
2) when crucible is warming up to 300 ℃, feed (per-cent by volume, 99.5%CO
2+ 0.5%SF
6) mixed gas carries out gas displacement, adds insulating covering agent (accounting for total batching 0.5% mass ratio) in crucible bottom then, and the pure magnesium batching that preheating is good puts into crucible, continues heating.
3) after the fusing of pure magnesium batching, add insulating covering agent (accounting for total batching 0.5% mass ratio) once more, add fine aluminium, aluminium manganese master alloy and pure zinc batching then successively, add the antimony powder batching of wrapping with aluminium-foil paper with strainer at last.
4) can stir after (following each operation all requires crucible temperature carrying out about 720 ℃) batching adds, leave standstill after stirring 5 minutes, at (99.5%CO
2+ 0.5%SF
6) draw out surface scum under mixed gas protected, the mixed gas add-on is a yardstick to guarantee that alloy surface does not burn.
5) draw slag and finish after, stop heating, in mould, continue to feed (99.5%CO
2+ 0.5%SF
6) mixed gas, cast molding simultaneously.
The smelting of Comparative examples A Z91 and AM60 alloy and cast molding process are identical with embodiment 1 alloy substantially, just do not have antimony powder in the batching, and other batching quantity is different.
III), the thermal treatment of foundry goods:
Embodiment 1 alloy and comparative example 1 alloy, comparative example 2 heat treatment of alloy can be divided into solid solution (T4), timeliness (T5), " solid solution+timeliness " (T6) three kinds:
1., with reference to magnesium-aluminum-zinc ternary alloy phase diagram (accompanying drawing 1) and finally definite by related experiment, the temperature of the T4 solution treatment of embodiment 1 alloy is advisable with 380 ℃, temperature is crossed low solid solution DeGrain, to such an extent as to the too high meeting of temperature undergoes phase transition and separates out alloying constituent and change; The T4 solution time can be taken as 20 hours, and the time, too short solid solution effect was undesirable, and grain growth can appear in overlong time; The sample that T4 handles takes out the back and adopts air cooling to room temperature.
The T4 treatment temp of Comparative examples A Z91 and AM60 is 410 ℃, and the time is 20 hours, and reason is the same; The sample that T4 handles takes out the back and adopts air cooling to room temperature.
2., embodiment 1 is all identical with the T5 ageing treatment of Comparative examples A Z91, three kinds of alloys of AM60.Temperature is taken as 180 ℃, and the time is 20 hours; The sample that T5 handles takes out the back and adopts air cooling to room temperature.
3., the T6 thermal treatment of embodiment 1 and Comparative examples A Z91, three kinds of alloys of AM60 is the combination of T4 and T5 mode.Every kind of alloy carries out 20 hours T4 solution treatment according to suitable temp separately earlier, and then carries out 20 hours T5 ageing treatment.
Different heat treatment mode (F, T4, T6) is seen accompanying drawing 3a-c to the influence and the evolutionary process thereof of embodiment 1 alloy microtexture.
IV), the specimen preparation of mechanical property and test:
The mechanics tensile property sample of alloy is to prepare for the regulation of sheet coupon with reference to the § 3.6.2 of GB GB 6397-86, and its structure and detailed dimensions are seen accompanying drawing 4,5.
The impact property of alloy is got the non-notch impact specimen of 10mm * 10mm * 55mm with reference to the regulation of GB GB/T229-1994.
Jin Shubushi experiment of hardness method is with reference to GB231-84, specimen size 15mm * 15mm * 5mm.
The as cast condition mechanical property of embodiment 1 alloy is as follows:
Tensile strength sigma
b=216MPa, yield strength σ
0.2=106MPa, unit elongation δ
5=8%.
The T4 attitude mechanical property of embodiment 1 alloy is as follows:
Tensile strength sigma
b=250MPa, yield strength σ
0.2=101MPa, unit elongation δ
5=11%.
The T5 attitude mechanical property of embodiment 1 alloy is as follows:
Tensile strength sigma
b=230MPa, yield strength σ
0.2=128MPa, unit elongation δ
5=7%.
The T6 attitude mechanical property of embodiment 1 alloy is as follows:
Tensile strength sigma
b=285MPa, yield strength σ
0.2=140MPa, unit elongation δ
5=10%, ballistic work α
k=20J, Brinell hardness HB=70.
Therefore, in each heat treatment state of embodiment 1 alloy, the comprehensive mechanical performance optimum of T6 attitude; In addition, embodiment 1 alloy and comparative example alloy A Z91, AM60 see accompanying drawing 6 in the mechanical property contrast situation of T6 heat treatment state.
Difference from Example 1 is:
Present embodiment alloy basic operational steps is as follows:
I), alloying constituent:
| Alloy designations | Constituent content (weight percent %) | |||
| Magnesium (Mg) | Aluminium (Al) | Zinc (Zn) | Manganese (Mn) | |
| | 88.7 | 6 | 5 | 0.3 |
II), alloy smelting and casting:
Reference example 1.The present embodiment alloy does not need to add at last the antimony powder batching of wrapping with aluminium-foil paper in the 3rd step of smelting procedure.
III), the thermal treatment of foundry goods:
Heat treatment section in the reference example 1.The temperature of the T4 solution treatment of present embodiment alloy is advisable with 370 ℃, and this temperature is with reference to the magnesium-aluminum-zinc ternary alloy phase diagram and finally determine that by experiment the too high meeting of temperature undergoes phase transition separates out.
IV), the specimen preparation of mechanical property and test:
The mechanical property specimen preparation is with described in the embodiment 1.
The as cast condition mechanical property of embodiment 2 alloys is as follows:
Tensile strength sigma
b=192MPa, yield strength σ
0.2=104MPa, unit elongation δ
5=6.2%.
The T4 attitude mechanical property of embodiment 2 alloys is as follows:
Tensile strength sigma
b=258MPa, yield strength σ
0.2=100MPa, unit elongation δ
5=10.5%.
The T5 attitude mechanical property of embodiment 2 alloys is as follows:
Tensile strength sigma
b=235MPa, yield strength σ
0.2=137MPa, unit elongation δ
5=6%.
The T6 attitude mechanical property of embodiment 2 alloys is as follows:
Tensile strength sigma
b=287MPa, yield strength σ
0.2=161MPa, unit elongation δ
5=8%, ballistic work α
k=22J, hardness HB=73.
Therefore, in each heat treatment state of embodiment 2 alloys, the comprehensive mechanical performance optimum of T6 attitude; In addition, embodiment 2 alloys and comparative example alloy A Z91, AM60 see accompanying drawing 7 in the mechanical property contrast situation of T6 heat treatment state.
Embodiment 3
Difference from Example 1 is:
Present embodiment alloy basic operational steps is as follows:
I), alloying constituent:
| Alloy designations | Constituent content (weight percent %) | ||||
| Magnesium (Mg) | Aluminium (Al) | Zinc (Zn) | Manganese (Mn) | Yttrium (Yt) | |
| | 88.2 | 4 | 7 | 0.3 | 0.5 |
II), alloy smelting and casting:
Reference example 1.The present embodiment alloy will add magnesium yttrium master alloy batching in the 3rd step of smelting procedure after adding fine aluminium, aluminium manganese master alloy batching, add pure zinc batching at last again.
III), the thermal treatment of foundry goods:
Heat treatment section in the reference example 1.The temperature of the T4 solution treatment of present embodiment alloy is advisable with 360 ℃, and this temperature is with reference to the magnesium-aluminum-zinc ternary alloy phase diagram and finally determine that by experiment the too high meeting of temperature undergoes phase transition separates out.
IV), the specimen preparation of mechanical property and test:
The mechanical property specimen preparation is with described in the embodiment 1.
The as cast condition mechanical property of embodiment 3 alloys is as follows:
Tensile strength sigma
b=202MPa, yield strength σ
0.2=115MPa, unit elongation δ
5=6.5%.
The T4 attitude mechanical property of embodiment 3 alloys is as follows:
Tensile strength sigma
b=248MPa, yield strength σ
0.2=110MPa, unit elongation δ
5=9.5%.
The T5 attitude mechanical property of embodiment 3 alloys is as follows:
Tensile strength sigma
b=231MPa, yield strength σ
0.2=132MPa, unit elongation δ
5=6.3%.
The T6 attitude mechanical property of embodiment 3 alloys is as follows:
Tensile strength sigma
b=260MPa, yield strength σ
0.2=149MPa, unit elongation δ
5=8%, ballistic work α
k=18J, hardness HB=72.
Therefore, in each heat treatment state of embodiment 3 alloys, the comprehensive mechanical performance optimum of T6 attitude; In addition, embodiment 3 alloys and comparative example alloy A Z91, AM60 see accompanying drawing 8 in the mechanical property contrast situation of T6 heat treatment state.
Claims (4)
1, a kind of preparation method of high-intensity high-tenacity cast magnesium alloys is characterized in that, by weight percentage, the principal element that is used for alloying is composed as follows: Mg content is the balance surplus; Aluminium content is 3～9%; Zinc content is 3.5～9%; Manganese content is 0.15～1.0%; 0＜antimony content≤2%; 0＜content of rare earth≤2%; Concrete steps are as follows:
1) earlier pure magnesium, magnesium rare earth intermediate alloy, fine aluminium, aluminium manganese master alloy, pure zinc, the various batchings of antimony powder are preheated to 140～160 ℃ in baking oven, insulating covering agent is put into baking oven simultaneously dries; Mould is preheated to 300～400 ℃ in other box-type furnace; Setting the crucible target temperature then is 710～730 ℃, begins heating;
2) when crucible is warming up to 280～320 ℃, feed CO
2Gas carries out gas displacement, adds the insulating covering agent that accounts for batching gross weight 0.3～2% in crucible bottom then, and the pure magnesium batching that preheating is good is put into crucible;
3) fusing of pure magnesium batching and etc. after crucible temperature is stabilized in 710～730 ℃, add the insulating covering agent that accounts for batching gross weight 0.3～2%, add fine aluminium, aluminium manganese master alloy, magnesium rare earth intermediate alloy and pure zinc batching then successively, add the antimony powder batching of wrapping with aluminium-foil paper at last;
4) the equal constant temperature of each operation carries out under 710～730 ℃ below, and batching can stir after adding, and leaves standstill after stirring 4～6 minutes, and per-cent by volume is at 99～99.5%CO
2+ 0.5～1%SF
6Draw out surface scum under mixed gas protected;
5) draw slag and finish after, stop heating, per-cent by volume is at 99～99.5%CO
2+ 0.5～1%SF
6Mixed gas protected cast molding down;
Through solution treatment, solid solution temperature is 350～390 ℃ with the cast magnesium alloys that obtains, and the solution treatment time is 16～24 hours, and air cooling is to room temperature; Perhaps ageing treatment, aging temperature is 160～200 ℃, and the ageing treatment time is 8～48 hours, and air cooling is to room temperature; Perhaps solution treatment adds the timeliness treatment combination, after carrying out solution treatment in 16-24 hour under 350～390 ℃, carries out 8～48 hours ageing treatment then under 160～200 ℃ earlier, and air cooling is to room temperature.
2, according to the preparation method of the described high-intensity high-tenacity cast magnesium alloys of claim 1, it is characterized in that: metal mold or sand mold casting are adopted in described cast molding, perhaps adopt pressure die casting or Extrution casting technique.
3, according to the preparation method of the described high-intensity high-tenacity cast magnesium alloys of claim 1, it is characterized in that: described solution treatment is carried out under protective atmosphere, and shielding gas is argon gas or sulfur hexafluoride.
4, according to the preparation method of the described high-intensity high-tenacity cast magnesium alloys of claim 1, it is characterized in that: described antimony powder is industrial star antimony.
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|---|---|---|---|
| CNB2004100205671A CN100338250C (en) | 2004-05-19 | 2004-05-19 | High strength and high toughness cast magnesium alloy and preparing process thereof |
| CNB2005800098757A CN100408709C (en) | 2004-05-19 | 2005-04-11 | High-strength-toughness magnesium alloy and its preparing method |
| US10/582,541 US20090068053A1 (en) | 2004-05-19 | 2005-04-11 | High strength and high ductility magnesium alloy and its preparation method |
| PCT/CN2005/000479 WO2005111251A1 (en) | 2004-05-19 | 2005-04-11 | A high-strength, high-toughness cast magnesium alloy and the method thereof |
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|---|---|---|---|
| CNB2004100205671A CN100338250C (en) | 2004-05-19 | 2004-05-19 | High strength and high toughness cast magnesium alloy and preparing process thereof |
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| CN100338250C true CN100338250C (en) | 2007-09-19 |
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| CN105039816A (en) * | 2015-07-20 | 2015-11-11 | 河南科技大学 | Low-cost, high-strength and heat-resisting magnesium alloy and preparation method thereof |
| CN105039816B (en) * | 2015-07-20 | 2017-05-31 | 河南科技大学 | A kind of high strength and low cost heat resistance magnesium alloy and preparation method thereof |
| CN108103334A (en) * | 2017-12-28 | 2018-06-01 | 重庆仟和镁业科技有限公司 | The production technology of whole magnesium alloy battery case |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005111251A1 (en) | 2005-11-24 |
| CN100408709C (en) | 2008-08-06 |
| US20090068053A1 (en) | 2009-03-12 |
| WO2005111251A8 (en) | 2006-03-02 |
| CN1699612A (en) | 2005-11-23 |
| CN1938441A (en) | 2007-03-28 |
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Assignee: Zhejiang Yongle Alloy Wheel Co., Ltd. Assignor: Institute of metal research, Chinese Academy of Sciences Contract record no.: 2010210000120 Denomination of invention: High strength and high toughness cast magnesium alloy and preparing process thereof Granted publication date: 20070919 License type: Exclusive License Open date: 20051123 Record date: 20100803 |
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