CN1174243A - Heat-resisting magensium alloy forming member, heat-resisting magnesium alloy for forming and forming method thereof - Google Patents
Heat-resisting magensium alloy forming member, heat-resisting magnesium alloy for forming and forming method thereof Download PDFInfo
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- CN1174243A CN1174243A CN97105000.7A CN97105000A CN1174243A CN 1174243 A CN1174243 A CN 1174243A CN 97105000 A CN97105000 A CN 97105000A CN 1174243 A CN1174243 A CN 1174243A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
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- 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
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Abstract
A heat-resistant magnesium alloy member having specially excellent molding property and elongation while keeping creep resistance property, which comprises 2 to 6% by weight of aluminum and 0.5 to 4% by weight of calcium, and the balance comprising magnesium and inevitable impurities, having a Ca/Al ratio of no more than 0.8, preferably no more than 0.6. The method of preparing the heat-resistant magnesium alloy member is characterized in a semi-solid injection molding at a range between a solidus temperaaature of the alloy and a liquidus temperature of the alloy.
Description
The present invention relates to a kind ofly when guaranteeing creep resistance, have excellent plasticity and the heat resistance magnesium alloy molded component of ductility, the heat resistance magnesium alloy that is used for described shaping and manufacturing process thereof especially.
In the present actual metallic substance that uses, the density of magnesium alloy is minimum, and people expect that especially magnesium alloy can be used as the light material that automobile is from now on used.Present most popular magnesium alloy is Mg-Al-Zn-Mn series alloy (for example, an AZ91D alloy).This alloy at room temperature intensity is big, and erosion resistance is good, is used as the material of wheel box that automobile uses, cylinder head etc.Yet in surpassing 120 ℃ temperature range, its strength characteristics begins to reduce, its creep-resistant property variation particularly, and this problem with the rust on bolt connecting portion junction surface in practicality etc. is relevant.
On the other hand, as improving stable on heating alloy, used the AS41 magnesium alloy of Mg-Al-Si series.Yet, though it is better than above-mentioned AZ91D about creep resistance aspect AZ41 magnesium alloy, but when use temperature during 150 ℃ of left and right sides, its characteristic is just perfect inadequately, and, its tensile strength characteristics under room temperature, high temperature is all low, in order to ensure desirable strength, has to increase wall thickness, produce like this, again and reduce the light-weighted effect of magnesium alloy.
Other is as the alloy that improves resistance toheat, though the alloy of the QE22 that adds silver and rare earth element etc. is arranged, its shortcoming is that this alloy costs an arm and a leg, and is unsuitable for die casting etc.
For this reason, there is the people to propose again to use to have the Mg-Al-Ca-Mn series alloy (spy opens flat 6-25790) of excellent hot strength.Here, if the ratio of Ca/Al is 0.7, preferably more than 0.75, the crystal structure form that then crystallization is separated out in the magnesium alloy changes, and crystallization goes out the Mg-Ca compound, demonstrates excellent hot strength characteristic.
But in the time of will doing the die casting shaping than high magnesium alloy with Ca/Al, such problem is still arranged: hot tearing takes place in die casting goods easily, easy scaling loss metal die when molten metal temperature is high.
The present invention is in view of problems of the prior art as mentioned above, its first purpose is, provide a kind of and have the rerum natura of the engine parts that are suitable for automobile etc., particularly when guaranteeing its creep resistance, have the excellent plasticity and the heat resistance magnesium alloy molded component of ductility.
Second purpose of the present invention be, provides a kind of replacement present widely used die casting method, is used for the suitable manufacturing process of above-mentioned heat resistance magnesium alloy molded component.
The 3rd purpose of the present invention is, provides a kind of and is suitable for making above-mentioned when guaranteeing its creep resistance, has the alloy composition of the heat resistance magnesium alloy molded component of excellent plasticity and ductility.
Present inventors are in order to solve above-mentioned problem, carried out all research, it found that: adopt the semi-melting manufacturing process that carries out injection forming under solid phase, liquid-phase mixing state to replace die casting as the magnesium alloy to Al-Ca series, then can prevent the scaling loss of metal pattern, simultaneously, make the parts of formed thereby have excellent intensity.But,, must greatly increase the addition of aluminium in order to keep described solid, liquid phase admixture.
On the other hand, the aluminium solid solution has shown time hardening in magnesium, and this is to add for the mechanical characteristics that improves alloy.But along with the carrying out that magnesium is added aluminium, the hot strength of this alloy has the tendency of decline, and in order to strengthen its hot strength, the someone recommends to add calcium, the Ca/Al ratio is remained on (spy opens flat 6-25790) more than 0.7.Yet present inventors find: the addition of calcium is big as described, casting takes place when being shaped easily split and the scaling loss metal die; And because crystallization goes out the Ma-Ca series compound in large quantities, the extension performance of molded article has the tendency of reduction, so, should select the Ca/Al ratio to remain on below 0.8.
Based on the opinion of two aspects as mentioned above, the present invention is a kind of aluminium 2-6% (weight) and calcium 0.5-4% (weight) of containing, and all the other compositions are magnesium and unavoidable impurities, wherein Ca/Al is than at the Mg alloy formed formed parts below 0.8; The invention reside in provides a kind of and is suitable for making above-mentioned when guaranteeing its creep resistance, has the excellent plasticity and the heat resistance magnesium alloy molded component of ductility.
It is generally acknowledged,, show time hardening, improve the mechanical characteristics of alloy, preferably aluminium is made an addition in the magnesium alloy with 2-10% (weight) for making its solid solution in magnesium.In the present invention, no doubt be necessary to add more than the aluminium 2% (weight), but when this addition surpassed 6% (weight), even then carry out the semi-melting injection forming, its extension performance was still low.For this reason, for reaching desired effect, when carrying out the semi-melting injection forming, this addition is controlled at below 6% (weight).On the other hand, the alloy high-temp intensity that reduces tendency appears, is in the interpolation of calcium when being accompanied by magnesium interpolation aluminium in order to improve, but in order not reduce the ductility of plasticity and formed parts, be necessary the Ca/Al ratio is controlled at below 0.8, so the addition of Ca is controlled at 0.5-4% (weight).
Strontium is used as fining agent in the casting of magnesium alloy, but owing in semi-melting injection molding method involved in the present invention, also can bring into play the thinning effect of solid phase, so, preferably add.Its addition is advisable with 0.15% (weight).
The crystal particle diameter of above-mentioned molded component is below 30 μ m, and its ductility/strength and has shown minimum creep rate 4 * 10 under 150 ℃ of test temperatures, test load 50MPa more than 180MPa (298K: with reference to Fig. 9)
-10The creep-resistant property (according to JIS Z 2271 " the extension creep test method of metallic substance ") of the excellence that/s is following.Therefore, be applicable to wheel box parts and the engine parts that automobile is used.Particularly, when Ca/Al than 0.6 when following, demonstrate the creep-resistant property of excellence.
Again, in the present invention, as the alloy material of above-mentioned Mg alloy formed parts shaping usefulness, contain aluminium 2-6% (weight) and calcium 0.5-4% (weight), all the other compositions are magnesium and unavoidable impurities, are preferably, and also contain below the Sr0.15% (weight).
Generalized theory, the invention reside in provide a kind of by Ca/Al than be adjusted in below 0.8, be more preferably Ca/Al than be adjusted in below 0.6, when guaranteeing its excellent creep resistance, have the excellent plasticity and the heat resistance magnesium alloy of ductility by the semi-melting moulding method.
Present inventors are special to be found, as alloy material, when being shaped with the semi-melting moulding method, the clipped wire or the metallic particles form that import internal strain are effective (with reference to Figure 10) to the crystallization refinement.As its working method, machining helps reducing cost.
Have again, when under adopting solid phase, liquid-phase mixing state, carrying out the semi-melting manufacturing process replacement die casting of injection forming, can under the cryogenic temperature that is lower than below the die casting liquidus line, implement described cast form.Therefore, the invention provides a kind of when guaranteeing its excellent creep resistance, manufacturing process with heat resistance magnesium alloy of excellent plasticity and ductility, it is characterized in that described magnesium alloy is to be lower than below the liquidus temperature in its temperature, to carry out semi-melting be shaped under solid phase, liquid-phase mixing state.
Die casting is normally when its temperature is higher than the above 30-50 of melt temperature ℃ temperature, molten metal is injected in the metal pattern, by contrast, because semi-melting injection forming of the present invention is to carry out injection forming when being lower than the temperature of liquidus line, therefore, its injection temperature is lower than the former 30-60 ℃ at least.Thus, can prevent scaling loss to metal pattern.
Can think that solidify script from the semi-melting state, therefore, it is little to solidify stress, thereby uses described method can suppress the generation of hot tearing.
Particularly, to the effect that prevents and suppress hot tearing of described metal pattern scaling loss in the semi-melting moulding method, when solid content 30% when following, it can suppress the generation of hot tearing effectively to the influence of length of flow significantly (with reference to Fig. 8).Therefore, when carrying out described semi-melting moulding method, the solid content under the semi-melting state is preferably in below 30%.
Usually, can think that when solid content is high more, it is to scaling loss and to solidify the influence of stress aspect also favourable, but in the present invention, the solid content height, then mobile poor, the reduction of filling properties takes place easily and cast cold shut, be difficult to obtain intact formed parts.
Particularly, the median size of these solidified structures is when 30 μ m are following, and its ductility value obtains improving especially significantly.
Above-mentioned magnesium alloy also can contain again 2% (weight) following, be selected from zinc, manganese, zirconium, and at least a element of silicon, and/or contain the rare earth element (for example, iridium, neodymium, lanthanum, cerium, contain the cerium mischmetal metal mixture) of 4% (weight).These elements can improve the intensity or the hot strength of above-mentioned magnesium alloy effectively below the described upper limit.
The working of an invention mode
Figure 1 shows that the one-piece construction of the forming mill 1 that is used for semi-melting moulding method of the present invention.In manufacturing process of the present invention, the loading hopper 8 that the magnesium alloy clipped wire that will be made by methods such as mechanical grindings or the raw material 3 of particle (diameter is more than 3mm) drop among the figure.Raw material 3 is supplied in the cylinder 4 from the inlet 7 of loading hopper 8 through argon gas.Raw material 3 nationality spiral 2 limits in this cylinder 4 are pushed to the place ahead, and the limit is heated.10 expression heating zone.When Heating temperature roughly reached liquidus line, raw material magnesium alloy 3 became molten state; When the temperature of Heating temperature below liquidus line, then as shown in the figure, this raw material becomes the semi-melting state of solid phase and liquid-phase mixing.In addition, as shown in the figure, the magnesium alloy that is in the semi-melting state stirs because of the rotation of spiral, and its shearing force is with solid phase segmentation, cut-out.At this moment, by the high speed injection structure 5 that places the rear portion spiral 2 is pushed towards the place ahead, then its solid phase molten metal that segmented, cut off, that be in the semi-melting state goes out from nozzle 9 high-velocity jet promptly as shown in the figure, is filled in the metal pattern 6.Here,, after solidify, solidifying, open mould, take out molded article keeping pressurization in the metal pattern.
Embodiment 1-7 and comparative example 1-5
Iron crucible is set on low-frequency furnace, makes SF
6 Gas 1% (all the other are dry air) flows at molten metal surface, and molten white silk makes the alloy of the composition of embodiment and comparative example.Cast these alloys onboard, process the particle that makes the 3-5mm diameter,, use above-mentioned forming mill, carry out semi-melting and be shaped used as raw material by lathe.Semi-melting is shaped and uses clamp force to reach 450 tons machine, and the injection speed when its condition is common the injection is 50m/s at metal pattern cast gate place, and injection pressure is about 700kg/cm
2, the alloy temperature of spray nozzle part is set at 550-580 ℃ below the liquidus temperature.Under aforesaid molding condition, make extension test piece (JIS4 test piece), according to the extension creep test method of JIS Z 2271, study its creep properties under 150 ℃, 50MPa condition.It the results are shown in Fig. 2.Can see that magnesium alloy of the present invention is compared with the AS41 that creep resistance is better than the AZ91D of comparative example 3, the former has more excellent creep resistance.
Table 1
| ??Al | ??Ca | ??Si | ??Mn | ?Sr | ???? | ||
| Embodiment | |||||||
| 1 | ????Mg-3Al-2Ca | ??2.98 | ??2.05 | ??0.30 | ??0.25 | ?- | Remaining |
| | ????Mg-4Al-2Ca | ??3.95 | ??2.02 | ??0.30 | ??0.32 | ?- | ????↑ |
| | ????Mg-4Al-3Ca | ??4.02 | ??3.06 | ??0.25 | ??0.28 | ?- | ????↑ |
| | ????Mg-6Al-3Ca | ??5.97 | ??3.10 | ??0.28 | ??0.30 | ?- | ????↑ |
| Embodiment 5 | Mg-4Al-2Ca-0.03Sr | ??3.87 | ??2.06 | ??0.25 | ??0.25 | ?0.03 | ????↑ |
| | Mg-4Al-2Ca-0.09Sr | ??4.02 | ??1.98 | ??0.30 | ??0.23 | ?0.09 | ????↑ |
| | Mg-4Al-2Ca-0.15Sr | ??4.05 | ??2.10 | ??0.23 | ??0.25 | ?0.15 | ????↑ |
| Comparative example 1 | Suitable ASTM AS41 | ??4.39 | ??- | ??0.45 | ??0.28 | ?- | ????↑ |
| Comparative example 2 | ????Mg-9Al-0.5Ca | ??8.70 | ??0.49 | ??0.90 | ??0.21 | ?- | ????↑ |
| Comparative example 3 | Suitable ASTM AZ91D | ??8.84 | ??- | ??0.02 | ??0.22 | ?- | ????↑ |
| Comparative example 4 | ????Mg-4Al-4Ca | ??4.02 | ??3.96 | ??0.32 | ??0.32 | ?- | ????↑ |
| Comparative example 5 | ????Mg-3Al-3Ca | ??2.75 | ??2.71 | ??0.27 | ??0.36 | ?- | ????↑ |
Under 25 ℃ of ram speed 10mm/ branches, probe temperature, record its ultimate strength and extension at break by Ying Site youth's strength tester again.It the results are shown in table 2.Aluminium content in the comparative example 2 surpasses the 2-6% (weight) of the scope of the invention, though the content of the aluminium of comparative example 4 and calcium within the scope of the invention, its Ca/Al is than surpassing 0.8.By contrast, aluminium 2-6% (weight), calcium 0.5-4% (weight), the Ca/Al of containing of the present invention is than having shown excellent extension performance at the embodiment below 0.8.
Table 2
| Al measures (weight %) | Ca measures (weight %) | Stretch (%) | |
| | ????3.95 | ????2.02 | ????6.7 |
| | ????4.02 | ????3.06 | ????7.0 |
| | ????5.97 | ????3.10 | ????5.2 |
| Comparative example 3 | ????8.70 | ????0.49 | ????0.8 |
| Comparative example 4 | ????4.02 | ????3.96 | ????1.2 |
In embodiment and comparative example, the relation between Ca/Al ratio and the above-mentioned elongation is shown in Fig. 3.As seen from the figure, when the Ca/Al ratio surpassed 0.8, elongation sharply reduced.
See again Ca/Al than and the minimized creep rate of straining between relation, then as shown in Figure 6, Ca/Al is than 0.6 when following (embodiment 2), creep strain speed is littler, has the creep resistance of excellence.
Again, use test metal pattern as shown in Figure 4, under the situation of guaranteeing flow of molten metal as shown, carry out semi-melting and be shaped, obtain result as shown in table 3.Along with Ca/Al than near 1, the casting hot tearing betides the portion of overflowing one side of cylindrical portion upper end, but compares less than 0.8 the time as Ca/Al, and aforesaid casting hot tearing does not then take place fully.
Table 3
| The Ca/Al weight ratio | Having or not of casting | |
| Embodiment | ||
| 1 | ????0.69 ????0.51 ????0.76 ????0.52 ????0.99 ????0.99 | Not having has |
Usually, the residence time during casting is long, and then the solid phase diameter sharply increases (embodiment 2 of Fig. 5), still, owing to add the effect that strontium can produce the crystallization of refinement body, therefore can be suppressed the increase of solid phase diameter by the adjusting of this residence time.
Use the alloy material of embodiment 2, change the temperature that semi-melting is shaped, and change the solid content in the molten metal, make molten metal enter as shown in Figure 7 metal flow evaluation metal pattern along illustrated direction, estimate this molten metal flow, its evaluation result is shown in Fig. 8.According to this result, when solid content surpasses 30%, then length of flow (flowing lenth) sharply descends.Hence one can see that, and owing to the organize crystal particle diameter of this molten metal flow to molded component exerts an influence, the semi-melting moulding method is preferably carried out under the state of solid content below 30%.
In semi-melting is shaped; use is the magnesium alloy materials of clipped wire or particle form; but; this clipped wire is owing to its inner reason such as machining produces the processing strain; heating generates the nuclear of recrystal grain in the near future; increased the solid phase diameter; so; make comparisons with using situation as using the situation of not processing the strained clipped wire with processing strained clipped wire; then as shown in figure 10 as can be known; the growth rate difference of its solid phase, its latter effect aspect the refinement of molded component crystal particle diameter is more excellent.
By as mentioned above as can be known, according to the present invention, be in the heat resistance magnesium alloy parts at Mg-Al-Ca, control Ca/Al ratio, the molded component that can obtain having the creep resistance characteristic under the excellent high temperature.So the engine parts of the wheel box parts of using with automobiles such as the manufacturing of light-weight magnesium alloy such as clutch separation piston and clutch drums and reciprocating lever etc. can make it have sufficient durable wear-resistant.
In addition, in the present invention, carry out semi-melting when tying up to the temperature that is lower than liquidus line and be shaped, can solve die casting produced in the past the hot tearing and the problem of metal pattern scaling loss, simultaneously, can keep it as previous methods or than the normal temperature and the hot strength of previous methods excellence and the elongation of extending.
The simple declaration of accompanying drawing
Figure 1 shows that the forming mill structural representation that is used for semi-melting moulding method of the present invention and injection molding method.
Figure 2 shows that the creep characteristic curve figure that is used for more various Mg alloy formed parts.
The Ca/Al that Figure 3 shows that various Mg alloy formed parts than with room temperature under the extend graph of a relation of elongation.
Figure 4 shows that the synoptic diagram of casting cracking test with metal pattern.
Figure 5 shows that the graph of a relation of solid phase diameter and residence time.
Figure 6 shows that the minimized creep emergent property speed of various Mg alloy formed parts.
Figure 7 shows that the synoptic diagram of the metal pattern of the flow of molten metal that is used to estimate various magnesium alloy.
Figure 8 shows that the solid content and the long graph of a relation that flows in the alloy composition of the embodiment 2 that records with Fig. 7 metal pattern.
Figure 9 shows that the average crystalline particle diameter of the member that is shaped with the alloy component of embodiment 3 and the graph of a relation of tensile strength.
Figure 10 shows that the grow up synoptic diagram in stage of solid phase when use not having processing strained clipped wire and processing strained clipped wire being arranged.
Among the figure, 1 expression injection machine, 2 expression spirals, 3 expression feed particles, 4 expression cylinders, 5 expression high speed injection structures, 6 expression metal patterns, the material passage that cylinder is led in 7 expressions, 8 expression loading hoppers, 9 expression nozzles, 10 expression heating zone.
Claims (12)
1. heat resistance magnesium alloy parts with excellent anti creep properties, it is characterized in that, this is a kind of by containing aluminium 2-6% (weight) and calcium 0.5-4% (weight), and all the other compositions are magnesium and unavoidable impurities, wherein Ca/Al compares at the Mg alloy formed molded component below 0.8.
2. the heat resistance magnesium alloy parts with excellent anti creep properties as claimed in claim 1 is characterized in that, the Ca/Al of described alloy has the minimum creep rate 4 * 10 under 150 ℃ of test temperatures, test load 50MPa than below 0.6
-10The creep-resistant property of the excellence of/s.
3. the heat resistance magnesium alloy parts with excellent anti creep properties as claimed in claim 1 or 2 is characterized in that, described alloy also contains the following Sr of 0.15% (weight).
4. each described heat resistance magnesium alloy parts as claim 1-3 is characterized in that the average crystallite particle diameter of described alloy is below 30 μ m.
5. each described heat resistance magnesium alloy parts with excellent anti creep properties as claim 1-4 is characterized in that, described Alloy Forming parts are automobile wheel box parts or engine parts.
6. heat resistance magnesium alloy with excellent anti creep properties, it is characterized in that, this is a kind of aluminium 2-6% (weight) and calcium 0.5-4% (weight) of containing, all the other compositions are magnesium and unavoidable impurities, and the heat resistance magnesium alloy with excellent anti creep properties that makes by the semi-melting injection forming under the temperature below the liquidus line of solid phase and liquid-phase mixing.
7. a heat resistance magnesium alloy as claimed in claim 6 is characterized in that, described alloy also contains the following Sr of 0.15% (weight).
8. one kind as claim 6 or 7 described heat resistance magnesium alloys, it is characterized in that, the Ca/Al of described alloy is than below 0.8.
9. a heat resistance magnesium alloy as claimed in claim 8 is characterized in that, the Ca/Al ratio of described alloy is below 0.6.
10. each described heat resistance magnesium alloy as claim 6-9 is characterized in that described alloy is clipped wire or the particle form that imports internal strain.
11. manufacturing process with heat resistance magnesium alloy molded component of excellent anti creep properties, it is characterized in that, each described heat resistance magnesium alloy of claim 6-10 under the temperature that is lower than the liquidus line that solid phase and liquid-phase mixing exist, is carried out the semi-melting injection forming.
12. the manufacturing process of heat resistance magnesium alloy parts as claimed in claim 11 is characterized in that, when carrying out described semi-melting injection forming, the solid content during the semi-melting state is below 30%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP082832/1996 | 1996-04-04 | ||
| JP082832/96 | 1996-04-04 | ||
| JP08283296A JP3415987B2 (en) | 1996-04-04 | 1996-04-04 | Molding method of heat-resistant magnesium alloy molded member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1174243A true CN1174243A (en) | 1998-02-25 |
| CN1065003C CN1065003C (en) | 2001-04-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN971050007A Expired - Fee Related CN1065003C (en) | 1996-04-04 | 1997-04-04 | Heat-resisting magensium alloy forming member, heat-resisting magnesium alloy for forming and forming method thereof |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20020020475A1 (en) |
| EP (1) | EP0799901B1 (en) |
| JP (1) | JP3415987B2 (en) |
| KR (1) | KR970070224A (en) |
| CN (1) | CN1065003C (en) |
| DE (1) | DE69706737T2 (en) |
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| FR2642439B2 (en) * | 1988-02-26 | 1993-04-16 | Pechiney Electrometallurgie | |
| DE69007920T2 (en) * | 1989-08-24 | 1994-07-21 | Norsk Hydro As | High-strength magnesium alloys and processes for their production through rapid solidification. |
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- 1996-04-04 JP JP08283296A patent/JP3415987B2/en not_active Expired - Fee Related
-
1997
- 1997-04-04 EP EP97105641A patent/EP0799901B1/en not_active Expired - Lifetime
- 1997-04-04 KR KR1019970012613A patent/KR970070224A/en not_active Application Discontinuation
- 1997-04-04 CN CN971050007A patent/CN1065003C/en not_active Expired - Fee Related
- 1997-04-04 DE DE69706737T patent/DE69706737T2/en not_active Expired - Lifetime
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2001
- 2001-09-12 US US09/949,621 patent/US20020020475A1/en not_active Abandoned
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| CN109957692A (en) * | 2019-03-27 | 2019-07-02 | 东北大学 | A kind of cast magnesium matrix composite material with high calcium and high aluminum content and preparation method thereof |
| CN109913720B (en) * | 2019-03-27 | 2020-11-24 | 东北大学 | A kind of high-calcium and high-aluminum content magnesium-based composite material with high elastic modulus and preparation method |
| CN109913720A (en) * | 2019-03-27 | 2019-06-21 | 东北大学 | A kind of high-calcium and high-aluminum content magnesium-based composite material with high elastic modulus and preparation method |
| CN111155011A (en) * | 2020-02-21 | 2020-05-15 | 江苏理工学院 | High-performance Mg-Al-Ca magnesium alloy and preparation method thereof |
| CN112725673A (en) * | 2020-12-28 | 2021-04-30 | 中信戴卡股份有限公司 | Mg-Al alloy and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR970070224A (en) | 1997-11-07 |
| JP3415987B2 (en) | 2003-06-09 |
| JPH09272945A (en) | 1997-10-21 |
| US20020020475A1 (en) | 2002-02-21 |
| CN1065003C (en) | 2001-04-25 |
| EP0799901B1 (en) | 2001-09-19 |
| EP0799901A1 (en) | 1997-10-08 |
| DE69706737D1 (en) | 2001-10-25 |
| DE69706737T2 (en) | 2002-07-04 |
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