CN1306052C - High corrosion resisting as cast magnalium and preparation method - Google Patents
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Abstract
The present invention involving a high corrosion resisting as cast magnalium and preparation method which belongs to magnalium alloy field.The alloy composition(wt%) is:Al 7.5-10.5,Mn 0.2-1.0,La 0.1-0.8,Ce 0.1-0.8,Pr 0.05-0.3,Y 0.1-0.8,Zn 0.1-0.5,Sr 0.2-0.5,the allowance is Mg and impurity elements.The preparing method is either using CO[2]+SF[4]to protect atmosphere melting or solvent method melting the temperature of which is 710-750 DEG C.The prepared alloy consists of Alpha phase,Mg[17] Al[11] phase containing Sr and Mg Al La Pr Ce Y Sr complex intermetallic compound.The hign magnalium alloy which salt acid test corrosion rate is only 0.1 mg/cm[2]days or so is superior to the corrosion performation of the AZ91(Mg-9Al) and Mg-9Al-1Re,also the ac impedance value of the alloy is higher than the above comparison alloy significantly.
Description
Technical field
The present invention relates to a kind of high corrosion resistant casting magnesium aluminium alloy and preparation method, high aluminium content cast magnesium alloy and preparation method that to relate to a kind of aluminium content or rather be the 7.5-10.5 mass percent belong to the magnesium alloy field.
Background technology
Magnesium alloy has that density is little, specific tenacity, specific rigidity height, good capability of electromagnetic shielding and damping performance, good casting and processing characteristics, at 3C Product (computers such as aerospace, automobile and electronic information, communication product and consumption electronic product) field obtained application more and more widely, and its usage quantity is with annual 20% speed increment in recent years.
But the corrosion resisting property difference of magnesium alloy is the significant obstacle of its application.Magnesium alloy is because its corrosion potential is very negative; at the aqueous solution or moist environment; under the saliniferous environment galvanic corrosion takes place very easily particularly; the precipitated phase of magnesium alloy is with respect to magnesium alloy substrate α cathodic often mutually; this will cause inevitable little galvanic corrosion; and the natural oxide film of magnesium alloy is loose porous, can not provide effective protection to alloy substrate.Therefore make further applying of magnesium alloy be very restricted.
Closely during the last ten years, the research that improves the corrosion stability of magnesium alloy energy obtains the great attention of various countries scientific circles such as America and Europe, Japan, industrial community, and has accomplished tangible results.By suitable alloying, the content of minimizing and control beavy metal impurity element and thermal treatment etc. can significantly improve and improve the solidity to corrosion of magnesium alloy.But the solidity to corrosion of existing magnesium alloy is still not enough; be difficult to adapt to widely used requirement under the various physical environments; for solving the anti-corrosion problem of magnesium alloy; except the magnesium goods being imposed the surface protection processing; improve the solidity to corrosion of magnesium alloy itself, develop high corrosion-resistant magnesium alloy more anti-corrosion, that do not need surface protection to handle and have prior meaning.
At this on the one hand, the magnesium alloy patent application of some better corrosion resisting properties has been proposed in recent years.(application number: 02130182.4) [JP252764/2001] patent application has proposed a kind of " magnesium alloy and magnesium alloy element with high anti-corrosion " as CN1401805A, the composition range of its corrosion-resistant magnesium alloy is: Al:5～7mass%, Ca:2～4mass%, Mn:0.1～0.8mass%, Sr:0.001～0.05mass% and rare earth element 0.1～0.6mass%, remainder are Mg and unavoidable impurities.Alloy corrosion speed is pressed the 100 hours weightlessness after the salt-fog test and is calculated, and in alloy component range, erosion rate is 0.1 milligram/centimetre
2. about day.
Japanese Patent JP2003166031 has proposed " high corrosion resistance magnesium alloy and its manufacture method ", the compositing range of its corrosion-resistant magnesium alloy is: Al:1～8mass%, Mn:0.1～1.5mass%, Ce or La:0.1～0.9mass%, surplus is Mg and unavoidable impurities, weight-loss metering after its solidity to corrosion is soaked in 5mass%Nacl solution with alloy sample, the erosion rate of this alloy＜0.1 milligram/centimetre
2. day.
But because magnesium alloy adopts casting forming or semi-solid-state shaping processing usually, require alloy that higher flowability and castability are arranged, consider from castability and mechanical property, the most frequently used cast magnesium alloys is to contain Al to reach the AZ91 type magnesium alloy of 9mass% (its principal constituent scope is: Al:8.5～9.5mass%, Mn:0.17～0.4mass%, Zn:0.45～0.9mass%, Si:＜0.05mass%, impurity:＜0.01mass%).Consider that from desired alloy high workability of casting forming high rate of finished products and castability the Al that contains of alloy measures and should improve as far as possible, so the Al that contains of diecast magnesium alloy measures requirement 〉=9mass% usually.
The Al content of above-mentioned two kinds of patent alloys all≤8mass%, consider from castability and over-all properties, these two kinds of alloys can not replace the AZ91 alloy fully, but as bringing up to＞8mass% containing the Al amount for improving castability, then these two kinds of patent alloys just can not keep high anti-corrosion.
For the high Al magnesium alloy of Al content＞8mass%, its solidity to corrosion is all poor usually.Our test shows: the AZ91D alloy, the corrosion rate of its 100 hours salt-fog tests is usually above 10 milligrams/centimetre
2. day.
The test-results of the alloy that relates in above-mentioned two patent applications also shows: when the Al amount of containing of alloy reaches 8mass% when above, the corrosion rate of alloy is also bigger.
Documents 2 (JP2003166031) shows: when the near 9mass% of the Al of alloy content, its corrosion rate is also greater than 0.3 milligram/centimetre
2. day.
Therefore, when the Al of alloy content reached better castability of maintenance and the desired 8-9mass% of mechanical property, corrosion stability of magnesium alloy is relatively poor to be a still open question.
Summary of the invention
The objective of the invention is to demand, provide Al content in the high Al content range of 7.5-10.5mass%, anti-corrosion magnalium and alloying approach thereof at industrial community.
The present invention is the composite alloying by polynary a spot of rare earth element and alkaline-earth metal Sr, and the precipitated phase that makes the Mg-Al alloy is by reinforcing yin essence polar Mg
17Al
12Change into mutually cathodic that disperse distributes very weak contain multielement rare earth, Sr, Mg; compound phase between the composition metal of Al; thereby significantly reduce little galvanic corrosion of Mg-Al alloy, promoted to have the formation of the complex oxide film of passivity and protectiveness simultaneously, make alloy of the present invention have good solidity to corrosion.
Therefore the invention provides the high cast magnesium alloy of a kind of solidity to corrosion, it consists of the element that contains following mass percent: Al:7.5～10.5, Mn:0.2-1.0, La:0.1～0.8, Ce:0.1～0.8, Pr:0.05～0.3, Y:0.1-0.8, Zn:0.1～0.5, Sr:0.2～1.5, the remainder of above-mentioned magnesium alloy is made up of Mg and unavoidable impurities.
The unavoidable impurities element mainly is in this magnesium alloy: Si, Cu, Fe, Ni.Its content is: Si≤0.05mass%, Cu≤0.004mass%, Ni≤0.002mass%, Fe≤0.004mass%.
This alloy can adopt protective atmosphere (CO
2+ SF
6) melting, also can adopt the solvent method melting.The raw material that uses is: Mg, and Al, Zn adopts the technical pure metal, Mn can adopt Al-Mn master alloy or electrolytic manganese, La, Pr, Ce, it is the rich La of Mg-of 15-25% that Y adopts content of rare earth, the rich Pr of Mg-, the rich Ce of Mg-, the master alloy of rich Y of Mg-or the rich LaPrCe of Mg-, Sr adopts technical pure Sr or AlSr10 master alloy, is smelted into alloy with above-mentioned preparation of raw material.And La: Ce: Pr=6 in the rich LaPrCe master alloy of Mg-: 3: 1.Concrete preparation is to melt Mg and Al in the solvent stove earlier, adds the rich La of Mg-again, the rich Pr of Mg-, and the rich Ce of Mg-, the rich Y of Mg-or Mg-richness LaPrCe and Al-Mn intermediate metal or electrolytic manganese and Metal Zn add technical pure metal Sr or AlSr10 master alloy at last.
The refining solvent that described solvent method uses, its composition (wt%) contains: KCl25-30, NaCl5-10, CaCl
25-10, CaF
225-30, MgO2-3, surplus is MgCl
2
Described protective atmosphere Co
2: SF
6=100-200: 1.
The smelting temperature of alloy is 710～750 ℃, and the teeming temperature of alloy is 680～720 ℃.Alloy can pour into alloy pig under casting temp, also the alloy liquid temp can be controlled at 680～720 ℃ and carry out high-pressure casting and become magnesium alloy product.Perhaps ingot casting is heated to (560～590) ± 2 ℃, alloy is in solid rate to be 50% or to carry out semi-solid casting when following, or after alloy is processed into bits sheet bits piece and is heated to (560～590) ± 2 ℃, make alloy be in solid rate be 50% or following semi-solid state form carry out injection forming, make magnesium alloy product.
Made alloy is by the α phase, contains the Mg of Sr
17Al
11Mutually and contain complicated intermetallic compound that Sr and La, Pr, Ce, Y, Al, Mg form mutually---the MgAlLaPrCeYSr formation.
Alloy provided by the invention has excellent corrosion resistant performance, and the corrosion rate of its salt-fog test is 0.1 milligram/centimetre
2. about day.(seeing Fig. 2 and table 1)
A) corrosion rate of salt-fog test
The solidity to corrosion of alloy adopts the corrosion rate of general salt-fog test to measure.Alloy is at the salt fog of 5mass%NaCl, and 35 ℃ corrosion is after 100 hours down, and the weightlessness of measuring before and after corroding is calculated corrosion rate.The corrosion rate of alloy provided by the invention and comparative alloy AZ91 (Mg-9Al) and Mg-9Al-1RE alloy is shown in Fig. 2 and table 1.
B) electrochemical AC impedance is measured
The polarization resistance Rp value that electrochemical AC impedance is measured is represented corrosion resistance (its inverse is corrosion rate), and the Rp value is big more, and the expression alloy is corrosion-resistant more.Electrochemical AC impedance is measured at pH10.5,25 ℃, in the 3.5%NaCl solution, measures with SolartronSI1287 electrochemistry interface and 1255B frequency response instrument after soaking 35 minutes.The complex number plane figure of 4 embodiment of the present invention and comparative alloy and Rp value are shown in Fig. 3 and table 2.
Alloy that table 1. embodiment of the invention provides and comparative alloy Mg-9Al and Mg-9Al-1RE (RE is about 50% mishmetal for Ce content) are at the corrosion rate of 5mass%NaCl35 ℃ of salt-fog test
| Alloy | Corrosion rate (milligram/centimetre 2. day) |
| Comparative alloy AZ91 (Mg-9Al) | ＞10 |
| Comparative alloy Mg-9Al-1RE (RE:Ce is main mishmetal) | 0.232 |
| | 0.057 |
| Embodiment 2 | 0.115 |
| Embodiment 3 | 0.068 |
| Embodiment 4 | 0.096 |
The Rp value that table 2. magnalium provided by the invention and comparative alloy electrochemical impedance are measured
| Alloy | Alternating-current impedance (Rp) value (Ω cm 2) |
| Comparative alloy Mg-9Al alloy | 263 |
| Comparative alloy Mg-9Al-1RE (RE:Ce is main mishmetal) | 986 |
| The present invention | 1250 |
From Fig. 3 and table 2 as can be seen: the Rp value of alloy provided by the invention is apparently higher than correlated AZ91 alloy (Mg-9Al) and Mg-9Al-1RE (RE:Ce accounts for the mishmetal more than 50%).Therefore alloy provided by the invention has stronger solidity to corrosion.
Therefore, the solidity to corrosion of alloy provided by the invention significantly surpasses general AZ91 alloy, is that the solidity to corrosion of Mg-9Al-1RE alloy of main mishmetal is also much better than adding Ce, and it is the Mg-Al alloy with excellent corrosion resistance.
In addition, the mechanical property of patent alloy provided by the invention and comparative alloy (AZ91) is as shown in table 3.
The mechanical property of table 3. alloy provided by the invention and comparative alloy (AZ91)
| Alloy | The room temperature tensile strength sigma b(Mpa) | Unit elongation (δ %) | Impelling strength Ak (J joule) |
| The present invention | ＞170 | ＞6 | ＞4 |
| Comparative alloy AZ91 | ＞160 | ＞3 | ＞4 |
Therefore, the mechanical property of alloy provided by the invention equals or good and AZ91 comparative alloy.
In sum, magnesium alloy contrasts such as high aluminium content magnalium provided by the invention and AZ-91 have good solidity to corrosion and preparation technology is similar to general magnesium alloy.
Description of drawings
The metallography microscope structure (X500) of the magnalium of Fig. 1 high alumina provided by the invention
The solidity to corrosion of Fig. 2 embodiment 1-4 of the present invention and two kinds of comparative alloy relatively
The electrochemical AC impedance complex number plane figure of Fig. 3 magnalium provided by the present invention and comparative alloy relatively
Embodiment
Below by specific embodiment, further illustrate substantive distinguishing features of the present invention and marked improvement, but the present invention only is confined to embodiment by no means.
The preparation composition (mass percent) of alloy is: Al:9.0%, La:0.6%, Ce:0.3%, Pr:0.1%, Y:0.33%, Mn:0.3%, Zn:0.4%, Sr:1.0%.Inevitably the magazine element is restricted to: Si≤0.05%, and Cu≤0.004%, Ni≤0.002%, Fe≤0.004%, all the other are Mg.
Adopt pure magnesium, commercial-purity aluminium, Mg-LaPrCe master alloy (La, Pr, the total amount of Ce accounts for 20%, wherein La: Ce: Pr ≈ 6: 3: 1), and Mg-Y master alloy (Y:21%), Al-Mn master alloy, technical pure Zn, metal Sr presses the mentioned component alloyage.Protective atmosphere (CO2: 200: 1 mixed atmosphere of SF6 ≈) in the Mg alloy smelting furnace, earlier fusing Mg and Al, treat the magnesium alloy fusing after; add Mg-LaPrCe again, Mg-Y, Al-Mn master alloy and Zn; add metal Sr at last, treat alloying element all after the fusing, (being about 710 ℃); heat up,, left standstill 30 minutes to 730 ℃; controlled temperature is no more than 750 ℃; the alloy liquid temp is reduced to about 710 ℃, skim ingot casting.When carrying out die casting, the alloy liquid temp is controlled at 700 ℃ carries out high-pressure casting and become magnesium alloy product.Perhaps ingot casting is heated to 580 ℃, alloy is in solid rate to be 50% or to carry out semi-solid casting when following, or alloy is processed into bits sheet bits piece, be heated to 580 ℃ after, make alloy be in solid rate be 50% or following semi-solid state form carry out injection forming, make magnesium alloy product.The present embodiment alloy is 0.052 milligram/centimetre at the corrosion rate of 5%NaCl salt-fog test
2. day, its room temperature tensile strength is 175MPa, and unit elongation is 6.3%, and impelling strength is 5J (joule).
Embodiment 2
The preparation composition (mass percent) of alloy is: Al:10%, La:0.3%, Ce:0.15%, Pr:0.05%, Y:0.26%, Mn:0.6%, Zn:0.4%, Sr:0.5%, the unavoidable impurities element is restricted to: Si≤0.05%, Cu≤0.004%, Ni≤0.002%, Fe≤0.004%, all the other are Mg.Adopt pure magnesium, commercial-purity aluminium, (total amount of LaPrCe accounts for 20% to the Mg-LaPrCe master alloy, La: Ce wherein: Pr ≈ 6: 3: 1), Mg-Y master alloy (Y:21%), Al-Mn master alloy, industrial-purity zinc, metal Sr presses the mentioned component alloyage.Protective atmosphere (CO2: 200: 1 mixed atmosphere of SF6 ≈) in the Mg alloy smelting furnace, earlier fusing Mg and Al, treat the magnesium alloy fusing after; add Mg-LaPrCe, Mg-Y again, Al-Mn master alloy and Zn add metal Sr at last; after treating that alloying element all melts, (being about 710 ℃), heat up; to 730 ℃; left standstill 30 minutes, controlled temperature is no more than 750 ℃, and the alloy liquid temp is reduced to about 710 ℃; skim ingot casting.When carrying out die casting, the alloy liquid temp is controlled at 680～720 ℃ carries out high-pressure casting and become magnesium alloy product.Perhaps ingot casting is heated to 560 ± 2 ℃, alloy is in solid rate to be 50% or to carry out semi-solid casting when following, or alloy is processed into bits sheet bits piece, be heated to 560 ± 2 ℃ after, make alloy be in solid rate be 50% or following semi-solid state form carry out injection forming, make magnesium alloy product.The present embodiment alloy is 0.132 milligram/centimetre at the corrosion rate of 5%NaCl salt-fog test
2. day, its room temperature tensile strength is 180MPa, and unit elongation is 6%, and impelling strength is 4J (joule).
Embodiment 3
The preparation composition (mass percent) of alloy is: Al:9.2%, La:0.8%, Ce:0.6%, Pr:0.2%, Y:0.53%, Zn:0.2%, Mn:0.4%, Sr:0.6%, the unavoidable impurities element is restricted to: Si≤0.05%, Cu≤0.004%, Ni≤0.002%, Fe≤0.004%, all the other are Mg.Adopt pure magnesium, commercial-purity aluminium, the Mg-LaPrCe master alloy (total amount of LaPrCe accounts for 20%, wherein La: Ce: Pr ≈ 6: 3: 1), and Mg-Ce master alloy (Ce:20%), Mg-Y master alloy (Y:21%), Mg-Pr master alloy (Pr:10%), Al-Mn master alloy, industrial-purity zinc, metal Sr presses the mentioned component alloyage.At protective atmosphere (CO
2: SF
6200: 1 mixed atmosphere of ≈) in the Mg alloy smelting furnace, earlier fusing Mg and Al, treat the magnesium alloy fusing after, add Mg-LaPrCe again, Mg-Ce, Mg-Pr, Mg-Y, Al-Mn master alloy and Zn add metal Sr at last, after treating that alloying element all melts, (being about 710 ℃), heat up, to 740 ℃, left standstill 30 minutes, controlled temperature is no more than 750 ℃, the alloy liquid temp is reduced to about 710 ℃, skim ingot casting.When carrying out die casting, the alloy liquid temp is controlled at 680～720 ℃ carries out high-pressure casting and become magnesium alloy product.Perhaps ingot casting is heated to 590 ℃, alloy is in solid rate to be 50% or to carry out semi-solid casting when following, or alloy is processed into bits sheet bits piece, be heated to 570 ± 2 ℃ after, make alloy be in solid rate be 50% or following semi-solid state form carry out injection forming, make magnesium alloy product.The present embodiment alloy is 0.073 milligram/centimetre at the corrosion rate of 5%NaCl salt-fog test
2. day, its room temperature tensile strength is 180MPa, and unit elongation is 6.5%, and impelling strength is 5.3J (joule).
Embodiment 4
The preparation composition (mass percent) of alloy is: Al:8.5%, La:0.8%, Ce:0.8%, Pr:0.30%, Y:0.60%, Mn:0.3%, Zn:0.4%, Sr:1.5%, the unavoidable impurities element is restricted to: Si≤0.05%, Cu≤0.004%, Ni≤0.002%, Fe≤0.004%, all the other are Mg.Adopt pure magnesium, commercial-purity aluminium, the Mg-LaPrCe master alloy (total amount of LaPrCe accounts for 20%, wherein La: Ce: Pr ≈ 6: 3: 1), and Mg-Ce master alloy (Ce:20%), Mg-Pr master alloy (Pr:10%), Mg-Y master alloy (Y:21%), Al-Mn master alloy, industrial-purity zinc, metal Sr presses the mentioned component alloyage.Adopt the solvent method melting, use special-purpose refining solvent, its composition (wt%): MgCl
225, KCl 25, and NaCl 10, CaCl
28, CaF
230, MgO 3.In Mg alloy smelting furnace, earlier fusing Mg and Al, treat the magnesium alloy fusing after, add Mg-LaPrCe again, Mg-Ce, Mg-Pr, Mg-Y, Al-Mn master alloy and Zn add metal Sr at last, after treating that alloying element all melts, (being about 710 ℃), heat up, to 730 ℃, left standstill 30 minutes, controlled temperature is no more than 750 ℃, the alloy liquid temp is reduced to about 710 ℃, skim ingot casting.When carrying out die casting, the alloy liquid temp is controlled at 680～720 ℃ carries out high-pressure casting and become magnesium alloy product.Perhaps ingot casting is heated to (560～590) ± 2 ℃, alloy is in solid rate to be 50% or to carry out semi-solid casting when following, or alloy is processed into bits sheet bits piece, after being heated to (560～590) ± 2 ℃, make alloy be in solid rate be 50% or following semi-solid state form carry out injection forming, make magnesium alloy product.The present embodiment alloy is 1.02 milligrams/centimetre at the corrosion rate of 5%NaCl salt-fog test
2. day, its room temperature tensile strength is 173MPa, and unit elongation is 6%, and impelling strength is 5J.
The solidity to corrosion of above four embodiment provided by the invention and comparative alloy relatively is summarized in table 1 and Fig. 2.
Claims (7)
1. high corrosion resistant casting magnesium aluminium alloy, it is characterized in that consisting of of alloy contain the element of following mass percent: Al 7.5-10.5, Mn 0.2-1.0, La 0.1-0.8, Ce 0.1-0.8, Pr 0.05-0.3, Y 0.1-0.8, Zn 0.1-0.5, Sr 0.2-1.5, surplus is Mg element and impurity element.
2. by the described high corrosion resistant casting magnesium aluminium alloy of claim 1, it is characterized in that the mass percent of described impurity element is respectively: Si≤0.05, Cu≤0.004, Ni≤0.002 and Fe≤0.004.
3. by the described high corrosion resistant casting magnesium aluminium alloy of claim 1, it is characterized in that alloy is by the α phase, contains the Mg of Sr
17Al
11Phase and MgAlLaPrCeYSr are complicated, and intermetallic compound constitutes mutually.
4. the method for preparing the described high corrosion resistant casting magnesium aluminium alloy of claim 1 is characterized in that concrete processing step is:
(a) mass percent of pressing alloy is formed: Al 7.5-10.5, Mn 0.2-1.0, La 0.1-0.8, Ce 0.1-0.8, Pr 0.05-0.3, Y 0.1-0.8, and Zn 0.1-0.5, Sr 0.2-1.5, surplus is the Mg batching, is smelted into alloy;
(b) adopt CO
2+ SF
6Protective atmosphere melting or solvent method melting; the smelting temperature of alloy is 710～750 ℃; teeming temperature is 680～720 ℃; alloy or under casting temp, pour into alloy pig; or the alloy liquid temp is controlled at 680～720 ℃ carries out high-pressure casting and become magnesium alloy product or ingot casting is heated to 560-590 ℃; alloy is in solid rate to be 50% or to carry out semi-solid casting when following; or after alloy is processed into bits sheet bits piece and is heated to 560-590 ℃; make alloy be in solid rate be 50% or following semi-solid state form carry out injection forming, make magnesium alloy product.
5. press the preparation method of the described high corrosion resistant casting magnesium aluminium alloy of claim 4, it is characterized in that molten alloy is earlier in smelting furnace, melt Mg and Al earlier, add the rich Y of rich Ce, Mg-of rich Pr, Mg-of Mg-rich La, Mg-or the rich LaPrCe of Mg-and Al-Mn intermediate metal or electrolytic manganese and Metal Zn again, add technical pure metal Sr or AlSr10 master alloy at last.
6. by the preparation method of claim 4 or 5 described high corrosion resistant casting magnesium aluminium alloys, it is characterized in that the protective atmosphere molten alloy is at CO
2: SF
6=100-200: 1 mixed atmosphere protection is carried out down; The solvent that the solvent method melting is used, its quality percentage composition is: KCl 25-30, NaCl 5-10, CaCl
25-10, CaF
225-30, MgO 2-3, surplus is MgCl
2
7. press the preparation method of the described high corrosion resistant casting magnesium aluminium alloy of claim 5, it is characterized in that the LaPrCe total amount is about 15-25% in the rich LaPrCe master alloy of Mg-, and La: Ce: Pr=6: 3: 1, the rich La of Mg-, the rich Ce of Mg-, the rich Pr of Mg-, contain La respectively in the rich Y master alloy of Mg-, Ce, Pr, Y are 15-25%.
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| PT2000551E (en) * | 2007-05-28 | 2010-10-21 | Acrostak Corp Bvi | Magnesium-based alloys |
| CN100519799C (en) * | 2007-12-29 | 2009-07-29 | 中国科学院长春应用化学研究所 | Cerium lanthanum containing high-strength anti-corrosion die-casting magnesium alloy |
| CN104498796A (en) * | 2014-12-15 | 2015-04-08 | 苏州昊卓新材料有限公司 | Preparation method of Mg alloy |
| CN104388785A (en) * | 2014-12-15 | 2015-03-04 | 苏州昊卓新材料有限公司 | Preparation method of high-strength Mg alloy |
| CN111593244A (en) * | 2020-06-11 | 2020-08-28 | 哈尔滨理工大学 | Novel multi-element corrosion-resistant magnesium alloy and preparation method thereof |
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