EP3097217B1 - Alliages de magnésium résistants au fluage et à haute performance - Google Patents
Alliages de magnésium résistants au fluage et à haute performance Download PDFInfo
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- EP3097217B1 EP3097217B1 EP14879634.5A EP14879634A EP3097217B1 EP 3097217 B1 EP3097217 B1 EP 3097217B1 EP 14879634 A EP14879634 A EP 14879634A EP 3097217 B1 EP3097217 B1 EP 3097217B1
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 162
- 239000000956 alloy Substances 0.000 claims description 162
- 229910052726 zirconium Inorganic materials 0.000 claims description 34
- 239000011575 calcium Substances 0.000 claims description 33
- 229910052727 yttrium Inorganic materials 0.000 claims description 32
- 229910052779 Neodymium Inorganic materials 0.000 claims description 31
- 229910052791 calcium Inorganic materials 0.000 claims description 27
- 239000011777 magnesium Substances 0.000 claims description 25
- 238000005266 casting Methods 0.000 claims description 23
- 229910052749 magnesium Inorganic materials 0.000 claims description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
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- 238000004512 die casting Methods 0.000 claims description 16
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- 230000032683 aging Effects 0.000 claims description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 230000001747 exhibiting effect Effects 0.000 claims description 9
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000005242 forging Methods 0.000 claims description 8
- 238000005495 investment casting Methods 0.000 claims description 8
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- 230000000052 comparative effect Effects 0.000 description 26
- 230000007797 corrosion Effects 0.000 description 22
- 238000005260 corrosion Methods 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 238000012360 testing method Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 9
- 230000035882 stress Effects 0.000 description 9
- 229910052761 rare earth metal Inorganic materials 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052688 Gadolinium Inorganic materials 0.000 description 5
- 238000005275 alloying Methods 0.000 description 5
- 229910000765 intermetallic Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
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- 229910052684 Cerium Inorganic materials 0.000 description 3
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- 238000007906 compression Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
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- 229910052719 titanium Inorganic materials 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910000583 Nd alloy Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910000946 Y alloy Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
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Images
Classifications
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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
- C22C23/06—Alloys based on magnesium with a rare earth metal 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
- 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
Definitions
- the present invention relates to creep-resistant magnesium-based alloys for applications at high temperatures which exhibit good castability, particularly suitable for high-pressure die casting, but advantageously used also in a processes comprising sand casting, investment casting, permanent mold casting, as well as direct chill casting or twin-roll casting.
- magnesium industry is experiencing dramatic growth, in part due to the demands of the transportation industry to improve fuel economy and emissions.
- a great progress in weight reduction has been made in consumer applications of magnesium alloys such as power hand tools, lawn and garden equipment, electronic and optical equipment, etc.
- new advanced alloys are required.
- High pressure die casting is the dominant form of casting due to its productivity and suitability for mass production.
- most common and new magnesium alloys that are being used for HPDC process are Al containing alloys. However, these alloys cannot serve at temperatures higher than 150-170°C under high stresses of 60-100 MPa.
- US 6,193,817 describes magnesium-based alloys containing 0.1-2.0 wt% Zn, 2.1-5.0 wt% RE elements (Ce based mishmetal) up to 0.4 wt% of a combination of at least two elements chosen from the group consisting of Zr, Hf and Ti, and optionally up to 0.5 wt% Mn and up to 0.5 wt% Ca.
- EP 1866452 discloses magnesium based alloys containing 1.5-4.0% RE elements, 0.3-0.8% Zn, 0.02-0.1% Al, 4-25 ppm Be and optionally up to 0.2% Zr, 0.3% Mn, 0.5%Y, and 0.1% Ca.
- WO 2009/086585 relates to magnesium based alloys containing 2-5% RE elements (primarily La and Ce, wherein La content is higher than Ce content) and 0.2-0.8% Zn.
- the alloys contain optionally Y, Gd, Zr, Mn, Ca, and Be. These alloys are also designated for high-pressure die casting but exhibit very low values of elongation, TYS, and UTS.
- SU 1,360,223 discloses Mg-based alloys containing 0.1-2.5% Zn, 0.3-1.0% Zr, 0.8-4.5% Nd, 0.5-5.0% Y, 0.8-4.5% Gd, and 0.01-0.05% Mn.
- the alloys are intended for sand casting process and exhibit optimal properties after full T6 treatment.
- US 4,116,731 describes heat treated and aged magnesium based alloys containing 0.8-6.0 wt% Y, 0.5-4.0 wt% Nd, 0.1-2.2 wt% Zn, 0.3-1.1 wt% Zr, up to 0.05% Cu, and up to 0.2% Mn. Due to relatively wide concentration ranges claimed by the above patent, the alloys exhibit very diverse properties; in addition, they are designated only for sand casting process
- EP 1329530 discloses magnesium-based casting alloys containing 0.2-0.8 wt% Zn, 0.2-0.8 wt% Zr, 2.7-3.3 wt% Nd, 0.0-2.6 wt% Y, and 0.03-0.25% Ca.
- the alloys exhibit high strength and high creep resistance after gravity casting and after full T6 heat treatment, as well as after extrusion and forging. However, the HPDC is not addressed.
- CN 1752251 describes magnesium alloys containing 0.35-0.8 wt% Zr, 2.5-3.6 wt% Nd, 0.0-0.4 wt% Zn, 0.0-0.5 wt% Ca, and 0.0-0.02 wt% impurities.
- the alloys are prepared by a two-stage process including a step of preparing intermediate master alloys Mg-Nd, Mg-Ca, and Mg-Zr, and a step of alloying said master alloys by Nd, Ca, and Zr.
- the complexity of the technology significantly increases the cost of the final alloy product.
- EP 1641954 describes creep resistant alloys containing 2.0-4.5% Nd, 0.2-1.0% Zr, 0.2%-7.0% HRE (Heavy Rare Earth Elements of atomic numbers 62-71), optionally up to 0.4% of other RE elements, up to 0.5% Y, up to 1.3% Zn, up to 0.5% Mn, and up to 0.4% Hf or Ti.
- the alloys are mainly designated for sand casting and, in addition, they are expensive due to the use of heavy rare earth elements, such as Gd in amounts of 1.0-1.6%.
- US 2009/0081313 relates to biodegradable magnesium alloys containing 1.5-5.0% Nd, 0.1-4.0% Y, 0.1-2.0% Ca, and 0.1-1.0 % Zr.
- the alloys are designated for manufacturing medical implants by extrusion.
- the high Ca content results in increased porosity, embrittlement and hot cracking in HPDC processes.
- WO 2010/038016 relates to magnesium alloys containing 2.0-4.0% Y, 0.5-4.0% Nd, 0.05-1.0% Zr, 0.0-5.5% Gd, 0.0-5.5% Dy, 0-5.5% Er, 0.0-0.2% Yb, and 0.0-0.04% Sm.
- the total content of Gd, Dy and Er is in the range of 0.3-12 wt.%.
- the alloy is dedicated for sand casting, and it can also be used as a wrought alloy. The alloy is unsuitable for HPDC process. Furthermore, the high content of heavy rare earth elements leads to high cost of these alloys.
- WO 2011/117628 describes magnesium alloys containing 0.0-10.0% Y, 0.0-5.0% Nd, 0.00-1.2% Zr, 0.0-0.3% Gd, and 0.0-0.2% Sm, wherein the total content of Ho, Lu, Tm and Tb is in the range of 0.5-5.5 %.
- the alloy is dedicated for manufacturing medical implants. Due to very wide concentration ranges of Y, Nd, and heavy rare earth elements Ho, Lu and Tm, the alloys exhibit very diverse properties. The alloys are not suitable for HPDC process and are expensive.
- Aghion et al. ( Aghion E. et al.: J. Mater. Sci. 2008, vol. 43, pp. 4870-4975 ) studied effects of Y in the range of 0.48-2.45 wt.% on the strength and corrosion behavior of Mg-Nd alloys and found that Y in this range improved said parameters but not affected castability.
- the invention provides a lightweight alloy for high-pressure die casting (HPDC) process, consisting of at least 94.8 wt% magnesium, 2.5 to 4.6 wt% neodymium, 0.05 to 0.40 wt% yttrium, 0.03 to 0.65 wt.% zirconium, optionally up to 0.02% Ca, and incidental impurities.
- invention further
- the alloy according to the invention comprises essentially no heavy rare earth (HRE) elements with the atomic number from 61 to 70.
- the alloy according to the invention comprises essentially no cerium, lanthanum, and praseodymium.
- the alloy according to the invention comprising essentially no zinc.
- the alloy according to the invention contains Nd and Y in an amount higher than 4.3 wt.%.
- Said incidental impurities usually comprise Si, Fe, Cu, and Ni in an amount of up to 0.02 wt%.
- the lightweight alloy according to the invention is suitable for prolonged operations at high temperatures of up to 200°C.
- the alloys for HPDC and other applications according to the invention exhibit superior casting properties, high strength, high creep resistance, high corrosion resistance, and the articles manufactured from the alloys show superior performance at high temperatures.
- the alloy according to the invention is usable for high pressure dies casting (HPDC), but it may be also used for a process selected from the group consisting of sand casting, investment casting, and permanent mold casting.
- the alloy according to the invention are also usable for a process comprising either twin roll casting with subsequent rolling, or direct chill casting with subsequent forging, extrusion or rolling.
- the lightweight alloy is advantageously used for HPDC.
- the alloy suitable for HPDC contains 2.8 to 4.3 wt% Nd, 0.06 to 0.25 wt% Y, 0.05 to 0.4 wt% Zr, and 0.0 to 0.02 wt% Ca.
- the alloy used for HPDC exhibits a tensile yield strength (TYS) at 200°C of at least 153 MPa, a compression yield strength (CYS) at 200°C of at least 152 MPa, a minimum creep rate of not more than 1.5x10 -10 /s at 200°C under stress of 100 MPa, and a corrosion rate of not more than 2.65 mpy.
- the alloy according to the invention preferably exhibits a castability of at least 96%.
- the invention relates to an article cast of the alloy containing 2.8 to 4.3 wt% Nd, 0.06 to 0.25 wt% Y, 0.05 to 0.4 wt% Zr, and 0.0 to 0.02 wt% Ca, the article exhibiting a superior combination of strength and ductility after T5 treatment which includes direct aging at 150-250°C for 1-10 h.
- said article exhibits a superior combination of strength and ductility after T5 treatment which includes direct aging at 175-225°C for 1-6 h.
- the alloy according to the invention is also suitable for sand casting, investment casting, permanent mold casting, and low pressure modifications thereof; in one embodiment, the alloy contains 2.7 to 3.4 wt% Nd, 0.15 to 0.40 wt% Y, 0.3 to 0.6 wt% Zr, and 0.0 to 0.02 wt% Ca.
- the invention relates to an article cast of said alloy, the article exhibiting a superior combination of performance properties after full T6 heat treatment comprising solid solution heat treatment at 520-560°C for 1 to 16 hrs, followed by cooling in a quenching medium and by subsequent aging at 200-270°C for 1 to 16 h.
- said article exhibits a superior combination of performance properties after full T6 heat treatment comprising solid solution heat treatment at 535-545°C for 3 to 5 hrs, followed by cooling in a quenching medium and by subsequent aging at 225-250°C for 3 to 6 h.
- the alloy according to the invention may be advantageously used for forging, extrusion, and rolling; in one embodiment, the alloy contains 2.8 to 3.8 wt% Nd, 0.20 to 0.40 wt% Y, 0.35 to 0.60 wt% Zr, and 0.0-0.02 wt% Ca.
- the invention relates to an article cast in said alloy, the article exhibiting a superior combination of performance properties after T5 heat treatment comprising aging at 200-250°C for 1 to 16 h.
- the present invention provides creep-resistant magnesium-based alloys designated for applications at temperatures as high as 200-250°C, which exhibit good castability and low susceptibility to hot tearing, which are strong and are corrosion resistant, and have excellent ductility.
- the invention provides a process for manufacturing a lightweight alloy for prolonged operation at high temperatures of up to 200°C, comprising steps of i) alloying magnesium with neodymium and zirconium at 765-785°C under intensive stirring; ii) settling the melt for 20-40 minutes to allow iron to settle; iii) adding yttrium, while avoiding intensive stirring to prevent the formation of Y-Fe intermetallic compounds; iv) optionally adding calcium prior to settling; v) settling the molten alloy for 30-60 minutes; and v) casting into desired form; wherein the steps are performed under a protective atmosphere of CO 2 + 0.5% HFC134a till solidification; the amount of magnesium in the alloy being at least 94.8 wt%, of neodymium from 2.5 to 4.6 wt%, of yttrium from 0.05 to 0.40 wt%, of zirconium from 0.03 to 0.65 wt.%, and of calcium 0.00 to 0.02%.
- the alloys according to the invention contain more than 94 wt% magnesium, from 2.5 to 4.6 wt% neodymium, from 0.05 to 0.40 wt% yttrium, from 0.03 to 0.65 wt% zirconium, optionally calcium up to 0.02 wt%, and incidental impurities.
- the alloys usually contain up to 0.007 wt% iron, up to 0.001 wt% nickel, up to 0.003 wt% copper, up to 0.015 wt% silicon, and eventually other incidental impurities.
- the alloys of the invention exhibit an excellent combination of high tensile and compressive yield strength, and high ductility.
- the great advantage of new alloys is related to their high creep rupture stress, creep strength and low minimum creep rate, as well as low corrosion rate measured under GM 9540 cyclic corrosion test.
- the alloys of the present invention combine superior performance properties, good castability, and relatively moderate cost.
- Articles according to the invention are preferably subjected to T5 or T6 heat treatments depending on preceding casting process and plastic forming operations.
- magnesium based alloys comprising neodymium, zirconium, yttrium, and optionally calcium, impart to the alloys superior properties, particularly for high pressure die casting. These properties include excellent combination of high tensile and compressive properties with high ductility, outstanding corrosion resistance, and creep properties allowing to achieve service temperatures up to 250°C.
- the above combination of properties can be realized at high-pressure die casting, at sand casting, as well as at direct-chill casting or twin roll casting followed by plastic forming processes such as forging, extrusion and rolling.
- Magnesium-based alloys of the instant invention contain 2.5 to 4.6 wt% neodymium. It was found by the inventors that if the Nd content is less than 2.5 wt%, the alloys have insufficient strength at ambient and elevated, and their creep resistance is not sufficient for serving at 250-300°C temperatures; Nd content higher than 4.6 wt% results in low ductility due to excessive amount of intermetallic compounds which are sources of cracks initiation and propagation.
- An alloy according to the present invention contains 0.05 to 0.40 wt % yttrium. It was found that yttrium content less than 0.05 wt% makes the alloy prone to oxidation and results in increased susceptibility to burning during molten metal handling at 700-780°C.
- Zirconium is mainly used to remove iron in the case of high pressure die casting process. In the case of gravity casting (sand casting, investment casting, and permanent mold casting) it also serves as a grain refiner. It has been found that 0.03 wt.% of Zr is sufficient to ensure low iron content in the alloy, while at least 0.3 wt% of zirconium is required for grain refining. The upper limit for the zirconium content is about 0.65 wt% due to its limited solubility in Mg-Nd-Y alloys.
- the alloys of the present invention contain substantially no zinc; it would deteriorate creep resistance and corrosion performance due to the formation of Zn-Y-Nd-Zr coarse intermetallics. Furthermore, the alloys of the instant invention do not contain rare earth elements with low solubility in solid magnesium such as Ce and La. The presence of those elements results in deterioration of mechanical properties, and particularly of ductility, due to the formation of coarse intermetallic compounds. An admixture of calcium in the alloys of the invention of up to 0.02% may improve oxidation resistance.
- the Ca content is limited to 0.02% because higher Ca content leads to increased micro-porosity and embrittlement of the alloys.
- the alloys of instant invention also do not contain heavy rare earth elements with atomic number higher than 60, they would increase the alloy price without remarkably improving the alloy performance.
- the magnesium alloys according to the invention were examined along with comparative alloys. The results show that the new alloys exhibit better oxidation resistance and fluidity, as well as lower susceptibility to die sticking than comparative alloys. Neither burning nor oxidation was observed on the surface of ingots made of alloys according to this invention. In contrast, the preparation of comparative alloys was sometimes accompanied by significant oxidation and undesirable losses of alloying elements.
- the alloys according to the invention reached between 96 and 100% on the relative castability scale, when evaluating oxidation resistance, fluidity, and die sticking of the alloy on casting (see Examples below), in comparison with 73 and 83% of comparative alloys whose composition differed more or less from the composition of the invention.
- the alloys according to the invention are very suitable for HPDC; it was found that they develop excellent properties after direct T5 aging at 150-250°C for 1-10 h, preferably at 175-225°C for 1-6 h. As for wrought alloys, it was found that the alloys according to the invention achieve very good properties after direct aging at 200-250°C for 1-16 h.
- the alloys according to the invention also provide excellent mechanical properties on sand casting after full T6 heat treatment; particularly, good results were obtained when the heat treatment comprised solid solution heat treatment at 520-560°C for 1 to 16 hrs, followed by cooling in a quenching media and by subsequent aging at 200-270°C for 1 to 16 h, preferably after solid solution treatment at 535-545°C for 3 to 5 hrs, followed by cooling in a quenching media and by subsequent aging at 225-250°C for 3 to 6 h.
- the alloys of the present invention were prepared in 150 l crucible made of low carbon steel.
- the mixture of CO 2 + 0.5% HFC134a was used as a protective atmosphere.
- the raw materials used were as follows:
- the alloys of the present invention have been prepared using pure Nd and pure Ca that significantly simplifies the process, reduces its duration and markedly lowers the alloy cost.
- Neodymium and zirconium were added typically at 770-780°C with intensive stirring of the melt. After addition of zirconium, the melt was held for 20-40 minutes to allow iron to settle. Yttrium was added after the iron settling, without intensive stirring, to prevent the formation of Y-Fe intermetallic compounds, which leads to excessive loss of yttrium.
- a strict temperature control was provided during the alloying in order to insure that the melt temperature will not increase above 785°C, thus preventing an excessive contamination by iron from the crucible walls, and to ensure that the temperature will not decrease below 765°C, thus preventing an excessive loss of zirconium. Calcium was added prior to settling. After obtaining the required compositions, the alloys were held for 30-60 minutes for homogenization, and settling of iron and non-metallic inclusions, and then they were cast into the 15 kg ingots. The casting was performed with gas protection of the molten metal during solidification in the molds by CO 2 + 0.5% HFC134a mixture. The die casting trials were carried out using an IDRA OL-320 cold chamber die casting machine with a 345 ton locking force.
- the castability was evaluated based on observed fluidity, oxidation resistance and die sticking or soldering.
- the casting temperature was 710°C.
- Each of the properties (fluidity, oxidation resistance, die sticking) was evaluated by assigning from 0 to 10 points on a relative scale, the higher the better (see Table 2).
- the sum of the points for an alloy divided by 30 and multiplied by 100 provides "castability coefficient", a relative assessment having a value between 0 and 100%, which characterizes the overall suitability of an alloy for die casting.
- the alloys according to the invention had castability coefficient between 96 and 100%, while comparative examples, even if differing only slightly from the new alloys of the invention, had castability coefficient between 73 and 83%.
- Creep rupture stress is the stress resulting in specimens rupture at a selected testing temperature for a certain time, usually 100 h.
- minimum creep rate at a steady state (MCR) was used to evaluate creep performance.
- Corrosion behavior was evaluated as per GM9540 cyclic test for 40 days ( Fig.9 ).
- the test procedure includes three main stages, combining both wet-dry transition and short sprays of light electrolyte solution. In this test a gradual increase of temperature is applied during the cycle.
- the die cast plates with dimensions of 140x100x3 mm were used. The plates were degreased in acetone and weighed prior to the test. Five replicates of each alloy were tested. At the end of the test the corrosion products were stripped in a chromic acid solution (180 g CrO 3 per liter solution) at 80°C about three minutes and the weight loss was determined. The weight loss was used to determine the average corrosion rate in mpy (milli-inch per year).
- Tables 1 to 4 illustrate chemical compositions, castability parameters, and properties of alloys for HPDC according to the invention and of comparative alloys.
- the new alloys of the invention demonstrate significantly better die castability evaluated by tendency to oxidation, fluidity and susceptibility to die sticking (Table 2), reflected by a castability coefficient of minimally 96%.
- Table 3 the new alloys are superior in tensile yield strength (TYS) and compressive yield strength(CYS) over the comparative alloys at both ambient and elevated temperatures.
- TYS values of the new alloys according to the invention at 200°C are 150 MPa or more, usually 153 MPa or more, whereas the comparative alloys have lower values.
- new alloys exhibit much better combination of strength and elongation than comparative alloys. Corrosion resistance of the new alloys determined under GM 9540 cyclic test conditions ( Fig. 9 ) also surpasses that property of the comparative alloys; the corrosion rate of the new alloys is less than 2.9 mpy, usually less than 2.7 mpy, such as 2.65 mpy or less (Tab. 3). In addition, new alloys also exhibit excellent creep resistance in the temperature range 200-250°C, outperforming the comparative examples (Table 4). The creep rupture strength of the new alloys for HPDC is typically about 200 MPa or more at 200°C, and about 105 MPa or more at 250°C.
- the MCR values of the new alloys are 1.5x10 -10 /s or less at 200°C and 100 MPa, usually 1.0x10 -10 /s or less; the comparative alloys have higher values even if differing only slightly in composition from the new alloys (Tab. 4).
- Tables 5-6 demonstrate chemical compositions and properties of alloys for sand casting according to the invention and of comparative alloys subjected to full T6 heat treatment.
- the alloys of the instant invention exhibit superior combination of TYS and Elongation in comparison with comparative examples.
- the compressive strength of new alloys is also higher both at ambient and elevated temperatures.
- a great advantage of the alloys of this invention is that they combine excellent mechanical properties with outstanding corrosion resistance which outperforms corrosion resistance of comparative alloys.
- Tables 7-8 illustrate chemical composition and mechanical properties of forged alloys of instant invention.
- the alloys of present inventions and comparative alloys were direct chilled cast, homogenized, forged and T5 heat treated.
- the forged alloys of the present invention exhibit higher TYS and UTS values than comparative alloys at both ambient temperature and 200°C. It is important that they the alloys according to the invention have also superior elongation and significantly higher compressive yield strength.
Claims (14)
- Alliage léger pour applications haute température, constitué dei) au moins 94,8 % en poids de magnésium,ii) de 2,5 à 4,6 % en poids de néodyme,iii) de 0,05 à 0,40 % en poids d'yttrium,iv) de 0,03 à 0,65 % en poids de zirconium,v) facultativement jusqu'à 0,02 % en poids de calcium, etvi) des impuretés accidentelles.
- Procédé de fabrication de lingots en alliage de magnésium comprenant de 2,5 à 4,6 % en poids de Nd, de 0,05 à 0,40 % en poids d'Y, de 0,03 à 0,65 % en poids de Zr, et facultativement de 0,0 à 0,02 % en poids de Ca et le reste étant du magnésium et des impuretés inévitables, dans lequel le Nd est ajouté sous agitation intense à 770 à 780 °C tandis que l'Y est ajouté après sédimentation à ces températures sous agitation douce.
- Alliage selon la revendication 1, utilisable pour un procédé choisi dans le groupe constitué de la coulée sous haute pression (HPDC), de la coulée en sable, du moulage en cire perdue et de la coulée en moule permanent.
- Alliage selon la revendication 1, utilisable pour un procédé comprenant soit une coulée entre cylindres avec laminage ultérieur, soit une coulée semi-continue avec forgeage, extrusion ou laminage ultérieur(e).
- Alliage léger pour applications haute température selon la revendication 4 utilisable pour HPDC.
- Procédé de coulée sous haute pression d'un alliage de magnésium comprenant de 2,5 à 4,6 % en poids de Nd, de 0,05 à 0,40 % en poids d'Y, de 0,03 à 0,65 % en poids de Zr, et facultativement de 0,0 à 0,02 % en poids de Ca et le reste étant du magnésium et des impuretés inévitables, dans lequel un alliage présente une coulabilité d'au moins 96 %, lorsqu'elle est mesurée en unités relatives caractérisant la résistance à l'oxydation, la fluidité, et la tendance au collage.
- Alliage selon la revendication 5, qui contient de 2,8 à 4,3 % en poids de Nd, de 0,06 à 0,25 % en poids d'Y, de 0,05 à 0,4 % en poids de Zr, et de 0,0 à 0,02 % en poids de Ca.
- Article coulé d'un alliage selon la revendication 5, présentant une combinaison supérieure de résistance et de ductilité après un traitement T5 qui inclut un vieillissement direct à 150 à 250 °C pendant 1 à 10 h.
- Article selon la revendication 8, présentant une combinaison supérieure de résistance et de ductilité après un traitement T5 qui inclut un vieillissement direct à 175 à 225 °C pendant 1 à 6 h.
- Alliage selon la revendication 3 adapté à une coulée en sable, un moulage en cire perdue, une coulée en moule permanent, et des modifications de ceux-ci à basse pression, contenant de 2,7 à 3,4 % en poids de Nd, de 0,15 à 0,40 % en poids d'Y, de 0,3 à 0,6 % en poids de Zr, et de 0,0 à 0,02 % en poids de Ca.
- Article coulé d'un alliage selon la revendication 10, présentant une combinaison supérieure de propriétés de performance après un traitement thermique T6 complet comprenant un traitement thermique en solution solide à 520 à 560 °C pendant 1 à 16 h suivi d'un refroidissement dans un milieu de trempe et d'un vieillissement ultérieur à 200 à 270 °C pendant 1 à 16 h.
- Article selon la revendication 11, présentant une combinaison supérieure de propriétés de performance après un traitement thermique T6 complet comprenant un traitement thermique en solution solide à 535 à 545 °C pendant 3 à 5 h, suivi d'un refroidissement dans un milieu de trempe et d'un vieillissement ultérieur à 225 à 250 °C pendant 3 à 6 h.
- Alliage selon la revendication 4, adapté au forgeage, à l'extrusion et au laminage, qui contient de 2,8 à 3,8 % en poids de Nd, de 0,20 à 0,40 % en poids d'Y, de 0,35 à 0,60 % en poids de Zr, et de 0,0 à 0,02 % en poids de Ca.
- Article coulé d'un alliage selon la revendication 13, présentant une combinaison supérieure de propriétés de performance après un traitement thermique T5 comprenant un vieillissement à 200 à 250 °C pendant 1 à 16 h.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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IL230631A IL230631A (en) | 2014-01-23 | 2014-01-23 | High performance creep resistant magnesium alloys |
PCT/IL2014/050649 WO2015111035A1 (fr) | 2014-01-23 | 2014-07-17 | Alliages de magnésium résistants au fluage et à haute performance |
Publications (3)
Publication Number | Publication Date |
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EP3097217A1 EP3097217A1 (fr) | 2016-11-30 |
EP3097217A4 EP3097217A4 (fr) | 2017-09-20 |
EP3097217B1 true EP3097217B1 (fr) | 2018-12-19 |
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EP14879634.5A Active EP3097217B1 (fr) | 2014-01-23 | 2014-07-17 | Alliages de magnésium résistants au fluage et à haute performance |
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US (1) | US20160304996A1 (fr) |
EP (1) | EP3097217B1 (fr) |
JP (1) | JP6590814B2 (fr) |
CN (1) | CN105934529B (fr) |
IL (1) | IL230631A (fr) |
WO (1) | WO2015111035A1 (fr) |
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CN106756371B (zh) * | 2017-02-15 | 2018-10-23 | 苏州慧金新材料科技有限公司 | 一种高耐蚀镁合金 |
CN109022984B (zh) * | 2018-09-25 | 2021-01-19 | 中国科学院海洋研究所 | 一种含Zn元素的耐腐蚀稀土镁合金及其制备方法 |
CN113308632A (zh) * | 2021-05-27 | 2021-08-27 | 长春理工大学 | 一种高温抗蠕变压铸镁合金及其制备方法 |
CN115637363B (zh) * | 2022-11-04 | 2023-07-21 | 南昌航空大学 | 一种高性能耐热耐蚀镁合金铸件及其制备方法 |
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AU544762B2 (en) * | 1981-03-25 | 1985-06-13 | Luxfer Group Limited | Magnesium base rare earth alloy |
GB9502238D0 (en) * | 1995-02-06 | 1995-03-29 | Alcan Int Ltd | Magnesium alloys |
JP2003055719A (ja) * | 2001-08-13 | 2003-02-26 | Honda Motor Co Ltd | マグネシウムまたはマグネシウム合金の鋳造方法 |
IL147561A (en) * | 2002-01-10 | 2005-03-20 | Dead Sea Magnesium Ltd | High temperature resistant magnesium alloys |
TW200641150A (en) * | 2005-04-04 | 2006-12-01 | Cast Centre Pty Ltd | Magnesium alloy |
CN1814837A (zh) * | 2006-02-23 | 2006-08-09 | 上海交通大学 | 高强度耐热镁合金及其制备方法 |
MX2008013652A (es) * | 2006-04-28 | 2009-01-29 | Biomagnesium Systems Ltd | Aleaciones de magnesio biodegradables y usos de las mismas. |
IL177568A (en) * | 2006-08-17 | 2011-02-28 | Dead Sea Magnesium Ltd | Creep resistant magnesium alloy with improved ductility and fracture toughness for gravity casting applications |
CN100469930C (zh) * | 2007-07-04 | 2009-03-18 | 北京有色金属研究总院 | 抗蠕变镁合金及其制备方法 |
CN101255517A (zh) * | 2007-11-28 | 2008-09-03 | 兰州理工大学 | 一种镁合金 |
GB0817893D0 (en) * | 2008-09-30 | 2008-11-05 | Magnesium Elektron Ltd | Magnesium alloys containing rare earths |
KR101646267B1 (ko) * | 2010-05-28 | 2016-08-05 | 현대자동차주식회사 | 내크리프 특성이 우수한 중력주조용 내열 마그네슘 합금 |
EP2481825B1 (fr) * | 2011-02-01 | 2013-05-08 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Alliage de magnésium contenant des métaux de terres rares |
-
2014
- 2014-01-23 IL IL230631A patent/IL230631A/en active IP Right Grant
- 2014-07-17 EP EP14879634.5A patent/EP3097217B1/fr active Active
- 2014-07-17 CN CN201480073926.1A patent/CN105934529B/zh active Active
- 2014-07-17 JP JP2016548228A patent/JP6590814B2/ja active Active
- 2014-07-17 US US15/102,019 patent/US20160304996A1/en not_active Abandoned
- 2014-07-17 WO PCT/IL2014/050649 patent/WO2015111035A1/fr active Application Filing
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WO2015111035A1 (fr) | 2015-07-30 |
CN105934529B (zh) | 2017-09-05 |
JP6590814B2 (ja) | 2019-10-16 |
IL230631A (en) | 2016-07-31 |
EP3097217A1 (fr) | 2016-11-30 |
CN105934529A (zh) | 2016-09-07 |
EP3097217A4 (fr) | 2017-09-20 |
JP2017507245A (ja) | 2017-03-16 |
IL230631A0 (en) | 2014-04-30 |
US20160304996A1 (en) | 2016-10-20 |
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