US3024108A - Magnesium-base alloy - Google Patents

Magnesium-base alloy Download PDF

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US3024108A
US3024108A US9936A US993660A US3024108A US 3024108 A US3024108 A US 3024108A US 9936 A US9936 A US 9936A US 993660 A US993660 A US 993660A US 3024108 A US3024108 A US 3024108A
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alloy
magnesium
zinc
rare earth
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George S Foerster
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Dow Chemical Co
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • C22C23/04Alloys based on magnesium with zinc or cadmium as the next major constituent

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  • magnesium-base alloy containing zinc and manganese which possesses, in rolled form, good longitudinal and transverse properties in both directions of rolling have heretofore been unsuccessful.
  • Magnesium-zincmanganese alloys have shown poor rollability when the zinc content exceeds about 3 percent.
  • Magnesium-base magnesium-zinc-manganese alloys containing less than about 3 percent of zinc have been satisfactorily hot rolled but at the same time have exhibited poor cold workability, and as the Zinc content is decreased, the alloys in rolled form possess increasingly poorer mechanical properties.
  • the poor properties of conventional magnesium-base magnesium-zinc alloys are believed due to heterogenous deformation which occurs when the alloy is strain hardened as by cold rolling.
  • the invention is based on the discovery that in certain limited ranges of proportions of zinc and manganese, herein shown, the addition of rare earth metal to the magnesium-base alloys containing these metals greatly improves their properties.
  • the addition of a critical amount of rare earth metal the amount by weight being from 0.04 to 0.2 as much rare earth metal as zinc, the balance being magnesium
  • a magnesium-base alloy is obtained which in rolled form exhibits good ductility, toughness, formability, resistance to corrosion, and satisfactory weldability without stress relief and the rolled products have substantially the same high tensile and compressive strengths in both the longitudinal and transverse directions of rolling.
  • the invention then consists of the improved magnesium-base alloy herein described and particularly pointed out in the claims.
  • rare earth metals which ordinarily adversely affect extrudability and room temperature mechanical properties of magnesium-zinc alloys in cast form, is decidedly beneficial to the magnesium-zinc alloys in rolled form.
  • Rare earth metal additions improve hot rollability of the high zinc alloys, apparently by decreasing the concentration of the low-melting magnesium-zinc phase(s) and markedly improve cold workability and resultant properties, apparently through promotion of more homogeneous deformation.
  • the proportion of rare earth metal added is critical and the addition of too much rare earth metal adversely effects transverse strength, formability, and mechanical properties generally.
  • a notable feature of the addition of rare earth metal in the critical concentration range herein disclosed is the effect on the longitudinal and transverse properties of the alloy in rolled form.
  • the transverse properties of the said magnesium-zinc-manganese alloys are quite generally higher than the longitudinal properties.
  • the longitudinal properties of the resulting compositions in rolled form are found respectively to be successively larger While at the same time the transverse properties respectively are found successively to approach a maximum value and then to decrease to values smaller than that of the longitudinal properties.
  • the compositions in the range in which the values of the longitudinal and transverse properties of the alloy approach, become equal, and diverge slightly are those herein disclosed and claimed.
  • Suitable rare earth metal to zinc ratios for the present alloy are those from 0.04 to 0.2 and preferably from 0.06 to 0.12. These ratios are illustrated graphically in the appended drawing.
  • the single figure shows a rectangular coordinate graph in which percent zinc is plotted along the ordinate scale and percent rare earth metal is plotted along the abscissa.
  • the range of proportions of rare earth metal and zinc in the alloy herein disclosed and claimed is graphically represented by the closed area bounded by the lines connecting points A, B, C and D, said alloy including from 0.1 to 2 percent of manganese and the balance magnesium.
  • the preferred range of proportions of rare earth metal and zinc is graphically represented in the same drawing as the closed area bounded by the lines connecting points E, F, G and H.
  • m agnesium-zinc-manganese-rare earth metal alloys in rolled form and 1) having rare earth metal-zinc ratios corresponding to the region generally below the line AD exhibit low mechanical properties (2) having ratios corresponding to the region to the right of the line CD generally exhibit low transverse properties, (3) having ratios corresponding to the region above the line BC exhibit poor rollability and weldability, and (4) having ratios corresponding to the region to the left of the line AB exhibit low longitudinal properties and poor rollability.
  • the rare earth metals suitable for use in preparing the present alloy are: cerium, lanthanum, praseodymium, neodymium or misch metal. Misch metal with from 35 to percent of cerium, the balance being rare earth metal and up to 5 percent of non-rare earth metal, is the preferred rare earth metal ingredient of the alloy. Any of the foregoing rare earth metals may be used alone or in any combination in compounding the alloy.
  • thorium may be substituted for all or a portion of the rare earth metal content of the alloy with no loss in properties. Substitution by thorium, however, is on the basis of an equal atomic percent which corresponds on a weight basis to the use of an amount of thorium equal to about 1.6 times the weight of the rare earth metal replaced.
  • the alloy may be made in the desired proportions according to the invention by melting together the alloying perature at which cracking would result if
  • These rolling slabs were scalped to about 1% inches thickness, heated to about 800 to 850 F. and cross-rolled to a thickness of about 1 inch, then turned 90 degrees and rolled to about A; inch thickness, and annealed for one hour at 700 F.
  • the annealed strips were then cold rolled in multiple passes at l to 2 percent per pass to a thickness of about 0.1 inch, then annealed for one hour at 700 F. and cold rolled an additional 40 percent.
  • the rolled strip was finally heat treated for one hour at 275 F.
  • Table 1 The properties set forth in Table 1 were determined on the so-prepared rolled strip.
  • TS u1timate tensile strength.
  • An amount of zirconium by weight from 0.001 to 0.05 percent of the weight of the alloy is effective. Larger amounts of zirconium are to be avoided as likely to cause precipitation of part of the desired manganese content of the alloy.
  • the cast metal In rolling the cast metal, it is desirable first to scalp the cast metal so as to present a smooth clean surface to the rolls of the rolling mill.
  • the clean rolling stock is heated to a suitable rolling temperature, e.g., about 800 to 850 F.
  • the heated metal is then reduced in thickness by passes between the rolls of the mill, the rolling being stopped 50 to 100 Fahrenheit degrees short of the temthe rolling were continued without reheating the metal.
  • the tern perature to which the metal may decline as it is being rolled before cracking occurs is readily determined by trial and varies with the proportions of the alloying ingredients.
  • the metal In general in hot rolling, the metal should be reheated when its temperature declines to about 600 or 650 F., if rolling is to be continued without cracking.
  • Reductions in thickness of the cast metal of to percent may be made per pass while the metal is at a suitable rolling temperature.
  • the hot rolled metal may be cold rolled (warm rolls, e.g., 180 F.) as much as to 50 percent by making thickness reductions of 1 to 2 percent per pass.
  • cold rolled warm rolls, e.g. 180 F.
  • Examples of the alloy according to the invention were cast in rolling slabs 2 inches by 4 inches by 8 inches.
  • compositions of the alloy containing about 2 percent or more of zinc are desirably worked, as by extruding, before forming into rolled products.
  • Extrudes, of these compositions, in the form of slabs make desirable rolling stock and permit making rolled products by either hot or cold rolling.
  • ingot of the alloy is heated to and extruded at about 600 and 800 F. depending upon the amount of reduction to be made. That is, for high reductions the higher temperatures of the range are used; small reductions may be made at the lower temperatures of the range.
  • the extrude (slab) Prior to rolling, the extrude (slab) is heated to between about 800 and 850 F. for example.
  • the heated extrude is rolled in a number of passes without reheating until the metal requires reheating to avoid cold cracking.
  • Table 2 set forth specific examples of the alloy and their properties in the form of pre-extruded rolled strip.
  • MM misch metal used consisted of 48% Ge, 18% Nd, 5.5% Pr, and 28.5% La which included minor amounts of other rare earth metals.
  • an alloy having the light weight characteristic of magnesium and possessing formability, corrosion resistance and good weldability.
  • a magnesium-base alloy consisting of from 1.25 to 3 percent of zinc, from 0.1 to 2 percent of manganese, and rare earth metal in an amount in percent by Weight which is from 0.04 to 0.2 of the zinc percentage, the balance of the alloy being magnesium.
  • a magnesium-base alloy consisting of from 1.25 to 3 percent of zinc, from 1 to 2 percent of manganese, and
  • a magnesium-base alloy consisting of 1.75 to 2.5 percent of zinc, from 1 to 2 percent of manganese, and rare rare earth metal in an amount in percent by weight which is from 0.04 to 0.2 of the zinc percentage, the balance of the alloy being magnesium.
  • earth metal in an amount in percent by weight which is from 0.04 to 0.2 of the zinc percentage, the balance of the alloy being magnesium.
  • a magnesium-base alloy consisting of 1.75 to 2.5 percent of zinc, from 1 to 2 percent of manganese, and rare earth metal in an amount in percent by weight which is from 0.06 to 0.12 of the zinc percentage, the balance of the alloy being magnesium.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Metal Rolling (AREA)

Description

March 6, 1962 G. s. FOERSTER MAGNESIUM-BASE ALLOY Filed Feb. 19, 1960 I l l I l I I l 0 5 Wely/v 2 Per Gen/Rare Ear/6 Me/a/ INVENTOR. George .5 Foe/1s rer fiGENT States hce 3,024,108 MAGNESIUM-BASE ALLOY George S. Foerster, Midland, Mich, assignor to The Dow Chemical Company, Midland, Micl1., a corporation of Delaware Filed Feb. 19, 1960, Ser. No. 9,936 8 Claims. (Cl. 75l68) This invention relates to magnesium-base alloys. It more particularly concerns an improved magnesium-base alloy containing zinc and manganese.
The beneficial effects obtained upon alloying zinc with magnesium are well known. However, attempts to develop a magnesium-base alloy containing zinc and manganese which possesses, in rolled form, good longitudinal and transverse properties in both directions of rolling have heretofore been unsuccessful. Magnesium-zincmanganese alloys have shown poor rollability when the zinc content exceeds about 3 percent. Magnesium-base magnesium-zinc-manganese alloys containing less than about 3 percent of zinc have been satisfactorily hot rolled but at the same time have exhibited poor cold workability, and as the Zinc content is decreased, the alloys in rolled form possess increasingly poorer mechanical properties. The poor properties of conventional magnesium-base magnesium-zinc alloys are believed due to heterogenous deformation which occurs when the alloy is strain hardened as by cold rolling.
It is the principal object of the invention to provide an improved magnesium-base alloy containing both zinc and manganese which is readily rollable and which in rolled form exhibits desirably high tensile and compressive properties in both the longitudinal and transverse directions of rolling.
Other objects and advantages of the invention will become apparent as the description of the invention proceeds.
The invention is based on the discovery that in certain limited ranges of proportions of zinc and manganese, herein shown, the addition of rare earth metal to the magnesium-base alloys containing these metals greatly improves their properties. In particular it has been found that in magnesium-base alloys containing from 1.25 to 3 percent of zinc (preferably 1.75 to 2.5 percent), and from 0.1 to 2 percent of manganese (preferably 1 to 2 percent), the addition of a critical amount of rare earth metal, the amount by weight being from 0.04 to 0.2 as much rare earth metal as zinc, the balance being magnesium, a magnesium-base alloy is obtained which in rolled form exhibits good ductility, toughness, formability, resistance to corrosion, and satisfactory weldability without stress relief and the rolled products have substantially the same high tensile and compressive strengths in both the longitudinal and transverse directions of rolling. The invention then consists of the improved magnesium-base alloy herein described and particularly pointed out in the claims.
The addition of rare earth metals, which ordinarily adversely affect extrudability and room temperature mechanical properties of magnesium-zinc alloys in cast form, is decidedly beneficial to the magnesium-zinc alloys in rolled form. Rare earth metal additions improve hot rollability of the high zinc alloys, apparently by decreasing the concentration of the low-melting magnesium-zinc phase(s) and markedly improve cold workability and resultant properties, apparently through promotion of more homogeneous deformation. However, the proportion of rare earth metal added is critical and the addition of too much rare earth metal adversely effects transverse strength, formability, and mechanical properties generally.
A notable feature of the addition of rare earth metal in the critical concentration range herein disclosed is the effect on the longitudinal and transverse properties of the alloy in rolled form. The transverse properties of the said magnesium-zinc-manganese alloys are quite generally higher than the longitudinal properties. Yet upon making small, but increasingly larger additions, to a typical example of the said Mg-Zn Mn alloy, of rare earth metal covering the said critical concentration range, the longitudinal properties of the resulting compositions in rolled form are found respectively to be successively larger While at the same time the transverse properties respectively are found successively to approach a maximum value and then to decrease to values smaller than that of the longitudinal properties. The compositions in the range in which the values of the longitudinal and transverse properties of the alloy approach, become equal, and diverge slightly are those herein disclosed and claimed.
It has not been previously shown that upon varying the proportions of a minor component of an alloy the relative magnitudes of the transverse and longitudinal properties are reversed. Nor is it expected in the art that such a change is produced by such small changes in the proportions of a minor component.
As the zinc content of the alloy is increased, the amount of rare earth metal needed to bring about the transposition of the magnitudes of transverse and longitudinal properties of the alloy is proportionately increased. To produce an alloy having the desired combination of properties, it is therefore necessary to add an amount of rare earth metal proportionate to the zinc content. Suitable rare earth metal to zinc ratios for the present alloy are those from 0.04 to 0.2 and preferably from 0.06 to 0.12. These ratios are illustrated graphically in the appended drawing.
In the drawing the single figure shows a rectangular coordinate graph in which percent zinc is plotted along the ordinate scale and percent rare earth metal is plotted along the abscissa. The range of proportions of rare earth metal and zinc in the alloy herein disclosed and claimed is graphically represented by the closed area bounded by the lines connecting points A, B, C and D, said alloy including from 0.1 to 2 percent of manganese and the balance magnesium. The preferred range of proportions of rare earth metal and zinc is graphically represented in the same drawing as the closed area bounded by the lines connecting points E, F, G and H.
Again referring to the drawing, m agnesium-zinc-manganese-rare earth metal alloys in rolled form and 1) having rare earth metal-zinc ratios corresponding to the region generally below the line AD exhibit low mechanical properties (2) having ratios corresponding to the region to the right of the line CD generally exhibit low transverse properties, (3) having ratios corresponding to the region above the line BC exhibit poor rollability and weldability, and (4) having ratios corresponding to the region to the left of the line AB exhibit low longitudinal properties and poor rollability.
The rare earth metals suitable for use in preparing the present alloy are: cerium, lanthanum, praseodymium, neodymium or misch metal. Misch metal with from 35 to percent of cerium, the balance being rare earth metal and up to 5 percent of non-rare earth metal, is the preferred rare earth metal ingredient of the alloy. Any of the foregoing rare earth metals may be used alone or in any combination in compounding the alloy.
If desired, thorium may be substituted for all or a portion of the rare earth metal content of the alloy with no loss in properties. Substitution by thorium, however, is on the basis of an equal atomic percent which corresponds on a weight basis to the use of an amount of thorium equal to about 1.6 times the weight of the rare earth metal replaced.
The alloy may be made in the desired proportions according to the invention by melting together the alloying perature at which cracking would result if These rolling slabs were scalped to about 1% inches thickness, heated to about 800 to 850 F. and cross-rolled to a thickness of about 1 inch, then turned 90 degrees and rolled to about A; inch thickness, and annealed for one hour at 700 F. The annealed strips were then cold rolled in multiple passes at l to 2 percent per pass to a thickness of about 0.1 inch, then annealed for one hour at 700 F. and cold rolled an additional 40 percent. The rolled strip was finally heat treated for one hour at 275 F. The properties set forth in Table 1 were determined on the so-prepared rolled strip.
Table 1 Properties of the alloy in rolled form Percent composition, bal. Mg
Alloy Longitudinal Transverse Zn MM Th Mn Per- TYS CYS TS Per- TYS OYS TS cent E cent E Percent E percent elongation. TYS=tensile yield strength,
at 0.2 percent deviation from the modulus line.
TS=u1timate tensile strength.
All strengths listed in thousands of p.s.i
MM=miseh metal used consisted of 48% Co, 18% Nd, 5.5%
of other rare earth metals.
to the melt, prior to the settling stage, to improve the malleability of the alloy in rolling slab form. An amount of zirconium by weight from 0.001 to 0.05 percent of the weight of the alloy is effective. Larger amounts of zirconium are to be avoided as likely to cause precipitation of part of the desired manganese content of the alloy.
In rolling the cast metal, it is desirable first to scalp the cast metal so as to present a smooth clean surface to the rolls of the rolling mill. The clean rolling stock is heated to a suitable rolling temperature, e.g., about 800 to 850 F. The heated metal is then reduced in thickness by passes between the rolls of the mill, the rolling being stopped 50 to 100 Fahrenheit degrees short of the temthe rolling were continued without reheating the metal. The tern perature to which the metal may decline as it is being rolled before cracking occurs is readily determined by trial and varies with the proportions of the alloying ingredients. In general in hot rolling, the metal should be reheated when its temperature declines to about 600 or 650 F., if rolling is to be continued without cracking.
Reductions in thickness of the cast metal of to percent may be made per pass while the metal is at a suitable rolling temperature.
By annealing the hot rolled cast metal, as for example, by heating for one hour at 700 F., the hot rolled metal may be cold rolled (warm rolls, e.g., 180 F.) as much as to 50 percent by making thickness reductions of 1 to 2 percent per pass. Before proceeding with the final 40 to 50 percent cold reduction by rolling, it is generally desirable to use a preliminary total cold roll of about 15 percent, obtained in multiple passes, followed by annealing at about 700 F. for one hour to improve the subsequent cold rollability and mechanical properties.
Examples of the alloy according to the invention were cast in rolling slabs 2 inches by 4 inches by 8 inches.
Pr, and 28.5% La which included minor amounts Compositions of the alloy containing about 2 percent or more of zinc are desirably worked, as by extruding, before forming into rolled products. Extrudes, of these compositions, in the form of slabs make desirable rolling stock and permit making rolled products by either hot or cold rolling. For example, for making rolled products, ingot of the alloy is heated to and extruded at about 600 and 800 F. depending upon the amount of reduction to be made. That is, for high reductions the higher temperatures of the range are used; small reductions may be made at the lower temperatures of the range. Prior to rolling, the extrude (slab) is heated to between about 800 and 850 F. for example. The heated extrude is rolled in a number of passes without reheating until the metal requires reheating to avoid cold cracking. On annealing the hot rolled product so obtained, for one hour at about 700 F., for example, it may be cold rolled (warm rolls 180 F.) as much as 45 to 50 percent thinner. The data in Table 2 set forth specific examples of the alloy and their properties in the form of pre-extruded rolled strip.
In making this rolled strip, four ingots, each of a different alloy, were cast into three inch diameter billets. These were machined to a diameter of 2 inches, heated to 750 F., then extruded at 700 F. into strip inch by 2 inches for rolling stock. The extruded strip was heated to 800 F cross-rolled in several passes to a thickness of inch, turned and rolled parallel to the direction of extrusion to a thickness of about 0.1 inch, reheated, and rerolled at 850 F. in one pass to a thickness of A inch. The rolled strip was annealed for one hour at 700 F. The annealed strip so obtained was cold rolled about 1 to 2 percent thinner per pass, the total cold reduction being about 40 percent. The cold rolled strip was heat treated one hour at 275 F., then the properties set forth in Table 2 were determined.
Table 2 Properties of preextruded rolled alloy Percent composition, balance Mg Alloy No. Longitudinal Transverse Zn MM Mn Perlgcnt TYS CYS TS Pelfient TYS CYS TS Percent E =percent elongation.
TS tensile strength. All strengths listed in thousands of p.s.i.
MM =misch metal used consisted of 48% Ge, 18% Nd, 5.5% Pr, and 28.5% La which included minor amounts of other rare earth metals.
Among the advantages of the invention are that an alloy is provided having the light weight characteristic of magnesium and possessing formability, corrosion resistance and good weldability.
This is a continuation-in-part of my copending application Serial No. 746,411, filed July 3, 1958, now abandoned.
I claim:
1. A magnesium-base alloy consisting of from 1.25 to 3 percent of zinc, from 0.1 to 2 percent of manganese, and rare earth metal in an amount in percent by Weight which is from 0.04 to 0.2 of the zinc percentage, the balance of the alloy being magnesium.
2. The alloy as in claim 1 in which the rare earth metal is misch metal.
3. The alloy as in claim 1 in which up to 100 percent of the rare earth metal content is rep-laced by thorium, the amount of thorium by weight being about 1.6 times the weight of rare earth metal replaced.
4. A magnesium-base alloy consisting of from 1.25 to 3 percent of zinc, from 1 to 2 percent of manganese, and
5. A magnesium-base alloy consisting of 1.75 to 2.5 percent of zinc, from 1 to 2 percent of manganese, and rare rare earth metal in an amount in percent by weight which is from 0.04 to 0.2 of the zinc percentage, the balance of the alloy being magnesium.
earth metal in an amount in percent by weight which is from 0.04 to 0.2 of the zinc percentage, the balance of the alloy being magnesium.
6. A magnesium-base alloy consisting of 1.75 to 2.5 percent of zinc, from 1 to 2 percent of manganese, and rare earth metal in an amount in percent by weight which is from 0.06 to 0.12 of the zinc percentage, the balance of the alloy being magnesium.
7. The alloy as in claim 6 in which up to percent of the rare earth metal content is replaced by thorium, the amount of thorium by weight being about 1.6 times the weight of rare earth metal replaced.
8. A magnesium-base alloy containing about 2 percent of zinc, 0.15 percent of misch metal, and about 1.5 percent of manganese, the balance being magnesium.
References Cited in the file of this patent UNITED STATES PATENTS

Claims (1)

1. A MAGNESIUM-BASE ALLOY CONSISTING OF FROM 1.25 TO 3 PERCENT OF ZINC, FROM 0.1 TO 2 PERCENT OF MANGANESE, AND RARE EARTH METAL IN AN AMOUNT IN PERCENT BY WEIGHT WHICH IS FROM 0.04 TO 0.2 OF THE ZINC PERCENTAGE, THE BALANCE OF THE ALLOY BEING MAGNESIUM.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5167917A (en) * 1990-09-21 1992-12-01 Sugitani Kinzoku Kogyo Kabushiki Kaisha Magnesium alloy for use in casting and having a narrower solidification temperature range
WO2000063452A1 (en) * 1999-04-03 2000-10-26 Volkswagen Aktiengesellschaft Highly ductile magnesium alloys, method for producing them and use of the same
US11496789B2 (en) 2004-04-07 2022-11-08 Tivo Corporation Method and system for associating video assets from multiple sources with customized metadata

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2788272A (en) * 1954-04-26 1957-04-09 Magnesium Elektron Ltd Magnesium base alloys
US2829973A (en) * 1953-04-09 1958-04-08 Magnesium Elektron Ltd Magnesium base alloys

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2829973A (en) * 1953-04-09 1958-04-08 Magnesium Elektron Ltd Magnesium base alloys
US2788272A (en) * 1954-04-26 1957-04-09 Magnesium Elektron Ltd Magnesium base alloys

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5167917A (en) * 1990-09-21 1992-12-01 Sugitani Kinzoku Kogyo Kabushiki Kaisha Magnesium alloy for use in casting and having a narrower solidification temperature range
WO2000063452A1 (en) * 1999-04-03 2000-10-26 Volkswagen Aktiengesellschaft Highly ductile magnesium alloys, method for producing them and use of the same
US11496789B2 (en) 2004-04-07 2022-11-08 Tivo Corporation Method and system for associating video assets from multiple sources with customized metadata

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