CA1151908A - Oxidation resistant magnesium alloy - Google Patents
Oxidation resistant magnesium alloyInfo
- Publication number
- CA1151908A CA1151908A CA000348593A CA348593A CA1151908A CA 1151908 A CA1151908 A CA 1151908A CA 000348593 A CA000348593 A CA 000348593A CA 348593 A CA348593 A CA 348593A CA 1151908 A CA1151908 A CA 1151908A
- Authority
- CA
- Canada
- Prior art keywords
- percent
- weight
- magnesium alloy
- alloy
- beryllium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 59
- 230000003647 oxidation Effects 0.000 title claims description 20
- 238000007254 oxidation reaction Methods 0.000 title claims description 20
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 89
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011701 zinc Substances 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 19
- 230000004907 flux Effects 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 69
- 239000000956 alloy Substances 0.000 claims description 69
- 229910052748 manganese Inorganic materials 0.000 claims description 41
- 239000011572 manganese Substances 0.000 claims description 41
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 40
- 235000002908 manganese Nutrition 0.000 claims description 40
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 34
- 235000001055 magnesium Nutrition 0.000 claims description 33
- 229910052749 magnesium Inorganic materials 0.000 claims description 33
- 239000011777 magnesium Substances 0.000 claims description 33
- 229940091250 magnesium supplement Drugs 0.000 claims description 33
- 238000004512 die casting Methods 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000005260 corrosion Methods 0.000 claims description 15
- 230000007797 corrosion Effects 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000004090 dissolution Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims 2
- 230000008018 melting Effects 0.000 claims 2
- 230000001681 protective effect Effects 0.000 abstract description 5
- 229940058494 beryllium Drugs 0.000 description 59
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- 239000000155 melt Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000005266 casting Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- -1 0.12% Chemical compound 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052614 beryl Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000063 preceeding effect Effects 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Continuous Casting (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
ABSTRACT
Magnesium alloys containing from up to 12%
aluminum, up to 1.5% zinc, up to 1.5% silicon, up to 0.18% manganese, 0.0025% to 0.015% beryllium are die cast without need for protective flux coverings. Die cast products that do not contain harmful flux inclu-sions are produced thereby.
Magnesium alloys containing from up to 12%
aluminum, up to 1.5% zinc, up to 1.5% silicon, up to 0.18% manganese, 0.0025% to 0.015% beryllium are die cast without need for protective flux coverings. Die cast products that do not contain harmful flux inclu-sions are produced thereby.
Description
~19~
Oxidation resistant magnesium alloY
The invention generally relates to magnesium alloys that contain beryllium and are sufficiently resistant to oxidation in the molten condition to obviate the need for the use of protective flux covers to prevent excessive melt oxidation or burning when exposed to oxygen-containing atmospheres. Beryllium functions to reduce the propensity of molten magnesium alloys to oxidize when exposed to oxygen-containing atmospheres such as air.
The elimination of the need to employ a protective flux cover for molten magnesium alloys is advantageous from at least several respects. First of all, the elimination of flux covers results in a significant cost reduction. In addition, the absence of flux covers means that flux particles cannot become mixed into the molten magnesium metal and then become trapped in the resultant casting in the form of flux inclusions. The absence of flux covers also results in increased magnesium yields because entrapment and subsequent loss of molten magnesium in the flux covering are eliminated.
It is known in the art to add beryllium to magnesium base alloys for various purposes. United States Patents Numbers 2,380,200; 2,380,201; 2,383,281; 2,461,229 and 3,947,268 as well as an article by F. L. Burkett entitled "Beryllium in Magnesium Die Casting Alloys" which appeared . .
.
~' 9~
in AFS Transactions, Volum~ 62, pages 2-4 (]954) disclose the addition o~ beryllium to magnesium base alloys. Of the above cited information, United States Patents Numbers
Oxidation resistant magnesium alloY
The invention generally relates to magnesium alloys that contain beryllium and are sufficiently resistant to oxidation in the molten condition to obviate the need for the use of protective flux covers to prevent excessive melt oxidation or burning when exposed to oxygen-containing atmospheres. Beryllium functions to reduce the propensity of molten magnesium alloys to oxidize when exposed to oxygen-containing atmospheres such as air.
The elimination of the need to employ a protective flux cover for molten magnesium alloys is advantageous from at least several respects. First of all, the elimination of flux covers results in a significant cost reduction. In addition, the absence of flux covers means that flux particles cannot become mixed into the molten magnesium metal and then become trapped in the resultant casting in the form of flux inclusions. The absence of flux covers also results in increased magnesium yields because entrapment and subsequent loss of molten magnesium in the flux covering are eliminated.
It is known in the art to add beryllium to magnesium base alloys for various purposes. United States Patents Numbers 2,380,200; 2,380,201; 2,383,281; 2,461,229 and 3,947,268 as well as an article by F. L. Burkett entitled "Beryllium in Magnesium Die Casting Alloys" which appeared . .
.
~' 9~
in AFS Transactions, Volum~ 62, pages 2-4 (]954) disclose the addition o~ beryllium to magnesium base alloys. Of the above cited information, United States Patents Numbers
2,380,200 and 2,380,201, and the surkett article teach that beryllium reduces the propensity for molten magnesium alloys to oxidize. These prior efforts to reduce oxidation do not involve beryllium additives at the levels of the invention and do not appear to involve the imposition of a restriction of manganese content to permit increased beryllium solubility in the magnesium alloy. Moreover, the Burkett article suggests that higher beryllium levels must be avoided.
According to one aspect of the invention there is provided a magnesium alloy characterized by having good resistance to oxidation in the molten state, good corro-sion resistance and good tensile strength, said alloy consisting essentially of up to 12 percent by weight of aluminum, up to 1.5 percent by weight of zinc, up to 1.5 percent by weight of silicon, not more than 0.15 percent by weight of manganese, and a given amount of dissolved beryllium, the given amount constituting from 0.0025 percent to 0.0125 percent by weight of the alloy, balance essentially magnesium, and wherein the manganese content of the alloy is sufficiently low that it does not prevent dissolution of the given amount of beryllium.
According to another aspect of the invention there is provided a method of producing a magnesium alloy die casting, comprising the steps of: a. providing a molten pool of a magnesium alloy characterized by having good resistance to oxidation in the molten state, good cor-rosion resistance and good tensile strength, said alloy consisting essentially of up to 12 percent by weight of aluminum, up to 1.5~ by weight percent of zinc, up to 1.5 percent by weight of silicon, not more than 0.15 percent by weight of manganese, and a given amount of dissolved beryllium, the given amount constituting from 0.0025 )8 -- 2~ -percent to n.Ol25 percent by weight of the alloy, balance essentially magnesium, and wherein the manganese content of the alloy is suf~iciently low that it does not prevent dissolution of the given amount of beryllium; b. protecting said molten pool by exposing it to a nitrogen-containing atmosphere; and c. die casting said molten magnesium alloy to form a die casting characterized by being essentially free of flux inclusions.
It is preferred to restrict the manganese content to a maximum of about 0.05% when the beryllium content ranges between about 0.012% and 0.015% to increase the solubility of beryllium in molten magnesium to an extent sufficient to enable the above mentioned amount of beryllium to be dissolved in the magnesium. For exampler about 0.15%
manganese will permit the dissolution of from about 0.007%
beryllium in molten magnesiu~.
It is preferred to maintain manganese from about 0.04%
to 0.15% and beryllium from about 0.005% to 0.0125% in the magnesium alloys of the invention to enhance corrosion resistance of the alloy. It is further preferred to restrict manganese from about 0.08% to 0.15% and beryllium from about 0.006% to 0.01% to further enhance corrosion resistance of the magnesium alloys.
The principles of the invention are readily adaptable . ~ ,, 0~
for use in the production of magnesium alloy die casting.
Magneslum die casting alloys typically contain from 2% to 12% aluminum, up to 1.5% zinc, up to 1.5% silicon, from 0.2% to 1.0% manganese, balance essentially magnesium.
The manganese content of the alloys of the invention is important because of its influence upon the solubility and ease of alloying of beryllium in molten magnesium.
Because this influence was not heretofore recognized, AZ9lB, a widely used die casting alloy having a nominal composition of 9% aluminum, 0.7~ zinc, 0.2% manganese, 0.5% silicon maximum, 0.3% copper maximum, 0.03% nickel maximum, balance essentially magnesium has contained less than 0.001% beryllium. It has been discovered that ber-yllium is soluble in AZ91B magnesium alloys to an extent greater than previously believed. In any event, a beryl-lium level of on the order of 0.001% is considered to be inadequate for purposes of achieving good protection of the molten magnesium. Rather it has been determined that about 0.0025~ to about 0.015% beryllium should be dissolved in molten magnesium or its alloys to inhibit burning, with the amount of beryllium being increased with increasing oxygen content of the atmosphere. Accordingly, the mang-anese content should not exceed more than about 0.18%, preferably no more than about 0.15%. When nitrogen atmos-pheres and short exposure times are involved, additions of from about 0.0025% to 0.005% beryllium are sufficient to provide protection of molten magnesium. However, when longer exposure times or significant air leakage into the nitrogen atmosphere occurs, beryllium contents on the order of from about 0.005% to 0.01% are recommended. On the other hand, should it be desired to inhibit the burning of molten magnesium or magnesium alloys held in air, a beryl-lium content of about 0.012% to 0.015% is preferred. Such beryllium contents require manganese to be restricted to no more than about 0.05%.
19~8 The beryllium level used depends upon the a~ount o~ oxygen in the atmosphere over the melt. For exam~le, if the molten magnesium is exposed to air with-out a cover, the oxygen content of the atmosphere willre~ain at about 20~, and, accordingly, high beryllium levels, on the order of 0.01% to 0.015%, will be needed to avoid excessive oxidation or burning. Should the molten magnesium be ex~osed for prolonged periods, it may be desirable to periodically add beryl'ium to ccm-pensate for beryllium that is oxidized or to add larger amounts of beryllium; e.g., 0.02% in order that the excess above the solubility limit will gradually dis-solve to compensate for oxidation losses and thereby maintain the beryllium at or close to the saturation level in the molten magnesium.
T~ reduce the berylliu~ level reouired for good melt protection it is desirable to J;eep the oxygen level as low as is practical. Placement of a lid or hood over the molten magnesium is helpful in this regard.
Reaction of the molten metal with oxy~en in the enclosed air will lower the o~ygen content of the atmosphere. If the system is very tight and the resultant oxygen content becomes very low, beryllium levels as low as 0.0025~
will provide adequate protection. If the system is not tight or is periodically opened for brief periods for operations such as ladling, it may be desirable to intro-duce sufficient nitrogen or other inert gases to main-tain the low oxygen contents. In such situations an intermediate beryllium level, e.g., 0.005% to 0.01~, may be used. Other protective gases such as SF2, ~2~ and various inert gases may also be used, although nitrogen is preferred due to its relative availability.
Impurities such as iron tend to for~ insoluble intermetallic compounds with beryllium and accordingly should be minimized. Because manganese, when in the presence of aluminum contents on the order of 1~ to 12%, f orms a relatively insoluble phase with iron which then settles to the bottom of the melt, small quantities of ~0 manganese such as 0.1% may be included in die casting X
19~8 alloys for puriflcatlon purposes. However, the manga-nese level should not be hiqh enough to precipitate beryllium. ~ypically, man~anese contents should be decreased from 0.18~ to O.Q5% as the beryllium level increases from 0.0025~ to 0.015~ in magnesium alloys containing about 9% al~minum.
The following experimental results il]ustrate certain o~ the principles of the invention.
A magnesium test alloy containing about 9%
aluminum, about 0.7~ zinc, and about 0.0025% berylli~n was held under a hood for 8 hours without burning or excessive oxidation.
A 130 lb. batch of an alloy containing 7.1%
aluminum, 0.71~ zinc, 0.05~ manganese, balance magnesi~l was melted, covered with a flux and held under a hood at 1250 F. Followirg removal of the flux by skimming, burning of the molten alloy occurred after 1 minute.
The burning was then extinguished with the establish-ment of a flux cover. The hood was closed and nitrogen was flooded over the surface of the flux-covered molten bath at a rate of 30 cfh for about 5 minutes. The hood was closed, the flux cover removed, and nitrogen flow was continued at a rate of 30 cfh. After 30 minutes, blooms (localized areas of high oxidation) began to form and increase in size. After 51 minutes the blooms began to burn slowl~ and emit a bright light. The hood door was then hriefly opened periodically to permit ladling and casting of test bars. Burning became more vigorous after 5 minutes of casting and very intense after 15 minutes.
Additional tests were conducted by adding various amounts of beryllium to the molten ma~nesium test alloy descri~ed in the preceeding paragraph. In general, the tests indicated that beryllium additions decrease the tendency of the molten alloy to burn. I~hen on the order of 0.008% beryllium was incorporated, the alloy was held satisfactorily under a 30 cfh nitrogen flow and then die cast into test bars. This alloy was ~0 also held in air without burning for approximately 15 .
minu~es. As the beryllium content was increased during the various tests, it was noted that the oxidation re sistance of the molten ma~nesiu~ alloy increased and tha~ lessened rates of nitrogen flo~ were re~uired for satisfactory operation. I^~hen about 0.01].% to 0.013~
berylli~m was incorporated into the molten alloy, the surface of the alloy became silvery in apnearance and was satisfa~torily held under exposure to air and then die cast. I~hen the silvery protective surface fil~ wa deliberately disrupted, a new film formed instantly, indicatinq that the protective function of berylli~m was still operative. Following exposure to air for about 1 hour, however, oxide blooms began to form and grow slowlv.
t~hen 0.00~5~ beryllium was alloyed into the magnesium test alloy, the melt was satisfactorily held under a nitrogen flow of 30 cfh with door closed and then was cast into test bars. Pollowing 15 minutes, the molten maqnesium alloy was heavily bloomed and commencing to burn. ~?hen 0.007~ to 0.01~ beryllium was alloyed, the castin~ run was successfully completed without the occurrence of bloo~ins with 60 cfh nitrogen. ~he door of the hood was then held open for 15 minutes without bloon fo mation. ~itrogen flow was then stopped and the molten alloy was held for an additional 15 minutes with-out bloom formation. After the alloy was saturated with ab~ut 120-130 ppm berylliu~ at 1200 - 1300 F, it was held in air with the door o~en for over 30 minutes with-out bloom formation and was then successfully cast ~:ith-out a nitro~en atmosphere. ~xtended holding, however, finally led to bloo~ for~ation.
To determine the compatibility of manganese and beryllium in magnesium alloys, two AZ9lB ingots con-taining about 0.2~ manganese were added to the melt.
.his addition reduced the beryllium content to about0.008~ an~ increased the manganese content to 0.12~.
~he molten alloy was successfully die cast with a flow of 6Q cfh nitrogen and the hooA door opened only as re-~0 quired. ~ portion of the melt was poured in air into a ;~
.
large ingot mold. ~o discoloration h~as noted on themetal surface as it slowly solidified.
Ano~her AZ9lB ingot was added to the molten alloy with a resultant lowering of the beryllium con-tent to about 0.007% and an increase in the man~anese level to about 0.1S%. Test bars were again cast under 60 cfh of nitrogen. Several blooms had formed at the end of the run.
The variations in manganese and beryllium level had no apparent effect upon the castability of the magnesium test alloy. Some improvement in fluidity and surface appearance appears to result from increas-ing beryllium content because of less oxidation of the molten material.
Five die cast bars of each alloy were tested in tension to determine the effect of beryllium and man-ganese. ~he results set forth in ~able I indicate that lower manganese and higher beryllium function to increase both ductility and tensile strength of the magnesium test alloy.
Sanded test bars of each alloy were also immersed in salt water (3% NaCl) for 3 days to de-termine corrosion resistance. The bars were sanded to remove the cast surface. The results in Table II
indicate that beryllium additions reduce the salt water corrosion rate of the magnesium test alloy to the same low level obtained by manganese additions. Small amounts of manganese, e.g., 0.12%, reduce the amount of beryllium re~uired for good corrosion resistance.
The improvement effected by beryllium can be attributed to a reduction in iron content.
:'........ .
t~08 Ta~le I
6 Be % ~ ~ E T~S TS
0 0.05 6 21,50036,300 0.00~5 0.05 7 22,90038,900 0.0086 0.05 6 22,70036,800 ~0 0.0113 0.04 7 21,00038,200 0.0125 0.04 5 22,00037,800 0.0081 0.12 6 22,70039,000 O.OQ71 0.15 8 21,90040,500 0.0006** 0.2 4 21,70034,600 Pounds per 5quare Inch (AZ9lB) ~y .
191~8 Table I I
% Be % Mn % Fe Corrosion Rate-IPY*
-- 0.05 0.015 1.30 0.0025 0.05 O.OlS 0.95 0.0086 0.05 0.008 0.17 0.0113 0.04 0.005 0.03 0 . 0125 0 . 04 0 . 005 0 . 03 0 . 00~1 0 . 12 0 . 006 0 . 03 0 . 0071 0 . 15 0 . 007 0 . 03 0 . 0006** 0 . 2 0 . 003 0 . 03 * i nches per year * * (A Z 9 lB ) x~-~' :~ ~L5~0~
~UPPLEMENTARY DI~CLOSUR~
The principal. discl.osure describes and claims a mag-nesium alloy characterized by having good resistance to oxidation in the mo]ten state, good corrosion resistance and good tensile strength, said alloy consisting essen-tially of up to 12 percent by weight of aluminum, up to 1.5 percent by weight of zinc, up to 1.5 percent by weight of silicon, not more than 0.15 percent by weight of man-ganese, and a given amount of dissolved beryllium, the given amount constituting from 0.0025 percent to 0.0125 percent by weight of the alloy, balance essentially mag-nesium, and wherein the manganese content of the alloy is sufficiently low that it does not prevent dissolution of the given amount of beryllium.
It has now been determined that a magnesium alloy of the same characteristics can be obtained which has a zinc content up to 30~. Thus, the present invention in its expanded form provided a magnesium alloy characterized by having good resistance to oxidation in the molten state, good corrosion resistance and good tensile strength, said alloy consisting essentially of up to 12 percent by weight of aluminum, up to 30 percent by weight of zinc, up to 1.5 percent by weight of silicon, not more than 0.15 percent by weight of manganese, and a given amount of dissolved beryllium, the given amount constituting from 0.0025 percent to 0.0125 percent by weight of the alloy, balance essentially magnesium, and wherein the manganese content of the alloy is sufficiently low that it does not prevent dissolution of the given amount of beryllium.
In another form the invention provides a method of producing a magnesium alloy die casting, comprising the steps of: a. providing a molten pool of a magnesium alloy characterized by having good resistance to oxidation in the molten state, good corrosion resistance and good tensile strength, said alloy consisting essentially of up to 12 percent by weight of aluminum, up to 3O% by weight - IOa -percent of zinc, Up to ~.5 percent by weight o~ ~ilicon, not more than O.l5 percent by weight of manganese, and a given amount of dissolved beryllium, the given amount constituting from 0.0025 percent to 0.0125 percent by weight of the alloy, balance essentially magnesium, and wherein the manganese content of the alloy is sufficiently low that it does not prevent dissolution of the given amount of beryllium; b. protecting said molten pool by exposing it to a nitrogen-containing atmosphere; and c.
die casting said molten magnesium alloy to form a die casting characterized by being essentially free of flux inclusions.
All other features of the invention as described in the principal disclosure also relate to those alloys containing between 1.5~ and 30% zinc.
According to one aspect of the invention there is provided a magnesium alloy characterized by having good resistance to oxidation in the molten state, good corro-sion resistance and good tensile strength, said alloy consisting essentially of up to 12 percent by weight of aluminum, up to 1.5 percent by weight of zinc, up to 1.5 percent by weight of silicon, not more than 0.15 percent by weight of manganese, and a given amount of dissolved beryllium, the given amount constituting from 0.0025 percent to 0.0125 percent by weight of the alloy, balance essentially magnesium, and wherein the manganese content of the alloy is sufficiently low that it does not prevent dissolution of the given amount of beryllium.
According to another aspect of the invention there is provided a method of producing a magnesium alloy die casting, comprising the steps of: a. providing a molten pool of a magnesium alloy characterized by having good resistance to oxidation in the molten state, good cor-rosion resistance and good tensile strength, said alloy consisting essentially of up to 12 percent by weight of aluminum, up to 1.5~ by weight percent of zinc, up to 1.5 percent by weight of silicon, not more than 0.15 percent by weight of manganese, and a given amount of dissolved beryllium, the given amount constituting from 0.0025 )8 -- 2~ -percent to n.Ol25 percent by weight of the alloy, balance essentially magnesium, and wherein the manganese content of the alloy is suf~iciently low that it does not prevent dissolution of the given amount of beryllium; b. protecting said molten pool by exposing it to a nitrogen-containing atmosphere; and c. die casting said molten magnesium alloy to form a die casting characterized by being essentially free of flux inclusions.
It is preferred to restrict the manganese content to a maximum of about 0.05% when the beryllium content ranges between about 0.012% and 0.015% to increase the solubility of beryllium in molten magnesium to an extent sufficient to enable the above mentioned amount of beryllium to be dissolved in the magnesium. For exampler about 0.15%
manganese will permit the dissolution of from about 0.007%
beryllium in molten magnesiu~.
It is preferred to maintain manganese from about 0.04%
to 0.15% and beryllium from about 0.005% to 0.0125% in the magnesium alloys of the invention to enhance corrosion resistance of the alloy. It is further preferred to restrict manganese from about 0.08% to 0.15% and beryllium from about 0.006% to 0.01% to further enhance corrosion resistance of the magnesium alloys.
The principles of the invention are readily adaptable . ~ ,, 0~
for use in the production of magnesium alloy die casting.
Magneslum die casting alloys typically contain from 2% to 12% aluminum, up to 1.5% zinc, up to 1.5% silicon, from 0.2% to 1.0% manganese, balance essentially magnesium.
The manganese content of the alloys of the invention is important because of its influence upon the solubility and ease of alloying of beryllium in molten magnesium.
Because this influence was not heretofore recognized, AZ9lB, a widely used die casting alloy having a nominal composition of 9% aluminum, 0.7~ zinc, 0.2% manganese, 0.5% silicon maximum, 0.3% copper maximum, 0.03% nickel maximum, balance essentially magnesium has contained less than 0.001% beryllium. It has been discovered that ber-yllium is soluble in AZ91B magnesium alloys to an extent greater than previously believed. In any event, a beryl-lium level of on the order of 0.001% is considered to be inadequate for purposes of achieving good protection of the molten magnesium. Rather it has been determined that about 0.0025~ to about 0.015% beryllium should be dissolved in molten magnesium or its alloys to inhibit burning, with the amount of beryllium being increased with increasing oxygen content of the atmosphere. Accordingly, the mang-anese content should not exceed more than about 0.18%, preferably no more than about 0.15%. When nitrogen atmos-pheres and short exposure times are involved, additions of from about 0.0025% to 0.005% beryllium are sufficient to provide protection of molten magnesium. However, when longer exposure times or significant air leakage into the nitrogen atmosphere occurs, beryllium contents on the order of from about 0.005% to 0.01% are recommended. On the other hand, should it be desired to inhibit the burning of molten magnesium or magnesium alloys held in air, a beryl-lium content of about 0.012% to 0.015% is preferred. Such beryllium contents require manganese to be restricted to no more than about 0.05%.
19~8 The beryllium level used depends upon the a~ount o~ oxygen in the atmosphere over the melt. For exam~le, if the molten magnesium is exposed to air with-out a cover, the oxygen content of the atmosphere willre~ain at about 20~, and, accordingly, high beryllium levels, on the order of 0.01% to 0.015%, will be needed to avoid excessive oxidation or burning. Should the molten magnesium be ex~osed for prolonged periods, it may be desirable to periodically add beryl'ium to ccm-pensate for beryllium that is oxidized or to add larger amounts of beryllium; e.g., 0.02% in order that the excess above the solubility limit will gradually dis-solve to compensate for oxidation losses and thereby maintain the beryllium at or close to the saturation level in the molten magnesium.
T~ reduce the berylliu~ level reouired for good melt protection it is desirable to J;eep the oxygen level as low as is practical. Placement of a lid or hood over the molten magnesium is helpful in this regard.
Reaction of the molten metal with oxy~en in the enclosed air will lower the o~ygen content of the atmosphere. If the system is very tight and the resultant oxygen content becomes very low, beryllium levels as low as 0.0025~
will provide adequate protection. If the system is not tight or is periodically opened for brief periods for operations such as ladling, it may be desirable to intro-duce sufficient nitrogen or other inert gases to main-tain the low oxygen contents. In such situations an intermediate beryllium level, e.g., 0.005% to 0.01~, may be used. Other protective gases such as SF2, ~2~ and various inert gases may also be used, although nitrogen is preferred due to its relative availability.
Impurities such as iron tend to for~ insoluble intermetallic compounds with beryllium and accordingly should be minimized. Because manganese, when in the presence of aluminum contents on the order of 1~ to 12%, f orms a relatively insoluble phase with iron which then settles to the bottom of the melt, small quantities of ~0 manganese such as 0.1% may be included in die casting X
19~8 alloys for puriflcatlon purposes. However, the manga-nese level should not be hiqh enough to precipitate beryllium. ~ypically, man~anese contents should be decreased from 0.18~ to O.Q5% as the beryllium level increases from 0.0025~ to 0.015~ in magnesium alloys containing about 9% al~minum.
The following experimental results il]ustrate certain o~ the principles of the invention.
A magnesium test alloy containing about 9%
aluminum, about 0.7~ zinc, and about 0.0025% berylli~n was held under a hood for 8 hours without burning or excessive oxidation.
A 130 lb. batch of an alloy containing 7.1%
aluminum, 0.71~ zinc, 0.05~ manganese, balance magnesi~l was melted, covered with a flux and held under a hood at 1250 F. Followirg removal of the flux by skimming, burning of the molten alloy occurred after 1 minute.
The burning was then extinguished with the establish-ment of a flux cover. The hood was closed and nitrogen was flooded over the surface of the flux-covered molten bath at a rate of 30 cfh for about 5 minutes. The hood was closed, the flux cover removed, and nitrogen flow was continued at a rate of 30 cfh. After 30 minutes, blooms (localized areas of high oxidation) began to form and increase in size. After 51 minutes the blooms began to burn slowl~ and emit a bright light. The hood door was then hriefly opened periodically to permit ladling and casting of test bars. Burning became more vigorous after 5 minutes of casting and very intense after 15 minutes.
Additional tests were conducted by adding various amounts of beryllium to the molten ma~nesium test alloy descri~ed in the preceeding paragraph. In general, the tests indicated that beryllium additions decrease the tendency of the molten alloy to burn. I~hen on the order of 0.008% beryllium was incorporated, the alloy was held satisfactorily under a 30 cfh nitrogen flow and then die cast into test bars. This alloy was ~0 also held in air without burning for approximately 15 .
minu~es. As the beryllium content was increased during the various tests, it was noted that the oxidation re sistance of the molten ma~nesiu~ alloy increased and tha~ lessened rates of nitrogen flo~ were re~uired for satisfactory operation. I^~hen about 0.01].% to 0.013~
berylli~m was incorporated into the molten alloy, the surface of the alloy became silvery in apnearance and was satisfa~torily held under exposure to air and then die cast. I~hen the silvery protective surface fil~ wa deliberately disrupted, a new film formed instantly, indicatinq that the protective function of berylli~m was still operative. Following exposure to air for about 1 hour, however, oxide blooms began to form and grow slowlv.
t~hen 0.00~5~ beryllium was alloyed into the magnesium test alloy, the melt was satisfactorily held under a nitrogen flow of 30 cfh with door closed and then was cast into test bars. Pollowing 15 minutes, the molten maqnesium alloy was heavily bloomed and commencing to burn. ~?hen 0.007~ to 0.01~ beryllium was alloyed, the castin~ run was successfully completed without the occurrence of bloo~ins with 60 cfh nitrogen. ~he door of the hood was then held open for 15 minutes without bloon fo mation. ~itrogen flow was then stopped and the molten alloy was held for an additional 15 minutes with-out bloom formation. After the alloy was saturated with ab~ut 120-130 ppm berylliu~ at 1200 - 1300 F, it was held in air with the door o~en for over 30 minutes with-out bloom formation and was then successfully cast ~:ith-out a nitro~en atmosphere. ~xtended holding, however, finally led to bloo~ for~ation.
To determine the compatibility of manganese and beryllium in magnesium alloys, two AZ9lB ingots con-taining about 0.2~ manganese were added to the melt.
.his addition reduced the beryllium content to about0.008~ an~ increased the manganese content to 0.12~.
~he molten alloy was successfully die cast with a flow of 6Q cfh nitrogen and the hooA door opened only as re-~0 quired. ~ portion of the melt was poured in air into a ;~
.
large ingot mold. ~o discoloration h~as noted on themetal surface as it slowly solidified.
Ano~her AZ9lB ingot was added to the molten alloy with a resultant lowering of the beryllium con-tent to about 0.007% and an increase in the man~anese level to about 0.1S%. Test bars were again cast under 60 cfh of nitrogen. Several blooms had formed at the end of the run.
The variations in manganese and beryllium level had no apparent effect upon the castability of the magnesium test alloy. Some improvement in fluidity and surface appearance appears to result from increas-ing beryllium content because of less oxidation of the molten material.
Five die cast bars of each alloy were tested in tension to determine the effect of beryllium and man-ganese. ~he results set forth in ~able I indicate that lower manganese and higher beryllium function to increase both ductility and tensile strength of the magnesium test alloy.
Sanded test bars of each alloy were also immersed in salt water (3% NaCl) for 3 days to de-termine corrosion resistance. The bars were sanded to remove the cast surface. The results in Table II
indicate that beryllium additions reduce the salt water corrosion rate of the magnesium test alloy to the same low level obtained by manganese additions. Small amounts of manganese, e.g., 0.12%, reduce the amount of beryllium re~uired for good corrosion resistance.
The improvement effected by beryllium can be attributed to a reduction in iron content.
:'........ .
t~08 Ta~le I
6 Be % ~ ~ E T~S TS
0 0.05 6 21,50036,300 0.00~5 0.05 7 22,90038,900 0.0086 0.05 6 22,70036,800 ~0 0.0113 0.04 7 21,00038,200 0.0125 0.04 5 22,00037,800 0.0081 0.12 6 22,70039,000 O.OQ71 0.15 8 21,90040,500 0.0006** 0.2 4 21,70034,600 Pounds per 5quare Inch (AZ9lB) ~y .
191~8 Table I I
% Be % Mn % Fe Corrosion Rate-IPY*
-- 0.05 0.015 1.30 0.0025 0.05 O.OlS 0.95 0.0086 0.05 0.008 0.17 0.0113 0.04 0.005 0.03 0 . 0125 0 . 04 0 . 005 0 . 03 0 . 00~1 0 . 12 0 . 006 0 . 03 0 . 0071 0 . 15 0 . 007 0 . 03 0 . 0006** 0 . 2 0 . 003 0 . 03 * i nches per year * * (A Z 9 lB ) x~-~' :~ ~L5~0~
~UPPLEMENTARY DI~CLOSUR~
The principal. discl.osure describes and claims a mag-nesium alloy characterized by having good resistance to oxidation in the mo]ten state, good corrosion resistance and good tensile strength, said alloy consisting essen-tially of up to 12 percent by weight of aluminum, up to 1.5 percent by weight of zinc, up to 1.5 percent by weight of silicon, not more than 0.15 percent by weight of man-ganese, and a given amount of dissolved beryllium, the given amount constituting from 0.0025 percent to 0.0125 percent by weight of the alloy, balance essentially mag-nesium, and wherein the manganese content of the alloy is sufficiently low that it does not prevent dissolution of the given amount of beryllium.
It has now been determined that a magnesium alloy of the same characteristics can be obtained which has a zinc content up to 30~. Thus, the present invention in its expanded form provided a magnesium alloy characterized by having good resistance to oxidation in the molten state, good corrosion resistance and good tensile strength, said alloy consisting essentially of up to 12 percent by weight of aluminum, up to 30 percent by weight of zinc, up to 1.5 percent by weight of silicon, not more than 0.15 percent by weight of manganese, and a given amount of dissolved beryllium, the given amount constituting from 0.0025 percent to 0.0125 percent by weight of the alloy, balance essentially magnesium, and wherein the manganese content of the alloy is sufficiently low that it does not prevent dissolution of the given amount of beryllium.
In another form the invention provides a method of producing a magnesium alloy die casting, comprising the steps of: a. providing a molten pool of a magnesium alloy characterized by having good resistance to oxidation in the molten state, good corrosion resistance and good tensile strength, said alloy consisting essentially of up to 12 percent by weight of aluminum, up to 3O% by weight - IOa -percent of zinc, Up to ~.5 percent by weight o~ ~ilicon, not more than O.l5 percent by weight of manganese, and a given amount of dissolved beryllium, the given amount constituting from 0.0025 percent to 0.0125 percent by weight of the alloy, balance essentially magnesium, and wherein the manganese content of the alloy is sufficiently low that it does not prevent dissolution of the given amount of beryllium; b. protecting said molten pool by exposing it to a nitrogen-containing atmosphere; and c.
die casting said molten magnesium alloy to form a die casting characterized by being essentially free of flux inclusions.
All other features of the invention as described in the principal disclosure also relate to those alloys containing between 1.5~ and 30% zinc.
Claims (32)
1. A magnesium alloy characterized by having good resist-ance to oxidation in the molten state, good corrosion resistance and good tensile strength, said alloy consisting essentially of up to 12 percent by weight of aluminum, up to 1.5 percent by weight of zinc, up to 1.5 percent by weight of silicon, not more than 0.15 percent by weight of manganese, and a given amount of dissolved beryllium, the given amount constituting from 0.0025 percent to 0.0125 percent by weight of the alloy, balance essentially mag-nesium, and wherein the manganese content of the alloy is sufficiently low that it does not prevent dissolution of the given amount of beryllium.
2. The magnesium alloy of Claim 1, wherein said alloy contains from 0.04 percent to 0.15 percent by weight of manganese.
3. The magnesium alloy of Claim 1, wherein said alloy contains from 0.005 percent to 0.01 percent by weight of dissolved beryllium.
4. The magnesium alloy of Claim 1, wherein said alloy contains not more than 0.15 percent by weight of man-ganese and from 0.006 percent to 0.01 percent by weight of dissolved beryllium.
5. The magnesium alloy of Claim 4, wherein said alloy contains from about 7 percent to about 9 percent by weight of aluminum, about 0.7 percent by weight of zinc, up to about 0.12 percent by weight of manganese, and about 0.008 percent by weight of dissolved beryllium.
6. The magnesium alloy of Claim 1, wherein said alloy contains not more than 0.05 percent by weight of manganese and from 0.011 percent to 0.0125 percent by weight of dissolved beryllium.
7. A die casting which is produced by melting the magnesium alloy of Claim 1 in a nitrogen-containing atmosphere, and die casting the molten magnesium alloy.
8. The die casting of Claim 7 wherein said magnesium alloy contains from 0.04 percent to 0.15 percent by weight or manganese.
9. The die casting of Claim 7, wherein said magnesium alloy contains from 0.005 percent to 0.01 percent by weight of dissolved beryllium.
10. The die casting of Claim 7 wherein said magnesium alloy contains not more than 0.15 percent by weight of manganese and from 0.006 percent to 0.01 percent by weight of dissolved beryllium.
11. The die casting of Claim 10, wherein said magnesium alloy contains from about 7 percent to about 9 percent by weight of aluminum, about 0.7 percent by weight of zinc, up to about 0.12 percent by weight of manganese, and about 0.008 percent by weight of dissolved beryllium.
12. The die casting of Claim 7, wherein said magnesium alloy contains not more than 0.05 percent by weight of manganese and from 0.011 percent to 0.0125 percent by weight of dissolved beryllium.
13. A method of producing a magnesium alloy die casting, comprising the steps of:
a. providing a molten pool of a magnesium alloy char-acterized by having good resistance to oxidation in the molten state, good corrosion resistance and good tensile strength, said alloy consisting essentially of up to 12 percent by weight of aluminum, up to 1.5% by weight percent of zinc, up to 1.5 percent by weight of silicon, not more than 0.15 percent by weight of man-ganese, and a given amount of dissolved beryllium, the given amount constituting from 0.0025 percent to 0.0125 percent by weight of the alloy, balance essentially magnesium, and wherein the manganese content of the alloy is sufficiently low that it does not prevent dissolution of the given amount of beryllium;
b. protecting said molten pool by exposing it to a nitrogen-containing atmosphere; and c. die casting said molten magnesium alloy to form a die casting characterized by being essentially free of flux inclusions.
a. providing a molten pool of a magnesium alloy char-acterized by having good resistance to oxidation in the molten state, good corrosion resistance and good tensile strength, said alloy consisting essentially of up to 12 percent by weight of aluminum, up to 1.5% by weight percent of zinc, up to 1.5 percent by weight of silicon, not more than 0.15 percent by weight of man-ganese, and a given amount of dissolved beryllium, the given amount constituting from 0.0025 percent to 0.0125 percent by weight of the alloy, balance essentially magnesium, and wherein the manganese content of the alloy is sufficiently low that it does not prevent dissolution of the given amount of beryllium;
b. protecting said molten pool by exposing it to a nitrogen-containing atmosphere; and c. die casting said molten magnesium alloy to form a die casting characterized by being essentially free of flux inclusions.
14. The method of Claim 13, wherein said nitrogen-containing atmosphere contains a greater proportion of nitrogen than that contained in air.
15. The method of Claim 13, wherein said magnesium alloy contains from about 0.005 percent to 0.01 percent by weight of dissolved beryllium.
16. The method of Claim 13, wherein said magnesium alloy contains from about 0.01 percent to 0.0125 percent by weight of dissolved beryllium and up to 0.05 percent by weight of manganese and said molten pool is exposed to air.
Claims supported by the supplementary disclosure:
Claims supported by the supplementary disclosure:
17. A magnesium alloy characterized by having good resist-ance to oxidation in the molten state, good corrosion resistance and good tensile strength, said alloy consisting essentially of up to 12 percent by weight of aluminum, up to 30 percent by weight of zinc, up to 1.5 percent by weight of silicon, not more than 0.15 percent by weight of manganese, and a given amount of dissolved beryllium, the given amount constituting from 0.0025 percent to 0.0125 percent by weight of the alloy, balance essentially mag-nesium, and wherein the manganese content of the alloy is sufficiently low that it does not prevent dissolution of the given amount of beryllium.
18. The magnesium alloy of Claim 17, wherein said alloy contains from 0.04 percent to 0.15 percent by weight of manganese.
19. The magnesium alloy of Claim 17, wherein said alloy contains from 0.005 percent to 0.01 percent by weight of dissolved beryllium.
20. The magnesium alloy of Claim 17, wherein said alloy contains not more than 0.15 percent by weight of man-ganese and from 0.006 percent to 0.01 percent by weight of dissolved beryllium.
21. The magnesium alloy of Claim 20, wherein said alloy contains from about 7 percent to about 9 percent by weight of aluminum, about 0.7 percent by weight of zinc, up to about 0.12 percent by weight of manganese, and about 0.008 percent by weight of dissolved beryllium.
22. The magnesium alloy of Claim 17, wherein said alloy contains not more than 0.05 percent by weight of manganese and from 0.011 percent to 0.0125 percent by weight of dissolved beryllium.
23. A die casting which is produced by melting the magnesium alloy of Claim 17 in a nitrogen-containing atmosphere, and die casting the molten magnesium alloy.
24. The die casting of Claim 23 wherein said magnesium alloy contains from 0.04 percent to 0.15 percent by weight of manganese.
25. The die casting of Claim 23, wherein said maynesium alloy contains from 0.005 percent to 0.01 percent by weight of dissolved beryllium.
26. The die casting of Claim 23 wherein said magnesium alloy contains not more than 0.15 percent by weight of manganese and from 0.006 percent to 0.01 percent by weight of dissolved beryllium.
27. The die casting of Claim 26, wherein said magnesium al]oy contains from about 7 percent to about 9 percent by weight of aluminum, about 0.7 percent by weight of zinc, up to about 0.12 percent by weight of manganese, and about 0.008 percent by weight of dissolved beryllium.
28. The die casting of Claim 23, wherein said magnesium alloy contains not more than 0.05 percent by weight of manganese and from 0.011 percent to 0.0125 percent by weight of dissolved beryllium.
29. A method of producing a magnesium alloy die casting, comprising the steps of:
a. providing a molten pool of a magnesium alloy char-acterized by having good resistance to oxidation in the molten state, good corrosion resistance and good tensile strength, said alloy consisting essentially of up to 12 percent by weight of aluminum, up to 30 % by weight percent of zinc, up to 1.5 percent by weight of silicon, not more than 0.15 percent by weight of man-ganese, and a given amount of dissolved beryllium, the given amount constituting from 0.0025 percent to 0.0125 percent by weight of the alloy, balance essentially magnesium, and wherein the manganese content of the alloy is sufficiently low that it does not prevent dissolution of the given amount of beryllium;
b. protecting said molten pool by exposing it to a nitrogen-containing atmosphere; and c. die casting said molten magnesium alloy to form a die casting characterized by being essentially free of flux inclusions.
a. providing a molten pool of a magnesium alloy char-acterized by having good resistance to oxidation in the molten state, good corrosion resistance and good tensile strength, said alloy consisting essentially of up to 12 percent by weight of aluminum, up to 30 % by weight percent of zinc, up to 1.5 percent by weight of silicon, not more than 0.15 percent by weight of man-ganese, and a given amount of dissolved beryllium, the given amount constituting from 0.0025 percent to 0.0125 percent by weight of the alloy, balance essentially magnesium, and wherein the manganese content of the alloy is sufficiently low that it does not prevent dissolution of the given amount of beryllium;
b. protecting said molten pool by exposing it to a nitrogen-containing atmosphere; and c. die casting said molten magnesium alloy to form a die casting characterized by being essentially free of flux inclusions.
30. The method of Claim 29, wherein said nitrogen-containing atmosphere contains a greater proportion of nitrogen than that contained in air.
31. The method of Claim 29, wherein said magnesium alloy contains from about 0.005 percent to 0.01 percent by weight of dissolved beryllium.
32. The method of Claim 29, wherein said magnesium alloy contains from about 0.01 percent to 0.0125 percent by weight of dissolved beryllium and up to 0.05 percent by weight of manganese and said molten pool is exposed to air.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US4180279A | 1979-05-23 | 1979-05-23 | |
| US041,802 | 1979-05-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1151908A true CA1151908A (en) | 1983-08-16 |
Family
ID=21918397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000348593A Expired CA1151908A (en) | 1979-05-23 | 1980-03-27 | Oxidation resistant magnesium alloy |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS55158248A (en) |
| AU (1) | AU5622780A (en) |
| BR (1) | BR8003132A (en) |
| CA (1) | CA1151908A (en) |
| DE (1) | DE3018531A1 (en) |
| FR (1) | FR2457329A1 (en) |
| GB (1) | GB2051129A (en) |
| IT (1) | IT1149295B (en) |
| NO (1) | NO801121L (en) |
Families Citing this family (2)
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|---|---|---|---|---|
| AU3463293A (en) * | 1992-02-04 | 1993-09-01 | Japan As Represented By Director General Of Agency Of Industrial Science And Technology | Method of flameproofing molten magnesium material, and alloy thereof |
| NO312106B1 (en) * | 1999-07-02 | 2002-03-18 | Norsk Hydro As | Method of improving the corrosion resistance of magnesium-aluminum-silicon alloys and magnesium alloy with improved corrosion resistance |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH257160A (en) * | 1944-06-23 | 1948-09-30 | Stone & Company Limited J | Process for obtaining molten magnesium-based alloys intended to be die-cast. |
| DE1019093B (en) * | 1953-07-31 | 1957-11-07 | Fuchs Fa Otto | Use of cast magnesium alloys with low beryllium additions |
| FR1108980A (en) * | 1954-10-06 | 1956-01-19 | Magnesium Elektron Ltd | Magnesium alloys |
| DE1027410B (en) * | 1955-03-08 | 1958-04-03 | Fuchs Fa Otto | Use of cast magnesium alloys with low beryllium additions |
| GB963073A (en) * | 1962-04-12 | 1964-07-08 | Magnesium Elektron Ltd | Improvements in or relating to magnesium base alloys |
| SU393343A1 (en) * | 1971-06-01 | 1973-08-10 | MAGNESIUM ALLOY |
-
1980
- 1980-03-06 AU AU56227/80A patent/AU5622780A/en not_active Abandoned
- 1980-03-21 IT IT20859/80A patent/IT1149295B/en active
- 1980-03-27 CA CA000348593A patent/CA1151908A/en not_active Expired
- 1980-04-18 NO NO801121A patent/NO801121L/en unknown
- 1980-04-21 FR FR8008932A patent/FR2457329A1/en not_active Withdrawn
- 1980-05-14 DE DE19803018531 patent/DE3018531A1/en not_active Withdrawn
- 1980-05-19 JP JP6546980A patent/JPS55158248A/en active Pending
- 1980-05-20 BR BR8003132A patent/BR8003132A/en unknown
- 1980-05-20 GB GB8016671A patent/GB2051129A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| BR8003132A (en) | 1980-12-23 |
| JPS55158248A (en) | 1980-12-09 |
| AU5622780A (en) | 1980-11-27 |
| DE3018531A1 (en) | 1980-12-04 |
| FR2457329A1 (en) | 1980-12-19 |
| IT8020859A0 (en) | 1980-03-21 |
| GB2051129A (en) | 1981-01-14 |
| NO801121L (en) | 1980-11-24 |
| IT1149295B (en) | 1986-12-03 |
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