US2633419A - Process for the treatment of melted magnesium and magnesium alloys - Google Patents
Process for the treatment of melted magnesium and magnesium alloys Download PDFInfo
- Publication number
- US2633419A US2633419A US79725A US7972549A US2633419A US 2633419 A US2633419 A US 2633419A US 79725 A US79725 A US 79725A US 7972549 A US7972549 A US 7972549A US 2633419 A US2633419 A US 2633419A
- Authority
- US
- United States
- Prior art keywords
- magnesium
- iron
- crucible
- chromium
- treatment
- 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 - Lifetime
Links
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims description 31
- 229910052749 magnesium Inorganic materials 0.000 title claims description 31
- 239000011777 magnesium Substances 0.000 title claims description 31
- 238000000034 method Methods 0.000 title claims description 7
- 229910000861 Mg alloy Inorganic materials 0.000 title description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 63
- 229910052742 iron Inorganic materials 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- 239000011651 chromium Substances 0.000 claims description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- 238000011109 contamination Methods 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NDUKHFILUDZSHZ-UHFFFAOYSA-N [Fe].[Zr] Chemical class [Fe].[Zr] NDUKHFILUDZSHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005269 aluminizing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- -1 magnesium-aluminium-zinc-manganese Chemical compound 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
Definitions
- magnesium which is free from iron available as the initial material.
- thermal methods of production in which magnesium is obtained in the form of crystals which ar formed from magnesium vapour, or where the magnesium is produced by electrolytic fusion methods and purified by distillation the metal fulfils these requirements for practical purposes, since in th s case the iron content is less than 0.001%.
- the re-meltin and alloying or other treatment of melted magnesium as in the cas of production by electrolysis is preferably carried out in apparatus consisting of iron or iron alloys free from nickel.
- the most suitable apparatus appears to be an apparatus of austenitic steel with a high manganese and high carbon content, but even in this case it is not possible to prevent the absorption of iron entirely whilst in certain cases the presence of manganese may be accompanied by disadvantages. A certain absorption of iron always occurs however.
- the iron content usually amounts to about 0.03%.
- crucibles'of chromium-iron are employed which are free from nickel and have a high chromium content up to 28%.
- rate of solution of the iron is reduced without its being possible however, to prevent the absorption of iron in a satisfactory manner.
- crucibles of this kind are unsuitable on account of the fact that they become brittle in the course of time and there is also a danger of crack formation.
- the effect produced by the protective layer of chromium according to the invention can be increased in accordance with the latter by the heat treatment of the parts of the apparatus or crucible in question in such a way that at a raised temperature the diffusion of the chromium is increased before the apparatus or crucible is taken into service for the required purpose.
- crystallized magnesium obtained by the condensation of magnesium vapour and containing 0.000392 iron can be remelted in an electrolytically chromated crucible of iron. Only after a large number of melts have been carried out in the crucible was it possible to notice a certain though slight increase of the iron content in the remelted metal. Not more than 0.0007% iron could be traced in the metal. Furthermore, the
Description
Patented Mar. 31, 1953 PROCESS FOR THE TREATMENT .OF-MELT-ED MAGNESIUM AND MAGNESIUM ALLOYS Sven Christian Pyk, Nyna'shamn, Sweden No'Drawing- Application March 4, 1949, Serial No.79,725; In 'SwedenMarch.11,-1948 2 Claims.
It is well-known that the presence of iron,
"nickel 'and'cobalt in magnesium and magnesium jalloys, even in very 'small quantities, causes an appreciable deterioration'in the resistance to cor- 'rosion.
In pure magnesium, for example, the rate of corrosion increases extremely rapidly when the iron content rises above 0.016%. Thus, with 0.020% it will be about five hundred times greater in a 3% salt solution than with 0.016% iron in the metal.
For magnesium-aluminium-zinc-manganese alloys this transitional value lies at about 0.002
Thus, it is very important in many cases to have magnesium which is free from iron available as the initial material. With thermal methods of production in which magnesium is obtained in the form of crystals which ar formed from magnesium vapour, or where the magnesium is produced by electrolytic fusion methods and purified by distillation the metal fulfils these requirements for practical purposes, since in th s case the iron content is less than 0.001%.
The re-meltin and alloying or other treatment of melted magnesium as in the cas of production by electrolysis is preferably carried out in apparatus consisting of iron or iron alloys free from nickel. In this respect the most suitable apparatus appears to be an apparatus of austenitic steel with a high manganese and high carbon content, but even in this case it is not possible to prevent the absorption of iron entirely whilst in certain cases the presence of manganese may be accompanied by disadvantages. A certain absorption of iron always occurs however. Thus, in magnesium of the ordinary commercial type the iron content usually amounts to about 0.03%.
When overheating the molten magnesium alloys for the purpose of obtaining a fine grain, or when introducing alloying substances which require a high temperature, the absorption of iron will increase. On introducin zirconium as an alloying constituent, for example, this iron absorption is particularly troublesome as dinicultly fusible zirconium-iron compounds occur in the melt which even when they are partially removed together with the iron, nevertheless increase the amount of zirconium employed.
It is already known that the iron absorption can be limited by aluminizing the crucible in which the metal is treated. As aluminium is soluble in magnesium, however, the aluminium layer in the crucible is rapidly dissolved so that at the outset magnesium containing aluminium 'isproduced, this being followed "by'ircn absorption. In some cases it is also desirable to obtain a product free from aluminium, this being the case, for example, in magnesium alloys containing' zirconium.
In other Processes crucibles'of chromium-iron are employed which are free from nickel and have a high chromium content up to 28%. In consequence of the greater resistance to oxidation thereby obtained with a consequent reduction in the scaling of the crucible material the rate of solution of the iron is reduced without its being possible however, to prevent the absorption of iron in a satisfactory manner. Furthermore, crucibles of this kind are unsuitable on account of the fact that they become brittle in the course of time and there is also a danger of crack formation.
It has now been surprisingly confirmed that the iron absorption can be prevented entirely Whilst at the same time the brittleness due to the chromium with the consequent risk of cracks can be avoided, thereby allowing magnesium which is substantially free from iron to be obtained, if the treatment of the magnesium or magnesium alloys is carried out in an apparatus, crucibles or the like, which at least as far as the part or parts which come into contact with the magnesium or magnesium alloys in a molten condition are concerned, is provided with a protectiv layer of chromium free from iron. This protective layer may be produced in a known manner for example, by the precipitation of chromium electrolytically or by chemical means by treating the apparatus with a gaseous mixture of chromium chloride and hydrogen or with chromium carbonyl.
It is also found that when re-melting the ma nesium in iron crucibles having a protective layer according to the invention and even after a long period of use after the chromium layer has flaked off, for example, in connection with the cleaning of the crucible or by oxidation, the action remains unaffected on account of the fact that while the crucible is in use chromium has been diffused into the outer surface of the iron crucible to a sufficient depth. The effect produced by the protective layer of chromium according to the invention can be increased in accordance with the latter by the heat treatment of the parts of the apparatus or crucible in question in such a way that at a raised temperature the diffusion of the chromium is increased before the apparatus or crucible is taken into service for the required purpose.
By way of example it may be mentioned that crystallized magnesium obtained by the condensation of magnesium vapour and containing 0.000392 iron can be remelted in an electrolytically chromated crucible of iron. Only after a large number of melts have been carried out in the crucible was it possible to notice a certain though slight increase of the iron content in the remelted metal. Not more than 0.0007% iron could be traced in the metal. Furthermore, the
metal was free from chromium and irom the point of view of corrosion was equal to magnesium purified by distillation. Magnesium remelted in an iron crucible of this kind which had not been treated according to the invention was found to contain 0.25% iron.
I claim:
1. In the art of handling pure molten magnesium without contamination thereof, the process which comprises melting pure magnesium in a .ferrous metal crucible having all parts thereof which come into contact with the molten magnesium covered with a heat treated layer of metal .lic chromium free from iron precipitated on the ferrous metal in direct contact with and partially difiused by heat treatment into the under- '4 lying metal, whereby contamination of the molten magnesium with iron is prevented.
2. In the art of handling pure molten magnesium without contamination thereof, the process which comprises melting pure magnesium in a ferrous metal crucible having all parts thereof which come into contact with the molten magnesium electroplated with a heat treated layer of metallic chromium free from iron and partially diffused by heat treatment into the underlying metal, whereby contamination of the molten magnesium with iron is prevented.
SVEN CHRISTIAN PYK.
REFERENCES CITED The following references are of record in the file oi? this patent:
UNITED STATES PA'IEN'I'S
Claims (1)
1. IN THE ART OF HANDLING PURE MOLTEN MAGNESIUM WITHOUT CONTAMINATION THEREOF, THE PROCESS WHICH COMPRISES MELTING PURE MAGNERSIUM IN A FERROUS METAL CRUCIBLE HAVING ALL PARTS THEREOF WHICH COME INTO CONTACT WITH THE MOLTEN MAGNESIUM COVERED WITH A HEAT TREATED LAYER OF METALLIC CHROMIUM FREE FROM IRON PRECIPITATED ON THE FERROUS METAL IN DIRECT CONTACT WITH AND PARTIALLY DIFFUSED BY HEAT TREATMENT INTO THE UNDERLYING METAL, WHEREBY CONTAMINATION OF THE MOLTEN MAGNESIUM WITH IRON IS PREVENTED.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE2633419X | 1948-03-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2633419A true US2633419A (en) | 1953-03-31 |
Family
ID=20426679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US79725A Expired - Lifetime US2633419A (en) | 1948-03-11 | 1949-03-04 | Process for the treatment of melted magnesium and magnesium alloys |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2633419A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4353535A (en) * | 1980-12-29 | 1982-10-12 | The American Tank & Fabricating Company | Crucibles for molten magnesium and method of forming |
| US4424436A (en) | 1980-12-29 | 1984-01-03 | American Tank & Fabricating Company | Method of forming crucibles for molten magnesium |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1608694A (en) * | 1925-08-10 | 1926-11-30 | John R Cain | Corrosion-resistant article and method of making the same |
| US1995349A (en) * | 1933-05-26 | 1935-03-26 | Western Electric Co | Apparatus provided with a protective coating for handling molten metal |
| US2205854A (en) * | 1937-07-10 | 1940-06-25 | Kroll Wilhelm | Method for manufacturing titanium and alloys thereof |
| US2257668A (en) * | 1934-11-10 | 1941-09-30 | Becker Gottfried | Formation of protective layers on iron and steel articles |
| US2262220A (en) * | 1940-08-30 | 1941-11-11 | Dow Chemical Co | Melting magnesium-base alloy |
-
1949
- 1949-03-04 US US79725A patent/US2633419A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1608694A (en) * | 1925-08-10 | 1926-11-30 | John R Cain | Corrosion-resistant article and method of making the same |
| US1995349A (en) * | 1933-05-26 | 1935-03-26 | Western Electric Co | Apparatus provided with a protective coating for handling molten metal |
| US2257668A (en) * | 1934-11-10 | 1941-09-30 | Becker Gottfried | Formation of protective layers on iron and steel articles |
| US2205854A (en) * | 1937-07-10 | 1940-06-25 | Kroll Wilhelm | Method for manufacturing titanium and alloys thereof |
| US2262220A (en) * | 1940-08-30 | 1941-11-11 | Dow Chemical Co | Melting magnesium-base alloy |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4353535A (en) * | 1980-12-29 | 1982-10-12 | The American Tank & Fabricating Company | Crucibles for molten magnesium and method of forming |
| US4424436A (en) | 1980-12-29 | 1984-01-03 | American Tank & Fabricating Company | Method of forming crucibles for molten magnesium |
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