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United States Patent (19) 11) Patent Number: 4,770,697 Zurecki 45) Date of Patent: Sep

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United States Patent (19) 11) Patent Number: 4,770,697 Zurecki 45) Date of Patent: Sep United States Patent (19) 11) Patent Number: 4,770,697 Zurecki 45) Date of Patent: Sep. 13, 1988 54 BLANKETING ATMOSPHERE FOR 722978 10/1978 U.S.S.R. MOLTEN ALUMNUM-LITHIUM ALLOYS 697252 11/1979 U.S.S.R. ............................. 164/66.1 OR PURE LITHIUM OTHER PUBLICATIONS 75) Inventor: Zbigniew Zurecki, Allentown, Pa. Aluminum-Lithium Alloys II, Second International 73) Assignee: Air Products and Chemicals, Inc., Al-Li Conference, 1983, pp. 657-673. Allentown, Pa. "Phase Composition of Surface Films on Al Alloys (21) Appl. No.: 925,652 with Li..', Tarasenko et al., UDC 669.71'884:539.216.2, American Society for Metals. 22 Filed: Oct. 30, 1986 "Casting Problems Specific to Al-Li Alloys', Divecha 51 Int. Cl." ....................... C22B 21/00; B22D 11/00 et al., Metallurgical Society/AIMF. 52 U.S. Cl. .................................... 75/68 R; 420/528; Primary Examiner-Nicholas P. Godici 164/66.1; 164/68.1; 164/475 Assistant Examiner-Richard K. Seidel 58) Field of Search .................... 164/66.1, 67.1, 68.1, Attorney, Agent, or Firm-Willard Jones, II; James C. 164/259, 415, 475; 75/68 R; 420/528 Simmons; William F. Marsh 56) References Cited (57) ABSTRACT U.S. PATENT DOCUMENTS Blanketing of molten aluminum-lithium alloys is per 3,467,167 9/1969 Mahin .......... 164/56 formed under a nontoxic and noncorrosive dichlorodi 3,484,232 12/1969 Karinthi et al 75/45 fluoromethane containing gas atmosphere, which pro 3,640,702 2/1972 Karinthi et al. 75/59 4,200,138 4/1980 Hildebrandt .......................... 164/66 duces a thin self-passivating fluxing film on the melt 4,248,630 2/1981 Balmath ................................ 75/135 surface. The blanketing atmosphere protects the melt 4,389,240 6/1983 Erich et al. .. 75/0.5 B from oxidation, burning, and lithium evaporation, im 4,402,741 9/1983 Pollet et al. ........................ 75/68 R proves alloy cleanliness and can be used in any furnace, 4,522,784 6/1985 Enright et al. ... ... 420/590 transfer or casting operation. The blanketing atmo 4,532,106 7/1985 Pickens ............................... 420/528 sphere can be applied in the entire range of commercial 4,534,807 8/1985 Field et al. ......................... 48/20.3 or master aluminum-lithium alloys including pure lith 4,556,535 12/1985 Bowman et al. .................... 420/580 ium melts. The dichlorodifluoromethane concentration 4,582,118 4/1986 Jacoby et al. ....................... 164/475 in the blanketing atmosphere can range from 0.05 to 100 FOREIGN PATENT DOCUMENTS vol % with the remainder being an inert gas such as 59-19507 2/1984 Japan . argon. 2129345 5/1984 United Kingdom................ 164/475 1124540 6/1986 United Kingdom ............... 75/68 R 20 Claims, No Drawings 4,770,697 1. 2 lithium charge, inert blanketing, lithium evaporation BLANKETING ATMOSPHERE FOR MOLTEN and melt hydrogen pick-up. Both systems suffer from ALUMNUM-LITHIUM ALLOYS OR PURE the lack of proper melt surface protection for inert gas LITHIUM bubbling and handling operations. Batch processes utilizing molten salt fluxes are an FIELD OF THE INVENTION alternative to the continuous systems, discussed above, This invention relates to the production of aluminum which are expensive and inflexible in operation, particu lithium alloys, and more particularly to the protective larly when operating ranges or alloy changes are re atmospheres for the operations of melting, holding, quired. These fluxes, which are comprised primarily of alloying, stirring, degassing, mold casting, and direct 10 lithium chloride or lithium fluoride, are applied to the chill casting of aluminum-lithium alloys. surface of the lithium containing bath whereby they eliminate a part of the problem related to the lithium BACKGROUND OF THE INVENTION reactivity and still achieve a lithium recovery of ap The production of aluminum-lithium alloys has be proximately 80 wt %. Unfortunately, disruptions in the come of commercial interest, due to the combination of 15 bath surface whether by-stirring or degassing or any mechanical properties and light weight which these other movement in the bath breaks the flux layer and alloys exhibit. Unfortunately, molten aluminum-lithium exposes the metal to ambient air resulting in violent alloys are very reactive with air which makes their oxidation of the lithium. Also, fluxes are highly corro production and fabrication correspondingly difficult, sive to the refractory linings of the furnace and related The surface of an Al-Libath reveals chemical behav 20 casting equipment and materials of construction. The ior of molten lithium rather than aluminum thus causing fluxes are also known to deteriorate the metal cleanli the bath to: (1) burn on contact with air thus forming an excessive dross layer with the generation of toxic fumes ness and contaminate the environment as well as the resulting in poor lithium recovery and hazardous work equipment including melting, mixing, holding, and al conditions; (2) attract hydrogen from the atmosphere, 25 loying furnaces, metal transfer troughs, casting stations, including traces of water vapor, which increases hydro direct-chill liners and molds. Difficulties associated gen absorption and results in higher porosity levels and with storage and handling of the fluxes frequently cause a loss of the desired mechanical properties; and (3) be a carry over of moisture into the aluminum-lithium melt come practically unskimmable thus preventing proper and the subsequent oxidation and hydrogen pick-up. stirring and degassing of the melt since any disruption Other solutions such as blanketing with a pure dry of the generated dross will increase the rate at which inert atmosphere eliminate the flux method drawbacks, further quantities of dross are formed. To overcome however, these require tightly enclosed pots and these enumerated difficulties, several solutions have troughs and therefore are not flexible enough to be used been offered in the literature. in various stages of aluminum-lithium fabrication. Fur U.S. Pat. No. 4,248,630 discloses a process for adding 35 thermore, inert atmosphere blanketing does not de alloying elements, including highly reactive metals such crease lithium evaporation from the bath, which results as lithium, to molten aluminum so that normally occur in substantial lithium losses and creates a potential ha ring oxidation reactions of such elements with the atmo zard. Inert atmosphere blanketing does not provide flux sphere is minimized. Basically, the process requires that layer cleaning properties such as preventing the hydro all other alloying elements except lithium be added to gen just removed from the bath during degassing from the molten aluminum and the melt be degassed and freely back-diffusing into the uncovered alloy, and/or filtered. Upon completion of the degassing/filtering allowing nonmetallic inclusions which have moved to step, the lithium is introduced into a mixing crucible as the bath surface during inert gas stirring to be inter the final step prior to casting. The desired concentration cepted by the flux layer. of the lithium is achieved by controlling the relative 45 amount of lithium and the alloyed melt. Uniformity of SUMMARY OF THE INVENTION the mixture is achieved by mechanical stirring. The The present invention is a protection process for use mixing crucible and all other crucibles in which lithium in melting, holding, alloying, stirring, degassing, melt may be present are kept under an argon blanket. transfer and casting processes for molten aluminum U.S. Pat. No. 4,556,535 discloses a process for form 50 lithium alloys or lithium. The process of the present ing aluminum-lithium alloys which comprises continu invention comprises blanketing the top of a molten ously monitoring the ingot casting rate and continu aluminum-lithium alloy or lithium bath with an effec ously adding a measured and controlled amount of tive amount of a nontoxic, reactive, dichlorodifluoro molten lithium beneath the surface of the molten alumi methane containing, gas atmosphere. The dichlorodiflu num stream as it flows to the ingot casting station. At 55 oromethane reacts with primarily the lithium in the melt the contact location of the lithium and aluminum, a and rapidly forms a thin fluxing layer on the surface of mixture of argon and chlorine and/or other inert and the bath. This thin layer prevents oxidation of the melt, reactive fluxing gases is injected through a vaned, rotat hydrogen absorption into the melt, and the formation of ing dispenser. The patent further discloses that the in a heavy dross layer; the thin layer is easily skimmed troduction of the lithium into the aluminum must be from the surface if necessary. The layer develops even below the surface of the aluminum in order to minimize if not all of the ambient air is evacuated from above the the occurrence of oxidation, fuming and hydrogen ab melt. sorption. Alternatively, other substitute blanketing atmo Both U.S. Pat. Nos. 4,248,630 and 4,556,535 counter spheres containing an effective amount of a halogen balance the detrimental effects of lithium reactivity by 65 compound having at least one fluorine atom and one means of minimizing time between the alloying and other halogen atom selected from the group consisting casting, however, neither process deals effectively with of chlorine, bromine and iodine, or an atmosphere com the problems of submerged injection of a premelted prising fluorine or a fluorine-containing compound and 4,770,697 3 4. one other halogen or halogen-containing compound The CCl2F2/inert gas blend is useable for the entire wherein said halogen is selected from the group consist range of aluminum-lithium alloys and aluminum-lithium ing of chlorine, bromine and iodine will work in the process of the present invention. The use of these alter master alloys up to 100% wt of lithium. The blend is native atmospheres would result in the same protective not, however, recommended for pure aluminum melts, layer.
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