US2616800A - Method of making cupro-titanium - Google Patents

Description

Nov 4, 1952 F. s. wMfrMANy METHOD OF MAKING CQPRO-TITANIUM Filed Nov. 22

M m MR Wm .mm M m ATTORNEY Patented Nov. 4, 1952 lMETHOD or MAKING CUPRo-TTTANIUM Frank S. Wartman, Tucson, Ariz., assigner to the United States of America as represented by the K Secretary of the Interior Application November 22, 1949, Serial No. 128,897

1v claim.v (o1. 75;,164) (Grantedv under the' act of March 3, 1883, as

amended April 30, 1928; 370 O. G. 757) ,Y The invention described herein may bev manufactured and used by or for the Government of the United States for governmental purposes Without the payment to me of any royalty thereon in accordance with the provisions of the act of April 30, 1928 (Ch. 460, 45 Stat. L. 467).

This invention relates to the manufacture of metal alloys, and more particularly, to the production of alloys containing copper and titanium.

Heretofore, alloys of copper and titanium have' been produced by the reaction of titanic acid withv a molten alloy containing copper and aluminium, for example, by the process shown in U. S. Reissue Patent No. 12,764 in the name of AL J. Rossi. Alloys of copper and titanium have great utility inthe arts, not only for fabrication but also for employment as deoxidizing agents' in the manufacture of copperalloys generally.V

Alloys of copper with titanium are also useful as master alloys for purposes of grain refinement, hardening and the like, when added to other alloys of copper. It has now been found that alloys of copper with titanium of controlled composition can be prepared by va simple and novel method susceptible of large scale operation.

Accordingly, this invention has for an objectv the productionof alloys of copper with titanium. Another object is to prepare such alloys containing between about 22 and 27% titanium by weight which are capable of melting at a relatively low temperature. Still another object ls to prepare alloys of copper with titanium by a processutilizing titanium chloride as a rawmaterial. Further objects willl be apparent or will appear as the ensuing description proceeds.

These objects are accomplished in accordance with this invention which provides a process for the production of an alloy of copper with titanium wherein an alloy of copper with magnesium is heated to fusion temperature while protecting the same from contact with the atmosphere, then titanic chloride is passed through said fused alloy in an amount sufiicient to react with the magnesium metal, the reaction mass is l cooled and the formed cupro-titanium is separated from the formed magnesium chloride., In one preferred embodiment the original alloy of copper with magnesium contains a suficient quantity'of magnesium such that ywhen reactedv with titanic chloride, there will result a cupro titanium alloy containing between 22 and 27% by weight of titanium. i. Y

While it is not vdesired to limit the invention to any particular theory of reaction, from information presently available, it appears that the V metallic magnesium, when heated to fusion tern' perature in the form of an alloy with copper, reacts with titanium tetrachloride or other titanium halide. to yield a magnesium halide'salt while liberating metallic titanium. lliorthwith,l the liberated metallic titaniumy alloys with the molten copper and the liberated magnesium chloride or other magnesium halide floats to the' top of the fused alloy. For each percent by weight of magnesium in the original copper-mag# nesium alloy, there results 0.986% by Weight,l of metallic titanium in the final copper-titanium alloy produced, provided, of course, that suiiicient titanium chloride is passed into the empre-magi nesium alloy toreact completely with themag'- nesium content thereof. Preferably, in the preparatlon of cupro-titanium in accordance" with this invention, a slight excess of titanium tetrahalide is introduced into the molten cupro-magnesiumalloy, say 1% excess, in order to insure substantially complete reaction of the magnesium content. Y

During the course of the reaction between the copper-magnesium alloy and the introducedti-v tanium tetrachloride, it is necessary to protect the fused metallic mass from contact with the atmosphere'or other contaminating gases. "As

is` known, titanium rapidly reacts with such diverse gases as oxygen, nitrogen, hydrogen, carbon monoxide, carbon dioxide and the like. Ac-w cordingly, the reaction mixture isenveloped in an inert gas, by preference one of the so-called rare gases: argon, krypton, and preferably helium, may be employed as a protective atmos` phere since none of these gases substantially rel' act with magnesium or titanium. Similarly, the

heated reaction mixture must be protected fromv contact with metals, otherwise the cupro-tif tanium and cupro-magnesium alloys will, in turn,r

alloy with metallic components. f Since titanium tetrachloride is highly corrosive to metals gena erally, it is desirable that the reaction mixture and heated conduits through which titanium 'tej-n trachloride is introduced be made of graphite or other inert refractory materials.

Reference is made to the acompanying drawing;V

wherein is shown an elevation partly in section of apparatus suitable for carrying out the profduction of cupro-ttanium in accordance with this invention. In the drawing is shown a closedk furnace I having a burner 2 for admission of air and fluid fuel. Near the lower portion ofthe furnace l there is shown a port 3 from which is withdrawn the produced` cupro-titanium vand magnesiumchloride. asrwill be describedin more` detail hereinafter. A flue 4 in the upper portion of the furnace I permits spent combustion gases to emerge. AXially positioned in the furnace I is a metallic receptacle supported by a refractory column 6 resting on the bottom of the furnace I. The receptacle 5 is provided with a graphite lining 'I which is drawn out to form a tapping spout 8 horizontally projecting therefrom at the bottom thereof. The spout 8 during heating of the charge is surrounded by a toroidal manifold 9 provided with apertures about its inner periphery for cooling the spout 8 with cold air. The manifold 9 is attached to and supported by an air pipe Ill. During tapping of the charge there is utilized a launder I I which is removable and employed only during tapping. Projecting from the receptacle 5 is a closed cylinder I2 which extends upwardly out through the top of the furnace I and provides a chamber for the admission of helium or other inert gas into the receptacle 5. Surrounding the cylinder I2 a1; the top of the furnace is a water jacket I3 provided with an inlet pipe I4 and an outlet pipe I5 for passage of water or other cooling iiuid therethrough. A metal pipe I5 projectsV upwardly from the cylinder I2 and is positioned axially therein to provide for the admission of helium and titanium chloride into the receptacle 5. The pipe I6 terminates at the upper portion of the furnace I but is continued by a graphite tube I'I which extends nearly to the bottom of the receptacle5 so as to introduce titanium tetrachloride or helium at the bottom of the receptacle 5. The pipe I5 is terminated at its upper end-by a valved inlet I8 for the initial admission of helium' or other insert gas into the receptacle 5 -whereby air is displaced. Radially projecting from nthecylinder vI2 above the Water jacket I3 is avalved outlet I9 for withdrawal of air and excess helium from the receptacle 5 and the cylinder I2. An additional valved inlet 20 projects from the` top of the cylinder I2 for the admission of heli-um simultaneously with the admission of titanium tetrachloride through the pipe IB. Above thetop of the cylinder I2 a valved inlet pipe 2I projects radially from the pipe I5 below the valved inlet I8 in order toV introduce titanium tetrachloride into the pipe I6 through the. graphite tube I1 into the receptacle 5. A iiow meter 22 may be provided in the inlet pipe 2I for metering the ow of titanium tetrachloride. A tank 23 adapted to contain titanium tetrachloride is supported on weighing scales 24 and connected by means of a flexible tube 25 through the flow meter 22 to the valved inlet 2I.

In operation of the above described apparatus,

the furnace I is heated by the burner 2 while the tap hole 8 is cooled by means of air coming through the pipe I9 and being directed against the tap hole 8 by the toroidal manifold 9. For initial operation, a quantity of magnesium chloride is introduced into .the receptacle 5 where it is melted and a gob thereofis solidified in the tap hole 8 by means of the air jet manifold 9. Thus, the receptacle 5 may now be charged with cupromagnesium. The top cover 2 6 on the cylinder I2 is removed and granulated cupro-magnesium alloy is dropped through the cylinder I2 into the receptacle 5. Thereupon the cover 29 is replaced, the cooling jacket I3 is provided with a circulation of water or other cooling fluid and helium is passed intothe valve inlet I8. At thisl time, the titanium tetrachloride inlet EI is closed, as

is the inlet 20, and the outlet I9 is opened. ItA

will be seen that helium passes downwardly through the pipe i5 and the tube- I1 to the' bottom of the receptacle 5 and the air in the receptacle 5 is displaced out of the apparatus through the outlet I9. Upon heating to a suitable temperature of say 950 C., the cupro-magnesium alloy in the receptacle 5 becomes molten. Thereupon, valved inlet 2I is opened to permit the ingress of titanium tetrachloride from the storage tank 23 through the iiow meter 22 and thence downwardly through the pipe I6 to the bottom of the receptacle 5. The titanium tetrachloride forthwith reacts with the fused metal and converts the magnesium content thereof to magnesium chloride which floats above the metal as an upper layer 2'I. As required in order to maintain a slight pressure, additional helium is introduced through the inlet 20 concurrently with the introduction of titanium tetrachloride. The rate of introduction of titanium tetrachloride is controlled by means of the scales 24 and the iiow meter 22 in order to maintain complete reaction in the receptacle 5. Generally, the receptacle 5 is heated for about an hour after the required quantity of titanium tetrachloride has been passed into the fused metal. Upon completion of the reaction, the air supply to the inlet I0 and toroidal manifold 9 is shut 01T and the launder II is inserted into the furnace so that the tap hole 8 `will-discharge its contents through the launder II into the receiver 28. As soon as the plug of magnesium chloride in the tap hole 3 melts, it, together with the product, cuprotitanium alloy, Passes out through the tap hole 8 into the launder I I and thence to the receiver 28. The operator upon observing that `all of the metal and most of the magnesium chloride Table Pounds Cupra-magnesium charged Time required for bringing to temperature. .liours Time required for addition of TiCli.. lo..- Pounds TiCl4- added i i Pounds cupio-titanium made Analysis oi alloy made:

Element .i Fe Mg C Percent by weight 0.2 0.1 0.04

While the technique and apparatus described above have proved quite suitable for the intermittent operations used in developing the process, many variations come to mind which might be desirable in steady operation. Time might be saved by adding the charge of cupro-magnesium to the reaction chamber as soon as the products of the previous run had been removed and the tap hole plugged. The charge of cupro-magnesium might even be added in uid condition by having a bath of it ready and molten in a second furnace. The tight cover and protective atmosphere of helium described might be dispensed with and a loose cover and thick fused layer of low melting chlorides used as a protective cover. For continuous operation it probably would also be advantageous to substitute an alloy resistant to oxidation at high temperatures for the mild steel used for the outer shell of the reaction chamber.

While the above description embodies the principle of the invention in its presently visualized preferred embodiment, various changes may be made as will occur to one skilled in the art with- 5 out departing from the spirit and scope of the invention.

What is claimed is:

A cyclic process for the production of a cuprotitanium alloy that consists in heating a vessel having a bottom tap hole, establishing a body of molten magnesium chloride therein and cooling the tap hole portion of the vessel to solidify part of the magnesium chloride therein and thus seal the tap hole; introducing a body of copper magnesium alloy into the vessel, blanketing said alloy with inert material and continuing to heat the vessel while cooling the tap hole portion thereof to establish a hot pool of fused alloy in the bottom of the vessel; passing into the fused alloy a quantity of liquid titanium tetrachloride in slight stoichiometric excess with respect to the magnesium of the alloy and continuing to heat the charge until the magnesium of the alloy is converted to magnesium chloride; discontinuing the cooling of the tap hole portion of the vessel to REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 1,321,684 Turner et al Nov. 11, 1919 1,648,954 Marden Nov. 15, 1927 2,157,979. Cooper et al May 9, 1939 2,193,363 Adamoli Mar. 12, 1940 2,205,854 Kroll June 25, 1940

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