USRE12764E - Process of producing alloys or compounds of copper and titanium - Google Patents

Description

UNITED STATES" PATENT oFFIoE,

Aucusrs .l. iiossi, OENEW'YORK, N. Yi, ASSIGNOPQBY MESNE- ASSIGNMENTS, TO THE TITANIUM ALLOY MANUFAorUaInGc-oMPANY, A CORPORATION or Mains.

PROCESS OF PRODUCING ALLOYS OR GOMPOUNDS OF COPPER AND TITANIUM.

i specification of Reissued Letters Patent. Beissued Mar. 17, 1908. 7

Original No. 700,244, dated Kay 30, .1902, No. 39,331. Application for reissue filed. January 8i, 1908.

" Y i Serial No. 411,000.

To all whom it may concern:

Be it known that I, AUGUsrE J Rossr, a" citizen ofthe United States, residing in theborough of Manhattan, city, county, and State of New York, have invented a new and useful article of manufacture, being a compound or alloy of copper and titanium, and a new and useful recess for the production' thereof and Uf'kmdred alloys derived from metals in the metallic state combined with metals reviously in an oxygenated state, of which t e follo mg is'a specification.

The object (if my invention isto produce not only the aforesaid compound or alloy of cop er and titanium, but. also a simple, rea il-y-carried-out, and industrially-economical process forroducing the same, as well as other kindred alloys into whichare combined a desired metal normall available in its metallic state with anot er metal or metals existing in the form of oxids.

My invention consists, among other things, in utilizing in the production of said alloys a bath consisting of molten aluminium and another molten metal or metals introduced into the charge in themetallic state, then introducing into the bath the oxygenated metal or metals and apgliying to the molten mixture while suppor such heat as to cause the separation of the oxygen'from the said oxygenated metal and its combination with the aluminium, whereby the in edients of the charge become separatedmto two general divisions, the one consisting of the molten metal, which was introduced in its metallic state other thari'the' aluminium is readily as combine, or alloyedf'with the metal which was introduce in its oxygenated statei and the other consisting of a slag-cemp of the combined oxygen" and al'ummi um in the form of alumina; and also-other impurities present in the charge, which slag arable from the said alloy. Letters atent of the 'United States No. 648,439 were granted to me on the 1st da of May 1900, for a process for producin'gal oys of iron and titanium which process consisted,'- broadly, in introducing titanic acid into (a bath of molten iron and aluminium' and supplying to the mixture while supported eat sufficient to institute the requisite reaction between the aluminium and the oxygen of 'the acid, and I then believed that 'if not indispensable part in facilitating and promotin the said reaction; but I have since discoveret l sential or indispensable in the charge, but that other molten metals.as, for instance, molten copper-may be substituted therefor without impairing the reduction of the titanic regard being had to the application and maintenance of the required heat, an alloy of titanium and copper or of such other metals may be readily and economically produced and the arts.

by myprevious Letters Patent, depends in a measureu on the fact that the heat of a varies at different temperatures, dimmlshing;v generally as the latter rise, and that -While the heats of such combination of formation in the case of two given metals may be identical at a certain very high temperature such heats vary absolutely, and particularly' relatively to each other as the temperatures vary, so that at lower temperatures said heat of oxid formation of the one metal used in my process as the reducing agent may be enormously greater than the corresponding heat at the same temperature of another similarly-used metalor 'substance' as, for instance, assuming" that the temperatures of oxid formation of carbon and are substantially. identical at the temperature of 2,00'0f centi'grade or tli'er'eabout, at therethirty thousand calories andthat of carbon only twenty-eight thousand calories, while at temperatures above 2,000 centigrade the heat of formation of carbon monoxid bebon: begins to decompose alumina. From this it follows that-certain, metals may be employed with eat advantage under-contit nium, for instance, and my, experiments an tests have demonstrated such to be the fact. f

' I amaware-that aluminium is a very the molten iron as such played an important powerful reducing agent and has long been My present invention, like that covered comes greater than that of alumina and car-' that molten or any iron is not es-.

acid by the aluminium, and that thus, due Y on an industrial scale for use in manufacture given meta s combination with oxygen aluminium per one atomic'weight of oxygen duced temperature-ofl'say, 0 ce'ntigrade to 500 centigrade the heat of formation of alumina is substantially one hundred and ditlons hereina ter described as reducing I agents for such'a refractory oxid as that of.

known as such, and that it hasbeenprior to ably .aluminium), thezheat of the formation my said invention used to a limited extent of the oxid of which is at a certain hightemsfor the-reduction'of metallic oxids; but acperature, presumably eater ,than that of cording -to my information. the aluminium k the formation of the OXlCl of the said oxygen- 5 and oxids involved have insuch cases beenated metal-that is to say, in a crucible or preliminarily reduced to a state of ,impalother convenient supporting vessel I prepare pable powder and intimately. mixed or sub a bath of molten aluminium by utilizing for. jected to the action of additional reagentsthat purpose in any convenient manner tem- V as, for instance, fluorids of the alkaline 'peratures sufficient to reduce the aluminium 0 metals and aluminium. In this manner to and retain it in molten state. I then fur- 75 under ordinary temperature one point of the ther introduceinto the crucible'and into such mixture has been raised to a temperature molten aluminium such proportion of one of suificiently high to commence the desired the metals to be allo ed aswill be required to reaction, whereupon the latter is then conform an alloy of the composition desired. tinued exothermally until complete'that is, This metal being in the metallic state I like- 80 without the assistance of any external heat; wise meltit down'in the crucible, so that it but the expense of the aforesaid previous shall become a com onen-t of the bath.' I preparation of .the aluminium has proved next introduce into the bath such proportion prohibitory of industrial utilization of such ofthe oxygenated metalas ,f for instance,

reaction at least inmany fields, among them rutile-as will insure in the resulting alloy 35 conspicuously those in which it has been 'dethe desired proportion of such'metal'as, for I sired to produce alloys of titanium with instance, titan1umand it will be vobserved other metals, and, moreover, the-comparathat the ingredients thus entering into the tively brief duration of the great heat probath are introducedt herein not necessarily duced by the said reaction and the combmain a powdered condition, but merely in their 90 tion of the oxygen of the metallic oxid withnatural condition of such coarse subdivision I the reducing metal has proved inadequateto as will tend to accelerate their reduction to V secure such reaction completely in all inthe molten state; I 'next raise the temperagredients of the charge su ject thereto, theture of theba'th so constituted to apoint suf- .30- comprehensiveness of the extent of reaction .ficiently high to\ insure' the commencement of 5 secured in such cases being dependent upon the reaction in which the refractory oxygen+ and proportional to the mtimateness with ated metal parts with its oxygenand the latwhich the powdered articles of the reducing" tercombines with the aluminium to form metal are mechanica ly approximated to and alumina. 'The intense heat resulting fronr commingled with the corresponding OW' the saidreaction supplements un'injuriously dered particles of the oxygenated met I thetem erature already previously'secured, am not aware that it hasever prior-to my and in-Pact this exothermal excess of heat present invention been even attempted to would during its continuance permit of the produce alloys even of iron and titanium" reductionof the temperature first applied to y the use of such processes involving the the charge asaforesaid were such reduction preliminary reduction of the reducing and of any economical importance; but it will be refractory oxygenated metal into conditions observedthat as the exothermalh'eat of the l of finepowder to insure mechanical mixture reaction diminishes I take pains to supply and dependent. thereafter upon the 'exo from the original external source such con A5 thermal heat developed by the reaction; but tinuance or addition of heat as to maintain o .I am satisfied from experiments made by me the ingredients of the charge at the tempera- 1 that aside from the expense involved in-such ture re uisite to insure fluidity, and the fullpreliminary pre aration of the niaterialsaccomp ishment of the aforesaid -react1ona an expense pro ibiting the application of amon such particles of the-charge as may such processes on an industria scalesuch have ailed to become requlsltely associated. 5 processes are incapable of producingeither during 'the com aratively'brief duration of with certainty or with any re uislte unithe exothermal reat arising from the said reformity "that completeness 0 reaction action taking-place in the major portion of through all parts of thecharge re uisite to .charge. I r

-- insure the production of an alloy of t e metal V The result of my aforesaid improved proc- 120 sought to be combined with the normally ess and treatment of the ingredients of the oxygenated metal, free from uncombined charge is as follows: As the oxygenated com-- remnants of the reducing metal as well as pound becomes reduced its molten metalhc other undesirable impurities constituentsbecome associated with the The process of producing the alloys inmolten metal with which it is sought to make 12 volved in my present invention is as follows: ,the alloy, while the liberated oxygen s I provide in any convenient Way for the supsimultaneously taken up by the alumnnum, port of the oxygenated metal and the metal producing an alumina slag whlch either to be alloyed therewith a bath consisting in floats upon the surface of the bath and can be whole or in part of a liquefied metal, (preferthus separated and withdrawn by any of those numerous methods whichwillbeobvious. to those skilled inthe' art or readily the oxygenated metal or the metal to be alloyed therewith, or both, will on the sufficient continuance of the high temperature required enter into and become constituents of the said slag, into which, on the one hand;

will become incorporated substantially all.

impurities of the charge, leaving, on the other hand, in the nether portions of the bath a substantially pure metallic alloy of the desired metals. As regards temperature, the requirements are the application of an ex- --ternal initial heat sufficiently high not only to liquefy the metallic constituents of the charge, but also to set up the aforesaid reaction. While the exothermic action is 00- curring, and consequently high temperaturesgenerated thereby, the amount of external eat may, if desired, be diminished; but

upon the termination of the exothermic action the heat derived, from an external source should be again raised to such a temperature as to insure the continued fluidity of the charge, and'thus the extension of the reaction to all particles capable of ,participating therein. Such being 'the requirements of temperature in the use of my process, I find it preferable to derive the required heat through the instrumentality of an electricall -derived temperatures, since such means of eating are morereadlly controlled during the various stages of my process than any other with which'I am acquainted. ;A convenient manner of utilizin 1n the application of my process such e ectrically-de- -rived heat consists in supporting thej'ingradients of the charge in a crucible contained in a furnace and surrounded'by caron August 23, J 898; but it will be understood that any other means of producing in the charge, electrically or otherwise the required high temperatures will be suflicient. The amount 0 heatrequired is merely such as to insure the li( uefaction of the metallic "constituents of t e charge and the raising of the bath of aluminium to and its maintenance ata su'ificiently high temperature to reach the point of the heat of formation of alumina as a maximum, which is supposed to be in the vicinity of 2 ,000 centigrade, or thereabout.

The relative proportion of the ingredients of the charge. cannot be stated by any hard and fast rule,;',but would depend in each as instance upon the varying qualities of the electric furnace or other application of high bon, into which are rojected the electrodes, eing illustrated in the,

process W1 stood processes.

ingredients, as well .as the res ective ercenta es of the combined meta s desired in the al oy. The intensity of the external heat to --be supplied during the operation of my I depend in all cases on the more or less refractory character of the alloy intended to be obtained,'and experiment'and practice alone can teach in each case which form of heat is the most convenient or best adapted therefor. As a general rule it may be stated that the oxy enated' metal or a in such ro or'- tion relative to the aluminium of the at as to insure the complete combination on the reaction of all aluminium and oxygen in the charge. Experiment will be required in each case of varying materials to determine in advance this proportion; but one of the advantages of my process consists in the facility with which any residuum of alumini-' um remaining in the charge after the completion of there action may be refined out of the alloy merely by the addition-of furthermetallic oxids while the temperature and molten condition of the charge is'maintained'. M preference for performing my process by tile aid of heat derived from an electrical source is not to be taken as excluding other heating means. In many-cases I find that for certain ferro metals the high temperatures of an electric furnace are notrequired, but that those of an open-hearth furnace or any other similar metallurgical contrivance by means of which sufficiently high temperatures can be produced will prove 'suflicient, [100 theonly limitation being that the source of heat shall be of sucha character and capacity as to maintain the alloy in-a molten. condition after the reduction of the oxids'by the aluminium and long enough to insure the separation of ingredients of the charge above de-: scribed andthe resulting purification of the allo In all cases of the application of m sai process and whatever may be the meta lic oxid reduced the aluminium oxidized into alumina at the ex use of the oxygen of such oxids forms,- as I ave stated, a slag which is readily separated from the alloyed metals underneath it when cooled or which can be tapped out of the furnace, if desired. This 15 melted alumina as a sort of artificial corun-' dumforms an excellent abrasive material somewhat akin to natural corundum, which is im ure alumina, and this byroduct of the 'a o is valuable for use as suc abrasive 12o materia or it may be treated as bauxite is in order. to remove such impurities as may be associated with it as resultant slag from my process, impurities derived from the gangues of the metallic oxids used, and thus prac- 1 25 tically ure alumina produced read .to be I reduce to aluminium again by wel under- I have in'this manner recovered from the use of the aluminium bath in my processeighty to ninety per cent. of

the aluminium used as a reducer, which appreciably increases the economy'of my said process. My experiments have also demonstrated that my'process is particularly applicable, as stated, to the introduction of metals other than iron into combination or alloy with titanium. For instance, I have loys have proved even at their surface,sufli- As an illustranium, which alloy I have named cuprotitanium. In such cases I have substituted for the bath-of iron, specified as essential in my aforesaid Letters Patent for,the production of ferro-titanium, a bath ofmolten copper and have charged into the furnace containing the same (preferably, though not necessarily, an electric furnace for the reasons given above) aluminium in ingots in quantity sufficient to accomplish the requisite reaction and have added to the charge in the requisite proportions, as above stated, to insure a complete reaction titanic acid in moderately-coarse grains, and initiating and maintaining in the charge a temperature sufficient to insure, first, liquefaction of the metallic constituents, next, the inception of the reaction between the aluminium and the oxygen of the oxid, and, finally, the continued maintenance of the charge in a molten condition until the requisite separation between the constituents has been secured have thus. obtained the said new alloy of copper and titanium. I have thus obtained such alloy containing in different instances, accordingto requirement and constitution of the :charges, copper and, respectively, 5.55 per cent.,' 8.45 per cent., and 14.15 per cent. of titanium and possessing such properties of toughness as not to bend even under a heav sledge-hannner blow, and some of. which ai ciently hard to'scratch glass. tion-of practically successful working charges forthus producing cupro-titanium Inlay mention the following: Copper, one hundred pounds; rutile, nine pounds; aluminium, five pounds. Copper, one hundred pounds; rutile sixteen pounds, aluminium, eight pounds. Copper, one hundred pounds, rutile, thirty pounds; aluminium, fifteen pounds. in the case of the first two mixtures thus constituted I was able to operate successfully the application of the process in a wind-furnace with a strong blast, the resulting cupro-titanium alloy containing, respectively, five per cent. and eight per cent. of titanium and being sufficiently fluid even under the heat thus employed to be poured off in waffles. In the case of the last mixture above mentioned I used with equal success the heat of an electric furnace. Should it be desired to introduce nickel, molybdenum, chromium, vanadium, or any other metal into alloy with the copper, the'oxids of such other metals should be substituted for it the titanic oxid, taking care that the said oxids so substituted shall be as free from purities as ava lable or even in some cases specially process. 11 the case that molybdenum is used for instance molybdic acid, iin the case of vanadium, vanadic acid, &c.;, might be used. f

What I claim as new, and" desire to secure by Letters Patent, is the following, viz: 1. The process of producingalloys of meturified for the purposes of theals assembled in the metallic state with metciently high to insure'the requisite reaction between said reducing metal'and the oxygen .ofthe oxygenated metals leaving the liquefied metallic residuum of the latter to become alloyed with the liquefied metals which were introduced in the metallic state, substantially as and. for the purposes described.

2. The process of producing alloys of metals assembled in themetallic state with met- "als in oxygenated. state, which consists in introducin into a bath of aluminium and of such metals in the metallic state molten to gether the oxigenated metal and then developing in the c arge a temperature sufficiently lngh to insure the requisite reaction between the said moltenaluminium and the oxygen of said metals in the oxygenated stateleaving the metallic residuum of said last men-,

tioned' metals to become alloyed with the said liquefied metal which was introduced in its, metallic state'into the charge other than aluminium, while the latter combines with the oxygen of said oxygenated metals and as an alumina slag containing also otherimpurities of. the charge is separated from the metallic alloy aforesaid, substantially as and for the purposes described. i

3. The process of producing an alloy or compound of copper and titanium which consists in introducing, into a; bath of aluminium and copper molten together, titanic acid and then develo ing in the charge a temperature sufficiently iiigh to insure the requisite reaction betweenthe said molten'aluminium and the oxygen of the titanic acid leavin the molten titanium to become alloyed wit the molten cop r while the aluminiumv combines with t 1e oxygen-of the said titanic acid and as an alumina slag containing also other impurities of the charge is separated from the said alloy of copper and titanium, substantially as and for the purposes described.

4. As a new article of manufacture a compound or alloy containing an important or com ound of copper and titanium, subquantity pf l(iopper say (pot less than 10 per stentia 1y as and for the purposes described. centum o t e mass an titanium in industrially im ortant proportions that is to say AUGUSTE E0881 5 not less t an 5 per centum of the mass, sub- Witnesses:

stentially as and for the purposes described. ED. AD. BRUCKNER,

5. As a new article of manufacture anelloy J. GERBER.