Патент USA US2067507код для вставки
Patented Jan. '12, 1937 2,067,507 UNITED STATES. PATENT OFFICE 2,067,507 - rnocnss or rename LEAD AND man ALLOYS George 0. Smith, East Orange, N. 1., assignor to Bell Telephone Laboratories, Incorporated, New York, N. Y., a corporation of New York No Drawing. Application August 28, 19:0, . 7 ‘Serial No. 478,551 25 Claims. (01. 75-166) This invention. relatesv to,.,a method of im such, as bromides,‘ ?uorides, and iodides react proving‘: the mechanical properties of lead and similarly to the chlorides. ‘ lead alloys and more particularly to a method‘ Thus, when small quantities of chlorides of of alloying certain high, melting-point metals high melting-point metals, such as copper, silver, with lead or lead alloys at comparatively low nickel, cobalt and others, are added to a large 5 temperatures. ' bath of molten lead, the lead‘replaces all of the A certain kind oi?v commercial pig lead, such as high melting-point metal of the salt to form Southeastern Missouri District lead, contains lead chloride and theliberated high melting metallic impurities consisting of very smallquan point metal ‘then alloys with the lead. There- ,\ titles of high melting-point metals, such as “cop quired temperature‘for the reaction ‘need only 10 per, silver, nickel and cobalt, and has been, be slightly above the melting point of lead chlo found to have physical properties which make ride.” Similarv vreactions take place when, the this kind of lead especially desirable for certain chlorides are added. either to a bath of molten, purposes, as for example, for cable sheath alloys. antimony or to a bath ‘of molten lead antimony" I 15, Another kind of commercial pig lead, such as alloy; _ ‘ 16 Bunker Hill lead, has a high degree of purity Certain oxides, which do not readily react with and is particularly characterized bythe almost lead in a process such as that described, have‘ ' total absence of‘theumetals referred to above. been found to react‘with‘ antimony in such a This high purity lead has been found’ not to process. When copper oxide is in contact with possess the desirable physical properties to as molten lead at a temperature of approximately go high a degree as the first mentioned lead. It 500° C. metallic copper and lead oxide are formed has furthermore been observed that when lead and, when there is an excess of lead, an alloy is alloyed with’ 1% of antimony, as for use in of lead and ‘copper results. ‘Oxides of copper, cable sheaths, the presence of the small quan cobalt, nickel and iron react similarly with mol tity‘of high melting point ‘metals has an addi- ' ten'antimony resulting in alloys which'mayxbe 25 tional advantageous effect, upon the physical used‘ as addition products in the manufacture properties of the alloy. 7 _ r The di?'erence in physical properties may con I ‘of lead antimony alloys containing these metals; or'the oxides can be brought into contact with a sequently be ascribed to‘ the presence of the metallic impurities referred to, which appear to impart to ‘the lead as well asto the lead alloy greater tensile strength, higher percentage elongation, and better fatigue resisting prop erties. ‘ ' , 35 V In accordance with the invention a method the'alloy‘will reduce the oxides and the copper, cobalt, nickel and iron will enter the melt. The by-products of the reaction is antimony oxide. An important feature of the method resides in the fact that practically the total amount of as is_ provided by which certain high melting-point metal added in the form of salt or oxide enters metals, such as copper, silver, nickel and cobalt, into the lead. Another important feature resides in the fact that the process may be carried out at temper atures considerably below the melting points of 40 the metal to be added,_the highest necessary tem perature used in the process being not much above the melting point of lead. This fact is of ad may be added to lead or to certain lead alloys, . such as antimony‘lead, at comparatively low temperatures and inexact, small quantities to ‘produce lead alloys ‘with improved physical properties. . During an extensive investigation of lead and 45 lead antimony alloy ‘whereupon, at a tempera ture of approximately500° C.,'the antimony in 30 lead antimony alloys it was found that com paratively small quantities of oxides and certain salts, such as chlorides, of these high melting vantage in a commercial process‘ in that the process is simpli?ed thereby and is made ‘more ‘5 economical. ’ point metals are practically completely reduced A further advantage observed in connection in the presence of the lead or antimony-‘under ‘with the use of chlorides is due ‘to the mum . the application of heat, that is, the free metal lead chloride formed during the reaction is not w to present replaces and liberates the one contained . miscible with lead and therefore readily separates ' in the salt or the oxide, 'at least in. those in from the lead product without contaminating it.‘ stances where the heat of formation‘of the new ‘ The‘lead chloride formed ?oats on the molten salt 'or oxide is higher than'that of the original metal and serves as a ?ux. Certain other can- . salt or oxide. Certain other salts of these metals, pounds oflead, such as-lead-phosphide and lead It 2,087,507 sulphide do not possess the property of not con- place in the mold ‘by maintaining a sumcient taminating the ?nal product. casting temperature. - It is well known in the art to reduce metallic salts or oxides in the ‘presence of other metals, What is claimed is: but the prior methods have 'either been in the nature of laboratoryexperiments, or thealloy ing constituents or thetemperatures have been di?erent from those used in the present process as de?ned by the appended claims. the chloride of which has a-heat of<formation , less than that of lead chloride in an amount less than 5% by weight of the lead which comprises . Inv practicing the process in accordance with the invention, silver, copper, nickel and cobalt i have been alloyed with lead by adding the chlo reducing a quantity of chloride of said metal in 10 a bath of said lead, free of alkaline metals, at a temperature between the melting point of said lead and 600° C., said quantity of chloride of said metal containing the approximate de sired amount of said metal to be added. 15 ride of these metals. ~ Antimony has also been alloyed with silver, copper, nickel and cobalt .15 by the addition of the chlorides of these metals. Copper has been added to lead as well as to anti mony by adding copper oxide tothe metallic lead and antimony. The percentage of high melting point metal that may be added by thisprocess is di?erent for the different metals and varies from less than .5% to‘ a few percent of the lead , , I In preparing these alloys one procedure .was to melt pure lead and heat to 525° C. in a cru cible, remove the crucible from the furnace and skim the dross of! thesurface of the melt;v the chlorides or oxides of the metals to be incora porated were then added; themolten metal was stirred and when its temperature was about ‘410°. 80 C. the? dross was removed again and‘ the alloy was castinto molds. ' . ' A free of alkaline metals, another metal having a higher. melting point than that oflead and 10 or antimony. ' 1. A method of alloying with a body of lead ’ Another procedure, which has been used suc cessfully, involved theaddition‘of 1% orslightly more of'antimony to'the molten lead; the proc 35 ess was then continued as just described. In. _ 2. A method of alloying a de?nite small quan tityof copper with lead, which comprises adding together in a container lead, antimony and chloride of copper, both said lead and said an timony being free of alkaline metals, and main taining the temperature of the contents of. said container at about 400° to 500° C. for at least a 20" .few minutes. ‘ 3.‘ A method ofv alloying cobalt with lead in t a desired amountof not more than .4% of the leadv which comprises- maintaining. a bath of molten lead, whichv is free‘of alkaline vmetals at a temperature [not more than about 100° C. above the melting-point of lead chloride, and addingthe amount of cobalt in'the form voi.’ 30 cobalt ~‘chloride to the bath. ‘ ’ 4. Aymethod of alloyingw'copner ‘with lead a desired amount of, not‘ more than.1%, of the‘ ' lead'which comprises maintaining. a bath of molten lead, free of alkaline 'metals,fat a tem 35 thisprocedure antimOny chloride will be formed perature not more than; about 100° ‘C. abovev during, the ‘reaction instead of lead chloride, for,‘ ‘the meltingv pointv of lead chloride and adding . whichreason a loss of antimony must be antici; the amount of copper in theiorm of copper‘ pated. ‘ ‘ ' ‘ chloride to the bath. 1 ' Stillanother-procedure, which has been used ' s. A 'method?of alloying silver with lead in a, 40 h desired amount of not more than 1% of the lead, whichv comprises adding v together lead, mony or as an addition alloy’ of lead and anti “which is free of alkaline metals, and the‘ amount " 5' mony,.tothe molten lead immediately after the of silver inv the form of silver chloride and main 45 small quantities of the other metals ‘have been taining the lead at a temperature not 'more..' successfully involves the addition of one percent or moreof antimony, either ‘as’ metallic anti incorporated. ’ . , , - In some cases antimony was used instead of than‘ about 100° C. above the vmelting point of i v: . lead chloride fora few minutes after'said adding. ‘ ' lead for alloying with the highfmelting-point 6. A method of alloying silver and, copperw'ith metal, the procedure being substantially the same ‘ leadv in desired amountse‘achof not more than 50 as when lead was used and the resultingalloy 1% of the lead which comprises adding together lead,‘ free of alkaline metals, and the amounts of was It in‘ should turn added be understood to lead. . that other _ metals, _ silver, and copper in the form‘ of chlorides and . than those described may be. added to lead or maintaining the lead at'a temperature not more than about 100° C. above the melting point of antimony by this process; for example, arsenic, 55 lead, bismuth, and iron may be added to anti-i ~ lead chloride for a few minutes after said adding. ' '7. A method of alloyingwith lead in a desired mony ‘by means of their chlorides; arsenic may be added vto lead by means of its. chloride; and amount of ‘not more than 1%. of the lead which . arsenic; bismuth, cobalt,’ iron, lead and nickelv comprises maintaininga bath of ‘molten lead, 60 maybe added to. antimony vby means of their, free of alkaline metals, at‘ a temperature not ,. oxides, . ‘ _ e I It should also be understood that the process may: be varied’ from the described proce 65 dures. Thus the temperature mayv be increased considerably above 500° C., but for practical pur poses it would not be advantageous to increase the temperature much beyond 600° C. It ‘is - , also possible to add the ingredients to the lead or the antimony at ordinary room temperature 70 and then heat to'about 500° C. .It is also within the scope of the invention toadd the chlorides of the desired metals to the lead invthe mold, by, for examplev ?rst placing the chlorides in the mold '_-and thenvpouring the lead or lead alloy ‘into the mold, permitting the reaction to take more than about 100° C. above the melting point of lead halide and adding the amount of copper in the form of a halide to the bath. ' ' - 6.0 ' ' p 8. A method of improving the physical proper; ties‘ of lead by the addition thereto of a small quantity of a metal having a higher melting point than that of lead, said method 'comprising'add 65 ing to the lead,‘ which is free of ‘alkaline metals, a quantity of a compound comprising said metal a " and anon-metallic constituent selected from the group which consists of oxygen, ?uorine, chlorine, 70 “bromine and iodine, said compound‘ having a I - lower heat of formation than the compound com prising- lead and said ‘non-metallic constituent, said last mentioned compound being not readily miscible with said lead and said lead being main 75 2,067,507 , 3 tained at aitemperature, between the melting‘ at a temperature below the boiling point of said ' point of said lead and the boiling point .of the compound comprising lead and said non-metallic constituent. > 9.,A, method of improving‘ the physical-prop-_ erties of. alloys comprising chieiiylead by the "addition thereto of’ small quantities of metal having a higher, melting point than that of the compound comprising lead and said non-metallic constituent. » ‘ ‘ 14. The method of forming an alloy compris ing copper and lead which comprises subjecting a molten bath‘of metallic lead, which is free "of alkaline metals, ‘to the action of an amount of copper chloride equivalent to about 1.2 pounds alloy, said method comprising'adding to the‘ of copper per ton of lead in the bath said bath being maintained at a temperature‘ below the 10 , quantity of ‘the halide ‘of said ‘metal at a term boiling point ‘of lead chloride. perature between the‘ melting'point of said alloy ‘ » 15. A method of alloying copperwith lead com and the boiling point of the corresponding halide prising: subjecting'a chloride‘ of’ copper‘ to a of lead, said halidecf said metalhaving a lower molten bath of an alloy comprising lead and a heat of formation'thansaid corresponding halide m'etalother than a member, of the ‘alkaline group of lead and said halide oflead being not readily which reacts with the chloride of copper to form metallic copper and the chloride of said metal. miscible with said alloy. _ said bath being maintained at a temperature 10. A method of improving the physical prop I erties of lead alloy by the addition thereto of below the boiling point of lead chloride. 16. A method of forminga lead alloy compris 20 small quantities of a metal having a higher melting point than that of the alloy, said method ing subjecting an alloy consisting of lead and comprising adding to the alloy, which is free of elements having a higher melting point than alkaline metals, a desired quantity of the halide that of lead to the action of a compound com of said metal, said halide having a lower heat of prising a metal having a higher melting point 25 formation than the corresponding halide of lead, than that of lead and a non-metallic constituent‘ 25 said halide of lead not being readily miscible with - selected from the group which consists of ?uorine, 10 alloy, which is free of alkaline metals, a desired said alloy, and heating said mixture to a tem , chlorine, bromine and iodine and oxygen at a perature approximately between the melting temperature between the melting point of said alloy and the boiling point of the compound point of said lead halide and 100° C. higher. 30 . 11. The method of forming an alloy comprising ' .comprising lead and said non-metallic constitu a copper and lead which comprises subjectingv a ent, said compound of said metal having a lower molten bath maintained at a temperature be heat of formation than the corresponding com 7 low. the boiling point of lead chloride and con taining metallic lead, which is free of alkaline metals, to the action of a chloride of copper pound of lead. . , 1'7. A method of incorporating metals having a higher melting point than that of lead in lead, thereby to e?'ect the precipitation‘ and dispersion said method comprising subjecting an alloy con of metallic copper in the molten bath. 12. A method of incorporating a metal having sisting of , lead and elements having a higher ‘ a higher melting point than that of lead in an 40 alloy comprising metallic lead, said method com melting point than that of lead to the action of the halide of a metal having a higher melting point than that of lead at a temperature between 40 prising subjecting a molten bath of said alloy the melting point of said alloy and the boiling to the action of a compound comprising said point of lead halide, the halide of said metal metal and a‘ non-metallic constituent selected having a lower heat of formation than the corre from the group which consists of oxygen, ?uorine, sponding halide of lead. 18. A method of incorporating copper in lead 45 chlorine, bromine and iodine, said compound having a lower heat of formation than the com vcomprising subjecting a molten bath of an alloy pound comprising lead and said non-metallic consisting of lead and elements having a higher, ‘ constituent, said compound comprising said metal ‘melting point than that of lead maintained at a reacting with said metallic lead to disperse said temperature below the boiling point of lead halide to the action of a halide of copper whereby cop 50 50 metal in said alloy and to form a compound com prising lead and said non-metallic constituent, per is dispersed throughout said alloy. 19. A method of incorporating a metal having ‘ whichv is substantially non-miscible in said alloy in’ the absence of sumcient alkaline metals in said a higher melting point than thatof lead in an bath to introduce the desired'amount of said high alloy comprising metallic lead, said method com 55 melting point metal by the interaction of said prising subjecting a molten bath of said alloy 55 alkaline metals‘ with said compound comprising to the action of a halideof said metal in the said high melting point metal, at a temperature absence of sufficient alkaline metals in said bath to introduce the desired amount of said high below the boiling point ‘of said compound com so prising lead. M . 13. The method of forming’ an alloy compris ing copper and lead which comprises , sub melting point metal by the interaction of said alkaline metals with said halide, said halide hav ing a lower heat of formation than the corre jecting a molten bath comprising metallic lead sponding lead halide at a temperature below the to the action of a compound comprising copper boiling point of ‘ said metal halide whereby said and a non-metallic constituent, said compound metallic lead reacts with ‘said halide of said high melting point metal to disperse said metal 65 65 having a lowerlieat of formation than the com pound comprising lead and said non-metallic in said alloy and to form lead halide. 20. A method of, alloying cobalt with lead constituent, said compound comprising copper reacting with said metallic lead to form metallic which comprises adding together in a container copper and a compound comprising lead and lead, antimony and cobalt chloride, both_ said said non-metallic constituent which does vnot lead and said antimony being free of alkaline 70 contaminate the resulting alloy in the absence metals, and maintaining the temperature of the contents of said container at about 400° C. to of su?icient alkaline metals in said bath' to in troduce the desired amount of copper by the 500° C. 21. A method of alloying silver with lead which interaction of said alkaline ‘metals with said copper compound, said bath being ‘maintained comprises adding together in a container lead, 4 2,007,507 antimony and silver chloride, both‘ said lead and said antimony being free or alkaline metals, and maintaining the temperature of the contents of said container-‘at about 400° to 500° C. r > '22. The method of forming an alloy comprising cobalt ‘and lead which ‘comprises subjecting I a molten bath maintained at a temperature below precipitation and. dispersion of metallic silver in the molten bath. a 24; A method 0! incorporating cobalt in- lead comprising subjecting a molten bath of an alloy, consistingof lead-Iandelementsl having a higher’ melting'point than-‘that of lead and maintained the boiling point of‘, lead chloride and containing at a temperature below'the boiling point of lead ’, or a chloride of cobalt thereby to ‘effect the pre cipitation-and dispersion of metallic cobalt in the cobalt is dispersed throughoutsaid alloy; ‘25. A method incorporating silver in lead com- I lead which is free of alkaline metals to the action a halide to the action of ‘a halide of cobalt whereby - ‘ moltenibath.‘ > a prising subjecting a molteribathof an alloy con- ’ 273. The method of forming ‘lament-mas, sistinghlof lead andelements' having a higher ing, silver and lead which comprises subjecting’ melting point than thatof lead and‘maintain‘ed a molten nbathlmaintained at a'temperature below at atemperature below the boiling, point of lead 15 the boiling point of I lead chloride and containing halide to the action of a halide ‘of silver whereby , metallic lead which is free of alkaline metal to silver is ‘dispersed throughout said alloy. f 1 ~ themaction of silver chloride thereby toe?ect the v , a p, ' JGEoRGnQsm'm.