1224
INDUSTRIAL AND ENGINEERING CHEMISTRY
121) Vennerholm, G.,iMetaE Progress, 51, 1163 (1946). '122) Vollmer, L. W.,and Wescott, B. B., IND.ENQ.CHLM..28. 1379 (1936). 123) Wachter, A.,and Smith, I?. S., Ibid., 35,358 (1943). 124) Wahlquist, €1. W., Corrosion, 1, 119 (1945). '125) \Vainer, E.,Am. Cwam. SOC.Bull., 25,248 (1946). 126) Waiiier, E.,and Baldwin, W. J., J. Am. Ceram. Soc., 28, 317 (1945). 1271 Walthall. J. H.. Miller, P., and Striplin, M. M., Trans. .4m Inst. Chem. Engrp.. 41.6.5. 71. 99. 111 (1945).
Vol. 39, No. 10
Westcott, B. B., Steel. 112,No.3,66 (1943). Williams, E. C., Trans. Am. Inst. Chem. Engrs., 37, 182 (1941, Woldman, N. E., and Metzler, R. J., "Engineering Alloys.' Sect. I1 and 111, Cleveland, Am. SOC.Metals, 1945. Woodward, E. R., Petroe, G. A,. and Vincent, G. P.. Trans Am. Inst. Chem. Engrs., 40,271 (1944). Yale, W. D., Corrosion, 2,85 (1946). Zander, J. M.,Better Enameling, 15, No. 10,4 (1944). Zirna, A. G., Trans. Am. Inst. Mining Met. Engrs., 117. 3!Jb (1935).
Lead, Tin, Zinc, and Their Alloys I
_I-
_
GEORGE O . HIERS,
_
_
-
_
_
~
-
_
_
I
_
_
&atiorru/
Lead Company, Brooklyn I , 1'. Y.
R
ESTRICTEU U-P i ~ t i k m t iwcb1s ha- caused vaiioua chaiige~ in their interrelations. I n the early part of Korld \Tar II ead was readily available for general use (9). The need of chemi.ale for war purposes created an unusual demand for lead equipnent. As zinc was in great demand for cartridge bracs. It waneplaced by lead, to a degree, for coatings on iron and steel Lead slloys likewise were used more extensively for die caqtinps ( 1 0 wrtll in place of zinc alloy die ca4npc. GENERAL ASPECTS
Yecauae of the difficulty of obtaining tin in the United StLtLea -he use of electrotinned iron for food cans became important iwnrding to a statement by .Khetzel (74) in 1944, this nen xocess accounted for one fourth of the enrire output of tin plat. snd saved 20,000,000 pounds of metal. . Prior t o 1946 the rating by use consumption of zinc galianizing, brass making, and die castings. I n 1946, for the firs. ;ime, die castings replaced braes in the second place. Such menion is appropriate here because the two major uses of zinc aintimately related with corrosion resistance. Zinc affords protvion to iron, primarily because of its o n n resistance and seco~du i l j because of its galvanic or sacrificial action. The *4.S.T.lI. m t h twenty years of continuous research, has proved that iht access of the zinc alloy die casting industry is vitally dependent ipon high purity alloys in prevenling corrosion failures due t o the xesence of certain metal impurities, lead and tin, which miiit 111 --+ricted to less than 0.010% eaeh. CHEMICAL INDUSTRY
CARBON13. I n the decomposition of carbonates for the -&tionof carbon of atomic weight 13, lead equipment is used. 1 .s believed that this new variety of carbon can be used as a trarvr n the preliminary studies for the relief of cancer. SYNTHETIC BEID C~TALYSTP (68). The Socony \ acuurii 1 JII 2ompany makes 50 tons of bead catalysts daily for use in ilit 'ecently developed Thermofor cracking process. Various tvpr>f lead equipment are employed for making alum and handling d u m solutions as part of the processing. The plant has si:, 42,000-gallon lead-lined steel tanks for alum and acid solutiona In addition, there are thirty-two lead-lined bead-forming toners. These are tile-covered for insulation. This plant uses about 125 Gens of lead pipe and equipment. The following comments on thik Drowse were made by Fettri Y
~
T
(46): Originally, the tank for making alum was lined with inch chemical lead. The tank is heated and cooled two to three times per day, the maximum temperature being 240-260 a F. After only 8 to 10 months of service this lining sagged and failed. Failure appeared attributable t o an insufficiency of lead-covered steel st,rap supports. The second linings were 3/8-inch thick tellurium lead strapped every 2 feet on sides and bottoms. To date, after about 2 years of service, the lining wh3 evidently rntirely satisfactory and showed no signs of deterioration. Recently Wormser (77), in his paper on lead equipment ilsed 111 the chemical industry, listed hhirt,y-one chemicals satisfactorily used with lead. He also discussed lead alloys, including one or more nf the following elements: antimony, tellurium, tin. and silver. Kilkinson (?6), in his study of the use of metals in handling sulfuric acid in petroleum processing, appears to prefer koniogeneous lead linings, wherein the lead is fused to the steel, to brieh iinings which he finds too expensive. On the other hand, Burke and Mantius (37) find brick linings adviaab!e for certain steps in the concentration of sulfuric acid They give a thorough discussion of the equipment used in the vacwum distillation of the acid. For their processing, brick linings me used inside of the lead linings when the acid is over 4OC; strength. Since the inception of this Simonson-Mantius prowsf in 1921, there has been continuous development to date in making the equipment more efficient'. I n addition to using 6% antimoniai lead and chemical lead for heating pipes, they also use Karbate. high silicon iron, and other materials. Recently Dowtherm has been adopted for some purposes, using 575-590' F. at' 20-25 pounds per square inch gage. About 5 years life for the brick linings is obtained lsit,h concentrations of 92-937, acid, with moderate maintenance costs. They find that leakage of acid betweer the bricks does not impair the lead if the seepage is more or lev Ttagnant, but currents of acid on the lead beneath the bricks caus rxeessive corrosion. Fifteen years of service has been reported i r some cases for brick linings. Discussions by American Institu.:G of Chemical Engineers members accompany the article. Potassium metabisulfite is now made in lead-lined equipmeni . ~ 2 ) .Sulfuric acid is now made in improved chambers (MillsPackard towers, 19). Description of a lead lined tank for treating tallow has been given (20). The design is simple and intended to minimize construction and maintenance costs. I n sewage treatment. and disposal, lead equipment is involved. The handling of copper sulfate has been discussed (7), and the use of lead in cbimnej- and condensers a t a disposal plant, is described (8).
October 1947
1225
INDUSTRIAL AND ENGINEERING CHEMISTRY
Recent photographic sink de-ign with ]rad lining hay hrrn mrn.icinrd (6). Various articles wferring to thevries and tests havr been pre.enred. They ail1 help in progress hut are here omitled a%not *wtinent. Linings of pure sheet tin are u v d in tanks for the chemical Idustry for handling foodstuffs. d nen alloy, 9 2 5 tin and 8 c 0 rinc, is apparently used in England for milk bottle caps. I t is niployed as foil of 0.0016-inch thirknrqs and is qaid to replace iliiniinuni and zinc (301. ELECTROPLATING AND PICKLING EQUIP.MEhT
.\ccording to Eckhardt (.$SI, cast insoluble anodes for chru:niiim plating prrform better after a Furface fusion produced xith 3 11osyhydrogt,n torch. Rrcently introduced is a neiv dwign 01’ gntimonial lead anode for chromium plating ( 2 7 ) . This anode :s an estruded and serrated product with seventy-one sharp edge -idges. These, being placed vertically, are said to increase the +hroning power and also to increase the plating efficiency by an -$timated 10%. The use of a large lead pan under an electrcjolating shop floor appears neFv (21). .In anodizing tank holding 2 0 5 sulfuric acid has been dcscribed. I t is lined rvi-ith tellurium lead 3,’16-inch thick and provided with -cooling coils of the same metal using direct expansion refrigeration (24). InPoluble anodes have been developed using 6 5 antimonial lead in the form of hollow cylinders of prrfornted sheet
‘17).
Ifantius exemplified good lead lining practice in general in hie gitwxiption of a pickling tank (63). The use of lead-covered tie rods for acid pirkling tRnks (23) and leaching tanks ha.s hren drarribed (13). HOT DIP-COATED AhL) ELECTROYL4TED IROh AhD STEEL
Galvanized products are largely made by hot dip coating or electroplating. For the first method, Prime Western zinc, conraining about ly0 lead, is satisfactory for use. Soluble zinc anodes are preferably of a higher quality to reduce anode qludge ormation. As mentioned before, lead was used to some extent T O replace zinc for coating steel and iron. Tin-coated iron is uutstanding in its desirability and use for containers for foods and beverages. For this purpose lead and zinc coatings are unYatisfactory. Terne plate prior t o 10 years ago contained 15 to 25% tin and ’he balance lead as an alloy coating for steel or iron. It competed with tin plate for cans designed to contain products other than .oods. Because of its cost, competition with galvanized iron xas somen hat limited. Horever, tin restrictions have reduced the :ontent of terne plate to about one third as much as formerly. +me commercial lead alloy coatings contain only 2.5% tin. I n addition to the use of hot dip lead-tin alloy coatings of about .jcy tin and 95% lead on iron and steel, there is a development in The use of similar alloy coatings formed by electroplating. Mor-a1 ( 6 7 ) made a valuable survey of lead coatings. This is s u p 7lemented by others (14, 15, 25, 39, 42-44)who have discussed .his production and use of such coatings. Pray (32) reported for *he X.S.T.M. the results of the atmospheric corrosion tests of ead plated coatings of various thicknesses for about 2l,’*years. Yo appreciable damage occurred to the steel base although some If the coatings were only 0.00008 inch thick originally. I n general, the life of coatings is directly related t o their thickwss, assuming fair quality. Hogaboom (56) stated, “Due to the uoro-ity of either hot dipped or electroplated coatings on steel, *hrough rhich rust stains appeared, it was considered that lead IflTered no protection. Later it was found that the ‘rust’ in the pores of the lead coating was insoluble: The pores indeed were illed with a product that gave better protection against corrosion *han lend itself! KO wonder lead coatings were adopted and lead became an important substitntr for zinc for lining containers for
COURTCSV, NEW JERIEV Z I N C COMPANY
.ipplication of a Finish Chromate Dip on ElectrozincCoated Steel Shells
overseas ,hipment, and for protecting n ire, strapping, arid telegraph and telephone pole hardware. On fence wire it not onl) gives good protection agairiqt corrosion but does not affect the physical properties of the steel core.” I n order to offsct any niisuriderstanding of the relative amount3 of coated metals (under diqcusqion here) used in the United Statec: for the year 1945, the 1917 issue of Metal Statistics is quotrd: :545 Cse of Use of Use of Cse of
lead i n terne plate tin In terne plate tin i n t i n plate zinc in gal\anizing
5,000 tons 741 tons 26,080 tons 337,181 tons
Galvanizing or zinc coating is a n ell knonn process, and rnanj books and articles have been published about the> subject. Electroplating to produce zinc coatings or electrogalvanizing has been devcloped, and therefore some references are cited (50,?‘3). Various phosphate and rhroniatr coatings have been applied to zinr coatings to improve their durdhility or to increase the life of paint films applied over them ( 6 4 ) . Apparently four of the method. are trade-named-Anozinc, Iridite, Cronak, and Bonderite. Khetzel discussed the electrolytic tin plate recently developed ( 7 4 ) . A development in inipioving the product by melting the tin on the surface with chilling to prevent denetting is attributed to Armour Inqtitute ( S I ) . h preliminary discourse on electrotinning appeared as a Biitish publication in 1939 (34). -4thorough discussion of the subject nas given by Luecak and Brighton in 1944, along v ith eleven references (62). Remarkable progress was made in quickly setting up plants for high speed electrotin
1226
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 39, No. 10
TABLE I. RESULTS OF OUTDOOR CORROSION TESTS(35) Designation
u cc EE AA BB
HH
Relative Position 1
2 3 4 5 6
Material Lead (chemical) Antimony-lead alloy Tin Zinc (Prime Western) Zinc (commercial) Zinc (spec. high grade)
Composition
99 2% Pb, 0.06 Cu 1.0% Sb, 99% P b 99 8% Sn 99% Zn, 0.85% P b 99.9% Zn 99.99% Zn
Graded Summary Corrosion Penetration, I n . X io-4-Industrial or Semi-industrial Sea Coast Altoona, Kew York, Sandy Hook, Key West, LaJolla. Pa. N. Y. N . J. Fla. Calif. C C 2.140 C C 1.24a CC 1.QOb HI-I 1 . 5 0 U 1.625 U 2.67" U 1.67 U 2.00) BB 1.79 CC 2.36" EE 6.03 EE 4.71 HH 5.44 A A 2.05 HH 4.81 HH 17.50 HH 19.13 A.4 5.54 cc 2 050 BB 6.29 $A 19.10 AA 19.32 B B 5.59 I: 2 , l e a AA 6.85 BB 19.31 BB 20.21 EE 7 . 0 0 b E E 8.11 EE 9.05
Rural State College, Pa. C C 1.290
EE 1.75 U
1.88"
BB 3.42 "3.57 AA 4.20
Phoenix. Aril. HH 0 . 4 t i
BB 0.70
U 0.94" A A 0.99 cc 1.090 EE 1.2R
4 Pitting depth, 0.001 t o 0.003 inch. b Estimated values; epecimens lost.
plating (4, 6 , 29, 36, 62, 60, 70, 7 1 ) . Plating speeds of over 1000 feet per minute were obtained. It F a s found that the same plating machinery could be used for zinc plating, if a change were desired. The zinc plating is usually applied heavier and somewhat more slowly (28). Fusion of the zinc on the surface, contrary to the tin practice, is not believed necessary. The British suggest the use of an electrodeposit of 0.00003 inch of tin plate as an undercoat for paint (55). The use of a protective coating from a hot alkaline bath of chromates and phosphates (Protecta tin) is also advocated and described elsewhere (54). Tin is said to be markedly beneficial as an undercoat for zinc or cadmium but less SO under nickel (72). SPRAYED COATINGS
Such coatings can be applied with a Schoop spray gun (01 modernized variety) wherein the wire is fed in, melted, and blown as a powder. Prepowdered metal is also blown through a torch device known as the Shorie gun. Because of the porous nature of such deposits, they must be applied thick for corrosion protection. The pores can be filled with paint or by insoluble chemical compounds precipitated therein. Zinc coating by spraying has been useful on ducts for conveying white powders. The protection adequately prevents rusting and discoloration. Sprayrd zinc coatings on ship ventilators are now used in considelable quantity. .4t the Pearl Harbor Navy Yard experimental lead spraying was recommended to prevent the corrosion of steel, with the ftrllowing thicknesses to be used for various environments: 0 03-0 04 inch for high humidity, COz and SO2 0 02-0 03 incb against brine and sea water 0 015-0 02 inch against salt water atmospheres
Pores were filled with lasticote (51). The life of equipment has been increased with lead sprayed coatings, both for pumps and pipes used for handling acid mine water ( I d ) and for the coating of filter plates handling zinc sulfate ~i~lutions.Worn spots in the coatings are readily resprayed ( 1 2 ) . PRIMARY CELLS AND LEAD STORAGE BATTERIES
United States S a v y wakeless torpedoes were propelled by power from lead storage batteries (18). Primary cells with lead dioxide and lead plates were developed with a perchloric acid electrolyte. Such batteries were used with weather observation balloons (76). Improved corrosion resistance of the positive grid metal in storage batteries is disclosed in a patent (35) relating to the use of silver in the antimonial lead alloy. A new design of lead linings with wood staves, for tanks for cutting storage battery acids, has been described (26). The lead
lining is brought out, as flanges between the staves, for cooling by increased radiation. SOFT SOLDERS
Tin restrictions necessitated the use of substitutes for tin-rich solders. One solder used in considerable quantity was the eutevtic 2.3% silver, 9i'.i'yO lead. Two difficulties, however, developed. The more serious one was failure of joints due to atmospheric corrosion of unsheltered equipment. A new A.S.T.M. specification suggests ly0tin, 1.57: silver, and 97.57.. lead as a better working and safer alloy. The second difficulty is encountered when 2.5% silver-lead alloy iused in baths on canning machines. The alloy picks up tin and throws out an insoluble silver-tin compound as a wastc sludge This trouble is eliminated by starting with an alloy with H maximum of 1.5% silver (63). The iT7ar Metallurgy Committee decided from accuniulated evidence that the lead solders (including those up to 98% lead) for food cans do not involve a health hazard (48). The substitute and low tin solders required more skill in their successful application. Better fluxes resulted and have been on the mnrkw 4nce then. BEARING METALS, BABBITT VARIETY
Restrictions prohibited the use of more than 10% tin in babbit 1 metal for most purposes. The substitutes or replacements proved satisfactory and will probably continue to be used. One t o ten per cent tin appears desirable to offset corrosion that might othorwise result from the breakdown of hot lubricating oils. A stwl back lined by 0.020-inch thick electroplated silver was developed For aircraft engine bearings. On top of the silver 0.001 inch of lead was electrodeposited to prevent shaft seizures, and finally about 0.00001 inch of indium was deposited on the lead as a corrosion inhibitor. Better fluxes and soldering techniques aided in the bonding of the linings to the backs. New methods in lead coating steel arid cast iron and applying tin have revolutionized bonding practict.. Fused halogen salts or decarburizing fused salts constitute two of the new methods. Accompanying pickling and dipping methods are prescribed. One method developed in the United States is known as the Kolene process (59). Another method was developed both here and abroad (40). ATMOSPHERIC CORROSION
In 1944 the A.S.T.M. (53) reported data (Table I) for outdoor corrosion tests for a ten-year period. The 9 X 12 inch sheet metal specimens were originally about 0.03 inch thick. Weight losses were determined and calculated as corrosion penetration.
October 1947
INDUSTRIAL AND ENGINEERING CHEMISTRY
Since neither tin nor tin plate are extensivelv used outdoors in an unprotected or unpainted state, the comparison betiyeen lead and Tine merits discussion. I n rural atmospheres lead is definitely less corroded. On the sea coast the grades of zinc are subject to tnice as much corrosion as lead and antimonial lead. I n industrial or aemi-industrial atmospheres the leads show a corrosion rate markedly less than the zincs; this indicates the leads to be 700 to 1 5 0 0 ~ superior. o The 1% antimonial lead alloy appears slightly superior to tht, canemica1 lead. I n recent years the greatest amount of sheet lead -old in the United States for roofing has been6Co antimonial lead. Sheet zinc in pure or alloy form is albo used in considerable quantity for roofing, vieat her-stripping, and containers. Lead coatings to resist atmospheric corrosion predominate a5 hot dip terne coatings. -4s mentioned before, the terne coatings ale currently in the realm of 2 to 10% tin, the balance lead. Lead coatings produced by electrodepositon are coming to the fore and hequently are either pure lend or about 5% tin and 95% lead. EJigh speed production has been attained by lead electroplating. RS well as with tin and zinc, as mentioned elsewhere. The relative performance of galvanized metal and terne coating\ (also pure lead coatings with or without copper undercoatings) is being studied by A.S.T.M. committees. Such coatings and their behavior have been previously mentioned in this article. UNDERGROUND CORROSION
The use of lead-sheathed electric cables for communication and pon-er purposes has involved many types of installations with various kinds of coverings on lead (2, 49). The use of pure zinc anodes as galvanic protective measures has been discussed ($9,66) with additional references given (67). Magnesium lts a protective anode has been described (69). Other features of underground corrosion (1, 3, 58) and cathodic protection (41, 66, 6 6 ) have been presented. The National Bureau of Standards has studied the corrosion of nietals underground for many years. Among the materials that werc tested are different kinds of lead and zinc and also coatings, using the same metals. A recent summat’ionof all the test data iyas published in book form (61). Heavy double-coated galvniiizing gave 10 years’ protection. I n some of the soils, lead of sutjstantial thickness was appreciably corroded in 10.years. Since the lead coat,ings mere thin and imperfect, their performance was not good under the same test conditions. For the relatively noncorrosive types of soils the performance of both was good. These data, accordingly, are consistent with the fact that, in many places in the United States, lead pipes have been used uiiderground for 50 to 100 years without substantial deterioration due ?o soil corrosion. British tests for 10 years’ exposure underg m i n d were recently reported (47). Where lead was severely ci,rrodeci in a few of the locations, it was found that completr protection mas afforded by a loose bitumen wrapping. Because of the cost of underground installations of metal pipe or sheathing, this precaution appears economical for installations in soils known to be corrosive. Patents on lead alloys for cable sheath (57) and lead alloy for pipe (38) have been obtained. These alloys Tvere designed for increased strength and creep resistance. To round out this section, the use of lead pipe to convey oil and giiaoline from the British Isles to the European coast is cited (16). Thi,c “Operation Pluto” expedited the end of the World War 11. .Ilthough there vere relatively few innovations in the use of Iracl, tin, and zinc and their alloys in recent years, many general improvements are now in evidence. The war brought about gowrnmcnt restrictions on the use of these metals, and research \vas stimulated in an effort t o conserve strategic materials and, a t the same time, t o keep pace with national defense demands. With respect to coatings, development’s were made for each of t n c rhrw metals. Hot dip coatings of high lead cont,ent (93-955
1227
Pb, 7-3y0Sn) were made possible by improved pickling and fluxing techniques. Electrotin coatings saved many tons of tin in the tin can industry, and the use of steel artillery shells with zinc coatings instead of brass shells became a strategic necessity. Greater production efficiency, improvements in equipment design, and new applications represent some of the major advancements made in the chemical industry. LITER-ITURE CITED
.Ilbano, V. J., Katl. Assoc. Coriosion Engrs., paper presented
Apr. 1947. Albano, V. J., and Pope, R., Corrosion, 3, No. 5,221-6 (1947). iindrexs, A. G., Xatl. Assoc. Corrosion Engrs., paper presented Apr. 1947.
Anonvmous, Blast Furnace Steel Plant, 32, KO.3, 2 3 2 4 (1944). Ibid., 32, 343-5 (1944). .4nonymous, Lead (Lead Ind. -4ssoc ) . 11, Nc.4 , s (1941). Ibid., 11, KO.6 , 2 (1941). Ibid., 11, N o . i , 2 (1942). Ibid., 13, No. 1,5 (1943). Ibid., 13, No. 4,2-3 (1943) Ibid., 13, N o . 4 , 4 (1943). I b i d . , 13, No. 6, 3 (1943).
Ibid., 13, No. 6, 8 (1943) Ibid., 14, No. 1, 5 (1944) Ibid
14. N o . 5 4 (1914)
Ibid., 15: No. 4, 4 (1945). Ibid., 15, N o . 6 , 2 (1945). Zbid.. 15, N o . 6. 3 (1945). Ibid., 16, NO.1, 4-6 (19461. Ibid., 16, No. 2, 2 (1946). Ibid., 16, N o . 2, 3 (1946). Ibid., 16, No. 2, 7-8 (1946). Ibid., 16, N o . 3, 4 (1946). Ibid., 16, No. 5, 3 (1946). Ihid. 16. No. 6 3 (1946). Ibid., 16: No. 6: 8 (1946). Anonvnious, Metal Finishing, 45, S5 (1947). Anonymous, Steel, 114, No. 6,154-6 (1944). rlnonymous, Tin and I t s Uses (Internatl. Tin Research Council) p 2 (July 1941). Ibid.. NO. 15, 15-16 (1944). Armour Institute, MetalInds., p. 394 (Dec. 14,1945). Am. Soc. for Testing Materials, Rept. of Subcomm. I1 of Comm. B-8 on performance tests, Preprint 15 (1947). Ibid., Subcomm. VI of B-3 Rept., Proc. 44,229 (1944). Baier, S.,Internatl. Tin Research and Development Council, Pub. 92 (Apr. 1939). Boese, 9.B., U. S.Patent 2,233,072 (Feb. 25,1941). Brighton, K. W., Iron SteeZEngr., 22,37-9 (1945). Burke, J. F., and Mantius, E., Chem. Eng. Progress, 43, NO. 5, I
237-46 (1947).
Butcher, W. T., and Lloyd, A., U.S. Patent 2,409,SO (Oat. 15, 1946).
Carlson, A. E., and Kane, J. M., Monthly Rev.Am. Electroplaters’ SOC.,33, 255-261 (1946).
Cresswell. R. A,. Brit. Iron Steel Inst., adv. copy (Feb. 1946); Metal Progress, 51, N o . 5, 802, 804 (1947). Dictae, I. C., Natl. Assoc. Corrosion Engrs., paper presented Apr. 1947. Diggin, M ,B., Metal Finishing, 41,418 (1943). Downie, C. C., Chem. Products, 8, 81, 82, 90 (1945). DuKose, 9. H., Trans, Am, Electrochem. SOC.,89,417 (1946). Eckhardt, Ray, Metal Finishing, p. 313 (June 1940) Fetter, E. C., Chem. & Met.Eng., 53, No. 5, 231 (1946). Gilbert, P. T., J . f n s t . Metals, 13, 139-74 (1946). Gillett, Cameron, and Griggs, Metal Progress, 3, 420-1, 454 I
(1943).
Gorinan, L. J., Corrosion, 1, No. 4, 163-77 (1945). Gray, Allen, Steel, 117, 108, 109, 158, 161, 162, 164, 168, 170 (Oct. 8 ) : 129, 130, 132,.134 (Oct. 22); 110, 112, 114, 146 (Oct. 29); 142, 144, 182, 184, 186 (Nov. 5 ) ; 132, 134, 136 (Nov. 12, 1945).
Grupp, G. W., X e t a l Finishing, 43, No. 11,450-1 (1945). Hall, W.F., Steel, 115,99-100,121 (1944). Harper, R. G., MetalZnd. (London), 6 4 , 2 4 2 4 (1944). Hedges, E. S., and Hoare, H. E., Metal Treatment, 13, No. 47, 197-205; NO.48,286-289 (1946). Hedges, E. S.,and Jordan, L. A., Iron andsteel, 18,691 (1946). Hogaboom, G. B., MetalProgress, 50, No. 5, 1065 (1946). Johnson, G. E., and Bassett. W. H., Jr., U. 8 . Patent 2,300,788 (NOT’.3, 1942).
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INDUSTRIAL AND ENGINEERING CHEMISTRY
(68) Kahn, F., and Phelps, H. S., Natl. .Issoc. Corrosion Engrs., paper presented Apr. 1947. (59) Lekbera. C. H.. I n d . Gas. 25. 11. 27-9 11947). (60) Lewis, W.R., T i n and Its Gaes (Inteinatl. Tin Research Coun-
cil), KO.16, 5-7 (Sept. 1945). (61) Logan, K. H., "Underground Corrosion," Govt. Printing Office, C'irc. C450 (Nov. 27, 1945). (62) Lueck, R. H., and Brighton, K. IT., I s n . ESG.CHEY.,36,532-40 (1944). (63) Mantius, Ernest, Steel, 106, KO. 10, 69-70, 82 (1940). (64) Maxon, S. E., X e t a l Finishing, 43,148-9 (1945). (65) Miller, M. C., Elec. Light and Power, 22, Xo. 5,46-51: S o . 6, 92-4,96,99, 102 (1944). (66) AMiller. M. C., PdroleumEngr., 17, No. 8, 55-8 (1946).
Vol. 33, No. 10
(67) ,Morral, F. R., Products Finishing, 40-2 (Jan. 1916). (68) Porter, R. TV., Chem. & Met. Eng., 53,No.4,94-8 (1946). arid Fatherly, R. L., Corrosion, 3,No. 7, 348(69) Robinson, H. 9.,
57 (1947). (70) Silnian, H., Sheet MetalInds., 21, 1031-36 (1945). (71) Timby, T. G., Iron Stcel Engr., 22,40-48 (1945). (72) Wernick, S., J . Electrodepositors Tech. Soc., 20, 47-60 (19441. Metal Inds.. 67.235-6 (1946). (73) Wernick, S., sheet Metal'lnds.: 21,443-6, 626-9 (1945). (74) Whetzrl. J. C., Metals, 15, 12-14 (1944). (75) White, J . C., Power, W.R., McMurtrie. R. L., and Pierce, Et T., Electro-Chem. Soc., Preprint, 91-2 (,4pr. 1947). (76) Wilkinson, E. R., Corrosion, 3,No. 5,252-62 (1947). (77) Wormsrr, F. E., Metal Progress. 43,223, 262, 268 (1943)
Nickel and HighNickel Alloys -
____
W. Z. FRIEND, The International Mckel Co., tnc., ,Yew Y o r k , N . I-.
L
ARGELY because of accelerated reseaxch during the war pe-
riod, new developments in nickel and nickel alloys have been more numerous during the last three or four years than in some preceding periods of similar duration. The field of nickel alloys in general is a very large one, and this summary is limited to a consideration of nickel and high-nickel or nirkel-base alloys containing more than about 50% nickel. Some of the more common high-nickel alloys now in commercial production, with their nominal chemical compositions, are listed in Table I. Mechanical and physical properties, as well as some data on the corrosion resisting properties of these materials, are given in the references shown in the table. Most of the lower nickel alloys will be covered by other authors dealing with the stainless steels and iron-base alloys, or with copper-base alloys. Considerable work has been done with high-cobalt alloys, or materials containing both cobalt and nickel which are not iron-base alloys. Since these materials possibly may not fit into other categorics, some attention is given to them in this summary. The subject matter falls naturally into three general classifications: development of new alloys or improvement in the composition of older alloys; developments in the fabrication of these alloys; and new or especially enlarged fields of application, particularly as applied to the chemical and process industries. N E W OR IMPROVED ALLOYS
HIGH TEiUPERATCRE . ~ L L O Y S . The greatest amount Of experimental work wit,h new or improved nickel alloys undoubtedly was done in the search for materials having maximum physical and mechanical properties, and oxidation resistance a t high temperatures in connection with jet engine, gas turbine, and supercharger developments (8, 15, 16, 18, 23, 31, 33,4.5, 47, 60. ?5, 88, 89, 92, 97, 99). In American developments in this field the outstanding higher nickel alloys were Hastelloy B, Inconel, Inconel B, and Inconel X. These materials were used in some models of jet engines, Hast,elloy B and Inconel S for turbine buckets or blades, and Inconel, Inconel B, and Inconel X for combustion chamber linings. I n the case of Hastelloy B and Inconel, use was made of alloys which had been in large scale production for a number of years as corrosion and heat resistant materials. Hastelloy B is a n age-hardenable material, and principal improve-
ments w r e in the heat treatment of this alloy to give masiniuna physical properties a t high temperature. INCOSEL5. Inconel X is an age-hardenable nickel-chromium alloy developed particularly for jet engine and gas turbine work. and now being applied to a variety of uses a t high temperaturei. Precipita.tion hardening characteristics are obtained by additions of titanium and aluminum. For gas turbine blades it has beel! used chiefly as forgings but is available in other wrought forms such as sheet, strip, wire, seamless tubing, hot rolled rod and flats. and forged billets. .kiter suitable heat treatment, Inconel X ha.* high strength at, all operating temperatures up to 1500" F. Its merit at, temperatures higher than 1500" F. has not been explored fully as yet, but its inherent hot-hardness probably will make it useful in some forms, as in sheets, up t,o 1700' or 1800" F., or perhaps higher. I t s resistnnce to oxidation is of a high order. Incone1 X shows low creep rates a t 1200°, 1350°, and 1500" F. X three-stage heat treatment is recommended for development oE maximum mechanical properties (54). INCOSEL B. Another alloy developed primarily for use in thc heat-resisting field is Inconel B, a nickel-chromium alloy now available in a variety of wrought forms. This is a modification of the older alloy Inconel, in which the chromium content is increased from 12-14% up to 16-180& Inconel B is not agehardenable but has the high level of mechanical properties whict would be expected from its chromium content. It was developed to provide increased oxidation resistance in such applications a? exhaust manifolds and heaters of heavy duty aircraft, and as combustion chamber linings of jet engines where operating temperatures continually are being pushed to higher and higher levels. It also has shown good test performance in some elevated temperature corrosion-resisting applications, such as the continuous h>drolysis of fats and distillation of fatty acids. Further investigation doubtless viill reveal other suitable applicat,ions in the hen1 resisting and corrosion resisting fields. KIMOSICALLOYS. In England considerable use was m d i . 01 the Simonic alloys in jet engine work (1, 2, 5 ) . These allo eosentia,lly of the 80 nickel-20 chromium composition, n.ith certain alloy additions to make them age-hardenable. Sirnonic 8 1 has been the standard material for blades of all Britis!i-huiIt gw turbine engines, Ximonic 75 has been used for combus:ioii ch:inibers and nozzle guide vanes.
