NICKEL-METAL, O X I D F LITERATURE CITED
Queneau, P. E., Trans. Can. Inst. Mining Met., 51, 356-67 (1948).
Brenner, A . , Burkhead, P., and Seegmiller, S., J . Research Natl. Bur. Standards, 39, 351-83 (1947). Brenner, A., Couch, D. E., and Williams, E., Plating, 37, 36, 161 (1950). Brenner, A., and Riddell, G. E., J . Research Nall. Bur. Standards, 39, 385-95 (1947). Butler, J. A. V., “Electrocapillarity,” p. 161, London, Methuen and Co., 1940. Hothersall, A. W., and Gardam, G. E., J . Electrodepositors, Tech. Soc., 27, advance copy (1951). I r o n Age, 163, No. 23, 49 (1949). Kolthoff, I. M.,and Lingane, J. J., “Polarography,” p. 45, New York, Interscience Publishers, 1941. Oholm, L. W., Finska Kemistsamfundets Medd., 45, 122-8 (1936). Parkinson, W . , J . Electrodepositors’ Tech. Soc., 27, advance copy (1951). Pinner, W. L.. Soderberg. G.. and Baker. E. M.. Trans. Electrochem. Soc., 80,539-68 (1941).
Renzoni, L. S. (to International Nickel Co., Inc.), U. S. Patent 2,394,874 (Feb. 12, 1946). Robinson, R. A., and Jones, R. S., J . Am. Chem. SOC.,58, 959-61 (1936).
Stokes, R. H., Trans. Faraday SOC.,44, 295-307 (1948). Wesley, W. A., Plating, 37, 949-53 (1950). Wesley, W. A., Cam, D. S., and Roehl, E. J., Ibid., 38, 1243-60 (1951).
Wesley, W. A., and Copson, H. R., J . Electrochem.
Soc., 94, 20-3 1 ( 1948). Wesley, W. A., and Roehl, E. J., Trans. EEectrochem. Soc., 86, 79 (1944). Wesley, W. A., Sellers, W. W., and Roehl, E. J., Proc. A m . Electroplnlers’ Soc., 36, 79-92 (1949). Zitek, C., and McDonald, H., Trans. Electrochem. Soc., 89, 433-41 (1946).
EECEIVED for review October 17, 1861.
.4CCsPTED
Eebruary 25, 1952.
CORROSION-RESISTING NICKEL ALLOYS AND CHEMICAL PROGRESS W. Z. FRIEND
AND
F.
L. LAQUE
The lnternationel Nickel Co., Inc., New York, N. Y. period of great development of the chemical and process industries during the past quarter century has coincided with the period of commercial development of most of the corrosion-resisting metals and alloys for process equipment. M a n y of these alloys contain nickel as an essential alloying element, not only because of the corrosion-resisting properties of the metal itself but also its metallurgical compatibility with a good many other metals. Following a summary of the corrosion-resistingcharacteristics of the principal nickel-containing alloys, examples are given of specific applications of these alloys in the manufacture of a number of chemical products, including products involving halogens such as chlorine, bromine, fluorine, and hydrogen fluoride; synthetic textiles such as viscose rayon, cellulose acetate rayon, and nylon) dyestuff manufacture and textile dyeing and Rnishing, synthetic plastics such as phenolics, alkyds, polystyrene, and organic chloride polymers) antibiotics such as penicillin, streptomycin, and chlorumycetin; fatty acid products; and corn products.
NY study of the progress of the chemical and chemical proo-
A
ess industries during the past quarter-century and of trhe rapid development of new processes to the continuous large scale production of many useful products, should give recognition to the part played by the availability of suitable corrosion-resisting metals and alloys for the construction of process equipment. It probably is not a matter of coincidence but of some direct relationship that this period of great chemical activity has coincided with the period of development of many af the corrosion-resisting materials which now are considered indispensable for the large volume economical manufacture of chemical products of good quality. From a historical standpoint i t might be said that our greatest period of chemical development in this country began around 1920 with the commercial production of such materials as the rayons, phenol-formaldehyde resins, and new synthetic dyes and dye intermediates. Our greatest period of activity in the de-
May 1952
velopment of corrosion-resistant metals and alloys began at about the same time with the commercial production of rolled nickel and Monel in 1921, stainless steels about 1923, and some aluminum alloys. Since that time we have seen the production of a host of metallic corrosion-resistant materials including Haatelloy alloys A, B, C, and D; Ni-Resist alloys; Worthite; Illium; Durichlor ; cupronickel alloys; Chlorimet alloys; Inconel and other nickel-chromium alloys; tantalum; magnesium; agehardenable aluminum alloys; rolled aluminum bronze alloys, nickel steels, and a variety of new stainless steel products including such highly alloyed materials as Durimet 20, Aloyco 20, and Carpenter 20. Recently we have seen the commercial introduction of wrought titanium (7), zirconium ( 7 ) , and molybdenum (77), which give great promise as corrosion-resisting metals of the future. A considerable number of the materials listed above contain nickel as an essential alloying element. This is due not only to the corrosion-resisting properties of the metal itself but also to the fact that it is metallurgically compatible with a good many other metals. It is significant that many of these materiah, except for the few made only as castings, are available in a variety of wrought forms and in a range of sizes. They have high mechanical strength and can be readily fabricated by welding, machining, bending, rolling, and other common means. This, almost as much as corrosion resistance, has contributed to their value as chemical engineering materials. NICKEL ALLOYS
Nickel and High-Nickel Alloys. The approximate compositions of the principal high-nickel alloys used for corrosion-resisting applications are given in Table I. Although commercial nickel has useful resistance t o corrosion by a large number of chemicals and chemical solutions (8,6f, 77), a large portion of the present use of this material for chemical process equipment is based upon its particular resistance to the following corrosives:
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NICKEL-METAL, OXlDF Commercially dried chlorine and bromine over a considerable range of temperatures ( 6 g ) . Hot wet organic chlorides and chlorinated solvents where small amounts of hydrochloric acid are formed by hydrolysis ( 5 2 ) . Fluorine and fluorides a t elevated temperatures (69). Hot aqueous solutions of inorganic neutral and acid chloride salts except oxidizing salts. Caustic alkalies a t all temperatures and concentrations ( 5 0 ) . Molten salts such as sodium and potassium chlorides and sodium nitrate. Molten alkali metals such as sodium and potassium but not lithium ( 6 ) .
tions of Inconel are in the high temperature field, where it provides a combination of high temperature strength with resistance t o oxidation, nitriding, ammonia atmospheres, carburization, halogen-containing atmospheres, and molten halide salts. Inconel X is an age-hardenable alloy providing unusual creep and stress rupture strength a t temperatures up to 1500" F. in addition to the corrosion resistance of Inconel (44). The Hastelloy alloys (SO, 61, 7 7 ) were developed specifically to handle certain severe corrosives for which no other strong metallic material was available a t the time. Hastelloy B is a nickel-base alloy containing 26 to 30% m o l y b d e n u m . It is usefully resistant to boiling hydrochloric Table I. Nomine1 Compositions of High-Nickel Alloys acid solutions of all concentraOther MolybSiliManChroNick- Coptions and to wet hydrogen chloElements, denum, Iron, con, ganese, Carbon, per, mium, ela, % % % % % % Material % % % ride, fields which i t shares only .. 1.4 0.1 1 67 30 .. 0.15 with tantalum and some of the .. 29 .. 0.9 0.50 0.75 0.15 A1 2 . 7 k ; ' T i 0.5 66 p r e c i o u s m e t a l s a m o n g the .. 3 31 .. 2.0 0.75 0.1 ... 63 .. 4 30 .. 2 0.76 0.1 ... 63 wrought c o r r o s i o n - r e s i s t a n t .. 0 15 0.1 .. 0.03 0.2 0.1 ... 99 4 .. 0.02 .. 0.05 0.2 0 . 0 2 max. 0.15 99.5 materials. Hastelloy B has been .. A1 4.4;' T i 0 . 5 0.0: 0.35 0.60 0.30 0.17 93.7 used for the lining of reactors and 0.2 ii.3 .. 0.23 0.25 0.08 76 .. A1 0.90; ' T i 2.5 0.03 15 0.40 0.5 0.04 73 accessory equipment for isomeri... ,. e 1 1 0 , 12 inax. 28 60 1 17 1 0 . 1 2 max. W 4.5 e 51 ... 17 zation of hydrocarbons in the .. A1 1 .. 10 1 0.12max. 4 .. 85 production of aviation gasoline 3 inax. 1 1 ... .. 32 0.10 ... 63 3 niax. 1 1 0.07 . .: 8 23 18 18 60 . (15), the alkylation of benzene 56 w-1 3 21 IlliumC 60 to ethylbenzene in the produc0 Includes small amount of < sbs!t. tion of styrene, and in other b Also available i n form of clad iteel. Trade mark rpgistered. Friedel-Crafts type syntheses J .-\r.nilsblein cast form only. using aluminum chloride-hydrogen chloride complexes as catalysts. This alloy also shows good resistance to boiling concentrated pure phosphoric acid soluKickel generally imparts some added resistance to most of these corrosives to the alloys to which i t is added in significant amounts tions and to hot nonoxidizing sulfuric acid solutions. Chlorimet 2 ( $ 1 )is a somewhat similar alloy available in cast form. and roughly in proportion to the amount of nickel in the alloy. Hastelloy C, a nickel-base alloy containing approximately 17% Duranickel, an age-hardenable alloy, G nickel, a high-carbon cast chromium, 17% molybdenum, and normally 4% tungsten, is usegall-resisting material, and low-carbon nickel, all are essentially fully resistant to wet chlorine up to about 140' F., strong hypothe same as commercial nickel in corrosion resistance. chlorites, ferric chloride up to about 170" F., cupric chloride to Monel (a, 61, 77), because of its high nickel content, is someabout 110' F., and similar severe corrosives to which no other what similar to nickel in resistance to the above corrosives except wrought metals except tantalum and titanium are suitably rethe molten salts and alkali metals. Because of its copper content sistant. I-Iastelloy C reactors, coils, and other equipment are used i t has superior resistance t o nonoxidizing chloride salt solutions in a variety of wet chlorinations at moderate temperatures, inand to hot dilute solutions of such nonoxidizing mineral acids as cluding the chlorination of acetic acid to produce chloroacetic hydrochloric (52), sulfuric (49), and phosphoric ($3). Many of acid in the production of 2,4-D. This material also demonstrates its particular applications are in the handling of these acids as in good resistance to boiling concentrated solutions of some organic the pickling of iron and steel, production of ammonium sulfate, acids and to sulfurous acid solutions, Chlorimet 3 ($1) is a someand handling of sulfonated organic compounds in the production what similar alloy available in cast form. of detergents (24). I n addition, Monel demonstrates good reHastelloy D is a cast nickel-silicon alloy having useful resistsistance t o unaerated hydrofluoric acid solutions of most concenance to boiling sulfuric acid solutions of most concentrations It trations and temperatures (26'1. It is used for the handling and has been used for cast heating coils in equipment employed in the regeneration of this acid in plants for the hydrofluoric acid alkylaconcentration of sulfuric acid by evaporation in petroleum retion of petroleum hydrocarbons (19, 34). Keither Monel nor fineries ( 1 1 ) and other plants, where the only other resistant nickel is resistant to oxidizing acids such as nitric or to solutions of metallic materials that have been used or considered are the cast oxidizing salts such as cupric or ferric sulfates or chlorides. K high-silicon irons and tantalum. Monel, an age-hardenable alloy, and S and H Monels, cast siliconThere are a number e€other complex nickel-base alloys concontaining gall-resisting materials, are essentially the same in taining also chromium and molybdenum, such as Illium (S5), corrosion resistance as commercial wrought Rlonel. Durco D-10, and LaBour 55, which are usefully resistant to a conInconel, a high-nickel alloy containing 14 to 17% chromium siderable number of complex oxidizing acid solutions such as mix(9, 61, 77), is resistant t o many of the same corrosives as comtures of nitric or chromic acids with sulfuric acid, crude phosmercial nickel and Monel including hot caustic alkalies but usuphoric acid, cupric and ferric sulfate, and a number of complex ally not as resistant to hot chloride solutions or any of the hot sulfate solutions such as viscose rayon spinning baths. These alnonoxidizing mineral acids. It is more resistant to oxidizing soluloys are used chiefly in cast form for such equipment as pumps, tions than either of these other materials. It shows a high degree fittings, and agitators, although Illium is available in some of resistance to many organic compounds, and frequently is used wrought forms. in the handling of such materials where it is desired to keep metalCupro-Nickel Alloys. The cupro nickel alloys containing from lic contamination of the product a t a minimum. Specific ap70 to 90% copper with balance mainly nickel are most notable for plications in these fields are in the high temperature splitting of their resistance to corrosion and fouling by sea water (54). The fatsand distillationof fatty acids (26),in the productionof pharma70-30 cupronickel alloy with controlled iron content greater than ceuticals such as vitamins and antibiotics (67), and the proc0.25% and the 90-10 cupronickel alloy with controlled iron conessing of various food products. The most significant applica-
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. NICKEL-METAL, OXIDE tent of 0.75 to 2.0%, show maximum resistance to impingement attack by high-velocity sea water. These materials are used for construction of coolers and condensers on ships and in coastal power, industrial, and chemical plants (66, 76). I n addition they provide high-copper alloys of good strength and weldability for use with nonoxidizing chemical solutions involving low concentrations of hydrochloric, hydrofluoric, sulfuric, phosphoric, acetic, and formic acids.
in neutral chloride solutions and in hot strong organic acids such as acetic, lactic, and fatty acids. When both molybdenum and copper or silicon are added and the nickel content is increaeed, as in Carpenter 20 (IS), Aloyco 20 (I), Durimet 20 (It?), or worthite (8I), there is a further increase in resistance to these corrosives at elevated temperatures. The stainless steels normally are not used in hydrochloric acid or hot acid chlorides because of a strong tendency to pitting attack and to stress-corrosion cracking (3, 60,7S, 77). ' The addition of columbium to the stainless steels, as in Type 347, or of titanium, Table II. Compositions of Wrought Chromium-Nickel Stainless Steels as in Type 321, or the lowering of carbon AISI' Chemical Composition, Per Cent content to 0.0370 maximum, as in Types Mn Si Type 304L (extra low carbon) and 316L, avoids C Max. Max. Cr Ni Other elements No. 301 Over 0.08-0.20 2.00 1.00 16.00-18.00 6.00-8.00 ...... a type of intergranular attack that may 302 O w r 0 .08-0. 20 2.00 1 .OO 17.00-19.00 8.00-10.00 . .. .. .. .. .. occur in certain media if the steels have 302B Over0.08-0.20 2.00 2.00-3.00 17.00-19.00 8.00-10.00 . 303 0.15max. 2.00 1.00 17.00-19.00 8.00-10.00 b been subjected to certain sensitizing tem0.08 max. 2,OO 1.00 18.00-20.00 8.00-11.00 304 peratures during hot working, welding, 304L 0.03 max. 2.00 1 .OO 18.0620.OO 8.00-11.00 2.00 1.00 17.00-19.00 10.00-13.00 ...... 305 0.12 mas. or heat treatment. 2.00 1.00 19.00-21.00 10.00-12.00 308 0.08max. 2.00 1.00 309 0.20max. 22.00-24.00 12.00-15.00 Ni-Resist Alloys. The Ni-Resist alloys 309s 0.08max. 2.00 1.00 22.00-24.00 12.00-15.00 ...... listed in Table I11 are cast iron-base mate3 10 0.25max. 2.00 1.50 24.00-26.00 19.00-22.00 ...... 2.00 3106 0.08max. 1.50 24.00-26.00 19.00-22.00 19.00-22.00 .... . rials containing nickel, chromium, and in 2.00 1.50-3.00 23.00-26.00 314 0.25max. 316 0.lOmax. 2.00 1.00 16.00-18.00 10.00-14.00 M o 2 some types also copper (48). These alloys TS 316 0.lOmax. 2.00 1.00 16.00-18.00 10.00-14.00 Mo1.75-2.50 316L 0.03max. 2.00 1.00 . 16.00-18 00 10 00-14 00 M o l 75-250 are used for pumps and valves handling 317 0.lOmax. 2.00 1.00 18.00-2O:OO 11 :00-14:00 Mo 3:0-4.60 hot caustic soda up to 50% concentration 321 0.08max. 2.00 1.00 17.00-19.00 8.00-11.00 Ti 5 X C min. 347 0.08max. 2.00 1.00 17.00-19.00 9.00-12.00 C b l O X C m i n . and with other alkaline solutions. They TS 347 0.08 max. 2.00 1 .OO 17.00-19.OO 9.00-12.00 Cb 8 X C min. 0.08 max. 2.00 1.00 17.00-19.00 9.00-12.00 Cb-Ta8XCmin. are used with a variety of cold solutions TS 347A Containing Smd1 amounts Of sulfuric, hya TS 316 TS 347 and TS 3478 are tentative standard type numbers; remainder of type numbers are drochloric, phosphoric, and other nonstandard b Phosphorus, t i p e numbers. sulfur, or selenium, 0.07% minimum; zirconium or molybdenum, 0.60% maximum. oxidizing acids, and have shown good performance in the pumping of brines and sea water ( 7 1 ) . Type 3Ni-Resist has a low Austenitic Chromium-Nickel Stainless Steels. The austenitic thermal expansion coefficient and is particularly used for such chromium-nickel stainless steels, listed in Table 11, are the most parts as filter press plates and filter drums and grids where cyclic widely used of the corrosion-resisting alloys, because of their changes from cold to hot solutions require a cast material resistresistance t o a variety of corrosives (8, 16, 42, 889,good mechaniant to cracking by thermal shock. The new ductile iron process cal properties, and moderate cost. Primarily because of chro(magnesium treating) when applied to Ni-Resist results in a mium content, they perform best under oxidizing conditions which marked improvement in strength, elongation, and toughness (71). are most harmful to ordinary steel and to many of the nonferrous Nickel Alloy Steels. The principal nickel alloy steels, those metals and alloys. The addition of nickel to the stainless steels containing 3.5, 5, and 8.5% nickel (4, 6) were developed primarily increases the passivating effects of chromium in oxidizing soluas materials with greater ductility than carbon steel for low temtions such aa nitric acid and a t the same time improves the reperature applications. The 3.5 and 5% nickel steels have useful sistance of the alloys to reducing conditions (66). Nickel also has ductility a t temperatures down to about - 150" and -200 F., reindirect effects related to its role in promoting the desifable ausspectively, the former material being used for such applications as tenitic structure and in maintaining such a structure during and the storage of liquefied hydrocarbon gases and for reactors in the following the heating and cooling to which the alloys may be subproduction of Butyl rubber, temperatures in the latter case varyjected during manufacture, fabrication, and use. ing from -1150' to f150" F. The 8.5% nickel steel was deThe straight chromium-nickel stainless steels such as Types 302 veloped as a material having suitable ductility below -200" F. and 304 are used to handle oxidizing acid solutions such as those However, its principal applications, along with 5% nickel steel, containing nitric acid, peroxides, chromates, and cupric, ferric, have been for corrosion-resisting applications such as tubing in and mercuric sulfates. They also are used with a variety of petroleum oil and distillate wells (10) and the evaporation and organic acids and compounds a t moderate temperatures, as in the handling of alkaline solutione such as black liquor in sulfate pulp food and pharmaceutical industries. They normally are not mills (87). resistant to reducing acid conditions as in hot sulfuric, phosNickel Plating. Considerable use now is being made of nickel phoric, or hydrochloric acids or halogen salt solutions. Types 309 and 310 and their modifications Table 111. Composition Range of Ni-Resist Alloys are used mainly for resistance to oxidation and sulfidation a t high Type 4 Type 2 Type 2b Ty e 3 Heat- and &inType 5 temperatures. Name Type lo 20% Nicdelb Heat-Resistht 30% k c k e l Resistant Minovar B .60max. 2.40 max. The addition of molybdenum T.o.tal carbon 3.00max. 3.00max. 3.00 max. 2.75 max. Sllicon 1.00-2.50 1.00-2.50 1.00-2.60 1.00-2.00 5 00-6.00 1.00-2.00 to the chromium-nicke1 Manganese 1 .OO-1.50 0.80-1.50 0.80-1.50 0.40-0.80 0.40-0.80 0.404.80 steels as in Types 316 and 317 Nickel 13.50-17s50 18.00-22.00 18.00-22.00 28.00-32.00 29.00-32.00 34.00-36 00 Copper 5.50-7.50 0.50max. 0.50max. 0.50 max. 0.50 max. 0.50 max. expands the p w i v i t y range, reChromium 1 .75-2.50 1.76-2.50 3.00-6.000 2.50-3.50 4.5-5.5 0.10max.d duces the t' pit, and a Where presence of copper offers corrosion resistance advantages 1 and l a are recommended. Q For handling caustics, food, eta., where copper contamination cannot be tolerated, Types 2 and 2a are recomimproves c o r n i o n r e s i s t a n c e mended. particularly in such mineral acids C Where 8ome machining is required, 3.0 to 4.0 chromium level is recommended. d Where higher hardness and greater strength are desired, chromium may be 2.5 to 3.0% a t expense of inas sulfuric, sulfurous, and phoscreased expamlvity. phoric a t moderate temperatures, e
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NICKEL-METAL, OXIDE plating of O.OO5-inch thickness or heavier over steel, copper, or other base metals rn a means of preventing corrosion of chemical process equipment. Among such applications of nickel-plated equipment cited by Prine (69) are: wire return rolls, kamyr rolls, screen plates, and beater bars in paper mills; cooking kettles, pasteurizer coils, apple pulpers, and candy molds in the food industry; tubing in petroleum condensate wells; filter plates, piping, bobbin trays, immersion rolls, dry cans, and dye sticks in the textile industry; dryer rolls for photographic film and sheet plastics; plastic press plates; and molding dies. Internally nickel-plated steel piping, particularly in sizes over 2.5-inch diameter, is used in a variety of plants and industries. PLANT APPLICATIONS
An effective way to illustrate further the part played by nickel and nickel alloys in the progress of the chemical industries is to cite Borne of the additional use9 to which these materials have been put as process equipment in several of these industries, as revealed by the literature and experience dealing with plant practice. Chlorine and Organic Chlorinations. Among the end products based upon organic chlorinations me the following, cited by Deutsch ( 1 7 ) : Chlorinated solvents from acetylene and ethylene Trichloroethylene Carbon tetrachloride Chlorobenzenes and toluenes Ethylene glycol Antiknock fluid Synthetic rubbers Refrigerants Lubricant aids Chlorinated naphthalene DDT and 2,4-D Intermediates and miscellaneous pi oducts j
It has been pointed out that nickel and Monel are resistant to commercially dried chlorine, Hastelloy C to wet chlorine, and Hastelloy B to wet hydrogen chloride and hydrochloric acid. All these materials are used to a considerable extent for reaction equipment in accomplishing the various types of chlorinations. There is a large field of chlorinations a t moderate temperatures in which the chlorine and organic reactants are commercially dried and where steel equipment might be used, providing the drying is always complete. However, where there are likely to be temporary lapses in the performance of drying equipment or where the presence of iron in the product is objectionable, the fact that nickel and Monel are more resistant than iron to the chlorine with relatively high degree of water saturation is utilized to provide insurance against serious corrosion. Uses of nickel and Monel reactors have been recorded particularly in the chlorination of paraffin and olefin hydrocarbons and of such aromatics as benzene, toluene, phenol, and amines ( 3 7 ) . They are not useful in the chlorination of organic acids such as acetic or of alcohols. In these particular chlorinations and in some wet chlorinations below about 140' F., Hastelloy C is successfully used. At higher temperatures glass-lined equipment frequently is used. Some types of chlorinations are carried out with such chlorine carriers as phosphorus chlorides, nitrosyl chloride, and sulfuryl chloride. Nickel and the high-nickel alloys are particularly useful in the production of these materials and with reactions involving them. Nickel and lead are the only two common metals which have shown a high degree of resistance to phosphorus halides (SQ),including the trichloride, pentachloride, oxychloride, and others. I n the production of these products nickel is used for much of the equipment contacting chlorine-containing reactants and products including reactors, coolers, piping, valves, storage tanks, tank cars, and shipping drums. I n a plant producing nitrosyl chloride ( 4 6 ) Inconel is found particularly useful for handling this chemical, being used for such equipment as tubular column heaters, piping, valves, flowmeters, and other fittings 968
Nickel cylindeis and valves ale used in the shipment of the product. Reference previously was made to the use of Hastelloy B and C equipment handling Friedel-Crafts type reactions nith aluminum chloridehydrogen chloride catalyst. Trescder and Wachter ( 7 6 ) found that bhe addition of as little as 0 2 % by weight of antimony or arsenic to the reaction mixture greatly reduced corrosion in a hydrocarbon isomerization process of this type and describe the use of hfonel and nickel plant reaction equipment where an aluminum chloride-antimony chloride catalyst is used. The test results and plant experience reported by Brown, DeLong, and Auld (9) show that nickel, Inconel, and Hastelloy B are usefully resistant to continuous exposure to dried chlorine and to dried hydrogen chloride at temperatures up to itbout 1000° F. The resistance of these high-nickel materials apparently is due to the high melting point and low vapor prcssuro of nickel chloiide formed on the metal surface Recorded ( 3 7 ) uses of nickel reaction equipment include: chlorination of heptane a t temperatures up to 300" C., and pressures up to 1000 pounds per square inch; nickel tubes lined with sulfur-free carbon for chlorination reaction a t 1500 F.; and cooling-jacketed nickel reaction tubes handling chlorine at inlet temperatures of 2000" F. Where sulfur compounds are present or high-temperature strength is required Inconel may be used for some high-temperature chlorinations There are numerous applications of nickel, Monel, and their clad steels in the storage, handling, distillation, and condensation of chlorinated hydrocarbons, for resistance to the small concentrations of hydrochloric acid which may be formed by hydrolyaia when some water is present. A partial list includes acetyl chloride, acetylene tetrachloiide, allyl chloride, amyl chloride, aniline hydrochloride, benzoyl chloride, benzyl chloride, cacodyl chloride, carbon tetrachloride, chloroacetic acid, chlorobenzenes, chloroform, chloronaphthalenes, chlorophenols, chloroprene, ethyl chloride, ethylene dichloride, hexachloroethane, methyl chloride, methylene chloride, perchloroethylene, trichloroethylene, and vinyl chloride Bromine. Work reported by Haines (29) has shown that nickel and Monel are suitably resistant for long-time exposure to bromine just saturated with water at atmospheric temperature and are highly resistant to bromine commercially dried with 60 to 80% sulfuric acid. As a result of this and other plant experience ( 4 7 ) , nickel is used for the construction of tank cars and tank trucks handling liquid bromine and ethylene dibronude, and for the pumping of liquid bromine. Monel and nickel are standard materials for shipping drums handling liquid bromine (29) Fluorine and Hydrogen Fluoride, Nickel and Monel aie considered t o be the most suitable materials for handling fluorinr a t elevated temperatures, principally because they acquire a very adherent thin fluoride coating which remains piotective wen under velocity conditions. I n the work now being done in the field of fluorination chemistry, numerous references are made t o the use of nickel and None1 reaction equipment ( 3 6 ) , including nickel-lined pressure vessels for the fluorination of carbon tetrachloride. Applications recorded (41, 65, 70,84) for nickel, Duranickel, Monel, K Monel, or S Monel in the handling of liquid or gaseous fluorine a t pressures up to 600 pounds per square inch include: storage vessels, compressors, piping, valves. flowmeters, and pressure arid temperature recorders and controllers. I n tests reported by Myers and DeLong (69) nickel and Monel showed good resistance in fluorine up to 500' C . and in hydrogen fluoride these materials and Inconel were resistant a t 600" C. Nickel and nickel-plated surfaces are used in the handling of uranium hexafluoride ( 7 3 ) . Inconel, Illium, and Hastelloys are used in the high temperature treatment of minerals with hydrogen fluoride and other halogens. I n these high temperature applications nickel and Monel cannot be used above about 600 F. if sulfur compounds are present, because of a tendency of these materials to intergranular sulfide embrittlement a t higher temperatures. O
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NICKEL-METAL, O X I D F Synthetic Textiles. In the production of viscose rayon considerable use is made of corrosion-resistingmaterials (38)for process equipment in order to avoid contamination by such elements as iron and copper which will adversely affect the aging, spinning, and dyeing qualities of the product. Applications of nickel alloys in the steeping unit for resistance t o caustic solutions include: nickel or nickel-clad steel for caustic soda storage, steep liquor coolers, and dialyzer frames; Type 2 Ni-Resist for pumps; and nickel- or Type 304 stainless-clad steel for aging cans. Type 304 stainless sometimes is used in carbon bisulfide systems and xanthating churns. In the handling of viscose solution, nickel or nickel-clad steel is used for storage and piping, filter press wires, candle filters, and spinner goosenecks; Ni-Resist and nickelplated cast iron are used for filter plates and frames; H Monel and nickel-plated bronze are used for spindles or “mushrooms” in spinning pots. Hastelloy C is used for spinning pots in the special high temperature spinning baths producing high-tensile fibers. I n the handling and recovery of sulfuric acid spinning baths, alloys such as Durimet 20, Worthite, and Illium are used for pumps and valves; nickel for evaporator tubes and tube sheets. Fabricated carriers of Type 317 stainless commonly are used for handling the viscose rayon cake through the various steps of washing, desulfurizing, chlorine bleaching, and treatment with antichlor and soaping solutions. Plants for the production of cellulose acetate rayon are equipped with considerable amounts of stainless steels (67), because of the resistance of these materials, particularly Type 316, to acetic acid solutions. Stainless equipment includes pretreaters for cellulose with glacial acetic acid, piping, acetylators, washing belts, spinneret nozzles, and stills for recovery of acetic acid, acetic anhydride, and acetone. Durimet and Worthite pumps, valves, and fittings handle acetate slurries. In order to supply the demand for such chemicals as acetic acid, acetone, acetaldehyde, formaldehyde, and alcohols in synthetic fiber and plastics industries and others there has been within recent years a considerable increase in the plant facilities for production of these chemicals by controlled oxidation of hydrocarbon gases (31, 32). These plants have installed large amounts of stainless steel equipment, much of it Type 316 stainless, for the distillation and purification of these chemical products, particularly acetic acid and formaldehyde. The original plants for the production of nylon (79) and the nylon salt,. hexamethylene diammonium adipate, used stainless steel, much of it Type 347,for almost all of the equipment which came into contact with these products during processing in order to protect the purity and clarity of the products. Inconel is used for ammonia superheaters. Recent developments in the methods of manufacture of nylon salts require considerable amounts of nickel and Monel equipment. The stainless steels have now become practically standard materials for the construction of equipment used for the dyeing and finishing of all types of textiles, Types 304 and 347 stainless are used for equipment in cotton, silk, and rayon dyeing and peroxide bleaching. Type 316 stainless is used for equipment in wool dyeing, carbonizing, aging, and chlorine bleaching. Equipment of these alloys has no effect upon the color of the dyes and can be readily cleaned when changing from one color to another. The production of dyestuffs and dye intermediates requires the use of almost every conceivable type of metallic and nonmetallic corrosion-resisting material. A very limited study (40)reveals the following among applications of nickel-containing process equipment: nickel and nickel-clad steel for caustic and brine storage; nickel, Inconel, and nickel-alloy cast irons and steels for caustic fusions; Inconel for diazotization vessels and coupling vats; Hastelloy B cooling coils in reactions involving hydrochloric and sulfuric acids; Monel and nickel reaction vessels for phosphorus trichloride chlorinations; Monel for sulfonation coolers; and stainless and nickel for standardization vessels. Synthetic Plastics. I n the manufacture of synthetic resins and
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plastics considerable use is made of nickel-containing materials for corrosion resistance and particularly for protection of the color and quality of the products. The choice of material for reactors or kettles often will depend upon the nature of the catalyst used. Phenol-formaldehyde resins are produced in stainless steel, nickel, or Monel kettles (28,67) equipped with agitators and condensers of the same materials. With melamine and urea-formaldehyde resins (61), stainless steel is used for steam-jacketed reaction kettles and agitators, pipelines, mixers, and pumps handling liquid resins and formaldehyde. Two of the processes for production of synthetic phenol use monochlorobenzene as a starting material (66, 62). I n one process chlorobenzene is hydrolyzed with diluted caustic soda under about 4000 pounds per square inch pressure and 750’ F. to form sodium phenolate. I n one plant (66) Inconel reaction tubes and low-carbon nickel heat exchangers were used in this process, while in another plant nickel steel tubes are used. In the production of synthetic phenol by reaction of fused caustic soda (78) with benzene sulfonic acid, low-carbon nickel and Inconel are used for continuous caustic soda evaporators and nickel-alloy steels and nickel-cast irons are used for caustic fusion vessels. Nickel and Inconel or their clad steels commonly are used for the h a 1 distillation, condensation, storage, and transportation of purified phenol to protect the purity and color of the product. Analyses of phenol stored in nickel and nickel-clad steel tanks show nickel content in one case of 0.15 p.p.m. in an 8000-gallon tank over 24 days, and in another case of 0.21 p.p.rn. in a 10,000-gallon tank over 28 days (22). Types 304 and 347 stainless steel or stainless-clad steel kettles commonly are used in the production of alkyd resins. A plant for production of polymethyl methacrylates is equipped largely with stainless steel equipment, most of it Type 347 (79). Monel and nickel are used in production of methyl acrylate polymer from ethylene chlorohydrin (46). Stainless steel kettles were used in the production of polystyrene by emulsion polymerization using potassium persulfate as catalyst (67) and for continuous massive polymerization of styrene. Polyiaobutylene w ~ 9produced continuously on an endless stainless belt (67). A number of important synthetic plastics and elastomers are based upon chlorinated hydrocarbon monomers such aa vinyl chloride, vinylidine chloride, and chloroprene. High-nickel alloys find considerable use in the production and hot working of these plastics. Hastelloy B is used for handling hydrochloric acid coming from chlorination reactors and elsewhere. In production of polyvinyl chloride, nickel wm used for reaction kettles in a batch process and for helical spiral vacuum evaporators in a continuous process (67). I n the production of polyvinylidine chloride (47) and copolymers nickel and Inconel are used extensively for handling the wet polymers. I n the hot extrusion of saran, Hmtelloy B and Duranickel are used for cylinder liners and screws and agehardened Durahickel for dies (64). I n order to prevent corrosion and contamination of the product in the manufacture of ethylcellulose, all equipment in the ethylation plant (14) including alkali treating troughs and conveyors, autoclaves, purification vessels, pipelines, pumps, centrifugala, and dryers are of nickel or Monel, solid or lined. I n all, this plant contains more than 100 tons of these two metals. In the hydrochloric acid plant and ethyl chloride plant, Hastelloy B is used for trim on valves and pumps. Antibiotics. The manufacturers of pharmaceuticals and drugs are large users of stainless steels and of other corrosion-resisting materials such as Inconel and nickel, chiefly t o protect the purity of their products. This is illustrated in the production of antibiotics such as penicillin, streptomycin, and chloromycetin. I n a penicillin plant described by Callaham (1.2) much of the process equipment is stainless steel, including carbon absorption tanks, bulk containers, racks, trays, assaying cylinders, filling machines, and numerous centrifugals and filters. In this plant, carbon steel is used for fermentation tanks and glass-lined steel
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NICKEL-METAL, OXIDE for solvent extraction of penicillin concentrate, for solvent recovery and storage equipment. I n another penicillin plant (67) Inconel is used for deep-fermentation tanks together with temperature control coils and agitators. Porter ( 6 7 ) described a plant for the production of streptomycin in which much of the process equipment is of stainless steel including pipes, valves, pumps, tanks, filters, and product containers. I n the elution process involving the use of an acidified solvent such as alcohol plus hydrochloric acid, rubber-lined elution tanks are used with porcelain pipe and fittings, Durichlor pumps, and Hastelloy B and rubber-lined filters. After neutralization of the streptomycin hydrochloride the product can be handled in stainless steel or Inconel evaporators. Much of the finishing and packaging equipment is of stainless steel. I n a plant for production of chloromycetin, described by Olive ( 6 3 ) , almost all of the process equipment is constructed of Incone1 or Inconel-clad steel. This includes jacketed preseed tanks; seed tanks; fermentation tanks equipped with agitators, baffles, and cooling coils; filter feed tanks; pressure filters; and filter cake receivers. Chloromycetin is extracted from the filtrate with amyl acetate in stainless steel extractors, the concentrate collected in Type 316 stainless tanks, and further concentrated in Inconel evaporators. Finishing and packaging equipment for all of these antibiotics is largely Types 302 or 304 stainless. Fatty Acids. Another chemical development has been the enlarged use of fractionated fatty acids as starting materials for the production of a variety of chemicals as well as for the production of soap by continuous processes. These uses require the production of fatty acids of a high degree of purity. Several articles (25, 68, 66, 68, 80) have described the use made of stainless steels and other nickel alloys in the production and processing of the fatty acids. The incoming fats and oils are hydrolyzed by two processes: ( I ) Twitchell splitting by batch operation in Monel tanks in the presence of boiling dilute sulfuric acid; (2) continuQUS hydrolysis with water and steam under about 700 pounds per square inch pressure and a t 450’ to 500’ F. Columns are constructed of Type 316 or 316L stainless in either solid or clad form, and of Inconel either clad or lined. Associated feed tanks and piping are of the same materials. Continuous vacuum fatty acid fractionating stills and columns are constructed of Type 316 or 316L stainless or Inconel with preheaters, condensers, and piping of the same materials. Types 304, 304L, and 347 stainless are used for distillate piping and storage. Type 2 Ni-Resist is used for vacuum booster and ejector diffusers and nozzles, for castings in some of the older type batch fatty acid stills, for red oil filter plates and frames, and for pumping cooled fatty acids. Pumps and valves of Durimet 20, Aloyco 20, and Worthite are used for handling hot sulfuric acid-treated feed stocks with Hastelloy B trim on pressure control valves. Nitriles are prepared from fatty acids by reaction with superheated ammonia, first in a reactor a t 465’ F., then in a converter with catalyst a t 680’ F. Stainless steels are used for reactor, converter, reflux condenser, vapor superheater, pitch column, and all connecting piping and valves. Fatty acids are hydrogenated in 18-8 stainless autoclaves at 300” F. under 200 pounds per square inch pressure. I n the esterification of fatty acids, stainless steel is used for reaction kettles with coils, agitators, condensers, mixing tanks, filters, and flakers. I n the concentration of glycerol from sweet water stainless is used for evaporators and nickel and nickel-clad steel for finishing stills, I n the production of synthetic glycerol from refinery gases (48),nickel aQd nickel-clad steel are used for the handling of alkyl chloride, and for the evaporation, distillation, and storage of glycerol. Ziels and Schmidt (83) determined that nickel and aluminum are the only common metals which have no pro-oxidant effect upon vegetable oils and fats. Nickel and stainless steel equipment commonly isused in the deodorization of fats and oils. Corn Products Refining. The corn products industry is an-
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other in which considerable amounts of the stainless steels, particularly Type 316, must be used, especially for resistance to the dilute sulfurous acid conditions which exist in the wet processing of corn. Flournoy (20) described the performance of metals in corn products refining. Carpenter 20 was the only stainless type alloy which showed satisfactory performance in towers for absorption of sulfur dioxide in water. I n plant practice wood, acidproof brick, and stoneware frequently are used. Types 316 and 317 stainless give satisfactory service in starch wash filtrates, Type 316 stainless steel and aluminum bronze as gluten slurry centrifugals, and Types 304 and 316 stainless as steep water evaporators. Cast stainless steels of the chromium-nickel-molybdenum type show satisfactory performance in dextrose converters in the presence of sulfuric acid. Converter inlet valves with Ni-Resist body and Type 316 stainless trim are used. Types 304, 316, and 317 stainless give satisfactory performance in ion-exchanged corn sirup liquors where cast iron body valves failed in a few months. Types 316L and 318 stainless were the only metallic materials showing satisfactory performance in feed dryer vapor ducts. Hightower (33) and Starr (72)have described the application of these and other corrosion-resistant materials in two corn products plants. Teeple (?4) gave a complete summary of the uses of nickelcontaining alloys in the pulp and paper industry, where these materials have been in common use for a number of years. Among recent developments are the use of Type 316 stainless linings for sulfite pulp digesters and of Inconel and Type 347 stainless-clad or lined digesters for sulfate pulp service. These are, of course, but a few of the examples which could be chosen to represent the part being played by the corrosion-resisting nickel alloys in the progress of the chemical and process industries. The examples were chosen principally to illustrate the variety of chemicals and processes being handled by these materials. It would be possible to cite numerous other applications in the industries referrea to and in others such as petroleum refining, food processing, high temperature fields, and chemical manufacture in general. I n the past it has been customary for new alloys or modifications of existing ones to be developed to fill the special needs of the advancing chemical industries. It is reasonable to expect that this custom will continue in the future and the chemical industry can still depend upon the metallurgical industry to provide it with materials of construction that will permit the promising results of laboratory size operations to be translated into commercial production on any required scale. LITERATURE CITED
(1) Alloy Steel Products Co., Tech. Information Bull. 2 , “Aloyco 20.” (2) Am. Soc. Metals, “Metals Handbook,” 1948. (3) Am. Soc. Testing Materials, Philadelphia, Symposium on Stress Corrosion Cracking, 1944. (4) Armstrong, T. N., and Brophy, G. R., “Some Properties of Low
Carbon 81/1 Per Cent Kickel Steel,” Natl. Conference on Petroleum Mechanical Engineering, Am. Soc. Mechanical Engrs., Houston. Tex., Oct. 5-8, 1947. (5) Armstrong, T. N., and Gagnebin, A. P., Trans. Am. SOC.Metals, 2 8 , l - 2 4 (1940). (6) Atomic Energy Commission, Washington, D. C., “Liquid Metals Handbook,” 1950. (7) Broughton, D. B., IXD. ENG.CHEM., 4 2 , 2 0 2 3 4 (1950). (8) Brown, M. H., and DeLong, W.B., I b i d . , 39, 1248-53 (1947); 40,1812-19 (1948); 41,2139-46 (1949). (9) Brown, M. H., DeLong, W.B., and Auld, J. R., Ibid., 39,839-44 (1947). (10) Buchan, R. C., Corrosion, 6 , 178-85 (1950). (11) Burke, J. F., and Mantius, E., Chem. Eng. Progress, 43, 237-46 (1947). (12) Callaham, J. R., C h e m & Met. Eng., 51, No. 4 , 94-8 (1944). (13) Carpenter Steel Co., “Carpenter Stainless Steel No. 20,” 1948. (14) Chem. & Met. Eng., 52, No. 9, 129-36 (1945). (15) Cheniceck, J. A., Iverson, J. O., Sutherland, R. E., and Weinert, P. C., Chem. Eng. Progress, 43,210-18 (1947). (16) DeLong, W.B., and Permar, P. H., IND.ENG.CHEW,42, 200919 (1950). (17) Deutach, Z. G., “Encyclopedia of Chemical Technology,” Vol. 1, p. 382, New York, Interscience Encyclopedia, 1947.
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NICKEL-METAL, OXIDE(18) D.wiron Co., Bull. 112, “Durimet 20.” (19) Findlay, R. A., Natl. Petroleum News (Tech. Section), 37, 326-8, 386,388 (May 2,1945). (20) Flournoy, R. W., Corrosion, 7, 129-33 (1951). (21) Fontana, M. G., Chem. Eng.,53, No. 10,114-15 (1946). (22) Friend, W. Z., Ibid., 58, No. 8,222 (1951). (23) Friend, W. Z., Chem. & Met. Eng.,No. 9,203-6 (1946). (24) Friend, W. Z., J. Am. Oil Chemists SOC.,25, NO. 10, 353-8 (1948). (25) Friend, W. Z., and Mason, J. F., Jr., Corrosion, 5,355-68 (1949). (26) Friend, W. Z., and Teeple, H. O., Oil & Gas J., 44, 87-101 (March 16,1946). (27) Gergstrom, R. E., and Lientz, J. R.,.Paper Trade J . , 124, No. 1, 42-6 (1947). (28) Groggins, P. H., “Unit Processes in Organic Chemistry,” Chap. XIII, Polymerization, New York, McGraw-Hill Book Co., 1947. e (29) Haines, G. S., IND. ENG.CHEM., 41,2792-7 (1949). (30) Haynes Stellite Division, “Hastelloy High Strength, NickelBase Corrosion-Resistant Alloys,” 1950. (31) Hightower, J. V., Chem. Eng., 55, No. 7, 105-7 (1948). (32) IbidE., 56, No. 1 , 9 2 4 (1949). (33) Ibid., 56, NO.6, 92-6 (1949). (34) Holmberg, M. E., and Prange, F. A,, IND. ENG.CHEM.,37,103033 (1945). (35) Illium Corp., “Illium Corrosion Data,” Bull. 105-A (1946). ENG.CHEM.,39,236-434 (1947). (36) IND. (37) International Nickel Co., Corrosion Reptr., 3, No. 3 (July 1948); “Chlorinations, Dry, Moist, 8.79Wet.” (38) Ibid., 4, No. 1 (January 1949); Notes on Cellulose and Viscose Rayon.” (39) Ibid., 4, No. 3 (June 1949); “Phosphorus and Some of Its Compounds.” (40) Ibid., 5, No. 2 (November 1950); “Dyes, Reflectors of Light and Learning.” (41) Ibid., 5, No. 3 (February 1951); “Fluorine Comes Out of Its Corner Fighting.” (42) International Nickel Co., Inc., “Corrosion-Resisting Properties of the Austenitic Chromium-Nickel Stainless Steels,” 1949. (43) International Nickel Co., Inc., “Engineering Properties and Applications of Ni-Resist,” 1949. (44) International Nickel Co., Inc., “Inconel X. A High Strength, High Temperature Alloy,” 1949. (45) International Nickel Co., Inc., Process Industries Quart., 6, No. 3 (1941). (46) Ibid., 10, No. 3 (1947). (47) Ibid., 11, No. 2 (1948). (48) Ibid., 13, No. 1 (1950). (49) International Nickel Co., Inc., Tech. Bull. T-3 (1948).
(50) Ibid., T-6 (1949). (51) Ibid., T-13 (1948). (52) Ibid., T-29 (1945).
(53) Landau, R., and Rosen, R., ISD. ENG.CHEM.,39, 281-6 (1947). (54) LaQue, F. L., and Clapp, W. F., Trans. Electrochem. Soc., 87, 103-25 (1945). (55) LaQue, F. L., and Mason, J. F., Jr., Proc. 16th Mid-Year Meetinn. Div. of Refining, Am. Petroleum Inst., 30 MIII, 103-19 (1950). (56) Lee, J. A., Chem. Eng., 54, KO.9,122-4 (1947). (57) Lee, J. A., “Materials of Construction for Chem-cal Process Intries,” New York, McGraw-Hill Book Co., 1950. (58) McBride, G. W., Chem. Eng., 55, No. 10, 94-7 (1947). (59) Myers, W. R., and DeLong, W. B., Chem. Eng. Progress, 44, 359-62 (1948). (60) Nathorst, H., “Stress Corrosion Cracking of Stainless Steels,” Bull. 6, Welding Research Council, New York, 1950. (61) O’Conner, J. A., Chem. Eng., 56, No. 12,88-91 (1949). (62) Olive, T. R., Chem. & Met. Eng., 47, No. 11,770-5 (1940). (63) Olive, T. R., Chem. Eng.,56, No. 10, 107-12 (1949). (64) Palmer, J. A., ModernPZastics, 21, No. 11, 141-8 (1944). (65) Paul, R. J., Corrosion, 5,43942 (1949). (66) Pilling, N. B., and Ackerman, D. E., Trans. Am. Inst. Mznzny Met. Engrs., 83,248 (1929). (67) Porter, R. W., Chem. Eng., 53, fio. 10, 94-8 (1946). (68) Potts, R. H., and McBride, G. W., Ibid., 57, No. 2, 124-7 (1950). (69) Prine, W. H., Materials &Methods, 30, No. 12,43-6 (1949). (70) Rudge, A. J., Chemistry &Industry, 16,247-53 (1949). (71) Sefing, F. G., Petroleum Refiner, 29, KO.1,97-101 (1950). (72) Starr, B., Chem. Eng., 56, No. 8, 92-5 (1949). (73) Stout, W. W., “Secret,” Chrysler Corp., 1947. (74) Teeple, H. O., Paper Trade J., 131; No. 19, 28, 30-2; No. 20, 19-23; NO.21, 14, 15, 18, 19,21-5 (1950). (75) Tracy, A. W., and Hungerford, R. L., Proc. Am. SOC.Testing Materials, 45,591-617 (1945). (76) Treseder, R. 8. and Watchter, A., Corrosion, 5, 383-91 (1949)’. (77) Uhllg, H. H., “Corrosion Handbook,” New York, John Wiley & Sons, 1948. (78) Weiss, J. M., Heat Eng. (October, November, December 1944). (79) Williams, R., Jr., Chem. Eng., 55, No. 9, 118-21 (1948). (80) Ibid., 56, NO.7,92-4 (1949) (81) Worthington Pump & Machinery Corp., “Technical Information, on Worthite,” BUZZ. W-350-B4E (1951). (82) Zapffe, C. A,, “Stainless Steels,” Am. Soc. Metals, Cleveland, 1949. (83) Ziels, N. W., and Schmidt, TV. H., Oil & Soap, 22,327 (1945). (84) Zima, G. E., and Doescher, R. N., Metal Progress, 59, KO. 5. 660-3 (1951). RECEIVED for review October 17, 1951. ACCEPTED January 15, 1954
METALLURGICAL NICKEL ANALYSIS W. D. MOGERMAN Batten, Barton, Durstine, and Osborn, 383 Madirion Ave., New York, N.
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historical review is given of analytical difficulties that delayed general recognition of Cronstedt’s discovery of nickel. The nickel methods most widely used in metallurgical laboratories for determining nickel in both small and large quantities are discussed. Some practical hints are proposed fcr eliminating certain sources OF error in gravimetric work.
ART of the purpose in this symposium is to do honor to Axel Fredrik Cronstedt, who discovered nickel in 1751 and is chiefly remembered today on that account (6). In his own day Cronstedt was probably better known as the author of an unusual book on mineralogy, published in 1758 (3). Cronstedt’s proposed new element, nickel, was not accepted as a demonstrable fact by many of his scientific colleagues and so i t tended to be overlooked for a long time (9). Some of his skeptical colleagues thought that Cronstedt was being deceived by a tricky mixture of
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copper and iron. The blue color of the substance in ammoniacal solution was attributed to copper, and its magnetism to the presence of iron. Some experimenters actually reported that the new substance was not magnetic. Nevertheless, these were the most reasonable opponents n ith whom Cronstedt contended, because they based their doubts on laboratory evidence, faulty though that evidence may have been. There were others who based their arguments against nickel on the theory that there could be no additional metallic elements because six “true metals” had been known since Biblical days, and six “half metals” already existed. That made twelve metals altogether, and to discover more would conflict with the twelve signs of the zodiac. So the controversy continued, fueled for a half century or more by bad analysis. But Cronstedt’s book, though i t was also controversial, was an indisputable fact that could not be dismissed with logic of this
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