Ferrous Metallurgy

ing techniques rather than basically new methods. There is no reliable criterion for the proportion of fundamental analytical research carried out by ...
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(196) Schaff, K., Brennsto~-~urnte-Kraft 8,371-80 (1956). (197) Schoniger, W., Alikrochemie ver. Milzrochim. Acta 39, 229-33 (1952) (198) Schuhknecht, W., Kuna, H., Brennsto.f-Chenz. 38, 313 (1957). (199) Schuhknecht, W., Schinkel, H., Ibid., 38, 275-7 (1957). (200) Schwab, G. M., Neuwirth, O., Chem. Ing. Tech. 29, 345-7 (1957). (201) Sharvin, Yu. V.,Andrianov, V. P., Sharova, E. A., Zavodskaya Lab. 21, 853-5 (1955); Rejerat. Zhur. Khim. 1956, Abstract 32940. (202) Shmuk, E. I., Zzvest. Akad. Nauk S.S.S.R., Otdel. Tekh. Nauk 1957, NO. 8, 126-8. (203) Shubnikov, -4.K., Soboleva, G. N.,

Bronovets, T. U.,Khrisanfova, A. I., Khim. i Tekhnol. Topliva i Masel 1957, KO.10, 1-5. (204) ShumilovskiI, K. N., Yarmolchuk, G. G., Podzemnaya. Gazifikatsiya Uglei 1957, NO.2, 61-4. (205) Sindelar, J., Paliva 37, 381-4 (1957). (206) Siniramed, C., Manci, C., Riv. combustibili 1 1 , 366-79 (1957). (207) Skalska, S., Held, S., Chem. Anal. (Warsaw) 1 , 294-300 (1956). (208) Sommer, O., Bergfreiheit, 383-8, September 1957; Mines belg. 79 (January 1958). (209) Spencer, C. F., Baumann, F., Johnson, J. F., ANAL.CHEX 30, 1473-4 (1958). (210) Stach, E., Brennstofl-Chem. 39, 15-20 (1958).

(211) Stach, E., Takahashi, R., A r ~ m y d Kydkaishi 37, 351-60 (195s). (212) Steinbrecher, H., Mozumder, A. K., Brennsfofl-Chem. 38, 175-8 (1957). (213) Stephens, J. N. , Australia, Commonwealth Sri. Ind. Research Organiza-

tion, Fuel Research, Physical, and Chemical Survey of the Natural Coal Resources, M 130, June 1957; Gas W o r l d 146, 720 (1957). (214) Stevens, C. W.,Power Eng. 61, 94-6 (1957). (215) Strain, H. H., ASAL. C H m f . 30, 622-4 (1958). (216) Strambi, E., Calore 24, 111-18 (1954). (217) Strambi, E., Chim. & Ind. (Paris) 72, 450 (1954). (218) StrizhevskiI, I. I., Zaitseva, V. P., Zavodskaya Lab. 22, 546-7 (1956). (219) Sugawara, K., Tanaka, M., Kozawa, A,, Bull. Chem. SOC. Japan 28, 492-4 (1955). (220) Szonntilgh, J., FarBdy, L., JBnosi, A., Magyar Kbm. Folybirat 61, 312-14 (1955) (221) Taniewski, M., Chemik (Gliwice) 10, 242-3 (1957). (222) Toren, P. E., Heinrich, B. J., Ax.4~.CHEW29, 1854-6 (1957). (223) T6th, J., GrBf, L., Magyar Kdm. Folydirat 63, 216-21 (1957); Bdnycisz. Kutato’ Zntdzet Kozlemdnyei 1, 117-25 (1956); Hung. Tech. Abstr. 9, No. 4, Abstr. 21 (1957). (224) Turowska, A . , Jedrzejczyk, B., Gaz, Woda i Tech. Sanit. 31, 229-33, 266-9 (1957). (225) Turowska, A., Jgdrzejczyk,B., Prace

last. Minisfersfwa Hutnictwa 9 , 87-92 (1957). (226) United Nations, Economic Commission for Europe, E/ECE/247, E/ ECEICOALII 10: Publ. Sales, No. 1956, I1 E.’4 (1956). ‘ (227) Ura, Mitsuru, Nippon Kagaku Zasshi 78, 316-20 (1957). (228) Ussar, M., Gaswarme 5, 216-20 (1956). (229) Vandy, D., Petrol. Eng. 29, C18, C20-23 (February 1957). (230) Verrien, J., ‘Compt. rend. congrks ind. gaz, Y2nd Congrbs, Strasbourg 1955, 267-97. (231) Verrien, J., Rev. inst. franG. pdtrole. et Ann, combustibles liquides 11, 641-83 (1956). (232) Voinov, A. P., Gazovaya Prom. 1958, KO.4. 48. (233) Tqarner, C. W., Am. Gas J . 184, NO. 12, 33-7 (1957); NO. 13, 31-4 (1957);’ 185, NO. 2, 23-7 (1958); No. 4, 27-33 (1958). 1234) Stefan, Chem. Anal. (Warsaw)Waszak, 2, 376-84 (1957). \

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(235) Weaver, E. R., Am. Gas ASSOC., ‘ Pioc. 38, 476-82 (1956). (236) Wencke, Karla, Chem. Tech. (Berlin) 8, 728-30 (1956); 9, 404-6 (1957). (237) Wilkinson, H. C., Fuel 36, 39-42 (1957). (238) Zbid., 37, 116-18 (1958). (239) Wngkowska, Lidia, Chem. Anal. (Warsaw) 1 , 301-10 (1956). (240) Zolotukhin, A. I., Lazovskii, I. M.,

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Review of APPLIED

M

I

H. F. Beeghly Jones

4

Laughlin Corp., Pittsburgh 27, Pa.

of analyzing ferrous metals described for the first time in the period November 1, 1956, to October 31, 1958, are, on the whole, refinements and improvements of existing techniques rather than basically new methods. There is no reliable criterion for the proportion of fundamental analytical research carried out by t,he metals industries as compared to that in applied and “fire drill” or “crash” type analytical methods development. The effort devoted to the former probably is much less than to the latter. Development of apparatus for the analyst has become a substantial business in the past two decades. The mass spectrometer and the electron probe microanalyzer, still less common 706

ETHODS

ANALYTICAL CHEMISTRY

and more expensive than the now well established emission and x-ray spectrograph, are beginning to be considered along with photometers, gas analysis equipment, and the ion exchange column as practical supplements to the relatively simple equipment available to the metals analyst 20 years ago. Requirements for metals are becoming increasingly severe. For critical uses, metal cleanliness and consistently high quality are imperative from one production lot to another. To meet these requirements, knowledge of composition from raw material to finished product is essential. Much more complete information is needed today than was required 10 years ago about the minor constituents. Their functions in such phenomena as response to

thermal treatment, work hardening, scaling and corrosion in different environments, and to nuclear radiation are now recognized as very important. Solvent extraction (27, 125), ion exchange (98, 106, 167), and other methods (66, 68, 97, 158, 171) for eliminating interfering constituents were described. Reviews and useful reference books (1-8) were published. These include such subjects as gases in metals (76, 1 1 7 ) ~activation (41, 51), trace analysis (17‘8), electroanalytical chemistry (42, 108), microchemical methods ( l a l ) , sampling and analysis of cast (28) and pig iron (174, analysis of high purity iron (81), analysis of deep drawing steel (119), and x-ray spectroscopy (108).

An especially interesting series of papers on the role of an analysis group in an industrial organization was published (1%$). ALUMINUM

Xluniinum, in trace amounts, in cast iron was determined by titration after separating a major part of the iron by a butyl acetate extraction. Other interfering elements \\-ere removed by extraction of their diethyldithiocarbamate complexes with chloroform. The pH was adjusted, the fluoride ion added, and the aluminum titrated (29). An ion exchange column was used to separate the iron from an 8N hydrochloric acid solution. The aluniinum was then precipitated and ignited to the oxide (6‘7). I n another method, the aluminum was extracted as the cupferrate with chloroform a t pH 4.5 and determined polarographically (142). Prior to the extraction, most of the iron was removed as the diethyldithiocarbaniate by extraction with chloroform. The spectrograph was used in determining the aluminum content of iron-aluminum alloys containing up to 12% aluminum (143). A method for the production control analysis of steel for aluminum was described (150). ARSENIC

Arsenic was determined by the molybdenum blue method (36). By one procedure, reduction to the blue complex with ascorbic acid was enhanced by addition of bismuth sulfate (89). The color was then extracted with n-amyl alcohol. I n other procedures the arsenic was reduced to the metal and determined polarographically (I??’), by titration with iodine (163), or by precipitation as quinolinearsenimolybdate (120). A procedure for measuring the arsenic content of residues isolated from steel was published ( I S ) . BERYLLIUM

The reaction of Eriochrome Cyanine

R in the presence of sodium Versenate a t p H 9.7 to 9.8 was used in the analysis ,of steel for beryllium. The intensity of the color was measured a t 512 mp (83)* BORON

Kern reagents for reaction with boron to form color complexes include diaminoantlirarufin, tribromoanthrarufin, and diaminocrysazin (31). Titanium was the only metal found to interfere with these reactions. The fluoride ion and oxidizing ions such as nitrate or dichromate must be absent. Ion exchangers were used to remove iron from a hydrochloric acid solution containing boron (65). The reaction

of dianthramide in concentrated sulfuric acid was then used to estimate the amount of boron present. Two other reagents for reaction with boron to form a color complex are 5-benzamido6’-chloro-l, 1‘-bis (anthraquinolyl)amine, which has a mavimuni absorption band a t 635 mp) and 5-toluidino-6’-chloro1,l’-bis(anthraquinoly1)aminewhich has an absorption band a t 720 mp (76). The boron content of alloy steel was determined by use of quinalizarin in concentrated sulfuric acid (90). Titanium interferes a t low boron contents. This interference can be eliminated by use of titanium in the blank The absorption of the boron quinalizarin compound was measured a t 615 mp, after 2-hour standing. The boron contents of iron-free solutions were measured by use of the polarograph (102). The color reaction of carmine with boron in the phosphoricsulfuric acid solution was also utilized (116). I n another method, interfering elements were removed by passing an acid solution first through a cation exchange (IR-120-H form) and then through an anion exchange resin (IRA400-C1 form). The boron content of the effluent was then measured by titration or by a color reaction (127). The large absorbing capacity of boron for neutrons was made the basis for its determination (39). By addition of copper fluoride to specimens of steel containing boron and silicon, these elements can be distilled preferentially to most constituents of the steel, from a deep crater supporting electrode (134). This is the basis for a method of determining these elements in the concentration range of 0,001 to 0.020% with coefficients of variability of =k3% for ~ silicon. boron and ~ t 3 . 2 7for The addition of boron-10 to stainless steels has created the need for an accurate method of analysis for the boron-10 isotope. The total boron content may be estimated in the usual way. The boron-10 (n, alpha) lithium7 reaction was made the basis for determination of boron-10 burnup, by use of the flame photometer for determining the lithiam content (4s).

specimen is burned in oxygen in a platinum crucible at a temperature in the range of 1300” to 1400” C. and at a pressure of 133 mm,of mercury. The carbon dioxide is frozen out in liquid nitrogen (&), This method is said t o be good for concentrations of 0.003 to 0.03 mg. of carbon. The conductometric method, in general use for higher carbon materials, has been evaluated and modified so that improved accuracies can be obtained for extremely loiv carbon contents (63). The inert gas fusion method was simplified and found useful for determining extremely small amounts of carbon (73). The carbon-12 ( p , gamma) nitrogen13 reaction was made the basis for a specific method for determining carbon in loiv carbon iron (61). The vacuum spectrograph, now comn~erciallyavailable, and the mass spectrometer also offer good possibilities for the analysis of metals for extremely small amounts of carbon. CHROMIUM

Chromium +G can be extracted from 1N hydrochloric acid solution 1,5-Diwith 4-methyl-2-pentanone. phenylcarbohydrazide added to the extract forms a color complex with chromium, the intensity of which can be measured a t 540 mp (38). This method is said to be especially suited to concentration ranges of 1 to 10 y and for estimating micro amounts of this element in cast iron and steel. After removal of interfering elements by extraction from an aqueous solution a t pH 2.0 with a 1 to 1 mixture of acetylacetone and chloroform, the chromium remaining in aqueous solution was refluxed with acetylacetone and the metal organic complex was extracted with a fresh mixture of acetylacetone and chloroform. This solution has a red-violet color which was made the basis for the colorimetric determination of chromium in concentrations above 0.20%. Smaller amounts of chromium were determined by means of the color reaction with diphenylcarbazide 1110). COBALT

CARBON

The determination of very small amounts of carbon in steel continues to be an important problem. One method, used where the amounts are of the order of 0.01 to O.l%, is to burn the specimen contained in a porous thimble, absorb the sulfur trioxide in a silver vanadate solution, collect the carbon dioxide in sodium hydroxide, and measure the change in conductivity of this solution (18). This procedure is said to permit a carbon determination in 4 to 6 minutes. I n another method, the

Activation of cobalt by exposure to a neutron flux was made the basis for determination of cobalt contents of the order of 0.01%. The cobalt activity was measured with a gamma spectrometer (146). I n another isot,ope method, a cobaltinitrite separation was made in conjunction with the use of the isotope dilution technique and the anodic deposition of cobalt (147). The precipitation of cobalt with acridine and ammonium thiocyanate &-as used. The precipitate was dissolved in acetone, ammonium acetate was added, and the cobalt was titrated with EDTA [(ethylenedinitrilo) tetraacetic acid] VOL. 31, NO. 4, APRIL 1959

707

using ammonium thiocyanate as indicator (170). NIOBIUM

A method for the combined determination of niobium and tantalum in steel involves acid solution, separation of the two elements by hydrolysis, and final determination of the niobium by means of a color reaction (6). The method is designed for routine production control. The reaction of niobium in a solution adjusted to pH in the range of 4.5 to 5.5 t o form a precipitate with cupferron was made the basis for separation of this element from tantalum, which is not precipitated (112). Titanium, if present, remains with the niobium and must be separated by other means. Ion exchange resins (Dowex-2) were useful for separating niobium from tantalum. The separation was made from an aqueous solution containing 36 grams of hydrochloric acid and 45 grams of oxalic acid per liter (82, 159). The effectiveness of the separation was measured by use of the niobium-95 and/or tantalum-182 isotopes. COPPER

By reaction of copper with bicyclohexanone oxalyldihydrazone a t pH 7.5 in ammonium citrate solution, a color complex is formed which can be measured without separation of the copper from the steel (80,172). Copper can be separated from ferrous alloys by use of fluoboric acid (50%), which dissolves cast iron leaving the copper behind in insoluble form. The copper was dissolved and the amount measured following electrodeposition (130). I n a phosphoric-sulfuric acid solution, copper was complexed with 2, 2'biquinoline and extracted with n-amyl acetate. The absorption was measured (166). This method is applicable to copper contents up to 1% and in the presence of such elements as cobalt, manganese, nickel, and tungsten. For low alloy steels, the reaction of copper with diethyl dithiocarbamate was used without separation of the copper from the iron. Cobalt and manganese interfere. EMISSION SPECTROSCOPY

The spectrograph has continued to be applied to analysis of industrial materials in production. The direct reading spectrograph has been useful in analyzing alloy cast irons (7, 1-40). By use of germanium as a reference element, powders with a wide range of compositions were analyzed with a n accuracy of &15% (10). An air blast in the spark gap and also ultraviolet or radioisotope radiation were found to stabilize the gap breakdown voltage

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and to enhance the reproducibility of the method (21, 62). I n routine control, it was found practical t o feed a powdered sample onto an adhesive tape which passed continuously through the spark gap. This provided a source for quick and continuous analyses of slags and various ore materials during beneficiation (36). By using a moving electrode, a larger sample area was sampled. This minimized the errors due to segregation (45). The use of solutions in acid to provide a homogeneous sample continued to find application. These were used in either cup electrodes (55) or the rotating electrode (136). An air stream has been found t o be a valid method for feeding powdered specimens into the arc (144). This method gave a tenfold increase in sensitivity. The order of consecutive volatilization of the elements was changed by this method. The vacuum spectrograph has become commercially available and promises to permit the analyst more nearly to approach his goal of using a single specimen for the determination of all elements required (22). By use of a spark in an inert atmosphere and analysis of the spectra in vacuum, the determination of such elements as carbon, phosphorus, and sulfur in steel appears feasible (175). Commercial argon appears of sufficient purity for use in the spark gap. Radioisotopes were incorporated into specimens for use in studying the distillation of elements in the arc (180). To obtain increased sensitivity, specimens were vacuum distilled and condensed on a water-cooled copper or graphite electrode, and these electrodes used as the specimen. A method for analyzing residues isolated from steel was described (162). GASES AND NONMETALLIC COMPOUNDS

The importance of the gases hydrogen, nitrogen, and oxygen in metals is being recognized to an increasing extent both as the source of certain deficiencies in mechanical properties and, in the case of nitrogen, as a useful alloying element. Two reviews of methods for the analysis of metals for these gases were published (76, 117). The precautions necessary to obtain a representative specimen from molten metal for analysis have been recognized and three studies of the sampling procedure were described (86, 93, 161). Hydrogen in steel is especially difficult to handle, because of the rapid diffusion rate of this element a t room temperatures (86). HYDROGEN

Simple apparatus for measuring the

diffusion rate of hydropen has been described (16,47). Abrasion of mild carbon and stainless steels with emery paper in the usual laboratory atmosphere a t room temperature was found to increase the hydrogen content of the specimen significantly (34). In another experiment, when thin specimens, of the order of 20 mils thick, were abraded with emery moistened with deuterium oxide, the deuterium passed through the steel specimen and could be detected with the mass spectrometer (58). A thorough discussion of methods for determining hydrogen in titanium will be of interest to persons concerned with analysis of steel. This paper critically reviews methods and the operating characteristics of different procedures and gives an indication of the precision and accuracy to be expected (111). I n another study the retention of hydrogen in different alloys was studied (155). OXYGEN

I n the determination of oxygen in a 4y0 silicon and 0.3y0aluminum steel by chlorination a t 500" C., it was observed that most of the aluminum nitride remained undecomposed after a 20hour exposure and it was suggested as a possibility for separating the aluminum, titanium, and silicon nitrides from steel (6). A microvacuum fusion method suitable for handling 10- to 20-mg. samples was used to analyze metal for both oxygen and hydrogen. A platinum bath improved the recovery (16). The reaction of bromine in the presence of carbon a t 125' C. in a helium atmosphere provided a reliable method of determining oxygen. The oxygen was absorbed as carbon dioxide in Ascarite and weighed (30). By direct current arc excitation in an argon atmosphere, the oxygen was liberated from metals and could be determined with the emission spectrograph (67). A concentration range from 10 to 2000 p.p.m. could be handled. The reaction of sulfuryl chloride with oxygen in a nitrogen atmosphere was utilized for the determination of oxygen in steel (94). Various procedures for determining gases in metal were evaluated and the applicability of each was indicated (113). For determination of extremely small amounts of oxygen and nitrogen, in metals it was found that the gases could be extracted in the usual vacuum fusion equipment and analyzed by means of a mass spectrometer connected directly to the vacuum fusion equipment (116). The method was found to be especially applicable to quantities of less than 0.001%. The limits of detection were 0.0001%. The inert gas or carrier gas fusion

method devised by Smilcy was modified slightly and has been found acceptable for the determination of oxygen in steels (136, 163). The equipment is both siinple and sufficiently rapid for routine use. For most steels the platinum bath was found not to be necessary and a dry bath technique very similar to that proposed by FT'alter was adequate. For certain alloys, the platinum bath provided a inore satisfactory method and has been used in both vacuum f u w n equipment and in the inert gas technique (17'3). T h tmission spectrograph has been used with the direct current arc excitation and a special electrode assembly in conjuliction with a molten platinum bath fur the determination of oxygen. The precision was comparable to that of vacuum fusion and the method was much faster than other techniques (56). .In improved vacuum fusion apparatus and analytical system, designed primaril?. for titanium, which includes use of a platinum bath, simplified the operation and reduced the time necessary for obtaining reliable oxygen anal!-sc. ( 9 ) . NITROGEN

Methods used for production control and for research on electric furnace steels were described (8, 32, 135). The reaction of ammonia with sodium hypochlorite and sodium phenolate to form a blue color provided a satisfactory basis for estimating the amount of nitrogen present (23). For extremely small amounts of nitrogen, steam distillation in micro-Kjeldahl apparatus, and the reaction of ammonia with pyrozalone in benzene (101) or with chloramine T and a mixture of l-phenyl-3-methyl-2pyrazolone-5-one and bis-l-phenyl-3methyl 11) razolinone in pyridine was used (91). This complex was extracted with carbon tetrachloride and the absorption was measured a t 460 nip The u\e of the vacuum fusion technique, in conjunction with the mass spectrometer, to estimate the amount of nitrogen liberated was found satisfactory (92). Various procedures have been used to decompose the compounds of nitrogen with different alloying constituents in steel. Vanadium nitride was found to be insoluble in 6 S hydrochloric acid (128). Heat treatment at 950" C.made liberation of nitrogen as ammonia easier (114). Silicon nitride retained nitrogen in the usual Kjeldahl procedure and was affected by thermal treatment (64). Fusion with sodium peroxide and sodium or potassium carbonate liberated the nitrogen (11). Alternatively a 1 to 1 mixture of lead chromate and lead oxide and fusion a t 1000" C. was used. il comparison was made between the solution distillation and vacuum fusion

methods for the determination of nitrogen in titanium and tantalum carbides, in the borides of zirconium and titanium, and in certain intermetallics as chromium-titanium, cobalt-chromium, and also in chromium nitride (65). The relationship between the ammonia content of the distillate and the conductivity was used for the nitrogen determination (154). The solubility of nitrogen in ironchromium alloys was measured (166).

solution, a copper sulfate cathode with potassium bromate, and a sodium citrate anode solution (95). A 15% sodium chloride-12.570 tartaric acid (96), hydrochloric acid plus a 5% citric acid (149) solution and a 5% sodium citrate solution containing 0.025% dibenzyl sulfoxide, o.0570 of a sulfonate wetting agent, and 0.1% of sodium fluoride were used (176). The carbides were separated by flotation and magnetically from an alcoholic suspension.

NONMETALLIC COMPOUNDS

LEAD

The importance of nonmetallic constituents of metals continues to increase as better methods for their detection and identification are developed. The newest technique to become commercially available permits identification of certain constituents without their removal from the metal. This involves the electron probe and micro x-ray fluorescence techniques (12, 24). Areas of the order of 1 to 3 microns can be studied. Such techniques are valuable in investigating mass transfer, identification of corrosion reactions, etc. The use of replicas has continued t o be an important means for attacking the nonmetallic compound problem (14). I n these, inclusions of the order of 10 microns in diameter may be identified. The usual method is to polish and selectively etch until the desired constituents are in relief above the metal matrix. These are then identified by x-ray, electron diffraction, or x-ray fluorescence. .4n over-all procedure for the examination of precipitates and inclusions in steel has been described (16). Sulfides are important and several methods for their isolation have been outlined (17). There has been much interest in the isolation and identification of carbides in steels. One procedure utilizes a 10% hydrochloric acid solution in alcohol and electrolysis a t 0.08 ,4.per sq. cm. current density and a t a maximum temperature of 40' C. (20). I n another study, the relation between grain gronth and residual aluminum was established by isolation of aluminum nitride and use of x-ray diffraction (25). Alcoholic bromine was used for the isolation of nonmetallic constituents (89). iilcoholic hydrobromic acid solution was found to be useful in isolation of carbides by electrolysis. The residue obtained was dried in vacuum and the oxygen and nitrogen contents of the residue were determined by vacuum fusion (84). Different electrolytes for isolation of the cementite phase were evaluated (77). These include potassium chloride-tartaric acid, ferrous sulfate-sodium chloride to which potassium sodium tartrate was added, a copper sulfate anode solution, a sodium thiosulfate plus sodium citrate cathode

Solutions were used to obtain a representative sample for determination of lead in steel. I n one instance, the lead 4057.82-iron 4017.15 A. line pair was applicable for a concentration range from 0.05 to 0.5% (54). I n another, thP rotating disk electrode in a nitric acid solution and the 2833.07 lead-2827.9 A. iron line pair was used (1%). The electrodeposition of lead from a nitric acid solution was suitable for determination of lead in manganese and ferromanganese ( 7 1 ) . Platinum electrodes were used; the deposition time was 6 hours. For estimating extremely small concentrations of lead and bismuth in cast iron (concentration ranges of the order of 0.0001 lead and 0.00005% bismuth) most of the iron was removed by extracting the ferric chloride with butyl acetate, The remaining iron was reduced with hydroxylamine chloride. Then, sodium tartrate, potassium cyanide, and sodium diethyl dithiocarbamate were added. The pH was adjusted to 11 with ammonium hydroxide and the lead and bismuth were extracted with a chloroform solution. Their concentration was measured polarographically ( 1 4 1 ) . Ferric iron must be completely absent, because it interferes with the lead and bismuth extractions. For larger amounts of lead, a similar extraction may be made of the dithiozone complex from an ammonium citrate solution and the determination is completed polarographically (70) or by measurement of the color intensity a t 520 mp after extraction with a benzene solution (168). MAGNESIUM

Localized segregations of magnesium in cast iron were detected by use of a high frequency spark of low amperage and spectrographic techniques (122). MANGANESE

A radium-beryllium neutron source for the activation of manganese in ferromanganese was made the basis for an analytical method (88). After an 18-hour exposure, the activity found was due to the 2.58-hour manganese-56 VOL. 31, NO. 4, APRIL 1959

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isotope, A 6-gram sample was used and no separations or preliminary operations were necessary to measure the manganese content with a mean error of 2.5%. For small amounts of manganese (rtliquots containing less than 0.01 mg. of manganese and less than 0.3 mg. of chromium) the manganese was titrated with 0.1N mercuric nitrate and a solution of 0.05N in sulfuric acid containing 1.5% of sodium fluoride (99). MOLYBDENUM

The color formed by the reaction of molybdenum with phenylhydrazine was made the basis for determination of this element in steel (182). The color complex was extracted with n-butyl alcohol. PHOSPHORUS

Methods for estimating the phosphorus content of residues extracted from steel have been described ( I S ) . The spectrograph has been useful for determining phosphorus. The 2149 A. line was used in air; others may be used with the vacuum spectrograph below 2000 A. (44). Prior to use of the molybdenum blue color method for phosphorus, arsenic was removed by distillation from a hydrobromic acid solution (48). Without resorting t o the vacuum spectrograph, it was found that use of a constant exposure time and a reference line permitted improved precision. Concentration ranges of the order of 0.01 to 0.07% were covered with a coefficient of variation of the order of 2 t o 4% (106). The conditions under which the yellow molybdophosphate precipitate is obtained in the presence of iron and other constituents in steel and basic slags were explored (160). RARE EARTHS

The rare earths and yttrium were determined by use of the arsenazo color reaction following removal of iron group elements by a mercury cathode separation and a diethyl dithiocarbamate extraction (61). Sulfasaliuylate was used as a masking agent to avoid interference from aluminum. I n the presence of calcium and magnesium, absorption measurement was made at pH 5. This avoids interference from these elements a t some sacrifice of sensitivity. Chromium, zirconium, and titanium, m hich are not separated with the mercury cathode, interfere. Arseneazo was used as an indicator for the EDTA titration of rare earths and yttrium in weakly acid solutions (60). Aluminum, which interferes, was masked by sulfosalicylate. Interference from calcium and magnesium

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was avoided by control of pH at 5.5. Interference from large amounts of iron, was avoided by extraction of the diethyl dithiocarbamate complexes with a chloroform solution. SILICON

Following removal of iron from an acid solution with an ion exchange resin, the molybdenum blue color was developed with stannous chloride and the intensity measured (40). Stannous oxalate was used as the reducing agent and the intensity of the molybdenum blue color was measured a t 650 mp. I n this procedure the iron was not separated from the silicon (7'9). A porous porcelain thimble of the type commonly used for recovery of graphite from cast iron was found useful for filtration of silicon following dehydration in the usual way (104). I n another procedure, the molybdenum blue color was developed and the intensity was measured a t 820 mp for less than 0.01% and a t 650 mp for larger amounts of silicon. A blank solution (129) was used in the reference cell of the spectrophotometw. I n still another molybdenum blue method, the color was developed by reduction with the ferrous iron present in the sample and the intensity of the resulting blue color was measured a t either 620 or 665 mp (148). The reaction of silicon to form potassium silicofluoride with subsequent titration was found to give results that were as reproducible as and considerably more rapid than those of the gravimetric method for silicon in ferrosilicon (166). For small amounts of silicon, copper fluoride volatilization and the spectrograph were used (134). SLAGS AND REFRACTORIES

The fusion of slags with a mixture of sodium carbonate and borax was found to provide a homogeneous solution with which to start spectrographic analysis ($3, 126). I n another spectrographic method, cobalt was used as the internal standard and the slags were formed into pellets with graphite (158). This method was also used for sinter. The flame photometer and a hydrochloric acid solution were found useful for determining the magnesium and calcium contents of slags (74). The use of EDTA with eriochrome black T as the indicator, for measuring the magnesium content of basic slags, was described (49). This method was used for determination of calcium (50), in conjunction with ion exchange or an ether or mercury cathode removal of iron. A procedure was described in which the powdered specimen containing sulfur is mixed u i t h an oxide powder

and heated in a stream of nitrogen to liberate sulfur. The liberated gases were absorbed in a mixture of hydrochloric acid, potassium iodide, and starch; and the absorbed sulfur was titrated with potassium iodide (100) Temperatures in the range of 980" to 1000" C. are needed for ores and in the range of 1020' to 1030" C. for slags. The analysis of iron and steel for extremely small amounts of sulfur was carried out by burning in oxygen a 10to 20-mg. specimen a t a temperature of 1350' C. (145). The gases liberated were absorbed in a standard potassium dichromate solution containing diphenvlcarbazide. The color intensity of the absorbing rolution mas measured a t 540 mp. The reduction in chromate content was proportional to the sulfur content. The reaction vias not stoichiometric and empirical standardization was necessary. The reaction sulfur-32 (n, p ) phosphorus-32 was used as the basis for determination of sulfur in steel (161). TITANIUM

The reaction of titanium with alizarin sulfonate was utilized for determining titanium in steel (72). TUNGSTEN

By reaction of the steel specimen with a sulfuric-phosphoric acid solution followed by reaction with dithiol in the presence of hydrochloric acid and of stannous chloride, tungsten was extracted with a butyl acetate solution (107). The absorption of this solution a t 635 mp increases with the amount of tungsten present. This method is good for =t0.005yO tungsten in the concentration range of 0.05 to 0.5% and about =kO.OOlyo a t concentrations of less than 0.05%. A routine method for determining tungsten in steel that does not contain niobium or tantalum was described (19). URANIUM

The uranium content of stainless steel was determined in a n acid solution by use of x-ray fluorescence. The Kalpha line of strontium, added as an internal standard, and the L-alpha line of uranium were used (157). VANADIUM

Vanadium was extracted with a chloroform acetylacetone solution. ilbove pH 2.0, the extraction of vanadium +3 was almost quantitative (109). The reaction of vanadium to form tungstovanadophosphate was made the basis of a quantitative method (152). Compensation must be made for the chromium, tungsten, and

iron in the solution. The intensity of the color developed in a phosphoricsulfuric acid solution after oxidation with perchloric acid and following separation of the iron rvith a mercury cathode was measured at 390 mp and related to the vanadium content (169). X-RAY SPECTROSCOPY

X-ray fluorescence began to find a place in the industrial analytical laboratory when direct reading equipment became available. The use of x-rays for diffraction (59,87),spectroscopy, and other specialized techniques has been increasing a t a very rapid rate. X-ray methods are nondestructive, but they are not absolute methods. Standards, once established, are permanent and can be retained as references. They are important and should be available in a matrix like that of the unknown specimen (4, 37, 125, 137, 167). Solid or liquid samples are used. Powdered specimens have been compressed into pellets (bf?), collected on ion exchange membranes ( I S I ) , or on resins. These latter techniques are capable of considerably Ivider application. Recent refinements in equipment provides a very fine electron beam to excite the characteristic x-rays from a n extremely small area (of the order of 1 mm. in diameter). This equipment enables individual segregates, in a steel surface, to be identified as to composition (24, 118, 131). The method of excitation is more sensitive than that of fluorescent excitation from primary x-ray beams and this lowers the limits of detectability. Few electron beam microanalyzers have been available to ixdustrial laboratories. The laboratories which have sufficient demand for such equipment, \vi11 find it a valuable analytical tool. ZIRCONIUM

The zirconium mandelate precipitate can be dried and weighed directly to give a quantitative measure of the zir(*oniumit contains (78). Insoluble residues from steel containing zirconium were fused with a carbonate-borax flux and the color reaction of zirconium with p-dimethylaminoazophenylarsonic acid used. Absorption was measured at 560 mp to give a quantitative indication of the zirconium content (1%). The absorption of the yellow color of the morin complex in 0.4 to 0.7N hydrochloric acid was measured at 463 mp to give a n indication of the zirconium content (164). Iron, nickel, chromium, and cobalt were first reduced with ascorbic acid. Zirconium mas reacted with pyrocatechol to form a blue color, the intensity of which was measured at 650 mp (17’9). Aluminum, titanium, and vanadium interfered seriously in this

reaction. Small amounts of iron could be tolerated. This review does not include all articles published in the period covered. It is intended to include only references to work that, with a minimum of modification, could be used in the modern industrial or control laboratories. When used in conjunction with earlier reviews in this journal beginning in 1949, a rapid coverage of published methods for the analysis of ferrous materials is obtained.

(31) Cogbill, Everett C., Loe, John €I., Ibid., 29,1251-8 (1957). (32) Colin, R. H., Snelling, G. H., Elect. Furnace Steel Proc., 16th Conf., . . 21-26 (1957). (33) Convenor, A. A., J . Iron Steel Inst. (London) 189, 49-55 (1958). (34) Cooke, F., Shanahan, C. E. A., J . A p p l . Chem. (London) 7,388-92. (35) Craven, S. W.,et al., J . Iron Steel Inst. (London) 188.331-7 (1958). (36) Danielsson, 411an, Progr. in ’Mineral Dressing, Trans. Intern. Mineral Dressing Congr., Stockholm, 727-37,1957. (37) Davis, C. M.,Clark, G. R., Pror. 6th. Conf. Ind. Appl. X-Rag Anal., 351-66, Denver, 1957. (38) Dean. J. A.. Beverlv. hI. L.. AKAL.

LITERATURE CITED

(1) Am. SOC. Testing Materials, Phil-

adelphia, Comm. E-3 on Chemical Analysis of Metals, STP195, “IonExchange and Chromatography in Analytical Chemistry,” 1958. (2) Ibid., STP222, “Gases in Metals.” (3) Ibid., STP238, “Solve,?t Extraction in the .Inalyses of Metals, 1958. (4) Anger, E. RI., Martin, J. P., Jr., Elect. Fzirnace Steel Proc., 15th Conf., 165-74 (1957). (5) Armson, F. J., Bennett, H. L., J . Iron Steel Inst. (London) 188,132-7 (1958). (6) Bagshawe, B., et al., Ibid., 187, 341-3 f,195il. --I

(7) Bartel, Roger, Goldblatt, Alan, Spectrochzm. Bcta 9, 227-34 (1957). (8) Beeghly, H. F., Elect. Furnace Sfeel Proc., 15th Conf.,37-44 (1957). (9) Bennett, S.” J., Covhgton, I,. C., ASAL. CHEX 30.363-5 flt)58). (10) Biher, H. E.,’ Levy, ’S.) J . Opt. SOC. A V L47,381-5 . (1957). (1 1) Billy, Michel, Lamure, Jules, Compt. ‘ rend. 245, 2889-90 (1957). (12) Birks. L. S.. Brooks. E. J . . Reat. ’ S R L Prog., 9-18, May 1957. (13) Bohnstedt, U., Budenz, R., 2.anal. Chem. 159, 12-21, 95-102 (1957). (14) Hooker, G. R., Norbury, J., Brzt. J . A p p l . Phys. 8, 109-13 (1957). (15) lbild., 9, 361-4 (1958).

(16) Booth, E., Bryant, F. J., Parker, h., Analyst 82,50-61 (1957). (17) Born, Kurt, Arch. Eisenhzittenw. 29,179-87 (1958). (18) Boulin, R., Chim. anal. 40, 72-6 (1958). (19) British Iron and Steel Research Assor., Methods of Analysis Comm., J . Iron Steel Inst. (London) 190, 51-4 (1958). (20) Brown, J. F., Clark, W.D., Parker, A., Aletallurgia 56, 215-23 (1957). (21) Bryan, F. R., Runge, E. F., B p p l . Spectroscopy 12,38-9 (1958). (22) Calkins, H. TV., Hasler, AI. F., Elect. Furnace Steel Proc., 15th Conf.,

181-90 (1957). (23) Calmettes, J., Drain, J., Rev. met. 53, 682-8 (1956). (24) Castaing, R., Philibert, J., Crussard, C., J . Metals 9, Am. Inst. Mining, M e t . Petrol. Engrs. Trans. 209, 389-94 (1957). (25) Chatterjee, A. B., Kijhawan, B. R., Trans. I n d i a n Inst. Metals 8. 225-51 (1945-85). (26) Chu, G. P. IC., I n d . Eng. Chem. 50, 59A-60A f 1958’). (27) Claasei, A,,’ Bastings, L., Z. anal. Chem. 160, 403-9 (1958). (28) Clarke, W. E., Metallurgia 56, 47-52 (1957). (29) Clarke, W.E., Rooney, R. C., Brit.

Cast Iron Research Assoc. J . Research and Develop. 6,606-9 (1957). (30) Codell, Maurice, Norwita, G., ANAL.

CHEM. 28,2006-11 (1956).

Proc. Na Pamr S o . AI! (40) Degtyarenko, Ya. A., OshchapovskiI, V. V., Nauch. Zapiski L’vov. Polztekh. Inst. 22, 107-10 (1956). (41) DeHaan, Abel, Am. Soc. Testing Materials, Spec. Tech. Publ., No. 215, 54-61 (1958). (42) D$ahay, Paul, “Inptrumental Analyses, lZacmillan, ?;em York, 1957. (43) Dutina, Dragomar, A N ~ L CHEM. . 30,2006-8 (1958). (44) Eckhard, Siegfried, Arch. Ezsenhziltenzu. 29, 89-94 (19%). (45) Eckhard, Siegfried, Koch, Walter, Ibzd., 28, 731-8 (1957). (46) Edgerton, J. H., Davis, H. G., U. S. Atomic Energy Comm., ORNL-2211 (1957). (47) Eichenaeur, Walter, Kdnzig, Herbert, Pebler, Alfred, 2. illetallk. 49, 220-5 f 1958). (48) El&dl, \T. T., Wilson, H. S . ,Analyst 82,453-41 (1957). (49) Endo. Yoshihide. Hattori. Kunihiro, ’ Bunseki‘Kagaku 6, 243-5 (1957). (50) Endo, Yoshihide, Tanihari, Hidetaro, Hattori, Kunihiro, Ibid., 6, 224-8 (1957). (51) Extermann, R. C., ed., “Radioisotopes in Scientific Research,” \-01. I , “Research with Radioisotopes in Physics and Industry,” p. 761. T’ol. 11, “Research with Ra$oisotopes in Chemistry and Geology, p. 741, Pergamon Press. Xew York. 1958. (52) Fagel, John,’ Jr., Balis, E. W., Bronx, L. B., A N A L . CHEY. 29, 1287-9 (1957). (53) Fall, William, Powder Met. Bull. 7,88-9 (1956). (54) Polley, E. W., Galletta, F. il., ANAL.CHEM.29. 1778-9 (1957). ’ (55) Ibid., 30, 502-3 (19583. (56) Fassel, V. A.: Gordon, W.A., Ibid.. 30. 179-82 f 1958). (57) ’Fassel, V . .4., Tabeling, It. W., Specfrochim. Acta 8 , 201-17 (1966). (58) Frank, R. C., Swets, D. E., J . A p p l . Phys. 28, 380 (1957). (59) Franks, A., Brit. J. A p p l . Phys. 9, 349-52 (1958). ( 6 0 ) Fritz, J. S., Oliver, R. T., Pietrzyk, D. J., ANAL.CHEXJO, 1111-14(1958). (61) Fritz, J. S., Richard, &I. J., Lane, W.J., Ibid., 30, 1776-9 (1958). (62) Fry, D. L., Schreiber, T. P., A p p l . Spectroscopy 11, 1-6 (1957). (63) Fryxell, R. E., ANAL.CHEW 30, 273-5 (1958). (64) Fryxell, R. E., Galitzine, N., Gardner. F. S.. J . Iron Steel Inst. (London) 189,327-32 (1988). (65) Gardner, L. E., Ibid., 189, 227-32 (1958). (66) Geilmann, W.,Z . anal. Chem. 160, 410-26 (1958). (67) Gilfrich, J. V., AXAL. CHEM. 29, 978-80 (1957). VOL. 31, NO. 4, APRIL 1959

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(68) Ginsburg, Leonard, Miller, Kay, Gordon, Louie, Zbid., 29, 46-8 (1957). (69) Gorlich, H. K., Schienck, Hermann, Stahl u. Eisen 76, 1479-86 (1956). (TO) Goto, Hidehiro, Hirokawa, Kichinosuke, Sci. Repts. Research Insts., Tohoku C’niv. 10, 10-19 (1958). (71) Goto, Hidehiro, Kakita, Yachio, Zbid., Ser. A, 9, 131-7 (1957). (72) Goto, Hidehiro, Kakita. Yachivo, Hirokawa, Kichinosuka, Nippon Kal aaku Zasshi 78. 1337-9. 1340-7f 1957). (79, Goto, Hidehiro, Waianabe, Toshio, Suzuki, Kyohei, Bunseki Kagaku 6, ($30-4 i19.57)

Kido, Genzaburo, himura, Takanori, Semento Gisutsu S e n p a 9, 118-21 (1955). (75) Grob, R. I,., Yoe, J. H., Anal. Chim. Acta 14, 253-622 (1956). (76) Guldner, W. G., Vakuum-Tech. 5, 13-66 (1956). Christakos, J., Stricker, (77) Gurry, R. W., C. D., Trans. Am. Soc. Metals, Preprint S o . 24 11957). (78) Hahn, R.’B., Elaginski, E. S., Anal. ChinI . Acta 14,45-7 (1956). (79) H all, M. T., Chemist Analyst 46, 64, 66 (1957). (80) H aywood, L. J. il., Sutcliffe, P., A?lalyst81, 651-5 (1956). (81) Heffelfinger, R. E., Chase, D. L., Rengstorff, G. W. P., Henry, W. M., (741, GOLk -&zuo,

ASAL. CHRM 1 12-1- 4 -. 3 -1-3. --- iR.W\ (82) Herrm ann, >I., Ind. chint. belge 23, 123-30 ( I 958). (83) Hill, IJ. T., ANAL.CHEM.30, 521-4 f 1958). (84) Hobeon, J. D., ilnalyst 82, 708-10 (1957). (85) Hobson, J. D., J . Iron Steel Inst. (London) 189, 315-21 (1958). (86) Hobson. J. D.. Swinburn., D.., Analvst . 83, 376-7 (1958): (87) Holmquist, S. B., Berry, T . F., Zwell, L., Am. Ceram. Soc. Bull. 37, 317-21 (1958). ( 8 8 ) Issa, I. AI., Handy, M., Hadidy, A, Chemist Analyst 47,44 (19%). (89) Jean, M.,Anal. Chim. Acta 14, 17282 (1956). (90) Jones, .4. H.. ANAL. CHEU. 29, . 1101-5 (‘1957). ’ (91) Kamada, Hitoshi, Sato, Ken, Bumeki Kagaku 6, 150-4 (1957). (92) Kato, Eiichi, Rept. Castings Research Lab., Waseda Univ., No. 8, 81-4 (1957). (93) Kimura, Shin, Bzinseki Kagaku 6, 232-7 11957). (94) Kleher, K.E., L’krain. Khim. Zhur. 22, 809-12 (1956). (95) Klvachko. Y. A.. Labina. 0. D..’ ’ Zavodikaya Lab. 22, i409-15 (i956). (96) Klyachko, Yu A., Shapiro, &I. M., Ibid., 23, 140-3 ( 1 9 5 3 (97) Koch, Walter, Malissa, Hans, Ditges, Dagmar, Arch. Eisenhiittenw. 28, 785-94 (1957). (98) Kunin, R., “Ion-Exchange Resins,” 2nd ed., 466 pages, Wiley, New York, 1958. (99) Kusaka, Yuzuru, Bull. Chem. SOC. Japan 31,216-96 (1958). (100) Lamure, J., Gelis, P. de, Congr. intern. auim. ind.. Madrid. 1955. (101) Lea;, J. B., hellon, hI. G., ANAL. CHEM.29,293-5 (1957). (102) Lewis, D. T., Analyst 81, 531-6 (1956). (103) Lingane, J. J., Ann. Priestley Lectures, 27 (1953); -4NAL. CHEM. 30, 1716-23 (1958). (104) Lingelbach, Gisela, Giesereitechnik 3, 133-4 (1957). (105) Logie, D., Chem. & Ind. (London) 225-7 (1957). (106) Lounamaa, Kilo, Appl. Spectroscopy 12,53-4 (1958). I

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(107) Wachlan, L. 8.,Hague, J. L., J . Research iVatl. Bur. Standards 59, 415-20 (1957). (108) Mack, Marian, Norelco Repfr. 3, 37-9 ( 1 956). (109) McKaveny. J. P., Freiser, Henry, .4X.4L. CHEX. 30, 526-9 (1958). (110) Ibid.. aa. 1965-8 (111) r\fcKihiey, T. n.,Trans. M e t . soc. AZME 212, 563-7 (1958). f112) Mainmtiar. .4. K.. Chowdhurl-. ’ J. B. R . ) Saturwissens~haften44, 420 (1957). (113) Mallett, 11. W.,Steel 139, (15) 95-8 11956). (114) Marot, J., Ind. chim. belge 22, 1161-74 (1957). (115) Martin, J. F., Friedline, J. E.. Melnirk. L. AI.. Pellissier. G. E.. Trans. Met. So;. AZJZh 212 , 514-19 (1658). (116) Martynchenko, I. U., Bondarenko, H. Xf., Zhur. Anal. Khim. 12, 495-8 ( 1957). (117) RIntoha, Yukio, hIantani, Shiro, Bunseki Kaqaku 5, 111-88 (1956). (118) Rlelford. D. A.. Duncumb. P.. ‘ Metullitrgza 57, 159-61 (1958). (119) hielnick, L. M.,,4m. Inst. Min. Met. Petrol. Engrs., Inst. Met. Div. Spec. Rept., Ser. No. 6, 63-70, 1957. (120) hleyer. S., Koch, 0. G., 2. anal. Chem. 158, 434-8 (1957); 160, 253-8 (1958). (121) Milner, G. ITr. C., Edwards, J. W Metals Rev. 2. 109-55 f1957’1. (122) Mirkin, ‘I. L., ‘Rikman, E. P., Zavodskaya Lab. 22, 930-6 (1956). (123) Mitchell, B. J., Proc. 6th Conf. Ind. Appl. X-Ray .4nal., 253-70, Denver, (19.57) ,_”_ ,.

(124) Mitchell, J., Jr., et al., J . Chent. E ~ u c35, . 1-17, 76-94 (1958). (125) Morrison, G. H., Freiser, H., “Solvent Extraction in Analytical Chemistrv,” 269 pp., Wiley, New York. 1957. (126) XIuir, S., Ambrose, A. D., Mefallirrgio 56, 255-7 (1957). (127) hlnto, Satoru, Bull. Chem. Soc. Javan 30. 881-5 (1957). (128) Narita. Kichi, Nippon Kagaku Zasshi 78, 705 (1957). (129) Ibid.. 78. 1367-7 (1957). (130) Sordling, Walter D., Chemist ilnnlyst 47, 45. 47 (1958). (131) X‘orton, J. F., Proc. 6th Conf. Ind. P ppl. 1 - R a y Anal., 219-29, Denver, (1957)

(132) -Pagliassotti, J. P., ANAL. CHEJI. 28, 1774-6 (1956). (133) Paterson, J. E., Ibid., 29, 526-7 (1!?,5i)

(134)-Pateraon, J. E., Grimes, W. F., Ibid., 30, 1900-2 (1958). (135) Peifer, 117, .4,, Elect. Furnace Steel Proc., 15th Conf., 27-36 (1957). (136) Peterson, J. I., Melnick, F. A., Steers, J. E., Jr., AN.4L. CHEM.30, 1086-9 (1958). (137) Peterson, Lennart, Jernkontorets Ann. 142, 203-8 (1958). (138) Pittaell, I. K., Appl. Spectroscopy 12, 54-7 (1958). (139) Pirs, hl., “ J . Stefan” Inst. Repts. Ljubljana 3, 175-8 (1956). (140) Richards, C. L., Levesque, Henry, Elect. Furnace Steel Proc., 15th Conf., 175-80 (1957). (141) Rooney, R. C., Analyst 83, 83-8 (1958). (142) Ibid.. pp. 547-54. (143) Runge, E. F., Bryan, F. R., J .

Metals 8,Am. Inst. Mining, Met. Petrol. Engrs. 206, 1674-6 (1956). (144) Rusanov, .4. K., Khitrov, V. G., Zavodskaya Lab. 23, 175-84 (1957). (145) Sakihama, Akira, Bunseki Kagaku

6, 439-42 (1957).

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