Steel and related materials - ACS Publications - American Chemical

Anal. Chem. 1991, 63,65R-86R

Steel and Related Materialst Thomas R. Dulski Carpenter Technology Corporation, R b D Center, P.O. Box 14662, Reading, Pennsylvania 19612-4662

INTRODUCTION This review continues the biennial series written by William Straub, both alone and with his colleague, J. K.Hurwitz, over the past decade and a half, under the title, "Ferrous Metallurgy". Steel chemists everywhere are indebted for their yeoman service. The material covered in this current review was extracted from Chemical Abstracts beginning with Vol. 109, No. 23, and endin with Vol. 113, No. 8. Supplemental coverage was extractef from Metals Abstracts between Jan 1989 and July 1990. Most of the review is organized by elemental analyte; papers that treat multiple analytes or that emphasize instrumental parameters are organized by technique. In addition there are several miscellaneous categories to cover thoae areas that require separate treatment. The last 2 years have shown a continued acceleration of the trend away from classical "wet chemical" techni ues in favor of high-s eed, low overhead instrumentation. %ith the exception ora few techniques based on fundamental approaches, t h e high-speed instrumentsare dependent upon comparative methodology that requires calibration and validation with traceable standard reference materials. The loas of experience and knowledge in the area of classical analytical chemistry upon which so many of the extant reference materials are based remains a crisii of o proportions. Nowhere is thii trend greater than in the%.S?%ere the classical wet chemical laboratory is vanishing from the steel industry. In developing countries, such as China, classical wet chemical techniques are still widely employed and certain European countries apparently remain cognizant of the importance of maintaining capability in this area. In the instrumental area, the cutting edge of --speed service to the needs of production is molten metal analysis, in which the product is analyzed while it is being produced. In this review a separate section is devoted to this rapidly growing technolop The review in this journal remtuns the most comprehensive source of information related to the analysis of steel (l), but several important reference compilations have a peared in Japan (21, Germany (31, and the USSR (4). fieviews of s v o g r a p h c techniques in Poland (5)and Germany (6) and e &on optical techniques in the U.K.(7)and Japan (8)have appeared. A review of trace methods (9) and a metals analysis handbook (10) were published. A comparison of spectroa hic techniques for the analysis of austenitic stainless steels 11 and a review of laboratory organization in a steelworks (12) have also been issued. The automation of steel analysis laboratories is a general topic widely discussed in the literature. Hardware and software advances have led to systems for rapid spectrographic control of steel and iron-making processes in Ja an (13,14), Germany (15-18), Czechoslovakia (191, Sweden 501, and the U.K.(21). Systems for rapidly sorting mixed steel are important tools, especially in a production environment where numerous grade compositions are routinely handled. Today this problem is largely handled by using spectrometers designed for use in the mill environment, although spark testing (where the color and pattern of sparks produced by grinding the steel are used), chemical spot testing, and sim le magnet and hardness tests are still employed in some pLces. One paper on spectrographic sorting (22) and one general review of the subject (23)have appeared. One general review that covers the a plication of atomic spectroscopy to minerals, refractories, clemicals, and metals has appeared (24). Another paper describes spectrometers (optical emission and X-ray fluorescence; simultaneous and

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'In the references, a shortcut version of citations in Chemical Abstracts and Metal Abstracts is given. If ex anded, the correct citation would be (for example,in ref 1) Chem. Ibstr. 1989,110 (26), 241643g.

sequential) suited for use in foundry control (25). Numerous papers describe specific control laboratory installations (26-28).

ALUMINUM Aluminum is present in many steels both as an all0 ed metallic constituent and as a precipitated compound, o&n the oxide or nitride. The importance of distinguishin these separate forms is emerging from the specialized f i e d of inclusion analysis (see Inclusions and Second Phases) and is becoming a concern for the rapid control of steel-makin processes. Work in this area is progressing rapidly, althoug much remains to be done. By using an optical emission approach with both a 20-9 prespark and no pres ark, one investigator has determined total aluminum antfnonmetallic aluminum, res ectively. Metallic aluminum is calculated by difference (Alf X-ray fluorescence has been applied to the problem by using a mathematical eak unfolding procedure to separate a series of overlapping% #I bands. By using this approach, metallic aluminum, aluminum oxide, and aluminum nitride can be determined but only to a detection limit of O M % , which is insufficient for practical metallurgical control (A2). A review of the roblem as it relates the continuous casting of aluminum-kiid steels, covering classical methods and electron probe microanalysis, as well as X-ray fluorescence and optical emission, has been written (A3). A eneral review of the analytical behavior of aluminum oxide incf&ions in steel has also appeared (A4). Certain sulfo com ounds have been used to enhance the optical absorption o!aluminum in the flameless atomic absorption determination of aluminum in steels (A5). Japanese investigators have employed a flameless AA approach using magnesium sulfate as a matrix modifier to determine trace amounts of aluminum in iron and steel (A6). Fluorometric techni ues are sometimes used for aluminum determination has been in stee(ts. 2-Hydroxy-5-sulfoaniline-N-salicylidene used as the fluorometric reagent to determine aluminum down to 2.5 ppm (A7). Spectrophotometricmethods for the determination of low levels of aluminum have been common in the industry for decades. A new reagent, m-bromocarboxyazo m, which forms a colored complex which is stable for 24 h, has been ap lied to steel, iron, and iron alloys (A8). As in most such metRods, aluminum must first be isolated from the iron matrix. Chrome Azurol S has been a lied to steels containing vanadium. In this approach, in a f fition to the removal of iron, the effect of vanadium is eliminated by stabilizing its +V oxidation state with excess hydrogen peroxide (A9). Chloro hosphonazo reacts with aluminum to form a complex that agsorbs at 600 nm. Biscyclohexanoneoxalyldihydrazonewas used to remove some interferences by precipitation and lycol bis(#I-aminoethyl ether)-N,"-tetraacetic acid was atded to the isolated aluminum to mask rare earths (AlO). Dibromonitrochlorophosphonazo has also been used to form a complex with aluminum in a solution buffered at pH 4.4-6.4 with hexamethylenetetramine buffer (All). A new reagent, Chromazo-BRZ-4-(N,N-dicarboxymethyl)aminobenzyl-( l-azo-2')1',8'-dioxynaphthalene-3,6'-disulfo acid is less affected by interferences than many other aluminum complex formers, and it has been applied to a spectrophotometric method for steel (A12).

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ANTIMONY Antimony has been determined by an energy-dispersive X-ray fluorescence ap roach usin both the Ka and La lines. Results were verifiea by optic3 emission using both the 206.838- and 259.806-nm lines. Both methods were found suitable up to a concentration of 0.5% (A13). Anodic stripping voltammetry was applied to the determination of antimony

0003-2700l91l0363-65~~09.50lO0 1991 American Chemical Society

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STEEL AND RELATED MATERIALS

(simultaneously with tin) after solvent extraction separation and then reextraction into the aqueous phase. The results obtained agreed with those obtained by atomic absorption (A14). Two associated dyes, crystal violet and rhodamine 6G, were used in the solvent extraction/fluorometric determination of antimony. The method is free of common interferences, except titanium (A15). The colored complex formed by antimon with dibromophenylfluorone in the presence of the emuls$er OP was used as the basis of a new spectrophotometric method. Interferences were eliminated by evolution and collection of SbH, (A16). The red association complex of phenosafranine cation and chloroantimonate anion was exploited in a spectrophotometric method. The colored species were extracted with a mixture of cyclohexane and butanone, and the absorbance was measured at 532 nm (A17, A18). In another approach, antimony was separated as the iodide by extraction with toluene. A portion of the extract was reacted with 2-(5bromo-2-pyridylazo)-5diethylaminophenol in ethanol, diluted with ethanol, and measured at 610 nm (A19).

ARSENIC For many years various techniques for arsenic determination have exploited the evolution of arsine gas from an acid solution of the sample matrix to isolate this important tramp contaminant of steel. More recently the evolution of ASH, has been adapted for direct introduction of the analyte into an atomic absorption or inductively coupled plasma optical emission instrument. One recent pa er utilizes the atomic absorption a proach with a micro hygide generation system into which tEe sample and KBH4 reagent system are introduced with micropi ts ( B O ) . Another paper utilizes the ICP approach combin&th a prelim' isolation of the arsenic by means of solvent extraction o f t e iodide com lex into x lene. The extracted arsenic is then mixed on-Ine with d&H4 in DMF solution and acetic acid and injected into the plasma by means of a gas-liquid continuous separation device that removes most of the organic phase vapor. Cast iron was successfully analyzed for arsenic by using this technique (A21). In a hydride method for nickel-based alloys, a microcolumn of strong cation-exchange resin was placed in-line before a flame-heated quartz tube atomic absorption spectrophotometer to remove the matrix before it could suppress the arsenic signal (A21a). A polarographic method for trace arsenic in steels and irons has been published (A22). There has also appeared a method based on coulometric titration following a solvent extraction of the arsenic-bromide complex (A23). Finally, a spectrophotometric method has appeared based on the arsenieantimony-molybdate which absorbs at 690 nm. The

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lower limit of the method (A24).

BISMUTH The determination of trace and ultratrace levels of bismuth is a critical concern in many sectors of the steel industry because of the element's deleterious effects on certain alloys. While instrumental approaches are now commonly employed, work still continues in spectrophotometric and polarographic techniques. The diethyldithiocarbamate complex was extracted into petroleum ether by one investigator to isolate it from the iron matrix, and then bismuth was determined by s ctrophotometric measurement of the ion association comp r x with iodide and rhodamine B in 0.016 M HNO,. The method has shown a detection limit of 0.00005% and is also applicable to nickel-base alloys (A25). The violet complex that bismuth forms with chlorophosphonazo I11 was applied to a s ctrophotometric procedure for cast irons. Rare earths are te only important interference (A26). A very sensitive method for steel was developed based on s ectro hotometric measurement of the ion association comptx wit! iodide and butylrhodamine B (A27). After removal of heavy metals from the matrix, bismuth was determined in a series of cast irons by square wave polarogra hy. Over the concentration range 0.0114~).00063%, a stanfard deviation of 0.00004-0.0006% was obtained ( A B ) . Bismuth has been determined in nickel, cobalt, and chromium alloys by means of solvent extraction 66R

ANALYTICAL CHEMISTRY, VOL. 63, NO. 12, JUNE 15, 1991

of the complex with 2-mercaptobenz.oimidazole in the presence of trichloroacetate anion and photometric measurement. Bismuth was determined over the range 0.0014-0.005% (A29). Bismuth was determined in low alloy steels over the range 0.0002-0.0050% by means of a continuous hydride generation-ICP optical emission system (A30). A microhydride generation system coupled to a microquartz cell for atomic absorption atomization has been used to determine bismuth in steels and nickel-base alloys. The effect of nickel and cobalt is removed by the addition of 8-hydroxyquinoline (A31).

BORON If an elemental component of modern steels were to be selected that presents the reatest overall challenge to the analytical chemist, it wouh probably be boron. It has a profound effect, even in trace quantities, upon the properties of most steels, and it can be present in a vanety of forms, some of them resistant to common acid dissolution procedures. The need for hi hly accurate boron determinations continues to generate a ost of new approaches in the literature. One review that com ares results from different procedures on the same standarzreference materials emphasizes the importance of classical wet chemical approaches in establishing accurate baseline data for national standards. Results from the curcumin spectrophotometric method, both direct and after solvent extraction, and from the 1,l'-dianthrimide spectrophotometric procedure after distillation of the methyl borate ester are compared (A32). Recent work in the determination of boron has been reviewed in another paper, covering photometric and instrumental techniques, as well as separation schemes and masking agents (A33). Methods for the spectrophotometric determination of trace amounts of boron in steel abound. One approach involves the formation of the ternary association complex with phenylhydroxyacetic acid and malachite green, which is extracted into benzene and measured (A34). Another involves distillation of the methyl borate ester into dilute caustic solution, which is evaporated to dryness. Curcumin is added to the dried salt, and the resultant complex is extracted into MIBK and measured ( A S ) . The curcumin method was also applied in a rapid approach in which the meth 1borate distillate was evaporated as it was collected ( A X ) . imethod based on the color reaction with 4,4'-disubstituted (R = OH or OCH,) dibenzoylmethane has been reported (A37). A study from the U.K. demonstrates some of the shortcomings of an established spectrophotometric method and makes a case for a new method based on dissolution of the sample in HC1 + HNOB, decomposition of boron compounds with H3P04 + H,S04 at 250 "C, reaction with coumarin, and measurement of the boron complex at 543 nm. Im roved linearity when these wet chemical results are plottea in spectrographic curves suggests that a number of reference materials may have been assigned erroneous values (A%). A spectrophotometric method based on the formation of the complex between boron and methylimino-H acid, after separation of interfering elements by precipitation with barium carbonate, has been published (A39). Acid-soluble boron in steels has been determined by extraction of the mandelic acid and malachite green complex with benzene and spectrophotometric measurement at 630 nm (A40). Novel approaches to boron determination in steel reflect the perceived importance of this field of study. In one paper the investigator used a fluoroborate ion selective electrode to measure the boron content of steel Sam les dissolved in a mixture of H,SO, and HBPO with the adxition of HF (A41). Two methods that utilize mofecular emission techniques have been published. In one, boron was determined in low alloy steel and nickel-base alloys by extraction from HCl into 2,4dimethyl-4,6-octanediol in toluene, followed by molecular emission determination at 546 nm with a H -NzO flame (A42). In the second, pulsed nebulization of small sample solution volumes into an air-H, flame are studied (A43). Boron was determined by dissolution of the steel sample in HzSOl and H 2 0 addition of EDTA, pH adjustment to 4, addition of disoaium chromotro ate and octyltrimethylammonium chloride and acetate guffer, and injection into an HPLC. Boron absorbance was measured at 350 nm (A44). A highperformance liquid chromatography method based on the anionic boron complex with H-resorcinol has been described (A45). Trace boron in nickel steels has been determined by

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STEEL AND RELATED MATERIALS l ” R. Dukkl is a Speclabt kr AnalytC cat Chemistry at the R&D Center of Carpenter Technology Cotporatkm, a producer of kon-, nlckel-, and cobalt-base specialty aC loys. In the past 28 years, he has been engaged tn nearty all aspects of the application of analytical chemistry to both basic and specialty steel productlon. He is the author of 10 pubilcatbns, including the book chapter, “ClassicalWet Analytical Chemistry”, in the Materials Characterlzatronvolume of the ASTM Metals Handbook. He has been awarded the CertMcate of Appreciation, the Lundell-Bright Award and the title of Fellow by ASTM, and the pharmacla Prize. He is currently active in ASTM Committee E-1 and serves as chairman of Committee S-17.

graphite furnance atomic absorption, using a strontiummagnesium mixed matrix modifier (A46). In certain special alloys, boron is added at high levels to achieve unique properties. This is a discrete area of concern for the analytical chemist. Several papers in this area have been published. The standard wet chemical approach involves formation of the boron-mannitol complex, which releases hydro en ions in direct proportion to the boron concentration, but a tigh phosphorus level in the alloy interferes seriously with this standard scheme. In one paper, a method is described in which boron is extracted with 2,2,4-trimethyl-2,4pentadiol and then back-extracted into dilute standard NaOH solution. Mannitol is added, and the released hydrogen ions consume a stoichiometric amount of NaOH. The excess NaOH is titrated with standard HC1 (A47). Boron was determined in neodymium-iron-boron magnet alloys by, first, removal of the iron and neodymium by precipitation with NaOH, expellin C02by boiling, neutralization, complexation of the boron wit! lycerol, and titration with standard NaOH to a phenolphthafein end point (A48). Boron in ferroboron was determined b fusing the sample with sodium peroxide ium carbonate. The iron precipitate from and potassium the leached fusion is filtered off, and the filtrate is directly measured by ICP optical emission (A49).

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CALCIUM Calcium is frequent1 determined by atomic absorption spectrophotometry. &e paper investigated the range 0.001-0.1% using a lanthanum solution to eliminate some interferences (BI). In another paper the surfactant, Triton X-100, was found to increase the atomic absorption signal of calcium by approximately 50%. The linear range of the calibration was also extended, and several interferences were suppressed (B2). In a third paper, the calcium atomic absorption si a1 was enhanced by 40% by the addition of potassium chgride solution. A detection limit of O.OOOl% was obtained. In addition it was discovered that the inclusion compound, Ca0*6A1203,which is insoluble in aqua regia, can be dissolved completely by the treatment with hydrofluoric acid followed by evaporation to fumes of perchloric acid (B3). Calcium was determined in iron ores by means of the color reactions with two reagents-chlorophosphonazo I11 and arsenazo 111. Both reactions occur in a slightly acidic 40% alcohol solution, and both calcium complexes have their maximum spectrophotometric absorbance at 650 nm (B4).

CARBON An interesting optical emission approach to the determination of carbon in steel involves measurement of the carbon spectral intensity at two different electrical discharge time bands in a spark made. An algorithm relates carbon content to the measured intensities (E). X-ray fluorescence has been used to determine the carbon content in pig iron. Reproducibility was better for white pig iron than for gray pig iron because of sample morphology. Identified sources of error include contamination of the vacuum chamber by vacuum pump oil and sample preparation technique. The method showed a precision (bM) of 0.050% over the concentration range 3.!5-4.7% (B6). The modem workhorse for carbon determination remains the technique based on inductive heating and combustion of

the sample in a stream of oxygen. The C02 roduced is measured in various ways but typically with a tRermal conductivity or an infrared absorption detector. Today, there is growing interest in carbon levels below 10 ppm, and one paper addresses the problems associated with determining carbon (and sulfur) in standard reference materials at these low levels (B7).Combustion techniques for carbon usually require the addition of a flux as an aid in coupling with the radiofrequency field and in releasing carbon from the sample. Several studies of fluxes have been published (B8-BIO). A new approach to combustion of the sample involved the construction of a continuous arc furnace for carbon (and sulfur) determination. The instrument automatically maintains a fixed arc length, and high temperature is achieved without the use of fluxes (BII). Carbon can be determined by wet chemical dissolution of the steel, evolution of carbon dioxide and its absorption in nonaqueous solvents, and subsequent titration. One paper described the use of sulfuric acid and hydrogen peroxide to dissolve the sample and evolve the CO ,which was absorbed in DMF containing 2-aminoethanol. %he COPwas titrated with tetrabutylammonium hydroxide. Activated Mn02was required to remove interference from SO2 (B12). Another team of investigators used sulfuric acid and potassium dichromate to dissolve the sample and employed a nonaqueous coulometric titration to measure the evolved C02 (B13). In the combustion/IR detection approach, temperature ramping can be used to distinguish between surface carbon and carbon in the metal substrate. One such study, which dealt with high-purity iron samples, revealed that some low carbon standard reference materials are certified at levels that appear to be too high (BI4). High carbon and low sulfur could be determined simultaneously in ferromanganese and ferrochromium using a combustion approach with a tungsten-tin accelerator (BI5).

CHROMIUM In the People’s Republic of China, there appears to be an interest in developing variations on the classical titration of chromium with ferrous ammonium sulfate. In particular, alternatives to the use of silver nitrate as catalyst in the oxidation of chromium with ammonium ersulfate are being sought (B16,B17). While chromium can [e less of a problem in flame atomic absorption analysis when a N 0-C2H2flame is used, many analysts wish to use an air-C2 flame. Hexamethylenetetramine has been shown to inhi it the interference of iron under these conditions (B18),and the addition of dimethyl ketone has been shown to enhance the sensitivity for chromium (BI9). Formation of chromium acetylacetonate and its atomization in an air-C2H2heated silica tube has allowed the detection of 0.2 ng of chromium in a steel matrix by atomic absorption spectrophotometry (B20). UV-visible molecular absorption spectrophotometry has always been a popular approach for low levels of chromium in steel. 2-(5-Bromo-2-pyridylazo)-5-diethylaminophenol forms a purple complex with chromium in sulfuric acid solution (B21). Diantipyrylstyrylmethane forms a violet-red complex with chromium in phosphoric acid solution (B22). Similarly, acid chrome blue K forms a chromium complex with maximum absorbance at 597 nm (B23). The bromides of cetyldimethylaminoacetic acid and tetradecyldimethylaminoacetic acid were shown to sensitize the color reaction between chromium and chrome azurol S (B24). A flow injection system based on the color reaction with tetramethylenebis(tripheny1phosphonium) bromide was applied to the determination of chromium in a ran e of steels (B25). A kinetic spectrophotometric method based on the oxidation of o-tolidine by Cr(V1) in the presence of hydrogen peroxide was applied to steel after an ion exchange separation (B26). A fluorometric method based on the reaction of chromium with 2-(a-pyridyl)thioquinaldinamidewas described (B27). Another fluorometric method that is based on the reaction between chromium(V1) and thiamine hydrochloride has been applied to the determination of chromium in cast iron (B28). A spectrophotometric method that exploits the blue-purple complex which forms between chromium(II1) and p-sulfophenylazochromotropic acid has been used for steel (B29). Alkyldimethylaminoaceticacid was studied as a sensitizer for the color reaction between chromium(II1) and eriochrome cyanine R, and the reaction was shown to be applicable to the

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ANALYTICAL CHEMISTRY, VOL. 63,NO. 12, JUNE 15, 1991 67R


spectrophotometric determination of chromium in steel (BO).

COBALT Cobalt can often be convenientl determined by molecular absorption spectrophotometry. $his is reflected in the literature with numerous papers describing colored complexes of cobalt that have been studied for application to steel analysis. In solutions a t H 6.8-7.8, p-meth lisonitrosoaceta henone forms a cobac complex that can 8e extracted into ckoroform and measured at 380 run. The procedure has been used for high-s ed steels and cast iron ( C l ) . 2Hydroxy-1-naphthalderyde guanylhydrazone forms a yellow complex in acid solution that absorbs at 416 nm (C2). 242Thiazolylazo)-5-diethylaminobenzoicacid reacts with cobalt

was applied to steels (C21). A sensitive test for the presence of co per in an aluminum-bearing ferrotitanium alloy was baselon dissolution in dilute sulfuric acid, addition of ammonium fluoride (to mask the matrix elements), and development of a thin-layer chromatagram with 2-propanoktetrah drofuran:50% (v/v) HNOB(3OA01.5). The TLC plate was praced in contact with NH vapor and then sprayed with ammonium sulfide solution. h e presence of 0.3ng of copper could be detected (C22).

GASES

This section has been reserved for gaseous elements in solid sam les of steel and related materials. Refer to Molten Metal pis,below, for a review of the extensive literature on the determination of gaseous elements in liquid metal baths. Argon. A commercial oxygenfnitrogendeterminator was modified for the determination of ar onfoxyqenfnitrogen in powder metallurgical materials. A mofecular sieve column was introduced between the absorption tra for H20and C02and the thermal conductivity detector. f i e nitrogen and ar on peaks were resolved with this arran ement. For 1-g samdes, the detection limit was 0.5 ppm (jl). Hydrogen. A gravimetric approach, based on the formation photometric technique was applied to the analysis of tool of H20 when urified oxygen is passed over a sample heated steels. The carrier stream contained 10% (wfv) ammonium to 90&1OOO O 8 , was applied to the determinationof hydrogen fluoride, and the rea ent stream contained ethylenebis(triin welding materials (02). Vacuum degassing of high-strength henylphosphoniumbromide and ammonium thiocyanate. steel over a range of temperatures showed three distinct peaks h o w injection extraction into chloroform was followed by of hydrogen evolution. The 450 and 800 K peaks were atmeasurement of the colored cobalt complex at 625 nm (0.tributed to physically bonded hydrogen, while the peak above Large amounts of cobalt, as occur in some highly alloyed 1000 K was attributed to hydrogen that was chemically steels, can be determined volumetrically. The oxidation of bonded in aluminum or silicon oxide inclusions (03).Chinese cobalt with ferricyanide anion is frequently employed. One investigators applied a US.-made commercial hydrogen denew approach is the oscillopolaro raphic titration of cobalt terminator to 18-8 type austenitic stainless steels, finding that at pH 9-9.5 with ferricyanide. Tke method showed better cost savi could be realized by reusing the crucible for 4-6 precision for magnet steels than the conventional potentiosamples;? hinese-made crucibles gave superior results in this metric titration (C8). approach ( 0 4 ) . Also in China, hydrogen was determined in stainless steels by emission spectrometric measurement of the COPPER intensity of the Ha line when a sample was heated to 800 f Spectro hotometric methods for co per are also very 50 OC in an argon-fded quartz discharge tube (05). Diffusible popular. !ow alloy steels were analyze$ by measuring the hydrogen in welded steel parta has been determined by placing copper complex with N-(phenyl)-2-thioquinaldinamide(C9). the welded s ecimen in a closed chamber and then analysis Another approach utilizes the complex with 3-(ltH-l’,2’,4’of the chamger atmosphere. Various temperatures can be triazolyl-3’-azo)-2,6-diaminotoluene in ethanol-water medium applied in the degassing step (06).Diffusible hydrogen in (ClO).4-(5’-Methyl-3’-isoaazolylezo)resorcinolalso reacts with steel parta has been determined by applying a nickelfnickel copper in ethanol-water solution and has been similarly apoxide polarizing electrode to the steel surface. Hydrogen is phed ( C l l ) . a,&y,6-Tetra(4-p ‘dy1)porphyrin forms a co per oxidized at the steel surface, and the current measured is com lex in the presence of hy$&4amiine,which has also k n related to hydrogen content. The method is sensitive to . +I oxidation state of copper d f o r steel samples ( ~ 1 2 )The Another hydrogen concentrations of less than 1 ppm (07). reacts with neocupferron, and the resultant com lex can be electrochemical robe for diffusible hydrogen uses palladium extracted in chloroform at pH 4.0. B adding hygoxylamine hydride or moly denum bronze as a reference electrode, hyhydrochloride, chrome azurol S, and guffer solution, a copper drogen uranyl phosphate tetrahydrate ((UO2)HPO44H10]as ion association complex is formed and then reextracted at pH solid electrolyte roton donor, and the Sam le or a thin foil 9.0 and measured at 600 nm (C13). Bathocuproine is a freof palladium in &ect contact with the sampye as the sensing quently employed spectrophotometricreagent for copper. In electrode (08). one pa er a study was made of the reaction of the copperNitrogen. Although commercial instruments based on (I)-bat\ocu roine complex with a series of fluorescein dethermal extraction of nitr en have large1 replaced chemical rivatives. d e approach was a plied to iron and steel analysis dissolutionfalkali-steam%tillation teciniques, the older, (CI4).Iron ore has been anafyzed for copper b employing classical approach is still used in some uarters. One rou the complex formed with 2-(3,5-dibromo-2-pyriiylazo)-5-di- of investigators found that a sulfuric aci& potassium c d o r i z ethylaminophenolin the presence of OP (CIS). Iron ore has medium was superior for dissolving a series of alloy steels also been analyzed utilizing the complex formed between containing various nitrides, as well as ball bearin steel (09). cop er and arsenazo I11 at H 6.3 (buffered with hexaOther workers have titrated the ammonium ions krmed after metiylenetetramine-HCl). Tge complex absorbs at 610 nm steel dissolution by using an am erometric approach with (C16). Copper was determined in iron and steels b extraction calcium hypochlorite as titrant &IO). Instruments for dewith carbon tetrachloride containin cobalt(I1r dithizone terminin nitrogen (and, simultaneously, oxy en) based on complex (in the presence of sodium ffuoride). Spectrophoheating t i e sample in a graphite crucible in ei&er a vacuum tometric measurement was made at 435 nm (Cl7). or an inert gas and measurement of the evolved Nz (and CO Traces of co per have been determined in powdered iron, or C02)with thermal conductivity and infrared detectors have iron oxide, a n t steel by means of a fluorescence quenching been calibrated in a new way. Dilute solutions of potassium method based on the copper(1) com lex with meso-tetrakisnitrate were micropipetted into low-gas content metallic cups (p-sulfophenyl) orphyrin (CIS). Fyame atomic absor tion (made of tin, nickel, copper, or alloys), dried, and analyzed. measurement o copper has been enhanced b the adchion The approach is an inexpensive alternative to calibration with of sodium dodecyl sulfate and aniline. The mecganism derives metal standards ( D l l ) . Use of a nickel-cerium bath in inert from the formation of volatile cop er complexes, which are gas fusion of solid samples was shown to correlate well with more easil atomized in the air-&Hz flame (Cl9). After the classical wet chemical approach (012). isolation gy means of solvent extraction with diantiOxygen. The development of an ASTM standard anayrlhe tane, copper (and cadmium and lead) was determined lytical method for oxygen in steel represents an important A?polarography versus a A fAgC1 reference electrode milestone in consensus standards testing. The work is based (820). A flow injection methotthat employs a thin-layer on commercially available inert gas fusion instrumentation electrolytic cell for the amperometric measurement of copper and covers the range 5-50 ppm oxygen. Two papers describe

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the efforts involved and the lessons learned from three interlaboratory teat pr arm conducted over a period of 6 years (013,014). The l a x o f standards for high concentrations of oxygen has led one group of investigators to study various synthetic standard systems. Benzoic aad/ethyl alcohol roved to be the most convenient and accurate medium for calitrating hi h oxygen levels (015). bviews. Three general review papers in the area of gases in metals have appeared. One paper summarizes ublished methodology between 1986 and 1988; it includes a $iscussion of carbon and sulfur determinations as well. One-hundred seventy-four sources are referenced (016). The second paper com ares chemical methods, vacuum and inert gas fusion, and . third paper covers methods for nuciar methods (017)The hydrogen, nitrogen, oxygen, and argon in high-temperature materials (018).

IRON In the steel industry, iron is commonly determined in a diverse ran e of materials-iron ore, slag,furnace dusts, acid pickling ba&, and many more-but only rarely in alloys. An important exce tion is in the specialty alloy industry, where iron is frequentfy determined as a major to minor component (and even as a trace contaminant) in complex high-temperature service superalloys. The best methods for major amounts of iron are volumetric, t ically redox titrations. A new volumetric ap roach for the ztermination of iron in iron ores is based on &ssolution of the sample in a mixture of sulfuric, hydrochloric, and hydrofluoric acids, followed by titration wth a stannous chloride solution (0.05 M) prepared in glycerol-ethanol (3:1), Molybdophos horic acid was used as an end oint indicator. The m e t h J i s simpler than the classic Snd2-HgC1 KzCrzO titration method and avoids the mercury compoungwaste disposal problem (019). It is often important to know the concentration of various oxidation states of iron in ores, slags, and other materials. QpicalIy, total iron is determined, and then a separate weight of the sample is dissolved with nonoxidizing acid under an inert atmosphere for the determination of iron(I1). Metallic iron is determined by reacting another weight of the sample with a solution (e.g., copper sulfate solution) that selectively dissolves iron(0) by ionic displacement. Iron(II1) is calculated by difference. Many variations on this scheme and other schemes are possible. For example, in one paper 5% ferric chloride solution is used to dissolve metallic iron in iron ores and agglomerates. The iron(I1) reaction product was titrated with potassium dichromate to a sodium diphenylamine end point (020).In another a roach, metallic iron is selectively dissolved with mercuric c/%ride-salicylic acid-ethanol solution, and the dissolved iron is uantified spectrophotometrically with sulfosalicylic acid (821).One investigator used a new ap roach for distinguishing the iron(I1) and iron(II1) states in bast furnace irons containing high titanium. After dissolution in dilute hydrochloric acid under a protective atmosphere, iron(II1) was determined spectro hotometrically as the thiocyanate complex and the iron( ) content was calculated by difference from total iron (022).Zinc-iron alloy galvanizing solutions were analyzed for ferrous and ferric ion concentrations. Iron(I1) was titrated with potassium perman anate solution, and in a separate portion of sample, ironhII) was titrated with titanous chloride solution (023). Rapid instrumental techniques for distinguishing and quantifyin the oxidation states of iron for process control of ore hantling operations are possible. In one paper the ferrous oxide content of ore sinter has been determined by measuring the magnetic permeability of the material (024). Also s ecialized, possibly semiempirical, tests have been de) 'magnetite iron" s c r i d for determining 'ore iron" (025and (026)in ores, beneficiation tailings, and other materials. LEAD Lead is an important tramp contaminant of nearly all steels used for critical applications. Carefully sorted scrap is a crucial requirement in steel production, since leaded steels (manufactured for their free-machining properties) and lead-bearing solders can contaminate the furnace charge and are difficult to refine out completely. Trace and ultratrace lead determination is, therefore, nearly always a concern in steel industry laboratories. In the U.S., Europe, and Japan, X-ray and optical emission and, especially, electrothermal atomic ab-

K

so tion are the dominant techniques employed, but sensitive m3ecular absorption spectro hotometric techniques and polarography are still viable Jternatives. Higher (alloyed) levels of lead are usually determined by flame atomic absor tion. &e color reaction of lead with potassium iodide and rhodamine B in the resence of gelatine and Triton X-100 has been utilized to &&ermine traces of lead in steels. The ion association complex was measured spectrophotometricall at 600 nm (El). Lead was also extracted from potassium i d d e solution into a 1:l mixture of cyclohexanone and methyl isobutyl ketone and then reacted to form an ion association complex with pyrogallol red and cetyltrimethylammonium bromide, which absorbs at 610 nm (E2).Cathodic strippin voltammetry was applied to the determination of traces of lea8 in steel. In the resence of selenium, in KHSO -K+301 buffer at pH 1.91, leazselenide was deposited at -0.6 and stripped cathodically at -1.0 V. A detection limit of 0.1 ppm was observed (E3). Square wave polarography was used to determine lead over the range 0.003-2.22% in cast irons and steels. The supportin electrol was 1 N HC1-0.12% ascorbic acid (E4). Leacf(and cat$!&, and copper) was also isolated by extraction of diantip ylheptane complexes and measured by AC polarography g16). Laser fluorescence spectrometry was applied to the determination of traces of lead in stainless steel. A YAG:Nd3+ pulsed laser was used for solid sample ablation. After a time delay of 1.5-5.0 ps, a dye pulsed laser excited the lead fluorescence at 233.3 nm. An estimated relative detection limit of 0.01 ppm was observed (E5).Lead was determined in steel by means of a double-tube graphite furnace atomic absorption k m a n background correction. spectrophotometer, emplo The inner (microsized) t u E composed of pyrolitic graphite. Improved sensitivity and less interference from matrix iron were observed (E6).

e

MANGANESE Manganese has been determined in steels by reaction of the +VI1 oxidation state with trimethylenebis(tripheny1phosphonium) bromide at pH 6.0. The ion pair is extracted into naphthalene in dimethyl ketone. A pink solid is filtered off, dissolved in chloroform, and measured spectrophotometrically at 548 nm (E7,E8). Manganese(II) forms a complex with mandelohydroxamic acid, which is extracted in trioctylmethylammonium chloride (Adogen 464)-toluene and measured spectro hotometrically (E9).Manganese(I1) also reacts with 8-hy8oxyquinoline to form a yellow com lex, which is extracted from alkaline solution with the liquii ion exchanger Aliquat 336 and measured (at 420 nm) (EIO). Another reaction involves the red-violet complex with 5,s'dithiodisalicylhydroxamic acid, which is extracted into Ad en 464-benzene and measured at 495 nm (Ell).A new azoyye, 5-amino-2-(2-quinolylazo)phenol,reacts with manganese(I1) in basic medium to form a red complex, which absorbs at 530 nm (E12).A spectrophotometric flow injection scheme was used to determine manganese in a range of steels. The carrier stream is 10% (w/v) ammonium fluoride, buffered at pH 6; the reagent stream is 0.25% (w/v) ethylenebis(tripheny1phosphonium) bromide. Manganese(VI1) in the sample reacts to form an ion association complex, which is extracted into chloroform and measured at 545 nm (E13). Use of high-order differentiation (d3e/dt3versus E) has allowed the determination of major amounts of manganese b oscillopolarographic titration. The method has been appfed to manganese-iron alloys and other alloys (E14).The manganese content of spM steel, galvanized iron, high tensile steel, and mild steel was cfetermined by neutron-activation analysis usin zazCfas a neutron source (E15).In the X-ray fluorescence etermination of low levels of manganese in high chromium steel, the interference of K /3 chromium radiation can be avoided by using a chemical separation approach (E16).

d

MOLYBDENUM There are many new procedures for the determination of this important alloying constituent. The complex formd with thiocyanate ion was exploited in a colorimetric procedure for medium and low alloy steel, high silicon steel, high tungsten steel, and high nickel-chromium steel. The color reaction was conducted in the presence of titanous sulfate and stannous chloride (El7). Another investigator found that the sensitivity ANALYTICAL CHEMISTRY, VOL. 63, NO. 12, JUNE 15, 1991

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of the color reaction with thiocyanate was reatly improved by adding OP (a nonionic surfactant) (El& Very low concentrations of molybdenum could be determined in steel and ores by forming an ion association complex between the anionic molybdenum thiocyanate moiety and Nile Blue in the presence of polyvinyl alcohol, Arabic gum, and dilute sulfuric acid. The s ectro hotometric measurement is made at 630 bfenum over the range 0.53-4.92% in highnm (E19). speed tool stee& was determined by formation of the thiocyanate com lex and extraction with butyltri henylhosphoniumtromide into microcrystalline benzop enone. !‘he solid is dissolved in chloroform, and its optical density is measured (E20). A fifth use of the thiocyanate complex was in a paper that described a hi h through ut (40 samples/ h) flow injection s tem in whi% solid steepsamples are dissolved electrolytic& by applying 200 mA of dc current for 8 s in a flowing carrier stream of 1.0 M KC1/0.1 M HCl. The molybdenum thioc anate complex is measured spectrophotometrically. Caliiration was performed with steel standard reference materials and was found to be linear over the range 0.7-2.7%. The system showed no baseline drift durin continuous operation for 4 h (E21). The ternar compfex of mol bdenum with thiocyanate and N-octyl-d phenylbenzami&ne in a benzene extract has been exploited in a spectro hotometric method (E22). Several coyor reactions that do not involve thioc anate were also reported. One group of investigators reacted d e dissolved sample with malachite green and dilute sulfuric acid (ascorbic and tartaric acids were added as masking agents) and then extracted it with 4,g-di-tert-but 1-3-methoxycatecholin toluene. The ion association comp ex was measured at 635 nm. The effect of tungsten was removed by an applied correction (E23). Another method involves the reaction of molybdenum with o-nitro henylfluorone and cetyltrimethylammonium bromide in dfute hydrochloric acid solution. The red complex absorbs at 530 nm (E24). Molybdenum also forms a complex with caffeic acid, which was extracted with Aliquat 336 (a liquid ion exchanger) at pH 4.0 and measured at 340 nm on a spectrophotometer, as well as by atomic absorption spectro hotometry (E25). The complexes between molybdenum an some anilides of merca to acids were exploited in a spectro hotometric ap roach 83%). Molybdenum reads with 9-(3,5-~bromo)salicy~uorone and cetyltrimethylammonium bromide to form a temary complex, which absorbs at 527 nm (E27). The complex between molybdenum and quinalizarin in the presence of cetylpyridinium chloride absorbs at 580 nm. The method has been applied to cob& and nickel-base alloys, as well as to steels (E28). A fluorometric method based on the complex with dibromophenylfluorene has been applied to iron and steel. The excitation was at 450 nm, and the emission wavelen h was 550 nm (E29). A kinetic chemiluminescence met od for molybdenum was reported based on the acceleration of the potassium bromate-potassium iodide-luminol reaction. A preliminary ion exchan e separation was used for steel samples (E30). A stripping-vokammetric method for trace amounts of molybdenum was applied to steel. Molybdenum was preconcentrated at a stationary mercury microelectrode, and then the current produced by cathodic polarization of the electrode was measured (E31, E32). In a solution of 8hydroxyquinoline, sodium nitrate, and malonic acid at pH 2.50, molybdenum was determined by polar0 raphy and applied to trace levels of the analyte in steel (g33). A similar approach was utilized by another group of investigators (E%), and a variant of the procedure was also published (E35). A volumetric method for major amounts of molybdenum was reported. It utilizes an aluminum-copper alloy to reduce the anal e, addition of a quantitative excess of ferric alum, and bac titration of the excess with potassium dichromate solution. The method was applied to the assay of ferromolybdenum (E36). After isolation by extraction with abenzoinoxime in chloroform, molybdenum was determined by thermometry by means of ita catalytic effect on the reaction between iodide ion and hydrogen peroxide (E37).

601

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NICKEL Dimethylglyoxime has been the reagent of choice for the gravimetric determination of nickel, but one paper has described the use of a new reagent, salicylaldehyde thiosemicarbazone, in this application. The new technique was applied 70R

ANALYTICAL CHEMISTRY, VOL. 63,NO. 12, JUNE 15, 1991

to the determination of nickel in stainless steel (F1).Amon the numerous new spectrophotometric procedures ia a methO i that involves formation of a 1:21 nickel:benzylamhe:xylenol orange complex, which absorbs at 600 nm (F2).After isolation of the nickel by extraction of the dimethyl lyoxime complex into chloroform, traces of nickel were r e a d w i t h hematoxylin in the presence of cetyltrimethylammonium bromide (which greatly sensitizes the color reaction) and measured at 608 nm (F3). After absorption on sulfh dry1 cotton and elution with 0.1 M HC1, nickel was reacteBPnth 2-(5-chloro-2-pyrid 1azo)-1,5-diaminobenzene in the presence of sodium decylbenzenesulfonate and Tween40 in ammonium acetate solution at pH 7.1. The red complex shows a maximum absorbance at 530-534 nm (F4). After removal of the iron matrix by extraction with MIBK, the nickel in steel alloys was determined by formation of the complex with 2-(3,5-dibromoyridylazo)-5-dimethylaminobenzoicacid in the resence of h i t o n X-100. The complex absorbs at 632 nm ($5). Nickel was also determined spectrophotometrically by measuring the ternary complex, nickel/3-(4’,5’-dimethyl-5’-thiazolylazo)2,6-dihydroxybenzoic acid c anide, which forms at pH 9.2 usin a borate buffer (k67. Nickel reacts with 3-(2pyrifyl)-5,6-di henyl-1,2,4-triazine at pH 6.8; the complex is then extracteg into 1,2-dichloroethane with ethyl tetrabromophenolphthalein to form an ion association complex, which is measured at 610 nm (F7).Other complex formin reagents that have been applied to the determination of nickf in steel are 3-(4’,5’-dimethyl-2’-thiazolylazo)-2,6-dihydroxybenzoic acid (F8), 2-(4,5-dimethylthiazolylazo)-5-dimethylaminobenzoic acid (F9), 2-(2-benzothiazolylazo)-5-diethylaminobenzoic acid (FIO),1-(5’-bromo-2’- yridyl)-5-thiocarbonyl-3-phenylformazan(FII),and 2-(6’-&omo-2’-benzothiazolylazo)-5-carboxyphenol(F12).A polarographic procedure based on the irreversible reduction of the nickel comlex with 2-amino-3-hydrox yridine has been applied to honel, Inconel-600, and staiTess steel (F13). A volumetric method for nickel levels above 6% in cobalt-free alloy steel has been described. Interferences are masked with sodium hexametaphosphate and potassium fluoride. An excess of standard chelating agent (EPTA) is added, along with CuEDTA, Tween-80, and Cu-PAN indicator. The solution is then back titrated with standard copper sulfate solution (F14).

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NIOBIUM Polarographic methods for niobium have appeared in the literature covering two distinct concentration ranges. Trace levels of the analyte are addressed by three papers. In one, the niobium-chlorosulfophenol S complex (in HC1/HN03 medium) is absorbed on a mercury drop electrode and yields a derivative wave at -0.77 V (versus a saturated calomel reference electrode) (F15).In another, the niobium-tartaric acid-nitrosulfophenol S complex (in HCl NaN03 medium) yields a catalytic wave peak potential of -0. 5 V (versus a SCE) (F16). In the third, niobium is shown to yield a catal ic polarographic wave at approximately +0.30 V (versus a S E) in an aqueous solution of 2 4 5-bromo-2-~dylazo)-5-(diethylamino)phenol, tartaric acid, and ED A at pH 2.2-2.7 (F17).The concentration range 0.51-2.08% Nb in steel and nickel-base alloys was addressed in another polarographic paper in which the effects of various mixed electrolyte media were studied (F18). Traces of niobium in iron ores were determined by a fluorescence quenchin approach. Niobium forms a nonfluorometric complex &at quenches the fluorescence of the dibromophenylfluorone-cetyltrimethylammonium bromide system. The exciting wavelength was 472 nm, and measurements were taken at 562 nm (F19).Several spectrophotometric methods have been published. In one, niobium is extracted with dichloromethane from an aqueous solution containing hydrochloric acid, potassium thiocyanate, and metoclopramide hydrochloride. The extracted complex absorbs at 385 nm (F20).In another paper, traces of niobium in iron and steel were determined by formation of the complex with phenylfluorone in the presence of cetylpyridinium bromide and measurement at 520 nm (F21). Niobium was determined in alloy steels over the range 0.003-0.12% in the presence of as much as 0.1% tantalum by solvent extraction of hexafluoroniobate, reextraction with water, and formation and measurement of the sulfochlorophenolS complex. In the presence of molybdenum and tungsten, a preliminary am-

4

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monia separation was required (F22).Niobium was determined in iron ores by a sensitive method that involves formation of the com lex with 2-(5-bromo-2-pyridylazo)-5-(diethylamino)pheno?inthe presence of tartaric acid at pH 1.0, adsorption on a resin, and-spectrophotometricmeasurement at 620 nm (F23).

PHOSPHORUS Because of troublesome interference and sensitivity problems with both o tical emission and X-ray fluorescence aproaches, the megod of choice for phosphorus in steel at levels h o w about 0.005% remains the "classic" s ctrophotometric technique based on the formation of the Kue (reduced) or, less frequently, the yellow (oxidized) phosphomolydate complex. Another alternative that is sometimes employed is based on colorimetric measurement of the phosphovanadomolybdate complex. One pa er examined certain problems with this latter ap roach, wkch has been adopted as the International Standarxs Organization (ISO) method for steel and irons. It was found that silicon produced a positive interference as did arsenic, chromium, hafnium, niobium, tantalum, and t The method was modified to eliminate the silicon pro lem; the remaining effects were also investigated (IC%). .An indirect atomic absorption method was published involving the formation of the bismuth0 hosphomolybdate complex, which was extracted into methyrisobutyl ketone and measured (F2.5). A new sensitive colorimetric system was described, based on the formation of an ion association complex: ethylrhodamine B-molybdophosphoric acid-polyvinyl alcohol. The complex absorbs strongly at 584 nm (F26). An automatic spectrophotometric analyzer was developed for trace phosphorus in steel. Sample dissolution is the only manually performed step. Phosphorus levels as low as 2 p m were determined in 6 min (F27).A paper on the reducefphos homolybdate method showed that the effect of arsenic in tEe sample can be eliminated by adding sodium thiosulfate (F28). Phosphorus in stainless steel slags was determined by dissolving the sample in hydrochloric acid to generate phoshine gas, which was collected in saturated bromine water. he excess bromine was removed, and the solution was measured by inductively coupled plasma optical emission spectrometry (F29).a article activation analysis, using an intemal standard and t i e method of standard additions, was shown to provide recise and accurate values for phosphorus in low alloy steels b30). Phosphorus se gation in solid steel pieces can be detected with a chemicalrimpre ated paper sheet. The specially prepared sheet is coated witEcid-treated pelatin and a triazine-type solidifyin agent. After drying, it is dipped in a mol bdate solution ($31). Interest in very i w levels of phosphorus in both steel and %h-temperature superalloys has spurred other developments. eae include a concentration technique in which hosphorus is collected in a beryllium hydroxide precipitate h32) and a method based on solvent extraction and s ectrophotometric measurement of the ion association compgx of crystal violet and phosphomolybic acid (F33).

The sample is cooled, diluted, treated with hydrazine dihydrochloride to reduce cerium, manganese, and vanadium, and further diluted. Yttrium is added as a coprecipitant, and the solution is treated with both hydrofluoric acid and ammonium hydrogen fluoride. The precipitated rare earths are collected on a 0.2-pm membrane filter that is then dried and measured. X-ray intensity ratios were measured against the yttrium as an internal standard. A relative standard deviation of 2% at the 0.075% concentration level and of 4% at the 0.0005% concentration level was obtained (G2). ICP emission spectrometry was applied to the determination of trace lanthanum, cerium, praseodymium, neodymium, and samarium in cast iron, and three different correction methods were applied to the removal of iron interference from the sample matrix (C3).Yttrium was determined in nickel-base superalloys down to 10 ppm concentration levels by using microwave-assisted dmolution (minimizing the amount of hydrofluoric acid employed) and measurement by ICP optical emission (G4). Neutron activation was employed to determine individual rare earths in steel first by solvent extraction removal of the iron and then by sorption of the rare earths on a deposit of calcium oxalate. After neutron activation, the rare earths on the deposit were measured by us' a Ge(Li) detector. Lanthanum, cerium, praseodymium, an neodymium were determined. The method is also applicable to i iron (125).A method based on the direct fluorescence ion in acid solution was applied to iron-base materials of after removal of the iron matrix by solvent extraction (C6). Spectrophotometric methods are common for the rare earths, and some are very sensitive, but almost none are completely element specific. Arsenazo I has been applied to raseodymium in pig iron and steel (0. Arsenazo I11 has en used for total rare earths in ferroalloys (G8), in stainless steels (G9),and for an electrographic test for rare earth elements diffused into a steel surface ((310). Arsenazo DBM was used for light rare earth elements in steel and iron (G11). Arsenazo DBC was applied to rare earths in iron ores (1312) and modular cast iron (1313).The compound, 2-(5-bromo-2pyridylazo)-5-(diethylamino)phenolfound a plication for total rare earths in cast iron, low all0 steel, antores (G14). Both the p- and m-isomers of fluorochoraphosphonazoform complexes with the rare earths. The -isomer was applied to steel (G15). Total rare earths in nod& cast iron were determined with bromophosphonazo-PSN (CIS). ChlorophosphonazoDBS was applied to total rare earths in alloy steels (G17). Similarly, chloro hosphonazo-p-Cl was used for iron and steel (GIB) and p-iocfochlorophosphonazo was a plied with and without a masking step to distinguish total "[eavy" and total "light" rare earths (G19). ChlorophosphonazomK was applied to the cerium subgroup in stainless steels (GZO). The ternary complexes that rare earths form with p-hippuric acid chlorophosphonazo and cet ltrimethylammonium bromide were exploited for steel ((7217.One paper described the synthesis of Arsenazo DBM, p-trifluoromethylchlorophosphonazo,pfluorochlorophosphonazo, and m-fluorochlorophosphonazo, and their application to the determination of rare earths in steel and alloys (G22).

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RARE EARTHS Methods for total rare earths, in which the chemically similar lanthanides (as well as scandium, yttrium, and lanthanum) are determined in sum, have been common and valuable in the steel and cast iron industries. While cerium show some usable redox behavior and chroic separations of the entire series are possible, most specific rare earth determinations are performed with some type of spectro aphic technique. One of the problems common to this worfis illustrated in a published paper on the determination of cerium in cast irons by X-ray fluorescence spectrometry. The nonhomo eneous distribution of cerium's com ounds with oxygen antsulfur led to poor results with solicfspecimens. The problem was solved by employing a wet chemical preconcentration technique in which the dissolved sample was reacted with oxalate and the precipitated cerium was measured (without ignition to the oxide) (GI). Another X-ray fluorescence approach was applied to the determination of lanthanum, cerium, praseodymium, neodymium, and samarium in steels. After dissolution of the sam le in a Teflon vessel and removal of the chromium as chrom ?chloride while heating to fumes of perchloric acid, the cooled: diluted sample is treated with phosphoric acid and again heated to fumes.

7

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smrcorv The majority of new work on silicon is in the area of molten metal analysis (see below); however, some new approaches with laboratory samples were published. Besides the classic gravimetric ap roach, the s ectrophotometric measurement of the silicomoPybdate compfex is robably the most widely used classical method. One paper &scribed a series of modifications that improved the reproducibility, linearity, and sensitivity of the calibration curve (G23).Another paper cou led the color reaction with a preliminary separation ste in SiF, is evolved from concentrated sulfuric acid wit[ a stream of au and collected in boric acid solution (C24).An automated procedure based on the photometric measurement of the silicomolybdate complex was also described (C25).Another publication described a flow injection-atomic absorption method for steels (G26). Other work describes a thermometric method for ferrosilicon and ferrosilicon manganese (G27). Ferrosilicon was also analyzed b dissolvin the sample in hydrofluoric acid which containeinitric acif and potassium fluoride. The recipitate of potassium hexafluorosilicate was filtered off antdissolved in a warm solution of sodium nitrate. After dilution to volume with sodium nitrate solution, an

with


71 R


aliquot was adjusted to pH 5.3-5.4, a total ion strength buffer was added, and the solution was titrated with standard lanthanum nitrate solution, using a fluoride specific ion electrode to detect the end point (G28).Silicon was determined in iron ore mixtures by using an energy dispersive X-ray fluorescence spectrometer with roll-compacted samples (G29).

STRONTIUM There was a surprising degree of interest in this element in the past 2 years, all of it from the Peop!e’s Republic of China. A polarographic method was described that is applicable to the range 0.005-1 % in steel. The iron matrix is eliminated with tetrameth lammonium hydroxide; then tetramethylammonium iodiJe in alcoholic aqueous solution serves as the sup orting electrolyte (at pH 8) ((330). Two related spectropiotometric methods, both applicable to 0.005-0).5%strontium in steels and both utilizing DCTA to mask interference from calcium and magnesium, have been reported. The first utilizes arsenazo 111, and the strontium complex is measured at 640 nm (G31); the second utilizes chlorophosphonazo111, and the complex absorbs at 660 nm (G32). Using dual-wavelength spectrophotometryand in the presence of acetone, sodium sulfate, and EDTA, another strontium com lex was ap lied to a silicon-iron alloy. The reagent is 2-(4P-chloro-2’-p\osphonaeo)-7-(2’,6’-dibromo-4’chloro henylazo)-l,8-dihydroxy-3,6-naphthalenedisulfonic acid. !he maximum absorbance is at 630 nm, and the procedure is not affected by the presence of other alkaline earth elements or of iron (G33). SULFUR In steel production laboratories, sulfur determination is nearly always linked to carbon determination since the combustion-based determinators usually measure these elements simultaneously. In these instruments the SO produced from the sample is usually measured by infrared aisorption; however, many older instruments based on an automated or semiautomated volumetric titration are still in use, and a few laboratories have applied a spectrophotometric finish to achieve very low detection limits. Several papers describing innovations in the determination of both sulfur and carbon have been discussed in the section on carbone(B7-B11, B15). One group of investigators determined sulfur in iron and steel by wrappin the Sam le in tin foil, placing it in a copper crucible wit! iron, moyybdenum silicide, and additional tin powder, and extracting the sulfur with an electric arc discharge. Measurement is by acid-base titration with sodium hydroxide solution to a mixed indicator (methyl orangebromocresol reen) end point (C34). Sulfur is afso determined by optical emission and X-ray fluorescence spectrometry. X-ray techniques, in particular, are subject to effects from the morphology of sulfur compounds in steel. One investigator discovered improved accuracy when a shallow mold was used to cast the analytical sample, if the near-surface, fie-grained portion was analyzed (G35). Sulfur was determined in cast iron by finishing the measurement with a new metallochromic indicator titration based on copper(I1) and 4-(3,5-dichloro-2-pyridylazo)-1,3diaminobenzene (G36). Sulfur in steel was also determined by molecular emission cavity analysis; however, man anese was found to impede the release of sulfur and may also fepress the molecular emission (G37). Sulfur can also be determined by dissolving the sample in h drochloric, nitric, and hydrofluoric acids, reducing the oxiiized sulfur compounds to HzS phosphorous and hydroiodic acids, and transporting g % t r e d gas to an absorbing solution by means of a stream of nitrogen. The absorbin solution contains zinc acetate, ferric ion, and NJV-dimethyfp-phenylenediamine,The latter reacts to produce methylene blue, which is measured s ec trophotometrically (C38).Sulfur was also determined)by absorbing the SOzevolved from combustion of the steel sample in a standard solution of potassium permanganate and measuring the degree of color loss spectrophotometrically (G39).

TIN Tin is an important tramp contaminant of nearly all steels. At very low levels it can present a particularly vexing problem for the analyst since many of the simpler, standard approaches 72R


are beset with either sensitivity roblems, matrix interference problems, or both. One commorfy employed route is to isolate the tin by distillation of the hydride (SnHJ. Traces of tin in tungsten steel and molybdenum steel were determined by combining hydride generation with nondispersive atomic fluorescence spectrophotometry (HI). In another procedure the evolved SnHl is carried over a gold porous electrode with a stream of nitrogen. The tin is oxidized, enerating a POtential proportional to ita concentration. he method was applied to iron ore analysis (H2). A direct method for tin in iron and steel is baaed on catalytic polarography in perchloric acid solution containing ammonium vanadate, potassium iodide, and ascorbic acid. It has been applied over the range O.OOO1-0.1% tin (H3). Two spectrophotometricmethods for tin show similar interference effects from molybdenum and tungsten. In one, tin is reacted with trihydroxy-4’-sulfazobenzene and cetyltrimethylammonium bromide in dilute sulfuric acid solution to form a com lex that absorbs at 470 In the other, tin is reacte1 with 9-cinnam 1-2,3,7nm (H4). trihydroxy-6-fluoroneand cetyltrimethylammonium gromide in dilute sulfuric acid solution to form a complex that absorbs at 508 nm (H5).

4

TITANIUM Titanium is frequent1 determined Spectrophotometrically as the peroxy complex. gerhaps the second most widel used colorimetric ap roach involves the complex with &antipyrylmethane. +his latter technique was recently studied for plain carbon and low alloy steel over the range 0.001-0.010% titanium (H6) and for cast irons, medium alloy steels, and copper-nickel alloys (Ha.Titanium also forms a colored complex with o-chlorophenylfluorone in the presence of the H9). nonionic surfactant Tween-80. It absorbs at 538 nm (H8, In the presence of cetyltrimethylammonium f2romide,ascorbic acid, and p ocatechol violet (in chloroacetic acid buffer solution at p g 3 ) , titanium forms a quaternary complex that absorbs at 295 nm (Hl0). Titanium also reacts with Nhydroxy-NJV’-diphenylbenzamidine and thiocyanate to form a yellow complex that can be extracted into chloroform from dilute sulfuric acid solution and measured at 390 nm (Hll). A fluorescence quenching method based on titanium, 5bromosalicylfluorone, and cetyltrimethylammonium bromide in dilute sulfuric acid was ap lied to iron and steel (H12). A similar method based on 4,5-&bromophenyMuoronehas been applied to stainless steels (H13).Oscillo olarographic measurement of a irreversible cathode wave rom the complex of titanium with 10-undecenehydroxamicacid has been reported (H14).An indirect polarographic method involves formation of 11-molybdotitanophosphoricacid, extraction with solvent, back extraction with base, and measurement of the molybdenum(V1) by its catalytic effect on the polarographic reduction of hydrogen peroxide (H15). Similarly, a titanium polar0 raphic catalytic wave in the system PAR-hydrogen peroxiiesodium bromate has been a lied to the trace determination of titanium in alloy steels ( B 6 ) . A working group in the Federal Republic of Germany conducted tests to optimize the determination of trace levels of titanium in steel by ICP o tical emission and X-ray fluorescence (HI7). Titanium(I8 in blast furnace slag was determined at high levels by first removing metallic iron and other active metals by ionic displacement with Cu2+salta and then measuring the hy produced by reacting the sample with phosphoric or hy rochloric acid (H18).

P

T

TUNGSTEN This element is often determined spectrophotometrically by measurement of its thiocyanate complex, but molybdenum and vanadium are serious interferences. The method has the advantage of relative simplicity, however, as compared to much more involved avimetric and volumetric methcds, and so it is often applief even to relatively high concentration samples. In one paper the interferences are handled by first removal of the iron matrix by precipitation of the hydroxide and then adding zinc chloride, titanium(II1) chloride, ammonium thiocyanate and adjusting the acidity prior to differential spectrophotometric measurement. The method was a plied to 6-20% tungsten in alloy steels and nickel-base J o y s (H19). In another version, sodium otassium tartrate is added, and the interferenta are added wten the calibration curve is prepared. The same paper addresses flame atomic


absorption determination of tun ten from hosphoric acid solution containing aluminum c#ride (H2Of In a variation of the thiocyanate rocedure, the tungsten(V)-thiocyanatediphenh dramine ydrochloride in association complex is extractei into chloroform and measured (H21). Other s ectrophotometric methods have also been reported. !‘he tungsten-phenylfluorone-cetyltrimethylammonium bromide com lex absorbs at 520 nm (H22). The tunpten-o%~~enyduorone-cetyltrimethyla”onium bromide comlex (in the presence of Tween-40) absorbs at 524 nm (H23). Fungsten also forms a colored complex with 4-sulfobenzeneazopyrocatechol in the presence of ascorbic acid and Flow injection spectrophotometry was utilized unithiol (H24). for tungsten usin dibromo henylfluorone and cetyltrimethylammonium%romide ( 25). Instrumental neutron activation using a %*Cfsource was applied to the determination of tungsten in steel between 0.017 An approach reported above in the section and 0.024% (H26). on molybdenum was similarly a plied to tungsten. An aluminum copper alloy is used to r&ce t ten m the presence of a known quantity of ferric alum, an the excess is back titrated with potassium dichromate solution. The method was applied to tungsten in ferrotungsten (E36).

can be removed by means of a precipitation with alkali (H43). Vanadium was determined in pig iron by dissolving the sample in sulfuric, phosphoric, nitric, and perchloric acids and heating to fumes. The oxidized vanadium is reacted with sodium diphenylaminesulfonatein 9.8 M H#04/8 M HSPO and measured at 540 nm (H44). Vanadium in ore, sl and steel was determined utilizin the color reaction wit 9-0chlorophen 1-1,6,7-trihydroxybuoronein the presence of cetyltrimethy&”onium bromide. The complex absorbs at 560 nm (He). Vanadium in vanadium titanferrous ores and slags was determined by chloroform extraction of the complex with 1-methoxy-N-phenyl-2-na hthohydroxamic acid and measurement at 540 nm (H46f

VANADIUM The literature is re lete with references on vanadium determination in steel. t h i s abundance of interest may relate to the interesting and difficult problems that this element’s aqueous chemistry often presenta to the steel analyst. One paper described a olarographic method based on reduction of the vanadium(Vkx ferron complex, using linear potential voltammetry (H27). n another, a highly sensitive polarographic catalytic wave of vanadium is produced in a system containing 3,5-dichloro-DMPAP, sodium bromate, and dilute sulfuric acid (H28).High concentrations of vanadium are frequently determined by redox titration. In a new variant, one a er describes the selective reduction of Cr(V1) and M n ( h 8 with absolute ethanol, thiourea, and sodium nitrite, followed by titration of V O with standard ferrous ammonium sulfate to a green N-phenylanthranilic acid indicator end point (H29). The bulk of the extensive literature on this element, however, is composed of spectrophotometric methods. The vanadium(V) catal zed oxidation of 3,5-diaminobenzoic acid dihydrochloride %y potassium bromate was ex loited in a sensitive kinetic method (H30). The complex getween vanadium and 2-(5-bromo-2-pyridylaz0)-5-(diethylamino)phenol in the presence of OP surfactant was ap lied to low alloy steels (H31). Vanadium forms a complex wit! mandelohydroxamic acid in the presence of oxalate, which is extracted in Andogen 464-toluene solution and measured (H32). After se aration of the iron matrix with methyl isobutyl ketone a n f t h e addition of EDTA to mask copper and aluminum, vanadium was reacted with ammonium aurine tricarboxylate to form a colored complex (H33). Vanadium reacts with 5,5’-dithiodisalicylhydroxamicacid to form a violet complex, which is extracted into a solution of Andogen 464 in toluene (H34). The complex with o-dianisidine absorbs at 440 nm (H35). The complex with chromotro ic acid absorbs at 420 nm (H36). The complex with 2,6-diR drox 3-(2’-thiazolylazo)benzoic acid absorbs a t 550 nm (d37).$he complex with furan-2hydroxamic acid is extracted with a toluene solution of trio c t y h e t h y h o n i u m chloride (Andogen 464)and measured The ternary com lex with N-hydroxy-Nat 530 nm (H38). p-chlorophenyl-N’-(2,3-dimethyl)[en 1-p-toluamidinehydrochloride and p-hydroxybenzaliehyie absorbs at 590 nm (H39). The ternary complex with N-p-aminophenyl-2-then lacrylohydroxamic acid and 3-(o-carboxy heny1)-1&e tern pgenyltriazene N-oxide absorbs at 455 nm (H40). complex with o-chlorophenylfluorone and cet Itrimethy ammonium bromide absorbs at 558 nm (H41). h2-pyrid;l ketone 2-pyridylh drazone, in the presence of EDTA, forms a stable red compfex with vanadium(I1) that has been used to determine the element in a high-strength low all0 The method shows very good sensitiwty and selectivity (Ih2). A trace catalytic method in which vanadium catalyzes the oxidation of henylhydrazine to benzenediazonium ion by otassium c d r a t e has been used for steel. A violet-red azo aye is formed from the reaction product, which is measured spectrophotometrically at 527 nm. Selenium interferes but

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ZIRCONIUM Spectrophotometric methods for zirconium in iron-base alloys are common-pyrocatechol violet, xylenol orange, and arsenazo I11 are, perhaps, the most frequently em loyed colored complex-forming agents. The last mentione compound was utilized in a paper that describes a procedure for trace zirconium in niobium-bearing steels and nickel-base all0 After dissolution, the iron is reduced with ascorbic acid a n z h e zirconium is extracted into thenoyltrifluoroacetone in x lene and then back extracted into 0.4 M HF/0.4 M The aqueous phase is reduced in volume, treated with nitric acid, and then diluted with water. Urea and arsenazo I11 are added, and the absorbance is measured at 670 nm (H47). In another approach iron is extracted away first as ita chloro complex into methyl isobutyl ketone, then potassium thiocyanate is added, and residual iron is extracted away. Arsenazo I11 is then added to the aqueous phase, and the zirconium complex is measured. This method has been apThe 2,4,6plied to the range 0.01-0.20% zirconium (H48). tribromo-, 2,6-dibromo and 4-chloro derivatives of arsenazo have also been utilized to determine zirconium in iron and steel (H49). Zirconium forms an ion association complex with thiocyanate and triflupromazine in dilute sulfuric acid, which can be extracted into chloroform and measured at 470 nm (H50). A fluorometric method based on the complex formed with morin in the presence of sodium dodecyl benzenesulfonate and dilute hydrochloric acid was described. The complex is excited with 507 nm light and emits at 421 nm

s

.

(H51).

MISCELLANEOUS ANALYTES This section has been reserved for analytes that appear sDarselv in the literature-usuallv as one or two references in the past 2 years. Elements. Cadmium. An AC polarographic method for cadmium (and comer and lead) was amlied to steels. The analyte was precdicentrated by solveni extraction with dianti yrylheptane in chloroform (C16). FEorine. Fluoride was determined in ores and slags by first sintering and then fusing the sample with sodium carbonate. After leaching the fused cake, the fluoride concentration was measured by means of a fluoride specific ion electrode, using a sam le ali uot buffered with citrate (11). GalEum. %he complex that gallium forms with morin was adsorbed on a mercury hanging drop electrode and then measured by cathodic strippin voltammetry. The method was used for steel, iron ore, an8 sla samples (12). Gallium was also determined in the nickel-Ease alloy, IN100, using nitric and hydrofluoric acid dissolution and a graphite furnace AA measurement, employing the L’vov platform (13). Germanium. A spectrophotometric method based on the ion association complex between ermanium(IV), mandelic acid, and malachite green was appfied to spiked carbon steel standards. Interferences from iron, titanium, tin, molybdenum, and antimony were masked by the addition of trans1,2-diaminocyclohexanetetraaceticacid and sodium diethyldithiocarbamate. The colored species was extracted into chlorobenzene and measured at 628 nm (14). Hafnium. An ICP o tical emission technique was applied to the determination o f h u m in ferrosiliconzirconium. The sample was dissolved in hydrofluoric, nitric, and sulfuric acids (15). Indium. Trace levels of indium in nickel-base heat resisting alloys (IN100, %ne 45, and MAR-M246) were determined by dissolution in hydrofluoric and nitric acids and measurement by a graphite furnace atomic absorption approach using the ANALYTICAL CHEMISTRY, VOL. 63, NO. 12, JUNE 15, 1991

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L'vov platform. A detection limit of 0.1 ppm was obtained (16).

Magnesium. Nodular cast iron can be anal zed for mago hotometric methdbased on the nesium employing a s complex formed wit xyli yl blue I in the resence of cetyltrimethylammonium bromide and OP ( 7). Sjmilarly, magnesium in rare earth containing nodular cast iron was determined spectrophotometrically, using the complex that magnesium forms with chlorophosphonazo I in the presence of potassium sodium tartrate and triethanolamine (which act as masking agents) (18). Palladium and Platinum. Iron ore samples dissolved in hydrochloric acid were reduced with stannous chloride, and the palladium and latinum were adsorbed on activated carbon. The activatexcarbon was then ashed, and the residue was mixed with graphite and calcium carbonate and arced in an o tical emission spectrogra h (19). Siruer. The catalysis by sirver ion of the oxidation of manganese(I1)to permanganate by ammonium persulfate was exdoited in a sDectroDhotometric method for silver in iron a i d steel (110): Tantalum. A spectrophotometric dual-wavelength method for tantalum in nickel-base alloys containing niobium has been developed. The colored complex is formed with 2-(5bromo-2-pyridylazo)-5-(diethylamino)phenol in citric acid and sulfuric acid medium. The wavelength pair used were 560 and 620 nm (111). Another spectrophotometric method for steels is based on the complex with tannin. Unfortunately, niobium, a fre uent accompanying element, interferes (112). Tantalum was jetermined in ferroniobium and a nickel-base alloy using a spectrophotometric procedure based on the analyte's reacin the presence tion with 4,5-dibromo-o-nitrophenylfluorone of citric acid, hydrogen peroxide, Triton X-100,and dilute sulfuric acid (113). Tellurium. A sensitive colorimetric method is based on the tellurium-potassium iodide-rhodamine B complex, formed in the presence of polyvinyl alcohol and phosphoric acid and measured at 600 nm (114). Trace levels of tellurium in cast iron were determined by adsorption from HF HC1 H 0 solution onto sulfhydryl cotton, elution with 1:l dN03:k26,and measurement b flame atomic absorption (115). Thallium. Thallium was determined in chalcopyrite ores utilizing a fluorometric approach. In the presence of dilute sulfuric acid and potassium bromide, thallium reacts with safranine T to form a complex that is extracted into isoamyl acetate. The complex absorbs at 525 nm and emits at 560 nm (116). Compounds and Empirical Analytes. Here the scope is restricted to common ore and mill roducts. Broader papers and those dealing with specializetf process-related sample materials are discussed in the next section, Miscellaneous Matrices. Empirical analytes refers to those species that have on1 a materials en ineering realit . &dcium Oxide. &ee calcium oxiie in iron ores and wustite briquets was determined by heating the sample in ethylene glycol for 30 min at approximately 80 OC. The solution is then titrated with standard 0.1 M hydrochloric acid to a mixedindicator end point (2:l methylene red:methylene blue, end point pH 5.4-5.6) (117). The acid titration test to assess uality in calcined lime and dolomite was studied and revised

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Moisture. Automatic probes to determine the moisture content of coke used for pig iron smelting were shown to have advantages over the ravimetric method (119). Sulfur Capacity. $he ability of oxide-fluoride sl s to remove sulfur from molten steel was assessed by m%ing copper containin varying amounts of sulfur with the slag sample in a molytdenum crucible (120).

MISCELLANEOUS MATRICES This section is devoted to those s ecial samples that many steel laboratories routinely monitor or various rocess control situations and to assess corrosion of the pro&ct in service. Corrosion. Ion chromato raphy was employed to determine chloride, fluoride, phospfate, and sulfate in the corrosion products of low alloy steel. The sample is fused in sodium carbonate, leached in water, passed throu h a cation-exchange column to remove sodium and then boilefto remove COz, and injected into an ion chromatograph. A conductivity detector was employed (JI). Nickel, cobalt, copper, zinc, lead, and

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manganese were determined in the corrosion products of low alloy steel by ion chromat aphy using s ectrophotometric detection of the complexesTrmed with P h at 520 nm (J2). A review of ion chromatographic applications in corrosion studies was also published (53).Potentiometry with an iodide-selective electrode was used to determine sulfates in corrosion products (54). An inert electrode was used to measure Fe3+in an aqueous heat transfer agent to assess the corrosion of steel structures (J5). Plating. A review of the applications of ion chromatography in the monitoring and control of various types of plat' baths has been published (J6). Phosphoric, sulfuric, a 3 chromic acids have been determined by ion chromatography in chromium plating baths and related polishing solutions. Improved accuracy resulted from close matching of the hydrogen ion concentration in standards and samples (J7). A general mide to the chemical analysis of plating- solutions was &so published (J8). Cleaning. The acid and metal-salt levels in steel pickling baths have been monitored by using y-ray spectrometry. The pickling solution is passed through a pipe and irradiated by a high-energy ('?'Cs).and a low-energy P A m ) source (59). Iron was determined in OEDF (hvdroxyethylidenedisulfonic acid)-a complexing agent used t o remove scale from steel surfaces-b direct photometry of the yellow com lex at 390 nm (JIO). 8ne review of techni ues for icklinggath monitoring and control has been puglished b11). Other Processes. Salt baths used for liquid carburizing were analyzed for cyanate and cyanuric acid. Cyanate was determined by a distillation-acid titration ap roach, and cyanuric acid was determined by decomposition o the cyanate, followed by residual clean-up with an absorption column and UV absorption measurement of the cyanuric acid (J12). Free sulfuric acid was determined in a coloring solution for stainless steels by an acid-base titration method that compensates for the effects of metal sulfates and the dissociation of CrO, (J13). The application of ion chromatography to the determination of anions in wastewaters, surface treatment baths, and rolling mill coolants (and for the determination of sulfur in steel) was described in a recent paper (J14).IR absorption was used to measure the dew point and carbon monoxide as concentration in a continuous annealing furnace (~15).dtrogen was determined in foundry sands by an inert gas fusion technique (J16).Magnesium and manganese were determined in production dusts in iron and steel production facilities by using an atomic absorption a proach. The effects of varyin amounts of aluminum ancfiron in the samples were m d (J17).

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MOLTEN METAL ANALYSIS If there is an area of intense research in the analysis of steel today it is in molten metal analysis. It has long been recognized that the economics and quality control of steel roduction depend critically on rapid chemical analysis o f inprocess metal. While most steel producers today still re1 on chill-cast molds or immersion samplers to obtain a solidlfor transport to a control laboratory, recent developments suggest that the future of steel process control analysis may be at the furnace side and in the control pulpit. Two apers consider the future of molten metal analysis ( K l , K27: however, much of this techno10 is still evolvmg, and many patents are being issued. Slight y over one-half of the references found in this category are from Japan; although there were a si ificant number of papers from the US. and Germany (FR!?+ GDR), these combined re resented only about 25% of the total. The other countries contributed to the literature-Norway, Canada, the U.K., Belgium, Brazil, the People's Republic of China, and the USSR-demonstrate the broad interest in this topic. Hydrogen. The new HYDRIS direct immersion probe for measurement of the hydrogen content of molten steel has been described (K3) and evaluated in service. The measurement reproducibility was superior to that obtained from laborato determination from samples obtained by using dual-wx samplers. The absolute accuracy of the technique, however, ical a lications at ladle and awaits further stud (K4) A direct measuring tundish sites have teen d e s % d robe was also developed at the British Steel Corporation's !winden laboratories; their pa er describes the device that is based on determination of t i e hydrogen content of a gas

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sam le which has been rapidly equilibrated with the molten

steef(K6). A similar probe technique has been developed at

Nippon Steel Corporation. The conversion calculation from hydrogen content of the equilibrated inert gas to h dro en content of the molten metal is based on Sievert's law (57, #8). Oxygen. If one can speak of a technology in molten metal anal is that is nearing maturity it is the oxygen robe, which has g e n in use in some plants for over a deca e. In Japan alone, oxygen sensors are being consumed at a rate increase of about 60000 ieces/year, with nearly a half-million conthese 52% were used in RH or DH ladles, sumed in 1985. 25% in basic converters, and 11% for secondary refining steps (K9).One review that covers the development of a new compact solid state sensor has been published (K10). The oxygen activities in iron and nickel-based metal melts containing chromium were studied, and Cr2O3 was found to be the key oxide phase controlling the oxygen activity (K11). Melt tem erature, oxy en concentration, and operating time were stuzied in the C evelopment f of Zr02 and Tho2 solid electrolyte based probes (K12). Needle concentration cells that use a molybdenum/molybdenum oxide reference and a zirconia calcium oxide solid electrolyte have been built and tested ( 13). Numerous patents and patent applications have been filed for probe designs employing a range of solid electrolyte, reference, and counter electrode materials (K14-Kl8). An exhaustive listing cannot be given in this review. The effect of electron conduction in yttria-stabilized zirconia was evaluated in the probes based on that ceramic (K19). Silicon. A paper from Japan describes the determination of silicon in molten pig iron by injecting w o n to generate fine p l e s that are transported to an ICP emmion s p o g r a p h . sults over the range 0.2-1.0% silicon agreed wit laboratory analysis. Total time for the determination was 80 s (K20). Potentiometric probes for silicon are also being developed. One version was used in molten i iron and showed a reOther designs have sponse time between 32 and 70 s &). been developed for iron and steel (K22-K26). Phosphorus. Control of hosphorus removal in converter steel refining was achieved \y monitoring the CO, C02, H2, and O2 content of the waste gas (K27). Direct measurement of hosphorus levels is also ossible with potentiometric These have been usec?for both molten pig iron and molten steel (K28, K29, K24). Other Work. Chromium activity in iron-base and nickel-base melts is a probe measurement oal for certain investigators (K30)and one patent in this fie6 has appeared (K31). A number of papers and patents have appeared describin on-line monitoring of molten steel composition by using IC% o tical emission measurement of nebulized metal particles. &e sample is often generated by an ultrasonic probe lowered into the molten metal (or by gas nebulization), and the nebulized particles are trans orted into the plasma by an inert gas stream (K32-K34). related ap roach involves chlorination of the molten steel surfaces anttransport of the metal chlorides to the plasma torch. The investigators reported that excess oxygen and oxide gases caused difficulties by extinguishing the torch and that molybdenum could not be determined (K35, K36). Pulsed laser excitation of the molten steel surface is being investigated foro tical emission analysis of the metal bath composition. For t e first microsecond, a continuum is emitted, after this, the light has analytical value. Japanese work employed a 2-5Q-switched laser pulse at 1.06 pm to determine 0.2-4.7% carbon, 0.15-0.50% silicon, 0.15-0.30% manganese, 0.02-0.07% sulfur, and 0.15-0.18% phosphorus at a blast furnace skimmer (K37). German workers saw detection limits of 10-100 ppm (K38).The light emitted by the flame above an alloy steel converter was examined b time-resolved optical spectroscopy. The measurement ed to information on gas consum tion, refractory linin wear, and carbon content of the m,e! among others (K397.Several publications describe a variety of molten metal probes that have been developed for monitoring various molten metal bath constituents: carbon, oxygen, and silicon (K25), ox en and s c u r (KlO),carbon,.silicon, and aluminum (K40),anToxygen, silicon, sulfur, aluminum, and phosphorus (K41).

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INCLUSIONS AND SECOND PHASES The scope of this section must be restricted to those topics that are primarily the concern of the analytical chemist (as

opposed to those that would interest a physical metallurgist). As a result, certain important instrumental techniques are treated lightly, and the reader is referred to the Fundamental Reviews issue of this journal for additional information. Another important source is Metals Abstracts. A review of chemical and ph sicochemical methods for characterizing steel inclusions h a s L n published. Dissolution methodology, rapid electrolysis, optical emission, and electrothermal atomic absorption spectroscopy are covered ( L l ) . A review has appeared covering electrochemical separation of carbide phases in tool steels and comparing their characterization by optical microscopy, scanning electron microecopy (SEM), electron microprobe analysis, and X-ray microstructural analysis (L2). A comparison of electrochemical isolation and analysis of steel precipitates and metallographicstudies concluded that the chemical ap roach is favored when determinin phase variation and c emical composition, while the medographical approach is better in determining general phase transformation (L3). Electrolytic dissolution of the metal matrix is one commonly employed means for isolating a variety of compounds from steel. Titanium, niobium, and vanadium carbonitrides were isolated from high-strength weldable steels by electrolysis at 0.3 V and 0.4 A/cm2 in 0.6 M HC1. Some solubility of the precipitates in the electrolyte was noted (L4). A new electrolyte containing 1% ascorbic acid and 0.5% tetramethylammonium chloride in methanol has been applied to the isolation of yttrium sulfide from low alloy and stainless steels (L5). A radioactive tracer technique was employed to determine the stability of cerium sulfide and cerium oxide during electrolytic isolation from steel (L6). The presence of CeC2 in some steels was proven by electrolytic isolation and application of metallography, Au er spectroscopy, X-ray diffraction, and electron micropro%e analysis (L7). Inclusions isolated from steel with iodinemethanol dissolution of the matrix can be analyzed for nitrogen by fusion in molten alkali and removal of the ammonia in an argon stream. The nitride nitro en is quantified by coulometric titration of the ammonia. 8r2N and ZrN are not completely decomposed by the alkali fusion technique (Ls).Boron nitride can be decomposed by a medium of ammonium sulfate, copper sulfate, and sulfuric acid by heating at fumes for 1h. In the resence of the dissolved steel matrix (as in determining total loron), phosphoric acid is added to the same mixture, which is heated at fumes for 25 min (L9). Sulfides of magnesium, calcium, barium, and rare earths and rare earth oxysulfides were determined b reduction with hydrogen at 600-900 OC and collection of t i e evolved hydro en sulfide in cadmium acetate solution. The cadmium sulkde is then determined polarographically (Ll0). A thermogravimetric analyzer with a calibration magnet reproducibly attached to the furnace for the thermoma netometry was used to demonstrate the presence of car%ideand nitride phases (by their Curie transitions) in carbonyl iron powder (L11). Detection limits, spatial resolution, and beam penetration were surveyed for electron microprobe instruments operated in various modes and configurations (L12). Both spatial information and chemical identity for individual ions removed from the sample surface are available from a new field ion microscope with a osition-sensitive detector (L13). Various electron beam and 8-ray microanalytical techniques have been utilized in new and improved methodologies to detect and quantify precipitates in steel (L14-Ll8). The need for rapid and accurate "soluble" and "insoluble" aluminum determinations (see Aluminum section, above) has highlighted the need for an umpire chemical method and reliable standards. This led one investigator to examine the solubility of various aluminum oxide compounds that occur in steel. Other parameters crucial to the problem (oxide particle size, temperature, the presence of the iron from the matrix, etc.) were also studied (L19). Twelve inclusion laboratories cooperated in testing two methods (electrolytic and acid dissolution isolation) for the determination of A1203,Si0 ,MgO, and FeO in low alloy steel. Spectrophotometric and methods were used to quantify the elements in the isolated residues (L20).Similar work by 13 laboratories for the determination of oxide inclusions in stainless steels was conducted (L21).Ten laboratories cooperated in testing a method for MnS in heavy rail steel (L22). A method for rare earth inclusions (and metallurgically dis-

K

ANALYTICAL CHEMISTRY, VOL. 63, NO. 12. JUNE 15, 1991

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solved rare earths) in carbon and low alloy steels has been developed. The method involves electrol ic isolation and s ctrophotometry using the Arsenazo-D F?C complex (1523). #e constituents of the carbide and y-prime hase isolates from nickel-base high-temperature alloys were letermined by means of an injection-flame atomic absorption approach ( L a ) .

SURFACE ANALYSIS

As in the previous section, here, as well, emphasis is placed

on chemistry at the expense of physical instrumental methods. For details on developments in surface characterization by Au er, ESCA, SIMS, and other similar methodologies, the reaier is ain referred to the Fundamental Reviews issue of Analytict?Chemistry in even-numbered years. This section covers both coatings and endogenous surface phenomena. Several ma'or review papers covering Auger electron spectroscopy, -ray photoelectron spectroscopy, secondary ion mass spectroscopy, Rutherford backscattering, ion scattering spectroscopy, sputtered neutral mass spectroscopy, and glow discharge optical emission spectroscopy have appeared in the last 2 years (MI-M6). The protective films produced by organic corrosion inhibitors have been studied by ESCA, Auger, SIMS, and LAMMA (M7).Passive films on iron, chromium, and their alloys were produced electrolytically, and then the specimens were transported under argon into the vacuum chambers of XPS and ISS instruments (M8). The plated layer on galvanized steel plates has been electrolytically removed in a water-methanol solution of ammonium nitrate, and the iron content of the zinc alloy layer was determined colorimetrically using the electrolyte (M9). X-ray fluorescence can be applied to iron determination and to determining adhesion in galvanized strip by measurin the Similarly, krRF same area before and after annealing (M10). has been used to determine the coatin weight of zinc phoshate films on steel by determining t i e zinc concentration TM11).The cathodic film on zinc plated steel sheet was dissolved in tetrahydrofuran, which is then evaporated and the residue ignited at low temperature. The residue is dissolved in nitric acid, and zinc is measured by flame atomic The Cr(II1) and Cr(V1) concentrations of absorption (M12). chromate layers on galvanized steel strip were determined colorimetrically and found to be practically free of Cr(V1) (M13).A combination of wet chemical analysis, infrared spectroscopy, and X-ray diffraction has been used to characterize zinc phosphate and manganese phosphate compounds as coatin s on steel and in the corresponding phosphatizing sludges (h14).Infrared spectroscopy is being used for the qualitative and uantitative analysis of thin inorganic and o anic f i whicpl me applied to steel for corrosion protection

k

(115). Glow discharge o tical emission spectroscopy has become

an important tool For surface studies of steel. One paper reviews its use in depth profiling of thin films and coatings. It can also be used to measure coating weights. Some applications described are the characterization of phosphate coatin s, oxide scale assive layers, and chromium-depleted zones b16). G D O dwas used for the depth-profile anal sis of zinc-iron and zinc-nickel alloy layers on steel sheet and for iron-nickel and cop rzinc on copper and iron (M18). In both studies, integrategmission intensities were used to obtain elemental coating weights. Glow discharge optical emission has also been used to depth-profile both carbon and nitr en in a recent study of nitrided layers in ure iron (M19). Anoxer recent paper describes the use of GD8ES to quantify elements in phosphate coatings on both cold-rolled and hot-dipped galvanized steel sheets (M20). GDOES has also been used to obtain elemental coating weights on terne steel and to characsheet electroplated with lead-tin alloy (M21) terize iron-zinc electroplate on steel sheets for automotive use (M22). X-ray fluorescence has been employed in surface studies to determine the thickness and to quantify the elemental com sition of electroplated la ers on steel. Coating weight can measured by recording eyemental intensities from two M24).Ellipsometry has been incident take-off angles (M23, used to measure the thickness of a film of hydrated chromium oxide on the surface of tin-free steel (M25) and to measure the thickness of assive films on austenitic stainless steels (M26).Ring-disi electrodes employed with stripping voltammetry have been used to determine the coating weight and

(d7)

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elemental composition of a number of electrode ited alloys, including NiFe, CoFe, NiSn, PbSn, CoCu, a n f i i C u (M27).

SAMPLING, SAMPLE PREPARATION, AND STANDARDS This rather eclectic section is united by the fact that the papers and patents described here are concerned with essential prerequisites to analytical measurement. A disk sampling probe was used to sample 100-ton pouring ladles before and after vacuum degassin operations. It was found that for optimum accuracy in t t e optical emission determination of carbon, manganese, silicon, sulfur, phoshorus, titanium, aluminum, and copper, 0.8-0.9 mm must polished off the steel surface (N1). A study has shown that a double-tube sampler for sampling molten steel for hydrogen determination is superior to the conventional quartz tube sampler. In the double-tubesampler, the hydro en normally lost during solidification is retained, yieldin v ues that are 2.5-3.5 times those obtained b the quartz t&e technique for certain grades of steel (N2). probe that has been used for basic oxygen fumace sampling yields a sample of two different thicknesses: 12 mm for spectrographic work and 4 mm for mechanical punching to produce pieces for carbon, sulfur,and nitrogen determination. Punching is performed with a pneumatic 10-ton press (N3). Another report describes a series of improvements to the samplin and sample preparation methods employed in a steelworfs. These include a rapid sampler for a continuous slab caster, a blast furnace slag sampler, a white pig iron sampler, and an automatic sampler for process plating solutions. Improvements in grinding and sievin operations are also described (N4).Another paper descri%esfour different sample molds used to roduce spectro raphic specimens from molten cast iron (55). !i review of errors related to the sampling of iron ores has been published (N6). Hi h carbon ferrochromium yielded better data for chromium tetermination when the sample was A new ground to a particle size coarser than 200 mesh (N7). and less labor-intensive method for sampling and reparing low carbon ferrochromium has been described ( 8). High carbon ferrochromium, ferrosilicon, ferromolybdenum, ferroniobium, and ferrovanadium have been prepared for X-ray fluorescence analysis by addin pure iron chi s and remelting in a high-frequency induction f m c e (N9). iron-titanium alloy used for hydrogen adsorption applications was oxidized, remelted, and then rapidly solidified to form a lassy specimen Anot er paper illusfor X-ray fluorescence analysis (NIO). trates the preparation of steel, p' iron, and cast iron samplea The e#ect of the loss of combined for spectrometry (N11). water and the oxidation of iron during lass bead preparation for X-ray fluorescence has been studief with iron ores (N13). Small diameter weld wires have been pressed into a flat solid suitable for X-ray fluorescence analysis. Comparison with remelted Sam lee showed better control of oxidizable alloy components A new method of sample preparation for gases in steel involves immersion of the sample m a nonconductive solution and cutting and polishing the specimen by using an electrical dischar e ap aratus that employs both cutting and polishing electrofes. $he technique avoids contamination by oxygen Mild steel samples (which are commonly and nitrogen (N14). stored in liquid nitrogen to revent the loss of mobile hydro en) were stored in EDTI, imidazole, and a commercial inhkitor with an active amino oup and tested for hydrogen content. Both imidazole and t f e commercial inhibitor minimized hydrogen pickup, while all three media decreased hydrogen loss (N15).A 1-g steel sample was digested under pressure at 150 O C for 40 min with a 1:1:3 mixture of hydrofluoric acid:nitric acid:hydrochloric acid in a Teflon-lined pressure bomb. The procedure was found to completely decompose all the aluminum content of the sample, includin oxide and nitride inclusions (N16).A variety of ore and smelter samples, includin blast furnace slag and chrome refractory, were dissolvedBby a standardized procedure involving sodium peroxide fusion in a zirconium crucible and acid dissolution of the cooled melt. ICP emission spectroscopy was employed in the analysis. Sulfur recovery was almost total (N17).Standard pig iron samples have been prepared by the melting of pure elements in an induction furnace. The molten material is poured into a cop er mold and then hot pressed. The standards prepared in si!t manner have been useful in

L!

i3

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refining X-ray fluorescence calibration curves (N18).High carbon steel standards were prepared by gas atomization of steel melts containing carbon at 1.5% and more. This a roach prevents graphite recipitation and im roves t e Komogeneity of carbon in t e resultant standar materials (N19).A aper that reviews the accuracy of the certified values of Ehmese standard reference materials has been published (N20).

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ATOMIC ABSORPTION For most steel making operations, atomic absorption spectrophotometry is not considered a sufficiently rapid technique for process control. It has an important place, however, in the verification of finished product analyses, in raw material testing, in the monitorin of chemical process solutions, and for air and water comp iance testing. In addition, electrothermal atomic absorption spectrophotometry has become the major technique in the f i i testing for residual levels of deleterious contaminants in critical end-use alloys. One review describes atomic absorption (and atomic emission) in its application to high-temperature alloy analysis (01). Sodium dodecyl sulfate was found to enhance the atomic absorption measurements of chromium and cop er and to eliminate the interference of iron and other ions in $e analysis Aluminum ion and chromium(V1) ion or aluof steels (02). minum ion and fluoride ion increased the sensitivity for titanium and vanadium using a nitrous oxide-acetylene flame. The additives also eliminated most interferences and increased the linear range of the calibration. The method was applied to low all0 steel and to titanium in an aluminum-chromium-iron J o y (03). Silicon in iron and nickel-base alloys was determined by a raphite furnace approach by using the method of standarcfadditions and calcium and lanthanum ions as matrix modifiers (04).Hi h alloy steel chips placed on a platinum substrate were diss8ved electrolytically. Tungsten and niobium were held in solution by the addition of tartaric acid and ammonium citrate. The method has been applied to the atomic absorption determination of trace levels of lead, tin, bismuth, and antimony (05). Methods for manganese, phosphorus, nickel, chromium, molybdenum, copper, vanadium, cobalt, titanium, aluminum, tin, lead, magnesium, calcium, zinc, bismuth, antimony, and tellurium were described in a Japanese publication (06). The use of pyrolytic graphite versus orous graphite furnace tubes in the electrothermal AA Zetermination of tin, antimony, lead, and bismuth was discussed in a recent paper. It was found that using electrospark dispersion to produce colloidal solutions of the steel sample allowed the porous graphite tubes to yie!d results equivalent to the use of acid dissolved samples in The spark-produced colloidal dispersion pyrolytic tubes (07). a proach to sample preparation for graphite furnace atomic agsorption measurement has been applied to nickel-based alloys, coppernickel alloys, and pure metals as well as to steels

f

(08,09).

Silver, bismuth, cadmium, lead, selenium, tin, tellurium, and zinc were determined in steels and superalloys by flame atomic absorption of methyl isobut 1 ketone extracts of the ion association complexes with iodiie and trioctylphosphine oxide (010). Arsenic and bismuth at levels between 0.5 and 200 ppm can be determined in steel by hydride generation atomic absorption. The effects of numerous method parameters were studied (011). Discrete nebulization of acid dissolved steel samples was employed to determine low levels of aluminum, antimony, arsenic, cobalt, lead, tin, and vanadium. The sensitivity for arsenic was increased by simultaneous nebulization of a sodium borohydride solution through Traces of manganese, one side of a branched capillary (012). cobalt, nickel, and copper were determined in iron ore by means of a solvent extraction AA a proach. The ammonium pyrrolidinedithiocarbamate com exes were extracted into meth 1 isobutyl ketone. The adchion of citrate (for cobalt, nicker and copper) and iron (for man anese and copper) prevented the coextraction of iron (01& While atomic absorption is usually associated with minor and trace elemental determinations, it is sometimes applied to major steel components. After dissolution in a mixture of phosphoric, hydrochloric, and nitric acids, sample solutions were evaporated to salta, cooled, and dissolved in water. Magnesium chloride, sulfosalic lic acid, and N-cyanoacylacetaldehyde hydrazone were ad&ed (to remove interference

P

from iron and silica) and measured by atomic absorption. The method was used to measure up to 2% manganese, 20% chromium, and 15% nickel (014). Manganese at 15-20% was determined by flame AA in a 15% chromium alloy. Careful adjustment of instrument arameters and closely matched standards was employed (815).

OPTICAL EMISSION Optical emission spectrometry, particularly in the form of the direct-reading polychrometer instruments, has been an essential technique for the steel indust? for many decades. Today, its utility as a rapid control tec nique, particular1 for the light atomic weight elements, remains unquestioned: And with the relatively recent commercial introduction of very stable high-temperature plasma excitation sources, optical emission techniques have extended their usefulness and versatility. One review of atomic emission applications to high-temperature all0 (which also covers atomic absorption) has been published ($1. Spectrographically measuring only the lowenergy portion of each spark discharge in the spark excitation of the sample has been shown to increase both the sensitivity and accuracy of the analysis. The method has been applied to the determination of carbon, hosphorus, sulfur, boron, and lead in steel (PI). Customizel excitation sources for areas of application include the high-energy prespark (HEPS) for major alloy components and spark analysis for traces (SAFT) (E?). An instrument system has been developed that accepts an unprepared solid sample. A robot prepares the sam le and presents it to an optical emission s ectrometer. Redigration is under computer control (P3). n a Swedish stainless mill, a robotically controlled argon-spark pistol and associated fiber-optic cable and spectrometer test about 60000 stainless plates/year. Total time is 30 s to identify the plate as one of about 100 grades of stainless steels (P4). An investigation to o timize the high-energy preexposure sparking of stainless steerwas conducted by using computer analysis (P5). Methods have recently been published for the determination of trace and low-level impurit elements in ferromolybdenum and ferrotungsten (p6)andin arsenic-bearing iron ores (p7)and for the determination of sodium and potassium in blast furnace slag (P8).The effect of matrix line interferences on the determination of sulfur in a cobalt-base superalloy has been studied in detail (P9).In other papers, the effects of sample the effeds of sample heat treatment (PII), temperature (PIO), and the use of a high-energy prespark (P12) were studied. The addition of wdered Teflon to powder samples with high iron, silicon, ancluminum contents was investigated for the dc arc determination of vanadium, titanium, and molybdenum (P13). The use of acid dissolved samples with inductively coupled plasma o tical emhion measurement is now a well-established methodoyogy that is in use throughout the world. Recent irons papers have described methods for low alloy steel (P14), nickel-based alloys (P16), and ferroalloys and steels (P15), (P17).A few laboratories now employ a system in which a high-voltage spark generates a metal aerosol from a solid sample; the aerosol is then swept by a flow of ar on into an ICP torch. One study for stainless steel showe a relative standard deviation of 0.48% at the 27% chromium level (P18). Another study examined the particles reachin the plasma by scanning electron microsco y and reveale that under optimal analytical parameters t L particles are aggregates of small (500-1500-& spheres (P19).A recent des@ system usea the se arate spark aerosol eneration in combination with a pulsef microwave-induce plasma. The system has been applied to the determination of nickel, manganese, and chromium in steels (P20).In another design, an atmospheric pressure capacitively coupled plasma both samples the solid specimen and serves as the spectral excitation (P21).The technique of hydride generation coupled to ICP optical emission has been applied in a multielement mode, in which trace levels of arsenic, bismuth, antimony, selenium, lead, tin, and cadmium in steel have been determined simultaneously. Further work is required, however, to optimize the technique (P22).Another study with multielement hydride/ICP measurement involved preliminary extraction of arsenic, antimony, and bismuth as the iodide complexes with methyl isobutyl ketone. The hydrides were enerated in the organic phase, diluted 1:l with formic acid. h#e' method was used for arsenic

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and antimon in a nickel-iron alloy (P23). A new design nebulizer/hy&ide generator system, incorporating a cyclone nebulizer, facilitates the generation of hydrides directly from organic media and has been used for arsenic and antimony determination of nickel-iron (P24). Anion exchange chromato raphy has been used to separate the components of nickef-base and cobalt-base high-temperature alloys, prior to measurement by ICP optical emission (P25). A temperature-controlled graphite crucible connected directly to an ICP torch has been used to determine trace quantities of nine elements (P26). Laser ablation has been used to generate aerosols for introduction into an ICP torch. The majority of the matrix interferences observed have been attributed to the ablation mechanism (P27).Precision is generally poorer than for spark emission (P28)but can be im roved by moving the sample to prevent a loss of focus of the &r beam (P29).The mobilization of stainless steel by laser ablation was studied (P30). The direct use of lasers to enerate sample spectra is under investigation by a number of workers. Optimum conditions are being sought in one study (P31),while another is using the technique to determine residual elements in scrap samples (P32). Another paper listed approximate detection limits of 0.002% chromium, 0.005% manganese, and 0.001% copper in iron and steel (P33). Glow discharge o tical emission spectroscopy is currently a very active area orstudy for both surface analysis (see section on this topic, above) and for ow tom ositional analysis. A three-electrode hollow cat ode disclarge lamp has been desi ned for the use of flat solid Sam les (P34). Manganese an8 chromium determination in steer has been attempted by using the dual-cathode-threeelectrode des* which separates the sample sputtering process from the excitation process. Modulation of a bias voltage which controls the sputtering process allows selective detection of the sample emission intensities (P35).Significant influence from the Sam le matrix has been documented in the determination of &con, carbon, phosphorus, sulfur, and vanadium In the analysis of medium alloy, high b glow diwh e (P36). ciromium, aghigh-speed tool steels, one study covers the kinetics involved in the sputtering of single elements and the relation of measured surface concentration and volume concentration (P37). Despite some shortcomings in regard to sample matrix effects, glow discharge emission spectroscopy shows considerable potential and has been used to determine 12 elements, with relative standard deviations spanning from 0.2% (for cobalt) to 2.0% (for carbon) (P38).

a

X-RAYFLUORESCENCE Modem high-speed steel production would not be possible without the computer-controlled simultaneous X-ray spectrometer. Similarly, sequential wavelength dispersive instruments have become an essential mainstay wherever time is not the critical issue. And ene dispersive units have made inroads in the competitive field r d o y sorting. The literature in this field centers around three areas: software, hardware, and practical applications. They will be considered in the following para raphs in reverse order (with allowances for some de ree o overlap). As with the other sections of this review wkch deal with instrumental approaches, for the most part only those papers that refer to multielement determinations will be considered here; sin le-element papers have been included in the appropriate e ement-specific sections. Three general review pa ers covering a plications in the area of high-temperature alroys (and other t i h-temperature materials) have been ublished. One covers t%e principles of X-ray fluorescence (&I, the second covers ener dispersive instruments (Q2),and the third covers wavelena dispersive instruments (Q3). Metallurgical treatments that produce vanadium, chromium, or tungsten carbide have been shown to affect the X-ray determination of numerous elements (P9). A fundamental parkmeters approach has been utilized to determine the major and minor alloying elements in nickelbased heat-resistin alloys. The calibration curves were obtained using a s m dsuite of standard reference materials, and the results were corrected by using theoretical a-coefficients. With the exception of aluminum, the relative standard deviations were all in the range 0.25-1.27% (Q4). The determination of carbon in steel remains an elusive problem that is under intensive study; la ered optical elements have been utilized with some success (&,Q6). Spotting an acid-dissolved

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sam le on a filter paper and analyzing the dried spot is an estahished approach for roducin "matrix-free" determinations. This method has$een appfied to the determination of neodymium, iron, and cobalt in a neodymium-iron-boron permanent magnet alloy (67) and, with the addition of a zinc internal standard, to nickel, chromium, titanium, and manganese in stainless steels and elastic alloy wires ( 8 8 ) . Highspeed steels were successfully analyzed by usi the DeJongh correction algorithm. Results were obtained or vanadium, chromium, manganese, cobalt, mol bdenum, and tun sten (89).Nickel-based heat-resisting d y s were analyzed y an acid dissolution/glass bead technique. Theoretical a coefficients were used to correct for interelement effects (910). Vanadium, silicon, phosphorus, manganese, and aluminum were determined in ferrovanadium by means of an oxidative fusion and the casting of a glass disk in a platinum mold (811). The effect of particle size distribution of iron ores on analytical results has been quantified and can be used to improve the accuracy of X-ray fluorescence data (Q12). Iron ores are typically either briquetted or fused for X-ray fluorescence analysis. One study showed that fusion with sodium tetraborate and casting a disk or pressing with a heated brass stamp yielded acceptable data (Q13). Other investigators found that with briquetted samples results were affected not only by particle size but also by the mineralogical influence of the a-F%03phaee (Q14). One study compared the resulta of X-ray fluorescence analysis of blast furnace slag and sinter (using pressed pellets) and wet chemical analysis (Q15). Electrosl remelting (ESR) fluxes containing rare earth elements as we as the slags they form in use have been successfully analyzed by X-ray fluorescence (816). A portable instrument for alloy sorting has been described. It utilizes a sealed gas pro ortional detector, a radioisotope source, and a programmabye microprocessor. Quantification is based on a modified Lucas-Tooth and price algorithm. The system has been used for sulfur in carbon steels and titanium and nickel in stainless steels. It is capable of rapidly sortin 7). A mercury(II7 stainless steels of similar composition (81 iodide detector has been tested for the determination of chromium, iron, nickel, niobium, and molybdenum in alloy and stainless steels (Q18). A scandium X-ray tube was compared to a rhodium X-ray tube for the determination of sulfur, phosphorus, silicon, aluminum, and carbon. Sensitivities obtained from the scandium tube were found to be twice those obtained from the rhodium tube (819). The scandium tube has been used to determine carbon over the range 0.76-1.23% in high-speed tool steels (620). A computer-based system for the quality control of XRF operations at a major U.S.basic steel producer's plant has been described. Inland Steel's East Chicago Works o rates three X-ray fluorescencespectrometers on an around-E-clock basis to analyze blast furnace iron and slag, sinter, iron pellets, and other furnace charge materials. Instrument data are archived in a data base management system, and rograms have been written to perform statistical analyses a n i generate plots that are useful both as a check on instrument calibration and to solve some production problems (Q21). In a basic experiment irregular particles of steel have been analyzed by embedding them in resin and measuring the analyte intensities, then slicin the resin into 0.5-mm sheets parallel to the plane of the d r a y beams and mapping the metal particles with an optical scanner. Fundamental parameter calculations are then used to obtain the count rates attributed to each pixel on the map (Q22). One aper describes the relationships between the correction coekcients in the Lachance, De Jongh and JIS (Japan Industry Standard) matrix effect algorithms (823). Based on theoretical models of the relationship between background intensity and matrix composition,a new technique for background correction has been applied to the determination of minor elements in stainless steels (Q24). Much current work focuses on the fundamental parameters approach to matrix effect correction. While known to be theoretically possible for many years, fundamental parameter calculations have only recently begun to realize their potential utility. Polychromatic primary X-ray excitation from the X-ray tube greatly complicates already formidable computations (825) that involve the instrument eometry, prim beam intensity, and other parameters. Pubfished work hayescribed the use of fundamental parameters for both wavelength dispersive and energy dispersive analyses of a number of sample types, in-

Y

%

Yl


in a single weight of high-speed steel was described. All were volumetric measurements, except molybdenum, which was measured colorimetrically (R18).Antimony, bismuth, cadmium, lead, tin, and zinc have been separated from an alloy steel matrix on Dowex 1x4 anion exchange resin. The ions are adsorbed from 1M hydrochloric acid-hydrobromic acid and desorbed with 1 M nitric acid (R19). Trace levels of arsenic, antimon , and bismuth were first separated as hyMISCELLANEOUS TECHNIQUES drides and then dtermined by anodic stripping voltammetry (R20). Arsenic and hosphorus were determined by voltamThis last section has been reserved as a “catch-all”for all metry of the molybtfotungstate heteropoly complexes when those notable papers that did not ap ear to belong in any of the arsenic concentration exceeds the phos horus concenthe preceding sections. An attempt {as been made to group tration. If phos horus exceeds arsenic, the pEosphorus comthem under a series of subheadings, but this ultimately gives plex is removezby extraction and measured spectrophotoway to the concluding Other Methods section, wherein the metrically, while the arsenic is measured voltammetrically unclassifiable are classified. (R21). A flow injection method for the determination of Several review papers seem to belon in this section; they hosphorus and sficon based on the formation of molybdenum include a summary of instrumental antchemical approaches h u e heteropol complexes has been applied to carbon and to the determination of bismuth, cadmium, copper, mercury, low alloy steel 6 2 2 ) . A review of flow in’ection methods that lead, antimony, tin, and zinc in (among other metals) steel, utilize ion pairing solvent extraction incjudes procedures for cast iron, and nickel-base alloys (RI). A similar review for manganese in steels and cobalt in tool steels (823). the determination of zirconium, hafnium, niobium, tungsten, Nuclear Methods. There are many pa rs in this category and molybdenum that covers nickel-base superalloys (R2)and that are concerned with elucidating morpglogical structures one for rare earths that covers steel, cast iron, and nickel in steel; these have been treatecblightly here and the reader su eralloys (R3) have also been published. is referred to the Fundamental Reviews issue for thorough hultielement Spectrophotometric Methods. Phenylcoverage. Chromium, cobalt, nickel, arsenic, zirconium, niofluorone forms temary complexes with tin, molybdenum, and bium, molybdenum, and antimony were determined simultitanium in the presence of CTMAB and dilute hydrochloric taneously in low alloy steel by instrumental hoton activation acid. By measuring the complex at five different wavelengths reaction as analysis, using 52Mnproduced by the “Fe &,p) (to decrease measurement error), the three elements have been an internal standard (R24). Aluminum, silicon, iron, mansuccessfully quantified in steel and modular cast iron (R4). ganese, and copper were determined in alloys, blast furnace A similar simultaneous approach has been applied to mo~ 1 %and other samples by neutron activation methods using lybdenum and tun sten complexes with hematein (R5) and a Am-Be source and either a cadmium filter or a paraffin to molybdenum and titanium complexes with phenylfluorone disk (R25). Twelve elements in low alloy steel were deterand Triton X-100 (R6). Low alloy steels and pig irons were mined by instrumental hoton activation analysis using 20analyzed for their vanadium and titanium content utilizing and 30-MeV bremsstrdlung radiation. The 20-MeV flux the complexes these elements form with N-BPHA (R7). encountered no interference reactions (R26). Limestone was Similarly, dual wavelengths are used to measure mixed commonitored for calcium content by using a y-albedo method plexes of tungsten (heteropoly-blue) and molybdenum (titawith a 141Amsource. Relative error was 1.72-3.63% of the nium phosphomol bdate) from alloy steel samples (R8). amount present (R27). The effect of particle size on the Niobium and tantafum in alloy steels were determined using y-albedo method for coal, limestone, and iron ore has been two complexing agents, salicylfluorone and 2-(5-bromo-2studied. A beam ener can be found for each material that pyridylazo)-5-(diethylamino)phenol,and a total of four Particle induced X-ray emission eliminates the effect wavelengths (R9). Vanadium and cobalt in all0 steels were (PIXE) using protons has been employed to determine indium determined by second-order derivative spectropiotomet of their complexes with 4-(1’H,1’,2’,4’-triazolyl-3’-az~-2- in steel for endodontics tools (R29). Manganese has been determined in spring steel, high tensile steel, mild steel, methylresorcinol (R10).Derivative s ectrophotometry was galvanized steel, and other samples b instrumental neutron also applied to the complexes that mogbdenum and tin form activation utilizing a 262Cfsource. 8wo different detection with o-chlorophenylfluorone and CTMAB (RII ). Titanium, modes to measure the %ln activity showed reasonably good zirconium, and hafnium have been isolated collectively by a reement (R30). Coke was pretreated with a solution of liquid ion exchangers; then titanium is determined as the dCe(N0S) and W e ( S 0 )2 and then used to carburize steel. perox complex (or by AA), zirconium as the alizarin red S A sample or the steel was then chlorinated to remove the metal compgx, and hafnium as the xylenol orange complex (R12). matrix and isolate the oxide inclusions that were measured Cobalt and co per and cobalt and nickel have been deterradiometrically to establish the de ree of coke ash contamimined in low J o y steels by differential kinetics measurements nation (R31). The application of hfossbauer spectrosco y to of the complexes formed with 3-(1’H-1’,2’,4’-triaolyl-3’ferrous metallurgy is covered in a recent review (R327. A azo)-2,6-diaminotoluene (R13). Cobalt and nickel have been statistical treatment of Mossbauer spectra from iron-chrodetermined separately in steel and ores b using a spectromium-nickel alloys has led to two methods for determining photometric procedure based on the comprexes with sodium the chromium concentration (R33). N-methylanabasyl-ru’-azo-2-naphthol-3,6-disulfonate (R14). Multielement Volumetric, Electrometric, and Related Mass Spectrometry. If there is an area poised for growth Methods. One paper described new procedures for trace levels in the analysis of steel, it is probably best represented by some of carbon, phosphorus, sulfur, and silicon in “clean”steels. of the newer mass spectrometric techniques. Inductively coupled plasma mass spectrometry (ICPMS), like the other Carbon was determined by nonaqueous titration and phosMS methodologies, shows high sensitivity and multielement phorus by first separating the analyte with activated alumina and then finishin colorimetrically,sulfur coulometrically after and by capability. It has been used for cobalt in steel (R34), combustion, ancfsilicon colorimetrically. Other rocedures using iron-base standard reference materials, spectral interwere also described (R15).Iron and cobalt were letermined ferences have been studied (R35). In a study with iron ore in Kovar and Alnico alloys by means of a successive volumetric standards, both sample and acid anion influences were ap roach. Iron(I1) is first titrated with EDTA at H 2; then evaluated (R36). A laser ablation-solid sam ling approach co!alt(II) complexed with either 1,lO-phenantfiroline or has been applied to ICPMS (as well as ICPO8S) and utilized 2,2’-bipyridyl is titrated at pH 4-5 with gold(II1) solution. for steels and slags as well as other materials (R37). By using Cop er interferes but is removed by electrolytic separation the laser ablation approach, background peaks are greatly (RI67. Titanium and vanadium were determined in vanadium reduced as compared to the solution ap roach (R38). Glow slags by first titratin the oxidized vanadium with ferrous discharge mass spectrometry (GDMS) [as been a plied to ammonium sulfate sofution to a 2-phenylaminobenzoic acid steel standard reference materials and in- rocess steepsamples. end point, then adding powdered iron to reduce the titanium Results are comparable to those from otter techniques, with to the +I11 oxidation state, and then titrating with potassium some exceptions that have been related to interference effects, dichromate solution to a neutral red indicator end point (blue sputter rate effects, and the oxidation of some refractory color) (R17).An analytical scheme for the determination of oxide-formin elements (R39). Spectral interferences due to tungsten, manganese, chromium, vanadium, and molybdenum the argon wo&ing gas can be circumvented by the use of neon

3

cludin steels (Q26, Q27), all0 steels [QZS), stainless ( 29) and hi&-speed tool steels (Q301 chromium-won-mckel oys (Q31), and ferromanganese and silicomanganese (Q32). Nonlinear correlation models have been successfully tested with iron-chmmium-nickel and iron-chmium-nickel-cobalt systems in which each component was determined over the range O-lOO% (Q33).

(b).

ANALYTICAL CHEMISTRY, VOL.

63,NO. 12, JUNE 15, 1901 79R


as an alternative. Lowering the argon ressure allows both ases to be used with nearly the same ebctronic parameters fR40). Spark source mass spectrometry (SSMS) conventionally employs two machined sample ieces as electrodes. One investigator obtained uivalent resu!ts for most elements in steel (and other materas) usin a sample and a counter electrode made of various materids ( M I ) . Other Methods. High-performance liquid chromatography has been used to determine chromium and cobalt in steel samples. The analytes are extracted into chloroform as the acetyl acetonates and reversed-phase separated on an ODS glass column using a methyl isocyanide/water (30 70) mobile phase. The eluted s cies were detected by a V(visib1e detector at 254 nm (fi2). HPLC has also found utilit for tb? anal sis of or anic brighteners and breakdown prducts in zinc p h n ba& (R43). A review of thermometric analysis techniques t i a t describes methods for chromium, molybdenum, titanium, and vanadium in ferrous industry materials has been published (R44). Diffuse reflectance Fouriertransform infrared spectroscopy has been used to characterize iron ores by computer comparison to data from well-characterized samples (R45).Laser induced fluorescence of the plasma plume from laser-ablated steel samples has been investigated in basic studies af laser microanalysis (R46).In such determinations of silicon, chromium, manganese, and magnesium in low alloy steel and other materials, the fluorescence intensity ratios were found to be independent of the matrix of the samples (R47).Manganese and nickel in zinc phosphate (hopeitel coatings on galvanized steel have been studied by using electron spin resonance (R48).

6

ACKNOWLEDGMENT I acknowled e Chemical Abstracts Service for providin access to STN &ernationaI to a d in the literature search use! in the preparation of thiswork. I thank Carpenter Technology Corporation for permission to publish this aper and Diane Dunkelberger who typed the manuscript. &st of all, I must thank my wife, Grace, for many long hours of patience with me. Registry No. Steel, 12597-69-2. LITERATURE CITED

INTROOUCTION (1) Straub, W. A. Anal. Chem. 1989, 61 (12), 14R-33R; CA110(26):24 1843g. 153-83 CA110(24):218638s. (2) Keto, K. m i W o 1980, 80 (I), (3) Prumbaum, R. Gbsserd 1989, 78 (23), 807-11; CAl12(12):110818m. (4) Kuz’mln, I.M.: PHm, Yu L.; Stepanovsklkh, V. V. Z e d . Lab. 1988, 55 (a), 5 - 9 CAl12(8):88704~. (5) Kllmckl. W. Zesz. Nauk. pdltech. Czestochow. 1988, 16, 171-8 CAI 12(22):209851d. (8)Schbbdd, K.; Puchlnger. A.; Krueger, F. New Hueite 1989. 34 (B), 2358; CAI 11(20):188329c. (7) Dyson, D. J. Fwty-Hgt chemfsts’ conk we me-^; Britlsh Steel: Grangetown, Middlesbrough. Cleveland, 1988; pp 21-31; CA112(10):90441c. (8) Tanino, M. Buns&/ 1989, (I), 80-5;CAI10(22):198922j. (9) Koch, K. H.; Ohls, K. Fresenlus’ Z . Anal. Chem. 1989, 335(7), 852-5; CA112(18):17118c. ( I O ) J. I . S.MmUak: kketalAnaW: Ironandsteel: Japanese Standards AMOC.: Tokyo, 1888;CA111(22):208402a. (11) Mwnt, C. R. AM/Y#c~~Tectm&3ueaIbr Mtwial cheracterlzetkn, RoOf InWnaHOnel Workshqp; World Sclentlfk Publlshhg: Slngapore, 1987; pp 281-4; CA111(14)126000d. (12) KlpSCh, D. Nws 1989, 34 (4). 141-3; CAI11(14):118645~. (13) Hato. T.; Aokl, M.: Tsuchlya, T. Bunsekl Kagaku 1988, 37 (1l), T1631170: CA11014\2714%(. (14) IstkaShl,-Y.iYo&&a, Y.: Satoh, S. Bunsekl Kapku 1988. 37(11), T 157-TI82: CA 11O( 12)107238e. (15) Verspohl, T.; b m h f f , R. Stah/ €/sen. 1988, 108 (24). 1211-4; CA 1101 . - 14k ~.,.. 1 . 1QO 1.In .... ( r e i ’ VWSPOM,T.; Kamphoff, R. T&. MM. ~ N p 1088. p 46 (I), 31-42 CAI lO(20t184837e. (17) VerSbhl, T.; Kamphoff. R. APT, kketal. Pbnt Techno/. 1988, 1 1 (8), 81-4; CA 1lO(20): 177217s. (18) Brauner, A.; Scheufbr, R. FacMw. Wsttenpax. MetaklvdtcKvererb 1988, 28 (lo), 914-16; CA110(12):89428v. (19) Zk(lIl.9. Wedzel, R. Hum. Lbty 1989, 44 (7), 503-5; CA112(2):15818n. (20) Lunner, S. E. FOTty-lkBt m t s ’ cOnlsrsncs-hcedngs; Brltlsh Steel: &aWetOWn, h#ddbSkOugh, Cleveland, 1988;pp 109-13 CA111(18): 186472r. (21) Mchard, G. S W Thus 1988, 218(5),245, 248; CA109(24):221425p. (22) Brauner, A.; Drekbach, V.; Scheutfisr, R. St& Thnes 1988, 216 (5), 248; CA10@(26):243144y.

s.;

80R


63,NO. 12, JUNE 15, 1991

(23) pusch, G. Mstahmhlhm# 1989, 43 (2), 38-8 MA22:23-0780. (24) Budtley, F.; Ramsey, M. H.; Rooke, J. M.; Hughes, H.; Norman, P. J . Anal. At. Smhn.1988, 3(6),203R-254R; MA22:23-0800. (25) EngUsh, G. R. M. FOCWX+Y Trade J . Int. 1988, 11 (3), 23-4, 26; MA2223-0201. (28) (Lelewdta. K.; Gaudnlk, J. Rz@. Spawahktwa 1988, 60 (g), 13-4; MA2223-0591. (27) Johansson, 0. Forty-fkst chemists’ Contefence-Rocedngs; Brltlsh Steel: GranQetown, Mlddlesbrough, - Cleveland, 1988; DD 115-20; MA2323-0049: (28) LI, J. Ye/in FMxi 1987, 7 (I), 83-5; CA112(24):228684t.

ALUMINUM (AI) Kalmar, E. Hung Tdps 1988, Hungary, HU 45817 A2. 28 July, 1988; CAI Io(20):185086g. (A21 Kbckenkaemper. R.; Koch, K. H. X-ray Specbwn. 1989, 18 (4), 17781;CAI 12(12):111075d. (A31 Gamage, C. F.; Tuscher, W.; Bassln, M. A. Fachber. Huenenprex. kket!?Mwe&mera&. 1988, 27(5), 397-8 CA111(8):81516e. (A4) Ravakre, D. Cah. Int. Tech.lRev. Metall. 1989, 86 (4), 351-80 CAI 12(18):150788z. (AS) Shevchuk, I.A.; Doroshenko, A. 1.; Alemasova, A. S.; Kovalenko, E. A. Z e V O d . Lab. 1988, 54 (9), 49-50 CA110(18):148779~. (A6) Naka, H.; Kwayasu, H.; Inokuma, Y. Bun&/ Kageku 1890, 39 (3), 171-5; CAI 12(22):210179~. (A7) Deguchl, M.; Ozono, J.; Kltabayashl, T.; Morlshlge, K.; Okamura, I. Ksnkw Mk&u-WOShh DabSkU KoaekubU 1988, 37 (1). 91-4 CAI 11(12): ioeiesq. (A8) ti, S.; Lw, H.; He, X . ; Zhang, a. Yejn Fenx/ 1987. 7 (I), 24-6 CA112114k -~ , 13132Oh. - --. (A9) Kurbatova, V. I.; Foklna, L. S.; Zakharova, T. N. Z e d . Lab. 1988, 54 (9). 3-5: CA110~16):148775t. (Al’Oj’ ”ng, C. i#ni Jhnyan, Huaxue Fence 1989. 25 (l), 2 0 CA113(2): 1707%. ( A l l ) Zhang, Y. L h a JIenyan. Huaxue Fence 1989, 25 (3), 167, 168; CAI 13(2)37072z. (A12) Basergln, N. N.; Zlbarova, Yu. F.; Zharova, V. M.; et al. Zevod. Lab. 1988, 54 (5), 22-4; MA2223-0184. ANTIMONY

(A13) Gomez, M. M.; Jlmenez, M. C.; Jlmenez, J. L. Rev. Metal. (Mew) 1988, 24 (5). 327-30; CAI 12(8):88902g. (A14) Lexa, J.; Stullk, K. Huh,. Llsty 1888. 43 (7), 495-7; CA110(18):18515%. (A15) Gong, G.; Wang, A.; Wang, H. Fenxl Huaxue 1989. 17 (S),524; CA 112(10):90727a. (A18) Uu, S.; Wang, Y. Yew Fenxi 1987, 7(2), 21-4; CA112(14):131394k. (A17) Kang, R. kbe/ W a n Daxue Xuebao. Zkan Kexueban 1988, (3), 88-93; CAI 1l(l8):145898~. (AM) Kang, R. Lhua Jhnyan, Huaxue Fence 1988, 24 (2), 87-8; CA113(4):34008y. (Al9) Ando. J. Kenkyu M&u-Kanagawa-ken Kogyu Shkensho 1989, 60, 50-2 CA113(2):17107q.

ARSENIC (A201 Xuan, W. Fenxi shlyenshi 1988. 7 , (12), 40-2; CA111(26):248993b. (A211 Garcla, A. M.: Sanchez, U. J. E.: Sanz-Medel, A. J . Anal. At. SpecIrom. 1989, 4 (7), 581-5; CA112(18):150910~. (A21a) Rlby, P. G.; ) 4 r s Y , S. J.; Qrzeskowtak, R. Pmwdnga of 4th Wennhl NaUonal Atomlc SpOCtrOecopy S y ” . ,/. Anal. At. Spechn. 1989, 4 (2), 181-4; MA2223-0791. (A22) Guan, C.; Xiao, W.; Xlao, C.; Liu, J. Ye/h Fenxi 1988, 8 (4), 47-8; CA112(4):299983h. (A23) Chen, L.; Fang, B.; Zhao, 0.;Wang, 2. Fenxl Shlyanshl1988, 7 (IO), 24-6; CA111(28):248977z. (A24) Xiao, M. U u a J&nyan, Huaxue Fence 1988, 24 (I), 19-20. 22; CA 112(28):245 1 9 b . BISMUTH

(A251 Yu, D. Ye/h FenXll988, 8 ( 5 ) , 18-21; CA112(8):68871w. (A281 Su, F. Ye/h Fenxi 1988, 8 (2), 9-12 CAI 12(4):2998Oe. (A27) U, X.; Ma, X . Fenxl Huaxue 1988, 16 (9), 797-800; CA110(24):224802a. (A281 Kulvdtova, H.; Stefanldesova, V.; Benetsky, M.; Tomlk, 8. Hum. Lbty 1988, 43 (1I), 805-7; CAI 11(22):208277p. (A29) Uvarova, K. A.; Zubtsova. T. J.; ChagkQalklna, T. S. Z e d . Lab. 1988, 54 (9), 6-10; MA22:23-0337. (A30) Flylo, 0. B.: Perelra. C. M. Quim. Nova 1989, 12(2), 142-7; C A I I S (4):33929q. (A31) Xuan. W.; Chen, M. Ye//n Fenx/ 1989, 0 (21, 38-9; CA112(24):22878). BORON

(A32) Amkose, A. D.; brine. M; Staats,0.: Welchart, E. S W R e s . 1989, SO@), 383-9; CA112(12):111046~. (A33) Lw, Y. Yejh FsnXi 1988, 8 (3), 34-8; CA112(8):47815a. (A341 Ding, Y.; Luo, F. Yejh Fenx/ 1988, 8(1), 53; CA112(8):47804m. (A351 Ishlkuro, M.; Klmura, J. Buns&/ Kapku 1988, 37 (IO), 498-502; CA 109(24):22 1 4 8 0 ~ . (A38) Takeuchi, M.; Hosoya, M. Bunsekl Kagaku 1988, 37 (9), T92-T95 CAl0@(24):221544b. (A37) Ischenko, A. V.; Stashkova. N. V.; Thnoteus, Kh. R.; Fsdsrova, S. F. Z e d . Lab. 1988, 54 (IO), 5-8 CA111(18)168335~. (A38) AmbrO88, A. D. F-th m t s ‘ Conference--; Brjtlah steek &angetown, Mlddlesbrough, Cleveland, 1987; pp 89-77; CAI 11(14):125907t.

STEEL AND RELATED MATERIALS (A39) Cao, X. YeJn F m l 1087, 7 (3), 48-7; CA113(2):17029r. (A401 He, A. Uwrr, Jlanven, Huaxue Fence 1088, 24 (l), 17-9; CA113‘ (4):33998m. (A41) Un, H, F m l ShlySnsM 1088, 7 (4), 57; CA111(22):208352). (A42) Pam. V. A.; s ” m k o , K. A.; Kuzyakov, Yu. Ya. Zh. Anal. K h h . 1088. 49 (5). 832-8; CA109(29):24314&. ( A W P a m , V. A.; softmmnko, K. A,; Kuzyakov, Yu. Ye. Zh. Anal. K h h . 1080, 14 (a), 1382-7; CA112(20):190870k. (AM) Jun. 2.; OShha, M.; Motomlru, S. Bun&/ Kagaku 1088, 37 (12), T228-T231; CAI 10(12):107284). (A451 MotOdzu, S.; M k n e , M.; Jun, 2. Analyst (London) 1000, 115 (4), 389-92 CA112(28):245254~. (A481 Jiang, Y.; Yao, J.; Huang, 8. Feml Shlyanshl 1088, 7 (12), 21-3 MA2223-0279. (A471 Ma, X.; Lu, C. Y e h FenxllO80, 9 (l), 17-21; CA112(8):88878d. (A481 Yen, G. Huaxue ShlM 1980, 30 (9), 405-7; CA113(4):33972y. (A49) Klute. W.; Flock, J.; Ohls, K. Fresenhs’ 2.Anal. Chem. 1088, 331 (7)- 897-708; MA22:23-0095. CALCIUM (81) Vrbenska, H.; Opravii. 0. Zvaracske Spravy 1080, 39 (l), 18-21; CAll1(28):247091t. (82) sheo. G.; U, J. Ouenopuxue Yu Gui?ngpu Fenxl 1088, 8 (5). 25-9; CA 111(14)128012). (83) hOkwnrr, Y.; Endo, J. 8lrnsekl Kagaku 1088, 37(10). 493-7; CA110(4):33081p. (84) YU, 0. Yew Fenxl1087, 7(2), 12-5; CA112(12):111100h. CARBON (85) Matsumoto, Y. Jpn. Kokal Tokkyo Koho 1980, Japan, JPO1013440 A2, 18 Jan, 1989, Helsei; CA111(24):224514u. (88) Sugknoto, K.; Aklywhl, T.; Kondou, T. Bunsekl Kagaku 1088, 37 (1I), 589-94; CAl10(10):87809~. (87) Ma-, R. W. Fwtklh chemlpts’ confwcMce-Pr-; Britlsh Steel: &angetown, Mlddbsbrough. Cleveland, 1987; pp 81-3; CAl11(14):125908u. (B8) Eretar, D.; Qdmaraer, N. L. 8mz. psdydo PI 1088, BrarH. BR8808299 A, 5 July 1988; CA110(10):87884f. (BO) Koedtl, I.; Hatakeyama, J. Jpn. Kokai Tokkyo Koho 1088, Japan, JP83154987 A2. 28 June, 1988; Showa; CAl09(28):243249m. (810) YOU. Q.; Wu, T. Yew Fenxl 1080, 9 (I), 34-6 CA112(8):88882a. (811) Xle. S.; Wng, F. Yejh Fenxl1987. 7(2), 58-9 CA112(14):131398q. (812) Ywhikawa, H.; Iwata. H. 8unsekl Kamku 1080. 38 (a), . . 389-94 . CA112(12): 111OlSj. (813) KuCeuml, H.; Ywhlori, T.; Tanaka, T. Anal. Sci. 1080, 5 (11, 95-100; CA111(4):32825z. (814) Chen. J. S.; Berth. U.; Qrellath, E. Fresenlus’ Z. Anal. (7”. 1989, 334 (2), 154-7; MA23:23-0127. (815) m n , Y.; Talbal. W. Yej/n Fenxl 1989, 9 (l), 34-8; MA22:23-0651.

CHROMIUM (818) U, C.; Few, A. Yejh FenxllO88, 8 (3), 8 0 CA112(6):47818s. (817) ZlWng, H. fmlW Tmmo 1088, 7(3), 80-2 CAl10(10):87582c. (818) Bslknl, N. L.; Mak, M. E.; Roso, E. Bd. Soc. Q u h . Peru 1088, 54 (3). 187-200 C A l 1l ( 14):126017q. (819) RuSOinov. I. K.; Pashadzhanov, A. M. Azerb. KMm. Zh. 1088, (2), 138-43; CAl12(8):89008e. (820) Castltlwo, J. R.; Mk, J. M.; Bendlcho, C. J . Anal. At. Specbwn. 1089, 4 (l), 105-8; CA110(28):241741n. (821) -0, X.; Llu, X.; Zhang, R.; Hu. 2. Huaxue 1088, 10 (3), 173-4; CA 110(10):87585f. (822) Sun, J.; h o , M.; h o , J.; Jlang, H.; Liu, a. Fenxl Shiyanshi 1088. 7 (3), 9-12; CA111(24):224343n. (823) Kong, F. Fenxl Shlyanshl1088, 7 (9). 81-2; CA112(8):88821e. (824) Yln, M.; sheo, G.; Chen, H. J. unlv. Iron Steel Technol. 1088. 10 (2), 283-70 CAI 10(24):224598d. (825) Bums, D. T.; Chlmpak, N.; Harrlott, M. Anal. Chlm. Acta 1080, 225 (l), 241-8; CA112(20):190880p. (828) Alba, F.; Estela, J. M.: Cerda. V. Qulm. Anal. (8arceha) 1088, 7(2), 219-30 CA111(12):108188k. (827) Pal, 8.;Chakrabartl, A. K.; Ahmed, M. J. U. M/kr&/m. Acta 1080, 1 (5-81, 393-401; CAll2(12):110983e. (828) Jb, N.; Yu, W. W ~ O ~ ) ~ H U 1000, ~ X U 7(2), # 71-3; CA113(8):51772n. (829) Kong, F. Lbua Jlanyan, Huaxue Fence 1088. 24 (2), 84-6 CA113(4):34005x. (830) Yln, M.; Shao. G.; Chen, H. 8eIlng Kejl Daxue Xuebao 1080, 11 (3), 270-6; CA113(8):70239k.

Wm

COBALT

(C1) Barhate, V. D.; Patll, M. R. Cum. Scl. 1089, 58 (e), 291-3; CA112(10):90737d. (C2) %llnar, F.; Berzas Nevado. J. J.; Esplnosa Mansllla, A. Anal. Lett. 1088. 21 (11). 2011-6 CAllM4B33074~. ( ~ 3 )&n, H.; ii, J. ~ & n g xudxiao HWXW xwbeo 1088, 9 (io), 10779; CAll0(20):185020n. (c4) Sun, Y.; W n , S. Y d h F ~ x1087, / 7(1), 27-9 CAl12(14):131403n. (c5) m n g ,M.; Chen, H. Lhua Jlanyan, Huaxue Fence 1080, 25 (4), 2192 0 CA113(4):33993f. (C6) Mvthy, 0.V. R.; Rsddy. T. S. Chlm. Acta T v c . 1080, 17(2), 189-94; CA113(2):17098n. (c7) Burns, D. T.; Chlmpak, N.; Hanlott, M. Anal. CMm. Acta 1080. 225 f 1). 123-8: CA 112f141:131450a.

COPPER

(Cg) Chakrabartl, A. K. J . Indlen Chem. Soc. 1080, 66(7), 497-8; CA112(18): 171187v. (C10) Aries. J. J.; Jlmlnez, F.; Jlminez, A. I . An. Quhr. Ser. 8 1088, 84 (3), 340-5; CA111(8):49545f. (C11) Sosa, Z.; Perez Trujlllo. J. P.; Arlas, J. J. Ann. Chim. (Rome) 1088, 78 (9-10), 585-92; CA111(2):18806p. (C12) Xu, M.; Pan. 2.; U, M. Fenxl SMyanshl1989, 8(1), 4, 8-10 CA112(21:15672a. CCi3i Yln. Q.: Lln. J. Wuhan Daxue Xuebao. Zken Kexwban 1988, (4). . 1is-8 CAl12(10):90835u. (C14) Buhl, F.; Kanla, K. Chem. Anal. (Warsaw) 1987, 32 (S), 1005-12; CAll1(22):208285q. ( C W Sal, Y.; Qing, 0.Fenxi Shtyanshl 1088, 7 (4). 34-8; CA111(141: , 126032r. -..._ (cis) wng, y. Lihua Jlanyan, Huaxue Fence 1989, 25 (5), 302, 304; CA113(2):17084e. (C17) Uang, L.; Yu, R.; Uu, H.; Wang, D. Yein Fenxi 1989, 9 (3), 8-11; CA112(28):245135g. (c18) CUI. w.; b n Q , L.; Shl. H. Fenxl M x u e 1080, 17 (a), 746-9; CAI 12(24):228888f. (Cl9) Wu, D.; Xu. J.; Shao, P. Zhebng &ngxueyuan Xuebao 1088, 39, 68-72; CA110(2):17822g. (C20) Petrov. 8. I.; Lesnov, A. E.; Shchrov, Yu. A.; Golubeva, E. V. Zawd. Lab. 1088. 54 (8). 13-5: CA110(81:88693v. (C21) Zhu, Y:; H&&, S.; Long, Y.:Llu, H.; ieng, L. Geoden~Xuexlao HuXuebao 1989. 10 (5). 554-8; CA112(6):47719n. (C22) Jin. X.; Uang. M.; Wu, F.; Zhang, Y.; Peng, X. Yejln Fenxl 1080, 9 (3), 49-51; CA112(24):228884h. QASS

(Dl) Graule, K.; Gallath. E. Freseniw’ Z . Anal. Chem. 1900, 335(3), 299303; CA112(14): 131459k. (D2) Bebushkin, P. L.; Persits, V. Yu. Odkrytlya, Izobret. 1989, U.S.S.R., 8111495898 Al. 23 July, 1989 CAll1(22):208432k. (D3) BreCheiS. U.; Hopf. H. D.; Lehmann, J. W s . Ber.-Akad. W k . D.D.R. Zentraht. Festkwpe?phys. Werkstofforsch. 1987, 34, 45-7; CA112(8):40382g. (D4) Guo, Y.; Llu, Y.; Zhou. S. Yejin Fenxi 1088, 8 (3), 57-8; CA112(12):110951z. (D5) Chen, G. Fenxl Swanshi 1988, 7 (a), 47-9; CA111(18):188298p. (D8) Qukrtana, M. A.; Dannecker, J. R. ASTM Spec. Tech. Publ. 962 (hym n Embrimement); ASTM: Phlladelphla. PA, 1988; pp 247-88; CA109(24):214137t. (D7) Berman, D. A.; Agarwala, V. S. ASTM Spec. Tech. Publ. 962 (&&ogen Embrittlement);ASTM: Philadeiphla, PA, 1988: pp 98-104; CA110(8):50325v. (D8) Mackor, A.; DeKreuk, C. W.; Schoonman, J. ASTM Spec. Tech. Pub/. 962 (Hy&cgan EmbrftMement);ASTM: Phlladelphla, PA, 1988; pp 90-7; CA110(8):88656p. (DQ) Zhong, J.; Wen. G. Lbngbel Oongxueyuen Xuebao 1080, 58, 75-9; CA112(8):88912k. (D10) Nwtrova. V. S.; Kurbatova. V. I.; Endeberya. T. S. ”9, Isobret. 1089, U.S.S.R., SU1522094 Al, 15 Nov, 1989; CA112(18):171382e. (D11) Clzek, 2.; Borek, P. Czech., CS257512 81, 15 Feb, 1989; CA111(24):224487j. (D12) Satonova, L. G.; Rybakov, V. S.; Shamraeva, V. V. Zawd. Lab. 1988, 54 (e), 100-2; MA22~23-0327. (D13) Diamondstone, 8. I.; Fllnchbaugh, D. A. ASTMSpec. Tech. publ. 987 (Effect of Steel Menufacturlng Processes on the Qual& of 8earfnB Steels); ASTM: Philedelphla, PA, 1988; pp 191-7; CA111(8):61523e. (D14) &em, W. B., Jr.; Diamondstone, 8. I.; Hoo,J. C. ASWSpec., Tech. Pub/. 987 ( E M of Steel Menufactwing Processes on the OUeUty of 8earlng Sreels); ASTM: Philadelohla, PA, 1988; DO . . 198-210 CA111(16):1/5918a. . (D15) Mwlta, 2.; Ueda. M. Techno/. Rep. Osaka UnAr. 1088, 38 (1909-19293, 89-76 MA22~23-0472. (DW) Ye, X. H. Fenxi Shiyanshl 1980, 8 (4), 128-36; MA23:23-0227. (017) Andreani. A. M. Ann. Chim., Sci. Meter. 1988, 13 (8), 839-46; MA22:23-07 15. (D18) Thornton, K. Chemlcel Chracterkatfon; Institute of Metals: London, 1988: pp 81-123; MA22:23-0144. IRON

(Dl9) Ma, X.; Me. Q.; Song, L. Tatyuan Qongye Daxue Xueb~o1088, 19(2), 50-8; CA 109(28):243188p. (D20) M u , J.; Gong, M. Yej/n FenxllO87, 7(2), 31-4; CA112(18):150865f. (D21) Wang, Q. Yejln Fenxi 1088, 8 (4), 21-3; CA112(8):47825u. (D22) XU, M. Femi Huaxue 1980, 17 (3), 257-9 CA111(28):247018~. (D23) Ono, A.; Midorlkawa, M. 8unsekl Kagaku 1088, 37(11), T142-T147; CAI 10(18): 185178q. (D24) De Almelde, C.; Peters, P. C.; Narahashl, Y. 8mz. Ped& P I 1087. Brazil, BR 8802960 A, 17 Nov, 1987; CA109(24):22156Od. (D25) Osoklna, (3. N.; Tarasova, T. N. Obopshch. Rud. (Len-d) 1988, 33 (5), 27-9; CA111(18):188340~. (D28) Osoklna. 0. N.; Kostousova, T. I.Zawd. Lab. 1088. 54 (8), 6-9; CA 110(12): 107189k. LEAD

(El) He, D.; Zhang, J.; Yu, F. Yejln Fenxl 1088, 8 (5). 10-2; CA112(14): 131340q. (E2) NembOotMri, K. K.; Remakrkha. T. V. ImSan J. Techno/. 1080. 27(4). 20 1-5; CA 112(12):11095% (E31 Wang, W.; Wu, E. Yejln Fenxi 1087, 7 (3), 10-3 CA112(24):228858c. ANALYTICAL CHEMISTRY, VOL. 83,NO. 12, JUNE 15, 1991

81 R

STEEL AND RELATED MATERIALS (€4) Zhu, 2.; Un, F. Yem Fenxl 1987, 7 (l), 43-5; CAl12(14):131408r. (€5) b v , 0. N.; Oshmkov, S. V.; Petrov, A. A. Zh. Ml. Spsktrosk. 1988, 49 (2). 300-12; CAl10(12):107199p. (€8)Sun, W.; Chen, M. G u ” f u e Yu Quangpu Fenxl 1989, 9 (2). 56-7; CA112(26):245148m. MANaIIEsL (€7) Bums, D. T.; Chlmpalee, D.; Chlmpak, N. Fresenhs’ Z.Anal. Chem. 1988, 332 (5), 453-5 CA110(22):204707k. (€8) Buns, D. T.: Chlmpslee, D.; Chlmpalee, N. Anal. Roc. (London) 1989, 26(1), 11; CA111(8):89989a. (€9) Salhs, F.; Martinez-Vklal, J. L.; Gonzalez-Murcla, V. Bull. Soc. Chlm. 8 d g . 1989, 98 (e), 387-0; CA112(20):190872n. (€10) Mem, S. K.; Agrawal, Y. K.; Desal, M. N. Talanta 1989, 36(6).8757; CAl12(18):150853a. (Ell) Mattkz-Vklal, J. L.; Qonzakz-Parra, J.; Salinas, F. Microchem. J . 1988. 37(3), 241-5; CA110(8):50312~. (€12) Tuakhanova. N. 1.;TaHpov, Sh. T.; Tulyaganova, M. M. Uzb. Khim. Zh. 1988, 33 (2), 5-8; CA112(8):47888~. (€13) Burns. D. 1.;Chlmpalee, N.; Harrlott, M.; McKlllen, G. M. Anal. Chlm. Acta 1989, 217 (l), 183-6 CA111(8):89978~. (€14) Yang, 2.; Yu, R.; Gao, H. Nanjlng Daxue Xuebao, Zkan Kexue 1080, 25 (I), 57-83. 87; CA112(10):90788q. (€15) RaJurkar, N. S.; Phulsundar, A. B. J . Radhnal. Nucl. Chem. 1089, 137 (2), 135-43; CA112(18):17122Og. (€16) Rajeev; MuralMhar. J. X-ray Spectrom. 1989, 18 (5), 211-4; MA23~23-0455.

MOLYBDENUM (E17) Tang, 2 . Ye/h Fenxl 1989, 9 (3), 39-40 CA112(22):210028x. (€18) LUO,0.; LI, D. Yelk, Fenxl 1987, 7 (2), 34-6 CA112(14):131395m. (El9) LI, 2. Fenxl Shlyenshi 1988, 7(8), 13-5; CA111(22):208348n. (€20) Burns, D. T.; Tungkananuruk, N. Anal. C h h . Acta 1989, 219 (2). 323-7; CAI 11(24):22440%. (€21) Bergamln F l h , H.; Krug, F. J.; Rels, 8. F.; Nobrega, J. A.; Mesqulta. M.; Souza, 1. G. Anal. C h h . Acta 1088, 214 (1-2), 397-400; CA110flOI:E76lgV. ,. -,.-. - .- .. (€22) Das, M.; Patel, K. S.; Mlshra, R. K. Analuskr 1989, 17 (9), 538-9; MA2323-0440. (€23) oehkne, M.; Nlshizakl, Y.; Motomlzu, S. 8unmkiKagaku 1988, 37(10), 554-7; CA110(4):33085t. (€24) b u , 2.; b o , X. Taianta 1988, 35 (12). 1007-9; CA110(22):204734s. (€25) Shah. N.; Menon, S. K.; Desal, M. N.: Agrawal. Y. K. Anal. Left. 1989, 22 (7), 1807-17; CA112(12):111028p. (€28) Ray, C.; MaJee, S.; Das, J. Chem. Anal. (Warsaw) 1988, 33 (6), 917-23; CA113(4):34025d. (€27) Xle, N.; Chen, R.; Gao, D. Yejin Fenxl 1089, 9 (3), 14-7; CA112(28):245 137). (€28) Tarek, M.; Zakl, M.; ECZawawy, F. M.; AbdeCKader, A. K.; Abdalla, M. M. Anal. Sci. 1990, 8(1), 81-5; CA112(26):245228n. (€29) Zhang, R.; Zhang, J.; Wang, H. Lanrhou Daxue Xuebeo, Z h n Kexueban 1988, 24 (4), 154-7; CA112(28):245128g. (E301 Zhang, X.; Lu, J.; Zhu, J.; Zhang. 2. Fenxl Huaxue 1988, 16 (Q),8088; CA110(26):241725k. (€31) Toropova. V. F.; Polyakov. N. Yu.; Mal’tseva, I . I. Zavod. Lab. 1988, 54 (lo), 12-4; CA110(18):185179t. (€32) Toropova, V. F.; Polyakov, N. Yu.; Mal’tseva, I. I.zh. Anal. Khlm. 1988. 43 (Q), 1653-6 CA111(14):125881e. (€33) Yan, 0.; Lu, W. Yejin Fenxil988. 8(8),24-7; CA112(2):15890e. (€34) Wang, L.; Zhang, H.; Chen, R.; Wen, S. Yejln Fenxl1988, 8 (l), 50-2; CA112(8):47803k. (€35) Toropova, V. F.; Polyakov, Yu. N.; Mal’tseva, I. I.; Mlkryukova, E. Yu. Zh. Anal. K h h . 1990, 45 (2), 273-8; CA112(26):245239~. (E361 Bhaskare, C. K.; anage, K. N. J. Indian Chem. Soc. 1988. 65 (9). 858-80; CAI 10(8):88715g. (€37) Vlllanueva Camanas, R. M.; Martinez Mora, 1. D.; Ramls Ramos, G.; AhrarezCoque, M. C. 0. Thermochlm. Acta 1090, 158 (2), 215-24; CA 112(22):210158q. NICKEL

(F1) Lek, S.; Perameswaran, G. Bull. Chem. Soc. Jpn. 1989, 62 ( l l ) , 3783-5; CA 112(18):171234q. (F2) Sukhan. V. V.; Gdach. V. F.; Lokhan’ko, 1.M. M r . Khkn. Zh. ( R w s . Ed.) 1988, 54 (a), 847-9; CAl11(16):145871e. (F3) Tar&, M.: Zakl, M.; Sedra, M. N. R.; Attlya. S. M. J . Chem. Techno/. Bktechnd. 1989, 44 (2), 155-82 CA111(14):128003g. (F4) Yang, K.; Sun, C. Ye/h Fenxl 1988, 8 (9, 13-5; CA112(8):88869b. (F5) S h , H.; U, W.; Ye, J.; Pan. X.; Jbo, F. Fenxl Huaxue 1988. 16 (l), 89-72; CA110(20):185013n. (F8) Sanchez. M. J.; Rodriguez, M. A.; Garcla-Montelongo. F. Anal. Left. 1989. 22 (Q),2075-82 CA112(20):190892~. (F7) Sakal, T.; Ohno, N.: Ichlnobe, N.: Sasakl. H. Anal. Chlm. Acta 1989, 221 (I), 100-15; CA112(8):88043~. (Fa) Garcb-MontebwO, F. J.; Sanchez, M. J.; Rodriguez, M. A.; Francisco, A. Ann. CMm. (Rome) 1989, 79(1-2), 59-71; CA111(18):1459371. (FO) Zhang, F.; X k . 2. Fenxl Huaxue 1988, 16 (8),729. 730-1; CA110(20): 185028~. (F10) Shen, H.; Li, J.; Zhang, J. Fenxl Shlyanshl 1988, 7 (2), 1-4; CA111(2433224332h. (F11) Wang, Y.; Yang, 0.; Llu. H.; Duan, Y. Fenxl Huexue 1989, 17 (a), 720-3; CA113(2):17035q. (F12) Zhang, Y.; Zhang, 0.; Han, X.; Wang. J.; Wang, X. L/hua Jianyan, Huaxue Fence 1988. 24 (l), 7, 8 , 1 2 CA113(8):70247m. (F13) Kumer. A.; Jorhl, A.; Shukla, R. K. Zh. Anal. Khlm. 1990, 45 (3). 557-61; CA113(2):17139b.

82R


(F14) Zhang, T.; Xu, D. LYnre Jlanyan, Huaxue Fence 1989. 25 (l), 24-5; CA113(2):17080a.

NIOBIUM (F15) Jlng, H. Yejin Fenxi 1988, 8 (2). 12-4; CA112(8):88861t. (F18) Lu, X.; Li, H.; LI, H. Lhue Jlanyan, Huaxue Feme 1988, 24 (4), 190201: CA113~8):516901. (F17) Tao, F. Yejin F&i 1988, 8(4), 46-7; CA112(8):47827w. (FIB) Kurbatov, D. I.; Yanchenko, M. Yu. Zh. Anal. Khim. 1988, 43 (8). 1453-7; CA110(16):146768t. (Fl9) Sei, Y.; Qlng, G. L. 1.Fenxl Huaxue 1989, 17 (S),558-80 CA112(10):907332. (F20) Ramappa, P. G.;Ramachandra, K. S. Asian J . Chem. 1989. 1 (I), 19-24; CAI 12(20):190868r. (F21) Shen, N.; Zhao, H. Yejn Fenxl 1988, 8(8),15-7; CA112(8):88891c. (F22) Poljakova, K.; Kllkova, J. H m . Lkry 1989, 44 (5), 385-8; CAl11(26):247088x. (F23) Peng, S.; He. J. Fenxl Huaxue 1980. 17 (3), 288-8; CA111(26):247017y.

PnosPnoRus (F24) Berglund, 8.; Wlchardt, C. Forty-Nrst Chemists’ ConferenceRoceedllngs ; British Steel: Qrangetown, Mlddlesbrough. Cleveland, 1988; pp 99-104; CA112(8):47899~. (F25) Ramchadran, R.; Gupta, P. K. Talanta 1988, 35 (e), 853-4; CA110(8):50333w. (F28) He. X.: Xu. S. Ylnwona Huaxue 1989. 6 (51, . . 39-43; CA112. (24):228948e. (F27) Shlratorl, K.; Shirata, N.; Tanaka, A.; Sew,K. Bun&/ Kagaku 1988, 37 (1I), T138-Tl41; CA1lO(14):127728m. (F28) Huang, D.; Zhu, 2.; Zhang, 0. Lhua Jianyan, Huaxue Fence 1989, 25 (3),175-6; CA113(2):17074b. (F29) Novaro, E.; Pagnoul, R.; Tomelllnl, R. Analyst (London) 1989, 114 (lo), 1335-8; CA112(14): 131417 ~ . (F30) Masumto, K.; Yagi, M. J . Redbanal. Nwl. Chem. 1989, 130 (2), 243-50 CA111(24):2243890. (F31) Funabashi, Y.; Matsumura, T.; Harlmaya, Y.; Asel, S. Jpn. Kokal To&kyo Kaho 1989, Japan, JP01181150 A2. 23 June, 1989, Helsel; CA112(6):47950f. (F32) Staskova. N. V.; Safenova, 0. E.; Skazetdkrova, A. S. Frdb. ForSchungsh 8 . Metall. WerkStOfftech. 1988. (B266), 82-6 MA2223-0783. (F33) Hongyao, C. Yejin Fenxi 1989, 9 (2). 12-4; MA23:23-0172.

-_ -

RARE EARTHS

(G1) Soflllc. T.: Malikovic. 198%. 18ll). . . 0. X-Rev. SDectrom. . , .. 25-9: CA111‘ (18):188392q. (G2) Inokuma, Y.; Endo, J. Bunseki Kamku 1988. 37(10). 503-8; CA110(4):33082q. (m) Ma, J.; Wang, Y.; Wu, Y. Ye/in Fenxl 1987, 7 (I), 38-9 CA112112k ,.-,.11 . .1 .103m .- -.... (04) Vozzella, P. A.; Condn, D. A. Anal. Chem. 1988, 60 (22), 2497-500; MA22:23-0 169. (05) Kaptabv, E. A.; Dogadkin, N. N.; Kuchlnskaya, 0. I.Zavod. Lab. 1889, 55 (12). 38-9; CA113(8):70284~. (G8) Uu, W. YeJn Fenxi 1988, 8 (5), 81-3; CA112(8):88874z. (G7) Kosturlak, A.; Gyepes, E. Acta Fac. Rerum Net. Unhr. Comnianae, Chim. 1987, 35, 133-47; CAllO(l2):107235~. (G8) Yao, J.; Zhu, T.; Ll, M. J . &ding Unlv. Iron Steel Techno/. 1988, 10 (l), 107-12; CA110(16): 148783~. (G9) Botella, J.; Baena, J. M.; Almohalla, T. Rev. Metal. (MeoHd) 1988. 24 (41, 271-5; CA111(20):188462r. (G10) Dal, L. Ye/ln Fenxl1988, 8 (9,37-40; CA112(8):47839b. (G11) Zhang. H.; Llang. Y. Zhonggtm Xitu Xuebao 1989, 7 (2), 88-8; CA112(12):1110911. (G12) He, J.; Qi, M. Yankuang Ceshi 1988, 7 (3), 207-9; CA111(24):2243 191. (G13) LI, S.; JI, D.; Wang, S.; Ren, J. Lhua Jlanyan, U x u e F e w 1988, 24 (l), 36-7; CA113(2):17089k. (G14) Wang, X.; Zhao, 0. Fenxl Huaxue 1988, 16 (l), 49-51; CA110( 18): 185218~. (615) Zhena. H.: XU. J. Zhonwuo Xitu X W ~ O1988.. 6 (4). . 89-90; CA111‘ (18):188$44a. (G16) brig, 2. Fenxl Shlyanshi 1988, 7 (11). 63-4; CA111(24):224387y. (G17) Xle, N.; Zhu, C.; Yu, X. Yejln Fenxi 1980. 9 (21, 24-7; CA112(24):228874e. (GIB) Pan, J.; Yang, R.; Xu, 2. Yejln Fenxl 1989, 9 (3), 5-8; CA112(281:245134f. (Gr‘9) ’Dal. H.; Guo, M. Yejln Fenxi 1987, 7 (l), 71-2 CA112(28):245119e. (020) Zhang, T. L h a Jianyan, Huaxue Fence 1988, 24 (9,303-4 CA113(8):51883). (G21) Del, H. Llhua Jianyan, Huaxue Fence 1088, 24 (l), 24-8; CA113(4):340008. (022) Zhang. H.;Li, X. Huaxue Shli 1989, 11 (8),323, 327-32; CA113(4):33897c. ’

--

I .

SlLlCW

(G23) Chen, T. Yejin Fenxl 1988, 8 (5), 80-1; CA112(8):88873y. ((324) Wana. B. Yeiln Fenxl1988. 8 (1). 8-11: CA112(8):88848s. iG25i Ptusklna, M: N.; Kryakhtunova, N. V. Vestn. Len/&. Unlv., Ser. 4 : Flz. KMm. 1990, (I), 83-7; CA113(4):34055p. (028) Li, M.; Zhang, H. L/hua Jianyan. Huaxue Fence 1989, 25 (I), 43-4, 49: CA112(24):228913s. (027). Matel. k. &cet. Mtal. 1987. 28, 349-52; CA111(24):224329n. (028) Nakamura, Y.; Yamaguchl, H.; Okochl, H. Trans. Net/. Res. Inst. Mst. (Jpn .) 1988, 30 (41, 234-9; MA23:23-0194.

STEEL AND RELATED MATERIALS ( a 9 ) Kochmula, N. M.; Bondarenko, A. I.Z e d . Lab. 1989, 55(4),41-4; MA2323-0023.

“IUM ((330) SU, J.; U, G. YO@ F W l 1989, 9 (3), 47-8; CAI 12(22):210032~. ((331) Uu, D.; Peng, B. Yejb Fmxl 1987, 7(1), 13-6 CA112(12):111102k. ((332) Llu. D.; Peng, 6.; Yang. S. Fenxl Wyenshl 1988, 7 (IO), 54-5:

CA111(24):224381r. ((333) theo. Y.; Ren, Y. Huaxue Xuebeo 1988. 46 (lo), 1035-8; CA110(18): 146814e.

SULFUR

(H36) Pandey. L. P.; Slngh, 6.; Padhi, K. K. J . Inst. Chem. ( I - ) 1988, BO (3), 101-2; CA110(8):68710b. (H37) Lopez Cancio, J.; Polo Conde, F.; Alemn Ruk, M. Qukn. AM/. (Bar&) 1988, 7(3), 331-9; CA111(18):188381k. (H38) Martinez-Videl, J. L.; (bnzalez-Pradas. E.; Vikfranca, M; Sallnes, F. Ann. Soc. Scl. Bnixehbs, Ssr. 1 1988, 101 (4), 165-72 CA111(8):49548g. (H39) Shah, R.; Mlshra, R. K. J . Indlen Chem. Soc. 1988. 65(11),818-17: CAI 11(8):69949u. (H40) Abbasi, S. A.; Hameed, A. S.; Nlpaney, P. C.; Soni, R. Amlyst(London) 1988, 113(10), 1581-5; CA110(14):127704~. (H41) Li, S.; Zhou, A.; Yang, X.; Dong, H. FenxiSh/yansh/1989, 8 ( 5 ) ,28-7, 39; CAI 13(8):70267t. (H42) Kavlentls, E. Anel. Lett. 1989, 22 (S), 2083-9; MA23:23-0190. (Ma) Pew, S.; Ruan, D. Lhua Jlanyan, Hu8xue Fence 1988, 24 (4), 197-8; CAI 13(8):70257a. (H44) Li, J.: Jing, T.’ Yeln Fenxl1988, 8 (3), 59; CA112(6):47815r. (H45) Xu, 0.; Yane, H. Fenxi Sh&enshi 1988. 7 (12), 33-4; CA112(2):15664z. (H46) Yu, J.; Wu, G.; Fan, X.; Hou, H. Fenxl Huaxue 1988, 16 (1 I), 1030-3 CAI 11(8):69987e.

((334) Zhane, 2.; Wu, X.; Ge,Y. Yejln Fenxl 1987, 7 (21, 89-70; CA112(22):2 1ooB8r. ((335) Lebedev, V. V. l e d . Lab. 1989, 55(8),98-100; CA112(4):29979t. ((338) Fontan, C. A.; Olslna, R. A. Telanta 1989, 36 (S), 945-9 CAII2114%131 - 389n. --((33’7) P w e z a , N.; Townshend, A.; Turner, P. S. Am/. Roc. (London) 1988, 25 (7), 244-6 CAI 10(18):148740C. ((338) Capah, T.; Szeja, K. R . Inst. Metal. Zsleu, 1988, 38 (3-4), 127-30 MA2223-0450. ((339) Lal, R.; Lal, Y.; Zhou, H.; Lin, Y. Lhua Jlenyen, Huaxue Fence 1988, 24 (8). 373; CA113(4):34019e.

2 I RCONIUM

TIN

(H47) Inokum, Y.; oide,A. BunseklKegeku 1988, 37(10), 514-8; CA110-

I

14t33063r.

(Hl) &ng, Y.; Lu, J.; Jln, X.; Chen, H.; Zhang, H. Yejln Fenxll988, 8 (5). 21-4; CAI 12(6):47836y. (H2) Peng, C.; Llu, M.; Ye, B. Fenxl huaxoe 1988, 16 (l), 43. 44-5 CAI 10(18): 165215b. (H3) Xlao, W.; Guan, C.; Zhang, J.; Qlu, R. Yejin Fenxl 1988, 8 (3), 31-3; CA 112(8):47810k. (H4) Yu, J.; Zeng, C. Lhua Jlenyen, Hwxue Fence 1989, 25 (2). 116-7, 119; CA113(6):51649c. (H5) Xu, 0.; Wang, 2. Fenxl Shly8nshl 1988, 7 (2), 17-9; MA22:23-0265.

TITANIUM (H6) Yln, D. Ye/h Fenxl1988, 8 (3). 45-8; CA111(26):24707k. (H7) Zhang. 2.; Liu, Y. Yejln Fenxl 1980, 9 (2), 48-7; CA112(22):210024t. (H8) Yang, J. YeB Fenxl 1988, 8 (3), 52-4; CAI 12(8):88857w. (H9) Yang. J. Lhua Jlanyen, Huaxue Fence 1988, 24 (4), 242; CAII3(4):34018b. (H10) Zhang. D.; Zeng, X. Fenxl Huaxoe 1989, 17 (e), 520-3; CA112(24):228835t. ( H l l ) Savarlar, C. P.; Vljayan, K. Telante 1989, 36 (IO), 1047-9; CA112(22):210049e. 0412) Li, S.; Zhang, H.; -0, D.; Ma, X. Llhua Jlenyan, Huaxue Fence 1989, 25 (3), 130-1; 164; CAI13(2):17087b. (H13) Ouyang, Y.; Cai, W.; Zhou, Y.; Xu, J. Fenxl Shlyanshl 1988, 7 (3), 12-4; CA111(24):224344p. (H14) Yang, 2.; Cheng, 0. Fenxl Shlyenshi 1989. 8 (2). 1-4; CA112(14): 131359~. (H15) Sanchez Batanero, P. Elechaemlysls (N.Y.) 1989, 1 (2), 181-4; CAI 11(18):145919b. (HI@ Zhang, C.; Lou, 0.; -0, P. Lhua JlanyEfn, Huaxue Fence 1988, 24 (5), 287-9; MA23:23-0473. (H17) Hlrshteld, D.; Thlerlg, D. Steel Res. 1990, 61 (5), 230-5; CA113(6):51755j. (H18) Xu, M.; Lei, Y.; Xu, Y. Huaxue Tongb8o 1988, 38 (4), 39, 54; CA110(8):8888 1t.

TU” (HI91 Aglanovlch, T. V.; Potklna, I.F. Frbbefg. Fwschungsh. B . 1988, B2B6. 79-81; CA112(4):29927~. (H20) Aglanovlch, T. V.; Federova, S. F. Zavod. L8b. 1089, 55 (4), 1-3; CAI 11(28):247023x. (H21) U, Y.; Wang, M. Ye@ Fenxll988, 8(4), 18-21; CA112(12):110952a. (H22) F. Yejh Fenxl1988, 8 (2), 58-9 CA112(8):68883~. (H23) Dlng, M.; Xla, D.; Wang, F.; He. Y. Fenxl Wyenshl 1988, 7 (2), 58; CAI 11(22):208345j. (H24) lataav, 0. A.; Abdukev, M. Sh.; Basargln, N. N.: Rozovskll, Yu. 0. OWWa I Z & O t . 1989, U.S.S.R., SUI503009 AI, 23 A g , 1989; CA112(8):89043q. (H2.5) y a g , J.; Del, G.; He, Z. Lhue Jleny8n. Huaxue Fence 1989, 25 (5). 284-6; CAI 13(2):17083d. (H26) Rajurkar, N. S.; Zlnjad, D. G. J . R e d b m l . Nucl. Chem. 1988, 127 (5), 333-40 CA109(24):221524~.

m,

VANADIUM

(H27) Wang, L.; Chen, R.; Wen, S. Yejin Fenxll987. 7 ( 1 ) ,48-50 CA112(4): 1314081. (H28) m n g , C.; Gu, Y. Fenxl Shiyenshll989, 8 (5). 17-9; MA2323-0165. (H29) Li, Q. Lhua Jlenyen, Huaxus Fence 1988. 24 (2). 83-4 CA11314k34004w.

( ~ i-zotou, ~ i A. c.; Papadopoulos. c. G. AIWWS~(London) 1990, 115 (3), 323-7; CAI 13(2):17133~. (H31) &u. Y.; J,’ H. ~ h u aJlenyt?n, HUXW Fence 1989, 25 (3), 180 CA113(2)17075c. (H32) MarUnez-Videl. J. L.; Gonzakz-Murcla, V.; Sallnas, F. Indlen J . Technol. 1989. 2719). 451-3: CA112118%1712190. (H33) Padhi, K. ‘K:; Panddy, L. P ’ N k Tech: J . 1988, 30 (I-4), 3-5; CA 112(10):90777s. (H34) Mertkrez-Videl, J. L.; Gonzabz-Parra, J.; Sallnas, F. Mlcrochem. J . 1988, 37 (a), 248-50; CAI 10(10):87585Z. (H35) Panday, L. P.; Slngh, 8.; Padhi, K. K. J . Ind/an Chem. Soc.1988, 65 (I 1). 817-8; CA111(4):32802q.

(His) ’ Llao, Xu, 2. Fenxl Huaxue 1989, 17 (7), 642-5; CA112112):111037t. (H50) ’Ramppa, P. G.; Manjappa, S. J . Inst. Chem. (I&) 1989, 61 (2), 47-8; CAI 12(22):210021q. (H51) Xu, J.; Wang, X.; Wang, H. Yejln Fenxl 1987, 7 (3). 19-21; CA112(24):228860x. MISCEUANEOUSANMYTES (11) Devev. P. J. A m / . Chlm. Act8 1989, 219 (2). . . 335-8: CA111(22):208381t. Unh. Iron Steel Techno/. 1988, 10 (3), (12) Yu, 2.; Huang. 2. J . 385-90; CAI 10(22):204748~. (13) Slmpson, R. T. At. Spectrosc. 1989, 10 (3). 82-4; MA2223-0588. (14) Sato, S.; Tanaka, H. Telanta lB89, 36(3), 391-4; CAl11(14):128037w. Hlavackova, H. M. Chem. Llsty 1989, 83 (S), 974-84; (15) Hlavacek, I.; MA23:23-0015. (16) Kobayshi, T.; Okochi, H. J. Jpn. Inst. Met. 1989, 53 ( l l ) , 1123-8; MA2323-0388. (17) Xlao, M. Lhua J&ny8n, HuaxueFence 1989, 25(1),8-10 27; CA113(6):51850w. (16) Guo, Y. Lhua J&ny8n, Hu8xue Fence 1988. 24 (3), 149. 156 CA113(4):33995h. (19) Xiong, J. Yejln Fenxl 1988, 8 (3), 20-4 CAI 12(8):47807q. (110) Luo. G.: Llu. S. Y e h Fenxi 1987. 711). 68: CA112(24):228853x. (11li R d n g , S.;Guiang, C.; Yanllng, L.”Yejh Fenxl 1980, 9 (2), 8-1 1; MA23:23-0171. (112) Pan@, L. P.; Slngh. B.; Padhi, K. K. J . Inst. Chem. (Indla) 1988. 60 (31, 99-100; CAI 10(10):87568j. (113) Wu. 2.; Hu, 2.: Jk, X. Anal. Chlm. Act8 1990, 231 (I), 101-6 1. MA23:23-050 .... .- ... (114) Llu, S.; Llu, 2. Oeodeng Xuexlao Huaxue Xueb80 1988. 9 (8). 774-9; CAI 11(8):89940j. (115) Wang, H.; Hue. P.; Yang, Y.; Zhang, A. Yejin Fenxi 1987, 7 (2), 62-3 CA 112(28):245 118d. (118) Mkaelyan, D. A.; Artsruni, V. Zh.;Khachatryan, A. 0. Arm. Khim. Zh. 1989, 42 (S), 568-71; CAI12(26):245208h. (1171 Kaleflchenko, T. Ya.; Sitka, A. I. ZeVOd. Lab. 1989, 55 (41, 16-7; CA111(28):247024y. (118) Carey, C. L.; Salter, P. Roc. Lime-Based Skgfomers, Reflnhg end Albyhg Powden, Cesting Mold Fluxes h Iron end Steel Industty Conf.; Press of Northeast University of Technology: Shenyang. 1988; MA23:230076. (119) M M , V. V.; Stdyar, A. A,; Chagan, A. V.; Polyanskii, D. S.; Osokin, N. A. Metak%g (Mascow) 1990, (1). 26; CA112(18):182473q. (120) Blktagtov, F. K.; Latah, Yu. V.; Levkov, L. Ye.; Voronln. A. E.; SbUC na, T. A.; Fetlsova, T. Rob/. Spets. Elekrometall. 1989. 5 (3), 8-11; CAI 12(12):102579~. ’

MISCEUANEOUS MATRICES (JI) Guo. H.; Chen, C. Ye/h Fenxl 1989, 9 (I), 59-60; CA112(8):888871. (J2) Chen, C.; OUO, H. Lhua Jlenyen, Huaxue Fence 1989, 25 (I), 28-9; CAI 13(2): 17081b. (J3) Andrew, B. E. Int. Corros. Conf. Ser., NACE-7(corrapkn InhlMHon) 1988, 185-92 CAI 12(24):228728k. (J4) Zura, L.; Gucds, A.; Kamradze, A.; Kukurs. 0. Law. PSRZlnat. Aked. Vestis, Kim. Ser. 1988. (5), 591-4; CA110(18):185172k. (J5) BysMtskll, A. L.: Bardln. V. V.; QI1Ikhes. M. S.; Drapkln, M. Ya.; Sokod k m 8 ,Izobret 1989, USSR, SU 1499189 Al, Aug, 1989 lOV. M. A. o CAI 11(22):199585h. (J6) . . Heberllno. S. S.: Carson. S.: CamDbeli. D. Met. F/nkh. 1989. 87 (9). .. 17-18, 20-2, 24-5; CA112(24):228681q. (J7) SOpok, S. R-. ARCCETR-88025; Order NO. ADA199410, Gov. Rep. Announce Index (US.) 1989, 89 (3) Abstr. No. 908778, 1988, AvaH. NTIS: CAI 11(18~:138805t. (J6) Hkbch, S.: kosensteln, C. Met. F/n/sh. 1988, 87 (1A) (Guidebook and Dlrectw), 549-79; MA22:23-0630. (J9) Bshrlnger, J; Evers, D.; Schoenert, D. Eur. Pat. Appl. 1989, Fed. Rep. Osr.. EP 300242 AI, 25 Jan, 1989; CA110(20):177548y.


83R

STEEL AND RELATED MATERIALS (J10) Msklakova, V. P.; Rychkova, V. I.; Kuznetsova, L. L.; Ratha, M. A. Zavcd. Lab. 1988. 54 (12), 19-21; CA111(20):186415c. (J11) Petetln, S. a h . Inf. Tech.IRev. &tan. 1990, 87 (2), 157-87; CA113(8):8297Ob. (J12) Hvo,K.; TwJknoto, J.; Kawatmra, A.; Wakida, S. oseke Kogvo w u S h k m Klho 1989, 40 (2), 93-102 CA111(28):237282S. (J13) Takaharl, T.; Dhtsuka, S. Tetsu to Mgnne 1989, 75 (I), 181-0; CA110(10):80111q. (J14) Tusset, V.; Hancert, J. Steel Res. 1989, 60 (0), 241-5; CA112(4):2997 1j. (J15) Iuchl, T.; HosMno, T. Roc. SPIE-Int. Soc. Opt. Eng. (Infrared Tech nOlosy 15), 1989, 1157, 309-17; CA112(28):245224k. (J18) Rentschler, R. G.; Draper, A. B.; Small, M. Trans. Am. fwndymen’s Soc. 1987, 95: MA2323-0389. (517) Indyk, L. I.; Melnk, V. V.; Nosenko, T. I. Zavod. Lab. 1989. 55(2), 41-3; MA22:23-0040. MOLTEN YEML ANALYSIS

(Kl) Sadti, M. BunsekllO88, (12), 912-7; CAl10(22):190912f. (K2) Fray, D. J. Roc. Conf. h48taM*gplcelprowsJea for the Yeer 2000and Beyond; TMS: Warrendale, PA, 1989; MA2223-0752. (K3) Stone, R. P.; Pleseers. J. €le&. fun. Conf. Roc. 1989, 46, 289-73; CA111(28):246870j. (K4) Zasowskl, P. J.; Branlon. R. V.; Mooney, D. C.; Stolnacker, W.; Stone, R. P. StOOhEkhQ Conf. Roc. 1989, 72, 393-400 CA112(10):908122. (K5) PleSSWS, J.; BljWOt. M. SmnWCt V , Pati I , Conf. Roc. 1989, 55775; MA2323-0054. (K8) Harvey, D. S.; Wilson, D. T. faly-fkst Chembts’ ConferenceR-; Brltlsh Steel: &angetown. Mlddlesbrough, Cleveland. 1988 pp 45-51; CA112(14):131353w. (K7) OMsubo, T.; Kawase, H.; Yamazaki, S. ASTMSpec. Tech. pub/. 962 ( W w E-t); ASTM: PhlIaddphla, PA, 1988; pp 105-16 CA110(8):88857q. (K8) Ono, A.; Klmura, H.; Onoyama, S.; Yamada, S.; Senoo, K.; Hayakawa, Y. Jpn. Kokal Tokkyo Koho 1989, Japan, JP 01213570 A2, 28 Aug, 1989, Heissl; CA112(10):90856s. (K9) Qoto. K. S.:Nagata. K.; Sum M. Conf. Roc. W . 0. FMbrookMem. synrpodum;Iron and Steel Society: Warrendale, PA, 1988; pp 147-55; MA23:23-0191. (K10) Uu, Q.; Worrell, W. L. SOW State I m k (Vdume Date 1987) 1988, 28-30 (Part 2), 1668-72 CAll1(8):49412k. (K11) Helm, M.; Koch, K.; Janke, D. Steel Res. 1889, 60 (0), 248-54 CA112(4):29892j. (K12) Ullmann, H.; Kuenstler, K.; Lang, H. J.; Burckhardt, W.: Herbst, K. Neue Hustte 1989. 34 (lo), 381-4; CA112(12):110909S. (K13) Zhaw, M.; Zhou, P. QBngtle 1988,23(9), 53-8 CAI10(24):210801~. (K14) Fuute, C.; Matsushlge, H.; Nagatsuka, T. Jpn. Kokal Tokkyo Koho 1989, Japan, JP 0173863 A2, 10 July, 1989, Heisel; CA112(22):210187y. (K15) Rsttlg, D.; Ullmann, H. Germany (East), DD 269017 A1 14 lune, 1989; CA112(10):90843k. (K16) Mucdk, R. -2. Fbdldo PI 1988, BrazH BR 8800201 A, 5 July, 1986 CA 11O( 10):8784 1w. (K17) Shlrdcura, T.; MetsusMge, H.; Ibukl, K. Jpn. K&a/ Tokkyo Koho 1988, Japan, JP 8329048 A2, 17 Oct 1988, Showa; CA110(28):241785y. (K18) Beam, P.: Johns, H. L.; Lebtner, H.; WrlgM, J. R.; Proch, R. US.. US. 4908349 A. 8 March, 1990 CA112(4):22904lt. (Kl9) Mokdchkov, A. V.; Luzgln, V. P.; Zlnkovskll Izv. V.U.Z. chemeye &tal. 1988. 31 (7), 41-5; MA22:23-0118. (K20) Ono, A.; Chlba, K.; Saekl, M.; Nlnbe, H.; Kasal, S. Tetsu to Hagnne 1989, 75 (e), 902-9; CAll1(8):81559~. (K21) (kmlyo, K. Jpn. Kdal TokkyO Koho 1988, Japan, JP 03191058 A2.8 Aug, 1988, Showa; CA110(4):27377e. (K22) Sasak, M.; Hamada, N. Jpn. Kaka/ Tokkyo Koho 1988, Japan, JP 83273055 A2, 10 Nov, 1988, Showa; CA111(14):128057c. (K23) Iwase, M. Jpn. Kaka/ Tokkyo Koho 1990, Japan, JP 02090052 A2, 9 April, 1990, Helsel; CAI13(4):34129r. (K24) Ham&,N.; Negetsuka, T. Eur. Pat. Appl. Japan, EP 295112 A2, 14 Dec, 1988; CA110(14):127703w. (K25) Romero, A. R.; Ichlhara, K.; Engell, H. J.; Janke, D. foun&y”9sses: 7?wk and Physk ( 1986); Plenum: New York, 1988; pp 219-38; CA112(4):29944~. (K26) Fuukawa, T.; Sumigama. Salt0 N.; et ai. Conf. Roc. 2nd S y ” on SPC and Sensors In 1)H, Steel Industry; CanadIan Instltute of Mining and Metallurgy: Quebec, 1988; pp 221-33; MA22:23-0750. (K27) Klyoshl, H. Jpn. Kokal Tokkyo Koho 1988, Japan, JP 83128109 A2, 31 May, 1988, Showa; CA112(4):23984u. (K28) Iwase, M.; Kushlma, Y. Jpn. Kokal Tokkyo Koho 1989, Japan, JP 01331449 A2, 24 M y , 1989; Helsel; CA112(8):69041n. (K29) Sasabe, M. Jpn. Kokai Tokkyo Koho 1989. Japan, JP 01203550 A2, 20 Oct, 1989, Helsel; CA112(20):191010y. (K30) Helnz, M.; Janke, D. Conf. Roc. W . 0 . Mem. Synrpodun; Iron and Steel Society: Warrendale, PA, 1988 pp 205-16 MA23:230192. (K31) Oklmura, T.; Fukul, K. Jpn. K&al Tokkyo Koho 1989, Japan, JP 01153954 A2, 18 June, 1989, Helsel; CA111(28):247139q. (K32) E. G. and 0. Idaho, Inc. Report, DOE/ID10155, Order No. M88014872 Avail. NTIS Energy Res. Abstr. 1988. Abstr. No. 54367. 1987; CA111(24):224248h. (K33) Ono, A.; Saekl, M. Jpn. Kokd Tokkyo Koho 1988, Japan, JP 83243871 A2, 11 Oct, 1988, Showa; Call1(2):18884n. (K34) Ono, A.; Saekl, M. Jpn. Kokal Tokkyo Koho 1988, Japan, JP 83243872 A2, 11 Oct, 1988, Showa; CA111(22):197213r. (K35) AklyOshl, T.; Takahashl, T.; Kondo, T. Bunsekl Kagnku 1989. 38 (10). 488-90 CA112(14):131429a. (K38) Tsukada, K.; Aklyoshl, T.; Kuralshl, T.; Takahashl, T. NKK Tech. Rep. 1989, 129, 79-83: MA23:23-0385.

84R


(K37) Tanimoto. W.; Yamamoto, A.; Twnoyama, K. Kawasakl Seitetsu 1989, 21 (2), 100-8; CA112(22):210057f. (K38) Carhoff, C.; Lorenzm, C. J.; W, K. P.; Sbbeneck, H. J. Proc. SPIE-Int. Soc. Opt. Eng. (Inprocess Optical Measurements) 1989, 1012, 194-6 CA111(18): 186416a. (K39) Persson, W.; Wendt, W.; Bmtheuwn, H. JOM1989, 41 (lo), 17-19; CA 112(4):238 101. (K40) Iwase, M. Tetsu to Hapne 1989, 75 (3, 379-88; CA110(20): 177000~. (K41) Iwase, M. A&. Ceram. 1988, 248(Sci. Technol. Zlrconla 3), 871-8 CA1lO(18): 158198t.

INCLUSIONS AND SECOND PHASES (Ll) Hocquaux, H. Cah. Inf. TechJRev. Metal. 1988, 85(12), 995-1008; CAl10(28):235091j. (L2) &man, D.; Klaentschl, N.; Solenthaler, C. Meter. Tech. ( L b s M , SwltZ.) 1988, 16 (4), 81-8; CA110(18):158100h. (L3) LOM, K.; Tuma, H.; VykUcky, M. Mem. EM.Sd.Rev. &tal. 1989, 86 (7-8). 445-7; CA112(10):81882e. (L4) Gruner, W.; Kaun, L.; Kunath, J.; LuR, 8. Wlss. Ber.-Akad. Wiss. D . D R . , ZWWdhSt. f W & m y S . WerkStOfforsch. 1987, 34, 22-4; CA111(14): 118912n. (L5) Wang. H.; Chen, M.; Shen, R.; Yao, Y. Yejin fenxi 1987, 7 (2), 24-8; CA112{18): 1711782. (L6) Hen, Q.; Wu, W.; Fang, K.; Hw, C.; Zhou, X. Repwt, ISTICTRC 000143; Order No. PB89-112808, Avail. NTIS Gov. Rep. Announce. Index (U.S.) 1989, Abstr. No. 904,357, 1987; CA112(8):68911). (L7) U. D.: CaO. S.: ZhenCr. 1988, 6 (1). -. L. zhonawo X l f ~X-0 . . 53-8; . CA 1Os(i0):23482lq. (L8) chino.A.; Ihlda, M.; Iwata, H. Tetsu to Hamne 1988, 74 (lo), 2041-6; . CA109(24O22155Ib. (L9) Kurayasu, H.; Inokuma, Y.; Nakayama, T. Tetsu to Mpne 1988, 74 (12), 2353-60; CA110(0):42091~. (L10) Han, Q.; Xlang, C.; ulou,D.; Sun, Y. J . W$hgIkriv. Iron Steel Technd. 1988, 10(4), 487-91; CA112(12):111093h. (L11) mung, K. H.; Wu, C. S.; Malawer, E. 0. 7Bmwchlm.Acta 1989. 154 (2), 195-204; CA112(18):171125e. (L12) Rek, A.; Stransky, K.; Svejcer, J. SkvaMnshri 1989, 37(3-4), 151-7; CA111(28):247087w. (L13) Cerezo, A.; Qdfrey, T. J.; Grovenor, C. R. M.; et al. J. Mwosc. (OXfo*d) 1989. 154 (3), 215-25; CA113(8):70146~. (L14) Murashko, G. M.; Smirnov, V. N. Apper. M e w Renrpnovskqp Anal. 1987, 36,54-8; CA111(20):188402~. (L15) Umada, M.; Fukuda, M.; Maauyama, F.; NisMmura, N. Jpn. Kaka1 Tokkyo Koho 1988, Japan, JP 83182544 A2,27 July, 1988, Showa; CA110( 16):146848s. (L10) Fukuda, Y.; Mkoguchl, S.:Hama&. H. Jpn. Kokai TokkyO Koho 1989, Japan, JP 01000751 A2, 11 Jan, 1989, Heisel; CA111(14):128088p. (L17) Hamada, H.; Tagushi, I. Jpn. Kdral Tokkyo Koho 1989, Japan, JP 01123146 A2, 10 May, 1989, Hdsei; CA111(28):247173w. (L18) Karagoz. S.; Lkm, I.; Bkhoff, E.; Fisdrmelster, H. F. Metal. Trans. A. 1989, 20A (12), 2095-701; CA112(10):81703n. (Ll9) Ravalne, D. Rev. Metal. Cah. Inf. Tech. 1989, 291-303, 351-80 MA22:23-07 11. (L20) Bdjbro Iron and Steel Reasarch Institute, Daye Iron and Steel Research Institute. Yelk, fenxl 5’ (2), 54-6 MA2323-0182. (L21) shet~halIron and Steel Roceas Technology Research Institute, TaC yuan Iron and Steel Research Instltute. Yelk, fm/1989, 9 (2), 59-80 MA23234184. (L22) Wuhan Iron and Steel Research Institute, Anshan Iron and Steel. Yejh Fenxi 1989, 9 (2), 57-8; MA2323-0183. (L23) Anshan Iron and Steel Research Institute, Baotw Rare Earth Research InstlMe. YeJn fenxi 1989, 9 (2), 60-1; MA23:234185. (L24) WYCblk, A. MkfOdtlm. Acta 1987, 1 (1-6), 201-9; MA22:23-0209.

--

SURFACE ANALYSIS

(Ml) FlSChmebtet, H. F. FreSenkrS’ 2.A M . Chem. 1988. 332(5), 421-32 CA1lo(l8): 148883m. K. H. VDI-EW., 702 (Phref. -ten &&bechsnschutr(M2) M&, SChbhten) 1988, 09-116 CAllO(1087497d. (M3) Ma&, S. Netsu shorll989, 20 (l), 32-8; CAl10(28):235112~. (M4) Koch, K. H.: Sommer,D.; mnenberg, D. Ra&xRundSd,. 1988, (2-3), 638-45; CA1lo(10): 1460741. (M5) PWk, D. M. Chomhl ChamcMzNun, Proc. ssml,., 2nd; InstlMe Of Mstals: London, 1988; pp 235-70; CAl10(10):87500~. (MB) Grant, J. T. Surface Interface Anal. 1989. 14 (8-7), 271-83; MA2223-0079. (M7) Holm, R.; Hottkamp, D.; Klelnstuck, R.; Rother, H. J.; Storp, S. FmenIUS’ Z . Anel. Chem. 1989. 333(4-5). 540-54 CA112(14):1234772. (M8) Haupt, S.; ShehMOw, H. H. -s. S C l . 1989, 29 (2-3), 183-82 CA110(22):201401q. (M9) Funabashhi, Y.; Jlnno, G.; Matsumua, T. Jpn. Kokal Tdrkyo Kdro 1988, Japan, JP 63033855 A2, 13 Feb, 1988, Showa; CAl10(18):185243). (M10) Matsumto, Y. Jpn. Kdal Tokkyo Koho 1988, Japan, JP 63317708 A2, 28 Dec, 1988, Showa; CA111(12):101202h. (MI 1) Shlbuya, T.: Hashlguchl, N.: Terajlma. K.; Tomatsu, I.; Nbhkawa, Y. Jpn. Kokal Tokkyo Koho 1988, Japan, JP 83217280 A2, 9 Sept, 1988, Showa; CAll1(2):18882k. (M12) ACamOvlC, N.; NOS~WOVIC. D. Hem. I n d . 1989, 19(1). 18-8; CA112(2): 15081~. (M13) Sdnabel. H. felngeraetetechnk 1989, 38 (7), 324-5; CA112(2): 10318e. (M14) Tonwaedu. K.; Veldefma. M.; Takkln. R.; Nemes. K. East/ NSV Toad. Akad. Tdm., Keem. 1989, 38 (2), 135-8; CA112(10):81834r. (M15) Molt, K.; Egdtraut. M.; Qottwald, K. H. “Mm.Acta (Volume Date 1987) 1988, 2 (1-0), 83-7; CA111(0):49504S.


..

(18):15801O$ (M17) IahlbashI, Y.; YoeMoke, Y. Tmna. Iron sted Inat. Jpn. 1988, 28(9), 773-8. . .- -, CAiiLU6k50311x -. .. .-,-,_ - - - . .... (M18) Too. W. B.: Hirokawa, K. SIA, svf. Interface Anal. 1988, 11(10), 533-8: CA110(181:1487481. (Ml@-R-&, E.; P.-MiR;oahkn. Acta 1989, 1(3-4), 197-212 CA112(4):29937c. (M20) Suzukl. K.; Yamamoto, M.; Saeki. M.; Fwkawa, A. &selkk!W 1989. 33(1), 10-5 CA111(2):10726r. (M21) -a, M.; Araki, S.; Okano, M.; Sato. S. NKK Tech. Rep. 1989, 128. 54-9: MA23:23-0208. - - - .-. (M22)-k&to, Y. Scmltomokkt. 1988, 40(2). 107-14: MA2223-0488. (M23) Matsunwto. Y. Roc. AESF Annu. Tech. Conf., 74th 0-2 1987; CA110(2):17789b. (M24) Yamamoto, A.: Tanimoto. W.; MakUshi, N.; Matwmwa, Y.: Who, Y. Kawasakl Se#etsu Qho 1989. 2 1 (2). 107-12 CA112(28):245169w. (M25) Yamamoto, M.; Asal, T.; Maeda, S. Kkoku h?mnm @”u 1988.39 (e), 452-7; CA 109(24):214072t. (M26) SwhOto. K.: Matsuda. S. StaM~ssSteek ‘87 Roc. Conf., Wthg meto 1987: Institute of Metals: London, U.K., 1988 pp 201-6; CA110(10):80295c. (M27) Andrlcacos, P. C.: Wong, K. H.; M a n s . J.; Romenklw, L. T. Roc.E ~ ~ I v c ~ &., w ~ . 90-8 -( S m on M ew&Mewa k , -, D e w s , 1989) (72-8, Electrochemistry) 1990, 373-85; CA113(6):48596c.

A$.

8AMPLINQ, SAMPLE PREPARATION, AND STANDARDS

(Nl) Smarskll, V. F.; Temchurin, V. M.; Kulakov, V. V.; Kharenko. V. P. Zavod. Lab. 1988. 54 (IO), 99-101; CA110(12):99426t. (N2) Akasaki, K.; Nakase, K.; Yamaguchl, H.; Tsuda, M. Tetsu to &@ne 1989, 75 (l), 175-80 CAl10(10):80005h. -noC Brltlsh (N3) Symonds,J. Forty-fht m t s ’ ; Steel: Grangetown, Mlddlesbrough. Cleveland. 1988 pp 63-6 CA111(22):208241x. (N4) Kondo, K.; Shlbazaki, T.; Aruga, M. Kawasakl Stsel Qho 1989, 21(2), 66-71; MA23:23-0350. (N5) Enrlquez, J. L.; del Pilar Echarrl, M. Fundlclon 1988, 34, 23-5; MA2223-0492. (N6) Pak. Yu. N.; Vdovkin. A. V.; Matveev. S. V. Izv. Vyssh. Uchebn. m.Zh.1989, 32(5), 4-8 CAl12(2):15591y. (N7) You, A.: Sun, 2. Yelk, Fenx/1987, 7(1), 69-70 CA112(24):228854y. (N8) Akhmanayev, S. 1.; Pervov. L. F.; Mosendz. N. N.; Chabanenko, N. I. Sov. Meter. Scl. Rev. 1988, 2 (2), 161-165 MA2223-0684. (N9) J o h a n m , G. Fortleth chemkts’ C o n m - P ; ~rftieh Steel: Grangetown, Mlddlesbrough, Cleveland, 1987; pp 85-92 CA111(14):125909V. (N10) Kuhara, K.; Matsuzaki, Y. Jpn. Kokai Tokkyo Koho 1988, Japan, JP63210758 A2, 1 Sept, 1988, Showa; CA110(10):87661c. (N11) Marqw de Cawalho, A. C.; Leal de Sene, M.; Qulmaraes, N. L.; Dias. S. C. 6raz. pedldo PI 1988; Brazil BR 8605342 A. 31 May. 1988 CA1lO(2): 17845s. (N12) Matsumto, Y.; Fullno. N.; Nasu, S. I S I J . Int. 1989. 29(11), 973-9; CA113(2):17059a. (N13) Lebedev, V. V. Zavod. Lab. 1988. 54 (a), 102-3; MA2223-0328. (N14) Sughnra, T.; Salto, K. Jpn. Kaka/, T&kyo Koho 1988, Japan, JP63228061 A2, 22 Sept, 1968, Showa; CA110(26):241762v. (N15) Sastd, V. S.; TJan, C. Werkst. K m 1988. 39 (lo), 482-4 CAlO9(26):234049n. (N18) NUtler. A. Czech. 08263378 B1, 14 July, 1989 CA113(2):17206w. (N17) b z k , J.; Maskery, D.; Maggs, S.; Susll, H.; SWh, F. E. Ana&st(London) 1989, 114 ( l l ) , 1401-3; CA112(14):131243k. (NIB) Kwk-Racan, M.; Matkovic, P. Mstakugile 1987, 26 (2-3), 59-65; MA22:23-07 17. (Nl9) FurUte, S.; Katagki, N.; Bandai, K.; Takada, J. Jpn. K&a/ Tokkyo Koho 1989. Japan, JP01191034 A2, 1 Aug, 1989, Heisek CA112(26):238906f. (N20) Wu. C. W. Ref. Meter. Roc. ISCRM‘89; Intematbnal Academic PubUcatkns: BeiJlng, 1989; pp 249-54; CAI 13(4):3389Ov. ATOMIC MSORPTION (01) Murphy, J. Chemhl Charactsnlsetfon;Institute of Metals: London, 1968 DD 14-60 MA2223-0143. (02) Fan,’J.; Chen,’X.; Wang, Y. o~engpuxunYU ~uengpuFenxi 1 ~ 8 8 8(4), , 55-8 CA111(8):4951IS. (03) Sun, M.; Zhu, P. Fenxl Shlyanshi 1989, 8 (l), 60-1; CA112(6):47769d. (04) Uuang, 2.; Xb, 2.; Zhou, H.; Lin, T. Xlamen Daxw Xuebao, Zkan Kexwban 1989, 28 (2), 180-4; CA112(28):245155p. (05) Karbmov, I. P.; Lebedev, V. I.; Persits, V. Yu. Zh.Ana/. KMm. 1989, 44 (I), 68-72 CA111(22):208289~. (06) HarhneVa. S. Tetsu to Heam 1988.. 74 (8). . . . 1540-5: CA109. (26):243165f. (07) Kherbmov, 1. P.; Karyekin, V. Yu. Zevcd. Lab. 1869, 55 (a), 38-8; CA112(8):479 182. (08) Karyakln, V. Yu.; Kharbmov, 1. P.: Pchekln, A. I.Zavod. Lab. 1988, 54 (4). 36-41: MA2223-0111. (09) i.‘vov. B. V.: Novlchikhln. A. V. At. Smcboec. 1990. 11 (1). . . 1-6 CAI 13(8):7029Ov. (010) LaMic, T.; OsojnWC, A.; Krlrtan, 2. Ze&za&/Zb. 1988, 22(4), 1598 6 CA11I f 161:146B12u. - - -(011)’ Kana J.; Dlng, C. Y O Fmxl ~ 1988, 8 (a), 24-8 CA112(6):47808r. (012) Batktoni. D. A.: Fucntes, M. I.: Smlchowskl. P. N. At. S m c m c . . 1889, 10(1), 12-6 CAl11(18):186383n. (013) Park, M.; Kim. Y. D.; Park. K. K. Taehan Hwabkhoe CM 1989, 33 (3), 315-20 CAI 12(10):90685k.

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.

- I

(014) AbdaHah. A. M.; Kabll, M. A. Chem. Anal. (Wafsaw) 1988, 33(1), 75-84; CA111(24):224207a. (015) Qlegorczyk, B.; Gralewska. K. Rezopl. Spwahhichvo 1989, 41 (a), 12-3 MA23:23-016 1.

OPTICAL EM188ION Hayashi, S.; Miyama, T. Ew. Pat. Appl. 1989, EP318900 A2, (PI) FUkUi, I.; 7 June, 1989; CA111(10):89463j. (P2) Slickers, K. A,; Wbach, V. Proc. Conf. Int. Metal/. congress,Innovatfon Wl.1988, 711-36 MA22:23-0511. (P3) SCheuM, R.; Brauner, A. Steel Techno/. Int. 1989, 381-3; MA23230511. (P4) Lunner, S. E. Forty-fkst Chemists' Conterence-Roceedlngs; Brltlsh Steel: Grangetown, Mlddlesbrough, Cleveland, 1989; pp 109-13; MA2323-0048. (P5) Yao, T. C)uet&aouxue Yu Ouengpu Fenxl 1989, 9 (4). 74-7; CA112(22):2 10052a. (P6) Tumanov, A. K.; Tumanova, T. G. Zevod. Lab. 1988, 54 (7), 113-4; CAI 1O(12):107201h. (P7) Zhuang, 6. Yem Fenxi 1988, B(4). 57-8; CA112(6):47831t. (P8) Rokosz, A.; Strycharski. P. Zesz. Ne&. Unlw. &g&bn.. R . (3”. 1988, 31, 111-7; CA111(8):49516Z. (Pg) Miksevk, M.; Rehak, N.; Gaal, F. Acta CMm. Hung. 1989, 126 (3), 369-75; MA23~23-0215. (P10) Azarenkov, E. A.; Nikol’skii, A. P.; Zamarev. V. P. Zevod. Lab. 1988, 54 (e), 31-3; CAI 10(10):87568C. (P11) Llang, Yu. Lhua Jknyan. Hauxua Fence lS89, 25 (I), 59, 60-2 CAI 12(26):245189c. (P12) NimbO, H.; Kurosaki, M.; Kasai, S. Bunsski Kagaku 1988. 37 (ll), T133-TI37; CAI 10)4):27 1 4 5 ~ . (P13) Ravcheva, Kh.; Tsobv, T.; Veseiinova, E. Acfa Chlm. Hung. 1989, 126 (3), 385-9; CA112(16):150829~. (P14) QlU, C. F m ~ / c e s MT-0 1988, 7(6), 68-71; CA111(10):89420t. (P15) Tohyama, M.; Uchlda, H. Kenkyu Mkoku-Kenagawa-kenKogyo ShkeMSh0 1988, 59, 114-5; CA111(14):125870a. (Pl6) Han, B. Fenx/ W y a M 1988, 7 (9), 20-3; CAI 11(26):246971t. (P17) Vaamonde, M.; Abnso, R. M.; Qarcla. J.; Izaga, J. J . Anal. At. Spectrm. 1988, 3(8), 1101-3 CA110(18):185197~. (P18) Rekner, H. Report, KCP-6134032, Order No. DE89003227, Avail. NTIS 1988 Energy Res. Abstr. 1989, Abstr. No. 4927; CAI 12(8):47786g. (Pl9) ReY, L. J.; Kdrtyohann, S. R. Appl. Specmc. 1968, 42(7), 1221-8 CA11~101:87580a. - .. .. ,. .,.- .- .-. (P20) Mohrrmed, M. M.; Uchlda, T.; Minami, S. Appl. Spectrosc. 1989, 43 (5). 794-800: CAI 12(10):90545a. ( p i l i ’ uang, 0; c.; la bed, M. w.’spectroch/m.~ c t a parf , B isas, 448 (IO), 1049-57; CAI 12(16):150823r. (P22) McIntyre, D. J. Forty-ht Chemkts’ Conference-Rocwd/ngs; British Stwk -town, Mlddlesbrough,Cleveland, 1988; pp 71-7; CA112(10):90695p. zheng, 2.; Zeng, X.; Huang, B. Fenxi Huaxue 1989, 17 (lo), 865-9; (P23) CA113(4):33955v. (P24) Huang, B.; Zeng, X.; Zheng, 2.; Liu, J. Spectroch/m. Acta 6 At. S p e c m C . 1988, 43 (4-5), 381-9; MA22~23-0369. (P25) Kohrl. M.: Kulkal. 0.: Yamada. K.: Okochi. H. Anal. Sc/. 1981).. 4 (3). . .. . 293-7; MA22:2&199. (P28) Ohls, K. D. Mkrochlm. Acta 1989, 3 (3-6), 337-48; CA113-

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IBP517A7h ,-,. .. .. ...

(P27) Thompson, M.; Chenery, S.; Brett, L. J . Anal. At. Specfrom. 1989, 4 (I), 11-6; CA110(26):241737r. (P28) Mochizukl, T.; Sakashb, A.; Iwata, H. Bunseki Kagaku 1988, 37 (IO), TlO9-TI 1 4 CA11018):66720e. (P29) Modrlzr;ki, T.; &kashita, A.; Aklyoshl, T.; Iwata, H. Anal. S d . 1989, 5 (5), 535-8 CA112(14):131433~. (P30) Chenery, S.; Thompson, M.; Timmins, D. Anal. Roc. R . Soc. Chem. 1988, 25 (3), 88-9 MA2223-0292. (P31) Lek, F.; sdorre, W.; KO, J. 8.; Nbmax, K. Mkfochlm. Acta 1989, 2 ( 4 4 , 185-99; CA 112(16): 1509312. (P32) Jones, J. G. S. Forty-ht Chemkts’ Conference-RWlngs; British Steel: Grangetown, Mlddbbrough, Cleveland. 1988; pp 67-70 CA 111(18):16647lq. (P33) Kegewa, K.; Nomure, H.; Aoki, K.; Yokoi, S.; Nakajlma, S. Bunko KOnkyU 1988, 37 (5), 380-5; CAI 11(14):125868f. (P34) Waaetsuma. K.: Hirokawa, K. Anal. Scl. 1988. 4 (2). . . 159-62: . MA22:280045. (P35) Wagatsuma, K.; Hkokawa, K. Anal. Chem. 1989. 61 (19). 2137-41; CA 260472. -. .1.i.i.l,l.Ab .,.i.- - ..-. (P36) Buravbv, Yu. M.; Zamaraev, V. P.; Chernyavskaya, N. V.; Voronova, T. V. Zh. MI. SpsMrOsk. 1990. 52(3). 368-74: CA113(4):33841e. (P37) Bwavlev, Yu. M.; Zamaraev, V. P.; Barkhum, A. EMtron. &ab. Meter 1989, (2), 46-50 CA111(18):157997p. (P38) Bwavbv, Yu. M.; Zamaraev. V. P. Zavcd. Lab. 1989, 55 (a), 44-8 CA 112(8):479 lab. X-RAY FLUORESCENCE

(01) Watson, K. E. Chemical Ck”tWlreH0n; Institute of Metals: London, 1988; pp 1-13 MA22:23-0142. (02) McKlndky, K. Cbmkal CharactWlretkn; Institute of Metals: London, 1988 p 124-83; MA2223-0145. (03) Rowen, T. E. Chemksl cheractertzetbn; Institute of Metals: London, 1988 pp 184-234; MA2223-0146. (44) Itoh, S.; &to, K.; Ids, K.; Okochi, H. Trans. NeH. Res. Inst. Mst. (&I 1987, .) 29 (3). 163-7; MA2223-0750. (05) Tanaka. T.; Ueda, Y.; Okashita, H. SMmedzu lfywon 1988, 45 (1/2), 43-9 CA110(20):184978s. (06) OUUbmot, J. C. A n a m 1988, 16 (7), 39-49; CA110(26):241692~. ANALYTICAL CHEMISTRY, VOL. 63,NO. 12, JUNE 15, 1991

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STEEL AND RELATED MATERIALS ((27) Nlng, D. X&ou Jhstw 1988, 7 (4), 305-7; CA110(24):224572r. (Q8) Dlng, H.; Chen, 0.; Xu, G. Lhue JIenyan, Hwxw fence 1989, 25 (2), 80-1; CAI 13(2): 17077e. (0s) Rajoev. Trans. I&n Inst. Met. 1988, 47 (l), 93-7; MA2223-0646. (Q10) Sato, K.; Itoh. S.; Nakamura, Y.; Okochl, H. Trans. Net/. Res. Inst. Met. (Jpn.) 1988, 30 (3), 146-51; MA2223-0601. ( a l l ) Yang, T. S . Techno/. Traln. (Telwan) 1989, 14(3), 25-31; MA23:230014. (412) Kochmoia, N. M.; Gotokhov, K. I. Zh. Anal. Khlm. 1990, 45 (I), 80-7; CA112(26):245235q. (413) Tarasova, E. G.; Flllppova, R. A.; Chalyl, K. I.; Shokhov, B. S.;Neuimln, Yu. A. Zavod. Lab. 1989, 55(9), 100-1; CA112(8):69010b. ((214) NovoseLRadovlc, V.; Sofillc, T.; Kocijanclc, J.; Pejnovic, M. Metakrg” (Slsek, Y w l . ) 1988, 27 (3), 57-60 CA111(10):69403q. ((215) Subrahmanyam, V. V. V.; Drishnaiah, D. S. R.; Srivastava, Y. P. Trans. I d a n Inst. Met. 1988, 41 (I), 87-92; MA2223-0645. ((216) W g ” o , G. M.; Ognyanlk, S. S.; Struina, T. A.; et ai. Rob/. Spets. Elekrrwnetall. 1988, 4 (2), 17-20 MA2223-0480. (Q17) Piorek, S. A&. X-fey Anal. 1989, 32, 239-50; CA113(6):51718z. (ala) Kelliher, W. C.; Maddox, W. G. A&. X-ray Anal. 1988, 31, 439-44; CA111(26):246942j. ((219) Tsujl, T.; Mochlzukl, T.; Ishibashi, Y.; Gunji, N.; Iwata, H. Bunsekl Kapku 1989, 38 (e), T123-Tl27; CA112(10):90803~. (Q20) Gunji, N.; Ishibashi, Y.; Mochizukl, T.; Tsujl, T.; Iwata, H. NKK Tech. Rep. lS89, 728. 34-9 MA23:23-0206. (Q21) Martln, J. E. ASTMSpec. Tech. publ. 973(ComputerizabbnandDeta Mnag3”t In the Metais Ana@& Laboratory);ASTM: PMledeiphia. PA, 1968; PP 92-101; CAl11(24):224228d. (Q22) Mantler, M.; Taut, T. X-ray Spectrom. 1989, 78(3), 105-8; CA112(8):66734d. (Q23) Tan, B.; Cui, X. J . Bedlng Unlv. Iron Steel Techno/. 1988, 10 (4), 48 1-6: CA 112(12): 1108894. ((224) Smagunova, A. N.; Mdchanova, E. 1.; Piiner, L. N.; Flnkei’shtein, A. L. X-ray Specbwn. 1988, 17 (5), 175-9; CAllO(6):50364g. (Q25) Fernandez, J. E.; Rubio. M.; Sanchez,J. H. Nucl. Instrum. Methods mys. Res., Sect. A (Volume Date 1988) 1989, A280 (2-3), 546-51; CA112(12): 111022). (Q26) Flnkel’shteln, A. L.; Gunlcheva, T. N.; Afonln, V. P.; Mkryukov, V. 0. Zh. Anal. Khlm. 1990. 45 (3). 527-34; CA112(26):245053dd. 0 2 7 ) Zhang, Y. fenxl Ceshl Tongko 1986, 7(3), 43-5; CA110(8);68708e. (Q28) LI, J.; Zhang. G.; Shu, 8. Yuenzlnmg Kexue Jlshu 1989. 23 (l), 15-9; CA113(6):51542n. ((229) Sasaki, A.; Enomoto. S. Radbkotopes 1989, 38 (4), 179-85; CA112(8):88844q. (Q30) Rozova, 0. F.; Molchanova, E. 1.; Smagunova, A. N.; Anislmova, L. D.; Goreva, E. 1. Appar. M e w RentgenovskogoAnal. 1988, 38, 7-14 CA112(6):47879q. (Q31) Wang, Y. fenxl Shly817ShllS89,8 (5), 35-39; MA23:23-0170. (Q32) Zagorcdnll. V. V.; Karmanov, V. I.; Gotdeeva, 0. L. Zh. Anal. Khlm. 1988, 43 (12). 2156-63; CA111(22):206272h. (Q33) Goiubev, A. A.; Pershln, N. V.; Moslchev, V. 1. Zavod. Lab. 1988, 54 (4), 26-30; MA22~23-0109.

MISCELLANEOUSTECHNIOUES (Rl) Wu, C.; Yen, J. Fenxl Shlyanshl 1988, 7 (5-7), 1-37; MA22:23-0275. (R2) Qln, G. fenxl Shlyanshl1988, 7 (5-7), 38-53 MA22:23-0278. (R3) Cheng, J.; Llu, J.: Jiang, 2. fenxl Shlyanshl 1988, 7 (5-7), 54-94 MA22:23-0277. (R4) LUO. C. fenxl, Shly8nShl 1988, 7 (1). 19-21; CAI 11(22):208328f. (R5) a n g , 2.; Huang, J. Yejln fenxl 1988, 8(1), 11-15; CA112(8):68847t. (R6) Zhao, S.;Che, W.; Wang, K.; Xue, X. Y e p fenxl 1989, 9 (I), 8-11; CA112(8):68877c. (R7) Hen, J. Llhua Jlanyan. Huaxue fence 1989, 25 (5), 308-9; CA113(4):33990c. (R6) Hu. J. Yejln fenxl 1987, 7 (3), 52-3 CA1113(2):17032m. (R9) Shl, H.; Ll, J.; XI, C. Oeodeng Xuexlao Huaxue Xwbao 1988. 9 (12), 1237-41: CAI 11(8):69999k. (R10) Jlmenez, A. i.;‘Jimenez, F.; Arias, J. J. Analyst (London) 1989, 174 (I), 93-6 CA110(24):2245741. (R11) Shl. H.; Kong, L.; XI, C.; LI. J. Fenxi Huaxue 1989, 77 (lo), 879-83; CA113(4):33957x. (R12) Sundaramurthl, N. M.; Shlnde, V. M. Ane/yst(London) 1989, 774(2), 201-205; MA22:23-0787.

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63,NO. 12, JUNE 15, 1991

(R13) Arias, J. J.; J i m z , A. I.; Jhnenez, F. h4krochh. Acta 1989. 1 (5-6), 303-11; CA112(14):131347~. (R14) Mansurk.ichodzhaev,U. M.; Dzhiyanbaeva, R. Kh.; Talipov, Sh. T. Uzb. K h h . Zh. 1990, (2), 87-90 CAl13(8):703071. (R15) Ishibashi, Y.; Yoshkawa, H.; Isobe, K.; Sato, S.; Iwata, H. NKK Tech. Rep. 1989, 728, 12-7; MA23:23-0204. (R16) Rao, B. V.; ooplnath, R. Tebnta 1989, 36(8), 867-8; MA23:23-0417. 0317) Han, J. Fenxl4Shlyanshl 1988, 7 (9), 6 4 CA111(26):246975x. (R18) Mho, J. Yejln fenxl 1989, 9 (3). 38-9 CA112(22):210027w. (Rl9) Orossman, M. A.; Ciba, J.; Jurczyk, J. Chem. Anal. (Warsaw) 1988, 33 (a), 933-9; CA113(8):51614n. (R20) Yang, S.; Zhang, S. fenxl Shlyanshl 1988, 7 (12), 11-4 CA111(24):224373x. (R21) Sorokina, L. V.; Tsyganok, L. P. Vopr. K h h . Khlm. T e k h d . 1967, 85, 51-5 CA110(12):107184e. (R22) Shen, J.; Mho, F. Yejln fenxll989, 9 (3), 30-3; CAl12(24):228883gg. (R23) Hanlott, M.; Burns, D. T. Anal. Roc. ( L o “ ) 1989, 26 (9). 315-7; CA 112(24):228686v. 0324) Hara, M.; Ilno, E.; Masumoto, K.; Yagi, M. Kakrnken Kenkyu Hdr&u (Tohoku D a b k u ) 1988, 27 (2), 236-42 CAI 11(26):247022w. (R25) Betra, R. J.; Garg, A. N.; Slnvhal, R. C. I d a n J . Techno/. 1989, 27 (6), 289-92; CA112(10):90769r. (R26) Hara, M.; Ilno, E.; Masumoto, K.; Yagi, M. Kakwken K e n W K&&u (TohokuD a b k u ) 1989, 22 (I), 51-61; CA112(20):190876s. (R27) Pak, Yu. N.; Portnov, V. S.; Vdovkin, A. V.; Terekhov, V. M. Izv. Vyssh. Ucheb. Zeved. a m . Zh. 1988, 37 (3), 17-21; CA109(26):243 143x. 6326) Pak, Yu. N.; Vdovkln, A. V. Izv. Vyssh. Uchebn. Zaved. Own. Zh. 1988, 37 (8). 6-9; CAll1(6):49492m. (R29) Oliver, A.; Mlranda, J.; Rlckards, J.; Cheang, J. C. Nud. Instrum. Methods mys. Res., Sec. B (Volume Date 1988) 1989, 840-841 (l), 627-9; CA111(26):247028a. (R30) Rajurkar, N. S.; Phulsundar, A. B. J. Radbanal. Nucl. Chem. Lett. 1989, 137 (2), 135-43 MA23:23-0081. (R31) Mns, J.; Mrazek, L.; Mayer, J.; Kralna. J. Czech, CS 251742 B1, 1 Oct, 1986; CA110(22):204795n. (R32) hlncipl, G.; Gauui, F. Metall. Ital. 1988, 80 (6), 511-23 CA110(2):11556b. (R33) Nagy, S.; Kuzmann, E.; Vertes, A.; Szabo, 0.; Konczos, G. Nml. Instrum. Methods Pnys. Res., Sect. B 1988, B34(2), 217-23 MA22:230056. (R34) Brown. R. M. fortbth Chemists‘ Contwence-Roc8dng.s; Britlsh Steel: Orangetown, Middlesbrwgh, Cleveland, 1987; pp 59-64; MA2223-

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IIRRR

(R35) Vaughan, M. A.; Horllck, G. J . Anal. A t . Speclrom. 1989. 4 (l), 455 0 CA110(24):224608g. (1336) Date, A. R.; Cheung, Y. Y.; Stuart, M. E.; Jln, X. J . Anal. A t . Spectram. 1988, 3 (5), 653-8; CA110(6):50308~. (R37) Mochlzukl, T.; Sakashita, A.; Iwata. H. NKK Tech. Rep. 1989, 128. 25-33; MA2323-0205. (R38) Mochlzukl, T.; Sakashita, A.; Iwata. H.; et ai. Anal. Scl. 1988, 4 (4), 403-9; MA2223-0197. (R39) Boettger. D. fort&th Chemists’ Contwence-Roce&/ngs; Britlsh Steel: Orangetown, Middlesbrough, Cleveland, 1987; pp 65-8 CA111H2k108169m. ,.-,. . - - .- -.... (R40) Jakubowski, N.; Stuewer, D. fresenlus’ 2.Anal. Chem. 1989, 335 (7). 680-6; CA112(18):171117d. (R41) Saito, M. Trans. Net/. Res. Inst. Met. (Jpn.) 1987, 29(4). 221-226 MA2223-0607. (R42) KMmakl, P. R.; Lajunen, L. H. J. flnn. Chem. Lett. 1988, 75 (5-6), 81-9 CAll1(6):49534b. (R43) Crotty. D.; Baanail. K. Plet. Surf. Rnlsh. 1988, 75 (11). . . 52-6: MA22:23-0241. (R44) LUPU, I.; LUPU,L. M e t e l ~ g h(Bucherest)1987, 39 (2), 59-60; CA110(12):99227d. (R45) Fredericks, P. M.; Doolan, K. J. Mmchlm. Acta (Volume Date 1987) 1988, 2 (1-6). 127-32; CA110(16):148795z. (R46) Sdorra. W.: Quentmeler. A.: Nlemax. K. Mkrochlm. Acta 1989..~2 ( 4 4 , 201-18 CA112(16):150932a. (R47) Quentmeier, A.; Sdorra. W.; Niemax, K. Spectrochh. Acta, Part B 1990, 458 (B), 537-46; CA112(24):226755~. (R48) Mlnaml, T.; &to, N. Hyomen K8Qaku 1988, 9 (e), 459-82 CA111(8):69928m.

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