aluminum, beryllium, titanium, and magnesium

Nonferrous Metallurgy 1. Light Metals: Aluminum, Beryllium, Titanium, and Magnesium Richard S. Danchik, Alcoa Research laboratories Aluminum Co. o f America, New Kensington, Pa. 7 5068

T

on nonferrous metallurgical analysis and covers the two-year period from September 1968 through August 1970 as documented by Chemical Abstracts and Analytical Abstracts. Also, the following journals were surveyed directly for the same period: ANALYTICAL CHEMISTRY,Analytica Chimica Acta, The Analyst, Analytical Letters, World Aluminum Abstracts, Journal of Analytical Chemistry of the USSR (a translation of Zhurnal Analiticheskoi Khimiii), and Talanta. As in the past (206), this review is limited to those analytical methods applied directly to materials of interest in the nonferrous metal industry. Many interesting methods potentially applicable to this field are not included because of space considerations. However, some general methods are included, possibly arbitrarily, because they appear particularly useful or novel. Books related, a t least partially, to methodology on analysis of light structural metals are as follows: “Analytical Chemistry of Beryllium (Analytical Chemistry of Elements)” (203), “Analysis of Ores of Nonferrous Metals and Products of Their Treatment” (240), and “The Chemistry of Titanium and Vanadium” (59). The analysis of nonferrous metals has also been reviewed by Hattori et al. (108) and Nishimura et al. (201). The determination of gaseous impurities in metals has been a subject of moderate interest. Fischer has reviewed various methods for determining gases in nonferrous metals with a specific application for the rapid determination of nitrogen (88). Bril and Dugain (49) discuss methods in which oxygen is determined by the addition of another metal t o a sample, thereby forming an alloy that melts a t a desired temperature. The applicability of gas chromatography t o the analysis of light metals has been reported by Cremer and Deutscher (66). With the exception of the alkali metals, all metals, after conversion to an organometallic compound, can be microanalyzed by gas chromatography below 450 “C. Among several noteworthy reviews were those by Tikhonova (269)on new photometric methods of determining HIS IS THE THIRTEENTH REVIEW

aluminum and by Albert (5) on the analysis of high-purity metals for trace impurities. A comparative study of various instrumental techniques for the analysis of aluminum and its alloys has been presented by Seco (235). The atomic fluorescence of beryllium was investigated by Robinson and Hsu (264) using a high-intensity beryllium hollow cathode lamp as a source and a newly designed burner assembly for NnO-acetylene and oxy-acetylene flames. Accompanying tables list methods referred to in the discussion along with other methods too numerous to mention individually. Table I shows the light metal materials for which compilations of procedures are available for determining miscellaneous alloying elements and impurities. I n Table 11, arrangement is according to the elements determined. Aluminum. Mustafin et al. (191) determined aluminum spectrophotometrically (580 nm) in various alloys using catechol violet. A 1:2 complex is formed preferably in a medium of p H 6.0 to 6.3 and Beer’s law is obeyed for 0.02 to 0.08 fig of aluminum per milliliter. A rapid chelometric method was developed for the determination of aluminum in its alloys without prior separation of the associated elements by Kiss and Doric (138). All metals (except the alkaline earths) were complexed a t p H 5.8 with E D T A with the excess E D T A being titrated with zinc solution in the presence of the Fea[FeCNeIz-benzidine indicator system; afterward the E D T A of the AI-EDTA chelate was liberated with sodium fluoride and determined by titration with the same indicator. A highly selective method for the separation and determination of aluminum has been developed by Villarreal (282). The procedure is based on the extraction of aluminum with N-benzoylN-phenylhydroxylamine (BPHA) into benzene from an ammonium carbonate solution containing several masking agents. Aluminum is back-extracted into 0.20M HCl, complexed with 8quinolinol, and the colored complex extracted into chloroform and measured a t 390 nm. Putnin and Lepin (220) developed an indirect polarographic method for deter-

mining aluminum using an alkalimetal nitrate as a basal electrolyte. Aluminum forms a complex with this nitrate, and the height of the reduction wave of the nitrate is proportional to the concentration of aluminum. The determination of aluminum in aluminum powder was reported by Lambert (150). The sample is dissolved in a HzSOl solution of Fe(II1) and Ce(1V). The Ce(1V) that remains after oxidation of the metallic aluminum is titrated with As(II1) by using an OsOccatalyst. The end point is detected by use of ferroin indicator or by a potentiometric system. Semimicro amounts of aluminum have been determined by Jaselskis and Bandemer (124) and Baumann (29) using the fluoride selective ion electrode. Aluminum in pH 3.8 (acetic acidacetate-NaC104 buffer solution) was titrated with 0.08M sodium fluoride to selected potential value using the fluoride activity and calomel electrodes. The amount of fluoride required to reach a potential of 80 mV is proportional to the concentration of aluminum. Paris and Delsey ($10) have developed a method for aluminum in bauxites by titrating samples with fluoride ion in an alcoholic medium saturated with sodium chloride. The end point is indicated by a pronounced change in the acidity of the mixture, which is determined electrochemically. A rapid complexometric method is presented for the determination of aluminum and titanium in bauxites by Nestoridis (199). An excess of E D T A is added to an acid sample solution, the pH is adjusted with hexamine, and the excess E D T A is titrated with a combined solution of copper and zinc in the presence of xylenol orange and PAN as indicators. For the simultaneous titration, fluoride is added to release E D T A combined with both aluminum and titanium. For the stepwise titration, phosphate is added to release the E D T A combined with aluminum. The method avoids the problem of titanium hydrolysis. Alumina. Anhydrous aluminas are identified and distinguished by the absorptions in the far-infrared region of their A1-0-A1 bonds and the aluminum hydroxides by the absorptions of their A1-OH-A1 bonds. Dorsey (73) presented characteristic spectra for fifteen different aluminas and aluminates.

ANALYTICAL CHEMISTRY, VOL. 43, NO. 5, APRIL 1971

109 R

~~~~~

Table 1.

Material A1

~

Methods for Nonferrous Metallurgical Materials

Constituents determined

Methods used.

References

S

Hi h purity

11

MS NA P MS Sb, Bi, Cd, Zn, Sn Fe, Cu, Si Review of im urities Mn, Pb, Cr, Ni Mg, Zn, Fe, General Mg, Zn, Fe, Cu, Mn, Pb, Cr, Ni Mg, Mn, Si, Fe, Zn, Cu, B, Ti, Ni M , Si, Mn, Cu, Fe, Zn, Ti, Sn, &a, Pb Cu, Fe, Al, Zn, Mg Cu, Ni, Fe, AI,Mg Si, P S, Cr, Mn, Ni, phases Zn, kd, Be, Cu, B, A1203 Fe, Mg, V, Ti, Ga, Si, Na, Ca, c u , Ag Fe, Si, Pb, Mg, Nn, Cu, Cd, In Cu, Pb, Zn, Sn, Na, Mn, In, Ga, M , Ca, Fe, Ni, Cr, Si Ni, Fe, Cr, Pb, Mg, Mn, Bi, Be, Ag Ti, Fe, Si, V, Na Ca, Cr, Fe, Mn, Si, Ti

&,

A1 alloys

80,

High urity A d Sintered A1 powder A1 nitride Bauxite

Be High purity Mg Mg alloys MgO Ti

Ti powder

Ti alloys

S P NA AA S AA S S AA AA EP C

S S S

S P S

Review of impurities

S

Si, Fe, Cu, Zn, Ti, V, Ga Cu, Mg, Ag, Fe, Ni, Pb, Mn, Si Cd, Zn Al, Si Si, Al, Fe, Ti, Ca Fe, Al, Ti, Ca, Mg Al, Si, Ti, Fe Si, Na, K, Ti, Mn, Cr, Al, Fe, Ca, Mg Review of impurities

S

Review of impurities Si, Cu, AI, Fe Al. Cu. Zn Al; Bi,'In, Cu, Ga, Mn, Pb, Sn, Si, Co, Fe, Ca, Sr, K, Na, Ba Mn, Sc, Cr, Fe, Co V, A1 Review of impurities Fe, Mn, Cr, Mg, Ni, Pb, Ca V, Al, Mn, Fe, Si Sb, As, Ba, Ca, Cr, Co, Cu, Ga, Au, Hf, Zn, In, Fe, Mn, Mo, Ni, K, Ag, Na, Ta, Th, W, U, rare earths Mn. In. U

S X X C EP

AA MS NA S S S NA NA NA S S

NA NA

x

X X MS S Ti hydride C a AA, atomic absorption; C, chemical; EP, electron robe; MS, mass spectrographic; NA, neutron activation; P, photometric; S, spectrograpgic; X, X-ray.

Van der Veen (27.4) reported t h a t the available alumina content of bauxites is linearly related to the gibbsite peak area as determined by DTA. The chemical method involving digestion with sodium hydroxide in a bomb is four to five times as precise as DTA, but D T A takes only 60% of the time needed for the chemical analysis. Levin (166) proposed a method for 110 R

the quantitative X-ray spectrographic determination of a-Al2Oa in bauxite with a n ionization diffractometer. The method is based on the fact t h a t the intensity of the diffraction pattern of the component is related to its concentration in the sample. Alumina in a n electrolyte was determined by Bystrova et al. (63) using a thermal reduction in vacuo by means of elemental carbon,


Metallic tin is added t o a n aliquot in a carbon case, and the system is vacuum heated t o 1800 "C. The CO evolved is burned to COz over CuO in a n oxidizing furnace at 400 "C, and the COI is measured volumetrically. Danchik and Oliver (67) have developed a semi-automatic spectrophotometric (550 nm) method for the determination of aluminum and hydroxide in aluminate solutions. Alkalone is used as the spectrophotometric reagent specific for the determination of hydroxyl ion. The free hydroxide is determined directly and the aluminum indirectly by using sodium gluconate as a complexing reagent with the release of a n equivalent amount of hydroxide. The simultaneous automatic determination of aluminum, fluorine, uncombined caustic, and carbonate in cryolite liquors has been developed by Wahl and Auger (287) using Technicon AutoAnalyzer components. The method is based on colorimetric procedures. A thermometric determination of aluminum oxide in aluminate liquors has been presented by Sajo etal. (9.30). Antimony. Meranger and Somers (180) developed a method for the determination of antimony content of titanium dioxide by atomic absorption spectrometry. The method is based on the extraction of antimony with isobutyl methyl ketone and has a limit of 25 ppm of antimony in a 0.1-gram sample. The determination of 0.2 to 10 pg of antimony in titanium dioxide with Rhodamine S has been studied by Jablonski and Watson (120). The complex is stable for at least 24 hours and only lead causes a n interference. Barium. Barium, strontium, and calcium were determined in magnesium salts by titration with E D T A after precipitation of magnesium with sodium hydroxide in the presence of EDTA, and after the selective extraction of each element with AT reagent (96). Beryllium. Khain and Fadeeva (133) have reviewed photometric and fluorometric methods for the determination of beryllium with various reagents. Methods for the preliminary separation of beryllium by precipitation or extraction and for masking interfering elements were also discussed. Various spectrographic, colorimetric, and fluorimetric methods have been presented by Keenan (131) for the analytical determination of beryllium. A tabulation of the chemical methods along with their individual applications is provided. Eristavi et al. (80) have described a method for determining beryllium in beryl and alloys based on an anion-exchange separation followed by a photometric determination with beryllon 11. A comparative evaluation by Eristavi

et al. (81) has also been made concerning the sensitivity and accuracy of the colorimetric determinations of beryllium with beryllon 11, thoron, and arsenaso I. Thomas and Chumnong (26’7) have determined beryllium in beryl using atomic absorption spectrometry. T h e absorption was measured in a NZOacetylene flame at 234.8 n m for t h e determination of 0.5 to 15% beryllium. Peterson (213) determined beryllium (0.002-0.007%) in aluminum alloys by atomic absorption spectrometry using a similar technique. Beryllium and N-methylanabasine (a’-azo-6)-m-aminophenol in a n acid medium (pH 1.8-3) form a colored 1 : 2 complex, which is suitable for the photometric determination of beryllium (76). The absorption maximum of the complex is a t 530 n m and Beer’s law is obeyed for 0.1 t o 0.8 pg of beryllium per milliliter. Bismuth. Bismuth and lead were determined by Crawford and Lush (65) in aluminum alloys either separately or in t h e presence of each other over a range of 0.05 to o,5yO.Diethyldithiocarbamate complexes are extracted from a n ammoniacal tartrate solution with the interfering elements being complexed with KCN, tartrate, and EGTA. The final determinations are made by titrating with EDTA. A simultaneous polarographic determination of bismuth and lead in aluminum alloys was developed b y Mukai (189). A detailed investigation of parameters was given. Boron. Tolk et a.Z. (271) developed a direct spectrophotometric method for the determination of traces of boron in aluminum alloys. I n this method t h e absorbance of the boron-curcumin complex formed in the sample solution is compared with the absorbance of another aliquot of sample solution, wherein the boron is rendered inactive with fluoride before curcumin is added. A spectrophotometric method for the determination of boron in aluminum and its alloys was investigated by Coedo and Seco (62). The method, which is applicable to samples containing 0.001 t o 1% of boron, is based on t h e procedure in which the absorbance of the BFd--methylene blue complex, extracted into 1,2-dichloroethane, is measured a t 660 nm. Calcium. Gorbenko a n d Degtyarenko (95) developed a method for t h e analysis of calcium in aluminum. The method is based on t h e extraction of calcium from a n alkaline medium with A T reagent, re-extraction of calcium with 0.1N HCl and a complexometric titration of calcium or its photometric determination with glyoxal bis(2hydroxyanil). Calcium has also been determined in aluminum metal by flame photometry (112). T h e sample is heated in a quartz boat in a stream of

Table 11. Methods for Elements in Nonferrous Metallurgical Materials Constituent Reagent or method References determined Material Photometric-catechol violet (191 ) Al Alloys Alloys Flame photometric (93) Chelometric Alloys (641 Alloys Chelometric (138) A1 salt Polarographic (8200) Pu-A1 alloys Electron microprobe (107) Titrimetric A1 powder (160) Sintered Al powder (278) X-ra diffraction A1 finishing solutions ConcLctometric (titration) (66) Anodizing solutions Titrimetric (111) AlFs Chelometric (863) AlzOs X-ray fluorescence (20) General Extraction-photometric-8($88) quinolinol F- selective ion electrode General (89, 184) Bauxite Potentiometric (titration) (210) Bauxite Chelometric (199) Mg alloys Chelometric (185) Photometric-eriochrome (106) MgO cyanine R Photometric-stilbaeo Ti Potentiometric T i alloys Photometric-aluminon Ti owder Photometric-cyanoformazan 2 Ti& Gasometric AlzOa AI powder Photometric-aluminon A1-Mg alloys Activation analysis Sintered A1 powder X-ray fluorescence AlFs Thermometric Aluminate solutions Photometric-alkalone I Aluminate solutions Potentiometric Aluminate solutions Photometric-aluminon Aluminate solutions Chelometric Aluminate solutions Potentiometric Aluminate solutions DTA Bauxite Activation analysis Bauxit.e X-ray spectrographic Bauxite Titrimetric-ZnSO4 Bauxite Chelometric-DCTA Bauxite Vacuum extraction Electrolyte Far-inf rared Hydrous Ah08 Atomic absorption Sb Ti02 Photometric-rhodamine S Ti09 Spectrographic Ti-Ni Titrimetric Titanates Ba Chelometric-EDTA Mg salts Atomic absorption A1 alloys Be Photometric-N-methylA1 alloys anabasine (a-azo-6)-maminophenol Atomic absorption Beryl Gravimetric Beryl E&ectrographic Beryl otometric-beryllon I1 Beryl Photometric-chrome azurol S Cu-Be alloys Photqmetric and fluorimetric General review Review General Fluorimetric General Photometric-review General Atomic absorption Process liquors Chelometric A1 alloys Bi Polarographic A1 alloys Photometric B Ah Mg Photometric-curcumin A1 alloys Photometric-BF4-methylene A1 alloys blue complex Flame photometric A1 Ca Photometric-glyoxal A1 salts bis(2-hydroxyanil) Atomic absorption A1 salts, A1203 Luminescence Mass spectrometric Charged particle activation A1 C analysis Gas-chromatographic Be Potentiometric and coulometric Ti alloys Photometric Ce-Mg alloys Ce Activation analysis c1 Ali01 X-ray fluorescence Ti Nephelometric Ti hydride

%?


111 R

~

Table II, Methods for Elements in Nonferrous Metallurgical Materials (Continued) Constituent determined Cr

Material A1 A1 alloys A1 alloys A1 alloys A1 salts, ALOB All01

C-~ O

cu

Mgd

A1 A1

A1

F Ga

Hf

H

HzO In

Fe

A1 alloys A1 alloys Sintered A1 powder Be Ti alloys Ti sulfate A1 electrolytes A1 AI A1 Aluminate solutions Bauxite A1 Ti Al, A1 alloys Al, A1 alloys Al, A1 alloys Al, A1 alloys A1 alloys Be0 Ti Be powder A1 Ti, TiOn A1 A1 ~~~

A1 A1 alloys A1 alloys

Cu-AI alloys All03

Pb Li Mg

Bauxite Ti, Mg Ti alloys Ticla TiClr A1 AlCh Li-AI allovs Alloys A1 alloys A1 alloys Al, A1 alloys A1 alloys Al, A1 alloys A1 alloys Mn-A1 alloys AI-Mg alloys Mg, Mg alloys A1 A1 A1

Ni

A1 alloys Ti Ti, Ti alloys A1 alloys

A1C13 Be0

E:,

hlg alloys

Reagent or method Atomic absorption Atomic absorption Activation analysis Photometric-diphenylcarbaside Atomic absorption Atomic absorption Spectrographic Photome tric-neocuproin Photometric-di-&quinolyl disulfide Photometric-Na-diethyldithiocarbamate Activation analysis Photometric Polarographic Activation analysis Polarographic Oscillographic polarographic Neutron absorption Activation analysis Photometric-rhodamine B Photometric-hematein Chelometric Photometric-Rhodamine B Activation analysis Activation analysis Vacuum fusion Vacuum heating Alutester apparatus Gassi method Vacuum melting Neutron irradiated-GC 5 ectrographic .“Iphermal decomposition Amalgam polarographic Activation analysis Titrimetric Photometric-oxalato complex X-ray fluorescenae Photome tric-0-phenanthroline Photometric-1,lOphenanthroline Atomic absorption Mossbauer Ex traction-chromatographicphotometric-sulfosalicylic acid Titrimetric Atomic absorption X-ray fluorescence Extraction-photometric Spectrographic Activation analysis Stripping analysis Atomic absorption Photometric-eriochrome black T Gravimetric or chelometric Photometric-chromotrope 2R Photometric-titan yellow Chelometric-CDTA Photometric-Calmagite X-ray spectrometric-direct electron excitation Chelometric Photometric General Photometric Square-wave polarographic Photome tric--8-mercaptoquinoline Photometric-triethanolamine Photometric Photometric-periodate Pho tornetric4-(Qpyridylaso)resorcinol Extraction-photometricdimethylglyoxime U-V spectrophotometric-cbenzoin oxime S ectrographic Pi0 tometric-dime thylglyoxime (Continued)

112 R


HC1 gas in order t o sublime AlCl,. Calcium chloride in the residue is dissolved in dilute HC1, LaCls solution and ethanol are added, the solution is diluted t o volume with water, and the calcium line intensity measured a t 422.7 n m with H-0 flame. A method of isotopic dilution for the analysis of calcium in titanium dioxide was developed by Miller and Poponova (181) using a mass spectrometer equipped with a thermal ionization source. Traces of calcium in alumina were determined by Marshall and West (166) using atomic absorption spectrometry with a microwave excited source and hollow cathode lamps. The limit of detection for calcium was 10 PPm. Carbon. A gas chromatographic determination of carbide carbon in metallic beryllium was studied by Nikol’skii et al. (200). The beryllium was dissolved in HC1 and the CH4 evolved is collected and determined by gas chromatography using a flame ionization detector and hydrogen as a carrier gas. Potentiometric and coulometric determinations of carbon in titanium and its alloys was developed by Ogneva et al. (204). Metallic titanium is combusted at 1250 OC in an oxygen stream and the evolved COz is absorbed in BaCl-NaOH solution a t p H 9.9. I n the potentiometric titration, base is added until the original p H 9.9 is re-established. The coulometric generation of base is monitored by a p H meter to keep the unchanged p H value 9.9 in the automatic variant of this method. The possibility of determining carbon impurities in aluminum using timedependent variable energy chargedparticle activation analysis is discussed by Rook and Schweikert (226) along with the current limitations of the method. Cerium. Siekierska (243) determined cerium in Ce-Mg master alloys by the photometric method based on the yellow color formed upon oxidation of Ce8+ t o Ce4+. The complex formed by the addition of a 5% HZOZsolution to the HC1 solution of the alloy is very stable. Chlorine. Miyakawa et al. (182) developed a method for a rapid determination of chlorine in sponge titanium. X-ray fluorescence analysis was carried out with the C1 K a line a t 64.95 “ C with no interferences from impurities such as F e and Mn. Application of neutron activation analysis and of electronic computation to the nondestructive determination of chlorine traces in alumina was described by Bussiere et al (52). The reproducibility of the method is better than 2% for 10-300 mg samples with a chloride content of 10 ppm. Chromium. Determinations for

the analysis of chromium in aluminum alloys b y neutron activation and by isotope dilution have been reported by Baishya and Heslop (23). Chromium, separated by oxidation t o dichromate, followed by solvent extraction, was substoichiometrically extracted with tetraphenylarsonium chloride into 1,2dichloroethane and assayed by measurement of its gamma emissions. An atomic absorption spectrometric method has been described by Elrod and Eaell (7'9) for the determination of chromium in alumina and aluminum metal. The addition of K2S208 was recommended t o permit a n accurate determination of chromium in the presence of large quantities of Al, Fe, and Ti. Chromium was also determined in alumina b y extraction of chromium(1V) into isobutyl methyl ketone, and aspiration of the extract into a n airacetylene flame for measurement of atomic absorption a t 359.3 nm (167). Chromium and zirconium were determined in aluminum alloys b y Wilson (290) using atomic absorption spectrometry. High intensity hollow cathode lamps are necessary for t h e determination, and a NzO-acetylene flame is needed to decrease interferences. Cobalt. T h e determination of trace amounts of cobalt in alumina b y atomic absorption spectrometry has been investigated by Fleet et al. (89). After the dissolution of alumina by HC1 in a sealed tube at 270 "C, traces of cobalt are determined at 240.7 nm. I n one of two procedures, cobalt (50 t o 250 ppm) is determined by aspiration directly into a n air-acetylene or N20-acetylene flame and in the other procedure, cobalt (10 to 100 ppm) is determined by co-precipitation on hydrated manganese dioxide, followed by extraction into isobutyl methyl ketone as its 8-hydroxyquinoline complex. The extract is sprayed into an air-propane flame. Cobalt has also been determined spectrographically as reported b y Verkhoturov Korshakevich (280). The lower limit of detection is 0.001% a t t h e 3543.5 A line using nickel as a n internal standard (3486 A). Copper. Stefan a n d Turkiewicz (261) determined copper (0.0005 t o 0.010%) in electrolytically pure aluminum. The copper complex of neocuproin was formed at p H 3-4 and extracted with pentanol and the absorbance of the orange color was measured at 454 nm. Copper has also been determined photometrically in aluminum alloys (161) by using a colored complex of copper and 2,2'-bicinchoninic acid (560 nm). A sensitive, precise, and accurate colorimetric analysis of aluminum for copper content was reported b y Branscomb (42). T h e method using N a diethyldithiocarbamate is extremely sensitive (0.0002 mg Cu/ml) and equal

~

Table

II. Methods for Elements in Nonferrous Metallurgical Materials (Continued)

Constituent determined Nb

Material AI-Mn alloys Ti

AlnOa,TiOt A1 nitride Ti T i carbide Ti carbide A1 A1 A1 A1-Mg- AlzOa-MgO Be Be

On

Be Be Ti Ti Ti

Ti

Pd

TI alloys Sintered A1 Dowder Ti alloys

P

Ti, Ti alloys A1 alloys

Al, AI alloys Al-Si alloys Ti Pu Rare earths DY Eu

Pu-A1 alloys AI-Dy alloys A1

La La La, Y

Ti A1 A1 alloys

sc R.E. R.E.

Bauxite AhOa Bauxite AI, A1 alloys A1 alloys A1 alloys Al-Si alloys A1203 Mg

Si

Ti Ti Ti Na

Na. K

S Th Sn

melts Ti

it:? A1 Al alloys

Nonferrous alloys

Reagent or method Pho tometric-arsenazo Photometric-4-(2-pyridylaao ) resorcinol Electron microprobe Mass spectrometric or titrimetric Nitrogen adsorption (BET met,hod) Kieldahl techniaue Activation analysis Dumas technique Comparison of methods Activation analysis Activation analysis Activation analysis Vacuum fusion Neutron activation analysis Activation analysis and photometric-brominemethanol Activation analysis Vacuum fusion Gravimetric and photometricdiantipyrinylmethane Gas extraction coulometric titration Spectrographic Activation analysis Pulsed heating Activation analysis Photometric-comparison of dimethylglyoxime and 1nitroso-2-naphthol Photometric-dimethylglyoxime Photometric-molybdovanadophosphate method Gravimetric and chelometric Pho tometric-molybdophosphate method Photometric-molybdovanadophosphate method X-ray fluorescence Chelometric Mass spectrometric-stable isotope dilution method Activation analysis Ex traction-complexometric Photometric-methylt hymol blue S ectrographic ray fluorescence Spectrographic Atomic absorption Atomic absorption Atomic absorption Thermometric Diffusion method Pho tometric-molybdenum blue method Titrimetric Photometric-molybdenum blue method Ex traction-photometric Activation analysis Flame photometric Flame photometric X-ray fluorescence Activation analysis Titrimetric

2

Spectrographic Activation analysis Titrimetric (iodometric) Activation analysis Polarographic Gas chromatographic separation (Continued)


113 R

Table 11. Methods for Elements in Nonferrous Metallurgical Materials (Continued)

Constituent determined Ti

Material A1 Al, A1 alloys Al, A1 alloys Al, A1 alloys Alloys A1 alloys A1 alloys A1 alloys A1 alloys A1 alloys, A1203 Si-A1 alloy

U

v

Zn

Zr

Fe-Cr-A1 alloys Bauxite Bauxite, alloys Ti alloys TiOn A1 A1 Al, bauxite Ti, TiO, Ti alloys TiClr A1 A1 A1 A1 alloys A1 alloys A1 alloys Ti02 Ti02 Alloys Al, A1 alloys Mg-Be alloys Ti-Zr Ti, Ti alloys

Reagent or method Polarographic Photometric-salicylfluorone Photometric-diantipyrylmethane Extractive-photometric 4,4’-diantipyrylmethane Photometric-tiron Photometric-tichromin Photometric Photometric-tipyrogin Photometric--B-acetoacetyl-1,4benzodioxan Photometric-Khimdu Photometric-N-phenylbenzo hydroxamic acid Polarographic Cathode ray polarographic Extractive-photometric Chelometric Difference-pho tometric-Hz02 Activation analysis Photometric-N-benzoy1-Nphenylhydroxylamine Potentiometric Activation analysis Electron microprobe Phenylanthranilic acid Pulse polarogra hic Photometric-Jthizone Extractive-dithizone Chromatographic-amperometric Chelometric Chelometric Polarographic Potentiometric and cathoderay polarographic

Photometric-l-(2-pyridylazo

2-naphthol X-ray fluorescence Pyrocatechol violet and acid chrome violet K Activation analysis Photometric-xylenol orange

t o or better than data obtainable from quantometric (spectrometric) analysis. Copper, cadmium, lead, and zinc were determined in sintered aluminum powder by Huertas (117) using polarography. A detailed procedure of analysis is presented. The determination of traces of copper in titanium sulfate was developed by Bragina and Zamyslov (41) using oscillographic polarography. Woelfle et al. (291) determined copper nondestructively b y y,y-coincidence counting in high-purity beryllium. The limit of detection was 6 pg of copper per gram of sample. Fluorine. A rapid determination of fluorine in aluminum electrolyte was developed by Akerman et al (3) using a n indirect neutron absorption technique. The limit of detection was 0.5 mg of fluoride per sample. Gallium. Soljic et al. (249) described a colorimetric method for t h e determination of gallium in bauxite using Rhodamine B. The concentrations of HCl, Rhodamine B, and Tic13 have a marked effect on the color intensity. Various studies were made concerning the reproducibility of the 114R

References

)-

absorbance of the Ga-chloro-Rhodamine B complex. Gallium (10 to 100 ppm) was determined in aluminum by Graffmann et al. (99) using a photometric technique with hematein. I n a n equilibrium reaction, which is dependent on pH and hematein concentration, gallium and hematein form 1 : l and 1:2 complexes. The absorbance a t 590 nm, the isobestic point between absorption bands of the two complexes, is measured for the determination of gallium because i t is independent of the position of the equilibrium. A method was developed by Busev et al. (61) for determining gallium and aluminum in aluminate solutions. A detailed chemical procedure is outlined for this analysis. Hafnium. Balsenc and Haerdi (24) proposed three methods for the determination of traces of hafnium in aluminum by neutron activation analysis. Lobanov et al. (167) also determined hafnium in titanium using neutron activation with a sensitivity of 10-6%. Hydrogen. A new apparatus for the analysis of hydrogen in aluminum and aluminum alloys is described by


Aschehoug et al. (18). Hydrogen is converted t o water by reaction with hot copper oxide, and the vapor is condensed in a cold trap. Subsequently, evaporation takes place in a small calibrated volume, and the pressure is determined by means of a n electric probe technique. Danilin (68) determined the hydrogen content in aluminum and its alloys by vacuum heating. Reaction tubes are described t h a t enable removal of the sample from the heating zone without disturbing the vacuum. The sensitivity and accuracy of the method were evaluated. Indium. Indium, manganese, and uranium in titanium and titanium dioxide were determined nondestructively or destructively using neutron activation by means of solvent extraction with tri-n-butyl phosphate (197). Destructively, the sensitivity for the determinations is enhanced by a factor of 20. An amalgam polarographic method for the determination of indium in aluminum was reported by Alimarin et al. (11, 16). The solution is electrolyzed for 30 minutes a t -1.2 V us. the SCE with a mercury drop on a silver wire as the cathode. The dissolution polarogram is recorded with a n oscillopolarograph. Iron. T h e determination of iron in titanium and magnesium by atomic absorption spectrometry was investigated by Sudo and Ikeda (257). A comparative study was made on conventional solvent extraction methods using various complexing agents with the oxine-iso-BuCoMe extraction of iron being most suitable. The extraction of iron with 1,lO-phenanthroline into propylene carbonate has also been studied for analysis of aluminum alloys (662). Lead. T h e determination of lead (10-6 gram) and titanium in highpurity aluminum was reported by Samadi and M a y (231). The activation analysis procedure is based on radioactivation with fast neutrons using a high flux reactor. The chemical separation processes are given. Lead was also determined in aluminum chloride by stripping analysis (126). The sample was dissolved in HC1 and electrolyzed on a mercury drop cathode us. SCE with a polarogram recorded from -0.7 t o -0.2 volt. Lithium. An atomic absorption spectrometric method was developed by Wheat (288) that is sufficiently precise and accurate for routine isotopic analysis of lithium in aluminum alloys. The basis for the method is the isotope shift in the absorption spectra for 6Li and 7Li. Magnesium. Shibata et al. (238) spectrophotometrically determined magnesium in aluminum alloys. Chromotrope 2R forms a pink complex

(570 nm) with magnesium in aqueous acetone medium a t p H 10.8; down to 0.01 ppm of magnesium can be determined. Photometric and direct extraction methods of determining small amounts of magnesium in aluminum and its alloys are reviewed by Natchev and Filipov (192). Magnesium in aluminum alloys has also been determined by Eriochrome Black T after an ion exchange separation (239). The absorbance of the 1:2 complex is measured a t 525 nm. Manganese. Square-wave polarography in triethanolamine-Na0H solution was used for the determination of manganese in aluminum (>O.O020j,) by Sudo and Okochi (266). A sample was heated with iron solution [lo0 mg of Fe ( f 3 ) per ml], 60% HC104, and water to white fumes, cooled, and triethanolamine added with KaOH. Air was bubbled through the solution to oxidize the manganese and a polarogram was recorded from -0.1 to -0.5 V us. the mercury pool. There was no interference from a I., Znd. Chim. Belge, 33,1126 (1968). (280) Verkhoturov, G. N., Korshakevich, I. I., Kauch. T r u d y sib. Nauchno-Isslcd. Proekt. Znst. Tsvet. hrletall., 2,234 (1968). (281) Vidal, G., Galmard, P., Lanusse, P., Rech Aerosp. No. 130,27 (1969). (282) Villarreal, R., Krsul, J. R., Barker, S. A., ANAL.CHEM.,41, 1420 (1969). (283) Vorozhoitskava. K. F.. Studens‘ kaya, L. S., T;, ‘Vses. Nauch.-Zssled I

,

Znst. Stand. Obraztsov Spektral. Etalonov, 3, 68 (1967). (284) Vos, G., Anal. Chim. Acta, 50, 323 (1970). (285) Vossen, P. G. T., ANAL.CHEM.,40, 632 (1968). (286) Wacehter, H., Znt. S y m p . “Reinstoffe. Wiss. Tech.,” Tagungsber, 2nd, 1965 (pub. 1966), 2,245. (287) Wahl, B. J., Auger, G., Advan. Automat. Anal. Technzcon Int. Congr., 1969 (Pub. 1970), 2,273. (288) Wheat, J. A,, U.S. At. Energy Comm. 1967, DP-AIS-67-62. (289) Wickbold, R., Fresenius’ 2.Anal. Chem.. 244 (6). 372 11969). (290) Wilson,’ L., Anal. Chim. Acta, 40, (291) 503 (1968). Woelfle, R., Herpers, C., Herr, W., Fresenius’ 2.Anal. Cheni., 233 (4), 241 (1968). (292) Wolna, J., Studencki, J., Rudy M e t ale A’iezelaz. 14 (4).207 (1969). (293) Wood, ’D. F.,’’Jone;, J. T., Analyst, 93, 131 (1968). (294) Yakovlev, P. Y. Zhukova, 11. P., Rlorein, N. G., Shashura, 11.V., Ozerskava. F. A.. Sovrem. Metodu. K h i m . Teihnol. Kontr. Proizvod., 14, 1468. (295) Yamauchi, F., Otaka, Y., Bunseki Kagaku, 17, 1384 (1968). (296) Yamaxaki, Y., ibid., 19, 187 (1970). (297) Yotsuyanagi, T., Yamada, 11., Aomura, K., ibid., 18, 1108 (1969). (298) Zadvornyi, A. S., Gorenko, A. F., Skakun, N. A,, Klyucharev, A. P., Z h . Anal. Khim., 2 5 , 346 (1970). (299) Zatsepina, E. hl., Lakokrasoch. Mater. Zkh. Prirnen. 5 , 4 4 (1968). (300) Zhechkova, L. A,, hlukhina, R. E., Romanova, N. S., Zavod. Lab., 34, 409 (1968). (301) Zhivopistsev, V. P., Petrov, B. I., Selexneva, E. A,, Gibiryakov, N. F., T r u d y K o m . Analit. Khini., 16, 80 (1968). (302) Zhukova, XI. P., Sb. T r . Tsent. Sauch.-Zsslcd. Inst. Chern. .lTet. No. 66.30 (1969). (303) Zimmer, K., Ikrenyi, K., JTagy. Kem. Foly., 76 (2), 78 (1970). (304) Zinchenko, V. A,, Vasil’eva, K. S., Zavod. Lab., 35, 1317 (1969). (303) Zuda, A., Jitea, I., Revta. Chim.,18 (6), 365 (1967).


119 R

aluminum, beryllium, titanium, and magnesium

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