The microchemical analysis of ferrous and non-ferrous alloys

Satisfactory methods are described for the determination of certain of the alloying constituents in small quantities of steels, aluminium alloys and white metals. In steels, lead is determined by using an extraction procedure with dithizone, whereas the stable colour produced by vanadium with 3 : 3' dimethylnaphthidine is used for determining this element. In aluminium alloys, absorptiometric procedures are recommended for determining copper, nickel, iron and manganese. The determination of silicon is advocated by the absorptiometric technique. For the determination of antimony, in white metals, a micro volumetric procedure with standard potassium bromate is recommended using α-naphthaflavone as indicator.     

Simultaneous determination of trace niobium, tantalum and tungsten in ferrous and non-ferrous alloys

A method is presented for the determination of niobium, tantalum and tungsten in steel and non-ferrous alloys, based on hydrolysis with sulphurous acid followed by X-ray fluorescence measurements. The limit of determination is about 0.002% and the standard deviation is 0.002 at the 0.05% level. Results below 0.01% by this method are only semiquantitative.     

The rapid spectrophotometric determination of copper in non-ferrous alloys

A very simple method has been established for the rapid determination of copper, employing the formation of the chlorocupric anion by means of concentrated hydrochloric acid. The absorption of the chlorocupric anion is measured spectrophotometrically at a wavelength of 950 mμ. The method is applicable to a wide variety of samples, including many non-ferrous alloys.     

Direct spectrophotometric determination of iron in non-ferrous alloys

Disodium 3-(2-pyridyl)-1,2,4-triazine-5,6-di(4'-phenylsulphonate) is used for determination of iron in metal analysis. High selectivity is achieved by using a ligand buffer and substoichiometric masking. Interference from 0.9 mg of Cu(II) can be completely eliminated by combined reduction and masking with ascorbic acid and thiosemicarbazide. Beer's law is obeyed over the range 0.4-1.6 mug/ml iron in the final solution, with a standard deviation of 0.02 mug/ml. The method has been successfully applied to determination of iron (without preseparation) in a number of non-ferrous metals and alloys, with a coefficient of variation of 1.2-5.0%.     

Determination of boron in glass by neutron transmission method

Neutron transmission method has been used for the determination of boron in borosilicate glasses. The method is sensitive and rapid to control the spatial homogeneities of glass-product in the melting furnace.Dedicated to Academician J. Csikai on his 60th birthday.This work was supported by the National Foundation for Research (Contact No. 259).     

Spectrophotometric determination of titanium with tannin and thioglycollic acid and its application to titanium-treated steels and ferrous and non-ferrous alloys

A sensitive spectrophotometric method for the determination of titanium by formation of its complex with tannin and thioglycollic acid at pH 4 has been developed. The intense yellow colour is measured at 400 nm and the system obeys Beer's law over the range 0.2-5 ppm titanium in the solution measured. The method is applicable to titanium-treated steels, stainless steels, permanent magnet alloys and duralumin alloys. The interference of Co, Ni, Cr, Mn, V, Mo and W can be eliminated by prior separation of titanium by controlled addition of cupferron in the presence of thioglycollic acid (TGA). Copper can be quantitatively separated by precipitation with TGA and determined complexometrically with EDTA, with PAN as indicator. Niobium interferes even in traces.     

Spectrophotometric determination of iron in aluminium metal and some non-ferrous alloys

A new, sensitive and selective spectrophotometric method is suggested for the determination of traces of iron(III) based on complex formation with hematoxylin in presence of cetyltrimethylammonium bromide (CTAB). Addition of CTAB shifted the absorption maximum of the iron-hematoxylin complex from 630 to 640 nm and increased its molar absorptivity from 9.88 × 10⁴ to 1.16 × 10⁵ 1·mol^–1·cm^–1. The method adhered to Beer's law up to 0.4 and 0.2 g/ml of iron in presence and absence of CTAB, respectively. The corresponding values of Sandell's sensitivity were 0.5 and 0.6 ng·cm^–2. The effect of reagent and surfactant concentrations, pH and standing time were investigated. EDTA, tartrate and sodium fluoride were used as masking agents for most of the interfering ions. The method was successfully used for the determination of iron in aluminium metal and some non-ferrous alloys.     

The determination of boron in biological materials by neutron irradiation and prompt gamma-ray spectrometry

A prompt-gamma neutron activation technique has been developed using the (n, ) apparatus situated at the O degree through-tube of the Imperial College CONSORT II Reactor with a thermal neutron flux at the target position of approximately 2×10⁶ n cm^–2 sec^–1, and a Compton-suppression system involving a lithium-drifted germanium (Ge(Li)) detector and a sodium iodide anti-Compton shield. Boron levels of 1–5 g g^–1 (detection limit 0.05 g B for 10,000 sec period of measurement) can be attained using the Compton-suppression system with graphical inter-polation correction for the 472 keV sodium-ray peak contribution to the Doppler-broadened 478 keV boron gamma-ray peak resulting from the¹⁰B(n, )⁷Li reaction. Very good agreement is reached for boron levels compared using this system for various Standard Reference Materials and other published values. Measurement of the boron content of bone and tooth samples from rheumatoid arthritis individuals shows lower levels, (p<0.05); 16.13±7.53 g g^–1, when compared with a control population; 19.79±4.18 g g^–1. A positive correlation existed between the boron content of bone and tooth material for each study group. Results indicate that boron availability may be associated with rheumatoid arthritis.     

The determination of boron in sedimentary rocks by neutron irradiation and prompt γ-ray spectrometry

Prompt γ-rays following the (n_th, α) reaction on¹⁰B have been measured to determine the boron content of sedimentary rocks. Employing an external reactor neutron beam with only modest flux, it is possible to assay boron at concentrations typically encountered in this material (>5 μg/g). The technique relies on the use of chemical standards and the values obtained for 9 North American shales are compared with measurements performed by emission spectrography. Detection limits and statistical errors as a function of beam time are also discussed. Department of Geology, Mcmaster University, Hamilton, Ontario (Canada)     

Monitoring of gamma emission and neutron transmission during boron neutron capture treatment delivery

The ability to map boron and hydrogen distributions in the body is paramount to the success of boron neutron capture therapy (BNCT). We investigated treatment-time quantitative mapping of these distributions by detecting (i) 0.48 MeV de-excitation photons from neutron capture by boron-10; (ii) 2.22 MeV photons from neutron capture by hydrogen; and (iii) transmitted neutrons. Monte Carlo simulations reported no detectable difference when ¹⁰B in tumour was varied from 0 to 50 ppm, and when the tumour size was varied from 0.0 to 9.5 cm³.     

Rapid spectrophotometric determination of copper in iron,steel and ferrous alloys

A rapid spcctrophotometric mcthod for the determination of copper in iron, steel and ferrous alloys without separating the copper has been developed. The sample is dissolved in acid and ammonium citrate is added to complex the iron and other alloying elements. The pH is then adjusted to 8.0–9,5 with ammonium hydroxide. A solution of bis-cyclohexanone-oxalyldihydrazone ia finally added and the absorbance of the blue copper complex formed is measured.     

Determination of aluminium in molybdenum and tungsten metals, iron, steel and ferrous and non-ferrous alloys with pyrocatechol violet

A method for determining 0.001-0.10% of aluminium in molybdenum and tungsten metals is described. After sample dissolution, aluminium is separated from the matrix materials by chloroform extraction of its acetylacetone complex, at pH 6.5, from an ammonium acetate-hydrogen peroxide medium, then back-extracted into 12M hydrochloric add. Following separation of most co-extracted elements, except for beryllium and small amounts of chroinium(III) and copper(II), by a combined ammonium pyrrolidincdithiocarbamate-cupfen-on-chlorofonn extraction, aluminium is determined spectrophotometrically with Pyrocatechol Violet at 578 nm. Chromium interferes during colour development but beryllium, in amounts equivalent to the aluminium concentration, does not cause significant error in the results. Interference from copper(II) is eliminated by reduction with ascorbic acid. The proposed method is also applicable to iron, steel, ferrovanadium, and copper-base alloys after preliminary removal of the matrix elements by a mercury cathode separation.     

Spectrophotometric determination of bismuth in concentrates and non-ferrous alloys by the iodide method after separations by diethyldithiocarbamate and xanthate extraction

A method for determining 0.0001-1% of bismuth in copper, molybdenum, lead, zinc and nickel sulphide concentrates is described. After sample decomposition, bismuth is separated from matrix and other elements, except lead and thallium(III), by chloroform extraction of its diethyldithiocarbamate complex, pH 11.5-12.0, from a sodium hydroxide medium containing citric acid, tartaric acid, EDTA and potassium cyanide as complexing agents. Following back-extraction of bismuth into 12M hydrochloric acid and reduction of thallium to the univalent state, bismuth is separated from co-extracted lead and thallium by chloroform extraction of its xanthate from a 2.5M hydrochloric acid-tartaric acid-ammonium chloride medium. Bismuth is then determined spectrophotometrically, at 337 or 460 nm, as the iodide. Interference from lead, which is co-extracted in mug-amounts as the xanthate and causes high results at 337 nm, is eliminated by washing the extract with a hydrochloric acid solution of the same composition as the medium used for extraction. The proposed method is also applicable to lead-, tin- and copper-base alloys.     

The determination of zirconium and aluminium in alloys slags and fumes by 14-mev neutron activation analysis

Aluminium and zirconium have beendetermined in alloys, slags and fumes by 14-MeV neutron activation analysis. Nuclear reactions with zirconium have been investigated, and the radioisotopes produced by 14-MeV neutron activation have been determined. The results for alloys and slags agree well with those obtained by chemical methods; precisions of 1.8% were obtained in ideal cases. The neutron activation method is capable of analysing 10–12 samples, in duplicate, per man-day.     

Accurate and efficient determination of boron content in volcanic rocks by neutron induced prompt gamma-ray analysis

An accurate and efficient analytical method using neutron-induced prompt γ-ray was developed for the determination of boron contents in volcanic rocks. We corrected the effect of sample geometry and flux fluctuation by using silicon as an internal standard. However, we found that the slopes of the calibration line vary among volcanic samples with different matrix. Because the increase of boron activity correlates positively with γ-ray count rate of hydrogen (water), we call this as the hydrogen effect. The hydrogen effect was confirmed by our experiment in which the boron activities showed systematic increase with the amount of added hydrogen (water). Most volcanic rocks, however, contain little water (<2 wt.%) to show this effect. We determined boron contents in various volcanic rocks in order to confirm the validity of the procedure that we established. The analyzed boron contents agreed well with the previous reported values. For efficient PGA of boron in volcanic rocks, we recommend JB-2 (GSJ standard rock) as a single geochemical standard, because of its high boron content (31.2 ppm).     

Nondestructive and destructive determination of manganese in nickel- and iron-base alloys by neutron activation analysis

Nondestructive and destructive methods are described for the determination, by neutron activation, of small amounts (more than about 0.001%) of manganese in nickel- and iron-base alloys. In the destructive method, thenoyltrifluoroacetone (TTA) extraction has been applied to the separation of manganese after irradiation.     

Spectrophotometric determination of traces of several metals in ferrous and nonferrous metals and alloys after isolation by iodide extraction

Methods are presented for the determination of traces of lead, cadmium, indium, bismuth, copper, and antimony in most of the important metals and alloys used in industry. The trace metals are isolated by hexone extraction of their iodides from 5% hydrochloric acid solution and then determined spectrophotometrically. The attractive feature of the proposed procedures is that the method used for each of the trace metals is applicable to all of the matrix metals and alloys being considered.