INAA for control of technology in producing Mo and W

INAA technique for the determination of impurities (O, F, Na, Mg, Al, Si, P, S, K, Sc, Cr, Mn, Fe, Co, Ni, etc.) and of some doping elements in molybdenum and tungsten with detections limits between 10^–12 and 10^–6g/g by using a nuclear reactor and a neutron generator have been developed. The methods have been used to control the products of processing of refractory materials, to study the dynamics of impurities and doping elements at all stages of the production process.     

Comparative PGAA and NAA results of geological samples and standards

Concentrations of major and trace elements in volcanic rock and soil samples, including geological standard reference materials, were determined by neutron activation analysis (NAA) and prompt gamma activation analysis (PGAA), both using the k ₀-standardization method. The paper highlights the different experimental procedures, such as sample preparation, data collection and spectrum evaluation. In geological samples, PGAA gives precise results for major elements (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K and—as a unique method—for H), for some of the light trace elements as B and Cl, as well as for Sc, S, Cr, Co, Ni, Cd, Nd, Sm and Gd. NAA is sensitive for the rare earth elements, and for many major (Ti, Al, Fe, Mn, Mg, Ca, Na, K) and trace elements (e.g.: Sc, V, Cr, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Zr, As, Sb, Ce, Ba, Hf, Ta, W). For most major elements the results obtained by the two methods show good agreement. The comparison of the results obtained for trace elements is not always possible, since PGAA is less sensitive and concentrations are often below its detection limits. Nevertheless, the complementarity of NAA and PGAA allows nearly panoramic analysis of geological materials.     

Findings of national proficiency test exercise for the determination of trace elements in edible mushroom reference material

This paper presents the results of the proficiency test exercise conducted in Pakistan for the determination of trace elements in mushroom reference material. Thirteen laboratories from different organizations of the country submitted trace elemental data on Al, As, Br, Ca, Cd, Ce, Cl, Co, Cr, Cs, Cu, Fe, Hg, K, Li, Mg, Mn, Na, P, Pb, Rb Sc, Si, Sm, Sr, Th, Zn. Results for Al, As, Br, Ca, Cd, Cl, Co, Cr, Cs, Cu, Fe, K, Mg, Mn, Na, Rb Sc, and Zn, in the mushroom material were reported by two or more participating laboratories and could be subjected to statistical evaluation. The original data of these trace elements was subjected to a computer program “Histo Version 2.1” provided by IAEA. The four outlier tests, i.e., Dixon, Grubbs, skewness and kurtosis were applied to the data sets. Consensus (overall) mean values, absolute standard deviation, relative standard deviation, standard error, median and range of values for these elements have been reported at a significance level of 0.05.     

South Aegean Volcanic Glass: Separation and Analysis by INAA and EPMA

Pumice from the major volcanic sources (Milos, Nisyros, Yali, Kos and Santorini) in the South Aegean region was investigated to reveal the differences between the composition of the bulk material, which contains a certain percentage of crystallites, and the pure glass phase, which is the main constituent. The knowledge of these differences is important for the identification of vitric tephra layers found in the Eastern Mediterranean region in archacological context, in deep sea drilling cores and lake sediments. Eruption products, deposited at some distance, show not only a decrease in their grain size, but also have usually lost their crystalline fraction due to gravity separation and consist only of glass shards. Major element distributions in such layers and in pumiceous glass are not sufficient for a reliable identification of the volcanic source, as several eruptions are known to have produced chemically very similar tephra layers in this region. Trace element data, especially of the rather immobile rare earth elements (REEs), can provide greater information on tephra originating from different volcanic eruptions. Therefore, a technique has been developed to separate the glass phase from different primary pumices to reveal differences in their trace element distributions. The concentrations of the major constituents, in particular Al, Ca, Fe, Mg, Mn, Na, Si, and Ti were determined by electron probe microanalysis (EPMA), those of Al, As, Ba, Ca, Ce, Co, Cr, Cs, Dy, Eu, Fe, Hf, K, La, Lu, Mn, Na, Nd, Rb, Sb, Sc, Sm, Ta, Th, Ti, U, V, Yb and Zr by instrumental neutron activation analysis. Subtle differences between the compositions of the glass phase and the bulk material are explained by differentiation during partial crystallization. Their applicability to the classification of tephra layers is demonstrated.     

Synthesis, structure, and properties of BaAl2Si2

Single crystals of BaAl2Si2 were grown from an Al molten flux and characterized using single-crystal X-ray diffraction at 10 and 90 K and neutron diffraction at room temperature. BaAl2Si2 crystallizes with the alpha-BaCu2S2 structure type (Pnma), is isostructural with alpha-BaAl2Ge2, and is an open 3D framework compound, where Al and Si form a covalent cagelike network with Ba2+ cations residing in the cages. BaAl2Si2 has a unit cell of a=10.070(3) A, b=4.234(1) A, and c=10.866(3) A, as determined by room-temperature single-crystal neutron diffraction (R1=0.0533, wR2=0.1034). The structure as determined by single-crystal neutron and X-ray diffraction (10 and 90 K) indicates that BaAl2Si2 (Pnma) is strictly isostructural to other (alpha)-BaCu2S2-type structures, requiring site specificity for Al and Si. Unlike BaAl2Ge2, no evidence for an alpha to beta (BaZn2P2-type, I4/mmm) phase transition was observed. This compound shows metallic electronic resistivity and Pauli paramagnetic behavior.     

Separation and Analysis of Theran Volcanic Glass by INAA, XRF and EPMA

 Pumice from the “Minoan eruption” on Thera (Cyclades, Greece) was investigated to reveal the differences between the composition of the bulk material, which contains a certain percentage of crystallites, and the pure glass phase. This is important for the identification of vitric tephra layers found in the Eastern Mediterranean region in archaeological context and in deep sea drilling cores. Eruption products, deposited at some distance, have usually lost their crystalline fraction due to gravity separation and consist only of glass shards. Only major element distributions in such layers and in pumiceous glass phases have been published up to now, but these data are not sufficient for a reliable identification of the volcanic source, as several other eruptions are known to have produced chemically very similar layers in this region (Milos, Nisyros, Yali, Kos). Therefore, a technique has been developed to separate the glass phase from the primary pumice to reveal differences in the trace element distributions obtained by instrumental neutron activation analysis (INAA). X-ray diffractometry and microscopical techniques were applied to check the purity of this fraction. The concentrations of the major constituents, in particular Al, Ca, Fe, K, Mg, Mn, Na, Si, and Ti were determined by X-ray fluorescence (XRF) and electron probe microanalysis (EPMA), those of Al, Ba, Ca, Ce, Co, Cr, Cs, Dy, Eu, Fe, Hf, K, La, Lu, Mn, Na, Nd, Rb, Sb, Sc, Sm, Ta, Ti, Th, U, Yb and Zr by instrumental neutron activation analysis and partly also by X-ray fluorescence. Subtle differences between the compositions of the glass phase and the bulk material are explained by differentiation during partial crystallization and their applicability to the classification of tephra layers is demonstrated.     

Studies in heavy ion activation analysis

¹⁸O induced radioactivation may be used for the trace detection of¹H via¹H (¹⁸O, n)¹⁸F. Matrices in which this reaction is interference-free include: Al, Si, S, K, Ti, V, Ni, Cu and Zn. However, due to numerous radioisotopes created at the bombarding energies used (E≥51 MeV), a post-irradiation chemical separation of¹⁸F is required.¹⁸O activation also appears as a promising means for the trace determination of S[S(¹⁸O, x)⁴⁷V], Si[Si(¹⁸O, x)^43–44Sc] and B[B(¹⁸O, x)³⁷Mg]. Part I: in Journal of Radioanalytical Chemistry, 53 (1979) 181.     

Structure and thermoelectric characterization of Ba8Al14Si31

A molten Al flux method was used to grow single crystals of the type I clathrate compound Ba8Al14Si31. Single-crystal neutron diffraction data for Ba8Al14Si31 were collected at room temperature using the SCD instrument at the Intense Pulsed Neutron Source, Argonne National Laboratory. Single-crystal neutron diffraction of Ba8Al14Si31 confirms that the Al partially occupies all of the framework sites (R1 = 0.0435, wR2 = 0.0687). Stoichiometry was determined by electron microprobe analysis, density measurements, and neutron diffraction analysis. Solid-state (27)Al NMR provides additional evidence for site preferences within the framework. This phase is best described as a framework-deficient solid solution Ba8Al14Si31, with the general formula, Ba(8)Al(x)Si(42-3/4x)[](4-1/4x) ([] indicates lattice defects). DSC measurements and powder X-ray diffraction data indicate that this is a congruently melting phase at 1416 K. Temperature-dependent resistivity reveals metallic behavior. The negative Seebeck coefficient indicates transport processes dominated by electrons as carriers.     

Neutron activation analysis for determination of trace elements in sediments in the Sea of Galilee,Israel

The feasibility of applying both thermal and epithermal neutron activation analysis for simultaneous determinations of elemental composition in sediments, collected from the Sea of Galilee (Kineret Lake), Israel, during 1988–1993, was experimentally investigated. In the present work, the concentrations of 30 elements (Al, Ba, Br, Ca, Ce, Co, Cs, Cr, Eu, Fe, Hf, K, La, Lu, Mg, Mn, Na, Nd, Rb, Sc, Si, Sr, Ta, Tb, Th, Ti, U, V, Yb and Zn) in sediments were determined. The validity of the method was checked by analyzing the U.S. NBS Standard Reference Material SRM-1633a; the elemental content found agreed well with the published certified data. Aluminium was determined by reactor neutron activation analysis (RNAA) taking into account the contribution of silicon to the total²⁸Al activity by the²⁸Si(n,p)²⁸Al reaction. Measurements of irradiated mixtures of Si and Al showed that the dependence of log SiAl mass ratio vs. log cadmium ratio (R _Cd) of²⁸Al is almost linear. The data can be analyzed more accurately by a parabolic correlation (log Si:Al mass ratio vs logR _Cd). The concentrations of fission radionuclide¹³⁷Cs, an activation radionuclide¹³⁴Cs (derived from Chernobyl accident) and the naturally occuring radionuclides⁴⁰K,²²⁶Ra and²³²Th in sediments were also measured by -ray spectrometry using Marinelli (Reentrant) Beaker-Sample Containers.     

A new family of oxide ion conductors based on tricalcium oxy-silicate

Tricalcium oxy-silicates, Ca3(SiO4)O and Ca2.93Mg0.07(Si0.98Al0.02O4)O0.99 [square]0.01, have been prepared as crystalline single phases. Ca3(SiO4)O and Ca2.93Mg0.07(Si0.98Al0.02O4)O0.99 [square]0.01 have triclinic and monoclinic structures, respectively. The samples show oxide anion conductivity with a small p-type electronic contribution under oxidizing conditions. At 1023 K, the oxide transport numbers range between 0.97 and 0.85 from reducing (dry 5%-H2-Ar/air gradient) to oxidizing (O2/air gradient) conditions in the 1023-1173 K interval. The thermal analyses showed a large weight loss on heating due to the presence of water in the materials. The monoclinic compound has ionic conductivities higher than those of the triclinic stoichiometric oxy-silicate, as expected due to the introduction of oxide vacancies. Typical total conductivities for these un-optimised solids are 10(-5)-10(-4) S cm(-1) at 1100 K. These compounds may contain a small amount of water, approximately 0.05 H2O moles per chemical formula, and they display an important proton contribution under a humidified atmosphere.     

Hydrothermal Stability of the Novel Zeolite Type LSX in Comparison to the Traditional 13X Modification

Ion‐exchanged LSX (Si/Al = 1.02) and 13X (Si/Al = 1.18) zeolite series (Li, Na, K, Rb, Ca, Sr, Ba exchanged) were hydrothermally treated at temperatures between 423 K and 513 K in liquid water under autogeneous water vapour pressure. Beside X‐ray powder diffraction, the molybdate method and the water sorption uptake have been used to characterize the treated samples. The LSX and 13X zeolites show a similar hydrothermal behaviour in spite of their different framework Si/Al ratios depending only on the type of introduced cations. Significant destabilizing effects were observed especially in presence of K and Rb cations as well as the bivalent Sr and Ba cations. The LSX zeolites are hydrothermally more stable than LTA zeolites of same cations despite their same chemical framework composition.     

焙烧对HZSM－5分子筛结构的影响

运用魔角自转固态核磁共振谱（ＭＡＳ－ＮＭＲ），研究了焙烧对ＨＺＳＭ－５分子筛结构的影响．结果表明，高温焙烧将引起ＨＺＳＭ－５分子筛骨架的脱铝，当焙烧温度从５００℃增加到７００℃时，ＨＺＳＭ－５的骨架Ｓｉ／Ａｌ比由１６．７增加至２２．７；而当焙烧温度由７００℃到８００℃时，骨架Ｓｉ／Ａｌ比则由２２．７增加到了４８．５．２７Ａｌ－ＭＡＳＮＭＲ结果表明，从骨架上脱下来的铝，部分地形成了ＮＭＲ不可见的无定形态．随着焙烧温度的升高，ＮＭＲ不可见铝增多     

Syntheses,structures and properties of five chiral quaternary sulfides,AlxLn_3(Si_yAl_(1-γ))S_7 (Ln=Y,Gd,Dy) and In_(0.33)Sm_3SiS_7

Five new quaternary isostructural rare-earth sulfides, Al0.57Gd3(Si0.27Al0.73)S7 (1), Al0.55Dy3(Si0.34Al0.66)S7 (2), Al0.50Y3(Si0.50Al0.50)S7 (3), Al0.44Gd3(Si0.70Al0.30)S7 (4) and In0.33Sm3SiS7 (5), have been synthesized by facile solid-state reactions. They crystallize in the 3-D ALn3EQ7 structure type in the hexagonal chiral space group P63. The structures feature a 3-D host framework constructed by Ln-S bicapped trigonal prisms, in which the octahedral and tetrahedral interspaces are occupied by A and E...     

Structural studies on thorium(IV)-titriplex IV-interacted 13X zeolite

A new zeolite derivative has been prepared by interacting Th(IV) and complexone in HCl medium and neutralising with aqueous ammonia. The amorphous and siliceous derivative showed a total mass loss of 29.25% in TG for stepwise dehydration, dehydroxylation and decomposition. Heats of reaction were 1167.6 J g^–1 at 88.7°C and 75.167 J g^–1 at 492.5°C for loss of volatile components and decomposition respectively.²⁹Si and²⁷Al MAS NMR spectra as well as XRD data of the derivative before and after calcination indicate presence of both four-coordinated and six-coordinated Al in varying ratios and the total loss of crystallinity.The author is grateful to Dr. Alan Dyer of the Department of Chemistry and Applied Chemistry, Salford University and to Dr. Jacek Klinowski of the Department of Chemistry, Cambridge University for providing the thermal data and NMR spectra respectively. He also acknowledges the comments received from Dr. N. Suryaprakash of the Sophisticated Instrument Facility, I.I.Sc., Bangalore on the²⁷Al and²⁹Si spectra of the derivatives.     

Determination of 21 elements by INAA for certification of SRM 1570a,Spinach

Analyses for certification have been made by instrumental neutron activation analysis (INAA) for the determination of 21 elements in the National Institute of Standards and Technology (NIST) Spinach renewal reference material, SRM 1570a. Elements determined included ones with short halflife products (Al, V, Ca, Mg), intermediate halflife products (Mn, Na, K, La), and long halflife products (Ba, Co, Cr, Cs, Eu, Fe, Rb, Sb, Sc, Se, Sr, Th, and Zn). For the first time a new robotic sample changer was used in the counting of long halflife indicator isotopes for certification of an SRM. Uncertainties obtained averaged±1.80% for the four major and minor constituents (Ca, K, Mg, Na); ±3.14% for elements with concentrations from 1 to 400 mg/kg (Al, Ba, Cr, Fe, Mn, Rb, Sr, and Zn); and±8.31% for the ultra trace elements (<1 mg/kg) (Co, Cs, Eu, La, Sb, Sc, Se, Th, and V).     

Application of nondestructive X-ray fluorescence analysis to determine the element composition of medicinal plants

A nondestructive X-ray fluorescence technique has been developed to determine Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr, Ba, and Pb in plants. The line element intensities were measured by an S4 Pioneer X-ray sequence spectrometer (Bruker AXS, Germany). The inversely proportional relationship was obtained between the analyte line intensity and mass of the plant, pressed on boric acid backing, for elements with an atomic number 11 < Z < 20. It was found that reduction of plant mass from 6 to 1 g leads to an increase in element determination sensitivity. The detection limits for 1 g of pressed plant were evaluated as μg/g: 5–20 (Na, Mg, Al); 1–4 (Si, P, S, Cl, K, Ca, Ti, Ba, Pb); 0.4-0.8 (Cr, Mn, Fe, Ni, Br, Cu, Zn, Rb and Sr). This technique was applied to determine the element composition of violets of Violaceae family, which are used in medicine.     

Determination of some trace elements in natural and fertilised Libyan soils using INAA and ED-XRF

Samples of natural and fertilised soils were collected from Al-Gheran region, west of Tripoli, Libya. The samples were investigated by means of INAA and ED-XRF for Al, Si, K, Ca, Sc, Cr, Mn, Fe, Co, Zn, Br, Rb, Sr, Y, Zr, Nb, Cs, Ba, Hf, Ta, Pb and Th. The results indicate that the concentrations of K, Ca, Zn, Sr and Pb are 2–4 fold higher in fertilised compared to natural soil, while the concentrations of Al, Si, Cr, Mn, Fe, Co, Rb, Y, Nb, Cs, Ba Ta and Th are nearly the same in all samples. Mn and Fe values in two arable soils have been found to be 4–6 times lower than the average concentration in the earth's surface soils. This study concludes that, although the levels of some trace elements important for human health are very low in both natural and fertilised soils. Further research is needed to understand the full significance of the distribution transfer and toxicity of trace elements introduced in imported fertilisers.     

Investigation of different types of filters for atmospheric trace elements analysis by three analytical techniques

Different atmospheric aerosol samples were collected on three types of filters. Disks of both loaded and clean areas of each kind of filter were investigated by XRF, PIXE and Scanning Electron Microscope (SEM) methods. The blank concentration values of the elements Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Br and Pb in the three types of fiters are discussed. It is found that for trace elemental analysis, the Nuclepore membrane filters are the most suitable for sampling. These have much lower blank element concentration values than the glass fibres and ash free filters. It was found also that the PIXE method is a more reliable analytical technique for atmospheric aerosol particles than the other methods.     

Comparison of different types of filters for atmospheric trace element analysis by three analytical methods

Different atmospheric aerosol samples were collected on three types of filters. From both of the loaded and clean areas of each kind of filter, different disks were cut and investigated by XRF, PIXE and scanning electron microscopy (SEM). The blank concentration values of the elements Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Br and Pb in the three types of filter are discussed. It is found that for trace elemental analysis, the Nuclepore membrane filters are the most suitable for sampling. These filters have much lower blank element concentrations than the glass fiber and ash free filters. It was found also that PIXE is a more reliable analytical technique for atmospheric aerosol particles than the other methods used.     

Ternary Rhodium Borides A3Rh5B2 (A = Mg,Sc) and Quaternary Derivatives A2MRh5B2. Preparation,Crystal Structure (M = Main Group and 3 d Elements), and Magnetism (M = Mn,Fe)

The new ternary rhodium borides Mg₃Rh₅B₂ and Sc₃Rh₅B₂ (P4/mbm, Z = 2; a = 943.4(1) pm, c = 292.2(1) pm and a = 943.2(1) pm, c = 308.7(1) pm, respectively) crystallize with the Ti₃Co₅B₂ type structure. Mg and Sc may in part be substituted by a variety of elements M. For M = Si and Fe, homogeneity ranges were found according to A_3–xM_xRh₅B₂ with 0 ≤ x ≤ 1.0 for A = Sc and with x up to 1.5 for A = Mg. Quaternary compounds with x = 1 (A₂MRh₅B₂: A/M in short) were prepared with M = Be, Al, Si, P, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Sn (Co, Ni only with A = Mg; Sn only with A = Sc; P, As with deficiencies). Single crystal X‐ray investigations show an ordered substitutional variant of the Ti₃Co₅B₂ type in which the M atoms are arranged in chains along [001] with intrachain and interchain M–M distances of about 300 pm and 660 pm, respectively. Measuring the magnetisation (1.7 K–800 K) of the phases Mg/Mn, Sc/Mn, Mg/Fe, and Sc/Fe reveals antiferromagnetic interactions in the first and dominating ferromagnetic intrachain interactions in the remaining ones. Interchain interactions of antiferromagnetic nature are evident in Sc/Mn and Mg/Fe leading to metamagnetism below T_N = 130 K, while Sc/Fe behaves ferromagnetically below T_C = 450 K. The overall trend towards stronger ferromagnetic interactions with increasing valence electron concentration is obvious.