Precipitated iron: a limit on gettering efficacy in multicrystalline silicon

A phosphorus diffusion gettering model is used to examine the efficacy of a standard gettering process on interstitial and precipitated iron in multicrystalline silicon. The model predicts a large concentration of precipitated iron remaining after standard gettering for most as-grown iron distributions. Although changes in the precipitated iron distribution are predicted to be small, the simulated post-processing interstitial iron concentration is predicted to depend strongly on the as-grown distribution of precipitates, indicating that precipitates must be considered as internal sources of contamination during processing. To inform and validate the model, the iron distributions before and after a standard phosphorus diffusion step are studied in samples from the bottom, middle, and top of an intentionally Fe-contaminated laboratory ingot. A census of iron-silicide precipitates taken by synchrotron-based X-ray fluorescence microscopy confirms the presence of a high density of iron-silicide precipitates both before and after phosphorus diffusion. A comparable precipitated iron distribution was measured in a sister wafer after hydrogenation during a firing step. The similar distributions of precipitated iron seen after each step in the solar cell process confirm that the effect of standard gettering on precipitated iron is strongly limited as predicted by simulation. Good agreement between the experimental and simulated data supports the hypothesis that gettering kinetics is governed by not only the total iron concentration but also by the distribution of precipitated iron. Finally, future directions based on the modeling are suggested for the improvement of effective minority carrier lifetime in multicrystalline silicon solar cells.

(Table 19, page 199) Minor constituents of one of the San Clemente iron concretions and its metallic core

The chemical and mineralogical composition of pelagic sediments from the East Pacific Ocean has been determined with the aim of defining the ultimate sources and the mechanisms of formation of the solid phases. The distribution of elements between sea-water, the pore solution and the various solid components of the sediments permits interpretations of the variations in time and space of the gross chemical composition of pelagic clays. For example, manganese, present in sea-water in a divalent form, is apparently oxidized at the sediment-water interface to tetravalent species which subsequently become a part of the group of ferromanganese oxide minerals which are found in the marine environment. It is suggested the rate of manganese accumulation in sediments is some function of the length of time the sediment surface is in contact with sea-water. The contribution of chemical species from the different geospheres is considered. The quantitative importance of pelagic clays in the major sedimentary cycle is studied on the basis of the distribution of the weathered igneous rock products between continental and pelagic deposits and sea-water. These analyses of a wide variety of pelagic clays allow a reformulation of the geochemical balance and it is concluded that pelagic clays account for approximately 13 per cent of the total mass of sediments produced over geologic time.

Anomalous scattering analysis of Agrobacterium radiobacter phosphotriesterase: the prominent role of iron in the heterobinuclear active site

Bacterial phosphotriesterases are binuclear metalloproteins for which the catalytic mechanism has been studied with a variety of techniques, principally using active sites reconstituted in vitro from apoenzymes. Here, atomic absorption spectroscopy and anomalous X-ray scattering have been used to determine the identity of the metals incorporated into the active site in vivo. We have recombinantly expressed the phosphotriesterase from Agrobacterium radiobacter (OpdA) in Escherichia coli grown in medium supplemented with 1 mM CoCl2 and in unsupplemented medium. Anomalous scattering data, collected from a single crystal at the Fe-K, Co-K and Zn-K edges, indicate that iron and cobalt are the primary constituents of the two metal-binding sites in the catalytic centre (alpha and P) in the protein expressed in E. coli grown in supplemented medium. Comparison with OpdA expressed in unsupplemented medium demonstrates that the cobalt present in the supplemented medium replaced zinc at the beta-position of the active site, which results in an increase in the catalytic efficiency of the enzyme. These results suggest an essential role for iron in the catalytic mechanism of bacterial phosphotriesterases, and that these phosphotriesterases are natively heterobinuclear iron-zinc enzymes.

Use of ultrasonic agitation in iron group alloy electrodepositions

The effects of ultrasonic agitation on deposition from two iron group alloy plating solutions, nickel-cobalt and bright nickel-iron, have been studied. Comparison has been made with deposits plated from the same solutions using controlled air agitation. The ultrasonic equipment employed had a fixed frequency of 13 KHz but the power output from each transducer was variable up to a maximum of 350 watts. The effects of air and ultrasonic agitation on hardness, ductility, tensile strength, composition, structure, surface topography, limiting current density, cathode current efficiency and macro-throwing power were determined. Transmission and scanning electron microscopy, electron-probe microanalysis and atomic absorption spectrophotometry have been employed to study the nickel alloy deposits produced. The results obtained show that the use of Ultrasonics increased significantly the hardness of both alloy deposits and altered their composition by decreasing the cobalt and iron contents from nickel-cobalt and nickeliron solutions respectively. The ductility of coatings improved but the tensile strength did not change very much. Ultrasonic agitation gave larger grained deposits than air and they seemed to have a lower stress. Dull cobalt-nickel deposits had a similar pyramidal surface topography regardless of the type of agitation but the bright appearance of the nickel-iron was destroyed by ultrasonic agitation; an unusual ribbed pattern was produced. The use of ultrasonic agitation permitted approximately a twofold increase in the plating current density at which sound deposits could be achieved but there was only a slight increase in cathode current efficiency. Macro-throwing power of the solutions was increased slightly by the use of ultrasonic agitation. ultrasonic agitation is an expensive means of agitating plating Solutions and would be worthwhile only if significant improvements in properties could be achieved. The simultaneous improvement in hardness and ductility is a novel feature that should have useful engineering applications.

(Table 2, Page 106-107) Composition of the HCl-soluble fraction in Barents Sea iron-manganese deposits

Ferromanganese concretions from ten stations in the Barents Sea have been analysed for 24 elements. The deposits occur as discoidal and flat concretions and as coatings, in the latter case on lithified or detrital material or as extensive pavements on the Svalbard shelf. The concretions are compositionally similar to Baltic concretions but differ considerably from deep-ocean nodules, particularly in Cu, Ni and Co contents. Statistical analyses reveal distinct correlations between Mn, Na, Ba, Ni and Cu; the Mn-rich coatings showed enrichment of Mo, Zn and possibly Co in a Mn-phase. The iron phase holds high concretions of P and As. Two iron-rich concretions with high contents of P, Ca, Sr, Y, Yb and La were found east and northeast of Spitsbergen Banken, probably indicating upwelling of nutrient-rich, cold polar water along the Svalbard shelf.

(Table 1, Page 1046-1047) Chemical composition of iron-manganese concretions from the Indian Ocean recovered by the R/V Vityaz and the R/V Ob

The data given in this and previous communications is insufficient to assess the quantitative role of these supplementary sources in the Indian Ocean, but they do not rule out their local significance. Elucidation of this problem requires further data on the characteristics of the composition and structure of nodules in various different metallogenic regions of the ocean floor. A study of the distribution of ore elements in nodules both depthwise and over the area of the floor together with compilation of the first schematic maps based on the results of analyses of samples from 54 stations) enables us to give a more precise empirical relation between the Mn, Fe, Ni, Cu, and Co contents in Indian Ocean nodules, the manganese ratio and the values of the oxidation potential, which vary regularly with depth. This in turn also enables us to confirm that formation of nodules completes the prolonged process of deposition of ore components from ocean waters, and the complex physico-chemical transformations of sediments in the bottom layer. Microprobe investigation of ore rinds revealed the nonuniform distribution of a num¬ber of elements within them, owing to the capacity of particles of hydrated oxides of manganese and iron to adsorb various elements. High concentration of individual elements is correlated with local sectors of the ore rinds, in which the presence of todorokite, in particular, has been noted. The appearance of this mineral apparently requires elevated Ca, Mg, Na, and K concentrations, because the stable crystalline phase of this specific mineral form of the psilomelane group may be formed when these cations are incorporated into a lattice of the delta-MnO2 type.

Description and composition iron-manganese concretions from the Pacific

One the most interesting features of ocean sedimentation is the manganese formations on the surface of the ocean floor in some areas. These are especially widespread in the Pacific Ocean as concretions, grains, and crusts on rock fragments and bedrock outcrops. Iron-manganese concretions are the most abundant as they completely cover about 10% of the bottom of the Pacific Ocean where there are ore concentrations. The concretions occupy from 20-50% of the bottom and up to 80-90% on separate submarine rises. Such concretions are found in different types of bottom deposits, from abyssal red clays to terrigenous muds, but they occur most widely in red clays and quite often in carbonate muds. Their shape and their dimensions are very diverse and change from place to place, from station to station, varying from 0.5-20 cm. They may be oval, globular, reniform, or slaggy and often they are fiat or isometric concretions of an indefinite shape. The concretions generally have nuclei of pumice, basalt fragments, clayey and tuffaceous material, sharks' teeth, whale ossicles, and fossil sponges. Most concretions have concentric layers, combined with dendritic ramifications of iron and manganese oxides.