A comparative study of diffusion samplers for the determination of hexavalent chromium by sequential injection spectrophotometry

A method is described for determining hexavalent chromium in high particulate-containing surface waters by sequential injection (SI). The relative performance of two membrane-based methods for sampling is compared. The first membrane approach is based on a commercial design known as the ‘supported capillary membrane sampler (SCMS)’ (Wolcott, D.K., US Pat. 5 317 932 (1995)) that uses tubular membranes; the second approach is based on a conventional parallel-plate dialyzer (PPD) design that uses planar membranes. The membranes are evaluated using the well-known colorimetric method for the determination of hexavalent chromium by complexation with 1,5-diphenylcarbazide (DPC). Thin-walled (∼200 μm) microporous (pore size ∼0.2 μm) polypropylene membranes are equilibrated with DPC during each sampling period. Formation of the DPC-Cr(VI) complex allows for efficient membrane transport; without the membrane, Cr(VI) transport decreases ∼90%. Factors optimized included reagent concentrations, sampling time, flow rate, and spectrophotometric conditions. Optimal conditions were 2.00 mM DPC and 0.100 M nitric acid for the reagent, and 600 and 900 s sampling times for the planar and tubular designs, respectively. The planar (PPD) design increased the sensitivity relative to the tubular (SCMS) design by ∼225%. The PPD-SI method was applied to the determination of dissolved Cr(VI) in high particulate-containing surface water samples. Figures of merit included a detection limit of <20 μg/l, precision of 1.1% R.S.D. at 100 μg/l (n=4), and selectivity for dissolved Cr(VI) in several surface water samples with high levels of particulate matter.     

Photo-induced phenomena in sputtered GeO2 films

Macroscopic and microscopic changes in sputtered GeO₂ films induced by band-gap light from an ArF excimer laser have been studied. When irradiated at 1 atm, the film thickness increases, surface-roughness increases, refractive-index decreases, hygroscopic enhancements, and Ge-O-Ge distance increases. Irradiations in vacuum make these changes smaller or undetectable. These photo-induced changes are discussed from phenomenological and structural viewpoints, and compared with characteristics in GeO₂-SiO₂ and GeS₂ films.     

Bubble transport in three-dimensional laminar gravity-driven flow - numerical results

This paper is the second part of a study on bubble transport, growth and shrinkage in three-dimensional gravity driven flow. Sample calculations with applications to glass melting furnaces are presented. First, a consistent set of thermophysical properties of the most common composition (74SiO₂-16Na₂O-10CaO (mol%)) of soda-lime silicate glass or similar compositions over the temperature range of 1000-2000 K is reported. The population balance equation is solved for the bubble density function using the backward method of characteristics. The zeroth to third order moments, i.e., number of bubbles, average radius, molar gas fraction, interfacial area, and void fraction are computed by numerical integration. Results for both transient and steady state operations are presented and analysed. Two cases are considered (1) bubbles containing only CO₂ and (2) bubbles containing a diffusing gas (O₂) and a non-diffusing gas (CO₂). The feasibility of such complex calculation is demonstrated and is in qualitative agreement with reported results.     

Infrared transmitting chalcogenide glass ceramics

Infrared glass ceramics transmitting light from 2 to 15 μm have been produced from a Ga-Ge-Sb-Se glass. The glass composition is selected in the middle of the glass forming region and the annealing temperature must be close to T_g to avoid excessive crystal growth. A heating time of the order of two weeks is necessary to see evolution of the thermal expansion coefficient of the composite while keeping the optical transmission properties of the glass.     

Chemical stability of Ni-enriched nanodomains in alkali borate glasses

The stability of Ni nanodomains observed in low alkali borate glasses (10 mol% alkali oxide) has been investigated at higher alkali contents using Ni K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. EXAFS data indicate that the Ni nanodomains disappear progressively when adding alkali oxide, whatever the nature of the alkali. This medium range reorganization around Ni is associated with a change of the local site from 6- to 5-fold coordination at 27-30 mol% alkali oxide and 4-fold coordination at higher alkali oxide content. Ni-Ni connections are still present for ^[5]Ni but no second neighbors are observed for ^[4]Ni in the EXAFS signal. The changes at both the local and medium range around Ni are likely associated to the disappearance of the large, rigid borate groups with the addition of alkali oxide.     

Structural investigation of SnO-B2O3 glasses by solid-state NMR and X-ray photoelectron spectroscopy

Local structure of the SnO-B₂O₃ glasses was investigated using several spectroscopic techniques. ¹¹B MAS-NMR spectra suggested that BO₄ tetrahedral units maximized at around the composition with 50 mol% SnO. The BO₄ units were still present at compositions with high SnO content (67 mol% SnO), suggesting that SnO acted not only as a network modifier but also as a network former. O1s photoelectron spectra revealed that the addition of small amounts of SnO formed non-bridging oxygens (NBO) (B-O?Sn) and the amounts of NBO increased with an increase in SnO content. ¹¹⁹Sn Mössbauer spectra indicated that Sn was present only as Sn(II) in the glasses. The structure of the SnO-B₂O₃ glasses was compared with that of conventional alkali borate glasses and lead borate glasses. The thermal and viscous properties of these glasses were discussed on the basis of the glass structure revealed in the present study.     

A Low-Temperature Approach for the Phase-Pure Synthesis of MIL-140 Structured Metal–Organic Frameworks

In a systematic investigation, the synthesis of metal–organic frameworks (MOFs) with MIL-140 structure was studied. The precursors of this family of MOFs are the same as for the formation of the well-known UiO-type MOFs although the synthesis temperature for MIL-140 is significantly higher. This study is focused on the formation of Zr-based MIL-140 MOFs with terephthalic acid (H₂bdc), biphenyl-4,4′-dicarboxylic acid (H₂bpdc), and 4,4′-stilbenedicarboxylic acid (H₂sdc) and the introduction of synthesis field diagrams to discover parameters for phase-pure products. In this context, a MIL-140 network with H₂sdc as linker molecule is first reported. Additionally, an important aspect is the reduction of the synthesis temperature to make MIL-140 MOFs more accessible even though linkers with a more delicate nature are used. The solvothermal syntheses were conducted in highly concentrated reaction mixtures whereby a targeted synthesis to yield the MIL-140 phase is possible. Furthermore, the effect of the often-used modulator approach is examined for these systems. Finally, the characteristics of the synthesized MOFs are compared with physisorption measurements, thermogravimetric analyses, and scanning electron microscopy.     

Neutron Generation in an Extended Cu Target Irradiated with 22 and 44 GeV Carbon Ions (Preliminary Results)

An extended Cu target was centrally irradiated with 22 and 44 GeV carbon ions for about 11 and 15 hours, respectively. The upper side of the target was in contact with a paraffin block for the moderation of secondary neutrons. Small holes in the moderator were filled with lanthanum salts (LaCl₃7H₂O) where the neutrons induced the ¹³⁹La(n,γ) ¹⁴⁰La reaction. The β-decay of ¹⁴⁰La(40h) was followed using radiochemical methods. The yields for the formation of ¹⁴⁰La agree within large errors with other experiments on extended targets carried out at the LHE, JINR (Dubna). To a first approximation, the breeding rate of ¹⁴⁰La doubles when the ¹²C energy is increased from 22 to 44 GeV. If results at 44 GeV are compared to those at 22 GeV, there cannot be excluded an excess of (20 ± 7)% in the experimentally observed ¹⁴⁰La production over theoretical estimates. A definite conclusion in this respect must await further experimental and theoretical work.

These experiments are the beginning of a research program to develop a subcritical reactor with neutron fluxes sufficiently high to permit the TRANSMUTATION of long-lived radioactive waste into short-lived or stable nuclei. Such transmutation would considerably relieve the ecological problems related to the final deposition of radioactive waste.     

Voronoi polyhedra analysis of MD simulated silicate glasses

The relationship between the volume and the surface of Voronoi polyhedra (VP) appeared to be an effective tool for the characterization of the structure of MD simulated silicate glasses. This feature was demonstrated on the series of binary potassium-silicate glasses with the alkali content ranging from 5 to 20 mol%. Moreover, the temperature dependence of the slope of the above dependence, when expressed for various types of central atoms (Si, O and K in our case) was studied. Each type of central atom is characterised by its own iron line linearly relating the volume of VP to its properly powered surface, so that new geometrical constrains to the VP was found.     

Enthalpy recovery, creep and creep-recovery measurements during physical aging of amorphous selenium

The physical aging behavior of amorphous selenium has been investigated using differential scanning calorimetry and conventional and interrupted creep experiments. As a result of physical aging, enthalpy decreases and the creep and recovery curves shift to longer times. The times required to reach equilibrium for enthalpy recovery and creep appear to have different temperature dependences resulting in enthalpy reaching equilibrium before creep at aging temperatures a few degrees below the nominal glass temperature. In the nominal glass transformation range, however, the times required to reach equilibrium are approximately the same. A general picture of aging behavior has emerged from our data on selenium coupled with past work on polyetherimide and polystyrene.