Comparison of three multivariate calibration methods as an approach to arsenic speciation by HG-AAS

This paper compares three multivariate calibration methods, namely classical least squares (CLS), inverse least squares (ILS) and Kaiman filter, applied to continuous-flow hydride generation with sodium tetrahydroborate(III) reducing agent and AAS detection for the purposes of speciation of As(III), As(V), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA). The precision of the three multivariate methods was compared in the calibration and prediction steps by standard error of prediction (SEP) and relative error of prediction (REP), respectively, for each analyte and no significant differences have been found for As(III), As(V), MMA, and DMA when the F-test was applied to compare the three multivariate calibration methods in pairs at the 95% confidence level. Determination of the As species was carried out in spiked drinking and sea water in the range 7–35 g 1^–1. Recoveries were in all cases around 100% and the detection limit for the least sensitive species was close to 5 g 1^–1.     

Effect of the particle size and solids volume fraction on the thermal degradation behaviour of Invar 36 feedstocks

Degradation kinetics and the thermal stability of Invar 36 powder injection moulding feedstocks (PIM) based on cellulose acetate butyrate (CAB) and polyethylene glycol (PEG) binders were investigated using simultaneous thermogravimetric analysis (STA) and differential scanning calorimetry (DSC). The initial decomposition temperature (IDT) and the integral procedure decomposition temperature (IPDT) were used to analyse the thermal stability of the binder system as a function of the solid loading content and powder particle size. The degradation kinetics was studied, and the process apparent activation energies were assessed using isoconversional methods. All the methodologies revealed changes in the thermal degradation behaviours of the feedstocks for solid loadings that were previously determined to correspond to optimal solid loadings using other experimental procedures. The studies also contrast previous similar findings with a ceramic powder. Therefore these results strengthen the proposal of thermodynamic degradation studies of feedstocks as an alternative or complementary technique to determine optimal solid loading contents in metal injection moulding (MIM).     

Thermal analysis of prealloyed Fe–3Cr–0.5Mo sintered steel

Thermal analysis was done to determine the temperatures of thermal reactions, phase transformations or melting reaction during continuous heating. These reactions are a direct response to the steel composition and to the sintering atmosphere. Simultaneous thermal analysis TG-DTA (STA) shows up the sintering behaviour of sintered low prealloyed chromium steels and their peculiarities. Given the high oxygen affinity of chromium, graphite additions can modify their thermal reactions, and hence the sintering behaviour of the steel. Evidence is given of the effect of carbon on the sintering process and the nature of the oxides.     

SQUID-based measuring systems

A program has been developed and initiated at the Indira Gandhi Centre for Atomic Research (IGCAR) for the utilization of SQUID sensors in various application areas. DC SQUID sensors based on Nb-AlO _x -Nb Josephson junctions have been designed and developed inhouse along with associated flux-locked loop (FLL) electronics. A compact low field SQUID magnetometer insertible in a liquid helium storage dewar has also been developed inhouse and is in use. Efforts to build a high field SQUID magnetometer, SQUID-DAC system, are in progress. A planar gradiometric DC SQUID sensor for non-destructive evaluation (NDE) application to be used in relatively unshielded environment has been designed and developed. An easily portable NDE cryostat with a small lift-off distance, to be used in external locations has been designed and tested. The magnetic field produced by a given two-dimensional current density distribution is inverted using the Fourier transform technique.     

Nanoelectromechanical systems

Nanoelectromechanical systems (NEMS) are nano-to-micrometer scale mechanical resonators coupled to electronic devices of similar dimensions. NEMS show promise for fast, ultrasensitive force microscopy and for deepening our understanding of how classical dynamics arises by approximation to quantum dynamics. This article begins with a survey of NEMS and then describes certain aspects of their classical dynamics. In particular, we show that for weak coupling the action of the electronic device on the mechanical resonator can be effectively that of a thermal bath, this despite the device being a driven, far-from-equilibrium system.     

Combining linear programming and automated planning to solve intermodal transportation problems

When dealing with transportation problems Operational Research (OR), and related areas as Artificial Intelligence (AI), have focused mostly on uni-modal transport problems. Due to the current existence of bigger international logistics companies, transportation problems are becoming increasingly more complex. One of the complexities arises from the use of intermodal transportation. Intermodal transportation reflects the combination of at least two modes of transport in a single transport chain, without a change of container for the goods. In this paper, a new hybrid approach is described which addresses complex intermodal transport problems. It combines OR techniques with AI search methods in order to obtain good quality solutions, by exploiting the benefits of both kinds of techniques. The solution has been applied to a real world problem from one of the largest spanish companies using intermodal transportation, Acciona Transmediterránea Cargo.     

Multinuclear NMR spectra and GIAO/DFT calculations of N-benzylazoles and N-benzylbenzazoles

The ¹H, ¹³C, and ¹⁵N chemical shifts of almost the whole series of N-benzyl azoles and benzazoles, with the exception of the unknown 1-benzyl-1H-pentazole (10) and the very unstable 2-benzyl-2H-isoindole (12), have been measured. In addition, the X-ray crystal structure of 1-benzyl-1H-indazole (14) was solved (monoclinic, space group P2₁/n), its geometry being very close to that used for the calculations. The absolute chemical shieldings were calculated at the gauge-independent atomic orbital (GIAO)/Becke, 3-parameter, Lee-Yang-Parr (B3LYP)/6-311++G(d,p) level and then transformed with very robust empirical equations into chemical shifts of the three nuclei showing an excellent agreement with the 313 experimental values.

     

Synthesis of a new 24-membered tetramide macrocycle and X-ray crystal structure determination

The synthesis and characterization of a new 24-membered tetramide macrocycle (6) related to Leigh's macrocycles and catenanes is reported. The replacement of p-xylylenediamine (Leigh) by m-xylylenediamine (this work) strongly modifies the geometry and properties of the new macrocycle. NMR spectroscopy (in DMSO?d₆ solution) and X-ray crystallography have been used to characterize compound 6. The structural features in the crystal (conformational aspects and H-bonding) have been discussed comparatively to two similar macrocycles NEWHIJ and UJUNOC.     

Anatomy of a polarization switch of a vertical-cavity semiconductor laser

Using a streak camera we have measured the three Stokes polarization parameters during a polarization switch of a vertical-cavity semiconductor laser. The switch occurs along a corkscrew path on the Poincare sphere and takes on average a few nanoseconds; this value agrees with a theoretical treatment based upon the Fokker-Planck equation.