Quantitative and high mass ToF-SIMS studies of siloxane segregation in hydrogel polymers using cryogenic sample handling techniques

This paper examines the capabilities of cryogenic sample handling to examine composition and structure of hydrogel materials where siloxane components are central to the analysis. XPS analysis of multicomponent polymers with cryogenic sample handling following exposure to aqueous environments has revealed the composition and kinetics of near surface reorganization for siloxane and fluorocarbon containing polymers. In this study we report results from a ToF-SIMS protocol for cryogenic sample handling applied to the analysis of surface changes upon hydration/dehydration of hydrogel polymers. Comparison of results from angle dependent XPS and ToF-SIMS are discussed for a range of commercial soft contact lens materials. Both methods detected changes in surface chemistry between the hydrated (frozen) and dehydrated surfaces. Analysis of the hydrated surfaces detected polymer components indicative of the commercial formulation as well as ice clusters. Analysis of the dehydrated materials detected changes in surface chemistry relative to the hydrated surface in addition to loss of water due to sample dehydration. A quantitative standard additions method for ToF-SIMS data was used to determine submonolayer amounts of PDMS impurities at the surface of the hydrogels. ToF-SIMS analysis of a series of seven poly (allyl methacrylate-g-dimethylsiloxane), AMA-g-DMS, graft copolymers in the hydrated state revealed high mass oligomeric ion distributions for systems with bulk PDMS content greater than 25 wt.%. This marks the first time that detection of high mass oligomeric ion distributions from hydrated (frozen) surfaces has been reported. Analysis of the dehydrated surface detected formation of high mass oligomeric ion distributions for systems with PDMS bulk content greater than 15 wt.%, but only detected these ion distributions in wet (frozen) samples when the bulk concentration was greater than 25 wt.%.     

Transport coefficients and defect structure of Sb2−xAgxTe3 single crystals

Incorporation of Ag in the crystal lattice of Sb₂Te₃ creates structural defects that have a strong influence on the transport properties. Single crystals of Sb_2−xAg_xTe₃ (x=0.0; 0.014; 0.018 and 0.022) were characterized by measurements of the temperature dependence of the electrical resistivity, Hall coefficient, Seebeck coefficient and thermal conductivity in the temperature range of 5-300 K. With an increasing content of Ag the electrical resistance, the Hall coefficient and the Seebeck coefficient all decrease. This implies that the incorporation of Ag atoms in the Sb₂Te₃ crystal structure results in an increasing concentration of holes. However, the doping efficiency of Ag appears to be only about 50% of the expected value. We explain this discrepancy by a model based on the interaction of Ag impurity with the native defects in the Sb_2−xAg_xTe₃ crystal lattice. Defects have a particularly strong influence on the thermal conductivity. We analyze the temperature dependence of the lattice thermal conductivity in the context of the Debye model. Of the various phonon scattering contributions, the dominant influence of Ag incorporation in the crystal lattice of Sb₂Te₃ is revealed to be point-defect scattering where both the mass defect and elastic strain play a pivotal role.     

High-pressure effect on the crystal and magnetic structure of LuMnO3: Correlation between a distortion of the triangular lattice and the symmetry of the magnetic state in hexagonal frustrated manganites

The effect of a high pressure (up to 6 GPa) on the crystal and magnetic structure of the hexagonal manganite LuMnO₃ is studied by neutron diffraction in the temperature range 10–295 K. It is found that, as the pressure increases, the ordered magnetic moment of Mn ions at T = 10 K decreases noticeably from 2.48 (0 GPa) to 1.98 μ_B (6 GPa). This decrease is due to an enhancement of the geometrical frustration effects on the triangular lattice. At the same time, the symmetry of the triangular antiferromagnetic state (the irreducible representation Γ₂) remains unchanged. A correlation is revealed between the distortion parameter of the triangular lattice formed by Mn ions and the symmetry of the antiferromagnetic state of hexagonal manganites RMnO₃. Based on this correlation, a generalized magnetic phase diagram of these compounds is constructed. The obtained phase diagram provides an explanation for the changes observed in the magnetic state of hexagonal manganites caused by high pressure and chemical substitution.     

The measurement of beta asymmetries at UNISOR/NOF using external plastic scintillator detectors

The performance of two external plastic scintillator detectors has been tested in an off-line mode using a source of¹⁰⁶RuFe at UNISOR/NOF. The measurement of beta asymmetries at various temperatures has resulted in the reproduction of the previously-determined magnetic dipole moment for the 1⁺ ground state of¹⁰⁶Rh and in addition the conclusion that the sign of this moment is positive.     

OPTIMAL INSTAR PARASITIZATION IN A STAGE STRUCTURED HOST-PARASITOID MODEL

A stage structured host-parasitoid model is derived and the equilibria studied. It is shown under what conditions the parasitoid controls an exponentially growing host in the sense that a coexistence equilibrium exists. Furthermore, for host populations whose inherent growth rate is not too large it is proved that in order to minimize the adult host equilibrium level it is necessary that the parasitoids attack only one of the larval stages. It is also proved in this case that the minimum adult host equilibrium level is attained when the parasitoids attack that larval stage which also maximizes the expected number of emerging adult parasitoid per larva at equilibrium. Numerical simulations tentatively indicate that the first conclusion remains in general valid for the model. However, numerical studies also show that it is not true in general that the optimal strategy will maximize the number of emerging adult parasitoid per larva at equilibrium.     

Probing microscopic chaotic dynamics by observing macroscopic transport processes

We derive the Kramers equation, namely, the Fokker-Planck equation for an oscillator, from a completely deterministic picture. The oscillator is coupled to a “booster”, i.e., a deterministic system in a fully chaotic state, wherein diffusion is derived from the sensitive dependence of chaos on initial conditions and friction is a consequence of the linear response of the booster to the action exerted on it by the oscillator. To deal with the Hamiltonian nature of the system of interest and of its coupling to the booster, we extend the earlier theoretical derivation of macroscopic transport coefficients from deterministic dynamics. We show that the frequency of the oscillator can be tuned to the microscopic frequencies of the booster without affecting the canonical nature of the “macroscopic” statistics. The theoretical predictions are supported by numerical simulations.     

Quantification of stable minor species in confined flames by cavity ring-down spectroscopy: application to NO

Cavity ring-down spectroscopy (CRDS) is used to measure the NO mole fraction formed in the burnt gases of low-pressure premixed flames. It is shown that the line-of-sight absorption is greatly increased by the contribution of the NO molecules surrounding the burner. This contribution has been quantified by developing a mathematical procedure taking into account the spatial and spectral features of the CRDS measurement. Calculations have been undertaken in the general case of a stable species not consumed in the flame. The most sensitive parameter is the temperature both in the flame and outside the flame. Simulations allow the selection of the best spectroscopic transitions for a given flame (i.e. a given temperature profile), ensuring the weakest influence of the inaccuracy affecting the temperature determination. High quantum states belonging to the A–X (0–1) band of NO have been found to be the most valuable and have led to a NO mole fraction determination with an accuracy of ±13%. NO absorption in the flame was completely masked using the A–X (0–0) band. Finally, the prompt-NO mole fraction formed in a methane/air flame stabilized at 33 Torr is obtained by combining CRDS and laser induced fluorescence techniques. Received: 12 October / Revised version: 1 February 2002 / Published online: 14 March 2002     

The phase composition of tin-nickel electrodeposited alloys

It was studied the tin phase composition of the electrodeposited alloys produced at different temperatures and current densities from an acid chloride/fluoride electrolyte and an acid chloride bath. Mössbauer spectra were consistent with a Ni₃Sn₄ intermetallic compound, dissolved tin, and a Cu?Sn intermetallic compound formed at the interface of the copper substrate.