A study of structural, compositional and optical properties of spray-deposited non-stoichiometric (Zn,Fe)S thin films

Non-stoichiometric ternary chalcogenides (Zn,Fe)S were prepared in the film form by pyrolytic spray deposition technique, using air/nitrogen as the carrier gas. The precursor solution comprised of ZnCl₂, FeCl₂ and thiourea. The depositions were carried out under optimum conditions of experimental parameters viz. carrier gas (air/nitrogen) flow rate, concentration of precursor constituents, nozzle substrate distance and temperature of quartz substrate. The deposited thin films were later sintered in argon at 1073 K for 120 min.The structural, compositional and optical properties of the sintered thin films were studied. X-ray diffraction studies of the thin films indicated the presence of (Zn,Fe)S solid solution with prominent cubic sphalerite phase while surface morphology as determined by scanning electron microscopy (SEM) revealed a granular structure.The chemical composition of the resulting thin films as analyzed by energy dispersive X-ray analysis (EDAX) reflected the composition of the precursor solutions from which the depositions were carried out with Fe at% values ranging from 0.4 up to 33.SEM micrographs of thin films reveal that the grain sizes of the thin films prepared using air as carrier gas and N₂ as carrier gas are in the vicinity of 300 and 150 nm, respectively.The diffuse transmittance measurements for thin films, as a function of wavelength reveal the dependence of direct optical band gap on Fe content and type of phase.     

Zero-sum constrained stochastic games with independent state processes

We consider a zero-sum stochastic game with side constraints for both players with a special structure. There are two independent controlled Markov chains, one for each player. The transition probabilities of the chain associated with a player as well as the related side constraints depend only on the actions of the corresponding player; the side constraints also depend on the player’s controlled chain. The global cost that player 1 wishes to minimize and that player 2 wishes to maximize, depend however on the actions and Markov chains of both players. We obtain a linear programming formulations that allows to compute the value and saddle point policies for this problem. We illustrate the theoretical results through a zero-sum stochastic game in wireless networks in which each player has power constraints     

Dynamic surface tension measurements of surfactant solutions using the maximum bubble pressure method – limits of applicability

One of the essential differences in the design of bubble pressure tensiometers consists in the geometry of the measuring capillaries. To reach extremely short adsorption times of milliseconds and below, the so-called deadtime of the capillaries must be of the order of some 10 ms. In particular, for concentrated surfactant solutions, such as micellar solutions, short deadtimes are needed to minimize the initial surfactant load of the generated bubbles. A theoretical model is derived and confirmed by experiments performed for a wide range of experimental conditions, mainly in respect to variations in deadtime and bubble volume.     

Topics in data assimilation: Stochastic processes

Stochastic models with varying degrees of complexity are increasingly widespread in the oceanic and atmospheric sciences. One application is data assimilation, i.e., the combination of model output with observations to form the best picture of the system under study. For any given quantity to be estimated, the relative weights of the model and the data will be adjusted according to estimated model and data error statistics, so implementation of any data assimilation scheme will require some assumption about errors, which are considered to be random. For dynamical models, some assumption about the evolution of errors will be needed. Stochastic models are also applied in studies of predictability.

The formal theory of stochastic processes was well developed in the last half of the twentieth century. One consequence of this theory is that methods of simulation of deterministic processes cannot be applied to random processes without some modification. In some cases the rules of ordinary calculus must be modified.

The formal theory was developed in terms of mathematical formalism that may be unfamiliar to many oceanic and atmospheric scientists. The purpose of this article is to provide an informal introduction to the relevant theory, and to point out those situations in which that theory must be applied in order to model random processes correctly.     

Reaction field model with free volume for the NMR chemical shift of129Xe dissolved in organic solvents

The temperature dependence of the NMR chemical shift of¹²⁹Xe dissolved in liquid alkanes is examined in the context of the reaction field model. An essential feature of the theory is the inclusion of the temperature dependence of the density of thesolvent. The theory of free volume for liquids is incorporated into the reaction field model to account for this temperature dependence. Comparison of the theory with previously reported measurements indicates the sensitivity of the¹²⁹Xe chemical shift to the free volume of liquids. Incorporation of free volume improves the agreement between measurement and theory for branched alkane solvents, and resolves the origin of the 62 ppm intercept in the plot of reaction field as a function of¹²⁹Xe chemical shift for the n-alkanes.     

Gelation of poly(n-butylisocyanate) in benzene

Poly (n-butylisocyanate)-benzene solutions prepared by solubilization at 45°C, followed by aging at room temperature were found to be metastable for months, although, eventually, they separated into a birefringent polymer-rich phase and an isotropic solution. These metastable solutions, as well as isothermally phase-separated biphasic samples, flowed and exhibited dynamic moduli indicative of low polymer connectivity. By contrast samples prepared by a freeze-thaw cycle were uniformly and highly birefringent and showed network (gel) behavior at room temperature. The mechanism of gel formation is most likely the exclusion of the polymer from the benzene crystal during crystallization, forcing the polymer to align and exist at grain boundaries. Films formed from solutions have different moduli than those formed from gels, and are consistent with the proposed mechanism.