Reversible Swelling/Deswelling Characteristics of Ethylene Glycol Dimethacrylate Cross-Linked Poly(acrylic acid-co-sodium acrylate-co-acrylamide) Superabsorbents

Poly(acrylic acid-co-sodium acrylate-co-acrylamide) superabsorbent polymers (SAPs) cross-linked with ethylene glycol dimethacrylate (EGDMA) were synthesized by inverse suspension polymerization. The SAPs were swollen in DI water, and it was found that the equilibrium swelling capacities varied with the acrylamide content. The SAPs were subjected to reversible swelling/deswelling cycles in DI water and aqueous NaCl solution, respectively. The effect of the addition of an electrolyte on the swelling of the SAP was explored. The equilibrium swelling capacity of the SAPs was found to decrease with increasing concentration of added electrolyte in the swelling medium. The effect of the particle size of the dry SAPs on the swelling properties was also investigated. A first order model was used to describe the kinetics of swelling/deswelling, and the equilibrium swelling capacity, limiting swelling capacity, and swelling/deswelling rate coefficients were determined.

Interdiffusion and the vacancy wind effect in Ni-Pt and Co-Pt systems

In this study, bulk and multifoil diffusion couple experiments were conducted to examine the interdiffusion process in Ni-Pt and Co-Pt binary alloy systems. Inter-, intrinsic-, and tracer-diffusion coefficients at different temperatures, and as a function of the composition, were estimated by using the experimental data. Results show that in both the alloy systems, Pt is the slower diffusing species, and hence the interdiffusion process is controlled by either Ni or Co. The thermodynamic driving force makes the intrinsic diffusion coefficients of Co and Ni higher in the range of 30-70 at.%. The low activation energy for Co and Ni impurity diffusion in Pt compared with Pt in Ni and Co indicates that the size of the atoms plays an important role. The vacancy wind effects on the diffusion process are examined in detail, and it was demonstrated that its contribution falls within the experimental scatter and hence can be neglected.

Interaction anisotropy and shear instability of aspirin polymorphs established by nanoindentation

Nanoindentation is applied to the two polymorphs of aspirin to examine and differentiate their interaction anisotropy and shear instability. Aspirin provides an excellent test system for the technique because: (i) polymorphs I and II exhibit structural similarity in two dimensions, thereby facilitating clear examination of the differences in mechanical response in relation to well-defined differences between the two crystal structures; (ii) single crystals of the metastable polymorph II have only recently become accessible; (iii) shear instability has been proposed for II. Different elastic moduli and hardness values determined for the two polymorphs are correlated with their crystal structures, and the interpretation is supported by measured thermal expansion coefficients. The stress-induced transformation of the metastable polymorph II to the stable polymorph I can be brought about rapidly by mechanical milling, and proceeds via a slip mechanism. This work establishes that nanoindentation provides ``signature'' responses for the two aspirin polymorphs, despite their very similar crystal structures. It also demonstrates the value of the technique to quantify stability relationships and phase transformations in molecular crystals, enabling a deeper understanding of polymorphism in the context of crystal engineering.

A New Iterative FIR Filter for Image and Video Restoration

Image and video filtering is a key image-processing task in computer vision especially in noisy environment. In most of the cases the noise source is unknown and hence possess a major difficulty in the filtering operation. In this paper we present an error-correction based learning approach for iterative filtering. A new FIR filter is designed in which the filter coefficients are updated based on Widrow-Hoff rule. Unlike the standard filter the proposed filter has the ability to remove noise without the a priori knowledge of the noise. Experimental result shows that the proposed filter efficiently removes the noise and preserves the edges in the image. We demonstrate the capability of the proposed algorithm by testing it on standard images infected by Gaussian noise and on a real time video containing inherent noise. Experimental result shows that the proposed filter is better than some of the existing standard filters

A DCT Based Filtering of Biomedical Images

Image filtering techniques have numerous potential applications in biomedical imaging and image processing. The design of filters largely depends on the a-priori knowledge about the type of noise corrupting the image and image features. This makes the standard filters to be application and image specific. The most popular filters such as average, Gaussian and Wiener reduce noisy artifacts by smoothing. However, this operation normally results in smoothing of the edges as well. On the other hand, sharpening filters enhance the high frequency details making the image non-smooth. An integrated general approach to design filters based on discrete cosine transform (DCT) is proposed in this study for optimal medical image filtering. This algorithm exploits the better energy compaction property of DCT and re-arrange these coefficients in a wavelet manner to get the better energy clustering at desired spatial locations. This algorithm performs optimal smoothing of the noisy image by preserving high and low frequency features. Evaluation results show that the proposed filter is robust under various noise distributions.

Thermodynamics of oxygen in liquid copper-tin alloys

The activity coefficients of oxygen in copper-tin alloys at 1 1 00°C have been measured by two different equilibrium methodsthe cell Pt, Ni + NiO I ZrOz solid electrolyte I O[Cu + Sn], cermet. Pt and the equilibrium between Cu + Sn alloys and SnO + SiO, slags established via SnO vapour. The results from both types of measurement confirm the work of Block and co-workers and show that other data are in error. The deoxidation equilibria for Sn in liquid copper, with solid SnO, as deoxidation product, have been evaluated at temperatures of interest in copper smelting.

Inverse models to analyze the spatiotemporal variations of chemical weathering fluxes in a granito-gneissic watershed: Mule Hole, South India

Water-rock reactions are driven by the influx of water, which are out of equilibrium with the mineral assemblage in the rock. Here a mass balance approach is adopted to quantify these reactions. Based on field experiments carried out in a granito-gneissic small experimental watershed (SEW), Mule Hole SEW (similar to 4.5 km(2)), quartz, oligoclase, sericite, epidote and chlorite are identified as the basic primary minerals while kaolinite, goethite and smectite are identified as the secondary minerals. Observed groundwater chemistry is used to determine the weathering rates, in terms of `Mass Transfer Coefficients' (MTCs), of both primary and secondary minerals. Weathering rates for primary and secondary minerals are quantified in two steps. In the first step, top red soil is analyzed considering precipitation chemistry as initial phase and water chemistry of seepage flow as final phase. In the second step, minerals present in the saprolite layer are analyzed considering groundwater chemistry as the output phase. Weathering rates thus obtained are converted into weathering fluxes (Q(weathering)) using the recharge quantity. Spatial variability in the mineralogy observed among the thirteen wells of Mule Hole SEW is observed to be reflected in the MTC results and thus in the weathering fluxes. Weathering rates of the minerals in this silicate system varied from few 10 mu mol/L (in case of biotite) to 1000 s of micromoles per liter (calcite). Similarly, fluxes of biotite are observed to be least (7 +/- 5 mol/ha/yr) while those of calcite are highest (1265 791 mol/ha/yr). Further, the fluxes determined annually for all the minerals are observed to be within the bandwidth of the standard deviation of these fluxes. Variations in these annual fluxes are indicating the variations in the precipitation. Hence, the standard deviation indicated the temporal variations in the fluxes, which might be due to the variations in the annual rainfall. Thus, the methodology adopted defines an inverse way of determining weathering fluxes, which mainly contribute to the groundwater concentration. (C) 2011 Elsevier B.V. All rights reserved.

Thermodynamic study of oxygen in liquid lead tin alloys

The activity coefficients of oxygen in liquid lead-tin alloys have been measured between 550 and 1100°C by use of solid oxide galvanic cells Pt, Ni-NiO I Zr02 Solid electrolyte I 0 (Pb + Sn), Cermet, Pt Pt, Fe-FeO I Zr02 Solid electrolyte I O(Pb + Sn), Cermet, Pt Alcock and Richardson's quasi-chemical equation, with the coordination number of atoms set to 2, is found to predict successfully the activity coefficients of oxygen in these alloys.The relative partial molar enthalpy and entropy of oxygen ?t 1 atom per cent in the alloys have been calculated from ttva variation of the activity coefficient with temperature. The addition of tin to an unsaturated solution of oxygen in lead is shown to decrease significantly both the partial molar enthalpy and entropy of oxygen. As the measurements were restricted to a narrow range between 750-1100'C in lead-rich alloys, however, the pronounced variation of the partial molar enthalpy of oxygen with temperature at constant alloy composition predicted by the quasi-chemical model could not be verified.

Quasichemical equations for oxygen and sulphur in liquid binary alloys

An equation has been derived for predicting the activity coefficient of oxygen or sulphur in dilute solution in binary alloys, based on the quasichemical approach, where the metal atoms and the oxygen atoms are assigned different bond numbers. This equation is an advance on Alcock and Richardson's earlier treatment where all the three types of atoms were assigned the same coordination number. However, the activity coefficients predicted by this new equation appear to be very similar to those obtained through Alcock and Richardson's equation for a number of alloy systems, when the coordination number of oxygen in the new model is the same as the average coordination number used in the earlier equation. A second equation based on the formation of “molecular species” of the type XnO and YnO in solution is also derived, where X and Y atoms attached to oxygen are assumed not to make any other bonds. This equation does not fit experimental data in all the systems considered for a fixed value of n. Howover, if the strong oxygen-metal bonds are assumed to distort the electronic configuation around the metal atoms bonded to oxygen and thus reduce the strength of the bonds formed by these atoms with neighbouring metal atoms by approximately a factor of two, the resulting equation is found to predict the activity coefficients of oxygen that are in good agreement with experimental data in a number of binary alloys.

Prediction of activities of oxygen in dilute quaternary solutions using binary data

Equations are developed for predicting the activity coefficients of oxygen dissolved in ternary liquid alloys. These are extensions of earlier treatments, and are based on a model in which each oxygen atom is assumed to make four bonds with neighboring metal atoms. It is also postulated that the strong oxygen-metal bonds distort the electronic configuration around the metal atoms bonded to oxygen, and that the quantitative reduction of the strength of bonds made by these atoms with all of the adjacent metal atoms is equivalent to a factor of approximately two. The predictions of the quasichemical equation which is derived agree satisfactorily with the partial molar free energies of oxygen in Ag-Cu-Sn solutions at 1200°C reported in literature. An extension of this treatment to multicomponent solutions is also indicated.

An entropy meter based on the thermoelectric potential of a nonisothermal solid electrolyte cell

The theory, design, and performance of a solid electrolyte twin thermocell for the direct determination of the partial molar entropy of oxygen in a single-phase or multiphase mixture are described. The difference between the Seebeck coefficients of the concentric thermocells is directly related to the difference in the partial molar entropy of oxygen in the electrodes of each thermocell. The measured potentials are sensitive to small deviations from equilibrium at the electrodes. Small electric disturbances caused by simultaneous potential measurements or oxygen fluxes caused by large oxygen potential gradients between the electrodes also disturb the thermoelectric potential. An accuracy of ±0.5 calth K−1 mol−1 has been obtained by this method for the entropies of formation of NiO and NiAl2O4. This “entropy meter” may be used for the measurement of the entropies of formation of simple or complex oxides with significant residual contributions which cannot be detected by heat-capacity measurements.

Alloy/Oxide Equilibria in Iron--Vanadium--Oxygen and Iron--Niobium--Oxygen Systems

An experimental characterization of three-phase equilibria in Fe--V--O and Fe--Nb--O systems at 1823, 1873 and 1923K has been carried out using a solid state cell and by analysis of quenched samples. The oxygen potentials corresponding to these three-phase equilibria were monitored by a solid state cell incorporating Y sub 2 O sub 3 doped ThO sub 2 with Cr + Cr sub 2 O sub 3 as reference electrode. Similar measurements were carried out for Fe--Nb--O alloys in equilibrium with a mixture of FeNb sub 2 O sub 6 and NbO sub 2 . These measurements permit evaluation of interaction parameters (e exp V sub O = --6590/T + 2.892 and e exp Nb sub O = --4066/T + 1.502) and activity coefficients of vanadiun and niobium in dilute solution (ln gamma exp O sub V = --35 320/T + 12.68 and ln gamma sub Nb exp O = --12 386/T + 4.34) in liquid iron. The results obtained in this study resolve a number of discrepancies in thermodynamic data reported in the literature, especially regarding the activity coefficients of V and Nb and the stability ranges for V sub 2 O sub 3 and VO sub 1+x . 18 ref.--AA

Investigation of dielectric, piezoelectric and ferroelectric properties of b-axis grown triglycine sulphate single crystal

Large single crystal of triglycine sulphate (dimension 100 mm along monoclinic b-axis and 15 mm in diameter) was grown using the unidirectional solution growth technique. The X-ray diffraction studies confirmed the growth/long axis to be b-axis (polar axis). The dielectric studies were carried out at various temperatures to establish the phase transition temperature. The frequency response of the dielectric constant, dielectric loss and impedance of the crystal along the growth axis, was monitored. These are typically characterized by strong resonance peaks in the kHz region. The piezoelectric coefficients like stiffness constant (C), elastic coefficient (S), electromechanical coupling coefficient (k) and d (31) were calculated using the resonance-antiresonance method. Polarization (P)-Electric field (E) hysteresis loops were recorded at various temperatures to find the temperature-dependent spontaneous polarization of the grown crystal. The pyroelectric coefficients were determined from the pyroelectric current measurement by the Byer and Roundy method. The ferroelectric domain patterns were recorded on (010) plane using scanning electron microscopy and optical microscopy.

Physically consistent simulation of mesoscale chemical kinetics: The non-negative FIS-alpha method

Biochemical pathways involving chemical kinetics in medium concentrations (i.e., at mesoscale) of the reacting molecules can be approximated as chemical Langevin equations (CLE) systems. We address the physically consistent non-negative simulation of the CLE sample paths as well as the issue of non-Lipschitz diffusion coefficients when a species approaches depletion and any stiffness due to faster reactions. The non-negative Fully Implicit Stochastic alpha (FIS alpha) method in which stopped reaction channels due to depleted reactants are deleted until a reactant concentration rises again, for non-negativity preservation and in which a positive definite Jacobian is maintained to deal with possible stiffness, is proposed and analysed. The method is illustrated with the computation of active Protein Kinase C response in the Protein Kinase C pathway. (C) 2011 Elsevier Inc. All rights reserved.

Identification and optimization of ammonia reactors through hybrid simulation

A hybrid simulation technique for identification and steady state optimization of a tubular reactor used in ammonia synthesis is presented. The parameter identification program finds the catalyst activity factor and certain heat transfer coefficients that minimize the sum of squares of deviation from simulated and actual temperature measurements obtained from an operating plant. The optimization program finds the values of three flows to the reactor to maximize the ammonia yield using the estimated parameter values. Powell's direct method of optimization is used in both cases. The results obtained here are compared with the plant data.