Methyl ethyl ketone plus water plus secondary butyl alcohol: A potential system for the exploration of a quadruple critical point

We report preliminary experiments on the ternary-liquid mixture, methyl ethyl ketone (MEK)+water (W)+secondary butyl alcohol (sBA)-a promising system for the realization of the quadruple critical point (QCP). The unusual tunnel-shaped phase diagram shown by this system is characterized and visualized by us in the form of a prismatic phase diagram. Light-scattering experiments reveal that (MEK+W+sBA) shows near three-dimensional-Ising type of critical behavior near the lower critical solution temperatures, with the susceptibility exponent (gamma) in the range of 1.217 <=gamma <= 1.246. The correlation length amplitudes (xi(o)) and the critical exponent (nu) of the correlation length (xi) are in the ranges of 3.536 <=xi(o)<= 4.611 A and 0.619 <=nu <= 0.633, respectively. An analysis in terms of the effective susceptibility exponent (gamma(eff)) shows that the critical behavior is of the Ising type for MEK concentrations in the ranges of 0.1000 <= X <= 0.1250 and X >= 0.3000. But, for the intermediate range of 0.1750 <= X < 0.3000, the system shows a tendency towards mean-field type of critical behavior. The advantages of the system (MEK+W+sBA) over the system (3-methylpyridine+water+heavy water+potassium Iodide) for the realization of a QCP are outlined.

Volume effects and associations in liquid alloys

The regular associated solution model for binary systems has been modified by incorporating the size of the complex as an explicit variable. The thermodynamic properties of the liquid alloy and the interactions between theA ?B type of complex and the unassociated atoms in anA-B binary have been evaluated as a function of relative size of the complex using the activity coefficients at infinite dilution and activity data at one other composition in the binary. The computational procedure adopted for determining the concentration of clusters and interaction energies in the associated liquid is similar to that proposed by Lele and Rao. The analysis has been applied to the thermodynamic mixing functions of liquid Al-Ca alloys believed to contain Al2Ca associates. It is found that the size of the cluster significantly affects the interaction energies between the complex and the unassociated atoms, while the equilibrium constant and enthalpy change for the association reaction exhibit only minor variation, when the equations are fitted to experimental data. The interaction energy between unassociated free atoms remains virtually unaltered as the size of the complex is varied between extreme values. Accurate data on free energy, enthalpy, and volume of mixing at the same temperature on alloy systems with compound forming tendency would permit a rigorous test of the proposed model.

Correlations between frequency of infra-red active vibrational modes and copper-oxygen distance in copper oxides. Application to superconductors

The infra-red spectra of a large number of ternary Cu(II) oxides with at least a quasi square-planar coordination of oxygen around the copper ions have been studied. The frequency of the bands with the highest frequency,v max, is found to correlate extremely well with the shortest Cu–O distance.v max increases at an impressive rate of sim20 cm–1 per 0.01 Å when the Cu–O distance becomes less than 1.97 Å, which is the Cu2+–O2– distance in square-planar CuO4 complexes as obtained from empirical ionic radii considerations. The marked sensitivity may be used as a ldquotitrationrdquo procedure not only to assign bands but also to obtain diagnostic information about local coordination in compounds derived, for example, from the YBa2Cu3O7–d structure such as LaCaBaCu3O7–d . The only example where this correlation fails is in the two-layer non-superconducting oxides derived from La2(Ca, Sr)Cu2O6. The significance of this result is discussed. The marked dependence of frequency on the bond-distance is qualitatively examined in terms of an increased electron-phonon coupling to account for the observed tendency of the superconducting transition temperature to go through a maximum as the average basal plane Cu–O distance is decreased.

Effect of amino acid substitutions at the subunit interface on the stabiity and aggregation properties of a dimeric protein: role of Arg 178 and Arg 218 at the dimer interface of thymidylate synthase

The significance of two interface arginine residues on the structural integrity of an obligatory dimeric enzyme thymidylate synthase (TS) from Lactobacillus casei was investigated by thermal and chemical denaturation. While the R178F mutant showed apparent stability to thermal denaturation by its decreased tendency to aggregate, the Tm of the R218K mutant was lowered by 5 degrees C. Equilibrium denaturation studies in guanidinium chloride (GdmCl) and urea indicate that in both the mutants, replacement of Arg residues results in more labile quaternary and tertiary interactions. Circular dichroism studies in aqueous buffer suggest that the protein interior in R218K may be less well-packed as compared to the wild type protein. The results emphasize that quaternary interactions may influence the stability of the tertiary fold of TS. The amino acid replacements also lead to notable alteration in the ability of the unfolding intermediate of TS to aggregate. The aggregated state of partially unfolded intermediate in the R178F mutant is stable over a narrower range of denaturant concentrations. In contrast, there is an exaggerated tendency on the part of R218K to aggregate in intermediate concentrations of the denaturant. The 3 A crystal structure of the R178F mutant reveals no major structural change as a consequence of amino acid substitution. The results may be rationalized in terms of mutational effects on both the folded and unfolded state of the protein. Site specific amino acid substitutions are useful in identifying specific regions of TS involved in association of non-native protein structures.

The contribution of polarons, bipolarons and intersite tunneling to low temperature conductivity in doped polypyrrole

The conductivity of highly doped polypyrrole is less than that of intermediately doped samples, by two orders of magnitude, at 4.2 K. This may be due to more number of bipolarons in highly doped samples. Bipolarons require four times more activation energy than single polarons to hop by thermally induced virtual transitions to intermediate dissociated polaron states than by the nondissociated process. The conduction process in these polyconjugated systems involve ionization from deep trapped states, having a View the MathML source dependence, hopping from localised states, having View the MathML source dependence, and intersite tunnel percolation, having T−1 dependence. The interplay of these factors leads to a better fit by View the MathML source. The mechanism for this exponential behaviour need not be same as that of Motts variable range hopping. Conduction by percolation is possible, if an infinite cluster of chains can be connected by impurity centers created by dopant ions. The tendency for the saturation of conductivity at very low temperatures is due to the possibility of intersite tunnel percolation is disordered polaronic systems.

A New Liquid Level Sensor for Process-Control Applications

Many process-control systems are air-operated. In such an environment, it would be desirable and economical to use pneumatic sensors. Bubble-back pressure sensors perform quite satisfactorily, but in case of viscous inflammable and slurry-like liquids with a tendency to froth, this level sensor is inadequate. The method suggested in this paper utilizes a pneumatic capacitor, one boundary of which is formed by the liquid level, to modulate a fluid amplifier feedback oscillator. The absence of moving parts and economy obtained makes this method attractive for process-control applications. The system has been mathematically modeled and simulated on an IBM 360/44 digital computer. Experimental values compare fairly well with the theoretical results. For the range tested, the sensor is found to have a linear frequency variation with the liquid level Extended running in the laboratory shows that the system is very reliable. This system has been found insensitive to temperature variations of up to 15ðC.

On characterization of deformation microstructure in Boron modified Ti-6Al-4V alloy

Addition of boron in small quantities to various titanium alloys have shown significant improvement in mechanical behavior of materials. In the present study, electron back-scatter diffraction (EBSD) techniques have been applied to investigate the deformation microstructure evolution in boron modified two-phase titanium alloy Ti-6Al-4V. The alloy was hot compressed at 750 degrees C up to 50% height reduction at two different strain rates (10(-3) s(-1) and 1 s(-1)). The EBSD analyses indicated significant differences in deformed microstructure of the base alloy and the alloy containing boron. A strong subgrain formation tendency was observed along with inhomogeneous distribution of dislocations inside large a colonies of Ti64. In contrast, a colonies were relatively strain free for Ti64 + B, with more uniform dislocation density distribution. The observed difference is attributed to microstructural modifications viz, grain size refinement and presence of TiB particles at grain boundary produced due to boron addition. (C) 2010 Elsevier B.V. All rights reserved.

A critical re-examination and a revised phase diagram of La1-xSrxCoO3

We report the results of a comprehensive study on dc magnetization, ac susceptibility, and the magnetotransport properties of the La1-xSrxCoO3(0 <= x <= 0.5) system. At higher Sr doping (x >= 0.18), the system exhibits Brillouin-like field cooled magnetization (M-FC). However, for x < 0.18, the system exhibits a kink in the M-FC, a peak at the intermediate field in the thermoremnant magnetization and a non-saturating tendency in the M-H plot that all point towards the characteristic of spin glass behavior. More interestingly, dc magnetization studies for x < 0.18 do not suggest the existence of ferromagnetic correlation that can give rise to an irreversible line in the spin glass regime. The ac susceptibility study for x > 0.2 exhibits apparently no frequency dependent peak shift around the ferromagnetic transition region. However, a feeble signature of glassiness is verified by studying the frequency dependent shoulder position in chi `' (T) and the memory effect below the Curie temperature. But, for x < 0.18, the ac susceptibility study exhibits a considerable frequency dependent peak shift, time dependent memory effect, and the characteristic spin relaxation time scale tau(0) similar to 10(-13) s. The reciprocal susceptibility versus temperature plot adheres to Curie-Weiss behavior and does not provide any signature of preformed ferromagnetic clusters well above the Curie temperature. The magnetotransport study reveals a cross over from metallic to semiconducting-like behavior for x <= 0.18. On the semiconducting side, the system exhibits a large value of magnetoresistance (upto 75%) towards low temperature and it is strongly connected to the spin dependent part of the random potential distribution in the spin glass phase. Based on the above observations, we have reconstructed a new magnetic phase diagram and characterized each phase with associated properties.

Influence of Starch Polysaccharide on the Remolded Properties of 2 Indian clay Samples

The reported presence in marine clays and the recognized role of polysaccharide as a bonding agent provided the motivation to examine the role of starch polysaccharide in the remoulded properties of nonswelling (kaolinite) and swelling (bentonite) groups of clays. The starch polysaccharide belongs to a group of naturally occurring, large-sized organic molecules (termed polymers) and is built up by extensive repetition of simple chemical units called repeat units. The results of the study indicate that the impact of the starch polysaccharide on the remoulded properties of clays is dependent on the mineralogy of the clays. On addition to bentonite clay, the immensely large number of segments (repeat units) of the starch polysaccharide create several polymer segment - clay surface bonds that cause extensive aggregation of the bentonite units layers. The aggregation of the bentonite unit layers greatly curtails the available surface area of the clay mineral for diffuse ion layer formation. The reduction in diffuse ion layer thickness markedly lowers the consistency limits and vane shear strength of the bentonite clay. On addition to kaolinite, the numerous polymer segment - clay surface bonds enhance the tendency of the kaolinite particles to flocculate. The enhanced particle flocculation is responsible apparently for a small to moderate increase in the liquid limit and remoulded undrained strength of the nonswelling clay.

Oxidative copolymerization: microstructure analysis of the terpolymer of styrene, methyl methacrylate, and oxygen

This paper reports the first study of the microstructure of a copolyperoxide by nuclear magnetic resonance spectroscopy. The copolyperoxides of styrene and methyl methacrylate (MMA) of various compositions have been synthesized. An analysis of the resonance signal of the backbone methylene protons gave the diad sequence probabilities which led to the calculation of the oxidative copolymerization reactivity ratios for styrene and MMA and the microstructural parameters like average chain length of the repeat unit sequences, run number, etc. The results point to the tendency of the SO1 and MO:! units to alternate in the chain. Compared to poly(styrene peroxide), the aromatic C1 seems to be stereosensitive in the terpolymers.

Folding of a Donor-Containing Ionene by Intercalation with an Acceptor

Cationic ionenes that bear electron-rich 1,5-dialkoxynaphthalene (DAN) units within the alkylene segment were allowed to interact with different types of electron-deficient, acceptor-containing molecules in an effort to realize intercalation-induced folding of the ionenes; the collapse of the chains was expected to occur in such a way that the donor and acceptor units become arranged in an alternating fashion. Several acceptor-bearing molecules were prepared by the derivatization of pyromellitic dianhydride and naphthalene tetracarboxylic dianhydride with two different oligoethylene glycol monomethyl ether monoamines. This yielded acceptor molecules with different water solubility and allowed the examination of solvophobic effects in the folding process. UV/Vis spectroscopic studies were carried out by using a 1:1 mixture of the DAN-ionenes and different acceptor molecules in water/DMSO solvent mixtures. The intensity of the charge-transfer (CT) band was seen to increase with the water content in the solvent mixture, thereby suggesting that the intercalation is indeed aided by solvophobic effects. The naphthalene diimide (NDI) bearing acceptor molecules consistently formed significantly stronger CT complexes when compared to the pyromellitic diimide (PDI) bearing acceptor molecules, which is a reflection of the stronger pi-stacking tendency of the former. AFM studies of drop-cast films of different ionene-acceptor combinations revealed that compact folded structures are formed most effectively under conditions in which the strongest CT complex is formed.

AB-initio study of alpha-silyl and beta-silyl substituent effects on vinyl radicals

The geometries of alpha- and beta-silyl substituted vinyl radicals and of alpha,beta-disilylvinyl radical have been optimised with the STO-3G and the STO-3G* basis sets. The relative stabilities of various conformers have been determined at the UMP2/6-31G* level. The stabilisation of vinyl radicals through alpha-silyl substitution is larger than that due to corresponding alkyl groups. The presence of an alpha-silyl group also leads to a tendency towards linearisation of the vinyl radical centre and a corresponding reduction in the inversion barrier. In marked contrast, the beta-silyl effect is negligible. The geometric, conformational and energetic consequences are insignificant. Overall, the silyl substituent effect at vinyl radicals is very different from that computed earlier for the vinyl cations, but qualitatively similar to that found in carbanions.

Kinetic evolution studies of silver nanoparticles in a bio-based green synthesis process

Silver nanoparticles are being extensively studied due to their widespread applications and unique properties. In the present study, the growth kinetics of silver nanoparticles as synthesized on reduction of silver nitrate solution by aqueous extract of Azadirachta indica leaves was investigated. The formation of silver nanoparticles was preliminarily monitored by measuring the absorption maxima at different time intervals after adding the reducing agent to the silver salt solution (0.5, 1, 1.5, 2, 2.5, 3, 3.5 and 4 h). At different time points characterization studies were conducted using X-ray diffraction studies, FT-IR techniques, zeta potential studies and transmission electron microscopy. The total available silver in the reaction medium was determined at different durations using ICP-OES. The changes in reduction potential in the medium were also monitored using potentiometric analysis. The results confirm a definite change in the medium pertaining to formation of the stable nanoparticles after 2 h, and a significant increase in the agglomeration tendency after 4 h of interaction. The growth kinetic data of the nanoparticles till 3.5 h was found to fit the LSW model confirming diffusion limited growth. (C) 2011 Elsevier B.V. All rights reserved.

Abrasive Jet Machining - Process variables and current applications

brusive Jet Machining (AJM) or Micro Blast Machining is a non-traditional machining process, wherein material removal is effected by the erosive action of a high velocity jet of a gas, carrying fine-grained abrasive particles, impacting the work surface. The AJM process differs from conventional sand blasting in that the abrasive is much finer and the process parameters and cutting action are carefully controlled. The process is particularly suitable to cut intricate shapes in hard and brittle materials which are sensitive to heat and have a tendency to chip easily. In other words, AJM can handle virtually any hard or brittle material. Already the process has found its ways Into dozens of applications; sometimes replacing conventional alternatives often doing jobs that could not be done in any other way. This paper reviews the current status of this non-conventional machining process and discusses the unique advantages and possible applications.

Scroll-Wave Dynamics in Human Cardiac Tissue: Lessons from a Mathematical Model with Inhomogeneities and Fiber Architecture

Cardiac arrhythmias, such as ventricular tachycardia (VT) and ventricular fibrillation (VF), are among the leading causes of death in the industrialized world. These are associated with the formation of spiral and scroll waves of electrical activation in cardiac tissue; single spiral and scroll waves are believed to be associated with VT whereas their turbulent analogs are associated with VF. Thus, the study of these waves is an important biophysical problem. We present a systematic study of the combined effects of muscle-fiber rotation and inhomogeneities on scroll-wave dynamics in the TNNP (ten Tusscher Noble Noble Panfilov) model for human cardiac tissue. In particular, we use the three-dimensional TNNP model with fiber rotation and consider both conduction and ionic inhomogeneities. We find that, in addition to displaying a sensitive dependence on the positions, sizes, and types of inhomogeneities, scroll-wave dynamics also depends delicately upon the degree of fiber rotation. We find that the tendency of scroll waves to anchor to cylindrical conduction inhomogeneities increases with the radius of the inhomogeneity. Furthermore, the filament of the scroll wave can exhibit drift or meandering, transmural bending, twisting, and break-up. If the scroll-wave filament exhibits weak meandering, then there is a fine balance between the anchoring of this wave at the inhomogeneity and a disruption of wave-pinning by fiber rotation. If this filament displays strong meandering, then again the anchoring is suppressed by fiber rotation; also, the scroll wave can be eliminated from most of the layers only to be regenerated by a seed wave. Ionic inhomogeneities can also lead to an anchoring of the scroll wave; scroll waves can now enter the region inside an ionic inhomogeneity and can display a coexistence of spatiotemporal chaos and quasi-periodic behavior in different parts of the simulation domain. We discuss the experimental implications of our study.