Rescaled mean spherical approximation structure factor for an aqueous suspension of polystyrene spheres

Rescaled mean spherical approximation (RMSA) has been used to calculate the structure factor for the aqueous suspension of polystyrene macroions with the interaction potential taken according to Derjaguin and Landau (1941) and Verwey and Overbeek (1948) (DLVO) model. The effects of charge over the macroion and size on the surface potential and therefore, the structure factor have been studied. The breakdown of the DLVO potential with an excess charge over the macroion (⩾800e) has been reported. The oscillation in the first peak height of structure factor versus wave vector curve with size has been correlated with the Debye length.     

Preparation of (CdO)1−x(PbO)x and (CdS)1−x(PbS)x thin films by spray pyrolysis technique and their characterization

Mixed thin films of (CdO)_1−x(PbO)_x and (CdS)_1−x(PbS)_x (x=0.25) were prepared on glass substrates by spray pyrolysis technique for various substrate temperatures 300, 320 and 340 °C. Structural and optical properties were studied. XRD studies reveal the formation of mixed films. The substrate temperature of 340 °C seems to be critical for the formation of CdO-PbO mixed films. It is observed that (CdS)_1−x(PbS)_x mixed films were formed at all the three substrate temperatures. The direct band gap value of (CdO)_1−x(PbO)_x and (CdS)_1−x(PbS)_x mixed films is about 2.6 and 2.37 eV, respectively.     

Study of interactions of various ionic species with solvents toward the design of receptors

In earlier studies, the interactions of isolated ionic species with various solvents were investigated using ab initio calculations. The ionic species investigated included cations (proton, hydronium, ammonium, and metal cations) and anions (single electron, hydroxide, and halide anions). However in the present study, we investigate the interactions of these ionic species with the solvent in the presence of other competing ionic species. We also elaborate on how the information obtained from these extensive studies have been employed in designing and synthesizing various kinds of novel ionophores and receptors.     

Order and chaos in soft condensed matter

Soft matter, like colloidal suspensions and surfactant gels, exhibit strong response to modest external perturbations. This paper reviews our recent experiments on the nonlinear flow behaviour of surfactant worm-like micellar gels. A rich dynamic behaviour exhibiting regular, quasi-periodic, intermittency and chaos is observed. In particular, we have shown experimentally that the route to chaos is via Type-II intermittency in shear thinning worm-like micellar solution of cetyltrimethylammonium tosylate where the strength of flow-concentration coupling is tuned by the addition of sodium chloride. A Poincaré first return map of the time series and the probability distribution of laminar length between burst events show that our data are consistent with Type-II intermittency. The existence of a ‘Butterfly’ intensity pattern in small angle light scattering (SALS) measurements performed simultaneously with the rheological measurements confirms the coupling of flow to concentration fluctuations in the system under study. The scattered depolarised intensity in SALS, sensitive to orientational order fluctuations, shows the same time-dependence (like intermittency) as that of shear stress.     

Thermal stability of shear-induced precursor structures in isotactic polypropylene by rheo-X-ray techniques with couette flow geometry

Combined in situ rheo-SAXS (small-angle X-ray scattering) and -WAXD (wide-angle X-ray diffraction) studies using couette flow geometry were carried out to probe thermal stabilty of shear-induced oriented precursor structure in isotactic polypropylene (iPP) at around its normal melting point (162 °C). Although SAXS results corroborated the emerging consensus about the formation of “long-living” metastable mesomorphic precursor structures in sheared iPP melts, these are the first quantitative measures of the limiting temperature at which no oriented structures survive. At the applied shear, rate = 60 s⁻¹ and duration t_s = 5 s, the oriented iPP structures survived a temperature of 185 °C for 1 h after shear, while no stable structures were detected at and above 195 °C. Following Keller's concepts of chain orientation in flow, it is proposed that the chains with highly oriented high molecular weight fraction are primarily responsible for their stability at high temperatures. Furthermore, the effects of flow condition, specifically the shear temperature, on the distributions of oriented and unoriented crystals were determined from rheo-WAXD results. As expected, at a constant flow intensity (i.e., rate = 30 s⁻¹ and duration, t_s = 5 s), the oriented crystal fraction decreased with the increase in temperature above 155 °C, below which the oriented fraction decreased with the decrease in temperature. As a result, a crystallinty “phase” diagram, i.e., temperature versus crystal fraction ratio, exhibited a peculiar “hourglass” shape, similar to that found in many two-phase polymer–polymer blends. This can be explained by the competition between the oriented and unoriented crystals in the available crystallizable species. Below the shear temperature (155 °C), the unoriented crystals crystallized so rapidly that they overwhelmed the crystallization of the oriented crystals, thus depleting a major portion of the crystallizable species and increasing their contribution in the final total crystalline phase. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3553–3570, 2006     

Design,synthesis, and characterization of main‐chain,aromatic polyesters based on 3,4‐ethylenedioxythiophene

A series of new thermoplastic polyesters based on 3,4‐ethylenedioxythiophene (EDOT) with flexible aliphatic spacers have been synthesized and characterized for the first time. The thermal properties of these polyesters based on EDOT are comparable to those of conventional polyesters based on the 1,4‐phenyl unit, indicating that EDOT is a viable replacement for the phenyl units. The glass‐transition and melting‐transition temperatures decrease monotonically with an increase in the spacer length. Theoretical calculations have revealed that the core angle for EDOT is comparable to that of unsubstituted thiophene and hence should be compatible with the formation of the mesophase. This has been confirmed experimentally by the synthesis of a main‐chain, thermotropic, liquid‐crystalline polyester based on EDOT that exhibits fluid birefringence. In fact, this is the first report in which a main‐chain, liquid‐crystalline polymer based on 3,4‐disubstituted thiophene has been successfully designed and synthesized. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3479–3486, 2006     

Structure–activity studies on the fungitoxicity of some triorganotin(IV) compounds

Seventeen triorganotin(IV) compounds, with the general formula R₃SnX, containing symmetrical and unsymmetrical combinations of alkyl and aryl groups on tin and with a wide variation in the non-carbon-bonded anionic (X) residues, were examined along with three formally pentacoordinated adducts of triaryltin chlorides with triphenylphosphine oxide for their antifungal activity against nine plant pathogenic and saprophytic fungi. The in vitro tests included inhibitory studies on radial growth, mycelial growth, spore germination, and germ tube elongation. A significant finding was the dependence of fungitoxicity on the nature of the X group in both the tributyltin and triaryltin series, in contrast to earlier published reports on the negligible influence of the X groups on overall toxicity relative to the R group. This suggests that the X group is significantly involved in transporting the biocide to the reactive sites, and that the X group which tends to confer increased solubility to the triorganotin compound gives rise to increased activity. In studies of R group variations, tri-iso-butyltin bromide was found to be much less fungitoxic than tri-n-butyltin compounds, a result which is reconcilable in terms of increased steric encumbrance at the tin site in the former case. The steric factor is also implicated in the reduced activities observed for tris(p-tolyl)tin and tris(p-chlorophenyl)tin compounds relative to (Ph₃SnX) towards most of the fungi screened in this study. In general, it was also noted that the triaryltins were more selective in their antifungal action than the trialkyltins, which exhibited broad spectral activity when applied at the concentration level of 10 μg cm^?3.     

Dielectric spectroscopy of a smectic liquid crystal

Complex dielectric spectroscopy (frequency range 5 Hz-13 MHz) has been used to analyse the frequency, temperature and bias-field dependences of the molecular dynamics of a very high-spontaneous-polarization ferroelectric liquid crystalline material exhibiting SmA, SmC* and unknown SmX smectic phases. Different smectic phase transition temperatures have been observed from the study of the temperature dependence of the dielectric strength and the relaxation frequency. The phase transition temperatures (crystalline to isotropic phases) have also been described very accurately from the temperature-dependent symmetric and asymmetric shape parameters of the relaxation function and also the dc conductivity. In a planar aligned cell, two symmetric modes (Goldstone mode and domain mode) have been observed in both the SmX and SmC* phases. One asymmetric mode (X-mode) observed in the SmC* and SmA phases could be related to the interaction of dipoles of the ferroelectric liquid crystals being affected by the surface of the cell. The soft mode, which usually appears very close to the SmC*-SmA phase transition was not observed until the bias field was applied. The second order nature of the SmC*-SmA phase transition was revealed.     

Radiation induced synthesis and swelling characterization of thermo-responsive N-isopropylacrylamide-co-ionic hydrogels

Two-component thermo-responsive hydrogels poly(N-isopropylacrylamide)-co-vinylbenzyltrimethylammonium chloride (NIPA-co-VBT) and poly(N-isopropylacrylamide)-co-p-sodium styrene sulphonate (NIPA-co-SSS) were prepared by using high energy gamma radiation. The gels were characterized by Fourier transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and sol-gel analysis. The presence of ionic monomers in NIPA leads to lower gel content. Introduction of ionic components in the matrix enhanced swelling extent but caused slower volume transition. The swelling studies in alcohol indicated that swelling extent was function of polarity of the swelling medium and all gels followed the order water > methanol > ethanol > iso-propanol. In mixed co-solvents (water-alcohol), they exhibit complex reentrant behavior. The co-polymer gels containing VBT swelled faster and to higher extent than those containing SSS. The dynamic swelling studies indicated that diffusion of water in PNIPA gel shifts from Fickian for PNIPA to anomalous for NIPA-co-ionic gels also the mean swelling time (MST) decreases for gels containing ionic monomers.