Modification of non‐Newtonian flow behavior of aqueous solution of poly(vinyl alcohol) by conducting polypyrrole prepared by in situ polymerization of pyrrole

The rheological behavior of an aqueous solution of poly(vinyl alcohol) (PVA) and polypyrrole (PPY) dispersions prepared by ferric chloride (FeCl₃)‐catalyzed polymerization of pyrrole was investigated at 12°C using a coaxial rotational viscometer. The results show that the addition of a low dose of FeCl₃ to the PVA solution greatly influences its rheology. The prominent shear‐thickening (dilatant) nature of PVA turns significantly pseudoplastic (shear thinning) in the presence of FeCl₃. Polypyrrole‐loaded PVA was obtained in a stable, optically clear dispersion by in situ polymerization of pyrrole in an aqueous PVA solution (5%) using FeCl₃ as the oxidative catalyst at 12°C. The PPY dispersions in aqueous PVA systems having a low loading of PPY and low Fe⁺³ content retain the dilatant character of an aqueous PVA solution; however, for an aqueous PVA system having a relatively high PPY loading and also a high Fe⁺³ content, prominent pseudoplastic (shear thinning) behavior is exhibited. The odd novel rheological patterns exhibited by a PVA solution in the absence and presence of FeCl₃ and the PVA–PPY dispersions containing FeCl₃ under different sets of conditions are explained on the basis of the complexation of PVA by Fe⁺³ and related ions and also as a consequence of some degree of H‐bonding and chemical grafting between the support polymer PVA and the PPY formed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3737–3741, 2004     

Investigation of Nucleation Mechanism and Tapering Observed in ZnO Nanowire Growth by Carbothermal Reduction Technique

ZnO nanowire nucleation mechanism and initial stages of nanowire growth using the carbothermal reduction technique are studied confirming the involvement of the catalyst at the tip in the growth process. Role of the Au catalyst is further confirmed when the tapering observed in the nanowires can be explained by the change in the shape of the catalyst causing a variation of the contact area at the liquid–solid interface of the nanowires. The rate of decrease in nanowire diameter with length on the average is found to be 0.36 nm/s and this rate is larger near the base. Variation in the ZnO nanowire diameter with length is further explained on the basis of the rate at which Zn atoms are supplied as well as the droplet stability at the high flow rates and temperature. Further, saw-tooth faceting is noticed in tapered nanowires, and the formation is analyzed crystallographically.     

Effect of silica doping on the densification and grain growth in zinc oxide

The ability of silica (SiO₂) in controlling the densification and grain growth behavior of nano crystalline zinc oxide (ZnO) has been systematically studied. It has been observed that SiO₂ acts as a sintering inhibitor in the ZnO–SiO₂ system up to 4 wt.% limiting value beyond which densification behavior of the system remains almost unchanged, especially above 1100 °C. The addition of SiO₂ to ZnO retards grain growth which in turn results a finer ultimate grain size as compared to the undoped ZnO. However, stabilization in grain size occurs at ≥4 wt.% SiO₂ addition. It has been observed that SiO₂ incorporation changes the grain growth mechanism up to 4 wt.% addition, beyond which no remarkable changes was noticed. The grain growth (n) shows distinctly different slopes as a function of sintering time for the SiO₂ doped ZnO systems than undoped ZnO. The different slopes tend to indicate that different diffusion mechanisms and probably the formation of a secondary phase (Zn–Si–O) at the grain boundary control the densification and grain growth. The thermal expansion coefficient of the system has been found to decrease substantially beyond 4 wt.% SiO₂ addition to ZnO.     

A partial Granger causality based method for analysis of parameter interactions in bioreactors

In this article, we utilize the concept of partial Granger causality to study the penicillin production process under several operating conditions. We propose a graph-theoretic template (causal network) based method for intelligent process monitoring. We validate our results with the aid of existing knowledge and available literature. The proposed method is quite general and can be extended to analyze several physical, chemical or biological systems.     

Photoelectrochemical performances of indium-doped CdS0.2Se0.8 thin film electrodes prepared by spray pyrolysis

Polycrystalline undoped and indium-doped CdS_0.2Se_0.8 thin films were deposited on FTO-coated glass substrates by spray pyrolysis. The cell configurations CdS_0.2Se_0.8/1 M (Na₂S + S + NaOH)/C and In:CdS_0.2Se_0.8/1 M (Na₂S + S + NaOH)/C were used to study a wide range of photoelectrochemical characteristics including capacitance–voltage in the dark, current–voltage characteristics in the dark and under illumination, photovoltaic power output and spectral response and to perform electrochemical impedance spectroscopy studies. The study reveals that the films exhibit n-type conductivity. Various PEC parameters such as the junction ideality factor under illumination, series and shunt resistances, fill factor and efficiency have been estimated for the PEC cells formed with CdS_0.2Se_0.8 and indium-doped CdS_0.2Se_0.8 thin films. The efficiency and fill factor of these PEC cells are found to be improved from 0.79% and 0.46 to 2.12% and 0.49, respectively, with indium doping in CdS_0.2Se_0.8 thin films. Electrochemical impedance spectroscopy studies show that doping of indium into CdS_0.2Se_0.8 thin film improves the performance of resulting PEC cells.     

Cleaning organized single-walled carbon nanotube interconnect structures for reduced interfacial contact resistance

A method is presented for significantly reducing the interfacial contact resistance of single-walled carbon nanotube (SWCNT) interconnects test-structures. Conventional lithographic cleaning steps are insufficient for complete removal of lithographic residues in SWCNT networks, leading to large interfacial contact resistance. Using improved purification procedures and controlled developing time, the interfacial contact resistance between SWCNTs and contact electrodes of Ti/Au were found to reach values below 2% of the overall resistance in two-probe test-structures of SWCNTs, demonstrating the importance of cleaning lithographic residues from the surface of SWCNTs before the fabrication of metal electrodes. These low-resistance contacts are quite stable over a large temperature range, and represent a step towards the implementation of SWCNTs as future interconnects.     

Morphology and properties of nylon 6 and high density polyethylene blends in presence of nanoclay and PE‐g‐MA

In this study, we report the synergistic effect of nanoclay and maleic anhydride grafted polyethylene (PE‐g‐MA) on the morphology and properties of (80/20 w/w) nylon 6/high density polyethylene (HDPE) blend. Polymer blend nanocomposites containing nanoclay with and without compatibilizer (PE‐g‐MA) were prepared by melt mixing, and their morphologies and structures were examined with scanning electron microscopy (SEM) and wide angle X‐ray diffractometer (WAXD) study. The size of phase‐separated domains decreased considerably with increasing content of nanoclay and PE‐g‐MA. WAXD study and transmission electron microscopy (TEM) revealed the presence of exfoliated clay platelets in nylon 6 matrix, as well as, at the interface of the (80/20 w/w) nylon 6/HDPE blend–clay nanocomposites. Addition of PE‐g‐MA in the blend–clay nanocomposites enhanced the exfoliation of clays in nylon 6 matrix and especially at the interface. Thus, exfoliated clay platelets in nylon 6 matrix effectively restricted the coalescence of dispersed HDPE domains while PE‐g‐MA improved the adhesion between the phases at the interface. The use of compatibilizer and nanoclay in polymer blends may lead to a high performance material which combines the advantages of compatibilized polymer blends and the merits of polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Wavelength conversion using rare earth doped oxides in polyolefin based nanocomposite films

Nanocomposites are a new class of polymeric materials which include organic or inorganic nano‐phase materials. These nanocomposite films can show interesting properties which have many applications for wavelength conversion and energy saving. In this paper, we present polyolefin based nanocomposite films prepared using wavelength‐converting red ‘phosphors’ such as Y₂O₃: Eu³⁺ and LiAl₅O₈:Fe³⁺ and blue ‘phosphor’ CaMgSi₂O₆: Eu²⁺. The durability of the polymer chain is unaffected by incorporation of inorganic nanoparticles as there is no direct interaction between them. The addition of surfactant in the nanocomposite film helps to improve the dispersion ability of the nanoparticles and increase the flexibility of the polymer film. Wavelength‐converting ‘nanophosphors’ incorporated in a polymer matrix help to increase the tensile strength of the film. The films show excellent wavelength conversion ability of UV light into the visible and near IR range. These nanocomposite films have great application in energy saving devices. Copyright © 2012 Society of Chemical Industry     

Polystyrene composites of single‐walled carbon nanotubes‐graft‐polystyrene

Single‐walled carbon nanotubes (SWCNTs) dispersed in N‐methylpyrrolidone (NMP) were functionalized by addition of polystyryl radicals from 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐ended polystyrene (SWCNT‐g‐PS). The amount of polystyrene grafted to the nanotubes was in the range 20‐25 wt% irrespective of polystyrene number‐average molecular weight ranging from 2270 to 49 500 g mol^?1. In Raman spectra the ratios of D‐band to G‐band intensity were similar for all of the polystyrene‐grafted samples and for the starting SWCNTs. Numerous near‐infrared electronic transitions of the SWCNTs were retained after polymer grafting. Transmission electron microscopy images showed bundles of SWCNT‐g‐PS of various diameters with some of the polystyrene clumped on the bundle surfaces. Composites of SWCNT‐g‐PS in a commercial‐grade polystyrene were prepared by precipitation of mixtures of the components from NMP into water, i.e. the coagulation method of preparation. Electrical conductivities of the composites were about 10^?15 S cm^?1 and showed no percolation threshold with increasing SWCNT content. The glass transition temperature (T_g) of the composites increased at low filler loadings and remained constant with further nanotube addition irrespective of the length and number of grafted polystyrene chains. The change of heat capacity (ΔC_p) at T_g decreased with increasing amount of SWCNT‐g‐PS of 2850 g mol^?1, but ΔC_p changed very little with the amount of SWCNT‐g‐PS of higher molecular weight. The expected monotonic decrease in ΔC_p coupled with the plateau behavior of T_g suggests there is a limit to the amount that T_g of the matrix polymer can increase with increasing amount of nanotube filler. Copyright © 2012 Society of Chemical Industry     

Effect of nanoclay on positive temperature coefficient to resistivity characteristics of high density polyethylene/silver‐coated glass bead composites

Positive temperature coefficient to resistivity characteristics of high density polyethylene (HDPE)/silver (Ag)‐coated glass bead (45 wt%) composites, without and with nanoclay, has been investigated with reference to HDPE/carbon black (CB) (10 wt%) composites. Plot of resistivity versus temperature of HDPE/CB (10 wt%) composites showed a sudden rise in resistivity (PTC trip) at ≈128°C, close to the melting temperature (T_m) of HDPE. However, for HDPE/Ag coated glass bead (45 wt%) composites, the PTC trip temperature (≈88°C) appeared well below the T_m of HDPE. Addition of 1 phr clay in the composites resulted in an increase in PTC trip temperature of HDPE/Ag‐coated glass bead (45 wt%) composites, whereas no significant effect of clay on PTC trip temperature was evident in HDPE/CB/clay composites. We proposed that the PTC trip temperature in HDPE/Ag‐coated glass bead composites was governed by the difference in coefficient of thermal expansion of HDPE and Ag‐coated glass beads. The room temperature resistivity and PTC trip temperature of HDPE/Ag‐coated glass bead (45 wt%) composites were found to be very stable on thermal cycling. Dynamic mechanical analyzer results showed higher storage modulus of HDPE/Ag‐coated glass bead (45 wt%) composites compared with the HDPE/CB (10 wt%) composites. Thermal stability of HDPE/Ag‐coated glass bead (45 wt%) composites was also improved compared with that of HDPE/CB (10 wt%) composites. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers