ESR and optical absorption spectra of Cu2+ in LiKSO4

ESR spectra of Cu²⁺ in LiKSO₄ have been studied at different temperatures. The measured g-values suggest a rhombic field for Cu²⁺ ion in the lattice. Optical absorption spectra of the crystal have been studied at room and liquid nitrogen temperatures. From the nature and position of the observed bands, they have been attributed to Cu²⁺ ions in D_2h symmetry. The orbital reduction parameters obtained indicate a substantial degree of covalency in the bonding of the copper ion.     

Magnetic phase evolution in Fe substituted GdBaCo2O5.5

Magnetization and magneto-resistance experiments have been carried out on well characterized samples of the GdBaCo_2−xFe_xO_5.5 series. Zero field cooled magnetization measurements in the low concentration Fe samples suggest, that the low temperature anti-ferromagnetic phase transforms sequentially to several ferromagnetic phases, before transforming to a paramagnetic state with increase in temperature. The anti-ferromagnetic to the first ferromagnetic phase transition is associated with a large negative magneto-resistance for Fe fractions upto x=0.075. Isothermal magnetization measurements in the ferromagnetic like region of the samples, suggests the presence of mixtures of two ferromagnetic phases. Similar measurements performed at low temperatures where anti-ferromagnetic-like phase is stabilised suggest the presence of a mixture of anti-ferromagnetic and ferromagnetic phases. Magnetization and magneto-resistance are seen to collapse for Fe fractions, x>0.1. Based on these studies a plausible scenario of the evolution of magnetism with Fe substitution in GdBaCo₂O_5.5, is suggested.     

Charge transport in polythiophene:fullerene:nanotube bulk heterojunction photovoltaic devices investigated by impedance spectroscopy

P3HT:PCBM bulk heterojunction devices incorporating SWNTs, which are predominantly metallic in character, have been analyzed using impedance spectroscopy to understand the effect of SWNTs on their charge carrier transport properties. SWNTs reduce the effective lifetime of injected charge carriers. Frequency dependence of capacitance and conductance of P3HT:PCBM devices show monotonic variations without any clear peak positions. Simulations of the complex admittance of the P3HT:PCBM devices under trap free space charge limited current within the framework of Scher–Montrol theory are used to qualitatively show that such characteristics are a signature of charge transport which is highly dispersive in nature. The position of peak τ_peak in the imaginary part of impedance Im(Z), which is essentially same as the first transition frequency of Cole–Cole plot, has a direct relation with the effective dc mobility of charge carriers which varies with dispersion parameters. Using the dc mobility values and the voltage variation of peak frequency of Im(Z), the ratio of τ_dc to τ_peak has been calculated. The magnitude of this ratio is indicative of the degree of dispersiveness in transport. It has been shown that, SWNTs at low concentrations tend to reduce the dispersiveness in charge transport.     

Magneto-resistance above 300 K in nano-crystalline Co–Ag metastable solid solutions

A series of nano-crystalline Co_xAg_100−x solid solutions have been prepared by NaBH₄ reduction of the corresponding metal salts at room temperature in Ar gas flow. Alloys heat-treated at 600 °C in Ar/H₂ (5%) show the evolution of metastable fcc Co precipitates in Ag. Magnetic studies indicate that all the compositions are ferromagnetic with Curie temperatures >400 K. For a nominal composition of Co₆₀Ag₄₀, heat-treated at 600 °C, an effective negative magneto-resistance (MR) ratio of the order of ∼21% at 350 K, at 2 T is observed. This could arise from the influence of magnetic field on the electron–phonon scattering effects near to T_c and to the spin-mixing scattering by magnons.     

Helix forming tendency of valine substituted poly-alanine: a molecular dynamics investigation

In this study, classical molecular dynamics simulations have been carried out on the valine (guest) substituted poly alanine (host) using the host-guest peptide approach to understand the role of valine in the formation and stabilization of helix. Valine has been substituted in the host peptide starting from N terminal to C terminal. Various structural parameters have been obtained from the molecular dynamics simulation to understand the tolerance of helical motif to valine. Depending on the position of valine in the host peptide, it stabilizes (or destabilizes) the formation of the helical structure. The substitution of valine in the poly alanine at some positions has no effect on the helix formation (deformation). It is interesting to observe the coexistence of 3 10 and alpha-helix in the peptides due to the dynamical nature of the hydrogen bonding interaction and sterical interactions.     

The Kolkata Paise Restaurant problem and resource utilization

We study the dynamics of the “Kolkata Paise Restaurant problem”. The problem is the following: In each period, N agents have to choose between N restaurants. Agents have a common ranking of the restaurants. Restaurants can only serve one customer. When more than one customer arrives at the same restaurant, one customer is chosen at random and is served; the others do not get the service. We first introduce the one-shot versions of the Kolkata Paise Restaurant problem which we call one-shot KPR games. We then study the dynamics of the Kolkata Paise Restaurant problem (which is a repeated game version of any given one shot KPR game) for large N. For statistical analysis, we explore the long time steady state behavior. In many such models with myopic agents we get under-utilization of resources, that is, we get a lower aggregate payoff compared to the social optimum. We study a number of myopic strategies, focusing on the average occupation fraction of restaurants.     

Metallic nanostructures in a polymer matrix and substrate fabrication and structural characterization

Metal nanostructures are of considerable interest in the field of plasmonics and metamaterials and could have a wider impact if they are successfully embedded in a stable, inert and flexible polymer matrix. Fabrication of such structures is challenging for a variety of reasons including thermal stability, material compatibility with processing steps and general handling of material. In this work we have demonstrated the fabrication of metal nanostructures and embedded them in a polymer. Furthermore, these structures were fabricated on a flexible polymer membrane and detached from a carrier substrate. Characterization of these structures was performed with SEM, TEM and EDS.     

Structure–property correlations of sulfonated polyimides. I. Effect of bridging groups on membrane properties

A series of six‐membered sulfonated polyimides were synthesized using 1,4,5,8‐naphthalenetetracarboxylic dianhydride, 4,4′‐diaminobiphenyl 2,2′‐disulfonic acid as the sulfonated diamine, and various nonsulfonated diamine monomers having different bridging groups. These bulky bridging groups have the capacity to increase hydrolytic stability and proton conductivity. Polyimides with bulky bridging groups showed increased solubility but exhibited lower thermal stability. The ion exchange capacity and water uptake reduced with increase in the bulkiness of the bridging group. This was attributed to the increase in the molecular weight of the repeating unit and hence effectively reduced the sulfonic acid content. In low temperatures, the conductivity was lower than Nafion®115 and, with increase in temperature, the conductivity rapidly increased and exhibited better conductivity than Nafion®115. Polyimides with bulky bridging groups 4‐amino phenyl sulfone, and 2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane showed higher conductivity than other polyimides and Nafion®115 despite low ion exchange capacity. The hydrolytic stability of the polyimides with bulky bridging groups was higher than the polyimides with less bulky atoms because of the imparted flexibility. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3612–3620, 2004     

Nanoindentation studies of polyimide thin films with various internal linkages in the diamine component

Polyimide thin films were synthesized from 3,3′,4,4′‐biphenyltetracarboxylic acid dianhydride (BPDA) and four different diamines (p‐phenylene diamine, 4,4′‐oxydiphenylene diamine, 4,4′‐biphenylene diamine, and 4,4′‐sulfonyldiphenylene diamine). The nanoindentation behavior of the resulting polyimides, namely, poly(p‐phenylene biphenyltetracarboximide) (BPDA‐PDA), poly(4,4′‐biphenylene biphenyltetracarboximide) (BPDA‐BZ), poly(4,4′‐oxydiphenylene biphenyltetracarboximide) (BPDA‐ODA), and poly(4,4′‐sulfonyldiphenylene biphenyltetracarboximide) (BPDA‐DDS), were investigated. Also, the morphological properties were characterized with a prism coupler and wide‐angle X‐ray diffraction and were correlated to the nanoindentation studies. The nanoindentation behavior and hardness varied quite significantly, depending on the changes in the chemical and morphological structures. The hardness of the polyimide thin films increased in the following order: BPDA‐DDS < BPDA‐ODA < BPDA‐BZ < BPDA‐PDA. For all the polyimide thin films, except that of BPDA‐BZ, the hardness decreased with an increase in the load. The birefringence, a measure of the molecular in‐plane orientation, increased in the following order: BPDA‐DDS < BPDA‐ODA < BPDA‐PDA < BPDA‐BZ. The X‐ray diffraction studies revealed that the crystallinity of the polyimide thin films varied with the changes in the chemical structure. The studies showed that the indentation response with an applied load and the hardness by nanoindentation for the BPDA‐based polyimides were closely related to the morphological structure. The nanoindentation and birefringence results revealed that the mechanical properties of the polyimide thin films were dependent on the crystallinity, which arose because of the chain order along the chain axis and the molecular packing order. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 861–870, 2004     

Novel thermooxidatively stable poly(ether-imide-benzoxazole) and poly(ester-imide-benzoxazole)

4-Hydroxy-5-nitrophthalimides were produced via nucleophilic aromatic substitution (NAS) of 4,5-dichloro phthalimide substituents by potassium nitrite. The use of a N-phenyl-phthalimide having a protected 4′-hydroxyl group allows concurrent deprotection and nitro reduction to amine to give the 4-hydroxy-5-amino-N-(4′-hydroxyphenyl) phthalimide. This key intermediate is the precursor to a poly (ether-imide-benzoxazole), and is the condensable monomer for a poly (ester-imide-benzoxazole). Benzoxazole monomer formation via condensation with p-fluorobenzoyl chloride afforded 2-(4′-fluorophenyl)-5,6,-N-[4′(-hydroxyphenyl) imide]-benzoxazole, which was polymerized under NAS conditions to produce a poly(ether-imide-benzoxazole) having an endothermic transition at 454°C with weight retention of 90% at 500°C in both air and nitrogen. Solution polycondensation of the 4-hydroxy-5-amino-N-(4′-hydroxyphenyl) phthalimide monomer with isophthaloyl chloride afforded a poly(ester-amide-imide) which was isolated and thermally cyclodehydrated in the solid state under vacuum to give a poly(ester-imide-benzoxazole) having 95% weight retention at 500°C in both air and nitrogen, with no detectable DSC transitions up to 500°C. © 1994 John Wiley & Sons, Inc.