Positron annihilation spectroscopic characterization of free-volume defects and their correlations with the mechanical and transport properties of SBR-PMMA interpenetrating polymer networks.

A series of interpenetrating polymer networks (IPNs) and semi-interpenetrating polymer networks (s-IPNs) of styrene butadiene rubber (SBR) and poly(methyl methacrylate) (PMMA) have been synthesized by adopting the sequential interpenetration and in situ polymerization method. The size and the concentration of free volume defects in these systems are monitored and their variations accurately traced using positron annihilation lifetime (PALS) and coincidence Doppler broadening spectroscopic (CDBS) measurements. The morphologies of the IPNs were analyzed with transmission electron microscopy (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Confocal Raman mapping had been employed to elucidate the mechanism of PMMA interpenetration in the SBR matrix with reference to the blend ratio. The results of free volume analysis lead to the conclusion that the increase of PMMA content in IPN was accompanied by enhancement of interpenetration in the system. Also the morphology changes from dispersed island pattern to a co-continuous one. Besides, the transport parameters and mechanical behavior of IPNs were studied in detail. The results of PALS and CDBS measurements have found to exhibit striking correlations with the sorption, mechanical properties and morphology of the polymer networks. The specific physics involved in the characterization protocol is effectively utilized to explore the chemistry of IPN formation. This new modality of characterization versus composition uplifts and widens the application prospects of elastomer-thermoplastic IPNs.

Magnetic performance and defect characterization studies of core-shell architectured MgFe2O4@BaTiO3 multiferroic nanostructures.

Multiferroics that permit manipulation of the magnetization vector exclusively by electric fields have spawned extensive interest for memory and logic device applications. In line with this understanding, we herein report the encapsulation of non-ferroelectric magnesium ferrite (MgFe2O4) nanoparticles in a ferroelectric shell of BaTiO3 to produce a system with engineered dielectric, magnetic, magneto-electric and ferroelectric properties. The interface effect on the strain transfer was observed to strongly influence the magneto-electric coupling and the electric and magnetic properties of the system. The model polyhedral image of MgFe2O4@BaTiO3 has helped to get an insight into the core-shell structure. The multiferroicity induced by the excellent coupling between the ferroelectric and magnetostrictive phases at the core-shell interface unlocks wide prospects for device downscaling and information storage applications. The influence of magnetostrictive stress on the magneto-electric coupling effects and domain dynamics was further studied using transmission electron microscopy (TEM) and atomic force microscopy images. Interestingly, the realization of a superparamagnetic multiferroic system has been a breakthrough and facilitates ultra high density magnetic data storage technologies. Evidence for spontaneous polarization and the ferroelectric trait exhibited by the multiferroic samples was revealed from the P-E hysteresis loop. The investigation of defect evolution in the system was carried out using positron annihilation lifetime spectroscopy (PALS) and coincidence Doppler broadening spectroscopy (CDBS) of annihilation radiation and the studies revealed thermal diffusion of positrons into the interfacial regions within the core-shell structure and the "formation and pick-off annihilation of orthopositronium atoms". It is concluded that interface engineering is a strong means for manipulation of the magnetic, dielectric and magneto-electric properties in multiferroic heterostructures for high density electrical energy and magnetic data storage.

Effects of process parameters on the defects in graphene oxide-polyaniline composites investigated by positron annihilation spectroscopy.

Graphene oxide (GO)-polyaniline (PANI) composites were prepared with different relative abundance of PANI and GO by in situ polymerization of aniline in the presence of GO and ammonium persulphate at different temperatures. In the process, GO also got reduced to graphene. Positron lifetimes and coincidence Doppler broadening of the electron-positron annihilation gamma ray spectra originating from the composite samples were measured and the results are reported. The positron lifetimes indicated the presence of very large size defects in the form of vacancy clusters within the samples. Another interesting observation was the increase of relative intensity of the defect specific positron lifetime component when an increase in relative abundance of PANI led to increased reduction of GO to graphene. The reduction also shrank the volume occupied by GO and the free volume thereby released added to the overall defect concentration, resulting in a simultaneous increase of the intensity of the positron lifetime component. The variation of the positron lifetime and its intensity with the synthesis temperature suggested an optimum temperature suitable for the process. The above observations are corroborated by other experimental investigations like electron microscopy, X-ray diffraction and electrical conductivity.

Mn(2+)-induced substitutional structural changes in ZnS nanoparticles as observed from positron annihilation studies.

Zinc sulfide nanoparticles doped with different concentrations of manganese ions (Mn(2+)) were synthesized at various temperatures to investigate the effects of substitution and the associated defect evolution. Positron lifetime and Doppler broadening measurements were used as probes. The initial stage of defect recovery was dominated by the occupation of Zn(2+) vacancies by Mn(2+) ions, bringing in characteristic changes in the positron lifetimes, intensities and Doppler broadened lineshape parameters. Detailed analyses considering the presence of one and two types of defects were carried out to identify the type of defects which trap positrons at the different dopant concentrations. Electron paramagnetic resonance studies indicated increased Mn-Mn interaction and the formation of Mn clusters with further doping. The results are in striking contrast to those for nanorods, where vacancy recombination transformed their interior into regions free of defects.

Mn-Doping in NiO Nanoparticles: Defects-Modifications and Associated Effects Investigated Through Positron Annihilation Spectroscopy.

Manganese-doped nickel oxide (Ni1-xMnxO) nanoparticulate samples with x in the range 0 (undoped sample) to 0.35 were synthesized by sol-gel method involving chemical reactions between the solutions of nickel nitrate hexahydrate and manganese acetate tetrahydrate. The nanocrystallites obtained after annealing of the precipitates for different durations were characterized by X-ray diffraction and high resolution transmission electron microscopy. The samples showed high degree of purity with no secondary phase up to 35 at.% (x = 0.35) of Mn-doping. At the initial doping concentrations, the crystallite sizes increased due to vacancy type defects being recombined with some of the doped Mn2+ ions. However, substitution-induced strain soon overtook the crystallite dynamics and the sizes rapidly started reducing again as an indirect consequence of the necessity to accommodate majority of the doped cations on the surfaces of the nanocrystallites. There was conspicuous changes in the lattice parameter too which could again be attributed to the strain and charge effects. The average sizes of the crystallites were obtained in the range 5.5 nm to 13.1 nm for the different samples. UV-Vis absorption studies indicated the formation of excitonic states in NiO on Mn-doping. The band gap energy (Eg) derived from the optical absorption spectra showed a continuous increase with increase of Mn-doping of the samples. Positron lifetime and Doppler broadening spectroscopic studies were carried out on those samples to characterize the vacancy type defects and defect clusters/complexes. There were also indications to suggest positron annihilation at the crystallite surfaces owing to their sizes of nanometer order. Positron lifetimes decreased upon increase of Mn-doping. The coincidence Doppler broadened ratio curves indicated definite shifts of the prominent oxygen-electron-annihilation peak and the variation of the lineshape parameter S also indicated clearly the effects of Mn-doping.

A positron annihilation spectroscopic investigation of europium-doped cerium oxide nanoparticles.

Doping in ceria (CeO2) nanoparticles with europium (Eu) of varying concentrations (0, 0.1, 0.5, …, 50 atom%) is studied using complementary experimental techniques and novel observations were made during the investigation. The immediate observable effect was a distinct reduction in particle sizes with increasing Eu concentration attributed to the relaxation of strain introduced due to the replacement of Ce(4+) ions by Eu(3+) ions of larger radius. However, this general trend was reversed in the doping concentration range of 0.1-1 atom% due to the reduction of Ce(4+) to Ce(3+) and the formation of anion vacancies. Quantum confinement effects became evident with the increase of band gap energy when the particle sizes reduced below 7-8 nm. Positron annihilation studies indicated the presence of vacancy type defects in the form of vacancy clusters within the nanoparticles. Some positron annihilation was also seen on the surface of crystallites as a result of diffusion of thermalized positrons before annihilation. Coincidence Doppler broadening measurements indicated the annihilation of positrons with electrons of different species of atoms and the characteristic S-W plot showed a kink-like feature at the particle sizes where quantum confinement effects began.

Positron annihilation spectroscopic studies of solvothermally synthesized ZnO nanobipyramids and nanoparticles.

Zinc oxide (ZnO) samples in the form of hexagonal-based bipyramids and particles of nanometer dimensions were synthesized through solvothermal route and characterized by x-ray diffraction and transmission electron microscopy. Positron annihilation experiments were performed to study the structural defects such as vacancies and surfaces in these nanosystems. From coincidence Doppler broadening measurements, the positron trapping sites were identified as Zn vacancies or Zn-O-Zn trivacancy clusters. The positron lifetimes, their relative intensities, and the Doppler broadened lineshape parameter S all showed characteristic changes across the nanobipyramid size corresponding to the thermal diffusion length of positrons. In large nanobipyramids, vacancies within the crystallites also trapped positrons and the effects of agglomeration of such vacancies due to increased temperatures of synthesis were reflected in the variation of the annihilation parameters with their base diameters. The sizes of the nanoparticles used were all in the limit of thermal diffusion length of positrons and the annihilation characteristics were in accordance with the decreasing contribution from surfaces with increasing particle size.

Positron annihilation studies of defects and interfaces in ZnS nanostructures of different crystalline and morphological features.

Nanostructures of ZnS, both particles and rods, were synthesized through solvothermal processes and characterized by x-ray diffraction and high resolution transmission electron microscopy. Positron lifetime and Doppler broadening measurements were made to study the features related to the defect nanostructures present in the samples. The nanocrystalline grain surfaces and interfaces, which trapped significant fractions of positrons, gradually disappeared during grain growth, as indicated by the decreasing fraction of orthopositronium atoms. The crystal vacancies present within the grains also trapped positrons. These vacancies further agglomerated into clusters during the thermal treatment given to effect grain growth. The positron lifetime was remarkably large at extremely small grain sizes (approximately 1.5 nm) and this was attributed to the occurrence of quantum confinement effects, as verified through optical absorption measurements. Positron lifetimes in ZnS nanorods increased with increasing content of cubic phase in the samples and this observation is assigned to the annihilation of positrons in sites with increased cubic unit cell volume. The Doppler broadened spectra also indicated qualitative changes consistent with these observations.