High ionic conductivity and ion conduction mechanism in ZIF-8 based quasi-solid-state electrolytes: a positron annihilation and broadband dielectric spectroscopy study.

The low ionic conductivity and electrode-electrolyte interface instability issues with solid polymer electrolytes jeopardize their electrochemical performances in lithium-ion batteries (LIBs). The use of quasi-solid-state electrolytes (QSSEs) with concentrated Li salt embedded inside the pore networks of metal organic frameworks (MOFs) can successfully address the aforementioned issues. Owing to the sieve effect of zeolitic imidazolate framework-8 (ZIF-8) towards selective cation permeability over anions through the interconnected pore network, a unique QSSE with LiTFSI salt concentrated in the ZIF-8 skeleton used as a filler in poly(ethylene oxide) has been synthesized. LiTFSI gets embedded inside the interconnected pore network of ZIF-8 that furnishes unhindered pathways for Li+ ion migration leading to a very high ionic conductivity of ∼6 × 10-4 S cm-1. The higher ionic conductivity is directly related to the Li+ ion conduction through the pore network of ZIF-8 which has been experimentally evident from complementary methods viz. Positron annihilation and broadband dielectric spectroscopy. The design route towards these types of QSSEs encompassing porous MOFs paves the way for realizing Li superionic conductors suitable for practical application in commercial LIBs with high safety and stability.

High cubicity of D2O ice inside spherical nanopores of MIL-101(Cr) framework: a neutron diffraction study.

Although cubic ice (ice Ic) is considered to be an important phase of water that impacts ice cloud formation in the Earth's upper atmosphere, its properties have not been studied to the same extent as those of hexagonal ice (ice Ih). This is because pristine ice Ic is not formed in simple laboratory conditions. Ice Ic formed in ambient conditions has a stacking disordered array of both hexagonal and cubic-structured hydrogen-bonded water molecules. It is therefore an active area of research to find ways of developing stacking disorder-free pure ice Ic. We demonstrate the evolution of almost pure ice Ic structure within the spherical nanopores of a hydrostable Cr-based metal-organic framework MIL-101(Cr) with an average pore size of 1 nm by low-temperature neutron diffraction study on D2O. It is observed that at temperatures below 230 K a fraction of liquid D2O transforms into ice and more than 94% of ice crystals evolved inside the pore are cubic in shape. This is a significantly high fraction of ice Ic formed under simple conditions inside the spherical pores of a Cr-based MOF. It is also observed that upon increasing the temperature, ice Ic remains stable until its melting point, without being transformed into ice Ih. This observation is in contrast to our previous observation of ice structure in the 2D cylindrical nanopores of MCM-41, where H2O ice after creeping out from the cylindrical channel was seen to be dominated by hexagonal shape. In the present study, the D2O molecules were confined into well-defined spherical nanopores, which hindered the growth of crystals above a certain size, thus minimizing the stacking disordered array. Nanoconfinement of water inside uniform spherical pores is therefore a promising method for the evolution of a significantly large fraction of cubic ice by minimizing the stacking disorder. This finding may open up the possibility of forming ice Ic with 100% cubicity under simple laboratory conditions, which will help in exploring the microphysics of ice cloud formation in the upper atmosphere.

Role of free volumes and segmental dynamics on ion conductivity of PEO/LiTFSI solid polymer electrolytes filled with SiO2 nanoparticles: a positron annihilation and broadband dielectric spectroscopy study.

The limited ionic conductivity of polymer electrolytes is a major issue for their industrial application. Enhancement of ionic conductivity in the poly(ethylene oxide), PEO, based electrolyte has been achieved by loading passive nanofillers such as SiO2 nanoparticles (NPs). To investigate the role of modifications in free volume characteristics and the polymer chain dynamics induced by the loading of passive fillers on the ionic conductivity of the PEO based ternary electrolyte, a systematic investigation has been carried out using positron annihilation and broadband dielectric spectroscopy. As a result of interfacial interactions, the loading of SiO2 NPs alters the semi-crystalline morphology of PEO resulting in a higher crystallinity at lower loadings due to the surface confinement of PEO chains, and the formation of smaller PEO crystallites at higher loadings due to interparticle nanoconfinement. These modifications are accompanied by a decrease in free volume fraction at the lowest loading (0.5 wt%) followed by an increase at higher loadings (≥2.0 wt%). The Almond-West formalism considering two different universalities in different temperature and frequency ranges has been used to explain the ion-conduction process at different NP loadings. The Li ion conductivity is observed to be maximum for a 5.0 wt% loading of SiO2 NPs. The enhancement in ionic conductivity is observed to be directly correlated with the free volume characteristics and segmental dynamics of the PEO matrix, confirming their role in ion transport in polymer electrolytes.

Probing the solute-drag effect and its role in stabilizing the orthorhombic phase in bulk La-doped HfO2 by X-ray and gamma ray spectroscopy.

The recent observation of ferroelectricity in ultra thin films of hafnium oxide (HfO2) has been attributed to the orthorhombic (o) phase of HfO2 with space group Pca21. Although this oxide is polymorphic in nature, this polar o-phase is known to be stabilized in the doped thin film oxide. The objective of the present experiment is to stabilize the o-phases in La doped bulk polycrystalline HfO2 and investigate their evolution with the doping concentration through Time Differential Perturbed Angular Correlation (TDPAC), X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) measurements. The present work reports the presence of both the polar Pca21 phase and the antipolar Pbca phase at different La-concentrations. Two o-phases of HfO2 with space groups Pca21 and Pbca, difficult to distinguish by other complimentary methods, could be unambiguously identified by utilizing the atomic scale sensitivity of the electric field gradient (EFG) embedded in TDPAC spectroscopy. The determination of the oxidation state and the local environment of La-atoms by XANES and EXAFS measurements illuminates the microscopic role of the dopant in stabilizing the o-phase. The "solute drag model" proposes a critical crystallite size for the nucleation of the o-phase in bulk HfO2 and explains the role of the La-dopant in stabilizing the o-phase. Thus the present study shows the possibility of stabilizing the polar o-phase and hence attaining ferroelectricity in bulk HfO2 to augment the scope of future application for this ferroelectric device.

Energetics of ice nucleation in mesoporous titania using positron annihilation spectroscopy.

The low temperature behavior of water and kinetics of ice nucleation in titania mesopores have been probed by positron annihilation lifetime spectroscopy as a function of pore filling. It is revealed that water undergoes complete freezing at around 220 K when more than 50% of the pore volume is filled and such freezing is hindered at lower hydration levels. A model describing progressive trapping of positronium by ice nuclei in liquid water during the phase transition is employed to estimate the energy associated with the nucleation under confinement. It is observed that the energy for ice nucleation in confinement is less than the activation energy for nucleation in bulk water because of the surface assisted nucleation inside the pore. Interestingly, energy for nucleation is seen to decrease with the lowering of hydration level and ascribed to the curtailed hydrogen bonding network of water at lower pore filling.

Unraveling doping induced anatase-rutile phase transition in TiO2 using electron, X-ray and gamma-ray as spectroscopic probes.

The present work reports the microscopic details of anatase (A) to rutile (R) phase transformation in a Mn-doped TiO2 system. Titanium dioxide (TiO2) powder was synthesized at three different dopant percentages, namely 1, 5, and 10 atom% of Mn, by a coprecipitation technique. Time differential perturbed angular correlation (TDPAC) spectroscopy was used to identify the formation of the rutile-like phase (R*) during the phase-transition process and revealed interface nucleation to be promoted by the Mn dopant. Electron paramagnetic resonance (EPR) spectroscopy, synchrotron-based X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) studies showed that Mn exhibited a mixed valence states of 2+ and 4+ at different stages of the annealing process. The rutile onset temperature gradually decreased with the increase in the Mn content. The present report proposes the mechanism for the phase transformation and details the effect of Mn on the A to R phase-transformation process. This can assist in gaining a fundamental understanding of the A to R phase-transformation process and the role of the dopant in stabilizing one phase over the other.

Defect induced ferromagnetism in MgO and its exceptional enhancement upon thermal annealing: a case of transformation of various defect states.

MgO particles of few micron size are synthesized through a sol-gel method at different annealing temperatures such as 600 °C (MgO-600), 800 °C (MgO-800) and 1000 °C (MgO-1000). EDX and ICP-AES studies confirmed a near total purity of the sample with respect to paramagnetic metal ion impurities. Magnetic measurements showed a low temperature weak ferromagnetic ordering with a TC (Curie temperature) around 65 K (±5 K). Unexpectedly, the saturation magnetization (Ms) was found to be increased with increasing annealing temperature during synthesis. It was observed that with J = 1 or 3/2 or S = 1 or 3/2, the experimental points are fitted well with the Brillouin function of weak ferromagnetic ordering. A positron annihilation lifetime measurement study indicated the presence of a divacancy (2VMg + 2VO) cluster in the case of the low temperature annealed compound, which underwent dissociations into isolated monovacancies of Mg and O at higher annealing temperatures. An EPR study showed that both singly charged Mg vacancies and oxygen vacancies are responsible for ferromagnetic ordering. It also showed that at lower annealing temperatures the contribution from was very low while at higher annealing temperatures, it increased significantly. A PL study showed that most of the F+ centers were present in their dimer form, i.e. as centers. DFT calculation implied that this dimer form has a higher magnetic moment than the monomer. After a careful consideration of all these observations, which have been reported for the first time, this thermally tunable unusual magnetism phenomenon was attributed to a transformation mechanism of one kind of cluster vacancy to another.

Unraveling the sub-nanoscopic structure at interphase in a poly(vinyl alcohol)-MOF nanocomposite, and its role in thermo-mechanical properties.

A microscopic model of the interfacial region is required to improve understanding of the role of local structure in bulk physical properties in metal organic framework-based polymer nanocomposites. A zeolitic imidazolate framework (ZIF-8)-based (loading 2-30 wt%) composite of poly vinyl alcohol (PVA) is studied as a model system to investigate the role of interfacial interaction in molecular packing, glass transition process and tensile properties. Attractive interfacial interaction between the surface of ZIF particles and PVA chains is established by Fourier transform infra red (FTIR) measurements. The morphology of the nanocomposites is characterized using X-ray diffraction and scanning electron microscopy (SEM), showing that aggregation of particles started from 5 wt% of ZIF-8. At low loadings, occurrence of two glass transitions measured using differential scanning calorimetry indicates two spatial zones, viz. interphase and bulk layers, of different packing density in the PVA matrix. With increase in loading, molecular packing throughout the polymer matrix is changed as the interparticle distance and interphase width become comparable. At the highest loading, PVA shows bulk glass transition temperature because of the non-significant volume fraction of interphase resulting from aggregation of ZIF. Molecular packing (free volume structure) of PVA in the nanocomposites is investigated using ortho-positronium lifetime distributions, which show that large vacant spaces are created at the interfacial region leading to a low-density interphase. The existence of a low-density interphase is also supported by bulk-density measurements of the nanocomposites. Tensile testing measurements show a decrease in ductility of the nanocomposites, indicating enhancement in rigidity of polymer chains at the interfacial region because of attractive interfacial interaction. This study indicates that the polymer chain framework at the interfacial region in PVA-MOF nanocomposites can be represented by a rigid but rather open network.

Effects of the molecular level dispersion of graphene oxide on the free volume characteristics of poly(vinyl alcohol) and its impact on the thermal and mechanical properties of their nanocomposites.

Poly(vinyl alcohol), PVA, reinforced with carbon nanofillers has shown drastic variations in thermal as well as mechanical properties. In order to establish structure-property correlations, these variations have been correlated with modifications in the hydrogen bonding structure as well as the crystallinity of the PVA matrix without paying much attention to molecular packing in the amorphous region of this semicrystalline polymer. In order to investigate the molecular packing in PVA-graphene oxide (GO) nanocomposites, free volume characterization of PVA-GO nanocomposites has been carried out using ortho-positronium (o-Ps) probe. The variations in free volume size, density and size distribution have been determined through o-Ps lifetime and the corresponding intensity as well as its lifetime distribution. The variation in hydrogen bonding and its effect on crystallinity has been determined by Fourier Transform Infra Red (FTIR) and X-ray diffraction (XRD) measurements. The variation in the thermal (glass transition temperature) and mechanical (Young's modulus, tensile strength and percentage strain at break) properties of the nanocomposites is explained in view of the free volume structure and crystallinity of the PVA matrix which are severely modified due to the molecular-level dispersion of GO sheets in the PVA matrix.

Investigation of nanolevel molecular packing and its role in thermo-mechanical properties of PVA-fMWCNT composites: positron annihilation and small angle X-ray scattering studies.

Carbon based nanofillers have shown phenomenal improvements in thermo-mechanical properties of poly vinyl alcohol (PVA) based nanocomposites depending on their interaction with PVA molecules and dispersion in the polymer matrix. In the present study, PVA based nanocomposites with amino-functionalized multi-wall carbon nanotubes (fMWCNTs, 0.2, 0.4, 0.8 and 1.0 wt%) were prepared by a simple casting method from aqueous solution. The relative increase in Young's modulus with 0.4% fMWCNTs was observed to be comparable with that for PVA-nanodiamond composite films which have been shown to have higher strength compared to nanotube and graphene oxide based nanocomposites. In order to investigate the nanolevel molecular packing (sub-nano level free volumes and nano level lamellar structure) and its role in thermal and mechanical properties, positron annihilation spectroscopy and small angle scattering have been used. The crystallinity and morphology of the samples were characterized using X-ray diffraction and scanning electron microscopy. The studies showed that interfacial interaction between PVA molecules and functionalities on the surface of fMWCNTs results in the formation of an ordered structure of PVA molecules which enhances load transfer between the PVA matrix and fMWCNTs leading to improved mechanical properties. The thermal properties of the composites were observed to be unaffected at the studied filler concentration.

Effect of interfacial interaction on free volumes in phenol-formaldehyde resin-carbon nanotube composites: positron annihilation lifetime and age momentum correlation studies.

The phenol-formaldehyde-carbon nanotube composites were characterized for their free volume properties and interfacial interactions between nanotubes and the polymer matrix. The base polymeric material was a novolac type phenol-formaldehyde (PF) condensation resin cross-linked with para-toluene sulfonic acid. Multi-wall carbon nanotubes (MWCNTs) were synthesized using a catalytical chemical vapor deposition method and characterized using high-resolution transmission electron microscopy. The PF resin-carbon nanotubes composites having 2, 5, 10 and 20% (w/w%) MWCNTs were prepared. The crystallinity and morphology of the samples were characterized using X-ray diffraction and scanning electron microscopy. The free volume size in the polymer nanocomposites was observed to increase with the increase in nanotube content. Positron age momentum correlation (AMOC) studies revealed the electronic environment around different positron annihilation sites. The studies showed that ortho-positronium principally annihilates from interfacial regions of polymer and nanotubes in the nanocomposite. The positron lifetime studies together with AMOC measurements indicate an increase in the free volumes at the interface of polymer and MWCNTs in the composite. The free positron intensities showed that the polymer and nanotubes are weakly interacting in this system.

Utilization of accelerator and reactor based nuclear analytical techniques for chemical characterization of automobile windshield glass samples and potential of statistical analyses using trace elements towards glass forensics.

Glass forensics is an important area in forensic crime investigations, wherein glass origin or source finding is necessary mainly through chemical composition. In the present work, Nuclear Analytical Techniques namely external (in air) Particle Induced Gamma-ray Emission (PIGE) and Instrumental Neutron Activation Analysis (INAA) were utilized for complete chemical characterization of twenty-five "as received" windshield glass samples of six car manufactures. Concentrations of four major elements (Si, Na, Mg and Al) by PIGE using proton beam and nineteen elements including sixteen trace elements by INAA using research reactor neutrons were determined. Both the methods were validated by analysing matrix matched glass certified (standard) reference materials. Trace elemental concentrations including rare earth elements (REEs) and ternary plot using concentrations of major, transition elements and REEs were utilized to obtain preliminary grouping of the analyzed glass samples. Statistical tools namely K-mean, Cluster Analysis and Principal Component Analysis (PCA) using trace elemental concentrations were utilized for grouping studies, important for forensic applications. Among these statistical analysis techniques, PCA results confirmed that windshield glasses from six manufactures clearly belong to six different groups.

Application of gamma-ray spectrometry, neutron multiplicity counting and calorimetry for non-destructive assay of U-Pu mixed samples.

This paper presents a standardless non-destructive method for simultaneous assay of uranium and plutonium in mixed samples relevant to nuclear safeguards, forensics and fuel cycle. The method is based on an in-situ absolute efficiency calibration of a γ-ray detector using plutonium γ-rays that can subsequently be used for quantification of uranium in the sample. The method was tested by assaying U-Pu samples with known amounts of U and Pu with varying mass, geometry, composition, reactor type, age and fissile isotope enrichment.

Evidence for confinement induced phase separation in ethanol-water mixture: a positron annihilation study.

We report an experimental evidence for the phase separation of ethanol-water mixture confined in mesoporous silica with different pore size using positron annihilation lifetime spectroscopy (PALS). A bulk-like liquid in the core of the pore and a distinct interfacial region near the pore surface have been identified based on ortho-positronium lifetime components. The lifetime corresponding to the core liquid shows similar behavior to the bulk liquid mixture while the interfacial lifetime shows an abrupt rise within a particular range of ethanol concentration depending on the pore size. This abrupt increase is attributed to the appearance of excess free-volume near the interfacial region. The excess free-volume is originated due to microphase separation of confined ethanol-water primarily at the vicinity of the pore wall. We envisage that probing free-volume changes at the interface using PALS is a sensitive way to investigate microphase separation under nanoconfinement.

Desorption of water from hydrophilic MCM-41 mesopores: positron annihilation, FTIR and MD simulation studies.

The desorption mechanism of water from the hydrophilic mesopores of MCM-41 was studied using positron annihilation lifetime spectroscopy (PALS) and attenuated total reflection Fourier transform infrared spectroscopy supplemented with molecular dynamics (MD) simulation. PALS results indicated that water molecules do not undergo sequential evaporation in a simple layer-by-layer manner during desorption from MCM-41 mesopores. The results suggested that the water column inside the uniform cylindrical mesopore become stretched during desorption and induces cavitation (as seen in the case of ink-bottle type pores) inside it, keeping a dense water layer at the hydrophilic pore wall, as well as a water plug at both the open ends of the cylindrical pore, until the water was reduced to a certain volume fraction where the pore catastrophically empties. Before being emptied, the water molecules formed clusters inside the mesopores. The formation of molecular clusters below a certain level of hydration was corroborated by the MD simulation study. The results are discussed.

Multifunctional pure and Eu(3+) doped ß-Ag2MoO4: photoluminescence, energy transfer dynamics and defect induced properties.

Pure and Eu(3+) doped ß-Ag2MoO4 were synthesized using a co-precipitation method at room temperature. The as prepared compounds were characterized systematically using X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, cyclic voltammetry (CV) and positron annihilation lifetime spectroscopy (PALS). It is observed that pure ß-Ag2MoO4 gives blue (445 nm) and green (550 nm) emission when irradiated with UV light. The origin of the green band was qualitatively explained from density functional theory (DFT) calculations using a suitable distortion model. It was observed that on doping europium ions, efficient energy transfer from molybdate to europium takes place. The excitation spectrum depicting f-f transitions (particularly 395 nm and 465 nm peaks) is much more intense than the CTB showing that Eu(3+) ions can be effectively excited by near UV-light. Based on DFT calculations it is proposed that due to the occurrence of Eu(3+) d-states in the conduction band (CB) as well as the strong contribution of Eu(3+) d-states to the impurity level present in the vicinity of the Fermi level, the host (ß-Ag2MoO4) to dopant (Eu(3+)) energy transfer is preferable. ß-Ag2MoO4 is also explored as a potential candidate for electrocatalysis of the oxygen reduction reaction (ORR). It was observed that the doping of europium ions in ß-Ag2MoO4 enhances the electrocatalytic activity toward the ORR. The presence of a large concentration of cation vacancies and large surface defects as suggested by positron annihilation lifetime spectroscopy (PALS) seem to be aiding the ORR.

Chitosan-transition metal ions complexes for selective arsenic(V) preconcentration.

Chitosan is naturally occurring bio-polymer having strong affinity towards transition metal ions. Chitosan complexed with transition metal ions takes up inorganic arsenic anions from aqueous medium. In present work, As(V) sorption in the chitosan complexed with different metal ions like Cu(II), Fe(III), La(III), Mo(VI) and Zr(IV) were studied. Sorptions of As(V) in CuS embedded chitosan, (3-aminopropyl) triethoxysilane (APTS) embedded chitosan, epichlorohydrin (ECH) crosslinked chitosan and pristine chitosan were also studied. (74)As radiotracer was prepared specifically for As(V) sorption studies by irradiation of natural germanium target with 18 MeV proton beam. The sorption studies indicated that Fe(III) and La(III) complexed with chitosan sorbed 95 ± 2% As(V) from aqueous samples in the pH range of 3-9. However, Fe(III)-chitosan showed better sorption efficiency (91 ± 2%) for As(V) from seawater than La(III)-chitosan (80 ± 2%). Therefore, Fe(III)-chitosan was selected to prepare the self-supported membrane and poly(propylene) fibrous matrix supported sorbent. The experimental As(V) sorption capacities of the fibrous and self-supported Fe(III)-chitosan sorbents were found to be 51 and 109 mg g(-1), respectively. These materials were characterized by XRD, SEM and EDXRF, and used for preconcentration of As(V) in aqueous media like tap water, ground water and seawater. To quantify the As(V) preconcentrated in Fe(III)-chitosan, the samples were subjected to instrumental neutron activation analysis (INAA) using reactor neutrons. As(V) separations were carried out using a two compartments permeation cell for the self-supported membrane and flow cell using the fibrous sorbent. The total preconcentration of arsenic content was also explored by converting As(III) to As(V).