Dhanadeep Dutta

Air quenching of positronium in mesoporous materials: positron porosimetry

The o-Ps lifetimes in mesoporous materials in vacuum and in the presence of air have been measured. The measured lifetimes are examined in terms of various available models for positron porosimetry. The o-Ps lifetimes measured in vacuum agree well with those predicted from the extended Tao–Eldrup model. In the presence of air, the o-Ps lifetimes are seen to reduce. The enhancement in the annihilation rate of positronium caused by air is seen to increase with decrease in the pore size. The positronium lifetimes measured in the presence of air in the present experiment and the literature data are fitted to a model based on the statistical probability of positronium interacting with the pore wall. This describes the increase in the quenching rate with decrease in pore size by taking into account the reactivity of air as well as the reduction in the average pore size due to adsorption of air on the pore surface. This simple model can be used in positron porosimetry for measurements carried out in the presence of air.

Structural aspects of synthetic zeolite: A comparative assay through positron annihilation and gas adsorption methods

Structural arrangement in alumino-silicate compounds (synthetic zeolite species), which encompasses large cavities and channels, have been discussed on the basis of their molecular organization and is further illustrated with the help of micrographs as perceived through transmission electron microscopic studies. The crystallinity aspects and structural defects were investigated through line broadening in x-ray diffraction and the grain sizes through the Debye-Scherrer method. Further, assays of the void size (micro- as well as mesopores) have been performed through positronium annihilation lifetime spectroscopy (PALS) and Brunauer-Emmett-Teller adsorption-desorption isotherm and compared. Despite of some of the limitations of the latter, the final results are in close agreement. The utility of PALS as a microprobe is illustrated through our models. Finally, it has been justified that PALS not only probes the subnanometer micropore sizes efficiently but it also senses the mesopores.

Effect Of Cross‐link Density On The Free Volume And Segmental Relaxation In Epoxy Resin Studied By Positron Annihilation Spectroscopy

The relations between the chemical and physical properties of a series of bisphenol‐A‐diglycidyl ether epoxy samples prepared by curing with polyetherdiamine of different chain length are reported. Glass transition temperature (Tg) decreased with the decrease in cross link density. The free volume hole sizes measured through positron annihilation lifetime spectroscopy increased with the increase in the chain length of curing agent or with decrease in cross link density. The water uptake by the polymer is influenced by free volumes, the chemical nature and the segmental relaxation in between the molecular chains.

Phase Transition of Water Confined in Saponites Using Positron Annihilation Spectroscopy

The temperature dependent Positron lifetime and Doppler broadening spectroscopy have been carried out to study the phase transition of water confined in interlamellar spaces of saponite clay in the temperature range 300K-200K. The change in slope/discontinuity in S-parameter and Ps lifetime as a function of temperature is an indication of phase transition. Two phase transition temperatures viz. above and below the bulk freezing temperature have been observed for water confined in saponite clay. This indicates the presence of two regimes of water confined in interlamellar spaces. The freezing-melting cycle is also marked by significant hysteresis.

Microstructural studies of poly (perfluorosulfonic acid) membrane doped with silver nanoparticles using positron annihilation spectroscopy

The Nafion -117 (H+ form) was converted to Ag+ form by ion exchange. The silver nanoparticles were formed in the membrane by reduction of Ag+ (of Ag+ form membrane) using an ionic reducing agent, NaBH4, and a neutral reducing agent, formamide. The free volume hole sizes in the nanoparticle doped and undoped Nafion were measured by positron annihilation lifetime spectroscopy (PALS). The surface modifications in the membrane by incorporation of nanoparticles were investigated using slow positron beam. The changes in the bulk free volume of Nafion with presence of nanoparticles were found to be nominal. In contrast, the surface microstructure appears to have undergone significant change.

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.

EPR Evidence of Liquid Water in Ice: An Intrinsic Property of Water or a Self-Confinement Effect?

Liquid water (LW) existence in pure ice below 273 K has been a controversial aspect primarily because of the lack of experimental evidence. Recently, electron paramagnetic resonance (EPR) has been used to study deeply supercooled water in a rapidly frozen polycrystalline ice. The same technique can also be used to probe the presence of LW in polycrystalline ice that has formed through a more conventional, slow cooling one. In this context, the present study aims to emphasize that in case of an external probe involving techniques such as EPR, the results are influenced by the binary phase (BP) diagram of the probe-water system, which also predicts the existence of LW domains in ice, up to the eutectic point. Here we report the results of our such EPR spin-probe studies on water, which demonstrate that smaller the concentration of the probe stronger is the EPR evidence of liquid domains in polycrystalline ice. We used computer simulations based on stochastic Liouville theory to analyze the lineshapes of the EPR spectra. We show that the presence of the spin probe modifies the BP diagram of water, at very low concentrations of the spin probe. The spin probe thus acts, not like a passive reporter of the behavior of the solvent and its environment, but as an active impurity to influence the solvent. We show that there exists a lower critical concentration, below which BP diagram needs to be modified, by incorporating the effect of confinement of the spin probe. With this approach, we demonstrate that the observed EPR evidence of LW domains in ice can be accounted for by the modified BP diagram of the probe-water system. The present work highlights the importance of taking cognizance of the possibility of spin probes affecting the host systems, when interpreting the EPR (or any other probe based spectroscopic) results of phase transitions of host, as its ignorance may lead to serious misinterpretations.

Exploring Defect-Induced Emission in ZnAl2O4: An Exceptional Color-Tunable Phosphor Material with Diverse Lifetimes

Activator-free zinc aluminate (ZA) nanophosphor was synthesized through a sol-gel combustion route, which can be used both as a blue-emitting phosphor material and a white-emitting phosphor material, depending on the annealing temperature during synthesis. The material also has the potential to be used in optical thermometry. These fascinating color-tunable emission characteristics can be linked with the various defect centers present inside the matrix and their changes upon thermal annealing. Various defect centers, such as anionic vacancy, cationic vacancy, antisite defect, etc., create different electronic states inside the band gap, which are responsible for the multicolor emission. The color components are isolated from the complex emission spectra using time-resolved emission spectroscopy (TRES) study. Interestingly, the lifetime values of the various defect centers were found to change significantly from milliseconds to microseconds upon thermal annealing, which makes the phosphors more diverse (i.e., either long-persistent blue-emitting phosphors or short-persistent white-emitting phosphors). Fourier transform infrared (FTIR) and diffuse reflectance spectroscopy (DRS) confirmed the presence of antisite defect centers such as AlZn+ or ZnAl- in the matrix. X-ray absorption fine structure (EXAFS) study showed that the spinel structure was more disordered in nature for low-temperature-annealed compounds. Electron paramagnetic resonance (EPR) and positron annihilation lifetime spectroscopy (PALS) studies were also carried out in order to characterize various anionic and cationic vacancies and their clusters present in the compounds. Antisite defect centers such as AlZn+ or ZnAl-, which act as an electron or hole trap, were found to be responsible for the diverse lifetime behavior. To gain insight about the electronic states inside the band gap, density functional theory (DFT)-based calculations were performed for both pure and various vacancy-introduced spinel structures. Finally, based on the theoretical and experimental results, for the first time, a detailed investigation of various defect-induced emission behavior in ZA is presented, which also explains the mechanism of color tunability and dynamic lifetimes.

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.

Effect of Crosslinkers on the Microstructure and Swelling Properties of the N-Isopropyl Acrylamide Gels: A Positron Annihilation Study

The Poly N-Isopropyl acrylamide (PNIPA) gels were prepared in different synthesis media by crosslinking with acrylate monomers with varying chain length. The microstructural characterization in terms of the free volume fractions and distributions were studied using positron annihilation lifetime spectroscopy (PALS). The equilibrium swelling of the PNIPA in distilled water was measured. An attempt has been made to understand the correlations between microscopic free volumes and the equilibrium swelling of the gels. The free volume fraction of the gels prepared in Dimethyl formamide (DMF) was directly correlated with swelling while it varied inversely with chain length of the crosslinker. The microstructure of the gels was found to be very sensitive to the solvent/medium used for polymerization. Our studies show that the swelling property is influenced by the free volumes, chain relaxation as well as the chemical nature of the cross linkers.