LiAlO2:Gd-Based Versatile and Ultrasensitive Detector for Gamma and Neutrons by Thermal and Optical Stimulation.

Considering the low-level dose detection requirement for neutron and γ radiation in cancer therapy, synthesis and exploratory studies have been performed on a newly developed phosphor LiAlO2:Gd. Our results reveal that the presence of both Li and Gd makes it sensitive to both gamma and thermal neutrons. The applicability of LiAlO2:Gd for beta, gamma, and neutrons in both thermally stimulated and optically stimulated modes has been verified by extensive experiments followed by kinetic parametric evaluation with theoretical calculations. The current work confirms that LiAlO2:Gd is a highly sensitive phosphor with a minimum detectable dose of 5.7 µSv for gamma and 92 µSv for themral neutrons. The phosphor is found to show very high sensitivity at low energy and dose. Its ability for detection and discrimination of both gamma and thermal neutrons makes it a potential material to be used in medical dosimetry.

Interparticle interaction-dependent jamming in colloids: insights into glass transition and morphology modulation during rapid evaporation-induced assembly.

Understanding the role of interparticle interactions in jamming phenomena is essential for gaining insights into the intriguing glass transition behavior observed in atomic and molecular systems. In this study, we investigate the jamming behavior of colloids with tunable interparticle interactions during evaporation-induced assembly (EIA). By manipulating the interaction among charged colloids using cationic polyethyleneimine (PEI) through electro-sorption and subsequent free polymer induced repulsion, we observe distinct jamming behavior in silica colloids during EIA, depending on the interparticle interactions. Silica colloids with strong repulsive interactions exhibit a repulsive colloidal glass state with a volume fraction of silica colloids in supraparticle ϕ ∼ 0.70. On the other hand, PEI-mediated attractive interactions among silica colloids lead to an attractive colloidal glass phase with a significantly lower ϕ ∼ 0.43. Free polymer induced repulsion of colloids at higher PEI concentration once again results in a repulsive glassy state with ϕ ∼ 0.61. Furthermore, we revealed that interparticle interactions not only influence the jamming behavior but also play a significant role in shaping the morphology of self-assembled structures during EIA, and the assembled structure undergoes a morphological reentrant transition from a doughnut-like shape to a spherical form and again back to a doughnut-like configuration. Jamming-dependent evolution of micropores and dynamics of the confined PEI have been probed using positron annihilation lifetime spectroscopy (PALS) and broadband dielectric spectroscopy (BDS). PALS reveals distinct variations in the micropores of the supraparticles with different PEI loadings, confirming the impact of jamming on the evolution of the micropores within the supraparticles. BDS measurements uncover non-monotonic dynamics of PEI molecules confined in the evolved pore network. It is revealed that the reentrant jamming behavior of colloids, modulated by PEI, holds profound significance for the long-term stability of supraparticles.

Performance of small- and wide-angle x-ray scattering beamline at Indus-2 synchrotron.

A Small- and Wide-Angle X-ray Scattering (SWAXS) beamline (BL-18) is installed and commissioned at a 1.5 T bending magnet port (5°) of Indus-2 synchrotron at RRCAT, Indore, India. The ∼40-m-long beamline has tunable x-ray energy in the range of 5-20 keV by using a double crystal monochromator. A 1.5-m-long toroidal mirror is used to focus the x-ray beam at the detector position. The beamline is equipped with a 6-m-long movable detector stage to access different wave-vector transfer ranges. At present, an online image plate area detector and a linear position-sensitive gas detector are installed for Small-Angle X-ray Scattering (SAXS) and Wide-Angle X-ray Scattering (WAXS) measurements, respectively. The beamline is operational in simultaneous SAXS/WAXS mode to probe the mesoscopic as well as molecular level structure over a wide range of wave-vector transfer. The specification of the beamline and its performance are reported here. A few recent experimental results, as obtained from BL-18, are also described in brief.

Hydrogen-bonded linear chain assemblies of palladium(II)-selenoether complexes: solid state aggregates as templates for nano-structural Pd17Se15 leading to efficient electrocatalytic activity.

A analogous series of 2-(3,5-dimethylpyrazol-1-yl)phenyl substituted selenoether complexes of palladium [PdCl2(RSeC6H4dmpz)]; (R = CH2COOH (1), CH2CH2COOH (2), and CH2CH2OH (3); dmpz = dimethylpyrazole) were ably synthesized in a facile manner and exhaustively characterized. Insight into molecular structures of these complexes was keenly probed through single crystal X-ray diffraction (XRD) analysis, unfolding the structural scaffolds and laying into molecular aggregation, availed through hydrogen bonding interactions borne out of tethered protic groups. The complexes were converted to capping free palladium selenide (Pd17Se15) nanoparticles through pyrolysis and evaluated for their electrocatalytic efficacy towards the hydrogen evolution reaction (HER), the oxygen evolution reaction (OER) and methanol oxidation reaction (MOR) in alkaline medium. In an alkaline medium, PSNP1 (Pd17Se15) obtained from the hydrogen bonded aggregate of complex PdCl2L1 (1) produced good HER activity. PSNP1 had a little decrease in current density after 300 continuous cycles, which proves that the catalyst presents high stability in the recycling process. For the electrocatalytic oxidation of CH3OH, the electrocatalytic rate constant (k) obtained was 0.3 × 103 cm3 mol-1 s-1.

Controlled Crystal Growth of All-Inorganic CsPbI2.2Br0.8 Thin Film via Additive Strategy for Air-Processed Efficient Outdoor/Indoor Perovskite Solar Cells.

The evolution of defects during perovskite film fabrication deteriorates the overall film quality and adversely affects the device efficiency of perovskite solar cells (PSCs). We endeavored to control the formation of defects by applying an additive engineering strategy using FABr, which retards the crystal growth formation of CsPbI2.2Br0.8 perovskite by developing an intermediate phase at the initial stage. Improved crystalline and pinhole-free perovskite film with an optimal concentration of FABr-0.8M% additive was realized through crystallographic and microscopic analysis. Suppressed non-radiative recombination was observed through photoluminescence with an improved lifetime of 125 ns for FABr-0.8M% compared to the control film (83 ns). The champion device efficiency of 17.95% was attained for the FABr-0.8M% PSC, while 15.94% efficiency was achieved in the control PSC under air atmospheric conditions. Furthermore, an impressively high indoor performance of 31.22% was achieved for the FABr-0.8M% PSC under 3200 K (1000 lux) LED as compared to the control (23.15%). With a realistic approach of air processing and controlling the crystallization kinetics in wide-bandgap halide PSCs, this investigation paves the way for implementing additive engineering strategies to reduce defects in halide perovskites, which can further benefit efficiency enhancements in outdoor and indoor applications.

Evidence of Size Stratification in Colloidal Glass Microgranules Realized by Rapid Evaporative Assembly.

Evaporation is a ubiquitous phenomenon. Rapid evaporation of the continuous phase from micrometric colloidal droplets can be used to realize nanostructured microgranules, constituting the assembled nanoparticles. One of the important aspects of such nonequilibrium assembly is the nature of the packing of nanoparticles in the microgranules. The present work demonstrates the evidence of size stratification of the nanoparticles in such far-from-equilibrium configurations. Small-angle X-ray scattering, in combination with particle packing simulation, reveals the "large on top"-type stratification in such assembled microgranules, where the larger particles get concentrated at the outer shell of the granules while the smaller particles reside in the core region. It also reveals the presence of local clusters in such a rapid evaporative assembly in aerosolized colloidal droplets.

Polyethyleneimine-assisted formation of Ag-SiO2 hybrid microspheres for H2O2 sensing and SERS applications.

Herein, we report a simple, cost-effective, and eco-friendly approach for producing polyethyleneimine (PEI)-assisted silver nanoparticle-supported silica microspheres through evaporation-induced assembly (EIA). The silica-PEI microspheres obtained through EIA consisted of highly trapped PEI molecules owing to their electrosorption onto oppositely charged silica colloids. The trapped PEI molecules in the microspheres played a crucial role in linking silver ions to form silver ion-PEI complexes, which were then reduced to form silver nanoparticles. Further, the complex interactions between PEI and silica colloids led to enhanced porosity in the microspheres, enabling the efficient adsorption of Ag ions. The characterization of the Ag-SiO2 microspheres was carried out using various techniques, including field-emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) spectroscopy, X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), and Fourier transform infrared (FTIR) spectroscopy, which confirmed the successful formation of Ag nanoparticles on microspheres, and a plausible formation mechanism is elucidated. The Ag-SiO2 microspheres exhibited good sensing properties for hydrogen peroxide (H2O2), with an estimated limit of detection of 1.08 mM and a sensitivity of 0.033 µA mM-1 mm-2. The microspheres were also used as a surface-enhanced Raman scattering (SERS) substrate, which demonstrated high sensitivity in detecting rhodamine 6G down to a concentration of 2 × 10-6 M. The present approach elucidates a promising alternative to conventional methods that face challenges, such as scalability issues, complex and cumbersome synthesis procedures, and the use of strong reducing agents. With the potential for industrial-level scalability, this method offers a viable strategy for producing Ag-SiO2 microspheres with possible applications in biomedical and sensing technologies.

Amphiphilic interaction-mediated ordering of nanoparticles in Pickering emulsion droplets.

For various industrial processes, the stabilization of an oil phase is crucial and demands a proper balance of complex interactions in an emulsion system. In Pickering emulsions, this is achieved by introducing nanoparticles, which become organized at the oil-water interface. The influence of interparticle interactions towards the formation of a stable emulsion and the ordering of the stabilizing nanoparticles is intriguing and needs attention. In this work, the role of amphiphilic interactions between hydrophilic silica nanoparticles and the Pluronic F127 tri-block co-polymer towards the spontaneous formation of a fairly stable Pickering emulsion has been studied using small-angle X-ray scattering. Unlike the usual random arrangements of the nanoparticles in a conventional Pickering emulsion, we observed highly organized silica nanoparticles at the oil-water interface. The established standard raspberry structural model of the Pickering emulsion fails to explain such strong ordering as observed in the present case. A plausible formation mechanism of the present Pickering emulsion with a high on-surface silica correlation is elucidated on the basis of the combined interactions of the block co-polymer and silica particles. A computer model is developed to elucidate the effects of size and distribution of the surface-decorating nanoparticles and their positional correlation.

γ-Resistant Microporous CAU-1 MOF for Selective Remediation of Thorium.

A simple solvothermal method was used to synthesize a metal-organic framework (MOF) with an Al metal entity, viz., CAU-1 NH2. The synthesized MOF was characterized using different techniques like X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy (SEM), field emission SEM (FE-SEM), transmission electron microscopy, small-angle X-ray scattering, positron annihilation lifetime spectroscopy, and X-ray photoelectron spectroscopy. The radiation stability was evaluated by irradiating the material up to a cumulative dose of 2 MGy using 60Co for the first time. The studies showed a remarkable gamma irradiation stability of the material up to 1 MGy. The porosity and surface area of the synthesized MOF were determined by Brunauer-Emmett-Teller, which showed a high specific surface area of 550 m2/g. The pH dependence study of Th uptake from an aqueous solution was performed from pH 2-8, followed by adsorption isotherm and adsorption kinetics studies. These results revealed that the Langmuir and pseudo-second-order kinetic models can be well adapted for understanding the Th uptake and kinetics, respectively. The synthesized MOF exhibited an ∼404 mg/g thorium adsorption capacity. Selectivity studies of adsorption of Th w.r.t. to U and different metal ions such as Cu, Co, Ni, and Fe showed that Th gets adsorbed preferentially as compared to other metal ions. In addition, the MOF could be used multiple times without much deterioration.

Insights into the CO2 Capture Characteristics within the Hierarchical Pores of Carbon Nanospheres Using Small-Angle Neutron Scattering.

Understanding adsorption processes at the molecular level has transformed the discovery of engineered materials for maximizing gas storage capacity and kinetics in adsorption-based carbon capture applications. In this work, we studied the molecular mechanism of gas (CO2, H2, methane, and ethane) adsorption inside an interconnected porous network of carbon. This was achieved by synthesizing novel macro-meso-microporous carbon (M3C) nanospheres with interconnected pore structures. The M3Cs showed a CO2 capture capacity of 5.3 mmol/g at atmospheric CO2 pressure, with excellent kinetics. This was due to fast CO2 adsorption within the interconnected hierarchical macro-meso-microporous M3C. In situ small-angle neutron scattering (SANS) under various CO2 pressures indicated that the macro- and mesopores of M3C enable fast diffusion of CO2 molecules inside the micropores, where adsorbed CO2 molecules densify into a liquid-like state. This strong densification of CO2 molecules causes fast CO2 diffusion in the macro- and mesopores of M3C, restarting the adsorption cycle for fresh CO2 molecules until all pores are completely filled. Notably, M3C also showed good capture capacities for hydrogen and various hydrocarbons, with excellent selectivity toward ethane over methane.

In situ crystal reconstruction strategy-based highly efficient air-processed inorganic CsPbI2Br perovskite photovoltaics for indoor, outdoor, and switching applications.

All-inorganic CsPbI2Br (CPIB) perovskite has gained strong attention due to their favorable optoelectronic properties for photovoltaics. However, solution-processed CPIB films suffer from poor morphology due to the rapid crystallization process, which must be resolved for desirable photovoltaic performance. We introduced phenethylammonium iodide (PEAI) as an additive into a perovskite precursor that effectively controls the crystallization kinetics to construct the preferred quality α-CPIB film under ambient conditions. Various photophysical and structural characterization studies were performed to investigate the microstructural, morphological, and optoelectronic properties of the CPIB and PEAI-assisted perovskite films. We found that PEAI plays a vital role in decreasing pinholes, ensuring precise crystal growth, enhancing the crystallinity, improving the uniformity, and tailoring the film morphology by retarding the crystallization process, resulting in an improved device performance. The device based on the optimized PEAI additive (0.8 mg) achieved a respectably high power conversion efficiency (PCE) of 17.40% compared to the CPIB perovskite solar cell (PSC; 15.75%). Moreover, the CPIB + 0.8 mg PEAI PSC retained ∼87.25% of its original PCE, whereas the CPIB device retained ∼66.90% of the initial PCE after aging in a dry box at constant heating (85 °C) over 720 h, which revealed high thermal stability. Furthermore, the indoor photovoltaic performance under light-emitting diode (LED) lighting conditions (3200 K, 1000 lux) was investigated, and the CPIB + 0.8 mg PEAI PSC showed a promising PCE of 26.73% compared to the CPIB device (19.68%). In addition, we developed a switching function by employing the optimized PSC under LED lighting conditions, demonstrating the practical application of constructed indoor PSCs.

Defect-Induced Adsorption Switching (p- to n- Type) in Conducting Bare Carbon Nanotube Film for the Development of Highly Sensitive and Flexible Chemiresistive-Based Methanol and NO2 Sensor.

Lightweight and flexible gas sensors are essentially required for the fast detection of toxic gases to pass on the early warning to deter accident situations caused by gas leakage. In view of this, we have fabricated a thin paper-like free-standing, flexible, and sensitive carbon nanotube (CNT) aerogel gas sensor. The CNT aerogel film synthesized by the floating catalyst chemical vapor deposition method consists of a tiny network of long CNTs and ∼20% amorphous carbon. The pores and defect density of the CNT aerogel film were tuned by heating at 700 °C to obtain a sensor film, which showed excellent sensitivity for toxic NO2 and methanol gas in the concentration range of 1-100 ppm with a remarkable limit of detection ∼90 ppb. This sensor has consistently responded to toxic gas even after bending and crumpling the film. Moreover, the film heat-treated at 900 °C showed a lower response with opposite sensing characteristics due to switching of the semiconductor nature of the CNT aerogel film to n-type from p-type. The annealing temperature-based adsorption switching can be related to a type of carbon defect in the CNT aerogel film. Therefore, the developed free-standing, highly sensitive, and flexible CNT aerogel sensor paves the way for a reliable, robust, and switchable toxic gas sensor.

Flexibility of Mixed Ligand Zeolitic Imidazolate Frameworks (ZIF-7-8) under CO2 Pressure: An Investigation Using Positron Annihilation Lifetime Spectroscopy.

Fine tuning of the pore architecture and flexibility of zeolitic imidazolate frameworks (ZIFs) is highly crucial for realizing their applications in molecular gas separation. Mixed ligand frameworks (ZIF-7-8) synthesized by mixing 2-methylimidazole (2meIm) and benzimidazole (bIm) ligands show enhanced gas separation performance, attributable to pore and flexibility tuning. In the present study, positron annihilation lifetime spectroscopy (PALS) measurements under CO2 pressure have been used to experimentally investigate the tuning of the pore architecture and flexibility of mixed ligand frameworks ZIF-7-8 having a ZIF-8 structure and similar morphology with varying bIm content up to 18.2%. The aperture and cavity of frameworks begin to open up with an increasing bIm ligand content followed by a decrease at a higher content. On the contrary, flexibility of the frameworks indexed from PALS measurements carried out under CO2 pressure shows a decreasing trend followed by an increase. The present study shows that mixed ligand frameworks having a larger aperture size are less flexible as a result of inherent open configurations of ligands in the framework lattice. On the other hand, frameworks having a comparatively smaller aperture size show higher flexibility as a result of a possibility of twisting of the ligands under CO2 pressure, resulting in aperture opening. The pore-opening phenomenon as a result of lattice flexibility under CO2 pressure is observed to be fully reversible for ZIF-7-8.

Hollow TiO2/SiO2 composite microspheres through reactive assembly across immiscible liquid interfaces.

Titania (TiO2) based photocatalysts have shown tremendous potential in tackling important issues related to energy, the environment, and water purification. The tunable morphologies of the TiO2 based multicomponent composites are promising for the improvement of photocatalytic characteristics for practical applications. In this work, we report a one-step facile approach to achieve hollow silica/titania microspheres through the process of reactive assembly at the immiscible interface of micrometer-sized droplets. Scanning electron microscopy and small-angle neutron scattering revealed the hierarchal structure of the microspheres. Elemental mapping of the composite microspheres provided direct evidence of the incorporation of silica nanoparticles into the microspheres. The diffusion of reactant molecules and hydrolysis/condensation reactions across the phase boundary of the interface of two immiscible liquids controls the morphology of the microspheres and the size of TiO2 nanoparticles. The silica/titania composite microspheres show excellent thermal stability against the anatase to rutile phase transition caused by inhibition of the growth of TiO2 nanoparticles due to proximity of the silica nanoparticles. The photoelectrochemical measurements show that TiO2-SiO2 microspheres exhibit superior photocatalytic characteristics compared to the TiO2 microspheres. The kinetics of dye degradation for TiO2-SiO2 microspheres is found to be significantly faster compared to TiO2 microspheres which confirms the superior photocatalytic properties of the composite microspheres.

Unravelling the polyethylenimine mediated non-monotonic stability behaviour of silica colloids: the role of competing electrostatic and entropic interactions.

Polymer-mediated interactions play an important role in the stability of colloids and are therefore paramount for both fundamental as well as scientific interests. The stability of colloids in the presence of neutral polymers depends on several parameters such as the adsorbing/non-adsorbing nature, molecular weight, concentration and temperature, and such systems are well studied. However, the stability behaviour of charged colloids in the presence of charged polyelectrolyte involves complex interaction mechanisms and hence needs attention. The present work reports the study of the stability behaviour of negatively charged silica colloids in the presence of cationic polyethylenimine (PEI) polyelectrolyte using small-angle neutron and X-ray scattering. The intriguing non-monotonic stability behaviour of silica colloids is observed with varying concentrations of PEI. In the low and intermediate PEI concentration regimes, electrosorption of PEI on the silica colloids causes partial screening of charges, leading to aggregation of colloids. The DLVO interaction potential at low and intermediate concentrations of PEI exhibit a reduced repulsion barrier which is responsible for aggregation. In the high concentration regime, the entropic interaction between the free PEI molecules and PEI decorated silica colloids leads to depletion re-stabilization. The combination of DLVO potential and adsorbed PEI mediated enhanced depletion repulsion in the presence of free PEI gives rise to an increased repulsion barrier responsible for the re-stabilization at high PEI concentrations.

Pattern of an Evaporated Colloidal Droplet on a Porous Membrane Dictated by Competitive Processes of Flow and Absorption.

Understanding the deposition pattern formed by an evaporated colloidal drop is of fundamental and technological interest. Such an evaporative process is important in various applications starting from inkjet printing to disease diagnosis. In this work, it is shown that the deposit pattern on a porous membrane can be tuned by varying the colloidal viscosity and membrane pore size. We have used small-angle X-ray scattering (SAXS) in scanning mode for profiling of deposit morphology and also for estimation of the interparticle correlation. It is demonstrated that low viscosity and small pore size favor a centrally dipped pattern owing to the coffee ring effect, which can be modified to a contrasting centrally peaked pattern by increasing the viscosity and pore size. To comprehend the experimental observations, a computer model has been developed using a continuity equation that well corroborates the experimental observations on the final deposited pattern and also provides the time evolution of the pattern. The work provides a way to tune the pattern of colloidal stain on a porous substrate by controlling flow and absorption.

Polyethylenimine assisted non-monotonic jamming of colloids during evaporation induced assembly and its implication on CO2 sorption characteristics.

We report a detailed study of hierarchically organized silica-polyethylenimine (PEI) microspheres achieved through evaporation-induced assembly. Due to complex interactions between oppositely-charged silica nanoparticles and PEI, non-monotonic jamming of the colloidal particles is manifested. With an increase in the polymer concentration, the local volume fraction of the silica particles decreases from 0.68 to 0.43 and then increases to 0.55 with further increase. The unusual jamming behaviour of the silica colloids in the presence of PEI provides an avenue for immobilizing PEI without reducing the porosity and specific area in contrast to the conventional impregnation approach. The resultant composite microspheres show good thermal stability and CO2 sorption characteristics. For a 33 wt% PEI loading, the microspheres exhibit a significant CO2 capture capacity of 65 mg g-1 even at room temperature and it is increased to 90 mg g-1 at 75 °C. The variation in the CO2 capture capacity at 0 °C as a function of PEI loading also demonstrated the signature of non-monotonicity owing to the structural modification in the silica-PEI microspheres. The composite microspheres demonstrated fast adsorption kinetics reaching 70% of the total capture capacity in one minute during the CO2 capture. The CO2 cycling adsorption-desorption studies showed good regeneration capability up to 20 cycles.

Jamming of Nano-Ellipsoids in a Microsphere: A Quantitative Analysis of Packing Fraction by Small-Angle Scattering.

The packing of particles is ubiquitous, and it is of fundamental importance, particularly in materials science in the nanometric length scale. It becomes more intriguing when constituent particles deviate from spherical symmetry owing to the inherent complexity in quantifying their positional and rotational correlation. For quantitative estimation of packing fraction, it requires a thorough analysis of the positional correlation of jammed particles. This article adopts a novel approach for determination of the packing fraction of strongly correlated nano-ellipsoids in a microsphere using small-angle scattering. The method has been elucidated through a quantitative analysis of structural correlation of nano-hematite ellipsoids in 3D micrometric granules, which are realized using rapid evaporative assembly. Owing to the deviation from spherical symmetry, the conventional analysis of scattering data fails to interpret the actual packing fraction of the anisotropic particles. The structural correlation gets smeared out because of orientation distribution among the packed anisotropic particles, which leads to an anomaly in the estimation of packing fraction using the conventional analysis approach. It is illustrated that consideration of an interparticle distance distribution function of the correlated nano-ellipsoids becomes indispensable in determining their packing fraction.

Elucidation of the sorbent role in sorption thermodynamics of uranium(VI) on goethite.

The sorption process of radionuclides, often conducted at ambient temperature, shows significant sensitivity to the surrounding temperature. Prediction of fate and transport in the environment, therefore, requires accurate thermodynamic data of their species defining sorption-desorption onto solid surfaces. Herein, we examined the thermodynamics of uranium(VI), U(VI), sorption onto goethite with particular emphasis on directly calculating the enthalpy of U(VI) surface species formed under slightly acidic pH conditions. To achieve this aim, a sorption study of U(VI) was carried out on goethite in the pH range 3-10 and modelled using a 2-pK single-site diffuse layer surface complexation model. A binuclear bidentate species of U(VI), (FeO)2UO2, reproduces the sorption profile at pH 3-5 while the sorption was under-estimated in the pH >5 region. Precipitation of schoeptite at pH 5-8 was attributed to the underestimation of the predicted sorption behaviour. The species complexation constant was employed in the analysis of heat consumed, measured using an isothermal titration calorimeter, in the titration of the goethite suspension with U(VI) at pH 4.5 ± 0.1. Enthalpy for the U(VI) species was found to be 41 ± 7 kJ mol-1, suggesting that sorption is an entropically driven process. Comparing thermodynamic data with that of similar U(VI)-iron oxide systems, binding energy of U(VI) surface species, surface hydration and hydrogen binding are suggested as main factors in the sorbent role towards the thermodynamics of the sorption process.

Polymer-mediated interaction between nanoparticles during hydration and dehydration: a small-angle X-ray scattering study.

Polymer-mediated interactions such as DNA-protein binding, protein aggregation, and filler reinforcement in polymers play crucial roles in many important biological and industrial processes. In this work, we report a detailed investigation of interactions between nanoparticles in the presence of high volume fractions of an adsorbing polymer. Small-angle X-ray scattering (SAXS) revealed the existence of a stable gel-like structure in the polymer-nanoparticle dispersion, whereby anchored polymer molecules on nanoparticles acted as bridging centres, while basic interactions between nanoparticles remained repulsive. Time-resolved SAXS measurements showed that the local volume fraction of nanoparticles increased during the drying of the dispersion owing to the shrinkage of the gel-like structure. Further, nanoparticle clusters in the dehydrated composite films showed percolated networks of nanoparticles, except for 5% loading that showed a phase-separated morphology as the volume fraction of nanoparticles remained lower than the percolation threshold. A significant restructuring of nanoparticle clusters occurred upon the hydration of nanocomposite films caused by the expansion of polymer networks induced by hydration forces. Temporal evolution of the volume fraction of nanoparticles during dehydration unveiled three distinct stages similar to the logistic growth function and this was attributed to the evaporation of free, intermediate, and bound water in the different stages. A plausible mechanism was elucidated based on the spring action analogy between anchored polymer chains and nanoparticles during hydration and dehydration processes.