We studied the formation mechanism of dendritic fibrous nanosilica (DFNS) that involves several intriguing dynamical steps. Through electron microscopy and real-time small-angle X-ray scattering ...studies, it has been demonstrated that the structural evolution of bicontinuous microemulsion droplets (BMDs) and their subsequent coalescence, yielding nanoreactor template, is responsible for to the formation of complex DFNS morphology. The role of cosurfactant has been found to be quite crucial, which allowed the understanding of this intricate mechanism involving the complex interplay of self-assembly, dynamics of BMDs formation, and coalescence. The role of BMDs in formation of DFNS has not been reported so far and the present work allows a deeper molecular-level understanding of DFNS formation.
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Spray drying is a facile technique to transform colloidal dispersion into micro-granules of controlled size, shape, and morphology. There is significant interest to understand the ...structural integrity, different morphology of the granules obtained post spray drying which find potential application in many technological fields. The shape of the constituent particles in the colloidal dispersion that is spray dried is expected to influence the micro-structural features of the micro-granules.
We investigate the formation of micro-granules consisting of nano-ellipsoids through controlled spray drying. The morphological features and the packing of ellipsoids in the granules are quantitatively analyzed by using small angle neutron scattering, small angle X-ray scattering and high-resolution field emission scanning electron microscopy. The time evolution of the micro-structure and the structural integrity of the granules are investigated by re-dispersing the powder granules in water.
The morphology of the granules are found to be strongly correlated with the aspect ratio of the ellipsoid. While the drying of droplets containing lower aspect ratio ellipsoids give rise to mostly spherical granules, in stark contrast, for higher aspect ratio ellipsoids, micro-granules of different morphologies are formed including doughnut shaped granules. A plausible mechanism explaining such an aspect ratio dependent shape transformation is proposed.
Since the starting of the year 2020, the whole world is facing a challenge due to an outbreak of an unprecedented COVID-19 pandemic owing to a novel coronavirus. Here, a modified ...susceptible–infected–recovered–dead model has been used to analyze the time series data of the pandemic for five countries. It is established that the present model is capable of simultaneously explaining the temporal evolution of active-infected, recovered, and dead population of all these five countries. The key parameters governing the temporal evolution of the spread of this pandemic are estimated and compared.
The authors report on the effect of manganese (Mn) substitution on the crystal chemistry, morphology, particle size distribution characteristics, chemical bonding, structure, and magnetic properties ...of cobalt ferrite (CoFe2O4) nanoparticles (NPs) synthesized by a simple, cost-effective, and eco-friendly one-pot aqueous hydrothermal method. Crystal structure analyses indicate that the Mn(II)-substituted cobalt ferrites, Co1–x Mn x Fe2O4 (CMFO, x = 0.0–0.5), were crystalline with a cubic inverse spinel structure (space group Fd 3 m ). The average crystallite size increases from 8 to 14 nm with increasing Mn(II) content; the crystal growth follows an exponential growth function while the lattice parameters follow Vegard’s law. Chemical bonding analyses made using Raman spectroscopic studies further confirm the cubic inverse spinel phase. The relative changes in specific vibrational modes related to octahedral sites as a function of Mn content suggest a gradual change of measure of inversion of the ferrite lattice at nanoscale dimensions. Small-angle X-ray scattering and electron microscopy revealed a narrow particle size distribution with the spherical shape morphology of the CMFO NPs. The zero-field-cooled and field-cooled magnetic measurements revealed the superparamagnetic behavior of CMFO NPs at room temperature. The sample with x = 0.3 indicates a lower value of blocking temperature (9.16 K) with the improved (maximum) value of saturation magnetization. The results and the structure-composition–property correlation suggest that the economic, eco-friendly hydrothermal approach can be adopted to process superparamagnetic nanostructured magnetic materials at a relatively lower temperature for practical electronic and electromagnetic device applications.
Apart from biocompatibility, poly(ethylene glycol) (PEG)-based biomedical constructs require mechanical tunability and optimization of microscale transport for regulation of the release kinetics of ...biomolecules. This study illustrates the role of inhomogeneities due to aggregates and structuring in the PEG matrix in the microscale diffusion of a fluorescent probe. Comparative analysis of fluorescence recovery after photobleaching (FRAP) profiles with the help of diffusion half-time is used to assess the diffusion coefficient (D). The observations support a nontrivial dependence of diffusion dynamics on polymer concentration (volume fraction, φ) and that of fillers carboxymethyl cellulose (CMC) and nanoclay bentonite (B). D values follow the Rouse scaling D ∼ φ–0.54 in PEG solutions. The diffusion time of the fluorescent probe in the PEG+bentonite matrix reveals the onset of depletion interaction-induced phase separation with an increase in bentonite concentration in the PEG matrix beyond 0.1 wt %. Beyond this concentration, structure factors obtained from prebleach FRAP images show a rapid increase at low Q. The two-phase system (PEG-rich and bentonite-rich) was characterized by the hierarchical structural topology of bentonite aggregates, and aggregate sizes were obtained at different length scales with phase contrast imaging, small-angle neutron scattering, and small-angle X-ray scattering. The microscale transport detection presented captures sensitively the commencement of phase separation in the PEG + bentonite matrix, as opposed to the PEG or PEG + CMC matrix, which are observed to be one-phase systems. This method of diffusion half-time and prebleach image analysis can be used for the fast, high-throughput experimental investigation of microscale mechanical response and its correlation with structuring in the polymer matrix.
We demonstrate for the first time the intrinsic role of nanoconfinement in facilitating the chemical reduction of metal ion precursors with a suitable reductant for the synthesis of metal ...nanoparticles, when the identical reaction does not occur in bulk solution. Taking the case of citrate reduction of silver ions under the unusual condition of citrate/Ag+ ≫ 1, it has been observed that the silver citrate complex, stable in bulk solution, decomposes readily in confined nanodomains of charged and neutral matrices (ion-exchange film and porous polystyrene beads), leading to the formation of silver nanoparticles. The evolution of growth of silver nanoparticles in the ion-exchange films has been studied using a combination of 110mAg radiotracer, small-angle X-ray scattering (SAXS) experiments, and transmission electron microscopy (TEM). It has been observed that the nanoconfined redox decomposition of silver citrate complex is responsible for the formation of Ag seeds, which thereafter catalyze oxidation of citrate and act as electron sink for subsequent reduction of silver ions. Because of these parallel processes, the particle sizes are in the bimodal distribution at some stages of the reaction. A continuous seeding with parallel growth mechanism has been revealed. Based on the SAXS data and radiotracer kinetics, the growth mechanism has been elucidated as a combination of continuous autoreduction of silver ions on the nanoparticle surfaces and a sudden coalescence of nanoparticles at a critical number density. However, for a fixed period of reduction, the size, size distribution, and number density of thus-formed Ag nanoparticles have been found to be dependent on physical architecture and chemical composition of the matrix.
Heterogeneous nanopore structure and distribution regulate the gas trapping, desorption kinetics, and diffusion in shale matrices. In shale, pores range from continuous micro- and mesopore size ...distributions, varying with organic (total organic matter-TOC) and inorganic constituents (clay content, Fe-bearing minerals, quartz,
etc.
). Previous research only showed a linear relationship of pore parameters with these intrinsic properties of shale, which limits our understanding of the concurrent influence of multiple intrinsic rock properties. As a result, in this work, we established multivariate dependency of nanopore structure, distribution, and complexity (from low-pressure N
2
and CO
2
sorption and small-angle scattering; SAXS/MSANS) in the previously little-studied Cambay shales and provided a better tool (partial least square regression) for analyzing the simultaneous effect of intrinsic shale properties on multiply connected pore-parameters. Furthermore, we discretized continuous pore-size distribution into individual pore families using deconvolution to understand the pore space better. Additionally, predicted shale formation environment in terms of deposition probability (
P
+
) and dissolution probability (
P
−
) using a dynamic model of the fractal interface by precipitation and dissolution. Our findings indicate that the Cambay shales have a high potential for future hydrocarbon exploration (
S
2
: 2.42–12.04 mg HC/g rock), “very good” (2-4 wt.%) to “excellent” (>4 wt.%) TOC content, and thermally mature type II–III admixed and type III kerogen. Deconvolution of the micro- and mesopore size distributions reveals that pore width (
w
) ranges ∼15.30–35 nm occupies greater than 50% of the total pore volume, and its pore volume increases with the presence of quartz, Fe-bearing minerals, and clay content. However, pores with
w
∼ 3.60–15.30 nm increase exclusively with TOC. In the micro- and early mesopore region, pore volume decreases with TOC from
w
∼ 0.30–0.75 nm and increases with TOC from
w
∼ 0.75–3.60 nm. Furthermore, TOC in shale increases the specific surface area and pore volume (micro-, meso-, and total pores), enhancing both sorption and free gas storage capacities. Cambay shales were likely deposited in three distinct environments, with precipitation probability (
P
+
) values of 1, 0.7–0.8, and 0.5, as revealed by a fractal dimension (
D
s
) analysis of multiple samples.
•Co-HMS-X catalyst showed catalytic activity for direct styrene epoxidation reaction.•Al, Ga and Tl (0.25mol%) are used as promoters in Co-HMS-X catalyst.•The highly active Ga-Co-HMS-X (Co/Ga=4) had ...large number of acidic sites.•The catalyst is stable up to three cycles.•It could epoxide cyclooctene with reasonably good conversion.
Atom efficient synthesis of various value added products has been focused as an intense research area after Kyoto protocol. Styrene epoxidation is a challenging reaction as styrene epoxide is an important monomer for large number of polymers. It has been found that surface acidity and redox property of the catalyst has a major contribution to the catalytic activity for oxidation reaction. In this study Co-HMS-X catalyst was prepared and characterized by BET surface area and porosity measurement, SAXS, SANS, FESEM, HRTEM, UV–vis spectra, FTIR, 29Si NMR, H2-TPR and NH3-TPD techniques. It is observed that 5mol% Co-HMS-X showed highest catalytic activity for styrene epoxidation reaction using molecular O2 as an oxidant. Interestingly it is found that among three different dopant (Al, Ga, Tl), the Ga promoted Co-HMS-X catalyst (Si:Co:Ga=100:5:1.25) showed highest catalytic activity in terms of styrene conversion (100%) and styrene epoxide selectivity (68%). The unusual trend of Al, Ga and Tl towards the activity of Co-HMS-X (5mol%) catalyst has been discussed from the results obtained in the H2-TPR and NH3-TPD study.
The influence of oleylamine (OLA) concentration on the crystallography, morphology, surface chemistry, chemical bonding, and magnetic properties of solvothermal synthesized CoFe2O4 (CFO) ...nanoparticles (NPs) has been thoroughly investigated. Varying OLA concentration (0.01–0.1 M) resulted in the formation of cubic spinel-structured CoFe2O4 NPs in the size-range of 20–14 (±1) nm. The Fourier transform spectroscopic analyses performed confirmed the OLA binding to the CFO NPs. The thermogravimetric measurements revealed monolayer and multilayer coating of OLA on CFO NPs, which were further supported by the small-angle X-ray scattering measurements. The magnetic measurements indicated that the maximum saturation (MS) and remanent (Mr) magnetization decreased with increasing OLA concentration. The ratio of maximum dipolar field (Hdip), coercivity (HC), and exchanged bias field (Hex) (at 10 K) to the average crystallite size (Dxrd), i.e., (Hdip/Dxrd), (HC/Dxrd), and (Hex/Dxrd), increased linearly with OLA concentration, indicating that OLA concurrently controls the particle size and interparticle interaction among the CFO NPs. The results and analyses demonstrate that the OLA-mediated synthesis allowed for modification of the structural and magnetic properties of CFO NPs, which could readily find potential application in electronics and biomedicine.
Nanoparticles confined in droplets of less than a picoliter are forced to organize in submicronic dry grains through solvent evaporation. The evolution of structures of the grains and the constituent ...nanoparticles during the slow drying process are investigated in situ with small-angle X-ray scattering (SAXS) for the first time. The scattering results have been explained on the basis of the equilibrium thermodynamics of the droplets in the drying tube. We demonstrate that this technique is really efficient in describing the internal arrangement of the nanoparticles inside the drying droplets. Distinction between an almost homogeneous repartition of the nanoparticles in droplets and formation of core shell like particles even in strongly polydispersed droplets can be made using SAXS.
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