Manmohan Kumar

Silver nanoparticle-loaded PVA/gum acacia hydrogel: synthesis, characterization and antibacterial study.

A simple one-pot method for in situ synthesis of silver nanoparticles (AgNPs), within polyvinyl alcohol/gum acacia (PVA-GA) hydrogel matrix, by gamma radiation-induced cross-linking is reported here. The synthesized hydrogels were characterized by FT-IR, thermogravimetry, dynamic light scattering and inductively coupled mass spectrometry method. The thermal stability was found to be more for the hydrogel loaded with silver nanoparticles and also the percentage silver loading was found to increase with increase in cross-linking density. The influence of gum acacia (GA) concentration on the equilibrium degree of swelling of the synthesized hydrogels, and also on the silver release from hydrogel matrix, was investigated. The size of the silver nanoparticles formed in the hydrogel matrix was in the range of 10-40 nm. The rheological gel point was found to be at 25.34 kGy of radiation dose, for a typical hydrogel synthesized, using 5% GA, 3% PVA and 1mM AgNO3. The antibacterial studies of the synthesized nanosilver-containing hydrogels showed good antibacterial activity against gram-negative bacterium, Escherichia coli.

Dilution induced thickening in hydrotrope-rich rod-like micelles

Dilution induced changes in the microstructure and rheological behavior of micelles formed by a cationic surfactant-anionic hydrotrope mixture has been investigated in the hydrotrope-rich region. The surfactant used is cetyltrimethylammonium bromide (CTAB) and the hydrotropic salt is sodium 3-hydroxy naphthalene 2-carboxylate (SHNC). The concentration of the mixture is varied from 0.5% to 10.0% w/w (φ=0.005-0.100) at a fixed weight ratio of hydrotrope to surfactant (85:15). Rheological studies indicate Newtonian flow behavior at low and high volume fractions (0.005 and 0.100) while a shear thinning behavior is observed at intermediate volume fractions. The zero-shear viscosity η(0) also passes through a maximum upon changes in the concentration. The most striking feature in our study is that a low viscosity Newtonian fluid transforms to a viscoelastic fluid, upon dilution, and then again to a Newtonain fluid. Small angle neutron scattering studies of 10.0% micellar solution show the presence of rod-like aggregates. Upon dilution, the scattering intensity per unit concentration shows an increase in the low q-region. The nature of pair distance distribution function and subsequent model fitting indicates a transition from rod-like micelles to unilamellar vesicles upon dilution. This behavior is explained in terms of the volume fraction dependant solubilization of hydrotropes in the rod-like micelles and consequent changes in the composition of the mixed micelles.

Resorcinol-formaldehyde coated XAD resin beads for removal of cesium ions from radioactive waste: synthesis, sorption and kinetic studies

A novel synthetic method was developed to synthesize resorcinol-formaldehyde (RF) resin in spherical form, of required mesh size, using XAD-4 as template beads. The synthesized RF-coated XAD (RF-XAD) beads were characterized, using different techniques. Suitable size and mechanical stability, along with their spherical shape, make these beads most appropriate for column operation. The efficiency of these beads was evaluated for removal of cesium from alkaline medium, in batch conditions, using a radioanalytical technique. The effect of sodium ion concentration, the initial cesium ion concentration and the contact time were also investigated. It was observed that the Kd value for Cs+ ions decreases with increase in Na+ ion concentration. The equilibrium data were fitted into different isotherm models, and were found to be represented well by the Langmuir isotherm equation, with a monolayer sorption capacity of 287 mg g−1. Kinetic modeling analysis, using pseudo first-order, pseudo second-order and intraparticle diffusion equations, shows that the pseudo second-order equation is the most appropriate model for the description of the sorption of cesium ions onto the RF-XAD beads. The rate constants were determined at different initial concentrations. The process mechanism was found to be complex, consisting of both surface sorption and pore diffusion.

An Organic Acid-induced Synthesis and Characterization of Selenium Nanoparticles

A simple wet chemical method has been developed to synthesize selenium nanoparticles (size 40–100 nm), by the reaction of sodium selenosulphate precursor with different organic acids in aqueous medium, under ambient conditions. Polyvinyl alcohol has been used to stabilize the selenium nanoparticles. The synthesized nanoparticles can be separated from its sol by using a high-speed centrifuge and can be redispersed in aqueous medium with a sonicator. UV-visible optical absorption spectroscopy, X-ray diffraction, energy dispersive X-rays, differential scanning calorimetry, atomic force microscopy, and transmission electron microscopy techniques have been employed to characterize the synthesized selenium nanoparticles.

Potassium cobalthexacyanoferrate–gel beads for cesium removal: kinetics and sorption studies

The hydrogel–sorbent composite beads of potassium cobalthexacyanoferrate (KCoHCF) were synthesized for separation of cesium from waste generated in the nuclear industry. Cross-linked sodium alginate, containing PVA, was used as a binding matrix for the synthesis of spherical beads of 2 mm diameter. The characterization of these beads was carried out, using TGA, SEM and BET surface area analysis techniques, which indicated the highly porous and hydrophilic nature of the beads. The sorption of cesium ions onto these synthesized beads was studied, using a radiotracer technique. To determine equilibrium sorption and kinetic parameters for different initial cesium ion concentrations, all the studies were conducted by a batch method. The experimental data were analyzed, using the different sorption isotherms, and found to be described the best by a Langmuir sorption isotherm. The monolayer capacity of KCoHCF–gel beads is found to be 15 mg g−1 of the dry beads. Sorption kinetics data were analysed, using different kinetic models. The results show that the sorption follows pseudo second-order reaction kinetics. The initial sorption rate and the rate constants for the pseudo first-order, pseudo second-order and intraparticle diffusion were evaluated, and discussed for different initial concentrations in the range 1–20 mg L−1. The mechanism of the sorption of cesium ions onto the synthesized beads was also investigated and film diffusion was found to be the rate determining step.

Pulse and gamma radiolytic studies on the formation of Cd, Pd and Cu clusters in aqueous solutions

Abstract Investigations on the formation of Cd, Pd and Cu sols using radiolytic techniques have been carried out. The reducing properties of the Cd particles were confirmed by dissolving MV 2+ , N 2 O and O 2 . By using high intensity electron pulses we observed the formation of the highly stable (approx. 8 days) Cd particles that showed absorption at both 270 and 450 nm. In the case of Cu, the stability of the sol depends on the type of reducing radical used, such as formate and isopropanol. It has been shown for Pd and Cd sols that the presence of both the stabilizer and agglomerated particles play an important role in stabilizing the small clusters.

Removal of americium from aqueous nitrate solutions by sorption onto PC88A—Impregnated macroporous polymeric beads

The removal of Am (III) ions from aqueous solutions was studied by solid-liquid extraction using indigenously synthesized Extractant Impregnated Macroporous Polymeric Beads (EIMPBs). These beads were prepared by an in situ phase inversion method using polyethersulfone (PES) as base polymer and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC88A) as an extractant. The synthesized EIMPBs were characterized by FTIR, TGA and SEM techniques. The batch equilibration study using these beads for the uptake of Am (III) was carried out as a function of parameters, like pH, equilibration time, Am (III) concentration, etc. The blank polymeric beads, without PC88A, have shown negligible sorption of Am (III) under the experimental conditions. The experimental data on the sorption behavior of Am (III) on the polymeric beads fitted well in the pseudo-second-order kinetics model. The synthesized polymeric beads exhibited very good sorption capacity for Am (III) at pH 3. The reusability of the beads was also ascertained by repetitive sorption/desorption of Am (III) up to 10 cycles of operation, without any significant change in their sorption characteristics.

The effect of UV radiation on polybenzoxazine/epoxy/OG-POSS nanocomposites

Degradation against atomic oxygen (AO), ultra-violet (UV) and vacuum ultra-violet (VUV) radiation has to be controlled in order to maintain the longevity and performance of light weight and high strength nanocomposites used in space and nuclear applications. With this in mind, a new synthetic route has been used to develop a semi-organic precursor, [polyhedral oligomeric silsesquioxane (POSS)] reinforced polybenzoxazine/epoxy (PBZ/EP) nanocomposites. PBZ/EP/POSS nanocomposites have been developed by reinforcing varying weight percentages of (0, 1.0, 3.0, and 5.0 wt%) POSS into 1 : 1 (w/w) ratio of BZ and DGEBA epoxy (EP) matrix via thermal curing. The developed nanocomposites were tested under UV irradiation at the wavelength of 365 nm for a period of one week. The values of tensile strength and morphological behaviour before and after exposure to UV irradiation have been determined in order to assess their radiation resistant behaviour. It was ascertained that the data obtained from the value of tensile strength for 5 wt% POSS reinforced PBZ/EP has changed only to an insignificant extent when compared to that of before UV irradiation. From SEM and XPS analysis, it was observed that a passive inert silica protective layer has been formed after radiation, which protects the composite materials from further deterioration due to radiation. Data from thermal and dielectric studies indicate that the POSS incorporated system possesses better thermal and low dielectric properties than those of the neat PBZ/EP matrix.

Studies on hydrolytic and radiolytic stability ofN,N,N´,N´-tetra-(2-ethylhexyl) thiodiglycolamide T(2EH)TDGA

Abstract Hydrolytic and radiolytic stability of T(2EH)TDGA solvent system has been investigated to establish its application in separation and recovery of palladium from High Level Liquid Waste (HLW) solutions. Hydrolysis of T(2EH)TDGA solvent system with nitric acid was not observed. Moreover, unlike other “S” donor extractants used for the said purpose, the oxidation of thioetheric sulphur to sulphoxide or sulphones was also not observed. However, radiolytic degradation was notably observed and found to increase with increase in absorbed dose. n-dodecane was found to sensitize the degradation of T(2EH)TDGA. At gamma radiation dose of 0.2 MGy, no significant loss of T(2EH)TDGA was observed. The degradation products were identified by GC-MS. The major products were found to be formed by cleavage of thioetheric and amidic bonds of T(2EH)TDGA molecule. The extraction studies of palladium with irradiated solvent indicate that with 0.025 M T(2EH)TDGA/n-dodecane, there was no significant change in DPd up to an absorbed dose of 0.2 MGy above which it decreases significantly. However, with 0.05 M T(2EH)TDGA/n-dodecane, there is gradual decrease in DPd with increase of absorbed dose. Further, the radiolysis does not affect the stripping behavior of palladium. Extraction studies of Pd(II) and other fission products from simulated high level liquid waste (SHLW) solutions to irradiated solvent system showed that, except palladium, any other element is hardly extracted thus retaining its remarkable selectivity.

Precursor concentration and temperature controlled formation of polyvinyl alcohol-capped CdSe-quantum dots

Summary Polyvinyl alcohol-capped CdSe quantum dots, with a size within their quantum confinement limit, were prepared in aqueous solution at room temperature, by a simple and environmentally friendly chemical method. The size of the CdSe quantum dots was found to be dependent on the concentrations of the precursors of cadmium and selenium ions, as well as on the aging time and the reaction temperature; all of which could be used conveniently for tuning the size of the particles, as well as their optical properties. The synthesized quantum dots were characterized by optical absorption spectroscopy, fluorescence spectroscopy, X-ray diffraction, atomic force microscopy and transmission electron microscopy. The samples were fluorescent at room temperature; the green fluorescence was assigned to band edge emission, and the near-infrared fluorescence peaks at about 665 and 865 nm were assigned to shallow and deep trap states emissions, respectively. The quantum dots were fairly stable up to several days.