Structural Characteristics and Electrical Conductivity of Spark Plasma Sintered Ytterbia Co‐doped Scandia Stabilized Zirconia

The effect of replacing Sc₂O₃ with Yb₂O₃ on the structural and electrical properties of xYb₂O₃–(12–x)Sc₂O₃–88ZrO₂ has been investigated. Spark plasma sintering technique is employed to fabricate dense bulk samples from the nano‐sized powders. X‐ray diffraction and transmission electron microscopy performed on pellets indicate the existence of cubic and rhombohedral phases in 12ScSZ, and a single cubic phase in all the co‐doped compositions. However, Raman spectroscopic studies suggest the presence of a metastable tetragonal t″‐phase along with rhombohedral phases in 12ScSZ, whereas a single cubic phase in all the co‐doped compositions. Significant enhancement in the conductivity of grain and grain boundary is observed on replacing Sc₂O₃ with Yb₂O₃. In the intermediate temperature range, 1Yb11ScSZ exhibits the highest, while 12ScSZ shows the lowest conductivity values, which is attributed to corresponding phases present in that range. Through co‐doping with >1 mol% Yb₂O₃ leads to conductivity decrease, but the value remains higher than that of 12ScSZ. A sharp conductivity change is observed in 12ScSZ and 1Yb11ScSZ samples, which is attributed to partial phase transition as well to the formation of cation‐vacancy complexes. In this work, the beneficial effect of Yb₂O₃ co‐doping in 12ScSZ on the phase and conductivity has been highlighted.     

TETRA-BUTYL-MALONAMIDE AND TETRA-ISOBUTYL MALONAMIDE AS EXTRACTANTS FOR URANIUM(VI) AND PLUTONIUM(IV)

ABSTRACT

Two new symmetrical diamides, namely straight-chain alkyl substituted neutral tetra-butyl-malonamide(TBMA) and sterlcally hindered branched-chain alkyl substituted tetra-isobutyl malonamide(TIBMA) were synthesised, characterised and used for the extraction of U(VI) and Pu(IV) from nitric acid media into n-dodecane. Both the cations were found to be extracted as their disolvates. Interestingly TBMA extracted more efficiently than TIBMA but afforded poor selectivity for Pu/U separation. The thermodynamic parameters involved in the extraction, determined by the temperature variation method, indicated the reactions in all cases to be enthalpy favoured. Entropy was found to be counteracting the extraction of U(VI) and favouring the extraction of Pu(IV). The recovery of diamides from the loaded actinides could be easily accomplished by using dilute oxalic acid or dilute U(IV) as the strippant for Pu(IV) and using dilute Na₂C0₃ as that for U(VI).     

Development of pellets of nifedipine using HPMC K15 M and κ-carrageenan as mucoadhesive sustained delivery system and in vitro evaluation

Polymeric mucoadhesive pellets of nifedipine were designed using computer software and they were prepared by extrusion-spheronization using HPMC K15M and κ-carrageenan with microcrystalline cellulose. A randomized rotatable two factor central composite design was applied for assessment of influence of two independent variables such as concentration of κ-carrageenan and HPMC K15M on dependent variables. Pellets were characterized by FTIR, DSC, SEM, flow properties, particle size, abrasion resistance, sphericity, drug content, percent production yield, in vitro drug release, ex vivo mucoadhesion, stability studies and similarity factor. The optimized formulation was selected based on criteria of sphericity nearest to 1.0 with maximum cumulative drug release percentage. Formulation NF6 exhibited sufficient porous spheres, free flowing and smooth surface mucoadhesion of 91.34 % and drug content 98.22 ± 0.37 %. Kinetic modeling revealed that the formulation followed the Higuchi model and showed the Quassi-Fickian drug release mechanism. The similarity factor, F2 value, was found to be 74 ± 6 and there was no significant change in drug content and ex vivo mucoadhesion after 90 days at 40 ± 2 °C, and 75 ± 5 % RH clearly indicated the optimized batch NF6 was stable. Thus, it can be concluded that use of κ-carrageenan, microcrystalline cellulose and HPMC K15M at the 20:35:10 w/w ratio could provide an effective carrier for enhancement of sphericity and sustained release of matrix pellets.     

The preparation and characteristics of surface treated barium sulfate extender pigment

This article deals with the treatment of barium sulfate extender pigment with iron oxide and its phenomenological adsorption mechanism in the presence of H⁺ and OH^? ions in solution. The pH range taken in the present study is 5–6. By depositing a ferric oxide layer on barium sulfate particles a novel pigment with better optical and functional performance is obtained. This pigment in various coating systems improves physicochemical performance and acts as an active barrier. The treated pigments can be suitably used in different architectural and industrial coatings. The experimental techniques of surface treatment are discussed, along with the instrumental analysis by SEM, EDAX, XRD, etc.     

Enhancement in CO oxidation activity of nanosized CexZr1−xO2 solid solutions by incorporation of additional dopants

The influence of Hf, Pr and Tb dopant cations on structural and catalytic properties of nanosized Ce_xZr_1?xO₂ solid solutions has been investigated. A wide range of analytical techniques are utilized to characterize the synthesized materials, and the catalytic activity is evaluated for CO oxidation. XRD, Raman, SEM and TEM results suggested formation of dopant cation incorporated ceria–zirconia solid solutions with highly homogeneous morphology and lattice defects. The CO-TPR measurements revealed an enhanced reducibility of Ce_xZr_1?xO₂ which is reflected in their better catalytic activity. The role of Tb⁴⁺/Tb³⁺ and Pr⁴⁺/Pr³⁺ redox couples in facilitating a higher activity has been addressed.     

Electrospinning of linear homopolymers of poly(methyl methacrylate): exploring relationships between fiber formation, viscosity, molecular weight and concentration in a good solvent

A series of seven linear homopolymers of poly(methylmethacrylate) ranging from 12,470 to 365,700 g/mol M_w, were utilized to further explore scaling relationships between viscosity and concentration in a good solvent at 25 °C and to investigate the impact of these relationships on fiber formation during electrospinning. For each of the polymers investigated, chain dimensions (hydrodynamic radius and radius of gyration) were measured by dynamic light scattering to determine the critical chain overlap concentration, c^*. The experimentally determined c^*, was found to be in good agreement with the theoretically determined value that was calculated by the criteria c^*∼1/[η], where the intrinsic viscosity was estimated from the Mark-Houwink parameters, K and a (at 25 °C in dimethyl formamide) obtained from the literature. The plot of the zero shear viscosity vs. c/c^* distinctly separated into different solution regimes, viz. dilute (c/c^*<1), semidilute unentangled (1<c/c^*<3) and semidilute entangled (c/c^*>3). The crossover between semidilute unentangled and semidilute entangled regimes in the present investigation occurred at c/c^*∼3, which, therefore, marked the onset of the critical chain entanglement concentration, c_e, according to the procedure utilized by Colby and co-workers [Colby RH, Rubinstein M, Daoud M. J de Phys II 1994;4(8):1299-310. [52]]. Electrospinning of all solutions was carried out at identical conditions to ascertain the effects of solution concentration, molecular weight, molecular weight distribution and viscosity on fiber formation and morphological features of the electrospun material. Only polymer droplets were observed to form from electrospinning of solutions in the dilute concentration regime due to insufficient chain overlap. As the concentration was increased, droplets and beaded fibers were observed in the semidilute unentangled regime; and beaded as well as uniform fibers were observed in the semidilute entangled regime. Uniform fiber formation was observed at c/c^*∼6 for all the narrow MWD polymers (M_w of 12,470-205,800 g/mol) but for the relatively broad MWD polymers (M_w of 34,070 and 95,800 g/mol), uniform fibers were not formed until higher concentrations, c/c^*∼10, were utilized. Dependence of fiber diameter on concentration and viscosity was also determined, viz. fiber dia∼(c/c^*)^3.1 and respectively. These scaling relationships were in general agreement with that observed by Mckee et al. [McKee MG, Wilkes GL, Colby RH, Long TE. Macromolecules 2004;37(5):1760-67. [33]].     

The role of castor oil in epoxy and polyamide systems for coating and adhesive application

Summary  Over the past few years, the challenges of globalisation, consolidation and economical point of view have meant that manufacturers of epoxy formulations have to constantly improve their capability to meet the needs of customers. An active area for advancement is that of epoxy and polyamide resin with castor oil. Generally, people working in the coating industries are familiar with castor oil, but this paper provides information on the new use of castor oil in epoxy and polyamide resin. This novel product (castor oil-modified epoxy resin/castor oil-modified polyamide) provides a previously unattainable combination and improved flexibility and toughness to a variety of ambient cure applications. This communication will review the performance of these castor oil-modified epoxy and polyamide resin surface coatings and adhesives. Based on the results of this study, these systems offer some advantages without much affecting the traditional properties of epoxy and polyamide resin in a variety of applications.     

Defect-mediated optical properties of Fe-substituted TiO2 nanoparticles

Here, sol–gel derived Fe–TiO₂ anatase nanoparticles with varying concentrations of Ti_(1–x)Fe_xO₂ (x = 0%, 1%, 5%, 10%) were prepared. The structural, morphological, and optical properties of prepared samples were studied. X-ray diffraction (XRD) patterns show the formation of pure anatase phase. The mean crystallite size of Fe–TiO₂ decreases with increase in the concentration of Fe. Fourier transform infrared spectroscopy (FTIR) spectra confirmed the presence of Ti–O vibrational band for all the samples. In Raman spectrum, peak broadening and red shifting linked with Eg ∼144 cm^–1 divulge the Fe substitution at Ti sites into host lattice structure. Photoluminescence (PL) spectra verified nine peaks related to near band-edge emission and various defect states. The UV–vis diffuse reflectance spectra represent redshift and reduction in the bandgap energy. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) investigations show that the size of the grains decreases with increase in Fe doping concentration. The study shows that Fe-doped TiO₂ anatase phase nanoparticles are suitable for photocatalytic activity and solar cell applications.     

Effect of morphology on the performance of metal-hydride electrodes

Electrochemical studies on AB₂ type Zr_0.5Ti_0.5V_0.6Cr_0.2Ni_1.2 metal hydride electrodes with varying particle size suggests that the electrodes with alloy particles of about 60 m yield the optimum performance. The values for diffusion coefficient of hydrogen in the alloy particles > 25 m are found to be nearly invariant. Both a.c. impedance and linear polarization data on electrodes with varying particle size suggest that the charge-transfer resistance depends on state-of-charge of the electrodes. A comparison of scanning electron micrographs of fresh electrodes and subsequent to their prolonged charge-discharge cycling suggests that the metal hydride particles develop stress-induced cracks owing to their inherent expansion and contraction during the hydriding/dehydriding processes.     

AC impedance and state-of-charge analysis of alkaline zinc/manganese dioxide primary cells

Alternating current impedance data of alkaline Zn/MnO₂ cells were analysed in view of identification of suitable parameters, which depend on the state-of-charge (SOC) of the cells. The impedance of a slightly discharged cell was found to possess impedance considerably lesser than that of an undischarged cell. The data in the form of Nyquist plot contained an inductance part at very high frequencies, a capacitive semicircle at high frequencies and a diffusion linear spike at low frequencies. The low frequency linear spike gradually transformed into a capacitive semicircle with the decrease of SOC of the cell, which was attributed to the nature of the reactions at the Zn anode. Of several impedance parameters that were examined, equivalent series capacitance (C_s) was found to have a strong dependence on SOC of the alkaline Zn/MnO₂ cells. There was a continuous change in a partially discharged cell during its ageing, which was reflected by transformation of low frequency data into a clear semicircle.