PNIPAAM grafted particle monoliths: parameters affecting structure and morphology

Crosslinked polystyrene latex particles generated with surfactant free emulsion polymerization were functionalized with thin layer of ATRP initiator on the surface. The functionalized particles were aggregated as physical networks using high shear techniques. The latex particles as well as the aggregated particles were used to successfully generate thermo-responsive monoliths by grafting PNIPAAM brushes from the surface of the particles by atom transfer radical polymerization and simultaneous crosslinking of these brushes. Different solid fractions and drying conditions were used in the generation of the monoliths and the effect of these variations on the structure and morphology of the monoliths was analyzed. Surprising morphologies consisting of tubes or channels were observed when higher solid fractions were used. This behavior was enhanced when the monoliths were dried at higher temperatures. By using proper solid fractions and drying conditions, homogenous porous monoliths could be achieve

Effect of the presence of excess ammonium ions on the clay surface on permeation properties of epoxy nanocomposites

Epoxy nanocomposites with commercially and self-modified montmorillonites of different cation exchange capacities carrying ammonium modifications of various chemical architectures were synthesized using solution casting approach. The commercially treated montmorillonites were observed to contain a large excess of unbound ammonium ions on the surface, which had a negative impact on the permeation properties of the composites owing to the suspected interactions of these unbound ammonium ions with the epoxy polymer. The permeation behavior was significantly improved when self-modified clays free of any excess ammonium modification were used. The microstructure development was unaffected by the physical state of the clay surface indicating that the potential changes in the polymer properties at the interface as well as interfacial interactions in the composites carrying the commercially modified clays may have led to increase in the free volume. Optimal preparation of the clay surface holds the key to achieve enhancement in the composite performanc

Using a Discrete Choice Experiment to Elicit the Demand for a Nutritious Food: Willingness-to-Pay for Orange Maize in Rural Zambia

Using a discrete choice experiment, this paper estimates the willingness to pay for biofortified orange maize in rural Zambia. The study design has five treatment arms, which enable an analysis of the impact of nutrition information, comparing the use of simulated radio versus community leaders in transmitting the nutrition message, on willingness to pay, and to account for possible novelty effects in the magnitude of premiums or discounts. The estimation strategy also takes into account lexicographic preferences of a subset of our respondents. The results suggest that (a) orange maize is well liked and can compete with white maize in the absence of a nutrition campaign, (b) there is a premium for orange maize with nutrition information, and (c) the mode of nutritional-message dissemination does not have a large impact on consumer acceptance, and (d) novelty effects do not translate into higher willingness to pay for orange maize.

Evidence for existence of Functional Monoclinic Phase in Sodium Niobate based Solid Solution by Powder Neutron Diffraction

We have carried out systematic temperature-dependent neutron diffraction measurements in conjunction with dielectric spectroscopy from 6 to 300 K for sodium niobate based compounds (1-x) NaNbO3 -xBaTiO3 (NNBTx). The dielectric constant is measured both as a function of temperature and frequency. It shows an anomaly at different temperatures in cooling and heating cycles and exhibits a large thermal hysteresis of 150 K for the composition x=0.03. The dielectric constant is found to be dispersive in nature and suggests a relaxor ferroelectric behavior. In order to explore structural changes as a function of temperature, we analyzed the powder neutron diffraction data for the composition x=0.03 and 0.05, respectively. Drastic changes are observed in the powder profiles near 30.6{\deg}, 32.1{\deg} and 34.6{\deg} in the diffraction pattern below 200 K during cooling and above 190 K in heating cycles, respectively.The disappearance of superlattice reflection and splitting in main perovskite peaks provide a signature for structural phase transition. We observed stabilization of a monoclinic phase (Cc) at low temperature. This monoclinic phase is believed to provide a flexible polarization rotation and considered to be directly linked to the high performance piezoelectricity in materials. The thermal hysteresis for composition x=0.03 is larger than x=0.05. This suggests that addition of BaTiO3 in NaNbO3 suppresses the thermal hysteresis. It is also observed that the structural phase transition temperature decreases on increasing dopant concentration.Comment: 16 Pages, 6 Figure

Dynamic characterization of cellulose nanofibrils in sheared and extended semi-dilute dispersions

New materials made through controlled assembly of dispersed cellulose nanofibrils (CNF) has the potential to develop into biobased competitors to some of the highest performing materials today. The performance of these new cellulose materials depends on how easily CNF alignment can be controlled with hydrodynamic forces, which are always in competition with a different process driving the system towards isotropy, called rotary diffusion. In this work, we present a flow-stop experiment using polarized optical microscopy (POM) to study the rotary diffusion of CNF dispersions in process relevant flows and concentrations. This is combined with small angle X-ray scattering (SAXS) experiments to analyze the true orientation distribution function (ODF) of the flowing fibrils. It is found that the rotary diffusion process of CNF occurs at multiple time scales, where the fastest scale seems to be dependent on the deformation history of the dispersion before the stop. At the same time, the hypothesis that rotary diffusion is dependent on the initial ODF does not hold as the same distribution can result in different diffusion time scales. The rotary diffusion is found to be faster in flows dominated by shear compared to pure extensional flows. Furthermore, the experimental setup can be used to quickly characterize the dynamic properties of flowing CNF and thus aid in determining the quality of the dispersion and its usability in material processes.Comment: 45 pages, 13 figure

Phase stability and structural temperature dependence in sodium niobate: A high resolution powder neutron diffraction study

We report investigation of structural phase transitions in technologically important material sodium niobate as a function of temperature on heating over 300-1075 K. Our high resolution powder neutron diffraction data show variety of structural phase transitions ranging from non-polar antiferrodistortive to ferroelectric and antiferroelectric in nature. Discontinuous jump in lattice parameters is found only at 633 K that indicates that the transition of orthorhombic antiferroelectric P (space group Pbcm) to R (space group Pbnm) phase is first order in nature, while other successive phase transitions are of second order. New superlattice reflections appear at 680 K (R phase) and 770 K (S phase) that could be indexed using an intermediate long-period modulated orthorhombic structure whose lattice parameter along direction is 3 and 6 times that of the CaTiO3-like Pbnm structure respectively. The correlation of superlattice reflections with the phonon instability is discussed. The critical exponent ({\beta}) for the second order tetragonal to cubic phase transition at 950 K, corresponds to a value {\beta}$\approx 1/3$, as obtained from the temperature variation of order parameters (tilt angle and intensity of superlattice reflections). It is argued that this exponent is due to a second order phase transition close to a tricritical point. Based on our detailed temperature dependent neutron diffraction studies, the phase diagram of sodium niobate is presented that resolves existing ambiguities in the literature.Comment: 21 Pages, 8 Figure

Enhancement of bulk second-harmonic generation from silicon nitride films by material composition

We present a comprehensive tensorial characterization of second-harmonic generation from silicon nitride films with varying composition. The samples were fabricated using plasma-enhanced chemical vapor deposition, and the material composition was varied by the reactive gas mixture in the process. We found a six-fold enhancement between the lowest and highest second-order susceptibility, with the highest value of approximately 5 pm/V from the most silicon-rich sample. Moreover, the optical losses were found to be sufficiently small (below 6 dB/cm) for applications. The tensorial results show that all samples retain in-plane isotropy independent of silicon content, highlighting the controllability of the fabrication process.Comment: 4 pages, 3 figures, 2 tables; Re-submitted to Optics Letter