Scrolls and nested tubes in multiwall carbon nanotubes

Recent high-resolution transmission electron microscopy (HREM) studies of multiwalled carbon nanotubes (MWCNTs) reveal a class of defects analogous to edge dislocations in a crystal. These defects are believed to mark the transition from scrolls on one side to nested tubes on the other. On the tube side, layer spacing becomes irregular. Analysis of the helicity of the tubes shows a strong correlation between diameter and helicity. This suggests that the organizing principle for the tubes is not Van der Waals forces, as in the case of graphite or turbostratic carbon, but preservation of helicity. Based on these observations and total energy calculations, the authors speculate that graphene monolayers initially form scrolls and subsequently transform into multiwall nanotubes through the progression of defects. Scrolls and nested tubes thus coexist within a single MWNT.     

Novel-stratified low reflectivity anti-reflective coatings derived from self-assembly of high refractive index nanoparticles

We describe new anti-reflective multilayer optical coatings formed from a single liquid coating solution in a single coating step. The nanoparticles in these coatings self-organize as the liquid coating dries on the substrate. The self-assembly of the nanoparticles results in the formation of a two-layer dielectric stack composed of alternating high and low refractive index layers. For the first time, using this process, an ultra-low reflectivity film can be inexpensively and simply formed using high refractive index titanium oxide nanoparticles and a low refractive index fluoropolymer. These films can be made scratch or abrasion resistant by the inclusion of silane coupling agents and low refractive index nanoparticles.     

Effect of interlayer potential on mechanical deformation of multiwalled carbon nanotubes

A study on the modeling and simulation of interlayer interaction in the multiwalled carbon nanotube (MWCNT) system is presented. We use an interlayer Morse potential previously developed from a local density approximation (LDA) treatment of a bilayer of graphite. We have fit this Morse potential to experimental high-pressure compressibility data for graphite and to a more extensive LDA equation of state (EOS) for graphite, and excellent agreement is observed. We employ this potential to treat the interlayer mechanics of MWCNTs, where the MWCNT is so highly deformed that interlayer separation well below approximately 0.34 nm, such as down to approximately 0.26 nm, is occurring. This, to our knowledge, is the first treatment that attempts to account for deformations that have the layers approaching each other at very high local (interlayer) stress levels. Since evaluating the interlayer potential for a large MWCNT system is computationally intensive, a continuum simulation approach is proposed that saves on computational time and thus on cost. Comparisons with experimental results of buckled and highly kinked MWCNTs are presented.     

Switching behavior of bulk,fast ion conducting,vitreous AgI-Ag2O-MoO3 solids with inert electrode

Developing efficient, fast performing and thermally stable Silver iodide-based fast ion conducting solids are of great interest for resistive switching applications, but still remain a challenge. Metallization in bulk, behavior of threshold voltage profile over composition, and corrosion reactions are few of the challenges. In this work, the switching behavior of bulk, fast ion conducting, vitreous (AgI)_x-(Ag₂O)₂₅-(MoO₃)_75-x, for 60 ≤ x ≤ 40 solids, has been investigated in order to understand the switching mechanism with the inert electrodes. By using inert electrodes, the switching becomes irreversible, memory type. The switching mechanism is the electrochemical metallization process. The inert electrodes restrain ionic mass transfer but exhibit low barrier to electron transfer allowing the cathodic metallization reaction to reach Nernst equilibrium faster. Cations involved in this process transport through the free volume within the solid structure and follows Mott-Gurney model for electric field-driven thermally activated ion hopping conductivity model. This model along with the thermal stability profile provides a narrow region within composition with better switching performance based on swiftness to reach threshold voltage and less power loss. Traces of anionic contribution to metallization are absent. Moreover, anodic oxidation involves reactions that cause bubble formation and corrosion.     

Studies on the synthesis and properties of hydroxypropyl derivatives of cassava (Manihot esculenta Crantz) starch

Cassava starch was subjected to hydroxypropylation in three different media, which included water, water in the presence of a phase transfer catalyst, and 2‐propanol, all at 30 ± 2 °C for 24 h. Propylene oxide was used in four different concentrations (50, 100, 150 and 200 g kg^?1 of starch dry weight). The products were characterized by determining their molar substitution (MS), structural and functional properties. The analyses were done in triplicate and the data were analyzed using the statistical package 8.01. The MS of the products ranged from 0.26 to 1.41. The MS of the hydroxypropyl derivatives were found to be higher when the reaction was carried out in the aqueous medium in the presence of tetrabutylammonium bromide, a phase transfer catalyst, when compared to the reaction in 2‐propanol, which was found to be not very effective at 30 ± 2 °C. The etherification altered the granular properties of starch, as could be seen from scanning electron micrographs. Hydroxypropylation resulted in starch pastes which were stable and with higher swelling volume, solubility, light transmittance and water binding capacity as compared to native starch. The hydroxypropyl starches showed significantly lower pasting temperatures and setback viscosities. The enzyme digestibility of the derivatives was seen to decrease with increase in MS and there was a significant reduction in the syneresis of the starch pastes of hydroxypropyl derivatives. Texture profile analysis showed that hydroxypropylated starch gels exhibited higher hardness, springiness (elasticity) and gumminess and lower cohesiveness than the native starch. Copyright © 2007 Society of Chemical Industry     

Determination of Amylose Content in Different Starches Using Modulated Differential Scanning Calorimetry

A simple calorimetric method for determination of amylose content in starch is reported. Starches were heated in the presence of two common surfactants, viz., sodium dodecyl sulphate (SDS) and cetyltrimethylammonium bromide (CTAB), and the enthalpies of melting of the amylose‐surfactant complexes were determined using Modulated Differential Scanning Calorimetry (MDSC). A large number of native starches including cereal, root and pea starches were examined. The results were compared with those obtained by iodimetry and gel permeation chromatography (GPC) for all the starches. There was a good correlation between the values from iodimetry and GPC with those obtained using the surfactants. Both surfactants seemed to work equally well, even for those starches with about 40% amylose content. However, in case of SDS higher standard deviations were usually obtained than for CTAB in the determination of transition enthalpies.     

Gelatinisation Properties of Cassava Starch in the Presence of Salts,Acids and Oxidising Agents

The effect of various cations, anions, acids and oxidising agents on the gelatinisation properties of cassava starch was studied and wide variation was observed in the pasting and swelling properties. Sodium chloride and sodium thiosulphate slightly lowered the peak viscosity of cassava starch with increase in concentration, whereas with sodium sulphite, calcium chloride and sodium hypochlorite, a more significant decrease in the viscosity and breakdown was observed. Ferrous sulphate, alum, aluminium chloride and acids enhanced the peak viscosity at lower concentrations followed by a decrease at 1% and above. Sodium metabisulphite elevated the viscosity at 0.05 and 0.1%, while sodium hypochlorite lowered the viscosity and breakdown. DSC studies showed that aluminium chloride, sodium sulphite, and sodium thiosulphate brought about an increase in T_onset, T_end and ΔH values at higher concentrations. A decrease in swelling volume was observed from 0.05 to 1% concentration of sodium chloride and above that there was a gradual increase. With sodium sulphite, a significant increase in swelling volume was observed at 2.5 and 5% levels. With 0.05 and 0.1% aluminium chloride and sodium metabisulphite an increase in swelling volume was noticed, but at higher concentrations there was a drastic fall. Sodium chloride, sodium sulphite, sodium thiosulphate and calcium chloride brought about decrease in starch paste clarity with increase in salt concentration, whereas ferrous sulphate, aluminium chloride, sodium hypochlorite, hydrochloric acid and acetic acid improved the starch paste clarity.     

Effect of graft-copolymerization with poly(acrylamide) on rheological and thermal properties of cassava starch

Graft copolymers of different grafting levels were synthesised by the free radical initiated reaction of cassava starch with acrylamide in presence of ceric ammonium nitrate. The viscosity properties of the native granular starch and the grafted starches were determined using a Rapid visco analyzer (RVA) and rheological properties by frequency sweep test under different conditions using a rheometer. Some of the grafted starches exhibited significantly higher and some others exhibited drastically reduced peak viscosity values irrespective of the percentage grafting. All the grafted starches exhibited very good viscosity stability as evidenced from the highly reduced breakdown and higher final viscosity values in comparison to native cassava starch. Thermal analysis of the pure granular cassava starch and grafted starches was carried out using a differential scanning calorimetry (DSC) and thermogravimetry. DSC studies showed that in comparison to native starch, the grafted starches showed lower temperatures of transition. The thermal stability of cassava starch was enhanced by grafting as observed from the thermogravimetric data. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of Cross‐linking with Epichlorohydrin on the Properties of Cassava (Manihot esculenta Crantz) Starch

Cassava starch was cross‐linked with epichlorohydrin (EPI) at 45°C for 2 h in three different media which include water, water in the presence of a phase transfer catalyst (PTC) and N,N‐dimethylformamide (DMF). The products were characterized by determining their physicochemical, thermal and retrogradation properties. In aqueous medium, the use of a PTC, tetrabutylammonium bromide (TBAB) produced derivatives with higher degree of cross‐linking than those prepared without the use of the catalyst. The degree of cross‐linking was found to be higher using the same concentration of EPI when the reaction was carried out in DMF. At low levels of cross‐linking, the peak viscosity of the cross‐linked starches increased in comparison to that of the native starch. With increasing degree of cross‐linking, the peak viscosity showed a significant reduction. The swelling volume, solubility and light transmittance of the starch pastes were lower for the modified starches. The cross‐linked starches showed slightly reduced values for the gelatinization temperatures, T_onset, T_peak and T_end. The enthalpy of gelatinization of the modified starches increased with increase in the degree of cross‐linking. The modified starches exhibited higher water‐binding capacities (WBC) than the native starch; but with increase in the degree of cross‐linking, there was a gradual decrease in WBC. The in vitro alpha amylase digestibility of the modified starches decreased gradually with increase in the level of cross‐linking.