Rolando Castillo

Metal particle catalysed production of nanoscale BN structures

Abstract Graphite-like nanostructures including nanotubes and encapsulated polyhedral particles have been obtained by arcing hexagonal boron nitride (h-BN) and tantalum in a nitrogen atmosphere. High resolution electron microscopy (HRTEM), electron energy loss spectroscopy (EELS) and X-ray diffraction studies have been used to study these new materials, which contain B:N ratios of ≈ 1:1. The observations reveal interesting new information on the dynamics of metal cluster catalysed nanostructure formation. The structures provide strong circumstantial evidence for the presence of B 2 N 2 squares at the tips, in addition to B 3 N 3 hexagons in the main body of the tubes.

Diffusing wave spectroscopy in Maxwellian fluids

We present a critical assessment of the diffusing wave spectroscopy (DWS) technique for obtaining the characteristic lengths and for measuring the loss and storage moduli of a reasonable well-known wormlike micelle (WM) system. For this purpose, we tracked the Brownian motion of particles using DWS embedded in a Maxwellian fluid constituted by a wormlike micellar solution made of cetyltrimethylam-monium bromide (CTAB), sodium salicylate (NaSal), and water. We found that the motion of particles was governed by the viscosity of the solvent at short times and by the stress relaxation mechanisms of the giant micelles at longer times. From the time evolution of the mean square displacement of particles, we could obtain for the WM solution the cage size where each particle is harmonically bound at short times, the long-time diffusion coefficient, and experimental values for the exponent that accounts for the broad spectrum of relaxation times at the plateau onset time found in the 〈Δr2(t)〉 vs. time curves. In addition, from the 〈Δr2(t) vs. time curves, we obtained G′(ω) and G″(ω) for the WM solutions. All the DWS microreological information allowed us to estimate the characteristic lengths of the WM network. We compare our DWS microrheological results and characteristic lengths with those obtained with mechanical rheometers at different NaSal/CTAB concentration ratios and temperatures.

HIGH RESOLUTION ELECTRON MICROSCOPY STUDIES IN CARBON SOOTS

Abstract A descriptive study using high resolution electron microscopy of fullerene-related carbon structures found in carbon soots is presented. Nanotubules, onions, small particles, carbon fibers, and tangled structures are some of the structures characterized here. Several methods, such as arc discharge, catalytic induced growth from vapor, heating, and electron irradiation were used to prepare the carbon soot samples. Several structures are reported here, such as tangled balls of graphite, self-arranged ellipsoidal graphite rings, and fiber structures grown from vapor. In the last case, we also show that the shape of the growing fiber layers is determined by the shape of the substrate particles.

Domain Growth, Pattern Formation, and Morphology Transitions in Langmuir Monolayers. A New Growth Instability

The aims of this study are the following two: (1) To show that in Langmuir monolayers (LM) at low supersaturation, domains grow forming fractal structures without an apparent orientational order trough tip splitting dynamics, where doublons are the building blocks producing domains with a seaweed shape. When supersaturation is larger, there is a morphology transition from tip splitting to side branching. Here, structures grow with a pronounced orientational order forming dendrites, which are also fractal. We observed this behavior in different Langmuir monolayers formed by nervonic acid, dioctadecylamine, ethyl stearate, and ethyl palmitate, using Brewster angle microscopy. (2) To present experimental evidence showing an important Marangoni flow during domain growth, where the hydrodynamic transport of amphipiles overwhelms diffusion. We were able to show that the equation that governs the pattern formation in LM is a Laplacian equation in the chemical potential with the appropriate boundary conditions. However, the underlying physics involved in Langmuir monolayers is different from the underlying physics in the Mullins-Sekerka instability; diffusional processes are not involved. We found a new kind of instability that leads to pattern formation, where Marangoni flow is the key factor. We also found that the equations governing pattern formation in LM can be reduced to those used in the theory of morphology diagrams for two-dimensional diffusional growth. Our experiments agree with this diagram.

Multiscale molecular dynamics simulations of micelles: coarse-grain for self-assembly and atomic resolution for finer details†

A positional interpolation/extrapolation method for the mapping of coarse-grained (CG) to atomistic (AT) resolution is presented and tested for single-component micelles formed by lysophospholipids of different chain length. The target CG nanoaggregates were self-assembled from random mixtures of surfactants in explicit MARTINI water and equilibrated by molecular dynamics simulations, at the microsecond time scale. The ambiguity inherent in the definition of the CG particles was explored by mapping the same CG structures to AT resolution surfactants of different size. After the conversion, the obtained AT micelles were simulated for 250 ns and the resulting trajectories were analyzed in detail. The mean lifetime of the surfactant–solvent interactions as well as the lateral diffusion coefficients of the surfactant molecules within the micellar aggregates were obtained for the first time. The results suggest that the individual molecules within the micelle behave like lipids in a fluid membrane. The employed mapping back method is efficient and versatile, as it can be applied to diverse combinations of force fields and systems with a minimum of code development. In a general context, this work illustrates the power of multiscale molecular dynamics simulations for the generation and subsequent examination of self-assembled structures, including the fine characterization of structural and dynamic properties of the resulting aggregate.

The Role of Boron Nitride in Graphite Plasma Arcs

Abstract Novel graphitic nanostructures (e.g. nanotubes, graphitic onions, polyhedral particles, hemitoroidal nanotube caps and branched nanotubes) are produced by arcing graphite electrodes, containing hexagonal-BN, in inert atmospheres. The introduction of BN or B inside the graphite anode generates long (≤ 20μm) and well graphitised carbon nanotubes exhibiting boron at their tips. High Resolution Electron Microscopy (HRTEM), Scaning Electron Microscopy (SEM), Electron Energy Loss Spectroscopy (EELS) and X-ray powder diffraction studies reveal the production of B4C crsytals, in addition to little amounts of BC3 nanotubes. Mass spectrometry (MS) studies over the generated soots indicate high yields of large fullerenes (e.g. C70, C76, and C84) and thermo-Gravimetric analysis (TGA) of the nanostructures show high oxidation resistance.

Microrheology and Characteristic Lengths in Wormlike Micelles made of a Zwitterionic Surfactant and SDS in Brine

We study the Brownian motion of probe particles embedded in a wormlike micellar fluid made of a zwitterionic surfactant N-tetradecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (TDPS), sodium dodecyl sulfate (SDS), and salty water to get structural and dynamical information of the micellar network. The motion of the probe particles was tracked with diffusing wave spectroscopy, and the mean square displacement as a function of time for the particles was obtained. This allowed us to obtain the long-time diffusion coefficient for microspheres moving in the micellar network and the cage size where each particle is harmonically bound at short times in that network. The bulk mechanical susceptibility of the fluid determines the response of the probe particles excited by the thermal stochastic forces. As a consequence, the mean square displacement curves allowed us to calculate the elastic (storage) and the viscous (loss) moduli as a function of the frequency. From these curves, spanning a wide frequency range, we estimated the characteristic lengths as the mesh size, the entanglement length, the persistence length, and the contour length for micellar solutions of different zwitterionic surfactant concentration, surfactant ratio ([SDS]/[TDPS]), salt concentration, and temperature. Mesh size, entanglement length, and persistence length are almost insensitive to the change of these variables. In contrast, the contour length changes in an important way. The contour length becomes shorter as the temperature increases, and it presents a peak at a surfactant ratio of ∼0.50-0.55. When salt is added to the solution, the contour length presents a peak at a salt concentration of ∼0.225 M, and in some solutions, this length can reach values of ∼12 μm. Scission energies help us to understand why the contour length first increases and then decreases when salt is added.

Langmuir monolayers of C17, C19, and C21 fatty acids: Textures, phase transitions, and localized oscillations

The phase diagrams of Langmuir monolayers of heptadecanoic (C17), nonadecanoic (C19), and heneicosanoic (C21) acids have been determined from pressure-area isotherms, and from direct observations of the monolayers using Brewster angle microscopy. In this paper, we describe the observed domains, textures and phase boundaries for all mesophases presented by these fatty acids between 2° and 45 °C. The phase diagrams of the three fatty acids can be superposed moving the temperature scale according to the number of carbons in the tail of the fatty acids. The L2/Ov phase transition, which is not detected through isotherms, was observed in all the fatty acids under study. At low temperatures, CS,L2′, and L2″ phases of C21 were observed, as well as, the transitions among them. Also, we observed in C21 a new phase located among the phases L2,L2′, and L2″. This phase was found recently, in the relative same place, in the fatty acid C20 with a tilting azimuth between the nearest-neighbor and the next nearest-neighbo...

Mean-square displacement of particles in slightly interconnected polymer networks.

Structural and viscoelastic properties of slightly interconnected polymer networks immersed in a solvent have been studied in two cases: when the polymer network is building up and when the polymer network is shrinking stepwise in a controlled way. To accomplish this goal, the mean square displacement (MSD) of embedded microspheres in the polymer network was measured as a function of time, with diffusive wave spectroscopy. Particle motion was analyzed in terms of a model, based on a Fokker-Planck type equation, developed for describing particles in Brownian motion within a network that constrain their movement. The model reproduces well the experimental features observed in the MSD vs t curves. The variation of the parameters describing the structure of the network can be understood as the polymerization comes about, and also after the successive volume contractions. In addition, from the MSD curves, the complex shear moduli were obtained in a wide range of frequencies when the network is building up, and at the different shrinking states of the network. Our microrheological results give an insight about the dynamics of embedded particles in slightly interconnected networks, which were also compared with similar results for polymers without interconnections and polymer gels.

Microrheology of solutions embedded with thread-like supramolecular structures

A family of methods uses colloidal particles as a mechanical probe for deforming the medium in conjunction with a procedure to trace the movement of the particles to get rheological information in a very wide frequency range. All of them are under the heading of microrheology. In the last decade, they have been developed up to the point of being a useful tool for understanding the structure and the dynamics of solutions with embedded thread-like supramolecular structures. This is the case of wormlike micellar solutions, which is the main interest of the paper. Here the impact of microrheology has been essential, providing structural information not easily obtained by other methods. Microrheology has also made an important contribution to the understanding of other threadlike system, as in the case of F-actin or fd virus solutions; they will also be discussed.