Cécile Zakri

Shape and Temperature Memory of Nanocomposites with Broadened Glass Transition

Shape-memory polymers can revert to their original shape when they are reheated. The stress generated by shape recovery is a growing function of the energy absorbed during deformation at a high temperature; thus, high energy to failure is a necessary condition for strong shape-memory materials. We report on the properties of composite nanotube fibers that exhibit this particular feature. We observed that these composites can generate a stress upon shape recovery up to two orders of magnitude greater than that generated by conventional polymers. In addition, the nanoparticles induce a broadening of the glass transition and a temperature memory with a peak of recovery stress at the temperature of their initial deformation.

Characterization of the growth of 2D protein crystals on a lipid monolayer by ellipsometry and rigidity measurements coupled to electron microscopy.

We present here some sensitive optical and mechanical experiments for monitoring the process of formation and growth of two-dimensional (2D) crystals of proteins on a lipid monolayer at an air-water interface. The adsorption of proteins on the lipid monolayer was monitored by ellipsometry measurements. An instrument was developed to measure the shear elastic constant (in plane rigidity) of the monolayer. These experiments have been done using cholera toxin B subunit (CTB) and annexin V as model proteins interacting with a monosialoganglioside (GM1) and dioleoylphosphatidylserine (DOPS), respectively. Electron microscopy observations of the protein-lipid layer transferred to grids were systematically used as a control. We found a good correlation between the measured in-plane rigidity of the monolayer and the presence of large crystalline domains observed by electron microscopy grids. Our interpretation of these data is that the crystallization process of proteins on a lipid monolayer passes through at least three successive stages: 1) molecular recognition between protein and lipid-ligand, i.e., adsorption of the protein on the lipid layer; 2) nucleation and growth of crystalline patches whose percolation is detected by the appearance of a non-zero in-plane rigidity; and 3) annealing of the layer producing a slower increase of the lateral or in-plane rigidity.

Anisotropic Thin Films of Single-Wall Carbon Nanotubes from Aligned Lyotropic Nematic Suspensions

Lyotropic nematic aqueous suspensions of single-wall carbon nanotubes can be uniformly aligned in thin cells by shearing. Homogeneous anisotropic thin films of nanotubes can be prepared by drying the nematic. Optical transmission between parallel or crossed polarizers is measured and described in order to estimate the dichroic ratio. The order parameter is measured using polarized Raman spectroscopy and found to be quite weak due to entanglement of the nanotubes and/or to an intrinsic viscoelastic behavior of the nanotube suspensions.

Phase behavior of nanotube suspensions: from attraction induced percolation to liquid crystalline phases

This article presents an overview of recent studies on the behavior of carbon nanotube dispersions. The effect of attractive interactions on the percolation threshold is investigated. Contrary to this, we show that carbon nanotubes experiencing repulsive interactions exhibit a different phase behavior including liquid crystallinity.

Correlation of properties with preferred orientation in coagulated and stretch-aligned single-wall carbon nanotubes

We report structure-property correlations in single-wall carbon nanotube (SWNT) fibers, among electrical, thermal, and chemical parameters with respect to stretch-induced preferential SWNT alignment along the fiber axis. Purified HiPco (high-pressure CO) conversion tubes are dispersed with the aid of an anionic surfactant and coagulated in the co-flowing stream of an adsorbing polymer. The fibers are then dried, rewetted under tensile load, and redried to improve the alignment. Complete removal of the polymer was assured by annealing in hydrogen at 1000°C. The degree of alignment was determined by x-ray scattering from individual fibers using a two-dimensional detector. The half width at half maximum describing the axially symmetric distribution of SWNT axes decreases linearly from 27.5° in the initial extruded fiber to 14.5° after stretching by 80%. The electrical resistivity ρ at 300K decreases overall by a factor ∼4 with stretching, for both as-spun composite and polymer-free annealed fibers. However, ...

Carbon nanotubes and liquid crystalline phases

This paper presents a review of the literature that deals with carbon nanotubes (CNTs) and liquid crystals (LCs) focusing on two main aspects. First, we describe the liquid crystalline behaviour of carbon nanotubes in solution. Via functionalization or absorption of amphiphilic molecules, CNTs can form nematic phases in water for concentrations above a few percents. Second, we explore the work done on the insertion of CNTs into thermotropic or lyotropic LCs. It is shown that it is possible to disperse small quantities of CNTs in various LC matrices and that the CNTs are responding to the LC director field. In some cases the CNTs are also strongly modifying the LC properties. These promising results indicate that carbon nanotubes and liquid crystals will certainly play an important role in the development of future applications and functional materials.

Graphene liquid crystal retarded percolation for new high-k materials.

Graphene flakes with giant shape anisotropy are extensively used to establish connectedness electrical percolation in various heterogeneous systems. However, the percolation behaviour of graphene flakes has been recently predicted to be far more complicated than generally anticipated on the basis of excluded volume arguments. Here we confirm experimentally that graphene flakes self-assemble into nematic liquid crystals below the onset of percolation. The competition of percolation and liquid crystal transition provides a new route towards high-k materials. Indeed, near-percolated liquid-crystalline graphene-based composites display unprecedented dielectric properties with a dielectric constant improved by 260-fold increase as compared with the polymer matrix, while maintaining the loss tangent as low as 0.4. This performance is shown to depend on the structure of monodomains of graphene liquid-crystalline phases. Insights into how the liquid crystal phase transition interferes with percolation transition and thus alters the dielectric constant are discussed.

Dispersion and film-forming properties of poly(acrylic acid)-stabilized carbon nanotubes.

We present a detailed study of the influence of pH on the dispersion and film-forming properties of poly(acrylic acid)-stabilized carbon nanotubes. Poly(acrylic acid) (PAA) is a weak polyelectrolyte, with a pH-responsive behavior in aqueous solution. We obtain quantitative UV-visible measurements to show that the amount of polyelectrolyte in optimal pH conditions is weak, showing a good efficiency of the polymer as a carbon nanotube dispersing agent. The best dispersion conditions are achieved at pH 5, a value close to the pK(a) of PAA. Apart from this tenuous pH value, the PAA is not efficient at stabilizing nanotubes and atomic force microscopy allows us to explain the delicate balance between the PAA adsorption and the suspension stability. This study finally permits optimal conditions for making homogeneous and conductive composite films to be determined.

Surface-Induced Polymerization of Actin

Living cells contain a very large amount of membrane surface area, which potentially influences the direction, the kinetics, and the localization of biochemical reactions. This paper quantitatively evaluates the possibility that a lipid monolayer can adsorb actin from a nonpolymerizing solution, induce its polymerization, and form a 2D network of individual actin filaments, in conditions that forbid bulk polymerization. G- and F-actin solutions were studied beneath saturated Langmuir monolayers containing phosphatidylcholine (PC, neutral) and stearylamine (SA, a positively charged surfactant) at PC:SA = 3:1 molar ratio. Ellipsometry, tensiometry, shear elastic measurements, electron microscopy, and dark-field light microscopy were used to characterize the adsorption kinetics and the interfacial polymerization of actin. In all cases studied, actin follows a monoexponential reaction-limited adsorption with similar time constants (approximately 10(3) s). At a longer time scale the shear elasticity of the monomeric actin adsorbate increases only in the presence of lipids, to a 2D shear elastic modulus of mu approximately 30 mN/m, indicating the formation of a structure coupled to the monolayer. Electron microscopy shows the formation of a 2D network of actin filaments at the PC:SA surface, and several arguments strongly suggest that this network is indeed causing the observed elasticity. Adsorption of F-actin to PC:SA leads more quickly to a slightly more rigid interface with a modulus of mu approximately 50 mN/m.

Liquid crystals of carbon nanotubes and graphene

Liquid crystal ordering is an opportunity to develop novel materials and applications with spontaneously aligned nanotubes or graphene particles. Nevertheless, achieving high orientational order parameter and large monodomains remains a challenge. In addition, our restricted knowledge of the structure of the currently available materials is a limitation for fundamental studies and future applications. This paper presents recent methodologies that have been developed to achieve large monodomains of nematic liquid crystals. These allow quantification and increase of their order parameters. Nematic ordering provides an efficient way to prepare conductive films that exhibit anisotropic properties. In particular, it is shown how the electrical conductivity anisotropy increases with the order parameter of the nematic liquid crystal. The order parameter can be tuned by controlling the length and entanglement of the nanotubes. In the second part of the paper, recent results on graphene liquid crystals are reported. The possibility to obtain water-based liquid crystals stabilized by surfactant molecules is demonstrated. Structural and thermodynamic characterizations provide indirect but statistical information on the dimensions of the graphene flakes. From a general point of view, this work presents experimental approaches to optimize the use of nanocarbons as liquid crystals and provides new methodologies for the still challenging characterization of such materials.