arXiv subjects

Patrick Davidson

Publications and source records attributed to Patrick Davidson.

17 recordsLinked to original sources

arXiv2023

Charge-Driven Liquid-Crystalline Behavior of Ligand-Functionalized Nanorods in Apolar Solvent

Concentrated colloidal suspensions of nanorods often exhibit liquid-crystalline (LC) behavior. The transition to a nematic LC phase, with long-range orientational order of the particles, is usually well captured by Onsager's theory for hard rods, at least qualitatively. The theory shows how the volume fraction at the transition decreases with increasing aspect ratio of the rods. It also explains that the long-range electrostatic repulsive interaction occurring between rods stabilized by their surface charge can significantly increase their effective diameter, resulting in a decrease of the volume fraction at the transition, as compared to sterically stabilized rods. Here, we report on a system of ligand-stabilized LaPO4 nanorods, of aspect ratio around 11, dispersed in apolar medium exhibiting the counter-intuitive observation that the onset of nematic self-assembly occurs at an extremely low volume fraction of around 0.25%, which is lower than observed (around 3%) with the same particles when charge-stabilized in polar solvent. Furthermore, the nanorod volume fraction at the transition increases with increasing concentration of ligands, in a similar way as in polar media where increasing the ionic strength leads to surface-charge screening. This peculiar system was investigated by dynamic light scattering, Fourier-Transform Infra-Red spectroscopy, zetametry, electron microscopy, polarized-light microscopy, photoluminescence measurements, and X-ray scattering. Based on these experimental data, we formulate several tentative scenarios that might explain this unexpected phase behavior. However, at this stage, its full understanding remains a pending theoretical challenge. Nevertheless, this study shows that dispersing anisotropic nanoparticles in an apolar solvent may sometimes lead to spontaneous ordering events that defy our intuitive ideas about colloidal systems.

cond-mat.soft↗

arXiv2019

Probing Permanent Dipoles in CdSe Nanoplatelets with Transient Electric Birefringence

Zinc-blende CdSe semiconducting nanoplatelets (NPL) show outstanding quantum confinement properties thanks to their small, atomically-controlled, thickness. For example, they display extremely sharp absorption peaks that make them very interesting objects for optoelectronic applications. However, the presence of a ground-state electric dipole for these nanoparticles has not yet been investigated. We therefore used transient electric birefringence (TEB) to probe the electric dipole of 5-monolayer thick zinc-blende CdSe NPL with a parallelepipedic shape. We studied a dilute dispersion of isolated NPL coated with branched ligands and we measured, as a function of time, the birefringence induced by DC and AC field pulses. The electro-optic behavior proves the presence of a large dipolar moment (> 245 D) oriented along the length of the platelets. We then induced the slow face-to-face stacking of the NPL by adding oleic acid. In these stacks, the in-plane dipole components of consecutive NPL cancel whereas their normal components add. Moreover, interestingly, the excess polarizability tensor of the NPL stacks gives rise to an electro-optic contribution opposite to that of the electric dipole. By monitoring the TEB signal of the slowly-growing stacks over up to a year, we extracted the evolution of their average length with time and we showed that their electro-optic response can be explained by the presence of a 80 D dipolar component parallel to their normal. In spite of the $\bar{4}$3m space group of bulk ZB CdSe, these NPL thus bear an important ground-state dipole whose magnitude per unit volume is twice that found for wurtzite CdSe nanorods. We discuss the possible origin of this electric dipole, its consequences for the optical properties of these nanoparticles, and how it could explain their strong stacking propensity that severely hampers their colloidal stability.

physics.app-ph↗

arXiv2017

Electric-field induced shape transition of nematic tactoids

The occurrence of new textures of liquid crystals is an important factor in tuning their optical and photonics properties. Here, we show, both experimentally and by numerical computation, that under an electric field chitin tactoids (i.e. nematic droplets) can stretch to aspect ratios of more than 15, leading to a transition from a spindle-like to a cigar-like shape. We argue that the large extensions occur because the elastic contribution to the free energy is dominated by the anchoring. We demonstrate that the elongation involves hydrodynamic flow and is reversible, the tactoids return to their original shapes upon removing the field.

cond-mat.soft↗

arXiv2016

Stable freestanding thin films of copolymer melts far from the glass transition

Thin polymer films have attracted attention because of both their broad range of applications and of the fundamental questions they raise regarding the dynamic response of confined polymers. These films are unstable if the temperature is above their glass transition temperature Tg. Here, we describe freestanding thin films of centimetric dimensions made of a comb copolymer melt far from its glass transition that are stable for more than a day. These long lifetimes allowed us to characterize the drainage dynamics and the thickness profile of the films. Stratified regions appear as the film drains. We have evidence that the stability, thinning dynamics and thickness profile of the films result from structural forces in the melt. Understanding the key mechanisms behind our observations may lead to new developments in polymeric thin films, foams and emulsions without the use of stabilizing agents.

cond-mat.soft↗

arXiv2015

Hybrid Nanocomposites with Tunable Alignment of the Magnetic Nanorod Filler

For many important applications, the performance of polymer-anisotropic particle nanocomposite materials strongly depends on the orientation of the nanoparticles. Using the very peculiar magnetic properties of goethite ({\alpha}-FeOOH) nanorods, we produced goethite-poly(hydroxyethyl methacrylate) nanocomposites in which the alignment direction and the level of orientation of the nanorods could easily be tuned by simply adjusting the intensity of a magnetic field applied during polymerization. Because the particle volume fraction was kept low (1-5.5 vol \%), we used the orientational order induced by the field in the isotropic phase rather than the spontaneous orientational order of the nematic phase. At the strongest field values (up to 1.5 T), the particles exhibit almost perfect antinematic alignment, as measured by optical birefringence and small-angle X-ray scattering. The results of these two techniques are in remarkably good agreement, validating the use of birefringence measurements for quantifying the degree of orientational order. We also demonstrate that the ordering induced by the field in the isotropic suspension is preserved in the final material after field removal. This work illustrates the interest, for such problems, of considering the field-induced alignment of anisotropic nanoparticles in the isotropic phase, an approach that is effective at low filler content, that avoids the need of controlling the nematic texture, and that allows tuning of the orientation level of the particles at will simply by adjusting the field intensity.

cond-mat.soft↗

arXiv2015

Magnetic Nanorods Confined in a Lamellar Lyotropic Phase

The dilute lamellar phase of the nonionic surfactant C$_{12}$EO$_5$ was doped with goethite (iron oxide) nanorods up to a fraction of 5 vol. %. The interaction between the inclusions and the host phase was studied by polarized optical microscopy (with or without an applied magnetic field) and by small-angle X-ray scattering. We find that, when the orientation of the nanorods is modified using the magnetic field, the texture of the lamellar phase changes accordingly; one can thus induce a homeotropic-planar reorientation transition. On the other hand, the lamellar phase induces an attractive interaction between the nanorods. In more concentrated lamellar phases (under stronger confinement) the particles form aggregates. This behavior is not encountered for a similar system doped with spherical particles, emphasizing the role of particle shape in the interaction between doping particles and the host phase.

cond-mat.soft↗

arXiv2015

Connectivity of the Hexagonal, Cubic, and Isotropic Phases of the C$_{12}$EO$_6$/H$_2$O Lyotropic Mixture Investigated by Tracer Diffusion and X-ray Scattering

The connectivity of the hydrophobic medium in the nonionic binary system C$_{12}$EO$_6$/H$_2$O is studied by monitoring the diffusion constants of tracer molecules at the transition between the hexagonal mesophase and the fluid isotropic phase. The increase in the transverse diffusion coefficient on approaching the isotropic phase reveals the proliferation of bridgelike defects connecting the surfactant cylinders. This suggests that the isotropic phase has a highly connected structure. Indeed, we find similar diffusion coefficients in the isotropic and cubic bicontinuous phases. The temperature dependence of the lattice parameter in the hexagonal phase confirms the change in connectivity close to the hexagonal-isotropic transition. Finally, an X-ray investigation of the isotropic phase shows that its structure is locally similar to that of the hexagonal phase.

cond-mat.soft↗

arXiv2015

Lyotropic Lamellar Phase Doped with a Nematic Phase of Magnetic Nanorods

We report the elaboration of a hybrid mesophase combining the lamellar order of a lyotropic system of nonionic surfactant and the nematic order of a concentrated solution of inorganic nanorods confined between the surfactant layers. Highly aligned samples of this mesophase can be obtained by thermal annealing, and the orientation of the nanorods is readily controlled with a magnetic field. High-resolution synchrotron X-ray scattering and polarized optical microscopy show that, compared to their isolated counterparts, both the nematic and lamellar orders are altered, demonstrating their interplay.

cond-mat.soft↗

arXiv2015

Short-range dynamics of a nematic liquid-crystalline phase

Using x-ray photon correlation spectroscopy, we studied the dynamics in the nematic phase of a nanorodsuspension. The collective diffusion coefficient in the plane perpendicular to the director varies sharply with the wave vector. Combining the structure factor and the diffusion coefficient, we find that the hydrodynamic function of the phase decreases by more than a factor of 10 when going from length scales comparable to the interparticle distance toward larger values. Thus, the collective dynamics of the nematic phase experiences strong and scale-dependent slowing down, in contrast with isotropic suspensions of slender rods or of spherical particles.

cond-mat.soft↗

arXiv2015

Slow dynamics of a colloidal lamellar phase

We used x-ray photon correlation spectroscopy to study the dynamics in the lamellar phase of a platelet suspension as a function of the particle concentration. We measured the collective diffusion coefficient along the director of the phase, over length scales down to the interparticle distance, and quantified the hydrodynamic interaction between the particles. This interaction sets in with increasing concentration and can be described qualitatively by a simplified model. No change in the microscopic structure or dynamics is observed at the transition between the fluid and the gel-like lamellar phases.

cond-mat.soft↗

arXiv2015

Repulsion Between Inorganic Particles Inserted Within Surfactant Bilayers

We study by synchrotron small-angle x-ray scattering highly aligned lamellar phases of a zwitterionic surfactant, doped with monodisperse and spherical hydrophobic inorganic particles as a function of particle concentration. Analysis of the structure factor of the two-dimensional fluid formed by the particles in the plane of the bilayer gives access to their membrane-mediated interaction, which is repulsive, with a contact value of about 4k$_{\text{B}}$T and a range of 14 {\AA}. Systematic application of this technique should lead to a better understanding of the interaction between membrane inclusions.

cond-mat.soft↗

arXiv2015

Morphology of gold nanoparticles determined by full-curve fitting of the light absorption spectrum. Comparison with X-ray scattering and electron microscopy data

UV-Vis absorption spectroscopy is frequently used to characterize the size and shape of gold nanoparticles. We present a full-spectrum model that yields reliable results for the commonly encountered case of mixtures of spheres and rods in varying proportions. We determine the volume fractions of the two populations, the aspect ratio distribution of the nanorods (average value and variance) and the interface damping parameter. We validate the model by checking the fit results against small-angle X-ray scattering and transmission electron microscopy data and show that correctly accounting for the polydispersity in aspect ratio is essential for a quantitative description of the longitudinal plasmon peak.

cond-mat.soft↗

arXiv2015

A two-dimensional nematic phase of magnetic nanorods

We report a hybrid mesophase consisting of magnetic nanorods confined between the non-ionic surfactant bilayers of a lamellar phase. The magnetic field-induced ordering of the nanorods was measured experimentally and modeled by a two-dimensional Onsager theory including the third virial coefficient. The nanorods are strongly confined in layers, with no orientational coupling from one layer to the next. At high volume concentration they exhibit spontaneous in-plane orientational ordering and form a stack of independent two-dimensional nematic systems. This isotropic-nematic transition is first-order.

cond-mat.soft↗

arXiv2015

The interaction of charged nanoparticles at interfaces

We study charged nanoparticles adsorbed onto surfactant bilayers using small-angle scattering of synchrotron radiation. The in-plane interaction of the particles is well described by a DLVO component (measured independently in solution) and a repulsive dipolar interaction due to the presence of the interface, with an amplitude close to the theoretical prediction. We prove that charged nanoparticles at soft interfaces are well described by the classical model of Poisson-Boltzmann and van der Waals terms; as a corollary, they do not experience the like-charge attraction reported in the literature for some systems of micron-sized spheres at interfaces.

cond-mat.soft↗

arXiv2014

Interplay of anisotropy in shape and interactions in charged platelet suspensions

Motivated by the intriguing phase behavior of charged colloidal platelets, we investigate the structure and dynamics of charged repulsive disks by means of Monte-Carlo simulations. The electrostatic interactions are taken into account through an effective two-body potential, obtained within the non-linear Poisson-Boltzmann formalism, which has the form of anisotropic screened Coulomb potential. Recently, we showed that the original intrinsic anisotropy of the electrostatic potential in competition with excluded volume effects leads to a rich phase behavior that not only includes various liquid-crsytalline phases but also predicts the existence of novel structures composed of alternating nematic-antinematic sheets. Here, we examine the structural and dynamical signatures of each of the observed structures for both translational and rotational degrees of freedom. Finally, we discuss the influence of effective charge value and our results in relation to experimental findings on charged platelet suspensions.

cond-mat.soft↗

arXiv2014

Infrared dichroism of gold nanorods controlled using a magnetically addressable mesophase

Gold nanorods have unique optical properties, which make them promising candidates for building nano-structured materials using a "bottom-up" strategy. We formulate stable bulk materials with anisotropic optical properties by inserting gold and iron oxide nanorods within a lamellar mesophase. Quantitative measurements of the order parameter by modelling the absorbance spectra show that the medium is macroscopically aligned in a direction defined by an external magnetic field. Under field, the system exhibits significant absorption dichroism in the infrared range, at the position of the longitudinal plasmon peak of the gold nanorods (about 1200 nm), indicating strong confinement of these particles within the water layers of the lamellar phase. This approach can yield soft and addressable optical elements.

cond-mat.soft↗

arXiv2014

Lamellar L{\alpha} Mesophases Doped with Inorganic Nanoparticles

The development of nanostructured hybrid systems is a flourishing area of research, which brings together chemistry, physics and materials science. These systems are composed of nanoparticles with interesting properties (e.g. optical, magnetic, catalytic) dispersed within an organic matrix. Control of both the position and orientation of the particles in a precise and reproducible way is an important goal. Towards this goal, the use of lyotropic liquid crystals as host phases is a promising strategy that has prompted sustained experimental work over the last decade. Here we briefly review this field, with an emphasis on the structure and the physical characterization of these novel materials.

cond-mat.soft↗