Influence of an adsorbing polymer in the aging dynamics of Laponite clay suspensions

Clay-polymer dispersions in aqueous solutions have attracted a great interest in recent years due to their industrial applications and intriguing physical properties. Aqueous solutions of bare Laponite particles are known to age spontaneously from an ergodic state to a non ergodic state in a time varying from hours to months depending on Laponite concentration. When a polymer species like Polyethylene Oxide (PEO) is added to the solution, it weakly adsorbs on clay particle surfaces modifying the effective interaction potential between Laponite particles. A dynamic light scattering study, varying polymer concentration at fixed polymer molecular weight (Mw=200.000 g/mol), has been performed in order to understand the effect of polymer on the aging dynamics of the system. The results obtained show that arresting phenomena between clay particles are hindered if PEO is added and consequently the aging dynamics slows down with increasing PEO concentration. This process is possibly due to the progressive coverage of the clay surface by polymers that grow with increasing PEO concentration and may lead to steric stabilization.Comment: 13 pages, 6 figures, manuscript accepted for publication on Philosophical Magazin

Routes to gelation in a clay suspension

The gelation of water suspension of a synthetic clay (Laponite) has been studied by dynamic light scattering in a wide range of clay weight concentration (Cw = 0.003-0.031). At variance with previous determination, indicating a stable liquid phase for Cw < Cw*=0.015-0.018, we find that the gelation takes actually place in the whole examined Cw range. More importantly, we find that Cw* marks the transition between two different routes to gelation. We hypothesize that at low concentration Laponite suspension behaves as an attractive colloid and that the slowing down of the dynamics is attained by the formation of larger and larger clusters while at high concentration the basic units of the gel could be the Debye Huckel spheres associated to single Laponite plates.Comment: 5 pages, 4 figure

More on phase diagram of Laponite

The phase diagram of a charged colloidal system (Laponite) has been investigated by dynamic light scattering in a previously unexplored range of salt and clay concentrations. Specifically the clay weight and salt molar concentrations have been varied in the ranges Cw=0.004- 0.025, Cs=(1x 10^-3- 5x 10^-3) M respectively. As in the case of free salt water samples (Cs= 1x 10^-4 M) an aging dynamics towards two different arrested phases is found in the whole examined Cw and Cs range. Moreover a transition between these two different regimes is found for each investigated salt concentration. It is clear from these measurements that a revision of the phase diagram is necessary and a new "transition" line between two different arrested states is drawn.Comment: 16 pages, 5 figures, submitted to Langmui

Polaron Crystallization and Melting: Effects of the Long-Range Coulomb Forces

On examining the stability of a Wigner crystal in an ionic dielectric, two competitive effects due to the polaron formation are found to be important: (i) the screening of the Coulomb force, which destabilizes the crystal, compensated by (ii) the increase of the carrier mass (polaron mass). The competition between the two effects is carefully studied, and the quantum melting of the polaronic Wigner crystal is examined by varying the density at zero temperature. By calculating the quantum fluctuations of both the electron and the polarization, we show that there is a competition between the dissociation of the polarons at the insulator-to-metal transition (IMT), and a melting towards a polaron liquid. We find that at strong coupling, a liquid state of dielectric polarons cannot exist, and the IMT is driven by the polaron dissociation. Next, taking into account the dipolar interactions between localized carriers, we show that these are responsible for an instability of the transverse vibrational modes of the polaronic Wigner crystal as the density increases. This provides a new mechanism for the IMT in doped dielectrics, which yields interesting dielectric properties below and beyond the transition. An optical signature of such a mechanism for the IMT is provided.Comment: 10 pages, 3 figures, to be published in Int.J.Mod.Phys.

Aging of the Nonlinear Optical Susceptibility of colloidal solutions

Using Z-scan and dynamic light scattering measurements we investigate the nonlinear optics response of a colloidal solution undergoing dynamics slowing down with age. We study the high optical nonlinearity of an organic dye (Rhodamine B) dispersed in a water-clay (Laponite) solution, at different clay concentrations (2.0 wt% - 2.6 wt%), experiencing the gelation process. We determine the clay platelets self diffusion coefficient and, by its comparison with the structural relaxation time, we conclude that the gelation process proceeds through the structuring of interconnecting clay platelets network rather than through clusters growth and aggregation.Comment: 4 figures, 4 page

Photodynamic Therapy of Necrobiosis Lipoidica - A Multicenter Study of 18 Patients

Background: Necrobiosis lipoidica (NL) is a granulomatous skin disease of unknown origin, and no reliably effective treatment option exists to handle this often disfiguring disease. Recently, a patient with long-lasting NL was reported to be cured by topical photodynamic therapy (PDT). Objective: To evaluate the overall potential of PDT in the treatment of NL on the lower legs. Methods: Retrospective study of 18 patients (aged 16 - 62 years) from 3 European university departments of dermatology treated with PDT for NL. Methyl aminolevulinate or 5-aminolevulinic acid were used as topically applied photosensitizers. Illumination followed with red light-emitting diode light. Results: Complete response was seen in 1/18 patients after 9 PDT cycles, and partial response in 6/18 patients (2 - 14 PDT cycles) giving an overall response rate of 39% (7/18). Conclusion: Although almost 40% of the cases showed some degree of response, PDT cannot currently be recommended as first-line therapy of NL. Subpopulations of therapy-resistant NL patients may, however, benefit from PDT. Copyright (C) 2008 S. Karger AG, Base

Charge-density wave formation in Sr_{14}Cu_{24}O_{41}

The electrodynamic response of the spin-ladder compound Sr$_{14-x}$Ca$_x$Cu$_{24}$O$_{41}$ ($x=0, 3, 9$) has been studied from radiofrequencies up to the infrared. At temperatures below 250 K a pronounced absorption peak appears around 12 cm$^{-1}$ in Sr$_{14}$Cu$_{24}$O$_{41}$ for the radiation polarized along the chains/ladders (${\bf E}\parallel {\bf c}$). In addition a strongly temperature dependent dielectric relaxation is observed in the kHz - MHz range. We explain this behavior by a charge density wave which develops in the ladders sub-system and produces a mode pinned at 12 cm$^{-1}$. With increasing Ca doping the mode shifts up in frequency and eventually disappears for $x=9$ because the dimensionality of the system crosses over from one to two dimensions, giving way to the superconducting ground state under pressure.Comment: One name added to author list 4 pages, 2 figures, email: [email protected]

Competing interactions in arrested states of colloidal clays

Using experiments, theory and simulations, we show that the arrested state observed in a colloidal clay at intermediate concentrations is stabilized by the screened Coulomb repulsion (Wigner glass). Dilution experiments allow us to distinguish this high-concentration disconnected state, which melts upon addition of water, from a low-concentration gel state, which does not melt. Theoretical modelling and simulations reproduce the measured Small Angle X-Ray Scattering static structure factors and confirm the long-range electrostatic nature of the arrested structure. These findings are attributed to the different timescales controlling the competing attractive and repulsive interactions.Comment: Accepted for publication in Physical Review Letter

Anisotropic Charge Modulation in Ladder Planes of Sr_14-xCa_xCu_24O_41

The charge response of the ladders in Sr_14-xCa_xCu_24O_41 is characterized by dc resistivity, low frequency dielectric and optical spectroscopy in all three crystallographic directions. The collective charge-density wave screened mode is observed in the direction of the rungs for x=0, 3 and 6, in addition to the mode along the legs. For x=8 and 9, the charge-density-wave response along the rungs fully vanishes, while the one along the legs persists. The transport perpendicular to the planes is always dominated by hopping.Comment: 4 pages, 3 figures, submitted to PRB R