Ramón G. Rubio

Salt-induced changes in the growth of polyelectrolyte layers of poly(diallyl-dimethylammonium chloride) and poly(4-styrene sulfonate of sodium)

Multilayers formed by the sodium salt of poly(4-styrene sulfonate), PSS, and poly(diallyldimethylammonium) chloride, PDADMAC, have been built by electrostatic self-assembly from polyelectrolyte aqueous solutions of different ionic strengths. The growth of the multilayers has been followed using dissipative quartz crystal microbalance and ellipsometry. Neutron reflectometry and XPS data indicate that the PSS and PDADMAC layers interpenetrate leading to an almost homogeneous polymer film. The results show that on increasing [NaCl] the growing process changes from a linear to a non-linear regime. The comparison of the thickness values obtained from QCM and ellipsometry has allowed us to calculate the water content of the polymer film. The results agree with those obtained by neutron reflectometry. The analysis of the QCM data has provided values of the complex shear modulus, which are typical of a rubber-like polymer system. The analysis of the mass adsorbed calculated by the ellipsometry measurements indicated that the charge compensation mechanism changes from intrinsic at low ionic strengths to mainly extrinsic at high ionic strengths. Finally, it was found that the response of a polymer film to a change in [NaCl] is rather different for films grown at low or at high ionic strengths.

Wettability of silica nanoparticle–surfactant nanocomposite interfacial layers

The hydrophobicity of a particle surface can be tuned by the addition of surfactants that change the surface free energy for their attachment to a liquid interface. In this work, we report an experimental study where the wettability properties of silica nanoparticles are modified by the adsorption of alkyltrimethylammonium surfactants (CnTAB, n = 12, 16) on the surface of the particles. We have pointed out that the wettability of the complexes is controlled by an intricate balance of electrostatic and hydrophobic interactions between the particle surface and the surfactant. These interactions play an important role in the structure of the surfactant–particle nanocomposite interfacial layer.

Particle laden fluid interfaces: Dynamics and interfacial rheology

We review the dynamics of particle laden interfaces, both particle monolayers and particle+surfactant monolayers. We also discuss the use of the Brownian motion of microparticles trapped at fluid interfaces for measuring the shear rheology of surfactant and polymer monolayers. We describe the basic concepts of interfacial rheology and the different experimental methods for measuring both dilational and shear surface complex moduli over a broad range of frequencies, with emphasis in the micro-rheology methods. In the case of particles trapped at interfaces the calculation of the diffusion coefficient from the Brownian trajectories of the particles is calculated as a function of particle surface concentration. We describe in detail the calculation in the case of subdiffusive particle dynamics. A comprehensive review of dilational and shear rheology of particle monolayers and particle+surfactant monolayers is presented. Finally the advantages and current open problems of the use of the Brownian motion of microparticles for calculating the shear complex modulus of monolayers are described in detail.

DILATATIONAL RHEOLOGY OF INSOLUBLE POLYMER MONOLAYERS : POLY(VINYLACETATE)

The dilatational rheology of the poly~vinylacetate! monolayer onto an aqueous subphase with pH52.0 has been studied between 1 °C and 25 °C. The combination of several techniques, relaxation after a step compression, oscillatory barrier experiments, electrocapillary waves, and surface light scattering ~SLS! by thermal capillary waves, has allowed us to explore a broad frequency range. The relaxation experiments show multiexponential decay curves, whose complexity increases with decreasing the temperature. A regularization technique has been used to obtain the relaxation spectra from the relaxation curves and the dilatational viscoelastic parameters have been calculated from the spectra. The oscillatory barrier experiments confirm the results obtained from the step compression experiments. The dilatational viscosity increases very steeply in the frequency range 0.1–0.001 Hz. The shapes of the relaxation spectra follow the qualitative trends predicted a model recently proposed by Noskov @Colloid Polym. Sci. 273, 263 ~1995!#. The temperature dependence of the fundamental relaxation time follows a Williams-Landel-Ferry equation above 14 °C. These results correspond to the many-chain dynamics regime. The kilohertz region has been explored by the SLS technique. These results are compatible with the existence of a single Maxwell mode, with a relaxation time that has an Arrhenius-type temperature dependence. In the intermediate-frequency regime ~10 Hz to 2 kHz! a further Maxwell process is found. It might correspond to the dynamics of loops and tails out of the surface plane. @S1063-651X~98!08012-X#

Adsorption Kinetics and Mechanical Properties of Ultrathin Polyelectrolyte Multilayers: Liquid-Supported versus Solid-Supported Films

Multilayers of sodium salt of poly(4-styrene sulfonate) (PSS) and poly(diallyl dimethyl ammonium) chloride (PDADMAC) have been built layer by layer (LbL) both at the solid/aqueous interface (solid supported) and the air/aqueous interface (liquid supported). For the solid-supported multilayers, the adsorption kinetics and the complex shear modulus were measured using a dissipative quartz crystal microbalance and a null ellipsometer. A bubble tensiometer was used to measure the adsorption kinetics and the elasticity modulus of the liquid-supported multilayers. At the solid/aqueous interface, adsorption kinetics changes with the number of adsorbed layers. However, at the air/aqueous interface, PSS dynamics were the same for all adsorbed layers except the first. Conversely, the adsorption kinetics of PDADMAC at the air/water surface differed between those layers close to the interface and those far from it. Multilayers grow at the air/water interface by an intrinsic-charge-compensation process, whereas, for the same ionic strengths, solid-supported layers deposit by the extrinsic-charge-compensation process. No significant differences were found between the recoverable dilational storage modulus of the liquid-supported multilayers and the real part of the shear modulus of the solid-supported ones built at the same ionic strength. The values of the modulus are in the MPa range, which corresponds to gel-like films. This result is in agreement with the strong hydration degree of the LbL films calculated from ellipsometry measurements.

pH-induced changes in the fabrication of multilayers of poly(acrylic acid) and chitosan: fabrication, properties, and tests as a drug storage and delivery system.

Multilayers of poly(acrylic acid), PAA, and chitosan, CHI, have been built by the layer-by-layer (LbL) method from aqueous solutions at different pH values and analyzed by the dissipative quartz crystal microbalance (D-QCM) and ellipsometry. The results showed that under all of the assembly conditions considered the growth of the films is nonlinear. The thickness of the PAA layers increases as the pH of the assembling solutions decreases, whereas the adsorption of CHI is almost unaffected by the pH conditions. The comparison of the thickness obtained by D-QCM and by ellipsometry has allowed us to calculate the water content of the films, showing that the multilayers are highly hydrated, with an average water content higher than 20%. The analysis of D-QCM data has provided high-frequency values of the complex shear modulus that are in the megapascal range and shows a transition from mainly viscous to mainly elastic behavior for the added PAA layers, depending on the pH. The monomer surface density in each layer (obtained from the combination of ellipsometry and differential refractive index measurements) indicated that the monomer density depends on the assembly conditions. It was found that the adsorption kinetics is a bimodal process, with characteristic times that depend on the number and nature of the layers. Finally, the possibility of using of these multilayers as a drug storage and delivery system has been evaluated.

Polymer-surfactant systems in bulk and at fluid interfaces.

The interest of polymer-surfactant systems has undergone a spectacular development in the last thirty years due to their complex behavior and their importance in different industrial sectors. The importance can be mainly associated with the rich phase behavior of these mixtures that confers a wide range of physico-chemical properties to the complexes formed by polymers and surfactants, both in bulk and at the interfaces. This latter aspect is especially relevant because of the use of their mixture for the stabilization of dispersed systems such as foams and emulsions, with an increasing interest in several fields such as cosmetic, food science or fabrication of controlled drug delivery structures. This review presents a comprehensive analysis of different aspects related to the phase behavior of these mixtures and their intriguing behavior after adsorption at the liquid/air interface. A discussion of some physical properties of the bulk is also included. The discussion clearly points out that much more work is needed for obtaining the necessary insights for designing polymer-surfactant mixtures for specific applications.

Polymer monolayers with a small viscoelastic linear regime: equilibrium and rheology of poly(octadecyl acrylate) and poly(vinyl stearate).

The equilibrium properties of monolayers of two polymers: poly(octadecyl acrylate) and poly(vinyl stearate) on water have been measured. The surface pressure (Pi) versus surface concentration (Gamma) curves indicate that the water-air interface is a poor solvent for both polymers. The thermal expansivity shows a sharp change near room temperature. This behavior is typical of a glass transition; this is the first time that such a plot is observed for Langmuir films. The Pi vs Gamma curves measured by the continuous compression method show strong anisotropy effects. They also show that the monolayer is brought into nonequilibrium states depending on the compression rate. Within the linear regime, the relaxation experiments were bimodal. The longest relaxation time strongly increases as T is decreased, which might be compatible with the high increase of viscosity in the glass transition. The oscillatory barrier experiments showed that the maximum strain of the linear regime is smaller than 3% for both monolayers. The Fourier-transform analysis of the oscillatory experiments beyond the linear regime points out the contribution of different harmonics in the response function. Oscillations in the nonlinear regime show hysteresis cycles. The results obtained indicate that some of the previously published data for these polymer monolayers correspond to nonequilibrium states.

Spreading of Aqueous Solutions of Trisiloxanes and Conventional Surfactants over PTFE AF Coated Silicone Wafers

Kinetics of spreading of aqueous trisiloxane surfactant T(n) (with n = 4, 6, and 8 ethoxy groups) solutions and conventional aqueous surfactant solutions (Tween 20, C12E4, SDS) over silicon wafers coated with PTFE AF is experimentally investigated. It has been found that trisiloxane solutions spread on highly hydrophobic PTFE AF coated silicone wafers; however, they do not show superspreading behavior on these highly hydrophobic substrates. Solutions of conventional nonionic surfactants investigated show kinetics of spreading similar to trisiloxanes. Three regimes of spreading have been identified (i) complete non-wetting during the spreading process at low concentrations, (ii) a transition from initial nonwetting to partial wetting at the end of the spreading process at intermediate concentrations, and (iii) partial wetting both at the beginning and the end of the spreading process at higher concentrations. Transition from the first regime (i) to the second regime (ii) takes place at the critical aggregation concentration (CAC) or critical micelle concentration (CMC), transition from regime (ii) to regime (iii) happens at the critical wetting concentration (CWC). In the case of regime (i) the spreading of nonionic surfactants solutions investigated on PTFE AF coated silicone wafers is slow and follows a theoretically predicted law (Starov; et al. J. Colloid Interface Sci. 2000, 227 (1), 185). In the case of regimes (ii) and (iii), the spreading of the nonionic surfactant solutions investigated proceeds in two stages: the fast short first stage, which is followed by a much slower second stage. It is shown that the slow stage develops according to a previously described theoretical model. According to this theory the surfactant molecules adsorb in front of the moving three-phase contact line (autophilic phenomenon), which results in a partial hydrophilisation of an initially hydrophobic substrate and a spreading as a consequence. We assume that the first stage of the spreading is related to the disintegration of surfactant aggregates in the vicinity of the moving three-phase contact line.

Dilational rheology of Langmuir polymer monolayers: Poor-solvent conditions

The viscoelastic moduli (elasticity and dilational viscosity) of monolayers of P4HS have been studied over a broad frequency range (0.1 mHz–200 kHz) using a combination of relaxation and capillary waves techniques. The analysis of the surface pressure, the elasticity and the viscosity in the semidilute regime show that the air–water interface is a poor (near-Θ) solvent for the monolayer. The results of viscoelastic moduli show that there is a broad relaxation process in the low-frequency range (ω<1 Hz), and another very intense relaxation process centered in the kHz region. This behavior contrasts with the one previously found for PVAc, a polymer for which the interface is a good solvent. For PVAc the relaxation found at low frequencies is much narrower, and two processes are clearly distinguished at higher frequencies: one centered at 500 Hz and another one at 40 kHz.