Adsorption of biopolymers onto nanocelluloses for the fabrication of hollow microcapsules

In this work, we studied the multilayer adsorption of cellulose nanocrystals and cellulose nanofibers with other polysaccharides such as xyloglucan and chitosan. We showed that the specific interactions between these biopolymers can be exploited to prepare three-dimensional functional materials. Quartz crystal microbalance studies showed that both biopolymers were adsorbed irreversibly on the nanocellulose surfaces. In aqueous media, the maximum amount of adsorbed polymer was higher for the smaller and more crystalline cellulose nanocrystals, compared to cellulose nanofibers. For both nanocelluloses employed, the amount of xyloglucan of the first bilayer was larger than the amount of chitosan adsorbed. Ellipsometry showed that both xyloglucan and chitosan were adsorbed on nanocellulose surfaces. However, at the second layer no mass change was detected by quartz crystal microbalance when xyloglucan was added, while for addition of successive layers of chitosan a decrease of frequency was detected. The water uptake of multilayers was higher for cellulose nanocrystals than for nanofibers, which was ascribed the presence of voids in the nanocrystal layer. Finally, we demonstrated that multilayer adsorption of these biopolymers can be performed on calcium carbonate sacrificial templates, which can then be removed to yield hollow polysaccharide microcapsules.

Structure and Dynamics of Highly Attractive Polymer Nanocomposites in the Semi-Dilute Regime: The Role of Interfacial Domains and Bridging Chains

Detailed molecular dynamics (MD) simulations are employed to study how the presence of adsorbed domains and nanoparticle bridging chains affect the structural, conformational, thermodynamic, and dynamic properties of attractive polymer nanocomposite melts in the semi-dilute regime. As a model system we have chosen an unentangled poly(ethylene glycol) (PEG) matrix containing amorphous spherical silica nanoparticles with different diameters and at different concentrations. Emphasis is placed on properties such as the polymer mass density profile around nanoparticles, the compressibility of the system, the mean squared end-to-end distance of PEG chains, their orientational and diffusive dynamics, the single chain form factor, and the scattering functions. Our analysis reveals a significant impact of the adsorbed, interfacial polymer on the microscopic dynamic and conformational properties of the nanocomposite, especially under conditions favoring higher surface-to-volume ratios (e.g., for small nanoparticle sizes at fixed nanoparticle loading, or for higher silica concentrations). Simultaneously, adsorbed polymer chains adopt graft-like conformations, a feature that allows them to considerably extend away from the nanoparticle surface to form bridges with other nanoparticles. These bridges drive the formation of a nanoparticle network whose strength (number of tie chains per nanoparticle) increases substantially with increasing concentration of the polymer matrix in nanoparticles, or with decreasing nanoparticle size at fixed nanoparticle concentration. The presence of hydroxyl groups at the ends of PEG chains plays a key role in the formation of the network. If hydroxyl groups are substituted by methoxy ones, the simulations reveal that the number of bridging chains per nanoparticle decreases dramatically, thus the network formed is less dense and less strong mechanically, and has a smaller impact on the properties of the nanocomposite. Our simulations predict further that the isothermal compressibility and thermal expansion coefficient of PEG-silica nanocomposites are significantly lower than those of pure PEG, with their values decreasing practically linear with increasing concentration of the nanocomposite in nanoparticles.

RuSseL: A Self-Consistent Field Theory Code for Inhomogeneous Polymer Interphases

In this article, we publish the one-dimensional version of our in-house code, RuSseL, which has been developed to address polymeric interfaces through Self-Consistent Field calculations. RuSseL can be used for a wide variety of systems in planar and spherical geometries, such as free films, cavities, adsorbed polymer films, polymer-grafted surfaces, and nanoparticles in melt and vacuum phases. The code includes a wide variety of functional potentials for the description of solid–polymer interactions, allowing the user to tune the density profiles and the degree of wetting by the polymer melt. Based on the solution of the Edwards diffusion equation, the equilibrium structural properties and thermodynamics of polymer melts in contact with solid or gas surfaces can be described. We have extended the formulation of Schmid to investigate systems comprising polymer chains, which are chemically grafted on the solid surfaces. We present important details concerning the iterative scheme required to equilibrate the self-consistent field and provide a thorough description of the code. This article will serve as a technical reference for our works addressing one-dimensional polymer interphases with Self-Consistent Field theory. It has been prepared as a guide to anyone who wishes to reproduce our calculations. To this end, we discuss the current possibilities of the code, its performance, and some thoughts for future extensions.

Deposition of Synthetic and Bio-Based Polycations onto Negatively Charged Solid Surfaces: Effect of the Polymer Cationicity, Ionic Strength, and the Addition of an Anionic Surfactant

The deposition of layers of different polycations (synthetic or derived from natural, renewable resources) onto oppositely charged surfaces has been studied using ellipsometry and quartz crystal microbalance with dissipation monitoring (QCM-D). Information about the thickness of the deposited layers and their water content was ascertained. The adsorption of the different polycations onto negatively charged surfaces was found to be a complex process, which is influenced by the chemical nature of the polymer chains, ionic strength, polymer concentration and the addition of additives such as surfactants. The experimental picture shows a good agreement with theoretical calculations performed using the Self-Consistent Mean Field (SCF) approach. The results show that the electrostatically-driven deposition can be tuned by modifying the physico-chemical properties of the solutions and the chemical nature of the adsorbed polymer. This versatile approach is a big step forward in aiding the design of new polymers for many industrial applications and, in particular, the design of sustainable washing formulations for cosmetic applications.

Capacitance of thin films containing polymerized ionic liquids

Electrode-polymer interfaces dictate many of the properties of thin films such as capacitance, the electric field experienced by polymers, and charge transport. However, structure and dynamics of charged polymers near electrodes remain poorly understood, especially in the high concentration limit representative of the melts. To develop an understanding of electric field–induced transformations of electrode-polymer interfaces, we have studied electrified interfaces of an imidazolium-based polymerized ionic liquid (PolyIL) using combinations of broadband dielectric spectroscopy, specular neutron reflectivity, and simulations based on the Rayleigh’s dissipation function formalism. Overall, we obtained the camel-shaped dependence of the capacitance on applied voltage, which originated from the responses of an adsorbed polymer layer to applied voltages. This work provides additional insights related to the effects of molecular weight in affecting structure and properties of electrode-polymer interfaces, which are essential for designing next-generation energy storage and harvesting devices.