Polymers with dynamic (transient) bonds, often called associating polymers, have been attracting significant attention in recent years due to their unique viscoelastic properties, self-healing ability, and recyclability. Nevertheless, understanding the mechanisms and the factors controlling their macroscopic properties remains limited due to the higher complexity introduced by the dynamic bonds. In this study, small-angle X-ray scattering (SAXS), broadband dielectric spectroscopy (BDS), and rheology were applied to unravel the structure and dynamics of telechelic associating polymers with different molecular weights. SAXS measurements revealed phase separation of the functional end groups with an average cluster size of ∼2–3 nm and the distance between clusters controlled by the chain length. Borrowing the interfacial layer model analysis of BDS data from the polymer nanocomposite field, we demonstrated the presence of an interfacial polymer layer with a thickness of ∼0.7–0.9 nm surrounding these clusters. Rheological measurements showed quantitatively that the presence of the interfacial layer significantly alters the viscoelastic behavior of these materials, indicating the crucial role of the interfacial layer in defining the macroscopic mechanical properties of the studied telechelic materials. The presented results emphasize that phase separation of the functional groups in associating polymers leads to very significant changes of the viscoelastic properties, opening a promising avenue in the design of novel functional materials.

We investigate freely expanding viscoelastic sheets. The sheets are produced by the impact of drops on a quartz plate covered with a thin layer of liquid nitrogen that suppresses shear viscous dissipation as a result of the cold Leidenfrost effect. The time evolution of the sheet is simultaneously recorded from top and side views using high-speed cameras. The investigated viscoelastic fluids are Maxwell fluids, which are characterized by low elastic moduli, and relaxation times that vary over almost two orders of magnitude, thus giving access to a large spectrum of viscoelastic and elastocapillary effects. For the purposes of comparison, Newtonian fluids, with viscosity varying over three orders of magnitude, are also investigated. In this study, d(max), the maximal expansion of the sheets, and t(max) the time to reach this maximal expansion from the time at impact, are measured as a function of the impact velocity. By using a generalized damped harmonic oscillator model, we rationalize the role of capillarity, bulk elasticity and viscous dissipation in the expansion dynamics of all investigated samples. In the model, the spring constant is a combination of the surface tension and the bulk dynamic elastic modulus. The time-varying damping coefficient is associated to biaxial extensional viscous dissipation and is proportional to the dynamic loss modulus. For all samples, we find that the model reproduces accurately the experimental data for d(max) and t(max).

Downsizing electronic and electric equipment requires the optimization of electric field distributions in order to avoid localized dielectric breakdown (also called partial discharges). This paper presents a novel dielectric composite material aimed at grading electrical local surface stress. This functional material has a conductivity which increases by several orders with the applied electric field giving the ability to distribute the field by itself. It is prepared for the first time by dispersing graphite nanoplatelets in a polymer and may be used as a resistive or capacitive field grading material in electronic and electrical applications. Mechanisms at the origin of the nonlinear behavior are discussed.

Pesticide sensing is an important object of study due to its increasing use worldwide. Herein, we report a SERS study of 4-nitrophenol (PNP), which is product of neutralization processes of various pesticides such as Paraoxon, and can be used as a target molecule for monitoring. PNP is also widely used in the chemical industry and due to its high toxicity is considered a concerning pollutant. The sensing was carried out with a reduced graphene oxide nanocomposite functionalized with cysteamine and Ag nanoparticles (rGOSHAg), and compared with raw reduced graphene oxide and a commercial SERS substrates (SERStrate (TM)). A mechanistic evaluation was also carried out, focused in the degradation of PNP caused by the different exciting laser lines, evidencing the PNP dimerization in substrates containing Ag NPs (under 532 nm laser), which has important outcomes for sensing purposes. The nanocomposite rGOSHAg presented the highest sensitivity towards PNP, detecting concentrations as low as 10(-6) mol L-1 and with a high potential for field applications and real-time measurements of molecules commonly present in pesticides and industrial contaminants.

PNIPAm microgels synthesized via free radical polymerization (FRP) are often considered as neutral colloids in aqueous media, although it is well known, since the pioneering works of Pelton and coworkers, that the vanishing electrophoretic mobility characterizing swollen microgels largely increases above the lower critical solution temperature (LCST) of PNIPAm, at which microgels partially collapse. The presence of an electric charge has been attributed to the ionic initiators that are employed when FRP is performed in water and that stay anchored to microgel particles. Combining dynamic light scattering (DLS), electrophoresis, transmission electron microscopy (TEM) and atomic force microscopy (AFM) experiments, we show that collapsed ionic PNIPAm microgels undergo large mobility reversal and reentrant condensation when they are co-suspended with oppositely charged polyelectrolytes (PE) or nanoparticles (NP), while their stability remains unaffected by PE or NP addition at lower temperatures, where microgels are swollen and their charge density is low. Our results highlight a somehow double-faced electrostatic behavior of PNIPAm microgels due to their tunable charge density: they behave as quasi-neutral colloids at temperature below LCST, while they strongly interact with oppositely charged species when they are in their collapsed state. The very similar phenomenology encountered when microgels are surrounded by polylysine chains and silica nanoparticles points to the general character of this twofold behavior of PNIPAm-based colloids in water.

When a microparticle is trapped at a fluid interface, particle's electrical charge and weight combine to deform the interface. Such deformation is expected to affect the particle diffusion via hydrodynamics boundary conditions. Using available models of particle-induced electrostatic deformation of the interface and particle dynamics at the interface, we are able to analytically predict particle diffusion coefficient values in a large range of particle's contact angle and size. This might offer a solid background of numerical values to compare with for future experimental studies in the field of particle diffusion at a fluid interface.

Supramolecular associations provide a promising route to functional materials with properties such as self-healing, easy recyclability or extraordinary mechanical strength and toughness. The latter benefit especially from the transient character of the formed network, which enables dissipation of energy as well as regeneration of the internal structures. However, recent investigations revealed intrinsic limitations in the achievable mechanical enhancement. This manuscript presents studies of a set of telechelic polymers with hydrogen-bonding chain ends exhibiting an extraordinarily high, almost glass-like, rubbery plateau. This is ascribed to the segregation of the associative ends into clusters and formation of an interfacial layer surrounding these clusters. An approach adopted from the field of polymer nanocomposites provides a quantitative description of the data and reveals the strongly altered mechanical properties of the polymer in the interfacial layer. These results demonstrate how employing phase separating dynamic bonds can lead to the creation of high-performance materials.