Correction: Migration of nanoparticles across a polymer-polymer interface: theory and simulation.

Correction for 'Migration of nanoparticles across a polymer-polymer interface: theory and simulation' by Nigel Gibbions et al., Soft Matter, 2021, 17, 7294-7310, https://doi.org/10.1039/D1SM00671A.

Migration of nanoparticles across a polymer-polymer interface: theory and simulation.

We proposed recently a theoretical description for hydrodynamic flows in inhomogeneous liquids in the vicinity of solid interfaces, consistent with current theoretical descriptions of the thermodynamical equilibrium of liquids in the vicinity of solid surfaces and with the Onsager formalism for linear response theory in out-of-equilibrium liquids. We showed that these equations allow for describing diffusio-osmosis along a capillary and also wetting/dewetting dynamics of liquids on a solid substrate. We now apply this physical model to the wetting/dewetting dynamics of nano-particles in polymer blends, showing how they reach equilibrium at the interface between two liquids at rest and how they migrate from the non-preferred polymer to the preferred one under applied flow.

Diffusio-osmosis and wetting on solid surfaces: a unified description based on a virtual work principle.

In order to account for diffusio-osmosis, Derjaguin proposed long ago that there is an excess pressure confined within a layer of typically a few nanometers in the vicinity of a solid surface immersed in a liquid and resulting from the interaction between the liquid and the surface. In the presence of a composition gradient in the liquid a confined pressure gradient parallel to the surface is therefore responsible for the diffusio-osmotic flow. This picture appears in contradiction with the contact theorem of colloidal science according to which such excess pressure does not exist. We propose a theoretical description for calculating hydrodynamic flows in inhomogeneous liquids in the vicinity of solid interfaces which is consistent with the contact theorem. This approach is based on a Gibbs free energy and a virtual work principle for calculating the driving forces in the liquid due to inhomogeneous composition along a capillary and to the interaction with the solid interfaces. Our approach allows us to show that the physics at play is the same in wetting or in diffusio-osmosis experiments, as one can go continuously from the latter to the former by making composition gradients sharper. We obtain an explicit expression for the diffusio-osmotic mobility which depends on the Gibbs free energy density in the vicinity of the interface and its dependance on the solute concentration in the liquid beyond the interfacial region, and which is inversely proportional to the liquid viscosity.

Efficient polynomial analysis of magic-angle spinning sidebands and application to order parameter determination in anisotropic samples.

Chemical shift tensors in 13C solid-state NMR provide valuable localized information on the chemical bonding environment in organic matter, and deviations from isotropic static-limit powder line shapes sensitively encode dynamic-averaging or orientation effects. Studies in 13C natural abundance require magic-angle spinning (MAS), where the analysis must thus focus on spinning sidebands. We propose an alternative fitting procedure for spinning sidebands based upon a polynomial expansion that is more efficient than the common numerical solution of the powder average. The approach plays out its advantages in the determination of CST (chemical-shift tensor) principal values from spinning-sideband intensities and order parameters in non-isotropic samples, which is here illustrated with the example of stretched glassy polycarbonate.

Mechanical properties of amorphous and semi-crystalline semi-aromatic polyamides.

We investigate the mechanical properties of amorphous and semi-crystalline semi-aromatic polyamides, polyphthalamides (PPA). Three relaxation processes have been identified by DMTA which is consistent with literature for polyamide. PPA exhibit a brittle-to-ductile transition from a low impact strength to a high impact strength. At room temperature, all the studied PPA are brittle. During both tensile and compression experiments, a strain hardening behavior is observed for all the studied samples and is more pronounced in compression. The testing temperature has an influence on the strain hardening modulus, contrary to the crystallinity. Strain hardening gives properties of stability and resistance to damage.

Mechanical and ultimate properties of injection molded cellulose acetate/plasticizer materials.

The mechanical properties of injection molded plasticized cellulose acetate polymers processed with two different plasticizers (Triacetine and Diethyl phthalate) and various weight fractions comprised between 15 and 30 wt % have been investigated. Plasticized cellulose acetate exhibit a brittle-to-ductile transition from a low impact strength to a high impact strength of order 40 kJ/m². Obtaining a high impact resistance at room temperature requires plasticizer content larger than 25 wt.%. An important strain hardening is obtained for samples with both plasticizers during tensile experiment. At 15 wt.% plasticizer content, the measured strain hardening modulus is around 148 MPa at 60 °C. Different parameters influencing the strain hardening behavior have been identified: the tensile direction as compared to that of the injection flow, the temperature and the plasticizer, consistent with studies on pre-strained samples of synthetic amorphous polymers.

Miscibility and dynamical properties of cellulose acetate/plasticizer systems.

Due to its biodegradability and renewability, a great interest has been devoted to investigating cellulose acetate in order to expand its potential applications. In addition, secondary cellulose acetate (CDA) could also be considered as a model system for strongly polar polymer system. The dynamical behavior of CDA is supposed to be governed by H-bonding and dipolar interaction network. Due to their high glass transition temperature, cellulose acetate-based systems are processed when blended with plasticizers. It is thus of utmost importance to study the miscibility and plasticizing effects of various molecules. We prepared CDA films via solvent casting method with diethyl phthalate as the plasticizer. Miscibility diagrams were established by calorimetry and thermo-mechanical (DMTA) experiments. Dynamical properties were analyzed by DMTA and broadband dielectric spectroscopy. We could identify the α-relaxation of these CDA-plasticizer systems in the frequency range from 0.06 Hz to 10(6)Hz, which allowed for describing the dynamics in the so-called Williams-Landel-Ferry/Vogel-Fulcher-Tammann regime.

Dielectric relaxation of thin films of polyamide random copolymers.

We investigate the relaxation behavior of thin films of a polyamide random copolymer, PA66/6I, with various film thicknesses using dielectric relaxation spectroscopy. Two dielectric signals are observed at high temperatures, the α process and the relaxation process due to electrode polarization (the EP process). The relaxation time of the EP process has a Vogel-Fulcher-Tammann type of temperature dependence, and the glass transition temperature, T(g), evaluated from the EP process agrees very well with the T(g) determined from the thermal measurements. The fragility index derived from the EP process increases with decreasing film thickness. The relaxation time and the dielectric relaxation strength of the EP process are described by a linear function of the film thickness d for large values of d, which can be regarded as experimental evidence for the validity of attributing the observed signal to the EP process. Furthermore, there is distinct deviation from this linear law for thicknesses smaller than a critical value. This deviation observed in thinner films is associated with an increase in the mobility and/or diffusion constant of the charge carriers responsible for the EP process. The α process is located in a higher-frequency region than the EP process at high temperatures but merges with the EP process at lower temperatures near the glass transition region. The thickness dependence of the relaxation time of the α process is different from that of the EP process. This suggests that there is decoupling between the segmental motion of the polymers and the translational motion of the charge carriers in confinement.

Nucleation and Growth of Ordered Copolymer Structures at Reactive Interfaces between PA6 and MA-g-HDPE.

We have studied the effect of the interfacial chemical reaction between PA6 and MA-g-HDPE in static conditions at a macroscopically flat interface. Interface destabilization and the growth of instabilities, somehow similar to myelin figures observed in surfactants put in the presence of water, are observed. For the first time in this system, it is shown that ordered microphase-separated copolymer domains, whose morphologies depend on the architecture of the copolymer, namely, essentially on the relative length of the blocks on each side of the interface, may nucleate and grow at a static interface between reactive polymers. We discuss the stability of the plane interface in the case of nonsymmetrical formed graft copolymers. The density of copolymers in the interface (coverage) can be estimated accurately from the long period of the formed structures. We confirm the predictions of Berezkin et al. This observation is very important since it confirms that nanometric domains are certainly generated during reactive extrusion, in addition to micrometric domains formed by rheological processes.