A density functional study on dielectric properties of acrylic acid grafted polypropylene

Influence of acrylic acid grafting of isotactic polypropylene on the dielectric properties of the polymer is investigated using density functional theory (DFT) calculations, both in the molecular modeling and three-dimensional (3D) bulk periodic system frameworks. In our molecular modeling calculations, polarizability volume, and polarizability volume per mass which reflects the permittivity of the polymer, as well as the HOMO-LUMO gap, one of the important measures indicating the electrical breakdown voltage strength, were examined for oligomers with various chain lengths and carboxyl mixture ratios. When a polypropylene oligomer is grafted with carboxyl groups (cf. acrylic acid), our calculations show that the increase of the polarizability volume α' of the oligomer is proportional to the increase of its mass m, while the ratio α'/m decreases from the value of a pure polymer when increasing the mixture ratio. The decreasing ratio of α'/m under carboxyl grafting indicates that the material permittivity might also decrease if the mass density of the material remains constant. Furthermore, our calculations show that the HOMO-LUMO gap energy decreases by only about 15% in grafting, but this decrease seems to be independent on the mixture ratio of carboxyl. This indicates that by doping polymers with additives better dielectric properties can be tailored. Finally, using the first-principles molecular DFT results for polarizability volume per mass in connection with the classical Clausius-Mossotti relation, we have estimated static permittivity for acrylic acid grafted polypropylene, assuming the structural density keeping constant under grafting. The computed permittivity values are in a qualitative agreement with the recent experiments, showing increasing tendency of the permittivity as a function of the grafting composition. In order to validate our molecular DFT based approach, we have also carried out extensive three-dimensional bulk periodic first-principles total-energy calculations in the frameworks of the density functional theory and density functional perturbation theory (DFPT) for crystalline acrylic acid grafted polypropylene. Interestingly, the computed electronic and dielectric properties behave very similarly between the simplified molecular DFT modeling and the more realistic 3D bulk periodic DFPT method. In particular, the static permittivity values [ε(r)(0)] from the molecular DFT-Clausius-Mossotti modeling are in excellent agreement with the high-frequency dielectric constant values (ε(∞)) from the DFPT method. This obviously implies that the chain-to-chain interaction to dielectric and electronic properties of acrylic acid polypropylene, to a first approximation, can be neglected, therefore justifying the usage of molecular DFT modeling in our calculations.     

All-cellulose multilayers: long nanofibrils assembled with short nanocrystals

Self-organized multilayer films were formed by sequential addition of oppositely charged cellulose I nanoparticles. The all-cellulosic multilayers were prepared via adsorption of cationicially modified cellulose nanofibrils (cat NFC) and anionic short crystalline cellulose (CNC) at pH 4.5 and pH 8.3. The properties and build-up behavior of layer-by-layer-constructed films were studied with microgravimetry (QCM-D) and the direct surface forces in these systems were explored with colloidal probe microscopy to gain information about the fundamental interplay between cat NFC and anionic CNC. The importance of the first layer on the adsorption of the consecutive layers was demonstrated by comparing pure in situ adsorption in the QCM-D with multilayer films made by spin coating the first cationic NFC layer and then subsequently adsorbing the following layers in situ in the QCM-D chamber. Differences in adsorbed amount and viscoelastic behavior were observed between those two systems. In addition, a significant pH dependence of cat NFC charge was found for both direct surface interactions and layer properties. Moreover the underlying cellulose layer in multilayer film was established to influence the surface forces especially at lower pH, where the cat NFC chains extensions were facilitated and overall charge was affected by the cationic counterpart within the layers. This enhanced understanding the effect of charge and structure on the interaction between these renewable nanoparticles is valuable when designing novel materials based on nanocellulose.     

Molecular Engineering of Fracture Energy Dissipating Sacrificial Bonds Into Cellulose Nanocrystal Nanocomposites

Even though nanocomposites have provided a plethora of routes to increase stiffness and strength, achieving increased toughness with suppressed catastrophic crack growth has remained more challenging. Inspired by the concepts of mechanically excellent natural nanomaterials, one‐component nanocomposites were fabricated involving reinforcing colloidal nanorod cores with polymeric grafts containing supramolecular binding units. The concept is based on mechanically strong native cellulose nanocrystals (CNC) grafted with glassy polymethacrylate polymers, with side chains that contain 2‐ureido‐4[1H]‐pyrimidone (UPy) pendant groups. The interdigitation of the grafts and the ensuing UPy hydrogen bonds bind the nanocomposite network together. Under stress, UPy groups act as sacrificial bonds: simultaneously providing adhesion between the CNCs while allowing them to first orient and then gradually slide past each other, thus dissipating fracture energy. We propose that this architecture involving supramolecular binding units within side chains of polymer grafts attached to colloidal reinforcements opens generic approaches for tough nanocomposites.     

Vibrational characterization of the 1:1 iodine-benzene complex isolated in solid krypton

The structure and properties of a 1:1 iodine-benzene complex isolated in an inert krypton matrix at low temperature have been studied with infrared and resonance Raman spectroscopy and with MP2 calculations. The structure of the ground-state complex is found to be unsymmetric, and the I-I vibrational frequency is found to be red-shifted by 3.94 cm(-1) upon complexation. The experimental data agree well with computational results, leading to the conclusion that the I2-Bz complex structure is not axial but of above-bond type, identically with other halogen-benzene complexes.