Macroscopic quantum phenomena such as high-temperature superconductivity, colossal magnetoresistance, ferrimagnetism and ferromagnetism arise from a delicate balance of different interactions among electrons, phonons and spins on the nanoscale. The study of the interplay among these various degrees of freedom in strongly coupled electron-lattice systems is thus crucial to their understanding and for optimizing their properties. Charge-density-wave (CDW) materials, with their inherent modulation of the electron density and associated periodic lattice distortion, represent ideal model systems for the study of such highly cooperative phenomena. With femtosecond time-resolved techniques, it is possible to observe these interactions directly by abruptly perturbing the electronic distribution while keeping track of energy relaxation pathways and coupling strengths among the different subsystems. Numerous time-resolved experiments have been performed on CDWs, probing the dynamics of the electronic subsystem. However, the dynamics of the periodic lattice distortion have been only indirectly inferred. Here we provide direct atomic-level information on the structural dynamics by using femtosecond electron diffraction to study the quasi two-dimensional CDW system 1T-TaS(2). Effectively, we have directly observed the atomic motions that result from the optically induced change in the electronic spatial distribution. The periodic lattice distortion, which has an amplitude of ∼0.1 Å, is suppressed by about 20% on a timescale (∼250 femtoseconds) comparable to half the period of the corresponding collective mode. These highly cooperative, electronically driven atomic motions are accompanied by a rapid electron-phonon energy transfer (∼350 femtoseconds) and are followed by fast recovery of the CDW (∼4 picoseconds). The degree of cooperativity in the observed structural dynamics is remarkable and illustrates the importance of obtaining atomic-level perspectives of the processes directing the physics of strongly correlated systems.

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Mechanical properties and deformation mechanisms of polypropylene (PP)/wood fiber (WFb) composites modified with maleated polypropylene as compatibilizer and styrene‐butadiene rubber (SBR) as impact modifier have been studied. The addition of maleated polypropylene to the unmodified polypropylene/wood fiber composite enhances the tensile modulus and yield stress as well as the Charpy impact strength. SBR does not cause a drop in the tensile modulus and yield strength because of the interplay between decreasing stiffness and strength by rubber modification and increasing stiffness and strength by good interfacial adhesion between the matrix and fibers. The addition of both maleated polypropylene and rubber to the polypropylene/wood fiber composite does not result in an improvement of effects based on maleated polypropylene and rubber, which includes possible synergism. The deformation mechanisms in unmodified polypropylene/wood fiber composite are matrix brittle fracture, fiber debonding and pullout. A polymeric layer around the fibers created from maleated polypropylene may undergo debonding, initiating local plasticity. Rubber particle cavitation, fiber pullout and debonding were the basic failure mechanisms of rubber‐toughened polypropylene/wood fiber composite. When maleated polypropylene was added to this composite, fiber breakage and matrix plastic deformation took place. Polym. Compos. 25:521–526, 2004. © 2004 Society of Plastics Engineers.

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Heterophasic copolymers comprised of polypropylene (PP) matrix and ethylene-propylene copolymer (EPC) dispersed phase were investigated with respect to the dispersed phase composition, i.e., ethylene/propylene ratio. The rheological properties, morphology, as well as thermal and mechanical relaxation behavior were studied to describe the structure evolution and phase interactions between the components of the PP copolymers. Decrease of the ethylene content of the EPC leads to a higher matrix-dispersed phase compatibility, as evaluated by the shift of the glass transition temperatures of EPC and PP towards each other. At ethylene content of EPC of 17 wt %, the glass transition temperatures of the both phases merged into a joint relaxation. The effect of the EPC composition on the internal structure of the dispersed domains and on the morphology development of the heterophasic copolymers was demonstrated. Decreasing ethylene content was found to induce a refinement of the dispersed phase with several orders of magnitude down to 0.18 m for propylene-rich EPC. Optical microscopy observations showed that the dispersed propylene-rich phase is preferably rejected at the interlamellar regions of the spherulites and/or at the interspherulitic regions, while the ethylene-rich domains are engulfed within the PP spherulites. Both of these processes impose an additional energetic barrier and influence the spherulite growth rate of the heterophasic materials.

ABSTRACT:The effect of grafting level of maleic anhydride (MA) in the maleated polypropylene (PPMA) on the fracture, deformation mechanisms, and mechanical properties of polypropylene (PP) wood flour composites was studied. Tensile strength, elongation at break, and impact strength are noticeably improved with addition of interfacial modifiers as maximum values of the examined mechanical properties were detected when concentration of MA in the compatibilizer was 1 wt %. To explore the microstructure and deformation mechanisms, scanning electron microscopy was employed. It was found that low concentrations of MA up to 1 wt % led to the creation of a thin and irregular polymer layer assisted formation of fibrillated plastic deformation zone around the wood particles, while the bulk PP matrix experienced voiding and brittle fracture. Higher concentrations of MA fetch to stronger interaction between PP and wood flour, the reason for brittle fracture and reduced ductility of the matrix. The impact fracture behavior of the composites during Instrumented impact tests is also discussed with respect to the interfacial bond strength.

The crystallization and the mechanical properties of polyethylene, which is one of the most important commodity polymers, are influenced by the crystalline α-relaxation. This process originates from the diffusive chain transport through the crystallites as mediated by local 180°flips. Recent studies have stressed the relevance of the chain folding morphology on the chain diffusion, but its relation to the rate of jumps of the individual repeat units has not yet been addressed. In this study, we compare samples with very different morphology, including nanocrystals as a unique new model system, and use proton low-field and carbon-13 high-field solid-state NMR spectroscopy to determine the rate of local jumps and the largescale crystalline−amorphous diffusion coefficient, respectively. We find that samples with tight folds (reactor powders and nanocrystals) display on average lower activation energies of the local jumps. Nanocrystals stand out in that they feature a significantly broader distribution of local jump rates, which we attribute to the location of stems in the finite nanocrystal. Our results for the crystalline−amorphous long-range diffusion are at partial variance with previous findings in that samples with tight folds do not generally exhibit the fastest diffusion, and we discuss the related ambiguities. Our data suggest that the higher chain mobility in the amorphous domain of melt-crystallized samples has an accelerating effect on intracrystalline chain dynamics at high temperatures but is accompanied by a more progressive slowdown at low temperatures due to cooperativity effects.

Nanoparticles with a defined shape and surface chemistry result from an encoding of crystal size directly in the polymer microstructure. This is brought about by carboxy groups spaced precisely on every 21st or 45th carbon atom of linear polyethylene chains synthesized by acyclic diene metathesis polymerization (ADMET) of precisely branched, long-chain α,ω-dienes. These hydrophilic functional groups form a layer on the nanocrystal surface, which interacts with the aqueous dispersing medium and, thus, self-stabilizes the nanocrystals. The nanocrystal thickness is directly predeterminded by the length of the long-chain methylene spacer between the functional groups.