Atomic Force Microscopy and Real Atomic Resolution. Simple Computer Simulations.

Using a simple computer simulation for AFM imaging in the contact mode, pictures with true and false atomic resolution are demonstrated. The surface probed consists of two f.c.c. (111) planes and an atomic vacancy is introduced in the upper layer. Changing the size of the effective tip and its registry with respect to the atoms of the crystal probed, images with completely different qualitative features are obtained. If the effective tip is a single atom the vacancy is clearly imaged. However, if the tip consists of several atoms and is in registry with the sample, a virtual atom appears instead of the vacancy and the crystal lattice is perfectly reproduced. If the tip is out of registry with respect to the sample, artifacts having the size of the effective tip are reported.

Stick and Slip Behaviour of Confined Oligomer Melts under Shear. A Molecular-Dynamics Study.

The flow behaviour of melts of short chains, confined in molecularly thin Couette flow geometries, is studied with molecular-dynamics simulations. The effect of wall attraction and confinement on the density and velocity profiles is analysed. In these highly inhomogeneous films, a strong correlation between the density and velocity profile is found. Sticking of the interfacial layer on the wall and slip on the wall and inside the film is manifested by changes in the velocity profile. The location of the slip is determined by the strength of the wall attraction.

Co-axial capillaries microfluidic device for synthesizing size- and morphology-controlled polymer core-polymer shell particles

An easy assembling-disassembling co-axial capillaries microfluidic device was built up for the production of double droplets. Uniform polymer core-polymer shell particles were synthesized by polymerizing the two immiscible monomer phases composing the double droplet. Thus poly(acrylamide) core-poly(tripropylenglycol-diacrylate) shell particles with controlled core diameter and shell thickness were simply obtained by adjusting operating parameters. An empirical law was extracted from experiments to predict core and shell sizes. Additionally uniform and predictable non-spherical polymer objects were also prepared without adding shape-formation procedures in the experimental device. An empirical equation for describing the lengths of rod-like polymer particles is also presented

Microfluidic synthesis and assembly of reactive polymer beads to form new structured polymer materials

Monodisperse and size-controlled polymer particles were produced without surfactant or wash-coat from O/W monomer emulsions and ‘‘on the fly’’ polymerization under UV irradiation in a very simple needle/tubing system. The effect of the viscosity of the continuous phase on the size of final particles was investigated. The capillary number ratio was found to be relevant to predict the size of the droplets. A relation between dimensionless numbers predicts particle diameter as a function of the needle inner diameter and both velocity and viscosity ratios of continuous and dispersed phases. A functional comonomer was incorporated in the monomer phase so as to obtain polymer microparticles bearing reactive groups on their surface. Polymer beads necklaces were thus formed by linking polymer particles together

Tuning of the luminescence in poly((silanylene)thiophene)s

Synthetic routes to alternating copolymers consisting of oligosilylene blocks and oligothiophene blocks (T-x; x = 1, 2, 3, 4, or 6 rings) are presented. Solubility requirements for obtaining acceptable molecular weights and, eventually, for film formation are met by the introduction of butyl groups replacing methyls on the silicon atoms and by employing T-6 blocks carrying two octyl substituents. Additionally, substituted oligothiophenes are synthesized as an aid in the interpretation of NMR, absorption, and fluorescence spectra. Regarding the electronic configuration of the oligothiophene blocks, NMR spectra show clear differences between plain oligothiophenes, end-substituted oligothiophenes, and polymers, indicative of pi-sigma interactions with the oligosilylene blocks and possible through-conjugation to adjacent blocks in polymers. Red shifts in optical spectra show a parallel trend across the various compounds based on the same oligothiophene unit, related to the stabilization of photoexcited states on the oligothiophene by the oligosilylene substituents. These effects are strong in T-2-based compounds and reduced fdr longer T-n. The main feature of the spectra is the decrease of the transition energies with the size of the oligothiophene blocks in the polymers. Since this effect is also found in fluorescence, it enables one to adjust the luminescence wavelength by choosing the proper block length (''chemical tuning''). Fluorescence quantum efficiencies in solution are found to be remarkably high in polymers based on T-2 blocks. Spin-coated films of T-2-based (or T-3-based) polymers show evidence of T-4 (T-6) impurity blocks that act as an exciton trap

Stability of Monitoring Weak Changes in Multiply Scattering Media with Ambient Noise Correlation: Laboratory Experiments

Previous studies have shown that small changes can be monitored in a scattering medium by observing phase shifts in the coda. Passive monitoring of weak changes through ambient noise correlation has already been applied to seismology, acoustics and engineering. Usually, this is done under the assumption that a properly reconstructed Green function as well as stable background noise sources are necessary. In order to further develop this monitoring technique, a laboratory experiment was performed in the 2.5MHz range in a gel with scattering inclusions, comparing an active (pulse-echo) form of monitoring to a passive (correlation) one. Present results show that temperature changes in the medium can be observed even if the Green function (GF) of the medium is not reconstructed. Moreover, this article establishes that the GF reconstruction in the correlations is not a necessary condition: the only condition to monitoring with correlation (passive experiment) is the relative stability of the background noise structure

Imaging of single polymer chains based on their elasticity

In this work we apply a force modulation technique to a standard atomic force microscope (AFM) in order to study the elasticity of individual polystyrene molecules. The sample mounted on a piezoelectric tube was forced to vibrate along the z direction. The corresponding modulation of the cantilever, which reflects the spring constant of the sample, was phase sensitively detected and measured as a function of the surface topography. The image contrast in these images is based on local variations of the surface elasticity. Compared to the conventional AFM topography image, the elasticity image shows an enhanced contrast with pronounced molecular structure.

Inhomogeneities in sheared ultrathin lubricating films

Nonequilibrium molecular dynamics computer simulations have been used to study nanoscopically confined oligomer films under shear. Beyond the well-known density layering across such films, other structural and dynamical inhomogeneities exist across such films and are discussed here. When these films are subjected to strong shear flows, slip appears at the confining surfaces or inside the pore, depending on the wall interactions. For strong wall affinities interlayer slip develops between the adsorbed layer and the free chains, resulting in a structural discontinuity; a molecular mechanism, involving shear induced conformational changes of the adsorbed chains, is associated with this interlayer slip. Moreover, the resistance to flow (quantified through an effective viscosity) changes considerably across the film, with a dramatic viscosity increase of the adsorbed layer near attractive surfaces. Shear thinning is mainly taking place inside this more viscous interfacial layer, whereas the dynamics in the middle of the film remain bulklike; thus, there also exists strong inhomogeneity in the dynamics of the system. A comparison with SFA experimental and theoretical studies is also made

Self-assembly of rod-coil block copolymers from weakly to moderately segregated regimes

Abstract.: We report on the self-assembly behaviour of two homologue series of rod-coil block copolymers in which, the rod, a π -conjugated polymer, is maintained fixed in size and chemical structure, while the coil is allowed to vary both in molecular weight and chemical nature. This allows maintaining constant the liquid crystalline interactions, expressed by Maier-Saupe interactions, ω , while varying the tendency towards microphase separation, expressed by the product between the Flory-Huggins parameter and the total polymerization degree, χN . Therefore, the systems presented here allow testing directly some of the theoretical predictions for the self-assembly of rod-coil block copolymers in a weakly segregated regime. The two rod-coil block copolymer systems investigated were poly(DEH-p-phenylenevinylene-b-styrene), whose self-assembly takes place in the very weakly segregated regime, and poly(DEH-p-phenylenevinylene-b-4vinylpyridine), for which the self-assembly behaviour occurs under increased tendency towards microphase separation, hereby referred to as moderately segregated regime. Experimental results for both systems are compared with predictions based on Landau expansion theorie