A Versatile Strategy to Synthesize Perfluoropolyether‐Based Thermoplastic Fluoropolymers by Alkyne‐Azide Step‐Growth Polymerization

Perfluoropolyether (PFPE)‐based thermoplastic fluoropolymers are synthesized by A₂ + B₂ step‐growth polymerization between PFPE‐diyne and fluorinated diazides. This versatile method allows synthesizing PFPE‐based materials with tunable physicochemical properties depending on the exact nature of the fluorinated segment of the diazide precursor. Semicrystalline or amorphous materials endowed with high thermostability (≈300 °C under air) and low glass transition temperature (≈−100 °C) are obtained, as confirmed by differential scanning calorimetry, thermogravimetry, and rheometry. Step‐growth polymerizations can be copper‐catalyzed but also thermally activated in some cases, thus avoiding the presence of copper residues in the final materials. This strategy opens up new opportunities to easily access PFPE‐based materials on an industrial scale. Furthermore, a plethora of developments can be envisioned (e.g., by adding a third trifunctional component to the formulations for the synthesis of PFPE‐based elastomers).

     

Identification de la relation de dispersion dans les barresIdentification of the dispersion relation in rods

Dispersion and attenuation of longitudinal waves in elastic or weakly viscoelastic rods are measured by analysing the resonant frequencies present in the strain spectrum due to an unknown loading. The method takes the finite measuring time of the test into account. It is applied to an aluminium bar, in which the dispersion relation is identified very accurately at frequencies up to 60 kHz. To cite this article: R. Othman et al., C. R. Mecanique 330 (2002) 849–855.     

Near-wall velocity measurements by particle-shadow tracking

We report a new method to measure the velocity of a fluid in the vicinity of a wall. The method, that we call particle-shadow tracking (PST), simply consists in seeding the fluid with a small number of fine tracer particles of density close to that of the fluid. The position of each particle and of its shadow on the wall are then tracked simultaneously, allowing one to accurately determine the distance separating tracers from the wall and therefore to extract the velocity field. We present an application of the method to the determination of the velocity profile inside a laminar density current flowing along an inclined plane.     

Self-assembled nanoribbons and nanotubes in water: energetic vs entropic networks

We present a comparative investigation of two opposite classes of self-assembled fibrillar networks. Ribbons and tubes having cross-sectional dimensions in the nanoscale can be formed in aqueous solutions of steroids derived, respectively, from deoxycholic (DC) and lithocholic (LC) acids. Rheological features distinguish energetic networks of DC ribbons rigidly fixed in cylindrical bundles and entropic transient networks of LC tubes weakly interacting in shear-sensitive suspensions. The two classes are characterized by their frequency sweep profiles, viscoelastic linear domains, scaling laws of the elastic shear modulus vs concentration, kinetics of formation of the networks, and their optical birefringence aspects. A theoretical context for networks of rigid fibers is used to account for the scaling exponents α in the G’ (and σ*) ∝C ^α laws (α=2.0 and 1.0, respectively, for DC and LC). The evolution observed in DC gels from ribbons to cylindrical fibers with monodisperse sections made up with four ribbons is an indication of an equilibrated balance between face-to-face attractions and untwisting elastic processes of the constitutive ribbons.Paper presented at the Annual Meeting of the European Society of Rheology, Grenoble, April 2005     

Phase Transition with the Line‐Tension Effect

We make the connection between the geometric model for capillarity with line tension and the Cahn‐Hilliard model of two‐phase fluids. To this aim we consider the energies where u is a scalar density function and W and V are double‐well potentials. We show that the behaviour of F _ε in the limit ε→0 and λ→∞ depends on the limit of ε log λ. If this limit is finite and strictly positive, then the singular limit of the energies F _ε leads to a coupled problem of bulk and surface phase transitions, and under certain assumptions agrees with the relaxation of the capillary energy with line tension. These results were announced in [ABS1] and [ABS2]. (Accepted November 5, 1997)     

Rheological characterization of a solder paste for surface mount applications

Solder pastes used in surface mount soldering techniques (SMT) are very complex suspensions containing high volumes of metallic powder in a carrier fluid. The rheological complexity results largely from the carrier fluid itself, which is a suspension of colloidal particles. In this work, we have characterized the rheological properties of a typical carrier fluid and its solder paste containing 64 vol.% metallic powder. A six-blade vane geometry was used to avoid wall slip and sample fracture. All measurements were carried out following pre-shearing and rest time in order to obtain reproducible results. Steady shear experiments showed that the solder paste was highly shear-thinning and thixotropic. In oscillatory shear, the linear viscoelastic domain was found to be very narrow for both the suspending fluid and the paste. Frequency sweep tests in the linear domain revealed a gel-like structure with a nearly constant G′ for the suspending fluid and a slightly increasing G′ for the solder paste. From creep experiments, a yield stress of about 40 Pa was determined for the suspending fluid at temperatures between 25 and 40°C, and of 100 Pa at 4°C. A much larger yield stress, 480 Pa, was determined for the solder paste at 25°C.     

Non-linear normal modes,invariance, and modal dynamics approximations of non-linear systems

Non-linear systems are here tackled in a manner directly inherited from linear ones, that is, by using proper normal modes of motion. These are defined in terms of invariant manifolds in the system's phase space, on which the uncoupled system dynamics can be studied. Two different methodologies which were previously developed to derive the non-linear normal modes of continuous systems — one based on a purely continuous approach, and one based on a discretized approach to which the theory developed for discrete systems can be applied-are simultaneously applied to the same study case-an Euler-Bernoulli beam constrained by a non-linear spring-and compared as regards accuracy and reliability. Numerical simulations of pure non-linear modal motions are performed using these approaches, and compared to simulations of equations obtained by a classical projection onto the linear modes. The invariance properties of the non-linear normal modes are demonstrated, and it is also found that, for a pure non-linear modal motion, the invariant manifold approach achieves the same accuracy as that obtained using several linear normal modes, but with significantly reduced computational cost. This is mainly due to the possibility of obtaining high-order accuracy in the dynamics by solving only one non-linear ordinary differential equation.