Continuous Controlled Radical Polymerization of Methyl Acrylate in a Copper Tubular Reactor

The use of copper tubing as both the reactor and as a catalyst source is demonstrated for continuous controlled radical polymerization of methyl acrylate at ambient temperature and at low solvent content of 30%. The high surface area provided by the copper walls mediates the reaction via the single electron transfer–living radical polymerization (SET‐LRP) mechanism. The polymerizations proceeded quickly, reaching 67% conversion at a residence time of 16 min. Ligand concentration could also be reduced without a sharp drop in polymerization rate, demonstrating the potential for decreased raw material and post‐process purification costs. Chain extension experiments conducted using synthesized polymer showed high livingness. The combination of living polymer produced at high polymerization rates at ambient temperature and low volatile organic solvent content demonstrate the potential of a copper reactor for scale up of SET‐LRP.

     

Dynamics of fracture in drying suspensions

We investigate the dynamics of fracture in drying films of colloidal silica. Water loss quenches the nanoparticle dispersions to form a liquid-saturated elastic network of particles that relieves drying-induced strain by cracking. These cracks display intriguing intermittent motion originating from the deformation of arrested crack tips and aging of the elastic network. The dynamics of a single crack exhibits a universal evolution, described by a balance of the driving elastic power with the sum of interfacial power and the viscous dissipation rate of flowing interstitial fluid.     

Quantum corrections to the semiclassical Hartree-Fock theory of a harmonically trapped Bose gas

An analytical approach is proposed to investigate the mechanism of implantation of size selected clusters into graphite, in order to explain the origin of linear variation of measured penetration depth with momentum or energy of incident cluster. In agreement with experimental observations, the cluster experiences, during its penetration, a force which consists in a component proportional with cluster velocity and a constant component. Expressions of these forces were obtained in the frame work of this approach. Regardless of whether the cluster breaks down into single atoms on the surface or not, there is evidence for existence of a wave generated under impact of cluster on the surface. Under the assumption that the cluster does not break up at impact on the surface, the penetration depth depends on the cross-section between the cluster and the surface, the cluster velocity and the properties of graphite. When the cluster fragments upon the impact on the surface, the generated wave is followed by a collective motion (??collective cascade??) of displaced atoms of target, including the constituents of cluster themselves, due to the transfer of cluster momentum. Thus, it is these displaced atoms which penetrate in the medium. During this collective penetration, some constituents of cluster can reach a certain depth which may be considered as the range of the deepest implanted constituents of cluster. It is shown that, the depth of penetration depends on the initial radius of cluster, its velocity and the properties of graphite. In addition, the depth varies non linearly with cluster velocity, for small clusters (n ?? 7), while for large clusters (n ?? 13), it varies (i) linearly with cluster velocity (or momentum) when the force proportional with speed of cluster is dominant. (ii) Linearly with the square of cluster velocity (or energy) if the constant force becomes dominant. It is shown that, a mechanism based on a collective motion of displaced atoms including the constituents of cluster themselves, induced by transfer of cluster momentum to the medium, permits to explain the behavior of measured depth of implanted clusters into graphite. This collective motion involves only one free parameter for all clusters of the same nature which are used as projectiles in the same experiment.     

Investigating the impact of operating parameters on molecular weight distributions using functional regression

Molecular weight distributions (MWDs) are inherently functional observations in which differential weight fraction is expressed as a function of chain length. Conventional approaches for analyzing and predicting MWDs include discretization and treatment as multi-response estimation problems, characterization using moments, and detailed mechanistic modeling to predict fractions for each chain length. However, these approaches can be sensitive to loss of information, complexity and problem conditioning. An alternative is to treat the MWDs as functional observations, and to use techniques from Functional Data Analysis (FDA), notably functional regression. The objective of this paper is to develop and apply empirical modeling techniques based on functional regression for investigating the impact of operating parameters on MWDs.     

Simulation of free radical high-pressure copolymerization in a multi-zone autoclave reactor: compartment model investigation

A compartment model is used to describe the complex flow of a high-pressure ethylene copolymerization process in an industrial multi-feed multi-zone autoclave reactor at steady state operation conditions. To capture the imperfect mixing effects due to fresh initiator injection, each zone is considered as a set of three interconnected well mixed CSTRs with recycle streams. Volumes of the reactors and the recycle flow are adjusted to get the best fit with results of steady state well mixed analysis for each zone. Once the temperature and conversion as state variables in each reaction volume are known, the properties of polymer produced in each zone and those of final polymer can be determined. Using a realistic set of kinetic mechanisms, temperature, monomer conversion, molecular weights and short and long chain branching frequencies in each zone and at the exit point of the reactor are estimated. Some of the model results are compared with experimental data obtained for an industrial reactor.     

Structural recovery of polymer glasses

The structural recovery of polystyrene glasses subjected to thermal cycles in the glass transition region is studied by differential scanning calorimetry and by dilatometry. Three different types of behaviour are observed in respect of the peak in the specific heat capacity or thermal expansion coefficient on heating, and are found to be in full agreement with the predictions of the KAHR model. First, for well-stabilized glasses, the dependence of the (main) peak temperature on heating rate and annealing time yields consistent values for the structure parameter x by means of the peak-shift method. Second, for poorly-stabilized glasses, the (upper) peak temperatures shift quite differently, but again consistently with theory. Third, for glasses intermediate between poorly-and well-stabilized conditions, both main and upper peaks can be observed simultaneously in the same endotherm.