Role of heat generation and thermal diffusion during frontal photopolymerization

Frontal photopolymerization (FPP) is a rapid and versatile solidification process that can be used to fabricate complex three-dimensional structures by selectively exposing a photosensitive monomer-rich bath to light. A characteristic feature of FPP is the appearance of a sharp polymerization front that propagates into the bath as a planar traveling wave. In this paper, we introduce a theoretical model to determine how heat generation during photopolymerization influences the kinetics of wave propagation as well as the monomer-to-polymer conversion profile, both of which are relevant for FPP applications and experimentally measurable. When thermal diffusion is sufficiently fast relative to the rate of polymerization, the system evolves as if it were isothermal. However, when thermal diffusion is slow, a thermal wavefront develops and propagates at the same rate as the polymerization front. This leads to an accumulation of heat behind the polymerization front which can result in a significant sharpening of the conversion profile and acceleration of the growth of the solid. Our results also suggest that a novel way to tailor the dynamics of FPP is by imposing a temperature gradient along the growth directio

The synthesis and some properties of nylon 4,T

The synthesis of nylon 4,T from tetramethylenediamine and a terephthalic acid derivative was studied in a two step-process: prepolymerization, followed by postcondensation in the solid state (4 h, 290°C). The prepolymers were prepared by the nylon salt method, ester polymerization method, interfacial method, and a low temperature solution method. A maximum ηinh of 1.52 was obtained. From a solution in trifluoroacetic acid, films were cast and on these films we studied its IR spectrum, WAXS, and melting behavior with DSC. A boiled up sample had a double melting transition at 434 and 475°C and a ΔH0 of 130 J/g

Process for interfacial polymerization of pyromellitic dianhydride and 1,2,4, 5-tetraamino-benzene Patent

Process for interfacial polymerization of pyromellitic dianhydride and tetraamino benzen

Immediate versus water-storage performance of Class V flowable composite restoratives

Objectives The aims of this investigation were to clarify the effects of 24 h water-storage and finishing time on mechanical properties and marginal adaptation to a Class V cavity of eight modern flowable resin-composites. Methods Eight flowable composites, plus two controls (one microfilled and one hybrid composite), were investigated with specimen sub-groups (n = 10) for each property measured. The principal series of experiments was conducted in model Class V cavities with interfacial polishing either immediately (3 min) after setting or after 24 h water-storage. After the finishing procedure, each tooth was sectioned in a buccolingual direction through the center of the restoration, and the presence or absence of marginal-gaps was measured (and then summed for each cavity) at 14 points (each 0.5 mm apart) along the cavity restoration interface (n = 10 per group; total points measured = 140). The shear bond-strengths to enamel and to dentin, and flexural strengths and moduli data were also measured at 3 min and after 24 h water-storage. Results For all flowable composites, polished immediately after setting, 14–30 summed gaps were observed (controls: 64 and 42). For specimens polished after 24 h, a significantly (p &#60; 0.05) reduced number of 8–17 summed gaps occurred for only 3 flowable composites; whereas for 5 flowable composites there were non-significantly-different (p &#62; 0.05) numbers (11–17) of summed gaps (controls: 28 and 22). After 24 h storage, shear bond-strengths to enamel and to dentin, flexural strengths and moduli increased highly significantly (p &#60; 0.001) for all materials, except Silux Plus. Significance A post-cure interval of 24 h resulted in enhanced mechanical and adhesive properties of flowable dental composites. In a minority of cases there was also a reduced incidence of marginal-gap formation. However the latter effect may be partly attributed to 24 h delayed polishing, even though such a delay is not usual clinical practice.</p

Nucleation in binary polymer blends: A self-consistent field study

We study the structure and thermodynamics of the critical nuclei in metastable binary polymer blends using the self-consistent field method. At the mean-field level, our results are valid throughout the entire metastable region and provide a smooth crossover from the classical capillary-theory predictions near the coexistence curve to the density functional predictions of Cahn and Hilliard (properly transcribed into expressions involving the parameters of the binary polymer blends) near the spinodal. An estimate of the free energy barrier provides a quantitative criterion (the Ginzburg criterion) for the validity of the (mean-field) self-consistent approach. The region where mean-field theory is valid and where there can be a measurable nucleation rate is shown to be poorly described by the existing limiting theories; our predictions are therefore most relevant in this region. We discuss our results in connection with recent experimental observations by Balsara and co-workers

Modeling morphology evolution during solvent-based fabrication of organic solar cells

Solvent-based techniques usually involve preparing dilute blends of electron-donor and electron-acceptor materials dissolved in a volatile solvent. After some form of coating onto a substrate, the solvent evaporates. An initially homogeneous mixture separates into electron-acceptor rich and electron-donor rich regions as the solvent evaporates. Depending on the specifics of the blend and processing conditions different morphologies are typically formed. Experimental evidence consistently confirms that the morphology critically affects device performance. A computational framework that can predict morphology evolution can significantly augment experimental analysis. Such a framework will also allow high throughput analysis of the large phase space of processing parameters, thus yielding insight into the process-structure-property relationships. In this paper, we formulate a computational framework to predict evolution of morphology during solvent-based fabrication of organic thin films. This is accomplished by developing a phase field-based model of evaporation-induced and substrate-induced phase-separation in ternary systems. This formulation allows all the important physical phenomena affecting morphology evolution during fabrication to be naturally incorporated. We discuss the various numerical and computational challenges associated with a three dimensional, finite-element based, massively parallel implementation of this framework. This formulation allows, for the first time, to model 3D morphology evolution over large time spans on device scale domains. We illustrate this framework by investigating and quantifying the effect of various process and system variables on morphology evolution. We explore ways to control the morphology evolution by investigating different evaporation rates, blend ratios and interaction parameters between components

Linear stability of an active fluid interface

Motivated by studies suggesting that the patterns exhibited by the collectively expanding fronts of thin cells during the closing of a wound [Mark et al., Biophys. J., 98:361-370, 2010] and the shapes of single cells crawling on surfaces [Callan-Jones et al., Phys. Rev. Lett., 100:258106, 2008] are due to fingering instabilities, we investigate the stability of actively driven interfaces under Hele-Shaw confinement. An initially radial interface between a pair of viscous fluids is driven by active agents. Surface tension and bending rigidity resist deformation of the interface. A point source at the origin and a distributed source are also included to model the effects of injection or suction, and growth or depletion, respectively. Linear stability analysis reveals that for any given initial radius of the interface, there are two key dimensionless driving rates that determine interfacial stability. We discuss stability regimes in a state space of these parameters and their implications for biological systems. An interesting finding is that an actively mobile interface is susceptible to fingering instability irrespective of viscosity contrast

Tuning the Mechanical Properties in Model Nanocomposites: Influence of the Polymer-Filler Interfacial Interactions

This paper presents a study of the polymer-filler interfacial effects on filler dispersion and mechanical reinforcement in Polystyrene (PS) / silica nanocomposites by direct comparison of two model systems: un-grafted and PS-grafted silica dispersed in PS matrix. The structure of nanoparticles has been investigated by combining Small Angle Neutron Scattering (SANS) measurements and Transmission Electronic Microscopic (TEM) images. The mechanical properties were studied over a wide range of deformation by plate/plate rheology and uni-axial stretching. At low silica volume fraction, the particles arrange, for both systems, in small finite size non-connected aggregates and the materials exhibit a solid-like behavior independent of the local polymer/fillers interactions suggesting that reinforcement is dominated by additional long range effects. At high silica volume fraction, a continuous connected network is created leading to a fast increase of reinforcement whose amplitude is then directly dependent on the strength of the local particle/particle interactions and lower with grafting likely due to deformation of grafted polymer.Comment: Journal Polymer Science (2011

Spontaneous symmetry breaking in active droplets provides a generic route to motility

We explore a generic mechanism whereby a droplet of active matter acquires motility by the spontaneous breakdown of a discrete symmetry. The model we study offers a simple representation of a "cell extract" comprising, e.g., a droplet of actomyosin solution. (Such extracts are used experimentally to model the cytoskeleton.) Actomyosin is an active gel whose polarity describes the mean sense of alignment of actin fibres. In the absence of polymerization and depolymerization processes ('treadmilling'), the gel's dynamics arises solely from the contractile motion of myosin motors; this should be unchanged when polarity is inverted. Our results suggest that motility can arise in the absence of treadmilling, by spontaneous symmetry breaking (SSB) of polarity inversion symmetry. Adapting our model to wall-bound cells in two dimensions, we find that as wall friction is reduced, treadmilling-induced motility falls but SSB-mediated motility rises. The latter might therefore be crucial in three dimensions where frictional forces are likely to be modest. At a supra-cellular level, the same generic mechanism can impart motility to aggregates of non-motile but active bacteria; we show that SSB in this (extensile) case leads generically to rotational as well as translational motion.Comment: 13 pages, 8 figures, 1 tabl

Microgravity Polymers

A one-day, interactive workshop considering the effects of gravity on polymer materials science was held in Cleveland, Ohio, on May 9, 1985. Selected programmatic and technical issues were reviewed to introduce the field to workshop participants. Parallel discussions were conducted in three disciplinary working groups: polymer chemistry, polymer physics, and polymer engineering. This proceedings presents summaries of the workshop discussions and conclusions