1,721,043 research outputs found
Thermoregulated gas transport through electrospun nanofiber membranes
No full textThermoregulation of gas transport using electrospun fiber membranes is demonstrated experimentally for the first time. The fiber membranes comprise three layers: a middle layer of electrospun polystyrene sandwiched between two outer layers of electrospun cellulose acetate mat as supports, bonded together by hot pressing. The electrospun polystyrene layer serves as a phase change material that blocks transport of gases though the membrane when the fibers de-vitrify. The membrane exhibited a reduction in oxygen flux at temperatures in excess of 140 °C. Using a blend of polysulfone and polystyrene resulted in an upward shift of the transition temperature to 250 °C. Modeling of transport was performed to estimate the impact of the morphological properties of the membranes such as tortuosity, fiber diameter, and porosity.Philip Morris Internationa
Mechanical and Structural Characterization of Semicrystalline Polyethylene under Tensile Deformation by Molecular Dynamics Simulations
No full textWe have studied tensile deformations of semicrystalline polyethylene (PE) with molecular dynamics simulations at two different strain rates and temperatures. Compared to earlier studies, the modeled systems were approximately 5 times larger, which allowed significantly larger strains up to about 120% to be examined. Two different modes of structural transformation of semicrystalline PE were observed at the higher temperature of 350 K, depending on the strain rate. At the faster strain rate of 5 × 10⁷ s⁻¹, cavitation in the noncrystalline region dominated, with little change in the crystalline region, resulting in monotonically declining stress with increasing strain after the yield point. However, in a small number of cases, significant deviations from the average stress–strain profile were observed that correlated with topological constraints, such as bridges and bridging entanglements connecting crystalline regions separated by the noncrystalline region, and destabilization of the crystalline region. At the slower strain rate of 5 × 10⁶ s⁻¹, we observed repeated melting/recrystallization events and significant oscillations in stress associated with variations of density in crystalline and noncrystalline regions and the displacement of polymer chains from crystalline to noncrystalline regions. When averaged over an ensemble of starting configurations for semicrystalline PE, the oscillations were found to be less coherent from microstate to microstate and offset one another. The postyield stress became notably smoother and began to resemble the plastic flow observed macroscopically, followed by stress hardening at the later stage of deformation. At the lower temperature of 250 K, cavity formation was the only mechanism observed, for both strain rates. The interplay between the thermodynamic stability of the crystalline region and the topological constraints imposed by bridges and entanglements in the noncrystalline region is crucial to understanding structural transformations of semicrystalline PE during tensile deformations.U.S. Army Research Laborator
Heterogeneous Nucleation of an n-Alkane on Tetrahedrally Coordinated Crystals
No full textHeterogeneous nucleation refers to the propensity for phase transformations to initiate preferentially on foreign surfaces, such as vessel walls, dust particles, or formulation additives. In crystallization, the form of the initial nucleus has ramifications for the crystallographic form, morphology, and properties of the resulting solid. Nevertheless, the discovery and design of nucleating agents remains a matter of trial and error because of the very small spatiotemporal scales over which the critical nucleus is formed and the extreme difficulty of examining such events empirically. Using molecular dynamics simulations, we demonstrate a method for the rapid screening of entire families of materials for activity as nucleating agents and for characterizing their mechanism of action. The method is applied to the crystallization of n-pentacontane, a model surrogate for polyethylene, on the family of tetrahedrally coordinated crystals, including diamond and silicon. A systematic variation of parameters in the interaction potential permits a comprehensive, physically based screening of nucleating agents in this class of materials, including both real and hypothetical candidates. The induction time for heterogeneous nucleation is shown to depend strongly on crystallographic registry between the nucleating agent and the critical nucleus, indicative of an epitaxial mechanism in this class of materials. Importantly, the severity of this registry requirement weakens with decreasing rigidity of the substrate and increasing strength of attraction to the surface of the nucleating agent. Employing this method, a high-throughput computational screening of nucleating agents becomes possible, facilitating the discovery of novel nucleating agents within a broad “materials genome” of possible additives.National Science Foundation (U.S.) (Award CMMI-1235109
Electrical Conductivity of Electrospun Polyaniline and Polyaniline-Blend Fibers and Mats
Full text linkSubmicrometer fibers of polyaniline (PAni) doped with (+)-camphor-10-sulfonic acid (HCSA) and blended with poly(methyl methacrylate) (PMMA) or poly(ethylene oxide) were electrospun over a range of compositions. Continuous, pure PAni fibers doped with HCSA were also produced by coaxial electrospinning and subsequent removal of the PMMA shell polymer. The electrical conductivities of both the fibers and the mats were characterized. The electrical conductivities of the fibers were found to increase exponentially with the weight percent of doped PAni in the fibers, with values as high as 50 ± 30 S/cm for as-electrospun fibers of 100% doped PAni and as high as 130 ± 40 S/cm upon further solid state drawing. These high electrical conductivities are attributed to the enhanced molecular orientation arising from extensional deformation in the electrospinning process and afterward during solid state drawing. A model is proposed that permits the calculation of mat conductivity as a function of fiber conductivity, mat porosity, and fiber orientation distribution; the results agree quantitatively with the independently measured mat conductivities.United States. Army Research Office (Institute for Soldier Nanotechnologies, Contract ARO W911NF-07-D- 0004
Molecular Dynamics Simulation of Surface Nucleation during Growth of an Alkane Crystal
Full text linkCrystal growth from the melt of n-pentacontane (C50) was studied by molecular dynamics simulation. Quenching below the melting temperature gives rise to propagation of the crystal growth front into the C50 melt from a crystalline polyethylene surface. By tracking the location of the crystal–melt interface, crystal growth rates between 0.02 and 0.05 m/s were observed, for quench depths of 10–70 K below the melting point. These growth rates compare favorably with those from a previous study by Waheed et al. [ Polymer 2005, 46, 8689−8702]. Next, surface nucleation was identified with the formation of two-dimensional clusters of crystalline sites within layers parallel to the propagating growth front. Critical nucleus sizes, waiting times, and rates for surface nucleation were estimated by a mean first passage time analysis. A surface nucleation rate of ∼0.05 nm⁻² ns⁻¹ was observed, and it was nearly temperature-independent. Postcritical “spreading” of the surface nuclei to form a completely crystallized layer slowed with deeper supercooling.National Science Foundation (U.S.) Division of Civil, Mechanical and Manufacturing Innovation (CMMI-1235109
Kinetic Model for Layer-by-Layer Crystal Growth in Chain Molecules
Full text linkA kinetic model is proposed to describe the structure and rate of advancement of the growth front during crystallization. Solidification occurs through the mechanisms of surface nucleation and lateral spreading of the solid phase within layers in the vicinity of the growth front. The transformation from liquid to solid within each layer is described by an equation similar to the two-dimensional variant of the Johnson–Mehl–Avrami (JMA) equation, but in which the finite size and shape of the critical nucleus and the dynamic evolution of the solid fraction of the underlying layers are taken into account. Connection to the regime theory of Hoffman and co-workers, for surface nucleation and spreading in one or two dimensions, is also made. Given only molecular level information regarding surface nucleation rates, lateral spreading rates, and critical surface nucleus geometry, the resulting set of coupled nonlinear equations for solidification in each layer is numerically integrated in time to obtain the structure and rate of advancement of the growth front, for arbitrarily large systems and long times. Using this kinetic model with input parameters obtained from molecular dynamics simulations, a multiscale modeling analysis of crystal growth in n-pentacontane (C50) is performed.National Science Foundation (U.S.) Division of Civil, Mechanical and Manufacturing Innovation (CMMI-1235109
Simulation of the structure and mechanics of crystalline 4,4′-diphenylmethane diisocyanate (MDI) with n -butanediol (BDO) as chain extender
No full textWe report molecular simulation, at the atomistic level, of crystalline 4,4′-diphenylmethane diisocyanate (MDI) with n-butanediol (BDO) as chain extender, henceforth denoted as MDI/BDO, which is one of the most important components of thermoplastic polyurethanes. This work studies the structure and properties of crystalline MDI/BDO at equilibrium and under deformation. An atomistic molecular model of the MDI/BDO unit cell was constructed from fractional coordinates available for related model compounds and space group symmetry, and bulk properties of the subsequently equilibrated crystal were estimated by molecular dynamics. Overall stress-strain behavior of the crystal to small strains was simulated. The full stiffness matrix of crystalline MDI/BDO was extracted, allowing for the complete characterization of the linear elastic behavior of the crystal. Keywords: Atomistic simulation; Crystal elasticity; Polyurethan
Free surface electrospinning from a wire electrode
Full text linkElectrostatic jetting from a free liquid surface offers an alternative to conventional electrospinning in which jets are emitted from spinnerets. In this work we analyze a system in which a wire electrode is swept (in a rotary motion) through a bath containing a polymeric solution in contact with a high voltage, resulting in entrainment of the fluid, the formation of liquid droplets on the wire and electrostatic jetting from each liquid droplet. Solutions of polyvinylpyrrolidone in ethanol were used as test systems to evaluate each stage of the process. The volumes of individual droplets on the wire were measured by photographic methods and correlated with the viscosity, density and surface tension of the liquid, and with system parameters such as electrode rotation rate and wire diameter. The local electric field in the absence of liquid entrainment was modeled using conventional electrostatics, and jet initiation was found to occur consistently at the angular position where the electric field exceeds a critical value of 34 kV/cm, regardless of rotation rate. Two operating regimes were identified. The first is an entrainment-limited regime, in which all of the entrained liquid is jetted from the wire electrode. The second regime is field-limited, in which the residence time of the wire electrode in an electric field in excess of the critical value is too short to deplete the fluid on the wire. The productivity of the system was measured and compared to the theoretical values of liquid entrainment. As expected, highest productivity occurred at high applied potentials and high rotation rates.Novartis-MIT Center for Continuous Manufacturin
Nanocarbon-Based Electrochemical Systems for Sensing, Electrocatalysis, and Energy Storage
No full textCarbon materials are important for many electrochemical applications due to their tunable electron-transfer and charge-storage properties. Judicious structural manipulation of carbon to modulate its chemical, electronic, and crystalline properties is key to the rational design of many high-performance electrochemical devices. Here we focus on three types of carbon nanomaterials of recent interest in electrochemistry, namely, carbon nanofibers, carbon nanotubes, and graphene. We concentrate on how structural variations in these carbon nanomaterials impact their electrochemical activities. In this review, following a brief overview of the synthesis methods for each class of carbon nanomaterials, we discuss their electrochemical applications for sensing, electrocatalysis, and energy storage, with emphasis on general carbon structure manipulation strategies that impart specific functionalities to suit each application area. Special attention is devoted to articulating how the electronic structure of carbon influences its electrochemical activity. Through the analysis of different electrochemical devices, we find that some of the modification techniques apply to more than one application area; thus structural manipulation methods in one class of electrochemical devices may be extended to other types
Production of core/shell fibers by electrospinning from a free surface
Full text linkElectrostatic fiber formation (“electrospinning”) is the leading technology for production of continuous fibers with submicron diameter. Applications such as drug delivery and sensors benefit from the ability to produce submicron fibers with a core/shell morphology from electrified coaxial jets of two liquids. However, low productivity of the conventional needle-based coaxial process is a barrier for commercialization. We present a novel technology that overcomes this limitation by the development of coaxial jets directly from compound droplets of immiscible liquids entrained on wires, and control of mass transfer processes to produce uniform, core/shell fibers. The enabling feature of controlled evaporation by design of solution properties is verified by a simple mass transport model. Electron micrographs confirm the formation of fibers with the desired morphology. The proposed technology creates the opportunity to produce nanofibers with core/shell morphology on an industrial scale for a wide variety of applications.Novartis-MIT Center for Continuous Manufacturin
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