The Size Dependence of Poymeric Materials in Confined 的大小依赖的聚合物材料在密闭的.pptVIP

Structure and Properties of Polyethylene Nanofibers from Molecular Dynamics Simulations Sezen Curgul, Krystyn J. Van Vliet, Greg C. Rutledge* Department of Materials Science and Engineering *Department of Chemical Engineering Massachusetts Institute of Technology Introduction Electrospinning: A versatile method to produce fibers with diameters in the nano range Advantages Small diameters (10 nm-10 mm) High surface area (1-100 m2/g) High porosity (ca. 90%) Small fiber-to-fiber distance Motivation Numerous applications postulated for nanofibers, but little fundamental investigation of the nanofiber properties Difficulty of characterization on the nanoscale Objectives Evaluate the fiber properties (including structural, mechanical, thermal) at the molecular level as a function of fiber size Understand the origin of transition from bulk-like behavior to nanomaterial behavior: How small is “nano”? Approach Constructing the simulation Step I: Equilibrium simulation in bulk using Periodic Boundary Conditions Step II: Increase box size in 2 directions. The system remains periodic only in Z-dimension Molecular Dynamics Simulation Polyethylene: the prototypical chain-like molecule (C50-C300) Total system size: 200 to 150,000 C atoms Compute engine: LAMMPS from Sandia National Laboratory Structural characterization NVT ensemble, 495 K Radial density profiles Interfacial Excess Energy Gibbs Dividing Surface applied to energy profile Calculate interfacial excess energy Eint=0.022±0.002 J/m2 (similar to thin film PE simulations1 and experiments2) Eint NOT dependent on fiber size* Molecular Conformations Measure of chain size: Radius of gyration Chains are confined* Confinement increases as Fiber size decreases Molecular weight increases Effect notable up to 2-4xRg Glass Transition Temperature (Tg) Determination Slow cooling (effective rate =1.97x1010 K/s) from 495 K down to 100 K Re-equilibrate at several temperatures to determine fiber radius and core