Biomedical subjects

Jack F Douglas

Publications and source records attributed to Jack F Douglas.

28 records · Page 2Linked to original sources

PubMed2004

Flow-induced properties of nanotube-filled polymer materials.

Carbon nanotubes (CNTs) are under intense investigation in materials science owing to their potential for modifying the electrical conductivity sigma, shear viscosity eta, and other transport properties of polymeric materials. These particles are hybrids of filler and nanoscale additives because their lengths are macroscopic whereas their cross-sectional dimensions are closer to molecular scales. The combination of extended shape, rigidity and deformability allows CNTs to be mechanically dispersed in polymer matrices in the form of disordered 'jammed' network structures. Our measurements on representative network-forming multiwall nanotube (MWNT) dispersions in polypropylene indicate that these materials exhibit extraordinary flow-induced property changes. Specifically, sigma and eta both decrease strongly with increasing shear rate, and these nanocomposites exhibit impressively large and negative normal stress differences, a rarely reported phenomenon in soft condensed matter. We illustrate the practical implications of these nonlinear transport properties by showing that MWNTs eliminate die swell in our nanocomposites, an effect crucial for their processing.

Complex Mixtures↗

PubMed2004

Breakup of a fluid thread in a confined geometry: droplet-plug transition, perturbation sensitivity, and kinetic stabilization with confinement.

We investigate the influence of geometrical confinement on the breakup of long fluid threads in the absence of imposed flow using a lattice Boltzmann model. Our simulations primarily focus on the case of threads centered coaxially in a tube filled with another Newtonian fluid and subjected to both impulsive and random perturbations. We observe a significant slowing down of the rate of thread breakup ("kinetic stabilization") over a wide range of the confinement, Lambda= R(tube)/R(thread) < or =10 and find that the relative surface energies of the liquid components influence this effect. For Lambda<2.3, there is a transition in the late-stage morphology between spherical droplets and tube "plugs." Unstable distorted droplets ("capsules") form as transient structures for intermediate confinement (Lambda approximately equal 2.1-2.5). Surprisingly, the thread breakup process for more confined threads (Lambda< or =1.9 ) is found to be sensitive to the nature of the initial thread perturbation. Localized impulsive perturbations ("taps") cause a "bulging" of the fluid at the wall, followed by thread breakup through the propagation of a wave-like disturbance ("end-pinch instability") initiating from the thread rupture point. Random impulses along the thread, modeling thermal fluctuations, lead to a complex breakup process involving a competition between the Raleigh and end-pinch instabilities. We also briefly compare our tube simulations to threads confined between parallel plates and to multiple interacting threads under confinement.

Journal Article↗

PubMed2004

Numerical path integration technique for the calculation of transport properties of proteins.

We present a new technique for the computation of both the translational diffusivity and the intrinsic viscosity of macromolecules, and apply it here to proteins. Traditional techniques employ finite element representations of the surface of the macromolecule, taking the surface to be a union of spheres or of polygons, and have computation times that are O(m(3)) where m is the number of finite elements. The new technique, a numerical path integration method, has computation times that are only O(m). We have applied the technique to approximately 1000 different protein structures. The computed translational diffusivities and intrinsic viscosities are, to lowest order, proportional respectively to N(-1/3)(R) and N(0)(R), where N(R) is the number of amino acid residues in the protein. Our calculations also show some correlation with the shape of the molecule, as represented by the ratio m(2)/m(3), where m(2) and m(3) are, respectively, the middle and the smallest of the three principal moments of inertia. Comparisons with a number of experimental results are also performed, with results generally consistent to within experimental error.

Algorithms↗

PubMed2004

Flory-Huggins model of equilibrium polymerization and phase separation in the Stockmayer fluid.

The competition between chain formation and phase separation in the Stockmayer fluid (SF) of dipolar particles is analyzed using a renormalized Flory-Huggins model of equilibrium polymerization. Calculated critical properties (T(c), phi(c), Z(c)) for the SF compare favorably with simulations over a wide range of the dimensionless dipolar (or "sticking") energy mu*. We find that the polymerization transition preempts phase separation for a large mu*, i.e., (mu*)2 >22.

Journal Article↗

PubMed2003

Growth of 'dizzy dendrites' in a random field of foreign particles.

Microstructure plays an essential role in determining the properties of crystalline materials. A widely used method to influence microstructure is the addition of nucleating agents. Observations on films formed from clay-polymer blends indicate that particulate additives, in addition to serving as nucleating agents, may also perturb crystal growth, leading to the formation of irregular dendritic morphologies. Here we describe the formation of these 'dizzy dendrites' using a phase-field theory, in which randomly distributed foreign particle inclusions perturb the crystallization by deflecting the tips of the growing dendrite arms. This mechanism of crystallization, which is verified experimentally, leads to a polycrystalline structure dependent on particle configuration and orientation. Using computer simulations we demonstrate that additives of controlled crystal orientation should allow for a substantial manipulation of the crystallization morphology.

Computer Simulation↗

PubMed2002

Amorphous solidification in polymer-platelet nanocomposites.

Computer simulations are used to understand the molecular basis of the rheology changes in polymer melts when loaded with platelet filler particles, specifically when the polymer and nanofiller interact attractively. With decreasing temperature, there is increasing aggregation between chains and filler and an increase in the polymer matrix structural relaxation time. These lifetimes are predicted to diverge at an extrapolated temperature, which we identify with the emergence of an amorphous solid state. Our findings suggest that filled polymers are phenomenologically similar to solutions of associating polymers and to supercooled liquids near their glass transition.

Journal Article↗

PubMed2002

What do we learn from the local geometry of glass-forming liquids?

We examine the local geometry of a simulated glass-forming polymer melt. Using the Voronoi construction, we find that the distributions of Voronoi volume P(v(V)) and asphericity P(a) appear to be universal properties of dense liquids, supporting the use of packing approaches to understand liquid properties. We also calculate the average free volume along a path of constant density and find that extrapolates to zero at the same temperature T0 that the extrapolated relaxation time diverges. We relate to the Debye-Waller factor, which is measurable by neutron scattering.

Journal Article↗

PubMed2002

Growth pulsations in symmetric dendritic crystallization in thin polymer blend films.

The crystallization of polymeric and metallic materials normally occurs under conditions far from equilibrium, leading to patterns that grow as propagating waves into the surrounding unstable fluid medium. The Mullins-Sekerka instability causes these wave fronts to break up into dendritic arms, and we anticipate that the normal modes of the dendrite tips have a significant influence on pattern growth. To check this possibility, we focus on the dendritic growth of polyethylene oxide in a thin-film geometry. This crystalline polymer is mixed with an amorphous polymer (polymethyl-methacrylate) to "tune" the morphology and clay was added to nucleate the crystallization. The tips of the main dendrite trunks pulsate during growth and the sidebranches, which grow orthogonally to the trunk, pulsate out of phase so that the tip dynamics is governed by a limit cycle. The pulsation period P increases sharply with decreasing film thickness L and then vanishes below a critical value L(c) approximately 80 nm. A change of dendrite morphology accompanies this transition.

Journal Article↗

PubMed2002

Nonequilibrium pattern formation in the crystallization of polymer blend films.

We show that the morphology of polyethylene oxide crystallization in thin films can be tuned to obtain circular spherulites, seaweed and symmetric dendrites, and fractal aggregation forms through the addition of clay particles and the amorphous polymer, polymethyl methacrylate. The thin-film polymer crystallization patterns are compared to a two-dimensional phase field model of dendritic growth in Ni/Cu alloys with a variable surface tension anisotropy epsilon. Some aspects of polymer crystallization patterns can be understood from the phase field calculations, but a more general model is required to describe the full range of observed patterns.

Anisotropy↗

PubMed2002

Beyond Flory-Huggins theory: new classes of blend miscibility associated with monomer structural asymmetry.

Flory-Huggins (FH) theory is restricted to polymer mixtures whose monomers are structurally identical, a situation limited to isotopic blends and computer simulations. We investigate the influence of monomer structure on blend miscibility and scattering properties using the lattice cluster theory generalization of the FH model. Monomer structural asymmetry is shown to profoundly affect blend miscibility (T(c),phi(c)), chain swelling (T(theta)), and the scale (xi) and intensity [S(0)] of composition fluctuations. Four distinct blend miscibility classes are identified and experimental evidence for these classes is discussed.

Kinetics↗