Meltblown fibers: Influence of viscosity and elasticity on diameter distribution

Both melt viscosity (η_o) and elasticity (correlated here with the longest melt relaxation time λ₁) were found to control the diameter distribution of meltblown fibers. Fibers were formed by melt blowing binary polystyrene (PS) blends containing widely differing component molecular weights using a custom-built laboratory apparatus. Varying the concentration and molecular weight of a high molecular weight PS provided independent control over η_o and λ₁. These rheological parameters influence the average diameter (d_av) and the distribution of diameters (coefficient of variation, CV) of meltblown fibers in different ways. Increasing η_o leads to an increase in d_av but has little impact on CV. On the other hand, increasing λ₁ beyond a threshold value reduces CV while simultaneously increasing d_av. A one-dimensional slender-jet theoretical model with both upper convected Maxwell and Phan–Thien and Tanner constitutive equations was developed to investigate the influence of viscoelasticity and processing parameters on the properties of meltblown fibers. This model predicts a strong dependence of fiber diameter on the air shear stress and variations in fiber diameter with viscoelasticity that are in qualitative agreement with the experimental results. We believe these results suggest that carefully controlling the viscoelastic profile of polymers used in melt blowing is a viable approach for producing nanofibers with narrow fiber diameter distributions using current commercial equipment.     

Cycloadditions of Bifunctional Vinyl Ethers with Electrophilic Alkenes through Tetramethylene Zwitterion Intermediates

Bifunctional vinyl ethers react with electron‐poor alkenes to cyclobutanes in good yields. The second C?C bond reacted with neither the cyclobutane nor its zwitterion intermediate, even on heating. Cyclobutanes formed from ‘tetracyanoethylene’ ( 8 ) were transformed into tetrahydropyridines by reaction of the corresponding zwitterion with MeCN as the solvent. In contrast, cyclobutanes formed from dimethyl (dicyanomethylidene)propanedioate ( 9 ) did not react with MeCN, which is ascribed to diminished stabilization of the zwitterion intermediate, and increased steric effects. These results extend the classical studies of Huisgen and his co‐workers.     

ABA triblock copolymers with a ring‐opening metathesis polymerization/macromolecular chain‐transfer agent approach

Block copolymers containing polystyrene and polycyclooctene were synthesized with a ring‐opening metathesis polymerization/chain‐transfer approach. Polystyrene, containing appropriately placed olefins, was prepared by anionic polymerization and served as a macromolecular chain‐transfer agent for the ring‐opening metathesis polymerization of cyclooctene. These unsaturated polymers were subsequently converted to the corresponding saturated triblock copolymers with a simple heterogeneous catalytic hydrogenation step. The molecular and morphological characterization of the block copolymers was consistent with the absence of significant branching in the central polycyclooctene and polyethylene blocks [high melting temperatures (114–127 °C) and levels of crystallinity (17–42%)]. A dramatic improvement in both the long‐range order and the mechanical properties of a microphase‐separated, symmetric polystyrene–polycyclooctene–polystyrene block copolymer sample was observed after fractionation. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 361–373, 2007     

Spectral analysis and multidimensional stability of traveling waves for nonlocal Allen-Cahn equation

In this paper, the spectrum of linearized operator about a traveling wave for the nonlocal Allen-Cahn equation is estimated and the result is applied to study multidimensional stability of planar waves.     

Existence and instability of spike layer solutions to singular perturbation problems

An abstract framework is given to establish the existence and compute the Morse index of spike layer solutions of singularly perturbed semilinear elliptic equations. A nonlinear Lyapunov-Schmidt scheme is used to reduce the problem to one on a normally hyperbolic manifold, and the related linearized problem is also analyzed using this reduction. As an application, we show the existence of a multi-peak spike layer solution with peaks on the boundary of the domain, and we also obtain precise estimates of the small eigenvalues of the operator obtained by linearizing at a spike layer solution.     

Synthesis and Antitumor Activity of Heterocycles Related to Carbendazim

Three types of compounds were synthesized from carbendazim ( 1 ), a benzimidazole derivative (Scheme 1 ). They included a group of esters at N1 prepared by treating carbendazim with isocyanates bearing ester groups ( 2a , 2b , 2c ), carboxyalkyl‐1,2,3,4‐tetrahydro‐s‐triazino[1,2‐a]benzimidazole‐2,4‐dione esters ( 3a and 3b , 3d and 3c derived from 3a . The antitumor potencies of the N1 esters were in the range of 7 to 40 μM, which compares favorably with carbendazim, but their water solubilities were low. The s‐triazine derivatives showed activity against pancreatic tumor cells, and one of them ( 3b ) was active in mice, but they were not effective against other tumor types. Treatment of carbendazim with 3‐bromopropionyl chloride produced 1‐methoxycarbonyl‐4‐oxo‐1,2,3,4‐tetrahydropyrimido[1,2‐a]benzimidazole ( 4 ), which gave 1‐(3‐aminopropionyl)benzimidazole 2‐methylcarbamates, substituted on the amino nitrogen ( 5a , 5b , and 5d ), when treated with amines. These products showed some antitumor activity in cell cultures, and an ethoxy derivative ( 5c ), obtained by treating 1‐methoxycarbonyl‐4‐oxo‐1,2,3,4‐tetrahydropyrimido[1,2‐a]benzimidazole with sodium ethoxide, was active in the 67–150 μM range. Some of the new compounds had good water solubility. Carbendazim kills tumor cells by inhibiting tubulin; however, s‐triazine 3b , which differs from it in size and functional groups, does not act by this mechanism.     

A displaced-line velocity diagnostic and its application in a visualization engine

A technique for measuring three-dimensional velocity by imaging the displacement of a marked fluid line is described, together with its use in an automotive visualization engine. In a flow seeded with 2–3 μ phosphorescing particles, a line is excited by a UV laser beam, deformed by the local velocity field, and detected by stereo low-light-level video cameras. The derivation of velocity from digitized images is discussed and capabilities of the diagnostic are assessed. Some image data taken in the engine are shown and quantitative two-component velocity plots along the line are presented.     

Polymeric cross-linked surface treatments for controlling block copolymer orientation in thin films

The orientation of cylinder-forming poly(styrene-block-methyl methacrylate) [P(S-b-MMA)] was investigated on two sets of polymeric surface treatments: 10 para-substituted polystyrene derivatives with <10 mol % poly(4-vinylbenzyl azide) and a series of poly(styrene-random-4-vinylbenzyl azide) [P(S-r-VBzAz)] copolymers with 5-100 mol % poly(4-vinylbenzyl azide). The copolymers were spin-coated to form thin films and then cross-linked by heating. The resulting films exhibited a range of surface tensions from 21 to 45 dyn/cm. Perpendicular orientation of P(S-b-MMA) cylinders was achieved with poly(p-bromostyrene) and all the [P(S-r-VBzAz)] copolymer surface treatments, most notably the homopolymer of poly(4-vinylbenzyl azide). Films made from these simple copolymers are as effective as random terpolymer alignment layers commonly made from both block monomers and a cross-linkable monomer.