Recent experiments suggest that short fibers in concentrated suspensions align more slowly as a function of strain than models based on Jeffery’s equation predict. We develop an objective model that captures the slow orientation kinetics exhibited by short-fiber suspensions. The standard moment-tensor equation of fiber orientation is used to find equations for the change rates of the eigenvalues and eigenvectors of the orientation tensor. As a phenomenological assumption, the growth rates of the eigenvalues are reduced by a constant scalar factor, while the rotation rate expressions for the eigenvectors are unchanged. The eigenvalue/eigenvector equations are then reassembled as a tensor equation. An equivalent kinetic theory is also developed. The new model is tested in a variety of flows, and found to exhibit slower kinetics than the standard model but similar steady-state orientations. The model provides an excellent fit to the shear stress transient in a shear reversal experiment with a 30% glass fiber filled polybutylene terephthalate resin melt, and we show how this experiment can be used to determine the parameters of the model.

While considerable effort has been expended on determining the health effects of exposure to typical urban concentrations of O3, little is known about the chemical events responsible for toxicity. Phospholipids containing unsaturated fatty acids in the cell membranes of lung cells are likely reaction sites for inhaled ozone (O3). In this study, we examined the reaction of O3 with 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) in unilamellar phospholipid vesicles. Reaction of ozone with the carbon-carbon double bond of POPC yielded an aldehyde and a hydroxy hydroperoxide. The hydroxy hydroperoxide eliminated H2O2 to yield a second aldehyde. Upon further ozonolysis, the aldehydes were oxidized to the corresponding carboxylic acids. A material balance showed that no other reaction consumed POPC and O3 or produced these products. As a mechanistic probe, we measured incorporation of oxygen-18 from 18O3 into aldehyde, carboxylic acid, and H2O2. Approximately 50% of the aldehyde oxygen atoms were derived from O3. Oxygen in H2O2 was derived solely from O3, where both oxygen atoms in a molecule of H2O2 were from the same molecule of O3. One of the carboxylic acid oxygen atoms was derived from the precursor aldehyde, while the other was derived from O3. These results support the following mechanism. Cleavage of the carbon-carbon double bond of POPC by O3 yields a carbonyl oxide and an aldehyde. Reaction of H2O with the carbonyl oxide yields a hydroxy hydroperoxide, preventing formation ozonide by reaction of the carbonyl oxide and aldehyde. Elimination of H2O2 from the hydroxy hydroperoxide yields a second aldehyde. Oxidation of the aldehydes by O3 yields carboxylic acids.

We present a finite element method for predicting the fiber orientation patterns in 3-D injection molded features, and compare the predictions to experiments. The predictions solve the full balance equations of mass, momentum, and energy for a generalized Newtonian fluid. A second-order tensor is used to describe and calculate the local fiber orientation state. A standard Hele-Shaw molding filling simulation is used to provide inlet boundary conditions for the detailed finite element models, which are limited to the local geometry of each feature. The experiments use automated image analysis of polished cross-sections to determine fiber orientation as a function of position. Predictions compare well with experiments on a transverse rib, where the detailed calculation can be 2-D. Results of a 3-D calculation for a flow-direction rib also show generally good agreement with experiments. Some errors in this latter calculation are caused by not simulating the initial filling of the rib, due to computational limits.

Proton spin-lattice relaxation and proton spin-lattice relaxation in the rotating frame were observed in the solid polycarbonate of l,l-dichloro-2,2-bis(4-hydroxyphenyl)ethylene from 150 to 400 K. This polymer is suited to this type of study since it contains only a single type of proton. The relaxation times are quantitatively interpreted as a function of temperature using a correlation function-spectral density approach. Two types of correlation functions that are somewhat successful result from the one-dimensional defect diffusion model (DDM) and the correlated states model (CSM). Both can adequately simulate the proton relaxation data but the CSM also successfully accounts for the temperature dependence of the second moment and accurately predicts the location and much of the width of the low-temperature mechanical loss peak. The activation energy of the fundamental process in the CSM is also close to that observed in dilute solutions of the same polycarbonate and close to that calculated by MNDO (modified neglect of diatomic overlap) applied to model compounds. The Hartree-Fock calculations in conjunction with the earlier proton line width study are used to consider the repeat unit level geometry of the motion causing both spin relaxation and mechanical loss.

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