Polymer chain stiffness versus excluded volume: A Monte Carlo study of the crossover towards the wormlike chain model

When the local intrinsic stiffness of a polymer chain varies over a wide range, one can observe both a crossover from rigid-rod-like behavior to (almost) Gaussian random coils and a further crossover towards self-avoiding walks in good solvents. Using the pruned-enriched Rosenbluth method (PERM) to study self-avoiding walks of up to $N_b=50000$ steps and variable flexibility, the applicability of the Kratky-Porod model is tested. Evidence for non-exponential decay of the bond-orientational correlations $<\cos \theta (s) >$ for large distances $s$ along the chain contour is presented, irrespective of chain stiffness. For bottle-brush polymers on the other hand, where experimentally stiffness is varied via the length of side-chains, it is shown that these cylindrical brushes (with flexible backbones) are not described by the Kratky-Porod wormlike chain model, since their persistence length is (roughly) proportional to their cross-sectional radius, for all conditions of practical interest.Comment: 6 pages, 5 figures, to be published in Europhys. Lett. (2010

Why polymer chains in a melt are not random walks

A cornerstone of modern polymer physics is the `Flory ideality hypothesis' which states that a chain in a polymer melt adopts `ideal' random-walk-like conformations. Here we revisit theoretically and numerically this pivotal assumption and demonstrate that there are noticeable deviations from ideality. The deviations come from the interplay of chain connectivity and the incompressibility of the melt, leading to an effective repulsion between chain segments of all sizes $s$. The amplitude of this repulsion increases with decreasing $s$ where chain segments become more and more swollen. We illustrate this swelling by an analysis of the form factor $F(q)$, i.e. the scattered intensity at wavevector $q$ resulting from intramolecular interferences of a chain. A `Kratky plot' of $q^2F(q)$ {\em vs.} $q$ does not exhibit the plateau for intermediate wavevectors characteristic of ideal chains. One rather finds a conspicuous depression of the plateau, $\delta(F^{-1}(q)) = |q|^3/32\rho$, which increases with $q$ and only depends on the monomer density $\rho$.Comment: 4 pages, 4 figures, EPL, accepted January 200

Tuning of emission color for blue dendrimer blend light-emitting diodes

Published versio

Freezing of Spinodal Decompostion by Irreversible Chemical Growth Reaction

We present a description of the freezing of spinodal decomposition in systems, which contain simultaneous irreversible chemical reactions, in the hydrodynamic limit approximation. From own results we conclude, that the chemical reaction leads to an onset of spinodal decomposition also in the case of an initial system which is completely miscible and can lead to an extreme retardation of the dynamics of the spinodal decomposition, with the probability of a general freezing of this process, which can be experimetally observed in simultaneous IPN formation.Comment: 10 page

Orthorhombic Phase of Crystalline Polyethylene: A Constant Pressure Path Integral Monte Carlo Study

In this paper we present a Path Integral Monte Carlo (PIMC) simulation of the orthorhombic phase of crystalline polyethylene, using an explicit atom force field with unconstrained bond lengths and angles. This work represents a quantum extension of our recent classical simulation (J. Chem. Phys. 106, 8918 (1997)). It is aimed both at exploring the applicability of the PIMC method on such polymer crystal systems, as well as on a detailed assessment of the importance of quantum effects on different quantities. We used the $NpT$ ensemble and simulated the system at zero pressure in the temperature range 25 - 300 K, using Trotter numbers between 12 and 144. In order to investigate finite-size effects, we used chains of two different lengths, C_12 and C_24, corresponding to the total number of atoms in the super-cell being 432 and 864, respectively. We show here the results for structural parameters, like the orthorhombic lattice constants a,b,c, and also fluctuations of internal parameters of the chains, such as bond lengths and bond and torsional angles. We have also determined the internal energy and diagonal elastic constants c_11, c_22 and c_33. We discuss the temperature dependence of the measured quantities and compare to that obtained from the classical simulation. For some quantities, we discuss the way they are related to the torsional angle fluctuation. In case of the lattice parameters we compare our results to those obtained from other theoretical approaches as well as to some available experimental data. In order to study isotope effects, we simulated also a deuterated polyethylene crystal at a low temperature. We also suggest possible ways of extending this study and present some general considerations concerning modeling of polymer crystals.Comment: 18 pages, RevTex, 18 figures, 3 tables, submitted to Phys. Rev.

Intrinsic profiles and capillary waves at homopolymer interfaces: a Monte Carlo study

A popular concept which describes the structure of polymer interfaces by ``intrinsic profiles'' centered around a two dimensional surface, the ``local interface position'', is tested by extensive Monte Carlo simulations of interfaces between demixed homopolymer phases in symmetric binary (AB) homopolymer blends, using the bond fluctuation model. The simulations are done in an LxLxD geometry. The interface is forced to run parallel to the LxL planes by imposing periodic boundary conditions in these directions and fixed boundary conditions in the D direction, with one side favoring A and the other side favoring B. Intrinsic profiles are calculated as a function of the ``coarse graining length'' B by splitting the system into columns of size BxBxD and averaging in each column over profiles relative to the local interface position. The results are compared to predictions of the self-consistent field theory. It is shown that the coarse graining length can be chosen such that the interfacial width matches that of the self-consistent field profiles, and that for this choice of B the ``intrinsic'' profiles compare well with the theoretical predictions.Comment: to appear in Phys. Rev.

Portfolio Vol. I N 2

Wiley, Thomas R. In the Cathedral, Mexico City . Picture. 2. Whitehead, Richard Jr. Izzy was a Lady, After All . Prose. 3. Beckham, Adela. Rain on a March morning . Poem. 6. Beckham, Adela. Heaven . Poem. 6. Deane, Dorothy. Temptation . Poem. 6. Kellogg, Elizabeth. Gruess Dich Gott . Prose. 7. Nadel, Norman. The Duchess . Poem. 8. Dick, Pewilla. The Sligo Fisherman . Prose. 9. Deane, Dorothy. Against the Winter . Poem 12. Flory, Doris Jean. A problem . Poem 12. Travis, Paul Bough. My First View of the Congo Forest . Picture. 13. Bellows, George. Stag at Sharkey\u27s . Picture. 13. B.C.W. Aspiration . Poem. 14. Stewart, John. On Record . Prose 14. Sweitzer, Harry J. Playing Around . Prose. 15. Ellsberg, Edward. Book Parade: Hell on Ice . Prose. 15. B.C.W. End of Winter . Poem. 16. Wiley, Thomas R. End of Winter . Picture. 16. Deeter, Robert. Television, How, Where, and When . Prose. 17. Brush, Jane. Love A La Mode . Poem. 20. Brush, Jane. Radio! . Poem. 20. Brush, Jane. Backward Glance . Poem. 20. Brush, Jane. Homo Paradoxus . Poem. 20. Brush, Jane. The Sardonic Slant . Poem. 20. Brush, Jane. Baths . Prose. 20. Wilson, Gordon. Brushword . Cartoon. 20

The effect of elevated carbon dioxide on a Sierra-Nevadan dominant species: Pinus ponderosa

The impact of increasing atmospheric C0{sub 2} has not been fully evaluated on western coniferous forest species. Two year old seedlings of Pinusponderosa were grown in environmentally controlled chambers under increased C0{sub 2} conditions for 6 months. These trees exhibit morphological, physiological, and biochemical alterations when compared to our controls. Analysis of whole plant biomass distribution has shown no significant effect to the root to shoot ratios, however needles subjected to elevated C0{sub 2} exhibited an increased overall specific needle mass and a decreased total needle area. Morphological changes at the needle level included decreased mesophyll to vascular tissue 91 ratio and variations in starch storage in chloroplasts. The elevated CO{sub 2} increased internal CO{sub 2} concentrations and assimilation of carbon. Biochemical assays revealed that ribulose-bisphosphate carboxylase specific activities increased on per unit area basis with C0{sub 2} treatment levels. Sucrose phosphate synthase (SPS) activities exhibited an increase of 55% in the 700 uL L{sup {minus}1} treatment. These results indicate that the sink-source relationships of these trees have shifted carbon allocation toward above ground growth, possibly due to transport limitations