Theory of gel point in real polymer solutions

We develop a new theory of gelation which takes into account (i) delay of the gel point and (ii) change of functionality due to ring formation. We show that the problem of finding the gel point in real polymer solutions reduces to the problem of calculating the total ring concentration and the extent of reaction of intermolecular reaction at the gel point. In this paper, we solve a special case of this problem, on the basis of the independence assumption between intermolecular reaction and cyclization which takes into account only (i) the delay of the gel point: making use of the asymptotic equality of the total ring concentration, we acquire an approximate solution for the gel point D_c as a function of the inverse concentration , the relative frequency of cyclization and dimension d. Applying the observed values of in linear polyesters, the theoretical result reproduces well the Wile and the Gordon-Scantlebury observations, showing the existence of a critical dilution beyond which gelation can not occur, and an asymptote . As the classical gel point is approached, the present theory reduces to the linear equation, which makes one-to-one correspondence with the real slope , suggesting the inequality which is just what polymer chemists have quested for so far, with the physical meaning having remained unknown. Receveid: 30 December 1997 / Revised: 28 May 1998 / Accepted: 12 June 1998     

Multiple conformations in polyampholytes

We study the configurational statistics of a ring polyampholyte chain made of N randomly charged monomers with elementary charge .To a large extent, the overall structure of a polyampholyte is controlled by a total sum Q of all charges. When the total charge is smaller than , the polyampholyte has a compact globular structure. At charges larger than , the configuration has the form of a ring of small globules (beads) connected by strings. Between Q₁ and Q₂ we find a remarkable diversity of meta-stable configurations having the shapes of irregular clusters of small globules connected by the strings. We estimate the number of these configurations and the energy barriers between them. Between Q₁ and Q₂, the minimum energy configurations are completely controlled by randomness in the charge distribution along the chain. There are hysteresis effects in the shapes of the clusters. As the total charge increases, the linearly extended configurations become dynamically more preferable. When the charge decreases, the circular shapes are preferred. We remark on the probable connection with the multiple phase transitions observed in polyampholyte gels. Received: 10 July 1997 / Accepted: 13 October 1997     

Drift of a polymer chain in a porous medium --A Monte Carlo study

We investigate the drift of an end-labeled telehelic polymer chain in a frozen disordered medium under the action of a constant force applied to the one end of the macromolecule by means of an off-lattice bead spring Monte Carlo model. The length of the polymers N is varied in the range 8 < N < 128, and the obstacle concentration in the medium C is varied from zero up to the percolation threshold C≈ 0.75. For field intensities below a C-dependent critical field strength B _c, where jamming effects become dominant, we find that the conformational properties of the drifting chains can be interpreted as described by a scaling theory based on Pincus blobs. The variation of drag velocity with C in this interval of field intensities is qualitatively described by the law of Mackie-Meares. The threshold field intensity B _c itself is found to decrease linearly with C. Received 20 August 2001 and Received in final form 19 November 2001     

Characterization of the structure and the size distribution of branched polymers formed by co-polymerization of MMA and EGDMA

Free radical co-polymerization of methyl methacrylate (MMA) and ethyl glycol dimethyl methacrylate (EGDMA) in solution leads to the formation of polydisperse branched PMMA which grows in size until the system gels. The structure and the size distribution of the PMMA aggregates were characterized at infinite dilution using static and dynamic light scattering and size exclusion chromatography (SEC). The reaction extent was measured using SEC and Raman spectroscopy. The results show that the structure and size distribution of PMMA aggregates formed close to the gel point are compatible with those of percolating clusters. The structure factor of semi-dilute solutions of PMMA aggregates is the same as that of dilute solutions at distance scales much smaller than the correlation length of the concentration fluctuations (). However, the cut-off function of the pair correlation function at for semi-dilute solutions is more gradual than the cut-off function at for dilute solutions. Received 11 May 1998 and Received in final form 22 October 1998     

Effects of ionic strength and charge annealing in star-branched polyelectrolytes

We have developed a scaling theory that describes the conformations of weak star-branched polyelectrolytes in dilute solutions. The dependences of the overall star size on the number of branches and on the ionic strength of the solution (tuned by the addition of low molecular weight salt) are analyzed. The intrinsic structure of the polyelectrolyte stars in salt-free and salt-added solutions is discussed in terms of concentration and elastic blobs. In contrast to neutral stars, the swollen corona of the polyelectrolyte star consists of blobs which are not closely packed. We have shown that the size of star polyelectrolytes is less sensitive to the variation in the ionic strength than the size of linear polyelectrolytes. The effects of the ionization-recombination balance in the star polyelectrolyte were taken into account. For polyelectrolytes with small ionization constant, the size of the star depends nonmonotonically on the number of branches and on the ionic strength of the solution due to recombination of counterions with charged monomers. Received: 10 November 1997 / Revised: 16 February 1998 / Accepted: 1st April 1998     

Swelling of two-dimensional polymer rings by trapped particles

The mean area of a two-dimensional Gaussian ring of N monomers is known to diverge when the ring is subject to a critical pressure differential, p _c ∼ N ^-1. In a recent publication (Eur. Phys. J. E 19, 461 (2006)) we have shown that for an inextensible freely jointed ring this divergence turns into a second-order transition from a crumpled state, where the mean area scales as 〈A〉 ∼ N, to a smooth state with 〈A〉 ∼ N ². In the current work we extend these two models to the case where the swelling of the ring is caused by trapped ideal-gas particles. The Gaussian model is solved exactly, and the freely jointed one is treated using a Flory argument, mean-field theory, and Monte Carlo simulations. For a fixed number Q of trapped particles the criticality disappears in both models through an unusual mechanism, arising from the absence of an area constraint. In the Gaussian case the ring swells to such a mean area, 〈A〉 ∼ NQ, that the pressure exerted by the particles is at p _c for any Q. In the freely jointed model the mean area is such that the particle pressure is always higher than p _c, and 〈A〉 consequently follows a single scaling law, 〈A〉 ∼ N ² f (Q/N), for any Q. By contrast, when the particles are in contact with a reservoir of fixed chemical potential, the criticality is retained. Thus, the two ensembles are manifestly inequivalent in these systems. An erratum to this article is available at .     

On the number of intersections of self-repelling polymer chains

We give a detailed analysis of the intersection properties of polymers. Using the renormalization group we provide a full crossover function for the dependence of the number of intersections in a single polymer on chain length and excluded volume strength. We compare our results with Monte-Carlo data and with exact calculations for a random walk, finding good agreement in all respects. Restricting to the vicinity of the eight ternary fixed points we also calculate the number of intersections between two chains placed at a fixed distance, including the two halves of a block-copolymer. The analysis of these systems confirms the interpretation of the different contributions to the number of intersections in a single chain. Due to the highly nontrivial character of the correlations in a polymer chain the correction exponents in both cases however are different. None of the results can be extracted from any Flory-type estimate. Received: 1 April 1997 / Revised: 24 October 1997 / Accepted: 29 January 1998     

Grafted polymers with annealed excluded volume: A model for surfactant association in brushes

We present an analytical self-consistent-field (SCF) theory for a neutral polymer brush (a layer of long polymer chains end-grafted to a surface) with annealed excluded volume interactions between the monomer units. This model mimics the reversible adsorption of solute molecules or aggregates, such as small globular proteins or surfactant micelles, on the grafted chains. The equilibrium structural properties of the brush (the brush thickness, the monomer density profile, the distribution of the end segments of the grafted chains) as well as the overall adsorbed amount and the adsorbate density profile are analyzed as a function of the grafting density, the excluded volume parameters and the chemical potential (the concentration) of the adsorbate in the solution. We demonstrate that, when the grafting density is varied, the overall adsorbed amount always exhibits a maximum, whereas the root-mean-square brush thickness either increases monotonically or passes through a (local) minimum. At high grafting densities the chains are loaded by adsorbed aggregates preferentially in the distal region of the brush, whereas in the region proximal to the grafting surface depletion of aggregates occurs and the polymer brush retains an unperturbed structure. Depending on the relative strength of the excluded volume interactions between unloaded and loaded monomers both the degree of loading of the chains and the polymer density profile are either continuous or they exhibit a discontinuity as a function of the distance from the grafting surface. In the latter case intrinsic phase separation occurs in the brush: the dense phase consists of unloaded and weakly extended chains and occupies the region proximal to the surface, whereas a more dilute phase consisting of highly loaded and strongly extended chains forms the periphery of the brush. Received 26 November 1998 and Received in final form 2 April 1999     

Log-periodic oscillations for biased diffusion of a polymer chain in a porous medium

A coarse-grained off-lattice bead-spring model is used to reveal the complex dynamics of a polymer chain in a quenched porous medium in the presence of an external field B. The behavior of the mean square displacement (MSD) of the center chain bead and that of the center of mass of the chain as a function of time is studied at different values of the barrier concentration C, the field strength B and the chain length N. In a field, important information on the way in which chains move between obstacles and overcome them is gained from the MSD vs. time analysis in the directions parallel and perpendicular to the flow. Instead of a steady approach to uniform drift-like motion at low C, for sufficiently strong field B we observe logarithmic oscillations in the effective exponents describing the time dependence of the MSD along and perpendicular to field. A common nature of this phenomenon with oscillatory behavior, observed earlier for biased diffusion of tracers on random lattices, is suggested. Received 7 August 1998     

Smoothening transition of a two-dimensional pressurized polymer ring

We revisit the problem of a two-dimensional polymer ring subject to an inflating pressure differential. The ring is modeled as a freely jointed closed chain of N monomers. Using a Flory argument, mean-field calculation and Monte Carlo simulations, we show that at a critical pressure, p_c ∼ N^-1, the ring undergoes a second-order phase transition from a crumpled, random-walk state, where its mean area scales as 〈A〉 ∼ N, to a smooth state with 〈A〉 ∼ N². The transition belongs to the mean-field universality class. At the critical point a new state of polymer statistics is found, in which 〈A〉 ∼ N^3/2. For p ≫ p_c we use a transfer-matrix calculation to derive exact expressions for the properties of the smooth state.     

Suppression of superconductivity in high-T c cuprates due to nonmagnetic impurities: Implications for the order parameter symmetry

We show explicitly that the broad histogram single-spin-flip random walk dynamics does not give correct microcanonical average even in one dimension. The dynamics violates the detailed balance condition by an amount proportional to the inverse system size. As a result, in distribution different configurations with the same energy can have different probabilities. We propose a modified dynamics which ensures detailed balance and the histogram obtained from this dynamics is exactly flat. The broad histogram equation relating the average number of potential moves to density of states is generally valid. Received 2 October 1998 and Received in final form 13 October 1998     

Risk analysis in investment appraisal based on the Monte Carlo simulation technique

This work has been prepared for the purpose of presenting the methodology and uses of the Monte Carlo simulation technique as applied in the evaluation of investment projects to analyze and assess risk. In the deterministic appraisal the basic decision rule for a project is simply to accept or reject the project depending on whether its net present value (NPV) is positive or negative, respectively. Similarly, when choosing among alternative (mutually exclusive) projects, the decision rule is to select the one with the highest NPV, provided that it is positive. Recognizing the fact that the key project variables (as: volume of sales, sales price, costs) are not certain, an appraisal report is usually supplemented to include sensitivity and scenario analysis tests. Both tests are static and rather arbitrary in their nature. During the simulation process, random scenarios are built up using input values for the project's key uncertain variables, which are selected from appropriate probability distributions. The results are collected and analyzed statistically so as to arrive at a probability distribution of the potential outcomes of the project and to estimate various measures of project risk. Received 25 September 2000     

New considerations on the role of covalency in ferroelectric niobates and tantalates

We consider the interaction of an homogeneous polyelectrolyte with an obstacle during electrophoretic drift. We explicitly take into account the hydrodynamic interactions generated by this mechanical trapping, and we evaluate their influence on the unhooking process. Important qualitative effects are pointed out in low and moderate field regimes. However, numerical simulations indicate that, in strong field, the existing simpler local force models, which neglect these hydrodynamic interactions, are quantitatively acceptable. Received: 18 March 1998 / Received in final form and accepted: 20 May 1998     

Deformation of globular polysoaps: extension, confinement and extensional flow

A theoretical model of the extension and confinement of globular polysoaps predicts novel force laws. Polysoaps are polymers comprising of a flexible hydrophilic backbone incorporating, at intervals, amphiphilic monomers. The equilibrium configuration of long polysoaps, that form numerous spherical intrachain micelles, is a spherical globule of close packed micelles. The coupling of the deformation to the hierarchical self organization of the chain gives rise to a distinctive force law involving, for extension, two plateau regimes. When the chain is stretched by extensional flow the two regimes merge and the polysoap exhibits a single globule-stretch transition. Received 16 June 1998 and Received in final form 19 November 1998     

Quantum-Monte-Carlo simulations of polyethylene

The diffusion Quantum-Monte-Carlo method of solving the Schr?dinger equation is applied to the vibrational ground state of a polyethylene molecule. The results for the ground state energy show good agreement with normal mode analysis. In addition to stretching, bending and torsional interaction van-der-Waals interaction is applied to a single chain showing a decrease of the energy of 5%. The decrease for a polyethylene system of 5 chains with 10 atoms per molecule at the positions of a unit cell is determined to be 4.8% per molecule. Finally first steps towards simulating excited states were performed. Received: 9 February 1998 / Revised: 2 April 1998 / Accepted: 23 April 1998     

Polymer adsorption on heterogeneous surfaces

The adsorption of a single ideal polymer chain on energetically heterogeneous and rough surfaces is investigated using a variational procedure introduced by Garel and Orland (Phys. Rev. B 55, 226 (1997)). The mean polymer size is calculated perpendicular and parallel to the surface and is compared to the Gaussian conformation and to the results for polymers at flat and energetically homogeneous surfaces. The disorder-induced enhancement of adsorption is confirmed and is shown to be much more significant for a heterogeneous interaction strength than for spatial roughness. This difference also applies to the localization transition, where the polymer size becomes independent of the chain length. The localization criterion can be quantified, depending on an effective interaction strength and the length of the polymer chain. Received: 29 October 1997 / Revised: 19 December 1997 / Accepted: 6 March 1998     

Hydrodynamic interactions in self similar structures, such as polymers

We study the hydrodynamic properties of polymers and more generally self-similar structures using a new recursion model. The hydrodynamic interaction between monomers is modeled by the standard Green's function of Stokes flow in which an ultrametric distance is substituted for the usual Euclidean distance. This leads to a model where the long-range hydrodynamic interactions and the long-range correlations of the polymer conformation can both be accounted for and yet allow for analytical solutions. We explore the asymptotic as well as the finite size corrections to the scaling behavior with this model. In order to compare the results of the present scheme with more conventional techniques a generalized version of the existing mean field results by Kirkwood and Riseman for the hydrodynamic drag is introduced. Received 26 August 1998 and Received in final form 7 December 1998     

Model of populations colonizing a new habitat

We propose a model suitable for investigating the conditions under which a population, adapted to a given environment, may colonize a new neighbouring, spatially separated, habitat. We find out how similar the two regions must be for such a colonization to succeed and what will be the spatial distribution of genetic pools of the two populations after the process. It is found that between the two populations each adapted to the different region, a hybrid zone, characterized by increased heterozygosity, may be formed. The dependence of the shape of the hybrid zone on the external (environmental) parameters is determined. When the differences between the two regions are significant, the populations are separated by a depopulated zone. We show that the conditions in the colonized habitat influence the genetic pool of the population living in the first region. Computer simulations based on the standard Monte Carlo technique are used. Received 11 December 1998 and Received in final form 17 December 1998     

Dynamic and static light scattering study of the formation of cross-linked PMMA gels

Free radical co-polymerization of methyl methacrylate (MMA) and ethyl glycol dimethyl metacrylate (EGDMA) was investigated in solution at different molar ratios R = [EGDMA]/[MMA] between 0 and 0.05. Initially mainly linear PMMA was formed with weight average molar mass 7.5 g/mol independent of R. At larger reaction extents branched polymers were formed and the systems gelled. The scattering intensity rose initially with the reaction extent, but reached a plateau value at larger reaction extents. The plateau value increased strongly with R. Dynamic light scattering showed the appearance of a slow relaxation not observed in linear PMMA solutions. The data can be interpreted by assuming that the excess scattering originates from the branching points and relaxes through self diffusion of the branched particles. The results agree with predictions of the percolation model for gelation and Rouse dynamics. Viscosity measurements corroborate this interpretation. Measurements on a progressively diluted sample quenched close to the gel point again showed quantitative agreement with the percolation model for gelation. Received 11 May 1998 and Received in final form 22 October 1998