Studying of the critical exponents around the glass transition in bulk polymerization of ethyl methacrylate by using fluorescence techniques

The glass transition during bulk polymerization was studied in free-radical crosslinking copolymerization (FCC) of ethyl methacrylate (EMA), using both the steady-state fluorescence (SSF) and the fast transient fluorescence (FTRF) techniques. Pyrene (Py) was used as a fluorescence probe. Changes in the viscosity of the pregel solutions due to gel formation dramatically enhance the fluorescent yield of Py molecules. The reaction time at which the Py intensity and lifetime exhibit a sudden increase corresponds to the reaction time at which the rate of polymerization becomes maximum resulting from the gel effect. This effect is used to study the gelation of EMA, as a function of time, at various crosslinker concentrations and different temperatures. The results were interpreted in the view of percolation theory. The gel fraction, β and weight average degree of polymerization, γ exponents β?=?0.37?±?0.01, γ?=?1.71?±?0.04 and β?=?0.36?±?0.002, γ?=?1.687?±?0.01 are found in agreement with percolation results for SSF and FTRF measurements, respectively.     

Ffast Transient Fluorescence Technique to Study Critical Exponents at the Glass Transition

The fast transient fluorescence (FTRF) technique was used to study critical exponents at the glass transition in free-radical crosslinking copolymerization (FCC) for two different monomeric systems, methyl methacrylate (MMA) and styrene (S). Pyrene (P_y ) was used as a fluorescence probe. The fluorescence lifetimes of P_y from its decay traces were measured and used to monitor the gelation process. Changes in the viscosity of the pregel solutions due to glass formation dramatically enhance the fluorescent yield of aromatic molecules. This effect is used to study the glass transition upon gelation of MMA and S monomeric systems as a function of time, at various temperatures and crosslinker concentrations. The results are interpreted in the view of percolation theory. The gel fraction and weight average degree of polymerization exponents β and γ are found to be 0.37 ± 0.02 and 1.66 ± 0.07 in agreement with percolation results.     

Network Forming Fluids: Yukawa Square-Well <Emphasis Type="Italic">m</Emphasis>-Point Model

Thermal and connectivity properties of the Yukawa square-well m-point (YSWmP) model of the network forming fluid are studied using solution of the multidensity Ornstein-Zernike and connectedness Ornstein-Zernike equations supplemented by the associative mean spherical approximation (AMSA). The model is represented by the multicomponent mixture of Yukawa hard spheres with m_s^am_{s}^{a} square-well sites, located on the surface of each hard sphere. To validate the accuracy of the theory, computer simulation is used to calculate the structure, thermodynamic and connectivity properties of the one-component YSW4P version of the model which is compared against corresponding theoretical data. In addition, connectivity properties of the model were studied using Flory-Stockmayer (FS) theory. Predictions of the AMSA for the thermal properties of the model (radial distribution functions (RDF), internal energy, pressure, fractions of the particles in different bonding states) are in good agreement with computer simulation predictions. Similarly, good agreement was found for the connectedness RDF (CRDF), except for the statepoints located close to the percolation threshold, where the theory fails to reproduce the long-range behavior of the CRDF. Results of both theories (AMSA and FS) for the mean cluster size are reasonably accurate only at low degrees of association. Predictions of the FS theory for the percolation lines are in a good agreement with computer simulation predictions. AMSA predictions of percolation are much less accurate, where corresponding percolation lines are located at a temperatures approximately 25% lower then those calculated using computer simulation.     

A fluorescence study on the critical exponents for the linear polymerization of butyl-methacrylate

The steady-state fluorescence (SSF) technique was used to study the sol-gel transition for the linear bulk polymerization of butyl methacrylate (BMA), carried out above the glass transition temperature of polybutylmethacrylate (PBMA) (T _g?=?20°C). Pyrene (P_y) was used as the fluorescence probe. The increase in P_y intensity was monitored during free radical polymerization of BMA by using SSF technique. Changes in the viscosity of the pregel solutions due to gel formation dramatically enhance the fluorescent yield of aromatic molecules. This effect is used to monitor the sol-gel transition of BMA, as a function of time, at various temperatures. The results are interpreted in the view of percolation theory. The gel fraction exponent β?=?0.39?±?0.02 agreed the best with the static percolation values for the linear bulk BMA polymerization carried out above T _g but weight average degree of polymerization exponent,?γ?deviated from the percolation results.     

Universal behaviour of glass transition exponents in various polymeric systems

The fast transient fluorescence (FTRF) technique was used to study the critical exponents during glass transition in free-radical cross-linking copolymerization (FCC). Methyl methacrylate (MMA), ethyl methacrylate (EMA) and various combinations of MMA with EMA were used during FCC experiments. Pyrene (Py) was used as a fluorescence probe and its fluorescence lifetimes from its decay traces were measured during glass transition. Changes in the viscosity of the pre-gel solutions due to glass formation dramatically increased the Py fluorescent lifetimes, which were used to study the glass transition of MMA, EMA and their mixtures as a function of time, at various temperatures and monomer concentrations. The results were interpreted in the view of percolation theory. The critical exponents, β and γ, were measured near the glass transition point and found to be around 0.37 ± 0.015 and 1.69 ± 0.05, respectively, in all systems studied, which are in good agreement with the static percolation results.     

Bulk transport properties and exponent inequalities for random resistor and flow networks

The properties of random resistor and flow networks are studied as a function of the density,p, of bonds which permit transport. It is shown that percolation is sufficient for bulk transport, in the sense that the conductivity and flow capacity are bounded away from zero wheneverp exceeds an appropriately defined percolation threshold. Relations between the transport coefficients and quantities in ordinary percolation are also derived. Assuming critical scaling, these relations imply upper and lower bounds on the conductivity and flow exponents in terms of percolation exponents. The conductivity exponent upper bound so derived saturates in mean field theory.Research supported by the NSF under Grant No. DMR-8314625Research supported by the DOE under Grant No. DE-AC02-83ER13044     

Incorporation of Effects of Diffusion into Advection-Mediated Dispersion in Porous Media

The distribution of solute arrival times, W(t;x), at position x in disordered porous media does not generally follow Gaussian statistics. A previous publication determined W(t;x) in the absence of diffusion from a synthesis of critical path, percolation scaling, and cluster statistics of percolation. In that publication, W(t;x) as obtained from theory, was compared with simulations in the particular case of advective solute transport through a two-dimensional model porous medium at the percolation threshold for various lengths x. The simulations also did not include the effects of diffusion. Our prediction was apparently verified. In the current work we present numerical results related to moments of W(x;t), the spatial solute distribution at arbitrary time, and extend the theory to consider effects of molecular diffusion in an asymptotic sense for large Peclet numbers, P_e. However, results for the scaling of the dispersion coefficient in the range 1<P_e<100 agree with those of other authors, while results for the dispersivity as a function of spatial scale also appear to explain experiment.     

The electrical conductivity of binary disordered systems,percolation clusters,fractals and related models

We review theoretical and experimental studies of the AC dielectric response of inhomogeneous materials, modelled as bond percolation networks, with a binary (conductor-dielectric) distribution of bond conductances. We first summarize the key results of percolation theory, concerning mostly geometrical and static (DC) transport properties, with emphasis on the scaling properties of the critical region around the percolation threshold. The frequency-dependent (AC) response of a general binary model is then studied by means of various approaches, including the effective-medium approximation, a scaling theory of the critical region, numerical computations using the transfer-matrix algorithm, and several exactly solvable deterministic fractal models. Transient regimes, related to singularities in the complex-frequency plane, are also investigated. Theoretical predictions are made more explicit in two specific cases, namely R-C and RL-C networks, and compared with a broad variety of experimental results, concerning, for example, granular composites, thin films, powders, microemulsions, cermets, porous ceramics and the viscoelastic properties of gels.     

Directed spiral site percolation on the square lattice

A new site percolation model, directed spiral percolation (DSP), under both directional and rotational (spiral) constraints is studied numerically on the square lattice. The critical percolation threshold p _c ≈ 0.655 is found between the directed and spiral percolation thresholds. Infinite percolation clusters are fractals of dimension d _f ≈ 1.733. The clusters generated are anisotropic. Due to the rotational constraint, the cluster growth is deviated from that expected due to the directional constraint. Connectivity lengths, one along the elongation of the cluster and the other perpendicular to it, diverge as p → p _c with different critical exponents. The clusters are less anisotropic than the directed percolation clusters. Different moments of the cluster size distribution P _s(p) show power law behaviour with | p - p _c| in the critical regime with appropriate critical exponents. The values of the critical exponents are estimated and found to be very different from those obtained in other percolation models. The proposed DSP model thus belongs to a new universality class. A scaling theory has been developed for the cluster related quantities. The critical exponents satisfy the scaling relations including the hyperscaling which is violated in directed percolation. A reasonable data collapse is observed in favour of the assumed scaling function form of P _s(p). The results obtained are in good agreement with other model calculations. Received 10 November 2002 / Received in final form 20 February 2003 Published online 23 May 2003 RID="a" ID="a"e-mail: santra@iitg.ernet.in     

Percolation of the Loss of Tension in an Infinite Triangular Lattice

We introduce a new class of bootstrap percolation models where the local rules are of a geometric nature as opposed to simple counts of standard bootstrap percolation. Our geometric bootstrap percolation comes from rigidity theory and convex geometry. We outline two percolation models: a Poisson model and a lattice model. Our Poisson model describes how defects--holes is one of the possible interpretations of these defects--imposed on a tensed membrane result in a redistribution or loss of tension in this membrane; the lattice model is motivated by applications of Hooke spring networks to problems in material sciences. An analysis of the Poisson model is given by Menshikov et al. ⁽⁴⁾ In the discrete set-up we consider regular and generic triangular lattices on the plane where each bond is removed with probability 1–p. The problem of the existence of tension on such lattice is solved by reducing it to a bootstrap percolation model where the set of local rules follows from the geometry of stresses. We show that both regular and perturbed lattices cannot support tension for any p<1. Moreover, the complete relaxation of tension--as defined in Section 4--occurs in a finite time almost surely. Furthermore, we underline striking similarities in the properties of the Poisson and lattice models.     

Universal crossing probabilities and incipient spanning clusters in directed percolation

Shape-dependent universal crossing probabilities are studied, via Monte Carlo simulations, for bond and site directed percolation on the square lattice in the diagonal direction, at the percolation threshold. In a dynamical interpretation, the crossing probability is the probability that, on a system with size L, an epidemic spreading without immunization remains active at time t. Since the system is strongly anisotropic, the shape dependence in space-time enters through the effective aspect ratio r _eff = ct/L ^z, where c is a non-universal constant and z the anisotropy exponent. A particular attention is paid to the influence of the initial state on the universal behaviour of the crossing probability. Using anisotropic finite-size scaling and generalizing a simple argument given by Aizenman for isotropic percolation, we also obtain the behaviour of the probability to find n incipient spanning clusters on a finite system at time t. The numerical results are in good agreement with the conjecture. Received 10 February 2003 Published online 20 June 2003 RID="a" ID="a"e-mail: turban@lpm.u-nancy.fr RID="b" ID="b"UMR CNRS 7556     

Erdös Rényi随机网络上爆炸渗流模型相变性质的数值模拟研究

基于改进的Newman和Ziff算法以及有限尺寸标度理论, 通过对表征渗流相变特征物理量的序参量、平均集团尺寸、二阶矩、标准偏差及尺寸不均匀性的数值模拟, 分析研究了Erdös Rényi随机网络上Achlioptas爆炸渗流模型的相变性质.研究表明: 尽管序参量表现出了不连续相变的特征, 但序参量以及其他特征物理量仍具有连续相变的幂律标度行为.因此严格地说, Erdös Rényi随机网络中的爆炸渗流相变是一种奇异相变, 它既不是标准的不连续相变, 又与常规随机渗流表现出的连续相变处于不同的普适类. 关键词： Erdös Rényi随机网络 爆炸渗流模型 相变 幂律标度行为     

Random walk statistics on fractal structures

We consider some statistical properties of simple random walks on fractal structures viewed as networks of sites and bonds: range, renewal theory, mean first passage time, etc. Asymptotic behaviors are shown to be controlled by the fractal (¯d) and spectral (¯d) dimensionalities of the considered structure. A simple decimation procedure giving the value of (¯d) is outlined and illustrated in the case of the Sierpinski gaskets. Recent results for the trapping problem, the self-avoiding walk, and the true-self-avoiding walk are briefly reviewed. New numerical results for diffusion on percolation clusters are also presented.     

Transport in a disordered medium: Analysis and Monte Carlo simulation

We consider a classical stochastic model describing particle transport on a lattice with randomly distributed nearest-neighbor transition rates. Applying an effective medium theory to the model, we determine average properties related to the particle's dynamics ind-dimensions. In particular, we calculate the mean-square displacement, and the fourth moment of the displacement in one-, two- and three dimensions. The results compare favorably with Monte Carlo simulations of the model. We also present preliminary results for the velocity autocorrelation function.An aspect of the bond percolation problem, which is a special case of the stochastic model is investigated; the average inverse cluster size, <N _c ^–1>, is calculated. In one dimension the expression for this quantity is exact and in higher dimensions our results are very accurate not too close to the percolation concentration.     

Fluctuation states and optical spectra of solid solutions with a strong isoelectronic perturbation

We propose an approach to describing the density of fluctuation states in a disordered solid solution with a strong perturbation introduced by isoelectronic substitution in the range of attraction-center concentrations below the threshold of percolation along the sites of a disordered sublattice. To estimate the number of localized states we use the results of lattice percolation theory. We describe a method for distinguishing, within the continuum percolation theory, among the various “radiating” states of the fluctuation-induced tail, states that form the luminescence band at weak excitation. We also establish the position of the band of radiating states in relation to the absorption band of the excitonic ground state and the mobility edge of the system. The approach is used to describe the optical spectra of the solid solution ZnSe_1−c Te_c, which at low Te concentrations can be interpreted as a system with strong scattering. We take into account the exciton-phonon interaction and show that the calculated and observed luminescence spectra of localized excitons are in good agreement with each other. Zh. éksp. Teor. Fiz. 115, 1039–1062 (March 1999)     

Percolation and fragmentation of excited atomic nuclei

We present an analysis which aims at explaining the similarities (and differences) which exist between a simple bond percolation process on a cubic lattice and the fragmentation of highly excited atomic nuclei. Emphasis is placed on discussing percolation in terms of concepts which are well known in nuclear physics such asQ-value and particle emission thresholds. Similarities and differences between the bond percolation process and nuclear fragmentation are discussed. An approximate expression for the microcanonical partition sum (number of microstates) corresponding to any given percolation partition is shown to provide a good starting point for predicting fragment size distributions.Communicated by: X. Campi     

Percolation of polyatomic species on a square lattice

In this paper, the percolation of (a) linear segments of size k and(b) k-mers of different structures and forms deposited on a square lattice have been studied. In the latter case, site and bond percolation have been examined. The analysis of results obtained by using finite size scaling theory is performed in order to test the universality of the problem by determining the numerical values of the critical exponents of the phase transition occurring in the system. It is also determined that the percolation threshold exhibits a exponentially decreasing function when it is plotted as a function of the k-mer size. The characteristic parameters of that function are dependent not only on the form and structure of the k-mers but also on the properties of the lattice where they are deposited.Received: 3 September 2003, Published online: 23 December 2003PACS: 64.60.Ak Renormalization-group, fractal, and percolation studies of phase transitions - 68.35.Rh Phase transitions and critical phenomena - 68.35.Fx Diffusion; interface formation     

Full Connectivity: Corners,Edges and Faces

We develop a cluster expansion for the probability of full connectivity of high density random networks in confined geometries. In contrast to percolation phenomena at lower densities, boundary effects, which have previously been largely neglected, are not only relevant but dominant. We derive general analytical formulas that show a persistence of universality in a different form to percolation theory, and provide numerical confirmation. We also demonstrate the simplicity of our approach in three simple but instructive examples and discuss the practical benefits of its application to different models.     

Hypergeometric series in a series expansion of the directed-bond percolation probability on the square lattice

The asymmetric directed-bond percolation (ADBP) problem with an asymmetry parameterk is introduced and some rigorous results are given concerning a series expansion of the percolation probability on the square lattice. It is shown that the first correction term,d _n,1 (k) is expressed by Gauss' hypergeometric series with a variablek. Since the ADBP includes the ordinary directed bond percolation as a special case withk=1, our results give another proof for the Baxter-Guttmann's conjecture thatd _n,1(1) is given by the Catalan number, which was recently proved by Bousquet-Mélou. Direct calculations on finite lattices are performed and combining them with the present results determines the first 14 terms of the series expansion for percolation probability of the ADBP on the square lattice. The analysis byDlog Padé approximations suggests that the critical value depends onk, while asymmetry does not change the critical exponent of percolation probability.     

Percolation Properties of the Non-ideal Gas

We estimate locations of the regions of the percolation and of the non-percolation in the plane (λ,β): the Poisson rate–the inverse temperature, for interacting particle systems in finite dimension Euclidean spaces. Our results about the percolation and about the non-percolation are obtained under different assumptions. The intersection of two groups of the assumptions reduces the results to two dimension Euclidean space, ℝ², and to a potential function of the interactions having a hard core. The technics for the percolation proof is based on a contour method which is applied to a discretization of the Euclidean space. The technics for the non-percolation proof is based on the coupling of the Gibbs field with a branching process.