Collapse transition of two-dimensional flexible and semiflexible polymers

The nature of the globule-coil transition of surface-confined polymers has been an issue of debate. Here this 2D collapse transition is studied through a partially directed lattice model. In the general case of polymers with positive bending stiffness (Delta>0), the collapse transition is first order; it becomes second order only in the limiting case of zero bending stiffness (Delta triple bond 0). These analytical results are confirmed by Monte Carlo simulations. We also suggest some possible future experiments.     

Force-induced desorption and unzipping of semiflexible polymers

The thermally assisted force-induced desorption of semiflexible polymers from an adhesive surface or the unzipping of two bound semiflexible polymers by a localized force are investigated. The phase diagram in the force-temperature plane is calculated both analytically and by Monte Carlo simulations. Force-induced desorption and unzipping of semiflexible polymers are first order phase transitions. A characteristic energy barrier for desorption is predicted, which scales with the square root of the polymer bending rigidity and governs the initial separation process before a plateau of constant separation force is reached. This leads to activated desorption and unzipping kinetics accessible in single molecule experiments.     

Giant nonmonotonic stretching response of a self-associating polymer in shear flow

Self-associating polymers are ubiquitous in synthetic and biological systems. Here, we use a combination of simulation and theory to show that these polymers exhibit a counterintuitive strong nonmonotonic stretching response in shear flow. Furthermore, we demonstrate that this behavior can be tuned by controlling the barrier for dissociation of the bonds and develop a quantitative and predictive theory based on conformational transitions to explain the observed behavior. Our results can be important in understanding previous experimental and theoretical observations and further aid in the development of novel smart materials.     

Free energy of semiflexible polymers and structure of interfaces

The free energy of semiflexible polymers is calculated as a functional of the compositional scalar order parameter and the orientational order parameter of second-rank tensor S_ij on the basis of a microscopic model of wormlike chains with variable segment lengths. We use a density functional theory and a gradient expansion to evaluate the entropic part of the free energy, which is given in a power series of .The interaction term of the free energy is derived with a random phase approximation. For the rigid rod limit, the nematic-isotropic transition point is given by , N and w being the degree of polymerization and the anisotropic interaction parameter, respectively, and the degree of ordering at the transition point is 0.33448. We also find that the contour length of polymer chains becomes larger in a nematic phase than in an isotropic phase. Interface profiles are obtained numerically for some typical cases. In the neighborhood of isotropic-isotropic interfaces, polymer chains tend to align parallel to the interface on the polymer-rich side and perpendicular on the poor side. When an isotropic region and a nematic region coexist, orientational order parallel to the interface is preferred in the nematic region. Received: 28 May 1998 / Revised: 12 August 1998 / Accepted: 8 September 1998     

Elongation and fluctuations of semiflexible polymers in a nematic solvent

We directly visualize single polymers with persistence lengths l(p), ranging from 0.05 to 16 microm, dissolved in the nematic phase of rodlike fd virus. Polymers with a sufficiently large persistence length undergo a coil-rod transition at the isotropic-nematic transition of the background solvent. We quantitatively analyze the transverse fluctuations of the semiflexible polymers and show that at long wavelengths they are driven by the fluctuating nematic background. We extract the Odijk deflection length and the elastic constant of the background nematic phase from the data.     

Slip at high shear rates

There are contradictory published data on the behavior of fluid slip at high shear rates. Using three methodologies (molecular dynamics simulations, an analytical theory of slip, and a Navier-Stokes-based calculation) covering a range of fluids (bead-spring liquids, polymer solutions, and ideal gas flows) we show that as shear rate increases, the amount of slip, as measured by the slip length, asymptotes to a constant value. The results clarify the molecular mechanics of how slip occurs. Furthermore, they indicate that in this limit, molecular dynamics simulations must accurately account for heat transfer to the solid.     

Potts model,Dirac propagator,and conformational statistics of semiflexible polymers

A new discretized version of the Dirac propagator ind space and one time dimensions is obtained with the help of the 2d-state, one-dimensional Potts model. The Euclidean version of this propagator describes all conformational properties of semiflexible polymers. It also describes all properties of fully directed self-avoiding walks. The case of semiflexible copolymers composed of a random sequence of fully flexible and semirigid monomer units is also considered. As a by-product, some new results for disordered one-dimensional Ising and Potts models are obtained. In the case of the Potts model the nontrivial extension of the results to higher dimensions is discussed briefly.     

Single crystal EXAFS at high pressure

Abstract

We present a new technique for structure characterization under high pressure conditions. The use of an undulator beam of the third-generation ESRF source of synchrotron radiation has enabled the first single crystal EXAFS experiments at high pressure using a diamond anvil cell as pressure generator. Taking advantage of the linear polarization of X-rays the technique becomes an orientation-selective probe of the local structure of materials. We describe the principle of the technique and some applications.     

Studying solutions at high shear rates: a dedicated microfluidics setup

The development of a dedicated small‐angle X‐ray scattering setup for the investigation of complex fluids at different controlled shear conditions is reported. The setup utilizes a microfluidics chip with a narrowing channel. As a consequence, a shear gradient is generated within the channel and the effect of shear rate on structure and interactions is mapped spatially. In a first experiment small‐angle X‐ray scattering is utilized to investigate highly concentrated protein solutions up to a shear rate of 300000 s^?1. These data demonstrate that equilibrium clusters of lysozyme are destabilized at high shear rates.     

Herd formation and information transmission in a population: non-universal behaviour

We present generalized dynamical models describing the sharing of information, and the corresponding herd behavior, in a population based on the recent model proposed by Eguıluz and Zimmermann (EZ) [Phys. Rev. Lett. 85, 5659 (2000)]. The EZ model, which is a dynamical version of the herd formation model of Cont and Bouchaud (CB), gives a reasonable model for the formation of clusters of agents and for actions taken by clusters of agents. Both the EZ and CB models give a cluster size distribution characterized by a power law with an exponent -5/2. By introducing a size-dependent probability for dissociation of a cluster of agents, we show that the exponent characterizing the cluster size distribution becomes model-dependent and non-universal, with an exponential cutoff for large cluster sizes. The actions taken by the clusters of agents generate the price returns, the distribution of which is also characterized by a model-dependent exponent. When a size-dependent transaction rate is introduced instead of a size-dependent dissociation rate, it is found that the distribution of price returns is characterized by a model-dependent exponent while the exponent for the cluster-size distribution remains unchanged. The resulting systems provide simplified models of a financial market and yield power law behaviour with an easily tunable exponent. Received 31 December 2001     

More on shear modulus collapse of lattices at high pressure

In his recent paper, Shear modulus collapse of lattices at high pressure, J. Phys. Cond. Matt. 16 (2004) L125, V.V. Kechin claims that the zero temperature shear modulus of a metallic solid vanishes at a high critical pressure, and the critical pressures for this shear modulus collapse lie in the range 0-250 Mbar for elemental metals. Here we demonstrate that Kechin's arguments contain an erroneous assumption, and therefore, do not prove that all metals become mechanically unstable at high pressures. Ab initio calculations and experimental results on a number of solids are analyzed to confirm our conclusion.     

Adhesion of semi-crystalline polymers: shear contribution to fracture energy

A study of the adhesion of two semi-crystalline polymers (EVOH and PEg (grafted polyethylene)) by peel has shown that local fracture energy, G_A, is virtually independent of peel angle. Adopting the Dugdale model for energy expenditure, we obtain an estimate of G_A^D of the order of magnitude of G_A. However, observation of fracture fronts suggests that supplementary energy losses occur after separation, due to shear stresses reorienting the fibrillar craze material. A simple model is proposed to estimate this shear contribution to fracture energy, G_A^S, suggesting the potential importance of shear effects in overall fracture energy. To cite this article: A. Guiu, M.E.R. Shanahan, C. R. Physique 3 (2002) 397–402.     

Longitudinal relaxation of initially straight flexible and stiff polymers

The relaxation mechanism of an initially straight flexible or stiff polymer chain of length N in a viscous solvent is studied through Brownian dynamics simulations covering a broad range of time scales. After the short-time free diffusion, the chain's longitudinal reduction R2(0)-R2 approximately Nt1/2 at early intermediate times is shown to constitute a universal behavior for any chain stiffness caused by a quasisteady T approximately Nt(-1/2) relaxation of tensions associated with the deforming action of the Brownian forces. Stiff chains with a persistence length E > or = N are shown to exhibit a late intermediate-time longitudinal reduction R2(0)-R2 approximately N2E(-3/4)t1/4 associated with a T approximately N2E(-3/4)t(-3/4) relaxation of tensions affected by the deforming Brownian and the restoring bending forces.     

Dissipated work in driven harmonic diffusive systems: General solution and application to stretching Rouse polymers

We study n-dimensional diffusive motion in an externally driven harmonic potential. For these systems the probability distribution of the applied work is a Gaussian. We give explicit expressions for its mean and variance, which are determined by a non-local integral kernel relating the time-derivatives of the applied forces. As illustrations, we specialize our results to dragging a colloidal particle through a viscous fluid and to stretching a Rouse polymer with different protocols.     

Single pion production by linearly polarized photons at high energies

There exists a one-to-one correspondence between the dependence of the single-pion-photoproduction amplitude on the linear polarization of the photons at high energies and small momentum transfer in the direct channelγ+N→π+N on one hand and the parity of the exchanged particle-system in the crossed channelγ+π→N+¯N on the other.     

Flame structure of composite pseudo-propellants based on nitramines and azide polymers at high pressure

The chemical and thermal structures of flame of composite pseudo-propellants based on cyclic nitramines (HMX, RDX) and azide polymers (GAP and BAMO–AMMO copolymer) were investigated at a pressure of 1.0 MPa by molecular beam mass spectrometry and a microthermocouple technique. Eleven species H₂, H₂O, HCN, CO, CO₂, N₂, N₂O, CH₂O, NO, NO₂, and nitramine vapor (RDX_v or HMX_v), were identified, and their concentration profiles were measured in HMX/GAP and RDX/GAP pseudo-propellant flames at a pressure of 1 MPa. Two main zones of chemical reactions in the flame of nitramine/GAP pseudo-propellants were found. In the first, narrow, zone 0.1 mm wide (adjacent to the burning surface), complete consumption of nitramine vapor and NO₂ with the formation of NO, HCN, CO, H₂, and N₂ occurs. In the second, wider high-temperature zone, oxidation of HCN and CH₂O by NO and N₂O with the subsequent formation of CO, H₂, and N₂ takes place. The leading reactions in the high-temperature zone of flame of nitramine/GAP pseudo-propellants are the same as in the case of pure nitramines. In the case of nitramine/BAMO–AMMO pseudo-propellants a presence of carbonaceous particles on the burning surface did not allow us to analyze the zone adjacent to the burning surface, therefore only one flame zone was found. Temperature profiles in the combustion wave of nitramine/azide polymer pseudo-propellants were measured at 1 MPa. The data obtained can be used to develop and validate a self-sustain combustion model for pseudo-propellants based on nitramines and azide polymers.