Search results for "Dynamic"
showing 10 items of 12329 documents
Phase transitions in polymeric systems: A challenge for Monte Carlo simulation
1995
Polymers are more difficult to simulate than small molecule systems, due to the large size of random polymer coils (and their slow relaxation, that is observed when dynamic simulation algorithms are used). However, variation of the chain length N of a flexible polymer chain provides a very useful additional control parameter, allowing stringent tests of theories, and new physical phenomena may emerge. As an example of these concepts, critical phenomena in polymer mixtures are described. It is shown that unmixing of symmetrical mixtures ( N A = N B = N ) is described by an equation for the critical temperature T c ( N ) = aN + b rather than T c ∝ N as claimed by some theories. While for fini…
The Efficiency of Polymer Fractionation at Lower Critical Solution Temperatures
1978
The efficiency of a single fractionation step (i.e. of the partition of a given polymer sample between the coexisting phases which form when its solution demixes) is governed by the variation of the mass ratio of the individual P-mers with chain length. These dependences have been measured for the system dimethoxymethane/diethylether/ polystyrene which exhibits lower critical solution temperatures by means of the Baker-Williams method and by means of g.p.c. Their comparison with the results of previous investigation on systems showing upper critical solution temperatures reveals no thermodynamic differences in the aptitude of upper and lower critical solution temperatures for fractionation …
Calculation of the Phase Behavior of Lipids
1998
The self-assembly of monoacyl lipids in solution is studied employing a model in which the lipid's hydrocarbon tail is described within the Rotational Isomeric State framework and is attached to a simple hydrophilic head. Mean-field theory is employed, and the necessary partition function of a single lipid is obtained via a partial enumeration over a large sample of molecular conformations. The influence of the lipid architecture on the transition between the lamellar and inverted-hexagonal phases is calculated, and qualitative agreement with experiment is found.
Cylindrical polyelectrolyte-comb-surfactant complexes
2006
Abstract Quaternized polymer combs based on poly(2-vinylpyridine-macromonomers) and the surfactant sodium dodecylsulfate are employed in the synthesis of a novel cylindrical polyelectrolyte-comb-surfactant complex (PECSC). The complex formed has 1:1 stoichiometry with respect to the ratio of dodecylsulfate to pyridinium units. It is soluble in organic solvents such as 2-butanol or chloroform. Characterization of single particle properties of the complex in organic solution is possible and yields a radius of gyration of 〈Rg〉z = 78.4 nm, a hydrodynamic radius of 〈1/Rh〉z−1 = 51.4 nm and a cross-sectional radius of Rg,cross = 3.9 nm in chloroform. The characteristic ratio γ = 〈Rg〉z/〈1/Rh〉z−1 de…
Natural gas hydrates vs. induced dysfunctions in the hydrocarbon extraction process
2021
Cantoned fluids in porous-permeable or fractured media of reservoirs have acquired during the geological time special properties. The fluids from the reservoir could be or not a mixture of reservoir water, liquid hydrocarbons and gaseous hydrocarbons. Considering if inside of a reservoir there are two types of substances like natural gas and reservoir water which may be in the form of vaporous than the condition of saturation of gases with water vaporous is fulfilled. This process is taking place due to thermodynamic equilibrium resulting the so-called gas humidity. This state corroborated with a certain chemical composition plus favourable values of pressure and temperature may be decisive…
Shear induced mixing/demixing: blends of homopolymers, of homopolymers plus copolymers, and blends in solution
2000
Shear may shift the phase boundary towards the homogeneous state (shear induced mixing, SIM), or in the opposite direction (shear induced demixing, SID). SIM is the typical behavior of mixtures of components of low molar mass and polymer solutions, SID can be observed with solutions of high molar mass polymers and polymer blends at higher shear rates. The typical sequence with increasing shear rate is SIM, then occurrence of an isolated additional immiscible area (SLD), melting of this island into the main miscibility gap, and finally SIM again. A three phase line originates and ends in two critical end points. Raising pressure increases the shear effects. For copolymer containing systems S…
Molecular motion, thermal expansion, and phase transitions in paraffins: A model for polymers
2007
Owing to their simple chemical structure paraffins are generally regarded as representing a system which is especially suitable for a model study of the thermal behavior of oligomeric and polymeric solids. Extensive investigations on the properties of n-tritriacontane (C33H68) provide an example. For this system an identification of several types of motional mechanisms become possible. Their presence leads to peculiarities in the thermal expansion and to the occurrence of solid-solid phase transitions. Paraffins and polyethylene exhibit a marked anisotropy in the lateral thermal expansion. An analysis of the molecular background can be based on a modified Gruneisen theory which connects exp…
Phase Separation of Colloid Polymer Mixtures Under Confinement
2013
Colloid polymer mixtures exhibit vapor-liquid like and liquid-solid like phase transitions in bulk suspensions, and are well-suited model systems to explore confinement effects on these phase transitions. Static aspects of these phenomena are studied by large-scale Monte Carlo simulations, including novel “ensemble switch” methods to estimate excess free energies due to confining walls. The kinetics of phase separation is investigated by a Molecular Dynamics method, where hydrodynamic effects due to the solvent are included via the multiparticle collision dynamics method.
Coil-bridge transition in a single polymer chain as an unconventional phase transition: theory and simulation.
2014
The coil-bridge transition in a self-avoiding lattice chain with one end fixed at height H above the attractive planar surface is investigated by theory and Monte Carlo simulation. We focus on the details of the first-order phase transition between the coil state at large height H ⩾ Htr and a bridge state at H ⩽ Htr, where Htr corresponds to the coil-bridge transition point. The equilibrium properties of the chain were calculated using the Monte Carlo pruned-enriched Rosenbluth method in the moderate adsorption regime at (H/Na)tr ⩽ 0.27 where N is the number of monomer units of linear size a. An analytical theory of the coil-bridge transition for lattice chains with excluded volume interact…
Orientational ordering transitions of semiflexible polymers in thin films: A Monte Carlo simulation
2011
Athermal solutions (from dilute to concentrated) of semiflexible macromolecules confined in a film of thickness D between two hard walls are studied by means of grand-canonical lattice Monte Carlo simulation using the bond fluctuation model. This system exhibits two phase transitions as a function of the thickness of the film and polymer volume fraction. One of them is the bulk isotropic-nematic first-order transition, which ends in a critical point on decreasing the film thickness. The chemical potential at this transition decreases with decreasing film thickness ("capillary nematization"). The other transition is a continuous (or very weakly first-order) transition in the layers adjacent …