Simple Polymer Chain Models

SINGLE CHAIN STUDIES Simple Polymer Chain Models 

The simplest possible polymer model for a flexible polymer chain is the freely jointed (or random flight) chain. In this model, it is assumed that each bond angle and each rotational angle may take with equal probability any value in the range 0-360°. The conformational energies are the same irrespective of conformation. The mean-squared, end-to-end distance of a chain in this approximation is given by 

Although bond angles may exhibit some variation because of the vibrational motion of the chain, their values are constrained close to a mean value, which is normally taken as the value of the bond angle. 

The model will accept unrealistic conformations in which two repeat units occupy the same volume. 

The model neglects intramolecular interactions, which affect the conformation of a real chain. 

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While for the dienes we have seen much information can be obtained from simple one unit active polymer chain models, this is less helpful in the case of vinyl monomers where microstructure depends on the relationship between two or more monomer units in the chain and orientation of the incoming monomer. Little work has been done in this field (18). A mechanism has, however, been proposed to explain the changes in microstructure observed in poly ot-methyl st yrene formed by lithium catalysis in THF which does... 

It should be emphasized that these features of the transition between coil and liquid-crystalline globule, as well as the expression (3.7) for the temperature of this transition, are not sensitive to the specific polymer chain model in the limits p S> 1 and N > 1. In particular, the above results remain valid for each of the models shown in Fig. 7b-d, i.e. the chain composed of rods connected by flexible spacers (Fig. 7 b), the flexible chain with the rodlike side groups (Fig. 7 c) and the persistant chain (Fig. 7d). Such universality can be proved by means of the following simple arguments. 

It had long been assumed that the solvent in a polymer solution provides a neutral hydrodynamic background, and that the properties of the solvent in a solution, such as viscosity, are the same as the properties found in the neat solvent. We know now that this simple assumption is incorrect Just as the solvent can alter properties of the polymer, so also do polymers alter the properties of the surrounding solvent Translational and rotational mobilities of solvent molecules may be reduced or increased by the presence of nearby polymer chains. Models for polymer dynamics that assume that the solvent has the same properties as the neat liquid are therefore unlikely to be entirely accurate. 

We present here a simple experiment, conceived to test both the reptation model and the minor chain model, by Welp et al. [50] and Agrawal et al. [51-53]. Consider the HDH/DHD interface formed with two layers of polystyrene with chain architectures shown in Fig. 5. In one of the layers, the central 50% of the chain is deuterated. This constitutes a triblock copolymer of labeled and normal polystyrene, which is, denoted HDH. In the second layer, the labeling has been reversed so that the two end fractions of the chain are deuterated, denoted by DHD. At temperatures above the glass transition temperature of the polystyrene ( 100°C), the polymer chains begin to interdiffuse across the... 

These models are designed to reproduce the random movement of flexible polymer chains in a solvent or melt in a more or less realistic way. Simulational results which reproduce in simple cases the so-called Rouse [49] or Zimm [50] dynamics, depending on whether hydrodynamic interactions in the system are neglected or not, appear appropriate for studying diffusion, relaxation, and transport properties in general. In all dynamic models the monomers perform small displacements per unit time while the connectivity of the chains is preserved during the simulation. 

FIQ. 1 Sketch of the BFM of polymer chains on the three-dimensional simple cubic lattice. Each repeat unit or effective monomer occupies eight lattice points. Elementary motions consist of random moves of the repeat unit by one lattice spacing in one lattice direction. These moves are accepted only if they satisfy the constraints that no lattice site is occupied more than once (excluded volume interaction) and that the bonds belong to a prescribed set of bonds. This set is chosen such that the model cannot lead to any moves where bonds should intersect, and thus it automatically satisfies entanglement constraints [51],... 

A particularly simple lattice model has been utilized by Harris and Rice [129] and subsequently by Stettin et al. [130] to simulate Langmuir mono-layers at the air/water interface chains on a cubic lattice which are confined to a plane at one end. Haas et al. have used the bond-fluctuation model, a more sophisticated chain model which is common in polymer simulations, to study the same system [131]. Amphiphiles are modeled as short chains of monomers which occupy a cube of eight sites on a cubic lattice and are connected by bonds of variable length [132], At high surface coverage, Haas et al. report various lattice artefacts. They conclude that the study... 

The molar mass dependence of the intrinsic viscosity of rigid chain polymers cannot be described by a simple scaling relation in the form of Equation (36) with molar mass independent of K and a. over a broad molar mass range. Starting from the worm-like chain model, Bohdanecky proposed [29] the linearizing equation... 

The structure of a simple mixture is dominated by the repulsive forces between the molecules [15]. Any model of a liquid mixture and, a fortiori of a polymer solution, should therefore take proper account of the configurational entropy of the mixture [16-18]. In the standard lattice model of a polymer solution, it is assumed that polymers live on a regular lattice of n sites with coordination number q. If there are n2 polymer chains, each occupying r consecutive sites, then the remaining m single sites are occupied by the solvent. The total volume of the incompressible solution is n = m + m2. In the case r = 1, the combinatorial contribution of two kinds of molecules to the partition function is... 

The deformation of polymer chains in stretched and swollen networks can be investigated by SANS, A few such studies have been carried out, and some theoretical results based on Gaussian models of networks have been presented. The possible defects in network formation may invalidate an otherwise well planned experiment, and because of this uncertainty, conclusions based on current experiments must be viewed as tentative. It is also true that theoretical calculations have been restricted thus far to only a few simple models of an elastomeric network. An appropriate method of calculation for trapped entanglements has not been constructed, nor has any calculation of the SANS pattern of a network which is constrained according to the reptation models of de Gennes (24) or Doi-Edwards (25,26) appeared. 

The focus of this chapter is on an intermediate class of models, a picture of which is shown in Fig. 1. The polymer molecule is a string of beads that interact via simple site-site interaction potentials. The simplest model is the freely jointed hard-sphere chain model where each molecule consists of a pearl necklace of tangent hard spheres of diameter a. There are no additional bending or torsional potentials. The next level of complexity is when a stiffness is introduced that is a function of the bond angle. In the semiflexible chain model, each molecule consists of a string of hard spheres with an additional bending potential, EB = kBTe( 1 + cos 0), where kB is Boltzmann s constant, T is... 

The continuous chain model includes a description of the yielding phenomenon that occurs in the tensile curve of polymer fibres between a strain of 0.005 and 0.025 [ 1 ]. Up to the yield point the fibre extension is practically elastic. For larger strains, the extension is composed of an elastic, viscoelastic and plastic contribution. The yield of the tensile curve is explained by a simple yield mechanism based on Schmid s law for shear deformation of the domains. This law states that, for an anisotropic material, plastic deformation starts at a critical value of the resolved shear stress, ry =/g, along a slip plane. It has been... 

For an estimate of the ultimate shear strength, r0, of a single domain based on the lattice parameters we use a simple shear plane system proposed by Frenkel [19]. As shown in Fig. 19 it consists of a linear array of periodic force centres resembling the polymer chain. According to this model the relation between the relative displacement x along the shear direction and the shear stress is given by... 

In view of the development of the continuous chain model for the tensile deformation of polymer fibres, we consider the assumptions on which the Coleman model is based as too simple. For example, we have shown that the resolved shear stress governs the tensile deformation of the fibre, and that the initial orientation distribution of the chains is the most important structural characteristic determining the tensile extension below the glass transition temperature. These elements have to be incorporated in a new model. 

Simulation methods have been proved to be useful in the study of many different molecular systems, in particular in the case of flexible polymers chains [ 14]. According to the variety of structures and the theoretical difficulties inherent to branched structures, simulation work is a very powerful tool in the study of this type of polymer, and can be applied to the general problems outHned above. Sometimes, this utility is manifested even for behaviors which can be explained with simple theoretical treatments in the case of linear chains. Thus, the description of the theta state of a star chain cannot be performed through the use of the simple Gaussian model. The adequate simulation model and method depend strongly on the particular problem investigated. Some cases require a realistic representation of the atoms in the molecular models [10]. Other cases, however, only require simplified coarse-grained models, where some real mon-... 

Figure 5.6 shows that the PDMS data perfectly match the prediction of the simple Rouse model up to the highest Q-values, whereas the PIB data show severe deviations from the Rouse model (Fig. 5.3) and the stiff chain model (Fig. 5.4). From the fact that two polymers with very similar structural parameters but strongly different torsional barriers display completely different relaxation behaviour the conclusion is compelling that there must be an addi-...

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