Lattice-Hole Theory: Bulk Properties and Surface Tension of Oligomers and Polymers

Jain, Rahul; Simha, Robert

doi:10.1006/jcis.1999.6316

Cited by 17 publications

(11 citation statements)

References 26 publications

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“…Theoretical methods have been reviewed and provide insight into various aspects of surface and interface properties. Theoretical interpretation has evolved over the years, and has been addressed by models that emphasize mainly entropic contributions, mainly enthalpic, or both . Conformational entropic contributions to surface tension as the polymer coil is distorted by the sharp gradient at the air/melt interface have been described theoretically, and will be discussed further below.…”

Section: Introductionmentioning

confidence: 99%

The cohesive energy density of polymers and its relationship to surface tension, bulk thermodynamic properties, and chain structure

Dee

Sauer

2016

J of Applied Polymer Sci

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The cohesive energy density (CED) and the internal pressure (Pi) have similar values for most liquids at low pressures. For most polymers CED cannot be directly measured, unlike Pi which is readily obtained in the melt from PVT or other related data. Directly measured CED are available for the oligomer linear alkane series over a moderate molecular weight (MW) range. Scaling CED with measured surface tensions (ɣ) leads to separation into two universal scaling curves, which provides a measure of surface configurational entropy, as does the MW dependence of experimental surface tensions for two polymer series. A novel polymer scaling curve based on CED is shown to provide improved accuracy in the prediction of ɣ for any polymer or solvent. For polymers that interact predominately through Van der Waals forces, correlations between the average interchain separation distances and the magnitude of CED (or Pi), are shown to give a universal derivation of CED. In contrast, polymers like P4VP having strong polar interactions provide dramatic evidence of the different physical basis of CED and Pi. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44431.

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Section: Introductionmentioning

confidence: 99%

The cohesive energy density of polymers and its relationship to surface tension, bulk thermodynamic properties, and chain structure

Dee

Sauer

2016

J of Applied Polymer Sci

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“…An important contribution of the theory is the inclusion of the volume and the temperature‐dependent hole fraction [ h = h ( V , T )]; which is a measure of the free volume. In addition to entering into the thermodynamic functions, h also serves as a link to the surface tension,14 the constant stress viscosity,15 the kinetics of volume relaxation,16 and so forth. The connection of h with the results of positronium annihilation spectroscopy has also been demonstrated 17…”

Section: Introductionmentioning

confidence: 99%

Statistical thermodynamics evaluation of polymer–polymer miscibility

Utracki

2004

J Polym Sci B Polym Phys

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The Simha and Somcynsky (S–S) statistical thermodynamics theory was used to compute the solubility parameters as a function of temperature and pressure [δ = δ(T, P)], for a series of polymer melts. The characteristic scaling parameters required for this task, P*, T*, and V*, were extracted from the pressure–temperature–volume (PVT) data. To determine the potential polymer–polymer miscibility, the dependence of δ versus T (at ambient pressure) was computed for 17 polymers. Close proximity of the δ versus T curves for four miscible polymer pairs: PPE/PS, PS/PVME, and PC/PMMA signaled the usefulness of this approach. It is noteworthy, that the tabulated solubility parameters (derived from the solution data under ambient conditions) propounded the immiscibility of the PVC/PVAc pair. The computed values of δ also suggested miscibility for polymer pairs of unknown miscibility, namely PPE/PVC, PPE/PVAc, and PET/PSF. In recognizing the limitations of the solubility parameter approach (the omission of several thermodynamic contributions), these preliminary results are auspicious because they indicate a new route for estimating the miscibility of any polymeric material at a given temperature and pressure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2909–2915, 2004

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“…For example, it correlates bulk properties with surface tension. [7,8] The interpretation of h as a particular type of free volume fraction has resulted in correlations of equilibrium with transport properties, specifically with the constant stress viscosity of melts and their mixtures, [9] and viscoelastic functions. [10] The h-function has moreover been significant in the formulations of the kinetics of volume relaxation.…”

Section: Introductionmentioning

confidence: 99%

Analytical Representation of Solutions to Lattice-Hole Theory

Utracki¹,

Simha

2001

Macromol. Theory Simul.

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The Simha and Somcynsky (S‐S) lattice‐hole theory has been shown to represent accurately the pressure‐volume‐temperature (PVT) surface of chain molecular melts and their mixtures. Proceeding beyond its original intent, it has led to correlations with other properties and extension into the steady state and relaxing glass. The equilibrium results appear as the solutions of two coupled equations, involving the variables of state and the hole fraction, h = h (V, T) – a kind of free volume quantity. These are to be solved numerically. Notwithstanding the theory's quantitative success, its implicit form has on some occasions been a practical limitation. We remedy this situation by fitting the scaled and thus general solutions of the coupled equations to accurate algebraic equations, V = V (T, P) and h = hV, T). In this manner, explicit analytical expressions for configurational thermodynamic functions and their derivatives are now available. The new expressions for V and h are simple to employ; the convergence of the non‐linear least‐squares fit is obtained in seconds. The numerical values of the scaling parameters so derived are nearly identical to those computed from the original coupled equations. Having h and V from the original theory, the cohesive energy density [CED = δ2V, T)] was also considered. The results are again well represented by a simple algebraic expression. An expression for the reduced solubility parameter δ = δ (T, P) is also given. The usefulness of these solutions is further illustrated by an application to the PVT surfaces of polystyrene and polyphenylene ether blends.

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Lattice-Hole Theory: Bulk Properties and Surface Tension of Oligomers and Polymers

Cited by 17 publications

References 26 publications

The cohesive energy density of polymers and its relationship to surface tension, bulk thermodynamic properties, and chain structure

The cohesive energy density of polymers and its relationship to surface tension, bulk thermodynamic properties, and chain structure

Statistical thermodynamics evaluation of polymer–polymer miscibility

Analytical Representation of Solutions to Lattice-Hole Theory

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