Polymer blends molecular interpretation

Block polymers, owing to the tendency for formation of regular strucmres tailored by molecular design, are ideal models for compatibilized, two-phase polymer blends or alloys. Blends do show similar rheological behavior, e.g., yield, pseudoplasticity, thixotropy, structural rearrangements, but since the morphology is more difficult to control, the interpretation of data could present serious difficulties. 

MISCIBILITY OF POLYMER-POLYMER BLENDS PHASE DIAGRAMS AND MOLECULAR INTERPRETATION... 

One convenient strategy to interpret these results is to review the molecular characteristics of binary blends as extracted from polymer melt rheology [40]. The influence of short chains (M < Me) is to effectively decrease the plateau modulus and the terminal relaxation times as compared to the pure polymer. Consequently, the molecular weight between entanglements... 

In Chapter 3, we used the Rouse model for a polymer chain to study the diffusion motion and the time-correlation function of the end-to-end vector. The Rouse model was first developed to describe polymer viscoelastic behavior in a dilute solution. In spite of its original intention, the theory successfully interprets the viscoelastic behavior of the entanglement-free poljuner melt or blend-solution system. The Rouse theory, developed on the Gaussian chain model, effectively simplifies the complexity associated with the large number of intra-molecular degrees of freedom and describes the slow dynamic viscoelastic behavior — slower than the motion of a single Rouse segment. 

Molecular dynamics (MD) is an invaluable tool to study structural and dynamical details of polymer processes at the atomic or molecular level and to link these observations to experimentally accessible macroscopic properties of polymeric materials. For example, in their pioneering studies of MD simulations of polymers, Rigby and Roe in 1987 introduced detailed atomistic modeling of polymers and developed a fundamental understanding of the relationship between macroscopic mechanical properties and molecular dynamic events [183-186]. Over the past 15 years, molecular dynamics have been applied to a number of different polymers to study behavior and mechanical properties [187-193], polymer crystallization [194-196], diffusion of a small-molecule penetrant in an amorphous polymer [197-199], viscoelastic properties [200], blend [201,202] and polymer surface analysis[203-210]. In this article, we discuss MD studies on polyethylene (PE) with up to 120,000 atoms, polyethylproplyene (PEP), atactic polypropylene (aPP) and polyisobutylene (PIB) with up to 12,000 backbone atoms. The purpose of our work has been to interpret the structure and properties of a fine polymer particle stage distinguished from the bulk solid phase by the size and surface to volume ratio. 

Maier et al. [39] took j8 to be a material-dependent parameter and determined its value for several polymers by fitting data for binary blends of samples having different molecular weight distributions. They assumed a single-exponential form for F tM) and found j8 = 3.3 for PMMA and j8 = 3.8 for polystyrene. The terminal relaxation time was assumed to be proportional to M , where a > 3. As we have seen, this can be interpreted as a very crude way of accounting for tube length fluctuations. 

---