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expensive. Polymer theories can aid in identifying the most important experimental
parameters to be varied, thus supporting the new perspective that theory and simula-
tion can be effectively applied in tandem with the high-throughput experimentation
to accelerate the material design process. With a powerful theoretical model in hand,
it is comparatively inexpensive to tackle the large parameter space and explore the
physical and thermodynamic properties of the new polymeric materials. However,
this is possible only when the theoretical model provides an accurate description of
the physical system, includes the details of the polymer architecture at the molecular
level, and the model parameters reconcile with experimentally realizable parameters.
The aim of this research is to develop such powerful theoretical models to probe the
properties of both bulk and inhomogeneous polymers. However, the primary focus is
only the microstructure, phase behavior and thermodynamics of these systems.

1.1.1 Molecular modeling of the thermodynamics and phase
behavior of bulk polymer systems

Understanding the phase behavior of the polymeric materials is an important
requirement of modern polymer science and technology. The phase state of poly-
meric systems determines their properties and subsequently their applications. For
example, according to the properties desired, polymer blends as used may be either
homogeneous polymer “alloys” or partially miscible, more or less finely dispersed
two-phase materials. Polymer blends show substantial improvements in performance



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