Rheological properties thermodynamics

In this chapter we have discussed the thermodynamic formation of blends and their behavior. Both miscible and immiscible blends can be created to provide a balance of physical properties based on the individual polymers. The appropriate choice of the blend components can create polymeric materials with excellent properties. On the down side, their manufacture can be rather tricky due to rheological and thermodynamic considerations. In addition, they can experience issues with stability after manufacture due to phase segregation and phase growth. Despite these complications, they offer polymer engineers and material scientists a broad array of materials to meet many demanding application needs. 

The dynamic behavior of fluid interfaces is usually described in terms of surface rheology. Monolayer-covered interfaces may display dramatically different rheological behavior from that of the clean liquid interface. These time-dependent properties vary with the extent of intermolecular association within the monolayer at a given thermodynamic state, which in turn may be related directly to molecular size, shape, and charge (Manheimer and Schechter, 1970). Two of these time-dependent rheological properties are discussed here surface shear viscosity and dynamic surface tension. 

In order to utilise our colloids as near hard spheres in terms of the thermodynamics we need to account for the presence of the medium and the species it contains. If the ions and molecules intervening between a pair of colloidal particles are small relative to the colloidal species we can treat the medium as a continuum. The role of the molecules and ions can be allowed for by the use of pair potentials between particles. These can be determined so as to include the role of the solution species as an energy of interaction with distance. The limit of the medium forms the boundary of the system and so determines its volume. We can consider the thermodynamic properties of the colloidal system as those in excess of the solvent. The pressure exerted by the colloidal species is now that in excess of the solvent, and is the osmotic pressure II of the colloid. These ideas form the basis of pseudo one-component thermodynamics. This allows us to calculate an elastic rheological property. Let us consider some important thermodynamic quantities for the system. We may apply the first law of thermodynamics to the system. The work done in an osmotic pressure and volume experiment on the colloidal system is related to the excess heat adsorbed d Q and the internal energy change d E ... 

This volume provides an overview of polymer characterization test methods. The methods and instrumentation described represent modern analytical techniques useful to researchers, product development specialists, and quality control experts in polymer synthesis and manufacturing. Engineers, polymer scientists and technicians will find this volume useful in selecting approaches and techniques applicable to characterizing molecular, compositional, rheological, and thermodynamic properties of elastomers and plastics. 

The systems selected for evaluation are the PDMS-C02 system studied by Gerhardt et al. (1997, 1998) and PS-gas systems studied by Kwag et al. (1999). Properties for these systems are listed in Table 11.1. The variation in physical properties between these systems provides a very broad basis for evaluating the rheological properties of polymer-gas systems. The PDMS C02 system exhibits a favorable thermodynamic affinity between the polymer and dissolved gas, and provides the opportunity to evaluate the rheology of melts with very high dissolved gas content (up to 21 wt %). Carbon dioxide is much less soluble in polystyrene than in PDMS, so the PS-C02... 

Analyzing the unit operations in the extruder to a satisfactory degree is only possible when sufficient information about the rheological and thermodynamic properties of the polymers and polymer compounds is available. However, providing these data is very difficult, particularly in zones with considerable changes in state. Therefore, it is frequently necessary to refer back to model investigations and trials [6]. 

The effect of the minor components was kinetic, rather than thermodynamic. Although the crystallization kinetics were altered, the structure and mechanical properties of milk fat were the same with or without the minor lipids. The samples reached the same SFC value and had a similar microstructure as observed visually and as characterized by the fractal dimension. The rheological properties of the fats were also similar. Neither the storage modulus nor the yield force was affected by removal of the minor components (Wright and Marangoni, 2003). Large changes in the... 

The structural and rheological properties of emulsions, blends, and foams are of great importance in the food, cosmetics, oil-field, and packaging industries. By definition, such fluids are thermodynamically unstable or at best metastable. Hence, conditions of preparation are of extreme importance to both the scientific study and the engineering of these fluids. 

This chapter deals almost exclusively with neat, or pure, diblock copolymer melts. Polymer blends are discussed in Chapter 9, micellar solutions in Chapter 12, and stabilized suspensions in Chapter 6. In the following, Section 13.2 briefly reviews the thermodynamics of block copolymers, and Section 13.3 describes the rheological properties and flow alignment of lamellae, cylinders, and sphere-forming mesophases of block copolymers. More thorough reviews of the thermodynamics and dynamics of block copolymers in the liquid state have been written by Bates and Fredrickson (1990 Fredrickson and Bates 1996). The processing of block copolymers and mechanical properties of the solid-state structures formed by them are covered in Folkes (1985). Biological applications are discussed in Alexandridis (1996). 

Thus, the important features of the structural-mechanical barrier are the rheological properties (See Chapter IX,1,3) of interfacial layers responsible for thermodynamic (elastic) and hydrodynamic (increased viscosity) effects during stabilization. The elasticity of interfacial layers is determined by forces of different nature. For dense adsorption layers this may indeed be the true elasticity typical for the solid phase and stipulated by high resistance of surfactant molecules towards deformation due to changes in interatomic distances and angles in hydrocarbon chains. In unsaturated (diffuse) layers such forces may be of an entropic nature, i.e., they may originate from the decrease in the number of possible conformations of macromolecules in the zone of contact or may be caused by an increase in osmotic pressure in this zone due to the overlap between adsorption layers (i.e., caused by a decrease in the concentration of dispersion medium in the zone of contact). 

At this point we want to describe briefly the thermodynamic precondition for the formation of thin liquid films and some of their physical properties which differ from the related liquid bulk phase. Further we report on the present state of knowledge on the rate of thinning of liquid films dependent on the related surface rheological properties. 

Thermodynamics also plays a dominant role in the interphasial phenomena, viz. the interfacial tension coefficient, thickness of the interphase, Al, the rheological properties of the interphase, the adhesion, etc. It is worth recalling that most... 

Incorporation of long-chain hydrocarbon hydrophobes into a cellulose ether backbone leads to an interesting new class of polymeric surfactants. Their enhanced solution viscosity can be explained in terms of intermolecular associations via the hydrophobe moieties. Entropic forces cause the polymer hydrophobes to cluster to minimize the disruption of water structure. The same thermodynamic principles that are used to explain the micellization of surfactants can be applied to explain the solution behavior of HMHEC. HMHECs interact with surfactants that modify their solution viscosities. The chemical nature and the concentration of the surfactant dictate its effect on HMHEC solution behavior. The unique rheological properties of HMHEC can be exploited to meet industrial demands for specific formulations and applications. 

S.R. Mulligan, The QCM/HCC and Applications in Studying the Thermodynamic and Rheological Properties of Polymer and Protein Thin Films at a Gas/Solid interface, PhD Thesis, Drexel University, Philadelphia, 2002. 

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