Polymer concentration effect parameters

In reversible polymerization, the critical concentration is equal to the equilibrium dissociation constant for polymer formation. This parameter is therefore independent of the number of polymers in solution. Confirmation comes from smdying reversible polymerization of ADP-actin when sonic vibration is applied to a solution of F-ADP-actin filaments at equilibrium with G-ADP monomers, no change is observed in the proportion of G- and F-actin (Carlier et al., 1985). Therefore, the only effect of sonic vibration is to increase the number of filaments without affecting the rates of monomer association to and dissociation from filament ends. 

Figure 3. The effect of degree of polymerization on surface coverage (fractional site occupancy) at various polymer concentrations. The solid lines represent the present model and the symbols correspond to the theory of Scheutjens and Fleer. The parameter values are the same as in Figure 2.

The rheological properties of a fluid interface may be characterized by four parameters surface shear viscosity and elasticity, and surface dilational viscosity and elasticity. When polymer monolayers are present at such interfaces, viscoelastic behavior has been observed (1,2), but theoretical progress has been slow. The adsorption of amphiphilic polymers at the interface in liquid emulsions stabilizes the particles mainly through osmotic pressure developed upon close approach. This has become known as steric stabilization (3,4.5). In this paper, the dynamic behavior of amphiphilic, hydrophobically modified hydroxyethyl celluloses (HM-HEC), was studied. In previous studies HM-HEC s were found to greatly reduce liquid/liquid interfacial tensions even at very low polymer concentrations, and were extremely effective emulsifiers for organic liquids in water (6). 

This treatment assumes that the forces between molecules in relative motion are related directly to the thermodynamic properties of the solution. The excluded volume does indeed exert an indirect effect on transport properties in dilute solutions through its influence on chain dimensions. Also, there is probably a close relationship between such thermodynamic properties as isothermal compressibility and the free volume parameters which control segmental friction. However, there is no evidence to support a direct connection between solution thermodynamics and the frictional forces associated with large scale molecular structure at any level of polymer concentration. 

Solution parameters such as viscosity of solution, polymer concentration, molecular weight of polymer, electrical conductivity, elasticity and surface tension, those are which attribute to polymer and its solution charaeteristies has important effect on morphology [18]. 

The above phenomenological description of the viscoelastic behaviour of polymer melts and concentrated solutions leads to the following important conclusions if one focuses on the behavioiu- in the terminal region of relaxation, what is usually done for temperature (time-temperature equivalence) may also be done for the concentration effects and the effects of chain length one may define a "time-chain length equivalence" and "time-concentration equivalence"[4]. For monodisperse species, the various shifts along the vertical (modulus) axis and horizontal (time or frequency axis) are contained in two reducing parameters the... 

In Stage 111, the reduction in >p and increase in d lead to a reduction in desorption coefficient with an increase in polymer-phase viscosity. For vinyl chloride emulsion polymerization the separate monomer phase disappears at about 70% conversion (AT,. = 0.7). Therefore, as soon as iVp reaches a constant value, the only parameter that changes for AT < is I. In fact, it is mainly the increase in that causes the acceleration in rate. For X > the situation is more complex, with both lc,p and falling as polymer concentration increases. For vinyl acetate, the separate monomer phase already disappears at 20% conversion. For X > X, is almost constant however [Mp], fe,p, and all decrease with conversion. These effects will he discussed in more detail later. 

Any attempts to obtain the parameters of the chromatograms and the physicochemical constants which are measurable in theory, by FFF, will be affected by the sample mass injected into the FFF channel. All of the concentration effects on the chromatograms discussed in the previous sections will be transferred, in turn, to those measured parameters and the physicochemical constants, such as the mass selectivity (S ), the common diffusion coefficient (D), the thermal diffusion coefficient (Dj-), and so forth. The increased retention of large polymers will result in enhanced mass selectivity in ThFFF. For a long time, this enhanced selectivity, in turn, the enhanced ThFFF universal calibration constant n, has led to confusion concerning the accuracy and repeatability of FFF, because different research groups have reported different data for selectivity and physicochemical constants measured by FFF for a given polymer-solvent combination [2,11]. Recent studies show that the enhanced selectivity and the different values of the physicochemical constants reported by different laboratories, measured by ThFFF, may be caused by different concentrations (sample mass) used by different laboratories. 

Chapter 4(71) focuses on the characterization of sorption kinetics in several glassy polymers for a broad spectrum of penetrants ranging from the fixed gases to organic vapors. The sorption kinetics and equilibria of these diverse penetrants are rationalized in terms of the polymer-penetrant interaction parameter and the effective glass transition of the polymer relative to the temperature of measurement. The kinetic response is shown to transition systematically from concentration independent diffusion, to concentration dependent diffusion, and finally to complex nonFickian responses. The nonFickian behavior involves so-called "Case II" and other anomalous situations in which a coupling exists between the diffusion process and mechanical property relaxations in the polymer that are induced by the invasion of the penetrant (72-78). ... 

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