Search results for "Concentration effect"

Toluene self-diffusion in solutions of linear and crosslinked polystyrene

1995

Toluene self-diffusion coefficients in solutions of linear and crosslinked polystyrene (PS) at concentrations up to 30 wt% polymer have been determined over the temperature range 143–230 K using the1H n.m.r. static gradient stimulated echo method. At similar polymer concentrations, the diffusion coefficient values of toluene were higher for mixtures with crosslinked PS than for solutions containing linear PS. On cooling and approaching the solution glass transition, the amplitude decays in diffusion and spin-relaxation measurements become non-exponential and are interpreted in terms of a two-component decomposition. The estimated fraction of the toluene motionally bound to polymer increases…

Aggregation Processes and Formation of Silico-calco-alkaline Gels under High Ionic Strength

2002

This paper presents a systematic in situ study of the process of formation of silico-calco-alkaline gels starting from a liquid colloidal solution containing different alkaline ions and different calcium concentration until the final gel state. The combined use of X-ray and neutron small-angle scattering (SAS) and dynamical rheometry techniques lead to a consistent description of the structure of the aggregates and of the mechanisms of aggregation involved in gel formation. SAS results indicate that the aggregates are fractal objects, their structure strongly depending on calcium ion concentration. The differences in gelation kinetics for systems containing different alkaline ions were attr…

A friction factor analysis of the coupling between polymer/solvent self- and mutual-diffusion: polystyrene/toluene

1996

The Bearman statistical mechanical theory, which couples the mutual-diffusion and self-diffusion coefficients via friction factors, has been applied to polystyrene/toluene solutions with polystyrene molecular weights of 18 kDa and 900 kDa. Toluene and polystyrene self-diffusion coefficients, obtained from the literature and measured here, along with polystyrene/toluene binary mutual-diffusion coefficients and thermodynamic data, were employed to independently calculate the three friction coefficients (ξ 12 , ξ 11 , and ξ 22 ) required to describe transport within binary solutions. Results reveal that the frequently used geometric mean approximation (GMA) for relating the friction coefficien…

Self-Diffusion of Small Molecules into Rubbery Polymers: A Lattice Free-Volume Theory

2010

In the framework of the Free Volume Theory, a new equation was derived for the evaluation of self-diffusion coefficients of small molecules in polymers above the mixture glass transition temperature. The derivation of the equation turned out to be straightforward once the equivalence between the free-volume and the unoccupied volume given by Thermodynamic Lattice Theories is assumed. A parameter evaluation scheme is proposed, which is substantially simpler compared to the conventional Vrentas-Duda approach, even without losing generality. The key assumption is discussed and its consistency is verified from a numerical viewpoint. A comparison with experimental solvent self-diffusion coeffici…

Experimental studies of the rheological behavior of a demixing biopolymeric sol

1995

Experimental data are presented concerning a large transient viscosity surge occurring in the course of spinodal demixing of agarose aqueous solutions. The study includes the effects of water perturbation by minor proportions of compatible cosolutes. Three observations are noteworthy. One concerns an upward or downward shift of the spinodal temperature, caused by cosolutes, which agrees with their expected modulation of solvent-induced forces. The second concerns the time of appearance of the viscosity surge. This is observed to follow a critical law, with an exponent independent of polymer concentration and solvent perturbation. The third concerns the inverse-power-law dependence of the vi…

1991

The polysoaps [CH 2 C(Me)(CO 2 R)] n (R=(CH 2 ) 11 N + Me 2 (CH 2 ) 3 SO 3 − , (CH 2 ) 11 N + Me 2 CH 2 CH 2 OH) are studied. Their aqueous solution properties are strongly influenced by added salts; the surface activity can be modified efficiently by an appropriate choice of ions. The interactions of salts and polyzwitterions observed in solution can be extended to the behaviour in bulk. It enables the preparation of uniform, non crystalline blends containing up to equivalent amounts of inorganic salt and polyzwitterions

Molecular surfaces: An advantageous starting point for the description of composition-dependent viscosities applied to polymer solutions

1999

The viscosity of polymer/solvent systems is modeled as a function of composition under the premises that the dissipation of energy is taking place at the molecular interfaces and that the friction between solvent and solute varies with composition due to a change in the flow mechanism (drainage of coils). The simple expression obtained in this manner contains three system-specific parameters: a geometric factor γ, which accounts for the differences of the surface to volume ratios of the components; a hydrodynamic parameter α, which measures the friction between solute and solvent in the case of fully draining polymer coils; and β, which corrects for changes in the friction between unlike mo…

Some aspects related to stability, critical concentrations and kinetics of flocculation of the calcium phytate colloid

1986

Abstract As 99mTcCa phytate is an important radiopharmaceutical and its colloidal nature presents problems, we investigated some of them. This work describes the study of the colloidal behaviour of the calcium phytate colloid in terms of its formation, stability and kinetics of flocculation. The study of spontaneous, and centrifugation-induced flocculation allows the determination of two critical concentrations of sol flocculation. The titrations of calcium phytate colloid at different concentrations provide information on the colloidal formation conditions. Moreover, a study on flocculation kinetics was made by turbidity measurements.

Competition between chain scission and branching formation in the processing of high-density polyethylene: effect of processing parameters and of sta…

2009

Two samples of high-density polyethylene with different molecular weight were processed in a batch mixer and the rheological and structural properties were investigated. In particular, the effect of different processing parameters and the eventual presence of different stabilizers were evaluated. Actually, two reactions may occur during processing: branching/crosslinking or chain scission. The results indicate that when the processing conditions promote a scarce mobility of the macromolecular chains (lower temperatures, lower mixing speed, and higher molecular weight), branching is more favored than chain scission. On increasing the mobility of the chain (higher temperature, higher mixing s…

On the effectiveness of different additives and concentrations on the re-building of the molecular structure of degraded polyethylene

2006

Mechanical recycling is an easy and economic way to re-use plastic waste as secondary materials, but, in general, their properties are worse with respect to the reclaimed materials and the virgin polymer. The aim of this work was to study the effect of concentration and reaction kinetics of two additives, an ethylene-co-glycidyl methacrylate (Lotader) and a hydroxylamine derivative (CGX), in the re-building of a degraded polyethylene. CGX is a nitroxyl radical generator able to form branching in polyolefins while the epoxy groups of Lotader can react with the functional groups present in the recycled polyethylene. The results indicate that the CGX has a higher reaction rate than Lotader, pr…