Transport of Matter Phenomena in Polymers

Permanent research personnel

M. Sanopoulou (Chemist, PhD), principal researcher

K.G. Papadokostaki (Chemist, PhD) principal researcher

Emeritus Researcher

J. H. Petropoulos (Chemist, PhD)

Collaborating researcher

V. Dimos (Chemical Engineer, PhD)

Ph.D. candidates

A. Stavropoulou (Chemist, MSc)
D. Soulas  (Chemist, MSc)
M. Herouvim (Food technologist, MSc)
A. Hassimi (Chemist )

The Laboratory of Transport of Matter Phenomena in Polymers is concerned with the study of micromolecular sorption and diffusion in polymeric materials by a combination of theoretical and experimental approaches. The aim of the work is to help create the basic scientific background for the optimization of the design of polymeric materials for important applications (controlled release systems, permselective membranes, packaging, microchip manufacture, etc).

Current Research Activities

A. Polymer-based Controlled Release Systems

Development  of controlled release devices aims at the regulated, prolonged delivery of  drugs, agrochemicals or other bioactive agents. Matrix-type controlled release devices consist of a swellable polymer matrix incorporating the requisite bioactive solute and are activated by the ingress of water when placed in an aqueous environment. These devices, although they have a low manufacturing cost due to their structural simplicity, are commonly characterized by a continuous decline of dose rate. The latter constitutes a substantial drawback for most practical applications. Research of our group in this area aims at the optimization of the functioning of these devices by a combination of modeling and experimental work. In particular, we have developed an advanced, realistic model,  simulating the strongly interacting fluxes of solvent and solute and,  hence, capable of predicting the resulting rate and kinetics of release. Theoretical work is supported by experimental studies on the effect of various system parameters (such as solute solubility, polymer degree of hydration, osmotic effect of solvent) on the kinetics of release and concurrent uptake of water. In addition, methods for approaching the desired constant dose rate are investigated (e.g. multilaminate systems).

B. Mechanisms of Micromolecular Non-Fickian Transport Kinetics in Glassy Polymers

Sorption and diffusion of micromolecular substances in glassy polymer films is of great importance in many technological applications (e.g. polymer film drying, lithographic step of integrated circuit production, polymeric controlled release systems, food packaging materials). Sorption kinetics in these systems exhibit a variety of deviations from normal Fickian behaviour, attributable to (a) slow viscous relaxations of the swelling polymer or (b) differential swelling stresses generated by the constraints imposed on local swelling during sorption. Our group has developed macroscopic models based on both mechanisms, capable of simulating all basic features of observed non_Fickian kinetic behaviour, including Case II kinetics. Experimental work includes

(i) sorption from the vapour phase. Carefully designed experimental protocols, consisting of series of successive integral or interval sorption kinetic experiments, supplemented by measurement of longitudinal swelling kinetics of the polymer film enable us to study various types of non-Fickian behaviour. On the basis of the models mentioned above, we developed general diagnostic criteria for distinguishing between the underlying mechanisms responsible for the observed behaviour and applied this methodoly  to particular cellulosic or methacrylic polymer systems.

(ii) sorption from the liquid phase. Various optical techniques are used in order to obtain information not only on the rate and kinetics of penetration but also on penetrant concentration profiles and parallel deformation and structural relaxation of the swelling polymer. Combination of these techniques enables us to study in detail various types of non-Fickian penetration such as stress-dependent diffusion and Case II kinetics.

C. Molecular Dynamics Simulation of Structure and Transport Properties of Poly(dimethylsilamethylene) Polymers

The project aims at the development of novel membrane materials for the separation of hydrocarbons in the petroleum and natural gas industry. Molecular Dynamics is used for computer simulation of hydrocarbon sorption and diffusion properties in polysilamethylene polymers. In addition, experimental evaluation of the transport properties is performed in collaboration with Topchiev Institute of the Russian Academy of Sciences.

D. Characterization of Transport and Thermal properties of polymer systems for specific applications.

In collaboration with the Institute of Microelectronics in Demokritos, we evaluate the swelling and/or dissolution behaviour of thin supported polymer films exposed to different vapour or liquid environments for the development of lithographic systems and silicon bilayer chemical sensors.


Research Facilities


  • Vacuum apparatuses for sorption and longitudinal dilation kinetic measurements on polymer samples during sorption of vapors at sub-atmospheric pressures. Sorption is measured by means of electronic microbalances (Cahn 2000 and MK2-M5 CI Electronics) or quartz spring balances. Longitudinal dilation kinetics is measured simultaneously with sorption kinetics on a separate strip of the polymer by means of inductive transducers (Schaevitz) attached to the film.
  • Polarizing and interferometric microscopes for studying penetration of liquids in polymer films. By a combination of optical methods, the kinetics of visible penetration and swelling fronts are obtained in conjunction with the corresponding concentration and birefringence profiles.
  • Optical microdensitometer
  • Tensile tester in conjunction with optical setup for studying mechanical and rheo-optical properties of polymer films
  • Thermal analysis instruments, including Temperature Modulated DSC, TMA and TGA.


Research Grants

  • NATO SCIENCE FOR PEACE PROGRAM “Novel Membrane Materials and Membranes for Separation of Hydrocarbons in Natural and Petroleum Gas” in collaboration with Molecular Modelling of Materials Laboratory (Project No 972638), 1999-2003
  • PLATO GREEK-FRENCH BILATERAL PROGRAM “Effect of Glass Transition on the transport mechanism of micromolecules in polymeric materials “, Project No 889, 2002-2003
  • Excellence in the Research Institutes supervised by gsrt “Advanced Functional Materials” (Project No1422/B1/3.3.1/362/2002), 2003-2005. 
  • STREP Program FP6, Priority 3, “Computer aided molecular design of multifunctional materials with controlled permeability properties” in collaboration with Molecular Modelling of Materials Laboratory (Contract no.: 013644), November 2004 –2007.

Selected Publications