Plasticization of Biobased Polymers: A Combined Experimental and Simulation Approach
Time: Fri 2021-04-23 10.00
Subject area: Fibre and Polymer Science
Doctoral student: Hüsamettin Deniz Özeren , Polymera material
Opponent: Professor Kim Bolton, University of Borås, Faculty of Textiles, Engineering and Business
Supervisor: Professor Mikael S. Hedenqvist, Polymera material; Universitetslektor Richard Olsson, Polymera material; Docent Fritjof Nilsson, Fiber- och polymerteknologi
The field of bio-based plastics has developed significantly in recent decades and there is an increasing demand for industries to shift from petrochemical to biobased polymers. Biobased polymers offer competitive properties, and in many cases have advantages in terms of cost. Thermoplastic starch is already commercially available, while wheat-gluten protein-based materials are considered to be promising candidates for commercial use.
Biobased materials can, however, have several drawbacks that have to be handled. Starch-based materials are, in general, brittle due to the stiff glucose-based molecular chain and hydrogen bond network. This is the case also for proteins (due to the stiff peptide bond, bulky side groups and hydrogen bond network), like for example gluten. These issues can, however, be resolved with effective compatible plasticizers. But in order to be able to optimize the choice of the right plasticizer for a specific polymer, there is a need for an increased understanding of the plasticizer mechanisms. Besides, a methodology for prediction of the plasticizer amount needed, as well as to be able to rank possible plasticizer candidates, based on their effectiveness.
As a part of the development of a methodology (based on the combination of experimental and molecular-dynamics simulations) for prediction of plasticization and to investigate and understand plasticizer mechanisms, the main material investigated was starch, but also wheat gluten, both plasticized with glycerol. The main plasticizer used to date for biobased polymer materials is glycerol, because of its effectiveness, stability and low cost. In addition, it is also a large byproduct of biodiesel production. A number of other plasticizer candidates were also studied for the starch system to see if the developed methodology could be used to rank plasticizers. Diols were tested in the starch system as plasticizers, but they had no or little plasticization effect. Nevertheless, they gave rise to unexpected structures and properties. Several techniques were used to determine the experimental properties of the bio-based films, including calorimetry, gravimetry, dynamic mechanical analysis, and tensile testing.
The results (based on mechanical and thermal properties) showed that the methodology could be used to rank plasticizers in terms of their effectiveness. It was also possible to predict the amount of plasticizer needed for effective softening. With the help of the simulations, the emollient effect could be studied in detail and largely explained by hydrogen bonding effects. The methodology was also developed to be able to predict from simulation not only trends in mechanical properties but also absolute values in stiffness and strength at elongation rates corresponding to experimental measurements.