Semester

Summer

Date of Graduation

2014

Document Type

Dissertation

Degree Type

PhD

College

Statler College of Engineering and Mineral Resources

Department

Chemical and Biomedical Engineering

Committee Chair

Rakesh K. Gupta

Committee Co-Chair

Sushant Agarwal

Committee Member

Robin Hissam

Committee Member

X. Y. Li

Committee Member

Edward M. Sabolsky

Abstract

There has been considerable scientific interest in both research and commercial communities as of late in the area of biologically based or sourced plastics. As the consumption of petroleum rises and concerns about climate change increase, this field is likely to grow even larger. One bioplastic that has received a great deal of attention is polylactic acid (PLA). In the past, this material was used mainly in medical or specialty applications, but advancements in manufacturing have led to a desire to use PLA more widely, especially in durable applications. Unfortunately, PLA has several drawbacks that hinder more widespread usage of the material as a durable item: it has low ductility and impact strength in bulk applications, along with poor stability in the face of heat, humidity or liquid media. To combat these deficiencies, a number of techniques were investigated. Samples were annealed to create crystalline domains that would improve mechanical properties and reduce diffusion, blended with graphene to create barriers to diffusion throughout the material, or compounded with a polycarbonate (PC) polymer phase to protect the PLA phase and to enhance the mechanical properties of the blend. If a material containing biologically sourced components with good mechanical properties can be created, it would be desirable for durable uses such as electronics components or as an automotive grade resin.;Crystallization experiments were carried out in a differential scanning calorimeter to determine the effects of heat treatment and additives on the rather slow crystallization kinetics of PLA polymer. It was determined that the blending in of the PC phase did not significantly alter the kinetics or mechanism of crystal growth. The addition of graphene to any PC/PLA formulation served as a nucleating agent which speeded up the crystallization kinetics markedly, in some cases by several orders of magnitude. Results obtained from these experiments were internally consistent, showing that no matter the treatment or formulation, PLA achieved a maximum of 30-35 percent crystallinity.;Samples receiving no treatment as well as those with annealing, the addition of graphene, and in some cases annealing/graphene were subjected to both solvent and hydrolytic degradation in order to find the most stable blend or treatment. Both pellets and molded parts of varying thicknesses were investigated to evaluate the effect of diffusional resistance on long term durability. It was determined that while the addition of crystallinity or graphene platelets can provide a temporary barrier against diffusion of attacking species, PLA polymer itself is not dimensionally stable over the long lifecycle required for durable applications such as for automotive parts. In fact, PLA-only molded panels aged in distilled water at 50°C for 42 days experienced over 99% viscosity loss regardless of which treatment was applied, and nearly all mechanical strength was lost during this time. Furthermore, while the addition of graphene and the heat treatment produced diffusion barriers which could slightly enhance PLA's degradation resistance, the treatments caused the already fragile polymer to become very brittle. Solvent degradation experiments also showed that molded parts containing more than 40% PLA loading lost in excess of 75% of the original viscosity no matter what treatment was used. This showed that these materials are likely to fail well before a sufficiently long lifecycle for durable goods is achieved.;Polycarbonate rich blends with less than 30% PLA as the dispersed phase showed excellent property retention after the accelerated aging tests. Formulations with up to 20% PLA content had degradation results that were nearly identical to those of 100% polycarbonate, which literature has shown to have useful lifecycles for durable applications of up to 20 years. By completely encapsulating the PLA in the polycarbonate matrix, which occurred at about 30% PLA by maximum, it was fully protected by the more stable phase.;Lastly, molded parts of differing thicknesses were hydrolytically degraded to examine the effects of diffusion resistance on the mechanical properties of untreated PC/PLA blends. It was determined that, similar to the droplet morphology study, the effect of PC content was the most dominating factor in the durability of the formulations. In fact, if molded parts reach a critical thickness, a transition from ductile to brittle failure modes can be observed. The rate of diffusion through the materials was also determined to be much faster than the rate of PLA hydrolysis.;It is concluded that the most effective way to create a durable material containing a significant bio-based content is to completely encapsulate PLA polymer with the more stable polycarbonate phase. Materials containing up to about 30% PLA at maximum were shown to be sufficiently durable so that they may be employed in similar automotive and electrical applications as for pure polycarbonate. (Abstract shortened by UMI.).

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