Deformation studies of polymers and polymer/clay nanocomposites

Abstract

Polymer clay nanocomposites have been a popular area of materials research since they were first introduced in the 1990s. The inclusion of clays into many different host polymers has been shown to improve the properties of matrix polymers in a number of ways including increased mechanical strength, thermal stability and improved barrier properties while keeping the composite light weight and transparent. Although there is a great deal of published work on the preparation and property measurements of polymer clay nanocomposites, there is no model to design a nanocomposite with a given set of properties for a specific end-use. While it is important to know the structure property relationships of materials, the understanding of how nanocomposites reach their final forms and properties is equally important. A thorough understanding of processing effects on the final structure of polymer clay nanocomposites is still missing. With this perspective, this thesis addresses building structure-processing relationships of polymer clay nanocomposites by analyzing multiaxial deformation behavior using in-situ x-ray scattering techniques. This thesis can be divided into two distinct parts. The first part concerns the design of the in-situ multiaxial deformation device (IMDD) used to create the deformation conditions that polymers go through during processing such as blow molding and thermoforming. The device was designed to overcome several concerns with in situ measurement by maintaining constant sample to detector distance, minimizing the material between the incident beam and the detectors, as well as exposing the same point on the sample throughout deformation. A new design to create biaxial deformation, termed in-situ biaxial deformation device (IBDD), is also introduced in this part of the thesis.. In addition, a new heating unit, attached to IBDD, is designed for higher temperature studies, up to 150°C, to imitate industrial processing conditions more closely. The second part of the thesis addresses the effect of strain, strain rate, and temperature as well as the amount of clay on the polymer morphology evolution during multiaxial deformation.. Two different polymer/clay systems were studied: poly(ethylene)/clay and poly(propylene)/clay. It was observed that the morphological evolution of polyethylene and polypropylene is affected by the existence of clay platelets as well as the deformation temperature and the strain rate. Martensitic transformation of orthorhombic polyethylene crystals into monoclinic crystal form was observed under strain but is hindered in the presence of clay nanoplatelets. The morphology evolution of poly(propylene) crystal structure during multiaxial deformation was more subtle where the most stable α-crystalline form went through strain induced melting. This was more noticeable in the nanocomposites with clays up to 5 wt%. It was also noted that the thickness of the interlamellar amorphous region increased with increasing strain at room temperature due to the elongation of the amorphous chains. The increase in the amorphous layer thickness is slightly higher for the poly(ethylene)/clay nanocomposites compared to neat poly(ethylene) while the increase in the lamellar long spacing is slightly higher for the neat poly(propylene) compared to poly(propylene)/clay nanocomposites. The rate of change in the characteristic repeat distance in both poly(ethylene) and poly(propylene) systems is higher at faster strain rates, at room temperature, where it remained constant during higher temperature deformations. Time dependent recovery after deformation studies have shown that poly(ethylene)/clay system reverts back to its initial configuration. The recovery in the amorphous chains was however observed to take longer in the clay added poly(ethylene)s. Crystalline relaxation was observed to happen almost instantly in the poly(ethylene)/clay system. On the other hand, amorphous chains in the poly(propylene)/clay system did not revert back to the initial configuration in the period of time that the recovery observations were performed while the crystalline configuration recovered back almost fully in the given time.