Polymer Crystallization at Curved Liquid/Liquid Interface
Authors:   , Wang Wenda , Li Christopher Y. 
Published: July 2021

Liquid/liquid interface, either flat or curved, is a unique template for studying self-assembly of a variety of nanomaterials such as nanoparticles and nanorods. The resultant monolayer films can be ordered or disordered depending on the regularity of the nanomaterials. Integration of nanoparticles into two-dimensional structure leads to intriguing collective properties of the nanoparticles. Crystallization can also be guided by liquid/liquid interface. Due to the particular shape of the interface, crystallization can happen in a different manner comparing to the normal solution crystallization. In this dissertation, liquid/liquid interface is employed to guide the crystallization of polymers, mainly focusing on using curved liquid/liquid interface. Due to the unique shape of the interface and feasibility to control the curvature, polymer crystallization can take place in different manner and lead to the formation of curved or vesicular crystals. Curved liquid/liquid interface is typically created through o/w emulsions. With the presence of surfactant, the emulsions are controlled to be stable at least for the polymer crystallization periods. The difference to normal solution crystallization is: the nuclei will diffuse to the curved interface due to the Pickering effect and guide the crystallization along the curved liquid/liquid interface. If the supercooling can be controlled to be very small, crystal growth in the bulk droplets can be avoided. The advantages of this strategy are: 1) the formation process of vesicular type crystals can be monitored by controlling the polymer supply; 2) curved crystals, bowl-like structures and enclosed capsules can be easily obtained comparing to the self-assembly method for vesicle formation; 3) the obtained vesicles will be made of polymer crystals, which will possess the extraordinary mechanical properties. Based on the nucleation type, this dissertation is divided into two parts. The first part is focused on the self-assembly behavior of single-walled carbon nanotubes (SWCNTs) at curved liquid/liquid interface and the crystallization behavior of polymers at curved liquid/liquid interface while SWCNTs in presence. A few crystalline polymers, such as polyethylene (PE), poly(l-lactic acid) (PLLA), and poly(3-hexylthiophene-2,5-diyl) (P3HT), and water/oil systems were used to study the behavior. The formation of nano speckle structure is a crystallization-driven process due to heterogeneous nucleation and crystal growth of polymers at curved liquid/liquid interface. The second part deals with the homogeneous nucleation and crystal growth at curved liquid/liquid interface. Both PE and PLLA were used to conduct the study. For PE, 1,2-dichlorobenzene (DCB), water, and sodium dodecylsulfate (SDS) were used for the emulsion system. The emulsification system for PLLA is p-xylene, water, and hexadecyltrimethylammonium bromide (CTAB). Surfactant concentration can be employed to control the droplet size, thus controlling the final crystal vesicle's size. By controlling the initial polymer concentration, crystal shells with different morphology, such as curved crystal, bowl-like crystals, and crystal vesicles (named lamellaesome) can be obtained. The formation of these unique structures was templated by the curved interface. The formation process and detailed crystal structure are analyzed based on electron diffraction data from different sized lamellaesomes. Mechanical properties of the crystal vesicles and their encapsulation abilities will be discussed. At the end of this dissertation, a summary of my work and future outlook will be given.