The spinning process of hollow fiber membranes was investigated with regards to two fundamental phenomena: flow (shear and elongation) and phase separation. Quantitative analysis of phase separation kinetics of binary (polymer/solvent) and ternary (polymer/solvent/volatile co-solvent) polymer solution was carried out with a newly developed microfluidic device. The device enables visualization of in situ phase separation and structure formation in controlled vapor and liquid environments. Results from these studies indicated that there was a weak correlation between phase separation kinetics and macroscopic defect (macrovoid) formation. In addition, the effect of shear and elongation on membrane morphology was tested by performing fiber extrusion through microfluidic channels. It was found that the membrane morphology is dominated by different factors depending on the rate of deformation. At high shear rates typical of spinning processes, shear was found to induce macrovoid formation through normal stresses, while elongation suppressed macroscopic defect formation. Furthermore, draw resonance, one of the key instabilities that can occur during fiber spinning, was investigated. It was found that draw resonance occurs at aggressive elongation condition, and could be suppressed by enhanced phase separation kinetics. These results can be used as guidelines for predicting hollow fiber membrane spinnability.

Hollow fiber membranes offer the opportunity to dramatically reduce the energy required to perform gas separations in the chemical industry. The membranes are fabricated from highly non-Newtonian precursor materials, including concentrated polymer solutions that sometimes also contain dispersed particles. These materials are susceptible to shear-induced microstructural changes during processing, which can affect the characteristics of the resulting membrane. This thesis explores several shear-related effects using materials and flow conditions that are relevant for fiber spinning. The findings are discussed as they relate to membrane processing, and also from the standpoint of enhancing our fundamental understanding of the underlying phenomena. First, the effect of shear on polymeric dope solutions was investigated. Shear-induced demixing—a phenomenon not previously studied in membrane materials—was found to occur in membrane dopes. Phase separation experiments also showed that shear-induced demixing promotes macrovoid formation. The demixing process was found to depend not only on the instantaneous shear conditions, but also on the shear history of the solution. This suggests that low-shear flow processes that occur in the upstream tubing and channels used for fiber spinning can affect macrovoid formation. The effect of viscoelastic media on dispersed particles was also explored. Shear-small-angle light scattering results showed that particles suspended in membrane dope solutions formed aggregated, vorticity-oriented structures when shear rates in the shear-thinning regime of the polymer solution were applied. Shear rates well below the shear-thinning regime did not produce any structure. In fact, the application of a Newtonian shear rate to a sample already containing the vorticity structure caused the sample to return to isotropy. Measurements using a highly elastic, constant-viscosity Boger fluid showed that strong normal forces alone are not sufficient to form the vorticity structures, but that shear thinning is also required. Lastly, a study was conducted examining cross-stream migration of particles dispersed in viscoelastic media. Fluids exhibiting varying degrees of shear thinning and normal forces were found to have different effects on the particle distribution along the shear gradient axis in Poiseuille flow. Shear thinning was found to promote migration toward the channel center, while normal stresses tended to cause migration toward the channel walls. In addition to hollow fiber spinning, many other industrially relevant applications involve polymer solutions and suspensions of particles in viscoelastic media. Often, the properties and performance of the material depend strongly on the internal microstructure. The results from the research described in this thesis can be used to guide the design of materials and processing conditions, so that the desired microstructural characteristics can be achieved.