Date of Award

8-2013

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Legacy Department

Chemical Engineering

Advisor

Husson, Scott M

Committee Member

Hirt , Douglas

Committee Member

Gooding , Charles

Committee Member

Bruce , Terri

Committee Member

Wickramasinghe , Ranil

Abstract

This dissertation focuses on the design, development and implementation of novel, advanced imaging protocols for the characterization of membranes in microfiltration applications. Oftentimes, membrane characterization studies are done with high resolution microscopy techniques like scanning electron microscopy or transmission electron microscopy. The results obtained by these popular imaging techniques are subject to error and their reliability might be, in some instances, compromised because they require drying and metallization of the sample; working under high vacuum and electron beam intensity; and extensive sectioning to retrieve internal information. These factors may disrupt the membrane structure or modify its features. As an alternative to these techniques, confocal microscopy stands out and has gained popularity recently in material studies because its features overcome the aforementioned limitations. Therefore, the primary objectives of my dissertation were to design, develop and implement novel confocal microscopy imaging protocols for the characterization of membranes and highlight opportunities to obtain reliable and cutting-edge information of microfiltration membrane morphology and fouling processes.
My strategy consisted of developing a cross-sectional confocal microscopy imaging protocol that combines minimal mechanical sectioning of the sample with optical sectioning to obtain images from just below the surface of the cross-section and avoid concerns about surface artifacts due to sample preparation. The application of this protocol allowed the visualization of the full thickness of symmetric and asymmetric membranes, overcoming the limit on depth of penetration inherent in confocal microscopy. Along with image analysis, it is possible to obtain information regarding, but not limited, to membrane morphology and fouling.
After a comprehensive introduction and review of confocal microscopy in membrane applications (Chapter 1), the first part of this dissertation (Chapter 2) details my work on membrane morphology characterization by confocal laser scanning microscopy (CLSM) and the implementation of my newly developed CLSM cross-sectional imaging protocol. Depth-of-penetration limits were identified to be approximately 24 microns and 7-8 microns for mixed cellulose ester and polyethersulfone membranes, respectively, making it impossible to image about 70% of the membrane bulk. The development and implementation of my cross-sectional CLSM method enabled the imaging of the entire membrane cross-section. Porosities of symmetric and asymmetric membranes with nominal pore sizes in the range 0.65-8.0 microns were quantified at different depths and yielded porosity values in the 50-60% range. It is my hope and expectation that the characterization strategy developed in this part of the work will enable future studies of different membrane materials and applications by confocal microscopy.
After demonstrating how cross-sectional CLSM could be used to fully characterize membrane morphologies and porosities, I applied it to the characterization of fouling occurring in polyethersulfone microfiltration membranes during the processing of solutions containing proteins and polysaccharides (Chapter 3). Through CLSM imaging, it was determined where proteins and polysaccharides deposit throughout polymeric microfiltration membranes when a fluid containing these materials is filtered. CLSM enabled evaluation of the location and extent of fouling by individual components (protein: casein and polysaccharide: dextran) within wet, asymmetric polyethersulfone microfiltration membranes. Information from filtration flux profiles and cross-sectional CLSM images of the membranes that processed single-component solutions and mixtures agreed with each other. Concentration profiles versus depth for each individual component present in the feed solution were developed from the analysis of the CLSM images at different levels of fouling for single-component solutions and mixtures. CLSM provided visual information that helped elucidate the role of each component on membrane fouling and provided a better understanding of how component interactions impact the fouling profiles.
Finally, Chapter 4 extends the application of my cross-sectional CLSM imaging protocol to study the fouling of asymmetric polyethersulfone membranes during the microfiltration of protein, polyphenol, and polysaccharide mixtures to better understand the solute-solute and solute-membrane interactions leading to fouling in beverage clarification processes. Again, cross-sectional CLSM imaging provided information on the location and extent of fouling throughout the entire thickness of the PES membrane. Quantitative analysis of the cross-sectional CLSM images provided a measurement of the masses of foulants deposited throughout the membrane. Moreover, flux decline data collected for different mixtures of casein, tannic acid and beta-cyclodextrin were analyzed with standard fouling models to determine the fouling mechanisms at play when processing different combinations of foulants. Results from model analysis of flux data were compared with the quantitative visual analysis of the correspondent CLSM images. This approach, which couples visual and performance measurements, is expected to provide a better understanding of the causes of fouling that, in turn, is expected to aid in the design of new membranes with tailored structure or surface chemistry that prevents the deposition of the foulants in 'prone to foul' regions.
Overall, results from my dissertation demonstrate that CLSM has strong potential for providing reliable and new information that conventional imaging techniques, at present, are not able to provide. Also, CLSM and the cross-sectional imaging protocol developed in this dissertation are worthy tools in, but not limited to, membrane morphology and fouling characterization studies.

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