Design of advanced reverse osmosis and nanofiltration membranes for water purification

Most commercially available reverse osmosis (RO) and nanofiltration (NF) membranes are based on the thin film composite (TFC) aromatic polyamide membranes. However, they have several disadvantages including low resistance to fouling, low chemical and thermal stabilities and limited chlorine tolerance. To address these problems, advanced RO/NF membranes are being developed from polyimides for water and wastewater treatments. The following three projects have resulted from my research. (1) Positively charged and solvent resistant NF membranes. The use of solvent resistant membranes to facilitate small molecule separations has been a long standing industry goal of the chemical and pharmaceutical industries. We developed a solvent resistant membrane by chemically cross-linking of polyimide membrane using polyethylenimine. This membrane showed excellent stability in almost all organic solvents. In addition, this membrane was positively charged due to the amine groups remaining on the surface. As a result, high efficiency (> 95%) and selectivity for multivalent heavy metal removal was achieved. (2) Fouling resistant NF membranes. Antifouling membranes are highly desired for “all” applications because fouling will lead to higher energy demand, increase of cleaning and corresponding down time and reduced life-time of the membrane elements. For fouling prevention, we designed a new membrane system using a coating technique to modify membrane surface properties to avoid adsorption of foulants like humic acid. A layer of water-soluble polymer such as polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyvinyl sulfate (PVS) or sulfonated poly(ether ether ketone) (SPEEK), was adsorbed onto the surface of a positively charged membrane. The resultant membranes have a smooth and almost neutrally charged surface which showed better fouling resistance than both the positively charged NF membranes and commercially available negatively charged NTR-7450 membrane. In addition, these membranes showed high efficiency for removal of multivalent ions (> 95% for both cations and anions). Therefore, these antifouling surfaces can be potentially used for water softening, water desalination and wastewater treatment in a membrane bioreactor (MBR) process. (3) Thermally stable RO membranes. Commercial RO membranes cannot be used at temperature higher than 45°C due to the use of polysulfone substrate, which often limits their applications in industries. We successfully developed polyimides as the membrane substrate for thermally stable RO membranes due to their high thermal resistance. The polyimide-based composite polyamide membranes showed desalination performance comparable to the commercial TFC membrane. However, the key advantage of the polyimide-based membrane is its high thermal stability. As the feed temperature increased from 25oC to 95oC, the water flux increased 5 - 6 times while the salt rejection almost kept constant. This membrane appears to provide a unique solution for hot water desalination and also a feasible way to improve the water productivity by increasing the operating temperature without any drop in salt rejection.

Computational modeling of laser-induced delamination testing of thin films

Thin film adhesion often determines microelectronic device reliability and it is therefore essential to have experimental techniques that accurately and efficiently characterize it. Laser-induced delamination is a novel technique that uses laser-generated stress waves to load thin films at high strain rates and extract the fracture toughness of the film/substrate interface. The effectiveness of the technique in measuring the interface properties of metallic films has been documented in previous studies. The objective of the current effort is to model the effect of residual stresses on the dynamic delamination of thin films. Residual stresses can be high enough to affect the crack advance and the mode mixity of the delimitation event, and must therefore be adequately modeled to make accurate and repeatable predictions of fracture toughness. The equivalent axial force and bending moment generated by the residual stresses are included in a dynamic, nonlinear finite element model of the delaminating film, and the impact of residual stresses on the final extent of the interfacial crack, the relative contribution of shear failure, and the deformed shape of the delaminated film is studied in detail. Another objective of the study is to develop techniques to address issues related to the testing of polymeric films. These type of films adhere well to silicon and the resulting crack advance is often much smaller than for metallic films, making the extraction of the interface fracture toughness more difficult. The use of an inertial layer which enhances the amount of kinetic energy trapped in the film and thus the crack advance is examined. It is determined that the inertial layer does improve the crack advance, although in a relatively limited fashion. The high interface toughness of polymer films often causes the film to fail cohesively when the crack front leaves the weakly bonded region and enters the strong interface. The use of a tapered pre-crack region that provides a more gradual transition to the strong interface is examined. The tapered triangular pre-crack geometry is found to be effective in reducing the stresses induced thereby making it an attractive option. We conclude by studying the impact of modifying the pre-crack geometry to enable the testing of multiple polymer films.