Matrimid was utilized for the preparation of membranes with asymmetric structures. A combination of well-known solvents for Matrimid which include 1- methyl-2-Pyrrolidone (NMP), tetrahydrofuran (THF), dichloromethane, tetrachloroethane as well as non-solvents n-butanol, xylene, and acetic acid were used. Cast solutions were prepared at room temperature for different combinations and compositions of polymer/solvent/non-solvent systems. PEG and Octa-(amino phenyl) POSS were introduced in some of the cast solutions. The membranes obtained were characterized by permeation test for gas permeabilities and selectivities, Scanning Electron Microscopy (SEM) and Nuclear Magnetic Resonance (NMR) Spectroscopy. The gas permeation test showed that the use of mixture of dichloromethane and tetrachloroethane as solvents with xylene non-solvent and acetic acid as stabilizer gave membranes with very high gas selectivity of 133 for CO2/N2 and 492 for CO2/CH4. Also, cast solutions containing PEG resulted in membranes with slightly enhanced selectivities from 30 to 42 for CO2/N2. Permeation results for CO2, N2 and H2 and the selectivities for gas pairs such as CO2/N2, CO2/CH4, are discussed in relation to the effect of pressure on the membrane permeance, they are also compared with existing results.

Master of Science / Department of Chemical Engineering / Mary Rezac / Polymeric membranes have been playing important roles in gas or liquid separations. Polyimide polymers are of interest due to their commercially availability along with good transport, thermal and mechanical properties. In this study, two common commercial polyimide polymers, Matrimid and P84 were blended, to combine the good transport property of Matrimid with the plasticization resistance of P84. Matrimid/P84 blend solutions ranging from 0-100 wt. % Matrimid were prepared to make blend films. Physical properties (density, d-spacing, thickness), transport properties (permeability of H2, N2, CH4, Ar, He, CO2, and gas pairs selectivity), thermal property (mass loss curves of TGA), and liquid solutes (water, methanol, toluene, butanol, 1-propanol, 2-propanol) desorption behavior were measured or characterized. Rules of changing behavior of the properties with mass fraction of Matrimid were investigated, summarized, and interpreted mathematically. As Matrimid mass fraction increases, there are more mobility and space between polymer chains, therefore there are smaller density, larger d-spacing, larger fractional free volume (FFV) and larger permeability. The selectivity-permeability relationship follows the trade-off line. Thermal mass loss curve of the blend films in air have presented intermediate characteristic with rising fraction of Matrimid compared to individual polymers. A partial-miscible behavior has been found from the correlation between permeability and FFV. The desorption behavior was found to be reasonably described by the case III model, where the diffusion rate is similar with relaxation rate of polymers.

Doctor of Philosophy / Department of Chemical Engineering / Mary E. Rezac / Polyimide membranes have been used extensively in gas separation applications because of their attractive gas transport properties and the ease of processing these materials. Other applications of membranes, such as membrane reactors, which could compete with more traditional packed and slurry bed reactors across a wider range of environments, could benefit from improvements in the thermal and chemical stability of polymeric membranes. This work focuses on blending polyimide and polybenzimidazole polymers to improve the thermal and chemical stability of polyimide membranes while retaining the desirable characteristics of the polyimide. Blended dense films and asymmetric membranes were fabricated and characterized. Dense film properties are useful for studying intrinsic properties of the polymer blends. Transport properties of dense films were characterized from room temperature to 200°C. Properties including miscibility, density, chain packing and thermal stability were investigated. A process for fabricating flat sheet blended integrally skinned asymmetric membranes by phase inversion was developed. The transport properties of membranes were characterized from room temperature to 300°C. A critical characteristic of gas separation membranes is selectivity. Post-treatments including thermal annealing and vapor and liquid surface treatments were investigated to improve the selectivity of blended membranes. Vapor and liquid surface treatments with common, benign solvents including an alkane, an aldehyde and an alcohol resulted in improvements in selectivity.

Master of Science / Department of Chemical Engineering / John R. Schlup / The cross-linking reaction of the polyimide Matrimid 5218 with ethylenediamine (EDA) in methanol was investigated using Fourier transform infrared (FTIR) spectroscopy. Peaks associated with breaking imide bonds and the formation of amide bonds were identified. Using an internal standard peak of 1014 cm⁻¹ allowed for quantitative analysis to be applied. The peak areas, calculated by slice area, were used for absorbance ratio analysis to follow the cross-linking reaction as a function of time. Lastly, the absorbance values for the decreasing peak 1718 cm⁻¹ were used to calculate the order of reaction for the reaction rate of the mechanism.

Commercial pure terephthalic acid (PTA) manufacturing generates process streams mainly containing acetic acid (HAc) and water. A large financial incentive exists to replace the costly and energy intensive distillation column used to recycle HAc-water mixtures. This work focuses on the development of pervaporation technology to separate HAc-water mixtures using a hollow fiber-based membrane unit. Currently a 250 m outer diameter Matrimid® hollow fiber is used in industry for gas separation. Due to the difference between gas and liquid separations, the fiber performance associated with high flux in pervaporation is limited by a pressure change inside the bore along the axial direction of the fiber. A mathematical model was developed to describe the bore pressure change in pervaporation in this work, which demonstrated that spinning a large bore size fiber was a good solution to minimize the bore pressure change. Spinning technology has been adapted to obtain a large bore size defect-free Matrimid® hollow fiber. In addition to a large bore size, the asymmetric fiber exhibits an intrinsically defect-free selective layer supported on an open porous substrate. This eliminates the post-treatment with a caulking layer and has a special advantage for aggressive liquid separation. A proof of concept was provided by testing both small and large bore size defect-free fibers with a model 20% wt HAc feed in a pervaporation system at 101.5oC. The membrane selectivity (~ 25) and water flux (~ 4.5 kg/m2hr) were increased by about 150% with a diameter (O.D. ~ 500 m) twice as large as the regular fiber. Further, a decrease in the HAc flux was observed with the increased bore size due to the reduction in HAc-induced plasticization. Sub-Tg thermal annealing was used to stabilize the fiber by suppressing HAc-induced plasticization. This improves the polymer discrimination of shape and size for penetrants although no chemical reaction occurs with thermal annealing. The resulting membrane selectivity was increased from 10 to about 95 using a large bore size defect-free annealed fiber with acceptable water flux (~ 1.5 kg/m2hr) for 20% wt HAc concentration feed streams. These improvements make Matrimid® hollow fiber membranes very attractive for future scale-up and commercial development.