​Abstract:

Natural gas is among the most dominant resources to provide energy supplies and Saudi Arabia ranks among the top 5 producers worldwide. However, prior to use of methane, natural gas has to be treated to remove other feed gas components, such as H2O, CO2, H2S, N2 and C2+ hydrocarbons. Most NG fields in KSA contain about 10 mol% carbon dioxide that has to be reduced to less than 2 mol% for pipeline delivery. 

The conventional unit operations for natural gas separations, that is, molecular sieves, amine absorption, cryogenic distillation, and turbo expansion exhibit some disadvantages in terms of economics, operational flexibility or system footprint. One of the most attractive alternative is membrane technology in either standalone- or hybrid system configuration. Currently, the only two membrane materials used in industrial natural gas applications are cellulose acetate and polyimide, which have moderate permeability and fairly low selectivity when tested under realistic industrial conditions. The goal for future research is to develop unique polymeric membranes, which can at least partially replace conventional gas processing in future natural gas projects. This will support global economics and specifically the economy of Saudi Arabia.

Newly developed polymeric materials must meet certain criteria to be used on a commercial scale. These criteria include: (i) high permeability and selectivity, (ii) processability into thin films, (iii) mechanical and thermal stability, and (iv) chemical stability against feed gas components.  This project focused on the removal of carbon dioxide from natural gas by developing and characterizing functionalized aromatic polyimide membrane materials that exhibit very high selectivity under aggressive mixed-gas conditions. 6FDA-DAR demonstrated a mixed-gas CO2/CH4 selectivity of 78 at a CO2 partial pressure of 10 bar with no pronounced indication of plasticization. Combining hydroxyl- and carboxyl groups in a miscible polyimide blend led to mixed-gas CO2/CH4 selectivity of 100 with no aging and no plasticization effects. This burgeoning membrane material has very high potential in large-scale natural gas separations with the best overall performance of any type developed to date.

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• CONTACTLinda J. Sapolu

​​​​​​ABSTRACT: Power supply in any electronic system is a crucial necessity. Especially so in fully compliant personalized advanced healthcare electronic self-powered systems where we envision seamless integration of sensors and actuators with data management components in a single freeform platform to augment the quality of our healthcare, smart living and sustainable future. However, the status-quo energy storage (battery) options require packaging to protect the indwelling toxic materials against harsh physiological environment and vice versa, compromising its mechanical flexibility, conformability and wearability at the highest electrochemical performance. Therefore, clean and safe energy storage solutions for wearable and implantable electronics are needed to replace the commercially used unsafe lithium-ion batteries.

This dissertation discusses a highly manufacturable integration strategy for a freeform lithium-ion battery towards a genuine mechanically compliant wearable system. We sequentially start with the optimization process for the preparation of all solid-state material comprising a ''Lithium-free'' lithium-ion microbattery with a focus on thinfilm texture optimization of the cathode material. State of the art complementary metal oxide semiconductor technology was used for the thinfilm based battery. Additionally, this thesis reports successful development of a transfer-less scheme for a flexible battery with small footprint and free form factor in a high yield production process. The reliable process for the flexible lithium-ion battery achieves an enhanced energy density by three orders of magnitude compared to the available rigid ones.

Interconnection and bonding procedures of the developed batteries are discussed for a reliable back end of line process flexible, stretchable and stackable modules. Special attention is paid to the advanced bonding, handling and packaging strategies of flexible batteries towards system-level applications.

Finally, this work shows seamless integration of the developed battery module in an effective integration strategy to incorporate them into a complex architecture such as orthodontic domain in the human body. The developed optoelectronic system embedded in a 3D printed smart dental braces for enhanced enamel healthcare protection and overall healthcare cost reduction. These findings complement and provide power solution options in which flexibility of electronics is an added beneficial dimensionality to wearable biomedical and implantable devices.

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• CONTACTMazen E. Mero

​Abstract:

Mixed Matrix Membranes (MMMs) have received worldwide attention during the last decades. This is due to the fact that the resulting materials can combine the good processability and low cost of polymer membranes with the diverse functionality, high performance and thermal properties of the inorganic fillers. This work explores the fabrication and application of MMMs. Various fillers and polymers have been combined in this work depending on the desired application. We focused on the design and fabrication of nanofillers to impart target functionality to the membrane for water treatment, protective coating and gas separation.

This thesis is divided into three sections according to the application including:

Water Treatment: This part is divided into three chapters (2, 3 and 4), two related to the membrane distillation (MD) (chapter 2 and 3) and one related to the oil spill (chapter 4). Three different nanofillers have been used: Periodic mesoporous organosilica (PMO), graphene and carbon nanotube (CNT). Those nanofillers were homogeneously incorporated into polyetherimide (PEI) electrospun nanofiber membranes. The doped nanoparticle not only improved the mechanical properties and thermal stability of the pristine fiber but also enhanced the MD and oil spill performance due to the functionality of those nanofillers. In these chapters, the antibacterial effect of graphene and the use the highly porous organosilica nanoparticles, which was further utilized to load the eugenol antimicrobial agent, showed an enhancement of the anti-biofouling properties of the membranes as well.

Protective coating: This part includes two chapters 5 and 6 describing the design and the fabrication of a smart antibacterial and anti-corrosion coating, respectively.

In the first project, we fabricated colloidal lysozyme-templated gold nanoclusters gating antimicrobial-loaded silica nanoparticles (MSN-AuNCs@lys) as nano-fillers in poly(ethylene oxide)/poly(butylene terephthalate) (PEO–PBT) amphiphilic polymer matrix. MSN-AuNCs@lys dispersed homogeneously within the polymer matrix with no phase separation and zero NPs leaching. The system was coated on a common radiographic dental imaging device (PSP plate) that is prone to oral bacteria contamination. This mixed-matrix coating can successfully sense and inhibit bacterial contamination via a controlled release mechanism that is only triggered by bacteria. Interestingly, the quality of the images obtained with these coated surfaces is the same as uncoated surfaces and thus the safe application of such smart coatings can be expanded to include other medical devices without compromising their utility.

In the second project, the coaxial electrospinning approach has been applied to fabricate smart core-shell nanofiber for controlled release of anti-corrosion material. Acetal-dextran was used as a pH controlled shell of the fibers and polyvinyl alcohol (PVA) as a hydrophilic core. Caffeine, as an anti-corrosion inhibitor was encapsulated in the fiber core to test its potential application as an anticorrosion coating. The almost negligible release was noticed at neutral pH. In acidic pH due to corrosion, the fibers quickly respond by releasing caffeine cargo.

Gas separation: We describe the synthesis and application of novel ethylene-diamine-based PMO. The gas adsorption properties of these materials were investigated for CO2, CH4 and N2 gases at different temperatures. PMO nanoparticles exhibited excellent CO2 uptake and selectivity. The novel PMO nanoparticles were homogeneously incorporated into polydimethylsiloxane to fabricate a MMMs thin layer on a porous polyacrylonitrile support.  Our results prove that our PMOs can be used as nanofillers to enhance the CO2 selectivity of the PDMS polymer.

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• CONTACTLinda J. Sapolu

​​​ABSTRACT: Zinc oxide (ZnO) semiconductors have been utilized by many researchers, due to its unique properties beneficial for functional devices. In particular, gadolinium (Gd)–doped ZnO exhibits high ferromagnetic and electrical properties, which is attributed to defect/impurity bands mediated by Gd dopants. In this dissertation, I study the effects of Gd concentration, oxygen pressure using pulsed laser deposition (PLD), and thermal annealing on the optical and structural properties of undoped and Gd-doped ZnO films and nanostructures. Moreover, as the growth of practical ZnO nanostructures-based devices without catalyst, while presently challenging, is highly important for many applications. Thus, for the first time, a novel method is developed for growing well aligned ZnO nanorods (NRs) by optimizing PLD conditions using Gd-doped ZnO target without any catalyst in a single st​ep. This study shows that, both the lattice orientation of the substrate and the Gd characteristics are significant in enhancing the NR growth. Our findings reveal that precise control of the NR density can be achieved by changing the oxygen partial pressure. Furthermore, due to the Gd incorporation, these NRs possess favorable electrical properties with a significant mobility of 177 cm2 (V.s)-1 compared to that reported in literature. Nonetheless significant challenges need to be overcome to achieve reproducible and stable p-type ZnO for commercial applications. Hence, several attempts based on n-type ZnO grown on foreign p-type substrates were made to achieve high-performance devices and overcome the issues arising when p-type doped ZnO is employed. Moreover, Growth of ZnO nanostructures on a foreign p-type substrates does not require a lattice-matched p-type substrate. Thus, for the first time, PLD conditions are improved to grow high quality ZnO nanotubes (NTs) with high optical, structural and electrical properties on a p-type Si (100) substrate without catalyst for high-performance devices. A fabrication of high performance UV photodetector (PD) based on ZnO NT/p-Si is demonstrated with superior responsivity (up to ~ 101.2 AW-1) compared to that reported in literature. This new and simple method demonstrates that the PLD system has a significant potential for improving the performance of materials used in a wide range of electronic and optoelectronic applications.​

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• CONTACTMazen E. Mero

​Abstract:

Well-defined silica supported bimetallic catalysts Pt100-x Pdx (where x is the molar ratio of Pd) are prepared by Surface Organometallic Chemistry (SOMC) via controlled decomposition of Pd2(allyl)2Cl2 on Pt/SiO2. For comparison purposes, Pt100-x Pdx bimetallic catalysts is also prepared by ion-exchange (IE). According to the results of STEM, XAS and H2 chemisorption, all bimetallic nanoparticles, prepared using neither SOMC nor IE, produce discrete formation of monometallic species (either Pt or Pd). Most catalysts exhibit a narrow particle size distribution with an average diameter ranging from 1 to 3 nm for samples prepared by IE and from 2 to 5 nm for the ones synthesized by SOMC. For all catalysts investigated in the present work, iso-butane reaction with hydrogen under differential conditions (conversions below 5%) leads to the formation of methane and propane (hydrogenolysis), n-butane (isomerization), and traces of iso-butylene (dehydrogenation).

The total rate of reaction decreases with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate (expressed as moles converted per total surface metal per second) of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the results suggest a selective coverage of Pt (100) surface by a Pd layer, followed by a buildup of Pd overcoat onto a Pd layer assuming that each metal keeps its intrinsic catalytic properties. There is no mutual electronic charge transfer between the two metals (DFT).  For the PtPd catalysts prepared by IE, the catalytic behavior cannot simply be explained by a surface coverage of highly active Pt metal by less active Pd (not observed), suggesting there is a formation of a surface alloy between Pt and Pd collaborated by EXAFS and DFT. The catalytic results are explained by a simple structure-activity relationship based on the previously proposed mechanism of C-H bond and C-C Bond activation and cleavage for iso-butane hydrogenolysis, isomerization, cracking and dehydrogenation.

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• CONTACTLinda J. Sapolu

​​​ABSTRACT: The solar cells market has an annual growth of more than 30 percent over the past 15 years. In the recent years, the cost of the solar modules diminished to meet both of the rapid global demand and the technological improvements. In particular for the crystalline silicon solar cells, the workhorse of this technology. The objective of this doctoral thesis is enhancing the efficiency of c-Si solar cells while exploring the cost reduction via innovative techniques. Contact metallization and ultra-flexible wafer based c-Si solar cells are the main areas under investigation.

First, Silicon-based solar cells typically utilize screen printed Silver (Ag) metal contacts which affect the optimal electrical performance. To date, metal silicide-based ohmic contacts are occasionally used for the front contact grid lines. In this work, investigation of the microstructure and the electrical characteristics of nickel monosilicide (NiSi) ohmic contacts on the rear side of c-Si solar cells has been carried out. Significant enhancement in the fill factor leading to increasing the total power conversion efficiency is observed.

Second, advanced classes of modern application require a new generation of versatile solar cells showcasing extreme mechanical resilience. However, silicon is a brittle material with a fracture strains <1%. Highly flexible Si-based solar cells are available in the form thin films which seem to be disadvantageous over thick Si solar cells due to the reduction of the optical absorption with less active Si material. Here, a complementary metal oxide semiconductor (CMOS) technology based integration strategy is designed using corrugation architecture to enable an ultra-flexible solar cell module from bulk mono-crystalline silicon solar wafer with 17% efficiency. This periodic corrugated array benefits from an interchangeable solar cell segmentation scheme which preserves the active silicon thickness and achieves flexibility via interdigitated back contacts. These cells can reversibly withstand high mechanical stress as the screen-printed metals have fracture strain >15%. Furthermore, the integration of the cells is demonstrated on curved surfaces for a fully functional system.

Finally, the developed flexing approach is used to fabricate three-dimensional domeshaped cells to reduce the optical coupling losses without the use of the expensive solar tracking/tilting systems.

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• CONTACTMazen E. Mero