Thesis (MScEng (Process Engineering))--University of Stellenbosch, 1997. / This study focuses on the preparation and characterization of palladium-silver-nickel composite membranes. Electroless plating was used to deposit thin metal films on aluminazirconia membrane supports. Palladium conversion, in the electroless palladium plating process, was optimized with the aim of minimizing expensive palladium losses. The effect of deposition order on alloy composition and heat treatment on structural characteristics of the composite membrane was investigated. The inorganic support membranes were thoroughly cleaned and pretreated prior to plating to catalyze the surface. Factorial designs were used to obtain the maximum palladium conversion. Tetra amine palladium nitrate gave better solution stability and resulted in higher conversions than tetra amine palladium chloride. Buffer pH values of 9 to 11 caused little variation in palladium conversion. Moving outside this range resulted in a sharp decline in palladium conversion. At a pH of 9 to 11 the stabilizer is in the correct ionic form (EDTA3 and EDTA4,) to best stabilize the palladium ions, and hydrazine acts as a proper reducing agent. Significant interactions existed between the EDTA concentration (stabilizer) and hydrazine concentration (reducing agent) and between EDTA and temperature. The EDTA concentration was the most sensitive variable. A 27.5 g 10% tetra amine palladium nitrate solution per liter plating solution was used. Conversions exceeding 80% were obtained after three hours plating with 20 ml plating solution at the following conditions: temperatures from 71 to 77 DC, 40-60% molar excess hydrazine, EDTA:Pd-salt molar ratios between 30:1 and 40: 1 and buffer pH = 11. Silver plating rates for two hours plating of up to 2 mg/cm2 were obtained using a dilute silver nitrate solution with hydrazine as reducing agent. Electroless nickel plating was performed in a low temperature bath (40 DC) with nickel sulphate as source of metal ions and sodium hypophosphite as reducing agent. Metal films were fully characterized before and after heat treatment for 5 hours in a hydrogen atmosphere at 650 dc. Scanning electron microscopy (SEM) was used to analyze the surface structure. X-ray diffraction (XRD) patterns were taken to examine alloying and detect changes in the crystal structure .after heating. Energy dispersive X-ray maps (EDS) were used to visualize the diffusion process and particle induced X-ray emission (PIXE) was used to construct concentration profiles across the thickness of the metal films. Palladium deposits were dense, but columnlike, with a purity of 99.75%. Silver deposits were non-homogeneous, in other words it did not cover the entire substrate. The purity of the silver films was 99.5%. The nickel films were about 97% pure, very dense and defect free. When silver was deposited on palladium, the alloy penetrated more than 3 microns into the support and the palladium and silver concentrations varied across the thickness of the film after heating. By depositing palladium on silver, there was very little penetration into the support membrane pores (about 1 micron) and the palladium to silver ratio remained constant across the thickness of the film after heating. Silver-palladium-nickel alloy films call be prepared by first depositing silver, then palladium and finally nickel. During heat treatment, a counter diffusion process took place and the smaller nickel atoms penetrated into pores and defects that might be present in the palladium-silver solid solution. By adding more than 3% nickel, dense defect free films can be prepared, which is much thinner than conventional palladium-silver films. This method makes it possible to reduce the film thickness of dense, non-porous films to less than 5 microns, reducing fabrication cost and increasing the hydrogen flux through the film. Dense, non-porous palladium-silver films are usually in the range of 10-15 microns.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2009. / AFRIKAANSE OPSOMMING: Die effek van teenpolsing op die aanvuiling van 'n 2.5-duim spiraal kruisvloei ultrafiltrasie element is eksperimenteel ondersoek. Teenpolseksperimente met 'n organiese (dekstraan) oplossing en 'n anorganiese (kaolien) suspensie is uitgevoer deur gebruik te maak van 'n polipropileenmembraan (100 000 molekulêre massa snypunt). Die konsentrasie van die dekstraanoplossing was tussen 250 en 750 mg/L en die konsentrasie van die kaolien oplossing was tussen 100 en 300 mg/L. Teenpolsing behels die aanwending van drukpolse van tussen 100 en 150 kPa aan die kant van die produk (permeaat). Die polstussenposes het gewissel tussen 1 en 15 s en die duur van die polse tussen 0.1 en 0.5 s. Die vloeitempo was tussen 500 en 1500 L/h, en die toegepaste druk was 100 kPa. Eksperimentele resultate het getoon dat terugpols effektief was vir die vermindering van membraanaanvuiling, en die verbetering van vloei deur die membraan. Met aanhoudende terugpolsing het die netto vloei toegeneem met toenemende terugpolsdruk. Daar was 'n effense toename met 'n toename in kruisvloeitempo en 'n sterk afname met toenemende voeroplossingkonsentrasie. Die beste terugpols parameters vir die twee verskillende aanvuilingsmateriale was soos volg: 0.2 s polsduur, 3 s polstussenpose en 150 kPa terugopolsdruk vir die dekstraanoplossing; en 0.2 s polsduur, 5 s polstussenpose en 150 kPa terugopolsdruk vir die kaoliensuspensie. Die beste resulate behaal vir vloei onder hierdie kondisies was 3-maal en 1.5-maal hoër as die vloei behaal sonder polsing, vir dekstraan en kaolien, onderskeidelik. Nadat die membraan aan aanvuiling, gevolg deur terugpolsing, blootgestel is, is dit skoongemaak deur skoon water met terugpolsing te gebruik. Die vloei van die skoon membrane wat voorheen met dekstraan en kaolien aangevuil is was 62% en 71% van die oorspronklike vloei, onderskeidelik. Die Taguchi metode met 'n L9 ortagonale reeks is gebruik om die belangrike terugpolsfaktore te bepaal wat 'n maksimum permeaatvloei tot gevolg gehad het. Die polsdruk het die grootste effek op die membraanvloei gehad. Polstussenpose en polsduur het 'n onbeduidende effek en die dwarsvloeitempo het 'n swak effek op membaanvloei gehad. Daar moet egter opgelet word dat hierdie waarnemings slegs van toepassing is binne die eksperimentele grense soos bepaal in die inleidende ondersoek van hierdie studie.

Thesis (MEng.)--University of Stellenbosch, 2000. / ENGLISH ABSTRACT: The aim of the thesis was to investigate the use of flow destabilization methods, combined with permeate backflushing (BIF) or on their own, on flux recovery and maintenance in capillary UF membrane systems under cross-flow (XF) and dead-end (DE) operating conditions. Various hydraulic and mechanical methods have been used to remove the accumulated cake layer and improve steady state process flux. Permeate backflushing (B/F) is the most widely used but the drawbacks are loss of product and extensive down-time. In a pilot plant study for ultrafiltration of surface waters containing high NOM, turbidity and cation loads, the use of flow destabilization, or feed flow reversal (FFR) combined with cross-flow B/F was able to improve the normalised flux by 10.7 ± 3.4 %, compared with 3.2 ± 1.6 % improvement for BIF without FFR. When a second B/F included FFR, the flux improvement was 7.0 ± 2.0 % compared with 4.3 ± 2.5 % for a B/F without FFR. The hypothesis was proposed that the flow destabilization caused slight lifting of the oriented cake layer, while the cross-flow B/F was able to sweep the lifted cake out of the lumen. If the flow destabilization may be effected by a simple but effective and low-cost method, and if this flow destabilization may be combined with reverse flow for short durations, the "lift-and-sweep" approach will be the ideal method of maintaining process flux and increasing membrane life. Such a flow destabilization method, now named "reversepressure pulsing" (RIP), was developed. The method involves circulation of feed water in a recycle loop for 2 s to gain momentum, followed by closure of a fast-action valve upstream of the modules. The momentum of the water in the concentrate loop carries it into an air-filled feed accumulator, while concentrate and reverse-flow permeate (which also lifts the fouling layer) are discharged to the atmosphere using the recycle pump for 15 s. When the valve opens again, the air in the accumulator forces the water under pressure through the membrane lumens, causing a pressure pulse and flow perturbations that lift, shift and break up the fouling layer. During 3 such "lift-and-sweep" events, the cake is lifted and the debris is swept out of the lumen. Experimental results for uninterrupted dead-end filtration at a UF pilot plant using RIP only on a severely fouled membrane, indicated that the RIP increased the flux by 18.4 % and decreased the dP by 8.2 % over a 7.2 h period. The method is effective in removing the cake layer intermittently and no long-term flux decline occurred for a period of 555 h since the previous chemical cleaning. / AFRIKAANSE OPSOMMING: Die doel van die tesis was om die gebruik van vloei-destabiliserings metodes, alleen of gekombineer met permeaat-terugwas, op vloed-herwinning en instandhouding in kapillêre UF membraan-stelsels tydens kruisvloei en doodloop bedryf, te ondersoek. Verskeie meganiese en hidrouliese metodes word gebruik in membraan stelsels om die koeklaag op die membraan se oppervlak te verwyder en die gestadigde-toestand vloed te verbeter. Vanhierdie metodes word permeaat-terugwas die meeste gebruik, maar het sy nadele insluitend verlies van produk en produksietyd. In 'n loodsstudie vir die ultrafiltrasie van oppervlakwaters wat hoë beladings NOM, turbiditeit en katione bevat, is die waarneming gemaak dat kruisvloei terugwas met vloeidestabilisering (voerrigting-verandering) die genormaliseerde vloed met 10.7 ± 3.4 % kon verbeter, vergeleke met 'n 3.2 ± l.6 % verbetering sonder voerrigting-verandering. Vir 'n tweede terugwas was die verbetering 7.0 ± 2.0 % vergeleke met 4.3 ± 2.5 % sonder voerrigtingverandering. Die hipotese was voorgestel dat die vloei-destabilisering die geoiënteerde koeklaag van die oppervlak gelig het, en die kruisvloei terugwas die geligde koeklaag uit die lumen kon vee. Indien hierdie vloei-destabilisering bewerk kan word deur 'n eenvoudige maar effektiewe manier, en indien dit gekombineer kan word met terugvloei van produk vir kort tydperke, sal hierdie "lig-en-vee" benadering die ideale metode wees om die membrane se vloed te verbeter en leeftyd te verleng. So 'n vloei-destabiliseringsmetode, nou genoem "terugdruk-pulsering", is ontwikkel. Die metode behels die sirkuiering van voer-water vir 2 s in 'n hersirkulasielus om momentum op te bou, gevolg deur die toemaak van 'n snel-aksie klep stroom-op van die modules. Die water in die konsentraat-lus se momentum dra dit vorentoe tot in In lug-gevulde voer-akkumulator, terwyl konsentraat en terug-vloei permeaat (wat ook tot 'n mate die koeklaag lig) ook na die atmosfeer gewend word vir 15 s deur die hersirkulasiepomp. As die klep weer oopgaan, ontspan die lug in die akkumulator, en forseer die water daarin onder druk deur die membraan-lumens. Die druk-puls en vloei-perturbasies lig, skuif en breek die koeklaag op. Tydens 3 agtereenvolgende "lig-en-vee" aksies word die koeklaag effektief opgebreek en uit die lumen gevee. Eksperimentele uitslae vir ononderbroke doodloop bedryf op uitermate aangevuilde membrane van 'n ultrafiltrasie loodsaanleg toegerus met terugdruk-pulsering, het getoon dat die vloed met 18.4 % verbeter kon word en die dP met 8.2 % verminder kon word in slegs 7.2 h. Die metode breek die koeklaag effektief op, en geen langtermyn vloed-afname is waargeneem vir meer as 555 h sedert die vorige chemiese was-prosedure nie.

Thesis (MEng)--Stellenbosch University, 2000. / ENGLISH ABSTRACT: Fouling is readily acknowledged as one of the most critical problems limiting the wider application of membranes in liquid separation processes. A better understanding of fouling layer formation and its monitoring is needed in order to improve on existing cleaning techniques. Plant operation can be optimised if fouling can be monitored by noninvasion means either on the plant itself or on an attached monitoring device. The overall scope of this research was to develop a non-destructive, real-time, in situ visualisation technique or device for concentration polarisation and fouling layer monitoring. Ultrasonic-time-domain-reflectometry (UTDR) was employed as a visualisation technique to provide real-time characterisation of the fouling layer. A 24 cm-long rectangular flat sheet aluminium cell was designed and used as separation device for a desalination system. The experimental results obtained using this module confirmed that there are an excellent correspondence between the flux decline behaviour and the UTDR response from the membrane. The ultrasonic technique could effectively detect fouling layer initiation and growth on the membrane in real-time. In addition to the measurement of fouling, the ultrasonic technique was also successfully employed for monitoring membrane cleaning. Since no real-time permeation data is available during cleaning operations in industrial applications, a UTDR monitoring device may prove to be a very valuable technique in optimising cleaning strategies. The technique was further tested on an 8-inch diameter spiral wrap industrial module and good results were obtained. Stagnant zones, as well as flux flow behaviour inside the module could be determined. However, more research IS needed to fully understand the complex phenomena inside a spiral wrap module. Overall, the UTDR technique and its use in monitoring devices have a major impact in the membrane industry due to its extremely powerful capabilities. / AFRIKAANSE OPSOMMING: Membraan-bevuiling of -verstopping is die grootste struikelblok wat die algemene aanwending van membrane vir verskillende watersuiweringsprosesse negatief beinvloed. 'n Beter begrip van membraan-bevuiling, asook beter metingsmetodes daarvan is nodig om op bestaande skoonmaaktegnieke te verbeter. Die hoofdoel van hierdie studie was die ontwikkeling van 'n nie-destruktiewe-in-lyn visuele tegniek vir die meting van konsentrasie polarisasie en membraan-bevuiling. Deur gebruik te maak van ultrasoniese klank golwe, is 'n tegniek ontwikkel wat 'n direkte visuele aanduiding kon gee van die toestand van membraan-bevuiling binnein die module. 'n Reghoekige aluminium-module, 24 cm lank, is ontwerp en gebou waarbinne die membraan geplaas is vir die skeidingsproses. Resultate dui daarop dat daar 'n uitstekende verband bestaan tussen die afname in permeaatvloei en die ultrasoniese eggo vanaf die membraan. Die ultrasoniese tegniek kon die vorming van en toename in membraan-bevuiling doeltreffend karakteriseer. In teenstelling hiermee, is die tegniek ook suksesvol aangewend om die skoonmaak-proses van membrane te ondersoek. Met min of geen data beskikbaar vir die skoonmaak-proses van membrane in die industriële sektor, het die tegniek enorme potensiaal in die optimisering van bestaande skoonmaak-tegnieke. Die tegniek is verder aangewend op 'n industriële 8-duim deursnee spiraal-module en goeie resultate is verkry. Stagnante sones asook vloed-vloei-patrone binne-in die module kon suksesvol bepaal word. Baie navorsing is egter nog nodig om die ingewikkelde data wat gegenereer word tydens die ondersoek van 'n spiraal-module ten volle te verstaan. Die enorme potensiaal en moontlikhede van die ultrasoniese tegniek kan die begin wees van 'n revolusie in die membraan-industrie.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: Immersed membrane systems hold many operational and environmental advantages in biological treatment of wastewater. However, immersed membrane filtration have only found application in niche markets to date because of higher capital and operating costs associated with membrane fouling. But with capital costs on the decline as membranes become less expensive, immersed membrane systems are increasingly considered as an attractive alternative to conventional treatment processes. Operating costs remain high however, since energy intensive techniques such as air-sparging are required to limit membrane fouling. Improving the air-scouring efficiency of air-sparged immersed membranes can significantly reduce operating costs and unlock the immersed membrane system technology to wider application. The aim of this study was to identify factors that will improve air-scouring efficiency in order to produce guidelines that will help in the development of an immersed microfiltration membrane system with a resulting lower operating cost. Although, the research was done on a flat-sheet microfiltration membrane, the guidelines obtained can be used for the development of any immersed microfiltration membrane arrangement. An airlift reactor set-up was chosen for this study. Six system hydrodynamic factors were evaluated in a factorial design to determine their effects on the cross-flow velocity profile. They were the downcomer area to riser area ratio, top clearance distance, bottom clearance distance, aeration intensity, water depth and air sparger location. It was found that the air-scouring efficiency was increased by generating a cross-flow velocity profile with increased magnitude and uniformity, but absolute uniformity of the cross-flow velocity profile was found to be a prerequisite for optimisation of air-scouring efficiency. Downcomer area to riser area ratio was found to be 99.9% significant in determining the magnitude of the cross-flow velocity profile. Two models were developed to respectively predict the relative magnitude and uniformity of the cross-flow velocity profile. By using these two models, a methodology was developed to design an airlift reactor set-up that would produce system hydrodynamics with an improved air-scouring efficiency. / AFRIKAANSE OPSOMMING: Gesonke membraanstelsels beskik oor talle bedryfs- en omgewingsvoordele in biologiese behandeling van afvalwater. Maar weens die hoër kapitaal- en bedryfskostes wat gepaardgaan met membraanbevuiling, kon gesonke membraanstelsels tot op hede nog net toepassing in nismarkte vind. Maar soos kapitaalkoste daal met al hoe goedkoper membrane beskikbaar, word gesonke membraanstelsels al hoe aanlokliker as ‘n alternatief vir konvensionele behandelingsprosesse. Bedryfskostes bly egter hoog aangesien energie-intensiewe tegnieke soos lugborreling benodig word om membraanbevuiling te vertraag. Deur die effektiwiteit van die skropaksie wat lugborreling aan gesonke membrane bied te verbeter, kan ‘n beduidende besparing in bedryfskostes teweeggebring word om sodoende die uitgebreide toepassing van gesonke membraanstelsel tegnologie moontlik te maak. Hierdie studie het ten doel gehad die identifisering van faktore wat lugskropaksie effektiwiteit kan verbeter en om riglyne op te stel vir die ontwikkeling van ‘n gesonke mikrofiltrasie membraanstelsel met gevolglik laer bedryfskostes. Alhoewel hierdie navorsing ‘n plat-blad mikrofiltrasie membraan gebruik het, kan die riglyne steeds vir enige gesonke mikrofiltrasie membraanuitleg gebruik word. Daar is besluit op ‘n lugligter-reaktor opstelling vir hierdie studie. Ses stelselhidrodinamika faktore is geëvalueer in ‘n faktoriale ontwerp om hul effekte op die kruisvloei snelheidsprofiel te bepaal. Hulle was die afvloei-area tot opvloei-area verhouding, topruimte-afstand, bodemruimte-afstand, belugtingsintensiteit, waterdiepte en belugterligging. Daar is bevind dat die lugskropaksie effektiwiteit verhoog word wanneer ‘n kruisvloei snelheidsprofiel geskep word met ‘n verhoogde grootte en gelykvormigheid, maar die absolute gelykvormigheid van die kruisvloei snelheidsprofiel is gevind om ‘n voorvereiste te wees vir optimale effektiwiteit. Afvloei-area tot opvloei-area verhouding is gevind om 99.9% beduidend te wees in die bepaling van die snelheidsprofiel se grootte. Twee modelle is ontwikkel om afsonderlik die relatiewe grootte en gelykvormigheid van die kruisvloei snelheidsprofiel te voorspel. Die modelle is in ‘n metodologie vervat vir die ontwerp van ‘n lugligter opstelling met stelselhidrodinamika wat verbeterde lugskropaksie effektiwiteit sal skep.

Nanoplasmonics has provided a way to control light with extremely high precision, into nanoscale volumes. In many circumstances, the nanoplasmonic devices which can be realised are fabricated using processing techniques which rely on planar technologies. This thesis provides a general method to make nanoplasmonic devices on a flexible membrane structure, which can be free standing, extremely thin (less than the wavelength of visible light), but retains the ability to be manipulated without loss of optical function. These devices are very pliant and conformable. Flexibility allows the integration of nanoplasmonic devices into many new applications where curved surfaces or the ability to conform to another object is required, as well as providing a route for post-fabrication tunability. Two specific applications are considered: lab-on-fibre technology and surface enhanced Raman spectroscopy. Lab-on-fibre technologies have been advancing the ability to miniaturise experiments which would normally require a whole laboratory. Fabricating a membrane and then later applying it to the fibre decouples the choice of fibre from the design of the device. Surface enhanced Raman spectroscopy is a powerful diagnostic tool which can uniquely identify an optical fingerprint of different molecules. The technique has been held back from widespread clinical adoption because of the difficulty of reproducibility of the substrates used. A repeatable and reliable rigid substrate is demonstrated, which can identify the concentration of a three component mixture of physiologically relevant biomolecules. This same design is then shown in a flexible form factor, which is applied to a non-planar landscape where it can identify the locations where a molecule of interest has been deposited. This thesis details the development of the fabrication protocol, the construction of experimental apparatus for characterisation, and the use of numerical modelling to advance the flexible nanoplasmonic membrane platform.

MSc report presented to the University of the Witwatersrand In the fulfillment of the requirements for the degree of Master of Science in Engineering School of Chemical and Metallurgical Engineering Faculty of Engineering and the Built Environment University of the Witwatersrand Johannesburg April 2017 / Oil and gas operations produce high volumes of wastewater in the form of finely dispersed oil/ water (o/w) emulsions, which have detrimental effects on the environment. The current most feasible method used to mitigate the environmental impacts caused by the emulsion (produced water) from oil and gas operations is polymer membrane technology. However, polymer membranes are susceptible to fouling and concentration polarization, which leads to the necessity for frequent membrane replacement, thus loss of operating time and high operation cost. This motivates the need to investigate ways of modifying the polymer membrane in order to make it more resistant to fouling and concentration polarization. This study is concerned with circumventing the challenges experienced by polymer membrane during crude oil/ water mixture ultra-filtration by infusing the polymer membrane with nano particles. The aim of the research was to investigate the influence of addition of CNTs on the modified membranes in treatment of waste water from petroleum source. The Wet Impregnation method was used for the preparation of the bimetallic catalyst (Fe-Co catalyst supported on Zeolite), Chemical vapor deposition (CVD) method was used to prepare the carbon nanotubes (CNTs) and Phase inversion (PI) method was used for the preparation of the polymer nanocomposite membrane. The bimetallic catalyst was characterized using scanning electron microscope (SEM) and X-ray diffraction (XRD). The CNTs were characterized using Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and Transmission electron microscopy (TEM). The prepared polymer nanocomposite membranes were characterized using SEM, FTIR, goniometer (for contact angles) and TAXT plus texture analyzer (for tensile strength test). Functionalized carbon nanotubes were used as membrane fillers or modifiers to improve the filtration properties of the polymeric membrane, ultimately forming nanocomposite polymer membranes. This increased hydrophilicity, chemical, mechanical and physical properties of the polymer membrane, made them to perform better during filtration than pristine polymer membranes. The performance of the nanocomposite membranes were evaluated and it was determined that the nanocomposite polymer membrane with a loading 0.4 wt.% functionalized carbon nanotubes performed better than pristine membrane and other CNTs loaded nanocomposite polymer membranes. The pristine membrane (0 wt% CNTs) showed a higher contact angle (79o) which crosses ponds to the inability to soak up water. The 0.4 wt% nanocomposite polymer membrane showed the lowest contact angle of 72 o, this validated an improvement in the properties of the membrane, in particular hydrophilicity. The 0.4 wt% nanocomposite polymer membrane showed a superior mechanical strength, with a breaking force at 4 N relative to the other membranes of the same thickness. 0.4 wt% nanocomposite polymer membrane showed the highest permeate flux of 120 L/m2.h compared to the pristine membrane, which showed a permeate flux of 63 L/m2.h. The permeate flux of 0.4 wt% nano-composite polymer membrane increased with the operating pressure. / MT 2018

ABSTRACT Recent global interests in developing hydrogen economy generate substantial research and development for hydrogen production worldwide. Pd membranes are especially suited for high temperature hydrogen separation and membrane reactor applications. Alloying Pd with Ag not only suppresses hydrogen embrittlement, but also increases the permeability of the alloy membrane. The main objective of this work was to carry out fundamental studies to understand the properties of the porous stainless steel (PSS), morphologies of Pd and Ag deposits on PSS, and the structural changes of the membrane layer upon heat treatment. Both coating and diffusion and co-plating techniques were employed in the study. The Pd-Ag membranes that had sandwiched Ag layers suffered from very low selectivity due to the voids formed because of high diffusion rate of Ag. Alloy membranes with high selectivity can be prepared by applying intermediate annealing after each Ag deposition. On the other hand, the homogeneity of the alloy depended very much on the thickness of the deposited layers and annealing temperature and time. A stable co-plating bath was developed to co-plate Pd and Ag simultaneously. Pd-Ag membranes were prepared from co-plating bath using ultrasound to accelerate the plating rate.

The very large number of distinct structures that are known for metal-organic frameworks (MOFs) and zeolites presents both an opportunity and a challenge for identifying materials with useful properties for targeted separations. In this thesis we propose a three-stage computational methodology for addressing this issue and comprehensively screening all available nanoporous materials. We introduce efficient pore size calculations as a way of discarding large number of materials, which are unsuitable for a specific separation. Materials identified as having desired geometric characteristics can be further analyzed for their infinite dilution adsorption and diffusion properties by calculating the Henry's constants and activation energy barriers for diffusion. This enables us to calculate membrane selectivity in an unprecedented scale and use these values to generate a small set of materials for which the membrane selectivity can be calculated in detail and at finite loading using well-established computational tools. We display the results of using these methods for >500 MOFs and >160 silica zeolites for spherical adsorbates at first and for small linear molecules such as CO₂ later on. In addition we also demonstrate the size of the group of materials this procedure can be applied to, by performing these calculations, for simple adsorbate molecules, for an existing library of >250,000 hypothetical silica zeolites. Finally, efficient methods are introduced for assessing the role of framework flexibility on molecular diffusion in MOFs that do not require defining a classical forcefield for the MOF. These methods combine ab initio MD of the MOF with classical transition state theory and molecular dynamics simulations of the diffusing molecules. The effects of flexibility are shown to be large for CH₄, but not for CO₂ and other small spherical adsorbates, in ZIF-8.

Polyimide membranes containing nickel dithiolenes were investigated for the separation of propylene and propane. Permeation and sorption experiments were conducted as well thermal property analyses. Results indicate that the dithiolene has an antiplasticizing effect on the polymers studied. Upon addition of the dithiolene there is a subsequent reduction in the permeability coefficient and the permeability selectivity remains relatively unchanged. There is some evidence of increases in solubility selectivity, but a larger decrease in diffusivity selectivity results in a decrease in the permeability selectivity. Investigation of the thermal and mechanical properties of dithiolene-containing films indicates a reduction in fractional free volume as well as the glass transition temperature when compared to the pure polymer. There is also an increase in the modulus of the films upon addition of the dithiolene. The implications of these results and their correlation with antiplasticization are discussed.