D.Phil. (Chemistry) / Please refer to full text to view abstract

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A microcomputer-based process controller has been developed to produce porous membrane material. The production process is based on stretching the material in a constant temperature solvent bath. This thesis describes the hardware and software designed to direct and monitor the process. A VIC 20 is used as the process-controlling microcomputer. The system features two dedicated motor controllers and two channels for controlling temperature. The motor controllers determine the material feed rate and rate of stretch. The temperature controllers keep the system at a selectable constant temperature. An interactive assembly language program directs the entire process and monitors the controlled variables. A complete description of the interface and temperature control circuitry is given. The software used to direct the process is also discussed and presented. / Master of Science

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.

The main theme of this dissertation is to engineer nanoporous materials and nanostructured surfaces for applications in gas separation membranes. Tunable methods have been developed to create inorganic hydroxide nanostructures on zeolite surfaces, and used to control the inorganic/polymer interfacial morphology in zeolite/polymer composite membranes. The study of the structure-property relationships in this material system showed that appropriate tuning of the surface modification methods leads to quite promising structural and permeation properties of the membranes made with the modified zeolites. First, a facile solvothermal deposition process was developed to prepare roughened inorganic nanostructures on zeolite pure silica MFI crystal surfaces. The functionalized zeolite crystals resulted in high-quality ̒mixed matrix̕ membranes, wherein the zeolite crystals were well-adhered to the polymeric matrix. Substantially enhanced gas separation characteristics were observed in mixed matrix membranes containing solvothermally modified MFI crystals. Gas permeation measurements on membranes containing nonporous uncalcined MFI revealed that the performance enhancements were due to significantly enhanced MFI-polymer adhesion and distribution of the MFI crystals. Solvothermal deposition of inorganic nanostructures was successfully applied to aluminosilicate LTA surfaces. Solvothermal treatment of LTA was tuned to deposit smaller/finer Mg(OH)₂ nanostructures, resulting in a more highly roughened zeolite surface. Characterization of particles and mixed matrix membranes revealed that the solvothermally surface-treated LTA particles were promising for application in mixed matrix membranes. Zeolite LTA materials with highly roughened surfaces were also successfully prepared by a new method: the ion-exchange-induced growth of Mg(OH)₂ nanostructures using the zeolite as the source of the Mg²⁺ ions. The size/shape of the inorganic nanostructures was tuned by adjusting several parameters such as the pH of the reagent solution and the amount of magnesium in the substrates and systematic modification of reaction conditions allowed generation of a good candidate for application in mixed matrix membranes. Zeolite/polymer adhesion properties in mixed matrix membranes were improved after the surface treatment compared to the untreated bare LTA. Surface modified zeolite 5A/6FDA-DAM mixed matrix membranes showed significant enhancement in CO₂ permeability with slight increases in CO₂/CH₄ selectivity as compared to the pure polymer membrane. The CO₂/CH₄ selectivity of the membrane containing surface treated zeolite 5A was much higher than that of membrane with untreated zeolite 5A. In addition, the use of metal organic framework (MOF) materials has been explored in mixed matrix membrane applications. ZIF-90 crystals with submicron and 2-μm sizes were successfully synthesized by a nonsolvent induced crystallization technique. Structural investigation revealed that the ZIF-90 particles synthesized by this method had high crystallinity, microporosity and thermal stability. The ZIF-90 particles showed good adhesion with polymers in mixed matrix membranes without any compatibilization. A significant increase in CO₂ permeability was observed without sacrificing CO₂/CH₄ selectivity when Ultem® and Matrimd® were used as the polymer matrix. In contrast, mixed matrix membranes with the highly permeable polymer 6FDA-DAM showed substantial enhancement in both permeability and selectivity, as the transport properties of the two phases were more closely matched.

Submitted in fulfillment of the academic requirements for the degree of Master of Technology in Engineering: Chemical Engineering, Durban University of Technology. Durban. South Africa, 2015. / The textile industry consumes large volumes of water and in turn produces substantial quantities of polluted effluents. Approximately 30% of reactive dyes used during the textile processing remain unfixed on fibres and are responsible for the colouration in effluents. Various conventional methods are being used to treat textile effluent. However, the disadvantage of these methods is that total colour removal is not achieved and chemical by-products are introduced from the use of chemicals. The water quality produced therefore does not meet the requirement for textile reuse. Membrane based processes provide interesting possibilities of separating hydrolysed dye stuff and dyeing auxiliaries, thereby reducing colouration and COD content. They can be employed to treat reactive dye bath effluent to recover the salts and water for the purpose of reuse. This study aimed at integrating membrane processes into the reactive dye bath of a textile industry. The objectives were to determine the quality of permeate produced in terms of removal of organics, ascertain its reusability for dyeing, investigate the production rate in terms of permeate fluxes and finally to investigate the cleanability and flux recovery of the membranes. Three effluent samples were chosen for this study based on the dyeing recipe; Light shade, Medium shade and Dark shade. Ultrafiltration (UF) and Nanofiltration (NF) membrane processes were employed to treat the reactive dye bath effluents to recover the salts and water. Investigations were conducted firstly with UF as a pre-treatment to NF. Secondly, evaluations were carried out on the performance of two types of NF membranes (SR90 and NF90) in terms of permeate quality and fluxes for the investigated samples. The effect of cleaning on membrane performance was done. A reusability test was carried out on the permeate samples for dyeing. It was found that the use of UF as a pre-treatment yielded an increase in permeate of 5–25% of the NF fluxes and 90% in organics reduction for all treated samples, hence increasing the water recovery. High rejection of ˃90% by NF90 for COD, TOC and colour were obtained for all the treated samples. SR90 rejection was 80–90% for colour and ˃90% for COD and TOC. Salt recovery for NF90 was 60–90% and for SR90 was 40–50%. The reusability tests carried out showed that permeate recycled from NF90 can be used for any section in the textile industry including the most critical such as dyeing on light shades, while that from SR90 can be used for dyeing dark shades only. It was then concluded that membrane based processes can be integrated into the dye bath of the textile process for the purpose of reuse, thereby saving on the cost of chemicals (salts), reducing fresh water usage and reducing the extent of final effluent treatment.

Thesis (MScIng)--University of Stellenbosch, 2003. / ENGLISH ABSTRACT: Both porous and dense hydrogen selective membranes have recently been an active area of research. The combination of a reactor and a separator in the form of a membrane reactor is seen as a feasible application in which to perform dehydrogenation reactions. These reactions are equilibrium limited so that the removal of the product H2 by a selective membrane can improve the process effectiveness. Early Pd-based membranes were made of thin-walled tubes. In an attempt to increase permeation rates, thin supported Pd membranes have been developed. This study investigated the development and performance of a catalytic membrane reactor. The membrane reactor consists of a tubular alumina membrane support coated on the inside with a film of palladium or a palladium-copper alloy. This reactor was used for the dehydrogenation of isopropanol. The thin film was coated on the alumina support using an electroless plating process. This process occurs in a liquid medium where palladium and copper are deposited by electrolysis or electroless means. With these methods alloys can also be deposited on the support. By plating a thin film of palladium on the alumina membranes, will attract hydrogen molecules from the reaction product, which will increase the reaction rate. The electroless plating process consists of four major components: (i) (ii) (iii) (iv) reducing agent ( 0.04 M hydrazine), temperature bath, stabilised source of metal ions, and support membrane (α-alumina). Heat treatment was carried out on the coated membranes for 5 hours in a hydrogen atmosphere at 450°C. The plated membranes supplied by Atech were characterised using X-ray diffraction (XRD), scanning electron microscopy (SEM) and particle induced Xray emission (PIXE) before and after heat treatment. SEM photographs showed that the pore size of the membranes was doubtful and due to that the films were not of a dense nature. XRD results revealed that heat treatment led to the formation of smaller Pd and Cu crystallites. The concentration profiles constructed from the PIXE results indicated that Cu and Pd penetrated deep into the pores of the membrane during film preparation. Different catalysts (Al2O3, MgO and SiO2) were tested and the best one was chosen as catalyst in the membrane reactor. These catalytic runs were done in a plug flow (fixedbed) reactor. Different particle sizes of catalysts were also tested. A 9.2 Cu wt % on silica achieved the highest acetone yields for the temperatures tested. Two different types of alumina membrane reactors were used. These were supplied from SCT. One membrane only coated with palladium and the other coated with palladium and copper. Selectivity and permeability tests were also carried out on these membranes. Selectivities of up to 90.6 could be reached with the palladium coated membrane. The palladium-copper plated membrane only achieved selectivities of up to 13. With heat treatment this value decreased even more. The palladium coated membrane also achieved much better conversion to acetone in the dehydrogenation of 2-propanol. The reason for that is its better selectivity. The palladium-copper membrane reactor did not show much better results than the fixed-bed reactor. / AFRIKAANSE OPSOMMING: Hierdie studie ondersoek die ontwikkeling en werk verrigting van ‘n katalitiese membraan reaktor. Die membraan reaktor bestaan uit ‘n dun film palladium of palladium-koper allooi wat aan die binnekant van ‘n silindriese alumina membraan geplateer word. Die alumina dien as membraanbasis. Hierdie reaktor sal gebruik word vir die dehidrogenering van isopropanol. Die dun films van metaal word neergeslaan op die alumina basis deur ‘n elektrodelose platerings proses. Hierdie proses vind plaas in ‘n vloeistof medium waar palladium en koper neerslag plaasvind op ‘n elektrodelose wyse. Met hierdie metode kan metaal allooie geplateer word op basis membrane. Deur ‘n dun palladium lagie aan die binnekant van die alumina membrane te plateer sal veroorsaak dat waterstof molekules uit die reaksie volume sal weg beweeg. Dit sal ‘n verhoging in reaksie tempo meebring. Die platerings proses bestaan uit vier komponente: (i) reduseermiddel (0.04M Hidrasien), (ii) temperatuur water bad, (iii) stabiliseerde bron van metaal ione (Pd/Cu kompleks oplossing), en (iv) basis membraan (α-alumina). Hittebehandeling vir 5 uur is uitgevoer op hierdie geplateerde membrane by 450°C in ‘n waterstofatmosfeer. Die geplateerde membrane is daarna gekarakteriseer- voor en na hittebehandeling. Dit is gekarakteriseer deur X-straal diffraksie (XRD), skanderings elektron mikroskopie (SEM) en partikel geïnduseerde X-straal emissie (PIXE). XRD eksperimente het gewys dat die koper en die palladium ‘n allooi gevorm het. Veranderinge in kristaltekstuur het voorgekom na hittebehandeling. Tydens hittebehandeling was kleiner palladium en koper kristalle gevorm. SEM resultate het getoon dat die film nie baie dig was nie en die porie grootte van die membrane was ook nie korrek nie. PIXE resultate het die konsentrasieprofiele van beide koper en palladium oor die dikte van die membraan bepaal. Dit het gewys dat die Cu en Pd diep binne die membraan penetreer het tydens voorbereiding van die membraan. Verskillende soorte kataliste (Al2O3, MgO and SiO2) is ondersoek vir die dehidrogenering van isopropanol. Hierdie katalitiese ondersoek is gedoen in ‘n propvloei reaktor. Die beste katalis is gekies om in die membraan reaktor te gebruik. Verskillende partikel groottes is ook ondersoek. ‘n 9.2 Cu massa % koper op silika katalis het die beste omsetting na asetoon verkry vir die temperature waarvoor toetse gedoen is. Twee tipes membraan reaktors is gebruik. Een met net ‘n palladium film, terwyl ‘n palladium-koper allooi op die ander membraan reaktor gedeponeer was. Selektiwiteits- en deurlaatbaarheids toetse is op altwee membrane gedoen. Selektiwiteite van 90.6% kon verkry word met die palladium membraan. Die palladium-koper membraan kon slegs ‘n selektiwiteit van 13% bereik. Met hittebehandeling daarvan het die selektiwiteit selfs meer afgeneem. Die palladium membraan het ook hoër omsettings na asetoon getoon. Die rede hiervoor is die membraan se hoë selektiwiteit. Die palladium-koper membraan het nie veel beter resultate as die propvloei reaktor gelewer nie.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2006 / Fouling is a serious problem in membrane filtration, caused by pore plugging and adsorption of rejected macromolecules or other solutes in the membrane system. This requires periodic cleaning of membranes, which can add considerably to the overall cost of plant operation owing to lost productivity related to down-time, the cost of the chemicals used in cleaning, higher pressures and associated pumping costs to maintain membrane productivity, as well as reduced lifetime of the membranes. Ultrasound has recently been suggested as a promising approach to combating fouling in membranes. In principle it can be used on-line and may even eliminate the use of chemical cleaning or alternative measures completely, which could lead to major advances in the development and implementation of membrane technology. The objective of this investigation was therefore to assess the feasibility of using ultrasound to mitigate fouling in capillary ultrafiltration systems applied to water containing natural organic matter. Experimental work was conducted with a small laboratory-scale capillary membrane module. Ultrasound was introduced into the system by means of an ultrasonic probe operating at a fixed frequency of approximately 30 kHz, generating a maximum acoustic power density of 130 W/cm2 with a nominal power output of 50 W (IKA Labortechnik Staufen, United Kingdom, U50). Five systems were investigated, viz. aqueous solution of Congo Red dye, ultrapure water, coloured ground water from the George region, water from the Steenbras dam, as well as an aqueous solution of dextran. In most cases, ultrasonication resulted in an increase in the permeate flux. This increase could partly be attributed to an increase in the temperature and thus a decrease in the viscosity of the fluid and partly to enhanced mass and energy transfer due to sonication. Based on experiments done with the Congo Red dye and ultrapure water, no damage as a result of ultrasonication could be discerned in the membrane filter, except when there was direct contact between the ultrasonic probe and the membrane materials. Permeate quality analyses confirmed that sonication does not damage the membrane material – no degradation of permeate quality was found specifically during sonication intervals. In conclusion, ultrasound indeed appeared to be an effective approach to remove foulants associated with natural organic matter from membranes. However, an issue not addressed by this study, but apparent from the literature, is that the effect of ultrasound is strictly local and this has major implications for the scaleup of such ultrasound systems.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2009. / ENGLISH ABSTRACT: The aim of this study was to modify the surface of polyethersulfone (PES) ultrafiltration (UF) membranes to produce a more hydrophilic membrane by cross-linking poly(vinyl alcohol) (PVA) with sodium tetraborate (Na2B4O7.10H2O) (SB) on the surface. Key preparation factors were identified as PVA molecular weight, concentrations of the PVA and SB, cross-linking reaction time, number of coatings and the mode of coating. The effect of these factors on the membrane performance (salt retention and permeate flux) is discussed. These PVA-SB membranes typically had 11.46% retention and 413.30 L/m2.h flux for a feed containing 2000 ppm NaCl (0.45 MPa, 20°C, 45 – 50 L/h). The coating was shown to be uniform and stable by Fourier transform infrared spectroscopy (FT-IR) analyses. Coating significantly increased hydrophilicity and a maximum flux increase of 500 L/m2.h was reached. Measurements showed a reduced water contact angle and this confirmed the obvious enhancement of surface hydrophilicity. As a control, the role of the PVA base layer without cross-linking and the effects of its drying and heating on the water permeability of the PES-UF membrane were also studied, in order to ascertain maximum treatment conditions. Retention and permeate flux were determined (feed solution: 2000 ppm NaCl, applied pressure 0.45 MPa, 25°C, 45 – 50 L/h). It was found that the heating had the largest effect on the reduction of water permeability and therefore 50°C was the limit for treatment of this specific PES-UF membrane. Thin-film composite (TFC) membranes were prepared by an interfacial polymerization (IP) reaction between a polyfunctional amine and tri- or di-functional carboxylic chloride and then evaluated for their reverse osmosis (RO) performance. The salt retention of the PVA-SB membranes was improved when covering the cross-linked PVA gel sub-layer with a polyamide (PA) layer. However, the permeate flux decreased to below 30 L/m2.h (2000 ppm NaCl, 1 – 2 MPa, 20°C, 45 – 50 L/h). Two TFC membranes made from trimesoyl chloride (TMC) with m-phenylenediamine (MPD) or 2,6-diaminopyridine (DAP) exhibited retentions of 96.71% to 89.65% and fluxes of 10.93 to 27.91 L/m2.h, depending on the type of diamine used, when tested with a 2000 ppm NaCl solution (2 MPa, 25°C, 45 – 50 L/h). Two TFC membranes made from a n ew 2,5-furanoyl chloride (FC) with MPD or DAP exhibited retentions of 34.22% to 58.54% and fluxes of 49.21 to 25.80 L/m2.h, depending on the type of diamine used, when tested with a 2000 ppm NaCl solution (1 MPa, 25°C, 45 – 50 L/h). Novel PVA-SB-DAP-FC membranes made from the DAP with FC had the highest hydrophilicity value and exhibited >58.54% NaCl retention and 25.80 L/m2.h flux, and 75.08% MgSO4 retention and 34.75 L/m2.h flux, when tested with (2000 ppm feed, 1 MPa, 25°C, 45 – 50 L/h). The effect of the chemical structures of the different amines and carboxylic chlorides used on the RO performances of the TFC membranes prepared by two amines reacting with TMC or FC, on the surfaces of the modified asymmetric PES-UF membranes, was investigated. FT-IR and water contact angle determination were used to characterize the chemical structure, morphology and hydrophilicity of the PA layers of the composite membranes. The response surface methodology (RSM) was used to optimize the preparation conditions that had the largest effects on the RO performance of the PVA-SB-DAP-FC membranes. Good membrane performance could be realized particularly by manipulating three variables: DAP concentration, FC concentration and polymerization time (PT). The regression equation between the preparation variables and the performance of the composite membranes was established. Main effects, quadratic effects and interactions of these variables on the composite membrane performance were investigated. The membranes were characterized in terms of pure water permeation (PWP) rate, molecular weight cut off (MWCO), solute separation and flux. Mean pore size (μp) and standard deviation (σp) of the membranes were determined using solute transport data. The results revealed that PVA-SB membranes have almost the same pure water permeation that PES-UF membranes have. The MWCO of the PES-UF membranes decreased from 19,000 to 13,000 Daltons when the membrane was coated with PVA. / AFRIKAANSE OPSOMMING: Die doel van hierdie studie is die modifikasie van die oppervlakte van poliëtersulfoon ultrafiltrasie (PES-UF) membrane om meer hidrofiliese membrane te berei deur die kruisbinding van polivinielalkohol (PVA) met natriumtetraboraat ((Na2B4O7.10H2O) (NaB) op die membraanoppervlakte. Sleutelfaktore in die bereidingsproses is geïdentifiseer, naamlik: PVA molekulêre massa, PVA en NaB konsentrasies, kruisbindingsreaksietyd, die aantal bestrykingslae, en die manier waarop die bestrykingslae aangewend is. Die invloed van hierdie faktore op die membraanontsouting en vloed is ondersoek, en word hier bespreek. Hierdie PVA-NaB membrane het die volgende tipiese resultate getoon: 11.46% ontsouting en 413.30 L/m2.h vloed (Kondisies: 2000 dpm NaCl oplossing, 0.45 MPa toegepaste druk, 20 °C, vloeitempo 45–50 L/h). Die deklaag was uniform en stabiel, soos bepaal d.m.v. FTIR. Die aanwesigheid van die deklaag het die hidrofilisiteit verhoog en 'n maksimum vloed van 500 L/m2.h is behaal. Die waterkontakhoek is ook gemeet; 'n laer waarde het 'n verbetering in die hidrofilisiteit van die oppervlakte bevestig. Die rol van die PVA basislaag, sonder kruisbinding (kontrole), en die effek van uitdroging en verhitting hiervan, is ook bestudeer, om sodoende optimale behandelingskondisies te bepaal. Membraanontsouting en vloed is bepaal (Kondisies: 2000 dpm NaCl oplossing, 0.45 MPa toegepaste druk, 25 °C, vloeitempo 45–50 L/h). Verhitting het die grootste effek gehad op die afname in vloed. Daar is bevind dat 'n maksimum temperatuur van 50°C geskik is vir die behandeling van hierdie spesifieke PES-UF membraan. Dunfilmsaamgestelde (DFS) membrane is berei d.m.v. 'n tussenvlakpolimerisasiereaksie tussen 'n polifunksionele amien en 'n di- of tri-funksionele karbonielchloried, en daarna is die tru-osmose (TO) gedrag bepaal. Die ontsouting van die PVA-NaB membrane was hoër nadat die kruisgebinde PVA jel sub-laag met 'n poliamied (PA) laag bedek is. Die vloed het egter afgeneem, tot onder 30 L/m2.h (Kondisies: 2000 dpm NaCl oplossing, 1–2 MPa toegepaste druk, 20 °C, vloeitempo 45–50 L/h). Twee DFS membrane is berei met trimesoïelchloried (TMC), naamlik met m-fenieldiamien (MFD) of 2,6-diaminopiridien (DAP). Afhangend van die diamien wat gebruik is, is die volgende ontsoutingsresultate en vloede verkry: 96.71% tot 89.65% en 10.93 to 27.91 L/m2.h (Kondisies: 2 000 dpm NaCl oplossing, 2 MPa toegepaste druk, 25 °C, v loeitempo 45–50 L/h). Twee DFS membrane is ook berei met 'n nuwe verbinding, 2,5-furanoïelchloride (FC), en MFD of DAP. Afhangend van die diamien wat gebruik is is die volgende ontsoutingsresultate en vloede behaal: 34.22% tot 58.54% en 49.21 tot 25.80 L/m2.h (Kondisies: 2000 dpm NaCl oplossing, 1 MPa toegepaste druk, 25 °C, vloeitempo 45–50 L/h). Die PVA-NaB-DAP-FC membrane het die hoogste hidrofilisiteit getoon: 58.54% NaCl ontsouting en 25.80 L/m2.h vloed, en 75.08% MgSO4 ontsouting en 34.75 L/m2.h vloed (2000 ppm NaCl oplossing, 1 MPa toegepaste druk, 25 °C, vloeitempo 5–50 L/h). Die invloed van die chemiese struktuur van die verskillende diamiene en karboksielsuurchloriedes wat gebruik is in die bereiding van die DFC membrane op die oppervlakte van die gewysigde PES-UF membrane is in terme van TO ondersoek. FTIR en kontakhoekbepalings is gebruik om die chemiese struktuur, morfologie en hidrofilisiteit van die PA lae van die saamgestelde membrane te bepaal. Die eksperimentele oppervlakte ontwerp metode is gebruik om die bereidingskondisies vir die TO aanwending van die PVA-NaB-DAP-FC membrane te optimiseer. Goeie resultate is verkry deur die volgende veranderlikes te manipuleer: DAP en FC konsentrasies en die tydsduur van die polimerisasie. 'n Regressie-vergelyking tussen die bereidingsverandelikes en die funksionering van die saamgestelde membrane is bepaal. Die volgende is ook ondersoek vir hul effek op die funksionering van die saamgestelde membrane: hoof-effekte, vierkantseffekte, en interaksie tussen veranderlikes. Die eienskappe van die membrane wat bepaal is, is: deurlatingstempo van suiwer water (DSW), molekulêre massa-afsnypunt (MMAP), skeiding van opgeloste sout en vloed. Deurlating van opgeloste sout data is gebruik om gemiddelde poriegrootte (μp) en standaard afwyking (σp) van die membrane te bepaal. Resultate het getoon dat die PVA-NaB membrane amper dieselfde DSW gehad het as die PES-UF membrane. Die MMAP van die PES-UF membrane het afgeneem van 19,000 tot 13,000 Daltons na behandeling met PVA.

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.