Co-continuous structures generated from the phase separation of polymer blends present many opportunities for practical application. Due to the large interfacial area in such structures and the incompatibility between the components, such non-equilibrium structures tend to coarsen spontaneously into larger sizes and eventually form dispersed morphologies. Here, we utilize various strategies to kinetically stabilize the co-continuous structures in polymer blend systems at nano- to micro- size scales. In the partially miscible blend of polystyrene and poly(vinyl methyl ether), we took advantage of the spinodal decomposition (SD) process upon thermal quenching, and arrested the co-continuous micro-structures by the addition of nanoparticles. In this approach, the critical factor for structural stabilization is that the nanoparticles are preferentially segregated into one phase of a polymer mixture undergoing SD and form a percolated network (colloidal gel) beyond a critical loading of nanoparticles. Once formed, this network prevents further structural coarsening and thus arrests the co-continuous structure with a characteristic length scale of several microns. Our findings indicate that a key to arresting the co-continuous blend morphology at modest volume fractions of preferentially-wetted particles is to have attractive, rather than repulsive, interactions between particles. For the immiscible blend of polystyrene and poly(2-vinyl pyridine) (PS/P2VP), we presented a strategy to compatibilize the blend by using random copolymers of styrene and 2-vinylpyridine, controlling the degree of immiscibility between PS and P2VP. Based on such compatibilization, co-continuous structured membranes, having characteristic size down to tens of nanometers, were fabricated in a facile way, via the solvent-induced macrophase separation of polymer blend thin films. The feature size was controlled by controlling the film thickness and varying the molecular weight of the PS homopolymer and the random copolymers. As the processing method (solution casting) is simple and the structures are insensitive to the solvent or substrate choices, this approach shows great potential in the large scale fabrication of co-continuous nanoscopic templates on flexible substrates via roll-to-roll processes. Moreover, we proposed a quasi-binary blend system based on the PS/P2VP pair with the addition of a common solvent. An experimentally accessible phase mixing temperature was achieved, and the co-continuous morphologies were generated via thermally induced spinodal decomposition. The addition of solid particles significantly slowed down the coarsening kinetics and, in some cases, arrested the co-continuous structures at ~6 &mum for a short period of time. This study suggests an alternative means to achieve co-continuous structures in polymer solutions and also provides better understanding of the thermodynamics and kinetics of polymer blend phase separation. Our research demonstrates several means of kinetically trapping the non-equilibrium interconnected structures at sub-micron to tens-of-nanometer size scales that are germane to several functions including active layers of photovoltaic cells and polymer-based membranes.

Room temperature ionic liquids (ILs) are a unique class of solvents which are characterized by non-volatility, non-flammability, electrochemical stability and high ionic conductivity. These properties are highly desirable for ion-conducting electrolytes, and much work has focused on realizing their application in practical devices. In addition, hydrophilic and ionophilic polymers are generally miscible with ILs. The miscibility of ILs with ion-coordinating polymers makes ILs effective plasticizers for gel polymer electrolytes. Due to their unique properties, ILs present a means to realize the next generation of energy storage technology. In this dissertation, the fundamental interactions between poly(ethylene oxide) (PEO) and a variety of room temperature ILs were investigated. ILs with acidic protons were demonstrated to form a stronger interaction with PEO than ILs without such protons, suggesting that hydrogen bonding plays a dominant role for PEO miscibility with ILs. The hydrogen bonding interaction is selective for the PEO block of a PEO-b-PPO-b-PEO block copolymer (BCP). Therefore, blending these copolymers with the strongly interacting IL 1-butyl-3-methylimidazolium hexafluorophosphate ([BMI][PF6]) induced microphase separation into a well-ordered structure, whereas the neat copolymer is phase mixed. At sufficient quantities, the interaction between [BMI][PF6] and PEO suppresses PEO crystallinity entirely. In addition, the induced microphase separation may prove beneficial for ion conduction. Therefore, microphase separated copolymer/IL blends were investigated as potential gel polymer electrolytes. Cross-linkable block copolymers which microphase separate when blended with [BMI][PF6] were synthesized by modifying PPO-b-PEO-b-PPO copolymers with methacrylate end-groups. Cross-linking these copolymers while swollen with an IL generates ion gels with high ionic conductivities. The copolymer/IL blends vary from a well-ordered, strongly microphase separated state to a poorly ordered and weakly microphase separated state, depending upon the molecular weight. Stronger microphase separation results in higher mechanical strength upon cross-linking. However, this does not greatly affect ion conductivity. Nor is conductivity affected by forming gels from cross-linked PEO homopolymers when compared to BCPs. It was found that BCPs can be beneficial in producing gel electrolytes by allowing sequestration of phase selective cross-linkers away from the conducting block. Cross-linker molecules that are selective for the PPO blocks can be used to increase the mechanical strength of the gels with only a small effect on the conductivity. When cross-linkers that partition to the mixed PEO/IL block are used, the conductivity decreases by nearly a factor of 2. These studies show how ILs interact with PEO and how gel polymer electrolytes can be constructed with the IL [BMI][PF6]. While BCPs cannot directly be used to increase ion conductivity, they do allow for greater mechanical strength without sacrificing conductivity. This suggests many new approaches that may be used to simultaneously achieve high ionic conductivity and mechanical strength in solid and gel polymer electrolytes.

The main theme of this research is to understand the structure-property evolution during crystallization of a semicrystalline thermoplastic polymer. A combination of techniques including rheology, small angle light scattering, differential scanning calorimetry and optical microscopy are applied to follow the mechanical and optical properties along with crystallinity and the morphology. Isothermal crystallization experiments on isotactic poly-1-butene at early stages of spherulite growth provide quantitative information about nucleation density, volume fraction of spherulites and their crystallinity, and the mechanism of connecting into a sample spanning structure. Optical microscopy near the fluid-to-solid transition suggests that the transition, as determined by time-resolved mechanical spectroscopy, is not caused by packing/jamming of spherulites but by the formation of a percolating network structure. The effect of strain, Weissenberg number (We) and specific mechanical work (w) on rate of crystallization (nucleation followed by growth) and on growth of anisotropy was studied for shear-induced crystallization of isotactic poly-1-butene. The samples were sheared for a finite strain at the beginning of the experiment and then crystallized without further flow (Janeschitz-Kriegl protocol). Strain requirements to attain steady state/ leveling off of the rate of crystallization were found to be much larger than the strain needed to achieve steady state of flow. The large strain and We >1 criteria were also observed for morphological transition from spherulitic growth to oriented growth. An apparatus for small angle light scattering (SALS) and light transmission measurements under shear was built and tested at the University of Massachusetts Amherst. As a new development, the polarization direction can be rotated by a liquid crystal polarization rotator (LCPR) with a short response time of 20 ms. The experiments were controlled and analyzed with a LabVIEWTM based code (LabVIEWTM 7.1) in real time. The SALS apparatus was custom built for ExxonMobil Research in Clinton NJ.

Ethylene copolymers are widely used as packaging materials, adhesives and specialty polymers for well-regarded cost savings, durability, chemical resistance, and hot melt character. This work examines the use of diester monomers known as malonates to determine the plausibility of utilizing an uncommon monomer class for producing novel ethylene copolymers. Ethylene is copolymerized with diethyl methylene malonate—a simple malonate representative of more complex and highly modified malonate monomers and macromers—to produce ethylene-co-diethyl methylene malonate in a range of molecular weights. Ethylene-co-diethyl methylene malonate is analyzed to determine physical properties such as glass transition temperature, chain length and monomer incorporation. Successful copolymerization occurred under a range of temperatures and pressures in tetrahydrofuran, diethyl carbonate, and dimethyl carbonate. The produced polymers were found to have a molecular weight of 15-46 kg/mol, a glass transition temperature of 7°C, a melting temperature of 108°C, and a cold crystallization temperature of 64°C. The high concentration of a radical source inhibitor in the diethyl methylene malonate monomer solution negatively impacted molecular weight and ethylene incorporation.

The blending or mixing is extensively utilized in diverse processes of polymers to bring about advantageous properties, but the behavior becomes intriguing when associations are involved and multi-solvents are used. Explanations based on chemistry-specific arguments are less than satisfactory in abstracting essential features, and lack the general applicability across various systems. So, this work focuses on capturing the physical force governing the phenomenon of interest by using a generic model. Highly non-trivial behaviors of polymers are often observed in multi-solvent solutions. It is known that polymers swell and dissolve in good solvents, while they tend to collapse and aggregate in poor solvents. But for some specific systems, polymers that collapse in two different poor solvents become soluble in their mixtures, corresponding to cosolvency, and conversely, polymers that swell in two different good solvents become insoluble in their mixtures, pertaining to cononsolvency. The finding suggests that cononsolvency effect relies on the interplay between polymer-cosolvent preferential adsorptions and solvent-cosolvent attractions, which are typically investigated individually. The utilization of cononsolvency effect can either modify or induce micellization, leading to significant differences in morphology and thermodynamic properties compared to conventional micelles driven solely by hydrophobic interactions. The cosolvency project reveals that it arises from the cross competitions of Van der Waals-type interactions and the associative interaction (e.g., hydrogen bonding). The molecular association has long been a classical problem in physical chemistry, as it often gives rise to ”abnormal” phenomena, such as the elevation of boiling points due to hydrogen bonding. But the understanding of its effect on polymer system still remains rudimentary. So, this work tries to answer three fundamental questions by choosing three representative systems: 1. How will supramolecular complexations change the thermodynamics equilibrium morphology; 2. What is the impact of supramolecular bonds on the free energy landscape during the transition process; 3. How will association influence the single chain coil-globule conformational transition. It is found that the association not only results in versatile morphology, but also brings about distinct transition pathways. Besides, the conformational transition shows the dependence on the association pattern, which is actually decided by the statistical nature.

Thesis (MSc)--University of Stellenbosch, 2007. / ENGLISH ABSTRACT: Silicone rubber, particularly poly(dimethylsiloxane) (PDMS), has been increasingly used in the manufacture of outdoor high voltage insulators in the recent years. PDMS offers several advantages that make it suitable for outdoor use, such as low weight, a hydrophobic surface, stability, and excellent performance in heavily polluted environments. PDMS surfaces can, however, become progressively hydrophilic due to surface oxidation caused by corona discharge, UV radiation and acid rain. In this study, PDMS samples of controlled formulations as well as six commercial insulator materials four PDMS based and two ethylene propylene diene monomer (EPDM) based were exposed to various accelerated weathering conditions for various periods of time in order to track changes in the material over time. The ageing regimes developed and used to simulate the potential surface degradation that may occur during in-service usage included needle corona and French corona ageing, thermal ageing, UV-B irradiation (up to 8000 hours) and acid rain (up to 200 days). Both the chemical and physical changes in the materials were monitored using a wide range of analytical techniques, including: static contact angle measurements (SCA), optical microscopy (OM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), gas chromatography (GC), gas chromatography/mass spectroscopy (GC/MS), size-exclusion chromatography (SEC), Fourier-transform infrared photoacoustic spectroscopy (FTIR-PAS) and slow positron beam techniques (PAS). A low molecular weight (LMW) uncrosslinked PDMS model compound was used to further study the chemical effects of corona exposure on PDMS materials. PDMS showed far better performance than EPDM, in terms of resistance to the various ageing regimes and “hydrophobicity recovery”. / AFRIKAANSE OPSOMMING: Silikoonrubber, spesifiek polidimetielsiloksaan (PDMS), is gedurende die afgelope paar jaar toenemend gebruik in die vervaardiging van buitelughoogspanningisolators. PDMS het baie voordele vir gebruik in elektriese isolators soos ‘n laer massa, ʼn hidrofobiese oppervlak, stabiliteit en uitstekende werking in hoogsbesoedelde omgewings. Die hidrofobiese oppervlakte kan egter gelydelik hidrofilies word weens oppervlakoksidasie as gevolg van korona-ontlading, UV-bestraling en suurreën. In hierdie studie is PDMS monsters van verskillende samestellings sowel as ses kommersiële isolators (vier PDMS en twee etileenpropileenrubber (EPDM)) blootgestel aan verskillende versnelde weersomstandighede vir verskillende periodes om die veranderinge in die materiale te monitor. Die verskillende materiale is gerangskik volgens hulle werking oor ‘n periode van tyd. Dit het ook ‘n geleentheid gebied om die eienskappe van die verskillende samestellings te bestudeer. Die tegnieke wat ontwikkel is om die moontlike oppervlakdegradasie te simuleer, het naald-korona, “French” korona, UVB-bestraling (tot 8000 uur) en suurreën (tot 200 dae) ingesluit. Beide die chemiese en die fisiese veranderinge in die materiale is gemonitor met behulp van verskeie tegnieke soos statiese kontakhoekbepaling, optiese mikroskopie, skandeerelektronmikroskopie, energieverspreidingsspektroskopie, gaschromatografie, grootte-uitsluitingschromatografie, foto-akoestiese Fouriertransforminfrarooi (PASFTIR) en stadige-positronspektroskopie (PAS). ʼn Lae molekulêre massa PDMS modelverbinding is gebruik om die chemiese effek van korona te bestudeer. Die PDMS materiale het baie beter vertoon teenoor die EPDM materiale in terme van hulle herstel van hidrofobisiteit.

Thesis (PhD (Chemistry and Polymer Science)--University of Stellenbosch, 2009. / The work presented in this dissertation describes the development of self-healing coatings based on thiol-ene chemistry. The approach was to synthesize capsules with thiol and ene compounds separately encapsulated. These capsules were embedded in various coating formulations and upon the formation of a crack with a razor blade, these capsules ruptured. This caused the healing agent to flow into the crack via capillary action and the thiol-ene healing mechanism was initiated. This resulted in recovery of the damaged coating and provided continued protection to the substrate. Pentaerythritol tetrakis(3-mercaptopropionate) (TetraThiol), 1,6-hexanediol diacrylate (DiAcrylate) and 1,6-hexanediol di-(endo, exo-norborn-2-ene-5-carboxylate) (DiNorbornene) are the thiol and ene compounds used in this study. Kinetic experiments indicated that both TetraThiol-DiAcrylate and TetraThiol-DiNorbornene monomer pairs undergo rapid polymerization and form a network within minutes upon exposure to UV radiation and with the addition of a photoinitiator. The TetraThiol-DiNorbornene monomer pair also showed a high rate of polymerization without the addition of a photoinitiator and/or exposure to UV radiation. Styrene-maleic anhydride (SMA) copolymers and chain-extended block copolymers with styrene (P[(Sty-alt-MAh)-b-Sty]) were synthesized via Reversible Addition-Fragmentation chain Transfer (RAFT)- mediated polymerization. These copolymers were used as surfactant in miniemulsification for the synthesis of core-shell particles with TetraThiol as the core material. It appeared that P[(Sty-alt-MAh)-b-Sty] block copolymers, sterically stabilized via the addition of formaldehyde, provide optimal stability to the core-shell particles. DiNorbornene is encapsulated via miniemulsion homopolymerization of styrene and well-defined, stable nanocapsules were obtained. TetraThiol and DiAcrylate microcapsules were synthesized via in-situ polymerization of urea and formaldehyde. Microcapsules with a particle size of one to ten micrometers and with a very smooth surface were obtained. These microcapsules and nanocapsules were embedded in poly(methyl acrylate) (PMA), styrene-acrylate and pure acrylic films and the self-healing ability of these coatings, after introduction of a crack with a razor blade, was assessed.

Thesis (MSc)--Stellenbosch University, 2002. / ENGLISH ABSTRACT: Multimedia was the buzzword of the previous decade. Electronic learning is the buzzword of this decade. Both concepts changed, and are still changing the way educators present knowledge and information to students, both locally and worldwide. South Africa, also standing in the midst of these technological changes, has its own unique opportunities regarding the teaching environment. Different factors are currently changing the educational scene in South Africa. With Curriculum 2000 and the Outcome-Based Education concept (OBE) came the opportunity to choose and incorporate relevant science and technology programmes into school curriculums. The introduction of Technology as a subject in junior secondary school, opened the door to bring students in contact with, for example, the vast world of material science. Senior secondary students, on the contrary, have little or no exposure to teaching programmes on modern materials; materials that rule their lives! There is a need for high quality, easily accessible and informative material science programmes. This provided the initiative to create this programme. Depending on the standard of students, "Fun with Polymers" can be used as: • a lecturing tool for teachers and lecturers • an encyclopeadia which students can interactively navigate to learn more about polymer science • a source of information to anyone curious about the interesting world of plastic materials. The name "Fun with Polymers" indicates that learning science can be fun (after ali!). The programme contains easy to use navigation buttons, helpfiles, hypertext, sound, animations and pictures to teach synthetic polymer material science. Content consists of the history of the development of polymer materials, basic polymer chemistry principles, information on the building of macromolecules, facts on synthetic polymer materials, and some questions and answers to test the student's knowledge. Practical experiments, with plastic materials, complement the theoretical information and provide students with hands-on experience. / AFRIKAANSE OPSOMMING: Multimedia was die gonswoord van die vorige dekade. Elektroniese leer is die gonswoord van die nuwe dekade. Beide hierdie konsepte het, en is nog steeds besig, om die wyse hoe kennis en inligting, plaaslik en wêreldwyd, aan studente oorgedra word, te verander. Suid-Afrika, as deel van hierdie tegnologiese veranderinge, bied unieke en uitdagende geleenthede op die gebied van onderwys. Verskillende faktore beïnvloed, op die oomblik, die plaaslike onderwys scenario. Die koms van Kurrikulum 2000 en Uitkomsgebaseerde Onderwys het die deur vir toepaslike wetenskap- en tegnologie programme, as deel van skoolleerplanne, geopen. Die toevoeging van Tegnologie, as vakgebied, tot die junior sekondêre fase, skep die geleentheid om studente in aanraking te bring met, byvoorbeeld, die enorme wêreld van materiaalkunde. Senior sekondêre studente het egter min tot geen blootstelling aan materiaalkunde leerprogramme ten spyte van die feit dat hul lewens daagliks deur moderne materiale beïnvloed en beheer word! Daar bestaan 'n behoefte aan hoë kwaliteit, maklik bekombare inligting oor moderne materiale en vandaar die dryfveer om hierdie program te skep. Afhangende van die standaard van die studente, kan hierdie program gebruik word as: • 'n onderrigprogram vir onderwysers en lektore • 'n bron van inligting wat studente interaktief kan navigeer om meer van polimeeerchemie te wete te kom • 'n bron van inligting vir enigiemand wat nuuskierig is oor die interessante wêreld van plastieke. Die naam van hierdie program: "Fun with Polymers" dui daarop dat die wetenskapleerproses pret kan wees! Die program bestaan uit maklik navigeerbare instruksies, hulplêers, hiperteks, klank, animasies, en foto's om lig te werp op die onderwerp van plastiek. Die inhoud beslaan die geskiedenis van die ontwikkeling van plastiek= materiale, basiese polimeerchemie beginsels, inligting oor die vorming van makro= molekules, feite oor sintetiese polimeermateriale, en vrae en antwoorde om die gebruiker te toets oor sy/haar kennis. Maklik uitvoerbare en toepaslike praktiese eksperimente komplimenteer die teoretiese inhoud van die multimedia program.

Thesis (MSc)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: Polystyrene-block-poly(ethylene oxide) (PS-b-PEO) copolymers contain a hydrophilic PEO block and a hydrophobic PS block. PS and PEO have different affinities for most organic solvents and as a result, the PS-b-PEO copolymers are difficult to characterize in solution. In order to achieve a complete characterization of their molecular heterogeneity different techniques have been used. Recently FFF has become a cutting edge technology for polymer analysis because it possesses a number of advantages over conventional SEC and other liquid chromatographic techniques. The mild operating conditions allow the analysis of delicate and sensitive complex analytes such as complex polymer assemblies. The ability to analyze polymers with ultrahigh molar masses has also contributed to its significance in the characterization of polymers. In this study, the FFF behaviour of PS-b-PEO copolymers as well as PS and PEO homopolymers was investigated using Thermal FFF in different organic solvents and AF4. The aim of the study was the correlation of the thermodynamic quality of the solvents and the elution behaviour of the polymers. Unfortunately, PEO homopolymers have been found to interact with the membrane in AF4. Therefore, they were best characterized in organic solvents using Thermal FFF. In contrast to AF4 no specific interactions occurred due to the absence of a membrane. Results for Thermal FFF showed that in all utilized solvents, PS and PEO homopolymers were separated in the direction of increasing molar mass. For PS-b-PEO copolymers the retention in selective (good) solvents for PS was dependent on the molar mass of the PS block in the block copolymer. This was explained by the fact that in poor solvents PEO adopts a collapsed coil conformation while PS is present in extended random coil conformation. Results also showed that polymer retention was dependent on the temperature programme utilized. The fractionations by Thermal FFF indicated that some of the PS-b-PEO copolymer samples contained PS and PEO homopolymers as by-products. After semi-preparative fractionation these homopolymers were qualitatively identified using FTIR spectroscopy. / AFRIKAANSE OPSOMMING: Polistireen-blok-poli(etileenoksied) (PS-b-PEO) ko-polimere bevat 'n hidrofiliese politetileen oksied (PEO) blok en 'n hidrofobiese polistireen (PS) blok. PS en PEO het verskillende affiniteite vir die meeste organiese oplosmiddels, dit bemoeilik die karakterisering van PS-b-PEO ko-polimere in oplossing. Ten einde 'n volledige karakterisering van hul molekulêre heterogeniteit te bepaal moet ‘n verskeidenheid van tegnieke gebruik word. Onlangs het veldvloeifraksionering (FFF) baie grond gewen tov polimeer analise, aangesien dit verskeie voordele het bo tradisionele chromatografiese tegnieke soos grootte-uitsluitingschromatografie (SEC). Die ligte operasionele omstandighede laat die ontleding van ‘n verskeidenheid van polimere toe, enige iets van delikate polimeer komplekse tot ultra hoë molekulêre massa. In hierdie studie is die FFF gedrag van PS-b-PEO ko-polimere asook PS en PEO homopolimere ondersoek met behulp van Termiese FFF(ThFFF) in verskillende organiese oplosmiddels en onsimmetriese vloei-veldvloeifraksionering(AF4). Die doel van die studie was om die verband tussen die termodinamiese gehalte van die oplosmiddels en die eluering gedrag van die polimere te bepaal. Analise van PEO homopolimere was onsuksesvol aangesien daar interaksie was met die membraan. PEO is dus net geanaliseer in organise oplosmiddels met behulp van ThFFF, aangesien daar geen membraan is nie. Analise met ThFFF het gewys dat skeiding plaasvind volgens ‘n toename in molekulêre massa in organise oplosmiddels. Vir PS-b-PEO ko-polimere die retensie in selektiewe (goeie) oplosmiddels vir PS was afhanklik van die molekulêre massa van die PS blok in die ko-polimeer. ‘n Moontlike teorie is dat die PEO blok ‘n ineengestorte spoel struktuur vorm terwyl die PS blok ‘n uitgestrekte lukraake vorm aan neem. Resultate het ook getoon dat die polimeer retensie afhanklik was van die temperatuur program wat gebruik is. Die fraksionering deur ThFFF het aangedui dat sommige van die PS-b-PEO kopolimeer monsters bestaan het uit PS en PEO homopolimere as by-produkte. Hierdie is kwalitatief bewys deur analise van die fraksies na fraksionering van die ko-polimere met behulp van FTIR spektroskopie.

Thesis (DPhil)--Stellenbosch University, 2002. / ENGLISH ABSTRACT: Freshwater is the most fundamental of all life-supporting resources that determine our social, economic and political wellbeing. It is, however, only a small percentage of the world's water resources and is also unevenly distributed. Arid regions make-up about forty percent of the world's land area and have a large proportion of the world population, however, they only have a small fraction of the freshwater compared to other areas. Conventional freshwater sources in arid environments such as surface water in rivers, lakes and dams are often seasonal, available mainly during the rainy season. Equally, only a small part of the rain (0 - 5% of rainfall) infiltrates into groundwater reserves, and even this groundwater displays high rates of salinisation such that the end-water is too saline for human consumption. The poor quality of groundwater in arid regions is generally understood, however, it is always assumed that this is mainly a problem in areas where surface water does not occur. The study investigates seasonal groundwater salinisation in ephemeral (seasonal) river sources in some parts of Namibia and aims to derive a better understanding of the nature of this problem and how it affects people in these areas. It also looks at some possible solutions to the problem with the aim of informing water managers and scientists who are responsible for formulating solutions for water supply to areas in arid regions. These solutions are designed to take advantage of available opportunities in the study areas namely; the abundant supply of solar energy, alternative sources of freshwater such as fog and general atmospheric moisture, and adaptations for water collection in animals that inhabit these regions. The results show that groundwater in shallow ephemeral river sources of the Namib Desert and the Cuvelai delta in North central Namibia display high seasonal variation in Total Dissolved Solids (TDS) and chemical composition. The lowest TDS values are recorded during the rainy season, mainly after the first rains in the high rainfall areas and only after flood events in the lower rainfall regions. The groundwater salinity increases during the remainder of the year and in most cases becomes too saline for drinking purposes. The investigations of possible solutions indicate that small-scale photovoltaic reverse osmosis; solar distillation and fog collection could be used to address the seasonal shortage of potable water in these areas. The low-pressure (6 bar) reverse osmosis desalination experiments show that it is possible to operate the unit on a solar-driven pump to produce enough water to cover the typical daily water demand of a village in the Namib Desert. This unit would produce about 4600 litres per day (l/day) of 500- mg/l TDS product water, which exceeds the water production of similar world-leading small-scale RO units in Australia and The Canary Islands. The results also show that the cost of solar distillation units (solar stills) can be reduced sufficiently to make them a viable option for water supply to individual households in these rural areas. The study also found that fog is a feasible alternative source of freshwater in some of the study areas. The fog water is generally of 'A' quality drinking water according to the WHO-derived Namibian Drinking Water Quality Guidelines (NDWQG) and can be used directly or mixed with the saline groundwater to provide potable water. Mixing of the above-mentioned waters is particularly suitable in the Central Namib Desert because the period of high groundwater salinity coincides with that of peak fog deposition. The results also show that fog water can be collected with vanous polymeric greenhouse shade netting that can be easily obtained, and provides guidelines on the correct percentage shade coefficient and weave of possible fog collector mesh to intending users of fog collection technology in areas where the polypropylene mesh that is used in Standard Fog Collectors is not available. The investigations of surface properties of fog-harvesting beetles and experiments with various prototype collectors show that it is possible to increase water production in fog collectors existing today. The hydrophobic surface conditions as were found on the cuticles of fog-basking beetles (Onymaeris unguicularis and Onymacris bieolor) would enhance formation and runoff of large fog droplets on the collector surface. The prototype extractor-fan- and cooling system-based collectors show that it is possible to increase fog collection on polymeric meshes about three times and also that a comparable volume of atmospheric moisture can be collected even when there is no fog, up to a relative humidity of about 40%. In conclusion the study emphasizes that groundwater salinity in arid regions is at times a seasonal problem that should be considered in water supply strategies for these regions. Also that atmospheric moisture is a feasible alternative source of freshwater in some arid regions that often exceeds rainfall several times and should be considered as an important aspect of the strategies to address water problems in these areas. The study strongly recommends that scientists, engineers and water managers in these regions should always investigate the available opportunities such as climatic conditions (e.g. fog deposition) and adaptations for water collection/conservation that are found in the endemic plants and animals in order to develop sustainable solutions to this problem. They should also constantly update themselves on developments/opportunities that arise in the larger water industry that could be of benefit to water supply initiatives for remote areas in developing countries. Lastly, the study serves to better the understanding of the nature of groundwater salinity in arid environments that are dependent on seasonal surface flow for water supply as well as to contribute to the formulation of solutions to this problem in these areas, particularly in west coast hyper arid environments where conventional sources of freshwater are most inadequate. It also emphasises the role of materials science (polymers) and environmental engineering as well as that of UNESCO associated scientific institutions in the formulation of sustainable solutions to some of the current water problems in arid regions. Keywords: Arid lands, hydrochemistry, sources of freshwater, desalination, atmospheric moisture / AFRIKAANSE OPSOMMING: Vars water is die mees fundamentele van aIle lewensonderhoudende natuurlike hulpbronne wat ons sosiale, ekonomiese, en politieke welstand bepaal. Dit is egter slegs 'n klein gedeelte van die totale waterbronne van die wereld, en is boonop baie oneweredig versprei. Natuurlike waterarm gebiede (woestyne en halfwoestyne) beslaan ongeveer veertig persent van die landoppervlakte van die aarde en word bewoon deur 'n relatief groot persentasie van die wereldbevolking, maar beskik oor slegs 'n klein gedeelte van die varswater in vergelyking met ander gebiede. Konvensionele bronne van varswater in waterarm gebiede, soos oppervlaktewater in riviere, mere en darnme, is dikwels seisoenaal, en slegs beskikbaar gedurende die reenseisoen. Verder beland slegs 'n klein gedeelte van die reenval (0 - 5%) in die ondergrondse waterreserwes, en selfs hierdie grondwater vertoon 'n hoe mate van versouting, sodat die eindproduk te brak is vir menslike gebruik. Die swak gehalte van grondwater in waterarm gebiede word algemeen verstaan, maar daar is tot nog toe aanvaar dat dit oor die algemeen slegs 'n probleem is in gebiede waar oppervlaktewater me voorkom nie. Hierdie studie ondersoek seisoenale grondwaterverbrakking in seisoenale rivierbronne in sekere dele van Namibie en beoog om 'n beter begrip te formuleer van die aard van die probleem en hoe dit die inwoners van hierdie gebiede raak. Daar word ook ondersoek ingestel na moontlike oplossings vir die probleem, met die doel om 'n inligtingsbron vir waterbestuurders en wetenskaplikes wat verantwoordelik is vir die formuleer van oplossings vir watervoorsiening in waterarm gebiede daar te stel. Hierdie oplossings is ontwerp om voordeel te trek uit die beskikbare geleenthede in die ondersoekgebiede, naamlik; die oorvloedige beskikbaarheid van sonenergie, altematiewe bronne van varswater soos mis (Eng. "fog") en atmosferiese vog in die algemeen en aanpassings (Eng. "adaptations") vir die opvang van water wat voorkom by diere, veral insekte, in hierdie gebiede. Die resultate toon dat grondwater in die vlak seisoenale rivierbronne van die Namibwoestyn en die Cuvelai-delta in noordsentraal Namibie hoe seisoenale variasie in totale opgeloste stowwe (TVS) en chemiese samestelling vertoon. Die laagste TVS-waardes word waargeneem tydens die reenseisoen, hoofsaaklik na die eerste reen in die hoe-reenvalgebiede en eers na vloede in die lae-reenvalgebiede, Die soutgehalte van die grondwater neem toe gedurende die res van die jaar en in die meeste gevalle verbrak die water tot ondrinkbare vlakke. Die ondersoek na moontlike oplossings dui aan dat kleinskaalse fotovoltaiesgedrewe tru-osmose, sondistillasie en die opvang van mis (Eng."fog collection") aangewend kan word om die seisoenale tekort aan drinkwater in hierdie gebiede aan te spreek. Die laedruk (6 bar) tru-osmose-ontsoutingseksperimente wys dat dit moontlik is om die eenheid met behulp van 'n sonkraggedrewe pomp te bedryf en voldoende water te lewer vir die tipiese daaglikse drinkwaterbehoeftes van 'n nedersetting in die Namibwoestyn. Hierdie eenheid sal sowat 4600 liter per dag (l/d) water, met 'n TVSwaarde van 500 mg/I, lewer. Dit is aansienlik meer as die lewering van soortgelyke eenhede in Australie en die Kanariese Eilande. Die resultate wys ook dat die koste van sondistillasie-eenhede genoegsaam verminder kan word om dit 'n lewensvatbare opsie vir watervoorsiening aan enkelhuishoudings in die plattelandse gebiede te maak. Die studie het ook bevind dat die opvang van mis 'n toepaslike alternatiewe bron van varswater is in sekere van die studiegebiede. Die miswater is oor die algemeen 'A' -gehalte drinkwater vol gens die Namibiese gehalteriglyne Vir drinkwater (gebasseer op bepalings van die Wereldgesondheidsorganisasie) en dat dit net so, of vermeng met brak grondwater, gebruik kan word as drinkwater. Vermenging is besonder geskik in die sentrale Namibwoestyn, aangesien die periode van hoe grondwaterverbrakking saamval met die piek van benutbare misneerslag. Die resultate toon ook aan dat miswater opgevang kan word met verskeie tipes polimeriese skadunet, wat maklik verkrygbaar is, en verskaf riglyne vir die optimale skadu-koeffisient en weefpatroon van moontlike misvangsnette vir voomemende gebruikers van misvangstegnologie in gebiede waar die polipropileennet wat in die standaard miskollekteerders gebruik word nie, beskikbaar is nie. Die ondersoek van oppervlakeienskappe van mis-koesterkewers (Eng. "fog harvesting beetles") en eksperimente met verskeie prototipe versamelaars toon dat dit moontlik is om die waterproduksie van bestaande kollekteerders te verhoog. Die hidrofobe oppervlaktetoestande soos gevind op die opperhuid van die mis-koesterkewers (Onymacris unguicularis en Onymacris bicolor) bevorder die vorming en afloop van groot misdruppels op die versameloppervlak. Die prototipe suigwaaier- en verkoelerstelselgebasseerde versamelaars toon dat dit moontlik is om die misvogversameling op polimeriese nette tot drie maal te verhoog en dat 'n vergelykbare volume atmosferiese vog versamel kan word, selfs in die afwesigheid van mis, tot by 'n relatiewe humiditeit van ongeveer 40%. Ten slotte benadruk die studie dat grondwatersoutgehalte in waterann gebiede soms 'n seisoenale probleem is, en dat dit in ag geneem moet word in watervoorsieningstrategiee vir sulke gebiede. Dit benadruk ook dat atmosferiese vog 'n bruikbare alternatiewe bron van varswater kan wees in sekere areas, waar dit dikwels verskeie male meer is as reenval, en gesien behoort te word as 'n belangrike aspek in strategiee om waterprobleme in hierdie gebiede aan te spreek. Die studie beveel sterk aan dat wetenskaplikes, ingenieurs en waterbestuurders in hierdie gebiede altyd die beskikbare geleenthede soos klimaatstoestande (bv. misneerslag) en aanpassings vir vogvangslbewaring wat voorkom by inheemse plante en diere sal navors om sodoende onderhoudbare oplossings vir die probleem te vind. Hulle behoort deurlopend op hoogte te bly met ontwikkelings/geleenthede wat ontstaan in die wyer waterindustrie, wat van waarde kan wees in by waterverskaffmgsinisiatiewe vir afgelee gebiede in ontwikkelende lande. Laastens dien die studie om 'n beter begrip daar te stel van die aard van grondwatersoutvlakke in waterarm gebiede wat afhanklik is van seisoenale oppervlaktevloei vir watervoorsiening sowel as om 'n bydrae te lewer tot die formuleer van oplossings tot die probleem in hierdie gebiede, veral in die hiperdroe omgewings aan die Namibiese weskus, waar konvensionele waterbronne mees onvoldoende is. Dit benadruk ook die rol van materiaalkundige wetenskappe (polimere) en omgewingsingenieurswese sowel as die UNESCO-geassosieerde wetenskaplike instellings in die formulering van volhoubare oplossings vir sommige van die huidige waterprobleme in waterann gebiede. Sleutelwoorde: Waterarm gebiede, hidrochemie, bronne van varswater, ontsouting, atmosferiese vog