No / Graded porous materials are of growing interest because of their ability to improve the impedance matching between air and material itself. Theoretical models have been developed to predict the acoustical properties of these media. Traditionally, graded materials have been manufactured by stacking a discrete number of homogeneous porous layers with different pore microstructure. More recently a novel foaming process for the manufacturing of porous materials with continuous pore stratification has been developed. This paper reports on the application of the numerical procedure proposed by De Ryck to invert the parameters of the pore size distribution from the impedance tube measurements for materials with continuously stratified pore microstructure. Specifically, this reconstruction procedure has been successfully applied to retrieve the flow resistivity and tortuosity profiles of graded porous materials manufactured with the method proposed by Mahasaranon et al. In this work the porosity and standard deviation in pore size are assumed constant and measured using methods which are applied routinely for homogenous materials characterisation. The numerical method is based on the wave splitting together with the transmission Green's functions approach, yielding an analytical expression of the objective function in the Least-square sense.

Yes / This study investigates the acoustic performance of materials made using various amounts of bio-binder (cis-1,4-polyisoprene). The filler used in making these materials was from recycled tyres which consist of nylon 6,6 fibres bonded to rubber grains known as tyre shred residue (TSR). The materials have shown high acoustical performance especially at low binder levels, due mainly to the open porosity of the tested samples. The paper begins with a discussion of materials made using recycled granulates. The macroscopic properties (e.g. flow resistivity, porosity, tortuosity, etc.) that control the acoustical behaviour of these materials are then defined as are methods for their measurements. The acoustical characterisation of porous media is considered next, followed by discussion of the acoustic performance of the materials. The characteristics of these novel materials are illustrated through experimental and theoretical models involving sound absorption and transmission.

Non-dilute salt strength solutions occur in many near surface geologic environments. In order to better understand the occurrence and movement of the water and salt, mathematical models for this non-ideal fluid need to be developed. Initial boundary value problems may then be solved to predict behavior for comparison with observations. Using the principles of equilibrium reversible and irreversible thermodynamics, relationships describing the thermo-physics of non-dilute saline solutions in variably saturated porous media are investigated. Each of four central chapters investigates a particular aspect of the flow of saline solutions through porous media. The first chapter derives the general relationships describing the effects of salt on the vapor content in the gas phase and also on the liquid pressure. The second chapter summarizes an example using the new theory for sodium chloride (NaCl) from zero to saturated strength. Additional terms beyond the dilute approximation are shown to be more important in very dry, fine textured soils with significant salt content. The third chapter derives the salt corrections for Darcy-type flow laws for variably saturated porous media, and an example for NaCl is given. Agreement between theory and experimental data is good, though there appear to be some unaccounted for effects. These effects may be the result of ionic interaction of the salt with the loamy sand used, and/or the effect of hysteresis of the water content-pressure relationship. The final chapter investigates two fundamental assumptions commonly used in process thermodynamics when considering mixtures described by porous media, saline water, and moist air. The first assumption is that temperature is the generalized intensive variable associated with entropy. The second assumption is that the form of the differential of total energy is known a-priori. It is shown that the first assumption is suspect under some circumstances, and a generalized notion of how to select extensive variables for a given system is introduced for comparison with the second assumption. Examples comparing the "usual" and new theories are accomplished for ideal gases and for isotropic Newtonian liquids, with results being favorable except possibly for the Gibbs-Duhem Relation of the Newtonian liquid for the "usual" theory. / Graduation date: 2005

Thesis (MScEng)--University of Stellenbosch, 2002 / ENGLISH ABSTRACT: A Representative Unit Cell (RUC) model for flow through two-dimensional porous media is presented and applied to two industrial related problems. The first application is to that of cross-flow in tube banks. Both staggered and square (inline) configurations are investigated and the model results are compared to experimental data. The second application is to flow through a stack in a timber-drying kiln. The RUC model is applied to the anisotropic timber stack ends and the centre part is modelled with a standard duct flow solution. The results of the models applied to a timber stack are compared to experimental data obtained from model tests undertaken in a wind tunnel. The results of the RUC and duct flow models are found to be in excellent agreement with the data of the experimental models. These models may be used to optimize kiln designs. / AFRIKAANSE OPSOMMING: 'n Verteenwoordigende Eenheid Sel (VES) model vir vloei deur twee-dimensionele poreuse media word weergegee en toegepas op twee industriële toepassings. Die eerste toepassing is op dwarsvloei deur banke van buise. Beide gestapelde en inlyn konfigurasies word ondersoek waarvan die model resulte met eksperimentele data vergelyk word. Die tweede toepassing is op vloei deur 'n stapel in 'n hout-droogoond. Die VES model word toegepas op die anisotropiese ente van houtstapels en die middelste seksie word gemodelleer deur 'n standaard kanaalvloei oplossing. Die resultate van die modelle toegepas op n 'houtstapel word vergelyk met eksperimentele data verkry uit model toetse wat in 'n wind-tonnel uitgevoer is. Die VES en kanaalvloei modelle se resultate stem uitstekend ooreen met die data van die eksperimentele modelle. Hierdie modelle kan gebruik word om die ontwerp van droogoonde te optimeer.

Orientador: Celso Valentim Santilli / Banca: Rodrigo Fernando da Costa Marques / Banca: Eduardo José Nassar / Resumo: A produção de aluminas com distribuição de tamanho e volume de poros controlados pela separação de fases líquido-sólido é um assunto emergente na área de cerâmicas porosas. As aluminas foram produzidas pelo processo sol-gel acompanhado de separação de fases, usando o óxido de polietileno (PEO) como agente indutor na separação de fases e o óxido de propileno para a gelatinização, para isso foram estabelecidas condições de controle cinético e termodinâmico desses eventos, através do controle do tempo de agitação e temperatura no meio reacional. Foram otimizadas rotas de síntese através do ajuste dos parâmetros de preparação variando a concentração do agente direcionador de poros PEO durante a transição sol-gel. Esta transformação foi acompanhada in-situ por SAXS revelando que o crescimento de objetos fractais com dimensionalidade de 1,7, que é característico do mecanismo e agregação controlado pela difusão. A calcinação em 700°C possibilitou a produção de aluminas da fase gama (-Al2O3) com textura porosa formada por macro e mesoporos. O uso do agente direcionador de poros PEO em proporção molar entre 0,01-0,07 mostrou-se eficiente no ajuste da macro-mesoporosidade. Entretanto quando se emprega proporções molares de PEO acima de 0,07 obtém-se apenas famílias de mesoporos com um decaimento do volume específico de poros quando a proporção molar aumenta de 0,08 para 0,1. Estas aluminas mesoporosas apresentaram maior área superficial especifica (Área BET máximo de  305 m²/g) e uma melhor relação OH/-O-Al em comparação com as macro-mesoporosas. / Abstract: The production of alumina with volume and size distribution of pores controlled by phase separation induced by the addition of the polymer polyethylene oxide (PEO) during synthesis is an emerging issue in the area of functional ceramics. The aluminas were produced by the sol-gel process followed by phase separation, and the PEO as inducing agent phase separation and propylene oxide to gelation. Conditions for kinetic and thermodynamic control over these events were kept by controlling the stirring time and temperature in the reaction medium. Synthesis routes have been optimized by adjusting the preparation parameters varying the concentration of pores directing agent (PEO) during sol-gel process. This transformation was accompanied by in-situ SAXS and the results reveal the growth typical of fractal objects starting from a diluted solution, whose dimensionality in the Porod region was 1,7, characteristic of aggregation controlled by diffusion and the distances between the growing particles is around 2,95 nm. Gamma alumina (-Al2O3) with diversified porous texture and macro-mesopores was obtained with thermal treatment up to 700 ° C, being supported by several techniques. The macro-mesoporosity can be adjusted by PEO driver pores agent in a molar ratio from 0,01 to 0,07. Molar ratios of PEO above 0,07 produces only mesopores, decreasing the cumulative volume of this pores when the molar ratio increases from 0,08 to 0,1. These mesoporous aluminas had higher specific surface area (BET Area  305 m² / g) and better ratio OH/O-Al compared to the macro-mesoporous. / Mestre

Thesis (PhD)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: The first part of this study describes the synthesis of new porous materials from basic building blocks. Five structurally related ligands namely: N,N'-bis(3-pyridylmethyl)-naphthalene diimide (L1), N,N'-bis(4-pyridylmethyl)-naphthalene diimide (L2), N,N'-bis(4-pyridylmethyl)- pyromellitic diimide (L3), N,N'-bis(3-pyridylmethyl)-pyromellitic diimide (L4) and 2-(pyridin-4- ylmethyl)-benzene tricarboxylic anhydride (L5) were synthesised. Ligands L1 and L2 were reacted with metal nitrates and carboxylates as co-ligands in a systematic manner with a view to obtaining potentially porous 3–D coordination polymers. Ten structurally diverse coordination polymers were obtained and they were characterised by single-crystal X-ray diffraction, powder X-ray diffraction and thermogravimetric analysis. Four of these compounds absorb moderate amounts of CO2 and, in addition, show sorption selectivity towards CO2 over N2. The reaction of L3 and L4 with transition metal halides yielded two 1–D chains, while the reaction of L5 with transition metal nitrates yielded seven coordination polymers of which four are 2–D and three are 1–D. Of the 2–D structures three are isostructural. The second part of this work describes a variable pressure study of a flexible metal-organic framework [Zn2(BDC)2(BPY)] (BPY = 4,4 -bipyridine and BDC = 1,4-benzene dicarboxylic acid). [Zn2(BDC)2(BPY)] is one of the few examples of a flexible metal-organic framework that undergoes phase transformations in response to gas pressure. The high pressure sorption recorded for this metal-organic framework displays two inflection steps in the pressure range 0 to 30 bar, possibly indicating two phase transformations. The gas-loaded structures for each phase transformation were determined by means of single-crystal X-ray diffraction. High-pressure differential scanning calorimetry was also carried out on the system in order to determine accurate gate-opening pressures, as well as the energies involved with each phase transformation. The results correlate with those obtained from single-crystal X-ray diffraction and high-pressure sorption. The final section reports the mechanochemical synthesis of two Werner complexes [NiCl2(4- PhPy)4] (1), [CoCl2(4-PhPy)4] (2) and their corresponding solid solution [Ni0.5Co0.5Cl2(4-PhPy)4] (3) (PhPy = phenyl pyridine). The solid solution could only be formed by mechanochemical synthesis and not by conventional solution crystallisation methods. The solid solution exhibits sorption properties that differ from those of the pure compounds. / AFRIKAANSE OPSOMMING: Die eerste deel van hierdie studie beskryf die sintese van nuwe poreuse stowwe uit basiese boublokke. Vyf struktureel verwante ligande naamlik: N,N'-bis(3-piridielmetiel)-naftaleen diimied (L1), N,N'-bis(4-piridielmetiel)-naftaleen diimied (L2), N,N'-bis(4-piridielmetiel)- piromellitien diimied (L3), N,N'-bis(3-piridielmetiel)-piromellitien diimied (L4) en 2-(piridiel-4- ielmetiel)benseen trianhidried (L5) is gesintetiseer. Ligande L1 en L2 is gereageer met metaal nitrate en karboksielsure as mede-ligande in 'n sistematiese wyse met 'n oog op die verkryging van potensieel poreuse 3–D koördinasie polimere. Tien struktureel diverse koördinasie polimere is verkry en hulle is gekarakteriseer deur enkel-kristal X-straal-diffraksie, poeier X-straal diffraksie en termo-analise (thermal analysis). Vier van hierdie verbindings het matige hoeveelhede CO2 geabsorbeer en, bykomend, wys sorpsie selektiwiteit van CO2 oor N2. Die reaksie van L3 en L4 met oorgangsmetaalhaliede het twee 1–D kettings gevorm, terwyl die reaksie van L5 met oorgangsmetaal nitrate sewe koördinasie polimere opgelewer het, waarvan vier 2–D en drie 1–D polimere is. Van die 2–D polimere het drie vergelykbare strukture. Die tweede deel van hierdie werk beskryf 'n veranderlike druk studie van 'n buigsame metaalorganiese raamwerk [Zn2(BDC)2(BPY)] (BPY = 4,4-bipiridien en BDC = 1,4-benseen dikarboksielsuur). [Zn2(BDC)2(BPY)] is een van die min voorbeelde van 'n buigsame metaalorganiese raamwerk wat fase transformasies (phase transformations) ondergaan in respons op ‘n verandering in gas druk. Die hoë-druk sorpsie aangeteken vir hierdie metaal-organiese raamwerk vertoon twee infleksie stappe in die gebestudeerde druk gebied (0 tot 30 bar), wat moontlik op twee fase transformasies dui. Die gas-gelaaide strukture vir elke fase transformasie is bepaal deur middel van enkel-kristal X-straal-diffraksie. Hoë-druk differensiële skandeer kalorimetrie (differential scanning calorimetry) is ook uitgevoer op die stelsel ten einde dié akkurate hekopenings druk, sowel as die energie betrokke by elke fase transformasie te bepaal. Die resultate stem ooreen met dié verkry vanaf enkel-kristal X-straal diffraksie en hoë-druk sorpsie. Die finale afdeling bespreek die meganochemiese sintese van twee Werner komplekse [NiCl2(4-PhPy)4] (1) en [COCl2(4-PhPy)4] (2) en hul ooreenstemmende vaste oplossing (solid solution) [Ni0.5Co0.5Cl2(4-PhPy)4] (3). Die vaste oplossing kan slegs gevorm word deur meganochemiese sintese en nie deur konvensionele oplossing kristallisasie metodes. Die vaste oplossing vertoon sorpsie eienskappe wat verskil van dié van die suiwer verbindings.

Thesis (PhD)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: Research on transfer processes in various types of porous media has become important for the optimization of high technology engineering devices and processes. In this study the micro-structural parameters of different types of porous media, namely granular media, foamlike media and fibre beds, are characterized and quantified. Existing analytical modelling procedures for the three different types of porous media have been unified and refined to improve their predictive capabilities. Deterministic equations are proposed for predicting the streamwise pressure gradient, permeability and inertial coefficient of each type of porous medium. The equations are applicable over the entire porosity range and steady laminar flow regime and well suited as drag models in numerical computations. It is shown that the improved granular model can be regarded as qualitative and quantitative proof of the extensively used semi-empirical Ergun equation. The proposed model is used to provide physical meaning to the empirical coefficients. An Ergun-type equation is also proposed for foamlike media by remodelling the interstitial geometric configuration and accompanying flow conditions. The range of applicability of the existing foam model has been extended by incorporating the effect of developing flow in the pressure drop prediction. An equation is proposed in which the variation in the cross-sectional shape of the fibres can be incorporated into the interstitial form drag coefficient used in the foam model. This serves as an improvement on the constant value previously used. The existing foam model is also adapted to account for anisotropy resulting from compression. Two case studies are considered, namely compression of a non-woven glass fibre filter and compression of a soft polyester fibre material. The significant effect of compression on permeability is illustrated. In each case study the permeability values range over more than an order of magnitude for the narrow porosity ranges involved. The pressure drop prediction of the foam model is furthermore adapted to account for the combined effects of compression and developing flow. The newly proposed model diminishes the significant over-prediction of the existing foam model. An equation is furthermore proposed for predicting the permeability of Fontainebleau sandstones in which the effect of blocked throats is accounted for. Lastly, equations are proposed for predicting diffusivity ratios of unconsolidated arrays of squares and cubes. The prediction of the diffusivity ratio proposed in the present study, as opposed to model predictions from the literature, takes into account diffusion that may take place in stagnant fluid volumes. It is shown that a specific weighted average model proposed in the literature is not adequate to predict the diffusivity ratio of fully staggered arrays of squares, since it is shown not to be applicable to rectangular unit cells. Instead a new weighted average model is proposed which is applicable over the entire porosity range and for both staggered and non-staggered arrays of solid squares and cubes. The proposed weighted average model provides satisfactory agreement with experimental data from the literature and numerical data generated in the present study. / AFRIKAANSE OPSOMMING: Navorsing op oordragsprosesse in verskeie tipes poreuse media het belangrik geword vir die optimisering van ho¨e-tegnologie ingenieurstoestelle- en prosesse. In hierdie studie word die mikro-struktuur parameters van verskillende tipes poreuse media, naamklik korrelagtige media, sponsatige media en veselbeddens gekarakteriseer en gekwantifiseer. Bestaande analitiese modelleringsprosedures vir die drie verskillende tipes poreuse media is verenig en verfyn om die voorspelbare bekwaamheid daarvan te verbeter. Deterministiese vergelykings is voorgestel vir die voorspelling van die stroomsgewyse gradi¨ent, permeabiliteit en inersi¨ele ko¨effisi¨ent van elke tipe poreuse medium. Die vergelykings is geldig oor die hele porositeitsgrens en gestadigde laminˆere vloeigrens en goed geskik as weerstandsmodelle in numeriese berekeninge. Dit is aangetoon dat die verbeterde korrelmodel beskou kan word as kwalitatiewe en kwantitatiewe bewys van die ekstensiewe gebruikte semi-empiriese Ergun vergelyking. Die voorgestelde model is gebruik om fisiese betekenis aan die empiriese ko¨effisi¨ente te gee. ’n Ergun-tipe vergelyking is ook voorgestel vir sponsagtige media deur hermodellering van die tussenruimtelike geometriese konfigurasie en gepaardgaande vloeikondisies. Die grense van toepaslikheid van die bestaande sponsmodel is uitgebrei deur die inkorporering van die effek van ontwikkelende vloei in die voorspelling van die drukval. ’n Vergelyking is voorgestel waarin die variasie in die deursnit vorm van die vesels ingesluit is in die sponsmodel. Dit dien as verbetering op die konstante waarde wat voorheen gebruik is. Die bestaande sponsmodel is ook aangepas om voorsiening te maak vir anisotropie as gevolg van kompressie. Twee gevallestudies is oorweeg, naamlik kompressie van ’n nie-geweefde glasvesel filter en kompressie van ’n sagte polyester veselmateriaal. Die beduidende effek van kompressie op permeabiliteit is aangetoon. In elke gevallestudie strek die permeabiliteit waardes oor meer as ’n grootte orde vir die skrale porositeitgrense betrokke. Die drukvalvoorspelling van die sponsmodel is verder aangepas om voorsiening te maak vir die gekombineerde effekte van kompressie en ontwikkelende vloei. Die nuwe voorgestelde model verminder die beduidende oor-voorspelling van die bestaande sponsmodel. ’n Vergelyking is verder voorgestel vir die voorspelling van die permeabiliteit van Fontainebleau sandsteen waarin die effek van geblokte porie¨e in ag geneem is. Laastens is vergelykings voorgestel vir die voorspelling van die diffusiwiteitsverhoudings van nie-konsoliderende rangskikkings van vierkante en kubusse. Die diffusiwiteitsverhouding voorspel in die huidige studie, teenoor modelvoorspellings vanaf die literatuur, neem diffusie in ag wat plaasvind in die stagnante vloeistofvolumes. Dit is aangetoon dat ’n geweegde gemiddelde model, voorgestel in die literatuur, nie in staat is om die diffusiwiteitsverhouding van ten volle verspringende rangskikkings van vierkante te voorspel nie, aangesien dit nie toepaslik is vir reghoekige eenheidselle nie. ’n Nuwe geweegde model is in plaas daarvan voorgestel wat toepaslik is oor die hele porositeitsgrens en vir beide verspringende en nieverspringende rangskikkings van soliede vierkante en kubusse. Die voorgestelde geweegde gemiddelde model bied bevredigende ooreenstemming met eksperimentele data uit die literatuur en numeriese data gegenereer in die huidige studie.

An equifield strength model has been established to elucidate the formation mechanism for the highly ordered alumina pore arrays and titanium oxide nanotubular arrays prepared via a common electrochemical methodology, anodisation. The fundamentals of the equifield strength model was the equilibrium between the electric field driven oxidation rate of the metal and electric field enhanced dissolution rate of oxide. During the anodic oxidation of metal, pore initiation was believed to generate based on dissolution rate difference caused by inhomogeneity near the metal/oxide interface. The ionic nanoconvection driven by the electric force exerted on the space charge layer in the vicinity of electrolyte/oxide interface is established to be the main driving force of the pore ordering at the early stage of the anodisation. While the equifield strength requirement governs the following formation of the single pore and the self-ordering of random distributed pore arrays during the anodisation process. Hexagonal patterned Al2O3 nanopore arrays and TiO2 nanotubular arrays have been achieved by anodisation of corresponding metal substrates in proper electrolytes. The two characteristic microstructural features of anodic aluminium oxide (AAO) and anodic titanium oxide (ATO) were investigated using scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). The observations of the hemispherical electrolyte/oxide and oxide/metal interfaces, uniform thickness of the oxide layer, as well as self-adjustment of the pore size and pore ordering can be well explained by the equifield strength model. Field enhanced dissociation of water is extremely important in determination of the porosity of anodic metal oxide. The porosity of AAO and ATO films was found to be governed by the relative dissociation rate of water which is dependent on anodisation conditions, such as electrolyte, applied voltage, current density and electric field strength. Using an empirical method, the relations between the porosity of the AAO (ATO) films and the anodisation parameters, such as electric field strength, current density and applied voltage, have been established. Besides, the extent that an external electric field can facilitate the heterolytic dissociation of water molecule has been estimated using quantum-chemical model computations combined with the experimental aspect. With these achievements, the fabrication of anodic metal oxide films can be understood and controlled more precisely. Additionally, the impacts of other factors such as the electrolyte type and the temperature effect on the morphology of the anodic products were also investigated. Some important experimental evidences on the pore diameters variation with applied voltage in the anodisation of aluminium and the titanium were obtained for future investigation of the anodic metal oxide formation processes.

The synthesis and properties of novel Metal Organic Frameworks were investigated and reported in this thesis. Thirteen new materials have been synthesized and their properties have been discussed with nine of the structures being solved. The most interesting and useful MOF among the thirteen materials is STAM-1, a copper-based Metal Organic Framework in which the starting linker (Benzene-1,3,5-tricarboxylic acid) undergoes selective in situ monoesterification during the synthesis. The monoesterified BTC can be recovered easily from the MOF, opening up MOF synthesis as a “protection” tool for unexpected selectivity in preparative chemistry that is difficult to accomplish using standard organic chemistry approaches. The selective linker derivatisation leads to the formation of a porous MOF with two types of accessible channel; one hydrophilic lined by copper and the other hydrophobic, lined by the ester groups. The unique structure of the pores leads to unprecedented adsorption behaviour, which reacts differently to gases or vapours of dissimilar chemistry and allows them to access different parts of the structure. The structural flexibility of STAM-1 shows significant differences in the kinetics of O₂ and N₂ adsorption, showing potential for new materials to be developed for air separation. Having two types of channel systems, adsorption can be switched between the two channels by judicious choice of the conditions; a thermal trigger to open the hydrophilic channel and a chemical trigger to open the hydrophobic channel. The storage and release capability of NO in STAM-1 was investigated for use in biomedical applications. Successful studies showed the strength of the antibacterial effects of NO loaded STAM-1, by using three different bacterial strains as a test of performance and were found to be bactericidal. Furthermore the antibacterial effects of NO free STAM-1 were also probed and found to be bactericidal even with low concentrations of the material such as 5 wt%. STAM-1 showed some complex magnetic behaviour by displaying strong antiferromagnetic properties at room temperature and ferromagnetic properties at lower temperatures. The antiferromagnetic coupling was observed within the dimer and ferromagnetic coupling between the dimers. This property of ferromagnetism can only be attributed to the corporation of magnetic dimers in the framework. STAM-2 displays a different magnetic behaviour than STAM-1 which shows paramagnetic properties at room temperature and antiferromagnetic properties at lower temperatures. Other novel MOFs were also successfully characterised and their properties were investigated for potential applications.

published_or_final_version / Mechanical Engineering / Doctoral / Doctor of Philosophy