0.7nm single wall carbon nanotubes have been synthesized within VPI-5 zeolite channels with sucrose as carbon precursor. VPI-5 molecular sieves are synthesized hydrothermally under conventional heating. X-ray powder diffraction, micro raman, scanning electron microscope (SEM), transmission electron microscope (TEM), Thermogravimetric analysis have been used to investigate the structure of zeolite and thermal decoposition process of carbon precursors. 0.4nm single wall carbon nanotubes have also been fabricated within AlPO4-5 nanopores. A key challenge is to produce high yield single wall carbon nanotubes with uniform diameter. In order to improve the carbon nanotube yield, different organic precursors are employed. Although the problem is still the repetition and low yield of CNTs, it is still an improvement for 0.7nm SWNTs synthesis with the new template prolysis method. The novel multilayer conductor/insulator/conductor structures have been fabricated. This structure might find potential application in DNA sequential reactions because each layer might be individually addressed with voltage. When bias is applied to the conductive layer, it can be chemically functionalized, which leads to membrane pore with multiple reaction sequences when the molecule traverses the membrane reactor. In this thesis, Carbon/polymer/carbon system and copper/polymer system will be introduced. O2 RIE was used to expose the edge of carbon/polymer/carbon structure. However, the conductivity of carbon layer is not high enough for electroplating. Copper pores etched by FeCl3 solution shows good conductivity, and can be electroplated with metal nanoparticles.

Porous zeolite, carbon and aluminophosphate powders have been colloidally assembled and post-processed in the form of monoliths, flexible free standing films and coatings for gas separation and odor removal. Zeolite 13X monoliths with macroporosites up to 50 vol% and a high CO2 uptake were prepared by colloidal processing and sacrificial templating. The durability of silicalite-I supports produced in a binder-free form by pulsed current processing (PCP) were compared with silicalite-I supports produced using clay-binders and conventional thermal treatment. Long-term acid and alkali treatment of the silicalite-I substrates resulted in removal of the clay binder and broadened the size-distribution of the interparticle macropores. Furthermore, strong discs of hydrothermally treated beer waste (HTC-BW) were produced by PCP and the discs were activated by physical activation in CO2 at high temperatures. The activated carbon discs showed high strength up to 7.2 MPa while containing large volume of porosities at all length scales. PCP was further used to structure aluminomphosphate powders (AlPO4-17 and AlPO4-53) into strong functional monoliths. The aluminophosphate monoliths had strengths of 1 MPa, high CO2 uptake and were easy to regenerate. Zeolite Y, silicalite and ZSM5 were selected as potential zeolite adsorbents for removal of sulfur containing compound, e.g. ethyl mercaptan (EM) and propyl mercaptan (PM). A novel processing procedure was used to fabricate free-standing films and coatings of cellulose nanofibrils (CNF) with a high content of nanoporous zeolite; 89 w/w% and 96 w/w%, respectively. Thin flexible free-standing films and coatings of zeolite-CNF on paperboards with thickness around 100 µm and 40 µm, respectively, were produced. Headspace solid phase microextraction (SPME) coupled to gas chromatography- mass spectroscopy (GC/MS) analysis showed that the zeolite-CNF films can efficiently remove considerable amount of odors below concentration levels that can be sensed by the human olfactory system. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Manuscript.</p>

South Africa produces an average of 154 million broilers (Gallus gallus domesticus) annually, arising to an estimated 886 million kg of broiler litter. The largest population of broilers are reared in the North West province. Various applications for this largely underexploited resource have been published, including forming part of ruminant diets and direct land application. This however has several disadvantages, as it could lead to eutrophication of fresh water sources and faecal contamination of produce. Windrow composting of broiler litter has previously been studied, and found to deliver a stabilized product free of pathogenic and phytotoxic effects, therefore making it an excellent soil conditioner. This study aimed to characterize the microbial community present during the windrow composting of broiler litter. Four different formulations of substrate were tested; these being broiler litter (Windrow 1), Windrow 1 with previously composted material (Windrow 2), Windrow 2 amended with woodchips (Windrow 3) and Windrow 3 with an additional 12.5% (w/w) zeolite (Windrow 4). Broiler litter used in this experiment had a C:N ration of 10.3:1, whilst the blue gum woodchips added as an amendment had a C:N ratio of 172:1. Windrow and environmental temperatures were monitored on a regular basis. Windrow 1 largely mimicked environmental temperature, and could not sustain a true thermophilic phase during the experimental period. Windrow 2 did achieve a short lived thermophilic phase during the first few days of the composting process, however could not sustain its temperature over the whole period. In contrast Windrows 3 and 4 sustained temperature above 40°C for the largest part of the experimental period, regardless of environmental temperature. No significant difference (p < 0.05) could be observed between average moisture levels in the 4 windrows. Internal moisture profiles were however found to differ significantly, especially on the surface of the windrows. Moisture was also lost faster in Windrows 1 and 2 compared to Windrows 3 and 4. Chemical analysis showed differences between the four windrows constructed. A higher amount of nitrogen was lost in Windrows 1 and 2, mostly due to a sub-optimal initial C:N ratio in these windrows. Windrow 2 contained the highest values for plant nutrients P, Mg, Ca, Mn and Cu. Microbial population dynamics were observed using PCR-DGGE of samples collected throughout the composting of various treatments. Various commercial DNA extraction kits where tested in a previous study for their ability to remove PCR inhibitory substances, such as humic acids. The Machery-Nagel Soil DNA isolation kit was used as it gave amplifiable DNA from all samples. Samples were amplified using a nested PCR approach primer sets 27f-1492r \ 341f(GC)-907r and EF3-EF4 \ EF4(GC)-fung5 (where “GC” indicates a GC-rich clamp) for prokaryotic and eukaryotic species respectively. The PCR products were analyzed by agarose gel electrophoresis, and equal amounts of product were subjected to denaturing gradient gel electrophoresis (DGGE). Bands obtained from these polyacrylamide gels where then re-amplified using the same secondary primer sets (without the GC-clamp), and sequenced. A total of 454 prokaryotic bands in 55 distinct rf-positions were observed. Seven distinct rf-positions were observed in eukaryotic DGGE profiles. Prokaryotic profiles were aligned and the microbial diversity was analyzed by means of Ward’s clustering algorithm and the dice coefficient of similarity, as well as Simpson’s reciprocal, Shannon-Weaver and Species richness indices. Canonical correspondence analysis (CCA) was also performed on both the banding patterns as well as the bands present, together with the physico-chemical results obtained. Several bands were successfully identified as being influenced by physico-chemical parameters. Temperature, C:N ratio, ash, and moisture showed a correlation on CCA bi-plots. Sixteen bands were sequence identified. These sequences were compared to two different databases. The 16S rRNA database for Bacteria and Archaea gave identities to genus level, however maximum identity scores were low. Of the 16 sequences, 12 sequences were identified as uncultured bacteria when compared to the nucleotide collection database. In comparing the sequences with sequences collected in the nucleotide collection database, 12 were either first described in composts and soils, or animal manures. Results indicated mostly members of the genus Bacillus and Paenibacillus. The addition of a carbon source greatly affected the microbial metabolism, resulting in a thermophilic phase being achieved in amended windrows. As no thermophilic phase was observed in windrows that were not amended with woodchips, it could be concluded that the use of a carbon source is irremissible when composting broiler litter. A zeolite amendment is also strongly advised, as this further increased temperatures within the windrow. / Thesis (MSc (Environmental Sciences))--North-West University, Potchefstroom Campus, 2013.

South Africa produces an average of 154 million broilers (Gallus gallus domesticus) annually, arising to an estimated 886 million kg of broiler litter. The largest population of broilers are reared in the North West province. Various applications for this largely underexploited resource have been published, including forming part of ruminant diets and direct land application. This however has several disadvantages, as it could lead to eutrophication of fresh water sources and faecal contamination of produce. Windrow composting of broiler litter has previously been studied, and found to deliver a stabilized product free of pathogenic and phytotoxic effects, therefore making it an excellent soil conditioner. This study aimed to characterize the microbial community present during the windrow composting of broiler litter. Four different formulations of substrate were tested; these being broiler litter (Windrow 1), Windrow 1 with previously composted material (Windrow 2), Windrow 2 amended with woodchips (Windrow 3) and Windrow 3 with an additional 12.5% (w/w) zeolite (Windrow 4). Broiler litter used in this experiment had a C:N ration of 10.3:1, whilst the blue gum woodchips added as an amendment had a C:N ratio of 172:1. Windrow and environmental temperatures were monitored on a regular basis. Windrow 1 largely mimicked environmental temperature, and could not sustain a true thermophilic phase during the experimental period. Windrow 2 did achieve a short lived thermophilic phase during the first few days of the composting process, however could not sustain its temperature over the whole period. In contrast Windrows 3 and 4 sustained temperature above 40°C for the largest part of the experimental period, regardless of environmental temperature. No significant difference (p < 0.05) could be observed between average moisture levels in the 4 windrows. Internal moisture profiles were however found to differ significantly, especially on the surface of the windrows. Moisture was also lost faster in Windrows 1 and 2 compared to Windrows 3 and 4. Chemical analysis showed differences between the four windrows constructed. A higher amount of nitrogen was lost in Windrows 1 and 2, mostly due to a sub-optimal initial C:N ratio in these windrows. Windrow 2 contained the highest values for plant nutrients P, Mg, Ca, Mn and Cu. Microbial population dynamics were observed using PCR-DGGE of samples collected throughout the composting of various treatments. Various commercial DNA extraction kits where tested in a previous study for their ability to remove PCR inhibitory substances, such as humic acids. The Machery-Nagel Soil DNA isolation kit was used as it gave amplifiable DNA from all samples. Samples were amplified using a nested PCR approach primer sets 27f-1492r \ 341f(GC)-907r and EF3-EF4 \ EF4(GC)-fung5 (where “GC” indicates a GC-rich clamp) for prokaryotic and eukaryotic species respectively. The PCR products were analyzed by agarose gel electrophoresis, and equal amounts of product were subjected to denaturing gradient gel electrophoresis (DGGE). Bands obtained from these polyacrylamide gels where then re-amplified using the same secondary primer sets (without the GC-clamp), and sequenced. A total of 454 prokaryotic bands in 55 distinct rf-positions were observed. Seven distinct rf-positions were observed in eukaryotic DGGE profiles. Prokaryotic profiles were aligned and the microbial diversity was analyzed by means of Ward’s clustering algorithm and the dice coefficient of similarity, as well as Simpson’s reciprocal, Shannon-Weaver and Species richness indices. Canonical correspondence analysis (CCA) was also performed on both the banding patterns as well as the bands present, together with the physico-chemical results obtained. Several bands were successfully identified as being influenced by physico-chemical parameters. Temperature, C:N ratio, ash, and moisture showed a correlation on CCA bi-plots. Sixteen bands were sequence identified. These sequences were compared to two different databases. The 16S rRNA database for Bacteria and Archaea gave identities to genus level, however maximum identity scores were low. Of the 16 sequences, 12 sequences were identified as uncultured bacteria when compared to the nucleotide collection database. In comparing the sequences with sequences collected in the nucleotide collection database, 12 were either first described in composts and soils, or animal manures. Results indicated mostly members of the genus Bacillus and Paenibacillus. The addition of a carbon source greatly affected the microbial metabolism, resulting in a thermophilic phase being achieved in amended windrows. As no thermophilic phase was observed in windrows that were not amended with woodchips, it could be concluded that the use of a carbon source is irremissible when composting broiler litter. A zeolite amendment is also strongly advised, as this further increased temperatures within the windrow. / Thesis (MSc (Environmental Sciences))--North-West University, Potchefstroom Campus, 2013.

This study revealed that ammonium ion exchange of natural zeolite could be a feasible method of nitrogen removal and recovery from permeate from anaerobic membrane bioreactors (AnMBRs). NaCl concentrations optimized for chemical regeneration in batch experiments did not match those in continuous column tests. Instead, the mass ratio of Na+ to Zeolite-NH4+-N was significant for improving regeneration efficiency in column experiments; this mass ratio was 750 g Na+/g Zeolite-NH4+-N required for regeneration efficiency over 90% in 2 hours at pH 9. ???To decrease the NaCl dose in regeneration of exhausted zeolite, a high pH regeneration method was developed using an NaCl concentration of 10 g/L at pH 12 (the mass of Na+ to Zeolite-NH4+-N of 4.2 ) which achieved a regeneration efficiency about 85%. The recovery of ammonium nitrogen from the exhausted zeolite was assessed with air stripping followed by ammonia collection in an acid scrubber. The effects of shaking and air stripping were investigated in batch tests and the results showed the superiority of air stripping over shaking. Liquid circulation and air flow rates were varied for optimization of ammonia recovery in a continuous zeolite-packed column combined with a regeneration chamber and a stripping column. The liquid circulation rate had no significant effect on either the regeneration efficiency or the ammonia transfer efficiency from ammonium nitrogen to ammonia gas, while the ammonia transfer efficiency significantly increased with the air flow rate.??? Furthermore, the effect of pH on ammonia recovery was tested. Both the regeneration efficiency and the ammonia transfer efficiency were significantly improved with increasing pH. When the pH was increased from 9.5 to 12, the regeneration efficiency increased from 9.2% to 84% and the ammonia transfer efficiency increased from 54% to 92%. The nitrogen recovery process that combines zeolite ammonium exchange and air stripping can decrease chemical costs for regeneration of exhausted zeolite and efficiently collect ammonium nitrogen to be reused as fertilizers. Hence, the integrated nitrogen process can resolve the challenge of nitrogen removal in anaerobic membrane bioreactors treating organic wastewater in sustainable manners.

Thesis (M. Pharm.)--North-West University, Potchefstroom Campus, 2009.

Understanding climatic and water-mineral chemistry affecting hominin habitats duringthe period 1.92 to 1.80 Ma in Paleolake Olduvai basin, Tanzania is of social and scientific interest. Previous Olduvai research reported climate cycles in bulk sample mineral analyses. Xray diffraction, X-ray fluorescence, and color analyses of Locality 80 Tuff Bed I samples tested the null hypothesis: Alteration mineralogy of Central Basin volcanic Tuffs IA through IF reflect salinity/alkalinity cycles. Such cyclicity was not found. Several primary authigenic minerals were confirmed, but not as previously reported. Tuffs are thoroughly altered, mostly to potassium-feldspars, zeolites, and carbonates, plus other feldspars and clay minerals (clays not in this study). Nevertheless, other findings reveal there is more to be learned. Results imply a majorgeochemical shift around 1.869-1.857 Ma, from non-zeolite forming environments to zeolite forming environments. A newly developed age model could aid re-analysis of past work and assist future research.

Zeolite membranes are considered to be a promising alternative to polymeric membranes and they have the potential to separate gases under harsh conditions. Silicalite-1 membranes in particular are easy to prepare and suitable for several industrial applications. In this research project, silicalite-1/ceramic composite membranes were prepared using the pore plugging hydrothermal synthesis method and supports with zirconium oxide and/or titanium oxide as active layers. The effect of the support’s pore size on the morphology and permeation performance of the prepared membranes was investigated using five supports with different active layer pore sizes in the range of 0.14 – 1.4 m. The prepared membranes were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), electron diffraction spectrometer (EDS), single gas and binary gas mixtures permeation tests. The results confirmed the presence of a typical silicalite-1 zeolite structure with a high internal crystalline order grown inside the pores of the active layer of the supports, with a dense film covering most of the supports active layers. Silicalite-1 crystals in the prepared membranes were preferably oriented with either a- or b-axes perpendicular to the support surface. Single gas permeation results illustrated that the observed permeances were not directly related to the kinetic diameter of permeants. Instead, the transport of the studied gases through the prepared membranes occurred by adsorption followed by surface diffusion mechanism. Binary gas tests performed with CO2 and N2 mixtures showed that the prepared membranes were selective and very permeable with CO2/N2 permselectivities up to 30 and a CO2 permeances in the order of 10-6 mol m-2 Pa-1 s-1. A model was developed, based on Maxwell−Stefan equations and Extended Langmuir adsorption isotherm, to describe the transport of binary CO2 and N2 mixtures through the prepared silicalite-1 membranes. The model results showed that the exchange diffusivities (D12 and D21) were less dependent on the feed pressure and feed composition compared to the permeances and the permselectivities. Hence, they are more appropriate to characterize the intrinsic transport properties of the prepared silicalite-1 membranes.

Thesis (M. Pharm.)--North-West University, Potchefstroom Campus, 2009.

MFI type zeolites, are the most widely studied zeolites for membrane separations. Conventionally, zeolite membranes are prepared in batch systems by hydrothermal synthesis in autoclaves. This method has several disadvantages for use in industrial scale for the synthesis of membranes with large areas and complex geometries that are commonly used in membrane modules. The objective of this study is to prepare MFI type zeolite membranes on tubular alumina supports in a continuous system where the synthesis solution is circulated through the tubular supports. Syntheses were carried out using clear solutions, at atmospheric pressure and at temperatures below 100&deg / C. The membranes were characterized by N2, SF6, n-butane and isobutane permeances, X-ray diffraction and scanning electron microscopy. A 2-&amp / #956 / m membrane was synthesized using the composition 80SiO2: 16TPAOH: 1536H2O at 95&deg / C in the continuous system. The membrane showed N2 permeance of 4.4 x 10-7 mol/m2.s.Pa and N2/SF6 selectivity of 11. The membrane synthesized in the batch system showed a N2 permeance of 3.4 x 10-7 mol/m2.s.Pa and a N2/SF6 selectivity of 27. Both membranes showed n-butane/isobutane mixture (50%-50%) selectivities of about 6 at temperatures of 150 and 200&deg / C. Among many zeolite membranes reported in literature, these membranes are one of the few zeolite membranes synthesized in a flow system and the first MFI type membranes synthesized in a continuous flow system with circulation of the synthesis solution. The permeances and selectivities of the membranes synthesized in the continuous system are comparable with the MFI type membranes synthesized in batch systems in literature.