Charge transport below the mobility edge, where the charge carriers are hopping between localized electronic states, is the dominant charge transport mechanism in a wide range of disordered materials. This type of incoherent charge transport is fundamentally different from the coherent charge transport in ordered crystalline materials. With the advent of organic electronics, where small organic molecules or polymers replace traditional inorganic semiconductors, the interest for this type of hopping charge transport has increased greatly. The work documented in this thesis has been dedicated to the understanding of this charge transport below the mobility edge. While analytical solutions exist for the transport coefficients in several simplified models of hopping charge transport, no analytical solutions yet exist that can describe these coefficients in most real systems. Due to this, Monte Carlo simulations, sometimes described as ideal experiments performed by computers, have been extensively used in this work. A particularly interesting organic system is deoxyribonucleic acid (DNA). Besides its overwhelming biological importance, DNA’s recognition and self-assembly properties have made it an interesting candidate as a molecular wire in the field of molecular electronics. In this work, it is shown that incoherent hopping and the Nobel prize-awarded Marcus theory can be used to describe the results of experimental studies on DNA. Furthermore, using this experimentally verified model, predictions of the bottlenecks in DNA conduction are made. The second part of this work concerns charge transport in conjugated polymers, the flagship of organic materials with respect to processability. It is shown that polaronic effects, accounted for by Marcus theory but not by the more commonly used Miller-Abrahams theory, can be very important for the charge transport process. A significant step is also taken in the modeling of the off-diagonal disorder in organic systems. By taking the geometry of the system from large-scale molecular dynamics simulations and calculating the electronic transfer integrals using Mulliken theory, the off-diagonal disorder is for the first time modeled directly from theory without the need for an assumed parametric random distribution.

Organic semiconductors are prime candidates for thermoelectric applications, because one can maximize the dimensionless figure of merit ZT (by maximizing the Seebeck coefficient and electrical conductivity) while simultaneously minimizing the thermal conductivity. In this work, we explore a few materials and try to find their thermoelectric characteristics. For the n-leg of the thermogenerator, we studied a modified fullerene (PCBM) which is doped with TDAE vapor. For the p-leg, we studied PEDOT and found the TDAE dedoping level at which the figure of merit is maximized.

No description available.

The coralline soils of atolls suffer from multiple nutrient deficiencies that severely limit crop growth. This study was conducted to assess the nutrient status of the soils of the inhabited atolls within the Marshall Islands (MI), and to determine what local materials could be used to correct deficiencies limiting crop growth. Surface and subsoils from 25 atolls were collected and analyzed for their chemical properties, and soil test results were evaluated with a missing element pot study. Soil tests revealed that the MI soils were severely deficient in K (0.12 cmol c kg -1 ) and marginally deficient in Cu (0.13 ug g -1 ). The missing element study showed that the soil was deficient in K, S, N, P, and Cu. An incubation experiment and a series of greenhouse experiments were conducted to evaluate the ability of locally available organic materials to mineralize N and supply adequate nutrients to crops. Vigna marina and fish meal showed the highest N mineralization capacity, and the Gompertz equation provided the best fit. Chinese cabbage plants grew as well in soils amended with chicken manure, Vigna marina , and copra cake as they did in soil treated with chemical fertilizers. Plants grown in soil amended with fish meal did not grow as well due to inadequate K supply. Nitrogen recovery was highest in V. marina treatment at 92% followed by the chemical control (83%), chicken manure (34%), fish-meal (18%), and copra cake (9%). Added coconut leaves immobilized N and resulted in very poor cabbage growth. Comparisons between relative growth rate (RGR) and nutrient relative accumulation rate (RAR) showed that nutrients supplied from the V. marina amendment to the cabbage plant matched plant demand. In a rate experiment in the greenhouse, adding 10.1 g kg -1 of V. marina leaves (dry weight) supplied 350 mg N kg -1 to 5 week-old corn plants representing 38% of the total amount of N added in the amendment. Splitting the application quantity improved corn growth at the highest addition rate. Copra cake showed less promise as a suitable organic amendment. Supplementing copra with chemical N and P, and V. marina leaves with and without Cu and B did not improve crop growth compared with copra alone. The soil exhibited low P adsorption capacity, and corn and lettuce growth responded to high Olsen P soil levels. The results of the greenhouse experiments showed that V. marina is a potential organic fertilizer material to correct soil nutrient deficiencies for good crop growth in the Marshall Islands.

This thesis describes the development of a novel method for the rapid identification of complex organic materials, including macromolecules, that involves a high temperature simultaneous hydrolysis and derivatisation reaction. In this procedure, aqueous quaternary alkylammonium hydroxides are made to react with a wide range of complex molecular species, including synthetic and natural polymers, under high temperature flash heating conditions. The hydrolysis products are converted to derivatives, such as alkyl esters or alkyl ethers. The reaction forms the basis for a modified pyrolysis gas chromatography (Py-GC) identification technique. Although the process is primarily intended for the rapid identification of polymers which are susceptible to hydrolysis, it is also valuable for characterisation of a variety of hydrolysable lower molecular weight species, such as polymer additives, triglycerides and natural waxes.The reaction takes place when an intimate mixture of an aqueous quaternary alkylammonium hydroxide solution is flash heated with the analyte in a conventional pyrolysis unit, and "on-line" GC-MS is used to separate and identify the reaction products. Analytes included synthetic polyester resins and phenolic polymers, natural products such as lipids and wood extractives, and natural polymers including lignocellulose, proteins and kerogen.Reaction variables, such as temperature, pH analyte particle size, substrate, and the derivatising reagent were studied, in order to find the optimum conditions for the reaction. While the reaction occurs at temperatures as low as 358 degrees celsius, a 770 degrees celsius reaction temperature was adopted to allow direct comparison with Py-GC data. A high pH of the derivatising reagent was found to be necessary to achieve an efficient hydrolysis of the macromolecule. Small particle size gives better conversion to derivatised ++ / products. The nature of the heating substrate did not appear to influence the reaction. Tetraalkylammonium hydroxides (TAAH) were found to be the most effective derivatising reagents for the reaction. Tetramethylammonium hydroxide (TMAH) was the most useful derivatising reagent, since the methyl derivatives of the hydrolysed products were conveniently chromatographed and usually had well known mass spectra. Other TA-AHs were useful for (i) producing higher molecular weight alkyl derivatives of low molecular weight side chains in some polymers, e.g., acetate groups in polyvinyl acetate, (ii) the purpose of determining sites of pre-existing methylation in natural products such as lignocellulose, or (iii) cases where methylation products could be confused with existing pyrolysis products.The reaction mechanism is believed to involve hydrolysis of the organic material, formation of the tetra-alkylammonium salt, and thermal degradation of the quaternary ammonium salt to alkylated derivatives. Some evidence is presented to support this mechanism, which is considered to be ionic in character, rather than a free radical reaction.A detailed study of the reaction of alkyd resins indicated that polyhydric alcohols, polybasic acids, degree of cure, oil length, and rosin acid and epoxy modification could be determined. The reaction of rosin modified phenolic resins (tert-butyl phenol formaldehyde and para-nonyl phenol formaldehyde), gave rosin acid methyl esters and easily identifiable products from the synthetic components.Fatty acid methyl esters could be obtained directly from lipids, such as vegetable oils, without time consuming preparative steps. The problems of base catalysed isomerisation of the double bonds in polyunsaturated fatty acids were overcome by reducing the amount of base used for the reaction. The reaction facilitated the identification of fatty acids in ++ / woolwax, the triglycerides in cosmetic products, and lipids in trace quantities of human fingerprint deposits.A more reliable representation of the chemical structure of lignocellulose in softwood and hardwood species was obtained by the reaction, as compared to conventional PyGC which underestimates the aromatic carboxylic acid moieties. Gymnosperm or angiosperm origin was indicated by the presence of solely guaiacyl, or both guaiacyl and syringyl derived groups, respectively. Other extraneous extractable material was identified simultaneously, including aliphatic and aromatic acids, which would not normally be detected by conventional Py-GC.An alternative method involved extracting the wood with TMAH, followed by pyrolysis of the extract, to give less complex but more specific GC profiles. The TMAH extraction procedure also indicated some characteristic biomarker species as well as guaiacyl and syringyl derived compounds. The pyrolysis of tetraethylammonium hydroxide (TEAH) extracts revealed the sites of pre-existing methylation in the Eucalyptus marginata species.The thermally assisted hydrolysis and alkylation method which has been developed is usually superior to the conventional Py-GC procedure for those polymers which are prone to hydrolysis, since it results in products which are more readily related to the polymer structure. For example, concerted hydrolysis and alkylation of polyester resins results in alkyl carboxylate esters and the alkyl ethers, whereas in conventional Py-GC the products are alkenes and carboxylic acids. Carboxylic acids are more difficult to chromatograph by GC, and aromatic carboxylic acids in particular are susceptible to decarboxylation under the pyrolysis conditions.The reaction procedure has provided an alternative approach to the characterisation of submicrogram quantities of a range of synthetic polymers, natural products and ++ / natural polymers, which has not previously been possible without lengthy chemical degradation procedures. Although it has not displaced the conventional Py-GC technique, it has given a new dimension to the characterisation of organic materials, providing a powerful tool for forensic science investigations and the analysis of complex materials.

South Africa is a country with very little prime farmland. A large percentage of this high agricultural capability land is generally acidic and nutrient poor, and situated in areas where large coal mining activities occur. Coal mining and agriculture are important industries in South Africa. They impact extensive land areas, and often compete for the same land. The surface mining of coal seriously damages the surface soil, local flora and fauna. Mining wastes viz. overburden, discards and mine effluents, have also created land degradation problems. Three of the most common factors that characterize degraded substrates are soil acidification, nutrient depletion and loss of biological activity. To ensure a healthy and productive vegetation, disturbed soils need to be ameliorated effectively. Using conventional methods is costly and is often not sustainable. The challenge is, therefore, to use potential alternative ameliorants in an economically, ecologically and socially sustainable manner. Fortunately, South Africa has plenty of industrial and organic by-products, which might be used as alternative ameliorants. There is an enormous amount of international literature on the use of class C fly ash, (Sub bitumious or lignite CCB – [Coal combustion byproduct]), and to a lesser extent class F fly ash (Bitumious CCB), as opposed to South African class F fly ash, which is predominantly produced in this country. Fly ash, either by itself, or together with other wastes such as biosolids, can serve as a soil ameliorant by providing a good source of micro-, macronutrients and organic material for the reclamation of land. Previous research has shown that when sewage sludge is mixed with class F fly ash and a suitable source of reactive lime in a specific ratio, sewage sludge pasteurization will occur. The SLudgeASH (SLASH) mixture has been extensively evaluated as a soil ameliorant and has proven to be viable for the reclamation of poor and marginal soils. This study, has focused on the effect of soil ameliorants on the chemical-, physical- and microbiological properties of degraded agricultural land, mine land and other mining wastes (tailings and discards) requiring rehabilitation. This study also evaluated the affects of class F fly ash and SLASH amelioration of soils and substrates on plant production and revegetation, in comparison with conventional liming and fertilization methods currently in use. Species such as maize (Zea mays) and wheat (Triticum aestivum); pasture legumes such as lucerne or alfalfa (Medicago sativa); sub tropical grasses such as Foxtail Buffalo grass (Cenchrus ciliaris), Rhodegrass (Chloris gayana) and Smutsfinger grass (Digitaria erianthra) have been evaluated. The success of enhanced plant production, re- vegetation and sustainability of once degraded soils / substrates is an indication of the amelioration success achieved. Seed germination, root development, plant yield, plant density, botanical diversity and biological activity are parameters which can all be used to support the conclusion that alternative substrate amendment practices can improve the plant growth medium. Based on the results obtained in this study, it was concluded that fly ash and fly ash/organic material mixtures (SLASH) improved soil chemical properties such as pH, ammonium acetate extractable K, Ca, Mg and Bray 1 extractable P levels. All parameters measured were significantly influenced by the fly ash and SLASH. For example, the pH of soils impacted by acid mine drainage was improved by 240% by the use of SLASH. Other results illustrate improvements in soil physical properties such as texture, bulk density, water infiltration rate and hydraulic conductivity, by class F fly ash based soil ameliorants. In addition to the beneficial effects on soil physical properties, the microbial properties were also improved, as indicated by the beneficiation of symbiotic relationship of the Rhizobium bacteria and the important host plant Medicago sativa. Improvements in crop yields, such as: wheat yields on SLASH and fly ash treatments were 270% and 150% better than the control respectively; yields of maize and alfalfa were improved by 130 % and 450% respectively, were also registered. Fly ash and SLASH ameliorated soils resulted in approximately 850%, 266% and 110% higher dry matter production on gold mine tailings, AMD impacted soil and acidic mine cover soil, respectively, relative to the control treatments. Results also clearly illustrated that the abundance of certain species can be related to the higher fertility levels of the rehabilitated soil. Data collected over the past seven years, illustrates how the botanical composition has changed, and that soils receiving class F fly ash and sewage sludge had a higher dry matter production, whereas the control (no treatment) had a better biodiversity. With respect to the reclamation of coal discard materials, significant increases in yield, of up to 200%, were noted for soils and discards treated with class F fly ash, relative to the untreated control. The pH of cover soil was the most strongly affected soil parameter during the experimental period. Class F fly ash and SLASH have the potential to improve the chemical, physical and microbiological properties of degraded soils and substrates. From this experimental work it can be concluded that class F fly ash from Lethabo definitely has a much higher CaCO3 equivalent than what was originally assumed and that other SA sources probably have an even better neutralizing value. Class F fly ash and SLASH, are good sources of micronutrients and some macro nutrients, and may play a significant role in neutralizing acidity due to their residual alkalinity, and thus ability to continuously change the soil chemical balance so that nutrients become more available for plant uptake and use, thereby enhancing growth. Agricultural, domestic and industrial byproducts unfortunately, vary greatly in nutrient content, trace metals and liming potential, and these factors can affect both re-vegetation success and the environmental impact of reclamation. Co-utilization of by-products can often combine beneficial properties of the individual by-products to eventually have a more pronounced effect on the degraded soil or substrate. / Thesis (PhD(Pasture Science))--University of Pretoria, 2008. / Plant Production and Soil Science / PhD / unrestricted

In this thesis, we deal with the application of transmission terahertz spectroscopy as an analysis tool for the study of molecular solids, in particular organic crystals of pharmaceutical interest. Most of the work has been performed using two computational packages aimed at the interpretation of the spectra, one based on molecular forcefields (DMACRYS), the other on solid state density functional theory (CASTEP). We compare low temperature determinations of several molecular organic crystals to calculated spectra, and attempt to assign calculated modes of vibrations to absorption peaks, based on the similarity in frequency between the measured and calculated peaks. One of the main aims of this work is to establish the limits of our forcefield approach, which is based on the approximation that the intramolecular degrees of freedom can be neglected. We analyse the normal modes of vibration calculated with CASTEP, evaluating the amount of rigid molecule rotational and translational contribution to each eigenvector as a function of frequency, in order to validate our forcefield approach. We also compare the two sets of eigenvectors from the DMACRYS and CASTEP calculations to assess the similarity between the two approaches. We perform the same eigenvectors analysis on several hydrate systems in order to understand the role of water in the lattice dynamics of crystalline hydrates. We attempt a classification of the eigenvectors based on the strength of the forces involved in the molecular vibrations and based on the amount of the water contribution to each normal mode. A set of isostructural crystals is analysed in order to understand the effect that small variations (in the molecular formula and in the unit cell arrangement) have on the measured and calculated absorption spectra of a crystal. Finally, we discuss the use and development of computational methods that allow us to have a more realistic description of the molecular electrostatic in DMACRYS.

A collection of 4,10-chrysene derivatives was prepared via the BHQ (Bull-Hutchings- Quayle) reaction, their electronic and morphological properties analysed and assessed for suitability as organic semiconductor (OSC) materials. Larger polycyclic aromatic hydrocarbons (PAHs) such as benzo[k]tetraphenes and dinaphtho[1,2,-b:1',2'- k]chrysenes were then prepared and similarly characterised. An acene-based OSC material TMTES-pentacene was also prepared. It is proposed that non-linear PAH- based OSC materials may provide an alternative to popular acene-based materials; offering advantages in stability, diversity and handling.

Main objectives of the present dissertation can be divided in two parts. The first part deals with setting up a spectroscopic technique for reliable and accurate measurements of the two-photon absorption (2PA) cross section spectra. In the second part, this firmly established experimental technique together with conventional spectroscopic characterization, quantum-chemical computations and theoretical modelling calculations was combined and therefore used as a tool to gain information for the so-called structure-property relationship through several molecular compounds. / Die Hauptziele der vorliegenden Dissertation lassen sich in zwei Teile gliedern. Der erste Teil befasst sich mit dem Aufbau einer spektroskopischen Technik zur zuverlässigen und genauen Messung der Zwei-Photonen-Absorptionsquerschnittsspektren (2PA). Im zweiten Teil wurde diese fest etablierte experimentelle Technik zusammen mit konventioneller spektroskopischer Charakterisierung, quantenchemischen Berechnungen und theoretischen Modellrechnungen kombiniert und damit als Werkzeug genutzt, um über mehrere molekulare Verbindungen Informationen für die sogenannte Struktur-Eigenschafts-Beziehung zu gewinnen.

Conjugated polymer based electronics, a type of flexible electronic devices, can be produced from solution by traditional printing and coating processes in a roll-to-roll format such as papers and graphic films. This shows great promise for the emerging energy generation and conversion. The device performance of polymer electronics is largely dependent of crystalline structures and morphology of photoactive layers. However, the solution crystallization kinetics of conjugated polymers in the presence of electron acceptor nanoparticles has not been fully understood yet. In this study, solution crystallization kinetics of poly (3-hexylthiophene) in the presence of carbon nanotubes and graphene oxide has been investigated by using UV-visible absorption spectroscopy and transmission electron microscope. Various kinetics parameters such as crystallization temperature, polymer solution concentration and nanoparticle loading will be discussed. The crystallization rate law and fold surface free energy will be addressed by using polymer crystallization theory of heterogeneous nucleation. This fundamental study will provide a foundation of fabricating high efficiency polymer based electronics.