Die Diphthalocyanine der Seltenerdmetalle werden durch Reaktion von Seltenerdmetallacetat mit o-Phthalsaeuredinitril hergestellt. Die Diphthalocyanine existieren in zwei Formen, die sich in der Existenz eines delokalisierten freien Elektrons (Radikalform) oder eines ¨zusaetzlichen¨ Wasserstoffatoms unterscheiden. Die Charakterisierung der beiden Diphthalocyaninformen erfolgt mittels der IR-Spektroskopie und UV/VIS/NIR-Spektroskopie. Detailliert wird das spektroskopische Verhalten der Diphthalocyanine in unterschiedlichen Loesungsmitteln untersucht. ESR-spektroskopisch ist das freie Elektron der Radikalform nachweisbar. Zur Untersuchung des elektrochromen Verhaltens der Diphthalocyanine werden Schichten durch Sublimationsverfahren oder durch LB-Technik hergestellt. Die Analyse der Schichtstruktur erfolgt mittels HRTEM. Das elektrochrome Verhalten wird unter Beruecksichtigung des Schichtherstellungsverfahrens, der Diphthalocyaninform und der Art des verwendeten Elektrolyten untersucht. Die beobachteten Farbaenderungen reichen von violett, blau, gruen, blass-gelb, orange nach rot. Die entsprechenden UV/VIS-Spektren werden im Zusammenhang mit den ablaufenden Oxidations- und Reduktionsreaktionen diskutiert.

In der vorliegenden Arbeit wird die Synthese chromophorer Xerogele des Typs II auf Grundlage nucleophiler aromatischer Substitutionsreaktionen von Fluorarenen mit aminofunktionalisierten Trialkoxysilanen in Tetraethoxysilan als Lösungsmittel beschrieben. Die Herstellung von anorganisch-organischen Sol-Gel-Hybridmaterialien gelingt dabei in einer Eintopfreaktion. Neben kommerziell erhältlichen Fluoraromaten, wie z.B. 4-Fluornitrobenzen, wurden fluorfunktionalisierte Azomethine, Diazoverbindungen und Diphenylaminderivate eingesetzt. Die Synthese und Charakterisierung literaturunbekannter Fluoraromaten wird beschrieben. Besonderes Augenmerk lag auf der Reproduzierbarkeit der Xerogelsynthesen und der Charakterisierung der Xerogele durch Methoden der Festkörper-NMR- und UV/Vis-Spektroskopie sowie der Elektronenmikroskopie.

In den vergangenen Jahren löste die Nachfrage nach hochwertigen organischen Werkstoffen die Suche nach neuen Materialien mit maßgeschneiderten Eigenschaften für mögliche technische An-wendungen aus. In der vorliegenden Arbeit wurde ein Ansatz entwickelt, neue organische Materia-lien zu synthetisieren, wobei die Untersuchung der Copolimerisation von o-Phenylendiamin (OPD) mit o-Toluidin (OT) und m-Toluidin (MT) in wässriger Schwefelsäure im Vordergrund stand. Da-bei fand die zyklische Voltammetrie sowohl bei der elektrochemischen Synthese als auch für die Charakterisierung der Homo- und Copolymere auf einer Goldelektrode Anwendung. Die Copoly-mere wurden aus gemischten Monomerlösungen synthetisiert, die unterschiedliche OPD-Konzentrationen sowie eine konstante OT- oder MT-Konzentration aufwiesen. Die Voltammogr- amme zeigten ein unterschiedliches Verhalten für die verschiedenen OPD-Konzentrationen bei der Zugabe. Die Mischung der Monomerlösungen mit geeigneten Konzentrationen ergab ein Copolym- er mit einem großen potenziell nutzbaren Bereich der Redoxaktivität relativ zu den korrespondiere- nden Homocopolymeren. Die Homopolymere Poly-o-toluidin (POT) und Poly-m-toluidin (PMT) zeigten ähnliche elektrochemische Eigenschaften. Es wurden jedoch Unterschiede in den Eigensch- aften zwischen den OT- und MT-Copolymeren mit OPD beobachtet, die möglicherweise auf eine Abweichung in den Monomereinheiten und der Ausrichtung entlang der Copolymerkette zurückzu- führen sind. Die Copolymerisation der OPD wird offenbar gefördert, wenn OT statt MT als einer der Comonomere verwendet wird. Weiterhin wurde der Einfluss der Vorschubgeschwindigkeit (dE/dt) und des pH-Wertes auf die elektrochemische Aktivität untersucht. Die Copolymere waren oberflächengebunden, elektrisch aktiv und zeigten sogar bei einem pH-Wert = 8,0 bei Poly(OPT-co-MT) bzw. 9,0 bei Poly(OPT-co-OT) eine gute elektrochemische Aktivität. Die Messungen der in situ Leitfähigkeit unterstützte die Herausbildung eines neuen Stoffes (Copolymer), da die Copo-lymere Elektrodenpotenzialbereiche für eine maximale Leitfähigkeit besitzen, die sich völlig von jenen der Homopolymere unterscheiden. Die Leitfähigkeitswerte der Copolymere lagen zwischen den Werten der Homopolymere. Die in situ UV-Vis spektroelektrochemischen Untersuchungen der Copolymerisation von OPD mit OT und MT bei konstanter potenzieller Polymerisation auf mit Indiumzinnoxid (ITO) be-schichteten Glaselektroden zeigten, dass ein Kopf-Schwanz-verknüpfter p-Aminodiphenylamin (PPD)-Typ eines gemischten Dimers/Oligomers, der wahrscheinlich aus der Dimerisation der Kati-onenradikalen von OPD und OT oder MT resultiert, vorwiegend zu Beginn der Elektropolyme- risation der Mischlösungen entsteht. Ein Absorptionspeak bei λ = 497 nm in den UV-Vis-Spektren wurde diesen Zwischenprodukten zugeordnet. Es erfolgte eine Identifizierung der charakteristi-schen UV-Vis- und Raman- (λ = 647,1 nm) Eigenschaften der Copolymere, synthetisiert mit ver-schiedenen Zugabekonzentrationen auf ITO-beschichtetem Glas bzw. auf Goldelektroden, sowie eine Diskussion ihrer Abhängigkeit vom Elektrodenpotenzial. Die spektroelektrochemischen Er-gebnisse zeigten, dass die Hauptkette des Copolymers wahrscheinlich aus einer Mischung aus Co-polymerketten mit unterschiedlichen Monomergehalten und einer signifikanten Anzahl an Block-segmenten besteht. Die Eigenschaften der Copolymere erwiesen sich als sehr sensibel gegenüber der OPD Zugabekonzentration, so dass eindeutige Änderungen in den elektrochemischen und spektroelektrochemischen Eigenschaften der Stoffe aus Mischlösungen durch bloße Variierung der OPD-Konzentration bei der Zugabe beobachtet werden konnten. Die FT-IR-Spektralanalyse der Copolymere deutet auf die Anwesenheit von sowohl OPD- als auch OT- oder MT-Einheiten und daher auf die Copolymerbildung während der Elektrolyse der Misch-lösungen aus OPD und OT oder MT hin. Die zyklischen Strukturen des Phenazintyps erhöhen sich im Copolymer mit steigender OPD-Konzentration bei der Zugabe. / In recent years the demand for advanced organic materials has sparked the search for new materials with tailored properties for possible technological applications. In the present study an attempt has been made to synthesize new organic conducting materials by exploring the possibility of the copolymerisation of o-phenylenediamine (OPD) with o-toluidine (OT) and m-toluidine (MT) in aqueous sulfuric acid. Cyclic voltammetry was used both for the electrochemical synthesis and characterization of the homopolymers and copolymers on a gold electrode. The copolymers were synthesized from mixed solutions of the monomers having different concentrations of OPD and a constant concentration of OT or MT. The voltammograms exhibited different behavior for different concentrations of OPD in the feed. Mixing of the monomer solutions with appropriate concentrations resulted in a copolymer that shows an extended useful potential range of the redox activity relative to the corresponding homopolymers. The homopolymers poly(o-toluidine) (POT) and poly(m-toluidine) (PMT) show similar electrochemical properties. However, differences were observed in the properties between the copolymers of OT and MT with OPD that could be due to the variation in the monomer units and orientation along the copolymer chains. The copolymerization of OPD seems to be more facilitated if instead of MT, OT is present as one of the comonomers. The effect of scan rate and pH on the electrochemical activity was studied. The copolymers were surface confined, electroactive and showed good electrochemical activity even at pH 8.0 and pH 9.0 in case of poly(OPD-co-MT) and poly(OPD-co-OT), respectively. In situ conductivity measurements further suggest the formation of new material (copolymer) because the copolymers have electrode potential regions for maximum conductivity completely different from those of the homopolymers. The conductivity values of the copolymers were between the conductivities of the homopolymers. In situ UV-Vis spectroelectrochemical studies of the copolymerization of OPD with OT and MT at constant potential polymerization on indium tin oxide (ITO) coated glass electrodes reveal that head to tail coupled p-aminodiphenylamine (PPD) type of mixed dimers/oligomers, presumably resulting from the dimerization of OPD and OT or MT cation radicals, are predominantly formed during the initial stages of the electropolymerization of the mixed solutions. An absorption peak at λ = 497 nm in the UV-Vis spectra was assigned to these intermediates. Characteristic UV-Vis and Raman (λex = 647.1 nm) fea-tures of the copolymers synthesized with different feed concentrations on ITO coated glass and gold electrodes, respectively, have been identified and their dependencies on the electrode potential are discussed. Spectroelectrochemical results reveal that the copolymer backbone probably consist of a mixture of copolymer chains with different monomer contents and has significant number of block segments. The properties of the copolymers were found to be very sensitive to the OPD feed concentration and clear variations in the electrochemical and spectroelectrochemical properties of the materials from mixed solutions can be observed just by varying the concentration of OPD in the feed. FT-IR spectral analysis of the copolymers suggests the presence of both OPD and OT or MT units and thus formation of copolymer during the electrolysis of mixed solutions of OPD and OT or MT. The phenazine type cyclic structures increase in the copolymer with increasing OPD concentration in the feed.

This dissertation describes the electrochemical synthesis of conducting polypyrrole (PPy), poly(N-methylpyrrole) (PNMPy), poly(3-methylpyrrole) (P3MPy), poly(pyrrole-2,6-dimethyl-β-cyclodextrin) P(Py-β-DMCD), poly(N-methylpyrrole-2,6-dimethyl-β-cyclodextrin) P(NMPy-β-DMCD) and poly(3-methylpyrrole-2,6-dimethyl-β-cyclodextrin) P(3MPy-β-DMCD) films by electrode potential cycling on a gold electrode in aqueous and nonaqueous (acetonitrile) electrolyte solutions containing lithium perchlorate. The resulting products were characterized by cyclic voltammetry, in situ UV-Vis spectroscopy, ex situ FT-IR spectroscopy, in situ surface enhanced Raman scattering (SERS) and in situ resistance measurements. For electrosynthesis of polymers in the presence of cyclodextrin, a (1:1) (mole-mole) compounds (host-guest-complex) of β-DMCD with Py, NMPy and 3MPy, respectively; previously characterized with proton NMR spectroscopy was used as starting material. Different cyclic voltammetric behavior was observed for polymers in aqueous and nonaqueous solutions during electrosynthesis. The results show that in nonaqueous solutions the oxidation potential of Py, NMPy and 3MPy monomers increases in the presence of cyclodextrin. The same results were observed for P(Py-β-DMCD) and P(NMPy-β-DMCD) in aqueous solution. The slight shift of the oxidation peak for polymers in the presence of cyclodextrin (CD) compared to polymers in absence of CD may be a result of the hydrophobic monomer partly or entirely included in the CD hydrophobic interior cavity. In situ resistance measurements of the PPy and PNMPy show that films prepared in acetonitrile solution have less resistance than those synthesized in aqueous solutions. Meanwhile, the results show that the resistance of the polymer increased in the following order PPy < P3MPy < PNMPy and P(Py-β-DMCD) < P(3MPy-β-DMCD) < P(NMPy-β-DMCD). The FT-IR spectroscopy was used to identify the polymers and to find evidence for the presence of the CD in the material. The spectra suggests no CD incorporation in the P(Py-β-DMCD) and P(NMPy-β-DMCD) films. In situ UV-Vis spectroscopy and in situ SERS measurements for the study of the structure and properties of electronically conducting PPy, PNMPy, P3MPy, P(Py-β-DMCD), P(NMPy-β-DMCD) and P(3MPy-β-DMCD) were carried out in two different media. The in situ SERS spectra of polymers deposited on the roughened gold substrate with ORC (oxidation-reduction cycle) pre-treatment indicated both a marked increase in intensity and a better resolution. / Diese Dissertation beschreibt die elektrochemische Synthese von leitfähigem Polypyrrol (PPy), Poly-N-Methylpyrrol (PNMPy), Poly(3-Methylpyrrol) (P3MPy), Poly(Pyrrol-2,6-dimethyl-β-cyclodextrin) P(Py-β-DMCD), Poly(N-Methylpyrrol-2,6-dimethyl-β-cyclodextrin) P(NMPy-β-DMCD) und Poly(3-Methylpyrrol-2,6-dimethyl-β-cyclodextrin) P(3MPy-β-DMCD) auf einer Goldelektrode durch Potentialzyklen in wässrigen und nichtwässrigen (Acetonitril) Elektrolytlösungen mit Lithiumperchlorat als Leitsalz. Die erhaltenen Stoffe wurden mit zyklischer Voltammetrie, in situ UV-Vis-Spektroskopie, ex situ FT-IR Spektroskopie, in situ oberflächen verstärkter Ramanspektroskopie (SERS) und in situ Widerstandmessungen charakterisiert. Für die Elektrosynthese der Polymere in Gegenwart von Cyclodextrin wurden 1:1 (Molverhältnis) Verbindungen (Wirt-Gast-Komplex) von β-DMCD mit Py, NMPy und 3MPy resp., charakterisiert mit Proton-NMR-Spektroskopie, als Ausgangsmaterial eingesetzt. Die zyklischen Voltammogramme ergaben unterschiedliches Verhalten der Polymere in wässrigen und nichtwässrigen Lösungen während der Elektrosynthese. Die Ergebnisse zeigen, dass sich in nichtwässrigen Lösungen das Oxidationspotenzial von Py, NMPy und 3MPy-Monomeren bei Anwesenheit von Cyclodextrin erhöht. Dieselben Resultate ergaben sich für P(Py-β-DMCD) und P(NMPy-β-DMCD) in wässriger Lösung. Die leichte Verschiebung des Oxidationspeaks der Polymere bei Anwesenheit von Cyclodextrin (CD) verglichen mit den Polymeren bei Abwesenheit von CD könnte das Resultat der teilweise oder vollständig im hydrophoben Hohlraum der CD eingeschlossenen hydrophoben Monomere sein. In situ Leitfähigkeitsmessungen von PPy und PNMPy zeigen, dass Filme, die in Acetonitrillösungen hergestellt wurden besser leitfähig sind als die Filme, die in wässrigen Lösungen hergestellt wurden. Die Ergebnisse zeigen, dass der Widerstand der Polymere in der folgenden Reihenfolge steigt: PPy < P3MPy < PNMPy and P(Py-β-DMCD) < P(3MPy-β-DMCD) < P(NMPy-β-DMCD). Die FT-IR-Spektroskopie wurde verwendet die Polymere zu identifizieren und die Anwesenheit der CD in das Material. Die Spektren schlägt vor, keine CD-Aufnahme in den P (Py-β-DMCD) und P (NMPy-β-DMCD) Filme. In situ UV-Vis- und in situ SERS-Messungen zur Untersuchung der Struktur und der Eigenschaften der elektronisch leitfähigen PPy, PNMPy, P3MPy, P(Py-β-DMCD), P(NMPy-β-DMCD) and P(3MPy-β-DMCD) wurden in 2 verschiedenen Medien durchgeführt. Die in situ SERS-Spektren der Polymere, abgeschieden auf aufgerauhter Goldoberfläche und Substrat durch ORC (Oxidations-Reduktions-Zyklus) –Vorbehandlung zeigten sowohl eine deutliche Erhöhung der Intensität als auch eine bessere Auflösung.

The growing bacterial resistance against antibiotics creates a limitation for using traditional antibiotics and requests development of new approaches for treatment of bacterial infections. Among the bacterial infections that are most difficult to treat, biofilm-associated infections are one of the most hazardous. Consequently, the prevention of biofilm formation is a very important issue. One of the techniques that are widely investigated nowadays for this purpose is surface modification by polymer brushes that allows generating antifouling antibacterial surfaces. Previously, it was reported that salicylidene acylhydrazides (hydrazones) are good candidates as antivirulence drugs targeting the type three secretion system (T3SS). This secretion system is used by several Gramnegative pathogens, including Pseudomonas aeruginosa, to deliver toxins into a host cell. Furthermore, the chemical structure of these substances allows formation of complexes with metal ions, such as Fe3+ and Ga3+. The antibacterial activity of Ga3+ is well known and attributed to its similarity to the Fe3+ ion. It has also been shown that Ga3+ ions are able to suppress biofilm formation and growth in bacteria. In this thesis the chemistry of antibacterial and antivirulence Ga3+-Hydrazone complexes in solution was studied. First, to get insights in the solution chemistry, the protonation and the stability constants as well as the speciation of the Ga3+-Hydrazone complexes were determined. Additionally, a procedure for anchoring one of the hydrazone substances to antifouling polymer brushes was optimized, and the resulting surfaces were characterized. Results showed that the complexation with Ga3+ ions stabilizes the ligand and increases its solubility. Ga3+ ion binds to the hydrazone molecule forming a strong chelate that should be stable at physiological conditions. The different biological assays, such as Ga3+ uptake, antivirulence and antibiofilm effects, indicated very complex interaction of these complexes with the bacterial cell. Negatively charged and zwitterionic surfaces strongly reduced protein adsorption as well as biofilm formation. Therefore, the antifouling zwitterionic poly-[2-(methacryloyloxy)ethyl]dimethyl-3- sulfopropyl)-ammonium hydroxide (pMEDSAH) brushes were post-modified and successfully functionalized with bioactive substances via a block-copolymerization strategy. However, in order to maintain the availability of the bioactive substance after functionalization, the hydrophobic polyglycidylmethacrylate (pGMA) top block is probably better to functionalize with a lipophilic molecules to reduce diblock copolymer brush rearrangement.

We cool and study trans-Stilbene, Nile Red and Benzonitrile in a cryogenic (7K) cell filled with low density helium buffer gas. No molecule-helium cluster formation is observed, indicating limited atom-molecule sticking in this system. We place an upper limit of 5% on the population of clustered He-trans-Stilbene, consistent with a measured He-molecule collisional residence time of less than \(1 \mu s\). With several low energy torsional modes, trans-Stilbene is less rigid than any molecule previously buffer gas cooled into the Kelvin regime. We report cooling and gas phase visible spectroscopy of Nile Red, a much larger molecule. Our data suggest that buffer gas cooling will be feasible for a variety of small biological molecules. The same cell is also ideal for studying collisional relaxation cross sections. Measurements of Benzonitrile vibrational state decay results in determination of the vibrational relaxation cross sections of \(\sigma_{22} = 8x10^{-15} cm^2\) and \(\sigma_{21} = 6x10^{-15} cm^2\) for the 22 (v=1) and 21 (v=1) states. For the first time, we directly observe formation of cold molecular dimers in a cryogenic buffer gas cell and determine the dimer formation cross section to be \(\sim10^{-13} cm^2\). / Physics

In this study, polyelectrolyte membranes were prepared by layer-by-layer self-assembly on top of an interfacially polymerized polyamide substrate, and these thin-film-composite membranes were studied for pervaporative dehydration of ethylene glycol, ethanol and isopropanol. The performance of composite membranes based on polyethylenimine/poly(acrylic acid) (PEI/PAA) multilayers on a polyamide substrate showed good selectivity and stability for ethylene glycol dehydration. In order to understand the formation process of the polyelectrolyte multilayers, the growth of polyelectrolyte multilayers fabricated on the inner surface of cuvette was investiagted. The membrane surface became increasingly hydrophilic with an increase in the number of polyelectrolyte double layers, which favored water permeation for pervaporative dehydration of organic solvents. Water contact angle on the membrane surface decreased from 68?? to 20?? when 7 polyelectrolyte bilayers were deposited on the polyamide substrate. Although the (PEI/PAA) based polyelectrolyte membranes showed good performance for dehydration of ethylene glycol, these membranes did not perform well for the dehydration of ethanol and isopropanol at relatively high feed alcohol concentrations. This was found to be caused by insufficient stability of PEI/PAA bilayers and the polyamide substrate in the ethanol and isopropanol. To improve the performance of the composite membranes for dehydration of ethanol and isopropanol, the outermost surface layer was deposited with PEI, followed by crosslinking. A further improvement in the membrane selectivity was accomplished by substituting the PEI with partially protonated chitosan in the last few polyelectrolyte bilayers during membrane fabrication. It was demonstrated that using interfacially polymerized polyamide membrane as a substrate, polyelectrolyte membranes with less than 8 bilayers could be fabricated for the dehydration of alcohol and diol. This represents a siginificant advancement as a large number of polyelectrolyte bilayers (as many as 60) are often needed. Glutaraldehyde crosslinked polyelectrolyte self-assembled membranes comprising of chitosan and PAA were also prepared for isopropanol/water separation. The resulting membrane showed stable performance with good permeation flux and separation factor. The effects of crosslinking conditions (e.g., concentration and temperature of crosslinking agent, and crosslinking time) on the membrane performance were studied. Alternatively, using PEI as polycation, when anionic PAA was substituted with alginate in the last few polyelectrolyte bilayers during membrane fabrication, stable membranes with a good performance were obtained without the need of chemical crosslinking. The polyethylenimine/alginate self-assembly membranes showed good selectivity and stability for dehydration of ethanol. For instance, a permeation flux of 0.24 kg/(??? h) and a separation factor of 206 were obtained at room temperature at 10 wt% feed water concentration with a membrane comprising of 10 double layers of polyelectrolytes.

Techn. Universiẗat, Diss., 2006--Darmstadt.

Reactivators of acetylcholinesterase inhibited by organophosphate inhibitors play an important role in organophosphate poisoning therapy. There are a large number of reactivators being tested for their ability of penetration through blood-brain barrier (BBB) nowadays. The main aim of this thesis is to test this ability in four well know reactivators {--} HI-6, K-027, K-074 and TO-032. The 5% lethal dose (LD50) {--} therapeutic dose - of each reactivator was i.m. (intramuscularly) applied to experimental animals (Wistar rats) into right posterior thighs. Then the animals were sacrificed and the blood (plasma) and brain were collected for HPLC analysis. Subsequently, brain and plasma were frozen at -80 °C and stored until the assay. The reactivator concentrations were measured in plasma and four parts of the brain {--} frontal cortex (FC), basal ganglia (BG), ponto-medullar part (PM) and cerebellum (Ce). There were five animals for each group used for the purpose of the experiment. The concentrations of reactivators in plasma and blood samples were measured using HPLC-UV/VIS methodology. HI-6 concentrations CFC were on the average 4.29% of Caverage in plasma, CBG were on the average 1.9% of Caverage in plasma, CPM were on the average 2.3% of Caverage in plasma, and CCe were on the average 1.85% of Caverage in plasma. These rates were counted from all concentrations within the scope of particular observed parts of the brain. All the other tested reactivators were not quantified in brain at all.

Extensive research has been performed on the interaction of dithiocarbonates (xanthate) with a wide variety of substrates. This study the focuses on the interaction of trithiocarbonates (TTC) with pyrite and copper. The mechanism of adsorption of the xanthate is compared to that of the TTC. For the xanthate to adsorb it is necessary for an oxidant to be present, since xanthate adsorbs via charge transfer processes (electrochemical processes). It was found by the use of cyclic voltammetry and contact angle measurements that collector adsorption of the TTC can occur in both oxidising and reducing (thus the absence of an oxidant) conditions. Neither the TTC monomer nor the dimer could be detected on the surface by the use of Raman spectroscopy. The collector species on the surface was the TTC decomposition products namely the thiol or thiolate. Electrochemical impedance spectroscopy (EIS) confirmed that the TTC can interact under oxidising and reducing conditions. EIS showed that the rate of adsorption of the collector species for anodic currents increases relatively to the rate of adsorption for cathodic currents. Different adsorption mechanisms are realised for the different polarisation conditions. It is postulated that the TTC species serves as an intermediate for the adsorption of the thiol or thiolate on the surface, ultimately rendering the surface hydrophobic. Decomposition tests, performed by employing UV/Vis spectroscopy, indicated that the TTC is very unstable between a pH of 4 and 11. The thiol or thiolate however does not readily adsorb onto the substrates (indicated by the EIS measurements). Microflotation tests confirmed the thiolate’s inability to render pyrite hydrophobic. The microflotation tests also indicated that the TTC became less effective in recovering pyrite after it was left to decompose for a couple of hours. / Dissertation (MSc (Metallurgy))--University of Pretoria, 2008. / Materials Science and Metallurgical Engineering / unrestricted