Five well-known Zr-based alloys of the systems Zr–Cu–Al–(Ni–Nb, Ni–Ti, Ag) (Cu 5 15.4–36 at.%) with the highest glass-forming ability were comparatively analyzed regarding their pitting corrosion resistance and repassivation ability in a chloride-containing solution. Potentiodynamic polarization measurements were conducted in the neutral 0.01 M Na₂SO₄ 1 0.1 M NaCl electrolyte and local corrosion damages were subsequently investigated with high resolution scanning electron microscopy (HR-SEM) coupled with energy dispersive x-ray spectroscopy (EDX). Both pitting and repassivation potential correlate with the Cu concentration, i.e., those potentials decrease with increasing Cu content. Pit morphology is not composition dependent: while initially hemispherical pits then develop an irregular shape and a porous rim. Corrosion products are rich in Cu, O, and often Cl species. A combination of low Cu and high Nb or Ti contents is most beneficial for a high pitting resistance of Zr-based bulk metallic glasses. The bulk glassy Zr₅₇Cu₁₅.₄Al₁₀Ni₁₂.₆Nb₅ (Vit 106) and Zr₅₂.₅Cu₁₇.₉Al₁₀Ni₁₄.₆Ti₅ (Vit 105) alloys exhibit the highest pitting resistance.

Nowdays biofuels are becoming a good alternative for petroleum fuels due to environmental issues like high carbon dioxide emission and increasing vehicles population, together with the high price and fast depletion of petroleum oils. This project aims to investigate the corrosive effects of wood Pyrolysis oil on a special grade of nitrogen alloyed tooling steels to be used for injector nozzles in Diesel engines, where high stress and strain encounter high acidity and corrosivity of the Pyrolysis oil and cause breakdown over short periods. Vanax 35 and Vanax 75 manufactured in Uddeholm are two types of powder metallurgy high nitrogen alloyed martensitic stainless steel with a high combination of hardness (over 56HRC), low friction properties, wear resistance, anti-galling and corrosion properties. In this work, the newly developed Vanax material together with the tool steels Elmax and AISI O1 were tempered at various temperatures from 200°Cto 500°C. The tempered steels were then exposed in pyrolysis oil at 4 different temperatures, 20°C, 70°C, 95°Cand 130°C. The materials were investigated by means of corrosion rate measurements, microscopy (LOM, SEM, confocal) and Thermo-Calc calculations. The corrosion rate measurement proved that Vanax tempered at lower ranges (200°C, 400°Cand 450°C) showed the best corrosion resistance while higher tempering temperatures such as 500°C, Elmax and AISI O1 tempered at 200°Csuffered a great deal of general corrosion attack. Thermo-Calc calculations showed the formation of a hard phase, VN as primary nitrides instead of primary chromium carbides at austenizing temperature for the Vanax group. Higher amount of chromium is dissolved in solid solution in Vanax at austenizing temperature hence the martensite matrix has, after quenching, a higher chromium content that helps passivation. The loss in corrosion properties at higher tempering temperatures was due to the formation of CrN secondary phase at around 400˚C which reduces the chromium content of the martensite matrix. The results of light optical and confocal microscopy showed the presence of pits when tempering at 400˚C and 450˚C. No pits were observed at 200˚C. Elmax was not passivated at all which resulted in general corrosion attacks, due to a high chromium loss from the austenite solid solution at the austenizing procedure temperature and also the tempering temperatures. The chromium depletion from the austenite can be explained by a high carbon and a low nitrogen content in the composition which resulted in formation of a high amount of Cr7C3.

Ph.D. (Agriculture)) -- University of Limpopo, 2021 / The rind physiological disorders incidence such as rind pitting is a challenge to the citrus industry as it affects appearance; and ultimately, acceptability and purchase in both local and international markets. Although the internal quality is not directly affected by rind pitting, fruit damaged by this disorder are rejected in the fresh fruit market. The susceptibility to this disorder varies among citrus fruit cultivars. Other factors impacting rind physiological disorders include; pre-harvest environmental conditions and postharvest storage conditions. However, the main cause of this disorder is still unknown. In South Africa, ‘Benny’ valencias are the most prone orange cultivars to rind pitting disorder within the sweet-orange-type. Therefore, the aim of this study was to investigate production site and postharvest treatments’ effect on physico-chemical, biochemical properties, antioxidants, rind soluble sugars and gene expression in relation to rind pitting development of ‘Benny’ valencia citrus fruit. During 2016 and 2017 seasons, the study was conducted, whereby, ‘Benny’ valencia citrus fruit were harvested from Tzaneen, Groblersdal and Musina in South Africa. After harvesting, the fruits were transported to the Agricultural Research Council- Tropical and Subtropical Crops (ARC-TSC) postharvest laboratory in Nelspruit for sorting, grading treatment, cold storage and post-storage quality evaluation. After sorting and grading, fruits were subjected to the following treatments: T1 = no wax plus dehydration, T2 = wax plus dehydration and T3 = wax plus no dehydration. Dehydrated treatments were applied for 3 days at relative humidity of ±45%, thereafter, fruit were stored at -0.6 and 4.5°C for 28 days plus 7 days shelf-life. After removal from cold storage plus 7 days shelf-life, fruit were analysed for rind pitting incidence (RPI), weight loss percentage (WL), firmness, total electrolyte leakage (TEL), total soluble solids (TSS), titratable acidity (TA) and TSS: TA ratio. xxvi Afterwards, fruit were peeled to remove flavedo, thereafter; the flavedo peels were freeze-dried, milled and stored at -21°C for further physiological analysis. Freeze dried flavedo peel was analysed for total flavonoids, total phenolics, vitamin C, soluble sugars (glucose, fructose and sucrose), antioxidant assays (FRAP, DPPH, ABST and ORAC) and genes. The results showed that rind pitting incidence was high on fruit subjected to wax plus no dehydration across all storage temperatures and production sites. Furthermore, results showed that fruit harvested from Musina exposed to T1 had higher incidence of rind pitting than those from Groblersdal and Tzaneen, irrespective of storage temperature. Meanwhile, fruit harvested from Musina had the highest TEL when compared with Groblersdal and Tzaneen irrespective of treatments and storage temperatures. A significantly higher (P<0.05) WL was observed in Musina fruit harvested from Tzaneen exposed to T3 at both storage temperatures. Moreover, increased TSS was observed after storage across all production site and postharvest treatments. The study showed that production site and postharvest treatments had a significant influence on rind pitting and total electrolyte leakage. Additionally, fruit treated with no wax + dehydration was found to be more susceptible to rind pitting. However, fruit sourced from Tzaneen had significantly (P<0.0001) high TPC and TFC, irrespective of postharvest treatments therefore, low rind pitting incidence. While rind vitamin C was higher in fruit from Groblersdal when compared with Tzaneen and Musina. However, low RPI was also observed in fruit sourced from Groblersdal. Fruit from Musina subjected to wax plus dehydration had higher RSA and low RPI at both temperatures when compared with fruit sourced from Groblersdal and Tzaneen. Therefore, wax plus dehydration resulted in low rind pitting with an increased accumulation of rind biochemical concentrations, xxvii irrespective of cold storage temperatures. These results suggested that there is a link between rind pitting and rind biochemical concentrations in the ‘Benny’ valencia citrus fruit. Moreover, fruit from Musina subjected to wax plus dehydration had higher antioxidant measured by DPPH and low RPI at both low storage temperatures when compared with fruit harvested from Groblersdal and Tzaneen. Furthermore, fruit harvested from Musina and treated with no wax plus dehydration, thereafter, stored at -0.6°C had low RPI with high antioxidant activity measured by FRAP than Tzaneen and Groblersdal regions in both seasons. With respect to sugars, fructose was not significantly (P<0.05) affected by production sites, postharvest treatments and cold storage temperature, hence, the low pitting incidence. The highest glucose was observed in fruit harvested from Groblersdal, irrespective of treatments and cold storage temperatures when compared with those from Tzaneen and Musina, low RPI was also observed in fruit harvested from Groblersdal. However, fruit harvested from Groblersdal treated with wax plus dehydration and stored at 4.5°C had higher sucrose and low RPI when compared with Tzaneen and Musina. Moreover, this study suggested that soluble sugars in ‘Benny’ valencia flavedo during cold storage is involved in rind pitting tolerance mediated by wax plus dehydration treatment. Three homologic genes: CsCP gene; CsNAC-domain protein gene; CsCP-F gene; were chosen to examine the relationship between their expression and citrus rind pitting through quantitative RT-PCR analysis in pitting and no-pitting fruits. Results showed that the expression of CsCP, CsNAC and CsCP-F genes were all higher in the pitting rind fruit harvested from Tzaneen and low in fruit with low pitting. Groblersdal and Musina fruit had low expression of genes and low rind pitting was observed. Therefore, findings suggested that CsCP, CsNAC and CsCP-F genes may xxviii be linked to non-chilling rind pitting and could serve as targets for future investigation. Generally, the overall results obtained in this study provided an understanding into the previous unknown complexities of citrus non-chilling rind pitting. Moreover, the study revealed that the studied factors had an influence on non-chilling rind pitting and physico-chemical properties of ‘Benny’ valencia citrus fruit. In addition, postharvest treatments resulted in low non-chilling rind pitting with an increased accumulation of rind biochemical concentrations. The fruit with high antioxidant capacity were found to be tolerant to rind pitting, whereas, fruit with low antioxidant capacity were found to be susceptible to rind pitting. Furthermore, soluble sugars are believed to be involved in the defence mechanisms against non-chilling rind pitting in the fruit. Gene expression changes also provided clues about the possible mechanisms involved in non-chilling rind pitting development. / National Research Fund, Agricultural Research Council Tropical and Subtropical Fruit Crops and Citrus Academy

M. Tech. (Department of Metallurgical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / To meet the ever-increasing demand for maintenance of gear systems, industrial companies have traditionally depended on the shutdown of the machines before processing the fault diagnosis. Nowadays, online monitoring has proven to be effective in terms of machine state analysis and fault prediction. However, the application of such a technique in the analysis of combined multiple nonlinear faults is still a subject of research. The vibration signature of a coexisting nonlinear crack and pit in two-stage gear system is unknown, it can be regarded as one of the most difficult problems to extract and diagnose. Additionally, incorporating both a crack and a pit into numerical models is a time-consuming process that demands a breadth of mechanical understanding. Diagnostics of faulty gears, on the other hand, can be performed in the time and frequency domain or in the Time-Frequency domain, depending on the complexity of the vibration. Non-linear and non-stationary phenomena (Features) occur when repeated pitting and cracking faults occur, reducing the reliability of standard signal processing methods (Gear displacement and Fast Fourier Transform). This thesis solves each of these shortcomings by developing an eight-degree-of-freedom (DOF) gear model with a breathing crack and multiple pitted gear teeth. The identified spur-gear model enabled the investigation of the crack and pitting signatures and their effect on the ensuing vibrations independently of the action of other system components. Additionally, when pitting and cracking coexist, the study was conducted to determine the influence of such a failure on the transmission system. Theoretical results indicated that the presence of pitting and crack in the tooth of the gear resulted in a decrease in mesh stiffness. Additionally, the influence of the breathing pitting and crack results in material fatigue, which results in the generation of a random term in the vibration signal. To corroborate the acquired results, several experimental tests on a spur-gear test rig with a defined pit and crack size range were undertaken under a variety of conditions. In comparison to the presented methodologies, theoretical and experimental results indicate that 3D Frequency-RPM analysis is the most sensitive and resilient method for the early detection and identification of pit and crack faults. Furthermore, when crack or pit faults are studied individually, the STFT analysis yields interesting results. The feature analysis revealed that, when using the Time-Frequency technique, the crack and pit combination in a two-stage gear system is a priori more efficient than the other options.

[pt] Os aços inoxidáveis duplex (AID) possuem microestrutura com o balanço de fase aproximadamente iguais de ferrita (delta) e austenita (gama). A exposição desses materiais a elevadas temperaturas, em torno de 1000 graus C e 1100 graus C resultam em mudanças microestruturais significativas. Mudanças essas que podem variar desde a fração volumétrica das fases presentes, composição química, até precipitação de fases intermetálicas e relações de orientação presentes no material. Dependendo da fração volumétrica e morfologia das fases, haverá diferentes respostas a um determinado meio corrosivo, dentre eles o clorídrico. A composição química do material pode influenciar na formação das fases intermetálicas. E o empobrecimento local de determinados elementos influenciam no processo de repassivação do material. Em condições práticas de soldagem e tratamento térmico algumas propriedades microestruturais do material podem ficar sujeitas a alterações, dentre elas a resistência à corrosão por pites. Os materiais estudados no presente trabalho foram os AID UNS S32304 (lean Duplex) e o UNS S32750 (super duplex), ambos submetidos a tratamentos térmicos a 1000 graus C e 1100 graus C por 24 h seguidos de têmpera em água, os mesmos passaram por ensaio de corrosão segundo a norma ASTM G48-A. A presente dissertação utiliza como método de estudo a caracterização microestrutural através da técnica de microscopia eletrônica de varredura por meio da difração de elétrons retroespalhados (MEV/EBSD), para determinação das relações de orientação Kurdjumov-Sachs (K-S) e Nishiyama-Wassermann (N-W), correlacionando-as com o efeito do tratamento térmico nos aços estudados. Foi realizada a determinação da fração volumétrica das fases em função da temperatura de tratamento térmico. Foi identificada através da espectroscopia de energia dispersiva de raios-X a influência da composição química no material para iniciação da corrosão. A microscopia óptica foi realizada para análise da evolução morfológica e identificação das fases principais e intermetálicas. Foi verificada a precipitação da fase Sigma (sigma) no UNS S32750, e a constatação que os pites iniciaram na interface austenita secundária e sigma. Através da técnica de MEV/EBSD utilizando de uma análise qualitativa e semi-quantitativa verificou-se que o pite tem como local preferencial de iniciação junções triplas e/ou múltiplas de contorno de grão quando o PREN (Pitting Resistance Equivalent Number) das fases austenita e ferrita são próximos. Entretanto para grande variação no valor do PREN entre austenita e ferrita alguns pites iniciaram na fase com menor valor de PREN. / [en] Duplex stainless steels (DSS) have microstructure with approximately equal phase balance of ferrite (delta) and austenite (gamma). Exposure of these materials to high temperatures around 1000 degrees C and 1100 degrees C results in significant microstructural changes. These changes can vary from the volume fraction of the phases present, chemical composition, to precipitation of intermetallic phases and orientation relationship present in the material. Depending on the volume fraction and phase morphology, there will be different responses to a particular corrosive environment, including hydrochloric. The chemical composition of the material can influence the formation of the intermetallic phases. And the local impoverishment of certain elements influences the process of repassivation of the material. Under practical conditions of welding and heat treatment, some microstructural properties of the material may be subject to changes, including resistance to pitting corrosion. The materials studied in the present work were UNS S32304 (lean Duplex) and UNS S32750 (super duplex), both subjected to heat treatments at 1000 degrees C and 1100 degrees C for 24 h followed by quenching in water, the same underwent corrosion testing according to the ASTM G48-A standard. The present dissertation uses as a method of study the microstructural characterization through the technique of Scanning Electron Microscopy by means of electron backscattered diffraction (SEM/EBSD) to determine the Kurdjumov-Sachs (KS) and Nishiyama-Wassermann (NW) orientation relationships, correlating them with the effect of heat treatment on the studied steels. The determination of the volumetric fraction of the phases as a function of the heat treatment temperature was carried out. It was identified through energy dispersive spectroscopy X-ray the influence of the chemical composition on the material for corrosion initiation. light optical microscopy was performed to analyze the morphological evolution and identify the main and intermetallic phases. It was verified the precipitation of the Sigma phase (sigma) in UNS S32750, and the verification that the pits started at the secondary austenite and σ interface. Through the SEM/EBSD using a qualitative and semi-quantitative analysis, it was found that the pit has as its preferred initiation site triple and/or multiple grain boundary junctions when the PREN (Pitting Resistance Equivalent Number) of the austenite and ferrite phases are close. However, due to the large variation in the PREN value between austenite and ferrite, some pits started in the phase with the lowest PREN value.

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