PITTING MECHANISM OF MILD STEEL IN MARGINALLY SOUR ENVIRONMENTS: PIT PROPAGATION BASED ON ACIDIFICATION BY CATALYTIC OXIDATION OF DISSOLVED HYDROGEN SULFIDE

The present work studies pit propagation in marginally sour environments and proposes a credible mechanism. Both thermodynamic calculation and experimental measurement confirmed that H2S can be oxidized by traces of dissolved O2 into SO42- and H+ in the aqueous solutions near room temperature with the transitional metal ions serving as a catalyst. This acidification phenomenon would be more effective near the steel surface, especially inside a pit, where Fe2+ ions are most abundant. Therefore, the saturation degree of mackinawite would be lower inside the pit, which would prohibit the pitting from annihilation.

Development of a fiber optic sensor for hydrogen monitoring in transformers

<p>Electric vehicles and photovoltaic power generation are two of factors that are increasing the demands on the electrical grid. To cope with these challenges and to improve grid stability, the development of a transformer monitoring system as a fundamental part of the smart grid is necessary. Dissolved hydrogen in the transformer oil can serve as a primary indicator of the transformer health. Depending on the hydrogen concentration and rate of increase the transformer can be diagnosed. The goal of this thesis was to develop a highly sensitive hydrogen sensor for online health monitoring of transformers. The developed sensors are based on palladium and fiber Bragg gratings (FBG). Palladium expands with hydrogen absorption and this expansion is measured with an FBG. Detailed guidance for optimizing the sensor design is given. First, the selection of the working temperature is discussed. Second, the influence of the palladium geometry on the sensitivity is elaborated: by varying the cross-sectional area ratio of palladium to fiber the sensitivity can be tuned. Two different options to attach palladium are discussed: vapour deposition of palladium and adhesive bonding of palladium foils. The sensitivity of the palladium foil sensors was improved by improved manufacturing processes. The foil sensor have a sensitivity of up to 295 pm/% hydrogen and a resolution of 0.006% hydrogen in gas atmosphere at 90◦C and 1060 mbar. To further increase the hydrogen sensitivity two concepts for amplification of the signal are presented. One relies on palladium silver foils, which have an increased hydrogen solubility and therefore expansion compared to pure palladium, which achieved an increase in sensitivity of a factor of 17. This leads to sensitivity of over 4500 pm/% hydrogen, which is the most sensitive hydrogen sensor reported so far. The other concept relies on a novel concept for strain concentration using a pre-strained palladium foil and FBG, which achieved an amplification of a factor of 2.5. The sensors were characterised in gas and oil environment in a newly developed setup which is stable in pressure, temperature and gas concentration. In gas the sensors were tested at 60, 75, 90, 105, and 120◦C and for a hydrogen concentration range of 0.01 (100 ppm) to 5%. In oil the sensor was tested at 90◦C and for a hydrogen concentration range of 5- 4000 ppm dissolved hydrogen. Furthermore, the influence of carbon monoxide (CO) on the hydrogen sensitivity was examined. A slowed response could be observed, but CO had no impact on the precision of the sensor. Finally, the hydrogen calibration of the sensor is discussed by investigating the strain transfer between expanding palladium and fiber. Three different methods are elaborated to determine the coefficient of strain transfer: (a) via hydrogen measurement, (b) via temperature measurement, and (c) via strain measurement. Methods (a) and (b) were applied directly on the hydrogen sensor, and gave similar results. Method (c) was applied on a reference structure and used to verify method (b). A hydrogen sensor suitable for transformer health monitoring has been developed and characterised, and is currently being implemented in a transformer in the New Zealand network.</p>

Development of a fiber optic sensor for hydrogen monitoring in transformers

<p>Electric vehicles and photovoltaic power generation are two of factors that are increasing the demands on the electrical grid. To cope with these challenges and to improve grid stability, the development of a transformer monitoring system as a fundamental part of the smart grid is necessary. Dissolved hydrogen in the transformer oil can serve as a primary indicator of the transformer health. Depending on the hydrogen concentration and rate of increase the transformer can be diagnosed. The goal of this thesis was to develop a highly sensitive hydrogen sensor for online health monitoring of transformers. The developed sensors are based on palladium and fiber Bragg gratings (FBG). Palladium expands with hydrogen absorption and this expansion is measured with an FBG. Detailed guidance for optimizing the sensor design is given. First, the selection of the working temperature is discussed. Second, the influence of the palladium geometry on the sensitivity is elaborated: by varying the cross-sectional area ratio of palladium to fiber the sensitivity can be tuned. Two different options to attach palladium are discussed: vapour deposition of palladium and adhesive bonding of palladium foils. The sensitivity of the palladium foil sensors was improved by improved manufacturing processes. The foil sensor have a sensitivity of up to 295 pm/% hydrogen and a resolution of 0.006% hydrogen in gas atmosphere at 90◦C and 1060 mbar. To further increase the hydrogen sensitivity two concepts for amplification of the signal are presented. One relies on palladium silver foils, which have an increased hydrogen solubility and therefore expansion compared to pure palladium, which achieved an increase in sensitivity of a factor of 17. This leads to sensitivity of over 4500 pm/% hydrogen, which is the most sensitive hydrogen sensor reported so far. The other concept relies on a novel concept for strain concentration using a pre-strained palladium foil and FBG, which achieved an amplification of a factor of 2.5. The sensors were characterised in gas and oil environment in a newly developed setup which is stable in pressure, temperature and gas concentration. In gas the sensors were tested at 60, 75, 90, 105, and 120◦C and for a hydrogen concentration range of 0.01 (100 ppm) to 5%. In oil the sensor was tested at 90◦C and for a hydrogen concentration range of 5- 4000 ppm dissolved hydrogen. Furthermore, the influence of carbon monoxide (CO) on the hydrogen sensitivity was examined. A slowed response could be observed, but CO had no impact on the precision of the sensor. Finally, the hydrogen calibration of the sensor is discussed by investigating the strain transfer between expanding palladium and fiber. Three different methods are elaborated to determine the coefficient of strain transfer: (a) via hydrogen measurement, (b) via temperature measurement, and (c) via strain measurement. Methods (a) and (b) were applied directly on the hydrogen sensor, and gave similar results. Method (c) was applied on a reference structure and used to verify method (b). A hydrogen sensor suitable for transformer health monitoring has been developed and characterised, and is currently being implemented in a transformer in the New Zealand network.</p>

Hydrogen Nanobubble Water Delays Petal Senescence and Prolongs the Vase Life of Cut Carnation (Dianthus caryophyllus L.) Flowers

The short vase life of cut flowers limits their commercial value. To ameliorate this practical problem, this study investigated the effect of hydrogen nanobubble water (HNW) on delaying senescence of cut carnation flowers (Dianthus caryophyllus L.). It was observed that HNW had properties of higher concentration and residence time for the dissolved hydrogen gas in comparison with conventional hydrogen-rich water (HRW). Meanwhile, application of 5% HNW significantly prolonged the vase life of cut carnation flowers compared with distilled water, other doses of HNW (including 1%, 10%, and 50%), and 10% HRW, which corresponded with the alleviation of fresh weight and water content loss, increased electrolyte leakage, oxidative damage, and cell death in petals. Further study showed that the increasing trend with respect to the activities of nucleases (including DNase and RNase) and protease during vase life period was inhibited by 5% HNW. The results indicated that HNW delayed petal senescence of cut carnation flowers through reducing reactive oxygen species accumulation and initial activities of senescence-associated enzymes. These findings may provide a basic framework for the application of HNW for postharvest preservation of agricultural products.

Effect of Gas Bubbling Filtration Treatment Conditions on Melt Quality of AlSiMgCu Alloy

In this study, the optimal conditions of gas bubbling filtration (GBF) treatment for securing highly-clean molten Al-Si-Mg-Cu alloy were identified. The effects of GBF treatment time and stabilization time on the degree of molten metal cleanliness were examined by measuring melt quality parameters such as density index, bifilm index, porosity, and the amount of dissolved hydrogen [H]. A high melt quality was achieved when GBF treatment was performed on 10 kg melt for more than 10 min (i.e., 1 L gas/kg melt). However, as the stabilization holding time after GBF treatment increased to 10, 20, and 30 min, the melt quality degraded. GBF treatment for 30 min had a similar effect to treatment for 10 min, and the degree of deterioration of melt quality during the stabilization time was also similar. Considering the economics, 10 min GBF treatment and short holding time are required. Observations of the shape and volume of the largest pore suggested the cause of defect formation and confirmed that the volume of the largest pore can be used as an index of the melt quality.

Effect of hydrogen on the electrical resistance of NbSe2 in a wide temperature range

The electrical resistivity of niobium diselenide (NbSe2) with hydrogen was investigated in the temperature range Tc – 300 K. It was determined that hydrogen inhibits the formation of a charge density wave. It was shown that hydride phase with niobium is formed due to hydrogen in NbSe2 layers at low temperatures, which decomposes with increasing temperature to form a solid solution. The temperature dependence of the resistivity is approximated by the Bloch–Grüneisen function. The approximation parameters vary depending on the amount of dissolved hydrogen.