87 research outputs found

    Doctor of Philosophy

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    dissertationUnconventional resources (shale resources) have played a key role in increasing oil production in the past decade in the U.S. The sizes of pores in shales storing the oil are believed to be on the order of nanometers. It is believed that the fluids present in such small nanometer-scale pores have different properties compared to properties measured in the bulk. Fluid bubble points at given temperatures in the nano-sized pores are affected by the influence of pore walls in the vicinity of the fluid molecules. Bubble points affect the proportion of liquid or gas extracted from a given well and, thus, impact the economic viability of oil production. Hence, an accurate measure of a bubble point is important. Most studies on phase behavior of confined fluid systems have focused on modeling pore size dependence upon critical properties with no direct experimental evidence. In this work, direct bubble point measurements of hydrocarbon mixtures in several porous materials are provided. Two different synthesized mesoporous silica materials, SBA-15 and SBA-16, having nano-sized pores of about 4 nm, were used. Mesoporous monoliths with only nano-sized pores and no macro pores were also synthesized using a unique procedure developed in this study. Finally, to see the industrial application of this work, the Niobrara rock which is from one of the famous shale reservoirs in the U.S. was used. These porous materials were characterized well by X-ray diffraction (XRD), nitrogen adsorption/desorption isotherm (BET), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). Binary mixtures of hydrocarbons (decane-methane, octane-methane) with 90:10 mole ratio were employed. The phase diagrams of those hydrocarbon mixtures were modeled using a commercial thermodynamic simulator. The bubble point of bulk (no porous medium) mixtures of decane-methane and octane-methane, and the bubble point with porous materials (SBA-15, SBA-16, and mesoporous monoliths) were measured experimentally. Experiments were also performed with micrometer-sized sand particles and the Niobrara rock. The bubble point results of the hydrocarbon mixtures in the porous materials and the Niobrara rock were lower than those in the bulk, while the bubble points with sand were closer to those with bulk measurements. Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA) results showed that the boiling points of pure decane and decane saturated in the monolith were different, possibly due to the confinement effect. This study shows the phase behavior of hydrocarbons in a confined system is different from that in the bulk system

    Tail-robust factor modelling of vector and tensor time series in high dimensions

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    We study the problem of factor modelling vector- and tensor-valued time series in the presence of heavy tails in the data, which produce anomalous observations with non-negligible probability. For this, we propose to combine a two-step procedure with data truncation, which is easy to implement and does not require iteratively searching for a numerical solution. Departing away from the light-tail assumptions often adopted in the time series factor modelling literature, we derive the theoretical properties of the proposed estimators while only assuming the existence of the (2 + 2\eps)-th moment for some \eps \in (0, 1), fully characterising the effect of heavy tails on the rates of estimation as well as the level of truncation. Numerical experiments on simulated datasets demonstrate the good performance of the proposed estimator, which is further supported by applications to two macroeconomic datasets

    High-dimensional time series segmentation via factor-adjusted vector autoregressive modelling

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    Vector autoregressive (VAR) models are popularly adopted for modelling high-dimensional time series, and their piecewise extensions allow for structural changes in the data. In VAR modelling, the number of parameters grow quadratically with the dimensionality which necessitates the sparsity assumption in high dimensions. However, it is debatable whether such an assumption is adequate for handling datasets exhibiting strong serial and cross-sectional correlations. We propose a piecewise stationary time series model that simultaneously allows for strong correlations as well as structural changes, where pervasive serial and cross-sectional correlations are accounted for by a time-varying factor structure, and any remaining idiosyncratic dependence between the variables is handled by a piecewise stationary VAR model. We propose an accompanying two-stage data segmentation methodology which fully addresses the challenges arising from the latency of the component processes. Its consistency in estimating both the total number and the locations of the change points in the latent components, is established under conditions considerably more general than those in the existing literature. We demonstrate the competitive performance of the proposed methodology on simulated datasets and an application to US blue chip stocks data

    Current Trends in Korean Adolescents’ Social Purpose

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    In the research presented we investigated the features of Korean adolescents’ social purpose as compared with other life goals in terms of different aspects of psychological well-being (study 1). We also examine the perceptions of high achieving Korean adolescents on social purpose and factors affecting it (study 2).The results of study 1 showed that the pursuit of social purpose significantly predicted psychological well-being compared to the other two life goals. Results of study 2 showed Korean adolescents value and pursue social purpose as a life goal. They explicitly accepted their social responsibility to serve their country in line with idyllic Confucianism values and Collectivistic roles. However, further analysis revealed that they had implicitly pursued individualistic desires of materialistic wealth and fame in parallel with their explicit social purpose. Implications of the results are discussed from the socio-cultural perspective on social purpose in regards to how to understand the features of social purpose that Korean adolescents have and how to foster its development

    Ga-doped Pt-Ni Octahedral Nanoparticles as a Highly Active and Durable Electrocatalyst for Oxygen Reduction Reaction

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    Bimetallic PtNi nanoparticles have been considered as a promising electrocatalyst for oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells (PEMFCs) owing to their high catalytic activity. However, under typical fuel cell operating conditions, Ni atoms easily dissolve into the electrolyte, resulting in degradation of the catalyst and the membrane-electrode assembly (MEA). Here, we report gallium-doped PtNi octahedral nanoparticles on a carbon support (Ga-PtNi/C). The Ga-PtNi/C shows high ORR activity, marking an 11.7-fold improvement in the mass activity (1.24 A mgPt-1) and a 17.3-fold improvement in the specific activity (2.53 mA cm-2) compare to the commercial Pt/C (0.106 A mgPt-1 and 0.146 mA cm-2). Density functional theory calculations demonstrate that addition of Ga to octahedral PtNi can cause an increase in the oxygen intermediate binding energy, leading to the enhanced catalytic activity toward ORR. In a voltage-cycling test, the Ga-PtNi/C exhibits superior stability to PtNi/C and the commercial Pt/C, maintaining the initial Ni concentration and octahedral shape of the nanoparticles. Single cell using the Ga-PtNi/C exhibits higher initial performance and durability than those using the PtNi/C and the commercial Pt/C. The majority of the Ga-PtNi nanoparticles well maintain the octahedral shape without agglomeration after the single cell durability test (30,000 cycles). This work demonstrates that the octahedral Ga-PtNi/C can be utilized as a highly active and durable ORR catalyst in practical fuel cell applications

    Ga-doped Pt-Ni Octahedral Nanoparticles as a Highly Active and Durable Electrocatalyst for Oxygen Reduction Reaction

    Get PDF
    Bimetallic PtNi nanoparticles have been considered as a promising electrocatalyst for oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells (PEMFCs) owing to their high catalytic activity. However, under typical fuel cell operating conditions, Ni atoms easily dissolve into the electrolyte, resulting in degradation of the catalyst and the membrane-electrode assembly (MEA). Here, we report gallium-doped PtNi octahedral nanoparticles on a carbon support (Ga-PtNi/C). The Ga-PtNi/C shows high ORR activity, marking an 11.7-fold improvement in the mass activity (1.24 A mgPt-1) and a 17.3-fold improvement in the specific activity (2.53 mA cm-2) compare to the commercial Pt/C (0.106 A mgPt-1 and 0.146 mA cm-2). Density functional theory calculations demonstrate that addition of Ga to octahedral PtNi can cause an increase in the oxygen intermediate binding energy, leading to the enhanced catalytic activity toward ORR. In a voltage-cycling test, the Ga-PtNi/C exhibits superior stability to PtNi/C and the commercial Pt/C, maintaining the initial Ni concentration and octahedral shape of the nanoparticles. Single cell using the Ga-PtNi/C exhibits higher initial performance and durability than those using the PtNi/C and the commercial Pt/C. The majority of the Ga-PtNi nanoparticles well maintain the octahedral shape without agglomeration after the single cell durability test (30,000 cycles). This work demonstrates that the octahedral Ga-PtNi/C can be utilized as a highly active and durable ORR catalyst in practical fuel cell applications

    Is it necessary to delay antiviral therapy for 3-6 months to anticipate HBeAg seroconversion in patients with HBeAg-positive chronic hepatitis B in endemic areas of HBV genotype C?

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    Background/AimsSpontaneous HBeAg seroconversion occurs frequently in the immune reactive phase in HBeAg-positive chronic hepatitis B (CHB). Therefore, observation for 3-6 months before commencing antiviral therapy is recommended in patients with alanine aminotransferase (ALT) levels that exceed twice the upper limit of normal (ULN). However, HBeAg seroconversion occurs infrequently in patients infected with hepatitis B virus (HBV) genotype C. The aim of the present study was to determine whether the waiting policy is necessary in endemic areas of HBV genotype C infection.MethodsNinety patients with HBeAg-positive CHB were followed prospectively without administering antiviral therapy for 6 months. Antiviral therapy was initiated promptly at any time if there was any evidence of biochemical (i.e., acute exacerbation of HBV infection or aggravation of jaundice) or symptomatic deterioration. After 6 months of observation, antiviral therapy was initiated according to the patient's ALT and HBV DNA levels.ResultsOnly one patient (1.1%) achieved spontaneous HBeAg seroconversion. Biochemical and symptomatic deterioration occurred before 6 months in 17 patients (18.9%) and 5 patients, respectively. High ALT and HBV DNA levels were both independent risk factors for biochemical deterioration. Of 15 patients with HBV DNA ≥5.1×107 IU/mL and ALT ≥5×ULN, biochemical deterioration occurred in 7 (46.7%), including 1 patient receiving liver transplantation due to liver failure.ConclusionsSpontaneous HBeAg seroconversion in patients with HBeAg-positive CHB is rare within 6 months. Biochemical deterioration was common and may lead to liver failure. Immediate antiviral therapy should be considered, especially in patients with high ALT and HBV DNA levels in endemic areas of genotype C infection

    Effect of Pertussis Toxin and Herbimycin A on Proteinase-Activated Receptor 2-Mediated Cyclooxygenase 2 Expression in Helicobacter pylori-Infected Gastric Epithelial AGS Cells

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    Helicobacter pylori (H. pylori) is an important risk factor for chronic gastritis, peptic ulcer, and gastric cancer. Proteinase-activated receptor 2 (PAR2), subgroup of G-protein coupled receptor family, is highly expressed in gastric cancer, and chronic expression of cyclooxygenase-2 (COX-2) plays an important role in H. pylori-associated gastric carcinogenesis and inflammation. We previously demonstrated that H. pylori induced the expression of PAR2 and COX-2 in gastric epithelial cells. Present study aims to investigate whether COX-2 expression induced by H. pylori in Korean isolates is mediated by PAR2 via activation of Gi protein and Src kinase in gastric epithelial AGS cells. Results showed that H. pylori-induced COX-2 expression was inhibited in the cells transfected with antisense oligonucleotide for PAR2 or treated with Gi protein blocker pertussis toxin, Src kinase inhibitor herbimycin A and soybean trypsin inbitor, indicating that COX-2 expression is mediated by PAR2 through activation of Gi protein and Src kinase in gastric epithelial cells infected with H. pylori in Korean isolates. Thus, targeting the activation of PAR2 may be beneficial for prevention or treatment of gastric inflammation and carcinogenesis associated with H. pylori infection
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