Synthesis of M2AC (M = Ti, V, Cr, Nb, Zr, A = Al, Sn, S) (MAX) carbide phases and study of their physical behavior under extreme conditions

Materials known as Mn+1AXn phases, where n is 1, 2, or 3, and M represents an early transition metal, A an A-group element, and X is either Carbon and/or Nitrogen [1], are fast becoming technologically important materials due to the interesting combination of unique properties. However, a lot of important information about the high temperature and high pressure behavior of many of these compounds is still missing, which needs to be determined systematically. ^ In this dissertation the synthesis of M2AC (M = Ti, V, Cr, Nb, Zr) and A = (Al, Sn, S) compounds by arc melting, vacuum sintering and piston cylinder synthesis is presented along with the synthesis of Zr 2SC, which has been synthesized for first time in bulk form, by piston cylinder technique. The microstructural analysis by electron microscopy and phase analysis by x-ray diffraction is presented next. Finally, a critical analysis of the behavior of these compounds under the application of extreme pressure (as high as 50 GPa) and temperature (≈ 1000°C) is presented. ^ The high pressure studies, up to 50 GPa, showed that these compounds were structurally intact and their bulk moduli ranged from 140 to 190 GPa. The high temperature studies in the inert atmosphere showed that the M 2SnC compounds were unstable above 650°C and the expansion along the a-axis was higher than that along the c-axis, unlike the other phases. M2SC compounds on the other hand showed negligible difference in the thermal expansion along the two axes. The oxidation study revealed that Ti2AC (Al, S) compounds had highest resistance to oxidation while the M2SnC compounds had the least. Furthermore, from the oxidation study of these compounds, which were short time oxidation experiments, it was found that all of these compounds oxidized to their respective binary oxides. ^

Study of the physical properties of metals and oxides at extreme pressure and temperature conditions

The high-pressure and temperature investigations on transition metals, metal doped-oxide system, nanocrystalline materials are presented in this dissertation. The metal-doped oxide systems are technologically important because of their applications, e.g. LSC, opto electronic applications, luminescence from lasers, etc., and from the earth sciences point of view, e.g. the study of trace elements in the MgO-SiO2 system, which accounts for 50% of the Earth's chondritic model. We have carried out thorough investigations on Cr2O3 and on chromium bearing oxides at high PT-conditions using in situ X-ray diffractometry and florescence spectroscopy techniques. Having obtained exciting results, an attempt to focus on the mechanism of the coordination of transition metals in oxides has been made. Additionally, the florescence from the metals in host oxides was found to be helpful to obtain information on structural variations like changes in the coordination of the doped element, formation of new phases, the diffusion processes. The possible reactions taking place at extreme conditions in the MgO-SiO2 system has been observed using florescence as markers. A new heating assemblage has been designed and fabricated for a precise determination of temperature at high pressures. An equation combining pressure shifts of ruby wavelength and temperature has been proposed. We observed that the compressibility of nanocrystalline material (MgO and Ni) is independent of crystallite size. A reduction in the transition pressure of nanocrystalline ceria at high-pressure has been observed as compare to the corresponding bulk material. ^

Design principles of semantic binary database management systems

The Semantic Binary Data Model (SBM) is a viable alternative to the now-dominant relational data model. SBM would be especially advantageous for applications dealing with complex interrelated networks of objects provided that a robust efficient implementation can be achieved. This dissertation presents an implementation design method for SBM, algorithms, and their analytical and empirical evaluation. Our method allows building a robust and flexible database engine with a wider applicability range and improved performance. ^ Extensions to SBM are introduced and an implementation of these extensions is proposed that allows the database engine to efficiently support applications with a predefined set of queries. A New Record data structure is proposed. Trade-offs of employing Fact, Record and Bitmap Data structures for storing information in a semantic database are analyzed. ^ A clustering ID distribution algorithm and an efficient algorithm for object ID encoding are proposed. Mapping to an XML data model is analyzed and a new XML-based XSDL language facilitating interoperability of the system is defined. Solutions to issues associated with making the database engine multi-platform are presented. An improvement to the atomic update algorithm suitable for certain scenarios of database recovery is proposed. ^ Specific guidelines are devised for implementing a robust and well-performing database engine based on the extended Semantic Data Model. ^

The correlation of structure and electronic properties near the surface of transition metal oxides

The strong couplings between different degrees of freedom are believed to be responsible for novel and complex phenomena discovered in transition metal oxides (TMOs). The physical complexity is directly responsible for their tunability. Creating surfaces/interfaces add an additional ' man-made' twist, approaching the quantum phenomena of correlated materials. ^ The dissertation focused on the structural and electronic properties in proximity of surface of three prototype TMO compounds by using three complementary techniques: scanning tunneling microscopy, angle-resolved photoelectron spectroscopy and low energy electron diffraction, particularly emphasized the effects of broken symmetry and imperfections like defects on the coupling between charge and lattice degrees of freedom. ^ Ca1.5Sr0.5RuO4 is a layered ruthenate with square lattice and at the boundary of magnetic/orbital instability in Ca2-xSrxRuO4. That the substitution of Sr 2+ with Ca2+ causing RuO6 rotation narrows the dxy band width and changes the Fermi surface topology. Particularly, the γ(dxy) Fermi surface sheet exhibited hole-like in Ca1.5Sr0.5RuO4 in contrast to electron-like in Sr2RuO4, showing a strong charge-lattice coupling. ^ Na0.75CoO2 is a layered cobaltite with triangular lattice exhibiting extraordinary thermoelectric properties. The well-ordered CoO2-terminated surface with random Na distribution was observed. However, lattice constants of the surface are smaller than that in bulk. The surface density of states (DOS) showed strong temperature dependence. Especially, an unusual shift of the minimum DOS occurs below 230 K, clearly indicating a local charging effect on the surface. ^ Cd2Re2O7 is the first known pyrochlore oxide superconductor (Tc ∼ 1K). It exhibited an unusual second-order phase transition occurring at TS1 = 200 K and a controversial first-order transition at TS2 = 120 K. While bulk properties display large anomalies at TS1 but rather subtle and sample-dependent changes at TS2, the surface DOS near the EF show no change at T s1 but a substantial increase below TS2---a complete reversal as the signature for the transitions. We argued that crystal imperfections, mainly defects, which were considerably enhanced at the surface, resulted in the transition at TS2. ^

Enhanced biocompatibility of Nitinol via surface treatment and alloying

It is projected that by 2020, there will be 138 million Americans over 45, the age at which the increased incidence of heart diseases is documented. Many will require stents. This multi-billion dollar industry, with over 2 million patients worldwide, 15% of whom use Nitinol stents have experienced a decline in sales recently, due in part to thrombosis. It is a sudden blood clot that forms inside stents. As a result, the Food and Drug Administration and American Heart Association are calling for a new generation of stents, new designs and different alloys that are more adaptable to the arteries. The future of Nitinol therefore depends on a better understanding of the mechanisms by which Nitinol surfaces can be rendered stable and inert. In this investigation, binary and ternary Nitinol alloys were prepared and subjected to various surface treatments such as electropolishing (EP), magnetoelectropolishing (MEP) and water boiling & passivation (W&P). In vitro corrosion tests were conducted on Nitinol alloys in accordance with ASTM F 2129-08. The metal ions released into the electrolyte during corrosion tests were measured by Inductively Coupled Plasma Mass Spectroscopy (ICP-MS). Biocompatibility was assessed by observing the growth of human umbilical vein endothelial cells (HUVEC) on the surface of Nitinol alloys. Static and dynamic immersion tests were performed by immersing the Nitinol alloys in cell culture media and measuring the amount of metal ions released in solution. Sulforhodamine B (SRB) assays were performed to elucidate the effect of metal ions on the growth of HUVEC cells. The surfaces of the alloys were studied using Scanning Electron Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS) respectively. Finally, wettability and surface energy were measured by Contact Angle Meter, whereas surface roughness was measured by Atomic Force Microscopy (AFM). All the surface treated alloys exhibited high resistance to corrosion when compared with untreated alloys. SRB assays revealed that Ni and Cu ions exhibited greater toxicity than Cr, Ta and Ti ions on HUVEC cells. EP and MEP alloys possessed relatively smooth surfaces and some were composed of nickel oxides instead of elemental nickel as determined by XPS. MEP exhibited lowest surface energy and lowest surface roughness.

Electro and Magneto-Electropolished Surface Micro-Patterning on Binary and Ternary Nitinol

In this study, an Atomic Force Microscopy (AFM) roughness analysis was performed on non-commercial Nitinol alloys with Electropolished (EP) and Magneto-Electropolished (MEP) surface treatments and commercially available stents by measuring Root-Mean-Square (RMS) , Average Roughness (Ra), and Surface Area (SA) values at various dimensional areas on the alloy surfaces, ranging from (800 x 800 nm) to (115 x 115µm), and (800 x 800 nm) to (40 x 40 µm) on the commercial stents. Results showed that NiTi-Ta 10 wt% with an EP surface treatment yielded the highest overall roughness, while the NiTi-Cu 10 wt% alloy had the lowest roughness when analyzed over (115 x 115 µm). Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) analysis revealed unique surface morphologies for surface treated alloys, as well as an aggregation of ternary elements Cr and Cu at grain boundaries in MEP and EP surface treated alloys, and non-surface treated alloys. Such surface micro-patterning on ternary Nitinol alloys could increase cellular adhesion and accelerate surface endothelialization of endovascular stents, thus reducing the likelihood of in-stent restenosis and provide insight into hemodynamic flow regimes and the corrosion behavior of an implantable device influenced from such surface micro-patterns.

XML storage and retrieval using the semantic binary object -oriented database system (SEM-ODB)

Over the past five years, XML has been embraced by both the research and industrial community due to its promising prospects as a new data representation and exchange format on the Internet. The widespread popularity of XML creates an increasing need to store XML data in persistent storage systems and to enable sophisticated XML queries over the data. The currently available approaches to addressing the XML storage and retrieval issue have the limitations of either being not mature enough (e.g. native approaches) or causing inflexibility, a lot of fragmentation and excessive join operations (e.g. non-native approaches such as the relational database approach). ^ In this dissertation, I studied the issue of storing and retrieving XML data using the Semantic Binary Object-Oriented Database System (Sem-ODB) to leverage the advanced Sem-ODB technology with the emerging XML data model. First, a meta-schema based approach was implemented to address the data model mismatch issue that is inherent in the non-native approaches. The meta-schema based approach captures the meta-data of both Document Type Definitions (DTDs) and Sem-ODB Semantic Schemas, thus enables a dynamic and flexible mapping scheme. Second, a formal framework was presented to ensure precise and concise mappings. In this framework, both schemas and the conversions between them are formally defined and described. Third, after major features of an XML query language, XQuery, were analyzed, a high-level XQuery to Semantic SQL (Sem-SQL) query translation scheme was described. This translation scheme takes advantage of the navigation-oriented query paradigm of the Sem-SQL, thus avoids the excessive join problem of relational approaches. Finally, the modeling capability of the Semantic Binary Object-Oriented Data Model (Sem-ODM) was explored from the perspective of conceptually modeling an XML Schema using a Semantic Schema. ^ It was revealed that the advanced features of the Sem-ODB, such as multi-valued attributes, surrogates, the navigation-oriented query paradigm, among others, are indeed beneficial in coping with the XML storage and retrieval issue using a non-XML approach. Furthermore, extensions to the Sem-ODB to make it work more effectively with XML data were also proposed. ^

UBVRI Photometric Analysis of the Solar-Type Eclipsing Binary TYC 3034-299-1

TYC 3034-0299-1 (CVn) is a magnetically active, contact binary, ROTSE variable. UBVRcIc light curves are presented along with a period study and a simultaneous UBVRI light curve solution. Our light curves show eclipse amplitudes of 0.72 and 0.62 mags (V) in the primary and secondary eclipses. Modeled results include a dark spot region, found at longitude 51°, a 24% Roche lobe fill-out, and a mass ratio of 0.48. A total eclipse is found to occur in the secondary eclipse making TYC 3034-0299-1 a W-type (less massive star is hotter) W UMa variable.

An experimental study of the effects of double-diffusive convention processes during the solification of binary alloys

Experiments were conducted to show the effects of thermal and geometric boundary conditions on the liquid pool of a binary alloy system which is undergoing phase change, solidification. Transparent analogue solutions were selected for study and experimental apparatus were designed and built. Thermal distribution and concentration data were collected and analysed for the melt pool of various selected geometries and boundary conditions of the systems under study. The data indicate-that characteristic flows develop for both Hypereutectic and Hypoeutectic concentration levels and that the development of macrosegregation and microsegregation defects in continuous casting materials can be minimised by the adjustment of the process variables.

Digital signal processing implementation for near real-time wavelet transformation system for binary images

Communication has become an essential function in our civilization. With the increasing demand for communication channels, it is now necessary to find ways to optimize the use of their bandwidth. One way to achieve this is by transforming the information before it is transmitted. This transformation can be performed by several techniques. One of the newest of these techniques is the use of wavelets. Wavelet transformation refers to the act of breaking down a signal into components called details and trends by using small waveforms that have a zero average in the time domain. After this transformation the data can be compressed by discarding the details, transmitting the trends. In the receiving end, the trends are used to reconstruct the image. In this work, the wavelet used for the transformation of an image will be selected from a library of available bases. The accuracy of the reconstruction, after the details are discarded, is dependent on the wavelets chosen from the wavelet basis library. The system developed in this thesis takes a 2-D image and decomposes it using a wavelet bank. A digital signal processor is used to achieve near real-time performance in this transformation task. A contribution of this thesis project is the development of DSP-based test bed for the future development of new real-time wavelet transformation algorithms.

Enhanced Biocompatibility of NiTi (Nitinol) Via Surface Treatment and Alloying

It is projected that by 2020, there will be 138 million Americans over 45, the age at which the increased incidence of heart diseases is documented. Many will require stents. This multi-billion dollar industry, with over 2 million patients worldwide, 15% of whom use Nitinol stents have experienced a decline in sales recently, due in part to thrombosis. It is a sudden blood clot that forms inside stents. As a result, the Food and Drug Administration and American Heart Association are calling for a new generation of stents, new designs and different alloys that are more adaptable to the arteries. The future of Nitinol therefore depends on a better understanding of the mechanisms by which Nitinol surfaces can be rendered stable and inert. In this investigation, binary and ternary Nitinol alloys were prepared and subjected to various surface treatments such as electropolishing (EP), magnetoelectropolishing (MEP) and water boiling & passivation (W&P). In vitro corrosion tests were conducted on Nitinol alloys in accordance with ASTM F 2129-08. The metal ions released into the electrolyte during corrosion tests were measured by Inductively Coupled Plasma Mass Spectroscopy (ICP-MS). Biocompatibility was assessed by observing the growth of human umbilical vein endothelial cells (HUVEC) on the surface of Nitinol alloys. Static and dynamic immersion tests were performed by immersing the Nitinol alloys in cell culture media and measuring the amount of metal ions released in solution. Sulforhodamine B (SRB) assays were performed to elucidate the effect of metal ions on the growth of HUVEC cells. The surfaces of the alloys were studied using Scanning Electron Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS) respectively. Finally, wettability and surface energy were measured by Contact Angle Meter, whereas surface roughness was measured by Atomic Force Microscopy (AFM). All the surface treated alloys exhibited high resistance to corrosion when compared with untreated alloys. SRB assays revealed that Ni and Cu ions exhibited greater toxicity than Cr, Ta and Ti ions on HUVEC cells. EP and MEP alloys possessed relatively smooth surfaces and some were composed of nickel oxides instead of elemental nickel as determined by XPS. MEP exhibited lowest surface energy and lowest surface roughness.