Degree Discipline

Studies in regiospecific oxidation reactions of 1-methyl-pentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione. (open access)

Studies in regiospecific oxidation reactions of 1-methyl-pentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione.

Baeyer-Villiger oxidation of 1-methylpentacyclo[5.4.0.02,6.03,10.05,9] undecane-8,11-dione, performed by using m-chloroperbenzoic acid in 1:1 molar ratio, resulted in the formation of monolactone. The corresponding dilactone, was synthesized by reacting 1-methyl-PCU-8,11-dione with m-chloroperbenzoic acid in 1:2 molar ratio. 6-Methyl-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione was converted into the corresponding exo-6,7-monoepoxide via treatment with 30% aqueous hydrogen peroxide. Epoxidation of this monoepoxide by using m-chloroperbenzoic acid afforded the corresponding bis-epoxide. Ceric ammonium nitrate (CAN) promoted oxidation of 1-methyl-PCU-8,11-dione afforded "methylated lactones" and a "methylated alkene."
Date: May 2004
Creator: Vappala, Indu
System: The UNT Digital Library
Investigation of Structure and Properties of Low Temperature Deposited Diamond-Like Carbon Films (open access)

Investigation of Structure and Properties of Low Temperature Deposited Diamond-Like Carbon Films

Electrodeposition is a novel method for fabrication of diamond-like carbon (DLC) films on metal substrates. In this work, DLC was electrochemically deposited on different substrates based on an anodic oxidation cyclization of acetylene in liquid ammonia. Successfully anodic deposition was carried out for DLC onto nickel substrate at temperatures below -40°C. Comparative studies were performed on a series of different carbon sources (acetylene, sodium acetylide, and a mixture of acetylene and sodium acetylide). The films were characterized using a variety of methods including Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), XPS valence band spectra, and/or scanning electron microscopy (SEM). Raman spectroscopy is used as a bench mark technique to verify the presence of deposited DLC films, to access the films homogeneities, and to provide the ratio of the different carbon phases, mainly disordered graphite (D) and graphite (G) phases in the films. A combination of the Raman with FTIR and valence band spectra analysis allowed the distinction between hydrogenated DLC and unhydrogenated DLC films. Three different kinds of DLC [(1) hydrogenated DLC (a-C:H); (2) tetrahedral hydrogenated DLC (ta-C:H); and (3) graphitic-like DLC] were deposited depending upon the deposition conditions and substrates. Temperature and current density are …
Date: August 2004
Creator: Pingsuthiwong, Charoendee
System: The UNT Digital Library
Improvement of Homogeneity and Adhesion of Diamond-Like Carbon Films on Copper Substrates (open access)

Improvement of Homogeneity and Adhesion of Diamond-Like Carbon Films on Copper Substrates

Electrodeposition method is used to deposit diamond-like carbon (DLC) films on copper substrates via anodic oxidation at low temperature. These films are characterized using Raman spectroscopy, Fourier transform infrared spectroscopy and scanning electron microscopy. Homogeneity of these films is studied using Raman spectroscopy and scanning electron microscopy. Scotch tape peel tests indicate adherent film on copper substrate. Carbon phase transformation is studied using thermal annealing experiments in conjunction with Raman spectroscopy and scanning electron microscopy. A cathodic electrochemical method is also studied to deposit diamond-like carbon films on copper substrates. However, films deposited by the cathodic route have poor adhesion and quality compared to anodically deposited films. It is also possible to grow diamond phase on copper substrates using acetylene in liquid ammonia via electrodeposition route. An electrochemical method is proposed for boron doping into DLC films.
Date: August 2004
Creator: Vavilala, Suma
System: The UNT Digital Library
Thermodynamics of Mobile Order Theory: Solubility and Partition Aspects (open access)

Thermodynamics of Mobile Order Theory: Solubility and Partition Aspects

The purpose of this thesis is to analyze the thermochemical properties of solutes in nonelectrolyte pure solvents and to develop mathematical expressions with the ability to describe and predict solution behavior using mobile order theory. Solubilities of pesticides (monuron, diuron, and hexachlorobenzene), polycyclic aromatic hydrocarbons (biphenyl, acenaphthene, and phenanthrene), and the organometallic ferrocene were studied in a wide array of solvents. Mobile order theory predictive equations were derived and percent average absolute deviations between experimental and calculated mole fraction solubilities for each solute were as follows: monuron in 21 non-alcoholic solvents (48.4%), diuron in 28 non-alcoholic solvents (60.1%), hexachlorobenzene (210%), biphenyl (13.0%), acenaphthene (37.8%), phenanthrene (41.3%), and ferrocene (107.8%). Solute descriptors using the Abraham solvation model were also calculated for monuron and diuron. Coefficients in the general solvation equation were known for all the solvents and solute descriptors calculated using multilinear regression techniques.
Date: August 2004
Creator: De Fina, Karina M.
System: The UNT Digital Library