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Synthesis and characterization of molecules to study the conformational barriers of fluorocarbon chains (open access)

Synthesis and characterization of molecules to study the conformational barriers of fluorocarbon chains

Fluorocarbons are known to be stiffer than their hydrocarbon analogues, a property that underlines the extensive industrial application of fluorocarbon materials. Although there has been previous studies on the rotational barrier of molecules having fluorocarbon centers, a detailed systematic study is necessary to quantify flurocarbon stiffness. The molecules, Pyrene-(CF2)n-Pyrene, Pyrene-(CF2)n-F, Pyrene-(CH2)n-Pyrene and Pyrene-(CH2)n-H were therefore synthesized to enable the determination of the barrier to rotation of the carbon backbone in fluorocarbons. Conformational studies will be completed with steady-state and time-dependent emission spectroscopy.
Date: May 2000
Creator: Niyogi, Sandip
System: The UNT Digital Library
The Performance of Silicon Based Sensor and its Application in Silver Toxicity Studies (open access)

The Performance of Silicon Based Sensor and its Application in Silver Toxicity Studies

The silicon based sensor is able to detect part per trillion ionic silver in 0.0098% hydrofluoric acid based on the open circuit potential (OCP) measurement. The OCP jump of 100 ppt ionic silver solution is up to 120 mV. The complex agent can effectively suppress the ionic silver concentration and suppress the OCP signal. The ability of complex agent to suppress the OCP signal depends on the formation constant of the complex with silver. The complex adsorbed on the sensor surface induces a second OCP jump, the height of the second jump depends on the formation constant of the complex. The MINEQL chemical equilibrium modeling program is used to calculate the ionic silver concentration when complex agent presents, a discrepancy is found between the MINEQL simulation result and the OCP signal of the silicon based sensor. The toxicity of ionic silver to C. dubia is studied parallel to the OCP signal of silicon based sensor. Less toxicity is found when the complex agent is present similar to the OCP signal. Another discrepancy is found between the MINEQL simulation and the toxicity test when MINEQL simulation is used to predict and control the ionic silver concentration. The data from both biosensor …
Date: August 2000
Creator: Peng, Haiqing
System: The UNT Digital Library
Synthesis and characterization of molecules for electron transfer research. (open access)

Synthesis and characterization of molecules for electron transfer research.

Dimethoxynaphthalene (donor) and quinone (acceptor) have been chosen as a suitable redox pair and are bonded to either permethylated silane chains or corresponding permethylated alkyl chains to form Acceptor-(Bridge)-Donor molecules. The idea that the s-delocalization phenomenon of silane chains may greatly facilitate ET reactions will be tested. The starting material for the donor precursor, 4-(1,4-dimethoxynaphthyl)bromocyclohexane, was 1,4-naphthoquinone. After methylation and bromination, the Grignard reagent of the resulting bromide was reacted with cyclohexanedione, mono ethylene ketal. The resulting alcohol was changed to the donor precursor through the following functional group transformation steps: dehydration, hydrogenation, deketalization and bromination. 1,4-Dibenzyloxybromobenzene, the precursor for the acceptor, was synthesized from 1,4-hydroquinone through bromination and benzylation. The connection of the two precursors and either permethylated silane chains or permethylated alkyl chains will give the final target molecules for ET research. Progress on this is included.
Date: December 2000
Creator: Xiao, Wu
System: The UNT Digital Library
Substitution chemistry of the cobalt complexes RCCo3(CO)9 (R = H, CHO) with the diphosphine ligand: 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd). Syntheses, X-ray structures and reactivity. (open access)

Substitution chemistry of the cobalt complexes RCCo3(CO)9 (R = H, CHO) with the diphosphine ligand: 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd). Syntheses, X-ray structures and reactivity.

The reaction between the tetrahedrane cluster RCCo3(CO)9{R = CHO (1), H (3)} and the redox-active diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3- dione (bpcd) leads to the replacement of two CO groups and formation of RCCo3(CO)7(bpcd) {R = CHO (2), H (4)}. Clusters 2 and 4 are thermally unstable and readily transform into the new P-C bond cleavage cluster 5. All three clusters 2, 4, and 5 have been isolated and fully characterized in solution by IR and 31P NMR spectroscopy. VT 31P NMR data indicate that the bpcd ligand in RCCo3(CO)7(bpcd) is fluxional at 187 K in THF. Clusters 2, 4, and 5 have been structurally characterized by X-ray diffraction analyses.
Date: December 2001
Creator: Liu, Jie
System: The UNT Digital Library
NMR study of 2-ethylhexyllithium aggregate and 2- ethylhexyllithium/lithium 2-ethyl-1-hexoxide mixed aggregates. (open access)

NMR study of 2-ethylhexyllithium aggregate and 2- ethylhexyllithium/lithium 2-ethyl-1-hexoxide mixed aggregates.

A 1H, 13C, and 6Li NMR study of 2-ethylhexyllithium showed that 2- ethylhexyllithium exists solely as a hexamer in cyclopentane solution over the temperature range from 25 to -65 °C. Furthermore, 2-ethylhexyllithium and lithium 2- ethyl-1-hexoxide were shown to form mixed aggregates when the alkoxide was formed in situ by reacting 2-ethylhexyllithium with 2-ethyl-1-hexanol. A multinuclear, variable temperature NMR study of a sample with an O:Li ratio of 0.2 led to the identification of at least four such aggregates, one of which was found to be a hexamer with the composition R5(RO)Li6. Studies of samples with higher O:Li ratios, up to 0.8, showed additional mixed aggregates present. All solutions containing mixed aggregates were also shown to contain hydrocarbon soluble lithium hydride. A study of lithium 2-ethyl-1- hexoxide indicated that it aggregates in solution as well.
Date: December 2001
Creator: Petros, Robby A.
System: The UNT Digital Library
The preparation and characterization of thermo-sensitive colored hydrogel film and surfactant-free porous polystyrene three-dimensional network. (open access)

The preparation and characterization of thermo-sensitive colored hydrogel film and surfactant-free porous polystyrene three-dimensional network.

Polymer hydrogel films change their properties in response to environmental change. This remarkable phenomenon results in many potential applications of polymer hydrogel films. In this thesis colored thermo-sensitive poly(N-isopropylacrylamide) (PNIPAAm) hydrogel film was prepared by firstly synthesizing polymer latex and secondarily crosslinking the nanoparticles and casting the polymers onto glass. The shape-memory effect has been observed when changing the environmental temperature. The temperature-dependent of turbidity of polymer hydrogel film was measured by HP UVVisible spectrophotometer. This intelligent hydrogel might be used in chemomechanical systems and separation devices as well as sensors. Polymer adsorption plays an important role in many products and processes. In this thesis, surfactant-free three-dimensional polystyrene (PS) nanoparticle network has been prepared. The infrared spectroscopy and solubility experiment are performed to prove the crosslinking mechanism, also the BET method was used to measure the adsorption and desorption of polystyrene network. The BET constant (C) is calculated (C=6.32). The chemically bonded polymer nanoparticle network might have potential applications as catalyst or used for chromatographic columns.
Date: December 2001
Creator: Zhou, Bo
System: The UNT Digital Library
Synthesis of Crown Ether/Ammonium Salt for Electron Transfer Study (open access)

Synthesis of Crown Ether/Ammonium Salt for Electron Transfer Study

The theoretical model of Beratan and Onuchic predicts a large attenuation of ET rates through hydrogen bonds; however, the effect of individual hydrogen bond on electron transfer reaction has not been systematically studied. The organic complexes in this study are a series of crown ether/ammonium salt, which incorporate a redox partner on each component of the complex. The dimethoxynaphthalene redox donor was attached to the crown ether and a series of ammonium salts was synthesized which bear substituted quinone and naphthoquinone acceptor. The complexes characterization and preliminary electron transfer rate measurement were completed with UV/Vis and steady-state emission spectroscopy.
Date: May 2002
Creator: Han, Dong
System: The UNT Digital Library
An Analysis of the Effectiveness of Computer Assisted Instruction in General Chemistry at an Urban University. (open access)

An Analysis of the Effectiveness of Computer Assisted Instruction in General Chemistry at an Urban University.

The science-major General Chemistry sequence offered at the University of Houston has been investigated with respect to the effectiveness of recent incorporation of various levels of computer technology. As part of this investigation, questionnaire responses, student evaluations and grade averages and distributions from up to the last ten years have been analyzed and compared. Increased use of web-based material is both popular and effective, particularly with respect to providing extra information and supplemental questions. Instructor contact via e-mail is also well-received. Both uses of technology should be encouraged. In contrast, electronic classroom presentation is less popular. While initial use may lead to improved grades and retention, these levels decrease quickly, possibly due to a reduction in instructor spontaneity.
Date: May 2002
Creator: McGuffey, Angela
System: The UNT Digital Library
Fluorination Effect on the Conformational Properties of Alkanes (open access)

Fluorination Effect on the Conformational Properties of Alkanes

A Series of fluorophores of the general formular P(CF2)nP and P(CF2)n-1CF3 has been synthesized. Copper catalyzed coupling of 1-bromopyrene and the corresponding mono and di-iodoperfluoroalkanes were used in most cases. For the n=3 dimer, a novel 1,w-perfluoroalkylation of pyrene via bis-decarboxylation of hexafluorogultaric acid was utilized. These compounds, along with suitable hydrocarbon analogs, are being used to study the flexibility of fluorocarbon chains using emission. We have found that the excimer formation for the fluorinated pyrene monomers is highly dependent on concentration and is less efficient than for pyene. Excimer formation for the fluorinated pyrene dimers is much more efficient than for the fluorocarbon monomers and is only slightly concentraion dependent. Steady-state emission spectra indicate hydrocarbon dimers-models form excimers more efficiently than the fluorinated dimers suggesting the fluorinated chains are stiffer than the hydrocarbons. We conducted the temperature-dependent studies and quantified the conformational difference.
Date: May 2002
Creator: Xu, Wenjian
System: The UNT Digital Library
A Computational Study on 18+δ Organometallics (open access)

A Computational Study on 18+δ Organometallics

The B3LYP density functional has been used to calculate properties of organometallic complexes of Co(CO)3 and ReBr(CO)3, with the chelating ligand 2,3-bisphosphinomaleic anhydride, in 19- and 18-electron forms. The SBKJC-21G effective core potential and associated basis set was used for metals (Co/Re) and the 6-31G* basis set was used for all other elements. The differences of bond angles, bond distances, natural atomic charges and IR vibrational frequencies were compared with the available experimental parameters. The differences between the 19- and 18-electron systems have been analyzed. The results reveal that the 19th electron is mostly distributed over the ligand of 2,3-bisphosphinomaleic anhydride, although partially localized onto the metal fragment in 1 and 2*. Two different methods, IR-frequencies and natural atomic charges, were used to determine the value of δ. Present computed values of δ are compared with available experimental values, and predictions are made for unknown complexes.
Date: May 2002
Creator: Yu, Liwen
System: The UNT Digital Library
NMR Study of n-Propyllithium Aggregates (open access)

NMR Study of n-Propyllithium Aggregates

A variable temperature 1H, 13C, and 6Li NMR study of n-propyl-6Li-lithium showed five different aggregates, similar to that in the literature as (RLi)n, n= 6, 8, 9, 9, 9. There were also a number of additional new species, identified as lithium hydride containing aggregates. Unexpectedly, a series of 13C{1H} 1-D NMR experiments with selective 6Li decoupling showed evidence for 13C-6Li spin-spin coupling between the previously reported (RLi)n aggregates and various hydride species.
Date: December 2002
Creator: Davis, James W.
System: The UNT Digital Library
Synthesis and characterization of 2-chloro-3-benzylthiopyrrolo[1,2-a]- benzimidazol-1-one and 2,3-di(benzylthio)pyrrolo[1,2-a]benzimidazol-1-one. (open access)

Synthesis and characterization of 2-chloro-3-benzylthiopyrrolo[1,2-a]- benzimidazol-1-one and 2,3-di(benzylthio)pyrrolo[1,2-a]benzimidazol-1-one.

The reaction between o-phenylenediamine and 2,3-dichloromaleic anhydride has been probed and found to give 2,3-dichloropyrrolo[1,2-a]- benzimidazol-1-one as the major product. Chlorine substitution in 2,3-dichloropyrrolo[1,2-a]benzimidazol-1-one by added benzylthiol occurs in the presence of pyridine to provide the corresponding monosulfide and disulfide derivatives. The first benzylthiol ligand undergoes reaction at the C-3 position of the five-membered pyrrolo-1-one ring, with the addition of the second benzylthiol ligand occurring at the remaining chlorine-substituted carbon. The mono- and disulfide derivatives have been isolated and characterized in solution by NMR, IR, and UV-vis spectroscopies, and the solid-state structure of 2,3-di(benzylthio)pyrrolo[1,2-a]benzimidazol-1-one has been established by X-ray crystallography.
Date: December 2003
Creator: Huang, Shih-Huang
System: The UNT Digital Library
Investigation of the Pressure Dependence of SO3 Formation (open access)

Investigation of the Pressure Dependence of SO3 Formation

The kinetics of the pressure dependent O + SO2 + Ar reaction have been investigated using laser photolysis resonance fluorescence at temperatures of 289 K, 399 K, 581 K, 699 K, 842 K and 1040 K and at pressures from 30-665 torr. Falloff was observed for the first time in the pressure dependence. Application of Lindemann theory yielded an Arrhenius expression of k(T) = 3.3 x 10-32exp(-992/T) cm6 molecule-1 s-1 for the low pressure limit and k(T) = 8.47 x 10-14exp(-468/T) cm3 molecule-1 s-1 for the high pressure limit at temperatures between 289 and 842 K. The reaction is unusual as it possesses a positive activation energy at low temperature, yet at higher temperatures the activation energy is negative, illustrating a reaction barrier.
Date: December 2003
Creator: Naidoo, Jacinth
System: The UNT Digital Library
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
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
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
Electrochemical Study of Under-Potential Deposition Processes on Transition Metal Surfaces (open access)

Electrochemical Study of Under-Potential Deposition Processes on Transition Metal Surfaces

Copper under-potential deposition (UPD) on iridium was studied due to important implications it presents to the semiconductor industry. Copper UPD allows controlled superfilling on sub-micrometer trenches; iridium has characteristics to prevent copper interconnect penetration into the surrounding dielectric. Copper UPD is not favored on iridium oxides but data shows copper over-potential deposition when lower oxidation state Ir oxide is formed. Effect of anions in solution on silver UPD at platinum (Pt) electrodes was studied with the electrochemical quartz crystal microbalance. Silver UPD forms about one monolayer in the three different electrolytes employed. When phosphoric acid is used, silver oxide growth is identified due to presence of low coverage hydrous oxide species at potentials prior to the monolayer oxide region oxide region.
Date: August 2006
Creator: Flores Araujo, Sarah Cecilia
System: The UNT Digital Library
Computational Studies of Bonding and Phosphorescent Properties of Group 12 Oligomers and Extended Excimers. (open access)

Computational Studies of Bonding and Phosphorescent Properties of Group 12 Oligomers and Extended Excimers.

Density functional (ca, BLYP, BPW91, B3LYP and B3PW91), MP2 and CCSD(T) methods in combination with LANL2DZ or cc-pVxZ-PP (where x=D(double), T(triple) Q(quadruple), and 5(quintuple)) basis sets have been employed in computing electronic transition energies of zinc and cadmium monomers. CCSD(T)/aug-cc-pV5Z-PP combination finds values that are 150 cm-1 from the experimental value for the zinc monomer and 240 cm-1 remove from the cadmium monomer excitation experimental value. These method/basis set combinations are also used to find spectroscopic values (re, De, we, wexe, Be , and Te) that rival experimental values for dimers and excimers. Examples of this can be seen with the CCSD(T)/aug-cc-pV5Z-PP combination phosphorescent emission results. The values found are within 120 cm-1 of the zinc emission energy and 290 cm-1 of the cadmium emission energy. While this combination rigorously models spectroscopic constants for monomers, dimers, and excimers, it does not efficiently model these constants for larger clusters with available modern computational resources. It is important to show spectroscopic trends (bonding, phosphorescent excitation and emissions) as clusters increase as the monomer and dimer emission energies do not model solid state metallophilic interactions and phosphorescence. The MP2/LANL2DZ combinations show qualitative cooperative bonding trends in group oligomers and extended excimers as size …
Date: August 2008
Creator: Determan, John J.
System: The UNT Digital Library
Applications of Nanomanipulation Coupled to Nanospray Mass Spectrometry in Trace Fiber Analysis and Cellular Lipid Analysis. (open access)

Applications of Nanomanipulation Coupled to Nanospray Mass Spectrometry in Trace Fiber Analysis and Cellular Lipid Analysis.

The novel instrumentation of nanomanipulation coupled to nanospray mass spectrometry and its applications are presented. The nanomanipulator has the resolution of 10nm step sizes allowing for specific fine movement used to probe and characterize objects of interest. Nanospray mass spectrometry only needs a minimum sample volume of 300nl and a minimum sample size of 300attograms to analyze an analyte making it the ideal instrument to couple to nanomanipulation. The nanomanipulator is mounted to an inverted microscope and consists of 4 nano-positioners; these nano-positioners hold end-effectors and other tools used for manipulation. This original coupling has been used to enhance the current abilities of cellular probing and trace fiber analysis. Experiments have been performed to demonstrate the functionality of this instrument and its capabilities. Histidine and caffeine have been sampled directly from single fibers and analyzed. Lipid bodies from cotton seeds have been sampled indirectly and analyzed. The few applications demonstrated are only the beginning of nanomanipulation coupled to nanospray mass spectrometry and the possible applications are numerous especially with the ability to design and fabricate new end-effectors with unique abilities. Future study will be done to further the applications in direct cellular probing including toxicology studies and organelle analysis of …
Date: December 2008
Creator: Ledbetter, Nicole
System: The UNT Digital Library
Comparison of Homework Systems (Four Web-Based) used in First-Semester General Chemistry (open access)

Comparison of Homework Systems (Four Web-Based) used in First-Semester General Chemistry

Web-based homework systems are becoming more common in general chemistry as instructors face ever-increasing enrollment. Yet providing meaningful feedback on assignments remains of the utmost importance. Chemistry instructors consider completion of homework integral to students' success in chemistry, yet only a few studies have compared the use of Web-based systems to the traditional paper-and-pencil homework within general chemistry. This study compares the traditional homework system to four different Web-based systems. Data from eight, semester classes consisting of a diagnostic pre-test, final semester grades, and the number of successful and unsuccessful students are analyzed. Statistically significant results suggest a chemistry instructor should carefully consider options when selecting a homework system.
Date: May 2009
Creator: Belland, Joshua
System: The UNT Digital Library
Synthesis and Characterization of Platinum(II)(2-(9-anthracenylylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione)(dichloride), Platinum(II)(2-(9-anthracenylylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione(maleonitriledithiolate), and Platinum(II)(4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione)(4-Methyl-1,2-benzene dithiol) (open access)

Synthesis and Characterization of Platinum(II)(2-(9-anthracenylylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione)(dichloride), Platinum(II)(2-(9-anthracenylylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione(maleonitriledithiolate), and Platinum(II)(4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione)(4-Methyl-1,2-benzene dithiol)

Substitution of the 1,5-cyclooctadiene (cod) ligand in PtCl2(cod) (1) by the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) yields PtCl2(bpcd) (2). Knoevenagel condensation of 2 with 9-anthracenecarboxaldehyde leads to the functionalization of the bpcd ligand and formation of the corresponding 2-(9-anthracenylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (abpcd) substituted compound PtCl2(abpcd) (3), which is also obtained from the direct reaction of 1 with the abpcd ligand in near quantitative yield. The reaction of 3 with disodium maleonitriledithiolate (Na2mnt) affords the chelating dithiolate compound Pt(mnt)(abpcd) (4). The reaction of PtCl2(bpcd) (2) with 4-methyl-1,2-benzene dithiol under basic conditions affords Pt(tdt)(bpcd) (5). Compounds 2-5 have been fully characterized in solution by IR and NMR spectroscopies (1H and 31P), and their molecular structures established by X-ray crystallography. The electrochemical properties of 2‑5 have examined by cyclic voltammetry, and the nature of the HOMO and LUMO levels in systems 2-4 has been established by MO calculations at the extended Hückel level, the results of which are discussed with respect to electrochemical data and related diphosphine derivatives. In addition the new compounds 2-5 have been isolated by column chromatography and characterized by IR, UV-Vis spectroscopy.
Date: December 2009
Creator: Hunt, Sean W.
System: The UNT Digital Library
Electrochemical Deposition of Zinc-Nickel Alloys in Alkaline Solution for Increased Corrosion Resistance. (open access)

Electrochemical Deposition of Zinc-Nickel Alloys in Alkaline Solution for Increased Corrosion Resistance.

The optimal conditions for deposition of zinc-nickel alloys onto stainless steel discs in alkaline solutions have been examined. In the past cadmium has been used because it shows good corrosion protection, but other methods are being examined due to the high toxicity and environmental threats posed by its use. Zinc has been found to provide good corrosion resistance, but the corrosion resistance is greatly increased when alloyed with nickel. The concentration of nickel in the deposit has long been a debated issue, but for basic solutions a nickel concentration of 8-15% appears optimal. However, deposition of zinc-nickel alloys from acidic solutions has average nickel concentrations of 12-15%. Alkaline conditions give a more uniform deposition layer, or better metal distribution, thereby a better corrosion resistance. Although TEA (triethanolamine) is most commonly used to complex the metals in solution, in this work I examined TEA along with other complexing agents. Although alkaline solutions have been examined, most research has been done in pH ≥ 12 solutions. However, there has been some work performed in the pH 9.3-9.5 range. This work examines different ligands in a pH 9.3-9.4 range. Direct potential plating and pulse potential plating methods are examined for optimal platings. The …
Date: December 2009
Creator: Conrad, Heidi A.
System: The UNT Digital Library
Study of Silver Deposition on Silicon (100) by IR Spectroscopy and Patina Formation Study of Oxygen Reduction Reaction on Ruthenium or Platinum (open access)

Study of Silver Deposition on Silicon (100) by IR Spectroscopy and Patina Formation Study of Oxygen Reduction Reaction on Ruthenium or Platinum

To investigate conditions of silver electroless deposition on silicon (100), optical microscope, atomic force microscope (AFM) and attenuated total reflection infrared spectroscopy (ATR-FTIR) spectroscopy were used. Twenty second dipping in 0.8mM AgNO3/4.9% solution coats a silicon (100) wafer with a thin film of silver nanoparticles very well. According to AFM results, the diameter of silver particles is from 50 to 100nm. After deposition, arithmetic average of absolute values roughness (Ra) increased from ~0.7nm to ~1.2nm and the root mean square roughness (Rq) is from ~0.8nm to ~1.5nm. SCN- ions were applied to detect the existence of silver on silicon surface by ATR-FTIR spectroscopy and IR spectra demonstrate SCN- is a good adsorbent for silver metal. Patina is the general name of copper basic salts which forms green-blue film on the surface of ancient bronze architectures. Patina formation has been found on the surface of platinum or ruthenium after several scans of cyclic voltammetry in 2mM CuSO4/0.1M K2SO4, pH5 solution. Evidence implies that oxygen reduction reaction (ORR) triggers the patina formation. ORR is an important step of fuel cell process and only few sorts of noble metals like platinum can be worked as the catalyst of ORR. Mechanisms of patination involving …
Date: August 2009
Creator: Yang, Fan
System: The UNT Digital Library
Effect of Fluorine and Hydrogen Radical Species on Modified Oxidized Ni(pt)si (open access)

Effect of Fluorine and Hydrogen Radical Species on Modified Oxidized Ni(pt)si

NiSi is an attractive material in the production of CMOS devices. The problem with the utilization of NiSi, is that there is no proper method of cleaning the oxide on the surface. Sputtering is the most common method used for the cleaning, but it has its own complications. Dry cleaning methods include the reactions with radicals and these processes are not well understood and are the focus of the project. Dissociated NF3 and NH3 were used as an alternative and XPS is the technique to analyze the reactions of atomic fluorine and nitrogen with the oxide on the surface. A thermal cracker was used to dissociate the NF3 and NH3 into NFx+F and NHx+H. There was a formation of a NiF2 layer on top of the oxide and there was no evidence of nitrogen on the surface indicating that the fluorine and hydrogen are the reacting species. XPS spectra, however, indicate that the substrate SiO2 layer is not removed by the dissociated NF3 and NiF2 growth process. The NiF2 over layer can be reduced to metallic Ni by reacting with dissociated NH3 at room temperature. The atomic hydrogen from dissociated ammonia reduces the NiF2 but it was determined that the …
Date: May 2010
Creator: Gaddam, Sneha Sen
System: The UNT Digital Library