Metallurgy Commons^™

Electrochemical Evaluation Of Zinc Electrolyte, Rajesh Kumar Singh

Doctoral Dissertations

"The polarization characteristics of acidified zinc sulfate electrolyte with varying solution chemistries were examined by cyclic voltammetry. An attempt was made to correlate the polarization results with the morphological and current efficiency data in order to develop a better understanding of the more fundamental aspects of impurity and additive behavior during the zinc electrodeposition process.

A statistical screening design program was conducted to determine the effects of certain operating parameters on the nucleation potential of zinc from sulfate electrolyte. The variables studied included: solution temperature, H₂SO₄ and Zn concentration, and scan rate. The solution temperature was found to be the …

Mass Transport Considerations In Electrometallurgical Reactions, Jose Rolando Sami Cuzmar

Doctoral Dissertations

"The research program described is divided into three segments. In the first part, the morphology and kinetic studies of Cd²⁺ removal from ZnSO₄ solutions using Zn dust as a reducing agent are presented. In the absence of impurities, the morphology of the Cd deposit shows the formation of two-dimensional or leaf-like dendrites capable of interlocking and forming agglomerates or balls. The size and strength of the agglomerates depend on the initial Cd²⁺ concentration to Zn metal surface area ratio, the rate of Cd ²⁺ removal, and the reactor geometry. The presence of additives, like Cu²⁺ and …

The Influence Of Additives And Their Interactions On Copper Electrorefining, Chwan-Tsann Wang

Doctoral Dissertations

"Protein colloid (glue), thiourea, Avitone and chloride ion are the most common additives used electrorefining copper. The polarization behavior of these additives, single and combined, was studied by cyclic voltammetry techniques in conjunction with stationary and rotating disc electrodes. In the stationary electrode work, different protein colloids give substantially different results in polarization or interaction with other additives. The role played by Avitone is not clear, but it does somewhat modify other additives in the electrolyte. Thiourea can cause a depolarized peak and a polarized plateau depending on the concentration, the other additives present and the potential selected. Chloride ion …

The Effects Of Certain Impurities And Their Interactions On Zinc Electrowinning, Donald R. Fosnacht

Doctoral Dissertations

“The effects of germanium, antimony, arsenic, cobalt, glue, and free acid concentration were studied on both commercial and synthetic electrolytes. The effects of a single factor and the combined effects of multiple factors were elucidated. The temperature, zinc concentration, and current density were also varied. It was found that the acid concentration was the most critical factor when impurity levels were at normal plant solution concentrations. The ranges where the effect of the impurity became apparent were: greater than 20 ppb for antimony; 40 ppb for germanium; 120 ppb for arsenic; and 7-8 mg/l for cobalt for a solution containing …

Application Of Voltammetry To Copper Electrodeposition, Louis Francis Toth Jr.

Doctoral Dissertations

"A study was undertaken to determine the feasibility of using voltammetry and scanning electron microscopy techniques to characterize copper deposition from an acid-sulfate electrolyte. The main process variables investigated were temperature and addition agents (chloride ion, glue, separan or thiourea) at different concentrations, over a range of current densities. Cathodes employed were either polycrystalline titanium or copper. Some long-time copper deposits were also made using Ti cathodes and the orientations of these deposits were determined by x-ray diffraction.

Observations of copper crystals produced during voltammetry scans, on a Ti cathode, indicated that a characteristic morphology was associated with each type …

Corrosion And Electrochemical Behavior Of Indium And Indium-Bismuth Alloys In Hydrochloric Acid, Yar Ming Wang

Doctoral Dissertations

"The corrosion of In-Bi alloys was studied using X-ray, scanning electron microscopy, atomic absorption spectroscopy, and cyclic voltammetry techniques.

Calculated activation energy values indicated that the corrosion of In-Bi alloys was activation controlled. The effect of amine mixtures on the corrosion of In and In₂Bi (ß₁ phase) was studied. Morphological studies revealed that the porosity of the resulting physical surface structure was influential in determining the corrosion rate. In deaerated 3N HCl solutions, the selective dissolution of indium was the predominant mechanism in the corrosion of In-Bi alloys. The corrosion was always accompanied by a phase change …

The Morphology Of Cellular Precipitation In Magnesium Rich Magnesium-Aluminum Alloys, Jyong Shi Cho

Doctoral Dissertations

"The morphology of cellular precipitation in a Mg-9wt. %AI alloy has been investigated by light and electron microscopy. A study of the early stages of the cellular precipitation process indicated that cellular precipitate structure forms in Mg-Al alloys by Fournelle and Clark mechanism. "Replacive" motion indicative of the Tu and Turnbull mechanism for cellular precipitation was not seen"--Abstract, page 1.

Premartensitic Elasticity Of Fe-Ni Invars, Bryce Linn Shriver

Doctoral Dissertations

"The premartensitic temperature dependence of ultrasonic wave propagation in Fe-30 pct Ni polycrystals and Fe-32 pct Ni single crystals was measured by using a continuous wave technique. As the temperature was lowered to within 10°C of the M_s, a nonlinear decrease of the relative shear velocity was observed. This effect is related to dislocation stacking fault instabilities which may trigger the martensitic phase transformation. In addition, the single crystals show a frequency dependence of the shear elastic constant C' well above the M_s. The dispersion is believed to be caused by fluctuations in the anisotropic molecular …

Prebainitic Phenomena In Aisi 86b80 And 0.8c-5.3ni Steels, Chung Lim

Doctoral Dissertations

"An ultrasonic investigation shows that the prebainitic kinetics of AISI 86B80 and 0.8C-5.3Ni steels follow t^2/3 and or t¹ time laws in the lower bainite temperature region. The data analysis indicates that these kinetics signal carbon segregation to dislocations. The simple time laws are interrupted at the bainite start time. It is shown that at this time the carbon depleted regions around dislocations transform martensitically. The lower bainite reaction is thus initiated by the formation of supersaturated ferrite through carbon segregation and the subsequent local martensitic transformation"--Abstract, page iii.

The Morphology Of Cellular Precipitation In Aluminum Rich Aluminum-Silver Alloys, Santiago Ibarra Jr.

Doctoral Dissertations

"The morphology of cellular precipitation in Al-29.8wt%Ag alloy has been investigated in bulk specimens by transmission electron microscopy and in solution treated specimens by means of hot stage microscopy. Both cellular and general precipitation were observed to occur simultaneously in quench-aged and isothermally aged alloys. By studying the early stages of precipitation in the hot stage, the mechanism for the growth of cells in Al-Ag alloys was developed. According to this mechanism, the grain boundary allotriomorphs begin to form, the boundary then interacts with the allotriomorphs by bowing, and then either trailing precipitation forms on the allotriomorphs or new lamellae …

Grain Boundary Diffusion In Ionic Crystals, Kulwant Singh Sabharwal

Doctoral Dissertations

"The diffusion of ¹³¹I in single crystals and along the tilt grain boundaries of pure and calcium chloride doped (142±5 ppm) bicrystals of sodium chloride, grown by Czochralski technique, was investigated using a microtome sectioning technique. Results on bulk diffusion in pure NaCl agree well with the results of earlier investigators and are represented by the D=(504 cm²/sec)exp (-2.27 ev/kT). Enhanced diffusion of ¹³¹I is observed along the grain boundaries and the presence of the dopant lowers the grain boundary diffusivity over the entire temperature range of 430ºC - 570ºC studied in the present investigation. Thermal activation and electrical polarization …

Effects Of Cr-Plating And Environment On The Cracking Of Low Alloy Steels At High Temperatures, Robert C. Tooke

Doctoral Dissertations

"The cracking of low alloy Cr-Mo-V steels under cyclic stress at 1000-1100°C. was studied using a specially designed test apparatus. The results obtained from specimens plated with hard chromium are compared to those of unplated specimens. Tests conducted in gas mixtures of carbon monoxide and carbon dioxide showed that a high CO/CO₂ ratio retards cracking in both plated and unplated specimens. Both external and internal oxidation are used to explain these results. Inherent microcracks in the hard chromium plating promoted cracking in all CO/CO₂ environments. It was also found that these steels are severely embrittled in the presence …

The Effect Of Impurities And Additives On The Electrowinning Of Zinc, Haruhisa Fukubayashi

Doctoral Dissertations

"The effect of various impurities, commonly found in zinc electro-winning solutions, on the surface morphology of deposited zinc was investigated. Individual additions of the impurities Al, Ag, Cd, Co, Cr, Cu, Ge, Mn, Ni, Sb, Sn, Ti, PbO₂ , PbSO₄, and HCl were studied. In a few cases additives of animal glue, gum arabic, and Na₂SiO₃, were used individually or in combination, to determine their effect on the surface structure of the deposited zinc. Comparisons were then made with deposits from a pure electrolyte consisting of H₂SO₄ and Zn⁺², 200 and 65 g/l, respectively. The zinc was deposited on a …

The Genesis Of Cellular Precipitation In Copper Rich Copper-Indium Alloys, Raymond Albert Fournelle

Doctoral Dissertations

"The morphology of cellular precipitation in a Cu-9.5at.%In alloy has been investigated by light and electron microscopy and x-ray and electron diffraction. Both cellular and general precipitation were observed to occur simultaneously in quenched and aged alloys while only cellular precipitation was observed to occur in isothermally aged alloys. Because of the presence of wide, vacancy depleted precipitate free zones in the vicinity of grain boundaries, general precipitation was observed to have no effect on the early development of cellular precipitation. Hence, the early development of cellular precipitation was found to be identical for both types of heat treatment. By …

Thermal Lattice Expansion Of Various Types Of Solids, Jayantkumar Shantilal Shah

Doctoral Dissertations

"Thermal lattice expansion studies of various types of solids were carried out in this investigation and were corelated to their crystallographic and various other properties. The advantages and limitations of various methods of studying thermal expansion are discussed in detail. A new design for a versatile low temperature camera to study expansion by an X-ray method is proposed. The thermal lattice expansion of silicon was negative below 119ºK. This behavior is discussed in terms of crystal structure and interatomic bonding. Diamond exhibits no anomalous thermal expansion. Lattice parameter data for many metals at low temperatures are reported for the first …

Activation Volumes Of Carbon Diffusion In F.C.C. Iron-Nickel Alloys, James Raymond Keiser

Doctoral Dissertations

"The disaccommodation technique was used to determine the activation volume of carbon diffusion, ΔV, in six fcc iron-nickel alloys. Measurements were made at temperatures ranging from 68ºC to 90ºC and pressures up to six kilobars on samples having a nickel content between 31 and 63 at. %. A maximum activation volume of 3.9 cm³/mole was found at 34 at. % nickel. The compositional dependence of ΔV is satisfactorily reproduced by a magnetic energy continuum model in which it is assumed that the activation free energy of diffusion is essentially ferromagnetic in origin "--Abstract, page iii.

An Age Hardening Study Of Magnesium-Thorium-Manganese Alloys, Kuldip Singh Chopra

Doctoral Dissertations

"The age hardening processes in Mg-3.5 wt.% Th-1.0 wt.% Mn and Mg-1.0 wt.% Th-1.0 wt.% Mn alloys have been studied by light and electron microscopy, and by electron and X-ray diffraction. At aging temperatures of 300ºC and below, G.P. zone formation rapidly hardens these alloys followed by the precipitation of disc shaped plates during averaging. During aging above 300ºC, no G.P. zones form and the disc shaped precipitate grows to very large sizes. The combined results of X-ray and electron diffraction indicate that the disc shaped precipitate has a Mg₃Cd (DO₁₉) type structure. The basal plane of the Mg₃Th discs …

X-Ray And Neutron Diffraction Study Of The Holmium-Iron System, Michael Fred Simmons

Doctoral Dissertations

"Neutron diffraction and x-ray powder studies have been made of holmium-iron intermetallic compounds. The magnetic moments of Ho and Fe are in good agreement with measured spontaneous magnetization assuming a ferrimagnetic model with the Ho moments antiparallel to the Fe moments. The magnetic moments of the Fe atoms are found to be localized and thus independent of the rare earth content in the alloys. In contrast to HoCo₃, (00ℓ) type magnetic peaks in the neutron diffraction patterns are still prevalent at room temperature and gradually decrease as the Curie temperature is approached. This fact indicates that the easy direction of …

Electrode Reactions In Zinc Electrolysis, Ernest R. Cole

Doctoral Dissertations

"The effects of temperatures from 0°C to 50°C and current densities from 10 asf to 200 asf on the current efficiency in the electrolysis of pure zinc sulfate solutions (65 gpl Zn⁺⁺ - 200 gpl H₂SO₄) were determined. Pure platinum and platinum coated titanium anodes were used with an aluminum cathode. Platinum anodes were not inert at certain combinations of temperature and current density, and platinum acted as a low overvoltage impurity causing resolution of the cathode deposit. Orientation of the zinc deposits was found to vary with temperature and to have a distinct relationship to current efficiency. Preconditioning of …

The Oxidation Kinetics Of Liquid Lead And Lead Alloys, Thomas Edward Weyand

Doctoral Dissertations

"Liquid lead and lead-silver alloys were investigated to determine the rates and products of oxidation in pure oxygen at temperatures of 350 to 600°C. The kinetic data were determined using a Cahn electro-balance. Liquid lead was found to follow a cubic rate of oxidation between 350 and 400°C. A parabolic rate was found at temperatures above 400°C. 0.496% silver and 2.258% silver alloys followed a cubic rate of oxidation from 350 to 550°C and tended to approach a parabolic rate of oxidation above this temperature. Silver additions were found to increase the rate of oxidation as compared to the pure …

Voids In Neutron Irradiated Aluminum, Nicholas H. Packan

Doctoral Dissertations

"Void formation in high purity aluminum resulting from irradiation to fluences between 1.5 x 10¹⁹ and 1.6 x 10²² neutrons/cm² (E > 0 .1 MeV) at a temperature of 55 ± 5ºC was studied, primarily by means of transmission electron microscopy. In particular the effects of neutron fluence and flux were examined, as well as the possible influences of both preexisting and transmutation-produced impurities. A very low concentration of voids (about 10¹²/cm³) resulted from irradiation to 1.5 x 10¹⁹ neutrons/cm²; they averaged about 150 Å in diameter. Void concentrations and sizes increased with fluence, reaching values of 6 x 10¹⁴ voids/cm³ …

The Deformation Mechanisms In Sublimed Magnesium Under Cyclic Loading, Babu Narian Thakur

Doctoral Dissertations

"A detailed study of the deformation processes in sublimed magnesium under reverse bending fatigue in air at room temperature has been undertaken utilizing the light, scanning and transmission electron microscopy. The Principal deformation modes are the basal slip and {10Ī2} twinning. The proportion of twinning increases markedly with the increasing stress level and the number of cycles. The evidence for cross slip is seen on the basal slip bands. The extrusions are seen not only along the basal slip lines but also along the {10Ī2} twin boundaries. In the later stages of fatigue, the extrusions chip off producing a notch …

Diffusion Of Iron And Cobalt In Nickel Single Crystals, Charles Frederick Heuer

Doctoral Dissertations

"Diffusion coefficients of iron-59 in nickel have been determined in the temperature range 815°C to 1200°C. The temperature dependence can be represented by an Arrhenius type relationship,...The effect of the isotopic mass on the diffusion coefficient of cobalt in nickel has also been investigated. The isotope effect parameter, E, was found to vary from .26 to .84 over the temperature range 970.5°C to 1200°C. Both results are consistent with the single vacancy mechanism of diffusion. No evidence of divacancy contributions to the mass transport has been found"--Abstract, Page i.

Phase Equilibria And Thermodynamic Studies In The System Ca0-Fe0-Fe₂0₃₋Si0₂, Muharrem Timucin

Doctoral Dissertations

"A study of phase relations and thermodynamic properties of phases in the system CaO-FeO-Fe₂O₃-SiO₂ was conducted at 1450°C and 1550°C. The region of stability of the different phases was determined by microscopic examination of the specimens. The thermodynamic properties of liquid were determined by analyses of quenched samples equilibrated at oxygen pressures from about 10⁻¹¹ to 1 atm. Isothermal phase diagrams were constructed from data for 0, 5, 10, 20, and 30 weight percent silica sections of the CaO-FeO-Fe₂O₃-SiO₂ system, and the effect of temperature and increased silica additions on the oxygen solubility of the liquid oxides was measured. Multicomponent …

X-Ray Determination Of Lattice Parameters And Thermal Expansion Coefficients Of Aluminum, Silver And Molybdenum At Cryogenic Temperatures, Claude Lowell Woodard

Doctoral Dissertations

"A multiple exposure back reflection diffraction camera was designed to mount on the vacuum jacket of a pressurized helium gas "Cryomite". With this design it is possible to obtain six diffraction exposures on a single film at any temperature in the range of 180 to 25°K. temperatures within this range are reached in short intervals and exposure periods are less than 30 minutes in a 2.875 inch (73.03 mm) diameter camera. Some of the advantages of this design are; direct measurements, multiple exposures on a single film, short exposures, direct compensation of film length changes due to evacuation or processing …

Grain Boundary Self-Diffusion In Sodium Chloride, Kenneth Ray Riggs

Doctoral Dissertations

"The diffusion of ²²sodium and ³⁶chlorine along tilt and twist grain boundaries in pure and calcium chloride doped sodium chloride bicrystals was investigated. No enhanced diffusion of ²²sodium along the grain boundaries was observed. Between 400°C and 500°C the chlorine grain boundary diffusion parameter, D'Δ, is described by D'Δ = (D'Δ)₀exp (-Q_b/kT), where (D'Δ)₀ is approximately 10⁻⁷ cm³/sec and Qb is 1.15 ± .30 eV. The grain boundary angle, the grain boundary character (tilt or twist), and the calcium chloride concentration appear to have no pronounced effect upon the observed chlorine grain boundary diffusion. The ionic movement …

Calorimetry Of Room Temperature Deformed Copper, George Juri Filatovs

Doctoral Dissertations

"An adiabatic anisothermal differential calorimeter for the study of room temperature deformed 99.999% pure copper has been constructed. An annealed and a deformed specimen were heated at a constant rate in adiabatic surroundings and the differences in energy released between samples was obtained. The control circuits were automatic. Deformation was by elongation ranging from 12 to 40%, and the corresponding energy found was from 1.9 to 5.3 calories/gram-atom. No recovery energy was found. The results obtained generally agree with published results and, in particular, verify Gordon's isothermal annealing results. It is proposed that the criteria for the presence of recovery …

The Iron-Holmium Binary System And Related Magnetic Properties, Gerald J. Roe

Doctoral Dissertations

"The iron-holmium phase diagram was investigated to determine the alloying behavior of these two metals and to determine the magnetic properties of some of the iron-holmium alloys which formed intermediate phases. The iron-holmium binary system was determined by three experimental techniques, differential thermal analysis (DTA), x-ray diffraction, and metallography. A phase diagram with three eutectic points and four intermediate phases was constructed from the experimental data. The two phases, Ho₆Fe₂₃ and Ho₂Fe₁₇, melted congruently at 1322⁰C and 1343⁰C respectively. HoFe₂ and HoFe₃ melted incongruently at 1288⁰C and 1293⁰C respectively. Neutron diffraction investigations were made on the intermediate phases Ho₆Fe₂₃ and …

Surface Self-Diffusion On Nickel (111) By Radioactive Tracers, James Ronald Wolfe

Doctoral Dissertations

"Surface self-diffusion coefficients have been measured by a radioactive tracer method over the temperature range 614⁰ to 840⁰C on nickel (111) surfaces characterized by LEED. Previously unrecognized tracer evaporation during surface diffusion resulted in restricted spreading of the tracer at higher temperatures. A theoretical treatment of the tracer evaporation phenomenon is presented and subsequently used in the analysis of the data. The temperature dependence of the surface self-diffusion coefficient (D_s) for nickel (111) can be represented, over the experimental temperature range, by a single Arrhenius type relationship...Arguments are presented to justify an adatom surface diffusion mechanism which is …

Effect Of Micelles On Flotation Of Metal Ions, Uriel Michael Oko

Doctoral Dissertations

"A study of the anionic surfactant, sodium dodecyl sulfate (SDS), and the dependency of the adsorption of divalent metal counterions such as copper and zinc at the air-water interface on its concentration in the solution, was undertaken in order to better understand the process of ion flotation. The study is divided into two broad categories, the first of which consists of the evaluation of the extent of aggregation of the surfactant molecules into micelles, and the effect of the divalent metal counterion concentration on this aggregation and on the critical concentration at which micelles start forming (cmc). This was accomplished …