Thesis (M.Sc.) --University of Adelaide, 1951. / Typewr. copy.

ITC/USA 2007 Conference Proceedings / The Forty-Third Annual International Telemetering Conference and Technical Exhibition / October 22-25, 2007 / Riviera Hotel & Convention Center, Las Vegas, Nevada / As technological advances continue to be made in the commercial sectors of portable and wireless communication products, additional advancements in battery technology have also been made. These advancements have allowed for the rapid growth of a large variety of commercially available batteries which have the capability to meet or even exceed the current power and size requirements for numerous ballistic telemetry systems. The replacement of a custom built battery with a COTS battery would provide immediate advantages such as lower cost, shorter lead times and higher availability. The overall objective of this paper is to provide ballistic telemetry systems engineers and designers with multiple low cost, readily available alternatives to traditional custom made power sources.

Electrical double-layer formed at the interface between an electrode and an electrolyte has been a topic of innumerable studies. The electrical interface plays a crucial role in kinetics, mechanisms and applications in variety of electrochemical reactions. The electrical double-layer and electron-transfer reactions lead to many important applications of electrochemistry, which include energy storage devices, namely, batteries, fuel cells and supercapacitors. Electrochemical supercapacitors can withstand to higher power than batteries and deliver higher energy than the conventional electrostatic and electrolytic capacitors. A supercapacitor can be used as an auxiliary energy device along with a primary source such as a battery or a fuel cell for the purpose of power enhancement in short pulse applications. Among the various materials studied for electrochemical supercapacitors, carboneous materials, metal oxides and conducting polymers received attention. Among carboneous materials, various forms of carbon such as powders, woven cloths, felts, fibers, nanotubes etc., are frequently studied for electrochemical supercapacitors. Low cost, high porosity, higher surface area, high abundance and well established electrode fabrication technologies are the attractive features for using carboneous materials. However, specific capacitance (SC) of these materials is rather low. These electrodes store charge by electrostatic charge separation at the electrode/electrolyte interface. Electronically conducting polymers are interesting class of materials studied for supercapacitor application because of the following merits: high electronic conductivity, environmental friendliness, ease of preparation and fabrication, high stability, high capacitance and low cost. Polyaniline (PANI), polypyrrole and polythiophene are studied in this category. Transition metal oxides have attracted considerable attention as electrode materials for supercapacitors because of the following merits: variable oxidation state, good chemical and electrochemical stability, ease of preparation and handling. Hydrated RuO2 prepared by sol-gel process at low temperature has a specific capacitance as high as 720 F g-1 due to solid state pseudo faradaic reaction. However, high cost, low porosity and toxic nature limit commercialization of supercapacitors using this material. MnO2 is attractive as it is cheap, environmentally benign, its resources are abundant in nature and also it is widely used as a cathode material in batteries. An early study on capacitance behaviour of MnO2 was reported by Lee and Goodenough. Amorphous hydrous MnO2 synthesized by co-precipitation method exhibited rectangular cyclic voltammogram in various aqueous alkali salt solutions. A specific capacitance of 200 F g-1 was reported. Following this report, several reports appeared on capacitance characteristics of MnO2. According to the charge-storage mechanism reported, a specific capacitance of 1370 F g-1 is expected from MnO2. However, this value can be obtained in practice only when the mass of MnO2 is at the level of a few micrograms per cm2 area. At such a low thickness range, the utilization of the active material is high. As thin layers of MnO2 are uneconomical for practical capacitors, studies with a mass range of 0.4-0.5 mg cm-2 have been extensively reported. At this mass range, a maximum specific capacitance of about 240 F g-1 has been obtained. With an increase in mass per unit area, the specific capacitance of MnO2 decreases. The problem associated with low values of specific capacitance of thick layers of MnO2 is the following. The MnO2 deposits or coatings generally do not possess high porosity and the electrolyte cannot permeate into the coating. Only the outer layer of the electrode is exposed to the electrolyte. Consequently, the electrochemical utilization of the material decreases with an increase in thickness. Nevertheless, utilization of thick layers of the active materials is preferable for obtaining capacitance as high as possible in a given volume and area of the electrodes. Indeed, it would be ideal if specific capacitance of MnO2 is improved from its presently reported value of 240 F g-1 to a value equivalent to that of RuO2.xH2O, namely, 720 F g-1. In view of this, attempts are made to enhance specific capacitance of MnO2 by electrochemical deposition in presence of surfactants. Nanostructured MnO2 synthesized by inverse microemulsion route is also studied for electrochemical supercapacitors. The effect of crystallographic structure of MnO2 on the capacitance properties, studies on electrochemical deposition of MnO2 in acidic and neutral medium using electrochemical quartz crystal microbalance and capacitance characteristics of MnO2-polyaniline composites are also described in the thesis. Chapter 1 briefly discusses the importance of electrochemistry in energy storage and conversion, basics of electrochemical power sources, importance of MnO2, different synthetic procedures for MnO2 and its applications in energy storage and conversion in particular for electrochemical supercapacitors. Chapter 2 provides the experimental procedures and methodologies used for the studies reported in the thesis. In chapter 3, the effect of surface active agents, namely, sodium dodecyl sulphate (SDS) and Triton X-100 added to the electrolyte during electrodeposition of MnO2 on Ni substrate on capacitance properties is presented. Electrocrystallization studies show that MnO2 nucleates instantaneously under diffusion control and grows in three dimensions. The potentiodynamically prepared oxide provides higher specific capacitance than the potentiostatically and galvanostatically prepared oxides. Specific capacitance values of 310 and 355 F g-1 obtained for MnO2 electrodeposited in the presence of 100 mM SDS and 10 mM Triton X-100 are higher than the oxide electrodeposited in the absence of surfactants. Surfactant molecules adsorbed at the electrode/electrolyte interface alters structure of double-layer and kinetics of electrodeposition. Smaller particle size, greater porosity, higher specific surface area and higher efficiency of material utilization are the factors responsible for obtaining higher specific capacitance. Extended cycle-life studies indicate that the superior performance of MnO2 due to surfactants is present throughout the cycle-life tested. Chapter 4 pertains to electrochemical supercapacitor studies on nanostructured α-MnO2 synthesized by inverse microemulsion method and the effect of annealing. As synthesized nanoparticles of MnO2 was found to be in α-crystallographic structure with particles less than 50 nm size. Nanoparticles exhibited rectangular cyclic voltammograms between 0 and 1 V vs. SCE in aqueous 0.1 M Na2SO4 at sweep rates up to 100 mV s-1 due to the short diffusion path length. On annealing at different temperatures, a mixture of nanoparticles and nanorods with varying dimension is noticed. Specific capacitance of 297 F g-1 obtained during initial cycling decreases gradually on extended cycling. The capacitance loss is attributed to the increase in the resistance for intercalation/deintercalation of alkali cations into/from MnO2 lattice. MnO2 crystallizes into several crystallographic structures, namely, α-, β-, γ-, δ- and λ-structures. As these structures differ in the way MnO6 octahedra are interlinked, they possess tunnels or inter-layers with gaps of different magnitudes. Because capacitance properties are due to intercalation/deintercalation of protons or cations in MnO2, only some crystallographic structures, which possess sufficient gap to accommodate these ions, are expected to be useful for capacitance studies. The effect of crystal structure of MnO2 on its electrochemical capacitance properties is also included in chapter 4. Specific capacitance of MnO2 is found to depend strongly on the crystallographic structure, and it decreases in the following order: α ≅ δ > γ > λ > β. A specific capacitance value of 240 F g-1 is obtained for α-MnO2, whereas it is 9 F g-1 for β-MnO2. A wide (~ 4.6 Å) tunnel size and large surface area of α-MnO2 are ascribed as favorable factors for its high specific capacitance. A large interlayer separation (~7 Å) also facilitates insertion of cations in δ-MnO2 resulting in SC close to 236 F g-1. A narrow tunnel size (1.89 Å) does not allow intercalation of cations into β-MnO2. As a result, it provides very small SC. In Chapter 5, capacitance characteristics of PANI synthesized using (NH4)2S2O8, nanostructured MnO2 (α- and γ-form) and also PANI-MnO2 composites are presented. Morphology of PANI synthesized resembles the morphology of the MnO2 used as the oxidant. Electrochemical capacitance properties of PANI and composites are studied in a mixed electrolyte of 0.1 M HClO4 and 0.3 M NaClO4 between 0 and 0.75 V vs. SCE. Specific capacitance of 394 F g-1 is obtained for PANI synthesized using γ-MnO2. Chapter 6 describes the electrocatalytic behaviour of Mn3[Fe(CN)6]2 synthesized by ion-exchange reaction between MnSO4 and K3[Fe(CN)6] and the effect of annealing on its electrochemical capacitance properties. As prepared Mn3[Fe(CN)6]2 and also the sample heated at 100 oC exhibit redox couple in 0.1 M Na2SO4 electrolyte, corresponding to Fe(CN)64-/Fe(CN)63- present in the matrix. Mn3[Fe(CN)6]2 samples annealed at 150 oC and above decompose to oxides of manganese and iron, and hence exhibit capacitance characteristics in 0.1 M Na2SO4 electrolyte. A maximum specific capacitance of 129 F g-1 is obtained for Mn3[Fe(CN)6]2 annealed at 300 oC. Electrochemical quartz crystal microbalance (EQCM) investigations of kinetics of electrodeposition of MnO2 in acidic and neutral media, and capacitance behaviour are presented in chapter 7. Oxidation of Mn2+ to MnO2 is characterized by an anodic cyclic voltammetric peak both in acidic and neutral media. During the reverse sweep, however, reduction of MnO2 into Mn2+ occurs in two steps in the acidic medium and in a single step in the neutral medium. From EQCM data of mass variation during cycling, it is observed that the rate of electrodeposition of MnO2 is higher in the neutral medium than in the acidic medium. Specific capacitance of MnO2 deposited from the neutral medium is higher than that deposited from acidic medium owing to different crystallographic structures. Reversible insertion/deinsertion of hydrogen in to the layers of δ-MnO2 is observed in hydrogen evolution region. Details of the above studies are described in the thesis.

Thesis (M.S.)--University of Wyoming, 2008. / Title from PDF title page (viewed on Mar. 11, 2010). Includes bibliographical references (p. 42-45).

The aim of this project was to investigate the usage of manganese dioxide ore as a bio-filter media to remove metabolites in aquaculture closed system, and to determine whether manganese toxicity would at the same time represent a risk to fish. Initial work investigated the physical properties of manganese dioxide and its chemical interaction with ammonia and nitrite in the absence of biological activity. Subsequently, two pilot-scale pressurised filters were installed in a commercial scale hatchery in order to compare the metabolite removal performance of manganese dioxide against silicate sand in the presence of biological activity commonly found in aquaculture conditions. The investigation suggests that Mn medium is more reliable in converting ammonia to nitrate without producing a residual output of nitrite. The superior performance ofMn media compared with sand appears to be mainly related to the physical structure of the manganese ore. Furthermore, the Mn medium did not appear to be soluble in the ambient conditions normally found in aquaculture-closed system. From the design point of view, due to the higher ammonia and nitrite removal rates, a shorter retention time and a lower volume of media are required in the case of manganese dioxide technology compared with sand media. As a result, it is much easier to size a biofilter with Mn media. Manganese systems have a comparable total costs to conventional sand media, but using the Mn technology provides a more reliable control of toxic nitrite, thereby reducing risks offish loss and hence with reduced expected production costs.

International Telemetering Conference Proceedings / October 25-28, 1999 / Riviera Hotel and Convention Center, Las Vegas, Nevada / The rapid growth in portable and wireless communication products has brought valuable advancements in battery technology. No longer is a battery restricted to a metal container in cylindrical or prismatic format. Today’s batteries (both primary and secondary) can be constructed in thin sheets and sealed in foil/plastic laminate packages. Along with improvements in energy density, temperature performance, and environmentally friendly materials, these batteries offer greater packaging options at a significantly lower development cost. Under the Hardened Subminiature Telemetry and Sensor System (HSTSS) program these battery technologies have been further developed for high-g telemetry applications. Both rechargeable solid state lithium-ion polymer and primary lithium manganese dioxide batteries are being developed in conjunction with Ultralife Batteries Inc. Prototypes of both chemistries have been successfully tested in a ballistic environment while providing high constant rates of discharge, which is essential to these types of applications. Electrical performance and environmental data are reported.

The reaction between various forms of manganese dioxide and halide ions has been investigated. Analytical techniques for the study of this heterogeneous liquid-solid reaction have been developed. The appearance of the reaction products, I₂ and Mn²⁺, was monitored in the aqueous phase of the reaction mixture. I₂ was monitored using amperometry. Mn²⁺ was monitored by a novel application of flow injection analysis. A molecular mechanism was postulated which accounts for the complex pH dependence of the reaction and the inhibition of the reaction under conditions of lower hydrogen ion concentration. The potential of the manganese dioxide-iodide reaction for the metallurgical processing of ferromanganese nodules has been demonstrated. Studies show that there is a preferential dissolution of the manganese portion of the nodules by the action of iodide in acidic conditions. The use of deconvolution techniques for obtaining information from overlapping flow injection analysis peaks has been shown to be feasible. Deconvolution techniques allow an increase in the sampling rates which will broaden the application of flow injection analysis in kinetic studies.

Incorporation of magnetic microparticles (~ 1 um) at electrode structures increases electron transfer e¢ ciency, observed as increased current, for multiple electrochemical systems. Current increases occur with magnetic field. Inclusion of magnetic materials into the cathode matrix of alkaline MnO2 batteries requires the materials to be stable in the strong base electrolyte, typically 6 to 9 M KOH. Samarium cobalt magnetic particles sustain strong permanent magnetic fields and are stable in base without surface modification. Studies were undertaken at fast (C/2), moderate (C/3), and slow (C/5) constant current discharges. Here, alkaline MnO2 batteries generated increased power and energy when magnetic microparticles are incorporated into the cathode of the battery. Because of anode limitations in the battery, total coulombic output is not increased for the first electron discharge, but the available power and energy is significantly higher compared to nonmagnetic batteries at voltages above 0.9V. Constant current discharge curves of magnetic batteries demonstrate higher voltages than nonmagnetic batteries at a given time, which translates to greater power output. This effect is also observed by electrochemical impedance spectroscopy, where charge transfer resistance is less for magnetically modified cells. This work also developed voltammetric measurement protocols for acetone concentration collected in the liquid and vapor phase and measured in solution. Acetone on the breath is an indicator for physiological dysregulation. Measurements are demonstrated for acetone concentrations across the human physiological range, 1 uM to 10 mM at platinum electrodes in 0.5 M H2SO4. Effects arise through adsorption of acetone from the gas phase onto a platinum surface and hydrogen in acidic solution within the voltammetric butterfly region. The protocol is demonstrated to yield breath acetone concentration on a human subject within the physiological range and consistent with ketone urine test strip.

In this study, potassium permanganate was used as the oxidant to remediate TCE¡Vcontaminated groundwater. The objectives of this bench-scale oxidation study include the following: (1) evaluate the overall TCE oxidation rate with the presence of KMnO4, (2) assess the consumption rate of KMnO4, (3) evaluate the effect of the oxidation by-product, manganese dioxide (MnO2), on the TCE oxidation rate. The control factors in this study include (1) four different molar ratios of KMnO4 to TCE [designated as P, (KMnO4/TCE) = 2, 5, 10, and 20]; (2) four different TCE concentration (0.5, 5, 20, and 100 ppm); (3) three different initial pH values (2.1, 6.3, and 12.5); (4) three different oscillator mix rate (0, 50, and 200 rpm); (5) four different molar ratios of dibasic sodium phosphate (Na2HPO4) to Mn2+ [designated as D, (Na2HPO4/Mn2+) = 0, 50, 100, and 300D], and (6) two different medium solutions [deionized (DI) water and groundwater]. Moreover, the effects of D values on TCE oxidation rate and KMnO4 consumption rate were also evaluated. Experimental results indicate that a second-order reaction model could be applied to express the oxidation reaction of TCE by KMnO4, and the calculated rate constant equals 0.8 M-1s-1. Results also show that the higher the P value, the higher the TCE oxidation rate. Moreover, TCE oxidation rate was not affected under low pH conditions (pH = 2.10 and 6.3). However, TCE oxidation rate dropped under high pH condition (pH 12.5) due to the transformation of KMnO4 to manganese dioxide. The following three pathways would cause the production of manganese dioxide: (1) direct oxidation of TCE by KMnO4, (2) production of Mn2+ after the oxidation of TCE by KMnO4, and Mn2+ was further oxidized by KMnO4 to form manganese dioxide, and (3) transformation of KMnO4 to manganese dioxide under high pH condition. Results also show that more manganese dioxide was produced while groundwater was used as the medium solution. Results show that the produced manganese dioxide was 47.2% - 81.5% less with the addition of dibasic sodium phosphate. Moreover, the variations in D values would not affect the TCE oxidation rate. However, the increase in D value would decrease the consumption of KMnO4. Results also reveal that significant inhibition of manganese dioxide production was observed under low pH condition. Furthermore, no TCE oxidation byproducts were detected after the oxidation reaction. Key words: KMnO4, TCE, manganese dioxide and dibasic sodium phosphate

Nitrogen oxide in water was a critical factor of eutrophication. The poor tap-water quality in Taiwan was the result of ammonia nitrogen pollution. This research used manganese dioxide as the catalyst to degrade ammonia nitrogen content in water. Controlled factors in our experiment include basic test, optimal reaction condition test, and kinetics. Real water sample was drawn from the Love River for catalysis effect test. Results were then compared with the popularly used titanium dioxide. Significant findings in this research include: 1) when the manganese dioxide content in water was 2%, the ammonia nitrogen removal rates were 31.80% under UV irradiation, and 22.21 % without light interference; 2) under UV irradiation, manganese dioxide would not affect the catalysis effect due to pH changes; 3) silicate in the water had catalysis effect, while sulfate, phosphate, and nitrate had inhibition effect; 4) manganese dioxide had catalysis effect in seawater, yet the removal rate would decrease as the salt content increases; 5) the rise of water temperature would enhance the ammonia nitrogen removal rate; 6) manganese dioxide had catalysis effect on the treatment of the Love River water, and the ammonia nitrogen removal rate reached 89.50 %; 7) in the biological test, manganese dioxide could effectively degrade the ammonia nitrogen content in water, and improve the survival rate of larval shrimp; 8) comparing to titanium dioxide, manganese dioxide had advantages of low cost, with catalysis effect in both seawater and fresh water under no light condition. As a result, manganese dioxide has significant future application potentials. In the future, this research will conduct in-depth study on kinetics of degradability of manganese dioxide catalysis on ammonia nitrogen, and to design suitable catalytic reactor for water treatment. Moreover, it is of value to broadly research manganese dioxide related catalytic products, such as catalytic spray, catalytic paint, fluorescent tube, air filter, and catalytic fan...etc.