Characterization of a Coal Fly Ash-Cement Slurry by the Absolute Foam Index

This dissertation established a standard foam index: the absolute foam index test. This test characterized a wide range of coal fly ash by the absolute volume of air-entraining admixture (AEA) necessary to produce a 15-second metastable foam in a coal fly ash-cement slurry in a specified time. The absolute foam index test was used to characterize fly ash samples having loss on ignition (LOI) values that ranged from 0.17 to 23.3 %wt. The absolute foam index characterized the fly ash samples by absolute volume of AEA, defined as the amount of undiluted AEA solution added to obtain a 15-minute endpoint signified by 15-second metastable foam. Results were compared from several foam index test time trials that used different initial test concentrations to reach termination at selected times. Based on the coefficient of variation (CV), a 15-minute endpoint, with limits of 12 to 18 minutes was chosen. Various initial test concentrations were used to accomplish consistent contact times and concentration gradients for the 15-minute test endpoint for the fly ash samples. A set of four standard concentrations for the absolute foam index test were defined by regression analyses and a procedure simplifying the test process. The set of standard concentrations for the absolute foam index test was determined by analyzing experimental results of 80 tests on coal fly ashes with loss on ignition (LOI) values ranging from 0.39 to 23.3 wt.%. A regression analysis informed selection of four concentrations (2, 6, 10, and 15 vol.% AEA) that are expected to accommodate fly ashes with 0.39 to 23.3 wt.% LOI, depending on the AEA type. Higher concentrations should be used for high-LOI fly ash when necessary. A procedure developed using these standard concentrations is expected to require only 1-3 trials to meet specified endpoint criteria for most fly ashes. The AEA solution concentration that achieved the metastable foam in the foam index test was compared to the AEA equilibrium concentration obtained from the direct adsorption isotherm test with the same fly ash. The results showed that the AEA concentration that satisfied the absolute foam index test was much less than the equilibrium concentration. This indicated that the absolute foam index test was not at or near equilibrium. Rather, it was a dynamic test where the time of the test played an important role in the results. Even though the absolute foam index was not an equilibrium condition, a correlation was made between the absolute foam index and adsorption isotherms. Equilibrium isotherm equations obtained from direct isotherm tests were used to calculate the equilibrium concentrations and capacities of fly ash from 0.17 to 10.5% LOI. The results showed that the calculated fly ash capacity was much less than capacities obtained from isotherm tests that were conducted with higher initial concentrations. This indicated that the absolute foam index was not equilibrium. Rather, the test is dynamic where the time of the test played an important role in the results. Even though the absolute foam index was not an equilibrium condition, a correlation was made between the absolute foam index and adsorption isotherms for fly ash of 0.17 to 10.5% LOI. Several batches of mortars were mixed for the same fly ash type increasing only the AEA concentration (dosage) in each subsequent batch. Mortar air test results for each batch showed for each increase in AEA concentration, air contents increased until a point where the next increase in AEA concentration resulted in no increase in air content. This was maximum air content that could be achieved by the particular mortar system; the system reached its air capacity at the saturation limit. This concentration of AEA was compared to the critical micelle concentration (CMC) for the AEA and the absolute foam index.

HIGH VOLTAGE ELECTROPHORETIC DEPOSITION FOR ELECTROCHEMICAL ENERGY STORAGE AND OTHER APPLICATIONS

High voltage electrophoretic deposition (HVEPD) has been developed as a novel technique to obtain vertically aligned forests of one-dimensional nanomaterials for efficient energy storage. The ability to control and manipulate nanomaterials is critical for their effective usage in a variety of applications. Oriented structures of one-dimensional nanomaterials provide a unique opportunity to take full advantage of their excellent mechanical and electrochemical properties. However, it is still a significant challenge to obtain such oriented structures with great process flexibility, ease of processing under mild conditions and the capability to scale up, especially in context of efficient device fabrication and system packaging. This work presents HVEPD as a simple, versatile and generic technique to obtain vertically aligned forests of different one-dimensional nanomaterials on flexible, transparent and scalable substrates. Improvements on material chemistry and reduction of contact resistance have enabled the fabrication of high power supercapacitor electrodes using the HVEPD method. The investigations have also paved the way for further enhancements of performance by employing hybrid material systems and AC/DC pulsed deposition. Multi-walled carbon nanotubes (MWCNTs) were used as the starting material to demonstrate the HVEPD technique. A comprehensive study of the key parameters was conducted to better understand the working mechanism of the HVEPD process. It has been confirmed that HVEPD was enabled by three key factors: high deposition voltage for alignment, low dispersion concentration to avoid aggregation and simultaneous formation of holding layer by electrodeposition for reinforcement of nanoforests. A set of suitable parameters were found to obtain vertically aligned forests of MWCNTs. Compared with their randomly oriented counterparts, the aligned MWCNT forests showed better electrochemical performance, lower electrical resistance and a capability to achieve superhydrophpbicity, indicating their potential in a broad range of applications. The versatile and generic nature of the HVEPD process has been demonstrated by achieving deposition on flexible and transparent substrates, as well as aligned forests of manganese dioxide (MnO2) nanorods. A continuous roll-printing HVEPD approach was then developed to obtain aligned MWCNT forest with low contact resistance on large, flexible substrates. Such large-scale electrodes showed no deterioration in electrochemical performance and paved the way for practical device fabrication. The effect of a holding layer on the contact resistance between aligned MWCNT forests and the substrate was studied to improve electrochemical performance of such electrodes. It was found that a suitable precursor salt like nickel chloride could be used to achieve a conductive holding layer which helped to significantly reduce the contact resistance. This in turn enhanced the electrochemical performance of the electrodes. High-power scalable redox capacitors were then prepared using HVEPD. Very high power/energy densities and excellent cyclability have been achieved by synergistically combining hydrothermally synthesized, highly crystalline α-MnO2 nanorods, vertically aligned forests and reduced contact resistance. To further improve the performance, hybrid electrodes have been prepared in the form of vertically aligned forest of MWCNTs with branches of α-MnO2 nanorods on them. Large- scale electrodes with such hybrid structures were manufactured using continuous HVEPD and characterized, showing further improved power and energy densities. The alignment quality and density of MWCNT forests were also improved by using an AC/DC pulsed deposition technique. In this case, AC voltage was first used to align the MWCNTs, followed by immediate DC voltage to deposit the aligned MWCNTs along with the conductive holding layer. Decoupling of alignment from deposition was proven to result in better alignment quality and higher electrochemical performance.