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.

Determing the Effect of Thermal Treatment Timing on Ultra-High Performance Concrete Beams

The loss of prestressing force over time influences the long-term deflection of the prestressed concrete element. Prestress losses are inherently complex due to the interaction of concrete creep, concrete shrinkage, and steel relaxation. Implementing advanced materials such as ultra-high performance concrete (UHPC) further complicates the estimation of prestress losses because of the changes in material models dependent on curing regime. Past research shows compressive creep is "locked in" when UHPC cylinders are subjected to thermal treatment before being loaded in compression. However, the current precasting manufacturing process would typically load the element (through prestressing strand release from the prestressing bed) before the element would be taken to the curing facility. Members of many ages are stored until curing could be applied to all of them at once. This research was conducted to determine the impact of variable curing times for UHPC on the prestress losses, and hence deflections. Three UHPC beams, a rectangular section, a modified bulb tee section, and a pi-girder, were assessed for losses and deflections using an incremental time step approach and material models specific to UHPC based on compressive creep and shrinkage testing. Results show that although it is important for prestressed UHPC beams to be thermally treated, to "lock in" material properties, the timing of thermal treatment leads to negligible differences in long-term deflections. Results also show that for UHPC elements that are thermally treated, changes in deflection are caused only by external loads because prestress losses are "locked-in" following thermal treatment.

The Survival and Stock Performance of Emerging Country Firms in the United States

Many firms from emerging markets flocked to developed countries at high cost with hopes of acquiring strategic assets that are difficult to obtain in home countries. Adequate research has focused on the motivations and strategies of emerging country firms' (ECFs') internationalization, while limited studies have explored their survival in advanced economies years after their venturing abroad. Due to the imprinting effect of home country institutions that inhibit their development outside their home market, ECFs are inclined to hire executives with international background and affiliate to world-wide organizations for the purpose of linking up with the global market, embracing multiple perspectives for strategic decisions, and absorbing the knowledge of foreign markets. However, the effects of such orientation on survival are under limited exploration. Motivated by the discussion above, I explore ECFs’ survival and stock performance in a developed country (U.S.). Applying population ecology, signaling theory and institutional theory, the dissertation investigates the characteristics of ECFs that survived in the developed country (U.S.), tests the impacts of global orientation on their survival, and examines how global-oriented activities (i.e. joining United Nations Global Compact) affect their stock performance. The dissertation is structured in the form of three empirical essays. The first essay explores and compares different characteristics of ECFs and developed country firms (DCFs) that managed to survive in the U.S. The second essay proposes the concept of global orientation, and tests its influences on ECFs’ survival. Employing signaling theory and institutional theory, the third essay investigates stock market reactions to announcements of United Nation Global Compact (UNGC) participation. The dissertation serves to explore the survival of ECFs in the developed country (U.S.) by comparison with DCFs, enriching traditional theories by testing non-traditional arguments in the context of ECFs’ foreign operation, and better informing practitioners operating ECFs about ways of surviving in developed countries and improving stockholders’ confidence in their future growth.

Ownership Structure, Board Composition and Entrepreneurship : Evidence from Family Firms and Venture-Capital Backed Firms

The purpose of this article is to investigate how ownership structure, especially family and/or venture-capital involvement, as well as entrepreneurial activities, defined as strategic change and renewal, help explain the involvement of independent members on boards of directors. The CEOs of 2,455 small and medium-sized, private enterprises from practically all industries were contacted in a telephone survey, resulting in an exceptionally high response rate. The findings reveal that family firms are more reluctant to involve independent directors on their boards than non-family firms that presence of venture capitalists increases the frequency of independent board members and that ownership has an impact on board roles. The results do not support the hypothesised relationship that independent directors enhance entrepreneurial activities. One implication of our study is that the often-argued-for strategic contribution of outsiders to the boards in family firms may be overemphasised. Another implication is that family firms that choose to acquire additional capital should be aware that this could result in a change in the board composition and the loss of control of the business. However, new and external owners’ inclusion on the board seems to be negotiable since there are also venture capitalists that do not insist on board representation.

The Influence of Age and Size on Family-Owned Firms’ Financing Decisions: Empirical Evidence Using Panel Data

Based on four samples of Portuguese family-owned firmsdi) 185 young, low-sized family-owned firms; ii) 167 young, high-sized familyowned firms; iii) 301 old, low-sized family-owned firms; and iv) 353 old, high-sized family-owned firms d we show that age and size are fundamental characteristics in family-owned firms’ financing decisions. The multiple empirical evidence obtained allows us to conclude that the financing decisions of young, low-sized family-owned firms are quite close to the assumptions of Pecking Order Theory, whereas those of old, high-sized family-owned firms are quite close to what is forecast by Trade-Off Theory. The lesser information asymmetry associated with greater age, the lesser likelihood of bankruptcy associated with greater size, as well as the lesser concentration of ownership and management consequence of greater age and size, may be especially important in the financing decisions of family-owned firms. In addition, we find that GDP, interest rate and periods of crisis have a greater effect on the debt of young, low-sized family-owned firms than on that of family-owned firms of the remainder research samples.

The'cave' mineral oxammite: a high resolution thermogravimetry and Raman spectroscopic study

The thermal decomposition of natural ammonium oxalate known as oxammite has been studied using a combination of high resolution thermogravimetry coupled to an evolved gas mass spectrometer and Raman spectroscopy coupled to a thermal stage. Three mass loss steps were found at 57, 175 and 188°C attributed to dehydration, ammonia evolution and carbon dioxide evolution respectively. Raman spectroscopy shows two bands at 3235 and 3030 cm-1 attributed to the OH stretching vibrations and three bands at 2995, 2900 and 2879 cm-1, attributed to the NH vibrational modes. The thermal degradation of oxammite may be followed by the loss of intensity of these bands. No intensity remains in the OH stretching bands at 100°C and the NH stretching bands show no intensity at 200°C. Multiple CO symmetric stretching bands are observed at 1473, 1454, 1447 and 1431cm-1, suggesting that the mineral oxammite is composed of a mixture of chemicals including ammonium oxalate dihydrate, ammonium oxalate monohydrate and anhydrous ammonium oxalate.

Micropolar flow in a porous channel with high mass transfer

Two dimensional flow of a micropolar fluid in a porous channel is investigated. The flow is driven by suction or injection at the channel walls, and the micropolar model due to Eringen is used to describe the working fluid. An extension of Berman's similarity transform is used to reduce the governing equations to a set of non-linear coupled ordinary differential equations. The latter are solved for large mass transfer via a perturbation analysis where the inverse of the cross-flow Reynolds number is used as the perturbing parameter. Complementary numerical solutions for strong injection are also obtained using a quasilinearisation scheme, and good agreement is observed between the solutions obtained from the perturbation analysis and the computations.