In this study, polypyrrole (PPy) prepared by chemical and electrochemical polymerization was investigated as the electrode of electrochemical supercapacitor (ES). New strategies were developed for the fabrication of nano-structured PPy and PPy based nano-composites, which included discovery of advanced anionic dopants and multi-functional nano-crystals, and development of co-dispersing agents. These methods improved the capacitive performance and cycle stability of PPy electrodes. The results indicated that high material loading and good capacitance retention of PPy was achieved using an electrochemical polymerization method and Ni plaque as the current collectors. Nano-crystalline (CTA)2S2O8 formed by a chemical precipitation method from solutions, containing anionic oxidant (S2O82-) and cationic surfactant (CTA+), could be used as the oxidant to synthesize PPy nano-fibers. We demonstrated that multi-wall carbon nanotubes (MWCNT) can be efficiently dispersed using such nano-crystals. Application of multi-functional nano-crystals is a conceptually new approach for the fabrication PPy coated MWCNT. Moreover, safranin and malachite green were found as universal dispersing and charging agents for cataphoretic deposition of graphene, MWCNT and PPy nano-fibers. It opens new strategies in colloidal and electrochemical processing of PPy nano-composites for ES electrodes. PPy coated MWCNT, prepared by the multi-functional nano-crystals (CTA)2S2O8, was employed for the fabrication of N-doped activated carbon-coated MWCNT (N-AC-MWCNT). The obtained N-AC-MWCNT was uniformly coated and possessed with high surface area. The use of N-AC-MWCNT enabled the fabrication of ES electrodes with high mass loading and high active material to current collector mass ratio. Symmetric and asymmetric ES cells, fabricated by N-AC-MWCNT and aqueous Na2SO4 electrolyte, showed high specific capacitance, good capacitance retention and large voltage window. The positive electrode of asymmetric ES, MnO2 coated MWCNT, was successfully prepared by the chemical reaction between KMnO4 and N-AC-MWCNT. The problem of degradation of MWCNT was avoided by the use of N-AC as the sacrificial carbon. Significant progress on ES technology has allowed for the development of capacitive dyes removal (CDR) methods using ES devices. In our study, porous carbon materials, N-doped activated carbon coated MWCNT (N-AC-MWCNT) and N-doped activated carbon nano-fibers (N-AC-NF), were developed as the electrodes for CDR applications. The experimental results indicated that capacitive performance of ES cells was influenced by the chemical structure, size, charge-to mass ratio, concentration and redox-active ligands of the dyes. CDR is a promising method for removal of various cationic and anionic dyes, which offers advantages of energy saving and simple electrode regeneration. / Thesis / Doctor of Philosophy (PhD)

Polymer coatings are thin films of polymer deposited on different substrates for various applications. Such surface coatings can serve a functional purpose (adhesives, photographic films), protective purpose (anticorrosion), or decorative purpose (paint). Additionally, their composite coatings containing ceramic, or metal particles are often used to enhance durability, functionality, or aesthetics. Electrophoretic deposition (EPD) and dip coating are two promising methods for the fabrication of polymer and composite coatings due to the ease of fabrication, low cost, and high-volume production. EPD involves the electrophoresis of charged particles and their deposition on the electrode surface, which requires the colloidal particles to be charged in a stable suspension as a precursor solution for deposition. Many polymers cannot be deposited by EPD directly because of their charge neutrality and poor dispersion. Therefore, it is critical to develop efficient charging dispersants to modify electrically neutral polymers for their EPD. The approach was inspired by the strong solubilization power of bile acids in the human body. Two types of bile salts, cholic acid sodium salt and sodium chenodeoxycholate, and three types of biosurfactants, carbenoxolone sodium salt, glycyrrhizic acid, and 18β-glycyrrhetinic acid, which share similar structures with bile salts, were discovered for charging, dispersion, and EPD of different materials. The electrically neutral polymers (PTFE and PVDF), chemically inert materials (diamond, nanodiamond, graphene, carbon dots, carbon nanotubes and Zr-doped hydrotalcite (MHT)), and their composites can be well dispersed in suspension and deposited using these bio-surfactants as dispersants. It was found that the unique chemical structures of these biomolecules play vital roles in the surface modification and EPD of different materials. Moreover, the deposited polymer (PVDF, PTFE) and composite (PTFE-MHT) coatings can provide outstanding corrosion protection for stainless steel. The biomimetic and versatile strategy opens a way for the deposition of other electrically neutral materials through EPD. These findings also provide a promising strategy for selecting new dispersants for EPD. The deposition of high molecular weight (MW) polymers such as poly(ethyl methacrylate) (PEMA) at high concentrations in non-toxic solvents continues to be a challenge for dip coating. In this work, we firstly proposed using water-isopropanol as a co-solvent to dissolve high MW PEMA at high concentrations. It was found that water molecules can solvate carbonyl groups of PEMA and facilitate their dissolution. This method avoided the usage of toxic solvents and a long-time heating procedure for their removal. Moreover, it allows the fabrication of high-quality PEMA and composite coatings containing different flame retardant materials (FRMs), including double hydroxide LiAl2(OH)7.2H2O (LiAlDH), huntite, halloysite and hydrotalcite, through the dip coating method. A novel solid state synthesis method was proposed to fabricate LiAlDH, which is promising for the fabrication of other advanced DHs. Such composite coatings combined advanced properties of PEMA and functional properties of FRMs, such as corrosion inhibition and FR properties. / Thesis / Doctor of Engineering (DEng) / Polymer and composite coatings have been utilized for a wide range of applications due to their barrier properties, scratch and abrasion resistance, chemical resistance, and biocompatibility. Various techniques have been developed to fabricate polymer and composite coatings, such as electrophoretic deposition (EPD) and the dip coating method. However, limitations remain. EPD unitizes an electrical field to drive charged particles in a suspension toward conductive substrates to achieve film deposition. This process requires a stable suspension with charged particles, therefore, the electroneutral polymers present difficulties in their EPD. In addition, dissolving high molecular weight polymers at high concentrations in a non-toxic solvent is currently challenging, which is vital to utilize dip coating technique. The objective of this work was to develop advanced charging dispersants for EPD of electroneutral polymers and non-toxic solvents for dip coating of high molecular weight polymers. New biomimetic and versatile approaches have been developed for EPD of different electrically neutral polymers, chemically inert materials, and their composite coatings. A non-toxic co-solvent was proposed to dissolve high molecular weight polymer at high concentration for dip coating of the polymer and its composite coatings containing flame retardant materials. The results presented in this work showed the formation of high-quality films with multifunctionality and paved new strategies for further developments.

<p>Electrochemical deposition methods have been developed for the fabrication of organic － inorganic nanocomposite coatings. The methods are based on electrophoretic deposition of ceramic nanoparticles and polymers.</p> <p>EPD method has been developed for the deposition of nanostructured TiO₂ films using new dispersing agents. The stabilization and charging of the nanoparticles in suspensions was achieved using these organic molecules, which belong to catecholate and salicylate families. Anodic deposition was achieved using caffeic acid, 2,3－dihydroxybenzoic acid, 2,6－dihydroxybenzoic acid and 5－sulfosalicylic acid. Cathodic deposition was performed using 2,4 dihydroxycinnamic acid, p－coumaric acid and trans cinnamic acid. The deposition yield has been studied as a function of the additive concentration and deposition time. The deposition mechanism has been investigated. The fundamental adsorption mechanism is based on the complexation of metal ions at the surfaces of oxide nanoparticles. The method enabled the co-deposition of TiO₂ and other oxides and the formation of composite films.</p> <p>Electrophoretic deposition method has been used for the deposition of TiO₂ nanoparticles modified with organic dyes. Alizarin red, alizarin yellow, pyrocatechol violet and Aurintricarboxylic acid dyes were used for the dispersion and charging of TiO₂. The microstructures of the nanocomposite coatings were studied. The deposition yield was investigated under a variety of conditions. Obtained results could pave the way for the fabrication of dye-sensitized TiO₂ films.</p> <p>EPD method has also been developed for the fabrication of (Poly[3-(3-N,N-diethylaminopropoxy)thiophene]) PDAOT－TiO₂, (polyethylenimine) PEI－TiO₂ and PEI－hydrotalcite composite films. The microstructures of the nanocomposite coatings were studied by Scanning Electron Microscopy, Thermogravimetric Analysis, which showed the co－deposition of inorganic nanoparticles and organic polymer. Electrochemical test of the composite film has been conducted. The results showed that PEI film provided corrosion protection of the stainless steel substrates.</p> / Master of Science (MSc)

<p>Electrochemical methods show great promise in the deposition of biocompatible coatings for biomedical applications with advanced functionality. Consequently, methods of creating coatings of bioactive materials, such as halloysite nanotubes (HNT), hydroxyapatite (HA), chitosan, hyaluronic acid (HYH), poly-L-ornithine (PLO) and poly-L-lysine (PLL) and polyacrylic acid (PAA) have been developed through the use of electrophoretic deposition (EPD). The co-deposition of these materials are achieved at voltages ranging from 5 to 20 V on a 304 stainless steel substrate using suspensions of 0.5 and 1.0 gL^-1 biopolymer (chitosan, PAA, PLO, PLL) containing 0.3, 0.5 0.6, 1.0 and 2.0 gL^-1 bioceramic (HNT, HA). The resulting films were then investigated to further understand the kinetics and mechanics of deposition, determine their properties, and evaluate their suitability for physiological applications. The films were studied using X-Ray Diffraction (XRD), Differential Thermal Analysis and Thermogravimetric Analysis (DTA/TGA), Scanning Electron Microscopy (SEM), Quartz Crystal Microbalance (QCM) and Linear Polarisation. The results indicate that film thickness, composition and morphology can be controlled and modified at will, and that the deposition of composite films, multilayer laminates and functionally graded films are possible.</p> / Master of Applied Science (MASc)

Electrochemical supercapacitors (ESs) have attracted great attention due to the advantages of long cycle life, high charge/discharge rate and high power density compared to batteries. Significant improvement in ES performance has been achieved via development of advanced nanostructured materials, such as MnO2 and composite MnO2-MWCNT and PPy-MWCNT electrodes. In this dissertation, advanced dispersants were developed and investigated for the dispersion, surface modification and electrophoretic deposition (EPD) of metal oxides, multiwalled carbon nanotubes (MWCNT) and polypyrrole (PPy) in different solvents. Nature-inspired strategies have been developed for the fabrication of MWCNT films and composites. The outstanding colloidal stability of MWCNT, dispersed using anionic bile acids, allowed the EPD of MWCNT. Composite MnO2-MWCNT films were obtained by anodic EPD on Ni plaque and Ni foam substrates. Good dispersion of MWCNT during Py polymerization was achieved and allowed the formation of PPy coated MWCNT. The film and bulk electrodes, prepared by EPD and slurry impregnation methods, respectively, showed high capacitance and good capacitance retention at high charge-discharge rates. The mechanisms of dispersion and deposition were investigated. Cathodic and anodic EPD of MWCNT, MnO2, Mn3O4 was achieved using positively and negatively charged dispersants. Co-deposition of MWCNT and MnO2 was performed using a co-dispersant, which dispersed both MWCNT and MnO2 in ethanol. Composite films were tested for ES applications. The efficient dispersion was achieved at relatively low dispersant concentrations due to strong adsorption of the dispersants on the particle surface, which involved the polydentate bonding. We found the possibility of efficient dispersion of MWCNT in ethanol using efficient anionic dispersants. The electrostatic assembly method has been developed, which offers the benefit of improved mixing of MnO2 and MWCNT. The use of different anionic and cationic dispersants allowed the fabrication of electrodes with enhanced capacitance and improved capacitance retention at high charge–discharge rates and high active mass loadings. The asymmetric devices, containing positive MnO2–MWCNT and negative AC–CB electrodes showed promising performance in a voltage window of 1.6 V. We proposed another novel concept based on electrostatic heterocoagulation of Mn3O4- MWCNT composites in aqueous environment. In this case, various dispersants were selected for adsorption and dispersion of MWCNT and Mn3O4 and this allowed the formation of stable aqueous suspensions of positively charged MWCNT and negatively charged Mn3O4, which facilitated the formation of advanced composites with improved mixing of the components. Testing results showed promising performance of Mn3O4–MWCNT composites for applications in electrodes of electrochemical supercapacitors. / Thesis / Doctor of Philosophy (PhD)

<p> New electrophoretic deposition methods for the fabrication of advanced organic-inorganic composite coatings on metallic substrates for biomedical applications have been developed. In the proposed methods, chitosan was used as a matrix for the fabrication of multilayer and functional graded chitosan- hydroxyapatite (HA) coatings. The HA particles showed preferred orientation of c-axis parallel to the layer surface, which is similar to the bone structure. Electrochemical studies showed that the obtained coatings provided corrosion protection of the metallic substrates, such as stainless steel and Nitinol.</p> <p> The feasibility of co-deposition of chitosan and heparin has been demonstrated. Composite chitosan-heparin layers were used for the surface modification of chitosan-HA coatings. Obtained results paved the way for the electrophoretic fabrication of novel coatings for biomedical implants with improved blood compatibility.</p> <p> The feasibility of co-deposition of hyaluronic acid and HA has also been demonstrated. The co-deposition of hyaluronic acid and HA resulted in the fabrication of novel nanocomposite films by electrodeposition. The chemical composition, microstructure, corrosion protection, and other functional properties of the nanocomposites have been investigated. Co-deposition of hyaluronic acid and multiwalled carbon nanotubes has been studied by TGA/DT A and SEM studies.</p> <p> The feasibility of deposition of novel composites based on alginic acid has been demonstrated. New electrochemical strategies were used for the fabrication of alginic acid-HA, alginic acid-heparin and alginic acid -hyaluronic acid nanocomposites. The composition of these nanocomposite coatings can be varied by variation in bath composition for EPD.</p> <p> The electrochemical mechanisms for the fabrication of all these advanced organic-inorganic composite coatings have been developed.</p> / Thesis / Master of Applied Science (MASc)

No / Ten different mathematical models representing the electrophoretic mobility of analytes in capillary electrophoresis in mixed solvents of different composition have been compared using 32 experimental data sets. The solvents are binary mixtures of water-methanol, water-ethanol and methanol-ethanol, respectively. Mean percentage deviation (MPD), overall MPD (OMPD) and individual percentage deviation (IPD) have been considered as comparison criteria. The results showed that a reorganized solution model, namely the combined nearly ideal binary solvent/Redlich-Kister equation, is the most accurate model among other similar models concerning both correlation ability and prediction capability

Concrete is the most essential construction material due to its high availability, low costs, excellent compressive strength, and high durability nature. However, cement-based composites possess some disadvantageous features, notably brittleness and diminished flexural/tensile strength. To surmount these challenges, the integration of reinforcement into cementitious materials becomes imperative. One of the most promising reinforcement materials is high-strength carbon fiber (CF), which manifests in forms such as dispersed short fibers, rebar, and textile to fabricate the carbon fiber-reinforced cementitious composite (CFRC). As opposed to traditional steel-reinforced structural elements, the chemically inert CF does not demand a thick protective cover, which enables the creation of slender-walled, resource-conserving structural components. However, CFRC materials exhibit poor interfacial adhesion between hydrophobic CF and enveloping cementitious matrices, thereby limiting the efficient force transfer at the interface. The commonly used polymeric impregnation for the CF multifilaments is susceptible to degradation under heightened temperatures, a circumstance adverse to structural integrity, particularly in fire scenarios. As an alternative, thermally stable inorganic binders characterized by exceedingly fine particulates emerge as suitable candidates for impregnation. This finely dispersed suspension penetrates the CF roving housing multitudes of filaments, inducing enhancements in bonding interactions among CF filaments as well as between the roving and the cement matrix. The dissertation at hand suggests an innovative approach that utilizes fine mineral particles as a coating material. Its core objective revolves around the advancement of the electrophoretic deposition (EPD) method for nano-silica (NS) onto CF surfaces, with the intention of enhancing interfacial bonding with cementitious matrices. To achieve this, a comprehensive exploration into the effects of voltage, treatment duration, and pH value during surface modification on bond performance and fiber properties is undertaken. The bond-slip behavior of the modified CFs toward the cement matrix depending on the curing ages is systematically studied from various aspects of the single-fiber pullout curves. In extension to the experimental results, a numerical simulation is used to elucidate the stress distribution during the debonding process, while also serving to approximate and describe the force-displacement pullout curves. Furthermore, amorphous silica fume and micro-sized quartz are harnessed for electrophoretic modification of CF surfaces, allowing for a comparative evaluation with NS coating in terms of enhancing bond behavior. The morphological features of modified CF surfaces are scrutinized using scanning electron microscopy. Single fiber tension experiments and thermogravimetric analysis are performed to study the impact of EPD modification on the mechanical properties and temperature sensibility of CFs. Uniaxial quasi-static single-fiber pullout tests are conducted to provide profound insights into the interfacial interaction between CF and surrounding cement matrices at different stages during the pullout process. Within the EPD system, the kinetics of CF electrode reaction and the zeta potential of suspensions are examined through cyclic voltammetry experiments and zeta potential measurements, respectively. These investigations elucidate alterations in the surface chemistry of CFs and the quality of the coating under diverse treatment conditions.

In this work experimental design and tests were established to determine whether antibody production in guinea pigs injected with a bacterial antigen is Influenced by the environment of simulated high altitude with normoxic conditions. Hematological and electrophoretic studies were simultaneously run with the antibody determinations as a check on related responses of the animals.

Cette thèse s’intéresse principalement à la réalisation de nouvelles encres électrophorétiques pour les applications de type papier électronique couleur. Une méthode simple et peu contraignante basée sur la polymérisation en dispersion a été développée, permettant de réaliser de manière contrôlée et en milieu peu polaire des particules de polymère chargeables positivement ou négativement. Puis, grâce à ce nouvel outil, des particules électrophorétiques hybrides ont été synthétisées à partir de pigments inorganiques et caractérisées sous champ électrique. Enfin une nouvelle solution pour aller vers des dispositifs couleur a été proposée et la fabrication d’un démonstrateur test a été abordée. / The effective sharing of information is a key parameter in our actual society. Electronic paper based on the controlled motion of electrophoretic particles appears thus promising since it combines the advantages of the usual paper (flexibility, reflective display) and the capacity to refresh information on the same support like the more common LCD or OLED technologies. Electrophoretic inks are composed of coloured charged particles which migrate under an electrical field between two electrodes. Depending of the position of the particles on the front plane, the colour on the screen can be tuned. The design of electrophoretic particles based on pigment or dyed polymer and their integration in electronic devices were successfully achieved during the last decade but are still limited to a two colour-electrophoretic system. Up to date the majority of these particles were synthesized in aqueous media and the electrophoretic mobility was achieved by a ionic stabilizer or by a polyelectrolyte surfactant. Moreover the final electrophoretic particles incorporated in the electronic devices have to be dispersed in an organic media (paraffin oil) in order to achieve the desired stability of the display and thus leads to a large variety of problems during the phase exchange process.In this work our goals were to rationalize and improve the ink synthesis as well as to design electrophoretic inks with the full colour panel in order to realize the next generation of electrophoretic displays. We performed the particle synthesis by using an organic dispersion technique in aliphatic hydrocarbon solvents leading to chargeable electrophoretic particles with a good size control over a large range (from 75nm to 20µm) and a good stability. In order to obtain the full color panel, the encapsulation of several inorganic pigments was achieved by using the same technique and the electrophoretic behaviour of the resulting inks was characterized in a cell specially designed for electrophoretic measurements in organic media.