Multilayered iron electrodeposits composed of alternating layers of coarse-grained iron (grain size: 1.87 μm; (110) texture; hardness: 177 VHN) and fine-grained iron (grain size: 132 nm; (211) texture; hardness: 502 VHN), with layer thicknesses ranging from ~0.2-7 μm were successfully synthesized. The average hardness of the multilayered electrodeposits increased from 234 VHN to 408 VHN with decreasing layer thickness, consistent with a Hall-Petch type behaviour. In three-point bending tests, they failed in a macroscopically brittle manner although local ductility was observed in certain layers. Fractography analysis has shown that strain incompatibility between alternating layers contributes to the brittle nature of these materials. This study has demonstrated the possibility of applying a multilayered structure design to tailor the microstructure and mechanical properties of electrodeposited iron.

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Mercury amalgam microelectrodes, typically fabricated by electrodeposition of mercury onto metal (platinum, gold, silver) inlaid disks, possess certain advantageous properties for scanning electrochemical microscopy (SECM) and electroanalysis. But as applications require more and more precision, fundamental questions concerning the exact shape and constitution of the amalgam can become important for interpreting SECM experimental data. The purpose of this study is to analyze in depth the formation of the amalgam, in order to provide a better understanding of the key physical processes, and so be able to judge of the accuracy of the currently used models and refine them when necessary. The amalgam formation is the result of several processes that occur roughly at two different scales: the global scale, which is microscopic, and the local scale, of the order of few nanometers. On the global scale, the dominant physical process is the mass transport, driven almost entirely by diffusion, which determines the rate of mercury deposition. Other phenomena occur at the smaller local scale. Their understanding is essential to predict precisely the volume and shape of the amalgam at shorter times. Among these local phenomena, nucleation and droplet interactions appear critical. The former sets the formation rate and the size of the isolated mercury droplets that are initially formed at the surface of the electrode. An understanding of the latter is necessary to determine the droplet coalescence process. Among the specific accomplishments of this Master thesis work, a time scale analysis of the global phenomena has been performed leading to the conclusion that quasi-steady state diffusion of mercury ions in the bulk mainly defines the electrodeposition rate. Then, a series of analytical formulations for diffusion-limited electrodeposition current available in the literature has been quickly analyzed, leading to development of analytical/numerical models. These latter have been implemented, and results were critically compared with experimental data, leading to the conclusion that the early electrodeposition was not enough finely modeled. Mercury droplets nucleation and surface interaction have been identified as relevant processes of this period. They have next been investigated in detail, leading to the characterization of the nucleation process, and the derivation of two complimentary approaches on charged droplet stability. Regime maps have been developed, providing first explanations and quantitative information on charged droplet stability dependence on potential applied, electrolyte and droplet size. Finally, through analysis of theoretical predictions, a series of electroanalytical experiments have been proposed for the future validation of the suggested theoretical models.

Diamond-like carbon (DLC) film exhibits an extreme hardness, low friction coefficient, chemical stability, heat conductivity, high resistance, and high optical transparency. There properties lead to remarkable on industrial applications Diamond-like carbon films were deposited onto the silicon (100) and ITO glass substrates. Under the same deposition conditions, the characteristics of DLC films were evaluated by the variations of deposited parameters such as the applied voltage, deposition temperature the concentrations of electrolyte; acetic acid. The properties due to the different substrate were compared and discussed in detail. In experimental work, the properties of DLC film were conducted by various measurements. Scanning electron microscopy can make an insight into the surface morphology also to reveal the uniformity of the DLC films. For the I-t curves of DLC film growth, it can be used to study of the growth mechanism by correlation the surface morphology observed by Scanning electron microscopy (SEM). The transmission, refraction index and optical band gap of DLC film was measured by the N &K analyzer. Finally, the hydrogen content, composition and microstructure of DLC films were characterized by the FTIR and XPS analyze According to above results, DLC film using the electrolyte of acetic acid was more difficult to deposit on Silicon substrate because the very high activation energy and the high hydrogen ion existing in DI water firstly deposited on the surface of Si substrate. For FTIR measurement, The absorption wavenumber of various bonding observed were positioned at 610 cm-1,680 cm-1,1100 cm-1 and 3600 cm-1~3800 cm-1and to be cauterized as the bonding of Si-H¡BSi-O and O-H, respectively. The absorption peaks within the range from 2800 cm-1 to 3100 cm-1 were missing. Peaks observed were attributed to the bonding of Si-C¡B SP3 C-C¡B C-O¡BC-C¡BC=O and C=C and the CHn bonding was missing on the surface of substrate. The reaction mechanism of DLC deposition can be suggested from the results of measurements. As bias voltage applied, the acetic ion; CH3COO- were attracted by the Anode as the state of C¡]Anode¡^-OOCCH3, and then to give electron and form the CH3+ion»PCO2. The hydrogen ion and methyl ion were attracted by cathode. The competitive reaction was built between ions to deposited DLC films and/or to form Si-H. However, experimental results show that the last was preferred and for forming the DLC film was forbidden.

Nanoindentation has been widely used for measuring mechanical behavior of nanocrystalline (nc) metals that cannot be measured by tensile and compressive test. The hardness and elastic modulus are usually obtained by Oliver and Pharr method. However, this may not be true for materials showing viscoelastic characteristics. This study aims at clarifying the effect of testing parameters, especially loading rate and holding time, on the hardness and elastic modulus of a nanocrystalline Fe-51Ni coating obtained in nanoindentation tests as the material exhibits anelastic and creep characteristics. An analytical method based on the correspondence principle for linear viscoelasticity was developed. The holding displacement-time data obtained in indentation creep tests at a high loading rate of 20 mN/s were analyzed and material parameters related to the elastic, anelastic and creep characteristic were derived using a model containing one Maxwell unit and two Kelvin units. The anelastic deformation thus contains at least two relaxation processes having relaxation times of 0.37 s and 6.8 s, respectively and the creep deformation is described by a viscosity value of 4.2x104 GPa.s for the alloy in an as-deposited state. Moreover, electrodeposited (ED) Ni was analyzed by electron backscatter diffraction. Results indicated that the ED Ni exhibits a bimodal distribution of grain size. The grains having sizes larger than 2 £gm shows a strong fiber texture of <100>//ND, whereas the small grains (<2 £gm) are mainly randomly oriented.

Diamond-like Carbon (DLC) film exhibits an extreme hardness, low friction coefficient, chemical stability, heat conductivity, and high resistance. Their properties lead to remarkable applications on industry. In the experiment, we use electrondeposition to deposit the DLC film on Si substrate. Different concentrations of electrolyte were used to deposit on the of silicon substrates with different roughness surface. KOH solution was used to etch and to get the different roughness on the surface of silicon substrates. the morphology of surface were observed by SEM and AFM. Composition and microstructure of the DLC film were characterized by the Raman spectroscopy and XPS, repectively. The optical properties of DLC film were investigated by the N&K analyzer. From the AFM results, the surface morphology observed by KOH etching on the surface of silicon substrates during etching time as 0¡B20¡B40¡B60 min, the surface roughness increased from 2.64 to 14.07 nm. Based on thevariation of surface roughness, the growth rate was observed more quicker than the non etch surface. Moreover, to deposit the DLC film on the alkalinity solution was better then acid solution. However, the ID/IG ratio and the sp2/sp3 ratio obtained from Raman and XPS increase with the roughness surface from 1.09 to 1.82 and 0.985 to 2.15, respectively. It is because that the microstructure of DLC film varies and exchange to graphitization. The mixed the ammonia water and ammonium acetate into acetic acid solution was used to deposit DLC film on Si surface, and film shows with lower ID/IG ratio. Additionally, as the amount of ammonium acetate was varied in the solution, the ID/IG ratio of the films observed as decrease from 1.2 to 0.93 with increasing amount of ammonium acetate 10g to 40g. It was due to the methyl radicals increase in the solution. Besides, we can find the optical band gap decreased with DLC films changing to graphitization.

Recently, synthesis of Diamond-Like Carbon (DLC) films has received considerable interest. Owing to their similar characteristics of diamonds, such as extreme hardness, chemical stability, and high heat conductivity etc, DLC films are regarded as one of the most promising materials. But the practical applications have been limited due to their high internal stress and insufficient adhesion at the interface between DLC film and substrate. Several methods used to the deposition of Me-DLC films have been proposed. Studies have shown that the internal stress was released and the adhesion also improved by doping metallic element into DLC films. Conventionally, metal incorporation in DLC films were prepared by vapor deposition. The requirement of high vacuum equipment makes the process complicated. Besides, there are many merits in electrodeposition, such as low cost, simplicity of experimental set up, and availability for deposition on complex shapes substrate in large area. In this study, electrodepositing technique was used to synthesize the amorphous Cu-DLC films deposited on ITO substrate, in which the pH value of electrolyte varied, to study the characteristics and the composition of DLC films. According to the I-t curves of deposition, the end of current density was used for the impedance comparison of films. With the addition of Cu, the resistance of the electron transportation in Cu-DLC was reduced, and the awl-shaped surface morphology was observed by AFM measurement, which could enhance the electron field emission properties of thin films. For Raman analysis, the effect of Cu addition would promote the sp2 bonding¡F this result corresponds with the increasing ID/IG value. It indicates that film becomes graphitization due to the addition of Cu and leads the shift of G-peak position toward lower wavenumber. ESCA spectra of C1s and Cu2p indicate no obvious evidence of Cu-C formation. The sp2/(sp2+sp3) ratio increases with the pH value. In addition, we found that Cu-DLC in acidic environmental condition, or doping as [Cu(NH3)n]2+ complex is more conducive to the growth of copper metal in DLC films, and has the lowest optical band gap value deduced by n&k analyzer. Finally, we discussed the thin film growth mechanisms and the characteristic of electron field emission for the applications in the future.

The present study aims at clarifying the effects of processing parameters and substrate orientation on the epitaxial growth of Ni on polycrystalline Cu by electrodeposition from a sulfamate solution. The deposits were analyzed by scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), auger electron spectroscopy (AES) and transmission electron microscopy (TEM). Two morphologies: rough and smooth, of the substrate surface were introduced by electropolishing. Auger electron spectroscopy showed that Ni was deposited on both areas without preference. However, the deposition rate for the rough area was slightly higher at a low current density of 0.01 A/dm2. At higher current densities, both areas possessed the same rate of deposition. In-plane TEM results demonstrated that Ni deposited on Cu epitaxially regardless the orientation of the Cu grains, electrolyte temperature and current density. EBSD analysis indicated that the Ni epilayer with an orientation of <001>//ND grew epitaxially to as thick as 12 £gm, whereas randomly oriented Ni nucleated on the epilayer having orientations of <011>//ND or <-111>//ND on prolonging deposition at current of 10 A/dm2. In other words, the epitaxial growth of Ni on Cu cannot be sustained to a thickness of hundreds of micrometers without a <001>//ND orientation.

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For the theory of electrochemical analysis, a kinetic model that considers the ion transport limitations near the cathode of electrode is based upon a generalized Butler-Volmer equation and has been modified in theory and developed. The subjects of this study are the investigation of the kinetics mechanism of CdTe electrodeposition from an aqueous solution containing CdSO4, TeO2, and H2SO4 in cyclic voltammetry and applied to the optimal control of the composition and stoichiometric deviation of CdTe thin film by electrodeposition. The computer simulation is performed to understand the influences of electrodeposited parameters in the process, such as deposition temperature, pH value and concentrations of Cd2+ and HTeO2+ ions, is one of the focuses in this study. In this investigation, a novel electrochemical method for simultaneously measuring diffusion coefficient and ion transference number is applied in the simulation of CdTe electrodeposition for the first time. From the fitting of the experimental data, the values of the thermodynamic, kinetic and mass transport parameters of the electrodeposition process are obtained. In addition, the modified Butler-Volmer model predicts the potential of perfect stoichiometry (PPS) for electrodeposition of CdTe thin film, and a good agreement has been found between the calculated and experimental results. It also predicts the composition of electrodeposits for the electrodeposition of CdTe and other II-VI and III-V compounds from solutions containing reducible ions. Furthermore, the one that is worth mentioning in this investigation, a novel algorithm of stoichiometric deviation is also developed and applied to the electrodeposition for the first time. With the change of the parameter, the deviation of stoichiometry can be estimated accurately. The simulated results of mathematical model are verified experimentally using electrodeposition and can obtain two aspects. They are the accurate potential perfect stoichiometry (PPS) in which the intrinsic CdTe thin film can be electrodeposited and the stoichiometric deviation which can be dominated accurately in the adjustment of electrodeposited potential. Besides, the native non-degenerate p-type and n-type CdTe thin film can also be deposited. At PPS, well-connected granular CdTe thin films can be deposited and are predicted to be intrinsic, but are slightly p-type due to cadmium vacancies (VCd). The conversion of conductive type occurs only by defect redistribution and local defect reactions after annealing; the converted n-type layer shows lower resistivity and higher mobility. A film annealed at 350oC exhibits excellent crystallization.