Nanowires and nanotubes with single component such as gold and nickel were fabricated by electrochemical deposition method directed by the Anodic Alumina Membrane (AAO) as a template. A so called "polymer-free" method has been investigated to make striped nanowires with superlattice structure. Various methods have been used to characterize these nanomaterials, including SEM, FESEM TEM, STM and Optical Microscope. The aggregation of the nanowires and their alignment under the magnetic force were observed under the optical microscope.

Technological progress is determined to a great extent by developments of novel materials from new combinations of known substances with different dimensionality and functionality. We investigate the development of 3D ‘hybrid’ nanomaterials by utilizing graphene based systems coupled with transition metal oxides (e.g. manganese oxides MnO2 and Mn3O4). This lays the groundwork for high performance electrochemical electrodes for alternative energy owing to their higher specific capacitance, wide operational window and stability through charge-discharge cycling, environmental benignity, cost effective, easily processed, and reproducible in a larger scale. Thus far, very few people have investigated the potential of combining carbon sheets that can function as a supercapacitor in certain systems with transition metals that have faradaic properties to create electrochemical capacitors. Previous work by Wang et al. has focused on the structural combination of Mn3O4 and graphene based materials,1 and research by Jafta et al. studied the electrochemical properties of MnO2 with GO.2 We find that both physical and chemical attachment of manganese oxide on graphene allows for electrical interplay of the materials as indicated in electrochemical analysis and Raman spectroscopy. Attachment of the two materials is also characterized by scanning electron microscopy and X-ray diffraction.

Perchloroethylene (PCE) is a toxic contaminant that has been introduced into the environment over many years through industrial and agricultural wastes. Research has been done in the past to investigate PCE degradation by zero-valent iron (ZVI), green rust (GR) and a mixture of both. The combination of ZVI and green rust has been reported to be more effective for degrading PCE than either of them alone. Forming green rust electrochemically has the potential for depositing GR more effectively on the surface of ZVI where it will be able to more easily transfer electrons from ZVI to contaminants such as PCE. Therefore, the goal of this research was to determine the feasibility of electrochemically depositing green rust on zero-valent iron and to characterize it in terms of its composition, crystal properties and amount produced. XRD analysis was conducted to determine composition and crystal properties and a procedure was developed to measure the amount produced. Equipment was constructed to deposit green rust electrochemically onto ZVI. A chain of experiments with varying voltage, pH, time and amounts of ZVI were conducted to determine feasible experimental conditions for GR formation. Then, a method was developed to accurately measure the amount of surface oxides of iron deposited on the zero-valent iron substrate. This method was tested and found useful for measuring iron in: i) standard solutions of soluble iron with different concentrations of reagents; ii) suspensions with solid iron hydroxides by themselves; and iii) suspensions with solid iron hydroxides and ZVI. Electrochemical experiments were conducted and the amounts of iron hydroxides deposited on the ZVI surface were measured. XRD analysis of the deposits on the surface was conducted and the patterns of XRD-peaks were compared to that of type 2 – sulfate green rust.

Perchloroethylene (PCE) is a toxic contaminant that has been introduced into the environment over many years through industrial and agricultural wastes. Research has been done in the past to investigate PCE degradation by zero-valent iron (ZVI), green rust (GR) and a mixture of both. The combination of ZVI and green rust has been reported to be more effective for degrading PCE than either of them alone. Forming green rust electrochemically has the potential for depositing GR more effectively on the surface of ZVI where it will be able to more easily transfer electrons from ZVI to contaminants such as PCE. Therefore, the goal of this research was to determine the feasibility of electrochemically depositing green rust on zero-valent iron and to characterize it in terms of its composition, crystal properties and amount produced. XRD analysis was conducted to determine composition and crystal properties and a procedure was developed to measure the amount produced. Equipment was constructed to deposit green rust electrochemically onto ZVI. A chain of experiments with varying voltage, pH, time and amounts of ZVI were conducted to determine feasible experimental conditions for GR formation. Then, a method was developed to accurately measure the amount of surface oxides of iron deposited on the zero-valent iron substrate. This method was tested and found useful for measuring iron in: i) standard solutions of soluble iron with different concentrations of reagents; ii) suspensions with solid iron hydroxides by themselves; and iii) suspensions with solid iron hydroxides and ZVI. Electrochemical experiments were conducted and the amounts of iron hydroxides deposited on the ZVI surface were measured. XRD analysis of the deposits on the surface was conducted and the patterns of XRD-peaks were compared to that of type 2 – sulfate green rust.

Balun is a key component in radio frequency (RF) circuits. The conventional Si-based planar spiral balun presented a high insertion loss. To solve this problem, this thesis firstly develops a Si-based suspending spiral balun using electrochemical deposition and surface micromachining technology for the fourth generation of wireless communication system. To reduce the power dissipation of the conventional Si-based planar spiral balun, thesis utilized a suspending structure to reduce the power loss through the substrate and dielectric layer. The fabricated suspending spiral balun are constructed by three bottom GSG electrodes, thirty three supporting copper vias and a suspending spiral copper conducting layer. The main fabrication processes in this research including: (1) four thin-film deposition processes, (2) four photolithography processes, (3) two etching processes and (4) two copper electroplating processes. In addition, this thesis used the commercial software (Ansoft HFSS) to analysis the high frequency characteristic of Si-based suspending spiral balun. The finished Si-based suspending spiral balun were measured by a commercial network analyzer under 2~8 GHz testing frequency range. Based on the measurement results, the value of insertion loss is 1.26 dB at 5.2 GHz, magnitude imbalanced is lower than 0.86 dB, phase imbalanced is less than 3.4 degree and CMRR is more than 30 dB. Finally, this thesis successfully develops a Si-based suspending spiral balun using MEMS technology for the fourth generation wireless communication system.

Well-defined ultrathin films of palladium, with coverages ranging from submonolayer, ΘPd = 0.5 monolayer (ML), to multilayer, ΘP d = 8 ML, were electrochemically deposited on Pt(111) using potentiostatic and potentiodynamic methods. In both methods, between the coverage regimes studied, the growth of the Pd films follows the Stranski-Krastanov mechanism. The interfacial electrochemical properties associated with the film-to-bulk transition were characterized by conventional voltammetric techniques in combination with low-energy electron diffraction (LEED) and Auger electron spectroscopy (AES). The voltammetric peaks associated with H-atom adsorption and desorption on terrace sites indicate that the Pd electrodeposit starts to exhibit bulk-like properties at a coverage of 3 ML. Voltammetric cycling, in sulfuric acid solution, between the hydrogen evolution and the double-layer regions, was found to exert minimal influence on the annealing (smoothening) of the electrodeposited Pd films. However, cycling within the same potential region in the presence of bromide anions (at which Br- adsorption/Br desorption takes place) smoothens the initially rough Pd films essentially as well as high-temperature annealing. The influence of chemisorbed bromine on the anodic dissolution of Pd was also studied; this was for comparison with previous work on the anodic dissolution of Pd, in inert electrolyte, catalyzed by chemisorbed iodine. The present studies indicated that a small but measurable amount of bromine was desorbed along with dissolution of the Pd step atoms; bromine at the Pd terrace behaved identically to iodine in that the coverage of iodine is maintained regardless of the amount or origin of the of anodically stripped Pd. Atomically smooth, well-defined ultrathin Pd films were prepared by a constant potential deposition (CPD) method followed by multiple potential cycles, in dilute Brsolution, within the double-layer region and reductive removal of Brads, by simple emersion at a potential just before the hydrogen evolution reaction potential (EHER). A previously adapted method for the same purpose involved the chemisorption of iodine onto ultrathin PdCPD films, from dilute I- solution, followed by reductive desorption of Iads in iodide-free solution at pH 10 and at a potential just before EHER.

Οι μονοδιάστατες μεταλλικές νανοδομές, όπως νανοσύρματα και νανοσωλήνες, έχουν ελκύσει το ενδιαφέρον της επιστημονικής κοινότητας τα τελευταία χρόνια λόγο του σημαντικού ρόλου που παίζουν στην κατασκευή νανοσυσκευών, όπως ανιχνευτές, ηλεκτρονικά και οπτικά συστήματα και συστήματα αποθήκευσης πληροφορίας. Μια απλή και αποτελεσματική τεχνική για την κατασκευή μεγάλου αριθμού νανοσυρμάτων και νανοσωλήνων με μεγάλη αναλογία μήκους προς διάμετρο είναι η ονομαζόμενη «σύνθεση μήτρας», η οποία βασίζεται στην ηλεκτροχημική εναπόθεση μετάλλου μέσα στους πόρους κατάλληλου υλικού το οποίο λειτουργεί σαν μήτρα. Η πορώδης αλουμίνα είναι ένα υλικό που χρησιμοποιείται ευρέως για τον σκοπό αυτό λόγο της χημικής και μηχανικής της σταθερότητας και της αντοχής της σε υψηλές θερμοκρασίες. Επίσης, τα γεωμετρικά της χαρακτηριστικά μπορούν να ελέγχουν εύκολα κατά την διάρκεια της διαδικασίας παρασκευής της. Στην εργασία περιγράφεται η διαδικασία κατασκευής μεμβρανών πορώδους αλουμίνας με εξαγωνική κατανομή πόρων, ανοιχτών και στις δύο επιφάνειες και με συγκεκριμένα γεωμετρικά χαρακτηριστικά. Για να κατασκευασθούν οι μήτρες οι οποίες θα χρησιμοποιηθούν στην ηλεκτροεναπόθεση και για άλλες εφαρμογές εξήχθη η σχέση μεταξύ του ρυθμού ανάπτυξης της μεμβράνης πορώδους αλουμίνας και των παραμέτρων της ανοδίωσης (πυκνότητα ρεύματος, θερμοκρασία) για ανοδίωση σε υδατικό διάλυμα με περιεκτικότητα 0.3Μ οξαλικό οξύ. Επιπλέον, μελετήθηκε ο απαραίτητος χρόνος για την διάλυση του συμπαγούς διαχωριστικού στρώματος (barrier layer) της πορώδους αλουμίνας με την χρήση υδατικού διαλύματος 5%wt. φωσφορικού οξέος. Τέλος, στην εργασία αυτή μελετήθηκε η ανάπτυξη νανοσυρμάτων νικελίου σε πορώδης αλουμίνα με μέση διάμετρο πόρων 240nm. Για την καλύτερη κατανόηση των μηχανισμών ανάπτυξης των νανοσυρμάτων μελετήθηκε η σχέση της κρυσταλλογραφικής δομής των νανοσυρμάτων με την εφαρμοζόμενη τάση κατά την ανάπτυξη τους με την χρήση της τεχνικής dc ηλεκτροεναπόθεσης. Κατά την μελέτη αυτή αναπτύχθηκαν μονοκρυσταλλικά νανοσύρματα νικελίου προσανατολισμένα κατά την διεύθυνση [110] και πολυκρυσταλλικά νανοσύρματα με ισχυρό προσανατολισμό κατά την διεύθυνση [111]. / One-dimensional metallic nanostructured materials, like nanowires and nanotubes, have attracted extensive attention in recent years because of their importance in the fabrication of nanometer-scale devices such as sensors, electronics, and optics and information storage systems. A simple and effective technique to fabricate large number of metallic nanowires and nanotubes with high aspect ratio is the so called “template synthesis”, which involves electrochemically depositing metal into nanopores of a suitable material used as a template. Porous alumina membrane is a commonly used material for this purpose because of its chemical and mechanical stability and durability at high temperatures. Moreover, its geometrical characteristics are easily controlled during the fabrication process. In this work the fabrication process of free- standing porous alumina membranes with highly organized hexagonal structure and with specific geometrical characteristics is described. In order to fabricate templates for use in electrodeposition and other applications the dependence relation between the thickness growth rate and the anodization parameters (current density and temperature) for anodization in aqueous solution of 0.3M oxalic acid was derived. Furthermore, the time needed for barrier layer dissolution of porous alumina membrane with the use of hydrate solution of 5%wt. phosphoric acid. Finally, nickel nanowires were fabricated inside porous alumina membranes with mean pore diameter of 240nm. For better understanding of the nanowires growth mechanism the dependence of the crystal structure of nickel nanowire fabricated with dc electrodeposition from the applied voltage was studied. As a result, single crystal nickel nanowires oriented along [110] and polycrystalline nickel nanowires with a strong orientation along [111] have been fabricated.

<p>Electrochemical deposition finds applications in the electronics- and protective coating industries. The technique is a versatile tool for the synthesis of alloys and thin films. Knowledge of the fundamental aspects of the electrode processes enables the design of nanostructured materials. In this thesis, electrodeposition processes in solutions containing metal ion complexes were studied and new methods for the preparation of metal/metal-oxide coatings were developed and evaluated. </p><p>Metal/metal oxide coatings were electrodeposited from aqueous solutions containing metal complexes of hydroxycarboxylic acids under reducing conditions. The mass changes of the working electrode were monitored <i>in-situ</i> with the electrochemical quartz crystal microbalance (EQCM) technique and ellipsometry was used to detect the formation of Cu₂O. The coatings were further characterized with XRD, XPS, SEM, TEM, and Raman spectroscopy. Electrochemical methods, including reduction of Sb/Sb₂O₃ in an organic electrolyte, were also used to study the properties of the deposited materials. </p><p>Nanostructured coatings of Cu/Cu₂O were obtained during spontaneous potential or current oscillations in alkaline Cu(II)-citrate solutions. The oscillations were due to local pH variations induced by a subsequent chemical step and comproportionation between Cu and Cu²⁺. Well-defined layers of Cu and Cu₂O could be prepared by a galvanostatic pulsing technique, allowing independently controlled thickness of several hundred nanometers. Coatings, containing Sb and co-deposited, nanograins of Sb₂O_3, with a thickness of up to 200 nm were prepared from poorly buffered Sb(III)-tartrate solutions. Galvanostatic cycling showed that the latter material could be reversibly charged and discharged in a Li-ion battery for more than 50 cycles with a capacity of 660 mAh/g. </p><p>The results show that precipitations of metal oxides can occur due to local pH increases during electrochemical deposition from metal complexes with ligands containing hydroxyl groups. The ability to deposit metal oxides using cathodic deposition relies on a sufficiently slow reduction of the oxide. </p>

Selective laser sintering (SLS) is a commercial, powder-based manufacturing process that produces parts with complicated shape and geometry based on a computer solid model. One of the major drawbacks of SLSed inter-metallic and ceramic parts is their high porosity because of the use of binder system. High porosity results in poor mechanical, electrical and thermal properties of the preform and hence renders it unsuitable for various applications. This thesis attempts to infiltrate SLSed preforms by carrying out electrochemical deposition of metal ions inside the interconnected pore network. One of the major benefits of carrying out this novel process is low processing temperature as opposed to existing methods such as melt infiltration. Low temperature reduces both energy consumption and associated carbon-footprint and also minimizes undesirable structural changes. Both conductive and non-conductive preforms may be electrochemically infiltrated, and MMCs produced by this method have potential for use in structural applications. / text

Electrochemical deposition finds applications in the electronics- and protective coating industries. The technique is a versatile tool for the synthesis of alloys and thin films. Knowledge of the fundamental aspects of the electrode processes enables the design of nanostructured materials. In this thesis, electrodeposition processes in solutions containing metal ion complexes were studied and new methods for the preparation of metal/metal-oxide coatings were developed and evaluated. Metal/metal oxide coatings were electrodeposited from aqueous solutions containing metal complexes of hydroxycarboxylic acids under reducing conditions. The mass changes of the working electrode were monitored in-situ with the electrochemical quartz crystal microbalance (EQCM) technique and ellipsometry was used to detect the formation of Cu2O. The coatings were further characterized with XRD, XPS, SEM, TEM, and Raman spectroscopy. Electrochemical methods, including reduction of Sb/Sb2O3 in an organic electrolyte, were also used to study the properties of the deposited materials. Nanostructured coatings of Cu/Cu2O were obtained during spontaneous potential or current oscillations in alkaline Cu(II)-citrate solutions. The oscillations were due to local pH variations induced by a subsequent chemical step and comproportionation between Cu and Cu2+. Well-defined layers of Cu and Cu2O could be prepared by a galvanostatic pulsing technique, allowing independently controlled thickness of several hundred nanometers. Coatings, containing Sb and co-deposited, nanograins of Sb2O3, with a thickness of up to 200 nm were prepared from poorly buffered Sb(III)-tartrate solutions. Galvanostatic cycling showed that the latter material could be reversibly charged and discharged in a Li-ion battery for more than 50 cycles with a capacity of 660 mAh/g. The results show that precipitations of metal oxides can occur due to local pH increases during electrochemical deposition from metal complexes with ligands containing hydroxyl groups. The ability to deposit metal oxides using cathodic deposition relies on a sufficiently slow reduction of the oxide.