KI effects on the reversible electrodeposition of silver on poly(ethylene oxide) for application in electrochromic devices

A new approach to electrochromics, based on the reversible coating-dissolution of an oxide from an inorganic electrochromic electrolyte consisting of a silver-amine complex in a polymer electrolyte (PEO), has proven successful. The reversible electrodeposition of silver onto indium-tin oxide coated glass (ITO) was investigated and the influence of HClO(4) and KI was evaluated. Several characteristics of the electrolyte Ag-PEO make it suitable for use in electrochromic reversible silver electrodeposition devices, such as visible absorption spectrum with an absorbance variation of 60%, an electrochromic efficiency of 5.2 cm(2) C(-1) and an ionic conductivity 4.4 x 10(-4) S cm(-1). The addition of perchloric acid improved the transparency of Ag-PEO, and potassium iodide (KI) was fundamental in setting up the process of reversible silver electrodeposition in the PEO polymeric matrix. A description of the electrochemical processes implied is presented. A number of approaches focusing on the improvement of system performance are tested. (C) 2009 Elsevier Ltd. All rights reserved.

Engineering of metal oxide nanoparticles for application in electrochemical devices

The growing demand for materials and devices with new functionalities led to the increased inter-est in the field of nanomaterials and nanotechnologies. Nanoparticles, not only present a reduced size as well as high reactivity, which allows the development of electronic and electrochemical devices with exclusive properties, when compared with thin films. This dissertation aims to explore the development of several nanostructured metal oxides by sol-vothermal synthesis and its application in different electrochemical devices. Within this broad theme, this study has a specific number of objectives: a) research of the influence of the synthesis parameters to the structure and morphology of the nanoparticles; b) improvement of the perfor-mance of the electrochromic devices with the application of the nanoparticles as electrode; c) application of the nanoparticles as probes to sensing devices; and d) production of solution-pro-cessed transistors with a nanostructured metal oxide semiconductor. Regarding the results, several conclusions can be exposed. Solvothermal synthesis shows to be a very versatile method to control the growth and morphology of the nanoparticles. The electrochromic device performance is influenced by the different structures and morphologies of WO3 nanoparticles, mainly due to the surface area and conductivity of the materials. The dep-osition of the electrochromic layer by inkjet printing allows the patterning of the electrodes without wasting material and without any additional steps. Nanostructured WO3 probes were produced by electrodeposition and drop casting and applied as pH sensor and biosensor, respectively. The good performance and sensitivity of the devices is explained by the high number of electrochemical reactions occurring at the surface of the na-noparticles. GIZO nanoparticles were deposited by spin coating and used in electrolyte-gated transistors, which promotes a good interface between the semiconductor and the dielectric. The produced transistors work at low potential and with improved ON-OFF current ratio, up to 6 orders of mag-nitude. To summarize, the low temperatures used in the production of the devices are compatible with flexible substrates and additionally, the low cost of the techniques involved can be adapted for disposable devices.

The Leaching of Electrodeposition of Iron

Electrolytic iron as deposited is brittle and therefore must be annealed. After annealing, the material is ductile and closely resembles copper in its behavior under work. It is claimed to be more resistant to corrosion than dead soft iron. It also has the advantage of corroding uniformly ( or­dinary soft iron develops pin holes which shorten its life considerably). The extreme purity of electrolytic iron namely makes it very suitable as a base metal for alloys. Its ductility opens up a field for use in the manufacture of cold rolled strip, seamless tubes, and wire.

The Effect of Impurities on the Electrodeposition of Zinc from Zinc Sulfate Solution Containing Antimony.

It has been proven by research and years of experience, that before electrolytic zinc is possible, the electrolyte, as zinc sulfate solution must be prepared as pure as is economical. In other words, the ideal electrolyte must only be a solution of one metal - zinc. Every other metal and carbon must be excluded if good recovery and a firm deposit is to be obtained.

The Electrodeposition of Iron-Manganese Alloys

Although the alteration of properties resulting from the alloying of metals in their usual commercial forms has been extensively investigated, the field of electrodeposition of alloys is believed generally not to have received the atten­tion that it merits.

Electrodeposition of corrosion resistant zinc alloy coatings

With the increase use of de-icing salts on roads for safety, the need for improved corrosion resistance of the traditional galvanized automobile bodies has never been greater. In the present work, Zn alloy coatings (Zn-Ni and Zn-Co) were studied as an alternative to pure Zn coatings. The production of these deposits involved formulation of various acidic (pH of about 5.5) chloride based solutions. These showed anomalous deposition, that is, alloys were deposited much more easily than expected from the noble behaviour of Ni and Co metals. Coating compositions ranging from 0 to about 37% Ni and 20% Co were obtained. The chemical composition of the coatings depended very much on the electrolytes nature and operating conditions. The Ni content of deposits increased with increase in Ni bath concentration, temperature, pH and solution agitation but decreased considerably with increase in current density. The throwing power of the Zn-Ni solution deteriorated as Ni metal bath concentration increased. The Co content of deposits also increased with increase in Co bath concentration and temperature, and decreased with increase in current density. However, the addition of commercial organic additives to Zn-Co plating solutions suppressed considerably the amount of Co in the coatings. The Co content of deposits plated from Zincrolyte solution was found to be more sensitive to variation in current density than in the case of deposits plated from the alkaline Canning solution. The chromating procedures were carried out using laboratory formulated solution and commercially available ones. The deposit surface state was of great significance in influencing the formulation of conversion coatings. Bright and smooth deposits acquired an iridescent colour when treated with the laboratory formulated solution. However, the dull deposits acquired a brownish appearance. The correlation between the electrochemical test results and the neutral salt spray in marine environment was good. Non-chromated Zn-Ni coatings containing about 11-14% Ni increased in corrosion resistance compared to pure Zn. Non-chromated Zn-Co deposits of composition 4-8% were required to show a significant improvement in corrosion resistance Corrosion resistance was improved considerably by conversion coating. However, the type of conversion coating was very important. Samples treated in a laboratory solution performed badly compared to those treated in commercial solutions. Zn alloy coatings were superior to pure Zn, the Schloetter sample (13.8% Ni) had the lowest corrosion rate, followed by the Canning sample (1.0% Co) and then Zincrolyte (0.3% Co).Neither the chromium content of the conversion films nor the chromium state was found to have an effect on corrosion performance of the coatings.

Electrodeposition of cermets

Modern engineering requirements are frequently near the limits of application of conventional materials. For many purposes, particularly tribological, the most satisfactory solution is frequently the application of a resistant coating to the surface of a common metal. Electrodeposited cermet coatings have proved very satisfactory: some of the factors underlying the cernet electrodeposition process have been investigated. A ceramic particle in contact with an electrolyte solution will carry a charge which may affect the kinetics of the suspended particle under electroplating conditions. Measurerment has been made of this charge on particles of silicon carbide, chrornium diboride and quartz, in contiact with solutions of copper sulphate/ sulphuric acid in terms of the electrokinetic (zeta) potential and also as surface charge density. The methocl used was that of streaming potential and streaming current measurement

Effect of pulsed current on the electrodeposition of chromium and copper

This research was concerned with the effects of pulsed current on the electrodeposition of chromium and copper. In the case of the latter metal, a novel application has been studied and a theory proposed for the ability to improve throwing power by the joint use of organic additives and pulsed reverse current. During the course of the research, several improvements were made to the pulse plating unit.Chromium. A study was made of the effect of square wave pulsed current on various physical properties of deposits from three hard chromium plating electrolytes. The effect of varying frequency at a duty cycle of 50% on the mean bulk internal stress, visual appearance, hardness, crack characteristics and surface topography of the electrodeposits was determined. X-ray diffraction techniques were used to study the phases present in the deposits. The effect of varying frequency on the cathodic efficiencies of the electrolytes was also determined. It was found that pulsed current reduced the internal stress of deposits from the sulphate catalysed electrolyte. It also reduced or eliminated cracking of deposits and reduced deposit brightness. Under certain conditions, pulsed current was found to induce the co-deposition of hydrides of chromium. Deposit hardness was found to be reduced by the use of pulsed current. Cathodic efficiencies of the high efficiency electrolytes were reduced by use of pulsed current although this effect was minimised at high frequencies. The sulphate catalysed electrolyte showed an increase in efficiency over the frequency range where hydrides were co-deposited.Copper. The polarisation behaviour of acid copper solutions containing polyethers, sulphopropyl sulphides and chloride ions was studied using both direct and pulse reverse current. The effect of these additives on the rest potentials of copper deposits immersed in the electrolyte was also studied. Hole Throwing Power on printed circuit boards was determined using a specially designed test cell. The effect of pulsed reverse current on the hole throwing power of commercially produced printed circuit boards was also studied. Polyethers were found to have an inhibiting effect on the deposition of copper whereas the sulphopropyl sulphides produced a stimulating (i.e. depolarising) effect. Studies of rest potentials made when both additives were present indicated that the sulphopropyl sulphide was preferentially adsorbed. The use of pulsed reverse current in solutions containing both polyether and sulphopropyl sulphide was found to cause desorption of the sulphopropyl sulphide at the cathode surface. Thus, at higher current densities, the inhibiting effect of the polyether produced an increase in the cathodic polarisation potential. At lower current densities, the depolarisation effect of the sulphopropyl sulphide could still occur. On printed circuit boards, this effect was found to produce an increase in the `hole throwing power' due to depolarisation of the holes relative to the surface of the boards. Typically, using direct current, hole/surface thickness ratios of 40% were obtained when plating 0.6 mm holes in a 3.2 mm thick board at a current density of 3 A/dm2 whereas using pulsed reverse current, ratios of 80% could be obtained at an equivalent rate of deposition. This was observed both in laboratory tests and on commercially plated boards.

Biological activity of metal-edds (ethylenediaminedisuccinate) complexes in K562 and PBMC cells

The effect of S,S-ethylenediaminedisuccinic acid (edds) on the quenching of metal-catalyzed (metal = Mn, Fe, Co, Ni, Cu, Zn) oxidation of ascorbic acid was tested in vitro via oxidation of the fluorescent probe 1,2,3-dihydrorhodamine dihydrochloride. The pro-oxidant activity of iron was not fully suppressed, even at a four-fold molar excess of the ligand. The effect of serum on the toxicity to peripheral blood mononuclear cells (PBMC) and K562 cells was investigated. The cytotoxic effect of Fe-edds was abrogated in the presence of Trolox or serum proteins. The probable pathways of cell toxicity were investigated through blocking of the monocarboxylate transporters (MCT) in association with cell cycle studies by flow cytometry. Cells treated with metal complexes and alpha-cyano-4-hydroxycinnamic acid, a known MCT inhibitor, showed recovery of viability, suggesting that MCT proteins may be involved in the internalization of metal-edds complexes. The free acid induced cell cycle arrest in G0/G1 (PBMC) and S (K562) phases, suggesting direct DNA damage or interference in DNA replication.

Study of metal oxide-semiconductor capacitors with rf magnetron sputtering TiO(x) and TiO(x)N(y) gate dielectric layer

Metal oxide-semiconductor capacitors with TiO(x) deposited with different O(2) partial pressures (30%, 35%, and 40%) and annealed at 550, 750, and 1000 degrees C were fabricated and characterized. Fourier transform infrared, x-ray near edge spectroscopy, and elipsometry measurements were performed to characterize the TiO(x) films. TiO(x)N(y) films were also obtained by adding nitrogen to the gaseous mixture and physical results were presented. Capacitance-voltage (1 MHz) and current-voltage measurements were utilized to obtain the effective dielectric constant, effective oxide thickness, leakage current density, and interface quality. The results show that the obtained TiO(x) films present a dielectric constant varying from 40 to 170 and a leakage current density (for V(G)=-1 V, for some structures as low as 1 nA/cm(2), acceptable for complementary metal oxide semiconductor circuits fabrication), indicating that this material is a viable, in terms of leakage current density, highk substitute for current ultrathin dielectric layers. (C) 2009 American Vacuum Society. [DOI: 10.1116/1.3043537]

Electrodeposition of copper on titanium wires: Taguchi experimental design approach

Electrodeposition of thin copper layer was carried out on titanium wires in acidic sulphate bath. The influence of titanium surface preparation, cathodic current density, copper sulphate and sulphuric acid concentrations, electrical charge density and stirring of the solution on the adhesion of the electrodeposits was studied using the Taguchi statistical method. A L(16) orthogonal array with the six factors of control at two levels each and three interactions was employed. The analysis of variance of the mean adhesion response and signal-to-noise ratio showed the great influence of cathodic current density on adhesion. on the contrary, the other factors as well as the three investigated interactions revealed low or no significant effect. From this study optimized electrolysis conditions were defined. The copper electrocoating improved the electrical conductivity of the titanium wire. This shows that copper electrocoated titanium wires could be employed for both electrical purpose and mechanical reinforcement in superconducting magnets. (C) 2008 Elsevier B.V. All rights reserved.

Metallomics and chemical speciation: towards a better understanding of metal-induced stress in plants

Most metal ions are toxic to plants, even at low concentrations, despite the fact that some are essential for growth and play key roles in metabolism. The majority of metals induce the formation of reactive oxygen species, which require the synthesis of additional antoxidant compounds and enzymes for their removal. New techniques that have greatly improved the identification, localisation and quantification of metals within plant tissues have led to the science of metallomics. This advancement in knowledge should eventually allow the characterisation of plants used in the process of phytoremediation of soils contaminated with toxic metals.

The interaction of metal ions and Marimastat with matrix metalloproteinase 9

The effect of a range of metal ions on the ability of Marimastat to inhibit matrix metalloproteinase 9 (MMP-9) was examined in a fluorescence based proteolytic assay. Whilst none of the metals examined significantly affected the inhibitory ability of Marimastat, several metal ions did have a significant effect on MMP-9 activity itself. In the absence of Marimastat, Zn(II) and Fe(II) significantly inhibited MMP-9 activity at metal ion concentrations of 10 and 100 muM, respectively. In both the absence and presence of Marimastat, Cd(II) significantly inhibited MMP-9 at 100 muM. In contrast, 1 mM Co(II) significantly upregulated MMP-9 proteolytic activity. (C) 2003 Elsevier Science Inc. All rights reserved.