Quantum Dot-Sensitized Solar Cells Based on Directly Adsorbed Zinc Copper Indium Sulfide Colloids

Heavy metal-based quantum dots (QDs) have demonstrated to behave as efficient sensitizers in QD-sensitized solar cells (QDSSCs), as attested by the countless works and encouraging efficiencies reported so far. However, their intrinsic toxicity has arisen as a major issue for the prospects of commercialization. Here, we examine the potential of environmentally friendly zinc copper indium sulfide (ZCIS) QDs for the fabrication of liquid-junction QDSSCs by means of photoelectrochemical measurements. A straightforward approach to directly adsorb ZCIS QDs on TiO2 from a colloidal dispersion is presented. Incident photon-to-current efficiency (IPCE) spectra of sensitized photoanodes show a marked dependence on the adsorption time, with longer times leading to poorer performances. Cyclic voltammograms point to a blockage of the channels of the mesoporous TiO2 film by the agglomeration of QDs as the main reason for the decrease in efficiency. Photoanodes were also submitted to the ZnS treatment. Its effects on electron recombination with the electrolyte are analyzed through electrochemical impedance spectroscopy and photopotential measurements. The corresponding results bring out the role of the ZnS coating as a barrier layer preventing electron leakage toward the electrolyte, as argued in other QD-sensitized systems. The beneficial effect of the ZnS coating is ultimately reflected on the power conversion efficiency of complete devices, reaching values of 2 %. In a more general vein, through these findings, we aim to call the attention to the potentiality of this quaternary alloy, virtually unexplored as a light harvester for sensitized devices.

Application of chemical thermodynamics to the study of alloy formation, progress report for ...

"Work performed under Contract No. AT(30-1)-647"--p.2 of cover.

Morphological features of interfacial intermetallics and interfacial reaction rate in Al-11Si-2.5Cu-(0.15/0.60)Fe cast alloy/die steel couples

Soldering reactions are commonly observed during high pressure die casting of aluminium alloys, and involve the formation and growth of interfacial intermetallics between the die and the cast alloy. It is generally believed that close to 1% Fe is necessary in the aluminium alloy to reduce soldering. However, the role of iron in the interfacial reaction has not been studied in detail. In this investigation, reaction couples were formed between H13 tool steel substrates and an Al-11Si-2.5Cu melt containing either 0.15 or 0.60% Fe. Examination revealed distinctly different intermetallic layer morphology. The overall growth and chemistry of the reaction layer and the reaction rate measured by the consumption of the substrate were compared for the two alloy melts. It was demonstrated that a higher iron content reduces the rate of interfacial reaction, consistent with an observed thicker compact ( solid) intermetallic layer. Hence, the difference in reaction rate can be explained by a significant reduction in the diffusion flux due to a thicker compact layer. Finally, the mechanism of the growth of a thicker compact layer in the higher iron melt is proposed, based on the phase relations and diffusion both within and near the interfacial reaction zone. (C) 2004 Kluwer Academic Publishers.

Microstructure control in Sn-0.7mass%Cu alloys

Soldering alloys based oft the Sn-Cu alloy system are amongst the most favourable lead-free alternatives due to a range of attractive properties. Trace additions of Ni have been found to significantly improve the soldering characteristics of these alloys (reduced bridging etc.). This paper examines the mechanisms underlying the improvement in soldering properties of Sn-0.7 mass%Cu eutectic alloys modified with concentrations of Ni ranging front 0 to 1000 ppm. The alloys were investigated by thermal analysis during solidification, as well as optical/SEM microanalyses of fully solidified samples anti samples quenched during solidification. It is concluded that Ni additions dramatically alter the nucleation patterns and solidification behaviour of the Sn-Cu6Sn5 eutectic anti that these changes are related to the superior soldering characteristics of the Ni-modified Sn-0.7 mass%Cu alloys.

Influence of anodising current on the corrosion resistance of anodised AZ91D magnesium alloy

The thickness, chemical composition and microstructure of anodised coatings formed on magnesium alloy AZ91D at various anodising current densities were measured. It was found that all these parameters could be affected by anodising current density, and hence the coatings formed at different anodising current densities had different corrosion resistances. This suggests that the corrosion performance of an anodised coating could be improved if a properly designed current waveform is used for anodising. In addition, based on the experimental results, some physical, chemical and electrochemical reactions involved in the anodising process were proposed to explain the anodising behaviour in this paper. (c) 2005 Elsevier Ltd. All rights reserved.

Effect of manganese on grain refinement of Mg-Al based alloys

Manganese is a grain refiner for high purity Mg-3%Al, Mg-6%Al, Mg-9%Al, and commercial AZ31 (Mg-3%Al-1%Zn) alloys when introduced in the form of an Al-60%Mn master alloy splatter but the use of pure Mn flakes and ALTAB (TM) Mn75 tablets shows no grain refinement. Long time holding of the melt at 730 degrees C leads to an increase in grain size. The mechanism is attributed to the presence of all epsilon-AlMn phase (hexagonal close-packed) in the master alloy splatter. (c) 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Enhanced glass-forming ability of a Zr-based bulk metallic glass with yttrium doping

A significant enhancement in glass formation in a newly developed Zr51Cu20.7Ni12Al16.3 alloy has been achieved by yttrium doping. With just 0.5 at.% yttrium doping, the critical diameter of the as-cast alloys for glass formation has been increased from 3 mm to at least 10 mm. In the undoped, large-sized alloys, massive oxygen stabilized crystalline phases are observed but disappear in yttrium doped alloys. Very small amounts of stable alpha-Y2O3 phases found in the yttrium doped alloys, and their negligible effect on the metallic glasses' properties, provide a superior solution to achieve metallic glasses with a high glass formability. (c) 2006 Elsevier B.V. All rights reserved.

Development and evaluation of a non-destructive adhesion test

The object of this work was to further develop the idea introduced by Muaddi et al (1981) which enables some of the disadvantages of earlier destructive adhesion test methods to be overcome. The test is non-destructive in nature but it does need to be calibrated against a destructive method. Adhesion is determined by measuring the effect of plating on internal friction. This is achieved by determining the damping of vibrations of a resonating specimen before and after plating. The level of adhesion was considered by the above authors to influence the degree of damping. In the major portion of the research work the electrodeposited metal was Watt's nickel, which is ductile in nature and is therefore suitable for peel adhesion testing. The base metals chosen were aluminium alloys S1C and HE9 as it is relatively easy to produce varying levels of adhesion between the substrate and electrodeposited coating by choosing the appropriate process sequence. S1C alloy is the commercially pure aluminium and was used to produce good adhesion. HE9 aluminium alloy is a more difficult to plate alloy and was chosen to produce poorer adhesion. The "Modal Testing" method used for studying vibrations was investigated as a possible means of evaluating adhesion but was not successful and so research was concentrated on the "Q" meter. The method based on the use of a "Q" meter involves the principle of exciting vibrations in a sample, interrupting the driving signal and counting the number of oscillations of the freely decaying vibrations between two known preselected amplitudes of oscillations. It was not possible to reconstruct a working instrument using Muaddi's thesis (1982) as it had either a serious error or the information was incomplete. Hence a modified "Q" meter had to be designed and constructed but it was then difficult to resonate non-magnetic materials, such as aluminium, therefore, a comparison before and after plating could not be made. A new "Q" meter was then developed based on an Impulse Technique. A regulated miniature hammer was used to excite the test piece at the fundamental mode instead of an electronic hammer and test pieces were supported at the two predetermined nodal points using nylon threads. This instrument developed was not very successful at detecting changes due to good and poor pretreatments given before plating, however, it was more sensitive to changes at the surface such as room temperature oxidation. Statistical analysis of test results from untreated aluminium alloys show that the instrument is not always consistent, the variation was even bigger when readings were taken on different days. Although aluminium is said to form protective oxides at room temperature there was evidence that the aluminium surface changes continuously due to film formation, growth and breakdown. Nickel plated and zinc alloy immersion coated samples also showed variation in Q with time. In order to prove that the variations in Q were mainly due to surface oxidation, aluminium samples were lacquered and anodised Such treatments enveloped the active surfaces reacting with the environment and the Q variation with time was almost eliminated especially after hard anodising. This instrument detected major differences between different untreated aluminium substrates.Also Q values decreased progressively as coating thicknesses were increased. This instrument was also able to detect changes in Q due to heat-treatment of aluminium alloys.

Creep and fatigue of a single crystal nickel base superalloy

The introduction of single crystal casting techniques has led to the development of existing nickel-base superalloys to produce materials with optimum mechanical properties in the single crystal condition. As single crystals are known to be anisotropic, a study is needed to determine the general mechanical properties of these materials, and determine the effects of crystal orientation upon them. A study has been carried out to identify the effect of orientation and temperature on the creep and fatigue properties of a development single crystal superalloy, SRR 99. Creep testing and crystal rotation experiments have been made on SRR 99 and an earlier development alloy, SRR 9. Fatigue experiments at elevated temperatures have been carried out on both notched and un-notched specimens of alloy SRR 99. To aid in this analysis, several analytical techniques have been employed including Laue x-ray orientation analysis, measurement of strain by photographic methods and microstructural examination. Crystal rotation experiments have indicated that shear of 1 precipitates by lbrace111rbrace< 112> slip systems is operative during primary creep deformation at temperatures of 750oC and 850oC. The effect of orientation variation obtained by standard casting practices was not found to be significant. Creep rupture was found to be associated with multiple crack initiation from micropores. Fatigue crack initiation in un-notched specimens was found to be related to microporosity and microstructural defects. Failure was predominantly by crystallographic crack growth on lbrace111rbrace planes. The use of linear elastic fracture mechanics to describe fatigue crack propagation in alloy SRR 99 was found to be acceptable at temperatures up to 850oC. Variation of temperature, frequency and crystal orientation was found to have only moderate effect upon crack propagation rates.

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.

Autocatalytic deposition of composite coatings

The deposition and properties of electroless nickel composite coatings containing graphite, PTFE and chromium were investigated. Solutions were developed for the codeposition of graphite and chromium with electroless nickel. Solutions for the deposition of graphite contained heavy metal ions for stability, with non-ionic and anionic surfactants to provide wetting and dispersion of the particles. Stability for the codeposition of chromium particles was achieved by oxidation of the chromium. Thin oxide layers of 200 nm thick prevented initiation of the electroless reaction onto the chromium. A mechanism for the formation of electroless composite coatings was considered based on the physical adsorption of particles and as a function of the adsorption of charged surfactants and metal cations from solution. The influence of variables such as particle concentration in solution, particle size, temperature, pH, and agitation on the volume percentage of particles codeposited was studied. The volume percentage of graphite codeposited was found to increase with concentration in solution and playing rate. An increase in particle size and agitation reduced the volume percentage codeposited. The hardness of nickel-graphite deposits was found to decrease with graphite content in the as-deposited and heat treated condition. The frictional and wear properties of electroless nickel-graphite were studied and compared to those of electroless nickel-PTFE. The self-lubricating nature of both coatings was found to be dependent on the ratio of coated area to uncoated area, the size and content of lubricating material in the deposit, and the load between contacting surfaces. The mechanism of self-lubrication was considered, concluding that graphite only produced an initial lubricating surface due to the orientation of flakes, unlike PTFE, which produced true self-lubrication throughout the coating life. Heat treatment of electroless nickel chromium deposits at 850oC for 8 and 16 hours produced nickel-iron-chromium alloy deposits with a phosphorus rich surface of high hardness. Coefficients of friction and wear rates were intially moderate for the phosphorus rich layer but increased for the nickel-iron-chromium region of the coating.

Cracking in the welding of cupro-nickel alloys

The problem of variation in weld crack susceptibility caused by small variations in alloy and impurity elements for the 70-30 cupro-nickel alloy has been investigated. Both wrought and cast versions of the alloy have been studied, the main techniques employed being the Varestraint test and weld thermal simulation. In the wrought alloys, cracking has been found to occur mainly in the weld metal, whilst in the cast alloys cracking is extensive in both weld metal and heat affected zone. The previously reported effects of certain impurities (P,S,Si) in increasing cracking have been confirmed, and it has also been shown that Ti and Zr may both have a crack promoting effect at levels commonly found in cupro-nickels, whilst C can interact with several of the other elements investigated to produce a beneficial effect. The testing carried out using the weld thermal simulator has shown that a relationship does exist between hot ductility and weld cracking. In particular, the absence of the peak in ductility in the range 1100°C-900°C on cooling from a temperature near to the solidus is indicative of a highly crack susceptible alloy. Principal practical implications of the investigation concern the relationship of weld metal cracking to alloy composition, especially the level of certain impurities. It would appear that the upper limits permitted by the alloy specifications are unrealistically high. The introduction of lower impurity limits would alleviate the current problems of variability in resistance to cracking during welding.

Electrodeposition on magnesium alloy diecasting

Magnesium alloy diecasting AZ91CC, AZ61CC', AZ91HC and AZ71HC were electroplated using different pretreatment sequences which incorporated conventional zincate immersion processes. Satisfactory peel adhesion in excess of 7. 7 KNm -1 was achieved on AZ61CC using a sequence which was designated Canning. The comparatively low adhesion achieved on the AZ91HC was due to its poor surface quality as cast. Growth of deposits was monitored using a strip-and-analysis technique and the morphology of the various deposits were studied using scanning electron microscopy. Different pretreatment sequences resulted in different surface responses for the alloys but all alloys behaved in a similar manner in a particular sequence with regard to potential time-curves and the rate of zinc deposition. The role of fluoride in both the second stage solution and zinc immersion stages of the Canning pretreatment sequence was studied using techniques listed above and Auger electron spectroscopy. Complete coverage of the magnesium alloy surface with immersion zinc was achieved when fluoride was absent from the zincating solution. However, a zero adhesion value was indicated in both thermal cycling and peel tests. The presence of fluoride in the immersion zinc solution suppressed the rate of zinc deposition and affected the time taken to reach equilibrium during potential-time determinations. A mechanism is suggested to explain the significance of fluoride additions to the processing solutions. pH and composition of the zincating solution had a significant effect on the time taken to produce the step observed in the potential/time curves and hence equilibrium potential. Immersion zinc deposition occurred rapidly at first but then changed to a lower uniform rate at a point corresponding approximately to the step in the potential/time curve. Although the minimun levels of adhesion, using the Canning sequence, varied from 7.72 KNm-1 for alloy AZ61CC to 1.54 KNm-1 for alloy AZ91HC, all the alloys revealed ductile failure characteristics in the surface layer of the substrate after peel testing. Plated magnesium alloys exhibited good corrosion resistance when appropriately pretreated and overplated with adequate nickel chromium coatings. The immersion zinc layer was not preferentially attacked when pits penetrated to the coating/substrate interface. Hemispherical pits formed and attack on the substrate was severe. Of the pretreatment sequences investigated, the Canning one was the most premising with respect to peel adhesion and corrosion behaviour.