Highly Sensitive, Uniform, and Reproducible Surface-Enhanced Raman Spectroscopy from Hollow Au-Ag Alloy Nanourchins

A hierarchical nanoparticle strategy to simultaneously gain super Raman signal amplification, high uniformity, and reproducibility is presented. Using hollow Au-Ag alloy nanourchins, an ultrahigh sensitivity, e.g., down to 1 fM concentrations for DEHP molecule is obtained. A small standard deviation of <10% is achieved by simply dropping and evaporating sub-100 nm nanourchins onto a substrate.

Controlling alloy formation and optical properties by galvanic replacement of sub-20 nm silver nanoparticles in organic media

Galvanic replacement is a versatile synthetic strategy for the synthesis of alloy and hollow nanostructures. The structural evolution of single crystalline and multiply twinned nanoparticles <20 nm in diameter and capped with oleylamine is systematically studied. Changes in chemical composition are dependent on the size and crystallinity of the parent nanoparticle. The effects of reaction temperature and rate of precursor addition are also investigated. Galvanic replacement of single crystal spherical and truncated cubic nanoparticles follows the same mechanism to form hollow octahedral nanoparticles, a mechanism which is not observed for galvanic replacement of Ag templates in aqueous systems. Multiply twinned nanoparticles can form nanorings or solid alloys by manipulating the reaction conditions. Oleylamine-capped Ag nanoparticles are highly adaptable templates to synthesize a range of hollow and alloy nanostructures with tuneable localised surface plasmon resonance.

Comparison of nanostructures obtained from galvanic replacement in water and an ionic liquid for applications in electrocatalysis and SERS

We demonstrate potential applications for unusual dendrite like Au–Ag alloy nanoparticles formed via a galvanic replacement reaction in the ionic liquid [BMIM][BF4]. In comparison to Au–Ag alloy nanoshells synthesised via a similar reaction in water, the unusual branched structure of the dendritic materials led to increased electrocatalytic activity for the oxidation of both formaldehyde and hydrazine, and increased sensitivity and spectral resolution for the surface enhanced Raman scattering (SERS) of 4,4-bipyridal.

Preliminary mineralogy and ore petrology of the intermediate-sulfidation pallancata deposit, Ayacucho, Peru

Se investiga la compleja mineralogía del Yacimiento de Pallancata (6º productor de plata del mundo) y se establecen las condiciones de formación (P.T) basadas en la petrología de las menas comparada con los datos de mineralogía experimental y en la petrografía y microtermometría de inclusiones fluídas en la ganga silicatada, resultando un depósito típicamente caracterizado como epitermal de sulfuración intermedia.ABSTRACT:Pallancata is a world-class intermediate-sulfidation epithermal deposit, hosted by upper Miocene volcanics of the south-central Peruvian Andes in a sinuous N70ºW, ∼75º SW strike-slip structure, with wide (up to 35 m) pull-apart dilation zones related to bends of the vein strike. The structural evolution of the vein from earlier brecciation to later open space infill resembles the Shila Paula district (Chauvet et al. 2006). Fluid inclusion petrography and microthermometry show that ore deposition is related to protracted boiling of very diluted, mainly meteoric fluids, starting at 250–260 ºC, under ∼300 m hydrostatic head. The mineralogical-petrological study reveals a complex sequence of mineralization (eight stages) and mineral reactions consistent with Ag2S enrichment or Sb2S3 depletion, or both, during cooling over the temperature range 250–200 ºC: pyrite, sphalerite, galena, miargyrite, pyrargyrite-proustite, chalcopyrite, polybasite-pearceite, argentite (now acanthite), and Au–Ag alloy (“electrum”). This Ag2S enrichment and Sb2S3depletion during cooling may be explained by decay of a Ag-rich galena precursor at deeper levels (Pb2S2–AgSbS2 solid solution), which rapidly becomes unstable with decreasing temperature, producing residual (stoichiometric) PbS and more mobile Ag and Sb sulfide phases, which migrated upward and laterally away from the thermal core of the system. The core is still undisclosed by mining works, but the available geochemical evidence (logAg/log Pb ratios decreasing at depth) is consistent with this interpretation, implying a deeper potential resource. Data from sulfide geothermometry, based on mineral equilibria, document the thermal evolution of the system below 200 ºC (stephanite, uytenbogaardtite, jalpaite, stromeyerite, mckinstryite, among others). The end of the most productive stages (3, 4, and 5) is marked by the precipitation of stephanite at temperatures below 197 ± 5 ºC, but precipitation of residual silver continues through the waning stages of the hydrothermal system down to <93.3 ºC (stromeyerite) or in a supergene redistribution (stage 8, acanthite II).

Magnetic, electric, and dielectric properties of FeCo alloy nanoparticles dispersed in amorphous matrix

Nanocrystalline Fe53Co47 alloy was synthesized by a single-step transmetallation chemical method at room temperature. The Fe53Co47 alloy nanoparticles of 77 and 47 wt% were dispersed in silica matrix by the sol-gel process using tetraethyl orthosilcate. Structural studies reveal that the as-prepared alloy powders are in bcc phase and silica is in an amorphous state. The phase-transition temperature and Mossbauer spectra analysis of the Fe-Co alloy establishes the homogeneous alloy formation. A saturation magnetization of 218 emu/g was obtained for pure FeCo alloy at room temperature. Scanning electron microscopic analysis demonstrates the hollow-sphere morphology for FeCo alloy particles. Magnetic nanocomposite consisting of 47 wt% FeCo-silica shows enhanced thermal stability over the native FeCo alloy. Electrical and dielectric properties of 47 wt% FeCo-silica nanocomposites were investigated as a function of frequency and temperature. It was found that the dielectric constants and dielectric loss were stable throughout the measured temperature (310-373 K). Our results indicate that FeCo-silica nanocomposite is a promising candidate for high-frequency applications. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

A density functional theory study of carbon monoxide oxidation on the Cu3Pt(111) alloy surface: Comparison with the reactions on Pt(111) and Cu(111)

Alloying metals is often used as an effective way to enhance the reactivity of surfaces. Aiming to shed light on the effect of alloying on reaction mechanisms, we carry out a comparative study of CO oxidation on Cu3Pt(111), Pt(111), and Cu(111) by means of density functional theory calculations. Alloying effects on the bonding sites and bonding energies of adsorbates, and the reaction pathways are investigated. It is shown that CO preferentially adsorbs on an atop site of Pt and O preferentially adsorbs on a fcc hollow site of three Cu atoms on Cu3Pt(111). It is also found that the adsorption energies of CO (or O-a) decreases on Pt (or Cu) on the alloy surface with respect to those on pure metals. More importantly, having identified the transition states for CO oxidation on those three surfaces, we found an interesting trend for the reaction barrier on the three surfaces. Similar to the adsorption energies, the reaction barrier on Cu3Pt possesses an intermediate value of those on pure Pt and Cu metals. The physical origin of these results has been analyzed in detail. (C) 2001 American Institute of Physics.

Flexural behaviour and design of cold-formed steel beams with rectangular hollow flanges

Until recently, the hot-rolled steel members have been recognized as the most popular and widely used steel group, but in recent times, the use of cold-formed high strength steel members has rapidly increased. However, the structural behavior of light gauge high strength cold-formed steel members characterized by various buckling modes is not yet fully understood. The current cold-formed steel sections such as C- and Z-sections are commonly used because of their simple forming procedures and easy connections, but they suffer from certain buckling modes. It is therefore important that these buckling modes are either delayed or eliminated to increase the ultimate capacity of these members. This research is therefore aimed at developing a new cold-formed steel beam with two torsionally rigid rectangular hollow flanges and a slender web formed using intermittent screw fastening to enhance the flexural capacity while maintaining a minimum fabrication cost. This thesis describes a detailed investigation into the structural behavior of this new Rectangular Hollow Flange Beam (RHFB), subjected to flexural action The first phase of this research included experimental investigations using thirty full scale lateral buckling tests and twenty two section moment capacity tests using specially designed test rigs to simulate the required loading and support conditions. A detailed description of the experimental methods, RHFB failure modes including local, lateral distortional and lateral torsional buckling modes, and moment capacity results is presented. A comparison of experimental results with the predictions from the current design rules and other design methods is also given. The second phase of this research involved a methodical and comprehensive investigation aimed at widening the scope of finite element analysis to investigate the buckling and ultimate failure behaviours of RHFBs subjected to flexural actions. Accurate finite element models simulating the physical conditions of both lateral buckling and section moment capacity tests were developed. Comparison of experimental and finite element analysis results showed that the buckling and ultimate failure behaviour of RHFBs can be simulated well using appropriate finite element models. Finite element models simulating ideal simply supported boundary conditions and a uniform moment loading were also developed in order to use in a detailed parametric study. The parametric study results were used to review the current design rules and to develop new design formulae for RHFBs subjected to local, lateral distortional and lateral torsional buckling effects. Finite element analysis results indicate that the discontinuity due to screw fastening has a noticeable influence only for members in the intermediate slenderness region. Investigations into different combinations of thicknesses in the flange and web indicate that increasing the flange thickness is more effective than web thickness in enhancing the flexural capacity of RHFBs. The current steel design standards, AS 4100 (1998) and AS/NZS 4600 (1996) are found sufficient to predict the section moment capacity of RHFBs. However, the results indicate that the AS/NZS 4600 is more accurate for slender sections whereas AS 4100 is more accurate for compact sections. The finite element analysis results further indicate that the current design rules given in AS/NZS 4600 is adequate in predicting the member moment capacity of RHFBs subject to lateral torsional buckling effects. However, they were inadequate in predicting the capacities of RHFBs subject to lateral distortional buckling effects. This thesis has therefore developed a new design formula to predict the lateral distortional buckling strength of RHFBs. Overall, this thesis has demonstrated that the innovative RHFB sections can perform well as economically and structurally efficient flexural members. Structural engineers and designers should make use of the new design rules and the validated existing design rules to design the most optimum RHFB sections depending on the type of applications. Intermittent screw fastening method has also been shown to be structurally adequate that also minimises the fabrication cost. Product manufacturers and builders should be able to make use of this in their applications.

Fusionless scoliosis correction using shape memory alloy staples

Severe spinal deformity in young children is a formidable challenge for optimal treatment. Standard interventions for adolescents, such as spinal deformity correction and fusion, may not be appropriate for young patients with considerable growth remaining. Alternative surgical options that provide deformity correction and protect the growth remaining in the spine are needed to treat this group of patients 1, 2. One such method is the use of shape memory alloy staples. We report our experience to date using video-assisted thoracoscopic insertion of shape memory alloy staples. A retrospective review was conducted of 13 patients with scoliosis, aged 7 to 13 years, who underwent video-assisted thoracoscopic insertion of shape memory staples. In our experience, video-assisted thoracoscopic insertion of shape memory alloy staples is a safe procedure with no complications noted. It is a reliable method of providing curve stability, however the follow up results to date indicate that the effectiveness of the procedure is greater in younger patients.

Flexural behaviour and design of hollow flange steel beams

The LiteSteel Beam (LSB) is a new hollow flange channel section developed by OneSteel Australian Tube Mills using a patented Dual Electric Resistance Welding technique. The LSB has a unique geometry consisting of torsionally rigid rectangular hollow flanges and a relatively slender web. It is commonly used as rafters, floor joists and bearers and roof beams in residential, industrial and commercial buildings. It is on average 40% lighter than traditional hot-rolled steel beams of equivalent performance. The LSB flexural members are subjected to a relatively new Lateral Distortional Buckling mode, which reduces the member moment capacity. Unlike the commonly observed lateral torsional buckling of steel beams, lateral distortional buckling of LSBs is characterised by simultaneous lateral deflection, twist and web distortion. Current member moment capacity design rules for lateral distortional buckling in AS/NZS 4600 (SA, 2005) do not include the effect of section geometry of hollow flange beams although its effect is considered to be important. Therefore detailed experimental and finite element analyses (FEA) were carried out to investigate the lateral distortional buckling behaviour of LSBs including the effect of section geometry. The results showed that the current design rules in AS/NZS 4600 (SA, 2005) are over-conservative in the inelastic lateral buckling region. New improved design rules were therefore developed for LSBs based on both FEA and experimental results. A geometrical parameter (K) defined as the ratio of the flange torsional rigidity to the major axis flexural rigidity of the web (GJf/EIxweb) was identified as the critical parameter affecting the lateral distortional buckling of hollow flange beams. The effect of section geometry was then included in the new design rules using the new parameter (K). The new design rule developed by including this parameter was found to be accurate in calculating the member moment capacities of not only LSBs, but also other types of hollow flange steel beams such as Hollow Flange Beams (HFBs), Monosymmetric Hollow Flange Beams (MHFBs) and Rectangular Hollow Flange Beams (RHFBs). The inelastic reserve bending capacity of LSBs has not been investigated yet although the section moment capacity tests of LSBs in the past revealed that inelastic reserve bending capacity is present in LSBs. However, the Australian and American cold-formed steel design codes limit them to the first yield moment. Therefore both experimental and FEA were carried out to investigate the section moment capacity behaviour of LSBs. A comparison of the section moment capacity results from FEA, experiments and current cold-formed steel design codes showed that compact and non-compact LSB sections classified based on AS 4100 (SA, 1998) have some inelastic reserve capacity while slender LSBs do not have any inelastic reserve capacity beyond their first yield moment. It was found that Shifferaw and Schafer’s (2008) proposed equations and Eurocode 3 Part 1.3 (ECS, 2006) design equations can be used to include the inelastic bending capacities of compact and non-compact LSBs in design. As a simple design approach, the section moment capacity of compact LSB sections can be taken as 1.10 times their first yield moment while it is the first yield moment for non-compact sections. For slender LSB sections, current cold-formed steel codes can be used to predict their section moment capacities. It was believed that the use of transverse web stiffeners could improve the lateral distortional buckling moment capacities of LSBs. However, currently there are no design equations to predict the elastic lateral distortional buckling and member moment capacities of LSBs with web stiffeners under uniform moment conditions. Therefore, a detailed study was conducted using FEA to simulate both experimental and ideal conditions of LSB flexural members. It was shown that the use of 3 to 5 mm steel plate stiffeners welded or screwed to the inner faces of the top and bottom flanges of LSBs at third span points and supports provided an optimum web stiffener arrangement. Suitable design rules were developed to calculate the improved elastic buckling and ultimate moment capacities of LSBs with these optimum web stiffeners. A design rule using the geometrical parameter K was also developed to improve the accuracy of ultimate moment capacity predictions. This thesis presents the details and results of the experimental and numerical studies of the section and member moment capacities of LSBs conducted in this research. It includes the recommendations made regarding the accuracy of current design rules as well as the new design rules for lateral distortional buckling. The new design rules include the effects of section geometry of hollow flange steel beams. This thesis also developed a method of using web stiffeners to reduce the lateral distortional buckling effects, and associated design rules to calculate the improved moment capacities.