An Approach to a Bislactone Skeleton: A Scalable Total Synthesis of (+/-)-Penifulvin A

An efficient and scalable total synthesis of the architecturally challenging sesquiterpenoid (+/-)-penifulvin A has been accomplished via a 12-step sequence with an overall yield of 16%. For the construction of this structurally complex tetracyclic molecule, the key steps used included 1,4-conjugate addition, a Pd(0) catalyzed cross-coupling reaction between an enol phosphate and trimethyl aluminum, Claisen rearrangement using the Johnson orthoester protocol, Ti(III)-mediated reductive epoxide opening-cyclization, Lewis acid catalyzed epoxy-aldehyde rearrangement, and finally a substrate controlled oxidative cascade lactonization process.

Evaluation. of Transverse Piezoelectric Coefficient of ZnO Thin Films Deposited on Different Flexible Substrates: A Comparative Study on the Vibration Sensing Performance

We report on the systematic comparative study of highly c-axis oriented and crystalline piezoelectric ZnO thin films deposited on four different flexible substrates for vibration sensing application. The flexible substrates employed for present experimental study were namely a metal alloy (Phynox), metal (aluminum), polyimide (Kapton), and polyester (Mylar). ZnO thin films were deposited by an RF reactive magnetron sputtering technique. ZnO thin films of similar thicknesses of 700 +/- 30 nm were deposited on four different flexible substrates to have proper comparative studies. The crystallinity, surface morphology, chemical composition, and roughness of ZnO thin films were evaluated by respective material characterization techniques. The transverse piezoelectric coefficient (d(31)) value for assessing the piezoelectric property of ZnO thin films on different flexible substrates was measured by a four-point bending method. ZnO thin films deposited on Phynox alloy substrate showed relatively better material characterization results and a higher piezoelectric d(31) coefficient value as compared to ZnO films on metal and polymer substrates. In order to experimentally verify the above observations, vibration sensing studies were performed. As expected, the ZnO thin film deposited on Phynox alloy substrate showed better vibration sensing performance. It has generated the highest peak to peak output voltage amplitude of 256 mV as compared to that of aluminum (224 mV), Kapton (144 mV), and Mylar (46 mV). Therefore, metal alloy flexible substrate proves to be a more suitable, advantageous, and versatile choice for integrating ZnO thin films as compared to metal and polymer flexible substrates for vibration sensing applications. The present experimental study is extremely important and helpful for the selection of a suitable flexible substrate for various applications in the field of sensor and actuator technology.

Tailoring the Microstructural, Optical, and Electrical Properties of Nanocrystalline WO3 Thin Films Using Al Doping

We have studied the influence of Al doping on the microstructural, optical, and electrical properties of spray-deposited WO3 thin films. XRD analyses confirm that all the films are of polycrystalline WO3 in nature, possessing monoclinic structure. EDX profiles of the Al-doped films show aluminum peaks implying incorporation of Al ions into WO3 lattice. On Al doping, the average crystallite size decreases due to increase in the density of nucleation centers at the time of film growth. The observed variation in the lattice parameter values on Al doping is attributed to the incorporation of Al ions into WO3 lattice. Enhancement in the direct optical band gap compared to the undoped film has been observed on Al doping due to decrease in the width of allowed energy states near the conduction band edge. The refractive indices of the films follow the Cauchy relation of normal dispersion. Electrical resistivity compared to the undoped film has been found to increase on Al doping.

Field Emission with Ultra low Turn On Voltage from Metal Decorated Carbon Nanotubes

A simple and scalable method of decorating 3D-carbon nanotube (CNT) forest with metal particles has been developed. The results observed in aluminum (AI) decorated CNTs and copper (Cu) decorated CNTs on silicon (Si) and Inconel are compared with undecorated samples. A significant improvement in the field emission characteristics of the cold cathode was observed with ultralow turn on voltage (E-to similar to 0.1 V/mu m) due to decoration of CNTs with metal nanoparticles. Contact resistance between the CNTs and the substrate has also been reduced to a large extent, allowing us to get stable emission for longer duration without any current degradation, thereby providing a possibility of their use in vacuum microelectronic devices.

Impact dynamics of high Weber number drops on chemically modified metallic surfaces

Hydrophobic/superhydrophobic metallic surfaces prepared via chemical treatment are encountered in many industrial scenarios involving the impingement of spray droplets. The effectiveness of such surfaces is understood through the analysis of droplet impact experiments. In the present study, three target surfaces with aluminum (Al-6061) as base material-acid-etched, Octadecyl Trichloro Silane (OTS) coated, and acid-etched plus OTS-coated-were prepared. Experiments on the impact of inertia dominated water drops on these chemically modified aluminum surfaces were carried out with the objective to highlight the effect of chemical treatment on the target surfaces on key sub-processes occurring in drop impact phenomenon. High speed videos of the entire drop impact dynamics were captured at three Weber number (We) conditions representative of high We (We > 200) regime. During the early stages of drop spreading, the drop impact resulted in ejection of secondary droplets from spreading drop front on the etched surfaces resembling prompt splash on rough surfaces whereas no such splashing was observable on untreated aluminum surface. Prominent development of undulations (fingers) were observed at the rim of drop spreading on the etched surfaces; between the etched surfaces the OTS-coated surface showed a subdued development of fingers than the uncoated surface. The impacted drops showed intense receding on OTS-coated surfaces whereas on the etched surface a highly irregular receding, with drop liquid sticking to the surface, was observed. Quantitative analyses were performed to reveal the effect of target surface characteristics on drop impact parameters such as temporal variation of spread factor of drop lamella, temporal variation of average finger length during spreading phase, maximum drop spreading, time taken to attain maximum spreading, sensitivity of maximum spreading to We, number of fingers at maximum spreading, and average receding velocity of drop lamella. Existing models for maximum drop spreading showed reasonably good agreement with the experimental measurements on the target surfaces except the acid-etched surface. (C) 2014 Elsevier B.V. All rights reserved.

Low-Density Steels: The Effect of Al Addition on Microstructure and Properties

Density reduction of automotive steels is needed to reduce fuel consumption, thereby reducing greenhouse gas emissions. Aluminum addition has been found to be effective in making steels lighter. Such an addition does not change the crystal structure of the material. Steels modified with aluminum possess higher strength with very little compromise in ductility. In this work, different compositions of Fe-Al systems have been studied so that the desired properties of the material remain within the limit. A density reduction of approximately 10% has been achieved. The specific strength of optimal Fe-Al alloys is higher than conventional steels such as ultra-low-carbon steels.

Development of alloys with high strength at elevated temperatures by tuning the bimodal microstructure in the Al-Cu-Ni eutectic system

The development of high-strength aluminum alloys that can operate at 250 degrees C and beyond remains a challenge to the materials community. In this paper we report preliminary development of nanostructural Al-Cu-Ni ternary alloys containing alpha-Al, binary Al2Cu and ternary Al2Cu4Ni intermetallics. The alloys exhibits fracture strength of similar to 1 GPa with similar to 9% fracture strain at room temperature. At 300 degrees C, the alloy retains the high strength. The reasons for such significant mechanical properties are rationalized by unraveling the roles and response of various microstructural features. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Influence of Surface Texture and Roughness of Softer and Harder Counter Materials on Friction During Sliding

Surface texture influences friction during sliding contact conditions. In the present investigation, the effect of surface texture and roughness of softer and harder counter materials on friction during sliding was analyzed using an inclined scratch testing system. In the experiments, two test configurations, namely (a) steel balls against aluminum alloy flats of different surface textures and (b) aluminum alloy pins against steel flats of different surface textures, are utilized. The surface textures were classified into unidirectionally ground, 8-ground, and randomly polished. For a given texture, the roughness of the flat surfaces was varied using grinding or polishing methods. Optical profilometer and scanning electron microscope were used to characterize the contact surfaces before and after the experiments. Experimental results showed that the surface textures of both harder and softer materials are important in controlling the frictional behavior. The softer material surface textures showed larger variations in friction between ground and polished surfaces. However, the harder material surface textures demonstrated a better control over friction among the ground surfaces. Although the effect of roughness on friction was less significant when compared to textures, the harder material roughness showed better correlations when compared to the softer material roughness.

Surface Enhanced Raman Scattering on Anodized Alumina Templates for Bio-sensing Applications

SERS substrate was fabricated by depositing silver on anodized aluminum oxide (AAO) template. The thickness of the AA0 template was 200 nm with 40 nm circular pore and 15 nm spacing. SERS effect was observed on these metal coated structures due to electric field enhancement around the edge of the pores. Para-Nitrophenol (pnp) solution of 10(-6) M concentration was detected which refers to an enhancement factor of 10(4).

Study of Microstructure Evolution during Semi-Solid Processing of an In-Situ Al Alloy Composite

In the present work, effect of pouring temperature (650 degrees C, 655 degrees C, and 660 degrees C) on semi-solid microstructure evolution of in-situ magnesium silicide (Mg2Si) reinforced aluminum (Al) alloy composite has been studied. The shear force exerted by the cooling slope during gravity driven flow of the melt facilitates the formation of near spherical primary Mg2Si and primary Al grains. Shear driven melt flow along the cooling slope and grain fragmentation have been identified as the responsible mechanisms for refinement of primary Mg2Si and Al grains with improved sphericity. Results show that, while flowing down the cooling slope, morphology of primary Mg2Si and primary Al transformed gradually from coarse dendritic to mixture of near spherical particles, rosettes, and degenerated dendrites. In terms of minimum grain size and maximum sphericity, 650 degrees C has been identified as the ideal pouring temperature for the cooling slope semi-solid processing of present Al alloy composite. Formation of spheroidal grains with homogeneous distribution of reinforcing phase (Mg2Si) improves the isotropic property of the said composite, which is desirable in most of the engineering applications.

SIMULATION STUDY OF THE ADSORPTION DYNAMICS OF CYLINDRICAL SILICA GEL PARTICLES

The paper presents a simulation study of loose cylindrically shaped particles packed within a copper plate and aluminum fins. The model presented solves coupled heat and mass transfer equations using the finite volume method based on ANSY S FLUENT medium. Three different arrangements of cylindrical particles are considered. The model is validated with experimental data. It is found that the arrangements which represented monolayer configurations are only marginally better in heat transfer and uptake efficiency than the tri-layer configuration in the presence of fins. However, there is an appreciable difference in the uptake curve between monoand tri-layer configurations in the absence of fins. Finally, it is found that the fin pitch also plays an important role in determining the time constant for the adsorber design.

A rhodamine-based `turn-on' Al3+ ion-selective reporter and the resultant complex as a secondary sensor for F- ion are applicable to living cell staining

A newly designed fluorescent aluminum(III) complex (L'-Al; 2) of a structurally characterized non-fluorescent rhodamine Schiff base (L) has been isolated in pure form and characterized using spectroscopic and physico-chemical methods with theoretical density functional theory (DFT) support. On addition of Al(III) ions to a solution of L in HEPES buffer (1 mM, pH 7.4; EtOH-water, 1 : 3 v/v) at 25 degrees C, the systematic increase in chelation-enhanced fluorescence (CHEF) enables the detection of Al(III) ions as low as 60 nM with high selectivity, unaffected by the presence of competitive ions. Interestingly, the Al(III) complex (L'-Al; 2) is specifically able to detect fluoride ions by quenching the fluorescence in the presence of large amounts of other anions in the HEPES buffer (1 mM, pH 7.4) at 25 degrees C. On the basis of our experimental and theoretical findings, the addition of Al3+ ions to a solution of L helps to generate a new fluorescence peak at 590 nm, due to the selective binding of Al3+ ions with L in a 1 : 1 ratio with a binding constant (K) of 8.13 x 10(4) M-1. The Schiff base L shows no cytotoxic effect, and it can therefore be employed for determining the intracellular concentration of Al3+ and F-ions by 2 in living cells using fluorescence microscopy.

Rheological Behavior of Al-7Si-0.3Mg Alloy at Mushy State

In recent years, semisolid manufacturing has emerged as an attractive option for near net shape forming of components with aluminum alloys. In this class of processes, the key to success lies mainly in the understanding of rheological behavior of the semi-solid slurry in the temperature range between liquidus and solidus. The present study focuses on the non-Newtonian flow behavior of the pseudo plastic slurry of Al-7Si-0.3Mg alloy for a wide shear range using a high-temperature Searle-type rheometer. The rheological behavior of the slurry is studied with respect to relevant process variables and microstructural features such as shear rate, shear duration, temperature history, primary particle size, shape, and their distribution. The experiments performed are isothermal tests, continuous cooling tests, shear jump tests, and shear time tests. The continuous cooling experiments are aimed toward studying the viscosity and shear stress evolution within the slurry matrix with increasing solid fraction at a constant shear rate. Three different cooling rates are considered and their effect on flow behavior of the slurry was studied under iso-shear condition. Descending shear jump experiments are performed to understand the viscous instability of the slurry.

Influence of yttria and zirconia additions on spark plasma sintering of alumina composites

The mechanisms of densification and creep were examined during spark plasma sintering (SPS) of alumina doped with a low and high level of zirconia or yttria, over a temperature range of 1173-1573 K and stresses between 25 and 100 MPa. Large additions of yttria led clearly to in situ reactions during SPS and the formation of a yttrium-aluminum garnet phase. Dopants generally lead to a reduction in the densification rate, with substantial reductions noted in samples with similar to 5.5 vol% second phase. In contrast to a stress exponent of n similar to 1 for pure alumina, the doped aluminas displayed n similar to 2 corresponding to an interface-controlled diffusion process. The higher activation energies in the composites are consistent with previous data on creep and changes in the interfacial energies. The results reveal a compensation effect, such that an increase in the activation energy is accompanied by a corresponding increase in the pre-exponential term for diffusion.

Discharge Plasma Combined With Bauxite Residue for Biodiesel Exhaust Cleaning: A Case Study on NOx Removal

Experiments were conducted at laboratory level to treat the oxides of nitrogen (NOx) present in raw and dry biodiesel exhaust utilizing a combination of electric discharge plasma and bauxite residue, i. e., red mud, an industrial waste byproduct from the aluminum industry. In this paper, the adsorption and a possible catalytic property of bauxite residue are discussed. Nonthermal plasma was generated using dielectric barrier discharges initiated by ac/repetitive pulse energization. The effect of corona electrodes on the plasma generation was qualitatively studied through NOx cleaning. The plasma reactor and adsorbent reactors were connected in cascade while treating the exhaust. The diesel generator, running on biodiesel fuel, was electrically loaded to study the effectiveness of the cascade system in cleaning the exhaust. Interestingly, under the laboratory conditions studied, plasma-bauxite residue combination has shown good synergistic properties and enhanced the NOx removal up to about 90%. With proper scaling up, the suggested cascade system may become an economically feasible option to treat the exhaust in larger installations. The results were discussed emphasizing the role of bauxite residue as an adsorbent and as a room temperature catalyst.