Friction Stir-Welded Dissimilar Aluminum Alloys: Microstructure, Mechanical Properties, and Physical State

A356 and 6061 aluminum alloys were joined by friction stir welding at constant tool rotational rate with different tool-traversing speeds. Thermomechanical data of welding showed that increment in tool speed reduced the pseudo heat index and temperature at weld nugget (WN). On the other hand, volume of material within extrusion zone, strain rate, and Zenner Hollomon parameter were reduced with decrease in tool speed. Optical microstructure of WN exhibited nearly uniform dispersion of Si-rich particles, fine grain size of 6061 Al alloy, and disappearance of second phase within 6061 Al alloy. With enhancement in welding speed, matrix grain size became finer, yet size of Si-rich particles did not reduce incessantly. Size of Si-rich particles was governed by interaction time between tool and substrate. Mechanical property of WN was evaluated. It has been found that the maximum joint efficiency of 116% with respect to that of 6061 alloy was obtained at an intermediate tool-traversing speed, where matrix grain size was significantly fine and those of Si-rich particles were substantially small.

On Using Nanoporous Alumina Films as Tribological Coating

Anodization of aluminum alloys is a common surface treatment procedure employed for the protection against corrosion. A thin amorphous layer of alumina is formed on the surface of alloy, which seals the alloy surface from the surrounding. This alumina layer being harder than the base aluminum alloy can be useful as a tribological coating. But since this alumina layer is randomly formed with disordered voids and pores, predicting the mechanical properties is difficult. Specific anodizing conditions can be used to form highly ordered anodic nanoporous alumina films 1] on the aluminum alloy surface. These nanoporous alumina layer can be effectively used as a tribological coating, because of the highly ordered controllable geometry and the empty pores which can be used as reservoirs for lubricant.

Recrystallization and Ag3Sn Particle Redistribution During Thermomechanical Treatment of Bulk Sn-Ag-Cu Solder Alloys

Sn-Ag-Cu (SAC) solders are susceptible to appreciable microstructural coarsening during storage or service. This results in evolution of joint properties over time and thereby influences the long-term reliability of microelectronic packages. Accurate reliability prediction of SAC solders requires prediction of microstructural evolution during service. Microstructure evolution in two SAC solder alloys, such as, Sn-3.0Ag-0.5Cu (SAC 305) and Sn-1.0Ag-0.5 Cu (SAC 105), under different thermomechanical excursions, including isothermal aging at 150 degrees C and thermomechanical cycling (TMC) was studied. In general, between 200 and 600 cycles during TMC, recrystallization of the Sn matrix was observed, along with redistribution of Ag3Sn particles because of dissolution and reprecipitation. These latter effects have not been reported before. It was also observed that the Sn grains recrystallized near precipitate clusters in eutectic channels during extended isothermal aging. The relative orientation of Sn grains in proeutectic colonies did not change during isothermal aging.

Co-evolution of specific amino acid in sigma 1.2 region and nucleotide base in the discriminator to act as sensors of small molecule effectors of transcription initiation in mycobacteria

The transcription from rrn and a number of other promoters is regulated by initiating ribonucleotides (iNTPs) and guanosine tetra/penta phosphate (p)ppGpp], either by strengthening or by weakening of the RNA polymerase (RNAP)-promoter interactions during initiation. Studies in Escherichia coli revealed the importance of a sequence termed discriminator, located between -10 and the transcription start site of the responsive promoters in this mode of regulation. Instability of the open complex at these promoters is attributed to the lack of stabilizing interactions between the suboptimal discriminator and the 1.2 region of sigma 70 (Sig70) in RNAP holoenzyme. We demonstrate a different pattern of interaction between the promoters and sigma A (SigA) of Mycobacterium tuberculosis to execute similar regulation. Instead of cytosine and methionine, thymine at three nucleotides downstream to -10 element and leucine 232 in SigA are found to be essential for iNTPs and pppGpp mediated response at the rrn and gyr promoters of the organism. The specificity of the interaction is substantiated by mutational replacements, either in the discriminator or in SigA, which abolish the nucleotide mediated regulation in vitro or in vivo. Specific yet distinct bases and the amino acids appear to have co-evolved' to retain the discriminator-sigma 1.2 region regulatory switch operated by iNTPs/pppGpp during the transcription initiation in different bacteria.

Effect of chemical treatment on surface characteristics of sputter deposited Ti-rich NiTi shape memory alloy thin-films

NiTi thin-films were deposited by DC magnetron sputtering from single alloy target (Ni/Ti: 45/55 aL.%). The rate of deposition and thickness of sputter deposited films were maintained to similar to 35 nm min(-1) and 4 mu m respectively. A set of sputter deposited NiTi films were selected for specific chemical treatment with the solution comprising of de-ionized water, HF and HNO3 respectively. The influence of chemical treatment on surface characteristics of NiTi films before and after chemical treatment was investigated for their structure, micro-structure and composition using different analytical techniques. Prior to chemical treatment, the composition of NiTi films using energy dispersive X-ray dispersive spectroscopy (EDS), were found to be 51.8 atomic percent of Ti and 48.2 atomic percent of Ni. The structure and morphology of these films were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). XRD investigations, demonstrated the presence of dominant Austenite (110) phase along with Martensite phase, for untreated NiTi films whereas some additional diffraction peaks viz. (100), (101), and (200) corresponding to Rutile and Anatase phase of Titanium dioxide (TiO2) along with parent Austenite (110) phase were observed for chemically treated NiTi films. FTIR studies, it can be concluded that chemically treated films have higher tendency to form metal oxide/hydroxide than the untreated NiTi films. XPS investigations, demonstrated the presence of Ni-free surface and formation of a protective metal oxide (TiO2) layer on the surface of the films, in both the cases. The extent of the formation of surface oxide layer onto the surface of NiTi films has enhanced after chemical treatment. (C) 2014 Elsevier B.V. All rights reserved.

In Vivo Genotoxicity Assessment of Titanium Dioxide Nanoparticles by Allium cepa Root Tip Assay at High Exposure Concentrations

The industrial production and commercial applications of titanium dioxide nanoparticles have increased considerably in recent times, which has increased the probability of environmental contamination with these agents and their adverse effects on living systems. This study was designed to assess the genotoxicity potential of TiO2 NPs at high exposure concentrations, its bio-uptake, and the oxidative stress it generated, a recognised cause of genotoxicity. Allium cepa root tips were treated with TiO2 NP dispersions at four different concentrations (12.5, 25, 50, 100 mu g/mL). A dose dependant decrease in the mitotic index (69 to 21) and an increase in the number of distinctive chromosomal aberrations were observed. Optical, fluorescence and confocal laser scanning microscopy revealed chromosomal aberrations, including chromosomal breaks and sticky, multipolar, and laggard chromosomes, and micronucleus formation. The chromosomal aberrations and DNA damage were also validated by the comet assay. The bio-uptake of TiO2 in particulate form was the key cause of reactive oxygen species generation, which in turn was probably the cause of the DNA aberrations and genotoxicity observed in this study.

Synergistic electrochemical activity of titanium carbide and carbon towards fuel cell reactions

Titanium carbide (TiC) is an electrically conducting refractory interstitial compound possessing several unique properties. A cost-effective, efficient and non-Pt electrocatalyst based on TiC is explored and the multi-functionality of TiC towards various electrochemical reactions that are of significant interest in low temperature fuel cells is studied. Ameliorated activities towards oxygen reduction reaction (ORR) and borohydride oxidation are observed with TiC-carbon composites. High sensitivity and selectivity towards ORR have been demonstrated with very good methanol tolerance. The charge transfer interactions between TiC and carbon seem to play a vital role in the improved activity as compared to their individual counterparts. The present study opens up a way to realize completely Pt-free borohydride fuel cell architecture.

Exfoliated graphite/titanium dioxide nanocomposites for photodegradation of eosin yellow

An improved photocatalyst consisting of a nanocomposite of exfoliated graphite and titanium dioxide (EG-TiO2) was prepared. SEM and TEM micrographs showed that the spherical TiO2 nanoparticles were evenly distributed on the surface of the EG sheets. A four times photocatalytic enhancement was observed for this floating nanocomposite compared to TiO2 and EG alone for the degradation of eosin yellow. For all the materials, the reactions followed first order kinetics where for EG-TiO2, the rate constant was much higher than for EG and TiO2 under visible light irradiation. The enhanced photocatalytic activity of EG-TiO2 was ascribed to the capability of graphitic layers to accept and transport electrons from the excited TiO2, promoting charge separation. This indicates that carbon, a cheap and abundant material, can be a good candidate as an electron attracting reservoir for photocatalytic organic pollutant degradation. (C) 2014 Elsevier B.V. All rights reserved.

A Dinuclear Cadmium(II) Schiff Base Thiocyanato Complex: Crystal Structure and Fluorescence

A new dinuclear cadmium(II) complex, Cd(L)(NCS)](2) (1) has been synthesized using a potentially tetradentate Schiff base ligand HL, 2-((E)-(2-(diethylamino) ethylimino) methyl)-6-methoxyphenol, obtained by the condensation of 2-diethylaminoethylamine and o-vanillin, and characterized by different physicochemical techniques. Crystal structure of the title complex was unambiguously established by single crystal X-ray diffraction which reveals that metal centers are connected by bridging phenolato and chelating methoxy oxygen atoms of the coordinating Schiff bases and embedded in severely distorted octahedral geometries. Fluorescence properties of the ligand and its complex, studied at room temperature indicate that later may serve as strong fluorescent

Titanium promoted reduction of imines with Grignards, silanes, and zinc: identification of a new mechanism with silanes

Aldimines react with reducing agents, such as Grignards, phenylsilane or zinc in the presence of titanium(IV) isopropoxide to form amines and reductively coupled imines (diamines). Using deuterium labeled reagents, the mechanism of reduction to form amines is described. Reducing agents, such as the Grignard and zinc result in the formation of low valent titanium (LVT), which in turn reduces the imine. On the other hand, phenylsilane reacts by a distinctly different mechanism and where a hydrogen atom from silicon is directly transferred to the titanium coordinated imine. (c) 2014 Elsevier Ltd. All rights reserved.

Titanium nitride thin film anode: chemical and microstructural evaluation during electrochemical studies

TIN thin films with (200) fibre texture are deposited on Cu substrate at room temperature using reactive magnetron sputtering. They exhibit a discharge capacity of 172 mu Ah cm(-2) mu m(-1) (300 mAh g(-1)) in a non-aqueous electrolyte containing a Li salt. There is a graded decrease in discharge capacity when cycled between 0.01 and 3.0 V. Electron microscopy investigations indicate significant changes in surface morphology of the cycled TiN electrodes in comparison with the as deposited TiN films. From XPS depth profile analysis, it is inferred that Li intercalated TIN films consist of lithium compounds, hydroxyl groups, titanium sub oxides and TiN. Lithium diffusivity and reactivity decrease with increase in depth and the major reaction with lithium takes place at film surface and grain boundaries. (C) 2014 Elsevier Ltd. All rights reserved.

Azide/thiocyanate incorporated cobalt(III)-Schiff base complexes: Characterizations and catalytic activity in aerobic epoxidation of olefins

Reaction of cobalt(II) perchlorate hexahydrate with a potentially tetradentate Schiff base ligand, HL (2-methoxy-6-(2-diethylaminoethylimino)methyl]phenol) in presence of sodium azide and sodium thiocyanate yields two complexes Co( L)( HL)(N-3)]center dot ClO4 ( 1) and Co( L)( HL)(NCS)] center dot ClO4 ( 2); both being characterized by different physicochemical methods. Crystal structure of 1 was determined by single crystal X-ray diffraction while that of 2 was reported earlier. In 1, the central cobalt(III) adopts slightly distorted octahedral geometry with same donor set to that of 2. Catalytic efficacy of the complexes towards epoxidation of different alkenes under aerobic condition were investigated in homogeneous medium which reveals that 1 is better catalyst than 2 with respect to alkene oxidation, reflected from the turn over frequencies (TOF) measured at an optimum temperature of 60 degrees C in acetonitrile. (C) 2014 Published by Elsevier B.V.

Biodegradable Mg and Mg based alloys for biomedical implants

Mg and its alloys become natural biomaterials as the elemental Mg is found in the human body in abundance and their mechanical properties being akin to the natural bone as well as due to their inherent bioabsorbable/bioresorbable property. This paper discusses the development of new Mg alloys and their corrosion characteristics in detail. The latest advancements in coating of Mg alloys to control their degradation rate are also reviewed along with the future challenges that need to be addressed.

Mono- and Dialkyne Insertion Reactions of Cyclopalladated N,N `,N `'-Triarylguanidines kappa(2)(C,N)Pd(mu-Br)](2) and cis-/trans-kappa(2)(C,N)Pd(Lewis Base)Br]. Scaffolds for Enlarged, Rearranged, and Zwitterionic Palladacycles through Ring Contraction cum Amine-Imine Tautomerization

Insertion reactions of six-membered cyclopalladated N,N',N''-triarylguanidines, kappa(2)(C,N)Pd(mu-Br)](2) with various alkynes in CH2Cl2 under ambient conditions afforded diinserted eight-membered palladacycles, (kappa(2)(C,N):eta(2)(C=C)-PdBr] (1-11), in high yield (76-96%), while insertion reactions of six-membered cyclopalladated N,N',N''-triarylguanidines, kappa(2)(C,N)Pd(Lewis base)Br] (VI-XI), with various alkynes under the aforementioned conditions afforded monoinserted six-membered palladacycles, kappa(2)(C,N)-Pd(Lewis base)Br] (12-21), in high yield (81-91%) except for 14 (23%). The insertion reaction of VI with 2 equiv of dimethyl acetylenedicarboxylate (DMAD) and the insertion reaction of 12 with 1 equiv of DMAD in CH2Cl2 under ambient conditions resulted in the formation of a diinserted zwitterionic five-membered palladacycle, kappa(2)(C,C)Pd(2,6-lutidine)Br] (22), in 76% and 70% yields, respectively. Palladacycle 22 upon reaction with AgOTf in wet MeCN afforded the ionic palladacycle kappa(2)(C,C)Pd(2,6-lutidine)(H2O)]OTf] (23) in 78% yield. The ring size of the ``kappa(2)(C,N)Pd]'' unit in the structurally characterized diinserted palladacycles (1 center dot 2CH(2)Cl(2)center dot H2O, 2, 5, and 7), and monoinserted palladacycles (17, 18, and 20 center dot C7H8 H2O) is smaller than that anticipated for mono- and diinserted palladacycles, and this feature is mainly ascribed to the proclivity of III-XI to undergo ring contraction cum amine-imine tautomerization upon alkyne insertion. Palladacycle 22 represents the first diinserted product obtained in alkyne insertion reactions of kappa(2)(C,N)Pd(Lewis base)X] type palladarycles. The molecular structure of 22 center dot H2O determined by X-ray diffraction indicates that the positive charge on the guanidinium moiety is balanced by the negative charge on the palladium atom and thus represents the first structurally characterized zwitterionic palladacycle to be reported in alkyne insertion chemistry. Plausible mechanisms of formation of 12-21 and 22 have been outlined. The presence of more than one species in solution for some of the palladacycles in the series 1-7 and 12-21 was explained by invoking the C-N single-bond rotation of the CN3 unit of the guanidine moiety, while this process in conjunction with Pd-N(lutidine) bond rotation was invoked to explain the presence of four isomers of 15, as studied with the aid of variable-concentration H-1 NMR experiments carried out for 14 and 15.

Synthesis and Mechanism of Composition and Size Dependent Morphology Selection in Nanoparticles of Ag-Cu Alloys Processed by Laser Ablation Under Liquid Medium

We have synthesized Ag-Cu alloy nanoparticles of four different compositions by using the laser ablation technique with the target under aqueous medium. Following this, we report a morphological transition in the nanoparticles from a normal two-phase microstructure to a structure with random segregation and finally a core shell structure at small sizes as a function of Cu concentration. To illustrate the composition dependence of morphology, we report observations carried out on nanoparticles of two different sizes: similar to 5 and similar to 20 nm. The results could be rationalized through the thermodynamic modeling of free energy of phase mixing and wettability of the alloying phases.