Sphere to ring morphological transformation in drying nanofluid droplets in a contact-free environment

Understanding the transients of buckling in drying colloidal suspensions is pivotal for producing new functional microstructures with tunable morphologies. Here, we report first observations and elucidate the buckling instability induced morphological transition (sphere to ring structure) in an acoustically levitated, heated nanosuspension droplet using dynamic energy balance. Droplet deformation featuring the formation of symmetric cavities is initiated by capillary pressure that is two to three orders of magnitude greater than the acoustic radiation pressure, thus indicating that the standing pressure field has no influence on the buckling front kinetics. With an increase in heat flux, the growth rate of surface cavities and their post-buckled volume increase while the buckling time period reduces, thereby altering the buckling pathway and resulting in distinct precipitate structures. However, irrespective of the heating rate, the volumetric droplet deformation exhibits a linear time dependence and the droplet vaporization is observed to deviate from the classical D-2-law.

First principles study of structural stability and site preference in Co-3 (W,X)

Since the discovery 1] of gamma' precipitate (L1(2) - Co-3 (Al, W)) in the Co-Al-W ternary system, there has been an increased interest in Co-based superalloys. Since these alloys have two phase microstructures (gamma + gamma') similar to Ni-based superalloys 2], they are viable candidates in high temperature applications, particularly in land-based turbines. The role of alloying on stability of the gamma' phase has been an active area of research. In this study, electronic structure calculations were done to probe the effect of alloying in Co3W with L1(2) structure. Compositions of type Co-3(W, X), (where X/Y = Mn, Fe, Ni, Pt, Cr, Al, Si, V, W, Ta, Ti, Nb, Hf, Zr and Mo) were studied. Effect of alloying on equilibrium lattice parameters and ground state energies was used to calculate Vegard's coefficients and site preference related data. The effect of alloying on the stability of the L1(2) structure vis a vis other geometrically close packed ordered structures was also studied for a range of Co3X compounds. Results suggest that the penchant of element for the W sublattice can be predicted by comparing heats of formation of Co3X in different structures.

Multi-scale modelling of Suzuki segregation in gamma' precipitates in Ni and Co-base superalloys

The high temperature strength of alloys with (gamma +gamma') microstructure is primarily due to the resistance of the ordered precipitate to cutting by matrix dislocations. Such shearing requires higher stresses since it involves the creation of a planar fault. Planar fault energy is known to be dependent on composition. This implies that the composition on the fault may be different from that in the bulk for energetic reasons. Such segregation (or desegregation) of specific alloying elements to the fault may result in Suzuki strengthening which has not been explored extensively in these systems. In this work, segregation (or desegregation) of alloying elements to planar faults was studied computationally in Ni-3(Al, Ti) and Co-3(W, Al) type gamma' precipitates. The composition dependence of APB energy and heat of mixing were evaluated from first principle electronic structure calculations. A phase field model incorporating the first principles results, was used to simulate the motion of an extended superdislocation under stress concurrently with composition evolution. Results reveal that in both systems, significant (de) segregation occurs on equilibration. On application of stress, solutes were dragged along with the APB in some cases. Additionally, it was also noted the velocity of the superdislocation under an applied stress is strongly dependent on atomic mobility (i. e. diffusivity).

Modelling ternary effects on antiphase boundary energy of Ni3Al

The shearing of ordered gamma' precipitates by matrix dislocations results in the formation of antiphase boundaries (APB) in Ni-base superalloys. The APB energy is an important source of order-strengthening in disk and blade alloys where Ti and Ta substitute for Al in gamma'. While the importance of APB energy is well-acknowledged, the effect of alloying on APB energy is not fully understood. In the present study, the effect of Ti and Ta additions on the {111} and {010} APB energies was probed via electronic structure calculations. Results suggest that at low levels of Ti/Ta, APB energies on either plane increases with alloying. However, at higher Ti/Ta levels, the APB energies decrease with alloying. These trends understood by accounting for nearest neighbour violations about the APB and additionally, invoking the effect of precipitate composition on the energy penalty of the violations. We propose an Environment Dependent Nearest Neighbour Bond (EDNNB) model that predicts APB energies that are in close agreement to calculated values.

SWEETENING OF BIOGAS IN SPRAY TOWERS FOR POWER GENERATION

This paper presents the experience of the new design of using impinging jet spray columns for scrubbing hydrogen sulfide from biogas that has been developed by Indian Institute of Science and patented. The process uses a chelated polyvalent metal ion which oxidizes the hydrogen sulfide to sulfur as a precipitate. The sulfur generated is filtered and the scrubbing liquid recycled after oxidation. The process involves in bringing contact the sour gas with chelated liquid in the spray columns where H2S reacts with chelated Fe3+ and precipitates as sulfur, whereas Fe3+ gets reduced to Fe2+. Fe2+ is regenerated to Fe3+ by reaction of oxygen in air in a separate packed column. The regenerated liquid is recirculated. Sulfur is filtered and separated as a byproduct. The paper presents the experience in using the spray towers for hydrogen sulfide removal and further use of the clean gas for generating power using gas engines. The maximum allowable limit of H2S for the gas engine is 200 ppm (v/v) in order to prevent any corrosion of engine parts and fouling of the lubricating oil. With the current ISET process, the hydrogen sulfide from the biogas is cleaned to less than 100 ppm (v/v) and the sweet gas is used for power generation. The system is designed for 550 NM3/hr of biogas and inlet H2S concentration of 2.5 %. The inlet concentration of the H2S is about 1 - 1.5 % and average measured outlet concentration is about 30 ppm, with an average gas flow of about 300 - 350 NM3/hr, which is the current gas production rate. The sweet gas is used for power generation in a 1.2 MWe V 12 engine. The average power generation is about 650 - 750 kWe, which is the captive load of the industry. The plant is a CHP (combined heat power) unit with heat from the cylinder cooling and flue being recovered for hot water and steam generation respectively. The specific fuel consumption is 2.29 kWh/m(3) of gas. The system has been in operation for more than 13,000 hours in last one year in the industry. About 8.4 million units of electricity has been generated scrubbing about 2.1 million m3 of gas. Performance of the scrubber and the engine is discussed at daily performance level and also the overall performance with an environment sustenance by precipitating over 27 tons of sulfur.

Simultaneously targeting inflammatory response and parasite sequestration in brain to treat Experimental Cerebral Malaria

Malaria afflicts around 200 million people annually, with a mortality number close to 600,000. The mortality rate in Human Cerebral Malaria (HCM) is unacceptably high (15-20%), despite the availability of artemisinin-based therapy. An effective adjunct therapy is urgently needed. Experimental Cerebral Malaria (ECM) in mice manifests many of the neurological features of HCM. Migration of T cells and parasite-infected RBCs (pRBCs) into the brain are both necessary to precipitate the disease. We have been able to simultaneously target both these parameters of ECM. Curcumin alone was able to reverse all the parameters investigated in this study that govern inflammatory responses, CD8(+) T cell and pRBC sequestration into the brain and blood brain barrier (BBB) breakdown. But the animals eventually died of anemia due to parasite build-up in blood. However, arteether-curcumin (AC) combination therapy even after the onset of symptoms provided complete cure. AC treatment is a promising therapeutic option for HCM.

EFFECT OF AGING ON IMPRESSION CREEP BEHAVIOR OF Pb-FREE SOLDERS

During service and/or storage, Sn-Ag-Cu (SAC) solder alloys are subjected to temperatures ranging from 0.4 to 0.8 Tm (where Tm is the melting temperature of SAC alloys), making them highly prone to significant microstructural coarsening. The microstructures of these low melting point alloys continuously evolve during service. This results in evolution of creep properties of the joint over time, thereby influencing the long-term reliability of microelectronic packages. Here, we study microstructure evolution and creep behavior of two Sn-Ag-Cu (SAC) alloys, namely Sn-3.0Ag-0.5Cu and Sn-1.0Cu-0.5Cu, isothermally aged at 150 degrees C for various lengths of time. Creep behavior of the two SAC solders after different aging durations was systematically studied using impression creep technique. The key microstructural features that evolve during aging are Ag3Sn particle size and inter-particle spacing. Creep results indicate that the creep rate increases considerably with increasing inter-particle spacing although the creep stress exponent and creep activation energy are independent of the aging history.

Deployment strategy for controlled morphologies in sessile, mixed colloidal droplets

Colloidal systems offer an effective medium to micro-engineer complex structures without involving sophisticated fabrication procedures. This article presents a deployment strategy of multiple droplets of different colloidal composition and utilizes the inherent capillary flow driven self assembly of nanoparticles to construct stacks of multiple materials on a given glass substrate. Here we used aqueous nano-crystalline titania and nano-amorphous silica solutions as the two materials. Initially, a pure nanotitania (nanosilica) droplet is deployed and allowed to dry partially. Subsequently, a second droplet of pure nanosilica (nanotitania) is deployed co-axially on the partially dried precipitate. The proposed deployment strategy allowed significant morphological differences when the deployment order of nanosilica and nanotitania were interchanged. Compositional analysis performed using EDX (Energy Dispersive X-ray spectroscopy) showed preferential deposition of nanosilica and nanotitania along the radial as well as the axial plane of the final deposit pattern. The underlying mechanism for such a phenomenon could be attributed to the contact line dynamics of a sessile double droplet. We also observe heteroaggregation of the nanosilica-nanotitania interaction along a narrow interface which resulted in nanotitania particles clustering into isolated islands embedded into a matrix of nanosilica particles. Overall, this work elucidates the evaporation driven dynamics of a mixed colloidal system which displays both macroscopic as well as microscopic phenomena. Such a system could be used to generate ordered arrays of functional materials with engineered micro to nano-scale properties.

In-situ study of microscale fracture of diffusion aluminide bond coats: Effect of platinum

The influence of Pt layer thickness on the fracture behavior of PtNiAl bond coats was studied in situ using clamped micro-beam bend tests inside a scanning electron microscope (SEM). Clamped beam bending is a fairly well established micro-scale fracture test geometry that has been previously used in determination of fracture toughness of Si and PtNiAl bond coats. The increasing amount of Pt in the bond coat matrix was accompanied by several other microstructural changes such as an increase in the volume fraction of alpha-Cr precipitate particles in the coating as well as a marginal decrease in the grain size of the matrix. In addition, Pt alters the defect chemistry of the B2-NiAl structure, directly affecting its elastic properties. A strong correlation was found between the fracture toughness and the initial Pt layer thickness associated with the bond coat. As the Pt layer thickness was increased from 0 to 5 mu m, resulting in increasing Pt concentration from 0 to 14.2 at.% in the B2-NiAl matrix and changing alpha-Cr precipitate fraction, the initiation fracture toughness (K-IC) was seen to rise from 6.4 to 8.5 MPa.m(1/2). R-curve behavior was observed in these coatings, with K-IC doubling for a crack propagation length of 2.5 mu m. The reasons for the toughening are analyzed to be a combination of material's microstructure (crack kinking and bridging due to the precipitates) as well as size effects, as the crack approaches closer to the free surface in a micro-scale sample.

Growth mechanism of the interdiffusion zone between platinum modified bond coats and single crystal superalloys

Pt-modified beta-NiAl bond coats are applied over the superalloys for oxidation protection in jet engine applications. However, as shown in this study, it also enhances the growth of the interdiffusion zone developed between the bond coat and the superalloy along with brittle precipitates. Location of the Kirkendall plane indicates that a precipitate free sublayer grows from the bond coat, whereas another sublayer grows from the superalloy containing very high volume fraction of precipitates. With increasing Pt content, thickness of both the sublayers increases because of an increase in diffusion rates of the components. Quantitative electron probe microanalysis indicates high concentration of refractory components in the precipitates. Transmission electron microscopy shows that Rene N5 superalloy produces TCP phases mu and P, whereas CMSX-4 superalloy produces mu and sigma in the interdiffusion zone. With increasing Pt content in the bond coat, the average size of the precipitates decreases when coupled with Rene N5. Precipitates become much finer when the same bond coats are coupled with CMSX-4. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Growth mechanism of the interdiffusion zone between platinum modified bond coats and single crystal superalloys

Pt-modified beta-NiAl bond coats are applied over the superalloys for oxidation protection in jet engine applications. However, as shown in this study, it also enhances the growth of the interdiffusion zone developed between the bond coat and the superalloy along with brittle precipitates. Location of the Kirkendall plane indicates that a precipitate free sublayer grows from the bond coat, whereas another sublayer grows from the superalloy containing very high volume fraction of precipitates. With increasing Pt content, thickness of both the sublayers increases because of an increase in diffusion rates of the components. Quantitative electron probe microanalysis indicates high concentration of refractory components in the precipitates. Transmission electron microscopy shows that Rene N5 superalloy produces TCP phases mu and P, whereas CMSX-4 superalloy produces mu and sigma in the interdiffusion zone. With increasing Pt content in the bond coat, the average size of the precipitates decreases when coupled with Rene N5. Precipitates become much finer when the same bond coats are coupled with CMSX-4. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The effect of alloy composition on instabilities in the beta phase of titanium alloys

A metastable nano-scale disordered precipitate with orthorhombic symmetry has been identified using high resolution scanning transmission electron microscopy. The phase, termed O', is metastable, formed by a shuffle mechanism involving a {110}<1<(1)over bar>0> transverse phonon wave in samples of Ti-26Nb-2Zr (at.%) quenched from the beta phase. The addition of 2% Zr to Ti-26Nb appears to suppress significantly the stability of both the {11 (2) over bar}<111> shear and 2/3 <111> longitudinal phonon wave but promotes the {110}<1<(1)over bar>0> transverse shuffle. This results in the nano-size O' phase being homogeneously formed in the parent beta phase matrix rather than the massive alpha `' phase. (C) 2016 Elsevier B.V. All rights reserved.

Unimpeded permeation of water through biocidal graphene oxide sheets anchored on to 3D porous polyolefinic membranes

3D porous membranes were developed by etching one of the phases (here PEO, polyethylene oxide) from melt-mixed PE/PEO binary blends. Herein, we have systematically discussed the development of these membranes using X-ray micro-computed tomography. The 3D tomograms of the extruded strands and hot-pressed samples revealed a clear picture as to how the morphology develops and coarsens over a function of time during post-processing operations like compression molding. The coarsening of PE/PEO blends was traced using X-ray micro-computed tomography and scanning electron microscopy (SEM) of annealed blends at different times. It is now understood from X-ray micro-computed tomography that by the addition of a compatibilizer (here lightly maleated PE), a stable morphology can be visualized in 3D. In order to anchor biocidal graphene oxide sheets onto these 3D porous membranes, the PE membranes were chemically modified with acid/ethylene diamine treatment to anchor the GO sheets which were further confirmed by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and surface Raman mapping. The transport properties through the membrane clearly reveal unimpeded permeation of water which suggests that anchoring GO on to the membranes does not clog the pores. Antibacterial studies through the direct contact of bacteria with GO anchored PE membranes resulted in 99% of bacterial inactivation. The possible bacterial inactivation through physical disruption of the bacterial cell wall and/or reactive oxygen species (ROS) is discussed herein. Thus this study opens new avenues in designing polyolefin based antibacterial 3D porous membranes for water purification.

Developing and characterizing bulk metallic glasses for extreme applications

Metallic glasses have typically been treated as a “one size fits all” type of material. Every alloy is considered to have high strength, high hardness, large elastic limits, corrosion resistance, etc. However, similar to traditional crystalline materials, properties are strongly dependent upon the constituent elements, how it was processed, and the conditions under which it will be used. An important distinction which can be made is between metallic glasses and their composites. Charpy impact toughness measurements are performed to determine the effect processing and microstructure have on bulk metallic glass matrix composites (BMGMCs). Samples are suction cast, machined from commercial plates, and semi-solidly forged (SSF). The SSF specimens have been found to have the highest impact toughness due to the coarsening of the dendrites, which occurs during the semi-solid processing stages. Ductile to brittle transition (DTBT) temperatures are measured for a BMGMC. While at room temperature the BMGMC is highly toughened compared to a fully glassy alloy, it undergoes a DTBT by 250 K. At this point, its impact toughness mirrors that of the constituent glassy matrix. In the following chapter, BMGMCs are shown to have the capability of being capacitively welded to form single, monolithic structures. Shear measurements are performed across welded samples, and, at sufficient weld energies, are found to retain the strength of the parent alloy. Cross-sections are inspected via SEM and no visible crystallization of the matrix occurs.

Next, metallic glasses and BMGMCs are formed into sheets and eggbox structures are tested in hypervelocity impacts. Metallic glasses are ideal candidates for protection against micrometeorite orbital debris due to their high hardness and relatively low density. A flat single layer, flat BMG is compared to a BMGMC eggbox and the latter creates a more diffuse projectile cloud after penetration. A three tiered eggbox structure is also tested by firing a 3.17 mm aluminum sphere at 2.7 km/s at it. The projectile penetrates the first two layers, but is successfully contained by the third.

A large series of metallic glass alloys are created and their wear loss is measured in a pin on disk test. Wear is found to vary dramatically among different metallic glasses, with some considerably outperforming the current state-of-the-art crystalline material (most notably Cu₄₃Zr₄₃Al₇Be₇). Others, on the other hand, suffered extensive wear loss. Commercially available Vitreloy 1 lost nearly three times as much mass in wear as alloy prepared in a laboratory setting. No conclusive correlations can be found between any set of mechanical properties (hardness, density, elastic, bulk, or shear modulus, Poisson’s ratio, frictional force, and run in time) and wear loss. Heat treatments are performed on Vitreloy 1 and Cu₄₃Zr₄₃Al₇Be₇. Anneals near the glass transition temperature are found to increase hardness slightly, but decrease wear loss significantly. Crystallization of both alloys leads to dramatic increases in wear resistance. Finally, wear tests under vacuum are performed on the two alloys above. Vitreloy 1 experiences a dramatic decrease in wear loss, while Cu₄₃Zr₄₃Al₇Be₇ has a moderate increase. Meanwhile, gears are fabricated through three techniques: electrical discharge machining of 1 cm by 3 mm cylinders, semisolid forging, and copper mold suction casting. Initial testing finds the pin on disk test to be an accurate predictor of wear performance in gears.

The final chapter explores an exciting technique in the field of additive manufacturing. Laser engineered net shaping (LENS) is a method whereby small amounts of metallic powders are melted by a laser such that shapes and designs can be built layer by layer into a final part. The technique is extended to mixing different powders during melting, so that compositional gradients can be created across a manufactured part. Two compositional gradients are fabricated and characterized. Ti 6Al¬ 4V to pure vanadium was chosen for its combination of high strength and light weight on one end, and high melting point on the other. It was inspected by cross-sectional x-ray diffraction, and only the anticipated phases were present. 304L stainless steel to Invar 36 was created in both pillar and as a radial gradient. It combines strength and weldability along with a zero coefficient of thermal expansion material. Only the austenite phase is found to be present via x-ray diffraction. Coefficient of thermal expansion is measured for four compositions, and it is found to be tunable depending on composition.

Determination of dissolved oxygen in water with leukoberbelin-blue I. A quick Winkler method. [Translation from: Z.analyt.Chem. 262 97-99, 1972.]

The reaction of Mn(II) with water-dissolved oxygen, to a higher manganese hydroxide in an alkaline medium, as with the longstanding classic Winkler method, is the first step in the method described here. The assumption for faultless results by the conventional and modified Winkler method is clean water, which contains no organic substances by Mn(III) or Mn(IV). In many cases, however, eg. in river and lake-water tests, it can be seen with the naked eye that after some time the originally brown-coloured precipitate of manganese hydroxide becomes more and more colourless. Oxygen content was analysed in the water samples and evaluated by raising the amount of the leuko-base and giving the corresponding dilution of the colouring matter solution formed still higher oxygen contents can be measured.