Effect of thermal and thermo-mechanical cycling on the microstructure of Ni-rich NiTi shape memory alloys

Microstructural changes of Ni-rich NiTi shape memory alloy during thermal and thermo-mechanical cycling have been investigated using Electron Back Scattered Diffraction. A strong dependence of the orientation of the prior austenite grain on the misorientation development has been observed during thermal cycling and thermo-mechanical cycling. This effect is more pronounced at the grain boundaries compared to grain interior. At a larger applied strain, the volume fraction of stabilized martensite phase increases with increase in the number of cycling. Deformation within the martensite leads to stabilization of martensitic phase even at temperatures slightly above the austenite finish temperature. Modulus variation with respect to temperature has been explained on the basis of martensitic transformation.

Ultranarrow and Widely Tunable Mn2+-Induced Photoluminescence from Single Mn-Doped Nanocrystals of ZnS-CdS Alloys

Extensively studied Mn-doped semiconductor nanocrystals have invariably exhibited photoluminescence over a narrow energy window of width <= 150 meV in the orange-red region and a surprisingly large spectral width (>= 180 meV), contrary to its presumed atomic-like origin. Carrying out emission measurements on individual single nanocrystals and supported by ab initio calculations, we show that Mn PL emission, in fact, can (i) vary over a much wider range (similar to 370 meV) covering the deep green-deep red region and (ii) exhibit widths substantially lower (similar to 60-75 meV) than reported so far, opening newer application possibilities and requiring a fundamental shift in our perception of the emission from Mn-doped semiconductor nanocrystals.

Temperature dependence of indentation recovery ratios in austenitic and martensitic shape memory alloys

Instrumented microindentation (IM) on two Ni-Ti shape memory alloys (SMAs), where one is austenitic and the other is martensitic at room temperature, were conducted from 40 to 150 degrees C. Results show that the depth and work recovery ratios, eta(d) and eta(w) respectively, are complementary to each other. While eta(d) decreases gradually with temperature for austenite, it drops markedly for the martensite in the martensite-to-austenite transformation regime. These results affirm the utility of IM for characterizing SMAs.

Solvation dynamics of tryptophan in water-dimethyl sulfoxide binary mixture: In search of molecular origin of composition dependent multiple anomalies

Experimental and simulation studies have uncovered at least two anomalous concentration regimes in water-dimethyl sulfoxide (DMSO) binary mixture whose precise origin has remained a subject of debate. In order to facilitate time domain experimental investigation of the dynamics of such binary mixtures, we explore strength or extent of influence of these anomalies in dipolar solvation dynamics by carrying out long molecular dynamics simulations over a wide range of DMSO concentration. The solvation time correlation function so calculated indeed displays strong composition dependent anomalies, reflected in pronounced non-exponential kinetics and non-monotonous composition dependence of the average solvation time constant. In particular, we find remarkable slow-down in the solvation dynamics around 10%-20% and 35%-50% mole percentage. We investigate microscopic origin of these two anomalies. The population distribution analyses of different structural morphology elucidate that these two slowing down are reflections of intriguing structural transformations in water-DMSO mixture. The structural transformations themselves can be explained in terms of a change in the relative coordination number of DMSO and water molecules, from 1DMSO:2H(2)O to 1H(2)O:1DMSO and 1H(2)O:2DMSO complex formation. Thus, while the emergence of first slow down (at 15% DMSO mole percentage) is due to the percolation among DMSO molecules supported by the water molecules (whose percolating network remains largely unaffected), the 2nd anomaly (centered on 40%-50%) is due to the formation of the network structure where the unit of 1DMSO:1H(2)O and 2DMSO:1H(2)O dominates to give rise to rich dynamical features. Through an analysis of partial solvation dynamics an interesting negative cross-correlation between water and DMSO is observed that makes an important contribution to relaxation at intermediate to longer times.

Study on important diffusion parameters of binary Ni3Sn4 phase

Important diffusion parameters, such as-parabolic growth constant, integrated diffusivity, ratio of intrinsic diffusivities of species Ni and Sn, Kirkendall marker velocity and the activation energy for diffusion kinetics of binary Ni3Sn4 phase have been investigated with the help of incremental diffusion couple technique (Sn/Ni0.57Sn0.43) in the temperature range 200-150 degrees C. Low activation energy extracted from Arrhenius plot indicates grain boundary controlled diffusion process. The species Sn is three times faster than Ni at 200 degrees C. Further, the activation energy of Sn tracer diffusivity is greater than that of Ni.

Simultaneous measurement of mechanical and electrical contact resistances during nanoindentation of NiTi shape memory alloys

The nanoindentation technique can be employed in shape memory alloys (SMAs) to discern the transformation temperatures as well as to characterize their mechanical behavior. In this paper, we use it with simultaneous measurements of the mechanical and the electrical contact resistances (ECR) at room temperature to probe two SMAs: austenite (RTA) and martensite (RTM). Two different types of indenter tips - Berkovich and spherical - are employed to examine the SMAs' indentation responses as a function of the representative strain, epsilon(R). In Berkovich indentation, because of the sharp nature of the tip, and in consequence the high levels of strain imposed, discerning the two SMAs on the basis of the indentation response alone is difficult. In the case of the spherical tip, epsilon(R) is systematically varied and its effect on the depth recovery ratio, eta(d), is examined. Results indicate that RTA has higher eta(d) than RTM, but the difference decreases with increasing epsilon(R) such that eta(d) values for both the alloys would be similar in the fully plastic regime. The experimental trends in eta(d) vs. epsilon(R) for both the alloys could be described well with a eta(d) proportional to (epsilon(R))(-1) type equation, which is developed on the basis of a phenomenological model. This fit, in turn, directs us to the maximum epsilon(R), below which plasticity underneath the indenter would not mask the differences in the two SMAs. It was demonstrated that the ECR measurements complement the mechanical measurements in demarcating the reverse transformation from martensite to austenite during unloading of RTA, wherein a marked increase in the voltage was noted. A correlation between recovery due to reverse transformation during unloading and increase in voltage (and hence the electrical resistance) was found. (C) 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Combining indentation and diffusion couple techniques for combinatorial discovery of high temperature shape memory alloys

We demonstrate the possibility of accelerated identification of potential compositions for high-temperature shape memory alloys (SMAs) through a combinatorial material synthesis and analysis approach, wherein we employ the combination of diffusion couple and indentation techniques. The former was utilized to generate smooth and compositionally graded inter-diffusion zones (IDZs) in the Ni-Ti-Pd ternary alloy system of varying IDZ thickness, depending on the annealing time at high temperature. The IDZs thus produced were then impressed with an indenter with a spherical tip so as to inscribe a predetermined indentation strain. Subsequent annealing of the indented samples at various elevated temperatures, T-a, ranging between 150 and 550 degrees C allows for partial to full relaxation of the strain imposed due to the shape memory effect. If T-a is above the austenite finish temperature, A(f), the relaxation will be complete. By measuring the depth recovery, which serves as a proxy for the shape recovery characteristic of the SMA, a three-dimensional map in the recovery temperature composition space is constructed. A comparison of the published Af data for different compositions with the Ta data shows good agreement when the depth recovery is between 70% and 80%, indicating that the methodology proposed in this paper can be utilized for the identification of promising compositions. Advantages and further possibilities of this methodology are discussed.

Note: Effect of fluid phase compositions on the formation of substitutionally ordered solid phases from a binary mixture of oppositely charged colloidal suspensions

A binary mixture of oppositely charged colloidal particles can self-assemble into either a substitutionally ordered or substitutionally disordered crystalline phase depending on the nature and strength of interactions among the particles. An earlier study had mapped out favorable inter-particle interactions for the formation of substitutionally ordered crystalline phases from a fluid phase using Monte Carlo molecular simulations along with the Gibbs-Duhem integration technique. In this paper, those studies are extended to determine the effect of fluid phase composition on formation of substitutionally ordered solid phases.

An equivalent undercooling model to account for flow effect on binary alloy dendrite growth rate

A theoretical analysis is carried out to observe the influence of important flow parameters such as Nusselt number and Sherwood number on the tip speed of an equiaxed dendrite growing in a convecting alloy melt. The effect of thermal and solutal transfer at the interface due to convection is equated to an undercooling of the melt, and an expression is derived for this equivalent undercooling in terms of the flow Nusselt number and Sherwood number. Results for the equivalent undercooling are compared with corresponding numerical values obtained by performing simulations based on the enthalpy method. This method represents a relatively simple procedure to analyze the effects of melt convection on the growth rate of dendrites. (C) 2013 Elsevier Ltd. All rights reserved.

Strain-controlled fatigue in B-modified Ti-6Al-4V alloys

The strain-controlled fatigue behaviour of Ti-6Al-4V alloy with up to 0.11 wt.% B addition was investigated. Results show significant softening when the strain amplitudes, Delta epsilon(T)/2, are >= 0.75%. B addition was found to improve the fatigue life for Delta epsilon(T)/2 <= 0.75% as it corresponds to the elastic regime and hence is strength dominated. At Delta epsilon(T)/2 = 1%, in contrast, the base alloy exhibits higher fatigue life as TiB particle cracking due to strain incompatibility causes easy crack nucleation in the B-modified alloys. (C) 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Stability of fluctuating and transient aggregates of amphiphilic solutes in aqueous binary mixtures: Studies of dimethylsulfoxide, ethanol, and tert-butyl alcohol

In aqueous binary mixtures, amphiphilic solutes such as dimethylsulfoxide (DMSO), ethanol, tertbutyl alcohol (TBA), etc., are known to form aggregates (or large clusters) at small to intermediate solute concentrations. These aggregates are transient in nature. Although the system remains homogeneous on macroscopic length and time scales, the microheterogeneous aggregation may profoundly affect the properties of the mixture in several distinct ways, particularly if the survival times of the aggregates are longer than density relaxation times of the binary liquid. Here we propose a theoretical scheme to quantify the lifetime and thus the stability of these microheterogeneous clusters, and apply the scheme to calculate the same for water-ethanol, water-DMSO, and water-TBA mixtures. We show that the lifetime of these clusters can range from less than a picosecond (ps) for ethanol clusters to few tens of ps for DMSO and TBA clusters. This helps explaining the absence of a strong composition dependent anomaly in water-ethanol mixtures but the presence of the same in water-DMSO and water-TBA mixtures. (C) 2013 AIP Publishing LLC.

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.

Solvent Sensitivity of Protein Unfolding: Dynamical Study of Chicken Villin Headpiece Subdomain in Water Ethanol Binary Mixture

We carry out a series of long atomistic molecular dynamics simulations to study the unfolding of a small protein, chicken villin headpiece (HP-36), in water-ethanol (EtOH) binary mixture. The prime objective of this work is to explore the sensitivity of protein unfolding dynamics toward increasing concentration of the cosolvent and unravel essential features of intermediates formed in search of a dynamical pathway toward unfolding. In water ethanol binary mixtures, HP-36 is found to unfold partially, under ambient conditions, that otherwise requires temperature as high as similar to 600 K to denature in pure aqueous solvent. However, an interesting course of pathway is observed to be followed in the process, guided by the formation of unique intermediates. The first step of unfolding is essentially the separation of the cluster formed by three hydrophobic (phenylalanine) residues, namely, Phe-7, Phe-11, and Phe-18, which constitute the hydrophobic core, thereby initiating melting of helix-2 of the protein. The initial steps are similar to temperature-induced unfolding as well as chemical unfolding using DMSO as cosolvent. Subsequent unfolding steps follow a unique path. As water-ethanol shows composition-dependent anomalies, so do the details of unfolding dynamics. With an increase in cosolvent concentration, different partially unfolded intermediates are found to be formed. This is reflected in a remarkable nonmonotonic composition dependence of several order parameters, including fraction of native contacts and protein-solvent interaction energy. The emergence of such partially unfolded states can be attributed to the preferential solvation of the hydrophobic residues by the ethyl groups of ethanol. We further quantify the local dynamics of unfolding by using a Marcus-type theory.

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.

Anomalous phase transitions in soft colloid-polymer binary mixtures

We have shown earlier [1] that these PGNPs resemble star polymers or spherical brushes in terms of their morphology in the melt. However, these particles show dynamics in melt which is quite different from other soft colloidal particles. Since most of the work on soft colloidal particles have been performed in solutions we have now explored the phase behavior of the PGNPs in good solvent using microscopic structural and dynamical measurements on binary mixtures of homopolymers and soft colloids consisting of polymer grafted nanoparticles. We observe anomalous structural and dynamical phase transitions of these binary mixtures, including appearance of spontaneous orientational alignment and logarithmic structural relaxations, as a function of added homopolymers of different molecular weights. Our experiments points to the possibility of exploiting the phase space in density and homopolymer size, of such hybrid systems, to create new materials with unique properties.