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.

Composition dependent non-ideality in aqueous binary mixtures as a signature of avoided spinodal decomposition

We explore the potential energy landscape of structure breaking binary mixtures (SBBM) where two constituents dislike each other, yet remain macroscopically homogeneous at intermediate to high temperatures. Interestingly, we find that the origin of strong composition dependent non-ideal behaviour lies in its phase separated inherent structure. The inherent structure (IS) of SBBM exhibits bi-continuous phase as is usually formed during spinodal decomposition. We draw analogy of this correlation between non-ideality and phase separation in IS to explain observation of non-ideality in real aqueous mixtures of small amphiphilic solutes, containing both hydrophilic and hydrophobic groups. Although we have not been able to obtain IS of these liquids, we find that even at room temperature these liquids sustain formation of fluctuating, transient bi-continuous phase, with limited lifetime (tau less than or similar to 20 ps). While in the model (A, B) binary mixture, the non-ideal composition dependence can be considered as a fluctuation from a phase separated state, a similar scenario is expected to be responsible for the unusually strong non-ideality in these aqueous binary mixtures.

Composition dependent multiple structural transformations of myoglobin in aqueous ethanol solution: A combined experimental and theoretical study

Experimental studies (circular dichroism and ultra-violet (UV) absorption spectra) and large scale atomistic molecular dynamics simulations (accompanied by order parameter analyses) are combined to establish a number of remarkable (and unforeseen) structural transformations of protein myoglobin in aqueous ethanol mixture at various ethanol concentrations. The following results are particularly striking. (1) Two well-defined structural regimes, one at x(EtOH) similar to 0.05 and the other at x(EtOH) similar to 0.25, characterized by formation of distinct partially folded conformations and separated by a unique partially unfolded intermediate state at x(EtOH) similar to 0.15, are identified. (2) Existence of non-monotonic composition dependence of (i) radius of gyration, (ii) long range contact order, (iii) residue specific solvent accessible surface area of tryptophan, and (iv) circular dichroism spectra and UV-absorption peaks are observed. Interestingly at x(EtOH) similar to 0.15, time averaged value of the contact order parameter of the protein reaches a minimum, implying that this conformational state can be identified as a molten globule state. Multiple structural transformations well known in water-ethanol binary mixture appear to have considerably stronger effects on conformation and dynamics of the protein. We compare the present results with studies in water-dimethyl sulfoxide mixture where also distinct structural transformations are observed along with variation of co-solvent composition. (C) 2015 AIP Publishing LLC.

Ge composition saturation behavior during low-temperature Si1-xGex growth by disilane and solid Ge molecular beam epitaxy

Ge composition dependence on the Ge cell temperature has been studied during the growth of Si1-xGex by disilane and solid Ge molecular beam epitaxy at a substrate temperature of 500 degrees C. It is found that the composition x increases and then saturates when the Ge cell temperature increases, which is different from the composition-dependent behavior in growth at high temperature as well as in growth by molecular beam epitaxy using disilane and germane. The enhanced hydrogen desorption from a Ge site alone cannot account for this abnormal composition-variation behavior. We attribute this behavior to the increase of rate constant of H desorption on a Si site when the Ge cell temperature increases.

Crystallization studies on bulk SixTe100-x glasses

Bulk SixTe100-x (10 less-than-or-equals, slant x less-than-or-equals, slant 28) glasses have been prepared by the melt quenching technique. The crystallization of these glasses has been studied by using differential scanning calorimetry. The composition dependence of the glass transition temperature Tg, the recrystallization temperature Tcr and the melting temperature Tm show an unusual behaviour at the composition x congruent with 20. The glasses with 10 less-than-or-equals, slant x less-than-or-equals, slant 20 undergo double glass transition and double stage crystallization phenomena. On the other hand, glasses with 22 less-than-or-equals, slant x less-than-or-equals, slant 28 exhibit eutectic crystallization. The phases at different stages of crystallization have been identified by using X-ray diffraction techniques. The unusual behaviour at x congruent with 20 can be explained on the basis of the changes in the network topologies of IV-VI chalcogenide glasses.

Elastic properties of lead phosphomolybdate glassess

Elastic properties of lead phosphomolybdate [PbO-1bMoO3-1bP2O5] glasses have been investigated using ultrasonic velocity measurements at 10MHz. The composition dependence of elastic moduli, Poisson's ratio and the Debye temperature are found to be consistent with a structural model proposed earlier. According to this model lead acts both as a network former and as a network modifier in different composition regimes. It is suggested that the incorporation of lead into the network is accompanied by the conversion of three-connected [Image ] tetrahedra into four-connected Image tetrahedra in the network. lead; phosphorus; molybdenum

Evidence of an intermediate phase in ternary Ge7Se93-xSbx glasses

The compositional dependence of thermal properties, such as glass transition temperature (T-g), non-reversing enthalpy change (Delta H-NR) and the specific heat capacity change (Delta C-p) of melt quenched Ge7Se93-xSbx (21 a parts per thousand currency sign x a parts per thousand currency sign 31) glasses, has been studied using alternating differential scanning calorimetry (ADSC) which is analogous to modulated differential scanning calorimetry (MDSC). The glass transition temperature, T-g, which is a measure of global connectivity of the glass, has been found to increase with the addition of Sb. In addition, a change in slope has been observed in the composition dependence of T-g at an average coordination aOE (c) r > = 2.40. The experimentally observed compositional variation of glass transition temperature, has been compared with the theoretical predictions from the stochastic agglomeration theory (SAT) and has been found to be consistent. Further, a narrow thermally reversing window is seen in the compositional variation of the relaxation enthalpy (Delta H-NR), which is centered around aOE (c) r > = 2.40. The change in specific heat capacity (Delta C-p) at T-g is also found to exhibit a distinct minima at aOE (c) r > = 2.40, suggesting that the structural rearrangements for the liquid in the glass transition region are minimized around aOE (c) r > = 2.4.

High field electrical switching behavior of Ge10Se90-xTlx glasses

Electrical Switching Studies on bulk Ge10Se90-xTlx ( 15 <= x <= 34) glasses have been undertaken to examine the type of switching, composition and thickness dependence of switching voltages. Unlike Ge-Se-Tl thin films which exhibit memory switching, the bulk Ge10Se90-xTlx glasses are found to exhibit threshold type switching with fluctuations seen in their current-voltage (I-V) characteristics. Further, it is observed that the switching voltages (V-T) of Ge10Se90-xTlx glasses decrease with the increase in the Tl concentration. An effort has been made to understand the observed composition dependence on the basis of nature of bonding of Tl atoms and a decrease in the chemical disorder with composition. In addition. the network connectivity and metallicity factors also contribute for the observed decrease in the switching voltages of Ge10Se90-xTlx glasses with Tl addition. It is also interesting to note that the composition dependence of switching voltages of Ge10Se90-xTlx glasses exhibit a small Cusp around the composition x = 22. which is understood on the basis of a thermally reversing window in this system in the composition range 22 <= x <= 30. The thickness dependence of switching voltages has been found to provide an insight about the type of switching mechanism involved in these samples. (C) 2009 Elsevier B.V. All rights reserved

Effect of indium doping on the electrical switching behaviour of Ge-Te glasses

Bulk Ge15Te85-xInx (1 <= x <= 11) series of glasses have been found to exhibit a threshold switching behaviour for an input current of 2 mA. An initial decrease is seen in the switching voltages (V-T) with the addition of indium, which is due to the higher metallicity of indium. An increase is seen in V-T above 3 at.% of indium, which proceeds until 8 at.%, with a change in slope (lower to higher) seen around 7 at.%. Beyond x = 8, a reversal in trend is exhibited in the variation of V-T, with a well-defined minimum around x = 9 at.%. Based on the composition dependence of V-T, it is proposed that Ge15Te85-xInx glasses exhibit an extended rigidity percolation threshold. The composition, x = 3, at which the V-T starts to increase and the composition, x = 7, at which a slope change is exhibited correspond to the onset and completion, respectively, of the extended stiffness transition. Thermal studies and photoconductivity e85-xInx glasses. In addition, the minimum seen in V-T at x = 9 is associated with the chemical threshold (CT) of this glassy system.

Electrical switching and thermal studies on Ge22Te78-xIx chalcohalide glasses: The effect of iodine on network-topology

Investigations on the electrical switching behavior and thermal studies using Alternating Differential Scanning Calorimetry have been undertaken on bulk, melt-quenched Ge22Te78-,Is (3 <= x <= 10) chalcohalide glasses. All the glasses studied have been found to exhibit memory-type electrical switching. The threshold voltages of Ge22Te78-I-x(x) glasses have been found to increase with the addition of iodine and the composition dependence of threshold voltages of Ge22Te78-xIx glasses exhibits a cusp at 5 at.% of iodine. Also, the variation with composition of the glass transition temperature (Tg) of Ge22Te78-I-x(x) glasses, exhibits a broad hump around this composition. Based on the present results, the composition x = 5 has been identified as the inverse rigidity percolation threshold at which Ge22Te78-I-x(x) glassy system exhibits a change from a stressed rigid amorphous solid to a flexible polymeric glass. Further, a sharp minimum is seen in the composition dependence of non-reversing enthalpy (Delta H-nr) of Ge22Te78-I-x(x) glasses at x = 5, which is suggestive of a thermally reversing window at this composition. (C) 2007 Elsevier Ltd. All rights reserved.

Network topological thresholds in gallium doped As-Te glasses Electrical and thermal investigations

Electrical switching and differential scanning calorimetric studies are undertaken on bulk As20Te80-xGax glasses, to elucidate the network topological thresholds. It is found that these glasses exhibit a single glass transition (T-g) and two crystallization reactions (T-cl & T-c2) upon heating. It is also found that there is only a marginal change in T-g with the addition of up to about 10% of Ga; around this composition an increase is seen in 7, which culminates in a local maximum around x = 15. The decrease exhibited in T, beyond this composition, leads to a local minimum at x = 17.5. Further, the As20Te80-xGax glasses are found to exhibit memory type electrical switching. The switching voltages (VT) increase with the increase in gallium content and a local maximum is seen in V-tau around x = 15. VT is found to decrease with x thereafter, exhibiting a local minimum around x = 17.5. The composition dependence of T-cl is found to be very similar to that of V-T of As20Te80-xGax glasses. Based on the present results, it is proposed that the composition x = 15 and x = 17.5 correspond to the rigidity percolation and chemical thresholds, respectively, of As20Te80-xGax glasses. (c) 2007 Elsevier B.V. All rights reserved.

Elastic Properties of Alkali Phosphomolybdate Glasses

Ultrasonic velocities at 10 MHz have been measured in two series of lithium, sodium, and potassium phosphomolybdate glasses with two fixed P2O5 concentrations. Elastic moduli, Poisson's ratio, and Debye temperature have been calculated. The composition dependence of most of the properties of lithium glasses exhibits a trend opposite to that of potassium glasses. Properties of sodium glasses lie between the other two alkali systems. Alkali oxide modification is suggested to be accompanied by ring reformation in lithium and sodium glasses. Ring size effects have been shown to account for all of the composition dependence.

Elastic properties of phosphotungstate glasses

Elastic properties of potassium and lead phosphotungstate glasses have been investigated using ultrasonic velocity measurements. The composition dependence of elastic moduli in WO3-K2O-P2O5 glasses suggests that at low alkali oxide concentrations the atomic ring size increases by network modification, which results in the decrease of elastic moduli. In the highly modified regime, due to the presence of coulombic interaction, the rate of decrease of elastic moduli is reduced. In the WO3-PbO-P2O5 glasses the behaviour of elastic moduli suggests that PbO behaves both as a network former and network modifier. The incorporation of PbO into the network is quantitatively determined by the concentration of P2O5 in the system. The results are consistent with the structural model proposed earlier, based on characterization studies.

Activity–Composition Relations in the Nickel Oxide–Magnesium Oxide System at 1300 K by the Solid-State Galvanic Cell Technique

The activity of NiO in NiO-MgO rock salt solid solution has been measured at 1300 K by employing a solid-state galvanic cell: Pt,Ni+ NiO||(CaO)ZrO2||Ni + (Nix,Mgl-x)O, Pt. A high-density tube of Zr02-15 mol% CaO has been used as the solid electrolyte for the emf measurements. The activities of the component oxides in the rock salt solid solution exhibit negative deviation from ideality at the temperature of investigation. The solid solution obeys regular solution behavior at 1300 K. The value of the regular solution parameter is found to be -12000 ((l000) J mol-1. The composition dependence of ΔGEx obtained in this study agrees reasonably well with the calorimetric data reported in the literature for NiO-MgO solid solution.

Electrical switching and thermal studies on bulk Ge-Te-Bi glasses

Bulk, melt quenched Ge18Te82-xBix glasses (1 <= x <= 4) have been found to exhibit memory type electrical switching behavior, which is in agreement with the lower thermal diffusivity values of Ge-Te-Bi samples. A linear variation in switching voltages (V-th) has been found in these samples with increase in thickness which is consistent with the memory type electrical switching. Also, the switching voltages have been found to decrease with an increase in temperature which happens due to the decrease in the activation energy for crystallization at higher temperatures. Further. V-th of Ge18Te82-xBix glasses have been found to decrease with the increase in Bi content, indicating that in the Ge-Te-Bi system, the resistivity of the additive has a stronger role to play in the composition dependence of V-th, in comparison with the network connectivity and rigidity factors. In addition, the composition dependence of crystallization activation energy has been found to show a decrease with an increase in Bi content, which is consistent with the observed decrease in the switching voltages. X-ray diffraction studies on thermally crystallized samples reveal the presence of hexagonal Te, GeTe, Bi2Te3 phases, suggesting that bismuth is not taking part in network formation to a greater extent, as reflected in the variation of switching voltages with the addition of Bi. SEM studies on switched and un-switched regions of Ge-Te-Bi samples indicate that there are morphological changes in the switched region, which can be attributed to the formation of the crystalline channel between two electrodes during switching. (C) 2010 Elsevier B.V. All rights reserved.