Domain size correlated magnetic properties and electrical impedance of size dependent nickel ferrite nanoparticles

We report here the investigations on the size dependent variation of magnetic properties of nickel ferrite nanoparticles. Nickel ferrite nanoparticles of different sizes (14 to 22 nm) were prepared by the sol-gel route at different annealing temperatures. They are characterized by TGA-DTA, XRD, SEM, TEM and Raman spectroscopy techniques for the confirmation of the temperature of phase formation, thermal stability, crystallinity, morphology and structural status of the nickel ferrite nanoparticles. The magnetization studies revealed that the saturation magnetization (M-s), retentivity (M-r) increase, while coercivity (H-c) and anisotropy (K-eff) decrease as the particle size increases. The observed value of M-s is found to be relatively higher for a particle size of 22 nm. In addition, we have estimated the magnetic domain size using magnetic data and correlated to the average particle size. The calculated magnetic domain size is closely matching with the particle size estimated from XRD. Impedance spectroscopy was employed to study the samples in an equivalent circuit to understand their transport phenomena. It shows that nickel ferrite nanoparticles exhibit a non-Debye behavior with increasing particle size due to the influence of increasing disorders, surface effects, grain size and grain boundaries, etc. (C) 2015 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

A simple classical approach for the melting temperature of inert-gas nanoparticles

Like the metal and semiconductor nanoparticles, the melting temperature of free inert-gas nanoparticles decreases with decreasing size. The variation is linear with the inverse of the particle size for large nanoparticles and deviates from the linearity for small nanoparticles. The decrease in the melting temperature is slower for free nanoparticles with non-wetting surfaces, while the decrease is faster for nanoparticles with wetting surfaces. Though the depression of the melting temperature has been reported for inert-gas nanoparticles in porous glasses, superheating has also been observed when the nanoparticles are embedded in some matrices. By using a simple classical approach, the influence of size, geometry and the matrix on the melting temperature of nanoparticles is understood quantitatively and shown to be applicable for other materials. It is also shown that the classical approach can be applied to understand the size-dependent freezing temperature of nanoparticles.

Context-dependency of a complex fruit-frugivore mutualism: temporal variation in crop size and neighborhood effects

The quantity of fruit consumed by dispersers is highly variable among individuals within plant populations. The outcome Of Such selection operated by firugivores has been examined mostly with respect to changing spatial contexts. The influence of varying temporal contexts on frugivore choice, and their possible demographic and evolutionary consequences is poorly understood. We examined if temporal variation in fruit availability across a hierarchy of nested temporal levels (interannual, intraseasonal, 120 h, 24 h) altered frugivore choice for a complex seed dispersal system in dry tropical forests of southern India. The interactions between Phyllanthus emblica and its primary disperser (ruminants) was mediated by another frugivore (a primate),which made large quantities of fruit available on the ground to ruminants. The direction and strength of crop size and neighborhood effects on this interaction varied with changing temporal contexts.Fruit availability was higher in the first of the two study years, and at the start of the season in both years. Fruit persistence on trees,determined by primate foraging, was influenced by crop size andconspecific neighborhood densities only in the high fruit availability year. Fruit removal by ruminants was influenced by crop size in both years and neighborhood densities only in the high availability year. In both years, these effects were stronger at the start of the season.Intraseasonal reduction in fruit availability diminished inequalities in fruit removal by ruminants and the influence of crop size and fruiting neighborhoods. All trees were not equally attractive to frugivores in a P. emblica population at all points of time. Temporal asymmetry in frugivore-mediated selection could reduce potential for co-evolution between firugivores and plants by diluting selective pressures. Inter-dependencies; formed between disparate animal consumers can add additional levels of complexity to plant-frugivore mutualistic networks and have potential reproductive consequences for specific individuals within populations.

Effect of Structural Modification on the Quantum-Size Effect in II-VI Semiconducting Nanocrystals

The electronic structure of group II-VI semiconductors in the stable wurtzite form is analyzed using state-of-the-art ab initio approaches to extract a simple and chemically transparent tight-binding model. This model can be used to understand the variation in the bandgap with size, for nanoclusters of these compounds. Results complement similar information already available for same systems in the zinc blende structure. A comparison with all available experimental data on quantum size effects in group II-VI semiconductor nanoclusters establishes a remarkable agreement between theory and experiment in both structure types, thereby verifying the predictive ability of our approach. The significant dependence of the quantum size effect on the structure type suggests that the experimental bandgap change at a given size compared to the bulk bandgap, may be used to indicate the structural form of the nanoclusters, particularly in the small size limit, where broadening of diffraction features often make it difficult to unambiguously determine the structure.

Regional variation in the composition and structure of mixed-species bird flocks in the Western Ghats and Sri Lanka

Mixed-species bird flocks are attractive models for the investigation of geographical variation in animal communities, as they represent a subset of the avifauna in most forested regions of the world. Yet studies of the regional variation in flock size and the composition of flocks are few, due to the predominance of studies carried out at single study site. Here, we review nine studies of mixed-species flocks conducted at 16 sites along the Western Ghats in India and in Sri Lanka. We find that flock size varies as much within this region as it does globally, with observation time being a confounding variable. Flock composition, however, is predictably related to elevation. Flocks at high elevations (>1200 m) in the Western Ghats strongly resemble flocks at high elevations in the mountain ranges of Sri Lanka in their composition, especially at the family level. We compare these flocks to flocks of other regions and make recommendations on study methodology that can facilitate comparisons across studies.

Crystallite size effects in stacking faulted nickel hydroxide and its electrochemical behaviour

P-Nickel hydroxide comprises a long range periodic arrangement of atoms with a stacking sequence of AC AC AC-having an ideal composition Ni(OH)(2). Variation in the preparative conditions can lead to the changes in the stacking sequence (AC AC BA CB AC AC or AC AC AB AC AC) This type of variation in stacking sequence can result in the formation of stacking fault in nickel hydroxide. The stability of the stacking fault depends on the free energy content of the sample. Stacking faults in nickel hydroxide is essential for better electrochemical activity. Also there are reports correlating particle size to the better electrochemical activity. Here we present the effect of crystallite size on the stacking faulted nickel hydroxide samples. The electrochemical performance of stacking faulted nickel hydroxide with small crystallite size exchanges 0.8e/Ni, while the samples with larger crystallite size exchange 0.4e/Ni. Hence a right combination of crystallite size and stacking fault content has to be controlled for good electrochemical activity of nickel hydroxide. (C) 2008 Elsevier B.V. All rights reserved.

Diffusion of flexible, charged, nanoscopic molecules in solution: Size and pH dependence for PAMAM dendrimer

In order to understand self-diffusion (D) of a charged, flexible, and porous nanoscopic molecule in water, we carry out very long, fully atomistic molecular dynamics simulation of PAMAM dendrimer up to eight generations in explicit salt water under varying pH. We find that while the radius of gyration (R-g) varies as N-1/3, the self-diffusion constant (D) scales, surprisingly, as N-alpha, with alpha=0.39 at high pH and 0.5 at neutral pH, indicating a dramatic breakdown of Stokes-Einstein relation for diffusion of charged nanoscopic molecules. The variation in D as a function of radius of gyration demonstrates the importance of treating water and ions explicitly in the diffusion process of a flexible nanoscopic molecule. In agreement with recent experiments, the self-diffusion constant increases with pH, revealing the importance of dielectric friction in the diffusion process. The shape of a dendrimer is found to fluctuate on a nanosecond time scale. We argue that this flexibility (and also the porosity) of the dendrimer may play an important role in determining the mean square displacement of the dendrimer and the breakdown of the Stokes-Einstein relation between diffusion constant and the radius.

Approximate multipole coefficients of RF ion traps as functions of aperture size

In this study we present approximate analytical expressions for estimating the variation in multipole expansion coefficients as a function of the size of the apertures in the electrodes in axially symmetric (3D) and two-dimensional (2D) ion trap ion traps. Following the approach adopted in our earlier studies which focused on the role of apertures to fields within the traps, here too, the analytical expression we develop is a sum of two terms, A(n,noAperiure), the multipole expansion coefficient for a trap with no apertures and A(n,dueToAperture), the multipole expansion coefficient contributed by the aperture. A(n,noAperture) has been obtained numerically and A(n,dueToAperture) is obtained from the n th derivative of the potential within the trap. The expressions derived have been tested on two 3D geometries and two 2D geometries. These include the quadrupole ion trap (QIT) and the cylindrical ion trap (CIT) for 3D geometries and the linear ion trap (LIT) and the rectilinear ion trap (RIT) for the 2D geometries. Multipole expansion coefficients A(2) to A(12), estimated by our analytical expressions, were compared with the values obtained numerically (using the boundary element method) for aperture sizes varying up to 50% of the trap dimension. In all the plots presented, it is observed that our analytical expression for the variation of multipole expansion coefficients versus aperture size closely follows the trend of the numerical evaluations for the range of aperture sizes considered. The maximum relative percentage errors, which provide an estimate of the deviation of our values from those obtained numerically for each multipole expansion coefficient, are seen to be largely in the range of 10-15%. The leading multipole expansion coefficient, A(2), however, is seen to be estimated very well by our expressions, with most values being within 1% of the numerically determined values, with larger deviations seen for the QIT and the LIT for large aperture sizes. (C) 2010 Elsevier B.V. All rights reserved.

Size-Dependent Tuning of Mn2+ d Emission in Mn2+-Doped CdS Nanocrystals: Bulk vs Surface

We show that the characteristic Mn2+ d emission color from Mn2+-doped CdS nanocrystals can be tuned over as much as 40 nm, in contrast to what should be expected from such a nearly localized d-d transition. This is achieved surprisingly by a fine-tuning of the host particle diameter from 1.9 to 2.6 nm, thereby changing the overall emission color from red to yellow. Systematic experiments in conjunction with state-of-the-art ab initio calculations with full geometry optimization establish that Mn2+ ions residing at surface/subsurface regions have a distorted tetrahedral coordination resulting in a larger ligand field splitting. Consequently, these near-surface Mn2+ species exhibit a lower Mn2+ d emission energy, compared to those residing at the core of the nanocrystal with an undisturbed tetrahedral coordination. The origin of the tunability of the observed Mn2+ emission is the variation of emission contributions arising from Mn2+ doped at the core, subsurface, and surface of the host. Our findings provide a unique and easy method to identify the location of an emitting Mn2+ ion in the nanocrystal, which would be otherwise very difficult to decipher.

Effects of temper level on the dependence of fatigue crack growth threshold and crack closure on the prior austenitic grain size

An attempt has been made to systematically investigate the effects of microstructural parameters, such as the prior austenite grain size (PAGS), in influencing the resistance to fatigue crack growth (FCG) in the near-threshold region under three different temper levels in a quenched and tempered high-strength steel. By austenitizing at various temperatures, the PAGS was varied from about 0.7 to 96 μm. The microstructures with these grain sizes were tempered at 200 °C, 400 °C, and 530 °C and tested for fatigue thresholds and crack closure. It has been found that, in general, three different trends in the dependence of both the total threshold stress intensity range, ΔK th , and the intrinsic threshold stress intensity range, ΔK eff, th , on the PAGS are observable. By considering in detail the factors such as cyclic stress-strain behavior, environmental effects on FCG, and embrittlement during tempering, the present observations could be rationalized. The strong dependence of ΔK th and ΔK eff, th on PAGS in microstructures tempered at 530 °C has been primarily attributed to cyclic softening and thereby the strong interaction of the crack tip deformation field with the grain boundary. On the other hand, a less strong dependence of ΔK th and ΔK eff, th on PAGS is suggested to be caused by the cyclic hardening behavior of lightly tempered microstructures occurring in 200 °C temper. In both microstructures, crack closure influenced near-threshold FCG (NTFCG) to a significant extent, and its magnitude was large at large grain sizes. Microstructures tempered at the intermediate temperatures failed to show a systematic variation of ΔKth and ΔKeff, th with PAGS. The mechanisms of intergranular fracture vary between grain sizes in this temper. A transition from “microstructure-sensitive” to “microstructure-insensitive” crack growth has been found to occur when the zone of cyclic deformation at the crack tip becomes more or less equal to PAGS. Detailed observations on fracture morphology and crack paths corroborate the grain size effects on fatigue thresholds and crack closure.

Size dependence of the bulk modulus of semiconductor nanocrystals from first-principles calculations

The variation in the bulk modulus of semiconductor nanoparticles has been studied within first-principles electronic-structure calculations using the local density approximation (LDA) for the exchange correlation. Quantum Monte Carlo calculations carried out for a silicon nanocrystal Si87H76 provided reasonable agreement with the LDA results. An enhancement was observed in the bulk modulus as the size of the nanoparticle was decreased, with modest enhancements being predicted for the largest nanoparticles studied here, a size just accessible in experiments. To access larger sizes, we fit our calculated bulk moduli to the same empirical law for all materials, the asymptote of which is the bulk value of the modulus. This was found to be within 2-10% of the independently calculated value. The origin of the enhancement has been discussed in terms of Cohen's empirical law M.L. Cohen, Phys. Rev. B 32, 7988 (1985)] as well as other possible scenarios.

Microstructure evolution and hardness variation during annealing of equal channel angular pressed ultra-fine grained nickel subjected to 12 passes

The microstructure, thermal stability and hardness of ultra-fine grained (UFG) Ni produced by 12 passes of equal channel angular pressing (ECAP) through the route Bc were studied. Comparing the microstructure and hardness of the as-ECAPed samples with the published data on UFG Ni obtained after 8 passes of ECAP through the route Bc reveals a smaller average grain size (230 nm in the present case compared with 270 nm in 8-pass Ni), significantly lower dislocation density (1.08 x 10(14) m(-2) compared with 9 x 10(14) m(-2) in 8-pass Ni) and lower hardness (2 GPa compared with 2.45 GPa for 8-pass Ni). Study of the thermal stability of the 12-pass UFG Ni revealed that recovery is dominant in the temperature range 150-250A degrees C and recrystallisation occurred at temperatures > 250 A degrees C. The UFG microstructure is relatively stable up to about 400 A degrees C. Due to the lower dislocation density and consequently a lower stored energy, the recrystallisation of 12-pass ECAP Ni occurred at a higher temperature (similar to 250 A degrees C) compared with the 8-pass Ni (similar to 200 A degrees C). In the 12-pass Nickel, hardness variation shows that its dependence on grain size is inversely linear rather than the common grain size(-0.5) dependence.

Dependence of the strength of interaction of carbon monoxide with transition metal clusters on the cluster size

The interaction of CO with Cu, Pd, and Ni at different coverages of the metals on solid substrates has been investigated by He II and core-level spectroscopies, after the nature of variation of the metal core-level binding energies with the coverage or the cluster size is established. The separation between the (1 pi + 5 sigma) and 4 sigma levels of CO increases with a decrease in the size of the metal clusters, accompanied by an increase in the desorption temperature. In the case of Cu, the intramolecular shakeup satellite of CO disappears on small clusters. More importantly, CO dissociates on small Ni clusters, clearly confirming that metal-CO interaction strength increases with a decrease in the cluster size.

The nature of charge ordering in rare earth manganates and its strong dependence on the size of the A-site cations

Charge ordering in rare earth manganates of the type Ln(0.5)A(0.5)MnO(3) (Ln = rare earth, A = alkaline earth) is highly sensitive to the average radius of the A-site cations, [r(A)]. Tn the small [r(A)] regime (e.g., Y0.5Ca0.5MnO3), charge ordering occurs in the paramagnetic state, the transformation to an antiferromagnetic state occurring at still lower temperatures. At moderate [r(A)] values (e.g., Nd0.5Sr0.5MnO3), a ferromagnetic metallic state transforms to a charge-ordered antiferromagnetic state with cooling. These two distinct types of charge ordering and associated properties are explained in terms of the variation of the exchange couplings J(FM) and J(AFM) with [r(A)] and the invariance of the single-ion Jahn-Teller energy with [r(A)]. A qualitative temperature-[r(A)] phase diagram, consistent with the experimental observations, has been constructed to describe the properties of the manganates in the different [r(A)] regimes. (C) 1997 Academic Press.