Gd2Te3: an antiferromagnetic semimetal.

We report high-precision magnetization ([Formula: see text]), magnetic susceptibility ([Formula: see text]), specific heat (C p (T, H)) and 'zero-field' electrical resistivity, [Formula: see text], data taken on Gd2Te3 single crystal over wide ranges of temperature and magnetic field (H), with either [Formula: see text]-axis or [Formula: see text]-plane. [Formula: see text] and [Formula: see text] unambiguously establish that the b-axis is the easy direction of magnetization whereas any direction in the ac-plane is a hard direction. The [Formula: see text]-type anomaly in 'zero-field' specific heat, C p (T, H = 0), and an abrupt drop in [Formula: see text] (characteristic of the paramagnetic (PM) - antiferromagnetic (AFM) phase transition) are observed at the Néel temperature, [Formula: see text] K. [Formula: see text] and C p (T,H) clearly demonstrate that [Formula: see text] shifts to lower temperatures with increasing H irrespective of whether H points in the easy or hard direction. When [Formula: see text], the [Formula: see text] isotherms at temperatures in the range 2.5 K [Formula: see text] [Formula: see text] K reveal the existence of a field-induced spin-flop (SF) transition at fields 4.0 T [Formula: see text] [Formula: see text] [Formula: see text] 4.5 T. The first principles electronic band structure and density of states calculations, based on the density functional theory, correctly predict an AFM ground state (stabilized primarily by the 4f  Gd3+ - 5p  Te2-- 4f  Gd3+ superexchange interactions) and the observed semi-metallic behavior for the Gd2Te3 compound. Moreover, these calculations yield the values [Formula: see text] [Formula: see text] for the ordered magnetic moment per Gd atom at T = 0, [Formula: see text] mJ mol-1 K-2 for the Sommerfeld coefficient for the electronic specific heat contribution and [Formula: see text] K for the Curie-Weiss temperature, respectively. These theoretical estimates conform well with the corresponding experimental values [Formula: see text] [Formula: see text], [Formula: see text] mJ mol-1 K-2 and [Formula: see text] K.

Anomalous magnetoresistance in nanocrystalline gadolinium at low temperatures.

The results of a detailed investigation of electrical resistivity, ρ(T) and transverse magnetoresistance (MR) in nanocrystalline Gd samples with an average grain size d = 12 nm and 18 nm reveal the following. Besides a major contribution to the residual resistivity, ρ(r)(0), arising from the scattering of conduction electrons from grain surfaces/interfaces/boundaries (which increases drastically as the average grain size decreases, as expected), coherent electron-magnon scattering makes a small contribution to ρ(r)(0), which gets progressively suppressed as the applied magnetic field (H) increases in strength. At low temperatures (T ≲ 40 K) and fields (H = 0 and H = 5 kOe), ρ(H)(T) varies as T(3/2) with a change in slope at T(+) ≃ 16.5 K. As the field increases beyond 5 kOe, the T(3/2) variation of ρ(H)(T) at low temperatures (T ≲ 40 K) changes over to the T(2) variation and a slight change in the slope dρ(H)/dT(2) at T(+)(H) disappears at H ⩾ 20 kOe. The electron-electron scattering (Fermi liquid) contribution to the T(2) term, if present, is completely swamped by the coherent electron-magnon scattering contribution. As a function of temperature, (negative) MR goes through a dip at a temperature Tmin ≃ T(+), which increases with H as H(2/3). MR at Tmin also increases in magnitude with H and attains a value as large as ∼15% (17%) for d = 12 nm (18 nm) at H = 90 kOe. This value is roughly five times greater than that reported earlier for crystalline Gd at Tmin ≃ 100 K. Unusually large MR results from an anomalous softening of magnon modes at T ≃ Tmin ≈ 20 K. In the light of our previous magnetization and specific heat results, we show that all the above observations, including the H(2/3) dependence of Tmin (with Tmin(H) identified as the Bose-Einstein condensation (BEC) transition temperature, TBEC(H)), are the manifestations of the BEC of magnons at temperatures T ⩽ TBEC. Contrasted with crystalline Gd, which behaves as a three-dimensional (3D) pure uniaxial dipolar ferromagnet in the asymptotic critical region, ρ(H=0)(T) of nanocrystalline Gd, in the critical region near the ferromagnetic-paramagnetic phase transition, is better described by the model proposed for a 3D random uniaxial dipolar ferromagnet.

Critical behaviour of nanocrystalline gadolinium: evidence for random uniaxial dipolar universality class.

We report on how nanocrystal size affects the critical behaviour of the rare-earth metal Gd near the ferromagnetic-to-paramagnetic phase transition. The asymptotic critical behaviour of the coarse-grained polycrystalline sample (with an average crystallite size of L≅100 µm) is that of a (pure) uniaxial dipolar ferromagnet, as is the case with single crystal Gd, albeit the width of the asymptotic critical region (ACR) is reduced. As the grain size approaches ∼30 nm, the ACR is so narrow that it could not be accessed in the present experiments. Inaccessibly narrow ACR for L ∼ 30 nm and continuous increase in the width of the ACR as L decreases from 16 to 9.5 nm basically reflect a crossover to the random uniaxial dipolar fixed point caused by the quenched random exchange disorder prevalent at the internal interfaces (grain boundaries).

Magnetization processes in nanocrystalline gadolinium.

The thermal decline in magnetization, M(T), at fixed magnetic field (H) under 'zero-field-cooled' (ZFC) and 'field-cooled' (FC) conditions, the time evolution of ZFC magnetization, M(ZFC)(t), at fixed temperature and field, M(H) hysteresis loops/isotherms, and ac susceptibility have been measured on polycrystalline Gd samples with average grain sizes of d = 12 and 18 nm. The irreversibility in magnetization, M(irr), occurring below a characteristic temperature that reduces with increasing H, is completely suppressed above a grain-size-dependent threshold field, H*. At low fields (H ≤ 100 Oe), M(irr)(T), like the coercive field, H(c)(T), exhibits a minimum at ∼16 K and a broad peak at ∼50 K before going to zero at T ≃ T(C) (Curie temperature). At fixed temperature (T < T(C)) and field (H ≪ H*), where M(irr) is finite, M(ZFC) has a logarithmic dependence on time. The magnetic viscosity (S) at H = 1 Oe and T ≤ 290 K is independent of the measurement time above ∼2 ms but for t < 2 ms it is strongly time-dependent. S(T) peaks at T ≃ T(C) for H = 1 Oe. A magnetic field reduces the peak height and shifts the peak in S(T) to lower temperatures. All the above observations are put on a consistent theoretical footing within the framework of a model in which the intra-grain magnetizations overcome the energy barriers (brought about by the intra-grain and grain-boundary/interfacial magnetic anisotropies) by the thermal activation process. These field- and temperature-dependent energy barriers, that separate the high-energy metastable (ZFC) state from the stable minimum-energy (FC) state, are independent of time for t ≳ 2 ms and have a very broad distribution. We show that the shape anisotropy plays a decisive role in the magnetization reversal process, and that the magnetocrystalline and magnetostatic fluctuations, prevalent in the grain-boundary and interfacial regions, govern the approach-to-saturation of magnetization in nanocrystalline Gd.

Lattice instability and martensitic transformation in LaAg predicted from first-principles theory.

The electronic structure, elastic constants and lattice dynamics of the B(2) type intermetallic compound LaAg are studied by means of density functional theory calculations with the generalized gradient approximation for exchange and correlation. The calculated equilibrium properties and elastic constants agree well with available experimental data. From the ratio between the bulk and shear moduli, LaAg is found to be ductile, which is unusual for B(2) type intermetallics. The computed band structure shows a dominant contribution from La 5d states near the Fermi level. The phonon dispersion relations, calculated using density functional perturbation theory, are in good agreement with available inelastic neutron scattering data. Under pressure, the phonon dispersions develop imaginary frequencies, starting at around 2.3 GPa, in good accordance with the martensitic instability observed above 3.4 GPa. By structural optimization the high pressure phase is identified as orthorhombic B(19).

Magnons as a Bose-Einstein condensate in nanocrystalline gadolinium.

The recent observation [S. P. Mathew et al., J. Phys. Conf. Ser. 200, 072047 (2010)] of the anomalous softening of spin-wave modes at low temperatures in nanocrystalline gadolinium is interpreted as a Bose-Einstein condensation (BEC) of magnons. A self-consistent calculation, based on the BEC picture, is shown to closely reproduce the observed temperature variations of magnetization and specific heat at constant magnetic fields.

Bose-Einstein condensation of magnons in polycrystalline gadolinium with nano-size grains.

We report the observation of Bose-Einstein condensation (BEC) of magnons in nanocrystalline Gd. Employing a self-consistent approach, the variations with magnetic field (H) of the BEC transition temperature, T(c)(H), and the volume, V (H), over which the condensate wavefunction retains its phase coherence, the temperature and magnetic field variations of the chemical potential, µ(T, H), and the average occupation number for the ground state, [linear span]n(0)(T, H)[linear span], are accurately determined from the magnetization, M(T, H), and specific heat, C(T, H), data. The variation of T(c) with magnetic field has the functional form T(c)(H) = T(c)(H = 0) + aH(2/3) that is characteristic of BEC. In conformity with the predictions of BEC theory (i) for T ≤ T(c), the condensate fraction [linear span]n(0)(T, H)[linear span]/[linear span]n(0)(T = 1.8 K, H)[linear span] at constant H scales with the reduced temperature as [T/T(c)(H)](3/2), (ii) in the limit H−>0, µ(T, H) Í = 0 for T ≤ T(c) and abruptly falls to large negative values as the temperature exceeds T(c), and (iii) the magnetic-field-induced change in magnon entropy, deduced from both M(T, H) and C(T, H), follows the T(3/2) power law at low temperatures T<

Nano-adsorbents for the removal of metallic pollutants from water and wastewater.

Of the variety of adsorbents available for the removal of heavy and toxic metals, activated carbon has been the most popular. A number of minerals, clays and waste materials have been regularly used for the removal of metallic pollutants from water and industrial effluents. Recently there has been emphasis on the application of nanoparticles and nanostructured materials as efficient and viable alternatives to activated carbon. Carbon nanotubes also have been proved effective alternatives for the removal of metallic pollutants from aqueous solutions. Because of their importance from an environmental viewpoint, special emphasis has been given to the removal of the metals Cr, Cd, Hg, Zn, As, and Cu. Separation of the used nanoparticles from aqueous solutions and the health aspects of the separated nanoparticles have also been discussed. A significant number of the latest articles have been critically scanned for the present review to give a vivid picture of these exotic materials for water remediation.

Development of a novel circular secondary clarifier for improving solids liquid separation in wastewater treatment.

A novel circular secondary clarifier was developed to obviate the shortcomings of conventional clarifiers. The novel clarifier provides natural flocculation, which occurs as a result of hydraulic energy dissipation and the formation of sludge cloud referred to as plume. The efficiency of the clarifier depends on the stability of the plume, which in turn depends on the velocity gradient. For natural flocculation to occur, a velocity gradient of 10 to 15 s(-1) was found to be favorable. This velocity also keeps the plume-rise well below the free-surface. The mean particle size of mixed liquor suspended solids increases from 41 to 83 microm in the plume, which indicates agglomeration of particles and confirms that natural flocculation is occurring within the plume. The hydraulic improvement achieved by improving inlet design dissipates hydraulic energy, uniformly distributes flow, minimizes sludge blanket disturbances, and promote flocculation. The improved clarifier operates at 1-h hydraulic retention time.

Finite-size scaling in band ferromagnets with non-universal critical behavior.

The ultra-high sensitivity of the ferromagnetic resonance (FMR) technique has been fully exploited to study the finite-size effects in the critical region near the ferromagnetic to paramagnetic phase transition in Cr(75-x)Fe(25+x) (x = 0, 5) thin films of high structural and magnetic quality. Conclusive experimental evidence is provided for the validity of finite-size scaling. Irrespective of the film thickness and composition, the critical exponents ß, γ and ν for spontaneous magnetization, initial magnetic susceptibility and spin-spin correlation length retain their bulk values so that no dimensionality crossover occurs within the film thickness range covered in the FMR experiments. The present results indicate that (i) like Cr(75-x)Fe(25+x), the previously studied Fe, Co, Ni, and CoNi(3) thin films behave as itinerant-electron (band) ferromagnets in which the isotropic long-range interactions between spins decay as J(r)∼r(-(d+σ)) (σ>0), and (ii) the lattice dimensionality d, spin dimensionality m, and range of spin-spin interactions (via the material-specific parameter σ) decide the (non-universal) values of the critical exponents.

Structural and Mössbauer effect investigations of amorphous FeCuNbSiB alloys nanocrystallized (VITROPERM) in magnetic field.

Melt-spun amorphous ribbons of nominal composition Fe73Cu1Nb3Si16B7, annealed at 560-580 degrees C for 1 hour in a magnetic field (H) applied along the width in the ribbon plane, develop uniaxial magnetic anisotropy with easy axis along H and exhibit several novel attributes. The samples labelled as S20 and S150 are nanocomposites consisting of ferromagnetic nanocrystalline grains (volume fraction approximately equal to 84% and 81%) of mean size d = 13(2) nm embedded in a ferromagnetic amorphous matrix and possess a magnetic permeability as large as 20,000 and 150,000, respectively. While nearly 55% of the nanocrystalline grains have a cubic DO3 Fe3Si-like structure with actual Si concentration of about 22 at.%, the remaining 45% nanocrystalline grains have tetragonal Fe3B and hexagonal Fe2Si structure. Since the crystalline volume fraction of Fe3B and Fe2Si nanocrystals is more in the sample S20, this sample exhibits stronger local magnetic anisotropy and hence lower permeability.

Adsorptive separation of cadmium from aqueous solutions and wastewaters by riverbed sand.

Application of riverbed sand for the adsorptive separation of cadmium(II) from aqueous solutions has been investigated. Removal increased from 26.8 to 56.4% by decreasing the initial concentration of cadmium from 7.5 x 10(-5) to 1.0 x 10(-5)M at pH 6.5, 25 degrees C temperature, agitation speed of 100 rpm, 100 microm particle size and 1.0 x 10(-2) NaClO4 ionic strength. Process of separation is governed by first order rate kinetics. The value of rate constant of adsorption, k(ad), was found to be 2.30 x 10(-2)per min at 25 degrees C. Values of coefficient of mass transfer, beta L, were calculated and its value at 25 degrees C was found to be 1.92 x 10(-2)cm/s. Values of Langmuir constant were calculated. Values of thermodynamic parameters delta G0, delta H0 and delta S0 were also calculated and were recorded as -0.81 kcal/mol, -9.31 kcal/mol and -28.10 cal/mol at 25 degrees C. pH has been found to affect the removal of cadmium significantly and maximum removal, 58.4%, has been found at pH 8.5. Process can be used for treatment of cadmium(II) rich wastewaters.

Removal of basic dyes from aqueous medium using a novel polymer: Jalshakti.

Studies were carried out to remove basic dyes such as safranine T, methylene blue, crystal violet, light green, brilliant milling violet and patent blue VS from their aqueous solutions using biodegradable polymeric absorbent material, viz., Jalshakti (JS). Results showed that 93% safranine T, 98% methylene blue and 84% crystal violet were adsorbed on JS relative to their initial concentration (10 mg L(-1)). The optimum pH was found to be 6.0+/-0.5 and smaller size of particle of JS resulted better adsorptive removal of the dyes. IR spectroscopic and potassium ion release studies revealed that basic dyes were selectively removed through adsorption-ion-exchange mechanism involving carboxylic groups and K+ ions of JS.

Application of chemical, biological and membrane separation processes in textile industry with recourse to zero effluent discharge--a case study.

Environmental concerns associated with textile processing had placed the textile sector in a Southern State of India under serious threat of survival. The textile industries were closed under the orders of the Statutory Board for reason of inadequate compliance to environmental discharge norms of the State for the protection of the drinking water source of the State capital. In compliance with the direction of the Board for zero effluent discharge, advanced treatment process have been implemented for recovery of boiler feed quality water with recourse to effluent recycling/reuse. The paper describes to a case study on the adequacy assessment of the full scale effluent treatment plant comprising chemical, biological and filtration processes in a small scale textile industry. In addition, implementation of measures for discernable improvement in the performance of the existing units through effective operation & maintenance, and application of membrane separation processes leading to zero effluent discharge is also highlighted.

Physico-chemical treatment of wastewater from clusters of small scale cotton textile units.

Small scale industries can not own individual wastewater treatment facility due to non-availability of land and skilled manpower for operation and maintenance of wastewater treatment plants. A centralized wastewater treatment facility for clusters of small scale industries is appropriate. This concept is gaining popularity in recent years. In India, various textile process operations are undertaken by individual small scale units. The wastewater generated at these units is conveyed to a common effluent treatment facility comprising of equalization, flocculation-clarification, activated sludge process, secondary clarification and finally discharge into inland surface water bodies. The wastewater from small scale cotton textile processing units was highly coloured and alkaline with average BOD and COD concentration of 205 and 790 mg l(-1), respectively. Due to the presence of several dyes, particularly reactive dyes, the biological treatment is often found less effective. Therefore, applicability of various physico-chemical treatment methods needs to be investigated in pursuit of an alternative to biological treatment of textile wastewater. A physico-chemical treatment scheme, involving chemical coagulation-sedimentation, dual media filtration, activated carbon adsorption followed by chemical oxidation was investigated in this paper. The quality of final treated wastewater in terms of BOD and COD was 18-24 and 230-240 mg l(-1), respectively through this scheme. A scheme of treatment comprising coagulation-sedimentation, dual media filtration, activated carbon, chemical oxidation may be considered as an alternative to biological treatment of textile wastewater.

A zone-wise ecological-economic analysis of Indian wetlands.

In view of their sensitivity and importance, an ecological-economic analysis of wetlands has been carried out for various Indian states. Subsequently, the ecological wealths of different zones (north, south, east and west) have been computed and compared. Amongst states, Karnataka (7896.5 million US dollars yr(-1)), Gujarat (7689.4 million US dollars yr(-1)) and Andhra Pradesh (7670.9 million US dollars yr(-1)) are found to be the richest, whereas Nagaland (3.1 million US dollars yr(-1)), Meghalaya (5.9 million US dollars yr(-1)) and Sikkim (15.9 million US dollars yr(-1)) turn out to be the poorest. Amongst different zones, Southern Zone turns out to be the richest and the Northern Zone poorest. A ratio called ANR [Artificial (A) Wetland Wealth to Natural (N) Wetland Wealth Ratio (R)] has also been devised, which is the ratio of the ecological-economic values of artificial and natural wetlands. In other words, this ratio indicates the level of environmental concern of a given region. ANR ratio is found to be the highest for Madhya Pradesh (564.1) and Karnataka (159.8) states.

Common effluent treatment plant (CETP) for wastewater management from a cluster of small scale tanneries.

Effluent treatment plants need land for construction, capital cost, power and specialized manpower for their operation and maintenance. Because of these constraints, small scale tanneries can not afford to have their own effluent treatment facilities and therefore, combined effluent from all tanneries are to be brought to a centralized place for treatment. This facility is called a Common Effluent Treatment Plant (CETP). For operation and maintenance of CETP, small scale tanners formed a co-operative society. The expenses for operation and maintenance of CETP are being shared by participating tanneries. Wastewater management for the cluster of small scale tanneries was studied in details and various measures were incorporated to improve performance of the CETP and also to improve treated effluent quality to confirm standard prescribed by regulatory agencies. Performance of existing CETP was evaluated. Based on the results, bench scale laboratory treatability studies were conducted for improvement in treated effluent quality and also to suggest appropriate modifications to the CETP. These studies are detailed in this paper.

Comparison of decolorization of reactive microorganisms isolated from various sources.

Azo dyes are among the oldest man-made chemicals and they are still widely used in the textile, printing and the food industries. About 10% - 15% of the total dyes used in the industry is released into the environment during the manufacturing and usage. Some dyes and some of their N-substituted aromatic bio-transformation products are toxic and/or carcinogenic and therefore these dyes are considered to be envionmental pollutants and health hazards. These azo dyes are degraded by physico-chemical and biological methods. Of these, biological methods are considered to be the most economical and efficient. In this work, attempts were made to degrade these dyes aerobically. The organisms which were efficient in degrading the following azo dyes-Red RB, Remazol Red, Remazol Blue, Remazol Violet, Remazol Yellow, Golden Yellow, Remazol Orange, Remazol Black- were isolated from three different sources viz., wastewater treatment plant, paper mill effluent treatment plant and tannery wastewater treatment plant. The efficiency of azo dye degradation by mixed cultures from each source was analyzed. It was found that mixed cultures from tannery treatment plant worked efficiently in decolorizing Remazol Red, Remazol Orange, Remazol Blue and Remazol Violet, while mixed cultures from the paper mill effluent worked efficiently in decolorizing Red RB, Golden Yellow and Remazol Yellow. The mixed cultures from wastewater treatment plant efficiently decolorized Remazol Black.

Photocatalytic degradation of 2-chlorophenol: a study of kinetics, intermediates and biodegradability.

The kinetics of photocatalytic (TiO(2)/UV) degradation of 2-chlorophenol (2-CP), characterization of intermediates and induction of biodegradability in treated chlorophenol solutions is reported. Approximately 95% of the 2-CP is removed in approximately 2h at pH 5 and 0.2g TiO(2)l(-1) when the 2-CP concentration is < or =100mgl(-1); the pseudo-first-order rate constant (k) is estimated to be 0.0183 min(-1). GC-MS analyses detected phenol, catechol, hydroxyhydroquinone (HHQ), and chlorohydroquinone (CHQ) intermediates during the short irradiation time (<1h); however two other higher carbon intermediates 2-hydroxy-benzaldehyde (HB) and [1.1'-biphenyl]-2,2'-diol (BPD) are found as major intermediates over longer irradiation times. The biochemical oxygen demand (BOD) of treated 2-CP solutions improved substantially. A tentative mechanistic pathway to explain formation of higher carbon intermediates is presented.

Treatment of spent broth from an antibiotic manufacturing unit using anaerobic fixed film fixed bed reactor.

Studies on bench scale reactor were undertaken to determine its performance at various organic loading rate (OLR) and hydraulic retention time (HRT). The results indicated BOD and COD removals in the range of 67.2-77.4% and 57.8-69.1% respectively at the OLRs between 0.84 and 2.5 kgCOD/m3 d and HRT of 10 days. Daily gas production was measured by gas flow meter. Daily gas production varied between 0.268 and 0.326 m3/kgCOD added at the different OLRs. Studies were also carried out at lower HRT of 5 days. But BOD/COD removals reduced and correspondingly gas production also reduced. Gas composition remained constant at both the HRT and the Methane content was around 65-68% while the CO2 was around 32-35%. This paper discusses in detail the feasibility of upflow anaerobic fixed film fixed bed (UAFFFB) reactor system in treating the strong spent broth from the antibiotic industry.