Variation of the partial thermodynamic properties of oxygen with composition in YBa2Cu3O7−δ

The variation of equilibrium oxygen potential with oxygen concentration inYBa 2Cu3O7-δhas been measured in the temperature range of 773 to 1223 K. For temperatures up to 1073 K, the oxygen content of theYBa 2Cu3O7-δsample, held in a stabilized-zirconia crucible, was altered by coulometric titration. The compound was in contact with the electrolyte, permitting direct exchange of oxygen ions. For measurements above 1073 K, the oxide was contained in a magnesia crucible placed inside a closed silica tube. The oxygen potential in the gas phase above the 123 compound was controlled and measured by a solid-state cell based on yttria-stabilized zirconia, which served both as a pump and sensor. Pure oxygen at a pressure of 1.01 × 105 Pa was used as the reference electrode. The oxygen pressure over the sample was varied from 10-1 to 105 Pa. The oxygen concentrations of the sample equilibrated with pure oxygen at 1.01 × 105 Pa at different temperatures were determined after quenching in liquid nitrogen by hydrogen reduction at 1223 K. The plot of chemical potential of oxygen as a function of oxygen non-stoichiometry shows an inflexion at δ ∼ 0.375 at 873 K. Data at 773 K indicate tendency for phase separation at lower temperatures. The partial enthalpy and entropy of oxygen derived from the temperature dependence of electromotive force (emf ) exhibit variation with composition. The partial enthalpy for °= 0.3, 0.4, and 0.5 also appears to be temperature dependent. The results are discussed in comparison with the data reported in the literature. An expression for the integral free energy of formation of YBa2Cu3O6.5 is evaluated based on measurements reported in the literature. By integration of the partial Gibbs’ energy of oxygen obtained in this study, the variation of integral property with oxygen concentration is obtained at 873 K.

Compositional dependence properties change in S40Se60-x,Sb-x alloys

Bulk samples of S40Se60,Sb-x (with x=10, 20, 30 and 40 at. %) were prepared from high purity chemicals by melt quenching technique. The samples compositions were confirmed by using energy dispersive analysis of X-rays. X-ray diffraction studies revealed that all the samples have poly-crystalline phase. The variation in optical properties with compositional has been investigated by X-ray photoelectron spectroscopy and Raman spectroscopy. The optical band gap of the thin films is found to be decreased with composition. Increasing Sb content was found to affect the structural and optical properties of bulk samples. The intensity of core level spectra changes with the addition of Sb clearly interprets the optical properties change due to compositional variation. The Raman shift and new peak formation in these samples clearly show the structural modifications due to Sb addition.

Vegetation structure and composition of tropical evergreen and deciduous forests in Uttara Kannada District, Western Ghats under different disturbance regimes

In the present paper, we present the structure and composition of tropical evergreen and deciduous forests in the Western Ghats monitored under a long-term programme involving Indian Institute of Science, Earthwatch and volunteer investigators from HSBC. Currently, there is limited evidence on the status and dynamics of tropical forests in the context of human disturbance and climate change. Observations made in this study show that the `more disturbed' evergreen and one of the deciduous plots have low species diversity compared to the less-disturbed forests. There are also variations in the size class structure in the more and `less disturbed' forests of all the locations. The variation is particularly noticeable in the DBH size class 10 - 15 cm category. When biomass stock estimates are considered, there was no significant difference between evergreen and deciduous forests. The difference in biomass stocks between `less disturbed' and `more disturbed' forests within a forest type is also low. Thus, the biomass and carbon stock has not been impacted despite the dependence of communities on the forests. Periodic and long-term monitoring of the status and dynamics of the forests is necessary in the context of potential increased human pressure and climate change. There is, therefore, a need to inform the communities of the impact of extraction and its effect on regeneration so as to motivate them to adopt what may be termed as ``adaptive resource management'', so as to sustain the flow of forest products.

Influence of composition on the structure, electric and magnetic properties of Pd-Mn-P and Pd-Co-P amorphous alloys

The influence of composition on the structure and on the electric and magnetic properties of amorphous Pd-Mn-P and Pd-Co-P prepared by rapid quenching techniques were investigated in terms of (1) the 3d band filling of the first transition metal group, (2) the phosphorus concentration effect which acts as an electron donor and (3) the transition metal concentration.

The structure is essentially characterized by a set of polyhedra subunits essentially inverse to the packing of hard spheres in real space. Examination of computer generated distribution functions using Monte Carlo random statistical distribution of these polyhedra entities demonstrated tile reproducibility of the experimentally calculated atomic distribution function. As a result, several possible "structural parameters" are proposed such as: the number of nearest neighbors, the metal-to-metal distance, the degree of short-range order and the affinity between metal-metal and metal-metalloid. It is shown that the degree of disorder increases from Ni to Mn. Similar behavior is observed with increase in the phosphorus concentration.

The magnetic properties of Pd-Co-P alloys show that they are ferromagnetic with a Curie temperature between 272 and 399°K as the cobalt concentration increases from 15 to 50 at.%. Below 20 at.% Co the short-range exchange interactions which produce the ferromagnetism are unable to establish a long-range magnetic order and a peak in the magnetization shows up at the lowest temperature range . The electric resistivity measurements were performed from liquid helium temperatures up to the vicinity of the melting point (900°K). The thermomagnetic analysis was carried out under an applied field of 6.0 kOe. The electrical resistivity of Pd-Co-P shows the coexistence of a Kondo-like minimum with ferromagnetism. The minimum becomes less important as the transition metal concentration increases and the coefficients of ℓn T and T^2 become smaller and strongly temperature dependent. The negative magnetoresistivity is a strong indication of the existence of localized moment.

The temperature coefficient of resistivity which is positive for Pd- Fe-P, Pd-Ni-P, and Pd-Co-P becomes negative for Pd-Mn-P. It is possible to account for the negative temperature dependence by the localized spin fluctuation model and the high density of states at the Fermi energy which becomes maximum between Mn and Cr. The magnetization curves for Pd-Mn-P are typical of those resulting from the interplay of different exchange forces. The established relationship between susceptibility and resistivity confirms the localized spin fluctuation model. The magnetoresistivity of Pd-Mn-P could be interpreted in tenns of a short-range magnetic ordering that could arise from the Rudennan-Kittel type interactions.

Photo-assisted hydrosilylation of silicon nanoparticles: Dependence of particle size on grafting chemistry

Silicon nanoparticles between 2.5 nm and 30 nm in diameter were functionalized by means of photoassisted hydrosilylation reactions in the aerosol phase with terminal alkenes of varying chain length. Using infrared spectroscopy and nuclear magnetic resonance, the chemical composition of the alkyl layer was determined for each combination of particle size and alkyl chain length. The spectroscopic techniques were used to determine that smaller particles functionalized with short chains in the aerosol phase tend to attach to the interior (β) alkenyl carbon atom, whereas particles >10 nm in diameter exhibit attachment primarily with the exterior (α) alkenyl carbon atom, regardless of chain length. © 2011 American Chemical Society.

Raman scattering characterization of Mn composition and strain in Ga1-xMnxSb/GaSb epitaxial layers

Raman scattering (RS) experiments have been performed for simultaneous determination of Mn composition and strain in Ga1-xMnxSb thin films grown on GaSb substrate by liquid phase epitaxy technique. The Raman spectra obtained from various Ga1-xMnxSb samples show only GaSb-like phonon modes whose frequency positions are found to have Mn compositional dependence. With the combination of epilayer strain model, RS and energy dispersive x-ray (EDX) experiments, the compositional dependence of GaSb-like LO phonon frequency is proposed both in strained and unstrained conditions. The proposed relationships are used to evaluate Mn composition and strain from the Ga1-xMnxSb samples. The results obtained from the RS data are found to be in good agreement with those determined independently by the EDX analysis. Furthermore, the frequency positions of MnSb-like phonon modes are suggested by reduced-mass model. (C) 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Growth of nano-structures on composition-modulated InAlAs surfaces

InAs self-organized nanostructures were grown with variant deposition thickness and growth rate on closely matched InAlAs/InP by molecular-beam epitaxy. The structural properties. of InAs and InAlAs layer were studied. It is found that the InAs morphology is insensitive to the growth conditions. Transmission electron microscopy and reflectance difference spectroscopy measurements show that the InAlAs matrix presents lateral composition modulation which gives birth to surface anisotropy. Based on the dependence of the InAs morphology on the anisotropy of the InAlAs layer, a modified Stranski-Krastanow growth mode is presented to describe the growth of the nanostructure on a composition-modulated surface.

The dependence of GexSi1-x epitaxial growth on GeH4 flow using chemical vapour deposition

GexSi1-x epilayers were grown at 700-900 degrees C by atmospheric pressure chemical vapour deposition. GexSi1-x, Si and Ge growth rates as functions of GeH4 flow are considered separately to investigate how the growth of the epilayers is enhanced. Arrhenius plots of Si and Ge incorporation in the GexSi1-x growth show the activation energies associated with the growth rates are about 1.2 eV for silicon and 0.4 eV for germanium, indicating that Si growth is limited by surface kinetics and Ge growth is limited by mass transport. A model based on this idea is proposed and used to simulate the growth of GexSi1-x. The calculation and experiment are in good agreement. Growth rate and film composition increase monotonically with growth pressure; both observations are explained by the model.

Deviation from the stoichiometric composition of single-crystal 'Er2Co17'

The deviation from the stoichiometric composition of single-crystal 'Er2Co17' has been determined by theoretical analysis. It is found that the composition of this single-crystal 'Er2Co17' is rich in cobalt, and its real composition is suggested to be Er2-deltaCo17+2 delta (delta = 0.14) on the basis of a comparison of calculations based on the single-ion model with a series of experiments. The values of the Er-Co exchange field H-ex and the crystalline-electric-field (CEF) parameters A(n)(m) at the rare-earth (R) site in the 'Er2Co17' compound are also evaluated at the same time. The experiments provide the following data: the temperature dependence of the spontaneous magnetization of the compounds and the normalized magnetic moment of the Er ion, the magnetization curves dong the crystallographic axes at 4.2 K and 200 K, and the temperature dependence of the magnetization along the crystallographic axes in a field of 4 T.

Temperature and pressure dependence of phase separation of trans-decahydronaphthalene/polystyrene solution

The cloud-point temperatures (T-c1's) of ti-ans-decahydronaphthalene (TD)/polystyrene (PS, M-w = 270 kg/mol) solutions were determined by fight scattering measurements over a range of temperatures (1-16 degreesC), pressures (100-900 bar), and compositions (4.2-21.6 vol% polymer). The system phase separates upon cooling and the T-c1 was found to increase with the rising pressure for the constant composition. In the absence of special effects this finding indicates positive excess volumes. The special attention was paid to the demixing temperatures as a function of the pressure for the different polymer solutions and the plots in the T-volume fraction plane and P-volume fraction plane. The cloud-point curves of polymer solutions under changing pressures were observed for different compositions, demonstrates that the TD/PS system exhibits UCST (phase separation upon cooling) behavior. With this data the phase diagrams under pressure were calculated applying the Sanchez-Lacombe (SL) lattice fluid theory. Furthermore, the cause of phase separation, i.e., the influence of Flory-Huggins (FH) interaction parameter under pressure was investigated.

Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 6. Structure changes from smectic to columnar phases in a series of copolyethers containing odd and even numbers of methylene units in equal molar composition

A series of liquid crystalline copolyethers has been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane and different alpha,omega-dibromoalkanes [coTPP(n/m)]. In this report, coTPPs having n = 5, 7, 9, 11 and m = 12 are studied, which represent copolyethers having both varying odd number and a fixed even number of methylene units. The compositions were fixed at an equal molar ratio (50/50). These coTPPs(nlm) show multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. The undercooling dependence of these transitions is found to be small, indicating that these transitions are close to equilibrium, Although the coTPPs possess a high-temperature nematic (N) phase, the periodicity order along the chain direction is increasingly disturbed when the length of the odd-numbered methylene units decreases from n 11 to 5. in the coTPPs(5/12, 7/12, and 9/12), wide-angle X-ray diffraction experiments at different temperatures show that, shortly after the N phase formation during cooling, the lateral molecular packing improves toward a hexagonal lattice, as evidenced by a gradual narrowing of the scattering halo. This process represents the possible existence of an exotic N phase, which serves as a precursor to the columnar (Phi(H)) phase. A further decrease in temperature leads to a (PH phase having a long-range ordered, two-dimensional hexagonal lattice. In coTPP(11/12), the phase structures are categorized as highly ordered and tilted, smectic and smectic crystal phases, similar to homoTPPs, such as the smectic F (S-F) and smectic crystal G (SCG) phases. An interesting observation is found for coTPP(9/12), wherein a structural change from the high-temperature Phi(H) phase to the low-temperature S-F phase occurs. It can be proven that, upon heating, the well-defined layer structure disappears and the lateral packing remains hexagonal. The overall structural differences in this series of coTPPs between those of the columnar and highly ordered smectic phases are related to the disorders introduced into the layer structure by the dissimilarity of the methylene unit lengths in the comonomers.

Compositional dependence of the microphase separation transition in styrene-butadiene-styrene triblock copolymer/polystyrene blends

The change in the microphase separation transition (MST) temperature of a styrene-butadiene-styrene (SBS) triblock copolymer induced by the addition of polystyrene (PS) was investigated by small-angle X-ray scattering. It was found that the transition temperature was determined from the molecular weight (M(H)) Of the added PS in relation to that of the corresponding blocks (M(A)) in the copolymer. The MST temperature decreased with added PS if M(H)/M(A) < 1/4, while it increased with added PS when M(H)/M(A) > 1/4 Analysis of the theoretical expression based on the random phase approximation showed exactly the same tendency of change in the transition temperatures as that observed experimentally. The interaction parameter, chi(SB), obtained by nonlinear fitting of the scattering profiles of SBS/PS blends in the disordered state, was found to be a function of temperature and composition. Composition fluctuations were found to exist in SBS/PS blends, increasing with increasing addition of PS but diminishing with increasing molecular weight of the added PS.

Chemical composition of B-type supergiants in the OB 8, OB 10, OB 48, OB 78 associations of M 31

Absolute and differential chemical abundances are presented for the largest group of massive stars in M31 studied to date. These results were derived from intermediate resolution spectra of seven B-type supergiants, lying within four OB associations covering a galactocentric distance of 5-12 kpc. The results are mainly based on an LTE analysis, and we additionally present a full non-LTE, unified model atmosphere analysis of one star (OB 78-277) to demonstrate the reliability of the differential LTE technique. A comparison of the stellar oxygen abundance with that of previous nebular results shows that there is an off set of between similar to0.15-0.4 dex between the two methods which is critically dependent on the empirical calibration adopted for the R 23 parameter with [O/H]. However within the typical errors of the stellar and nebular analyses (and given the strength of dependence of the nebular results on the calibration used) the oxygen abundances determined in each method are fairly consistent. We determine the radial oxygen abundance gradient from these stars, and do not detect any systematic gradient across this galactocentric range. We find that the inner regions of M31 are not, as previously thought, very "metal rich". Our abundances of C, N, O, Mg, Si, Al, S and Fe in the M31 supergiants are very similar to those of massive stars in the solar neighbourhood.

Pressure dependence of spin fluctuations in metallic glasses Zrâ â Niâ â ,Zrâ â (Nix/Feâ â â -x)â â and /Zrx/feâ â â -x

The superconducting transition temperature Tc of metallic glasses ZrxFelOO-x (x=80, 75), Zr75(NixFelOO-x)25 (x=75, 50, 25), and CU2SZr75 were measured under quasi-hydrostatic pressure up to 8 OPa (80kbar). The volume (pressure) dependence of the electron-phonon coupling parameters Aep for CU25Zr75 was calculated using the McMillan equatio11. Using this volume dependence of Aep and the modified McMillan equation which incorporates spin-fluctuations, the volume dependence of the spin fluctuation parameter, Asf, was determined in Zr75Ni25, ZrxFelOO-x , a11d Zr75(NixFelOO-x)25. It was found that with increasing pressure, spinfluctuations are suppressed at a faster rate in ZrxFe lOO-x and Zr75(NixFelOO-x)25, as Fe concentration is increased. The rate of suppression of spin-fluctuations with pressure was also found to be higher in Fe-Zr glasses than in Ni-Zr glasses of similar composition.

Interactions between grain size and composition of sediments: two examples

Two contrasting case studies of sediment and detrital mineral composition are investigated in order to outline interactions between chemical composition and grain size. Modern glacial sediments exhibit a strong dependence of the two parameters due to the preferential enrichment of mafic minerals, especially biotite, in the fine-grained fractions. On the other hand, the composition of detrital heavy minerals (here: rutile) appears to be not systematically related to grain-size, but is strongly controlled by location, i.e. the petrology of the source rocks of detrital grains. This supports the use of rutile as a well-suited tracer mineral for provenance studies. The results further suggest that (i) interpretations derived from whole-rock sediment geochemistry should be flanked by grain-size observations, and (ii) a more sound statistical evaluation of these interactions require the development of new tailor-made statistical tools to deal with such so-called two-way compositions