On conduction mechanism in paramagnetic phase of Gd based manganites

Materials belonging to the family of manganites are technologically important since they exhibit colossal magneto resistance. A proper understanding of the transport properties is very vital in tailoring the properties. A heavy rare earth doped manganite like Gd0·7Sr0·3MnO3 is purported to be exhibiting unusual properties because of smaller ionic radius of Gd. Gd0·7Sr0·3MnO3 is prepared by a wet solid state reaction method. The conduction mechanism in such a compound has been elucidated by subjecting the material to low temperature d.c. conductivity measurement. It has been found that the low band width material follows a variable range hopping (VRH) model followed by a small polaron hopping (SPH) model. The results are presented here

Synthesis, Characterization and Applications of Modified TiO2 Systems

This thesis is divided in to 9 chapters and deals with the modification of TiO2 for various applications include photocatalysis, thermal reaction, photovoltaics and non-linear optics. Chapter 1 involves a brief introduction of the topic of study. An introduction to the applications of modified titania systems in various fields are discussed concisely. Scope and objectives of the present work are also discussed in this chapter. Chapter 2 explains the strategy adopted for the synthesis of metal, nonmetal co-doped TiO2 systems. Hydrothermal technique was employed for the preparation of the co-doped TiO2 system, where Ti[OCH(CH3)2]4, urea and metal nitrates were used as the sources for TiO2, N and metals respectively. In all the co-doped systems, urea to Ti[OCH(CH3)2]4 was taken in a 1:1 molar ratio and varied the concentration of metals. Five different co-doped catalytic systems and for each catalysts, three versions were prepared by varying the concentration of metals. A brief explanation of physico-chemical techniques used for the characterization of the material was also presented in this chapter. This includes X-ray Diffraction (XRD), Raman Spectroscopy, FTIR analysis, Thermo Gravimetric Analysis, Energy Dispersive X-ray Analysis (EDX), Scanning Electron Microscopy(SEM), UV-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS), Transmission Electron Microscopy (TEM), BET Surface Area Measurements and X-ray Photoelectron Spectroscopy (XPS). Chapter 3 contains the results and discussion of characterization techniques used for analyzing the prepared systems. Characterization is an inevitable part of materials research. Determination of physico-chemical properties of the prepared materials using suitable characterization techniques is very crucial to find its exact field of application. It is clear from the XRD pattern that photocatalytically active anatase phase dominates in the calcined samples with peaks at 2θ values around 25.4°, 38°, 48.1°, 55.2° and 62.7° corresponding to (101), (004), (200), (211) and (204) crystal planes (JCPDS 21-1272) respectively. But in the case of Pr-N-Ti sample, a new peak was observed at 2θ = 30.8° corresponding to the (121) plane of the polymorph brookite. There are no visible peaks corresponding to dopants, which may be due to their low concentration or it is an indication of the better dispersion of impurities in the TiO2. Crystallite size of the sample was calculated from Scherrer equation byusing full width at half maximum (FWHM) of the (101) peak of the anatase phase. Crystallite size of all the co-doped TiO2 was found to be lower than that of bare TiO2 which indicates that the doping of metal ions having higher ionic radius into the lattice of TiO2 causes some lattice distortion which suppress the growth of TiO2 nanoparticles. The structural identity of the prepared system obtained from XRD pattern is further confirmed by Raman spectra measurements. Anatase has six Raman active modes. Band gap of the co-doped system was calculated using Kubelka-Munk equation and that was found to be lower than pure TiO2. Stability of the prepared systems was understood from thermo gravimetric analysis. FT-IR was performed to understand the functional groups as well as to study the surface changes occurred during modification. EDX was used to determine the impurities present in the system. The EDX spectra of all the co-doped samples show signals directly related to the dopants. Spectra of all the co-doped systems contain O and Ti as the main components with low concentrations of doped elements. Morphologies of the prepared systems were obtained from SEM and TEM analysis. Average particle size of the systems was drawn from histogram data. Electronic structures of the samples were identified perfectly from XPS measurements. Chapter 4 describes the photocatalytic degradation of herbicides Atrazine and Metolachlor using metal, non-metal co-doped titania systems. The percentage of degradation was analyzed by HPLC technique. Parameters such as effect of different catalysts, effect of time, effect of catalysts amount and reusability studies were discussed. Chapter 5 deals with the photo-oxidation of some anthracene derivatives by co-doped catalytic systems. These anthracene derivatives come underthe category of polycyclic aromatic hydrocarbons (PAH). Due to the presence of stable benzene rings, most of the PAH show strong inhibition towards biological degradation and the common methods employed for their removal. According to environmental protection agency, most of the PAH are highly toxic in nature. TiO2 photochemistry has been extensively investigated as a method for the catalytic conversion of such organic compounds, highlighting the potential of thereof in the green chemistry. There are actually two methods for the removal of pollutants from the ecosystem. Complete mineralization is the one way to remove pollutants. Conversion of toxic compounds to another compound having toxicity less than the initial starting compound is the second way. Here in this chapter, we are concentrating on the second aspect. The catalysts used were Gd(1wt%)-N-Ti, Pd(1wt%)-N-Ti and Ag(1wt%)-N-Ti. Here we were very successfully converted all the PAH to anthraquinone, a compound having diverse applications in industrial as well as medical fields. Substitution of 10th position of desired PAH by phenyl ring reduces the feasibility of photo reaction and produced 9-hydroxy 9-phenyl anthrone (9H9PA) as an intermediate species. The products were separated and purified by column chromatography using 70:30 hexane/DCM mixtures as the mobile phase and the resultant products were characterized thoroughly by 1H NMR, IR spectroscopy and GCMS analysis. Chapter 6 elucidates the heterogeneous Suzuki coupling reaction by Cu/Pd bimetallic supported on TiO2. Sol-Gel followed by impregnation method was adopted for the synthesis of Cu/Pd-TiO2. The prepared system was characterized by XRD, TG-DTG, SEM, EDX, BET Surface area and XPS. The product was separated and purified by column chromatography using hexane as the mobile phase. Maximum isolated yield of biphenyl of around72% was obtained in DMF using Cu(2wt%)-Pd(4wt%)-Ti as the catalyst. In this reaction, effective solvent, base and catalyst were found to be DMF, K2CO3 and Cu(2wt%)-Pd(4wt%)-Ti respectively. Chapter 7 gives an idea about the photovoltaic (PV) applications of TiO2 based thin films. Due to energy crisis, the whole world is looking for a new sustainable energy source. Harnessing solar energy is one of the most promising ways to tackle this issue. The present dominant photovoltaic (PV) technologies are based on inorganic materials. But the high material, low power conversion efficiency and manufacturing cost limits its popularization. A lot of research has been conducted towards the development of low-cost PV technologies, of which organic photovoltaic (OPV) devices are one of the promising. Here two TiO2 thin films having different thickness were prepared by spin coating technique. The prepared films were characterized by XRD, AFM and conductivity measurements. The thickness of the films was measured by Stylus Profiler. This chapter mainly concentrated on the fabrication of an inverted hetero junction solar cell using conducting polymer MEH-PPV as photo active layer. Here TiO2 was used as the electron transport layer. Thin films of MEH-PPV were also prepared using spin coating technique. Two fullerene derivatives such as PCBM and ICBA were introduced into the device in order to improve the power conversion efficiency. Effective charge transfer between the conducting polymer and ICBA were understood from fluorescence quenching studies. The fabricated Inverted hetero junction exhibited maximum power conversion efficiency of 0.22% with ICBA as the acceptor molecule. Chapter 8 narrates the third order order nonlinear optical properties of bare and noble metal modified TiO2 thin films. Thin films were fabricatedby spray pyrolysis technique. Sol-Gel derived Ti[OCH(CH3)2]4 in CH3CH2OH/CH3COOH was used as the precursor for TiO2. The precursors used for Au, Ag and Pd were the aqueous solutions of HAuCl4, AgNO3 and Pd(NO3)2 respectively. The prepared films were characterized by XRD, SEM and EDX. The nonlinear optical properties of the prepared materials were investigated by Z-Scan technique comprising of Nd-YAG laser (532 nm,7 ns and10 Hz). The non-linear coefficients were obtained by fitting the experimental Z-Scan plot with the theoretical plots. Nonlinear absorption is a phenomenon defined as a nonlinear change (increase or decrease) in absorption with increasing of intensity. This can be mainly divided into two types: saturable absorption (SA) and reverse saturable absorption (RSA). Depending on the pump intensity and on the absorption cross- section at the excitation wavelength, most molecules show non- linear absorption. With increasing intensity, if the excited states show saturation owing to their long lifetimes, the transmission will show SA characteristics. Here absorption decreases with increase of intensity. If, however, the excited state has strong absorption compared with that of the ground state, the transmission will show RSA characteristics. Here in our work most of the materials show SA behavior and some materials exhibited RSA behavior. Both these properties purely depend on the nature of the materials and alignment of energy states within them. Both these SA and RSA have got immense applications in electronic devices. The important results obtained from various studies are presented in chapter 9.

Development, resistance and change. A point of view from Río Negro’s steppe

In this paper we search the concept of nonviolent resistance inquiring a rural experience from Rio Negro´s steppe. The initiative highlights the need to recognize  the context of the resistance exercise and the consideration of three aspects: the evaluation and interpretation of space, the dispute to public policy and the  restructuring of the family order. These three elements, which overlap material  and symbolic aspects, are discussed from an organization of trade domestic craft production. The notion of “development” is discovered on the basis of the  frameworks of values from which the reproduction of subordination is associated  with this idea, and even the challenge of change is the basis of the proposal which reviews that development idea, and illuminates from this complexity the notion  of “nonviolent resistance”.

Societies in change. Teacher's resource book.

Cumple con los requisitos del currículo nacional inglés para la etapa de 3 de secundaria (key stage 3). Este recurso proporciona al profesor distinto tipo de material didáctico sobre estrategias de enseñanza, organización del curso, formas de evaluación y, orientación sobre actividades y preguntas basadas en el libro del alumno. Este texto esta preparado para el Schools History Project creado en 1972 para mejorar el estudio de la historia entre estudiantes de trece a dieciséis años. Reconsidera las formas en que la historia contribuye a las necesidades educativas de los jóvenes, y por ello idea nuevos objetivos, nuevos criterios para la planificación y desarrollo del curso, así como de sus materiales de apoyo. Requiere nuevos criterios de evaluación y, por tanto nuevos exámenes y, adquirió mayor expansión con la introducción del General Certificate of Secondary Education (GCSE) en 1987.

Managing change in the urban environment : AS-A level resource pack : geography.

El objetivo de este recurso es ayudar en la enseñanza y en el aprendizaje de la geografía humana en los niveles AS y A, niveles que se cursan después de la etapa secundaria superior general. Consta de dieciocho temas, cada uno de los cuales comprende: unas notas para el profesor que establecen los fines y objetivos de cada lección, así como, las directrices y sugerencias sobre cómo organizar y presentarla y, también, distintas opciones y estrategias de enseñanza. Por su parte, las hojas informativas proporcionan definiciones y resúmenes de los términos clave y de las ideas y, facilitan, los datos pertinentes para la realización de los ejercicios de cada tema ó lección. En cuanto, a las hojas de trabajo consisten en una serie de ejercicios para los alumnos pues han sido diseñadas para desarrollar en ellos unas habilidades geográficas específicas.

Development and change : AS-A level resource pack : geography.

El objetivo de este recurso es ayudar en la enseñanza y en el aprendizaje de la geografía humana en los niveles AS y A, niveles que se cursan después de la etapa secundaria superior general. Consta de dieciocho temas, cada uno de los cuales comprende: unas notas para el profesor que establecen los fines y objetivos de cada lección, así como las directrices y sugerencias sobre cómo organizar y presentar cada tema y, también, distintas opciones y estrategias de enseñanza. Por su parte, las hojas informativas proporcionan definiciones y resúmenes de los términos clave y de las ideas y facilitan, además los datos pertinentes para la realización de los ejercicios de cada tema ó lección. En cuanto, a las hojas de trabajo consisten en una serie de ejercicios para los alumnos, pues han sido diseñadas para desarrollar en ellos unas habilidades geográficas específicas.

Rural change : AS-A level resource pack : geography.

Este recurso está orientado a ayudar a los estudiantes de los niveles de la etapa secundaria superior general, A y AS, a la comprensión profunda de los procesos geográficos que han dado forma al paisaje rural. Consta de veinte temas, cada uno de ellos organizado de la misma forma: notas orientativas para el profesor, con una introducción, unos objetivos y una planificación de la lección; también, incluye hojas con información detallada para explicar el tema en conjunto. Y, por último, las hojas de trabajo con ejercicios que alientan a los alumnos a pensar, preguntar y por tanto, a aprender, de forma activa, sobre los asuntos rurales.

Regional development and change : AS-A level resource pack.

Este recurso consta de dieciocho módulos y su objetivo es proporcionar un plan de enseñanza programado a los profesores de geografía de los niveles AS y A, niveles que se cursan después de la etapa secundaria superior general. Cada una de estas lecciones implica la realización de unas actividades que incluyen trabajo individual y en grupo, manejo de datos, comprensión, interpretación, análisis e informes, orales o escritos, para que los alumnos desarrollen unas habilidades concretas. Estos módulos están concebidos de forma independiente y siempre se presentan de la misma manera : con unas notas orientativas para el profesor y con hojas de ejercicios, que pueden fotocopiarse, con preguntas para los alumnos.

El pas del Paleolític Superior a Catalunya i la seva interpretació dins el context geogràfic franco-ibèric

S'ha analitzat el pas del paleolític mitjà al paleolític superior a Catalunya en base a l'estudi dels jaciments de la cova dels Ermitons (Sales de Llierca, Garrotxa) i de les coves del Reclau -Arbreda, Mollet i Reclau Viver-(Serinyà, Pla de l'Estany). En concret s'ha estudiat la cultura material i la fauna dels nivells mosterians tardans (paleolítc mitjà final) de les coves de l'Arbreda i dels Ermitons i dels aurinyacians (paleolític superior inicial) de les coves de l'Arbreda i de Mollet. Igualment s'han analitzat els territoris d'explotació de la cova dels Ermitons i de les coves del Reclau. D'aquesta anàlisi es desprén que els dos jaciments se situen en medis absolutament diferents. S'han analitzat els contextos geològics dels dos llocs, s'ha fet les descripció morfològica de cada un dels dos jaciments, així com l'estratigràfica i sedimentològica de cada cova. S'han datat els nivells mosterians i aurinyacians esmentats pel mètode del Carboni 14 AMS, així com també els aurinyacians de la cova del Reclau Viver. S'acompanyen aquestes dades amb les anàlisis paleoecològiques corresponents que s'han pogut efectuar: palinologia, antracologia, ictiologia, herpetologia, aus, quiròpters, insectívors i rosegadors. Es comparen les datacions obtingudes ambles d'altres jaciments i troballes catalans del mateix període: l'abric Romaní (Capellades, Anoia), la Roca dels Bous (Camarasa, la Noguera) i la mandíbula de Banyoles (Pla de l'Estany). Cim a conclusions s'estableixen les diferències a Catalunya entre el paleolític mitjà (cultura de l'home Neandertal) i el paleolític superior (cultura de l'home anatòmicament modern). En el segon apareix la tècnica de talla laminar, la indústria òssia ben elaborada, l'ornamentació, la decoració, es generalitza la importació del sílex com a matèria primera, es diversifica l'utillatge lític i hi ha una major utilització de les coves. S'interpreta aquest pas dins del context geogràfic franco-ibèric i es conclou que a Catalunya es caracteritza fonamentalment per dos fenòments: el reemplaçament abrupte i la contemporaneïtat. Aquesta abastaria entre 40.000 BP i el 33.000 BP segons cronologia radiocarbònica. Durant aquests temps la influència de la cultura del paleolític superior sobre la del paleolític mitjà seria escassa, encara que identificada per la presencia d'alguns útils de tipus paleolític superior en el tardomosterià de la cova dels Ermitons

Effect of ENSO phase on large-scale snow water equivalent distribution in a GCM

Understanding links between the El Nino-Southern Oscillation (ENSO) and snow would be useful for seasonal forecasting, but also for understanding natural variability and interpreting climate change predictions. Here, a 545-year run of the general circulation model HadCM3, with prescribed external forcings and fixed greenhouse gas concentrations, is used to explore the impact of ENSO on snow water equivalent (SWE) anomalies. In North America, positive ENSO events reduce the mean SWE and skew the distribution towards lower values, and vice versa during negative ENSO events. This is associated with a dipole SWE anomaly structure, with anomalies of opposite sign centered in western Canada and the central United States. In Eurasia, warm episodes lead to a more positively skewed distribution and the mean SWE is raised. Again, the opposite effect is seen during cold episodes. In Eurasia the largest anomalies are concentrated in the Himalayas. These correlations with February SWE distribution are seen to exist from the previous June-July-August (JJA) ENSO index onwards, and are weakly detected in 50-year subsections of the control run, but only a shifted North American response can be detected in the anaylsis of 40 years of ERA40 reanalysis data. The ENSO signal in SWE from the long run could still contribute to regional predictions although it would be a weak indicator only

Floodplain environmental change during the Younger Dryas and Holocene in Northwest Europe: Insights from the lower Kennet Valley, south central England

Many lowland rivers across northwest Europe exhibit broadly similar behavioural responses to glacial-interglacial transitions and landscape development. Difficulties exist in assessing these, largely because the evidence from many rivers remains limited and fragmentary. Here we address this issue in the context of the river Kennet, a tributary of the Thames, since c. 13,000 cal BP. Some similarities with other rivers are present, suggesting that regional climatic shifts are important controls. The Kennet differs from the regional pattern in a number of ways. The rate of response to sudden climatic change, particularly at the start of the Holocene and also mid-Holocene forest clearance, appears very high. This may reflect abrupt shifts between two catchment scale hydrological states arising from contemporary climates, land use change and geology. Stadial hydrology is dominated by nival regimes, with limited winter infiltration and high spring and summer runoff. Under an interglacial climate, infiltration is more significant. The probable absence of permafrost in the catchment means that a lag between the two states due to its gradual decay is unlikely. Palaeoecology, supported by radiocarbon dates, suggests that, at the very start of the Holocene, a dramatic episode of fine sediment deposition across most of the valley floor occurred, lasting 500-1000 years. A phase of peat accumulation followed as mineral sediment supply declined. A further shift led to tufa deposition, initially in small pools, then across the whole floodplain area, with the river flowing through channels cut in tufa and experiencing repeated avulsion. Major floods, leaving large gravel bars that still form positive relief features on the floodplain, followed mid-Holocene floodplain stability. Prehistoric deforestation is likely to be the cause of this flooding, inducing a major environmental shift with significantly increased surface runoff. Since the Bronze Age, predominantly fine sediments were deposited along the valley with apparently stable channels and vertical floodplain accretion associated with soil erosion and less catastrophic flooding. The Kennet demonstrates that, while a general pattern of river behaviour over time, within a region, may be identifiable, individual rivers are likely to diverge from this. Consequently, it is essential to understand catchment controls, particularly the relative significance of surface and subsurface hydrology. (c) 2005 Elsevier B.V. All rights reserved.

Abrupt climate change: ice sheets and oceans in action

Large temperature variations on land, in the air, and at the ocean surface, and highly variable flux of ice-rafted debris (IRD) delivered to the North Atlantic Ocean show that rapid climate fluctuations took place during the last glacial period. These quasi-periodic, high-amplitude climate variations followed a sequence of events recognized as a rapid warming, followed by a phase of gradual cooling, and terminating with more rapid cooling and increased flux of IRD to the north Atlantic Ocean. Each cycle lasted ˜1500 years, and was followed by an almost identical sequence. These cycles are referred to as Dansgaard/Oechger cycles (D/O cycles), and approximately every fourth cycle culminated in a more pronounced cooling with a massive discharge of IRD into the north Atlantic Ocean over an interval of ˜500 years. These massive discharges of IRD are known as Heinrich layers. “Heinrich events” are thus characterized as a rapid transfer of IRD from a “source,” the bed of the Laurentide Ice Sheet (LIS), to a “sink,” the North Atlantic.

Interactions between mass balance, atmospheric circulation, and recent climate change on the Djankuat Glacier, Caucasus Mountains, Russia

This paper reports recent changes in the mass balance record from the Djankuat Glacier, central greater Caucasus, Russia, and investigates possible relationships between the components of mass balance, local climate, and distant atmospheric forcing. The results clearly show that a strong warming signal has emerged in the central greater Caucasus, particularly since the 1993/1994 mass balance year, and this has led to a significant increase in the summer ablation of Djankuat. At the same time, there has been no compensating consistent increase in winter precipitation and accumulation leading to the strong net loss of mass and increase in glacier runoff. Interannual variability in ablation and accumulation is partly associated with certain major patterns of Northern Hemisphere climatic variability. The positive phase of the North Pacific (NP) teleconnection pattern forces negative geopotential height and temperature anomalies over the Caucasus in summer and results in reduced summer melt, such as in the early 1990s, when positive NP extremes resulted in a temporary decline in ablation rates. The positive phase of the NP is related to El Nino-Southern Oscillation, and it is possible that a teleconnection between the tropical Pacific sea surface temperatures and summer air temperatures in the Caucasus is bridged through the NP pattern. More recently, the NP pattern was predominantly negative, and this distant moderating forcing on summer ablation in the Caucasus was absent. Statistically significant correlations are observed between accumulation and the Scandinavian (SCA) teleconnection pattern. The frequent occurrence of the positive SCA phase at the beginning of accumulation season results in lower than average snowfall and reduced accumulation. The relationship between the North Atlantic Oscillation (NAO), Arctic Oscillation, and accumulation is weak, although positive precipitation anomalies in the winter months are associated with the negative phase of the NAO. A stronger positive correlation is observed between accumulation on Djankuat and geopotential height over the Bay of Biscay unrelated to the established modes of the Northern Hemisphere climatic variability. These results imply that the mass balance of Djankuat is sensitive to the natural variability in the climate system. Distant forcing, however, explains only 16% of the variance in the ablation record and cannot fully explain the recent increase in ablation and negative mass balance.

Top-down solar modulation of climate: evidence for centennial-scale change

During the descent into the recent ‘exceptionally’ low solar minimum, observations have revealed a larger change in solar UV emissions than seen at the same phase of previous solar cycles. This is particularly true at wavelengths responsible for stratospheric ozone production and heating. This implies that ‘top-down’ solar modulation could be a larger factor in long-term tropospheric change than previously believed, many climate models allowing only for the ‘bottom-up’ effect of the less-variable visible and infrared solar emissions. We present evidence for long-term drift in solar UV irradiance, which is not found in its commonly used proxies. In addition, we find that both stratospheric and tropospheric winds and temperatures show stronger regional variations with those solar indices that do show long-term trends. A top-down climate effect that shows long-term drift (and may also be out of phase with the bottom-up solar forcing) would change the spatial response patterns and would mean that climate-chemistry models that have sufficient resolution in the stratosphere would become very important for making accurate regional/seasonal climate predictions. Our results also provide a potential explanation of persistent palaeoclimate results showing solar influence on regional or local climate indicators.

Pollen ultrastructure in anther cultures of Datura innoxia. I. Division of the presumptive vegetative cell.

Ultrastructural features of embryogenic pollen in Datura innoxia are described, just prior to, during, and after completion of the first division of the presumptive vegetative cell. In anther cultures initiated towards the end of the microspore phase and incubated at 28 degrees C in darkness, the spores divide within 24 h and show features consistent with those of dividing spores in vivo. Cytokinesis is also normal in most of the spores and the gametophytic cell-plate curves round the presumptive generative nucleus in the usual highly ordered way. Further differentiation of the 2 gametophytic cells does not take place and the pollen either switches to embryogenesis or degenerates. After 48-72 h, the remaining viable pollen shows the vegetative cell in division. The cell, which has a large vacuole and thin layer of parietal cytoplasm carried over from the microspore, divides consistently in a plane parallel to the microspore division. The dividing wall follows a less-ordered course than the gametophytic wall and usually traverses the vacuole, small portions of which are incorporated into the daughter cell adjacent to the generative cell. The only structural changes in the vegetative cell associated with the change in programme appear to be an increase in electron density of both plastids and mitochondria and deposition of an electron-dense material (possibly lipid) on the tonoplast. The generative cell is attached to the intine when the vegetative cell divides. Ribosomal density increases in the generative cell and exceeds that in the vegetative cell. A thin electron-dense layer also appears in the generative-cell wall. It is concluded that embryogenesis commences as soon as the 2 gametophytic cells are laid down. Gene activity associated with postmitotic synthesis of RNA and protein in the vegetative cell is switched off. The data are discussed in relation to the first division of the embryogenic vegetative cells in Nicotiana tabacum.