On the role of acoustic plasmons in high Tc superconductors

The role of acoustic plasmons in the recently discovered high Tc superconductors is discussed. It is shown that the exchange of acoustic plasmons together with the usual phonon exchange between electrons can give rise to a Tc - 100 K.

Measurement of laser ablation threshold on doped BiSrCaCuO high temperature superconductors by the pulsed photothermal deflection technique

Laser‐induced damage and ablation thresholds of bulk superconducting samples of Bi2(SrCa)xCu3Oy(x=2, 2.2, 2.6, 2.8, 3) and Bi1.6 (Pb)xSr2Ca2Cu3 Oy (x=0, 0.1, 0.2, 0.3, 0.4) for irradiation with a 1.06 μm beam from a Nd‐YAG laser have been determined as a function of x by the pulsed photothermal deflection technique. The threshold values of power density for ablation as well as damage are found to increase with increasing values of x in both systems while in the Pb‐doped system the threshold values decrease above a specific value of x, coinciding with the point at which the Tc also begins to fall.  

The role of hierarchical morphologies in the superior gas sensing performance of CuO-based chemiresistors

The development of gas sensors with innovative designs and advanced functional materials has attracted considerable scientific interest given their potential for addressing important technological challenges. This work presents new insight towards the development of high-performance p-type semiconductor gas sensors. Gas sensor test devices, based on copper (II) oxide (CuO) with innovative and unique designs (urchin-like, fiber-like, and nanorods), are prepared by a microwave-assisted synthesis method. The crystalline composition, surface area, porosity, and morphological characteristics are studied by X-ray powder diffraction, nitrogen adsorption isotherms, field-emission scanning electron microscopy and high-resolution transmission electron microscopy. Gas sensor measurements, performed simultaneously on multiple samples, show that morphology can have a substantial influence on gas sensor performance. An assembly of urchin-like structures is found to be most effective for hydrogen detection in the range of parts-per-million at 200 °C with 300-fold larger response than the previously best reported values for semiconducting CuO hydrogen gas sensors. These results show that morphology plays an important role in the gas sensing performance of CuO and can be effectively applied in the further development of gas sensors based on p-type semiconductors. High-performance gas sensors based on CuO hierarchical morphologies with in situ gas sensor comparison are reported. Urchin-like morphologies with high hydrogen sensitivity and selectivity that show chemical and thermal stability and low temperature operation are analyzed. The role of morphological influences in p-type gas sensor materials is discussed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxygen mobility in Bi:Sr:Ca:Cu:O ceramic measured using anelastic relaxation methods

Since the discovery of YBaCuO, experiments have shown that its superconducting properties are strongly affected by the oxygen content. More recently, anelastic relaxation measurements in La2CuO4+δ, showed that the decrease in the oxygen content can be related to two events. One is the decrease in mobility between two adjacent CuO planes, and the other is the increase in the number of tilting patterns of the CuO6 octahedra. In the case of the bismuth-based ceramic, it is known that the oxygen content, within some limits, does not affect its superconducting properties. In order to evaluate the mobility and the effect of the oxygen content on this material we have prepared BSCCO ceramic and tested regarding its internal friction and electrical resistivity as a function of the temperature while the oxygen content was being reduced by a sequence of vacuum annelaing at 620 K. The samples were prepared in the Bi:Sr:Ca:Cu = 2212 and 2223 proportion, using powder obtained by the sol-gel route and conventional solid state reaction. The anelastic relaxation measurements were performed using a torsion pendulum operating with frequency about 15-35 Hz between 77 to 700 K. The diffraction pattern of the as sintered and the vacuum annealed material were also presented. The results have shown complex anelastic relaxation structures that were associated to the jump of interstitial oxygen atoms between two adjacent CuO planes. The vacuum annealing showed to be deleterious to the critical temperature of the superconducting ceramic.

Synthesis and properties of substituted Hg-based superconductors

This thesis is focused on studies of substituted Hg-based superconducting copper oxides ((Hg1-xMx)Ba2Can-1CunO2n+2+δ). These compounds are promising objects of investigation, not only from a fundamental point of view but also because of their high values of superconducting transition temperature (Tc) and irreversibility field (Hirr). The first part of the thesis is devoted to optimization of the synthesis procedure for Hg-based cuprates. The influence of different parameters (T, t, p(Hg), p(O2)) on the synthesis of these compounds in sealed silica tubes was studied. Optimal conditions yielded samples containing up to 95% of HgBa2Ca2Cu3O8+δ (Hg-1223). The formation of solid solutions with the formula (Hg1-xCux)Ba2Ca2Cu3O8+δ (where x <= 0.5) was also established. Another technique was developed, using LiF as a flux, for synthesis of samples containing up to 90% of the HgBa2CaCu2O6+δ (Hg-1212) phase. The second part concerns synthesis and studies of oxyfluorides using Hg-1212 and Hg-1223 as starting materials together with XeF2 as a fluorinating agent. It was found that oxyfluorides of both phases have a parabolic dependence of Tc vs. a parameter as well as enhanced Tc values (ΔT ≈ 3-4 K) in comparison with optimally doped non-fluorinated analogues. The crystal structure of Hg-1223 oxyfluoride was studied by X-ray powder and neutron diffraction methods. It is suggested that chemical modification of the crystal structure leads to a decrease in Cu-O distance without noticeable change in Cu-O-Cu angle (in the (CuO2) layers), which may be the significant factors influencing this Tc increase. Hg-1223 oxyfluoride was also studied under high pressure for first time. It was found that this compound has a record-high Tc value (≈ 166 K) at P ≈ 23 GPa. The last part describes the investigation of substituted Hg-based superconductors in the series (Hg0.9M0.1)Ba2CuO4+δ {(Hg,M)-1201}, where M = Tl, Pb, W, Mo, Nb and V. A comprehensive study of these compounds by various methods (X-ray powder diffraction, EDX, IR-, EXAFS- and XANES -spectroscopy) indicated that the change of charge carrier doping level is a crucial factor determining the irreversibility line. (Hg0.9Mo0.1)Ba2CuO4+δ showed the most improved irreversibility line position among the (Hg,M)-1201 compounds studied in this series.

The polymerization of lactic acid anhydrosulphite by anionic initiators

This thesis is primarily concerned with the synthesis and polymerization of 5-methyl-1;3, 2-dioxathiolan-4-one-2-oxide (lactic acid anhydrosulphite (LAAS)) using anionic initiators under various conditions. Poly(lactic acid) is a biodegradable polymer which finds many uses in biomedical applications such as drug-delivery and wound-support systems. For such applications it is desirable to produce polymers having predictable molecular weight distributions and crystallinity, The use of anionic initiators offers a potential route to the creation of living polymers. The synthesis of LAAS was achieved by means of an established route though the procedure was modified to some extent and a new method of purification of the monomer using copper oxides was introduced, Chromatographic purification methods were also examined but found to be ineffective. An unusual impurity was discovered in some syntheses and this was identified by means of 1H and 13C NMR, elemental analysis and GC-MS. Since poly-α-esters having hydroxyl-bearing substituents might be expected to have high equilibrium water contents and hence low surface tension characteristics which might aid bio-compatibility, synthesis of gluconic acid anhydrosulphite was also attempted and the product characterised by 1H and 13C NMR. The kinetics of the decomposition of lactic acid anhydrosulphite by lithium tert-butoxide in nitrobenzene has been examined by means of gas evolution measurements. The kinetics of the reaction with potassium tert-butoxide (and also sec-butyl lithium) in tetrahydrofuran has been studied using calorimetric techniques. LAAS was block co-polymerized with styrene and also with 1,3-butadiene in tetrahydrofuran (in the latter case a statistical co-polymer was also produced).

Major element oxides, trace element content and isotopic ratios of dolerites from the Schirmacher Oasis

New results on the petrochemistry and geochemistry of dolerites from the Schirmacher Oasis shed light on the development of the Karoo-Maud plume in Antarctica. The basalts and dolerites are petrologically identical to the rocks of western Dronning Maud Land (DML), which were previously studied and interpreted as a manifestation of the Karoo-Maud plume in Antarctica. The spatial distribution of the dikes suggests eastward spreading of the plume material, up to the Schirmacher Oasis for at least 10 Ma. The geochemical characteristics of magmas from the Schirmacher Oasis reflect the influence of crustal contamination, which accompanied both the ascent and spreading of the plume. The magmas of the initial stage of plume activity (western DML) appeared to be the most contaminated in crustal components. It was found that the geochemical characteristics of Mesozoic magmas from the Schirmacher Oasis are identical to those of enriched tholeiites from the Afanasy Nikitin Rise and the central Kerguelen Plateau (Hole 749), which indicates that their enrichment was related to the ancient material of the Gondwana continent. This was caused by the opening of the Indian Ocean under the influence of the Karoo-Maud plume. This process was peculiar in that it occurred in the presence of nonspreading blocks of varying thickness, for instance, Elan Bank in the central Kerguelen Plateau, and was accompanied by the formation of intraplate volcanic rises, which are documented in the seafloor relief of basins around Antarctica. The geochemical characteristics of igneous rocks from the resulting rises (Afanasy Nikitin, Kerguelen, Naturaliste, and Ninetyeast Ridge) indicate the influence of processes related to crustal assimilation. The magmatism that occurred 40 Ma after the main phase of the Karoo-Maud volcanism at the margins of the adjacent continents of Australia (Bunbury basalts) and India (Rajmahal trapps) could be generated by the Karoo-Maud plume flowing along the developing spreading zone. The plume moved subsequently and was localized at the Kerguelen Plateau, where it occurs at present as an active hotspot.

Mineral content, major oxides and trace elements concentrations in clay from different IODP Holes of 331-C0013, 331-C0017, East China sea shelf and different Taiwan rivers

The Okinawa Trough (OT) in the East Asian continental margin is characterized by thick terrigenous sediment and ubiquitous volcanic-hydrothermal activities. In this study, the clays collected during IODP Expedition 331 to the middle OT (Iheya North Knoll) were analyzed for mineralogical and geochemical compositions. By comparing with the clays from the East China Sea shelf and surrounding rivers, we examine different clay origins. The hydrothermal field in the mid-OT is dominated by Mg-rich chlorite, while the recharge zone has clay mineral assemblages similar to the shelf and rivers, showing high content of illite, subordinate chlorite and kaolinite and scarce smectite. Compared to the terrigenous clays, the hydrothermal clays in the OT have high concentrations of Mg, Mn and Zr but low Fe, Na, K, Ca, Ba, Sr, P, Sc and Ti, while the hydrothermal clays in the mid-ocean ridge are relatively enriched in Fe and V and depleted in Al, Mg, Zr, Sc and Ti. Different fractionation patterns of rare earth elements also register in the terrigenous and hydrothermal clays, diagnostic of variable clay origins. We infer that the OT hydrothermal clay was primarily formed by the chemical alteration of detrital sediments subject to the hydrothermal fluids. The remarkably different compositions of hydrothermal clays between the sediment-rich back arc basin like OT and the sediment-starved ocean ridge suggest different physical and chemical processes of hydrothermal fluids and fluid-rock/sediment reactions under various geologic settings.

Mineral composition, major element oxides and trace element concentration of sediments from ODP Leg 180 sites

Middle Miocene to Holocene fine-grained argillaceous sediments (clays, claystones/muds, and mudstones), which volumetrically dominated the sediment recovery in the Woodlark Basin during Leg 180, were chemically analyzed for major elements, trace elements, and some rare earth elements by X-ray fluorescence. Selected samples also underwent X-ray diffraction (XRD) analysis for mineral determination. The results shed light on sediment provenance when combined with shipboard sediment descriptions, smear slide study, and XRD. The oldest sediments recovered (Site 1108) of middle-late Miocene age include volcanogenic muds with distinctive high MgO and K2O, indicative of a relatively basic calc-alkaline source related to an inferred Miocene forearc succession. The forearc basement, composed of diabase and basalt, was locally exposed (Site 1109) and eroded in the late Miocene (<5.4-9.93 Ma), giving rise to fluvial conglomerates (Sites 1109, 1115, and 1118). Chemically distinctive fine-grained claystones and siltstones (with relatively high Ti, low K) are compatible with derivation from tropically weathered basic igneous rocks, correlated with the Paleogene Papuan ophiolite. Overlying latest Miocene-Pleistocene fine-grained sediments throughout the Woodlark Basin were partly derived from calc-alkaline volcanic sources. However, relatively high abundances of Al2O3 and related element oxides (K2O and Na2O) and trace elements (e.g., Rb and Y) reflect an additional terrigenous input throughout the basin, correlated with pelitic metamorphic rocks exposed on Papua New Guinea and adjacent areas. In addition, sporadic high abundances of Cr and Ni, some other trace metals, and related minerals (talc, crysotile, and chlorite) reflect input from an ophiolitic terrain dominated by ultramafic rocks, correlated with the Paleogene Papuan ophiolite. The source areas possibly included serpentinized ultramafic ophiolitic rocks exposed in the Papua New Guinea interior highlands. Chemical evidence further indicates that fine-grained terrigenous sediment reached the Woodlark Basin throughout its entire late Miocene-Holocene history. Distinctive high-K volcanogenic muds rich in tephra and volcanic ash layers that appear at <2.3 Ma (Sites 1109 and 1115) are indicative of high-K calc-alkaline volcanic centers, possibly located in the Dawson Strait, Moresby Strait, or Dobu Seamount area. Chemical diagenesis of fine-grained sediments within the Woodlark Basin is reflected in clay neomorphism and localized formation of minerals including dolomite, ankerite, and zeolite but has had little effect on the bulk chemical composition of most samples.