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This work uses numerical simulations of a thulium-doped optical fiber amplifier to predict various performance characteristics such as peak temperatures, expected output powers and efficiencies, presence of amplified spontaneous emission (ASE), and transverse mode instability (TMI) onset power thresholds. Single- and two-tone configurations are studied. In the latter case, the two laser sources are separated in frequency by the amount that corresponds to the peak Raman gain, and a few seed ratios at various total seed powers are examined. The goal is to provide the field with pertinent information on what is feasible for this type of amplifier.
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We describe the synthesis, crystal structure and lithium deinsertion-insertion electrochemistry of two new lithium-rich layered oxides, Li3MRuO5 (M = Mn, Fe), related to rock salt based Li2MnO3 and LiCoO2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m) where Li and (Li0.2Mn0.4Ru0.4) layers alternate along the c-axis, while the Li3FeRuO5 oxide adopts a near-perfect LiCoO2 (R3[combining macron]m) structure where Li and (Li0.2Fe0.4Ru0.4) layers are stacked alternately. Magnetic measurements indicate for Li3MnRuO5 the presence of Mn(3+) and low spin configuration for Ru(4+) where the itinerant electrons occupy a π*-band. The onset of a net maximum in the χ vs. T plot at 9.5 K and the negative value of the Weiss constant (θ) of -31.4 K indicate the presence of antiferromagnetic superexchange interactions according to different pathways. Lithium electrochemistry shows a similar behaviour for both oxides and related to the typical behaviour of Li-rich layered oxides where participation of oxide ions in the electrochemical processes is usually found. A long first charge process with capacities of 240 mA h g(-1) (2.3 Li per f.u.) and 144 mA h g(-1) (1.38 Li per f.u.) is observed for Li3MnRuO5 and Li3FeRuO5, respectively. An initial sloping region (OCV to ca. 4.1 V) is followed by a long plateau (ca. 4.3 V). Further discharge-charge cycling points to partial reversibility (ca. 160 mA h g(-1) and 45 mA h g(-1) for Mn and Fe, respectively). Nevertheless, just after a few cycles, cell failure is observed. X-ray photoelectron spectroscopy (XPS) characterisation of both pristine and electrochemically oxidized Li3MRuO5 reveals that in the Li3MnRuO5 oxide, Mn(3+) and Ru(4+) are partially oxidized to Mn(4+) and Ru(5+) in the sloping region at low voltage, while in the long plateau, O(2-) is also oxidized. Oxygen release likely occurs which may be the cause for failure of cells upon cycling. Interestingly, some other Li-rich layered oxides have been reported to cycle acceptably even with the participation of the O(2-) ligand in the reversible redox processes. In the Li3FeRuO5 oxide, the oxidation process appears to affect only Ru (4+ to 5+ in the sloping region) and O(2-) (plateau) while Fe seems to retain its 3+ state.
Assuntos
Ferro/química , Lítio/química , Manganês/química , Oxigênio/química , Compostos de Rutênio/química , Técnicas Eletroquímicas , Íons/química , Magnetismo , Oxirredução , Óxidos/química , Espectroscopia FotoeletrônicaRESUMO
Extensive molecular dynamics studies of 13 different silica polymorphs are reported in the isothermal-isobaric ensemble with the Parrinello-Rahman variable shape simulation cell. The van Beest-Kramer-van Santen (BKS) potential is shown to predict lattice parameters for most phases within 2%-3% accuracy, as well as the relative stabilities of different polymorphs in agreement with experiment. Enthalpies of high-density polymorphs - CaCl2-type, α-PbO2-type, and pyrite-type - for which no experimental data are available as yet, are predicted here. Further, the calculated enthalpies exhibit two distinct regimes as a function of molar volume-for low and medium-density polymorphs, it is almost independent of volume, while for high-pressure phases a steep dependence is seen. A detailed analysis indicates that the increased short-range contributions to enthalpy in the high-density phases arise not only from an increased coordination number of silicon but also shorter Si-O bond lengths. Our results indicate that amorphous phases of silica exhibit better optimization of short-range interactions than crystalline phases at the same density while the magnitude of Coulombic contributions is lower in the amorphous phase.
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We describe the synthesis, crystal structures, and optical absorption spectra of transition metal-substituted spiroffite derivatives, Zn(2-x)M(x)Te3O8 (M(II) = Co, Ni, Cu; 0 < x ≤ 1.0). The oxides are readily synthesized by solid state reaction of stoichiometric mixtures of the constituent binaries at 620 °C. Reitveld refinement of the crystal structures from powder X-ray diffraction (XRD) data shows that the Zn/MO6 octahedra are strongly distorted, as in the parent Zn2Te3O8 structure, consisting of five relatively short Zn/M(II)-O bonds (1.898-2.236 Å) and one longer Zn/M(II)-O bond (2.356-2.519 Å). We have interpreted the unique colors and the optical absorption/diffuse reflectance spectra of Zn(2-x)M(x)Te3O8 in the visible, in terms of the observed/irregular coordination geometry of the Zn/M(II)-O chromophores. We could not however prepare the fully substituted M2Te3O8 (M(II) = Co, Ni, Cu) by the direct solid state reaction method. Density Functional Theory (DFT) modeling of the electronic structure of both the parent and the transition metal substituted derivatives provides new insights into the bonding and the role of transition metals toward the origin of color in these materials. We believe that transition metal substituted spiroffites Zn(2-x)M(x)Te3O8 reported here suggest new directions for the development of colored inorganic materials/pigments featuring irregular/distorted oxygen coordination polyhedra around transition metal ions.
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We introduce two new lowest order methods, a mixed method, and a hybrid discontinuous Galerkin method, for the approximation of incompressible flows. Both methods use divergence-conforming linear Brezzi-Douglas-Marini space for approximating the velocity and the lowest order Raviart-Thomas space for approximating the vorticity. Our methods are based on the physically correct viscous stress tensor of the fluid, involving the symmetric gradient of velocity (rather than the gradient), provide exactly divergence-free discrete velocity solutions, and optimal error estimates that are also pressure robust. We explain how the methods are constructed using the minimal number of coupling degrees of freedom per facet. The stability analysis of both methods are based on a Korn-like inequality for vector finite elements with continuous normal component. Numerical examples illustrate the theoretical findings and offer comparisons of condition numbers between the two new methods.
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A remarkable hardening (~30 cm(-1)) of the normal mode of vibration associated with the symmetric stretching of the oxygen octahedra for the Ba(2)FeReO(6) and Sr(2)CrReO(6) double perovskites is observed below the corresponding magnetic ordering temperatures. The very large magnitude of this effect and its absence for the antisymmetric stretching mode provide evidence against a conventional spin-phonon coupling mechanism. Our observations are consistent with a collective excitation formed by the combination of the vibrational mode with oscillations of Fe or Cr 3d and Re 5d occupations and spin magnitudes.
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New phases of the type La2-xAx(l+)CUO4-y have been prepared where A(l+) is sodium or potassium. The sodium phases are superconducting for x values from 0.2 to 0.5 at temperatures up to about 40 K. In addition, there are unusual magnetic properties below about 10 K that may be indicative of spin glass behavior. Phases of the type La2-xKxCuO4-y could only be prepared with x values up to about 0.1, and these phases are not superconducting above 4.2 K.
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New high-temperature superconductors based on oxides of thallium and copper, but not containing barium, have been prepared. A transition temperature (T(c)) of about 85 K is found for (Tl(0.5)Pb(0.5)) Sr(2)CaCu(2)O(7) whereas (Tl(0.5)Pb(0.5))Sr(2)Ca(2)Cu(3)O(9) has a T(c) of about 120 K. Both materials possess tetragonal symmetry with a = 3.80 A, c = 12.05 A for (Tl(0.5)Pb(0.5))Sr(2)CaCu(2)O(7), and a = 3.81 A, c = 15.23 A for (Tl(0.5)Pb(0.5))Sr(2)Ca(2)Cu(3)O(9). A structure refinement of the latter phase has been carried out with single-crystal x-ray diffraction data.
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A new superconductor that displays onset behavior near 120 K has been identified as Bi(2)Sr(3-x)Ca(x)Cu(2)O(8+y), with x ranging from about 0.4 to 0.9. Single crystal x-ray diffraction data were used to determine a pseudo-tetragonal structure based on an A-centered orthorhombic subcell with a = 5.399 A, b= 5.414A, and c = 30.904 A. The structure contains copper-oxygen sheets as in La(2)CuO(4) and YBa(2)Cu(3)O(7), but the copper-oxygen chains present in YBa(2)Cu(3)O(7) do not occur in Bi(2)Sr(3-x)Ca(x)Cu(2)O(8+y). The structure is made up of alternating double copper-oxygen sheets and double bismuth-oxygen sheets. There are Ca(2+) and Sr(2+) cations between the adjacent Cu-O sheets; Sr(2+) cations are also found between the Cu-O and Bi-O sheets. Electron microscopy studies show an incommensurate superstructure along the a axis that can be approximated by an increase of a factor of 5 over the subcell dimension. This superstructure is also observed by x-ray diffraction on single crystals, but twinning can make it appear that the superstructure is along both a and b axes. Flux exclusion begins in our samples at about 116 K and is very strong by 95 K. Electrical measurements on a single crystal of Bi(2)Sr(3-x)Ca(x)Cu(2)O(8+y) show a resistivity drop at about 116 K and apparent zero resistivity at 91 K.
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There is now a new series of high-temperature superconductors that may be represented as (A(III)O)(2)A(2)(II)Can-1CunO2+2n where A(III) is Bi or Tl, A(II) is Ba or Sr, and n is the number of Cu-O sheets stacked consecutively. There is a general trend toward higher transition temperatures as n increases. The highest n value for a bulk phase is three and is found when A(III) is Tl. This compound, Tl(2)Ba(2)Ca(2)Cu(3)O(10), has the highest transition temperature( approximately 125 K) of any presently known bulk superconductor. The structure of Tl(2)Ba(2)Ca(2)Cu(3)O(10) has been determined from single-crystal x-ray diffraction data and is tetragonal, with a = 3.85 A and c = 35.9 A. No superstructure is observed, and the material is essentially twin-free. Electron microscopy in the Tl/Ba/Ca/Cu/O system has revealed intergrowths where n = 5; such regions may well be responsible for the superconducting onset behavior observed in this system at about 140 K.
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Fluorite-type Ce0.5Zr0.5O2 and Ce0.5Hf0.5O2 have been synthesized by a solution combustion route, and their oxygen release and reduction have been investigated up to 850 degrees C. On reduction, the zirconium system forms two pyrochlore phases, Ce2Zr2O7 (pyrochlore-I) and Ce2Zr2O6.2 (pyrochlore-II), while the hafnium system forms only a disordered fluorite phase with the composition Ce0.5Hf0.5O1.77, under the same experimental conditions. The crystal structures of the reduction products have been characterized by powder X-ray diffraction and Rietveld refinement, and their electronic structures have been investigated by photoelectron spectroscopy and electrical conductivity measurements. Pyrochlore-I (a = 10.6727(4) A) is a semiconductor, while pyrochlore-II (a = 10.6463(8) A) is a good conductor (with a nearly temperature independent resistivity of approximately 2.5 ohm.cm in the 400-1000 K range). X-ray photoelectron spectroscopy (XPS) shows an admixture of Ce(5d,6s) with Zr(4d) and O(2p) and a significant density of states near EF in the highly reduced pyrochlore-II phase. The changes have been rationalized in terms of a qualitative energy band scheme that brings out the special role of zirconium vis-à-vis hafnium in the reduction/oxygen release properties of Ce0.5Zr0.5O2 and Ce0.5Hf0.5O2.
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We describe the synthesis, crystal structures, and optical absorption spectra/colors of 3d-transition-metal-substituted α-LiZnBO3 derivatives: α-LiZn1-x MIIx BO3 (MII =CoII (0
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We report composition dependent structure evolution from SrTiO3 to SrFe0.5Ta0.5O3 by powder X-ray and neutron diffraction studies of SrTi1-2xFexTaxO3 (0.00 ≤ × ≤ 0.50) compositions. Structural studies reveal cubic (Pm3m) perovskite-type structure of the parent SrTiO3 for x up to 0.075 and cation disordered orthorhombic (Pbnm) perovskite-type structure for x ≥ 0.33. A biphasic region consisting of a mixture of cubic and orthorhombic structures is found in the range for 0.10 ≤ × ≤ 0.25. Dielectric studies reveal transformation from a normal dielectric to relaxor like properties with increasing Fe(3+) and Ta(5+) concentration. Dielectric response is maximum at x = 0.33 in the series. The results establish a protocol for designing new lead-free relaxor materials based on the co-substitution of Fe(3+) and Ta(5+) for Ti(4+) in SrTiO3. A complex interplay of strain effects arising from distribution of cations at the octahedral sites of the perovskite structure controls the dielectric properties.
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We describe the synthesis and structural characterization of new layered bismuth titanates, A[Bi(3)Ti(4)O(13)] and A[Bi(3)PbTi(5)O(16)] for A = K, Cs, corresponding to n = 4 and 5 members of the Dion-Jacobson series of layered perovskites of the general formula, A[A'(n)()(-)(1)B(n)()O(3)(n)()(+1)]. These materials have been prepared by solid state reaction of the constituents containing excess alkali, which is required to suppress the formation of competitive Aurivillius phases. Unlike the isostructural niobates and niobium titanates of the same series, the new phases reported here are spontaneously hydrated-a feature which could make them potentially useful as photocatalysts for water splitting reaction. On hydration of the potassium compounds, the c axis expands by ca. 2 Å and loses its doubling [for example, the tetragonal lattice parameters of K[Bi(3)Ti(4)O(13)] and its dihydrate are respectively a = 3.900(1) Å, c = 37.57(2) Å; a = 3.885(1) Å, c = 20.82(4) Å]; surprisingly, the cesium analogues do not show a similar change on hydration.
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Utilization of synthetic carnosine as a food additive is limited by both regulatory and economic hurdles. Therefore, the potential of producing carnosine-containing antioxidant extracts from an underutilized skeletal muscle source, mechanically separated pork (MSP), was investigated. Carnosine-containing MSP extracts were capable of inhibiting lipid oxidation both in vitro and in salted ground pork. Heating (60-80°C) the MSP extract removed iron and increased in vitro antioxidant activity. Isolation of a low molecular weight fraction of the MSP extract by ultrafiltration was effective at decreasing iron but did not substantially increase in vitro antioxidant activity. Freeze dried extracts (untreated, 80°C, ultrafiltration permeate) were capable of inhibiting both TBARS and lipid peroxide formation in ground, salted pork stored at -15°C. While MSP extracts were capable of inhibiting lipid oxidation both in vitro and in salted, ground pork, their antioxidant activity was low suggesting that their use as a food additive would be impractical.
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Classical anti-mitotic drugs have failed to translate their preclinical efficacy into clinical response in human trials. Their clinical failure has challenged the notion that tumor cells divide frequently at rates comparable to those of cancer cells in vitro and in xenograft models. Given the preponderance of interphase cells in clinical tumors, we asked whether targeting amplified centrosomes, which cancer cells carefully preserve in a tightly clustered conformation throughout interphase, presents a superior chemotherapeutic strategy that sabotages interphase-specific cellular activities, such as migration. Herein we have utilized supercentrosomal N1E-115 murine neuroblastoma cells as a test-bed to study interphase centrosome declustering induced by putative declustering agents, such as Reduced-9-bromonoscapine (RedBr-Nos), Griseofulvin and PJ-34. We found tight 'supercentrosomal' clusters in the interphase and mitosis of ~80% of patients' tumor cells with excess centrosomes. RedBr-Nos was the strongest declustering agent with a declustering index of 0.36 and completely dispersed interphase centrosome clusters in N1E-115 cells. Interphase centrosome declustering caused inhibition of neurite formation, impairment of cell polarization and Golgi organization, disrupted cellular protrusions and focal adhesion contacts-factors that are crucial prerequisites for directional migration. Thus our data illustrate an interphase-specific potential anti-migratory role of centrosome-declustering agents in addition to their previously acknowledged ability to induce spindle multipolarity and mitotic catastrophe. Centrosome-declustering agents counter centrosome clustering to inhibit directional cell migration in interphase cells and set up multipolar mitotic catastrophe, suggesting that disbanding the nuclear-centrosome-Golgi axis is a potential anti-metastasis strategy.