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Replacing lithium ions with sodium ions as the charge carriers in rechargeable batteries can induce noticeable differences in the electrochemical storage mechanisms of electrode materials. Many material parameters, such as particle size, morphology, and the presence of defects, are known to further affect the storage mechanism. Here, we report an investigation of how the introduction of titanium vacancies into anatase TiO2 affects the sodium storage mechanism. From pair distribution function analysis, we observe that sodium ions are inserted into titanium vacancies at the early stage of the discharge process. This is supported by density functional theory calculations, which predict that sodium insertion is more favourable at vacancies than at interstitial sites. Our calculations also show that the intercalation voltage is sensitive to the anion coordination environment of the vacancy. Sodiation to higher concentrations induces a phase transition toward a disordered rhombohedral structure, similar to that observed in defect-free TiO2. Finally, we find that the X-ray diffraction pattern of the rhombohedral phase drastically changes depending on the composition and degree of disorder, providing further comprehension on the sodium storage mechanism of anatase.

The single crystal study of CaBaCo4O7, a non collinear ferrimagnet (TC=64K), with a polar orthorhombic space group (Pbn21) between 4 K and 293 K, shows the appearance below TC of a large electric polarization along its c axis, reaching 17mC.m-2 at 10K. At 62.5K, a magnetic field driven giant variation of polarization, P(9T)-P(0T)=8mC.m-2, is observed. Moreover, the present magnetoelectric measurements, are fully consistent with the m'm2' magnetic point group, strongly supporting that this oxide is also ferrotoroidic. This ferrimagnetic oxide, which belongs to the '114' structural family, opens an avenue for the search of new magnetoelectrics., Comment: 6 figures

The comparative study of the substitution of zinc and lithium for iron in the "114" ferrites, YBaFe4O7 and CaBaFe4O7, shows that these diamagnetic cations play a major role in tuning the competition between ferrimagnetism and magnetic frustration in these oxides. The substitution of Li or Zn for Fe in the cubic phase YBaFe4O7 leads to a structural transition to a hexagonal phase YBaFe4-xMxO7, for M = Li (0.30 < x < 0.75) and for M = Zn (0.40 < x < 1.50). It is seen that for low doping values i.e. x = 0.30 (for Li) and x = 0.40 (for Zn), these diamagnetic cations induce a strong ferrimagnetic component in the samples, in contrast to the spin glass behaviour of the cubic phase. In all the hexagonal phases, YBaFe4-xMxO7 and CaBaFe4-xMxO7 with M = Li and Zn, it is seen that in the low doping regime (x ~ 0.3 to 0.5), the competition between ferrimagnetism and 2 D magnetic frustration is dominated by the average valency of iron. In contrast, in the high doping regime (x ~ 1.5), the emergence of a spin glass is controlled by the high degree of cationic disorder, irrespective of the iron valency., Comment: 2 tables, 7 figures

The study of the ferrites YBaFe4-xGaxO7 shows that the substitution of Ga for Fe in YBaFe4O7 stabilizes the hexagonal symmetry for 0.40 < x < 0.70, at the expense of the cubic one. Using combined measurements of a. c. and d. c. magnetization, we establish that Ga substitution for Fe in YBaFe4O7 leads to an evolution from a geometrically frustrated spin glass (for x = 0) to a cationic disorder induced spin glass (x = 0.70). We also find an intermediate narrow range of doping where the samples are clearly phase separated having small ferrimagnetic clusters embedded in a spin glass matrix. The origin of the ferrimagnetic clusters lies in the change in symmetry of the samples from cubic to hexagonal (and a consequent lifting of the geometrical frustration) as a result of Ga doping. We also show the presence of exchange bias and domain wall pinning in these samples. The cause of both these effects can be traced back to the inherent phase separation present in the samples., Comment: 25 pages, 10 figures

The d.c. magnetization and magnetic relaxation studies of the calcium doped samples, Y0.95Ca0.05BaCo2O5.5 and YBa0.95Ca0.05Co2O5.5, show the existence of a magnetic glass like behaviour in the family of cobaltites for the first time. Our investigations reveal glass-like arrest of kinetics at low temperature which prevents the system from reaching its magnetic ground state. We show that the low temperature state of these calcium doped phases, which consists of coexisting antiferromagnetic and ferro (or ferri) magnetic phase fractions, can be tuned in a number of ways. Our observations establish that the low temperature state of this oxide is not in thermal equilibrium. The glassy state is formed with the assistance of an external magnetic field, which makes it distinctly different from the more well known metastable state, the spin glass state. The cooling field can tune the fractions of the coexisting phases, and the glass-like state formed at low temperature can also be devitrified by warming the sample. The role of Ca doping in the appearance of these phenomena is discussed in terms of phase separation, involving Co3+ disproportionation into Co4+ ferromagnetic clusters and Co2+ antiferromagnetic clusters., Comment: 17 pages, 5 figures. Erratum DOI: 10.1103/PhysRevB.84.059904: "The authors did not cite a relevant and important reference. The cooling and heating in unequal field (CHUF) protocol that has been used and described in Sec. III B 2 of this paper was first published in Ref. 1 [arXiv:0805.1514]. We apologize for this omission."

An oxygen hyperstoichiometric ferrite CaBaFe4O7+\delta (\delta \approx 0.14) has been synthesized using "soft" reduction of CaBaFe4O8. Like the oxygen stoichiometric ferrimagnet CaBaFe4O7, this oxide also keeps the hexagonal symmetry (space group: P63mc), and exhibits the same high Curie temperature of 270 K. However, the introduction of extra oxygen into the system weakens the ferrimagnetic interaction significantly at the cost of increased magnetic frustration at low temperature. Moreover, this canonical spin glass (Tg ~ 166 K) exhibits an intriguing cross-over from de Almeida-Thouless type to Gabay-Toulouse type critical line in the field temperature plane above a certain field strength, which can be identified as the anisotropy field. Domain wall pinning is also observed below 110 K. These results are interpreted on the basis of cationic disordering on the iron sites., Comment: 23 pages, 9 figures

A comparative study of the effect of Fe and Ni doping on the bismuth based perovskite La0.6Bi0.4MnO3.1, a projected spintronics magnetic semiconductor has been carried out. The doped systems show an expressive change in magnetic ordering temperature. However, the shifts in ferromagnetic transition (TC) of these doped phases are in opposite direction with respect to the parent phase TC of 115 K. The Ni-doped phase shows an increase in TC ~200 K, whereas the Fe-doped phase exhibits a downward shift to TC~95 K. Moreover, the Fe-doped is hard-type whereas the Ni-doped compound is soft-type ferromagnet. It is observed that the materials are semiconducting in the ferromagnetic phase with activation energies of 77 & 82 meV for Fe & Ni-doped phases respectively. In the presence of external magnetic field of 7 Tesla, they exhibit minor changes in the resistivity behaviours and the maximum isothermal magnetoresistance is around -20 % at 125 K for the Ni-phase. The results are explained on the basis of electronic phase separation and competing ferromagnetic and antiferromagnetic interactions between the various mixed valence cations., Comment: 18 pages including figures

The triple "magnetic-transport-structural" transition versus temperature in three series of "114" cobaltites - Y1-xYbxBaCo4O7, Y1-xCaxBaCo4O7 and Yb1-xCaxBaCo4O7 - has been studied using magnetic, transport and differential scanning calorimetric measurements. The effect of the size mismatch {\sigma}2, due to cationic disordering at the Ln sites upon such a transition is shown for the first time in a triangular lattice. We show that increasing has an effect of increasing TS dramatically, while the size mismatch {\sigma}2 at the Ln sites decreases TS substantially. Moreover, the cationic mismatch at the Ln sites modifies the nature of the hysteretic transition by turning the sharp first order transition seen in the undoped samples into an intermix of first and second order transitions. These results are discussed on the basis of the particular nature of the high temperature form which exhibits a hexagonal close packed structure (space group: P63mc) with respect to the low temperature orthorhombic form (space group: Pbn21), the latter corresponding to a distortion of the former due to a puckering of the kagom\'e layers., Comment: 24 pages, 7 figures, 3 tables

The effect of oxygen content on the magnetic and transport properties of the ferromagnetic Eu0.9Ca0.1BaCo2O5.5+{\delta} has been carried out. Unlike the increase in TC with calcium content, paradoxally the TC value decreases with the increase in oxygen (Co4+) content as observed in the undoped phase. This result unveils the hidden generic magnetic feature of the LnBaCo2O5.5 system in the calcium doped phase. This behaviour supports strongly the appearance of Co3+ disproportion action into Co4+ and Co2+ and the magnetic phase separation scenario of ferromagnetic domains embedded in an antiferromagnetic matrix. All the samples covering a wide range of oxygen content, exhibit a p-type conductivity., Comment: 26 pages including figs

The substitution of zinc for iron in YBaFe4O7 has allowed the oxide series YBaFe4-xZnxO7, with 0.40 < x < 1.50, belonging to the "114" structural family to be synthesized. These oxides crystallize in the hexagonal symmetry (P63mc), as opposed to the cubic symmetry (F-43m) of YBaFe4O7. Importantly, the d.c. magnetization shows that the zinc substitution induces ferrimagnetism, in contrast to the spin glass behaviour of YBaFe4O7. Moreover, a.c. susceptibility measurements demonstrate that concomitantly these oxides exhibit a spin glass or a cluster glass behaviour, which increases at the expense of ferrimagnetism, as the zinc content is increased. This competition between ferrimagnetism and magnetic frustration is interpreted in terms of lifting of the geometric frustration, inducing the magnetic ordering, and of cationic disordering, which favours the glassy state., Comment: 24 pages, 10 figures

Investigation of the oxygen-deficient 112-type ordered oxides of the type LnBaCoMnO5+\delta (Ln = Nd, Eu) evidences certain unusual magnetic behavior at low temperatures, compared to the LnBaCo2O5+\delta cobaltites. One observes that the substitution of manganese for cobalt suppresses the ferromagnetic state and induces strong antiferromagnetic interactions. Importantly, NdBaCoMnO5.9 depicts a clear paramagnetic to antiferromagnetic type transition around 220 K, whereas for EuBaCoMnO5.7 one observes an unusual magnetic behavior below 177 K which consists of ferromagnetic regions embedded in an antiferromagnetic matrix. The existence of two sorts of crystallographic sites for Co/Mn and their mixed valence states favor the ferromagnetic interaction whereas antiferromagnetism originates from the Co3+-O-Co3+ and Mn4+-O-Mn4+ interactions. Unlike the parent compounds, the present Mn-substituted phases do not exhibit prominent magnetoresistance effects in the temperature range 75-400K., Comment: 23 pages including figures

CaBaCo4O7 represents a new class of ferrimagnets whose structure is built up of CoO4 tetrahedra only, similarly to other members LnBaCo4O7 of the 114 series, forming an alternate stacking of kagome and triangular layers. Neutron powder diffraction reveals, that this compound exhibits the largest distortion within the 114 series, characterized by a strong buckling of the kagome layers. Differently from all other members it shows charge ordering, with Co2+ sitting on two sites (Co2, Co3) and mixed valent cobalt Co3+/Co2+L sitting on two other sites (Co1, Co4). The unique ferrimagnetic structure of this cobaltite at 4 K can be described as the assemblage of ferrimagnetic triple chains (Co1 Co2 Co3) running perpendicular to the kagome layers, ferromagnetically coupled within the layers, and antiferromagnetically coupled with a fourth cobalt species Co4. The lifting of the geometrical frustration towards ferrimagnetism, which appears in spite of the triangular topology of the cobalt lattice, is explained by the very large structural distortion, charge ordering phenomena and large cobalt valence compared to other LnBaCo4O7 oxides., Comment: 19 pages, 7 figures

ABO3 perovskite multiferroic La0.5Bi0.5Mn0.5Fe0.5O3.09 where the B-site cations is responsible for the magnetic properties and the A-site cation with lone pair electron is responsible for the ferroelectric properties was synthesized at normal conditions. This oxide exhibits a ferromagnetic transition around 240 K with a well defined hysteresis loop, and a significant reversible remnant polarization below 67K similar to ferroelectric behavior. The magnetic interaction is interpreted by the ferromagnetic Fe3+-O-Mn3+ and antiferromagnetic Fe3+(Mn3+)-O-Fe3+(Mn3+) interactions competed each other, whereas the ferroelectricity is predominantly due to the polar nature introduced by the 6s2 lone pair of Bi3+ cations, Comment: Submitted to Applied Physics Letters, 7 pages, 3 figures

We have investigated the systematic transport properties of the layered 112-type cobaltite LaBaCo2O5.5 by means of electrical resistivity, magnetoresistance, electroresistance and thermoelectric measurements in various conditions. In order to understand the complex conduction mechanism of LaBaCo2O5.5, the transport data have been analyzed using different theoretical models. The system shows semiconductor-semiconductor like transition (TSC) around 326K, corresponding to ferromagnetic transition and in the low temperature region resistivity data follows the Motts variable range hopping model. Interestingly, near and below the room temperature this compound depicts significant change in electro- and magnetoresistance behavior, the latter one is noteworthy near the magnetic phase boundary. The temperature dependence of thermopower, S(T), exhibits p-type polaronic conductivity in the temperature range of 60-320K and reaches a maximum value of 303 uV/K (at 120K). In the low temperature AFM region, the unusual S(T) behavior, generally observed for the cobaltite series LnBaCo2O5.5 (Ln = Rare Earth), is explained by the electron magnon scattering mechanism as previously described for perovskite manganites., Comment: 18 pages including figs

The synthesis and structural study of the stoichiometric perovskite La0.5Ba0.5CoO3 have allowed three forms to be isolated. Besides the disordered La0.5Ba0.5CoO3 and the perfectly ordered layered LaBaCo2O6, a third form called nanoscale-ordered LaBaCo2O6, is obtained. As evidenced by transmission electron microscopy investigations, the latter consists of 112-type 90 degree oriented domains fitted into each other at a nanometer scale which induce large strains and consequently local atomic scale lattice distortions. These three ferromagnetic perovskites exhibit practically the same Tc (174-179 K), but differently from the other phases, the nanoscale-ordered LaBaCo2O6 is a hard ferromagnet, with Hc = 4.2 kOe, due to the strains which may pin domain walls, preventing the reversal of the spins in a magnetic field. The magnetotransport properties of these phases show that all of them exhibit a maximum intrinsic magnetoresistance, close to 6-7 % around Tc under 70 kOe but that the ordered phase exhibits a much higher tunnelling magnetoresistance effect at low temperature of about 15 % against 4 % due to the grain boundary effects., Comment: 26 pages, higher resolution figs (will be@chem. mat.2008)

The substitution of cobalt and nickel for manganese in the perovskite manganate LaBiMn2O6+d; has been realized, leading to the perovskites LaBiMn2-x(M)xO6+d, with M = Co, Ni and x =0-2/3. In contrast to the literature those phases are found to be orthorhombic with Pnma symmetry. More importantly, it is shown that ferromagnetism is enhanced, TC being increased from 80 K for the parent compound (x = 0) to 97 K for Ni-phase, and to 130 K for the Co-phase. Moreover, a strong competition between ferromagnetism and a glassy-ferromagnetic state in the case of nickel or a spin-glass behaviour in the case of cobalt is observed. These phenomena are interpreted in the frame of a phase separation scenario, where the ferromagnetic Mn4+/Ni2+ and Mn4+/Co2+ interactions reinforce the Mn3+/Mn4+ interactions. These compounds are found to be insulating with a relatively large positive value of thermoelectric power., Comment: 27 pages including table and figures

The effect of cobalt and nickel substitutions for manganese on the physical properties of the perovskite manganite La1.2Bi0.8Mn2-x(Ni/Co)xO6+d, with x = 0.0-0.8, has been investigated. It is observed that the ferromagnetism is enhanced, TC being increased from 103 K for the parent compound (x = 0.0) to 178 K for Ni-phase, and to 181 K for the Co-phase (x = 0.8). Moreover, the systems remain insulating and depict relatively large values of magnetoresistance effect at low temperatures (up to 67 % at 90K and 70 kOe, for x = 0.0 phase). These phenomena are interpreted by means of electronic phase separation, where the ferromagnetic Mn4+/Ni2+ and Mn4+/Co2+ interactions reinforce the Mn3+/Mn4+ interactions by super-exchange interaction. The dielectric measurements below the magnetic transition temperatures exhibit weak magneto-dielectric effect of around 0.25% at 80K, which may be due to spin-lattice interaction., Comment: 34 pages, parts of the work is published in JMC

Over the past ten years, the advent of information technology and multimedia has revolutionized language learning. Ever since it was founded, Auralog has been investing heavily in the technological and educational adventure. As a result, the company has become the reference for language learning with the integration of speech recognition technology into its software. Speech recognition offers the opportunity to practice oral and listening skills. Today, the growth of the Internet is opening up new territory; a new generation of language learning has been born, offering the opportunity to learn a foreign language online. Auralog, with Tell Me More Online, offers a complete language course online, containing all the advanced technology previously developed by the company. The course includes speech recognition, interactive dialogs, grammar, vocabulary, written exercises, videos, etc. Thanks to the Internet, learners also have the possibility of benefiting from the assistance of a personal tutor. This paper highlights: (1) the major stages of the evolution of language learning through the ages; (2) Tell Me More Online technology, including the advanced scoring system, S.E.T.S. (Spoken Error Tracking System), waveforms and pitch curves, and phonetic animations; (3) pedagogical content; (4) learning support, including the help of a tutor via Internet and the advantages of learning support combined with home study; and (5) available tutoring services. (Contains 13 references.) (MES)

A new nanoscale ordered perovskite cobaltite, which consists of 90 degree ordered domains of the layered-112 LaBaCo2O6 has been evidenced by high resolution- transmission electron microscopy. This new form, like the disordered La0.5Ba0.5CoO3 and ordered LaBaCo2O6, exhibits a ferromagnetic transition at TC around 179 K. However, it differs from the two previous forms by its strong magnetic anisotropy, and correlatively by its high value of coercivity (0.42 Tesla) at low temperature. We suggest that this behaviour originates from the locking of magnetic spins in the 90 degree oriented nano-domain. Moreover, one observes a semi-metal/semi-metal transition at TC with a maximum magnetoresistance of 6.5 % at this temperature., Comment: 16 pages including figures

A 59Co NMR study of CoO2, the x=0 end member of AxCoO2 (A = Na, Li...) cobaltates, reveals a metallic ground state, though with clear signs of strong electron correlations: low-energy spin fluctuations develop at wave vectors q different from 0 and a crossover to a Fermi-liquid regime occurs below a characteristic temperature T*~7 K. Despite some uncertainty over the exact cobalt oxidation state n this material, the results show that electronic correlations are revealed as x is reduced below 0.3. The data are consistent with NaxCoO2 being close to the Mott transition in the x -> 0 limit., Comment: 4 pages, submitted

The study of the ordered oxygen deficient perovskite EuBaCo2-xNixO5.50 shows that the doping of cobalt sites by nickel induces a strong ferromagnetic component at low temperature in the antiferromagnetic matrix of EuBaCo2O5.50. This system exhibits indeed phase separation, i.e. consists of ferromagnetic domains embedded in the antiferromagnetic matrix of EuBaCo2O5.50. Besides, a magnetic transition is observed for the first time at 40K in the undoped and nickel doped phases, which can be attributed to the ferromagnetic ordering of the Eu3+ moments below this temperature. Moreover sharp ultra magnetization multisteps are observed below 5K, characteristic of motion of domain walls in a strong pinning system and very different from any metamagnetic transition.

The magnetic and magnetotransport properties of the Sr3Fe2-xCoxO7-d system (0.2 <= x <= 1.0) were systematically investigated. This oxide system exhibits a giant magnetoresistance (GMR) effect at low temperatures, reaching up to 80% in 7 T at 5 K. Ac-susceptibility measurements show that there exists a strong competition between ferromagnetic (F) and spin glass states, and the balance between these two magnetic states can be controlled by varying cobalt (x) and/or oxygen contents (d). Importantly, the MR effect is closely related to the magnetic property: the development of magnetic disordering leads to enhancement in the negative MR effect. It is suggested that the compound segregates into F clusters embedded in a non-F matrix, being a naturally occurring analog of the artificial granular-GMR materials, as in the doped perovskite cobaltites, La1-xSrxCoO3 (x < 0.18)., Comment: 31 pages, 10 figures, to appear in J. Phys.: Condens. Matter

The magnetic and magnetotransport properties of the oxygen deficient perovskites, SrCo1-xMxO3-d with M = Nb and Ru, were investigated. Both Nb- and Ru-substituted cobaltites are weak ferromagnets, with transition temperatures Tm of 130-150 K and 130-180 K, respectively, and both exhibit a spin glass behavior at temperatures below Tf = 80-90 K. It is demonstrated that there exists a strong competition between ferromagnetism and spin glass state, where Co4+ induces ferromagnetism, whereas Nb or Ru substitution at the cobalt sites induces magnetic disorder, and this particular magnetic behavior is the origin of large negative magnetoresistance of these oxides, reaching up to 30% at 5 K in 7 T. The differences between Nb- and Ru-substituted cobaltites are discussed on the basis of the different electronic configuration of niobium and ruthenium cations., Comment: 32 pages, 9 figures, to appear in Phys. Rev. B

The oxygen-deficient perovskite cobaltite SrCo1-xNbxO3-d was synthesized by direct solid-state reaction and its magnetotransport properties were investigated. This cobaltite exhibits an unusual ferromagnetic behavior with a transition temperature Tm = 130-150 K and a spin glass like behavior below Tm. Importantly, this phase reaches a large magnetoresistance (MR) value, MR = -(rH - r0) / r0 = 30% at 5 K in 7 T. The large MR effect is believed to be related to the disordered magnetic state induced by the Nb-for-Co substitution., Comment: 14 pages, 5 figures, to appear in Appl. Phys. Lett