Temperature dependence of the magnetic properties and magnetoimpedance of nanocrystalline Fe<Subscript>73.5</Subscript>Si<Subscript>16.5</Subscript>B<Subscript>6</Subscript>Nb<Subscript>3</Subscript>Cu<Subscript>1</Subscript> ribbons

The temperature dependences of the magnetic properties and the magnetoimpedance effect of soft magnetic nanocrystalline Fe_73.5Si_16.5B₆Nb₃Cu₁ alloy ribbons are studied in the temperature range 24–160°C. A high temperature sensitivity of the impedance and the magnetoimpedance effect of the ribbons are detected in the ac frequency range 0.1–50 MHz. At an ac frequency of 50 MHz, the change in the impedance reaches 0.2 Ω/°C (0.5%/°C) in the temperature range 85–160°C. When the temperature increases, a monotonically decreasing character of the dependence of the magnetoimpedance effect on the applied magnetic field changes into a dependence having an increasing initial segment. The effect of temperature on the magnetoimpedance properties of the soft magnetic nanocrystalline ribbons is shown to result from temperature-induced changes in their electrical conductivity, magnetization, and effective magnetic anisotropy.     

Effect of high-temperature crystallization on the electrochemical properties of LiNi<Subscript>0.5</Subscript>Co<Subscript>0.2</Subscript>Mn<Subscript>0.3</Subscript>O<Subscript>2</Subscript> synthesized from a lithiated transition metal oxide precursor

The lithiated transition metal oxide precursor (LNCMO) with typical α-NaFeO₂ structure and imperfect crystallinity, obtained from a hydrothermal process, was pretreated at 500 °C and then subjected to sintering at 800–920 °C to synthesize the ternary layered LiNi_0.5Co_0.2Mn_0.3O₂ (NCM523). X-ray diffraction (XRD), scanning electron microscope (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge/discharge testing were used for investigating the effect of the high-temperature crystallization on the properties of the NCM523 cathode materials. The results show that the materials heated at 880–900 °C possess superior cation ordering, perfect crystallinity, and excellent electrochemical performances, among which the material heated at 900 °C delivers better performances, with the initial discharge capacity of 152.6 mAh g^?1 at 0.5 C over 3.0 to 4.3 V and the capacity retention of 95.5% after 50 cycles. Furthermore, the effect of the high-temperature crystallization on the Li⁺ diffusion coefficient, potential polarization, and electrochemical resistance are discussed.     

Influence of co-precipitation temperature on microstructure and electrochemical properties of Li[Li<Subscript>0.2</Subscript>Mn<Subscript>0.54</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>]O<Subscript>2</Subscript> cathode materials for lithium ion batteries

The layered Li-rich Mn-based cathode materials Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ were prepared by using co-precipitation technique at different temperatures, and their crystal microstructure and particle morphology were observed and analyzed by XRD and SEM. The electrochemical properties of these samples were investigated by using charge-discharge tests, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV), respectively. The results indicated that all samples are of high purity. When the precursors were co-precipitated at 50 °C, their cathode materials have the most uniform and full particles and exhibit the highest initial discharge capacity (289.4 mAh/g at 0.1C), the best cycle stability (capacity retention rate of 91.2 % after 100 cycles at 0.5C), and the best rate performance. The EIS results show that the lower charge transfer resistance of 50 °C sample is responsible for its superior discharge capacity and rate performance.     

Nano-SiC implantation into the structure of carbon/graphite materials made by pyrolysis (carbonization) of the precursor system coal tar pitch/poly(dimethylsiloxane)

Conversion of the air-cured poly(dimethylsiloxane) {–O–Si(CH₃)₂–}_n to SiC during co-pyrolysis with a coal tar pitch is studied with reference to the related SiO₂/pitch system. Each binary mixture is first homogenized at 160 °C followed by carbonization at 500 °C under argon to afford initial carbonizates. In both cases, one part of the initial carbonizate is further pyrolyzed at 1300 °C and another part at 1650 °C under an argon flow resulting in composite products. All products are studied with FT-IR, XRD, and XPS spectroscopic methods supplemented with SEM and ‘wet’ Si-analyses, when applicable. Carbothermally assisted conversion of both silicon precursors to nanocrystalline SiC embedded in the evolving C-matrix, i.e. nano-SiC/C composites, is evident only after the 1650 °C carbonization stage.     

Conference Report

Soil from Free-Air Carbon dioxide Enrichment (FACE) plots (FAL, Braunschweig) under ambient air (375 ppm; δ¹³C–CO₂?9.8‰) and elevated CO₂ (550 ppm; for six years; δ¹³C–CO₂?23‰), either under 100% nitrogen (N) (180 kg ha^?1) or 50% N (90 kg ha^?1) fertilisation treatments, was analysed by thermogravimetry. Soil samples were heated up to the respective temperatures and the remaining soil was analysed for δ¹³C and δ¹⁵N by Isotope Ratio Mass Spectrometry (IRMS). Based on differential weight losses, four temperature intervals were distinguished. Weight losses in the temperature range 20–200 °C were connected mostly with water volatilisation. The maximum weight losses and carbon (C) content were measured in the soil organic matter (SOM) pool decomposed at 200–360 °C. The largest amount of N was detected in SOM pools decomposed at 200–360 °C and 360–500 °C. In all temperature ranges, the δ¹³C values of SOM pools were significantly more negative under elevated CO₂ versus ambient CO₂. The incorporation of new C into SOM pools was not inversely proportional to its thermal stability. 50% N fertilisation treatment gained higher C exchange under elevated CO₂ in the thermally labile SOM pool (200–360 °C), whereas 100% N treatment induced higher C turnover in the thermally stable SOM pools (360–500 °C, 500–1000 °C). Mean Residence Time of SOM under 100% N and 50% N fertilisation showed no dependence between SOM pools isolated by increasing temperature of heating and the renovation of organic C in those SOM pools. Thus, the separation of SOM based on its thermal stability was not sufficient to reveal pools with contrasting turnover rates of C.     

Correlation between thermoluminescence emission and phase transitions of tridymite

ABSTRACT

Tridymite exhibits a complex 400?nm-induced thermoluminescence spectra consisting of five groups of components at (i) 90 and 130°C (due mainly to oxygen vacancies, substitution and interstitial atoms and/or impurities that create localized charge losses), (ii) 200°C (linked to a partial phase transition), (iii) 230°C (associated probably with alkali ions moving away from Al that leads to [AlO₄]° hole-like or [GeO₄/Li]° centers) and (iv) 320°C (caused by both phase transition and electron recombination with the unstable holes trapped at oxygen vacancies next to Al sites). The application of the T_m–T_stop protocol confirms a continuum in the trap structure not only because of the successive shifting of the maxima with the increase of the temperature, but also with the enhancement of the activation energy values that have been assessed by means of the initial rise method.     

Layered lithium-rich oxide nanoparticles: low-temperature synthesis in mixed molten salt and excellent performance as cathode of lithium-ion battery

Layered lithium-rich oxide, 0.5Li₂MnO₃·0.5LiMn_1/3Ni_1/3Co_1/3O₂, is synthesized in a mixed molten salt of KCl and LiCl under 750 °C. Its morphology and structure are characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption and desorption isotherm, and its performances as cathode of lithium-ion battery are investigated by charge–discharge test and electrochemical impedance spectroscopy, with a comparison of the samples synthesized via solid-state reaction. It is found that the resulting product consists of uniform nanoparticles, 50 nm in average, which possesses a well crystallite layered structure although its synthesis temperature is low and thus exhibits excellent cyclic stability and rate capability. The resulting product delivers an initial discharge capacity of 268 mAh g^?1 at 0.1 C and has a capacity retention of 82% after 100 cycles at 1 C, compared to the 243 mAh g^?1 and 73% for the sample synthesized by solid-state reaction under 900 °C.     

Synthesis of transparent BaTiO3 nanoparticle/polymer composite film using DC field

Transparent BaTiO₃ nanoparticle/polymer composite films were synthesized from titanium-organic film and barium ion in aqueous solution under direct current (DC) field. Titanium-organic precursor was synthesized from titanium isopropoxide, acetylacetone and methacrylate derivative. The UV treatment was effective to increase the anti-solubility of the titanium-organic film during DC processing. BaTiO₃ nanoparticles were crystallized in the precursor films on stainless substrates without high temperature process, as low as 40°C. The crystallite size of BaTiO₃ increased with increasing reaction temperature from 40 to 50 °C at 3.0 V/cm. BaTiO₃ nanoparticles also grew in size with increasing reaction time from 15 min to 45 min at 3.0 V/cm and 50 °C. Transparent BaTiO₃ nanoparticle/polymer films were synthesized on stainless substrates at 3.0 V/cm and 50°C for 45 min.     

Influence of temperature and initial ratio of the reactants on the formation of rusts in sulphated aqueous media

The investigation of the rusts obtained in sulphated aqueous media is done using the Mössbauer spectroscopy by simulating the corrosion process through the oxidation of ferrous hydroxide obtained by mixing FeSO₄ and NaOH in different initial ratios R=[FeSO₄]/[NaOH]. The influence of the temperature of oxidation is studied from 10°C to 60°C for various values of R scanning from 0.2 to 3. One notes strickingly that goethite is always present whereas magnetite and lepidocrocite are never observed together.     

Study of solid-state reactions and order-disorder transitions in Pd/α-Fe(001) thin films

The formation of the hard-magnetic ordered L1₀-FePd phase in thin bilayer Pd/α-Fe(001) films has been experimentally studied. Solid-state reactions initiated by thermal heating in bilayer Pd/α-Fe(001) films with a thickness of 50–60 nm (the atomic ratio Pd: Fe ≈ 50: 50) separated from the substrate have been studied using the in situ electron diffraction methods. It has been shown that the solid-state reaction between the palladium and iron layers in Pd/α-Fe(001) starts at 400°C with the formation of the disordered Fe-Pd phase. At 480°C, the ordered L1₀-FePd phase is formed. The order-disorder phase transition has been studied. It has been established that the transition of the ordered L1₀-FePd phase to the disordered FePd phase starts at 725°C. At 740°C, only the disordered FePd phase is present over the whole volume of the film. The observed temperature of the order-disorder phase transition is shifted from the equilibrium value by 35°C to higher temperatures. This effect is assumingly associated with the higher concentration of palladium atoms at the boundaries of the Fe-Pd crystal grains owing to the grain-boundary adsorption.     

Crystallization behaviour in a new multicomponent Ti16.6Zr16.6Hf16.6Ni20Cu20Al10 metallic glass developed by the equiatomic substitution technique

A new amorphous Ti_16.6Zr_16.6Hf_16.6Ni₂₀Cu₂₀A1₁₀ alloy has been developed using the novel equiatomic substitution technique. Melt spinning Ti_16.6Zr_16.6Hf_16.6Ni₂₀Cu₂₀A1₁₀ forms an amorphous phase with a large supercooled liquid region, ΔT=70°C. After isothermal annealing within the supercooled liquid region for 3 h at 470°C, the amorphous alloy crystallizes to form a fine-scale distribution of 2–5 nm nanocrystals, and the supercooled liquid region increases to ΔT=108°C. Atomic-scale compositional analysis of this partially crystalline material using a three-dimensional atom probe (3DAP) is unable to detect any compositional difference between the nanocrystals and the remaining amorphous phase. After annealing for 1 hr at 620°C, the amorphous alloy crystallizes to form 20–50nm equiaxed grains of a hexagonal-type C14 Laves phase with lattice parameters a = 5.2Å and c = 9.0 Å. 3DAP analysis shows that this Laves phase has a composition very close to that of the initial amorphous phase, suggesting that the alloy crystallizes via a polymorphic rather than a primary crystallization mechanism, despite the complexity of the alloy composition.     

The study of novel multi-doped spinel Li1.15Mn1.96Co0.03Gd0.01O4 + δ as cathode material for Li-ion rechargeable batteries

Novel spinel Li_1.15Mn_1.96Co_0.03Gd_0.01O_4 + δ was synthesized by high temperature solid-state reaction method. The product was identified as well-defined spinel phase by X-ray diffraction (XRD); the SEM images illustrated that the particle distribution was well-proportioned. The initial special capacity was 126.5 and 128.1 mAh g^? 1 at 25 and 50 °C. The fading rate was 0.017% and 0.098% per cycle under 0.5 °C at 25 and 50 °C, respectively. The results showed that Li_1.15Mn_1.96Co_0.03Gd_0.01O_4 + δ displayed excellent capacity and cycleability.     

Assessing the impact of IR stimulation at increasing temperatures to the OSL signal of contaminated quartz

The purpose of the present study is to identify the effect of the increasing temperature IR stimulation to the component-resolved OSL luminescence signal of mixed quartz-feldspars material. Post IR OSL signals measured at 110 °C were analysed via only general order kinetic terms, while IR signals obtained at increasing temperatures were de-convolved using the sum of general order kinetics plus a tunnelling component. By increasing stimulation temperature, it was demonstrated that IRSL at temperatures above 50 °C does not only stimulate feldspar but also stimulates both fast and medium quartz OSL components. In the temperature range between 175 and 250 °C, the IRSL initial intensity is dominated by the fast OSL component. Estimated equivalent doses using either Post-IR₁₇₅.OSL₁₁₀ as well as IRSL₁₇₅ (with the indices indicating the measurement temperature) are in good agreement between each other, due to both stimulating quartz. Finally, the physical meaningfulness of the fitting parameters for the tunnelling component is also discussed.     

Effect of sintering temperature on the elemental diffusion and electrical conductivity of SrTiO<Subscript>3</Subscript>/YSZ composite ceramic

The 50 vol% SrTiO₃/yttria-stabilized zirconia (YSZ) composite ceramic was prepared through powder sintering route in 1400～1500 °C. Only the cubic YSZ and SrTiO₃ phases are detected in all the sintered ceramics, and the typical XRD peak positions of both phases have varied dramatically. The grain sizes and relative densities of all specimens increase evidently with the sintering temperature. The width of the SrTiO₃/YSZ interfacial region increases from 100.4 to 468.8 nm as the sintering temperature rises from 1400 to 1500 °C. The total electrical conductivities of the sample sintered at 1500 °C are remarkably higher than those at 1400 and 1450 °C, while the ion transference numbers drop from 0.837 to 0.731 with sintering temperature from 1400 to 1500 °C. The variations in the electrical properties above can be interpreted based on the effects of sintering temperature on the elemental diffusions during the sintering process.     

Temperature dependent surface and spectral modifications of nano V<Subscript>2</Subscript>O<Subscript>5</Subscript> films

Nanocrystalline V₂O₅ films have been deposited on glass substrates at 300°C substrate temperature using thermal evaporation technique and were subjected to thermal annealing at different temperatures 350, 400, and 550°C. X-ray diffraction (XRD) spectra exhibit sharper and broader characteristic peaks respectively indicating the rearrangement of nanocrystallite phases with annealing temperatures. Other phases of vanadium oxides started emerging with the rise in annealing temperature and the sample converted completely to VO₂ (B) phase at 550°C annealing. FESEM images showed an increase in crystallite size with 350 and 400°C annealing temperatures followed by a decrease in crystallite size for the sample annealed at 550°C. Transmission spectra showed an initial redshift of the fundamental band edge with 350 and 400°C while a blue shift for the sample annealed at 550°C, which was in agreement with XRD and SEM results. The films exhibited smart window properties as well as nanorod growth at specific annealing temperatures. Apart from showing the PL and defect related peaks, PL studies also supported the observations made in the transmission spectra.     

Synthesis and electrochemical performance of Li1+xV3O8 as cathode material prepared by citric acid and tartaric acid assisted sol–gel processes

Lithium-ion battery cathode material Li_1+xV₃O₈ is synthesized by a citric acid/tartaric acid assisted sol–gel method and sintered at 350 °C, 450 °C and 550 °C for 3 h for the formation of Li_1+xV₃O₈ phase. The synthesized samples were fully characterized by FTIR, TG/DTA, XRD, SEM, EIS and charge–discharge tests. Li_1+xV₃O₈ material synthesized by tartaric acid assisted route and sintered at 450 °C for 3 h shows best electro-chemical performance. It shows a high initial capacity of 249 mAh g^?1 and still reserves a discharge capacity of 260 mAh g^?1 after 50 cycles. Moreover, in the case of tartaric assisted products, no capacity decadence is observed in 50 cycles. XRD together with TG/DTA measurements reveal that compared with citric acid assisted products, the adoption of tartaric acid as chelating agent effectively lowers the crystallization temperature of amorphous Li_1+xV₃O₈. Therefore, precursors obtained by tartaric acid route calcinated at 450 °C for 3 h exhibit lower crystallinity and smaller grain size, which contributes to the better electrochemical performance of the cathode electrodes. From EIS measurements, the bulk resistance is reduced, which favors the intercalation and de-intercalation of lithium ions while cycling.     

Electrode activation of anode-supported SOFCs with LSM- or LSCF-type cathodes

Electrode activation of SOFCs refers to one or more processes, which generally occurs during a first period of usually not longer than 100 h of applying a constant electrical load, and is associated with a decrease of the area specific resistance. To study this effect in relation to different starting-up and test conditions in more detail, the electrochemical performance between 650 and 900 °C of two types of anode-supported single cells, one with an La_0.65Sr_0.3MnO₃ (LSM) and the other with an La_0.58Sr_0.40Co_0.2Fe_0.8O_3−δ (LSCF) cathode, was evaluated.Both types of cells, when heated to and reduced at 800 °C, showed a decrease of the area specific resistance during the first 70 h at 800 °C of exposure under constant electrical load. The initial area specific resistance of cells heated to and reduced at 900 °C was comparable with that of the cells reduced at 800 °C and exposed for 70 h at 800 °C under constant electrical load. In other words, electrode activation is much faster at 900 °C than at 800 °C.     

Enhanced electrochemical performance of lithium vanadium phosphate as cathode by LiBOB/LiTFSI with additive in EC/EMC

A series of Li₃V₂(PO₄)₃/C (LVP/C) samples with monoclinic structure indexed to P2₁/n space group were synthesized using V₂O₃ as vanadium source by solid state reaction method by different sintering temperatures. It was found that the LVP/C sintered at 750 °C with a carbon content 3 wt.% was the optimum condition for this synthesis. The structural, morphological, superficial, and textural properties of LVP/C were characterized by XRD, SEM, TEM, and XPS. The electrochemical performance was evaluated by galvanostatic charge–discharge cycling using new high voltage electrolyte. The optimized cell delivered an initial discharge capacity of 187 mAh g^?1 in the higher cut-off voltage of 3.0–4.8 V vs. Li⁺/Li⁰ at 0.2 C rate, with a capacity retention of 88 %, 89 %, and 61 % after 50 cycles discharging at 1 C, 2 C, and 4 C, respectively. The capacity can be almost recovered at 0.5 C after long cycles. The excellent stability is contributed to the new high-voltage electrolyte.     

Investigation of structural features of hexadecafluorinated copper and zinc phthalocyanine films

The structural features of hexadecafluorinated copper and zinc phthalocyanine (MPcF₁₆) films (M = Cu, Zn) obtained by vacuum thermal deposition are investigated. The dependence of structural features of these films on the film thickness is studied by means of optical and Raman spectroscopy. It is shown that an increase in the thickness of MPcF₁₆ films, as well as film annealing under vacuum conditions at a temperature of 220°C, leads to the formation of the phase whose crystalline structure differs from that of the 20-to 50-nm-thick initial films.     

Atomic layer deposition of HfO2 on graphene from HfCl4 and H2O

Atomic layer deposition of HfO₂ on unmodified graphene from HfCl₄ and H₂O was investigated. Surface RMS roughness down to 0.5 nm was obtained for amorphous, 30 nm thick hafnia film grown at 180°C. HfO₂ was also deposited in a two-step temperature process where the initial growth of about 1 nm at 170°C was continued up to 10–30 nm at 300°C. This process yielded uniform, monoclinic HfO₂ films with RMS roughness of 1.7 nm for 10–12 nm thick films and 2.5 nm for 30 nm thick films. Raman spectroscopy studies revealed that the deposition process caused compressive biaxial strain in graphene, whereas no extra defects were generated. An 11 nm thick HfO₂ film deposited onto bilayer graphene reduced the electron mobility by less than 10% at the Dirac point and by 30–40% far away from it.