Reaction of SbPO4 with lithium in non-aqueous electrochemical cells: preliminary study and evaluation of its electrochemical performance in anodes for lithium ion batteries

SbPO₄, a phosphate with a layered structure, was tested as an electrode material for lithium cells spanning the 3.0-0.0 V range. Two main electrochemical processes were detected as extensive plateaus at ca. 1.6 and 0.7 V in galvanostatic measurements. The first process was found to be irreversible, thus excluding a potential intercalation-like mechanism for the reaction and being better interpreted as a decomposition reaction leading to the formation of elemental Sb. This precludes the use of this compound as a cathodic material for lithium cells. By contrast, the process at 0.7 V is reversible and can be ascribed to the formation of lithium-antimony alloys. The best electrochemical response was obtained by cycling the cell at a C/20 discharge rate over the voltage range 1.25-0.25 V. Under these conditions, the cell delivers an average capacity of 165 Ah/kg—a value greater than those reported for other phosphates—upon successive cycling.     

Microchemical Investigation of Archaeological Copper Based Artefacts Disclosing an Ancient Witness of the Transition from the Value of the Substance to the Value of the Appearance

In many Italian archaeological sites dated between the sixth and third centuries BC, unworked lumps of Cu-based materials are sometimes found, the so called Aes Rude, which according to archaeological considerations were appreciated as currency, as a medium of exchange and as a form of saving. The microchemical investigation of these ancient artefacts discloses their nature as apparently not usable for any functional applications or possible use. Indeed, Aes Rude resemble ordinary copper material, but microchemical results indicate that they are constituted by highly ferruginous leaded copper, making them useless for producing other metal objects by means of casting or hot and cold working. Notwithstanding this intrinsic negative feature, the production of these intractable Cu-based alloys was deliberately carried out to maximise the process yield in terms of produced metal from an impure and unselected metal ore by tailoring the smelting process parameters. With these considerations in mind, the microchemical investigation of these ancient iron–copper alloys gives evidence of the passage from the acceptance of an artefact value based on its true nature or potential use to the acceptance of the value based only on its appearance or form irrespective of its present or future use. This information could contribute to a better understanding of the evolution of human thought and economic and social interactions.     

Magnetotransport and magnetic properties of InAs/Mn digital alloys

We have investigated the magnetic and magneto-transport properties of a systematic sequence of five InAs/Mn digital alloys grown by a combination of molecular beam epitaxy and atomic layer epitaxy. The samples consist of 30 periods of Mn fractional monolayers (ML) (0.17–0.5 ML) separated by 14 ML thick InAs spacer layers in a superlattice configuration. Four samples show n-type electrical conduction while the fifth (0.25 ML Mn) is p-type. Squid magnetization measurements performed on these samples show remnant magnetization above room temperature, which is apparently related to a second phase.     

Coexisting antiferromagnetism and ferromagnetism in mechanically alloyed Fe-rich Fe–Ni alloys: implications regarding the Fe–Ni phase diagram below 400°C

Fe–Ni alloys below the Invar region with compositions Fe_100−xNi_x (x=21, 24, and 27 at%) were prepared by high-energy ball milling technique (mechanical alloying). The as-milled samples, characterized by X-ray diffraction and Mössbauer spectroscopy, contain a mixture of (BCC) and γ (FCC) phases, whereas the samples annealed at 650°C for 0.5 h show a single γ (FCC) phase displaying a single line Mössbauer spectrum at room temperature (RT). At low temperature, the Mössbauer spectra of annealed Fe₇₆Ni₂₄ and Fe₇₃Ni₂₇ alloys show the existence of a magnetically split pattern together with a broad singlet, which are ascribed to a high-moment ferromagnetic Ni-rich phase and a low-moment Fe-rich phase, respectively. The Fe-rich phase in annealed Fe₇₆Ni₂₄ alloy, which is paramagnetic at RT, undergoes antiferromagnetic ordering at 40 K, estimated from the dramatic line broadening of its spectrum, giving rise to a small hyperfine field (e.g. 2 T at 6 K). The coexistence of these phases is attributed to phase segregation occurring in these alloys as a result of enhanced atomic diffusion. The stability of these alloys towards martensitic (FCC→BCC) transformation at low temperatures is discussed in connection with the Fe–Ni phase diagram below 400°C.     

稀土及杂质元素对ZA27合金晶间腐蚀的影响

为了从本质上了解杂质与稀土元素对锌铝合金晶间腐蚀的影响 ,探索抑制合金晶间腐蚀的有效途径 ,依据晶界的大角度重位点阵理论编制出相应计算机软件 ,建立含稀土、杂质及 η相颗粒的α相大角度晶界原子集团模型 ,采用递归法计算了α相晶界间的电荷转移 ,由此讨论了杂质 (Pb、Sn、Cd)及稀土元素 (La、Y)对Zn、Al电极电位的影响 .结果表明 ,杂质Pb、Sn、Cd增大原子间的电荷转移量 ,提高Zn、Al电极电位差 ,加速合金的腐蚀 ,稀土元素减小原子间的电荷转移量 ,降低Zn、Al电极电位差 ,具有抑制晶间腐蚀的作用 .     

Theoretical investigation of Mössbauer hyperfine interactions in ordered FeNi and disordered Fe–Ni alloys

Electronic structure spin-polarized calculations were performed for 79-atoms embedded clusters representing the ordered intermetallic compound FeNi, the fcc Fe-rich disordered alloy Fe₈₅Ni₁₅ in an antiferromagnetic (AFM) configuration, and the ferromagnetic (FM) disordered alloy Fe₅₀Ni₅₀. The spin-polarized discrete variational method (DVM) in Density Functional theory was employed. Spin magnetic moments, as well as the ⁵⁷Fe Mössbauer hyperfine parameters isomer shift and magnetic hyperfine fields, were obtained from the calculations. For FM Fe₅₀Ni₅₀, the effect of pressure on the hyperfine field and on the isomer shift was investigated, for three different local atomic configurations surrounding the ⁵⁷Fe probe atom. In the case of the isomer shift, the calculated values were compared to reported experimental data.     

Annealing effects on the magnetization of Co–Ni–B amorphous nanoparticles

Chemically prepared (Co_xNi_1−x)_1−yB_y (x=0.5, 0.75, 1; y≈0.4) amorphous fine particles were characterized by X-ray diffraction, DTA and TGA, and in situ magnetic measurement as a function of annealing temperature in an inert atmosphere. Magnetic measurement performed in as-prepared and 150°C annealed samples shows an increase of the saturation magnetization and magnetic moment after thermal treatment. Room temperature magnetization increases by factors of 3.5, 1.8, and 1.5, for x=0.5, 0.75, and 1, respectively. These measurements may indicate a local re-ordering of the amorphous phase at temperatures much lower than the full crystallization temperature.     

Thermodynamic and surface properties of Sb-Sn and In-Sn liquid alloys

The thermodynamic properties of Sb-Sn and In-Sn liquid alloys have been studied using the quasi-chemical model for compound forming binary alloys and that for simple regular alloys. The concentration fluctuation S _cc(0) and the Warren-Cowley short-range order parameter (α ₁) were determined for the whole concentration range at a temperature of 770 K. The surface tensions of these liquid alloys were determined for the whole concentration range by using energetics determined from thermodynamic calculations. In all calculations, In-Sn manifested properties very close to alloys of ideal mixing, while Sb-Sn showed properties that are asymmetric about equiatomic composition. Our results suggest that a weak complex of the form SbSn₂ could be present in the Sb-Sn alloy at a temperature of about 770 K.     

Mössbauer, X-ray diffraction and magnetization studies of Fe–Mn–Al–Nb alloys prepared by high energy ball milling

Fe₆₀Mn₁₀Al₂₀Nb₁₀, (Fe₆₀Mn₁₀Al₃₀)₉₅Nb₅ and (Fe₆₀Mn₁₀Al₃₀)₉₀Nb₁₀ ball milled powdered alloys were investigated using X-ray diffraction, Mössbauer spectrometry, thermomagnetic (TGM) and magnetization measurements. We studied the influence of Nb content and of different milling times on the structural and magnetic properties. Two main features can be concluded: (1) the FeAlMn induces a BCC phase whatever the Nb content is, and (2) as both increasing Nb content and milling time give rise to an highly disordered state in conjunction with a decrease of the ferromagnetic behavior.     

Thermal evolution of ferromagnetic metallic glasses

A traditional TG apparatus was modified by placing two permanent magnets producing a controlled magnetic field (TG(M): Magneto Thermogravimetry). This technique proved to be useful to study both structural relaxation and crystallisation of ferromagnetic metallic glasses. Results obtained for the amorphous alloys Fe₄₀Ni₄₀P₁₄B₆ and Fe_62.5Co₆Ni_7.5Zr₆Nb₂Cu₁B₁₅, are reported in this paper. Structural relaxation can be evaluated by measuring changes in Curie temperature induced by thermal treatments. Crystallisation in TG(M) is detected through a change in the measured apparent mass (difference between the sample mass and magnetic force driving it upward). These results were confirmed by DSC analysis. Whether the obtained crystalline phase is ferromagnetic, it can be identified through its Curie temperature, measured by TG(M). In fact the value of 770°C measured as Curie temperature of crystallised Fe_62.5Co₆Ni_7.5Zr₆Nb₂Cu₁B₁₅led to conclude that the only ferromagnetic crystalline phase is a-Fe. These hypothesis was confirmed by XRD analysis, showing that the first crystallisation yields to a-Fe nanocrystals. This revised version was published online in July 2006 with corrections to the Cover Date.