Magneto-optical properties of transition metal compounds XPt3 (X = V, Cr, Mn, Fe, Co) and X3Pt (X = Fe, Co)

We have studied theoretically the electronic structure and magneto-optical Kerr effect (MOKE) of XPt₃ (X = V, Cr, Mn, Fe, Co) and X₃Pt (X = Fe, Co) compounds from first principles using the full potential linearized augmented plane wave (FPLAPW) method within the local spin density approximation. The calculated magneto-optical spectra show the features of the experimental spectra which can be attributed to electronic transitions. For the Pt based compounds of 3d transition metals, we find the largest Kerr angle of −1.17° for MnPt₃ in the polar geometry which is in good agreement with the experimental data. Our calculations show an increase in Kerr rotation for XPt₃ series which can be correlated to an increase in the unpaired valence d-electrons of 3d transition metal (X) up to MnPt₃ and then a decrease for FePt₃ and CoPt₃. The Kerr spectrum is analyzed to ascertain the origin of the various peaks in terms of optical transitions. In addition, the effect of interchanging X and Pt atoms in XPt₃ is also studied in order to have greater insight for the dependence of Kerr spectra on configuration and local environment of these two atoms.     

Microstructure and strength of B2-ordered (Ni,Co)Al

A transmission electron microscopy (TEM) investigation of the morphologies and crystal structures of precipitates in supersaturated B2-ordered (Ni,Co)Al has revealed that rod-like precipitates of the (Ni,Co)₂Al phase with a hexagonal structure form parallel to the <111> direction of the B2 matrix. By aging at temperatures below 973 K, a long period superlattice structure of hexagonal (Ni,Co)₂Al was formed. The (Ni,Co)Al hardens appreciably by the precipitation of these phases. An energy dispersive spectroscopy (EDS) was used to analyze the compositions of each phase formed in the B2-(Ni,Co)Al. The effects of the dispersion of the (Ni,Co)₂Al phase on the temperature dependence of the strength of the B2-(Ni,Co)Al have been investigated over a temperature range from 298 K to 1173 K.     

Li(Mn1/3Ni1/3Co1/3)1-yMyO2(M=Al,Mg,Ti)正极材料的制备及性能

采用液相共沉淀合成锰镍钴氢氧化物前驱体, 在前驱体中掺入元素M(M=Al, Mg, Ti), 与锂结合生成Li(Mn1/3Ni1/3Co1/3)0.98M0.02O2材料, 结果表明掺杂可有效提高材料的循环性能. X射线衍射结果表明 随掺钛量增大(0≤y≤0.15), 晶格畸变增大, 半高宽变大, 晶粒粒径增大; 其中掺钛量y=0.1的材料电化学性能表现最好, 以20 mA/g电流充放电, 在2.5～4.6 V电压区首次放电容量可达215 mA·h/g.     

Cycle stabilities of the La0.7Mg0.3Ni2.55−xCo0.45Mx (M = Fe, Mn, Al; x = 0, 0.1) electrode alloys prepared by casting and rapid quenching

In order to improve the cycle stability of La–Mg–Ni system (PuNi₃-type) hydrogen storage alloy, Ni in the alloy was partly substituted by Fe, Mn and Al, and the electrode alloys La_0.7Mg_0.3Ni_2.55−xCo_0.45M_x (M = Fe, Mn, Al; x = 0, 0.1) were prepared by casting and rapid quenching. The effects of the substitution of Fe, Mn and Al for Ni and rapid quenching on the microstructures and electrochemical properties of the alloys were investigated in detail. The results obtained by XRD, SEM and TEM indicate that element substitution has no influence on the phase compositions of the alloys, but it changes the phase abundances of the alloys. Particularly, the substitution of Al and Mn obviously raises the amount of the LaNi₂ phase. The substitution of Al and Fe leads to a significant refinement of the as-quenched alloy's grains. The substitution of Al strongly restrains the formation of an amorphous in the as-quenched alloy, but the substitution of Fe is quite helpful for the formation of an amorphous phase. The effects of the substitution of Fe, Mn and Al on the cycle stabilities of the as-cast and quenched alloys are different. The positive influence of the substitution elements on the cycle stabilities of the as-cast alloys is in proper order Al > Fe > Mn, and for as-quenched alloys, the order is Fe > Al > Mn. Rapid quenching engenders an inappreciable influence on the phase composition, but it markedly enhances the cycle stabilities of the alloys.     

Structure and electrochemical properties of Li(Ni_(0.5)Mn_(0.5))_(1-x)TixO_2 prepared by one-step solid state reaction

1Introduction Many efforts have been made to develop new materials as an alternative to LiCoO2due to the relatively high cost and toxicity of Co.Since OHZUKU and MAKIMURA[1]successfully synthesized LiNi0.5Mn0.5-O2with excellent performance by solid state …     

Raman active phonons of RFe3(BO3)4, R=La or Nd, single crystals

Oriented single crystals of RFe₃(BO₃)₄, with R=La or Nd, have been studied by Raman spectroscopy. Spectra with the relevant polarization configurations have been recorded in order to obtain the symmetry of the observed phonons. The factor group analysis and the correlation with the free (BO₃)³⁻ ion are done in order to identify most of the phonons associated with the two different types of (BO₃)³⁻ ion present in the crystal. The number and symmetries of the optical Raman active modes are 7A₁+19E, among which 4A₁+8E can be assigned as mostly due to (BO₃)³⁻ vibrations. 7A₁+18E modes were observed.

The highest energy peaks have been assigned to the regular planar (BO₃)³⁻ and to the three irregular (BO₃)³⁻ groups. The two lowest energy peaks of A₁ symmetry (around 180 and 300 cm⁻¹) are very probably related to the BO₃ rotatory mode and to Fe displacements. R ions do not participate in A₁ symmetry modes. The E mode around 90 cm⁻¹ (the lowest frequency mode) is probably due to the R ions which have the longest bonds and are the heaviest ions.     

新型复合贮氢合金Zr_(0.9)Ti_(0.1)(Ni,Co,Mn,V)_(2.1)的制备与电化学性能

采用熔铸方法制备母合金Zr0 .9Ti0 .1(Ni,Co ,Mn ,V) 2 .1,进而在母合金基础上添加吸氢剂B ,利用球磨制得 4种复合贮氢合金。X射线衍射结果表明 ,随着球磨时间的增加 ,复合合金由晶态转化为非晶态 ;电化学测试结果表明 ,复合合金经过 1～ 2次球磨就能完全活化 ,具有很好的活化性能 ;在 6 0mA/g电流下 ,复合贮氢合金C和D的稳定容量均可达到 44 0mA·h/ g左右 ,比母合金高出 80mA·h/ g ;但随着球磨时间的延长 ,所得的复合合金容量比铸态母合金的还低 ;在 30 0mA/g电流下 ,复合合金D具有较好的循环稳定性 ,经过 2 0 0次循环后其容量仅衰减 3 %。     

Behavior of residual carbon in Sm(Co, Fe, Cu, Zr)z permanent magnets

When sintered Sm(Co, Fe, Cu, Zr)_z permanent magnets are prepared by metal injection molding, some organic binders are added in alloy powder, which leads to much residual carbon in the magnets. The residual carbon decreases magnetic properties and destroys the microstructure of the magnets. In this paper, the behavior of carbon in Sm(Co, Fe, Cu, Zr)_z permanent magnets has been studied. The results indicate that Sm(Co, Fe, Cu, Zr)_z magnets can keep excellent magnetic properties when the carbon content is below 0.1 wt.%: Br ≥ 10 kGs, H_cj ≥ 22 kOe, BH_max ≥ 25 MGOe. When the carbon content is above 0.1 wt.%, Br, H_cj and BH_max decrease with increasing carbon content evidently. Carbon consumes Zr content and forms ZrC, which reduces the volume fraction of the lamella and Sm(Co, Cu)₅ phases. Thus, the cell size increases and the cellular microstructure deteriorates. When the carbon content reaches 0.43 wt.%, there is not enough Sm(Co, Cu)₅ phase to form a uniform cellular microstructure. Br, H_cj and BH_max are approximate to zero. Since carbon has little influence on the content of Sm₂(Co, Fe)₁₇ phase, Ms can keep a high value (≥100 emu/g). ZrC has high melting point (3420 °C) and acts as dispersion particle in the magnets, which prevents the grains of SEM structure growing and reduces the liquid content of green compacts during sintering. Therefore, the density of the magnets decreases.     

Composition dependence of structure and optical properties of Cu2ZnSn(S,Se)4 solid solutions: An experimental study

The evolution of structure and optical properties of Cu₂ZnSn (S_xSe_1−x)₄ (CZTSSe) solid solutions in a wide composition range (0 ≤ x ≤ 1) has not been fully elucidated. We have performed comprehensive characterization on the CZTSSe powders with different S/Se ratios, which were synthesized by the solid state reaction method. X-ray diffraction patterns demonstrate that the lattice parameters a and c of CZTSSe decrease lineally when S replace Se gradually, which obeys the Vegard's rule. The A₁ Raman modes of CZTSSe show a typical two-mode behavior. The absorption spectra reveal that the band gap of CZTSSe can be tuned monotonously between 0.96 and 1.5 eV with almost linearity, and a small band gap bowing constant (b ≈ 0.08 eV) is deduced.     

Synthesis and characterization of layered Li（Ni1/3Mn1/3CO1/3）O2 cathode materials by spray-drying method

Spherical Li(Ni_(1/3)Mn_(1/3)Co_(1/3))O_2 was prepared via the homogenous precursors produced by solution spray-drying method. The precursors were sintered at different temperatures between 600 and 1 000 ℃ for 10 h. The impacts of different sintering temperatures on the structure and electrochemical performances of Li(Ni_(1/3)Mn_(1/3)Co_(1/3))O_2 were compared by means of X-ray diffractometry(XRD), scanning electron microscopy(SEM), and charge/discharge test as cathode materials for lithium ion batteries. The experimental results show that the spherical morphology of the spray-dried powers maintains during the subsequent heat treatment and the specific capacity increases with rising sintering temperature. When the sintering temperature rises up to 900 ℃ , Li(Ni_(1/3)Mn_(1/3)Co_(1/3))O_2 attains a reversible capacity of 153 mA·h/g between 3.00 and 4.35 V at 0.2C rate with excellent cyclability.     

Microstructure and electromagnetic properties of Al18B4O33w/Co composite particles prepared by electroless plating method

Al₁₈B₄O₃₃w/Co composite particles were prepared successfully through electroless plating Co on Al₁₈B₄O₃₃ whiskers. The growth behavior of the coatings, the effect of the process parameters and the electromagnetic properties of the prepared Al₁₈B₄O₃₃w/Co composite particles were investigated. The reduced Co nucleated first on the pre-activated surface of the whiskers to form insular particles which then grew larger gradually and eventually merged together to form continuous coatings. The reaction rate increased but the mass gain decreased with the increase of the bath pH and the bath temperature. The crystallinity of the deposited Co decreased with the increase of phosphorous content as well as the bath temperature. The effect of loading is much weaker compare to that of bath pH and bath temperature. The permittivity and the permeability of the prepared Al₁₈B₄O₃₃w/Co composite particles are markedly higher than those of the raw Al₁₈B₄O₃₃ whiskers in microwave band. Relaxation resonance is found in the samples with thick Co coatings due to the presence of eddy current, which deteriorates the permeability of the Al₁₈B₄O₃₃w/Co composite particles.     

Influences of the substitution of Fe for Ni on structures and electrochemical performances of the as-cast and quenched La0.7Mg0.3Co0.45Ni2.55−xFex (x = 0–0.4) electrode alloys

In order to improve the cycle stability of the La–Mg–Ni system PuNi₃-type hydrogen storage electrode alloys, Ni in the alloy was partially substituted by Fe. The La_0.7Mg_0.3Co_0.45Ni_2.55−xFe_x (x = 0, 0.1, 0.2, 0.3, 0.4) hydrogen storage alloys were prepared by casting and rapid quenching. The effects of the substitution of Fe for Ni on the structures and electrochemical performances of the as-cast and quenched alloys were investigated in detail. The results of the electrochemical measurement indicate that the substitution of Fe for Ni obviously decreases the discharge capacity, high rate discharge capability (HRD) and discharge potential of the as-cast and quenched alloys, but it significantly improves their cycle stabilities, and its positive impact on the cycle life of as-quenched alloy is much more significant than on that of the as-cast one. The microstructure of the alloys analyzed by XRD, SEM and TEM show that the as-cast and quenched alloys have a multiphase structure which is composed of two major phases (La, Mg)Ni₃ and LaNi₅ as well as a residual phase LaNi₂. The substitution of Fe for Ni helps the formation of a like amorphous structure in the as-quenched alloy. With the increase of Fe content, the grain sizes of the as-quenched alloys significantly reduce, and the lattice constants and cell volumes of the alloys obviously increase.     

Magnetic and electronic properties of RCoxGe2 (R = Pr, Nd) compounds

Magnetization, magnetic susceptibility, neutron diffraction and X-ray photoemission spectroscopy measurements were performed on polycrystalline samples: PrCo_0.85Ge₂ and NdCo_0.82Ge₂, crystallizing in an orthorhombic structure of the CeNiSi₂-type. The magnetometric data indicate that both compounds are antiferromagnetic at low temperatures, PrCo_0.85Ge₂ below 5 K and NdCo_0.82Ge₂ below 2.1 K. The neutron diffraction data indicate an antiferromagnetic structure in PrCo_0.85Ge₂ at 1.5 K and give no evidence of any magnetic ordering in NdCo_0.82Ge₂. The X-ray photoemission data indicate that the valence bands are formed predominantly by R 4f5d6s and Co 3d bands. The spin-orbit splitting values determined from the Pr and Nd, 3d_5/2 and 3d_3/2 XPS spectra are equal to 20.9 eV for the Pr compound and 23.0 eV for the Nd compound. The analysis of these spectra performed on the basis of the Gunnarsson–Schönhammer model revealed a small hybridization between 4f-electrons of the rare earths with the conduction band which implies rather good stability of the f shell in these compounds.     

Synthesis, characterization and magnetic properties of complex oxides Ln2Mn2/3Re4/3O7 (Ln = Er, Y) and Y2Zn2/3Re4/3O7

Complex oxides Ln₂Mn_2/3Re_4/3O₇ (Ln = Y, Er) and Y₂Zn_2/3Re_4/3O₇ with a zirkelite structure and hexagonal unit cells (space group P3₁21, z = 6) have been obtained. Static and dynamic magnetic susceptibility measurements show that these oxides possess spin-glass behavior at low temperatures. Valence combinations of d-metals in the oxides are Mn²⁺(Zn²⁺)–Re⁵⁺. It is supposed that the examined specimens Ln₂Mn_2/3Re_4/3O₇ (Ln = Y, Er) contain the second magnetic phase of an unknown composition.     

Mechanochemical solid state synthesis of (Cd0.8Zn0.2)S quantum dots: Microstructure and optical characterizations

(Cd_0.8Zn_0.2)S quantum dots with a mixture of both cubic (Zinc-blende) and hexagonal (Wurtzite) phases have been prepared within 75 min by mechanical alloying the stoichiometric mixture of Cd, Zn and S powders at room temperature in a planetary ball mill under Ar. The Rietveld analysis of X-ray powder diffraction data reveals relative phase abundances of both cubic and hexagonal phases and several microstructure parameters like lattice parameters, particle sizes, lattice strains, concentrations of different kinds of stacking faults, etc. in both the phases. At the time of formation, hexagonal phase dominates over the cubic phase (molar ratio ∼0.6:0.4), but in course of milling up to 15 h, the hexagonal phase partially transforms to cubic phase and the molar ratio becomes ∼0.4:0.6. Particle sizes of hexagonal and cubic phases reduce to ∼4.5 nm and 12.5 nm, respectively, after 15 h of milling. The hexagonal phase contains a significant amount of lattice strain in comparison to cubic phase. The presence of different kinds of stacking faults is revealed clearly from the high resolution transmission electron microscope (HRTEM) images.     

First-principles investigations of isotope effects in thermodynamic properties of TiX2 (X = H, D, and T) system

As hydrogen, deuterium and tritium storage materials, a series of investigations of mechanical and thermal properties of titanium hydrides, deuterides and tritides have been performed, however, very limited theoretical studies of thermodynamic properties for them can be found. Based on density-functional theory (DFT) and density-functional perturbation theory (DFPT) we have discussed systematically the hydrogen isotope effects on the thermodynamic properties of TiX₂ (X = H, D, and T) system. Our calculations indicate that for evaluating accurately their physical properties at absolute zero temperature, such as the equilibrium lattice constants, bulk modulus, and heat of formation, the zero-point energy correction must be taken into account. By performing the phonon calculation within quasiharmonic approximation (QHA), we obtain their vibrational free energies, vibrational entropies, and temperature dependence of specific heat, thermal expansion, and bulk modulus. Those results demonstrate that comparing with TiH₂, TiT₂ and TiD₂ are more stable and the zero-point effects play an important role in their thermal expansion. The increase in the force constant between Ti and H causes the higher value of specific heat of TiH₂ during the phase transition from FCC to FCT. In addition, comparing with available experimental values, we can conclude that QHA is feasible for describing the thermal properties of TiX₂.     

A general hydrothermal route to synthesis of nanocrystalline lanthanide stannates: Ln2Sn2O7 (Ln = Y, La–Yb)

A general hydrothermal process with use of lanthanide (III) nitrates and Na₂SnO₃ as precursors has been proposed for synthesizing nanocrystalline lanthanide stannates with general formula: Ln₂Sn₂O₇ (Ln = Y, La–Yb). Stannates of all lanthanides except for the radioactive promethium were successfully synthesized. Characterization by XRD and TEM revealed that all the products were phase-pure nanocrystalline lanthanide stannates with pyrochlore-type structure. Photoluminescent properties of three samples (i.e. Tb₂Sn₂O₇, Dy₂Sn₂O₇ and Yb₂Sn₂O₇) are also presented. The mole ratio of Ln(NO₃)₃:Na₂SnO₃ and hydrothermal temperature were two key factors for this general hydrothermal route.     

Hydrogen disproportionation by reactive milling and recombination of Nd2(Fe1−xCox)14B alloys

Stoichiometric Nd₂(Fe_1−xCo_x)₁₄B alloys (x=0, 0.25, 0.5, 0.75 and 1) have been disproportionated into NdH_2+δ and bcc–(Fe,Co) (0≤x≤0.75) or fcc–Co (x=1), respectively, by milling in hydrogen at enhanced temperatures. Reactive milling leads to the disproportionation of the thermodynamically very stable Nd₂Co₁₄B alloy. This reaction is not possible via the conventional hydrogenation disproportionation desorption and recombination (HDDR) process. Grain sizes of disproportionated and recombined Nd₂(Fe,Co)₁₄B materials were found to be <10 nm and 40–50 nm, respectively — approximately an order of magnitude smaller than those of conventional-HDDR processed alloys. The recombined Nd₂Co₁₄B alloy shows on average slightly smaller grain sizes than the Nd₂Fe₁₄B compound. A more effective exchange coupling leading to enhanced remanences, possibly due to the slightly smaller grain size, has been observed for Nd₂Co₁₄B powders recombined at 600–700°C.