Polymeric sheets in Mg4C60

We present preliminary results on the preparation and structure of Mg₄C₆₀, a new fulleride polymer. A series of Mg_xC₆₀ compositions (0<x<6) were prepared by solid state reaction. While most samples were multiphase, a single phase material was obtained at the nominal composition Mg₄C₆₀. The X-ray diffraction pattern of Mg₄C₆₀ was successfully indexed and fitted to a rhombohedral structure based on two-dimensional polymeric sheets of C₆₀ ions. This result extends the family of fulleride polymers to the salts of multiply charged cations and thus opens a new direction in this field.     

Structure and magnetic properties of LaFe11.5−xCoxSi1.5C0.2 compounds for magnetic refrigeration near room temperature

The influence of cobalt on the microstructural, magnetic and magnetocaloric properties of LaFe_11.5−xCo_xSi_1.5C_0.2 (x=0.50–0.85) compounds was investigated. The ingots were prepared by using a vacuum induction melting furnace. Before annealing, a large amount of 1:13 phase was distinctly observed. Nearly single 1:13 phase was obtained after annealing at 1353 K for only 3 days. The easy formation of 1:13 phase in the annealing process could be attributed to carbon doping. The Curie temperature (T_C) increases linearly with increasing the cobalt content. Although the maximum magnetic entropy changes of the compounds decrease rapidly when T_C rises from 275 to 298 K, and it decreases mildly when T_C continues to rise. Two composite refrigerants based on the compounds are proposed. Their entropy changes remains approximately constant over the temperature range from 266 to 292 K and 289 to 309 K.     

Superconductivity in Hg-substituted BaPb0.75Bi0.25O3

A series of Hg-doped BaPb_0.75Bi_0.25O₃ (BPBO) with a nominal composition of BaPb_0.75 − xHg_xBi_0.25O₃ (x=0-0.40 with 0.05 intervals) has been synthesized by solid state reaction. The system shows a lattice parameter expansion and lattice symmetry distortion with Hg doping. Superconducting transition temperature Tc and superconducting volume fraction of the system decrease with Hg doping level in the low doping level region (0?x?0.25) and are nearly fully suppressed at x=0.25. However, the superconductivity is recovered with further increasing Hg content at x>0.3. The possible mechanisms of the superconductivity in the low doping level region and the recovery of superconductivity in the high doping level region for Hg-doped BPBO system have been discussed.     

Structural, magnetic and electronic transport properties of MnxGe1−x/Ge(0 0 1) films grown by MBE at 350 °C

We report on the structural, magnetic and electronic transport properties of thin Mn_xGe_1−x films grown at 350 °C. Isolated Mn₅Ge₃ nanoclusters, about 100 nm in size, were formed at the top surface of the film, dominating the magnetic properties of the whole film. Electronic transport properties show Mn doping effect indicating the presence of substitutional Mn ions dispersed in the Ge host, contributing to the formation of a Mn_xGe_1−x diluted phase. Electrical behaviour indicates a saturation effect with the raise of the nominal Mn concentration in the film, above x ≅ 0.03.     

Magnetic properties and Griffiths singularity in La0.45Sr0.55 Mn1−xCoxO3

The magnetic properties and the Griffiths singularity were investigated in Mn-site doped manganites of La_0.45Sr_0.55Mn_1−xCo_xO₃ (x=0, 0.05, 0.10 and 0.15) in this work. The parent sample La_0.45Sr_0.55MnO₃ undergoes a paramagnetic-ferromagnetic transition at T_C=290 K and a ferromagnetic-antiferromagnetic transition at T_N=191 K. The doping of Co ions enhances the ferromagnetism and suppresses the antiferromagnetism. The enhanced ferromagnetism results from the fact that the Co doping enhances the Mn³⁺-Mn⁴⁺ double-exchange interaction and induces the Co²⁺-Mn⁴⁺ ferromagnetic superexchange interaction. Detailed investigation on the magnetic behavior above T_C exhibits that the Griffiths singularity takes place in this series of Mn-site doped compounds. The correlated disorder induced by the Co ionic doping, together with the phase competition from the ferromagnetic and the antiferromagnetic interactions among Mn ions, is responsible for the Griffiths singularity.     

Effect of carbon doping on thermodynamic behavior of MgB2

The thermodynamic behavior of carbon doped MgB₂ has been studied using a rigid ion model (RIM). The model potential consists of the long-range Coulomb, the short-range repulsive and the van der Waals interactions. This model has successfully explained the cohesive and thermodynamic properties of Mg(B_1−xC_x)₂ (x=0.0, 0.02, 0.05, 0.075, 0.1, 0.2). The properties studied are the cohesive energy, molecular force constant, Restrahlen frequency, compressibility, Debye temperature and Gruneisen parameter. Our results on Restrahlen frequency and Debye temperature are in reasonably good agreement with the available experimental data. In addition, we have computed the specific heat C_p for Mg(B_1−xC_x)₂ (x=0.2) as a function of temperature T in the range 16 K?T?1000 K. We have also shown the variation of specific heat C_p with doping concentration at room temperature (300 K). The calculated specific heat C_p for Mg(B_1−xC_x)₂ (x=0.2) in the temperature range 16 K?T?22 K for which experimental results are available, agrees pretty well with the experimental data.     

Evidence of glassy ferromagnetic phase and kinetic arrest of electronic phase in Sm0.35Pr0.15Sr0.5MnO3 manganites

The effect of doping of rare earth Pr³⁺ ion as a replacement of Sm³⁺ in Sm_0.5Sr_0.5MnO₃ is investigated. Temperature dependent dc and ac magnetic susceptibility, resistivity, magnetoresistance measurements on chemically synthesized (Sm_0.5−xPr_x)Sr_0.5MnO₃ show various unusual features with doping level x=0.15. The frequency independent ferromagnetic to paramagnetic transition at higher temperature (∼191 K) followed by a frequency dependent reentrant magnetic transition at lower temperature (∼31 K) has been observed. The nature of this frequency dependent reentrant magnetic transition is described by a critical slowing down model of spin glasses. From non-linear ac susceptibility measurements it has been confirmed that the finite size ferromagnetic clusters are formed as a consequence of intrinsic phase separation, and undergo spin glass-like freezing below a certain temperature. There is an unusual observation of a 2nd harmonic peak in the non-linear ac susceptibility around this reentrant magnetic transition at low temperature (∼31 K). Arrott plots at 10 and 30 K confirm the existence of glassy ferromagnetism below this low temperature reentrant transition. Electronic- and magneto-transport measurements show a strong magnetic field—temperature history dependence and strong irreversibility with respect to the sweeping of magnetic field. These results are attributed to the effect of phase separation and kinetic arrest of the electronic phase in this phase separated manganite at low temperatures.     

Structure and magnetic properties of (Nd,Dy)16(Fe,Co)76−xTixB8 powders prepared by mechanical alloying

Nanocrystalline (Nd,Dy)₁₆(Fe,Co)_76−xTi_xB₈ magnets were prepared by mechanical alloying and respective heat treatment at 973–1073 K/30–60 min. An addition of 0.5 at % of Ti results in an increase of coercivity from 796 to 1115 kA m⁻¹. Partial substitution of Nd by Dy results in an additional increase of coercivity up to 1234 kA m⁻¹. Mössbauer investigations shows that for x?1 the (Nd,Dy)₁₆(Fe,Co)_76−xTi_xB₈ powders are single phase. For higher Ti contents (x>1) the mechanically alloyed powders heat treated at 973 K are no more single phase, and the coercivity decreases due to the presence of an amorphous phase. A heat treatment at a higher temperature (1073 K) for longer time (1 h) results in the full recrystallisation of powders. The mean hyperfine field of the Nd₂Fe₁₄B phase decreases for titanium contents of 0?x?1, and remains constant for x>1. This indicates that the Ti content in the Nd₂Fe₁₄B phase reaches its maximum value.     

A study of TaxC1−x coatings deposited on biomedical 316L stainless steel by radio-frequency magnetron sputtering

In this paper, Ta_xC_1−x coatings were deposited on 316L stainless steel (316L SS) by radio-frequency (RF) magnetron sputtering at various substrate temperatures (T_s) in order to improve its corrosion resistance and hemocompatibility. XRD results indicated that T_s could significantly change the microstructure of Ta_xC_1−x coatings. When T_s was <150 °C, the Ta_xC_1−x coatings were in amorphous condition, whereas when T_s was ≥150 °C, TaC phase was formed, exhibiting in the form of particulates with the crystallite sizes of about 15-25 nm (T_s = 300 °C). Atomic force microscope (AFM) results showed that with the increase of T_s, the root-mean-square (RMS) values of the Ta_xC_1−x coatings decreased. The nano-indentation experiments indicated that the Ta_xC_1−x coating deposited at 300 °C had a higher hardness and modulus. The scratch test results demonstrated that Ta_xC_1−x coatings deposited above 150 °C exhibited good adhesion performance. Tribology tests results demonstrated that Ta_xC_1−x coatings exhibited excellent wear resistance. The results of potentiodynamic polarization showed that the corrosion resistance of the 316L SS was improved significantly because of the deposited Ta_xC_1−x coatings. The platelet adhesion test results indicated that the Ta_xC_1−x coatings deposited at T_s of 150 °C and 300 °C possessed better hemocompatibility than the coating deposited at T_s of 25 °C. Additionally, the hemocompatibility of the Ta_xC_1−x coating on the 316L SS was found to be influenced by its surface roughness, hydrophilicity and the surface energy.     

Effect of K doping on the physical properties of La0.65Ca0.35−xKxMnO3 (0?x?0.2) perovskite manganites

The effects of K doping in the A-site on the structural, magnetic and magnetocaloric properties in La_0.65Ca_0.35−xK_xMnO₃ (0?x?0.2) powder samples have been investigated. Our samples have been synthesized using the solid-state reaction method at high temperature. The parent compound La_0.65Ca_0.35MnO₃ is an orthorhombic (Pbnm space group) ferromagnet with a Curie temperature T_C of 248 K. X-ray diffraction analysis using the Rietveld refinement show that all our synthesized samples are single phase and crystallize in the orthorhombic structure with Pbnm space group for x?0.1 and in the rhombohedral system with R3¯c space group for x=0.2 while La_0.65Ca_0.2K_0.15MnO₃ sample exhibits both phases with different proportions. Magnetization measurements versus temperature in a magnetic applied field of 50 mT indicate that all our investigated samples display a paramagnetic-ferromagnetic transition with decreasing temperature. Potassium doping leads to an enhancement in the strength of the ferromagnetic double-exchange interaction between Mn ions, and makes the system ferromagnetic at room temperature. Arrott plots show that all our samples exhibit a second-order magnetic-phase transition. The value of the critical exponent, associated with the spontaneous magnetization, decreases from 0.37 for x=0.05 to 0.3 for x=0.2. A large magnetocaloric effect (MCE) has been observed in all samples, the value of the maximum entropy change, |ΔS_m|_max, increases from 1.8 J/kg K for x=0.05 to 3.18 J/kg K for x=0.2 under a magnetic field change of 2 T. For x=0.15, the temperature dependence of |ΔS_m| presents two maxima which may arise from structural inhomogeneity.     

The effect of different temperature annealing on phase relation of LaFe11.5Si1.5 and the magnetocaloric effects of La0.8Ce0.2Fe11.5−xCoxSi1.5 alloys

The phase relation of LaFe_11.5Si_1.5 alloys annealed at different high-temperature from 1223 K (5 h) to 1673 K (0.5 h) has been studied. The powder X-ray diffraction (XRD) patterns show that large amount of 1:13 phase begins to form in the matrix alloy consisting of α-Fe and LaFeSi phases when the annealing temperature is 1423 K. In the temperature range from 1423  to 1523 K, α-Fe and LaFeSi phases rapidly decrease to form 1:13 phase, and LaFeSi phase is rarely observed in the XRD pattern of LaFe_11.5Si_1.5 alloy annealed at 1523 K. With annealing temperature increasing from 1573  to 1673 K, the LaFeSi phase is detected again in the LaFe_11.5Si_1.5 alloy, and there is La₅Si₃ phase when the annealing temperature reaches 1673 K. There almost is no change in the XRD patterns of LaFe_11.5Si_1.5 alloys annealed at 1523 K for 3-5 h. According to this result, the La_0.8Ce_0.2Fe_11.5−xCo_xSi_1.5 (0≤×≤0.7) alloys are annealed at 1523 K (3 h). The analysis of XRD patterns shows that La_0.8Ce_0.2Fe_11.5xCo_xSi_1.5 alloys consist of the NaZn₁₃-type main phase and α-Fe impurity phase. With the increase of Co content from x=0 to 0.7, the Curie temperature T_C increases from 180 to 266 K. Because the increase of Co content can weaken the itinerant electron metamagnetic transition, the order of the magnetic transition at T_C changes from first to second-order between x=0.3 and 0.5. Although the magnetic entropy change decreases from 34.9 to 6.8 J/kg K with increasing Co concentration at a low magnetic field of 0-2 T, the thermal and magnetic hysteresis loss reduces remarkably, which is very important for the magnetic refrigerant near room temperature.     

Magnetic/structural diagram, chemical composition-dependent magnetocaloric effect in self-doped antipervoskite compounds Sn1−xCMn3+x (0≤x≤0.40)

The effects of Mn substitutions on the crystal structure, magnetic properties, and magnetocaloric effect (MCE) of antiperovskite Sn_1−xCMn_3+x (0≤x≤0.40) have been investigated detailedly. Both the Curie temperature (T_C) and the magnetizations at 40 kOe decrease with increasing x firstly for x≤0.10, and then increase with increasing x further. The type of magnetic transition changes from first-order to second-order around x=0.10 with increasing x. Chemical composition-dependent MCE is also studied around T_C. With increasing x, the maximal magnetic entropy changes decrease and the magnetic phase transitions broaden. Accordingly, the relative cooling power (RCP) increases with increasing x, reaching the largest values of ∼0.56 J/cm³ (∼75 J/kg) and ∼1.66 J/cm³ (∼221 J/kg) with the magnetic changes of 20 kOe and 48 kOe, respectively. Considering the large RCP, inexpensive, and innoxious raw materials, these serial samples Sn_1−xCMn_3+x are suggested to be potential room-temperature magnetic refrigerant materials.     

Raman spectra of samarium-fullerene intercalation compounds

Samarium-fullerene intercalation compounds of nominal composition Sm_xC₆₀ (x=1,2,…,6) have been synthesized by a solid-state reaction method. We obtain a Sm_2.75C₆₀ superconducting phase with orthogonal structure and a Sm₆C₆₀ phase with body-centered cubic structure. The broadening and weakening of Raman peaks of the Sm_xC₆₀ compounds are due to the distortion of C₆₀ and electron-phonon interaction. The Raman measurements reveal that the distortion of C₆₀ decrease in Sm_xC₆₀ (x=3,4,5) exposed to air, although the fulleride solids have transformed into an amorphous state. The Raman results also show that the distortion of C₆₀ is still very large in the Sm₆C₆₀ exposed to air, or the C₆₀ molecules have been destroyed and become some amorphous carbide.     

Magnetic properties and room-temperature magnetocaloric effect in the doped antipervoskite compounds Ga1−xAlxCMn3 (0≤x≤0.15)

We report the effects of Al doping on the structure, magnetic properties, and magnetocaloric effect of antiperovskite compounds Ga_1−xAl_xCMn₃ (0≤x≤0.15). Partial substitutions of Al for Ga enhance the Curie temperature (from 250 K for x=0.0 to 312 K for x=0.15) and the saturation magnetization. On increasing the doping level x, the maximum values of the magnetic entropy change (−ΔS_M) decreases while the temperature span of −ΔS_M vs. T plot broadens. Furthermore, the relative cooling power (RCP) is also studied. For 20 kOe, the RCP value tends to saturate at a high doping level (for x=0.12, 119 J/kg at 296 K). However, at 45 kOe, the RCP value increases quickly with increasing x (for x=0.15, 293 J/kg at 312 K). Considering the relatively large RCP and inexpensive raw materials, Ga_1−xAl_xCMn₃ may be alternative candidates for room-temperature magnetic refrigeration.     

Dopings in the transition-metal aluminides OsAl2 to obtain materials with high spin polarization: A first-principles study

The doping effects of 3d transition metals on the magnetic properties of Os_1 − xCr_xAl₂ are studied by first-principles calculations. The Os_1 − xCr_xAl₂ alloys have high spin-polarizations at the Fermi level with the Cr concentration in the range of 0.0<x?0.625. At higher Cr concentration, the ferromagnetic phase transforms into a ferrimagnetic metallic phase.     

Temperature dependence of electrical resistivity for Ca-doped perovskite-type Y1−xCaxCoO3 prepared by sol-gel process

The temperature dependences of DC electrical resistivity for perovskite-type oxides Y_1−xCa_xCoO₃ (0?x?0.1), prepared by sol-gel process, were investigated in the temperature range from 20 K up to 305 K. The results indicated that with increase of doping content of Ca the resistivity of Y_1−xCa_xCoO₃ decreased remarkably, which was found to be caused mainly by increase of carrier (hole) concentration. In the whole temperature range investigated the temperature dependence of resistivity ρ(T) for the un-doped (x=0) sample decreased exponentially with decreasing temperature (i.e. ln ρ∝1/T), with a conduction activation energy ; the resisitivity of lightly doped oxide (x=0.01) possessed a similar temperature behavior but has a reduced E_a (0.155 eV). Moreover, experiments showed that the relationship ln ρ∝1/T existed only in high-temperature regime for the heavily doped samples (T?82 and ∼89 K for x=0.05 and 0.1, respectively); at low temperatures Mott's ln ρ∝T^−1/4 law was observed, indicating that heavy doping produced strong random potential, which led to formation of considerable localized states. By fitting of the experimental data to Mott's T^−1/4 law, we estimated the density of localized states N(E_F) at the Fermi level, which was found to increase with increasing doping content.     

Effect of Sn-doping on the structural,magnetic and magnetocaloric properties of La0.67Ba0.33Mn1−xSnxO3 compounds

Magnetocaloric effect (MCE) in fine-grained perovskite manganites of the type La_0.67Ba_0.33Mn_1−xSn_xO₃ (x=0.05, 0.1 and 0.15) were prepared by the solid-state method. The prepared samples remain single phase and exhibit paramagnetic to ferromagnetic phase transition (T_C) at 340, 325 and 288 K for x=0.05, 0.1 and 0.15, respectively. From the measured magnetization data of La_0.67Ba_0.33Mn_1−xSn_xO₃ compounds as a function of field (2 T), the associated magnetic entropy change close to their respective Curie temperatures and the relative cooling power (RCP) have been determined. Large MCE has been obtained in all samples and |ΔS_M|_max reached the highest value of 2.49 J/kg K at T_C (288 K) for the sample x=0.15, with H=2 T.     

Phase and electrical behaviour in the Bi14W1 − xLaxO24 − 3x/2 system

The compositional and thermal dependencies of phase and electrical behaviour of compositions in the system Bi₁₄W_1 − xLa_xO_{24 − 3x/2} (0.00 < x < 1.00) have been studied by X-ray powder diffraction, differential thermal analysis and a.c. impedance spectroscopy. The system exhibits polymorphism and phase separation, which shows both compositional and thermal dependence. Compositions with x = 0.25 and x = 0.50 exhibit a single phase tetragonal structure at room temperature. In contrast, the x = 0.75 composition at room temperature shows a mixture of a cubic phase and a secondary β-Bi₂O₃ related tetragonal phase. A full solid solution is observed at high temperatures, corresponding to the occurrence of a δ-Bi₂O₃ type phase. The appearance of the various phases correlates well with the observed electrical behaviour. The x = 0.75 composition exhibits exceptionally high conductivity at high temperatures (σ₈₀₀ = 1.34 S cm^− 1), but also shows significant phase separation at lower temperatures.     

The effect of Ru doping on the alkali-doped manganite Pr0.8Na0.2MnO3

Polycrystalline manganites Pr_0.8Na_0.2MnO₃ doped by ruthenium (0.0≤x_Ru≤0.2) were prepared by the sol-gel process. The magnetic field induced metamagnetism was observed to occur with a large resistivity drop at 3 K for x_Ru≤0.02 samples, which can be sorted into the kind of CMR phenomenon. It was found that the 0.01 Ru doping increased T_C and decreased the metamagnetic critical field than that of the undoped sample. The doped manganites show a quick increase in their magnetic moments as x_Ru increases from 0.01 to 0.04, but the larger fraction of Ru doping (0.04≤x_Ru≤0.2) reduces their M and T_C. All the five doped samples have larger magnetic moments than that of the host sample. Ru doping of x_Ru>0.01 results in a rapid disappearance for the observation of long range spin and charge ordering in the samples’ M-T curves, which is characteristic of the undoped sample. It was found that larger low-temperature MR favored decrease in the metamagnetic critical field. Finally, the phase diagram of Ru doping vs. transition temperatures is presented to summarize the experiments.     

Doping and temperature dependence of inversion symmetry breaking in La2−xSrxCuO4

The doping dependence of the Raman spectra of high quality La_2−xSr_xCu^16,18O₄ polycrystalline compounds has been investigated at low temperatures. It is shown that symmetry forbidden bands peaked at ∼150 cm⁻¹, ∼280 cm⁻¹, and ∼370 cm⁻¹ are activated in the (xx/yy) polarization Raman spectra due to the local breaking of the inversion symmetry mainly at low temperatures and for doping concentrations for which the compound is superconducting. The apparent A₁-character of the activated modes in the symmetry reduced phase indicates a reduction from the D_2h to C_2v or D₂ crystal symmetries, which associates the observed modes to specific IR-active phonons with eigenvectors mainly along the c-axis. The temperature and doping dependence of this inversion symmetry breaking and the superconducting transition temperature are very similar, though the symmetry reduction occurs at significantly higher temperatures.