The influence of lattice strain and Mg vacancies on the superconducting properties of MgB2 samples has been investigated. High quality samples with sharp superconducting transitions were synthesized. The variation in lattice strain and Mg vacancy concentrations were obtained by varying the synthesis conditions. It was found that high strain (~1%) and the presence of Mg vacancies (~ 5 %) resulted in lowering the Tc by only 2 K.
Bulk MgB2 samples were prepared under different synthesis conditions and analyzed by scanning and transmission electron microscopy. The critical current densities were determined from the magnetization versus magnetic field curves of bulk and powder-dispersed-in-epoxy samples. Results show that through a slow cooling process, the oxygen dissolved in bulk MgB2 at high synthesis temperatures can segregate and form nanometer-sized coherent precipitates of Mg(B,O)2 in the MgB2 matrix. Magnetization measurements indicate that these precipitates act as effective flux pinning centers and therefore significantly improve the intra-grain critical current density and its field dependence.
This work studies the influence of microstructures and crystalline defects on the superconductivity of MgB2, with the objective to improve its flux pinning. A MgB2 sample pellet that was hot isostatic pressed (HIPed) was found to have significantly increased critical current density (Jc) at high fields than its un-HIPed counterpart. The HIPed sample had a Jc of 10000 A/cm2 in 50000 Oe (5 T) at 5K. This was 20 times higher than that of the un-HIPed sample, and the same as the best Jc reported by other research groups. Microstructures observed in scanning and transmission electron microscopy indicate that the HIP process eliminated porosity present in the MgB2 pellet resulting in an improved intergrain connectivity. Such improvement in intergrain connectivity was believed to prevent the steep Jc drop with magnetic field H that occurred in the un-HIPed MgB2 pellet at H > 45000 Oe (4.5 T) and T = 5 K. The HIP process was also found to disperse the MgO that existed at the grain boundaries of the un-HIPed MgB2 pellet and to generate more dislocations in the HIPed the pellets. These dispersed MgO particles and dislocations improved flux pinning also at H<45000 Oe. The HIPing process was also found to lower the resistivity at room temperature.
The superconductivities of samples prepared by several procedures were found to degrade under ambient environment. The degradation mechanism was studied by measuring the change of surface chemical composition of dense MgB2 pellets (prepared by hot isostatic pressure, HIPed) under atmospheric exposure using X-ray Photoelectron Spectroscopy (XPS). Results showed that samples with poor connectivity between grains and with smaller grain sizes degrade with time when exposed to ambient conditions. In these samples, the Tc did not change with time, but the superconducting transition became broader and the Meissner fraction decreased. In contrast, our well-sintered and the HIPed samples remained stable for several months under ambient condition. The degradation was found to be related to surface decomposition as observed by XPS. We observed the formation of oxidized Mg, primarily in the form of a Mg hydroxide, the increase of C and O contents, and the reduction of B concentration in the surface layer of MgB2 samples.
We have studied thermodynamics of the Mg-B system with the modeling technique CALPHAD using a computerized optimization procedure. Temperature-composition, pressure-composition, and pressure-temperature phase diagrams under different conditions are obtained. The results provide helpful insights into appropriate processing conditions for thin films of the superconducting phase, MgB2, including the identification of the pressure/temperature region for adsorption-controlled growth. Due to the high volatility of Mg, MgB2 is thermodynamically stable only under fairly high Mg overpressures for likely growth temperatures. This constraint places severe temperature constraints on deposition techniques employing high vacuum conditions.
The electronic structure of BaFe2As2 doped with Co, Ni, and Cu has been studied by a variety of experimental and theoretical methods, but a clear picture of the dopant 3d states has not yet emerged. Herein we provide experimental evidence of the distribution of Co, Ni, and Cu 3d states in the valence band. We conclude that the Co and Ni 3d states provide additional free carriers to the Fermi level, while the Cu 3d states are found at the bottom of the valence band in a localized 3d10 shell. These findings help shed light on why superconductivity can occur in BaFe2As2 doped with Co and Ni but not Cu.