Preparation and Characterization of Mg1−x B2 Bulk Samples and Cu/Nb Sheathed Wires with Low Grade Amorphous Boron Powder

MgB₂ bulk and wire samples were prepared using cheap, low grade amorphous boron powders. Based on chemical analysis performed on the starting reagents, three nominal stoichiometries were studied. It was found that the structural and superconducting properties of the bulk samples were not affected by the composition, but that residual Mg was left in the wires for the nominal MgB₂ composition. In contrast, slightly Mg-deficient compositions were free from residual Mg and exhibited higher critical current densities. The MgB₂ phase formation kinetics was not influenced by the variations in the nominal powder composition.     

Progress in Critical Current Density (<Emphasis Type="Italic">J</Emphasis><Subscript><Emphasis Type="Italic">c</Emphasis></Subscript>) in Sintered MgB<Subscript>2</Subscript> Bulks

The present paper focuses on methods of further improving the flux pinning and critical current density of disk-shaped MgB₂ bulk superconductors by adding excess Mg metal in combination with an optimum silver content and optimized processing conditions. Bulk MgB₂ samples were produced by in situ solid-state reaction in Ar gas ambient using high purity commercial powders of Mg metal and 1.5 wt% carbon-coated amorphous B powders mixed in a fixed ratio of Mg/B = 1.1:2. Further, 4 wt% silver was added to improve flux pinning as well as mechanical performance of the bulk MgB₂ material. The magnetization measurements confirmed a sharp superconducting transition with T_c,onset at around 37 K, which is only by 1 K lower than in bulk MgB₂ material produced without carbon-coated amorphous boron. The critical current density (J_c) values significantly improved in the MgB₂ material with 4 wt% of silver and 1.5 wt% of carbon-coated amorphous boron, sintered at 775 ^°C for 3 h. At 20 K, this sample showed J_c at around 500 and 350 kA/cm² in the self-field and 1 T, respectively, which makes it suitable for several industrial applications.     

Kinetics analysis for the sintering of bulk MgB<Subscript>2</Subscript> superconductor

The pertaining kinetic characteristics during the sintering of bulk polycrystalline MgB₂ superconductors is essentially important for the improvement of properties. Here Differential Thermal Analysis was adopted to record the heat effect during the preparation of bulk MgB₂ samples. The reaction between Mg and B powders starts before the melting point of pure Mg and the evolution for the fractions of MgB₂ were determined as a function of sintering temperatures. After fitting with different kinetic mechanism functions assumed, the sintering process of bulk MgB₂ superconductors was attributed to a solid-state interface-reaction controlled mechanism with an apparent activation energy of 4.54 × 10⁵ J mol⁻¹. Combined with microstructural observations by scanning electron microscopy and phase identification by X-ray diffraction, the formation process of MgB₂ phase was classified into two different stages: (i) solid-solid reaction stage, in which Mg and B powder starts to react and the growth of MgB₂ grain is restricted by the pinning effects of pores; (ii) solid–liquid reaction stage, in which the molten Mg melt promotes the reaction process and the regular hexagon bulk MgB₂ grain forms in a solution-reprecipitation and growth mode.     

Influence of different boron precursors on superconducting and mechanical properties of MgB2

The superconducting, structural and mechanical properties of MgB₂ bulk samples have been studied as a function of precursor B powder particle size by means of AC susceptibility, XRD and microhardness measurements, respectively. The in situ processed MgB₂ samples have been prepared by means of conventional solid state reaction method with magnesium powder (99.8 %, 325 mesh) and four different types of boron powders (95.2, >95, 91.9 and 86.7 %) from two sources, Pavezyum and Sigma Aldrich. The XRD measurements showed that the diffraction peaks for our samples belong to the main phase of the MgB₂ diffraction patterns. The highest critical temperature T _c = 37.7 K was achieved for the MgB₂ sample which was fabricated by using >95 % purity amorphous boron. Microhardness measurements were performed to investigate the mechanical properties. Load independent hardness, Vickers microhardness, Young’s modulus, fracture toughness, and yield strength values were calculated separately for all samples. The results were analyzed by using the Meyer’s law, proportional sample resistance model, elastic–plastic deformation model, Hays Kendall approach, and indentation induced cracking (IIC) model. It was found that the IIC model is the most successful model to describe the mechanical properties of our samples.     

Mechanochemical synthesis of amorphous and crystalline magnesium diboride

We have studied the phase composition of materials obtained by mechanochemical processing and subsequent heat treatment of mixtures of magnesium and boron powders in the atomic ratio 1: 2. Differential dissolution, differential scanning calorimetry, and X-ray diffraction data indicate that, during mechanical processing, some of the magnesium reacts with boron to form amorphous magnesium diboride. During annealing of the activated powder mixture, X-ray amorphous magnesium diboride forms at 340°C and crystallizes at 480°C. As shown by high-resolution transmission electron microscopy, the unreacted crystalline magnesium is covered with an amorphous layer consisting of magnesium diboride and boron. The amorphous material obtained by milling contains nuclei of MgB₂ crystallites 3–5 nm in size. During subsequent heating of the activated mixture, magnesium and boron react further to form amorphous magnesium diboride and the amorphous phase crystallizes. Heating of mechanically activated mixtures to just below the crystallization temperature allow MgB₂ nanoparticles to be produced. The formation of nanocrystalline magnesium diboride nuclei along with the amorphous phase during mechanochemical processing facilitates mechanochemical synthesis compared to thermal synthesis.     

Formation of MgO whiskers on the surface of bulk MgB<Subscript>2</Subscript> superconductors during in situ sintering

Magnesium oxide (MgO) whiskers (with diameters of about 60–80 nm) formed on the surface of bulk polycrystalline MgB₂ superconductor at a relative low temperature (720 °C) during in situ sintering process. The reaction between Mg and B powders begins at a temperature below melting point of Mg and maintains till about 750 °C. The residual Mg powders evaporate and react with trace oxygen to form MgO vapor as the temperature exceeds the melting temperature of Mg and a low supersaturation is required for the growth of MgO whiskers. The preformed MgB₂ and MgO crystals act as substrates and the melted Mg powders on the surface of them serve as catalysts during the growth process of MgO whiskers. The growth process of MgO whiskers is dominated by a self-catalytic vapor–liquid–solid (VLS) mechanism.     

The role of various boron precursor on superconducting properties of MgB2/Fe

The superconducting properties of Fe sheathed MgB₂ wire has been studied as a function of precursor B powder particle size. The in situ processed MgB₂ samples were prepared by means of conventional solid state reaction method with magnesium powder (99.8%, 325 mesh) and three different types of amorphous boron powders (purity; 98.8%, >95% and 91.9%) from two sources, Pavezyum (Turkish supplier) and Sigma Aldrich. The particle sizes of Turkish boron precursor powder were selected between 300 and 800 nm. The structural and magnetic properties of the prepared samples were investigated by means of the X-ray powder diffraction (XRD) and ac susceptibility measurements. The XRD patterns showed that the diffraction peaks for our samples belong to the main phase of the MgB₂ diffraction patterns. The highest critical temperature, T_c = 38.4 K was measured for the MgB₂ sample which was fabricated by using the 98.8% B. The critical current density of this sample was extracted from the magnetization measurements and J_c = 5.4 × 10⁵ A cm⁻² at 5 K and B = 2 T. We found that the sample made by using the 98.8% boron showed almost 2 times higher J_c than that of obtained from 91.9% B powder.     

Solid-state reaction induced by milling of a mixture of cobalt and boron powders

A mixture of polycrystalline elemental cobalt and boron powders in the atomic ratio Co₆₇B₃₃ was mechanically milled for 150 h. The milled powders were examined by X-ray diffraction, extended X-ray absorption fine structure spectroscopy and differential scanning calorimetry. Two steps where energy was regulated by different full/void volume ratio in the vials were carried out. In the first milling step (f/v=1/1) amorphization involves only a portion of the starting powder and reaches a steady state after 25 h. More energetic conditions (f/v=1/5) lead to almost complete amorphization of the sample after 70 h, and in the final stages the formation of crystalline t-Co₂B is observed. Then a steady state, in which both amorphous and crystalline phases coexist, is reached.     

The Effect of Cu Addition on the Phase Formation and Critical Current Density in the Sugar Doped MgB2 Superconductor

With the aim of improving the critical current density (J _c ) in the MgB₂ superconductor, minor Cu (3?at%) was doped to the MgB₂ samples in-situ sintered with Mg powder and sugar-coated amorphous B powder. Combined with thermal analysis, phase identification, microstructure observation and J _c measurement, the effect of minor Cu addition on the sintering mechanism, microstructure and critical current density of sugar-doped MgB₂ superconductors were investigated. It is found that the minor Cu addition could obviously accelerated the MgB₂ phase formation and improve the growth of MgB₂ grains during the sintering process of sugar-doped MgB₂ due to the appearance of Mg?CCu liquid at low sintering temperature. On the other hand, the Mg?CCu liquid hindered the reactive C released from sugar entering in the MgB₂ crystal lattice. Hence, the connectivity between MgB₂ grains was improved accompanying with the C substitution for B is decreased. At 20?K, the J _c of co-doped samples at low fields was further increased whereas it is decreased at high fields, compared with the only sugar-doped samples.     

Comparison of Levitation Forces of Bulk MgB2 Superconductors Produced by Nano Boron and Carbon-Doped Nano Boron

MgB₂ bulk superconductors were prepared by hot press plus furnace heating method. Two types of boron powders were used, one is amorphous nano boron and the other is C-doped boron. Characteristics of superconductors were determined by XRD and resistance measurements. Systematic levitation force measurements were performed by using a modular system at low temperatures. These bulk superconductors showed around 9 N repulsive and 4 N attractive forces in the z-axis at 20 K at closest point to the cryostat lid which contains the MgB₂ superconductor. These values slightly decreased by increasing temperature to 24 and 28 K for both samples. Comparing two samples, nano boron MgB₂ showed slightly higher levitation force than C-doped MgB₂ although C-doped MgB₂ has higher attractive force value at the closest point. This situation points out that C-doped MgB₂ is much proper for attractive force applications (as guidance force) while the nanoboron MgB₂ sample is much appropriate for repulsive force (as levitation).     

On the study of phase formation and critical current density in superconducting MgB2

Superconducting bulk MgB₂ samples have been synthesized by employing sintering technique without using any additional process steps, generally undertaken in view of the substantial loss of magnesium, during heat treatment. Starting with Mg rich powders having different atomic ratios of Mg : B, as against the nominally required Mg : B = 1:2 ratio, we have obtained superconducting MgB₂ samples of different characteristics. The effect of excess Mg in the starting mixture and processing temperature on the phase-formation, transition temperature (T _C) and critical current density (J _C) have been investigated by electrical transport and a.c. susceptibility measurements. The X-ray diffraction and X-ray photoelectron spectroscopic analyses of MgB₂ bulk samples have been carried out to understand the role of excess Mg and the effect of processing temperature. It is established that MgB₂ samples with high critical current density can be synthesized from a Mg rich powder having Mg : B in 2:2 ratio, at temperatures around 790°C. Critical current density has been found to vary systematically with processing temperature.     

Fabrication and Properties of MgB2 Coated Superconducting Tapes

We present the formation of MgB₂ coatings by simple and novel aerosol deposition technique which has a potential to escalate towards the fabrication of long superconducting tapes. The thin MgB₂ coatings were produced by using pre-synthesized MgB₂ powder. The ability of this technique to form a precursor powder in a thin film form has greatly reduced the intricacies involved in the synthesis of MgB₂ by other techniques like hybrid physical chemical vapor deposition etc. The as-synthesized thin films were characterized by the x-ray diffraction technique to study the structural properties. The thin films were found to be x-ray amorphous in nature depicting the formation of frustrated structure which showed a superconducting transition onset at around 36 K.     

Synthesis and Characterization of MgB2–MgO Composite Superconductor

We reported a practical process to synthesize MgB₂–MgO composite superconductor from low-cost raw materials of fine Mg and B₂O₃ powder by a single-replacement reaction. Electrical resistivity measurement showed an onset of superconducting transition at 38.0 K and zero resistance at 36.7 K in the zero magnetic fields. The diamagnetic transition at 37 K was observed by ac susceptibility measurement. X-ray powder diffraction indicated mixed MgB₂ and MgO phases with a mass ratio of 1:2.6. This is particularly useful in studying the boundary and weak-link effects of MgB₂ grains on transport properties of the samples.     

The mechanism of accelerated phase formation of MgB2 by Cu-doping during low-temperature sintering

Thermal analysis, phase identification and microstructure observation were adopted to explore the accelerating sintering effect of Cu-doping on the low-temperature formation of MgB₂ below Mg melting. It is found that the Cu-doping sintering of MgB₂ bulk followed an activated sintering mechanism and thus obviously promoted the reaction between Mg and B forming bulk MgB₂. Accordingly, dense MgB₂ bulks with excellent T_c and J_c were successfully synthesized by the Cu-doping sintering at 575 °C for only 5 h. Further, a sintering model was proposed to illuminate the Cu-doping activated sintering mechanism. It is found that during the Cu-doping activated sintering process, the local Mg-Cu liquid generates firstly and then segregates to the interface between Mg and B particles, which can wet Mg particles and provide a rapid transport for the diffusion of neighboring Mg atoms into B particles resulting in the accelerated formation of MgB₂ phase.     

Nano-sized Spherical MgB2 Superconducting Powder Fabrication Using MHz Range Ultrasonic Spray Pyrolysis (USP) System

We have fabricated 40?C150 nm sized MgB₂ superconducting spherical powders by using a 2.4 MHz ultrasonic spray pyrolysis system and consecutive high temperature heating and powder collection chamber. Various chemical solutions, which contain Mg, B, de-ionized water, acetone and LAPSA in different concentrations and gas atmosphere, were used to obtain MgB₂ superconducting powders. Microstructural, transport and magnetic characterizations of the powders were performed using XRD, SEM-EDX, R-T, M-H analysis and critical current density calculations, which is found in the range of 10⁶ Acm^?2, indicating improved flux pinning properties.     

Fabrication and Transport Properties of MgB2 Thin Films and Tunnel Junctions

We report on fabrication and characterization of MgB₂ thin films and tunnel junction structures. The MgB₂ films were prepared on Al₂O₃, Si, glass, and plastic foil substrates by either vacuum codeposition of boron and magnesium, or high-temperature magnesium annealing of boron films. The crystalline structure of our films depended directly on the method of preparation. The films prepared by codeposition and postannealed in Ar atmosphere were amorphous with nanocrystal inclusions and were characterized by very smooth surfaces. On the other hand, the boron-precursor films annealed in magnesium vapor were rough, polycrystalline with approximately 1-μm-diameter single-crystal blocks. Because of their surface quality, the amorphous films were used for preparation of point contact junctions and for optical characterization. The point-contact spectra of tested junctions exhibited a two-gap structure. The MgB₂ polycrystalline films was used for bulk transport studies. The best films were characterized by the critical temperature T _c of up to 39 K and the current density j _c at 4.2 K of about 10⁷ A/cm².     

Comparative study on sintering behavior of Al86Ni6Y4.5Co2La1.5 mechanically alloyed amorphous powder and melt-spun ribbon

In this research work, the sintering characteristics of Al₈₆Ni₆Y_4.5Co₂La_1.5 mechanically alloyed amorphous powders and milled melt spun ribbon have been compared. Mechanically alloyed amorphous powders were synthesized via 200?h high energy ball milling. Melt spun ribbons were synthesized by single roller melt spinning technique and grounded to powder form by ball milling. Mechanically induced partial crystallization occurred in the ribbons during milling. Significantly higher amount of contaminations such as carbon, oxygen and iron were observed in the mechanically alloyed amorphous powders compared to the milled ribbons. Both powders were consolidated via spark plasma sintering. Superior particle bonding was found in the sample consolidated from milled ribbons, ascribed to the lower amount of contamination that could not effectively restrict the viscous flow and diffusion of atoms. Various complex crystalline phases evolved in the sample consolidated from milled ribbon particles due to the presence of crystalline phases in the powders which acted as nucleation sites, whereas the amorphous phase was mostly retained in its counterpart. Vickers microhardness of the consolidated alloys from milled ribbon and mechanically alloyed amorphous powders were 3.60?±?0.13?GPa and 2.53?±?0.09?GPa, respectively. The higher hardness in the former case was attributed to the superior particle bonding and distribution of hard intermetallic phases in the amorphous matrix.     

Ex Situ Spark Plasma Sintering of Short Powder-in-Tube MgB<Subscript>2</Subscript> Tapes with Open and Closed Ends

Short powder-in-tube tapes of MgB₂ in the Fe sheath were fabricated by ex situ route from a commercial powder containing some free Mg and MgO impurity phases. The final heat treatment was performed by spark plasma sintering (SPS). Tapes were with open (OT) or closed (CT) endings. Closed endings were made by folding and pressing. The MgB₂ core of the OT sample has shown a higher low-field critical current density, a higher maximum pinning force, a slightly higher disorder, smaller average MgB₂ crystallite size, a weak contact between Fe and MgB₂ core, and more macro-flux jumps. The upper and irreversibility fields were similar for OT and CT samples. In the center of the MgB₂ cores, the detected impurity phase is MgO, while at the interface with Fe, MgB₄ also occurs. Impurity phases found at interface, MgO and MgB₄, are present in the center of the bulk SPSed samples. Reactions and pinning-force-related parameters are discussed with respect to Mg behavior influenced by condition of endings. It is inferred that the presence of free Mg in the raw MgB₂ powder has an important contribution to observed differences, and its removal or control is recommended.     

Microwave direct synthesis of MgB2 superconductor

Intermetallic compound superconductor MgB₂ was synthesized from spherical magnesium powder and lower purity amorphous boron powder by microwave direct heating. Powder X-ray diffraction (XRD) analysis indicates that the phases of the synthesis sample are MgB₂ (major phase) and a small amount of MgO. Scanning electron microscope (SEM) observation shows that the MgB₂ grain size is homogeneous and the particle size is about several hundreds of nanometers. The onset superconducting transition temperature of the MgB₂ sample measured by the temperature dependence of magnetization measurement is about 37.6 K. The critical current density J_c calculated according to the Bean model are about 2.0 × 10⁵ A/cm² at 20 K in self-field and 1.0 × 10⁵ A/cm² at 20 K in 1 T applied field.     

Fabrication and Transport Properties of MgB2 Thin Films and Tunnel Junctions

We report on fabrication and characterization of MgB₂ thin films and tunnel junction structures. The MgB₂ films were prepared on Al₂O₃, Si, glass, and plastic foil substrates by either vacuum codeposition of boron and magnesium, or high-temperature magnesium annealing of boron films. The crystalline structure of our films depended directly on the method of preparation. The films prepared by codeposition and postannealed in Ar atmosphere were amorphous with nanocrystal inclusions and were characterized by very smooth surfaces. On the other hand, the boron-precursor films annealed in magnesium vapor were rough, polycrystalline with approximately 1-m-diameter single-crystal blocks. Because of their surface quality, the amorphous films were used for preparation of point contact junctions and for optical characterization. The point-contact spectra of tested junctions exhibited a two-gap structure. The MgB₂ polycrystalline films was used for bulk transport studies. The best films were characterized by the critical temperature T _c of up to 39 K and the current density j _c at 4.2 K of about 10⁷ A/cm².