Synthesis and analysis of PbO-modified Bi-Sr-Ca-Cu-O superconductors

High T _c superconducting materials based on a PbO-modified Bi-Sr-Ca-Cu-O system with various ratios between the oxides were prepared by calcination at 800 °C and firing at 855 °C. From X-ray powder diffraction analysis data, the ratio of low- and high-temperature phases was calculated. The material with the nominal composition Bi₂Pb_0.5Sr₂Ca_2.5Cu_3.5O _x was chosen for further experimental work. Samples fired at 800 °C contain mostly the low-temperature phase (2212). Higher firing temperatures lead to the formation of the high T _c phase (2223) with T _c(R=0) over 100 K. Some samples were cold pressed and refired which increased the specific density to over 80% of the theoretical density. The composition of samples was investigated by X-ray powder diffraction analysis and by energy dispersive X-ray spectroscopy. The main phase in the material fired at 800 °C, is the low T _c phase 2212, and secondary phases are Ca₂PbO₄, unreacted CuO and traces of 2223 phase. At higher firing temperatures, the main phase is the high-temperature phase 2223. The material is still heterogeneous and contains Ca₂PbO₄.     

Formation of the high-Tc phase in lead-doped Bi-Sr-Ca-Cu-O superconductors

The characteristics of Bi-Sr-Ca-Cu-O superconductors have been investigated as a function of the amount of Pb addition. The volume fraction of the high-T _c phase increases with increasing Pb addition up to x=0.3 in (Bi_1–xPb_x)₂Sr₂Ca₂Cu₃O_y and above that it decreases. The grain size is increased and density is decreased with increasing Pb addition, due to two-dimensional grain growth which results from formation of the high-T _c phase. The specimen with x=0.3 has a transition temperature of 104 K and high magnetic susceptibility due to the fact that most of the volume fraction is of the high-T _c phase. Pb addition cause formation of Ca₂PbO₄ as a secondary phase and it produces a partially melted liquid phase below the sintering temperature, which acts as a flux and promotes formation of the high-T _c phase.     

Stabilization of the high temperature phase in Bi-Ca-Sr-Cu-O system

Since the discovery of Bi-containing high-T _c superconductors, difficulties in obtaining monophase samples have been known. The study of phase formation in the system Bi₂Sr_(3−x)Ca _x Cu₂O _y , where 0.5<x<2.5 and conditions for raising HT phase (110 K) content by loading a superstoichiometric excess of Ca and Cu ions into the initial composition as well as by a substitution of lead for a part of bismuth is the object of the present paper.     

Enhancement of (Bi,Pb)-2223 HTS Formation by Boron-Doping

Influence of boron-doping on the superconducting properties of (Bi,Pb)-2223 HTS ceramics prepared in an alumina crucibles has been investigated. X-ray diffraction, resistivity, and AC susceptibility measurements were performed on the undoped and boron-doped compounds. Obtained results have shown that B₂O₃ addition in the Bi_1.7Pb_0.3Ca₂Sr₂Cu₃O _y precursor enhances the formation of high-T _c phase. The boron-doped samples with starting composition Bi_1.7Pb_0.3Ca₂Sr₂Cu₃B _x O _y (x=0.05 and 0.5) reveal significant improvement in the zero resistivity temperature compared to the undoped sample (from 72 K up to 100 K). Boron-doping level x=1.5 results in a substantial degradation of the (Bi,Pb)-2223 phase.     

Doping of Bi-Sr-Ca-Cu-O Compounds with Mn

Formation of the superconducting phases Bi-2212 and Bi-2223 has been studied for samples with nominal composition Bi_aPb_bMn_cSr₄Ca₅Cu₇O _x (a + b + c = 4). The influence of the stoichiometric replacement of Bi and/or Pb by Mn on the electric and magnetic properties of the Bi-based superconductors has been studied. The partial substitution of Mn for Bi in the samples without Pb did not promote the growth of the Bi-2223 phase. The samples with double substitution Pb-Mn for Bi revealed a large amount of the Bi-2223 phase.     

Doping of Bi-Sr-Ca-Cu-O superconductors with Pb,Sn and Ag

Basic and substituted superconductors in the homologous series Bi₂Sr₂Ca _n−1Cu _n O_2n+4+y , Bi_2−x/2Sr_2−x/2L _x Ca _n−1Cu _n O_2n+4+y and Bi₂Sr_2−x L _x Ca _n−1Cu _n O_2n+4+y (L=Sn, Pb or Ag,x=0−0.4,n=2, 3 or 4) have been synthesized. All the prepared ceramic samples show superconducting behaviour with zero resistance atT _c=70 to 85 K. The compounds withn=3 or 4 showed onset temperature around 115K indicating involvement of a disproportionate solid-state reaction and formation of a two-phase system. The phase involving tin or lead oxides showed similar superconducting properties. Final rapid quenching of samples contributed to preservation of the high temperature equilibria with higher solubility of tin oxide in the quaternary system Bi-Sr-Ca-Cu-O. Silver was not soluble but precipitated in a colloidal form at interfaces between the crystalline grains.     

Superconducting Properties of B<Subscript>2</Subscript>O<Subscript>3</Subscript>-Added (Bi,Pb)-2223 HTSs Prepared on Alumina Plates

Nominally pure and B₂O₃-added (Bi,Pb)-2223 HTS samples were synthesized in air on alumina plates. The influence of boron-doping as well as annealing conditions on the high-T _c 2223 phase evolution was studied using X-ray diffraction (XRD), resistivity and AC susceptibility measurements. The B₂O₃-added samples with starting composition Bi_1.7Pb_0.3Ca₂Sr₂Cu₃B _x O _y (x=0.05 and 0.5) reveal significant enhancement of 2223 phase formation compared to the undoped sample. Higher-level boron doping x=1.5 leads to the degradation of high-T _c 2223 phase.     

Influence of sintering time and quenching on the formation of highT c phase

Influence of sintering time and quenching in Bi_{2 −x} Pb _x Ca₂Sr₂Cu₃O _y (x=0.0, 0.1, 0.2, 0.25, 0.3 and 0.4) samples have been studied by resistance and XRD measurements. In samples sintered at 850°C for 4 days,T _c(0) increases with Pb concentration.T _c(0) increased from 81 K forx=0.0 to 109 K inx=0.30 sample and then decreased. Increasing the sintering time to 10 days decreased theT _c Quenching further decreased theT _c(0). From X-ray diffraction patterns, the intensity peaks of low and highT _c phases have been measured. The addition of Pb promotes highT _c-phase. Sintering time, slow cooling and rapid quenching studies show that there is an optimum sintering time and cooling rate to produce a highT _c-phase.     

Effect of Nb addition on magnetic,structural and superconducting properties of (Bi,Pb)-2223 superconductors

In this work, the effects of Nb₂O₅ addition with different ratios on the structural and magnetic properties of Bi_1.7?xPb_0.3Nb_xSr₂Ca₂Cu₃O_y (x = 0.00–0.20) superconducting samples were investigated. (Bi, Pb)-2223 superconducting samples were prepared by conventional solid-state reaction method. The phase formation, phase fraction and lattice parameters were determined from X-ray powder diffraction (XRD) measurements, the microstructure, surface morphology analyses of the samples were carried out using scanning electron microscope (SEM). Additionally, ac susceptibility measurements were done in order to determine the critical current density (J_c) and hole concentration (p) of the samples. AC susceptibility measurements were done at various ac fields (ranging from 20 to 160 A/m) to understand the effect of Nb addition on magnetic properties of Bi_1.7?xPb_0.3Nb_xSr₂Ca₂Cu₃O_y superconductor. Critical onset (T _c ^on ) and loss peak temperatures (T_p) were estimated from the ac susceptibility curves. It was observed from ac susceptibility measurements that the critical onset temperatures decreased from about 108–98 K with increasing Nb addition (x = 0.00–0.20). The imaginary part of susceptibility was used to calculate the intergranular critical current density (J_c) by means of the Bean’s model. X-ray diffraction analysis revealed that the samples consisted of a mixture of Bi-2223 and Bi-2212 phases as the major constituents and non-superconducting phase Ca₂PbO₄ as the minor. It was also shown from XRD measurements that volume fraction of high-T_c phase decreases with increasing Nb addition up to x = 0.20. The sample with Nb addition of x = 0.20 showed the highest volume fraction of Bi-2223 phase (86 %). When Nb addition was increased, the surface morphology and grain connectivity are found to degrade, the grain sizes decrease and porosity of the samples were observed to increase from SEM images except the sample with x = 0.20 Nb addition.     

Controlled grain orientation at the surface of Bi2Sr2CaCu2Ox superconducting glass-ceramics

Bi₂Sr₂CaCu₂O_x glass with Cu⁺/(Cu⁺ + Cu²⁺) = 0.76 was prepared by using a conventional melt-quenching method, and crystalline phases and grain orientations at the surface of superconducting glass-ceramics obtained by annealing at various atmospheres were examined. The grain orientation of the Bi₂Sr₂CaCu₂O_x phase (low-T _c phase) at the surface was severely affected by oxygen partial pressure in annealing. The favourable grain orientation, in which the plate-like grains of the low-T _c phase are oriented parallel to the surface plane, was first established in the samples obtained through a newly developed two-step annealing method: first annealing at 780°C in oxygen and second annealing at above 750°C in nitrogen. It was concluded that the favourable grain orientation of the low-T _c phase at the surface occurred due to the formation of a liquid phase in nitrogen.     

Synthesis and characterization of 110 K superconducting phase in Bi(Pb)-Sr-Ca-Cu-oxide

The temperatures and sequence of formation of superconducting phases within the composition Bi_1.6Pb_0.4Sr₂Ca₂Cu₄O _x were determined using simultaneous differential thermal analysis (DTA) and thermogravimetric analysis (TGA), X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). A single phase high-T _c ceramic was obtained by a solid state reaction using predetermined firing conditions, although a transmission electron microscopy (TEM) study showed a small amount of glass phase in the grain boundary tripoint regions. The unit cell of the high-T _c phase was refined asa=0.5413 nm,b=0.5414 nm,c=3.715 nm. The melting temperature of the high-T _c phase is in the region of 852–862°C. The effect of lead was believed to lower the temperature of formation of the high-T _c phase. Lead was also found to evaporate from the matrix during and after high-T _c phase formation, whereas bismuth was found to be stable in both the low-T _c phase and high-T _c phase compounds.     

Possibilities for formation of the 110 K phase 2223 in Sb or V doped Bi-Sr-Ca-Cu-O and Bi-Pb-Sr-Ca-Cu-O materials

Superconducting oxide materials with nominal composition Bi_2–x Sb _x Sr₂Ca₂Cu₃O_y (x=0.05–0.3) and Bi_1.6Pb_0.4–x V _x Sr₂Ca₂Cu₃O_y (x=0.1 0.4) were synthesized. It was found that after prolonged synthesis, formation of the 2223 phase in the Bi-Sb-Sr-Ca-Cu-O system is possible. However, the critical temperatures of the samples are around 90 K and are lower than those of the superconducting materials from the Bi-Pb-Sr-Ca-Cu-O and Bi-Pb(Sb)-Sr-Ca-Cu-O systems. It was also found that V inhibits the formation of the phase 2223, raises the resistance of the samples and has a negative effect on theT _c and the phase composition of the Bi-Pb(V)-Sr-Ca-Cu-O materials.     

Significant Improvement in Superconductivity by Substituting Pb at Bi-site in Bi2?xPbxSr2CaCu2O8 with x=0.0 to 0.40

Here we report the synthesis and superconducting properties of bulk Bi_2−x Pb _x Sr₂CaCu₂O₈ (x=0.0 to 0.4) compound. Though the superconducting transition temperature (T _c) decreases marginally, the critical current density under magnetic field J _c(H) increases with Pb content. An optimization is observed for x=0.16 with J _c(H) (7.894×10³ A/cm²) that is nearly doubled in comparison to the pristine compound. It seems that controlled substitution of Pb at Bi-site in bulk Bi-2212 (Bi₂Sr₂CaCu₂O₈) system can enhance the superconducting critical parameters. These results are explained on the basis of possible improved inter- and intra-granular properties with Pb substitution in Bi_2−x Pb _x Sr₂CaCu₂O₈ system.     

Phase evolution and gas-phase particle size distributions during spray pyrolysis of (Bi,Pb)SrCaCuO and Ag(Bi,Pb)SrCaCuO powders

Phase evolution, gas-phase particle size distributions and lead loss were studied during formation of (Bi,Pb)SrCaCuO powders and their composites with silver by spray pyrolysis starting from nitrate solutions. The 10 wt% Ag/90 wt% Bi_1.8Pb_0.44Sr₂Ca_2.2Cu₃O_x composite powders made at 700°C consisted of 20–60 nm grains of silver and mixed-oxide phases with a fine dispersion of Ag grains within the particles. At 700°C, the primary phases present in (Bi,Pb)SrCaCuO powders were (Bi,Pb)₂Sr₂CuO_x (2201), Ca₂PbO₄ (plumbate), (Bi,Pb)₂Sr₂CaCu₂O_x(2212), and (Bi,Pb)₃Sr₂Ca₂Cu₁O_x(3221). For T≥800°C, the powders were considerably depleted in lead, and the plumbate and 3221 phases were absent. For T = 900°C, a large number of ultrafine particles (<30 nm) were formed, probably from the PbO vapor released from the reactor walls. Using spray pyrolysis, it is easy to control stoichiometry and limit the phase segregation at the nanometer-scale so that homogeneous and phase-pure materials can be obtained rapidly during subsequent processing.     

Effect of Pb Doping on the Superconducting Properties of?(Cu0.5?xPbxTl0.5)Ba2Ca2Cu3O10?δ

The effect of Pb doping on the superconducting properties of (Cu_0.5−x Pb _x Tl_0.5)Ba₂Ca₂Cu₃O_10−δ (x=0.0, 0.15, 0.25, 0.35) samples has been investigated. Lead is doped in Cu_0.5Tl_0.5Ba₂O_4−δ charge reservoir layer and at the CuO₂ planar sites. A multiphase material is achieved with the doping of Pb at the CuO₂ planar sites; however, a predominant single-phase (Cu_0.5−x Pb _x Tl_0.5)Ba₂Ca₂Cu₃O_10−δ (x=0.0, 0.15, 0.25, 0.35) material is synthesized with the doping of Pb at the charge reservoir layers. Formation of multiphase material with the doping of lead at the planar sites showed that its substitution at the planar site is not possible and the formation of PbO₂ planes is less likely. In the samples doped at the charge reservoir layer, the zero critical temperature [T _c (R=0)] is systematically depressed with the increased concentration of lead. The T _c (R=0) and magnitude of the diamagnetism are enhanced after post-annealing the samples in oxygen atmosphere. An apical oxygen mode is observed around 438 cm⁻¹ in undoped samples, which is shifted to 457–461 cm⁻¹ in the Pb-doped samples. This shift in the peak position is most likely associated with the connectivity of apical oxygen atoms with Pb atoms of (Cu_0.5−x Pb _x Tl_0.5)Ba₂O_4−δ (x=0.0, 0.15, 0.25, 0.35) charge reservoir layers. The presence of Pb in the charge reservoir layer and its increased concentration, somehow, stops the flow of mobile carriers to the conducting CuO₂ planes. The decreased density of mobile carriers diminishes the critical temperature and magnitude of diamagnetism in the final compound. The increased oxygen diffusion in the unit cell achieved by post-annealing in oxygen replenishes the concentration of carriers in conducting CuO₂ planes, which increases the T _c (R=0) and the magnitude of diamagnetism. These experiments have shown that the density of mobile carriers plays a vital role in the mechanism of superconductivity and their depressed density suppresses the superconductivity parameters.     

Structural and Physical Properties of Nd Substituted Bismuth Cuprates Bi1.7 Pb0.3−x Nd x Sr2Ca3Cu4O12+y

BiPb-2234 bulk samples with nominal composition of the compound Bi_1.7Pb_0.3−x Nd _x Sr₂Ca₃Cu₄O_12+y (BSCCO) (0.025≤x≤0.10) have been prepared by the melt-quenching method. The effects of Nd substitution on the BSCCO system have been investigated by electrical resistance (R–T), scanning electron microscopy (SEM), X-ray diffraction (XRD) and magnetic hysteresis measurements. It has been the BSCCO (2212) low-T _c phase is formed for all the substitution levels, together with the BSCCO (2223) high-T _c phase. The results obtained suggest that with increasing Nd³⁺ doping for Pb²⁺ the (2223) phase existing in undoped BSCCO gradually transforms into the (2212) phase and hence all of the samples have a mixed phase formation. The R–T result of the samples show two-step resistance transition; first transition occurs at 100 K and second in an interval of 80–90 K, depending on the Nd concentration. We have found that the magnetization decreases with increasing temperature in agreement with the general characteristic of the high-T _c materials. The samples exhibit weak field dependence particularly after 2 T and changes on the magnetic hysteresis, M–H curve rather small compared to the conventional superconducting materials. The maximum critical current density, J _c, value was calculated to be 8.51×10⁵ at 4.2 K and J _c decreases with increasing temperature and the substitution level.      

Sintering period dependence of composition and superconducting properties of (BiPb)SrCaCu,1.8Ox system

The material system (Bi_0.7Pb_0.3)Sr₁ Ca₁ Cu_1.8O _x forms, at 840° C, two major phases having a highT _c (100K) and a lowT _c (70 K) both of which consist of platelets and a non-superconducting minor phase which has a rod-like shape and is isolated by the major phases. As the sintering period increases, the amount of highT _c phase increases accompanying the decrease in lowT _c phase while the amount of the non-superconducting phase is independent of sintering period, resulting in a superconductor withT _c of 100 K. Changes in compositions of each phase also occur during sintering due to evaporation of bismuth and lead.     

Rapid formation of the high-T c phase in (Bi,Pb)-Sr-Ca-Cu-O superconductor via the sol-gel method

Bi-Pb-Sr-Ca-Cu-O powder was synthesized by the oxalate gel method. A sample with the composition of Bi_1.7Pb_0.4Sr_1.6Ca_2.4Cu_3.6O_y was used in this study. After pyrolysis of the gel precursor at 500 °C for 5 h, the resulting powder was calcined at 850 °C for another 5 h. The black powder was pressed into pellets and sintered at 852 °C for 5 h. The high-T _c phase was formed more easily in the sample with excess calcium and copper than in the theoretical composition. (Bi,Pb)₂Sr₂Ca₂Cu₃O_y (above 90%) was prepared as above within a relatively short time. Characterization of (Bi,Pb)₂Sr₂Ca₂Cu₃O_y superconductor by X-ray diffraction, scanning electron microscopy, electron probe microanalysis, resistivity measurement and magnetic measurement, is reported.     

Improving the Physical Properties of (Bi,Pb)-2223 Phase by SnO<Subscript>2</Subscript> Nano-particles Addition

In this work, the effect of SnO₂ nano-particles (40 nm) addition to the physical properties of Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10+δ superconducting phase was studied. (Bi, Pb)-2223 superconductor phase added by SnO₂ nano-particles was prepared by a conventional solid-state reaction technique. The SnO₂ nano-particles concentrations x varied from 0.0 to 2.0 wt% of the sample’s total mass. The prepared samples were investigated by X-ray powder diffraction (XRD), scanning electron microscope (SEM) and electron dispersive spectroscopy (EDS) for analyzing phase formation and microstructure. Also, the electrical resistivity and transport critical current density, for investigated samples, were measured by standard dc four-probe method. Phase examination by XRD indicated that SnO₂ nano-particles enhanced the (Bi, Pb)-2223 phase formation up to x=0.4 wt%. On the other hand, the high concentrations of SnO₂ nano-particles retarded the phase formation. Granular investigation, from scanning electron microscope, showed that both number and size of voids decreased as x increased from 0.0 to 0.4 wt%. The superconducting transition temperature and transport critical current density were found to have optimal values at x=0.4 wt%. The enhancement rates in T _c and J _c were 12 and 58%, respectively, which had a maximum enhancement in both J _c and T _c for all investigated nano-particles.     

Enhanced Electrical Transport Properties of Nano NiFe2O4-added (Bi1.6Pb0.4)Sr2Ca2Cu3O10 Superconductor

The effect of nanometer sized NiFe₂O₄ (∼15 nm) addition in Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O₁₀ (Bi2223) superconductor was studied. The (Bi_1.6Pb_0.4)Sr₂Ca₂Cu₃O₁₀ superconductor was prepared through the co-precipitation method and 0.01 wt% to 0.05 wt% of nano NiFe₂O₄ was added. The critical temperature (T _c), critical current density (J _c), phase formation and microstructure were investigated. All samples showed a major Bi2223 phase with (Bi,Pb)₂Sr₂CaCu₂O₈ (Bi2212) as the minor phase. The sample with 0.01 wt% nano NiFe₂O₄ showed the highest T _c and J _c: of more than 3 orders of magnitude higher than the non-added sample at 77 K. A further nano NiFe₂O₄ addition (>0.01 wt%) leads to degradation of T _c and J _c. These results indicate that addition of an optimum amount of NiFe₂O₄ nanoparticles can effectively enhance the transport critical current density in this system.