Effect of processing temperature on the superconducting properties of acetone doped MgB2 tapes

Correlation of phase formation, critical transition temperature T_c, microstructure, and critical current density J_c with sintering temperature has been studied for acetone doped MgB₂/Fe tapes. Sintering was performed at 600–850 °C for 1 h in a flowing Ar atmosphere. High boron substitution by carbon was obtained with increasing the sintering temperature; however, the acetone doped samples synthesized at 800 °C contain large size MgB₂ grains and more MgO impurities. Incomplete reaction for the acetone doped samples heated at 600 °C result in bad intergrain connectivity. At 4.2 K, the best J_c value was achieved in the acetone doped sample sintered at 700 °C, which reached 24,000 A/cm² at 10 T and 10,000 A/cm² at 12 T, respectively. Our results indicate that the small grain size and less impurity were also important for the improvement of J_c–B properties besides the substitutions of B by C.     

Spectroscopic properties of Co2+: ZnAl2O4 nanocrystals in sol–gel derived glass–ceramics

Transparent glass–ceramics containing zinc–aluminum spinel (ZnAl₂O₄) nanocrystals doped with tetrahedrally coordinated Co²⁺ ions were obtained by the sol–gel method for the first time. The gels of composition SiO₂–Al₂O₃–ZnO–CoO were prepared at room temperature and heat-treated at temperature ranging 800–950 °C. When the gel samples were heated up to 900 °C, ZnAl₂O₄ nanocrystals were precipitated. Co²⁺ ions were located in tetrahedral sites in ZnAl₂O₄ nanocrystals. X-ray diffraction analysis shows that the crystallite sizes of ZnAl₂O₄ crystal become large with the heat-treatment temperature and time, and the crystallite diameter is in the range of 10–15 nm. The dependence of the absorption and emission spectra of the samples on heat-treatment temperature were presented. The difference in the luminescence between Co²⁺ doped glass–ceramic and Co²⁺ doped bulk crystal was analysed. The crystal field parameter D_q of 423 cm⁻¹ and the Racah parameters B of 773 cm⁻¹ and C of 3478.5 cm⁻¹ were calculated for tetrahedral Co²⁺ ions.     

Critical current density in MgB2 bulk samples after co-doping with nano-SiC and poly zinc acrylate complexes

The co-doped MgB₂ bulk samples have been synthesized using an in situ reaction processing. The additives is 8 wt.% SiC nano powders and 10 wt.% [(CH₂CHCOO)₂Zn]_n poly zinc acrylate complexes (PZA). A systematic study was performed on samples doped with SiC or PZA and samples co-doped with both of them. The effects of doping and co-doping on phase formation, microstructure, and the variation of lattice parameters were studied. The amount of substituted carbon, the critical temperature (T_c) and the critical current density (J_c) were determined. The calculated lattice parameters show the decrease of the a-axis, while no obvious change was detected for c-axis parameter in co-doped samples. This indicates that the carbon was substituted by boron in MgB₂. The amount of substituted carbon for the co-doped sample shows an enhancement compared to that of the both single doped samples. The co-doped samples perform the highest J_c values, which reaches 3.3 × 10⁴ A/cm² at 5 K and 7 T. It is shown that co-doping with SiC and organic compound is an effective way to further improve the superconducting properties of MgB₂.     

Influence of Zr and Ce doping on electromagnetic properties of (Gd,Y)–Ba–Cu–O superconducting tapes fabricated by metal organic chemical vapor deposition

(Gd,Y)Ba₂Cu₃O_x tapes have been fabricated by metal organic chemical vapor deposition (MOCVD) with Zr-doping levels of 0–15 mol.% and Ce doping levels of 0–10 mol.% in 0.4 μm thick films. The critical current density (J_c) of Zr-doped samples at 77 K, 1 T applied in the orientation of H 6 c is found to increase with Zr content and shows a maximum at 7.5% Zr doping. The 7.5% Zr-doped sample exhibits a critical current density (J_c) of 0.95 MA/cm² at H 6 c which is more than 70% higher than the J_c of the undoped sample. The peak in J_c at H 6 c is 83% of that at H 6 a–b in the 7.5% Zr-doped sample which is more than twice as that in the undoped sample. Superconducting transition temperature (T_c) values as high as about 89 K have been achieved in samples even with 15% Zr and 10% Ce. Ce-doped samples with and without Ba compensation are found to exhibit substantially different J_c values as well as angular dependence characteristics.     

Stoichiometry dependence of the critical current density in pure and nano-SiC doped MgB2/Fe tapes

The stoichiometry dependence of the microstructure and superconducting properties of pure and nano-SiC doped MgB₂/Fe tapes was systematically investigated. The tapes prepared with the composition of a slight deficiency of Mg (Mg_0.9B₂ and Mg_xB₂(SiC)_0.1 (x = 0.9 and 1.0)) showed the best transport J_c. Adding a slight excess of Mg like 5%, as being done by many researchers, was not beneficial for the J_c improvement as expected. The onset T_c was not significantly changed in both doped and undoped tapes by adding excess of boron or magnesium, but the transition widths were broadened due to the induced impurities. The slightly-Mg-deficient pure samples show smaller grain sizes, which corresponds to a better J_c–B performance at high magnetic field due to the enhanced grain boundary pinning. The field dependence of J_c in nano-SiC doped tapes was almost not influenced by varying the starting Mg content although microstructural difference can still be seen, suggesting that the flux pinning ability was mainly controlled by the carbon substitution effect for boron.     

Increase of critical current density with doping carbon nano-tubes in YBa2Cu3O7−δ

The effects of carbon nano-tubes (CNTs) on the crystal structure and superconducting properties of YBa₂Cu₃O_7?δ (Y-123) compound were studied. Samples were synthesized using standard solid-state reaction technique by adding CNT up to 1 wt% and X-ray diffraction data confirm the single phase orthorhombic structure for all the samples. Current–voltage measurements in magnetic fields up to 9 T were used to study the pinning energy U_J and critical current density J_c as a function of magnetic field at fixed temperature. We find that while T_c does not change much with the CNT doping (91–92 K), both U_J and J_c increase systematically up to 0.7 wt% CNT doping in a broad magnetic field ranges between 0.1 and 9 T and J_c in the 0.7 wt% CNT doped sample is at least 10 times larger than that of the pure Y-123. The scanning electron microscope image shows that CNTs are forming an electrical-network between grains. These observations suggest that the CNT addition to the Y-123-compounds improve the electrical connection between superconducting grains to result in the J_c increase.     

Large transport critical currents of powder-in-tube Sr0.6K0.4Fe2As2/Ag superconducting wires and tapes

We report the achievement of transport critical currents in Sr_0.6K_0.4Fe₂As₂ wires and tapes with a T_c = 34 K. The wires and tapes were fabricated through an in situ powder-in-tube process. Silver was used as a chemical addition as well as a sheath material. All the wire and tape samples have shown the ability to transport superconducting current. Critical current density J_c was enhanced upon silver addition, and at 4.2 K, a largest J_c of ～1200 A/cm² (I_c = 9 A) was achieved for 20% silver added tapes, which is the highest in iron-based wires and tapes so far. The J_c is almost field independent between 1 T and 10 T, exhibiting a strong vortex pinning. Such a high transport critical current density is attributed to the weak reaction between the silver sheath and the superconducting core, as well as an improved connectivity between grains. We also identify a weak-link behavior from the apparent drop of J_c at low fields and a hysteretic phenomenon. Finally, we found that compared to Fe, Ta and Nb tubes, Ag was the best sheath material for the fabrication of high-performance 122 type pnictide wires and tapes.     

MgB2 coated superconducting tapes with high critical current densities fabricated by hybrid physical-chemical vapor deposition

The MgB₂ coated superconducting tapes have been fabricated on textured Cu (0 0 1) and polycrystalline Hastelloy tapes using coated conductor technique, which has been developed for the second generation high temperature superconducting wires. The MgB₂/Cu tapes were fabricated over a wide temperature range of 460-520 °C by using hybrid physical-chemical vapor deposition (HPCVD) technique. The tapes exhibited the critical temperatures (T_c) ranging between 36 and 38 K with superconducting transition width (ΔT_c) of about 0.3-0.6 K. The highest critical current density (J_c) of 1.34 × 10⁵ A/cm² at 5 K under 3 T is obtained for the MgB₂/Cu tape grown at 460 °C. To further improve the flux pinning property of MgB₂ tapes, SiC is coated as an impurity layer on the Cu tape. In contrast to pure MgB₂/Cu tapes, the MgB₂ on SiC-coated Cu tapes exhibited opposite trend in the dependence of J_c with growth temperature. The improved flux pinning by the additional defects created by SiC-impurity layer along with the MgB₂ grain boundaries lead to strong improvement in J_c for the MgB₂/SiC/Cu tapes. The MgB₂/Hastelloy superconducting tapes fabricated at a temperature of 520 °C showed the critical temperatures ranging between 38.5 and 39.6 K. We obtained much higher J_c values over the wide field range for MgB₂/Hastelloy tapes than the previously reported data on other metallic substrates, such as Cu, SS, and Nb. The J_c values of J_c(20 K, 0 T) ∼5.8 × 10⁶ A/cm² and J_c(20 K, 1.5 T) ∼2.4 × 10⁵ A/cm² is obtained for the 2-μm-thick MgB₂/Hastelloy tape. This paper will review the merits of coated conductor approach along with the HPCVD technique to fabricate MgB₂ conductors with high T_c and J_c values which are useful for large scale applications.     

Significant enhancement of electrical transport properties of thermoelectric Ca3Co4O9+δ through Yb doping

We report the significant enhancement of the power factor of Ca₃Co₄O_9+δ through Yb doping. The pellets were prepared by pressing under 0.5 GPa and 2 GPa. The highest power factor of 553 μW m^?1 K^?2 due to the significant increase of electrical conductivity was obtained for Ca_2.9Yb_0.1Co₄O_9+δ pressed at 0.5 GPa. This is 2.3 times higher than that of Ca₃Co₄O_9+δ (246 μW m^?1 K^?2). Nanostructure examinations show that the pellets pressed at 0.5 and 2 GPa have different nano-lamella structures. This work suggests that Yb is an effective doping element for enhancing the electrical transport properties of Ca₃Co₄O_9+δ, and the optimum doping level is related to the nanostructure of the bulk pellets.     

The effect of pinning centers in Zn-doped CuBa2Ca3Cu4O12−y high-temperature superconductors

CuBa₂Ca₃Cu₄O_12−y (Cu:1234) high-temperature superconductors (HTS) doped with up to 2% Zn were grown using the high-pressure synthesis technique. Magnetization loops of the samples were measured at various temperatures between 5 and 77.3 K and magnetic fields up to 14 T. Critical current densities J_c of the samples were estimated using the critical state model. The results show that Zn-induced pinning centers increase J_c of Cu:1234 several times, depending on field and temperature. From the experimentally determined field-temperature region in which a higher Zn concentration lead to a higher J_c, we suggest the existence of a cross-over from quite efficient, extended (in the c-axes direction) pinning centers to point-like (inefficient) pinning centers at a certain temperature, depending on field. This effect can be attributed to the fact that, unlike other HTS, in Cu:1234 there is a second critical temperature T_c2 of about 70–80 K (in zero field, and 50–60 K in 15 T), related to the over-doping of pyramidal basal plane (outer CuO₂ plane).     

Effect of W-addition on pinning property of MgB2

The 5d transition metal W was added into the MgB₂ superconductor. The Mg, B and W were sintered at 1173 K for 30 min under H₂/Ar atmosphere in the electric furnace. The W_x(MgB₂)_1?x samples were prepared in the W concentration range of 0 ? x ? 0.05. Temperature and field dependences of magnetization were measured by the SQUID magneto-meter. The field and x dependences of J_c at 20 K were analyzed by the extended critical state model. The enhancement of J_c became maximum for the x = 0.02 sample.     

Preparation of solution-based YBCO films with BaSnO3 particles

The YBCO films with BaSnO₃ (BSO) particles were prepared on LAO (0 0 1) substrates by metal organic deposition using trifluoroacetates (TFA-MOD) via introducing SnCl₄ powders into the YBCO precursor solution. It was found that with the increase of the SnCl₄ contents, the slower decomposition and higher temperature for nucleation during the reaction were requested compared to that of pure YBCO film. The YBCO films with different contents of Sn with dense surface and well c-alignment were obtained under optimized heat treatment, and the BaSnO₃ phases were detected by XRD analysis. Litter effect of BSO particles on the T_c and J_c values of YBCO films was found. All YBCO films with BSO particles had T_c values over 90 K and J_c values over 1 MA/cm². A significant enhancement of J_c was observed for YBCO films with BSO particles compared to that of pure YBCO film by the field dependence of J_c values. The best property was obtained for YBCO film with 6 mol.% Sn at 77 K under magnetic field. The results showed that the J_c value of YBCO film with 6 mol.% Sn was enhanced by a factor of 2 in 2 T, and over a factor of 10 beyond 4 T compared to that of pure YBCO film.     

Effects of Y2O3 additions on the oxygen diffusion in top-seeded melt growth processed YBa2Cu3O7−y superconductors

To understand the effect of Y₂BaCuO₅ (Y211)/YBa₂Cu₃O_7?y (Y123) interfaces on the oxygen diffusion in single grain YBa₂Cu₃O_7?y superconductors, single grain Y123 superconductors with 0.05 and 0.3 moles of Y₂O₃ additions were fabricated by a top-seeded melt growth (TSMG) process. Y123 compacts with Y₂O₃ additions were subjected to melt growth heating cycles with a cooling rate of 1 °C/h through a peritectic temperature (1015 °C) and then annealed at 450 °C for 200 h in flowing oxygen. The superconducting temperature (T_c) and critical current density (J_c) were estimated for the three different regions (top surface (s), intermediate (i) and center (c)) of samples. The amount of Y211/Y123 interface area in single grain Y123 superconductors was successfully controlled by Y₂O₃ additions. The T_c values of s regions were higher than those of i and c regions, which indicates the presence of more oxygen at the sample surfaces. In addition, the T_c values of i and c regions of the Y123 sample with 0.3 mole Y₂O₃ addition were higher than those of the same regions of the Y123 sample with 0.05 mole Y₂O₃ addition due to the promoted oxygen diffusion through Y211/Y123 interfaces and other related defects. In spite of the promoted oxygen diffusion by Y₂O₃ addition, the large T_c difference among the regions still existed, which suggests sluggish oxygen diffusion into single Y123 grains.     

Reel-to-reel fabrication of meter-long YBCO coated conductor

YBa₂Cu₃O_7?δ (YBCO) superconductors were coated on the CeO₂/YSZ/Y₂O₃ buffered Ni-5at%W tapes by a reel-to-reel pulsed laser deposition (PLD). The process of a multi-layer deposition of YBCO film was explored. X-ray diffraction texture measurements showed good both in-plane and out of plane crystalline orientations in YBCO films. The average values calculated at a full width at half maximum (FWHM) of the peaks from phi-scans (φ) and omega (ω) scans for one meter-long YBCO tape were 7.49° and 4.71°, respectively. The critical current (I_c) was over 200 A/cm-width at 77 K and under self-field for meter-long YBCO tape. The critical transition temperature of the YBCO tape was typically as 90.1 K with 0.5 K transition widths.     

Epitaxial growth of Ce2Y2O7 buffer layers for YBa2Cu3O7−δ coated conductors using reel-to-reel DC reactive sputtering

Biaxially textured Ce₂Y₂O₇ (CYO) films were deposited on Ni–5at.%W (Ni–5W) tapes by a DC reactive sputtering technique in a reel-to-reel system. Subsequent YBa₂Cu₃O_7?δ (YBCO) films were prepared using pulsed laser deposition leading to a simplified coated conductor architecture of YBCO/CYO/Ni–5W. X-ray diffraction measurements revealed an epitaxial growth of the CYO buffer layer with a texture spread down to 2.2° and 4.7° for the out-of-plane and in-plane alignment, respectively. Microstructural investigations showed a dense, smooth and crack-free surface morphology for CYO film up to a thickness of 350 nm, implying an effective suppression of cracks due to the incorporation of Y in CeO₂. The superconducting transition temperature T_c of about 90 K with a narrow transition of 0.8 K and the inductively measured critical current density J_c of about 0.7 MA/cm² indicate the potential of the single CYO buffer layer.     

Improved critical current density in Zn doped YBCO single crystals

Magnetic measurements were made using pure YBCO and Zn doped YBa₂(Cu_1?xZn_x)₃O_7?σ. Single crystals with Zn concentration of 0.5%, 1.5%, 3.0% and 4.3%. The magnetic hysteresis loops for these samples were measured in the temperature range 0.1 ? T/T_c ? 0.96 under magnetic fields of 5 T using SQUID. It was found that the critical current density J_c increased for low Zn content samples up to 3% Zn concentration compared to pure YBCO sample and decreased for the higher Zn content samples. These values varied consistently when compared at magnetic fields of 1 T and 3 T. Moreover Zn doped samples showed significant values of J_c in the temperature range of 0.7–0.9T_c, close to critical temperature compared to pure YBCO sample. The irreversibility field H_irr was also enhanced in this temperature range showing consistent decrease with increase of Zn concentration. The peak field H_p above H_c1 and irreversibility field H_irr, both show power law dependence of the form H = m₁(1 ? T/T_c)^m2 in the temperature range of 0.75–0.96T_c. The values of parameter m₂ increased from 1.44 to 1.95 for the samples up to 3% Zn content and decreased to 1.37 for higher Zn contents. The ratio H_irr/H_p was found to be 3–4 for the lower Zn content samples and was 7–8 for the sample with high Zn content indicating more disorder for higher Zn content samples. The region between peak field H_p and irreversibility field H_irr was broadened with the increase of Zn concentration. The strong effect of Zn substitution in modifying behavior of these samples even at elevated temperatures is possibly due to the changes in the anisotropy of our samples with the increase of Zn concentration and also due to the locally induced changes in magnetic moments by Zn substitution.     

Sputtered magnesium diboride thin films: Growth conditions and surface morphology

Magnesium diboride (MgB₂) thin films were deposited on C-plane sapphire substrates by sputtering pure B and Mg targets at different substrate temperatures, and were followed by in situ annealing. A systematic study about the effects of the various growth and annealing parameters on the physical properties of MgB₂ thin films showed that the substrate temperature is the most critical factor that determines the superconducting transition temperature (T_c), while annealing plays a minor role. There was no superconducting transition in the thin films grown at room temperature without post-annealing. The highest T_c of the samples grown at room temperature after the optimized annealing was 22 K. As the temperature of the substrate (T_s) increased, T_c rose. However, the maximum T_s was limited due to the low magnesium sticking coefficient and thus the T_c value was limited as well. The highest T_c, 29 K, was obtained for the sample deposited at 180 °C, annealed at 620 °C, and was subsequently annealed a second time at 800 °C. Three-dimensional (3D) AFM images clearly demonstrated that the thin films with no transition, or very low T_c, did not have the well-developed MgB₂ grains while the films with higher T_c displayed the well-developed grains and smooth surface. Although the T_c of sputtered MgB₂ films in the current work is lower than that for the bulk and ex situ annealed thin films, this work presents an important step towards the fabrication of MgB₂ heterostructures using rather simple physical vapor deposition method such as sputtering.     

Flux pinning in columnar-structured and single crystalline MgB2 films

We have investigated the flux pinning effect of columnar grain boundary in columnar-structured and single crystalline MgB₂ films. The MgB₂ films with columnar structure showed much higher J_c than that of single crystalline thin film, and sample having smaller grain size had a higher J_c in high magnetic fields. At 5 K, the MgB₂ film with grain size of 460 nm showed an abnormal double-peak behavior in pining force density, F_p(B), caused by competition of different types of pinning sites, such as planar defects and point defects. Field dependences of F_p in columnar-structured films suggest that the columnar grain boundary is a strong pinning source in the MgB₂ film and it plays a crucial role in enhancing J_c over a wide range of magnetic fields and temperatures.     

Epitaxial growth of La2Zr2O7 buffer layers for YBa2Cu3O7−δ coated conductors on metallic substrates using pulsed laser deposition

In the present work, La₂Zr₂O₇ (LZO) buffer layers were deposited using pulsed laser deposition (PLD) on various metallic substrates including epitaxial pure Ni on a LaAlO₃ (LAO) substrate as well as highly textured Ni–5 at.%W tapes. It is shown that the LZO deposited on pure Ni-buffered LAO exhibits a mixed orientation while LZO on Ni–5 at.%W grows epitaxially. This difference may be explained by the existence of a sulphur superstructure on the surface of Ni–5 at.%W tapes, promoting the epitaxial (0 0 l) nucleation of seed layers. Highly textured YBa₂Cu₃O_7?δ layers were prepared either by using a single buffer layer of LZO or bilayer buffers of CeO₂/LZO on Ni–5 at.%W. The superconducting transition temperature (T_c) increases with the LZO thickness, reaching a value of 90 K with a very narrow transition width (1.5 K) for 240 nm thick LZO layers. Inductive J_c measurements at 77 K in self-field show a value of about 0.96 MA/cm² for the thickest LZO layers, which is comparable to the value observed on standard buffer architectures such as CeO₂/YSZ/Y₂O₃.     

Carbon doping of MgB2 by toluene and malic-acid-in-toluene

The decomposition of malic acid (C₄H₆O₅) in the presence of Mg and B was studied using Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA) which revealed that malic acid reacted with Mg but not B. Also, the addition of toluene (C₇H₈) to dissolve malic acid followed by subsequent drying resulted in no reaction with Mg, indicating that the malic acid had decomposed during the dissolution/drying stage. The total carbon contributed by toluene versus a toluene/5 wt.% malic acid mixture was measured using a LECO CS600 carbon analyzer. The toluene sample contained ～0.4 wt.% C while the toluene/malic acid mixture had ～1.5 wt.% C, demonstrating that the toluene contributed a significant amount of carbon to the final product. Resistivity measurements on powder-in-tube MgB₂ monofilamentary wires established that the toluene/malic acid doped sample had the highest B_c2. However, the toluene-only sample had the highest transport J_c over most of the magnetic field range (0–9 T), equaled only by that of toluene/malic-acid sample in fields above 9 T.