Formation of SrSnO3 shell-like inclusions in the Bi2Sr2CaCu2O8+x superconductor via chemical reaction

Superconducting composites Bi-2212–SrSnO₃ have been prepared by reacting between the Bi–Sr–Ca–Cu–O precursor and Sr₂SnO₄ or Ca₂SnO₄ at 800–950°C, followed by crystallisation of Bi-2212 from the partial melt at decreasing temperature. The samples have been characterised by powder X-ray diffraction, scanning electron microscopy and magnetic measurements. The materials consist of large Bi-2212 lamellae and complex-shaped fine inclusions of SrSnO₃. The composite obtained using Sr₂SnO₄ contains almost all the SrSnO₃ phase in the form of micron-sized spherical shells, which are partly included in Bi-2212 lamellae, partly agglomerated in-between. The shells are perforated, thus allowing the Bi-2212 crystals to grow through them. It has been found that the shell-like grains form at an early stage of the precursor thermal treatment between 800 and 850°C. A mechanism of the SrSnO₃ shell formation is proposed. The composites exhibit T_c in the range of 82–87 K and reveal up to five times better magnetic flux pinning at T≥30 K in comparison with the undoped Bi-2212 sample prepared using the same experimental procedure.     

Plan-view preparation of TEM specimens from thin films using adhesive tape

A simple plan-view sample preparation technique for transmission electron microscopy (TEM) specimens is proposed for thin films by tearing-off the film with adhesive tape. The demand for very thin samples is highest for nanostructured materials where the structure of 2-5 nm sized features (grains) needs to be resolved; therefore, overlapping of nanometer-sized features should be avoided. The method provides thin areas at the fracture edges of plan-view specimens with thickness in the range of the grain size in the film allowing for artifact free high-resolution TEM imaging. Nanostructured materials typically fracture between the grains providing areas with the thickness of the grain size. Besides the swiftness of the method, the samples are free of surface amorphization artifacts, which can occur in ion beam milling up to 1 nm depth even at low energy ion bombardment. The thin film tear-off technique is demonstrated on a CuMn alloy thin film with grain size of 2 nm.     

Umwandlungen glasförmiger BSCCO-Vorstoffe in den kristallinen Zustand

The glassy precursors were fabricated by quenching the melted materials with copper plates. In the case of heating the properties of the quenched samples were changed, because as a result of solid-state reactions formation of cuprate occurs. The amorphous samples were annealed in air and transformed to the crystalline state. This process can be seen by DTA and electric resistivity behaviours. The microscopic observation of the polished surfaces show the growth of the superconducting phase Bi₂Sr₂CaCu₂O_8+x (for composition Bi-2212) and Bi₂Sr₂CaCu₂O_8+x with Bi₂Sr₂Ca₂Cu₃O_10+x (for composition Bi-2223 and Bi-2234), respectively.     

Effect of mechanical activation on the thermal stability of polytetrafluoroethylene powder

It was found that processing in a planetary activator leading to amorphization of the structure of polytetrafluoroethylene powder was not accompanied by a noticeable decrease in its thermal stability. It was established that the temperature at the onset of melting drops slightly, the melting rate increases, and the enthalpy of the endoeffect declines noticeably heating.     

铋系2223相形成机理及单相块材的合成

在化学动力学基础上，指出了Ｂｉ系２２２３超导相的形成，经历了先由２２０１相与ＣａＯ、ＣｕＯ相互作用生成２２１２相，随后由２２１２相再与ＣａＯ及ＣｕＯ作用产生２２２３相的过程。同时，论证了ＣａＯ面进入２２１２相元胞是形成２２２３相的控制步骤，用分步法及加入籽晶的工艺，制备了２２２３单相块材。     

Metal-organic deposition of YBa2Cu3Ox and Bi2Sr2Ca1Cu2Ox films on various substrates starting from different fluorine-free metallorganic compounds

YBa₂Cu₃O_x (Y-123) and Bi₂Sr₂Ca₁Cu₂O_x (Bi-2212) films on various substrates have been prepared by Metal-Organic Deposition starting from different metallorganic fluorine-free compounds and using a very simple instrumentation. The processing conditions include a rapid pyrolysis step in air and an annealing step in oxygen for Y-123 and in air for Bi-2212. The films obtained have been characterized by X-ray diffraction (XRD) and the formation of a superconducting phase of Y-123 or Bi-2212 was confirmed measuring the critical temperature (T _c) with Ac-susceptibility and resistive measurements. Microstructure and final cationic ratios have been studied by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS).     

High temperature Ho<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZrO<Subscript>2</Subscript> insulation coatings on AgMg sheathed Bi-2212 superconducting tapes by sol–gel technique for magnet technology

High temperature 0, 5, 8 and 12 mol % Ho₂O₃–ZrO₂ insulation coatings were successfully deposited on Ag and AgMg/Bi-2212 superconducting tapes using sol–gel technique for magnet technologies. With this purpose, transparent solutions were prepared from Ho and Zr-based precursor materials and then Ho₂O₃ effect on thermal, structural and microstructural properties were observed and discussed in the present study. It was found that Ho₂O₃ additive has a propensity to generate tetragonal ZrO₂ and help to stabilize it. It was observed that insulation coatings with a mosaic structure having cracks were fully compatible with Ag/AgMg sheathed Bi-2212 tape substrates because of oxygen permeability, high and low actual temperatures and W&R process in comparison with the conventional insulation process. In addition, surface roughness decreased with increasing Ho₂O₃ content, thereby decreasing the grain size. Although porosity values vary considerably from one porosity mesurement expression to another, porosities of the insulation coatings can be estimated to be in the range of 3 and 30 vol %.     

Study on Phase-Formation Mechanism and Intergrowth for Bi(Pb)-Sr-Ca-Cu-O System

In this paper, the phase-formation mechanism of Bi-based superconductors was systematically investigated by using high-temperature X-ray diffraction, differential thermal analysis (DTA) and crystallization of amorphous state. The transformations among Bi-based 2201, 2212 and 2223 phases were observed, and the intergrown phenomenon of the 2201, 2212 and 2223 phases was explained. It was proposed that there exist a composition equilibrium between 2212 phase and Ca2CuO3 and a competition of thermody-namic stability among Ca2CuO3, 2212 and 2223 phases. This is why it is difficult to prepare the 2223 phase. After Pb was doped in Bi-Sr-Ca-Cu-O system, Ca2CuO3 phase in the Bi-Sr-Ca-Cu-O system was replaced by Ca2PbO4, so that the composition equilibrium and competition of thermodynamic stability mentioned above were avoided.     

Quantum tunneling of magnetization via well-defined Dy–Cu exchange coupling in a ferrimagnetic high-spin [Dy4Cu] single-molecule magnet

A centrosymmetric rectangular complex [Dy₄Cu] was prepared from dysprosium(III) 1,1,1,5,5,5-hexafluoropentane-2,4-dionate and copper(II) dimethylglyoximate. From magnetic studies, the Dy magnetic moments are all aligned parallel at the ground state via antiferromagnetic superexchange interaction with the central Cu spin. In pulsed-field magnetization measurements at 0.5 K, complex [Dy₄Cu] exhibited magnetization steps with hysteresis, which is typical of a single-molecule magnet. This behavior is explained in terms of a simple Ising model together with well-defined Dy–Cu exchange coupling (−0.64 K).     

Composites supraconducteurs “oxyde / oxyde”: Conditions de frittage et propriétés électriques de composites Bi-2212 / isolant

In order to improve the electrical and/or mechanical properties of bismuth cuprate superconductors, composites have been elaborated by pressing polycrystalline Bi₂Sr₂CaCu₂O_{8 + δ} (2212) mixed with two insulator oxides into pellets, which were sintered near 800 °C. A large domain of composition was investigated. The Bi₂CuO₄ (2001) oxide reacts with the Bi-2212, decreases its T_c value but can increase its mechanical resistance. The Bi₂Sr₃CaO₇ (2310) oxide seems not to react with the 2212. A zero resistance at low temperature (> 40K) is observed up to 30 vol.% of superconductor oxide (20 vol.% taking into account the insulating cavities) in the 2310/2212 composites.     

Gas vacuoles formation during the dehydration of trehalose dihydrate: A Raman microspectroscopy approach

Dehydration of trehalose dihydrate implemented by slow heating (1 K min⁻¹), has been monitored by Raman microspectroscopy from 25 to 110°C directly on single crystals. Between 90 and 120°C, gas initially trapped in irregular macroscopic defects, reorganizes to form spherical vacuoles. The Raman analysis of these vacuoles highlights that the areas in vicinity of the defects are the first affected by the dehydration mechanisms. Indeed, the progressive amorphization of the crystal starts around these defects.     

Oxygen exchange study in phase transformations of superconducting bismuth cuprates (Pb2212 and Pb2223)

The oxygen exchange between the condensed phase(s) and the gas phase was studied as a function of temperature for superconducting phases of the system (Bi,Pb)-Sr-Ca-Cu-O.An oxygen probe apparatus allowed confirmation that the variation in oxygen composition in the Pb2212 and Pb2223 superconducting phases is a reversible phenomenon on heating and cooling. It was demonstrated that the mass loss of both phases, for the 905 and 980°C isotherms, was due to the oxygen composition variation and to PbO loss (this latter phenomenon begin irreversible).     

Polarized Raman spectroscopic study of relaxed high density amorphous ices under pressure

We have made high density amorphous ice (HDA) by the pressure-induced amorphization of hexagonal ice at 77 K and measured the volume change on isobaric heating in a pressure range between 0.1 and 1.5 GPa. The volume of HDA on heating below ～0.35?GPa increases, while the volume of HDA on heating above ～0.35?GPa decreases. The polarized OH-stretching Raman spectra of the relaxed HDAs are compared with that of the unannealed HDA. The relaxed HDAs are prepared at 0.2 GPa at 130 K and 1.5 GPa at 160 K. It is found that the relatively strong totally symmetric OH-stretching vibration mode around 3100?cm(-1) exists in the depolarized reduced Raman spectrum χ(VH)(") of the unannealed HDA and that its intensity rapidly decreases by relaxation. The χ(VH)(") profiles of the relaxed HDA are similar to those of liquid water. These results indicate that the HDA reaches a nearly equilibrium state by annealing and the intrinsic state of HDA relates to a liquid state. The pressure-volume curve of the relaxed HDA at 140 K seems to be smooth in the pressure range below 1.5 GPa.     

稻秆半焦与CO2气化反应特性的研究

利用三种热解炉装置,分别在热解终温550℃～950℃、加热速率0.1K/s～500K/s下热解制取稻秆半焦。采用等温热重法,在STA409综合热分析仪上进行了稻秆半焦与CO₂的气化实验,考察了热解终温、热解速率以及气化温度对半焦气化反应性的影响。研究表明,热解条件对稻秆半焦的反应性影响很大。在热解终温为550℃～950℃时,随着热解温度的提高,其气化反应性呈下降趋势;热解速率越高,其气化反应性越好。在850℃～950℃,提高气化温度能提高稻秆半焦与CO₂的反应性。采用扫描电镜技术观测了0.1K/s和500K/s 两种热解速率下半焦的表面形貌。结果显示,后者具有更加丰富的孔隙结构,且大孔结构明显多于前者。采用混合反应模型描述了稻秆半焦与CO₂的气化反应过程,求取了反应动力学参数。     

Thermoanalytical studies of the processing of bulk and thin film BSCCO highT c superconductors by the Edita-Gel route

The decomposition of EDTA gel precursors for BSCCO superconductor manufacture has been studied using STA (TG/DTA) and dilatometry in conjunction with FTIR. Ther thermoanalytical data are discussed in relation to the sequence of phase formation necessary for the production of the 2223 BSCCO superconducting phase. Thin film preparation of Bi-based highT _c superconductors have been carried out on MgO (100). Grain orientation of oxide thin films has been investigated. Well orientated 2212 grains have been achieved, with the (001) planes parallel to the substrate. The EDTA-gel method has been modified by the addition of glycerol to achieve the appropriate viscosity for spin coating. STA has been used to study the decomposition of these modified gels for the formation of thin films.     

Thermal behaviors of poly(ethylene terephthalate)/SiO2 nanocomposites prepared by cryomilling

The thermal behaviors of poly (ethylene terephthalate) (PET)/SiO₂ nanocomposites prepared by cryomilling were studied, by comparing with the cryomilled PET and the raw PET. Cryomilling induced amorphization of crystalline PET matrix and the decrease of PET molecular weight. Cryomilled PET/SiO₂ nanocomposites have two abnormal phenomena in the DSC 1st heating thermogram due to the stored energy induced by cryomilling. During DSC cooling process, the dispersed nanometer SiO₂ particles play a role of nucleating agent in PET matrix, and the hot crystallization ability of PET/SiO₂ nanocomposites improves a lot. Besides, the heat stability of cryomilled PET/SiO₂ nanocomposites improves more much during reheating. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1351–1356, 2006     

Water's polyamorphic transitions and amorphization of ice under pressure

Transformations of water's high density amorph (HDA) to low density amorph (LDA) and of LDA's to cubic ice (Ic) have been studied by in situ thermal conductivity kappa measurements at high pressures. The HDA to LDA transformation is unobservable at p of 0.07 GPa, indicating that, for a fixed heating rate, an increase in pressure increases the temperature of HDA to LDA transformation and decreases that of LDA to ice Ic, causing thereby the two transformations to merge, and HDA appears to convert directly to ice Ic. Thus either LDA forms but converts extremely rapidly to ice Ic, or LDA does not form. At a fixed p and T, in the range of pressure amorphization of hexagonal ice, kappa continues to decrease with time. Therefore, the amorphization of ice Ih is kinetically controlled. When HDA at 1 GPa was heated from 130 to 157 K and densified to very HDA, its kappa increased by 3%. Our findings and a scrutiny of earlier reports show that a reversible transition between HDA and LDA does not occur at approximately 135 K and approximately 0.2 GPa. Since there is no unique HDA, it is difficult to justify the conjecture for a second critical point for water.     

Ceramic Tl-oxide based superconductors reinvestigated by magnetic separation technique and SQUID measurements

Ceramic samples of Tl₂Ba₂Ca₂Cu₃O₁₀ (Tl-2223) and TlBa₂Ca₂Cu₃O₉ (Tl-1223) superconductor were resynthesized by using several preparation procedures and investigated by means of magnetic separation technique, allowing evaluation of the superconducting critical temperature of individual grains as small as 25 μm. Although an onset of diamagnetism detected by SQUID measurements was observed around 130 K in Tl-2223 and 134 K in Tl-1223, no grains with T_c > 125 K were found for Tl-2223 and with T_c > 130 K for Tl-1223. Furthermore, the volume fraction of superconductivity of such ceramics was less than 5% and 3% in best samples of Tl-2223 and Tl-1223, respectively. Here we provide a detailed comparison of results obtained by magnetic separation technique with those by SQUID applied to individual grains and bulk samples.     

Effects of dehydration temperatures on moisture absorption and dissolution behavior of theophylline.

Anhydrous theophylline was prepared by heating theophylline monohydrate at temperatures between 60 degrees C and 140 degrees C. The effects of dehydration temperatures on the moisture absorption and dissolution behavior of anhydrous theophylline were investigated in this study. The hydration rate of anhydrous theophylline at 95% relative humidity and 25 degrees C decreased with increasing dehydration temperatures. From the fitting analysis of solid-state reaction models, the hydration reaction was found to be governed by the phase boundary reaction model for samples prepared at lower dehydration temperatures (<100 degrees C) but the reaction obeyed the growth of nuclei reaction model when samples were dehydrated at higher temperatures. The dissolution rates of various anhydrous theophylline samples were measured by the rotating disk method. The calculated solubility of anhydrous theophylline prepared by heating was about 2.5 times higher than that of theophylline monohydrate. The phase transformation rate from the anhydrous form to the monohydrate during dissolution tests decreased with higher dehydration temperatures. It was found that the anhydrous theophylline prepared at different dehydration temperatures transformed to the monohydrate by way of different growth of hydrate nuclei mechanism.     

Study of structural heterogeneity of HTSC Bi-ceramics

Using Bi-ceramics as an example, we estimate here the possibility of detemination of the structural heterogeneity of HTSC materials from X-ray powder diJjZaction data. me heterogeneity is due to the presence of alternating layers of different types within individual microcrystals. Explicit information on alternating fragments of diferent height is provided by the intensity distribution data of basal reflections, therefore we studied X-ray diffraction patterns of oriented specimens. The dipaction patterns from unidimensionally disordered structures were simulated based on a previously devised procedure for the calculation of dipaction profiles of mixed-layer minerals. The comparison of calculated and experimental dipaction patterns testifies that defects in the samples are really caused by the presence of layers of different heights corresponding to the 2212 phase built into the matrix of the basic 2223 phase. The concentration of such defects reaches 20% with a high segregation degree of both layer types.Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Geological Institute, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 5, pp. 133–146, September–October, 1993.Translated by T. Yudanova