The mechanisms and kinetics of the reduction of powdered Fe2O3 and Fe3O4 samples have been investigated under nonisothermal conditions to provide a detailed insight into the processes occurring. Both conventional linear heating temperature-programmed reduction (TPR) and constant rate temperature-programmed reduction (CR-TPR) techniques were utilized. Fe2O3 was found to reduce to Fe in a two-step process via Fe3O4. The mechanism of the prereduction step of Fe2O3 to Fe3O4 was found to follow an nth order expression where nucleation or diffusion was not the rate-controlling factor while the main reduction step to metal was described by a model involving the random formation and growth of nuclei. A CR-TPR rate perturbation method, “rate-jump”, was applied to the measurement of variations in apparent activation energy throughout the reduction processes, under near-equilibrium conditions and the activation energy measurements are compared with those obtained under conventional linear heating conditions.

Coupled magneto-optical imaging and local misorientation angle mapping have been used to demonstrate the percolative nature of supercurrent flow in YBa 2 Cu 3 O 7Ϫx ͑YBCO͒ coated conductors grown on deformation-textured Ni substrates. Barriers to current flow occur at many YBCO grain boundaries ͑GBs͒ which have propagated through the buffer layers from the underlying Ni substrate, and all Ni GBs with misorientation angles Ͼ4°initiate percolative current flow. This type of current barrier is characteristic of the conductor form and has been found to exist in samples with J c (0 T,77 K) values Ͼ2 MA/cm 2 . Sharpening of the local substrate texture or improving in low-angle GB properties should lead to higher J c values. © 2000 American Institute of Physics. ͓S0003-6951͑00͒00341-7͔High critical current density (J c ) conductors capable of operating in fields of several tesla at liquid-nitrogen temperature are critical to large-scale applications of hightemperature superconductors. Coated conductors ͑CCs͒ with biaxially textured YBa 2 Cu 3 O x ͑YBCO͒ respond to this need. [1][2][3] One widely employed approach today uses deformation texturing of a metal substrate, generally pure Ni, on which buffer layers and YBCO are grown. 1,2 Such architectures permit J c (0 T,77 K) values 1,2 Ͼ1 MA/cm 2 , but many samples have lower values. Here we couple magneto-optical imaging and local misorientation angle mapping to show that many such barriers to current flow occur at YBCO grain boundaries ͑GBs͒ which have propagated through the buffer layers from the Ni GBs in the underlying substrate. All Ni GBs with misorientation angles Ͼ4°were found to initiate percolative current flow. Since typical deformation-textured substrates have many GBs misoriented in the range of 5°-10°, this study shows that it will be very valuable for CC technology to further enhance substrate texture and/or to improve low-angle GB properties.Magneto-optical ͑MO͒ imaging, light microscopy, and backscattered electron Kikuchi pattern ͑BEKP͒ analysis of the local texture were conducted on a series of four CC samples grown on deformation-textured Ni substratres with in-plane and out-of-plane full width at half maxima of 6.6°-7.4°and 5.8°-8.7°, respectively, as measured by x-ray pole figures. The buffer and YBCO layers were deposited by pulsed-laser deposition ͑PLD͒ with architecture YBCO/CeO 2 /yttria-stabilized zirconia ͑YSZ͒/CeO 2 /Ni and thickness of 300-1200/100/500/100 nm for the respective oxide layers. The thickness of the YBCO layer varied from sample to sample without obvious differences in the properties measured by MO imaging and ac susceptibility. A 0.6-m-thick YBCO sample had a high transport J c (0 T,77 K) of 1.2 MA/cm 2 . The remaining samples were taken directly to other characterizations.A representative MO image of the granular fluxpenetration network obtained using standard imaging procedures 4,5 is shown in Fig. 1. This network is common to CCs with varying constructions from multiple sources. Among the variations are deformation-textured s...

A new system has been developed for the study of both bulk and surface metal oxides by temperature programmed reduction (TPR) under both conventional linear heating and constant rate thermal analysis (CRTA) conditions. It is shown that constant rate temperature-programmed reduction (CR-TPR) is capable of producing higher resolution of overlapping events, provides more insight into reduction mechanisms, and allows easier quantification of reduction processes than conventional TPR. The CR-TPR curves for both bulk and supported copper oxides confirmed that reduction followed a nucleation or autocatalytic mechanism. Bulk nickel oxide was found to reduce via a similar mechanism. Advantages of the CR-TPR “rate-jump” technique to determine reaction energetics are illustrated by investigation of the apparent activation energy (E a) of CuO reduction, and the results are compared with those obtained under linear heating conditions. Both approaches yield reasonable values of E a under the appropriate experimental conditions employed. However, the CR-TPR “rate-jump” technique allows variations in E a to be measured as a function of the extent of reduction, revealing changes in the reaction mechanism or kinetics. Our results suggest it is possible to estimate the apparent activation energy of both the nucleation and growth stages involved in reduction. The validity of the “rate-jump” technique employed is confirmed using the thermal decomposition of CaCO3, a widely investigated process. The TPR system uses a hygrometer cell to monitor the production of H2O as the sample is reduced. The sample temperature is controlled by a computer in such a way that the production of H2O, i.e., the rate of reduction, can be maintained at a constant preselected value for CR-TPR experiments. Important instrumental features include a fast response furnace, direct temperature measurement, a sensitive specific detector, and control and data analysis software developed specifically for this work.

Thermally induced reactions are of great importance in the manufacture and characterization of a very wide range of increasingly complex materials covering areas as diverse as ceramics and heterogeneous catalysts. Subsequently, there is a need for improved thermoanalytical methods that can provide enhanced resolution and a greater understanding of the energetics and mechanisms involved. This paper describes a new solid insertion probe mass spectrometer (SIP-MS) system that is designed to meet these needs by operating high vacuum with small sample masses. The SIP-MS system supports both conventional linear heating and a range of sample-controlled thermal analysis (SCTA) techniques including constant rate thermal analysis (CRTA). Its ability, in conjunction with the latter technique, to obtain reliable apparent activation energy measurements throughout a process under near-ideal experimental conditions is demonstrated. In addition, the system can discriminate between different reaction mechanisms and provide information on the often complex solid-state reactions found in calcination processes.