Veena Sahajwalla

Quantitative X-ray diffraction analysis and its application to various coals

A technique is presented to obtain the maximum structural information on carbonaceous materials from their X-ray scattering curves in the middle and high range of scattering angle. This technique involves a precise and systematic analysis of X-ray scattering curves. Four Australian black coals ranging in rank from semi-anthracite to HV bituminous are included in this study, and the results are compared with data in the literature. Based on qualitative observations, a simplified coal structure, in which only two types of carbon structures including crystalline carbon and amorphous carbon are considered, is suggested. The good agreement in intensity between experimental measurements and theoretical calculations demonstrates the validity of the simplified model. The quantitative analysis yields three structural parameters, viz., fraction of amorphous carbon (xA), aromaticity (fa) as well as crystallite size and its distribution (La, Lc, d002, pn). As expected, coal was found to contain a significant amount of highly disordered material, amorphous carbon, which gradually decreases during the coalification process. In agreement with the TEM observations, coal crystallites are found to be around 6 A in diameter and piled up by 2–4 aromatic layers on average, with the high rank coal being more condensed in terms of the inter-layer spacing. However, our measurements suggest that the average crystallite height increases with coal rank from 7.5 A for Coal1-DD to 13.75 A for Coal5-YD. The measured aromaticity, which agrees with the results of NMR spectroscopy, shows a good relationship with the hydrogen content in coal.

Concentration of precious metals during their recovery from electronic waste.

The rapid growth of electronic devices, their subsequent obsolescence and disposal has resulted in electronic waste (e-waste) being one of the fastest increasing waste streams worldwide. The main component of e-waste is printed circuit boards (PCBs), which contain substantial quantities of precious metals in concentrations significantly higher than those typically found in corresponding ores. The high value and limited reserves of minerals containing these metals makes urban mining of precious metals very attractive. This article is focused on the concentration and recovery of precious metals during pyro-metallurgical recycling of waste PCBs. High temperature pyrolysis was carried out for ten minutes in a horizontal tube furnace in the temperature range 800-1350°C under Argon gas flowing at 1L/min. These temperatures were chosen to lie below and above the melting point (1084.87°C) of copper, the main metal in PCBs, to study the influence of its physical state on the recovery of precious metals. The heat treatment of waste PCBs resulted in two different types of solid products, namely a carbonaceous non-metallic fraction (NMFs) and metallic products, composed of copper rich foils and/or droplets and tin-lead rich droplets and some wires. Significant proportions of Ag, Au, Pd and Pt were found concentrated within two types of metallic phases, with very limited quantities retained by the NMFs. This process was successful in concentrating several precious metals such as Ag, Au, Pd and Pt in a small volume fraction, and reduced volumes for further processing/refinement by up to 75%. The amounts of secondary wastes produced were also minimised to a great extent. The generation of precious metals rich metallic phases demonstrates high temperature pyrolysis as a viable approach towards the recovery of precious metals from e-waste.

Generation of copper rich metallic phases from waste printed circuit boards

The rapid consumption and obsolescence of electronics have resulted in e-waste being one of the fastest growing waste streams worldwide. Printed circuit boards (PCBs) are among the most complex e-waste, containing significant quantities of hazardous and toxic materials leading to high levels of pollution if landfilled or processed inappropriately. However, PCBs are also an important resource of metals including copper, tin, lead and precious metals; their recycling is appealing especially as the concentration of these metals in PCBs is considerably higher than in their ores. This article is focused on a novel approach to recover copper rich phases from waste PCBs. Crushed PCBs were heat treated at 1150°C under argon gas flowing at 1L/min into a horizontal tube furnace. Samples were placed into an alumina crucible and positioned in the cold zone of the furnace for 5 min to avoid thermal shock, and then pushed into the hot zone, with specimens exposed to high temperatures for 10 and 20 min. After treatment, residues were pulled back to the cold zone and kept there for 5 min to avoid thermal cracking and re-oxidation. This process resulted in the generation of a metallic phase in the form of droplets and a carbonaceous residue. The metallic phase was formed of copper-rich red droplets and tin-rich white droplets along with the presence of several precious metals. The carbonaceous residue was found to consist of slag and ∼30% carbon. The process conditions led to the segregation of hazardous lead and tin clusters in the metallic phase. The heat treatment temperature was chosen to be above the melting point of copper; molten copper helped to concentrate metallic constituents and their separation from the carbonaceous residue and the slag. Inert atmosphere prevented the re-oxidation of metals and the loss of carbon in the gaseous fraction. Recycling e-waste is expected to lead to enhanced metal recovery, conserving natural resources and providing an environmentally sustainable solution to the management of waste products.

Coal char reactivity and structural evolution during combustion—Factors influencing blast furnace pulverized coal injection operation

A fresh char was prepared and reacted with oxygen under conditions similar to those prevailing in the raceway region of the blast furnace (BF) during pulverized coal injection (PCI), using a well-characterized drop-tube furnace (DTF). Char combustion under the present conditions was found to be controlled by the combination of pore diffusion and chemical reaction. Both the char density and size gradually decrease with burnoff, while the char surface area increases up to a burnoff of 40 to 50 pct due to the formation of a large amount of meso- and micropores, which were observed by high-resolution field-emission scanning electron microscopy (FESEM) and gas adsorption measurements. Despite the obvious increase in surface area, the char combustion reactivity decreases with burnoff. This is due to the loss of the intrinsic reactivity of char during combustion, as confirmed by fixed-bed (FB) measurements of fresh char and chars partly burnt in a DTF. The structural characterization by quantitative X-ray diffraction analysis (QXRDA) shows that the amorphous concentration (fam) of the char decreases during combustion, while the aromaticity (far) and the average crystallite size (L002) of the char increase. The char becomes more ordered during combustion, which is in accordance with the observations made using high-resolution transmission electron microscopy (HRTEM). The char structural ordering observed was found to be responsible for the loss of char intrinsic reactivity during combustion. Based on the QXRDA, a char structure model has also been suggested to explain the char structural evolution observed during combustion. The implications of char structural evolution for char combustion during a PCI operation are also discussed.

Time‐temperature‐transformation study of a nanocrystalline Fe91Zr7B2 soft magnetic alloy

The structure, soft magnetic properties, magnetostriction, grain size and volume fraction of the residual amorphous phase have been studied for an amorphous Fe91Zr7B2 alloy annealed for periods of 60 s–1080 ks, at temperatures of 823–973 K. The highest permeability (at 1 kHz and 0.4 A/m) 31,000 and smallest coercivity 4.2 A/m are obtained for the sample annealed at 923 K for 60 s, where a small grain size (≊12 nm) and about 35% of the residual amorphous phase are measured. The coercivity of the nanocrystalline alloy varies as the 3rd power of the grain size, corresponding to the case where the magnetically coupled region has a dimensionality between two and three. This slightly low dimensionality is presumed to be due to the alignment of the magnetization in the sample plane.

The role of alloying elements in Cu-free nanocrystalline Fe-Nb-B soft magnetic alloys

Abstract In order to clarify the role of alloying elements in Cu-free nanocrystalline Fe-Nb-B soft magnetic alloys, we have examined the kinetics of primary crystallization, the microstructure after primary crystallization, the changes in Curie temperature (Tc) and the hyperfine interactions of the amorphous phase upon primary crystallization in Fe86 − xNbxB14(x = 0, 2, 4, 5, 6 and 8) alloys. The mean grain size after primary crystallization decreased drastically in the x range 4–6 at.%. The kinetic analysis of the primary crystallization reaction showed that the decrease in the grain size can be attributed to the commencement of homogeneous nucleation. Tc of the amorphous phase increased with the B enrichment during primary crystallization. Tc decreased with Nb content and the hyperfine field distribution of the residual amorphous phase after primary crystallization for the x = 6 sample showed the presence of a non-magnetic component. These results suggest that Nb plays a role in the formation of the nanostructure by accelerating nucleation, as does B in the generation of a strong intergranular magnetic coupling, through increasing the Tc of the residual amorphous phase.

Slag-graphite wettability and reaction kinetics. Part 1 Kinetics and mechanism of molten FeO reduction reaction

Abstract The present paper reports results relating to the kinetics and mechanism of FeO reduction by graphite, the data being obtained from experimental investigations into the wettability of graphite by molten slag containing FeO. The rate of FeO reduction was determined by measuring the volume of CO gas formed as a result of the reduction of FeO in experiments conducted in the same sessile drop apparatus. The reduction reaction initiated by direct slag–graphite contact produces CO gas which spreads into the molten slag droplet causing foaming of the slag; further reduction of FeO proceeds mostly via indirect reduction. The rate of reduction was found to depend directly on the initial FeO content. An increase in temperature improves the rate of reaction, which has an activation energy of 112·18 kJ mol-1. These results indicate that transport of FeO (Fe2+, O2- ) in the liquid slag phase is probably the slowest step.

Application of fly ash as a catalyst for synthesis of carbon nanotube ribbons

The larger diameter-based carbon nanotube (CNT) ropes and ribbons are currently synthesized by catalytic decomposition of hydrocarbons with transition metal-based catalysts e.g., Co, Ni, Fe and Mo at 1100-1200°C, using chemical vapour deposition (CVD) and electric arc methods. We produced CNT ribbons by fly ash (FA) catalyzed pyrolysis of a composite film of poly (vinyl alcohol) (PVA) with FA at 500°C for 10min under a nitrogen flow of 2L/min. Different geometrical structures, e.g.; knotted and twisted, U- and spiral-shaped CNT ribbons were observed in the images of scanning and transmission electron microscopy. The widths of the CNT ribbons measured varied in the ranges 18-80nm. X-ray photoelectron spectroscopy analysis showed five types of carbon binding peaks, C-C/C-H (∼77%), C-O-H (∼9%), -C-O-C (∼5%), C=O (∼5%) and -O-C=O (∼3%). The ratio of intensities of G and D bands, IG/ID was 1.61 analysed by Raman Spectroscopy. CNT ribbons grown on the surface of FA have potential for the fabrication of high-strength composite materials with polymer and metal.

The spout of air jets upwardly injected into a water bath

The spout region of gas jets in liquids has received little attention, although it has both theoretical and practical significance. In this study, the spout of upwardly injected gas jets in water was characterized experimentally in terms of gas fraction, bubble frequency, and axial velocity distributions for ultimate incorporation into turbulent recirculating flow models. The measurements were made with a two-element electroresistivity probe coupled to a microcomputer. For the turbulent flow conditions prevailing in the jet plume and spout, special hardware and software were developed to analyze the signals generated by contact of the bubbles with the sensor in real time. Correlations of the gas fraction with axial and radial position for different gas flow rates have been established from the measurements. The dimensions of the spout were obtained from time-exposure photographs; when compared with the gas-fraction measurements, the spout boundary always corresponded to values ranging from 0.82 to 0.86. The radial profiles of bubble frequency at different levels in the spout exhibit a bell shape; the bubble frequency decreases with increasing height. The velocity of the bubbles in the spout drops linearly with increasing axial position.

TWO-STAGE NANOSTRUCTURAL FORMATION PROCESS IN FE-NB-B SOFT MAGNETIC ALLOYS

The nanostructural formation kinetics in a soft magnetic Fe80Nb6B14 alloy have been investigated by means of differential scanning calorimetry, thermogravimetric analysis and transmission electron microscopy. Unlike nanocrystalline Fe–Zr–B soft magnetic alloys, where the nanocrystallite formation is governed mostly by a nucleation and growth mechanism, the nanostructural formation mechanism in the Fe–Nb–B alloy shows a change in the fraction transformed range 0.1–0.2. The first‐ and second‐stage nanostructural formation processes have been described by the nucleation and growth and grain‐growth models, respectively. This two‐stage nature in the nanostructural formation kinetics can be attributed to a high population density of the primary bcc nuclei.