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The following are abstracts from papers presented at the 4th Symposium on Respirable Dust in the Mineral Industries and· were produced through research funding under the Generic Mineral Technology Center for Respirable Dust. Full articles appear in the proceedings published in July 1996 in Applied Occupational and Environmental Hygiene. (Volume 11, Number 7). The two addresses included in the proceedings point to the progress, prospects, problems, and perspectives on control of respirable dust and dust-related disease in the mineral industries. The symposium papers deal with respirable dust issues that are longstanding such as characterization, health effects, control of airborne coal dust, new and emerging issues such as iron toxicity, diesel particulates, and sampling. The papers were grouped into the following topics: continuous dust monitoring, encompassing the development of a fixed-site monitor that will provide continuous information on instantaneous and time-weighted respirable dust concentrations; mechanisms involved in the generation of dusts in mine environments, important for dust control at the source; characterization and control of diesel emissions (particularly diesel particulates) in mine atmospheres; mining systems effects and models; dust control in mine working faces and in milling environments; characterization of the physical, chemical mineralogical, and biological properties of the dust and their relevance to health effects and sampling; dust-lung interactions, encompassing results from several biomedical studies dealing with acute and chronic inhalation of airborne dusts and associated lung responses; the role of iron in causing lung injury; and therapeutic strategies for ·the control of pulmonary disease. All papers submitted to the organizers were peer-reviewed. In the proceedings, we have not differentiated among the platform and poster papers; rather, they have been grouped into the above topical areas. Taken together, these papers reveal significant progress in the control of dust generation, characterization of dust, understanding of dust-lung interaction, and mining and milling practices to reduce dust exposure - all essential for reducing dust-related occupational hazards at the workplace.

Jan 1, 1998

By G. Binks

In 1997, the Zinifex Hobart Smelter ceased ocean disposal of jarosite and the flowsheet was converted to reject iron as paragoethite. This paper describes the evolution of the flowsheet since the changeover and considers future flowsheet developments. The major change to the flowsheet has been an increase in the silica content of the calcine resulting from treating increasing levels of Century concentrate. The high silica levels impacted on the paragoethite precipitation stage, causing a deterioration in the settling and filtration characteristics of the paragoethite and an increase in the contained zinc level. The implementation of a two stage neutral leach step has enabled the flowsheet to cope with the higher input silica levels. Future developments include an understanding of the form of the zinc in the paragoethite and options to lower the zinc level to improve the overall zinc recovery.

Jan 1, 2006

By M. Desjardins

The Hoyle Pond underground mine, located in the Porcupine Gold Camp, east of the city of Timmins, Ontario, Canada, is the cornerstone of Goldcorp Canada Ltd?s Porcupine Gold Mines. Cut and fill, shrinkage, longhole and panel mining methods are employed to excavate the narrow gold bearing structures. In order to meet increased flow requirements of 256 m3/s at the mine, a new Fresh Air Raise (FAR) and new surface fans were commissioned in early 2005. The newly acquired fans were capable of supplying the desired volume of air within a range of 1.5 and 2.0 kPa. Upon commissioning of the surface fans the total pressure was found to be exceedingly high; far beyond the design capabilities of the new installation. Consequently only one surface fan could be operated at any given time providing about half the required volume of air. Extensive work was immediately started aimed at reducing the system resistance in order to permit operation of the two fans in parallel and achieve the required mine flows. Larger booster fans were installed in parallel at the 900 m level, a 3 m raise bore linking the 450 and 900 m levels was developed to twin the existing fresh air circuit, and the FAR from surface to the 450 m level was twinned with the original FAR. This strategy, completed in 2012, resulted in a drastic reduction in system resistance and pressures, allowing the two surface fresh air fans to be safely operated in parallel and meeting the flow requirements. This paper describes details of the engineering design work and commissioning of the modified ventilation system, successfully ensuring the long term viability of the project.

Aug 1, 2013

By Ruben Piqueras, Juan Luis Magro, Jorge Vázquez, Santiago Martínez, Xavier Manjarín

The Parallel Thimble Shoal Tunnel project involves the construction of a bored tunnel under Thimble Shoal Channel in Chesapeake Bay (VA), between two artificial islands and parallel to the existing tube tunnel, built in the sixties. It will be the first transportation tunnel constructed in the Mid-Atlantic region using a Tunnel Boring Machine (TBM), a 44-foot-diameter Earth Pressure Balance (EPB) named "Chessie," manufactured by Herrenknecht, and which was assembled at the CBBT's southernmost island, with extremely limited room, live adjacent traffic, and difficult access. "Chessie" was successfully launched in February 2023 and this paper describes this complex and challenging process.

Jun 23, 2024

By H. Deveci

Bioleaching/biooxidation is essentially a dissolution process with the involvement of acidophilic bacteria acting as the "catalyst" to accelerate the dissolution of metals from sulfide minerals. The contribution of bacteria to the metal dissolution is closely controlled by the growth of bacteria, which is itself affected by the physico-chemical conditions within the bioleaching environment. There are a number of operating parameters controlling bioleaching processes, which are required to be maintained within a certain range in the leaching environment whereby the activity of bacteria with the resultant oxidation of sulfide minerals can be optimized. In this regard temperature, acidity, oxidizing conditions, availability of nutrients, oxygen and carbon dioxide, surface area and presence of toxic ions are of prime importance for control and optimization of bioleaching of sulfide ores/concentrates. Bioleaching processes are temperature and pH dependent with optimum metal dissolution occurring in a particular range where the bacterial strain is most active e.g. mesophiles at 35-40°C and pH 1.6-2.0. Provision of nutrient salts is required to maintain the optimnm growth and hence metal dissolution with the quantity of nutrients apparently being dependent on the availability of substrate i.e. head grade/pulp density of an ore/concentrate. Oxygen transfer is one of the most critical factors since the oxygen levels below 1-2 mgll may adversely affect the oxidizing activity of bacteria. Bioleaching rate tends to improve with increasing the surface area at low pulp densities but, in practice. the pulp density is limited to -20010 w/v. Increasing concentrations of ions such as cr may also adversely affect the oxidative activity of bacteria. Keywords: Bioleaching, Biooxidation, Acidophilic bacteria

Jan 1, 2003

By Renato P. Cunha

The paper presents the results of a comparative and parametric analysis in which a numerical program developed exclusively for groups of deep foundations under general loading (vertical, horizontal and moment loads) was used. This program, developed in the doctoral thesis work of Zhang (2000), extends the finite layer method to accommodate a simultaneous general loading on top of piled raft foundations, allowing the establishment of a coupled relationship between displacements (in all three directions), rotations (in two directions), and external loads. Zhang (2000) has extensively tested and validated this program against well known case histories, but has not applied it to piled rafts overlying unsaturated tropical soil materials. Hence, this paper further explores the applicability of this program by using it to simulate the behavior of experimental field loading tests carried out at the University of Brasilia (UnB) experimental site. At this site, Cunha and Sales (1998) and Sales (2000) carried out several loading tests on small scale isolated rafts (1 x 1m) and piles (L=5m, dia=0.15m), group of piles (4 piles, raft clear off the ground) and piled rafts (1 and 4 piles underneath a raft in contact with the soil). The authors adopt Zhang's program to backcalculate, hence simulate, this series of experimental field loading tests under vertical loading. They also use this set of results to "calibrate" the program for further parametric analyses. The parametric analyses were carried out with different piled raft configurations in this same soil type, trying to evaluate their field behavior under the effect of distinct (geometric) configurations of pile distribution.

Jan 1, 2002

By B Ghahreman‐Nejad, M Munro

Design of embankment dams often requires seismic analyses, or an assessment of earthquakeinduced ground and dam movements. There are a large number of cases where earthquakes have triggered sliding and lateral spreading of embankments, resulting in excessive crest settlements. In some instances, liquefaction and embankment failure has occurred resulting in loss of containment. Hence, evaluation of the effects of earthquakes on embankment dams is a critical design aspect. This paper discusses the methods and the results of a seismic liquefaction assessment and deformation analyses of a tailings dam. The tailings dam consists of a perimeter earth core rockfill starter dam which has been raised using upstream construction methods. The embankment raises (formed by an upstream clay blanket and an all-in rockfill body) are constructed over the impounded tailings, which are potentially liquefiable. Extensive field and laboratory tests were undertaken to assess the liquefaction potential of the tailings, and also determine the material properties required for seismic stability and deformation analyses. Numerical modelling of seismic liquefaction and deformation was carried out using FLAC (Itasca 2016) to predict the magnitude and spatial variation of deformations that may lead to an uncontrolled release of tailings. Primarily based on a parametric assessment of UBCSand and Finn-Byrne constitutive models, the results of the analyses are presented and compared for evaluation.

Jul 1, 2021

By C. Musingwini, M. Mohutsiwa

"SynopsisCapital cost estimates are important in decisions on whether a project will be approved, mothballed, or abandoned. In South Africa, junior coal miners do not have extensive databases of historical projects from which to estimate capital costs. The purpose of this paper is to establish formulae that can be used for estimating capital costs of developing coal mines in a coal-producing country, using South Africa as a case study. The costs are estimated to an error of magnitude level of -30% to +50%, which is suitable for a concept study level, using a parametric estimation technique. The study uses data from completed coal mining projects from selected coal-producing countries. Three formulae are developed and presented for estimating capital costs of underground bord and pillar, surface shovel and truck, and dragline operations.IntroductionCapital cost estimates play a critical role in deciding whether projects will proceed, be delayed, or abandoned. It is therefore important that capital cost estimates are carried out accurately as determined by the estimation guidelines based on the level of estimation conducted (Shafiee and Topal, 2012). The lack of literature on estimation of capital costs in many coal mining countries is adversely affecting junior coal miners, since they do not have an extensive database of historical projects on which to base estimations. In South Africa, the difficulty in estimating capital costs is attributable to lack of publicly available data on completed South African mining projects (Hall, 2013)."

Jan 1, 2015

The question of earth models has repeatedly arisen in our work. An accurate representation of the seismic properties is required for three reasons: 1.To be able to determine from a set of received arrival times, the location of a seismic source in the earth, and secondly the degree of accuracy required in the model used for calculating source location from the set of arrival time differences. 2. To be able to determine the expected arrival times at an array of geophones produced in response to a hypothetical source in the earth. 3. To be able to estimate received signal strengths more accurately. The work reported here on earth models is based on information from sever- al consultants and from others who expressed an interest in the problem and supplied information to us. II. COAL MINE GEOLOGY On one of our earlier assignments for the Bureau of Mines, Earth Science Research Inc. of Cambridge, Massachusetts prepared for us a short description of the lithology to be expected at coal mine sites. This description follows, together with the ranges of compressional seismic velocities (Figure I*) associated with typical materials comprising the layered structure of a coal mine area. Coal is primarily associated with fresh water sediments including sandstones, shales, and clays, and occasionally may be metamorphased to varying degrees. In the Appalachian Basin the coal beds occur within cyclical sequences of non-marine shales, sands tones, conglomerates, limes tones, and clays. The beds range in thickness from a few inches to 60 feet, averaging between 2 feet and 10 feet. They have generally broad areal extent, occasionally up to 5,000 square miles, and have an overall tabular or lens-like shape. Within a particular lens, local changes in thickness are normal.

Jan 1, 1974

By Clément F. Bernier

One of the chief sources of the world's supply of asbestos lies in a belt of ultrabasic rocks which runs northeastward through an area called the Eastern Townships, south of the St. Lawrence River in the Province of Québec. The productive portion of this belt extends from the town of Asbestos in the south, for a distance of some 9,5 km to beyond the village of East-Broughton. The first discovery of asbestos in this region was made in 1874. Only crude fibre was produced until 1888 when the first mill was erected near the town of Black Lake. Since the inception of the industry, almost 100 years ago, no less than 100 different compa¬nies have been formed and 46 different mines have been operated. There are presently 5 active companies in the area providing direct employment for 4100 workers, down from 6000 during the seventies.

Jan 1, 1984

By D. H. Forbes, H. M. Manasevit, F. L. Morritz

Single-crystal thin films of molybdenum have been grown. by the pyrolytic decomposition of molybdenum hexafluoride in a hydrogen ambient on various insulating substrates at temperatures front 650° to 900° C. Single-crystal discs of various orientations of magnesium aluminate spinel, a aluminum oxide, magnesium oxide, and the natural facets of beryllium oxide were all observed to exert epitaxial control on the depositing film. Determinations of the crystallographic relationships existing between film and substrates have been made, using X-ray diffraction three-circle goniometry and Laue back-reflection techniques. Using these data, crystallographic overlays have been constructed which suggest a possible interfacial geometry on the basis of a match between metal deposit atoms and metal ion sites in the substrate. A continuing program has been in effect in the Auto-netics Laboratories over the past several years aimed at the development of electronic materials in new and useful forms using chemical vapor deposition techniques. During the course of these investigations, the epitaxy of silicon1"5 and tungstenep7 on single-crystal metal oxide insulators was studied extensively. The deposition of molybdenum is a logical extension of the tungsten work since the crystal structure is identical and the lattice dimensions differ by less than 1 pct. The pyrolytic decomposition of molybdenum hexafluoride in hydrogen was used to grow molybdenum films on the oxide substrates AlzOs, MgA1~04, MgO, and Be0 at from 650" to 900°C, depending on the substrate material. Under the experimental conditions to be described, monocrystalline films of controlled orientation were obtained. The materials investigated and their crystal structure are listed in Table I. EXPERIMENTAL The molybdenum depositions were effected by the hydrogen reduction of molybdenum hexafluoride (MoFe) in a flowing system of hydrogen at atmospheric pressure. The schematic of the apparatus is shown in Fig. 1. The hydrogen, purified by passage through a heated palladium thimble, was mixed with the vapor of the liquid MoFe maintained in a steel bottle at room temperature (25°C). The mixture was passed over the substrate, which was heated by rf induction of a sup-

Jan 1, 1969

By P. T. Chiang

Chemical etching methods for the simultaneous revealing of the tellurium or selenium Phase and the chalcogenide grain boundaries of the alloy systems are given. A tellurium eutectic was found Present in zone-melted ingots. Similarly, a selenium monotectic was present in ingots. In general, the second phase (tellurium or seleniumn) occubies three different sites; viz., along the chalcogenide grain boundaries, as inclusions within the chalcogenide grain, and on the undersurface of the ingot. The detection limit for the tellurium phase is about 1 u in width. THERMOELECTRIC materials based on Group V (bismuth, antimony) and Group VI (selenium, tellurium) elements have aroused considerable interest in recent years in the practical application of thermoelectric cooling. In many cases, a small amount of excess tellurium (or selenium) was added to the material to optimize its thermoelectric properties. Then the question immediately arises as to the number of phases present in the resultant alloy. In the binary systems of Bi-Te, Sb-Te, and Bi-Se, the congruent melting compositions have been reported to be non-stoichiometric and are represented by Bi~Te respectively. It is to beexpected and known that Bi2Te3 and SbzTe3 crystallize from the melt with an excess of bismuth and antimony in the lattice and that tellurium forms a eutectic.~' The same could be assumed to take place in the pseudo binary systems of (Bi,Sb)zTe3 and Bi2(Se,Te)3 as well as in the system studiedby puotinen5 and other workers. Likewise, BiaSe3 crystallizes from the melt with an excess of bismuth in the lattice and selenium forms a monotectic.~ Therefore, in practice, alloys solidified from the melt often contain a second phase (tellurium or selenium) in one region or another of the solid mass even without the addition of excess tellurium (or selenium). ~u~~recht' studied the thermoelectric properties of (Bi,Sb)2Te3 alloys with excess tellurium and simultaneous additions of selenium. He mentioned that the materials show two phases because of the considerable excess of tellurium or selenium. However, he did not report as to how the tellurium or selenium phase was identified. It is generally believed that the presence of an excessive amount of tellurium or selenium phase in the alloy would adversely affect its thermoelectric properties and its uniformity. Consequently, there is a need for a simple method for the identification of the tellurium and selenium phase. The quantity of the second phase present is usually too small to be detected either by chemical analysis or by normal X-ray techniques. This investigation was therefore carried out, first, to devise a simple metallographic method for the identification of the tellurium or selenium phase coexisting with the chalcogenides and, second, to determine the distribution and specific location of the tellurium or selenium phase in the ingots. EXPERIMENTAL PROCEDURE The starting materials used for the alloy preparations were 99.999 pct pure bismuth, antimony, and tellurium and 99.997 pct pure selenium. The bismuth and antimony were obtained from Consolidated Mining and Smelting Co. of Canada Ltd., while the selenium and tellurium were obtained from Canadian Copper Refiners Ltd. The tellurium was purified further in the laboratory by zone refining. The elements were pulverized in a stainless-steel pestle and mortar. The amounts for the desired composition were weighed out each time on an analytical balance to make up a 100-g sample. Then the sample was introduced into a Vycor ampule (19 by 150 mm), pumped down to a vacuum of 10"5 Torr for 15 min, and sealed off. The ampule was then heated in a horizontal resistance furnace at 800" to 900°C for about 20 hr. During this period the assembly was rocked back and forth several times to ensure good mixing. At the end of the heating period, the ampule was quenched in cold water and then transferred to the zone-melting apparatus described in a previous publications to grow large-size aligned polycrystals. The background and ring-heater temperatures were adjusted to make the freezing solid-liquid interface slightly convex to the liquid. The recorded temperature gradient in the vicinity of the freezing solid-liquid interface was around 15°C per cm. The ampule was moved horizontally at a speed varying from 0.4 to 2 cm per hr so that the ring heater would cover the whole ingot length from end to end. A single zone-melting pass was used for the Bi-Te, Sb-Te, and Bi-Sb-Te ingots. Two passes in the forward and reverse directions were carried out for the Bi-Se and Bi-Se-Te ingots. Six passes in the forward and reverse directions were performed for the Bi-Sb-Se-Te ingot. The zone-melted ingots were found to contain several large crystals, with their basal planes (0001) approximately parallel to the growth axis. Samples of bismuth and antimony tellurides coated with a layer of tellurium, and bismuth selenide coated with a layer of selenium, were prepared for comparison in phase identification. These coatings were made by dropping a piece of the zone-melted ingot into some molten tellurium or selenium under argon atmosphere and allowing them to cool slowly to room temperature. The metallographic specimens were prepared by

Jan 1, 1969

By Edwin F. Brush, John Chipman

Published data on the activity of carbon in binary and ternary austenite at 1000°C are reviewed. The composition variables are . The coefficient, Vj, has the value for substitutional elements but may be assigned a ualue -1 for silicon to effect a simplification on the mathematical treatment. The activity coefficient PC = is obtained from gas equilibrium data. For the ternary systems studied the Henrian activity coefficient is given by the expression: The principle advantage in cornparison with the analogous expression in terms of atom fractions is found in the fact that for most systems the final term and in many the last two terms are zero. Values of the interaction parameters are tabulated and the graphical comparison of the equation with experirt~ental data is sho,wn in several figures. The thermodynamic properties of the solid solution, austenite, are of considerable importance in the heat-treatment of alloy steels and in other aspects of ferrous metallurgy. Early studies embodied in the Fe-C diagram have been extended to include other binary and some ternary diagrams. Our best hope of obtaining a useful thermodynamic treatment of reactions in complex alloy steels will not be found in quaternary and quinternary phase diagrams but in determinations of activities and interaction relations among the several solute elements. The foundation for such a development was laid by smith' in his early studies of the activity of carbon in Fe-C alloys and his subsequent work on Fe-C-Si, Fe-C-Mn, Fe-C-Ni, and Fe-C-Co solid solutions.2"4 Other observers have also made noteworthy contributions and these will be discussed and correlated here in the light of a somewhat simplified mathematical treatment of solute interactions. Fe-C AT 1000°C In a recent review of the thermodynamic properties of binary Fe-C austenite it was shown that the simple mathematical treatment employed by smith' was capable of describing all the published results on this solution. The treatment utilizes the atom ratio, yc = nC/nF,, rather than the atom fraction. The activity of carbon is proportional to the equilibrium gas ratio, either measured on a scalk in which the activity of graphite is taken as unity or, alternatively, aC may be set equal to yc at infinite dilution. In either case the ratio aC/y = (PC, the activity coefficient. It was found that the experimental data of smith1 and those of Diin-wald and wagner; Bungardt, Preisendanz, and Lehn-ert,' and Scheil, Schmidt, and Wiinnings at temperatures of 800" to 1200° C as well as reliable data on the solubilities of graphite and cementite could be represented by the equation for which graphite is the standard state: The data on alloyed austenite have been obtained at 1000°C. For this temperature, the "Henrian" activity coefficient (which is unity at infinite dilution) is: FOr an interstitial solute such as carbon in austenite it has been shown by statistical mechanicsg that the activity in the infinitely dilute solution is proportional to the ratio of the number of lattice sites occupied by carbon to the number of yet unfilled lattice sites. A variable zz proportional to this ratio serves as a useful measure of concentration:" in which b is the number of lattice sites provided by each atom of solvent; in austenite b = 1. The Henrian activity approaches zz at infinite dilution and the ratio a is the activity coefficient. The effect of a change in concentration is then given by: It has been shown further that in some systems the derivative in Eq. [4] remains constant over a wide range of concentrations. In such a case second-order terms become negligible and the Henrian activity coefficients is:

Jan 1, 1969

By A. Ghosh, T. B. King

The kinetics of the discharge reaction: 20'- (in silicate melt) = O,(g) + 4e- at a platinum anode in lithium silicate melts have been studied al 1350°C by galvanostatic methods. Plots of the sleady-state overpotential, q, as a function of the logarithm of the current density, i, showed injlections and were linear only at high current densities. The value of the overpotential was influenced by bubbling gas through the electrolyte. The ocer potential was also studied as a function of time. The rise and decay of overpotential were very slow processes. At low current densities transport is the likely rate-controlling process but at high current densities passivation of the electrode, Presumably by an oxide film on the surface, seems to be a contributory functor. IT is well-established that molten silicates behave as electrolytes'5 and, except in a few cases,6 conduction is entirely ionic. Moreover, it is supposed that a possible, and perhaps predominant, mechanism for phase boundary reactions between metals and slags is similar to that in corrosion whereby anodic and cathodic processes occur at unrelated sites, the metal serving to conduct electrons.1'8 Thus electrochemical studies of some slag-metal reactions would seem to be a useful way to diagnose the rate-controlling steps in the overall reaction. The electrochemical method is, in principle, a better diagnostic tool than the direct chemical method for the following reasons: 1) The partial electrochemical reactions, which are simpler than the overall reaction, may be studied individually. 2) The rate of reaction can be controlled at will and independently of the concentrations of reactants. 3) Fast reactions can be studied by relaxation methods.' Esin and his coworkers5'10"12 have pioneered such studies in silicates and have deviloped some ingenious techniques. Not all of their findings, however. can be accepted without a good deal of further work. In this investigation, the kinetics of the oxygen discharge reaction: 202- (in silicate melt) = Oz(g) + 4e- [I] at a platinum electrode were studied by both steady-state and transient galvanostatic techniques. Interest in this reaction was first developed as a result of the findings of Fulton and chipman13 that the reduction of silica, in a silicate slag, by carbon, dissolved in liquid iron, is a very slow reaction. Subsequent work, for example, by Rawling and ~lliott,'~ has demonstrated that the reaction under these conditions must be slow, because the rate is limited by diffusion of oxygen in the iron to the metal-crucible phase boundary at which a CO bubble may be nucleated. Further work by Tarassof,'~ in which the reduction of silica by aluminum dissolved in copper was studied, has shown that under these conditions, where carbon monoxide evolution is not involved, control of the reaction rate resides in diffusion of silica in the slag phase. However, there is no practical way of inducing sufficient convection in the system to make it clear that the phase boundary reaction is indeed fast. The overall reaction of silica reduction involves the discharge of silicon ions at cathodic sites and oxygen ions at anodic sites. In the examples cited, the discharged ions are dissolved in a liquid metal. In the present study of oxygen ion discharge, gaseous oxygen may be evolved at high current densities or oxygen may simply dissolve, possibly as oxygen molecules, in the silicate at very low current densities. The discharge of an oxygen ion at an anode must, in silicates less basic than the orthosilicate composition, be preceded by a reaction in the vicinity of the electrode, such as: which makes oxygen ions available. Platinum was chosen as the working electrode since it is comparatively inert to oxygen and is, therefore, expected to come rapidly into equilibrium with the electrolyte and with gaseous oxygen. Minenko, Petrov, and Ivanova16 have measured the electromotive force at a platinum electrode in molten silicates as a function of the partial pressure of oxygen in the atmosphere, the concentration of oxide ions in the melt, and the temperature. They found platinum to behave as a reversible oxygen electrode. At two different oxygen pressures, Po2 (I) and Pq (11). the electromotive force is given by: where F is the Faraday constant, equal to 23,060 cal per v equivalent, indicating that the electrode reaction is as written in Eq. [I.]. Platinum has been similarly used in molten silicates by other inve~ti~ators. "'~~ In this investigation platinum was used only as an anode, since a current deposits other elements on its surface and changes its characteristics.

Jan 1, 1970

By W. A. Oates, J. A. Lambert, P. T. GaIIagher

Monte Carlo methods have been used to compute the arrangements of interstitial atoms dissolved in tetrahedral sites in bcc lattices. It is assumed that the presence of an interstitial atom "blocks " a certain number of neighboring sites and prevents their occupancy. Sites "blocked" by more than one filled site are allowed for. The computed values of. the mean occupation number (defined as the ratio of the total number of sites blocked to the number of solute atoms are used to calculate the configurational entropies of the solutions. These entropies are compared with those resulting from previous theoretical studies of this problem and also with available experin~ental data for the p Zr-H, Nb-H, V-H, and Ta-H systems. Evidence is also given that the "blocking" explanation of low limiting compositions in these systems, rather than this being due to initial limitations on the number of sites available, is probably correct. THE ideal partial configurational entropy of mixing of an interstitial solute in a metal is given by: where p is the number of interstitial sites per metal atom and Xi is the atomic fraction of the interstitial. For the bcc lattice. which we shall be concerned with in this paper, the interstitial positions are shown in Fig. 1. It can be seen that for the tetrahedral sites, p=6. whereas for the octahedral sites, p = 3. Different emphasis has been placed on the relative importance of energy and entropy effects in determining deviations from ideality in interstitial solid solutions. In some cases the same system, e.g., Fe-C, has been described by the contradictory regular and athermal solution models indicating that the enthalpy and entropy functions, derived from equilibrium data, are frequently not accu.rate enough to differentiate between these treatments. However, for certain metal-hydrogen solutions the equilibrium data is available over sufficiently wide ranges of temperature and composition to permit a reasonably accurate determination of the compositional variation of the heats and entropies. Hoch&apos; has attempted to interpret the results of interstitial solid solutions in terms of a regular solution model. In the case of the Ta-H system where 13 = 6, this model entails fitting the experimental relative partial entropies of solution, asH, to the equation: where ASgs is the relative partial excess entropy of solution of hydrogen. Hoch found that the results of Mallett and Koeh1 could be fitted to this equation with an approximately constant value of AF up to XH = 0.25. However, it is apparent from the solubility isotherms in this system which become asymptotic to the composition TaH that, since (Xh /6 - ~Xh ) becomes infinite only at TaH6, it is necessary that AS<&apos; tends to infinity at TaH. In other words, the low saturation composition of TaH, instead of the anticipated TaH,, eliminates the possibility of applying regular solution theory to such systems. Rather large negative excess configurational entropies must exist at higher hydrogen concentrations in order to explain the lower saturation values. To account for these low limiting compositions and excess entropies two distinctly different approaches have been followed. Rees and many others1-l2 have assumed that not all interstitial sites are crystallographically equivalent with respect to the interstitial addition; that is, in Eq. [I] p is less than the value anticipated from geometrical considerations. To describe, say, a bcc metal-hydrogen system with a limiting composition of MH by this approach one would consider that p = 1 in the first instance instead of p = 6.&apos;j3 In some cases, nonintegral values of B have been taken in order to improve the fit with the experimental data over limited ranges of composition. The other approach which has been used to explain the low saturation compositions is to assume that, although all sites are available for occupancy, strong repulsive interactions exist between the neighboring interstitial atoms, and hence occupancy of any site excludes or blocks a certain number of neighboring sites from being occupied. Earliest treatments of this concept considered the exclusion of an integral number, of nearest-neighbor sites from being occupied at all concentrations. In this case, the partial configurational entropy is given by: These early treatments failed to allow for the overlap of the blocked sites which will arise at all but the very lowest concentrations. More recently attempts have been made to calculate the effect of this decrease in the number of blocked sites on the configurational entropy. Using the quasichemical treatment of interstitial solid solutions as given by Lacher and assuming that an infinite repulsive interaction energy existed between the solute atoms. atom obtained an approximate configurational entropy applicable to the blocking with overlap case:

Jan 1, 1970

By Shiro Ban-ya, John Chipman

The effects of many alloying eletnents on the acticity coefficient of sulfur in liquid iron have-been studied by the equilibriutn in the reaction Sfin Fe) + Hz = HzS at 1550°C&apos;. Results are expressed in terms of a concentration variable for a nonmetallic or for a substitutional metallic solute. Activity coefficient of sulfur, defined as increased by B, Al, C, Si, Ge, Sn, P, As, Sb, Mo, W, Co, and PI. It is decreased by Cu,Au, Ti. Zr, V, h&apos;b, Ta, Cr, ,23n, and Ni. Irulues oj. the interaction coejficient 0i = 6 In are labulated. The same interactions are expressed also in terms of atom fraction and of weight percent. The thermodynamic properties of sulfur in liquid iron have been fairly well established. Our recent paper1 reported new determinations of activity coefficient up an atom fraction of 0.12 and equations based on a careful review of all published data. The effects of alloying elements on the activity of sulfur have been studied by several investigators,2"11 especially by Morris and Williams for silicon,&apos; by Morris and Buehl for carbon,~ and by Sherman and Chipman for manganese. phosphorus, and al~minum.~ However, the effects of some important alloying elements remain to be determined. The purpose of this investigation was to determine the effects of many alloying elements on the activity of sulfur in Fe-S-j ternary systems. EXPERIMENTAL METHOD This study was based on experimental determination of equilibrium in the reaction at 1550°C: The same apparatus and procedure as described in our previous paper have been retained, and the same corrections were applied for dissociation of H2S. The alumina crucibles used in the experiments consisted of four separate compartments. In a given experimental run. kach of three alumina crucibles held four different samples of about 3 g each which reached equilibrium in the same gas atmosphere and temperature. The charges were made up of electrolytic iron, pure iron sulfide, and desired alloying elements, which were pure metal or master alloys made in the laboratory. The weighed samples were held for 4 to 12 hr in the prepared atmosphere at 1550°C. They were then low- ered to be cooled as quickly as possible. The quenched metal beads were crushed to avoid the errors of segregation in the ingot. The sulfur content was determined gravimetrically and alloy content by appropriate chemical analysis. CALCULATIONS The apparent equilibrium constants of Eq. [I] are expressed as follows from the corrected gas ratios and sulfur concentrations: The term K" is the observed equilibrium constant in any given ternary solution, K&apos; is the value for the Fe-S binary solution. and the limiting value of K&apos; in the infinitely dilute solution is designated by K, which is the true equilibrium constant in Eq. [I]. In the thermodynamic treatment of nonmetallic elements in a metallic solution, it has been suggested1&apos; that the lattice ratio has certain advantages over other variables to express the concentration of solute. In interstitial solid solutions the lattice ratio zj is proportional to the ratio of filled interstitial sites to those which remain unfilled. The equations derived for the activity of the solute using zj as the concentration variable are found also to be applicable to liquid solutions containing nonmetallic solutes when the nonmetal is treated as if it were interstitial. For this purpose we adopt the following definitions: The quantity vj which is negative for interstitial solutes is taken as -1 for nonmetallic and +1 for metallic solutes. For purposes of calculation however ; j may be assigned a value which results in a linear relation such as shown in Figs. 1 to 15. The activity coefficient of sulfur, Qs, and equilibrium constant. K(z). are defined as follows: According to a Taylor series expansion. the logarithm of the activity coefficient of sulfur in Fe-S-j ternary system is: However, the value of 6 In */6zi remains constant through a broad range of dilute solutions and the terms of higher order are negligibly small. As a consequence, Eq. [6] is simplified as follows:

Jan 1, 1970

By D. S. Tannhauser, I. Bransky

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of &apos;association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples&apos;-4 or thermogravimetric measurements. 5,8 Darken and Gurry&apos;s1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth&apos;s neutron-diffraction experiments. Roth&apos;s model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1&apos; used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.&apos; Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3&apos; states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By E. Furubayashi, T. Taoka, S. Takeuchi

Recrystallization textures developed from artificial nucleation around indentations were compared with spontaneously recrystallized textures in two rolled 3 pet Si-Fe single crystals with (111)[112] and (100) [011] orientations. Orientation of individual grains in some stages of their growth was also directly determined by a microetch-pit method. In both the crystals, the recrystallization texture was characteristic of each orientation regardless of any nucleation conditions, artificial or spontaneous, though artificially nucleated grains were more randomly oriented in finer stage. These results support the concept that the process of selection of growing grains controls the formation of the prejerred recrystallization texture. Discussion is given on the factors controlling the mobility of grain boundaries. Recrystallization textures are formed through a number of stages which are customarily called by the terms recovery, nucleation, and grain growth. Many experiments have been done to clarify the mech- anism of formation of recrystallization texture but no fully successful explanation has been proposed. The texture consists of oriented grains which nucleate at many sites of the deformed matrix and grow at the expense of the matrix during annealing. The current theories on the formation of recrystallization texture are based on the following two extreme hypotheses: 1) the oriented nucleation theory by Burgers et al.;1, 2 2) the oriented growth theory by Beck et al.3-5

Jan 1, 1968

By L. S. Darken

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of &apos;association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples&apos;-4 or thermogravimetric measurements. 5,8 Darken and Gurry&apos;s1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth&apos;s neutron-diffraction experiments. Roth&apos;s model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1&apos; used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.&apos; Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3&apos; states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By W. R. Bacon

"MAGNETITE HAS BEEN found in many .parts of the coastal area of British Columbia, but the more important deposits are on Vancouver Island and Texada Island. The locations of these deposits are shown on Figure 1.Interest in the magnetite deposits dates back to the 1870s, when land was acquired on the southwest coast of Texada Island by the Puget Sound Iron Company. This ground included the Prescott, Paxton, and Lake deposits. During the years 1885 to 1903, and 1908, 28,898 tons of magnetite ore was shipped to the company's blast-furnace plant at Irondale, Washington, U.S.A. This production was almost entirely from the Prescott open-pits.In the years following the Texada Island discoveries, other magnetite deposits were found in the coastal area, and various plans were proposed to utilize the local ores in the establishment of a steel industry in the Pacific Northwest. None was carried to fruition but, in 1951, open-pit mining was begun at Iron Hill, Vancouver Island, to furnish iron concentrates for steel mills in Japan. In 1952 mining of the Texada deposits was resumed to supply the same market. Production figures for these recent operations are as follows:"

Jan 1, 1949