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By Joel Bradley, Kot Unrug, Kyle Perry, Mark Klimek

"A West Kentucky mine operation in No. 11 seam, encountered floor heave, due to the localized increase of the thickness in the fireclay mine floor. Floor heave has overridden seals installed in two mined out panels. The third seal’s location was planned for isolating that area from the Mains. A plan of support has been developed to prevent repetition of the floor heave and related problems outby the seals. The applied ground control measures were successful. An attempt of a 3D numerical modeling was made, that it would match the observed behavior of the mine floor and could be used as a design tool in similar conditions. In the paper described are sequence of events, a mitigation ground control system applied, and the first stage of numerical modeling.IntroductionWest Kentucky coal mine operation in the No. 11 seam has approached an area where the fireclay floor thickness increases to about 5 ft. Delayed floor heave has been observed. In the first sealed area (Panel KK), floor heave has overridden the seals and has begun to progress outby. This could not be allowed at the new seal location PP described in this paper because such override would affect the mains. Previously numbers of standing support systems were used, but their effectiveness was not satisfactory as is illustrated in Figure 1, Figure 2, and Figure 3. Therefore, with sealing of the next area approaching, mine management was looking for a better solution that would eliminate the problem. In that stage, our team looked closely at the geology and strength of roof and floor, as well as the characteristics of ground failure around the seal at the first site. The technical literature has been searched as well Haramy et al. 1986 Hsiung and Peng 1987, Peng 2008, Santos & Bieniawski 1987. This led to the identification of factors responsible for the ground failure. It has been determined that increased fireclay thickness from typically less than 2 ft to about 5 ft, when compared to the previously mined parts of reserve, and the strong limestone strata just above the immediate roof composed of 2 ft of black shale, created conditions of failure. It appeared that, when pillars were punching into the mine floor, the strong roof did not break but was bending, exerting high pressure on outby pillars, causing rib failures and closure. This is a similar mechanism to a strong roof affecting longwall shields. The remedial action planned was additional support."

Jan 1, 2015

Magnetite cenospheres 40-270 I/m in diameter have been found during the combustion of pyrite concentrate.Micrographs of the surface and internal structures are presented together with comment on the mechanism of forrnation.The similarity to cenospheres found during the combustion of pulverized fuel was noted and speculation raised to their contribution to the dust and fume load in flash smelters.

Jan 1, 1980

By Ramon Silveira Assis Barros

Este trabalho foi realizado com o objetivo de se investigar o comportamento do aço inoxidável duplex UNS S32304 em meios contendo íons cloreto. Para tanto, foram realizados ensaios CST com carga e deformação constantes usando meios com concentrações distintas de cloreto de magnésio (MgCl2), em ebulição. Foram realizados também análises química, metalográfica e eletroquímica do material. Após os ensaios de CST, foi constatada a suscetibilidade à CST deste material, além da influência da concentração de íons cloreto na solução. Essa constatação foi reforçada após a análise microfractográfica dos corpos de prova ensaiados. A análise eletroquímica do material revelou a evolução de pites em potencial de, aproximadamente, 400mVECS.

Jan 16, 2018

By John Stankus

Regional high horizontal stress has long been recognized as an important factor affecting roof stability However, localized high horizontal stress, although causing many ground control problems, has not received due attention, Through many ground control studies and underground experiences, it has been round that localized horizontal stress can be created by abrupt changes of overburden and stream valleys. The magnitude of localized horizontal stress depends on the valley configuration and overburden depth. Utilizing the Jennmar Finite Element Analysis System (JFEA), this paper analyzes the mechanism of the localized horizontal stress concentration based on two cast studies.

Jan 1, 1999

By S. Y. Tan

The thermal stability of fully silicided NiSi with arsenic doping on silicon was investigated. The aims of the work were to investigate the Ni silicide phase-related issues associated with arsenic dopant and thermal annealing on Ni-FUSI/HfO2/Si and Ni-FUSI/HfSiO/Si gate stacks. It was found that arsenic-incorporation demonstrated some improvement in both morphology and phase stability of nickel silicided films at high processing temperatures regardless underlying gate dielectrics. The correlations of Ni-Si phase transformation and arsenic doapnt with their electrical and physical changes were established by sheet resistance measurements, X-ray diffraction (XRD), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) analysis. Furthermore, the modulation of the work function (WF) of Ni fully silicided gates by arsenic impurity is presented, comparing the effects of dopant (As) on the WF and silicide phases (NiSi and NiSi2). It confirmed that the work function of NiSi can be tuned by implanting arsenic dopant, but it ineffective for NiSi2 phase.

Jan 1, 2010

By Paul F. Kerr, Raymond F. Robinson

Uranium mineralization occurs in the footwall of the Sunshine vein from the 2900 to the 3700 level. Veinlets of uraninite associated with pyrite and jasper have been so extensively divided and recemented that units more than a few feet in length are seldom observed. The wall rock is St. Regis quartzite of the Belt series. The age of the uraninite, on the basis of isotopic analyses, is 750 * 50, which agrees with geological data suggesting that phases of the Sunshine mineralization are pre Cambrian. THE Sunshine mine in the Coeur d'Alene district, Idaho, is well known for its silver-bearing veins but prior to the summer of 1949 had not been recognized as a possible source of uranium. At that time, during a geiger counter reconnaissance by T. E. Gillingham, R. F. Robinson, and E. E. Thurlow, high radioactivity was noted and radioactive specimens were collected from the footwall of the Sunshine vein.' The detection led to the identification of uraninite-bearing veins, since explored jointly by the Atomic Energy Commission and the Sunshine Mining Co. After the occurrence was noted, the geology of the uranium deposit was studied by the Sunshine staff, and a laboratory examination of the ores was conducted at Columbia University. Several types of laboratory work were undertaken. Differential thermal curves were made of selected siderite samples and results from many more were secured through the work of Mitcham.2 X-ray diffraction and X-ray fluorescence analyses were employed on uraninite, jasper, and siderite. Chemical analyses were made through the cooperation of the Division of Raw Materials of the Atomic Energy Commission. General Geological Features Several silver-bearing veins cut the overturned north limb of the Big Creek anticline as mapped by Shenon and McConne1,³ while the Osburn fault, a long-recognized regional feature about a mile away, marks the north boundary of the Silver Belt. The Sunshine vein, Fig. 1, has a south dip more or less parallel to the 60" axial plane of the fold and cuts rocks of the Belt. Series, starting with the Wallace formation near the surface, continuing downward through the St. Regis formation, and probably extending into the Revett quartzite which lies below the bottom or 3700-ft level. The limb of the anticline is locally modified by secondary folds, one being prominently exposed in the uranian area along the Jewel1 crosscut near the Sunshine vein. Crumpling of the limb resulted from compression which formed the anticline and probably preceded the faults in which the vein deposits accumulated. Evidence of drag along these faults points to reverse movement in the uranium-bearing area and elsewhere. This is true of major faults in the mine workings, and the majority of faults which can be mapped, as pointed out by Robinson.' The St. Regis formation, as measured in the mine, appears to have an initial thickness of some 2000 ft, but the apparent thickness due to thickening during folding is some 3400 ft. Along the Sunshine vein the purple and green rocks characteristic of the Wallace formation in the nearby Military Gulch section p. 37 of ref. 5) have been completely bleached because of introduced sericite. Hydrothermal solutions acting on the wall rock have substituted for the original color a pale greenish cast, although no pronounced mineralogical change has resulted, as Mitcham has observed.' The silver and the uranium depositions appear to belong to distinct epochs resulting from several periods of emplacement. Likewise, multiple periods of deformation account for the faulting. Uraninite is generally associated with silicification, while silver . mineralization accompanies carbonate veins. Rarely, uraninite may be found in a matrix of siderite. Ordinarily uraninite formed prior to ar-gentian tetrahedrite. Where clusters of veins form a stockwork, uraninite-jasper veins often favor one trend while tetrahedrite-siderite veins favor another. During deformation, brecciation of the St. Regis quartzite provided openings between broken rock fragments for precipitation from vein-forming solutions. Fractures due to major breaks were filled during the first stages of vein formation, while later deformation displaced the first veins and provided new channels along which further mineralizing solutions proceeded. The uraninite veins, as the first formed, have suffered fracturing, displacement, and segmentation. Uranian vein segments uncut by faults and more than a few feet in length are rare or nonexistent. Siderite veins are more massive and often extend without a break for tens and even hundreds of feet. In general they show much less segmentation. While the siderite is usually later, there is an overlap in the periods of deposition, some earlier siderite veins being extensively segmented in much the same way uraninite veins have been broken. Vein silica is more extensively distributed than the uranium and iron mineralization it carries. Along the vein course concentrations of uraninite frequently fade away and barren white quartz continues, the transition often occurring within a few feet along strike or down dip. An example appears on the 3700-ft level where a uraninite vein, see Fig. 2a,

Jan 1, 1954

By Helen D. Robinson

The seawalls that surround Ellis Island were constructed in the early 1900s and now show varying degrees of deterioration. An innovative approach to the structural repair of the seawalls was developed, which consisted of the use of micropiles for stabilization of vertical and horizontal seawall movements. The micropiles were installed through the existing seawalls and penetrated through a thick overburden, consisting of soft alluvial deposits and relatively hard glacial till, and were bonded into Manhattan Schist. Drilling of the micropiles often encountered timber and other obstructions. The selection of micropiles for stabilization of the seawalls offered significant advantages over other foundation systems and over alternative soil improvement techniques. They allowed drilling through a variety of materials without the need for significant retooling or changes to the drilling procedure. This reduced the impact of foundation construction on the sensitive historical landscape and structures, and prevented the need for significant foundation work from the water side of the seawalls. In addition, micropiles offered relatively high installation rates and flexibility to adapt to the varying conditions along the seawalls.

Jan 1, 2008

By F. C. NINNIS

AT THE Belmont mill, the pregnant solution is de¬livered to a 30 by 10-ft. tank, from which it is pumped to three Merrill clarifying presses of the sluice-bar type, whence it flows through the meter to the precipitation supply tank. ?The solution for precipitation is pumped by a 10 by 10-in. Aldrich triplex pump and delivered through a 6-in. line to the forty-eight triangular frame Merrill presses at the head of the mill. Zinc dust is fed in at the pump suction and the solution precipitated to 0.01 to 0.02 oz. silver. The solution flowing from the presses is tested at 1-hr. intervals with sodium sulfide. All solution is precipitated to the same value; 4J tons of solution are precipitated for each ton of ore treated and the presses are cleaned every 15 days. The product from the presses' is dumped into steel cars having steam-jacketed bottoms, in which they are dried until the moisture content is between 15 and 17 per cent. when 8. per cent. of soda and .3 per cent. of borax are added and the contents thoroughly mixed. In the case of special clean-ups, the precipitate is tested and the flux is added to meet the requirements.

Jan 1, 1921

By D. G. Macintyre

"Potentially economic stratiform barite-sulphide deposits have recently been discovered in Devonian basinal facies rocks of the Kechika Trough of northeast British Columbia. This new mineral district is over 180 kilometres long and includes nine major occurrences, namely Driftpile Creek, Bear, Mount Alcock, Cirque, Fluke, Pie, Elf, Kwadacha and Sika. The Cirque is the largest known deposit, with reserves of atleast 30 million tonnes averaging 10per cent combined lead-zinc and 47 grams per tonne silver. The footwall rocks for the Cirque and other strati/rom barite-sulphide deposits in the area are rhythmically bedded baritic and pyritic carbonaceous black shales, siliceous argillites and cherts of probable Mid to Late Devonian age. These siliceous rocks overlie a succession of proximal to distal turbidites which are the basinal equivalent of Early to Mid Devonian carbonate reefs to the east. The siliceous facies is overlain by deeper-water black shales of probable Late Devonian to Mississippian age.Preliminary stratigraphic and sedimentological investigations suggest that the strati/arm massive pyrite and bedded barite deposits formed in third-order euxinic basins within a northwest-trending structurally controlled trough which, in the southern part of the district, was bounded by carbonate reefs. The exhalative event, which appears to have been accompanied by synsedimentary faulting, took place during the early stages of a major eastward-directed marine transgression that was probably related to rapid crustal subsidence. Dewatering of metal-enriched shales and subsequent brine discharge along fault zones within the trough, with the exhaled brines accumulating in seafloor depressions, is the mechanism envisaged for formation of the deposits. Convective circulation systems may have been established about the more deep-seated faults, in response to elevated heat flow levels."

Jan 1, 1982

By Amr M. Sallam

In recent years, with the increase of the number of high-rise buildings that are proposed and being built in Central Florida especially in Downtown Orlando, Augered Pressure Grouted Displacement (APGD) piles became a pronounced foundation option. The APGD pile is a bored displacement pile that does not result in drilling spoil. APGD piles are mostly suited for loose to medium granular soils and slightly silty/clayey sandy materials, such as those encountered in Central Florida. The case history presented in this paper involves the APGD piles recommended for a 35-story mixed-use condominium in Downtown Orlando. The subsoil condition was typical for the region; that is loose to medium fine sands underlain by thin layer of plastic sandy clays and plastic clays followed by mixed clayey sands and sandy clays with phosphates and traces of shells transitioned to the weathered limestone. Four APGD test piles were installed and were, statically, tested. Three of the tested piles failed to support the design load. Analysis of load test results showed that the bottom half of the test piles, below the plastic clay deposits, was not effective, which was attributed to structural deficiency resulted from possible pile necking due, in our opinion, to the increase of the porewater pressure within the plastic clays. Three additional test piles were constructed with modified reinforcement cage; that is to extend beyond the plastic clays with tighter stirrups. The additional test piles were, statnamically, tested and were able to sustain the design loads. The construction of the APGD piles through subsoil conditions similar to those of Downtown Orlando, where plastic clayey deposits are encountered, should account for the high porewater pressures that mostly will be developed within the plastic clay, hence, may cause pile necking. Extending the cage to penetrate through and pass the plastic clays reduced the necking potential and improved the test piles performance.

Jan 1, 2006

By R. C. Gilmore, S. A. Lolon, G. E. Bogin, S. A. Saki, J. F. Brune, J. W. Grubb

"Gob ventilation boreholes (GVBs) are widely used in underground coal mines for longwall gob degasification purposes. GVBs are often drilled within 10 to 30 m above the top of the coal bed into the fractured zone, completed with 20 cm (8 in.) diameter casing and 60 m of slotted pipe at the bottom. The purpose of this completion strategy is to create a pressure sink to capture the emissions before they can enter into the underground workplace. For GVBs to work effectively, they must be drilled close enough to the working areas to capture methane from the fractured zone while the setting depth must be kept above the caved zone to minimize the amount of ventilation air that is drawn into the GVBs. Well completion parameters are important for creating safe working conditions. In this paper, computational fluid dynamics (CFD) studies will be presented to analyze the effect of different practices for GVBs completion parameters for methane extraction, formation of explosive gas zones in the gob and methane concentrations at the longwall face and tailgate. Authors have identified the optimum completion parameters for GVBs, which can maximize the benefit and minimize fire and explosion risk. INTRODUCTION Coal mines may be considered gassy based on the presence of CH4. Gas from the mined coalbed or from rider seams above or below the mined coalbed can migrate into the gob and then potentially move towards the working areas. In longwall coal mines with high methane emissions, sufficient ventilation and additional methane control measures are usually required to reduce the methane concentration in working areas to below statutory levels. Several techniques or combinations of techniques are available to control the methane hazard. These may include mine face ventilation to dilute methane, coal bed degasification, nitrogen injection into the gob to render a methane atmosphere inert and the use of gob ventilation boreholes (GVBs). Longwall face ventilation and dilution alone can only handle methane emissions up to a certain amount. When methane emissions exceed the face ventilation capacity, additional control measures are required. Drilling horizontal or vertical methane drainage holes into the coal seams as well as gob ventilation boreholes from the surface into the gob area to extract methane are common practices. GVBs are usually drilled from the surface above the longwall panel ahead of mining. When the face moves outby the GVBs and the gob begins to form, methane production starts from the boreholes. It is important to control the performance of GVBs to maintain a safe working environment in the mine. The performance of GVBs depends on multiple factors, including borehole location, length and diameter of slotted casing, setting depth of casing above the coal seam being mined, wellhead vacuum pressure, and permeability of caved-fractured zones."

Jan 1, 2016

By D. D. Carda, S. Dunn, W. E. Dunn, T. Storbeck

Gold chlorination which will be presented in this paper is limited entirely to the use of gaseous chlorine in a fluidized bed reactor at elevated temperatures in the absence of aqueous water. The only water used in this process is that which is used in scrubbing the effluents. Low temperatures are defined as those below 500°C. All experimentation for this paper was carried out on a laboratory scale, with all calculations extrapolated frpm this. Some of the data is drawn from work with other projects which have been operated at pilot and larger scale.

Jan 1, 1998

By L. L. Newman

As soon as the Congress recognized the alarming rate at which our domestic oil resources were being depleted during the war, it took action to step up the rate of research and development which the Bureau of Mines had been conducting for several years on the production of synthetic liquid fuels from coals. Under Public Law 290, approved April 5, 1944, funds were authorized for the Bureau to proceed with research, development, design and construction of demonstration plants for the hydrogenation of coal, the synthesis of oil from carbon monoxide and hydrogen, and the distillation of oil from shale. During the latter part of 1944, when it became evident that the collapse of Germany was near, a Technical Oil Mission was organized to study the Ger- man techniques of synthetic oil production. Since the cost of hydrogen or synthesis gas is one of the major factors of expense in the operation of hydrogenation or synthesis gas processes, the Bureau of Mines considered it of prime importance to include on the mission gas engineers whose instructions were to examine closely the methods employed by the Germans in solving the problem of providing low- cost hydrogen or synthesis gas for their very extensive operations on synthetic liquid fuels. The Solid Fuels Mission and the Utilities Mission, as well as the Army and Navy Missions, also included teams for the study of German gas production. Although their objectives naturally differed from those of the Technical Oil Mission and from each other, it was recognized that there was considerable overlapping of their fields of investigation. Duplication of effort, however, was largely avoided through the close cooperation between the group leaders of these missions. For example, although I went to Europe as a member of the Technical Oil Mission, my first German assignment was actually made by Dr. Harry F. Yancey, leader of the Solid Fuels Mission- to investigate the brown-coal gasification methods in central Germany. The art of gasification in the United States and England, and to a large extent in the proximity of the coking-coal regions of Germany and the rest of continental Europe, depends essentially on two stages of operation; namely, carbonization and intermittent water-gas generation. As far as the United States is concerned, complete gasification in a single stage of operation is rarely practiced, except in gas-producer operations where the product is a relatively lean gas consumed close to the point of manufacture, and for water-gas production with anthracite as a generator fuel. Complete gasification of bituminous coal has been the subject of numerous investigations. Many relatively simple modifications of the water-gas generator have been tried to permit the direct gasification of low-cost bituminous coal instead of high- cost coke and anthracite for the production of water gas. Although varying degrees of success have been achieved and the water gas produced generally has been higher in calorific value, in only a few isolated in- stances has there been any sustained use of bituminous coal for water-gas production for public utility uses after the shortages of anthracite and coke have been lessened.

Jan 1, 1946

By John Relser

The production processes that are developed in the mining and minerals industry are manufactured to be exposed to very aggressive environments. Chemical, abrasion, and impact expose structures and equipment, steel or concrete, to a significant deterioration. This causes damage and adds high costs to operations that can be reflected in the destruction of equipment and structures in the arrest of the production process, which becomes very costly. Also, there is the potential for personnel accidents, which would require large sums of compensation for an employee, thus directly harming the image of the mining operation and company. Manufacturers of paints and coatings that have major centers for research and development (R&D Labs) distributed globally have developed high-tech products for durable protection from the elements for structures and equipment used in the mining industry. The difference between these paintings and coatings and what is normally known as conventional paints (e.g., those called domestic or decorative), is its chemical composition, structured around polymeric components that have highly resistant, chemical and physical properties to cope with extreme conditions to which they are exposed. With this, and only this, longer life of components can be achieved for equipment and structures used in the production processes of the mining industry. Today, in addition to the important features mentioned, some manufacturers of the paints and coatings dedicated to this highly modernized process have invested large sums of money in developing new products that add operational elements to the painting process. These coatings provide added value and significant performance to companies mining operations and that we can describe in three fundamental concepts:

Feb 1, 2014

By L. A. Neumeier

The Bureau of Mines evaluated the properties of a Zn-0.75 pct Cu-0.12 pct Ti alloy extruded at temperatures between 400° and 720° F. The extrusions were made with a reduction ratio of 28-to-l and at relatively slow speed. Rod was also extruded at 560° and 640° F with a reduction of 255-to-l. With increased extrusion, temperature, extrusion pressures decreased substantially and creep resistance of the rod improved significantly. Coefficients of thermal expansion were low in the long rod dimension. Microstructures, hardness, and tensile properties were also evaluated, and a limited evaluation was made of bend ductility at 32° F for the rod extruded with the 255-to-1 reduction.

Jan 1, 1969

By T. L. Joseph

The Bureau of Mines gas been studying the blast furnace for a number of years and has published detailed reports on various phases of its investigations. Inquiries frequently received for information of a more general character than that given in the detailed reports have promoted the preparation of an information circular to cover in a general way the important features of the Bureau of Mines blast-furnace investigations. SHAPE AND DIMENSIONS OF FURNACE The modern blast furnace approximate a refractory-lined steel cylinder about 90 feet in height and 25 feet in diameter. It actually consists of a number of cylinders and truncated cones superimposed upon each other. The shape and dimensions of a modern furnace are shown in figure 1. The bottom section, commonly referred to as the hearth or crucible, is a cylindrical section about 12 feet high. Liquid metal and slag collect in this part of the furnace and are withdrawn at regular intervals; iron is removed at a level about 2 feet above the bottom of the furnace and slag at a level about 5 feet higher. Depending upon on the size of tie furnace, 40,000 to 75,000 cubic feet of preheated air per minute is introduced through from 10 to 16 tuyeres equally spaced around the periphery of the hearth.

Jan 1, 1934

By J. Georgi

A number of infrastructure projects are on progress all around Greece at the moment. The common propose of these a project is the promotion of quality in: Design, construction and maintenance stages. They also comply with environmental management, which is, a method of organizing and implementing environmental protection measures. The paper includes by special reference on two important modern transport infrastructure projects for the development of Greece and its communication with Europe and the Balkans. Their landscape types and natural vegetation, local climate, geological conditions, altitudes, aspects and soil types vary As a result, upland landscapes in particular, are endangered. Due to the complex of nature of this environment, the development and the landscape design of the projects is a high challenging task. Wherever the nature of the projects requires intervention to the environment, they intend to follow the direct restoration of landscape and method for ecological balance. The implementation of landscape design of infrastructure projects, aims at restoring the landscape affected by construction works, incorporating transport works into the landscape, emphasizing on areas of particular interest (e.g. archaeological sites), while at the same time observing the principles of an efficient operation and safe use of the alignment. Landscape design provides, among others for the protection of slopes against surface erosion and the reinforcement of their stability, the improvement of road functionality, the aesthetic improvement of the landscape, adaptation of the road landscape to the greater environment, visual guidance of the user, screening of lights of the vehicles moving in the opposite direction, the protection against wind etc. The landscape design strategy and landscape applications are specified by special landscape guidelines and specifications that can be considered as part of the sustainable development of a alignment creating a high a esthetic scenery, ensuring the security of transportation and the environmental protection.

Jan 1, 2002

By M. F. Handley

This paper covers in situ stresses in the Earth?s crust prior to any man-made disturbances, such as mining. It introduces the Southern African Stress Database, which contains primitive stress measurements obtained from locations spread all over southern Africa. The measured stress data shows large variability without any visible trends, except a relationship with increasing depth. The stress database is reviewed briefly, establishing means to measure the variability or dispersion in the measurements, and showing that the dispersion is not as much a result of experimental error as it is a feature of primitive stress. The paper demonstrates from the beginning that the state of stress in rock is highly variable, but that there are well-defined maximum and minimum limits to all the stress components in rock. Formal error analysis is introduced to check the consistency of the database and to separate out a database of consistent stress measurements for use in a primitive stress model. The aim is to provide a picture of primitive crustal stress based on objective stress measurements together with interpretations of how the primitive stress can be affected by the five main influences; namely, depth, rock mass properties, tectonism, isostacy, and erosion. Four elementary models for primitive stress are introduced and compared with the measured data. It is quite clear that none of the elementary models is sufficient to describe the data. In the absence of a better model, this paper suggests a generic model based on the Hoek-Brown failure criterion and the consistent stress database, since it incorporates the variability in the stress tensor that is likely to be encountered underground all over southern Africa. Rock engineers should take every opportunity to obtain local primitive stress data at every mining operation and civil engineering project, and to adjust the proposed model accordingly Keywords primitive stress, Southern African Stress Database, error analysis, generic primitive stress model.

Jun 1, 2013

By H. H. Kellogg

Equations representing the standard free energy of formation as a function of temperature, for thirty metallic chlorides, are presented and plotted on a free-energy vs. temperature diagram. The use of these data for calculations on reduction of metallic chlorides, refining of metals with chlorine, and chlorination of metallic oxides and sulphides is illustrated. CHLORINE metallurgy' has attracted metallur- gists for more than a century because the unusual properties of the metallic chlorides—low melting point, high volatility, and ease of formation from the oxides—make possible many useful extractive processes. Interest in chlorine processes is undergoing a renaissance due to present availability of chlorine at relatively low prices, and to recent advances in technology. During the present century there have accumulated a considerable number of reliable values of the thermodynamic constants for the metals and their chlorides. These data permit the calculation of free-energy equations for many metallurgically important reactions. Consideration of free-energy values makes possible certain predictions of the direction and extent of a given reaction, as well as the effect of temperature, pressure, and composition upon the result. Reaction rate, although not predictable from free-energy data, is usually sufficiently great at elevated temperatures that diffusion of the reactants and products to and from the zone of reaction determines the actual rate. Thus, if the free-energy indication is favorable, the chances are good that a high temperature metallurgical reaction will proceed at a reasonable rate, if adequate provision for rapid diffusion has been made. This paper presents standard free-energy equations for a number of metallic chlorides, based on data which are scattered throughout the literature. The equations are presented in a form that simplifies their use, and typical examples are given of the application of free-energy data to metallurgical processes. Free Energy of Reaction The free-energy change (AG) of a reaction is the true measure of the "driving force" of the reaction under a given set of conditions, and this is related to the standard free-energy change (AGO) of the reaction as follows: For the reaction: bB + cC = dD + eE ?G = ?G°+RTln ADd. AEA / ABb. ACc where A, = activity of constituent (i) T = absolute temperature, OK R = gas constant The criterion of a spontaneous reaction from left to right, at constant temperature and pressure, is a negative value for the free-energy change (?G). The standard free energy of the reaction is equal to the free energy of the reaction when all the reactants and products are at unit activity, since under these conditions the second term on the right-hand side of eq 1 is equal to zero. The concept of activity is treated fully in many textbooks on chemical thermodynamics1 and in a recent article by Chipman.2 Briefly, the activity (A,) of a constituent (i) is a measure of the reactivity of this constituent relative to its reactivity in some arbitrary standard state. For liquids and solids the standard state most often used is the pure liquid or solid constituent. Thus the activity of a pure liquid or solid in a metallurgical reaction is equal to unity. Gases under moderate pressure and at elevated temperatures behave very nearly as 'idea1 gases,' and the standard state is chosen as the gas at 1 atm pressure. The activity of an ideal gas is therefore equal to its partial pressure, and this relation is sufficiently exact for real gases in most metallurgical reactions. For a liquid or solid solution there is in general no simple way to express the activity of a constituent as a function of its concentration, and activity must be determined by experiment. A few solutions follow a so-called 'ideal' behavior, and if the pure constituent is chosen as the standard state, the activity of a constituent in an ideal solution becomes equal to its mol fraction. When a reaction reaches a state of thermodynamic equilibrium at constant temperature and pressure, AG becomes equal to zero and eq 1 reduces to: [ADd . AEe ?G°=RTln Abb ¦ Ac c equilibrium [2] The brackets surrounding the activity term are used to emphasize that each of the activities is an activity under equilibrium conditions—not just any arbitrarily assigned value. The bracketed term is the equilibrium constant (K) of the reaction. Eq 2 makes possible the calculation of equilibrium activities for a given reaction, if AGO is known at the desired temperature. The standard free-energy equations presented in this paper were calculated from the fundamental thermodynamic values of enthalpy of formation at 298°K (AH°,), standard entropy at 298°K (So298), heat capacity as a function of temperature (Cp), and enthalpies of transition, fusion, vaporization, and sublimation for the various constituents. Where possible the data reported in the recent "Selected Values of Chemical Thermodynamic Properties," published by the Bureau of Standards," were used. A large number of data came from the publications

Jan 1, 1951

By A. H. Jones

(San Francisco Meeting, September, 1915). THE Belmont mill at Tonopah, Nev., was designed and constructed by the Belmont staff. Ground was broken in August, 1911, and milling operation started July 25, 1912. The metallurgical flow sheet, and the machinery adapted to carrying out operations in accordance with this plan, were decided upon from experience gained in the treatment of Belmont mine ores at the old Belmont mill at Millers, Nev. The detail drawings were made by the-engineering staff of the Tonopah-Belmont Development Co., under the supervision of Otto Wartenweiler, who also .had direct charge of the construction, consulting with the General Superintendent of the company, Frederick Bradshaw, and the writer.

Jan 8, 1915