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By H. I. Aaronson, H. A. Domian, G. M. Pound

The thernodyna,nics of I the Proeutectoid ferrite re-action ha1.e been investigated on the bases of three diifevent descviptions of the statistical thernzodynamics of interstitzal solid solutions. Especially at low ternperatures, substantial dijeretzces are found in the valltes of the extrapolated y/y + a and cr/a + y equilibriurn curls, and in the To- co7nposilion metastable eqliilibriunz curl-es thus co,npited. Although neither actiztity nor phase-diagram date are able to distingrish udeqiutely among the various descviptions, the statustics of Lacher, Fouller, and Guggenheinz provide the ?nost conplete epresentation az3ailable of the single carbon-ctrbon interaction energy (w) nzodel of an intevstitiril solid solution, and the relationships deduced frojrl then2 are accordingly pre.ferred. The findings tlzut w in austenite 'aries significu?ztly uith tenpevntrue and that phase-diagawr data arc not accurately con?palible usith eqcrctions deduced on the basis of actility infoation indicate, hou'e13er, that a wzore cornplex nlodel of the uustenite , und pvobably of the .feyrite, solirl solutions will have to forn the basis of f4tuve statistical t1.eat1nents. Some suggestions for such a ruodel arc advanced. Althoug11 w represents a vepltlsio energy in austozite, it was found to corvcsporzd in ferrite to a binding energy, in qualitatit.e accord zc,itlz the internal-friclion results of Keefer and wert. ThE transformation of austenite to proeutectoid fer-rite is becoming recognized as an exceptionally useful vehicle for quantitative studies of the kinetics of phase transformations.'" Reasons for this popularity include well-characterized microstructures which develop on a convenient scale with acceptable kinetics within a considerable temperature-composition region, the absence of great sensitivity to common impurities, and, especially. the availability of a unique wealth of the ancillary information indispensable for the quantitative interpretation of kinetic measurements, including phase diagram,3 crystallographies diffusivity,5 inter-facial energy,=17 elastiit," specific vlume, ''' and ativity'-' data. Development of considerable amounts of additional thermodynamic information from activity data is of particular importance with respect to kinetic studies, since much of this information is needed in temperature-composition regions not directly accessible to presently available techniques for the measurement of equilibrium properties. A generally useful approach to the thermodynamics of solid solutions, which is of especial value in this situation, is based upon the formulation of the free energy of such solutions as a function of temperature and composition. The free energy of solid solutions has been resolved into many components. Particularly in the case of interstitial solutions, with which we shall be concerned in the present study, however, only the positional entropy component has been intensively studied. The other components are conventionally taken into account by fitting equations for the activity of the interstitial species or the temperature-composition path of phase boundaries, derived principally from positional entropy considerations, to experimental information on these quantities through adjustment of one or more constants in the equations. A number of studies of the thermodynamics of interstitial solid solutions have been made primarily on this basis,'"25 but only Kaufman, Radcliffe, and cohenZ2 (hereafter KRC) and ener''% ave applied the results of such studies to develop relationships for the thermodynamic quantities of interest in the austenite —- proeutectoid ferrite transformation. KRC made use of a model developed by cheil'' (on the basis of a previous study by ohansson'), and subsequently rede-rived correctly by Speiser and retnak,' in which a carbon atom is considered to inhibit occupancy of a certain number of its nearest-neighboring interstitial sites. schei120 determined the number of sites in austenite thus excluded by matching calculated and experimentally measured curves for the variation of carbon activity with the mole fraction of carbon. zener17 used a different approach. He assumed that the positional entropy of carbon is ideal both in austenite and in ferrite (i.e., no excluded interstitial sites), and included all other contributions of carbon in a temperature-independent "free-energy change" accompanying the transfer of 1 mole of carbon between the two phases. This quantity was determined by "pinning" an equation derived for the boundaries of the a + y region to experimental data on the compositions of these boundaries at a single temperature. In the present investigation, three different approaches to the thermodynamics of the proeutectoid ferrite reaction are examined comparatively: I) the method of Zener; 2) the model employed by KRC and predecessors; and 3) the more detailed statistical thermodynamic treatment of the same model developed by acher and Fowler and uenheim, ' in which the problem of overlapping regions of influence of individual interstitial atoms is resolved. In order to make these comparisons, it is necessary to undertake an extension of one aspect of Zener's method; since the Lacher- Fowler -Guggenheim (LFG) treatment has not been previously used in the present context, the necessary thermodynamic "superstructure" for this treatment will be developed in parallel

Jan 1, 1967

By W. A. Krivsky, R. Schuhmann

Jan 1, 1962

By Robert H. Aborn, J. J. B. Rutherford

It is now well known that troublesome intercrystalline corrosion may occur in austenitic stainless steels following exposure of the metal to a temperature within the range 1000° to 1500° F. (540° to 815° C.). The present paper describes a satisfactory method of estimating the extent of such corrosion, based on the measurement of the electrical resistance of a specimen before and after attack. This new method enabled us to study quantitatively the effect of several factors upon intergranular corrosion in the 18 Cr, 8 Ni type of alloy. The results show that susceptibility to this attack increases with increasing carbon content and grain size and appears to pass through a maximum for certain combinations of temperature of sensitization and period during which the alloy was maintained at that temperature; and are in complete accord with our interpretation of the mechanism of this phenomenon. The method is probably applicable to other metals or alloys subject to intercrystalline attack, such as the aluminum alloys of the duralumin type. The methods hitherto in use for estimating the degree of intergranular attack fall into three types: (1) microscopic examinationll (2) macroscopic examination of fractures, and (3) determination of the time required for complete failure or disintegration.2 None of these lends itself very well to a measurement of the extent of corrosion. The first two are qualitative in nature and the third provides an arbitrary value largely dependent on individual judgment, since failure is a progressive phenomenon and not a sudden event. Our experience is that weight-loss determinations, although valuable in some types of corrosion investigations, bear no simple relation to intercrystalline corrosion in this type of alloy, as is to be expected since the phenomenon probably involves only the thinnest films between adjacent metallic grains. Measurement of electrical resistance has been used recently in the study of some types of corrosion,3 but seems not to have been applied to

Jan 1, 1932

By F. A. Olson, J. S. Cho, M. E. Wadworth

An infrared study of the states of hydration of MgSO4 revealed a hitherto unreported metustable dehydration state in the temperature range just below that of the stable anhydrous salt. Infrared, thermogvavimetric, and X-ray studies indicated that the state had bisulfate and hydroxide characteristics. A formula fitting all of the experimental evidence is hydrogen-bonded Mg(OH)HSO4, or possibly the chemically equivalent 1/2 Mg(HSO4)2. Mg(OH)2 Infrared spectra of the 7, 6, 1, and OH2O states of hydration are given as well as the spectra of the newly found state which is called the bisulfate state in this paper. Thermogvavimetric studies as a function of water-vapor pressure gave an enthalpy value of 16 cal per mole, and 25 eu for the conversion of the bisulfate state to that of the anhydrous salt. The free energies of the transition varied from 1.76 to 0.18 kcal per mole as the transition temperature varied from 279° to 336°C. The bisulfate state is believed to be of importance in catalytic dehydration phenomena using MgSO4 and may be of interest because of properties in sulfating reactions differing from those of the monohydrate. Also, an analogous state may exist as a hydration state of other sulfates. ANHYDROUS magnesium sulfate is a catalyst with a high degree of specificity for the dehydration of secondary alcohols.1'2 The only product obtained at the usual operating temperature range of 360" to 400°C other than the corresponding olefin is water. Thus, the bonding of water to the anhydrous salt as well as an understanding of the hydration states of MgSO4 became of interest in attempting to understand the catalytic mechanism better. In the process of this study using infrared, X-ray, and thermogravimetric analyses a dehydration state not previously reported was found. Proof of its existence, the nature of the state, and its role, if any, in the catalytic mechanism then became of interest. This paper is concerned principally with the first two aspects of this problem. Magnesium sulfate forms many hydrates, of which the monohydrate and heptahydrate (Epsom salts)3 are most important. Other hydrates4 are known with 1-1/4,5 l-1/2, 5 2, 4, 5, 6, and 12 H2O's. The hydrates with 1-1/4, 1-1/2, 2, 4, and 5 HzO's are unstable. The anhydrous salt is very stable thermally and has a strong affinity for water. It can be heated without additional decomposition to about 800°C.' At 900°C noticeable decomposition takes

Jan 1, 1964

By Robert Goodrich

THERE is a small area about Murray where bedded gold quartz veins occur in Prichard slate. The ore taken from the upper levels, during the early days, was free milling and was treated by stamp milling and amalgamation. There was likewise a considerable placer working. The report is current that tungsten (scheelite) was encountered, which interfered with the amalgamation in the stamp mills and which, in placering, collected in the riffles in the sluice boxes and. clogged them. Consequently, in the quartz mines, the scheelite, when encountered, was rejected, being thrown into the waste, sometimes inside the mine and at other times outside on the clump. The free surface ores became worked out and as the ore in depth became pyritic and rebellious to amalgamation the mines closed down. Last spring tungsten ore brought a high price, near $80 per unit, 60 per cent. W03 and up. This so stimulated the output of tungsten ore that old clumps were explored and waste stored in the mines was gone over. Tungsten was likewise mined from virgin ground. So the district produced quite heavily for a time. The condition now is different. The price is not so high, about $20 per unit W03, which makes profits questionable when mining in new ground. The accumulations from early clay mining have been exhausted and the output has greatly declined. The Golden Chest mine was the heaviest producer of tungsten. The months of June and July were spent at this mine studying the problem. Since the mine had produced both gold and tungsten, we looked forward to the problem of recovering both from what might be called a gold-tungsten ore. A study of the Golden Chest vein showed this not to be so there. While gold ore and tungsten ore come from the same vein, the tungsten ore is confined to a more or less disturbed or distorted portion

Jan 8, 1917

By Donald F. Saunders

Means and relative standard deviations were calculated for eU, eTh, K, and their ratios for aerial gamma-ray spectral data in 29 quadrangles at 1:250,000 scale. Known or suspected uraniferous provinces were characterized by: 1) Higher eU, eTh, and K means (due to generally higher radioelement concentrations); 2) Higher relative standard deviations for eU, eU/eTh, and eU/K (reflecting the presence of local uranium enrichments); and

Jan 12, 1979

By T. Smales, P. L. Wright, K. Barron

The results of field measurements using an air injection technique to investigate the integrity of three pillars in the Mclntyre Mines Ltd. 114 seam at Crande Cache, Alberta, are reported. These pillars are shown to be stable and an estimate is made of the strength of these pillars. Using these results, together with Hustrulid's pillar strength formulae, a general pillar strength equation for the 114 seam is developed. This equation takes into account the probability of failure that may be deemed tolerable within the design requirements. The variation of the minimum pillar dimensions with depth below surface for uniform pillar layouts is then examined for a range of tolerable failure probabilities. A general equation of the form B = 2.60 +B Z relates the minimum pillar design width, B metres, with the overburden depth, Z metres, where B is a parameter related to the tolerable failure probability. This equation only applies for 3.05m high pillars with 6.lm wide entries. Finally, the question of what failure probability is tolerable within the design of mine pillars is discussed. This will depend on the support role required of that pillar and the anticipated period over which the pillar must perform that role. Five categories of coal mine pillars are defined, each with a somewhat different role to perform. Tentative design criteria in the form of "tolerable probabilities of failure" are suggested for four of these five categories of pillar. The fifth category of pillar has no reliable support function to perform and support must be obtained by other means.

Jan 1, 1983

By T. A. Read, H. K. Birnbaum

STRESS-induced twin boundary motion in the AuCd ß'phase (52.5 at. pct Au 47.5 at. pct Cd having an orthorhombic structure (space group D h)' was discussed for the case of transformation twins.' Mechanical twinning, i.e., introduction of new twin orientations by the applied stress was sometimes observed in the ß' phase which contained two transformation twin orientations. (See Ref. 2 for experimental details.) The transformation twins terminated at the mechanical twin boundary; the two initial orientations having been twinned to the new orientation as shown in Fig. l. In a "hard" tensile instrument, formation of each mechanical twin was accompanied by a sharp drop in load (and an audible click) resulting in a typical serrated load-extension curve. The mechanical twins increased in width and additional twins were nucleated as the load increased until the entire specimen was occupied by the mechanical twin orientation. A restoring force2 caused the mechanical twin and transformation twin boundaries to return towards their initial configuration on releasing the load. In a stabilized specimen* the total strain introduced by mechanical twinning was recovered on releasing the applied stress. Initial and final microstructures were identical. After decreasing gradually to a critical width, mechanical twins suddenly disappeared accompanied by audible clicks and sharp increases in load (measured at a constant rate of crosshead motion in a "hard" machine). Mechanical twins could be stabilized in any position by maintaining the applied load for a sufficient time, indicating a decrease in restoring force with time similar to that observed for transformation twins.' Orientation relationships for mechanical and transformation twins were determined and are shown in Fig. 2. The mechanical twin, T3, was twin related to transformation twin, T,, by reflection in (1ll), and twin related to transformation twin, T2, by reflection in (111)T, . T, was related to T, by reflection in(ll1)T1 . The "average" mechanical twin composition plane lay several degrees from (1ll), . In every specimen which mechanically twinned, orientation T3 was most highly favored by the applied stress, i.e., it was the twin orientation which provided the greatest change in length compatible with the direction of applied stress

Jan 1, 1961

By G. M. Schwartz

THERE has been considerable controversy regarding the structure and mineral constituents produced when iron ore is sintered. This investigation was undertaken in order to establish the fundamental reactions that take place in the sintering process by determining the nature of the resulting minerals. The writer's immediate interest in the subject arose mainly from the request of E. W. Davis for information based on a microscopic study of sinter submitted by him in May, 1926. In the author's preliminary work, samples of iron-ore sinter were secured from the Minnesota School of Mines Experiment Station and from commercial plants. These were polished by the usual methods for polishing opaque ores. In order to study these surfaces satisfactorily, it is necessary to magnify them rather highly, a range from 100 to 1000 dia. being used. For the higher magnifications oil-immersion lenses and an intense source of light are necessary. After the preliminary study had shown the problems involved, a series of small samples were sintered under carefully controlled conditions and with analyzed materials. Variations in the relative amounts of ore, coal and water were made in order to study the effect of each constituent. The attempt has been to arrive at a clearer understanding of the sintering process and the reactions involved without reference to any preconceived notion as to sinter. It is clear that the study of polished surfaces has yielded results not possible with thin sections alone. The thin sections made in this work were found unsatisfactory at magnification greater than 75, whereas magnifications of 1000 were easily studied with reflected light on carefully polished surfaces. A rather complete statement of observed facts is made so that the reader may form his own conclusions. The writer's interpretations are suggested.

Jan 1, 1929

By T. P. Meloy

In a recent paper, Gaudin and Meloy1 derived a size distribution function for single, impact fracture. Mular2 extended the use of this size distribution to describe the output of carefully controlled grinding experiments. As it stands, the function is difficult to compute. Consequently, a series of tables of the function are presented below: where M(x) is the cumulative fraction finer than size x when x is particle size. Weight percents are tabulated for the single parameter, r, in three different size ranges: from 0 to 1, from 1 to 10 and from 10 to 100. Tables I, II and III are cumulative percent finer and Tables IV, V and VI are for weight percent passing screen size x, retained on the screen below. A number of conditions from the table are plotted in Figs. 1 and 2. Fig. 1 is a plot of the cumulative percent finer vs. size, and Fig. 2 is the weight per-

Jan 1, 1963

By Fred W. Gordon

Apart from the character of pig-iron to be manufactured, other than that it shall be well reduced and open-grained, the selection of the materials should be such as to produce it at the lowest cost. As a rule, the sources of fuels and limestones are not so extensively varied as those of the ores. Many Eastern furnaces are now using Lake Superior ores, and but recently a part of the supply came from foreign ports. It is, however, of the highest importance that the character of fuels and limestones, as well as ores, should be carefully considered in determining their value and making judicious selection among those available. The formulas here offered are based upon the assumption that the heat-requirements for a given mixture are measured by a constant required by the oxide of iron, added to that required for a unit of slag, multiplied by the weight of that slag per unit of iron. The heat-requirements for oxide of iron per unit of pig-iron made are assumed to be 2854 centigrade units. This is taken from the careful analysis of Sir Lowthian Bell, and, so far as the writer is able to determine, is very nearly correct. Dividing this by the quantity of heat that may be evolved and utilized within the furnace per unit of carbon, determines the quantity of carbon required per unit of pigiron ; and if to this be added the quantity of carbon absorbed by the pig-iron, the total requirements in carbon are determined, on the assumption that pure oxide of iron is reduced with pure carbon by the ordinary process of the blast-furnace. Calculating the quantity of slag that would be made from a given mixture of ores, smelted with a given impure fuel and fluxed with a given impure limestone, multiplying this weight of slag by the heat-requirements of its unit (taken at 1050 C. H. U.), and dividing the product by the heat-units evolved and utilized within the furnace per unit of carbon, will determine the quantity of carbon required per unit of pig-iron for the slag.

Jan 1, 1893

By R. D. Pehlke, J. V. Gluck

A study was made of the effect of small additions of metallic solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450o to 650°C. The experimental measurements were made in a multielectrode galvanic cell using. a fused LiCl-KCl electrolyte. The activity of zinc in binary solution exhibited a strong positive deviation from Raoult's law and obeyed Henry 's law to at least 0.050 mole fraction. The ternary addition of lead, gallium, or indium increased the activity of zinc. Cadmium or tin additions slightly decreased the zinc activity. Copper, mercury, silver, or antimony caused moderate decreases, while gold strongly decreased the zinc activity. The results are expressed in terms of Wagner's interaction parameter ejZn and a second-order cross-interaction parameter. The interactions for copper, gold, silver, and antimony showed a linear dependence with reciprocal absolute temperature, while the other interactions were essentially independent of temperature over the experimental range. Since tin and antimony decreased the zinc activity, the hypothesis of a purely periodic variation with atomic number was rejected. A semiquantitative explanation was possible with a free-electron model when relative electronegativities were used to express changes in the electron/atom ratio caused by the solute addition. Random solution and quasi-chemical models correctly predicted the majority of the interactions for which binary data were available to apply them. A knowledge of the thermodynamic interactions in liquid (and solid) metallic solutions is of considerable theoretical and experimental interest in the formulation of quantitative thermodynamic relations for metallurgical processes. The approaches to defining the interactions may be either phenomenological (i.e., "What mathematical function adequately describes observed behavior and permits extrapolation to new situations?") or theoretical, such as a specific model

Jan 1, 1968

By R. B. Moore

Page History................................ 708 What is Radioactivity?........................ 710 Disintegration Series.......................... 711 Radium Ore Deposits......................... 713 Metallurgical Treatment........................ 717 Methods of Ore Concentration..................... 722 Future Supply of Ore......................... 723 Uses of Radium............................ 723 Mesothorium as a Substitute for Radium................. 724 Discussion.............................. 725 Probably no other metal excites as much interest, among both scientific men and the general public, as radium. This is due partly to the high cost of radium salts and partly to the peculiar properties of the element. Since radium-bearing ores were discovered in the United States, the interest of American scientific men has been stimulated and, at the present time, more radium is extracted and refined in this country than in all the rest of the world together. HISTORY The property of radioactivity was discovered, partly by accident, by Henri Becquerel, the French physicist, in 1896. He was experimenting with certain fluorescent substances in order to find, if possible, a connection between fluorescence and the recently discovered X-rays. Among other chemicals which possess the property of fluorescence, he was using salts of uranium. His custom was to expose the fluorescent substance to the action of sunlight and then register the effect of possible penetrating radiation on a photographic plate protected from ordinary light. Bec-querel's experiments gave positive results at once, and he at first believed that he had discovered a relation between fluorescence and X-rays. Later he exposed a plate to a uranium salt which had not been previously exposed to sunlight. To his surprise, on developing this plate, he found that he had obtained the same effect as he had previously secured when

Jan 1, 1919

By K. A. Grace

Reserves are the basic foundation of any mining enterprise, but a lack of understanding of the concept of resources and reserves is still a frequent cause of failure in mining ventures. A review of the development of the resource-reserve concept emphasizes the necessity for a common language, and the classification system as set out by the US Geological Survey and Bureau of Mines is advocated as the basis for this. Because of its strong economic connotation, the term reserves should be severely restricted in its use, and should encompass mining and processing factors. Modifications to the basic definition of reserves to accomplish this are proposed. Caution must be used in the quantification of undiscovered or hypothetical resources, particularly in juxtaposition with known resources data.

Jan 1, 1985

By Robert H. Leach, C. H. Chatfield

THIS paper gives a brief summary of the process of manufacture of sterling silver, and some of its more important physical properties, as observed in commercial production of rolled sheet and wire. Although papers have been published by Turner and Smith,1 Rose,2 Sperry3 and Jordan,4 there are few technical data available, and unfortunately the time allowed for the preparation of this paper has not been sufficient to make it as comprehensive as the title might indicate. ANALYSIS OF STERLING SILVER Fine or pure silver is too soft for coinage and the manufacture of articles in which strength and resistance to wear are desired. From the earliest times of which we have record, copper has been the metal generally used to harden silver. Analyses of coins and silver articles from ancient tombs show varying amounts of copper, and old Roman silver objects in the British Museum have approximately the same analysis as our sterling. The first authentic record of the establishment of a stand¬ard alloy is during the reign of Henry II in England. During the twelfth and thirteenth centuries, the people in the Eastern Provinces of Germany had a reputation for the standard and purity of their silver coinage, and it is said that Henry II employed some of these Easterlings, as they were called, to improve and standardize the English coinage, which had become debased. The peculiar standard adopted is probably accounted for by the system of weights used. A troy pound contains

Jan 1, 1928

By J. P. G. Farr, R. Brownsword

THE role of solute segregation in the formation of cellular solidification substructures in tin and its dilute alloys is well-established, see, e.g., Ref. 1. Segregation has been shown to persist during cooling, enabling solidification structures to be studied from sections taken at some distance behind the interface. In the present work, a single crystal of commercial nickel, 99.965 pct, was examined in this way. The crystal was cut from the center of a rod given a single pass in an electron beam floating zone melter. Polished sections of a nickel specimen taken normal to the growth direction showed a very fine precipitate phase, the distribution of which varied over the section. The identification of the phase proved difficult because of the small amount present and the small particle size, about 1 p: but it was shown by probe microanalysis to contain only nickel and oxygen in detectable concentrations and was probably nickel oxide, NiO. Bulk analysis of the material before melting showed there to be only 3 to 4 ppm of oxygen present, thus demonstrating a very considerable segregation concentration effect. In some areas of the section the precipitate formed a discontinuous hexagonal network suggesting decoration of the cellular boundaries known to be present in the sample2 whereas in a restricted region the precipitate formed small clusters. Occasionally it could be seen that the clusters were at the intersections of an hexagonal network of cellular dimension. It was suggested3 that this was the result of enhanced segregation to the cell boundary intersections whereas general cell boundary segregation was insufficient to give a precipitate. Enhanced nodal segregation has since been demonstrated in a number of systems.1, 4-8 The development of a suitable electrolytic etching technique (perchloric acid 20 pct v/v; ethyl alcohol 70 pct; glycerol 10 pct; current below electropolishing plateau; 1 to 2 sec etching) suggested the association of the phase with regions of solute segregation (where ko < 1); in these regions anodic attack produced grooves or depressions. In a study of the variation of solidification substructures with degree of constitutional supercooling, Biloni et a1.&apos; appear to have used standard growth conditions and varied the solute concentration. They were able to produce in a series of individual tin crystals examples of substructure ranging from planar interface through various cellular structures to den- Fig. 1—Electroetched section taken normal to the rod axis; the center of the rod lies to the left and the periphery to the right of the micrograph. The variation of structure across the section is evident. Magnification 60 times. drites. It was possible in the present nickel crystal to observe a continuous range of substructures varying with degree of supercooling across a single section as shown in Fig. 1. Growth rate, 13 mm per min, and temperature gradient were essentially constant; the variation in structure is thought to be due to a radial gradient in solute concentration ahead of the solid interface. The liquid at the interface is likely to have been richer in solute toward the periphery of the zone, the result of curvature of this interface. The type of substructure was seen to vary with increasing constitutional supercooling as follows: a) region free of precipitate. top left, Fig. 1: 6) region of nodal precipitates which became arranged in hexagons on passing from the center of the rod: c) irregular hexagonal cells with incomplete boundary precipitation; d) regular hexagonal cells of decreasing size with complete boundary precipitation. Fig. 2 shows the transition from stage 6 and Fig. 3 shows the structure in stage d. Within stage 0, the range of conditions over which irregularly positioned nodes occur appears to be small and the nodes are soon recognizable as taking up positions at the intersections of an hexagonal network as the supercooling increases.

Jan 1, 1970

By M. Mortada

Nonsteady-state flow of slightly compressible liquids in porous media of non-uniform properties has been the subject of a number of recent studies. Most of these studies considered one-dimensional flow in systems with cylindrical geometry and with the properties of the porous medium varying with radial distance only. A. Houpeurt&apos; studied the problem in its general form by examining the solutions of the differential equation, In Eq. 1, the permeability k and the porosity + are arbitrary functions of radial distance. Houpeurt concluded that, except for special forms of the functions k and the problem is not well suited for mathematical treatment, but lends itself to high-speed digital computation. Carslaw and Jaeger&apos; discussed the solution of Eq. 1 for the case in which the permeability varies as a power of the radial distance. P. Albert3 studied analytically the pseudo steady-state solutions in systems of finite radial extent and non-uniform properties. He also obtained some numerical solutions for nonsteady-state flow using a high-speed computer. William Hurst4 examined the interference pressure drop due to a point sink located in an infinite system consisting of two permeability regions in series. In this case, the permeability changed at a radial distance r from the point sink. INTERFERENCE BETWEEN OIL FIELDS IN A NON-UNIFORM AQUIFER The interference pressure drop for oil fields located in an extensive aquifer of uniform properties is discussed in a number of places in the literature. This work considers the interference pressure drop for oil fields located in a non-uniform extensive aquifer comprising two regions of different properties as shown in Fig. 1. Region I of the aquifer extends from which is the radius of Oil Field A, to ar,,, where a>1. It has permeability k,, porosity +, and effective compressibility c,. Oil Field B is located in Region II which extends from ar, to infinity and has different properties from those of Region I, but the same formation thickness h. Region II has permeability k2, porosity and effective compressibility c2. The choice of this type of aquifer should not imply that it is of frequent occurrence. It is chosen primarily to illustrate the effects of non-uniform aquifer properties on oilfield interference. It is of interest to point out that a non-uniform radial aquifer in which both the permeability and the porosity are inversely proportional to the radial distance can be treated in a manner similar to a linear aquifer of uniform properties. The situation where only the permeability varies as the inverse of the radial distance is also amenable to analytical treatment. Both aquifers behave quite differently from a radial aquifer with uniform properties so far as the water influx and the interference pressure drop are concerned. METHOD OF SOLUTION The expression for the interference pressure drop in Oil Field B due to a constant rate of water influx in Oil Field A is developed in the Appendix. This is accomplished by the simultaneous solution of two partial differential equations describing the pressure in Regions I and 11. The two differential equations are solved subject to the following conditions: (1) at r,, the pressure gradient is constant; (2) at ar the pressure and

By Herbert H. Kellogg

The chemistry of sulfide roasting is analyzed to show those aspects of performance which Thecan be predicted from considerations of thermodynamic equilibrium. It is concluded that equilibrium calculations can serve as a yardstick for prediction of roaster-gas composition and sulfate formation in the calcine for fluid-bed roasting practice. A method of calculation which combines the equilibrium and stoichiometric factors is outlined, and illustrated by an example from the roasting of Cu-Fe sulfides. ON first examination the roasting of sulfides would not seem to be a process to which equilibrium calculations could be applied to yield results of practical value. The burning of sulfides is an ex-tremely spontaneous reaction, excess air is always used to obtain rapid reaction, and in most traditional roaster designs (hearth roasting) the temperature and gas composition vary widely from point to point in the roaster. These are all conditions which promote a non-equilibrium state in the roasting process. However, the introduction of the fluid-bed roaster1 has brought to roasting practice new conditions of operation, so that equilibrium calculations can be used to predict certain limited aspects of practical operation. The fluid bed is characterized by uniformity of temperature, gas composition, and calcine composition from point to point throughout the bed. These relatively uniform properties of the bed make the meaningful calculation of the equilibrium state of certain reactions in roasting possible. It is the purpose of this paper to analyze roasting from an equilibrium viewpoint, to show where the method may be expected to yield valuable information, where it fails, and to outline methods of calculation. Main Roasting Reaction The reaction MS (s) + 3/2 0, = MO (s) + SO, [I] might well be called the main roasting reaction. It adequately accounts for the well known facts that metal sulfide and air are the main reactants, and metal oxide and SO, the main products. Deviations from this simple stoichiometry will be discussed under side reactions. For all metal sulfides, Reaction 1 is strongly exothermic and the equilibrium position is far to the right. Since the reaction is exothermic, the equilibrium shifts in the right-to-left direction as the temperature is raised. However, at all practical roaster temperatures (between 500" and 1200°C), the amount of this shift is small, and the equilibrium position remains far to the right. The main roasting reaction is essentially irreversible, and the application of equilibrium considerations to this reaction will not be! a fruitful field of investigation. A knowledge of the rate of this reaction. although not the proper subject of this paper, is of great importance to the roasting process. Analysis of the factors which influence this rate shows that: 1) The rate will increase rapidly with increased temperature. 2) The rate will be proportional to the partial pressure of oxygen at the surface of the reacting particle. Because of diffusion effects, the partial pressure of oxygen at the particle surface may be considerably less than in the bulk of the roaster gas. For this reason, intimate contact between gas and solid and high relative velocity between gas and solid, such as can be obtained in a fluid bed or flash roaster, will markedly increase the rate of reaction. 3) The rate will be proportional to the surface area of metal sulfide. Therefore, smaller particle size will permit a more rapid rate per unit of weight. To achieve practical rates of roasting the partial pressure of oxygen in the roaster gases must be maintained at a finite level at all times. Even where the gas-solid contact is very good, as in the fluid-bed roaster, the oxygen content of the gas must not be allowed to drop below some limiting value (perhaps 1 pct), or the rate of the main roasting reaction will become too small for practical operation. Side Reactions in the Gas Phase The gas phase during roasting of metallic sulfides contains the elements oxygen, sulfur, nitrogen, by-

Jan 1, 1957

By Franc R. Joubin, D. H. James

Uranium exploration in the North Shore area of Lake Huron goes back to 1847 when J. L. LeConte, a distinguished American geologist, identified a pitchblende-like mineral which he called coracite from specimens sent from a locality north of Sault Ste. Marie. In 1948 a search for the LeConte occurrence resulted in discovery of the Camray field, some 70 miles north of Sault Ste. Marie. Prospecting the Camray field yielded about 30 pitchblende occurrences spread over approximately 200 sq miles. Almost without exception these discoveries consisted of narrow, short, pitchblende-filled fractures, within or along the contacts of diabase dykes cutting pre-Cambrian Archean granite and gneiss. Eight discoveries were diamond drilled and three were explored underground, but none proved to be of economic value. Uranium prospecting at this time spread far afield, and it was in 1949 that radioactive conglomerate was discovered in Long Township of the Algoma district midway between and 90 miles from Sault Ste. Marie and Sudbury. F. Joubin examined this discovery at that time but could not interest capital in its development.

Jun 1, 1956

By Robert Leach

THIS paper gives a brief summary of the process of manufacture of sterling silver, and some of its more important physical properties, as observed in commercial production of rolled sheet and wire. Although papers have been published by Turner and Smith,1 Rose,2 Sperry3 and Jordan,4 there are few technical data available, and unfortunately the time allowed for the preparation of this paper has not been sufficient to make it as comprehensive as the title might indicate. ANALYSIS OF STERLING SILVER Fine or pure silver is too soft for coinage and the manufacture of articles in which strength and resistance to wear are desired. From the earliest times of which we have record, copper has been the metal generally used to harden silver. Analyses of coins and silver articles from ancient tombs show varying amounts of copper, and old Roman silver objects in the British Museum have approximately the same analysis as our sterling. The first authentic record of the establishment of a standard alloy is during the reign of Henry II in England. During the twelfth and thirteenth centuries, the people in the Eastern Provinces of Germany had a reputation for the standard and purity of their silver coinage, and it is said that Henry II employed some of these Easterlings, as they were called, to improve and standardize the English coinage, which had become debased. The peculiar standard adopted is probably accounted for by the system of weights used. A troy pound contains

Jan 1, 1928