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By Keith R. Bock, Norman Parlee, Albert M. Barloga

Coils of pure iron and iron-carbon alloy wire (0.05 to 0.80 pct C) and sufficient sulfur to saturate the solid phase were equilibrated in evacuated or argon filled tubes. After rapid cooling, and removal of the outside nonmetallic layer, the wires were analyzed for carbon and sulfur and the data used to construct an Fe-S binary and isotherms of the Fe-C-S ternary in the range 1149° to 1427°C. THE solid solubility of sulfur in steel is of interest in connection with such phenomena as hot shortness, burning, and so forth. "Burning," the more or less permanent damage that some steels suffer when heated for forging or rolling, has been shown to be related closely to the behavior of sulfur and less closely to carbon and oxygen.' Attempts to interpret burning phenomena in steels fail because of lack of data on the Fe-C-S and the more complex systems in this family. Rosenqvist and Dunicz 2 and Turkdogan, Ignatowicz, and pearson3 have largely elucidated the Fe-S diagram in the region of interest but no information on the Fe-C-S diagram in this region appears to be available in the literature. This paper deals with the elucidation of the Fe-C-S diagram in these interesting ranges. The method employed is different from those used by previous workers2'3 on the Fe-S system. EXPERIMENTAL METHOD Pure iron wires (Ferrovac E) or iron carbon alloy wires of 1 mm in diam were cleaned with acid and acetone, coiled, and placed in silica tubes (7 mm OD and 5 mm ID) previously closed at one end. Enough sulfur was added to assure saturation of the solid iron phase. The filled tubes were either simply evacuated and sealed, or filled with argon at a reduced pressure and sealed. The argon was required at the higher temperatures to prevent collapse of the tubes. The filled and sealed tubes were placed in the middle uniform temperature zone of a Globar tube furnace and equilibrated at temperatures ranging from 2100°F (1149°C) to 2720°F (1493°C). After equilibration the tubes were removed from the furnace and quenched in air or water, the form of quenching being found to have no effect on the results. The tubes were broken open and the coils were placed in a 1 : 1 HC1 solution to remove the sulfide-rich layer. The coils were then cut into small pieces and analyzed for sulfur and carbon. In the early stages of the investigation different equilibration times ranging up to 17 hr were tried and the cores of the wires were analyzed to test for saturation. One hour appeared to be sufficient to reach maximum sulfur content at 1454°C and 2 hr sufficient at 1149°C. The practice adopted was to use at least 3 hr at the higher temperatures and at least 5 hr at the lower temperatures. The iron-carbon alloy wires used were made by carburizing pure iron wire with carbon monoxide gas in a one inch diameter ceramic tube at about 1204°C. Differing carbon contents were obtained by allowing fairly large coils to react with the gas for varying lengths of time at a flow rate of 800 cc per min. The reacting times ranged from 15 min to 4 hr depending upon the amount of carbon desired. The furnaces used were controlled by means of Leeds and Northrup Speedomax Type H instruments with D.A.T. Control attachment. Thermocouples were calibrated against the melting points of gold and copper. The temperatures recorded appear to be accurate within i2.7OC. Starting with run No. 85 and continuing with the

Jan 1, 1962

THE refining period of an open-hearth heat blends imperceptibly into the finishing period, during which final adjustments are made in slag composition, in bath action and temperature, and in composition of the steel, in order to prepare it for casting into ingots. Operations must be governed by the consideration that alterations in the character of the heat during the finishing period must be held to a minimum. In a broad sense, the finishing and deoxidation period of a heat may be said to be- gin when the action of the last ore addition has ceased, and to end when the teeming of the ingots is completed. INGOT STRUCTLIRES A survey of the relative advantages and disadvantages of different types of ingot structure is required because deoxidation treatments during the finishing period control the amount of gas evolved during solidification and consequently determine the type of ingot structure. Four classes of ingots are recognized, de- pending upon the degree of deoxidation to which the steel has been subjected. These types are killed, semikilled, capped, and rimmed; typical examples of their structures are represented by ingots 1, 2, 5, and 7, respectively, of Fig 9-1. The actual ingots from which these cross sections were sketched were all poured to the same height (indicated by the dotted lines) in the same type and size of bottle-top molds. The eight drawings of the figure represent selected types of ingot structure in a continuous series from "dead killed" to "wild," resulting from variations in the total quantity of gas evolved, from none at all to copious amounts, during solidification of the steel in the mold. Killed and semikilled steels are adjacent at the "quiescent" end of the ingot structure series where only small amounts of gas are evolved. The term "quiescent" describes the action of the molten metal during and subsequent to the teeming of killed and semikilled steels. Capped and rimmed steels are adjacent at the

Jan 1, 1964

By Alex Boozenny

The results of potential measurements between 1) a titaniurn electrode in NaCl-TiCl, melts and a graphite-cizlorine reference electrode and 2) a titanium electrode in NaC1-Nu "melts and a graphite-chlorine reference electrode show that the following relationship expresses the equilibrium relationship between the TiCl, and the dissolved metallic sodium concentrations, expressed in mole fraction units, in dilute NaCl welts at 850°C. The results of potential measurenments between a graphite electrode in NaCl-TiCl, melts that were saturated with TiCl, and a graphite-chlorine reference electrode, when combined with the standard free energy data given in literature, gave the following expression for the equilibrium relationship between the TiCl, and TiCl, concentrations, expressed in mole fraction units, in dilute NaCl melts at 850°C. These relationships are for melts in equilibrium with pure titanium. In impure systems, less sodiurn and more TiCI, can be copresent with a given concentration of TiCl,. AFTER 10 years of existence, the titanium metal industry still relies on the original Kroll and the sodium reduction processes for the only important means of converting titanium-bearing ores to titanium metal via production of titanium tetrachloride as an intermediate. Through years of modification and development these two processes have evolved to a point where any further major economic advances in the field of titanium metal production must be achieved through implementation of processes which are distinct departures from simple magnesium or sodium reduction of titanium tetrachloride. Concurrently with the refinement of the Kroll and sodium reduction processes, industries and government have sponsored research and development in the field of producing titanium by electrolysis of oxides,' carbides,' and halides3'4 in fused salt media. However, the incomplete understanding of the physical chemistry of fused salt systems has in many cases hindered the development of promising new titanium production processes to the point where they will have a clear advantage over the processes presently employed. Fortunately the volume of information on fused salt physical and electrochemistry is increasing at an accelerating pace. The first approaches tbward investigating the electrochemical behavior of fused salt systems have been the measurements of equilibrium potentials of metals immersed in melts containing their halides.' Some work on the kinetics of fused salt electrochemical processes has been reported.'09" Some descriptions of the structural composition of fused salt systems are also available. The work described herein is a continuation of the study of metal electrode potentials in fused salts. Specifically, this contribution to the growing store of fused salt chemistry information presents a description of the equilibrium relationships between the concentrations of titanium dichloride, titanium trichloride, and metallic sodium in fused sodium chloride. The investigation of the titanium dichloride-titanium trichloride equilibrium relationships is not completely new. Kellog and Krye and Melgren and opie15 have presented the results of chemical analysis of salts containing titanium chlorides. Flengas and lngrahaml' have published the results of an investigation of these equilibrium relationships obtained by measurement of electrode potentials in a fused NaCl-KC1 mixture. The investigation described herein differed from that of Flengas and Ingraham principally in the use of straight NaCl as the solvent in place of the more costly and more difficult to purify mixture. This investigation was conducted in three parts. First, the equilibrium potentials of titanium in sodium chloride containing known concentrations of titanium dichloride were measured. A graphite-chlorine electrode was employed as reference. Second, the equilibrium potentials of titanium immersed in sodium chloride containing known concentrations of elemental sodium were measured. Third, the equilibrium potentials of graphite immersed in titanium tetrachloride-saturated sodium chloride containing known concentrations of titanium trichloride were measured. The results of these three related investigations are presented in the above order. The results are combined with the thermodynamic properties of titanium chlorides and sodium chloride, obtained from literature, to give the titanium dichloride-titanium trichloride-elemental sodium equilibrium concentration relationships. In the test, whenever a melt contains titanium chlorides in predominantly divalent form, the melt

Jan 1, 1962

By H. B. Pulsifer

ABOUT 15 varieties, or modifications, of the best magnesium available were prepared and subjected to etching tests, then examined for microstructure. Of the 30-odd etching reagents that were tried, nearly half, mostly ammonium salts, etched the metal satisfactorily. The surfacing and etching of magnesium is shown to be a very simple and quick operation. The density and hardness of magnesium were determined. The most interesting new observations relate to the finding of the hexagonal etch figures, the crystal laminations, and the fact that the metal is plastic, cold, when restrained or quickly deformed. Under slowly applied pressure cold metal deforms slightly, then shears to fracture without plastic flow: The chief structural features of magnesium are presented in two reduced photographs and 30 photomicrographs.

Jan 1, 1927

By Fritz Wald, Martin Weinstein, Herbert E. Bates

ONE of the methods for preparing a fiber-reinforced composite is that of directional solidification of a eutectic melt. Its major drawback lies in the fact that the matrix in this case is a pure constituent (or a terminal solid solution of fixed concentration) and the ratio of fiber to matrix volume is fixed. Only very few, if any, pure metal matrices possess technically useful properties, and the necessity for alloying is the inevitable consequence of this fact. Nevertheless, structures similar to binary eutectic ones can be obtained in higher-order systems by pseudoeutectic reactions of a type where crystallites and a solid-solution matrix are simultaneously precipitated from a liquid.1"3 Trials to solidify such alloys directionally—the matrix consisting of a solid solution of chromium, nickel, and silicon and the reinforcing phase being Cr3C2— will be reported elsewhere.4 This note describes constitutional studies carried out primarily to determine -the position of the pseudoeutectic and further to insure that no undesirable reactions between the reinforcing phase and components of the matrix occur in the solid state at elevated temperatures. In the investigation it was specifically desired to reinforce a matrix which is as close as possible to the 80/20 Nichrome composition with Cr3C2 to insure good oxidation resistance and improve the strength at high temperatures. No konstitutional information on the quaternary C-Cr-Ni-Si svstem in the range of interest was found in the literature. Nevertheless, the two most important ternaries c-cr-Ni5 and have been completely investigated. On C-Cr-Si some investigations have been conducted,7"9 and C-Ni-Si was studied with a few alloys in the course of the present investination 9 Eight alloys were prepared to investigate the changes in the constitution of the ternary C-Cr3Ce-yNi eutectic5 with silicon contents up to 10 wt pct. Five alloys were made with varying chromium and carbon contents around compositions containing -60 to 70 wt pct Ni and 5 to 6 wt pct Si. The latter alloys were designed to locate the y(Ni-Cr-Si-C)-Cr3C2 pseudoeutectic reaction and to determine the maximum chromium content in solid solution compatible with a two-phase equilibrium between y and Cr3C2 only. The alloys were prepared from electrolyte nickel, semiconductor-grade silicon, high-purity chromium (99.999 pct pellets), and semiconductor-grade graphite. They were melted inductively in high-purity alumina crucibles under flowing argon. Twenty-gram charges were prepared and investigated by optical microscopy (including hot-stage investigations), X-ray powder methods, and electronmicroprobe analysis. The alloys were studied in the as-cast condition and also after a homogenization annealing treatment of 48 days at 900°C in evacuated quartz ampoules. The structures of all alloys based on the ternary eutectic plus silicon in the as-cast state consisted generally of an inhomogeneous solid solution and at least two other phases. Annealing of the alloys showed that the solid solution was homogenized but that an incomplete solid-state reaction had taken place in all alloys with silicon contents over 5 wt pct. This reaction is clearly visible in Fig. 1 around the large Cr3C2 crystals (gray areas). Below this concentration, the alloys consisted of a homogeneous matrix and precipitates of Cr3C2 plus graphite, Fig. 2. The Cr3C2 was entirely unreacted here. From these observations and subsequent X-ray and microprobe investigations, it was deduced that the

Jan 1, 1969

The performance of a two-horizon depletion-type reservoir produced through combination wells is analyzed. By introducing some simplifying approximations, it has been possible to obtain formulas which are easy to handle. Only ordinary differential equations are used, and the development of the analysis can be followed without difficulty by the non-specialist. A rigorous analysis has been made of this problem. It has been found that the approximations introduced in the simplified analysis are fully justified and that errors seldom will be more than 2 per cent. The report shows the effect of the rate of withdrawal upon the relative depletion of the two horizons. Numerical examples are given. INTRODUCTION In its simplest form an oil reservoir consists of a continuous, homogeneous body of porous and permeable rock, enclosed at the top and the bottom by impermeable material. The flow of fluid through such a reservoir has been the subject of numerous papers, and the mathematical analysis of well performance, pressure build-up, etc., has reached a high degree of refinement. One of the basic assump tions introduced into these analyses is the homogeneity of the reservoir. In non-homogeneous reservoirs, these computations still can be carried out satisfactorily, provided small irregularities in the physical properties of the rock are distributed in a random fashion. The flow equations are derived as solutions of the continuity equation, and their solutions are dependent upon the assumption of many constant factors in the reservoir: permeability to oil, compressibility of the reservoir fluid, viscosity saturation, etc. When these axe assumed to be constant, the continuity equation can be solved rigorously. When these assumptions do not hold and corrections are introduced, it becomes very difficult and often impossible to solve analytically. The present analysis is concerned with production from a two-layer depletion-type reservoir in which the layers have different permeabilities. Instead of using the continuity equation, results were derived from some simple physical ideas. In a single-layer reservoir in which the oil is at a pressure above the bubble point, the rate of production often has been assumed to be directly proportional to the pressure drawdown. In the simplified analysis it has also been assumed that the drop in average reservoir pressure is directly proportional with the cumulative withdrawal. These considerations in the past have been the basis of the analysis of reservoir performance and have been applied to a variety of problems, often with marked success. In the problem under investigation these relationships are shown to be compatible with the equation of continuity, but the approach has the advantage of leading to ordinary differential equations in which changes in constants can be introduced without making the analytical solution impossible. It has the additional advantage that it can be understood more readily by the large group of engineers who are not reservoir specialists. For that reason, detailed steps in the mathematical developments have been shown in full. SCOPE OF ANALYSIS The analysis in this paper has been applied to a two-layer depletion-type reservoir in which both horizons are produced simultaneously in the same well. Because of the difference in permeability, it is obvious that the depletion of the two zones will proceed at different rates. For various problems it may be of interest to know the degree of depletion of the two zones at any arbitrary time and to in-

By I. W. Alcorn

THE cost of drilling in the past few years of proration and ever decreasing allowables has received increasing thought and study. It seems to parallel the strides made with respect to pumping problems in 1932 and 1933. Low profit margins stimulate the search for economies. Any discussion of slim-hole drilling involves a multitude of abstract values, and the problem can be attacked only by a study of records and rational thinking. In a measure, traditional methods must be studied with a questioning attitude. The words "slim hole" may be somewhat misleading, as the term is entirely relative. For that reason I wish to define it as used in this discussion. On the Gulf Coast, I would define a normal hole as one in which 10 3/4-in. surface casing has been set and below which a 9 7/8-in. hole is dug. With this as a datum, holes of larger diameter below surface would be called "large holes," with 12 1/4 in. as the "extra large" class and holes of smaller diameter classed in the slim-hole range, 6 1/4 in. representing about the minimum size. The optimum size has not been definitely determined, but the preference is for a program that would call for setting 8 5/8-in. surface casing and digging a 7 3/4-in. hole. Different sections of the country might very properly deviate from this practice because of differences in depth, formations, regulations, or other factors. This paper will be confined to a discussion of the drilling of exploratory wells, as the drilling of this class of wells is quite a different problem from that of drilling a proven field, although many of the same considerations apply in both cases, as will be apparent. Although for many years shallow slim-hole and core-test holes of small diameter had been dug, it was not, I believe, until the fall of 1937 that serious consideration was given to its application in drilling wells 7000 ft., 8000 ft. and 9000 ft. deep on the Gulf Coast. This does not mean that nearly all such wells drilled on the Gulf Coast now are of the slim-hole variety, but only that efforts have been aimed in that direction with very encouraging results and there has been a very definite trend to reduce the size of holes, a trend that probably will continue. As to exploration policy, there appear to be two distinct and opposite views. The one usually followed in the past was more or less designed to "shoot the works" on one well. Generally on the Gulf Coast, the depth at which production might be obtained is limited by the drilling equipment and economics. With this thought in mind, wildcat wells are often planned with the idea of carrying the depth to 10,000 ft., or even 15,000 ft. All of the possible hazards are anticipated and the general drilling and casing programs are so predicated. Such wells contemplate the drilling of large-diameter holes; the setting of at least one protective string of casing and an extensive coring policy, all of which finally adds up to an expensive well. As opposed to this general policy is the slim hole. This, on the Gulf Coast, recognizes that new discoveries represent gam-

Jan 1, 1941

By O. A. E. Jackson

In all three principal dunite dikes, minute disseminated grains of pyrrhotite are to be seen in the fresh rock in amounts less than 1 pct. Traces of nickel have been reported from many such specimens. Nickeliferous pyrrhotite is the principal nickel-bearing mineral, although olivine contains very minor amounts of nickel in solid solution, substituting for magnesium and iron. Such occurences are of no economic significance. Nickel analyses of possible economic significance (up to 3 pct Ni) have been returned from samples taken near the margins of the two large western dunite dikes. These samples were from schistose zones along and within the dike walls. The mineralized shear zones, up to 30 ft wide, strike N 30 W and dip from 65" to 90" west. They consist of layers of hard, fresh, green-gray dunite, mineralized with finely disseminated pyrrhotite. These layers alternate with layers of soft, black, oxidized schistose dunite up to 1 ft wide, well mineralized with pyrrhotite and tabular-fractured pentlandite in crystals up to 1/4-in. diam. Sulfides identified in polished sections were chiefly pyrrhotite and pentlandite, with much smaller amounts of chalcopyrite. There are two varieties of pyrrhotite. One develops a fine polish and conforms to published descriptions. The other is slightly darker and browner, does not polish as well, and displays flamelike growth or intergrowth structure when etched with nitric acid fumes. Pyrrhotite and pentlandite crystallized contemporaneously in the form of veins in the olivine and as fillings of the interstices of euhedral olivine crystals. Chalcopyrite replaces the other sulfides. The most striking feature of the deposits is their occurrence in intimately fractured and schistose zones in the dunite where faulting has been localized along the contacts of the sediments and the dunite dikes. Though far too little detailed work has been done to be certain, there appears to be a higher concentration of sulfides in the shear zones along the margins of dike apophyses, sediment reentrants, and strike and dip irregularities. Much more study would be required in order to submit a plausible theory of formation of the nickel deposits, supported by laboratory and field evidence. Results of the present study, especially localization of the metals by fracturing, certainly indicate that the nickel concentrations were brought about by precipitation of nickel sulfides from fluids that used the fractures as a means of ingress. Studies of nickel sulfide deposits throughout the world have demonstrated that such sulfides were deposited at considerable depths and at temperatures of several hundred degrees. This would rule out the possibility of groundwater as the transporting medium. The two possible sources of hot nickel-bearing fluids are quartz diorite and gabbro. The first possibility is that large volumes of fluids, expelled from the quartz diorite magma during its crystallization, obtained a supply of nickel by altering the nickeliferous olivine of the dunites. The likelihood of this process is lessened by the recognition that, although the dunites show some alteration to serpentine, talc, and trem-olite, they are for the most part remarkably fresh outside the schistose zones. The worldwide association of nickel with basic rocks, together with the presence of pyrrhotite in thin films on joint planes of the gabbro on Jumbro Mountain, favors the gabbro source. The writer extends thanks to C. Phillips Purdy, Jr., project chief of American Metal Climax Inc., for giving him the opportunity to study these deposits. He is also indebted to the officers of American Metal Climax Inc. and Discovery Mines Inc. for permission to publish this article.

Jan 1, 1961

By Robert B. Sosman

THE relative temperature distribution within a coke oven and among the ovens in a battery can be obtained automatically for the operator's guidance by sighting a total-radiation pyrometer on the face of the coke as it is pushed out, and recording the surface temperature. Keeping the instrument clean and keeping its view of the coke unobstructed by smoke and dust are the principal problems. Typical records from three plants are presented in this paper, showing that the temperature patterns are reproducible. DEVELOPMENT OF METHOD The method of coke pyrometry described in this paper was introduced in 1936 by E. A. Lee, then Assistant Superintendent, now Superintendent, of the Coke Plant at Lorain Works, National Tube Co., Lorain, Ohio. At the request of the Coke Committee of the United States Steel Corporation, the Research Laboratory of the Corporation undertook to adapt the method to the somewhat different conditions met with at the Gary Works of the Carnegie-Illinois Steel Corporation, Gary, Ind., and at the Clairton Works of the same Corporation at Clairton, Pa. This work was done in cooperation with the Leeds and Northrup Co. of Philadelphia and later with the Brown Instrument Co. Division of Minneapolis-Honeywell Regulator Co., Philadelphia. We of the Research Laboratory wish to express our appreciation of the courtesies extended by Mr. Lee, by A. N. Cole, Superintendent of the Gary coke plant, and by D. P. Finney, Assistant General Superintendent in charge of coke-plant operations at Clairton. We are also indebted to the instrument companies for the loan of a part of the equipment. At Gary and Clairton the instruments were installed and various experiments were made by J. W. Bain, of the Research Laboratory of the United States Steel Corporation. PYROMETRY OF COKE The coke inside a by-product oven is almost completely inaccessible to pyrometric instruments. The temperature in the walls can conceivably be measured with thermocouples, but the atmosphere is usually strongly reducing, a condition well known to be destructive to the accuracy of the customary high-temperature couples. In some plants, periodic readings are taken with an optical pyrometer sighted into the top of the combustion flues. This is a useful measure for safety and general control, as it tends to prevent the damage that would result from overheating of the ovens. It does not, however, tell much about the temperature of the coke itself, because of the continually changing gradient in the wall between the coke and the combustion chamber. The best indication of the temperature of the coke itself must therefore be obtained by observation of the product as it is pushed out of the oven. The human eye is very sensitive to variations in brightness of a surface, and particularly to differences in brightness over a continuous hot surface.

Jan 1, 1942

By L. A. Willey

Although the interierometric method for the determination of length changes was devised by Fizeau more than three quarters of a century ago, it has not achieved the widespread use in the metallurgical field that its precision and simplicity would seem to warrant. The interferometer and the basic principle are both very simple. When optically plane surfaces held at a very slight angle to each other are illuminated by monochromatic light, rectilinear, equally spaced interference fringes arc formed. Each fringe corresponds to a defiuitc thikness of the wedge formed by the optical flat.;. The difference in wedge thickness between two consecutive fringes is cqual to one half the wave length of the illuminating light. Instruments for vicwing the intertero~ncter have passed through a number of modifications. Outstanding among the improvements were those Abbe. in 1884. His improved instrument permitted micrometric mcasurements to the order of one-hundredth of the width of an interference fringe (i.e., lengths were measured to the order of one two-hulldredth of the mave length of light ). It also permitted the consecutive use of light of several wave lengths. which made possible the determination of the order number of any fringe and therefore the absolute thickness of the wedge at any point. The Abbe dilatometer and methods of measuretment, including corrections to he applied for the change of index of refraction with change in tempcrature and barometric pressure in an air wedge, have been thoroughly described by Pulfrich.' Pulfrich2 made further improvements in the interference measuring apparatus. His instrument embodied all the features of the Abbe dilatometer but was made more versatile by its complete mechanical separation from the interferorneter. The introduction of an Amici prism in the piece permitted the simultaneous observ tion of the whole set of fringe systems developed in the interferometer from the visible light of a geisler tulle. .Also, the introduction of a direct-vision, reflecting prism made it possible to set the fringes parallel to the two vertical fiducial line. of the instrument without the necessity of rotating the interierometcr. Interferometric methods employed ill this country have been developed and dcscribed by Priest, Pelers and Cragoe," Austin,5 Merritt,= Saunders,? and Nix and MaNair. Since none of these authors used the type of instrument that was employed in the present investigation, they Will not be discussed here. This paper will be limited to the description of the interfernmetric apparatus and method used at the Aluminum Research Laboratories and to the presentation of data so obtained. Apparatus and Procedure A general view of the dilatometer, not including equipment for controlling and

Jan 1, 1945

INTRODUCTION Mineral explorationists range throughout the world looking for mineral deposits which can subsequently be made into mines. Mines are not found! Mines are made, usually at great cost and not often without significant risk. The process of making a mineral deposit into a mine involves a great deal more than a complete appraisal of the deposit. The making of a mine demands detailed feasibility studies of many factors, any one of which, if shown to be negative, could prevent the deposit from becoming a successful mine. Total feasibility analysis involves at least three major fields of study: (1) economic analysis, (2) financial analysis, and (3) political and environmental analysis. Economic analysis is essential for proper decision making at many stages in the evaluation of a mineral deposit. It is the yardstick by which the proposed mining project and alter- native investment opportunities are measured. Economic analysis is concerned with costs and potential profits and can be applied at various stages in the evaluation of a mineral deposit to determine if the project merits the additional funds necessary to bring about each succeeding stage. The nearer any deposit approaches to becoming a mine, the more carefully the economic analysis should be made. Financial analysis has reference to how, where, and at what cost the investment funds can be obtained to finance the proposed mine project. Political and environmental analysis has reference to the many intangible factors that can affect the making of a successful mine. These factors loom larger today than ever before, due to the profusion of government regulations and various environmental constraints now imposed upon the mineral industry both by law and by the weight of public opinion. Ultimately, many of these intangible factors can be resolved back into the economic analysis as an added cost to mine development, but more and more often they have become insurmountable obstacles to any development of certain deposits. The role of financial analysis and the analysis of intangible factors must never be underestimated when making a feasibility study upon which to base investment decisions; however, the emphasis of this text will be upon economic factors. THE PARAMETERS OF MINERAL ECONOMIC ANALYSIS The two major elements of economic analysis are: 1) The potential earnings or annual generated cash flow of the project. 2) The investment costs necessary to realize such earnings. If the difference between the two elements is large enough, i.e., if the return on investment from the cash flow is high enough to attract investors, the project can be said to be financially feasible. The mineral economic analysis must take into consideration many parameters, some of which are known or knowable within certain limits, and others of which are unknown or unpredictable within certain limits and for which estimates must be made. Because both known and estimated parameters enter into the same analytical computations, it is important for the analyst to realize the nature of each when considering the results of an analysis. Some parameters such as the grade of mining block, although estimated, are said to be known within mathematically defined limits. Other parameters, such as the future price for minerals produced, etc., can only be estimated or "guestimated" within reasonable limits for which no precision can be assigned. Known or Knowable Mineral Economic Parameters Known or knowable parameters are: 1) Tonnage and grade of valuable minerals for the total mineral body and for individual mining blocks. 2) Metallurgical recovery of valuable mineral. 3) Minimum operating life of mineral de- posit at any specified production rate. 4) Royalty schedule, property payments, etc. 5) Sales-purchasing agreements, smelter schedules, marketing contracts, etc.

Jan 1, 1980

By F. W. Jessen, N. Lamont

The effect of an existing fracture or joint plane, which may exist in a rock, on the extension of a hydraulically induced fracture through the rock has been investigated in the laboratory. By use of a series of models made from various outcrop rocks, the width and orientation of existing fractures do not alter the extension or direction of the hydraulic fracture. The results, which conform quite well with the Grifith theory of failure, are illustrated by a series of photographs of the various models. INTRODUCTION The process of hydraulic fracturing has been widely used in the oil industry since its introduction in 1948 and has made possible the production of many reservoirs which would have been uneconomical prior to this process. Numerous studies of the mechanics of the process2-h nd of the effects of oriented fractures on recovery'.' have appeared in the literature. The increased recoveries led to attempts to predict the orientation of hydraulic fractures at the wellbore and to the development of methods to control this orientation. Field tests have been devised"." which indicate the validity of theoretical predictions of fracture orientation at the borehole. The direction of extension of hydraulic fractures from the borehole has not received much attention since most studies have predicted, at least implicitly, that a fracture will continue in the same plane unless a change of state of stress in the rock occurs. Since such predictions are based on the assumption of rock homogeneity, the effects of rock heterogeneities are left unknown. Most sedimentary rocks are composed of layers which reflect the changing depositional conditions of geological time. In addition, the more competent rocks frequently are fractured and jointed as the result of structural deformations or tectonic movements. Evidence of such joint systems exists in many surface outcrops, and it can be assumed that similar systems occur in many subsurface rocks, although the individual joints may be rather tightly closed due to overburden forces. This paper investigates the effect that an existing fracture in a rock would have on the direction or orientation of an extending or advancing hydraulic fracture when it intersects the existing fracture. The study was conducted on small rock models under triaxial stress conditions. The results indicate that an existing fracture will have little effect on the hydraulic fracture. THE MODEL STUDY The rock model represents an elemental portion of the earth containing an existing fracture which is located at some distance from a borehole from which hydraulic fracture is being extended. A generalized view of a model is presented in Fig. 1. The models were constructed from cement blocks and natural rocks. The various materials tested and some of the physical properties are listed in Table 1. The rocks were cut into rectangular blocks with dimensions of 11/2 X3Y2 X4 to 8 in. An initial slot was cut into the end face of each block along the longitudinal axis normal to the top face. The slot was filled with plastic aluminum along its outer edge to a depth of 1/16 in. A hole of 3/8-in. diameter was drilled into the sealed slot at the center of the end face to serve as an entry port for the fracturing fluid. Existing fractures of various types were simulated in the models. A "hairline" fracture with essentially zero width was created by cutting the model into two parts with a diamond saw and replacing the two parts together along the cut. A finite-width fracture was created by placing a layer of sand grains between the two faces of the cut just described (see Fig. 12). A large open fracture (similar, perhaps, to a vug) was created by cutting the model in two parts and removing a portion of the downstream block to a depth of % in. See Fig. 13. For a fourth

By B. A. Rogers

THE etching effect which is produced on a piece of polished iron or steel when it is heated in hydrogen or in a vacuum seems to have been observed first by Osmond,1 who believed that he could distinguish four systems of grain boundaries on a piece of steel which had been heated in hydrogen. In a number of other investigations, samples of pure iron were found, after heating, to have complex networks in which two or three systems of grain boundaries could be detected. It was further noticed that samples that had been polished plane before being placed in the furnace were, after treatment, roughened and undulating over their entire surfaces. From a comparison of the temperature of heat treatment with that of the A 3 transformation, it was concluded that the changed appearance of the samples was definitely related to the latter phenomenon. Certain other deductions were made but these are not of importance here and only observations on the appearance of the samples will be reviewed. Ewen2 heated a strip of polished iron in a vacuum in such a way that one end was maintained at a temperature of 1000° C. and the other at 580° C. On the cooler end there was outlined a simple polyhedral network, and at the hotter there appeared the complex system of lines and the undulating surface characteristic of iron which has passed through the A3 transformation. He found that in going from the cooler toward the hotter end the sample maintained much the same character of surface up to the beginning of the transformed area, but that near this region double grain boundaries were of frequent occurrence. Rawdon and Scott' concluded that the simple type of network brought out by heating a sample of pure iron in a vacuum was of the same type as that developed by ordinary etching methods. They also confirmed the observations of

Jan 1, 1929

By Y. A. Chang

Heat content values of tantalum monocarbide and tungsten monocarbide have been determined from 325" to 985°K by means of a drop-type diphenyl ether calorinzeter. Based on the values obtained in the present study and those available in the literature, best values lected and computed from 298. 15°K to temperatures close to their respectiue melting points. At temperatures higher than 1700°Kfor TaC and 27000 K for WC, values of Cp and related thermodynamic quantities were extrapolated based on the two Debye parameters: one corresponds to the metal sublattice and the other to the carbon sublattice. The contrzbutzon In the total specific heat due to lattice dilation was evaluated using the Nernst-Lindemann relalionship. The calculated values of Cp were in good agreement with the In view of their refractoriness, tantalum monocar-bide (TaC) and tungsten monocarbide (WC) are of con- experimentally determined ualues. Furthermore, the calculated values of the absolute entropies at 298.15"K were 5.03 and 4.15 in comparison to the experimental values of 5.05 and 4.15, all expressed in the unit of cal per degg-atom. Using the same Debye parameters, values of the linear coefficients of ther mal expansion for TaC and WC were calculated from absolute zero to their respective melting points using the Grüneisen equation. The calculated values are in excellent agreement with the experimental values available in the literature. Finally, the values of the bulk modulus of TaC from room tenzperature to temperature near its melting Point were also calculated using the equation recently derived by Anderson. No cot~ipari-son between the calculated and experimental values can be made due to lack of experimental data. siderable practical interest. In order to completely define these materials, it is necessary to know their thermal properties as a function of temperature. Tantalum rnonocarbide having a NaCl structure (B-1 type) melts congruently at 4250PK,1 while tungsten monoearbide with a simple hexagonal structure (Bh type) melts per itectically at 3049°K into melt and graphite.2 In the present study, the heat content values (from which

Jan 1, 1968

By D. A. Thomas, E. S. Meieran

Tungsten wires were examined by transmission electron microscopy after drawing and after high-temperature annealing. Drawn wire consists of highly elongated grains called fibers, whose long axis is parallel to [110]. Each fiber is ribbon-shaped, with the wide dimension of the ribbon parallel to (001) and the narrow dimension parallel to (110). Furthermore, most fibers are bent about [I10] and twisted along their length. The fibers are divided into cells, which in some cases contain a platelet substructure lying on (110) planes. The misorien-tations of these platelets accumulate to allow the macroscopic twist of the fibers. During annealing, several competing reactions occur, starting at different temperatures and progressing at different rates. Among these processes are fiber-boz~ndary migration, polygonization, dislocation rearrangement, and possibly impurity segregation. The fiber-boundary migration accompanied by the formation of transverse boundaries during polygonization leads to an equiaxed grain structure although recrystal-lization does not occur. There is a relationship between the flow stress of the wires and their average subgrain width in the form sy = s0 + kyd-1/2 . Also, there appears to be a relatio'nship between wire ductility and the formation of transverse boundaries during annealing at about 800°C. THERE have been many investigations of the structures and properties of tungsten wires1-4 due to their commercial importance for use as lamp filaments. The structural studies have so far been limited to optical microscope and replica electron-microscope studies. due to the difficulty of .-me- paring from wires thin foils which can be examined by transmission electron microscopy. However, this difficulty has been recently overcome,5 and it is now possible to examine tungsten wires by transmission electron microscopy as well as by other techniques. In this paper, the structure of drawn tungsten wire is described, as are the changes in the structure during high-temperature annealing. Some discussion of the relationship between structures and properties is also given. EXPERIMENTAL MATERIALS AND PROCEDURES Commercial 0.030-in.-diam doped tungsten wires drawn at progressively decreasing temperatures between about 1400° and about 800°C were examined. The composition, mechanical properties, and optical microstructures are described in detail elsewhere.' All experimental materials were vacuum-annealed for 10 ot 30 min at temperatures at 100°C intervals between 700° and 2000°C. Specimens were thinned for examination in the Siemens Elmiskop I electron microscope by the method of Meieran and Thomas.5 STRUCTURE OF AS-DRAWN WIRE The optical microstructure of as-drawn tungsten wire has been described by Peck and Thomas.7 They observed that wire in longitudinal section consists of highly elongated grains called fibers whose width varies between 1 and 10 µ, while in transverse section the fibers appear to be elliptical in cross section and bent about their common [110] wire axis. They explained this unusual appearance as being due to the drawing of a bcc material with a [110] texture, and predicted that the wide and narrow planes of the fiber cross section would be parallel to (001) and (110), respectively. The fibers apparently bend about the [110] axis during drawing to maintain grain boundary continuity during drawing. Transmission electron microscopy offers a way of checking these predictions as well as providing a more detailed picture of the wire structure. Figs. 1, 2, and 3 are typical electron micrographs of

Jan 1, 1965

By P. R. Swann, J. G. Parr

Quenched structures were studied in alloys containing up to 12.5 pct cobalt. The subsequent decomposition of a 10 pct cobalt retained-ß phase alloy was investigated using metallographic and X-ray diffraction methods. Hardness measurements also were made during the decomposition process. Precipitation of Ti2Co is by nucleation and growth; and an activation energy of 50,000 cal per mole was determined. The values of the coefficient ß suggest that the precipitate is pearlitic at temperatures between 450 and 475°C, and spheroidal between 500 and 525°C. THIS paper describes part of a series of invesligations into phase transformations in binary alloys of titanium with transition elements. The general approach is similar to that taken in work on titanium-iron and titanium-nickel alloys.' Previous investigators'' have established the titanium-rich end of the titanium-cobalt phase diagram, reproduced in Fig. 1. Orrell and Fontana' showed that alloys containing more than about 6 pct" cobalt quenched from the ß range, produced 100 pcl retained-p phase. The isothermal decomposition of alloys containing between 0.8 pct Co and 15.5 pct CO was investigated by the same workers in the temperature range 650 to 1000°C. They reported that these alloys transformed into a or Ti,Co depending on the cobalt content, but no quantitative data were given. In the work to be described a series of alloys containing 0.8 pct Co to 12.5 pct Co was examined in the quenched condition. The 10 pct Co alloy (the lowest cobalt content to retain 100 pct ß on quenching) was selected for further work on the tempering kinetics of the ß decomposition. Experimental Procedure Since our own melting equipment was not installed at the outset of this work, the Physical Metallurgy Division of the Department of Mines and Technical Surveys (Ottawa, Canada) prepared the alloys. These were made of Japanese sponge, (which when melted had a value of 103 DPH, using a 1-kg load), and electrolytically prepared cobalt. The al- loys, made up to contain 0.8, 1.6, 3.3, 5.8, 8.3, 10.0 and 12.5 pct Co, were homogenized by swaging into rods at 900°C. Filings were taken from the rods, and any iron chips from the file were separated magnetically. Size fractions of both plus and minus 200 mesh (about 75p) were shown by their constitution, after annealing just below the eutectoid temperature, to contain the same cobalt content. Consequently, it was permissible to use the —200-mesh fraction, knowing it to be representative of the rod composition. Quenching in argon was carried out in a newly designed furnace, whose features include (1) an Inconel furnace tube, (2) a positive pressure of argon maintained at all times in the furnace—even when a sample is removed or inserted. The furnace is shown in Fig. 2 and is described in the Appendix. The tempering processes were carried out on powder samples sealed in evacuated quartz capsules. Since the highest tempering temperature was 525OC, no protection against reaction with the quartz was necessary. (Tests were made on filings of iodide titanium and showed no hardness increase after equivalent heat-treatments.) A thermocouple was attached to the capsule, which was heated to the

Jan 1, 1959

By Charles H. Jacoby

In 1774 a Swedish chemist, C. W. Schule, first recognized manganese as an element. That same year Schule's associate, J. G. Gahn, isolated the element manganese for the first time. In 1856 the Bessemer process of steelmaking gave birth to the economic importance of manganese. Later, in 1882, Robert Hadfield discovered high manganese steels. Although the primary use of manganese is in the ferroalloy industry, two additional important uses for manganese are making chemicals and dry cell batteries. Manganese is also vital to plant and animal life. Various chemical compounds of manganese are used in fertilizers, feeds, glass manufacture, paints, varnishes, and for numerous medicinal and chemical purposes. For the study of industrial minerals and rocks, only the chemical and battery grade material is of- concern, but for the sake of comparison, metallurgical aspects are included in this presentation. Although currently the world's largest consumer of manganese, the United States is producing only minor amounts of ore at the present time. This is due primarily to the fact that although huge deposits of manganese occur within our borders, all are of such low grade as to be economically unfeasible to mine. For many years various government agencies and segments of private industry have devoted sizable sums of money and time in an attempt to upgrade ores from the various deposits, and also in an attempt to recover manganese from blast furnace slags. In view of current world prices, and the quantity of high grade material available, there is little likelihood that any of these approaches will be found to be economically feasible in the near future. Geology and Mineralogy Mineralogy There are over one hundred minerals that contain manganese. These minerals vary from those with compositions that are predominantly manganese to those having only minor percentages. [Chemical Mineral Composition % Mn Hausmannite Mn304 72 Polianite MnO2, 63.1 Pyrolusite MnO24 60-63 Cryptomelane KR8O16R (R=Mn) Variable PsilomelaneBa Mn Mn8O16 (OH).45-60 CoronaditePb R8O16R (R=Mn) Variable Hollandite Ba R8O16R (R=Mn) Variable Manganite Mn2O3•H20 62 Braunite 3 Mn2O3•MnSiO3 62 Tephroite 2 MnO•SiO2 54.3 Rhodochrosite MnCO3 47 Rhodonite MnSiO3 42 Spessartite 3 MnO•AI2O3•3SIO2 33.3 WadHydrous Mn OxidesVariable Franklinite(Fe Mn Zn)O(Fe Mn)sO3 Variable Asbolan Cobaltiferous wad Variable AlabanditeMnS63.14] Geology From a geological standpoint most manganese deposits are complex. In general, it can be said that all primary deposits of manganese are carbonates or silicates. The most productive and profitable have been those of sedimentary origin and residual concentrations. Examples of these residual types of deposits are associated with the metamorphosed lodes of Madhya, Pradesh, India, and the lateritic deposits of Orissa and Bihar, India; nodules in the residual clays of the Philippine Islands, US southern Appalachians and Arkansas, Ghana, and Brazil. Sedimentary manganese deposits are best exemplified by the Nikopol district of Russia and the Tchiatouri area of Georgia, USSR. Hydrothermal replacements are characterized by the rhodochrosite deposits of Butte and Phillipsburg, MT. In general, the hydrothermal type deposit has not resulted in any large tonnages being produced, but may have given

Jan 1, 1983

By D. O. Wyble

Five water-driver fields, for which pressure predictions had been made within a few years after discovery, were re-studied when four to five years of additional pressure and production data became available. It was fortnd that forecasts of the pressure in water-dri~fe reservoirs may be subject to considerable unccrtainty. Predictions car be erroneous when there is insufficient presswe history to define the cllaracteristics of the aquifer, and when there are errors in the pressure, production or geologic data. INTRODUCTION The efficient operation of an oil or gas reservoir requires that the important characteristics of the reservoir be determined soon after its discovery. It is especially desirable to evaluate the pressure-production relationship quickly, for this relationship provides a basis for deducing the type of production mechanism that is operative, and for making pressure predictions. The pressure predictions, in turn, provide a basis for calculating efficient rates of production, determining whether water or gas should be injected, etc. The importance of pressure prediction is such that forecasts should be made as accurate as possible, and the limits of error well defined. Historically, pressure forecasts for some fields have proved very accurate, while for others the forecasts were so erroneous that they resulted in the adoption of wrong, or at best, unnecessary production practices. Pressure predictions made for water-drive fields are especially subject to error. Accurate forecasting for these fields requires that much be known not only about the reservoir proper but about the adjacent water-filled rock as well. The water-containing rock, or aquifer, may extend for many miles, and often there is only meager data regarding its thickness, permeability and porosity. Much of the information must be inferred from the previous pressure behavior of the reservoir. A brief pressure history may provide little information about the characteristics of the aquifer. Hence, pressure predictions made early in the life of water-drive fields can be incorrect. The work described in this paper was done to determine the degree of reliability which can be expected of pressure predictions made within a few years after water-drive fields are discovered. Five fields, for which the original pressure predictions had been based on less than seven years' history, were re-examined with the aid of four to five years of additional pressure data. Where the predictions were inaccurate, the reasons for failure were ascertained. The studies were accomplished by use of the electric reservoir analyzer.' The analyzer was first adjusted to repeat the original pressure-production match using the same values for the various parameters as were used in the original study. Then, the actual production rates experienced during the time elapsed since the initial study were set into the analyzer, and the pressure behavior indicated by the machine for this period was compared with that which actually OCcurred. Where the pressure profile traced out by the analyzer deviated from the observed field behavior, the analyzer was readjusted to obtain a better over-all match. The old and the new solutions were compared to determine the reasons for any differences. COMPARISON OF PREDICTED RESERVOIR PRESSURE BEHAVIOR WITH ACTUAL PERFORMANCE Field A The original pressure-production match is entirely adequate as evidenced by the pressure match of the field's history subsequent to Jan., 1952 (see Fig. 1)'.

By Thomas Fraser

There are large coal reserves in Argentina, Brazil, Chile, Colombia, Peru and Venezuela, and growing productive industries in Brazil, Chile, Peru and Colombia. The paper describes current activities in these coal fields, and improvement programs that are in progress, or are planned. Special emphasis is placed on improvements in mining and preparation practice, and expansion of production that have been accomplished by American equipment and technical assistance.

Jan 4, 1951

By A. L. Lee, M. H. Gonzalez, R. F. Bukacek

Experimental viscosity data for methane are presented for temperatures from 100 to 340F and pressures from 200 to 8,000 psia. A summary is given of the available data for methane, and a comparison is presented for that data common to the experimental range reported in this paper. Correlation of the data is presented, and predicted values are given for temperatures up to 460F and pressures up to 10,000 psia. INTRODUCTION The increasing ranges of temperature and pressure at which fluids are produced, transferred and processed in the petroleum and chemical industries stress the need for accurate information on physical properties, both for engineering calculation and for improving the methods used to estimate physical properties. A survey of the literature reveals that disagreements between published data on the viscosity of methane are common and that most investigations have been conducted over restricted temperature and pressure ranges. This situation made it desirable to undertake an investigation with a scope common to most of the literature data available. APPARATUS AND MATERIALS The apparatus used in this investigation was the capillary tube viscometer'described by Dolan,10 with modifications introduced in the general design and operation of the instrument. It has an effective pressure range from 14.7 to 10,000 psia and a temperature range from room temperature to 400F. The design of the viscometer is based on the establishment of a manometric head between two vessels containing the test fluid and a volume of mercury. The reservoirs are connected by a capillary tube through which the test fluid flows and a tube through which mercury flows. A pressure gradient is established by elevating one of the vessels above the other, the resulting flow of mercury displacing the test fluid through the capillary. The schematic diagram of the system (Fig. 1) shows the arrangement of the equipment auxiliary to the viscometer. The density cells assembly (E, Fig. 1) was not used in this investigation since reliable data are available on methane. 23 The assembly consists of a bank of eight 316 stainless steel pycnometers. Experimental values of the density of a natural gas19 and i-butane14 samples have been obtained for pressures up to 8,000 psia and temperatures up to 340F. The methane used was obtained from the Southern California Gas Co. Mass spectrometric analysis showed a composition of 99.8 percent CH4, 0.1 percent C2H6 and 0.1 percent C3H8. EXPERIMENTAL VALUES AND ACCURACY OF DATA Determinations were carried out at several temperatures. With the temperature in the cabinet controlled at a given level, a series of runs were made at various pressures. To establish pressures lower than that obtained from the methane cylinder, it was necessary to vent the gas slowly to the atmosphere until the desired pressure was reached. The consistency of the test run time for a particular condition can be used as a criterion for the accuracy of the data. A further check is obtained by comparison of the viscosity values obtained using different driving heads. To establish the instrument's reproducibility, a large number of runs were made at three completely different conditions of temperature and pressure. Data obtained were analyzed statistically to determine the most reliable value for the variance of the experimental data. It was found that the variances of the data taken at different experimental conditions were not statistically equivalent, but they were small. The largest variance was found at 8,000 psia and 100F, where the standard deviation was 0.385 micropoise. Therefore, 99.9 percent of the data can be expected to fall within 1.15 micropoises of the population mean, except for the intervention of systematic errors in operation.