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By Warren E. Morrison

The first major evaluation of the nation's raw materials prospects after World War II was completed by the President's Materials Policy Commission (Paley Commission) in 1952 and submitted to the President in June of that year, as a five-volume study entitled Resources for Freedom. The bulk of the report was devoted to an analysis of the past, present, and probable future of the Nation's mineral supply industries. The Commission's evaluation of the future situation regarding minerals was derived from its forecasts of the probable domestic demand for the major minerals in the 1970's. This demand analysis was made in the context of probable worldwide demand. Several crucial assumptions were made by the Commission's fore-casters. It was assumed in 1950 that the next 20 to 30 years would see no major wars and be a period of sustained economic growth. Another assumption was that the anticipated demand for raw materials must be supplied at essentially no increase in real cost in order to avoid crucial supply problems. The Commission's forecasts were derived within the context of the country's expected future rate of economic activity. The gross national product (GNP) growth to 1975 was derived from projections of the number of people in the labor force, hours of work, and an index of probable production measured per unit of labor input. It was believed labor hours would decrease and labor productivity would increase. The result was a forecast GNP growth rate of 3 percent.

Jan 1, 1970

By R. E. Hobart

THE development of the Hauto power plant and the claims made by various engineers that electricity was more economical than steam for power purposes in and about the mines; led the Lehigh Coal and Navigation Co., in 1911, to conduct a test to ascertain the consumption of power used by a large steam hoisting engine. The question being one on which no reliable information could be found, and the opinion of various engineers differing to such an extent, it was decided that a test under actual operating conditions was necessary. This was arranged for at one of the collieries. The engine selected was a 30 by 60-in. (76.2 by 152.4-cm.) piston-valve engine of modern type, and comparatively new. The boiler plant from which the hoist received its power was about 600 ft. (182 m.) from the engine, the latter being fed by a 10-in. (25.4-cm.) steam line insulated with magnesia pipe covering. Two batteries of the boiler plant, aggregating 1200 hp., were cut off and fed into a separate steam line leading direct to the hoist engine. Steam auxiliaries, consisting of feed-water pump and blowers, were fed by the boilers in test, and their consumption charged against the hoist. A barrel weighing device was installed, as it was felt that this would be the most accurate way of determining the consumption of water. The fuel, No. 3 buckwheat, was carefully weighed, and every precaution was taken to make the test accurate in every particular. The test was run for 1 week, or a total of 168 hr. A record was kept of the number of trips hoisted or lowered, and continuous indicator cards were taken. One particular set of cards was taken with the hoist operating balanced, and also with the hoist operating with no counterweight other than the empty cage, the coal in the car being weighed. The speed of the hoist was taken by means, of a graphic recording instrument which registered the number of revolutions every 5 sec. From this record, speed-time curves were plotted.

Jan 2, 1918

By R. P. Alger, J. S. Wahl, C. W. Johnstone, J. Tittman

To overcome the problems of mudcake and hole irregularities, the new compensated formation density logging device employs two detectors spaced at different intervals from the source. The detector at the shorter spacing is particularly sensitive to the density of material immediately adjacent to the face of the pad. The contribution of this material, which includes mudcake and minor wall irregularities, affects the response of each detector to a different degree. The signals from both detectors are combined to give automatically a density correction which is added to the uncompensated density information from the detector at the longer spacing. Both the compensated density measurement and the amount of compensation are then recorded on the log. With the unwanted borehole effects removed, the measurement is recorded directly in terms of bulk density on a linear scale. INTRODUCTION Formation density is a very useful and diagnostic parameter for formation evaluation. When the matrix lithology is known, porosity is accurately and readily computed from density data.'-" hen the density measurements are used with other porosity-responsive measurements, such as Sonic and Neutron logs, both lithology and porosity may be defined with good accuracy."'" In the past, however, application of density logs was complicated by the need for corrections to obtain true formation densities from the log values. Mudcakes on permeable formations and roughness of the borehole walls have been particularly troublesome since, in each case, the device was prevented from direct contact with the formation. ~ttempts have been made to correct for such conditions by making a simultaneous caliper log, estimating pad standoff, and assuming knowledge of the composition of the intervening materials. While such corrections are frequently accurate, they are not always reliable because of uncertainties in the pad standoff and material composition. A further complication was the necessity for manual conversion of log counting rates to density. The newly introduced compensated formation density logging device (FDC) automatically corrects for mudcake and minor wall irregularities, and provides a log that is scaled directly in bulk density. The purpose of this paper is to discuss briefly the equipment, to explain the theoretical considerations involved in the compensation, and to present field examples of this new log. COMPENSATED FORMATION DENSITY EQUIPMENT The FDC tool incorporates two major advances over previous density logging devices: a second detector, spaced closer to the gamma ray source to provide increased sensitivity to material close to the pad; and the automatic derivation of a corrected formation density from the two counting rates. The arrangement of the source and detectors is shown in Fig. 1. The longer spacing detector is at the same spacing from the source and gives the same response as the single detector in the previous uncompensated device. By appropriate combination of the outputs of the two detectors, the FDC tool is able to compensate in large measure for effects of mudcake and hole rugosity. This is achieved, as will be described later, without specific knowledge of either the thickness or the nature of material between the pad and formation. To obtain corrected formation density, the two count rates are automatically processed by an analog computer in the surface panel. More specifically, the computer derives a value of uncompensated formation density from the long-spacing counting rate, computes a density correction p using both the long and the short spacing count-

Jan 1, 1965

By J. S. Lasater

Resu1ts of experinmental measurernents of heat capacities and thermal conductivities of some typical porous rocks are presented. Measured heat capacities agree closely with va1ues calculated front known chenlical . compositions of the rocks. On the basis of this agreement, heat capacitir.7 of fluid-satttrated rocks were calc~ililted. Therrnal conductivities of the rock samples were measured under varioits conditions of fluid saturation. From these data therrnal dif-fvsivities were calculated. A significant variation of thermal diflusivity with trnlperature is indicated. Knowledge of the thermal characteristics of fluid-bearing porous rocks has become increasingly important with the development of thermal oil-recovery processes. Reliable thermal data for petroleum reservoir rocks are not available and approximate values are generally assumed for reservoir calculations. 'The effects of temperature, pressure and fluid saturation on thermal properties of porous rocks have not been carefully studied. The purpose of the present work was to measure and report the thermal characteristics of some typical porous rocks. A group of eight sedimentary rock samples, including limestone, shale, sandstone and silt-stone, was selected for the study. Properties reported include heat capacities, thermal conductivities and thermal diffusivities. The effect of fluid saturation on these properties was also considered. Determinations of thermal properties require precise measurements which are time consuming and difficult to reduce to a routine basis. Methods have not been developed for measurement of thermal proper-ties under conditions of pressure, temperature, and fluid saturation, which may be encountered in thermal recovery processes. As one approach to these problems, some preliminary work on methods of estimating thermal properties from other more readily measurable characteristics of the rock-fluid system is reported. The samples selected for the studies were oilfield cores from within, or closely associated with oil-productive zones. Descriptions of individual samples are given in Table 1. Clay minerals present in the samples were determined by differential thermal analysis (DTA). Quartz content was estimated from DTA cooling curves. For all but the thermal conductivity tests, a representative 200-gm sample of each core was disaggregated, thoroughly extracted in diox-ane and oven dried at 100°C. The cleaned and dried sample was care- fully split into appropriate portions for the several tests. Chemical analyses of the samples were obtained to permit calculations of heat capacities by methods which are outlined later. Resuits of chenlical analyses are given in Table 2. Heat contents of the test samples were measured by a Runsen-type calorimeter. The heat content of the unknown sample is measured relative to the known heat content of platinum. The apparatus is referred to as a relative error type because of the comparative measurements, and has the advantage of canceling systematic errors. Experimental results are reproducible within 0.5 per cent. A temperature base of 298.16 K is taken for heat content measurements. Measurements were made at five temperatures (260, 440, 620, 800 and 980° F). It was necessary to preheal the sample above the maximum experimental temperature to eliminate volatile constituents. Assuming the weight loss on pre-heat, ing was mostly water, a correction to the observed heat content was made to account for the water originally present in the sample. This latter procedure was followed in the determination of calculated heat contents as will be described later. The apparatus and the method of measure-

By L. D. Wooddy, W D. Moore

Water drives may be natural or artificial. For the case of a natural water-drive reservoir, the volume of water influx corresponding to reservoir pressuve-production history may be calculated by means of the material bal-ance-unsteady state equation. For the artificial water drive or pattern injection water flood, the material balance equation is sufficient to determine the reservoir pressure-production, injection history. However, for both cases to reliably predict reservoir performance, it is necessary to calculate the saturation distribution of the reservoir fluids at different stages of depletion. This paper consolidates the various equations used to determine the performance of water-drive reservoirs into one approach that is applicable to any reservoir that has a natural water drive or is to be produced by water injection. The numerical procedure has been simplified considerably, and the solution is adaptable to either hand calculations or digital computer operation. INTRODUCTION A water-drive reservoir is one in which the predominant source of energy for production of oil results from the encroachment of water into the oil zone. The water drive may be either natural or artificial. Water invasion takes place by expansion of water in the aquifer as a result of the pressure decline transmitted from the oil reservoir. Because water is practically incompressible, a natural water drive requires an extensive aquifer containing a volume of water many times the volume of oil in the reservoir. Provided the permeability of the formation is reasonably high, a moderate decline of reservoir pressure usually causes adequate water influx. If the reservoir pressure decline becomes excessive because of low permeability or a high rate of production, part of the oil production may result from the liberation of dissolved gas which may cause excessive quantities of free gas to be produced along with the oil. In extreme cases, reservoir pressure may decline so rapidly as to cause the oil to be produced predominantly by dissolved gas drive, leading to abandonment of the reservoir before the advancing water has had a chance to flush the entire reservoir. In reservoirs that are not connected to extensive aquifers, an artificial water drive may be created by injecting water into or around the lower edges of a reservoir. Sometimes water is injected within the reservoir through wells interspersed among the producing wells. When injection is carried out in such fashion, the reservoir is in effect subdivided into a number of separate producing segments, in each of which the displacement of oil is simultaneously taking place, and the shapes of which are fixed by the well patterns employed. Because of the natural tendency of oil and water to segregate according to their relative densities, water will tend to migrate downdip regardless of where injected. Accordingly, the injected fluids can be retained within the intended reservoir segments only when conditions are unfavorable to their migration under the force of gravity. Pattern injections are usually confined, therefore, to reservoirs having low structural relief, or low permeability, or when production and injection rates are such that fluid movements in the reservoir are dominated by the pressure gradients rather than by the force of gravity. In the case of natural water-drive reservoirs and artificial water-drive reservoirs in which the water is in-

Jan 1, 1958

By J. Kucera, J. Vreštál

DIFFERENT authors1 ' have been engaged in meas-uring the vapor pressure of pure cobalt. The results of their measurements satisfy the expected temperature dependence of vapor pressure and are in mutual agreement, with the exception of the results by De Dyk Man and ~esmejanov.~ The latter authors, by using the effusion method, have achieved considerably higher values than other workers. By using the isotope exchange method they obtained much lower values than other authors. The determination of thermodynamic functions of the binary Ni-Co system was carried out, as far as we know, only by De Dyk Man and Nesmejanov.4 This determination was based on extremely low values of vapor pressure over pure cobalt obtained by the isotope exchange method. Therefore we considered it useful to repeat these measurements. Furthermore, the reliable values of thermodynamic functions should complement the migration characteristics, the inner magnetic field data obtained by Miissbauer effect measurements, specific heat data, and the K effect and positron annihilation characteristics that have been achieved for the Ni-Co system in the Institute of Metallurgy of the Czechoslovak Academy of Sciences in Brno.5-9 The measurements in this paper were performed by the isotope exchange method. In this method, as has been shown by analysis,10-'3 the vaporization rate, w, can be calculated from the relation w = k/1oSw [1] i0Sw) [1] where L, is the activity per unit mass of the source, S is the area of evaporation, k is the tangent at the point t = 0 to the curve giving the radioactivity de-pendence of the target vs annealing time, t, and wis the probability for the tracer atom condensation on the target surface. The value for cc. can be obtained from the equation w = a + 2P(l-a) [2] where P is Clausing's coefficient and a is the condensation coefficient. In the present work the cylinder shaped containers for annealing the samples were used, characterized by the ratio 1:d = 1.06. Here 1 is the length and d the diameter of the container. For this ratio P = 0.514 and w =0.5, and w is independent of the condensation coefficient. The vaporization rate is related to the vapor pressure p by the relation where R is the gas constant, T is the absolute temperature, and M is the molecular weight of the component investigated. Measurements of the vapor pressure of the i component over the pure metal, p!, and the alloy, pi, at the given temperature and composition enable one to calculate the thermodynamic activity of this component from the equation ai=pi/pi [4] is and the activity coefficient ri=ai/xi [5] xi where xi is the molar fraction of the investigated alloy component. EXPERIMENTAL Evaporization rate measurements were carried out with pure cobalt and eight different Ni-Co alloys, which were kindly delivered by the Centre National de Recherches Me'tallurgiques Liege, Belgium. The composition of the alloys is given in Table I. The cobalt used in these alloys contained the following impurities: 0.016 wt pct Fe, 0.014 wt pct Cu, 0.01 wt pct Mn. Other elements were present in much lower concentrations. From the melts, samples in the form of small cylinders of 12 mm in diam were ma-chined. The thickness of the targets and sources was 2.5 and 1.2 mm, respectively. The lower thickness of the sources was chosen to make their over-all ac-tivity as low as possible. Sources were activated in

Jan 1, 1970

By Carlos G. Valenzuela

The value generally accepted for stacking-fault energy, of copper has been approximately 40 ergs per sq cm based on Fullman's2 value for the coherent twin-boundary energy and the assumption that is twice the twin boundary energy However, Thornton and coworkers8 determined that the lower limit of for copper is approximately 60 ergs per sq cm, based on measurements of dislocation-node radii. They suggested that the assumption of = 2t is invalid. It is the purpose of this note to present results which indicate that the values of obtained by measurement of twin-grain boundary intersections and the values obtained by measurement of dislocation-node radii are actually compatible. The most reliable values for of the a brasses, based on electron-microscope observation of dislocation nodes, are probably those values reported by Smallman and Green6 who applied the Siems correction (1961) to data obtained by Howie and Swann.3 These values shown in Fig. 1 give an extrapolated value of approximately 70 ergs per sq cm for pure copper. In the present work, Fullman's method for determining the stacking-fault energy of copper was extended to the a brasses. High-purity copper (99.999 pet) and high-purity zinc (99.999 pet) were mixed in proportioned amounts and melted in sealed and evacuated quartz tubes. The alloys were homogenized for a week at 750°C and chemically analyzed by means of X-ray fluorescence. These alloys, along with a specimen of pure copper, were rolled to 98 pet reduction and a thickness of 0.009 in., resealed, and annealed for 40 hr at 715°C. Values for the ratio of twin-boundary energy to the grain-boundary energy, it gb, were obtained from measurements of dihedral angles formed at the intersections of twin boundaries and grain boundaries by using Fullman's2 mechanical analogy of surface tensions acting at the intersection of an annealing twin and a grain boundary. The angles between the twin traces and the grain boundaries were measured for a large number of twin-grain boundary intersections at a magnification of X500 using a rotating mechanical stage on a Reichert metallograph. The rotary stage has a calibrated angle scale with vernier so that measurements can be made to 0.1 deg. The mean twin-grain boundary energy and standard deviation were calculated for copper and each of the brasses by the use of an IBM 7072 computer. It was found that the mean value of gb stabilized after approximately 100 twin-angle measurements. This was determined by plotting the mean against the number of angles measured. Since the measured angles deviate from true dihedral angles, a correction factor for grain orientation, discussed below, was applied. The stacking-fault energy was then calculated from these values and the values of grain-boundary energy derived by Taylor.7 The data obtained are tabulated in Table I. Values for stacking-fault energy are plotted in Fig. 1. The value of gb for the specimen of 1.03 pet Zn is close to the value obtained by Fullman2 for OFHC (99.98 pet) copper, 0.045. It is believed that the purity of the copper affects gb significantly. The 99.999 pet purity Cu used in this investigation yielded a value of yt/ygb, 0.76, which is much higher than that obtained by Fullman. Additional evidence suggesting that the purity of

Jan 1, 1965

By W. L. Kerlie, J. H. Richards

The variation in hydrogen content of basic open-hearth steels during refining and the effect of changing from steam to air atomization were studied. The water content of the furnace atmosphere, the slag basicity, and the degree of oxidation of the slag-metal system largely control the hydrogen in the steel. SMALL amounts of hydrogen have an adverse effect on the ductility of steel and a wide range of hydrogen contents has an adverse effect on the internal soundness of both ferrous and nonferrous castings. This has been of major concern to the metal industry, both manufacturers and fabricators, for many years. As one of the results of continuing investigations of the hydrogen problem, much has been learned about methods of reducing the hydrogen content of liquid metals below the relatively high levels that are normally associated with such phenomena as rising ingots and excessive porosity in sand casting. However, it was not until a reliable and simple method for sampling and analyzing liquid metal was developed that much progress was possible in quantitatively evaluating the effect of steelmaking practice on hydrogen contents at levels below 6 to 8 ppm. Throughout all the work described in the following presentation the Geffner pintube technique was used to obtain samples of liquid metal1 * and the tin-fusion method, developed at Massachusetts Institute of Technology,2 was used to analyze the samples. Before attempting a systematic experimental program for minimizing the hydrogen content of open-hearth steels, it was necessary to determine the variation in hydrogen in the open-hearth bath during the normal processing of a heat. The logs of ten heats are illustrated in Figs. 1 through 7. The number at each point on the graphs refers to the number of pintube samples analyzed for hydrogen. An increase in the hydrogen content of the liquid metal during the early period of refining is apparent in all heats. There is evidence of a decrease in hydrogen later in the refining period, see Fig. 2, for example. Therefore, the existence of a maximum hydrogen content at some intermediate time during the refining period is anticipated. To test for the existence of a maximum, the data illustrated in Figs. 1 to 5 were grouped together so that they could be examined on a collectively comparable basis. The grouping was effected, as illustrated in Fig. 8, by superimposing Figs. 1 to 5 so that the apparent hydrogen maxima coincided at a fixed position, indicated by the zero on the time axis. Also, by vertical adjustment until the graphs appeared to the eye to be superimposed, the hydrogen scale was made to show the change in hydrogen content. That is, a standard amount was subtracted from the hydrogen values for each heat. Therefore, Fig. 8 represents a generalized presentation of the data and, for this reason, cannot be used to predict the actual hydrogen content of the bath during refining, but rather to show the probable rate of change in hydrogen during refining. Statistical examination of the grouped data in Fi.g. 8 shows that the apparent. increase and suhsequent decrease in hydrogen are real and confirms the existence of a maximum in general. The average increase In hydrogen during the early period of refining is between 0.8 and 1.3 ppm per hr, and the

Jan 1, 1958

By Pedro Bolsaitis, Paul M. Sullivan

The activities of zinc in liquid Zn-A1 alloys in the temperature range of 1000' to 1160°K were determined by means of the isopiestic technique. The results are in reasonable agreement with the previous values determined by the radioactive tracer dew point method. Slightly negative excess entropies of mixing were found. The measured activities suggest that the a function for these alloys is not a constant, as has frequently been assumed, but is better represented by two straight line segments of different slopes. THE thermodynamic data of Al-Z alloys have been the subject of investigation by many authors. However, in the recent compilation of such data by Hult-gren et al.,5 the conclusion is reached that none of the previous measurements are reliable or consistent with each other. Since then two new sets of measurements have been reported,2, 8 both laying claim to good accuracies, yet showing very significant disagreement in the measured activity coefficients of zinc in Zn-A1 alloys and in the magnitude and sign of the excess entropies of mixing. Information on the thermodynamics of the system is of particular interest for interpreting results of the Bureau of Mines research on refining of zinc by distillation of die cast scrap. The present study was undertaken as an independent check on the recent values obtained from dew point measurements 8 and electromotive force measurements.' The isopiestic method, first introduced by Herasy-menko,' was chosen because it is one of the few thermodynamic techniques which, in principle at least, is carried out under perfect equilibrium conditions. The disadvantage of the method is that data are obtained at various random compositions and temperatures, which makes the interpretation somewhat cumbersome. The random errors arising from temperature gradients and fluctuations appear to be comparable to those of other techniques, as evidenced by the magnitude of the estimated uncertainties in the calculated integral thermodynamic quantities. An advantage of the method is that each run provides a relatively large amount of data; thus, it is less time consuming than those methods where samples of each composition must be measured individually. EXPERIMENTAL PROCEDURE The activities of zinc in liquid Zn-A1 alloys were measured by the isopiestic method which uses the principle of the tendency toward equilibrium of a series of samples at various temperatures under an imposed vapor pressure of the more volatile component (i.e., zinc, in this case). The basic apparatus is shown in Fig. 1. The small graphite crucibles that contained the metal samples were 15 mm ID and 13 mm deep with approximately 3 mm wall thickness. Each crucible was notched at the top and bottom to allow easy passage of vapor from one to another. At the beginning of an experiment each crucible was weighed on an analytical balance. Zinc and aluminum of spectrographic purity (99.999 pct) were then weighed into the crucibles. The amounts of each metal added were such that initial compositions varied above and below equilibrium values. One crucible contained only pure zinc. After weighing, the crucibles were stacked with the pure zinc on the bottom (corresponding to the lowest temperature in the furnace) and richest aluminum alloys at the top. The entire stack of crucibles was then placed in the silica glass container "E" which was then sealed under vacuum. Sixteen to twenty calibrated Chromel-Alumel thermocouples were attached by wire along the length of the silica tube, one or more adjacent to each sample.

Jan 1, 1970

By P. Bevilacqua, M. C. Williams, T. P. Meloy

We will bet you that, without prior programming within 10 minutes, we can design and simulate a 10,000 unit operation separation circuit. We will even do it at your place. We do it all the time. [ ] There are no tricks; we do it in a spreadsheet. We do it in those user friendly spreadsheet such as Quattro Pro. Spreadsheets must be user friendly. Accountants use them as do managers, business men, lawyers, doctors and salesmen. What these users seldom realize, is how powerful a mathematical tool a spreadsheet is. Among their other capabilities, spreadsheets can do a finite element analysis. That is why they are useful for accounting. That is also why they are more useful to engineers in the mineral industry. Spreadsheets are ideally suited for the engineering problems in the mineral industry. We have used then for solving problems in: a) mine ventilation; b) circuit design and optimization of dense media, flotation and sizing; c) comminution circuit design; d) shaking tables; e) Humphrey spirals; f) sluice ways and channel flow; g) lock particle and liberation problems; h) tunnel and shaft stress problems; i) cascadograph simulation; j) complex heat transfer problems; k) flow in porous media; and sheet flotation (Figure 1). Mineral industry problems presented on or with a spreadsheet are an excellent teaching instrument, problem statement and solution tools and sales devices. Spreadsheets answer easily, quickly and reliably many mineral industry engineering problems. What makes spreadsheets so useful to the mineral industry. The short answer is: they are easy to use; mineral industry problems fit the spreadsheet format. Those reasons are part of the answer. The real answer lies with the structure of the spreadsheet itself. Essentially, a spreadsheet is a "finite element analysis" form of computer software. Many mineral industry problems are readily solved by finite element analysis techniques. While some in the mineral industry may think they have never heard of finite element analysis, most use it weekly if not daily. Any profit and loss statement is essentially a finite element instrument. In fact, any array of numbers where one number is related to another may be construed as a finite element analysis product. Finite element analysis is a common daily activity. To get an appreciation of a finite element analysis, think of a monthly sales forecast for the next year. For each product and for each month, there exists a dollar figure for the forecasted amount of sales. In the forecast statement, for a given product in a given month, there is a "box" where the forecasted figure is presented. The forecast figure in that box was arrived at through some type of formula. The formula probably required some information from other neighboring boxes in the master forecast statement. Voila, one has a finite element analysis. Today the analysis would be done in a spreadsheet. A typical mineral industry problem is ventilation in an underground mine. Think of a rectangular room and pillar mining operation. Each room has air entering at a given pressure and velocity and air leaving at another pressure and velocity. During steady state, the air entering and leaving the room is determined by conditions in the adjacent rooms. One can readily model the room and pillar mine layout in a spreadsheet, and then find the flow in and out of each room at steady state. Change the flow by moving a brattice cloth or blocking off a path way and one gets a new air flow profile. Change the numbers on the spreadsheet that reflect

Jan 1, 1993

By M. T. Simnad, C. E. Birchenall, M. H. Davis

The transport mechanisms previously proposed in wustite and hematite have been confirmed by movement of inert markers during the growth of these phases. By similar measurements the mechanism for magnetite has been determined. The rates of growth of multilayer scales on iron, magnetite and hematite on wustite, and hematite on magnetite have been measured. All rates are found to be diffusion controlled under the conditions of the experiments. MANY studies have been made of the rate of oxidation of iron in both the low temperature, film-forming region and the high temperature scaling range. The interpretation of the results has been greatly complicated by the formation of multi-layered scales containing the various phases of iron oxides. In most cases no attempt has been made to determine the composition of the scale and its dependence on time of oxidation in a quantitative manner. However, several recent studies'" have taken this variable into account. It is generally agreed that the growth of thick scales on iron follows a parabolic rate law for the increase of total thickness. In the thin film region agreement has been claimed with parabolic equations of various forms and with logarithmic equations. The discussion here will be concerned only with the formation of scales of considerable thickness, greater than several microns, although some of the conclusions may be applicable to thin films. A brief survey will be given of the solid phases of the iron-oxygen system, the stability of wiistite in bulk and in thin films, the relative densities of iron in the metal and oxides, and the kinetics of forma- tion of oxide scales on iron. New experimental results will be introduced at several points during the discussion, and an attempt will be made to formulate a mechanistic picture consistent with these observations. The experimental techniques are described in an appendix. Iron-Oxygen System Fig. la shows the iron-oxygen phase diagram. Wüstite ("FeO"): The lowest of the oxides has a NaCl type cubic lattice formed by close-packing of the relatively large oxide ions with the smaller iron ions arranged in the interstices. The ionic radius for 0' is about 1.3 A, while Fe++ has a radius of about 0.8A and Fe"' about 0.7A. Its range of existence on the phase diagram is very wide for an ionic material of this type and does not seem to include the stoi-chiometric composition FeO. These deviations appear to be well established as vacancies on iron lattice sites by the comparison of lattice parameters and densities for a series of compositions by Jette and Foote.4 The limits of the field are disputed, but the work which seems most reliable" indicates vacancies in from 5 pct to more than 12 pct of the iron sites. In order for the crystal to be electrically neutral, there must be electron holes which correspond to the formation of trivalent iron ions equal to twice the number of vacancies. Magnetite ("Fe³O4"): Considerable disagreement also exists in the literature about the stable range of the Fe³O4 field. Some diagrams show the Fe³O4 composition to be lower in oxygen than the formula indicates, but Schenck6 gives a diagram from the

Jan 1, 1952

By V. Anthony Cammarota

MINERALS INFORMATION PROGRAM Mineral data collection by the Federal Government actually began in 1882 with an appropriation by Congress to the U.S. Geological Survey (USGS). Although the Bureau of Mines was instituted in 1910, it was not until 1924 that the collection, interpretation, and dissemination of worldwide information on production, consumption, and availability of minerals became the responsibility of the Bureau. The objective of the Bureau's minerals information program is to maintain and provide reliable, timely, and comprehensive data for analysis of national minerals problems. This program is implemented by a staff of specialists who cover about 100 mineral commodities and the mineral industries of 168 countries. Data are also provided on the minerals industry on the State and county level. The specialists analyze information to identify trends and problems, forecast future U.S. and world supply and demand for the nonfuel minerals, and relate trends and developments to their impact on the domestic minerals industry. Data Sources and Publications The primary sources of data concerning the domestic minerals industry are the companies that produce, use, and trade in these minerals. Approximately 60,000 survey forms are sent to industry, on a monthly, quarterly, semiannual, or annual basis, to obtain the data. Domestic trade data are provided by the Bureau of the Census, U.S. Department of Commerce. Information on mineral developments abroad is developed by Bureau specialists from mineral reports supplied by U.S. embassies worldwide, from primary source documents, from a review of the technical mining literature, and from onsite mine and plant visits in foreign countries. The information is disseminated through a number of Bureau publications: "Mineral Industry Surveys" provide aggregated data on a monthly. quarterly, or semiannual basis to give timely information on the most important mineral commodities. "Mineral Commodity Summaries," published each January, provides preliminary annual data on supply and demand and discusses significant events of the previous year. The final data are published later in the "Minerals Yearbook," which is the definitive historical record for mineral statistics. "Mineral Facts and Problems," an encyclopedic work issued every 5 years, covers industry structure, technology, supply-demand analysis. economic factors, reserves, and forecasts of U.S. and world demand for individual commodities. "Mineral Perspectives" and "Mineral Issues" cover important international mineral developments and significant issues of current U.S. policy as they relate to minerals. Discussions and analyses of mineral trends and developments also appear in other Bureau publications, such as "Minerals and Materials" and "Information Circulars." These publications provide the basis for analysis and policy determinations by the Bureau and by virtually every Federal agency concerned with minerals, defense issues, the national economy, and foreign relations. The data are also used by industry in planning capital investments in mines and processing plants, by financial analysts, by U.S. delegations in their work with international commodity groups, and by a host of other minerals related organizations. Data Bases The data bases used by the specialists for preparing publications or in response to a continuous stream of inquiries include both those that contain individual commodity data from respondents, and those that are summary data bases on production, trade, capacity, employment and a number of other minerals-related items, not all of which are derived from data reported to the Bureau of Mines. The data bases maintained on the mainframes are not accessible by non- Bureau users. A 10-year data base of supply- demand data, published each year as an update of tables that appear for each commodity in Mineral Facts and Problems, is available on a floppy

Jan 1, 1987

By A. D. Rich

The term "bleaching clay" or "bleaching earth," as used in the oil industries, refers to clays that in their natural state, or after chemical or physical activation, have the capacity for adsorbing coloring matter from oil. There are three common types of bleaching clays: fuller's earth, activated clays, and activated bauxite. Fuller's earth, or naturally active clay, is prepared from bentonites (see Chap. 5) that possess natural activity. It is not activated commercially; in fact, earths of this type ordinarily do not respond satisfactorily to acid activation. Fuller's earth is prepared in pulverized as well as granular form for use in the contacting and percolation processes, respectively. Acid-activated clays also are of bentonitic origin. The basic raw clay, however, is of a type that has a very low natural activity but is highly activable by treatment with mineral acid. Commercial acid-activated clays generally possess several times the decolorizing power (bleaching efficiency) of the best quality of fuller's earth. The former are prepared commercially only in the pulverized grade because of the difficulties in obtaining a satisfactory granular product, and hence are used only in the contact process. Activated bauxite is made by heat-treating bauxite ore, which in its natural state has very little natural activity. The commercial product is prepared in granular form for use in the percolation process on petroleum oils. For the most part, bleaching clay is used commercially in the decolorization of animal, vegetable and petroleum oils, fats and waxes. It is applied in two ways: (1) by the percolation method and (2) by the contacting method. Percolation refers to the passage of oil through a bed of granular clay whereas contacting refers to direct agitation of oil and pulverized clay followed by removal of the clay from the oil by filtration. In either case, the decolorizing effect is obtained by intimate contact between the liquid oil and the solid adsorbent. Petroleum oils are treated commercially by either the percolation or the contact process. Animal and vegetable oils are treated by the contact process only. Composition The raw clays from which both fuller's earth and acid-activated clays are prepared are composed of hydrous aluminum silicates containing varying quantities of magnesium, iron, calcium and other elements. These raw materials are usually nonswelling bentonites derived from volcanic ash or lava by weathering and hydrothermal chemical reactions. The bentonites have as their chief mineral constituent montmorillonite, which has the formula [(OH)4Si6A14O20•nH2O], according to Grim. (See Chap. 5, ref. 6, p. 91.) The underlying reasons are not fully known for the natural activity of the fuller's earth type of clay and its usual failure to further activate with mineral acid in contrast to the natural inactivity of the activatable type of clay. However, it may be said that the bentonites that are responsive to the acid-activation treatment generally have not undergone any drastic metamorphism. The chemical composition is not a reliable means of discrimination between a nonactive, a naturally active, and a nonactive but activable clay, therefore it is not possible to forecast the ultimate quality of a clay on the basis of the raw-clay analysis alone. Table 1 gives typical analyses of representative clays of the foregoing classifications.

Jan 1, 1960

By H. D. Attra

The effects of phase behavior on reservoir economics is a function of both fluid composition and flow properties of the reservoir rock. In some operations such as gas injection into volatile crude-oil resertoirs, the stock-tank recovery derived from vaporization of the reservoir oil by the displacing gas can approach the recovery derived from the displacement mechanism. In other cases of gas-cycling reservoirs, the dry injected gas can effectively vaporize a retrograde liquid phase, allowing a substantial reduction in cycling pressure with no appreciable loss in recoverable liquids. Because of these effects, it is essential that phase behavior be considered in developing the economics of any secondary recovery program in which gas is the injected fluid. The inclusion of phase behavior in conventional calculation procedures has been retarded because of the complexity of the calculation and the large volume of laboratory data required. However, by applying high-speed computers and new laboratory techniques, the phase-behavior displacement calculation has been developed to economically include this basic fundamental of gas displacement. The calculation is performed by reducing the reservoir to a series of one-dimensional segments. Phase changes, saturation distributions and changing fluid properties are evaluated for each segment as a function of time. The relative volumes of equilibrium liquid and gas displaced from each segment are determined by a trial-and-error procedure to meet the requirements of phase equilibrium and two-phase flow. The produced fluids are flashed through conditions of surface separation approximating those in the field to obtain actual values for stock-tank liquid recovery and producing gas-oil ratios. Based on the results of successful field studies, the technique appears to have application to reservoirs producing under a nonmiscible gas-displacement mechanism and should substantially increase the reliability of this type of analysis when phase behavior is an important factor. Predicting reservoir performance under gas-injection operations involves three basic principles of reservoir engineering. First, a material balance exists between the displacing gas and the displaced reservoir fluid. Second, the oil and gas flow in relationship with the two-phase flow property of the reservoir rock; and third, phase equilibrium exists between the displacing gas and the native reservoir fluid. To illustrate these three principles, consider the one-dimensional reservoir shown in Fig. 1. The reservoir is divided into a series of segments representing a one-dimensional cross section between an injection area and a producing area. So represents the oil saturation, Cw represents the connate-water saturation and Sg represents the displacing gas saturation. The gas is moving into Segment 1 and the reservoir oil is being produced out of Segment N. Consider the case when gas has just moved into Segment 1 and the displacing gas-oil contact is at position a-a The volume of oil pushed out of Segment 1 is a function only of mobility and the two-phase flow properties of the reservoir rock, that is, Kg/Ko and µo/µg. Behind the front if the injected gas is foreign to the reservoir oil (a nonequilibrium gas), there will either be vaporization of the oil into the gas or condensation of the gas into the oil. In either case the net result is a mass transfer and a re-distribution of composition and liquid and gas saturation. If the displacement is at constant pressure and is continued, the gas moves into new segments, proceeding succesively into Segment 2, 3, etc. The total volume of oil produced from the reservoir

By T. S. Lundy, J. Askill

J. Askill and T. S. Lundy (Oak Ridge National Laboratory)—Moore has proposed a simple correlation between the activation energy for solute diffusion in fee metals and the atomic volume of the diffusing species using both tracer and chemical-diffusion data. The first point we wish to make is that it is wrong to attempt such correlations without separating the two types of data. Activation energies obtained using tracer techniques cannot, in general, be directly compared with those obtained from chemical-diffusion experiments. A knowledge of the variations of chemical potentials with composition is necessary and chemical-diffusion data must be corrected for such variations, even for dilute alloys, before a comparison is possible. Secondly, for nickel, iron, aluminum, and lead, Moore neglected a number of recently published works, e.g., Al26 and Mn54 in aluminum,46 cr51 in nickel,47 and Fe55 in iron.48 These and others should have been used. If one considers only the tracer diffusion data, there is left no simple correlation of the type proposed by Moore. For example, in the case of solute diffusion in aluminum the only reliable tracer data listed by Moore are for zinc and aluminum. The nickel, cobalt, and iron data of Agarwala49 are representative of near-surface diffusion-not bulk diffusion. In conclusion we suggest that for tracer diffusion data in these fee metals there is no justification for proposing any simple correlation of activation energy with atomic volume using the limited data that are presently available. R. H. Moore (author's reply)—The writer has proposed a simple correlation which is useful in estimating the internal consistency of diffusion data. The accuracy of the correlation is, of course, a function of the number of data available. Lundy and Askill take issue with the writer's decision to include data for the systems: nickel, iron, aluminum, and lead, taking the view that the data are insufficient to establish the correlation. The writer agrees that the data are insufficient and has cau- tioned the reader that the correlation is tentative in these instances. Inclusion of these systems is justified by the interesting trends the correlation reveals. For example, the distinction between interstitial and substitutional diffusion may be clearly established, Figs. 4 and 6, and the behavior of transition elements and nontransition elements is indicated to parallel the behavior illustrated by the silver and copper systems. Lundy and Askill have singled out the aluminum system for special criticism. The writer chose to discuss the data for diffusion of iron, nickel, and cobalt in aluminum in the terms used by the original authors9 and has included the comments of Balluffi.l0 The writer did not intend the reader to conclude that data for these elements should correlate with data for the nontransition elements as Lundy and Askill have evidently assumed. Iron, nickel, and cobalt form intermetallic compounds with aluminum, so the activity coefficients of these elements may be expected to deviate markedly from unity. This may account for the low frequency factors observed by Hirano.9 The nontransition elements, on the other hand, yield relatively simple phase diagrams with no evidence for intermetallic compound formation as in the case of iron, nickel, and cobalt. In dilute solution, Henry's law should be closely obeyed, the activity coefficients should not deviate markedly from unity, and the effect on the activation energy should not be large. The accuracy of the correlation applied to these systems will improve as the data is extended. It does not seem unreasonable to conclude that its extension should be encouraged.

Jan 1, 1965

By Klaus M. Zeitler

INTRODUCTION One cannot discuss the subject of "Raising Capital in the 1990s" without having a crystal ball and a reliable fortune teller. This discusses "Raising Capital for the 1990sW, which is what Metal1 Mining Corporation did in 1987. We raised (3166 million in an IPO (initial public offering) that was originally planned for only some (375 million. Why did we raise this money? How did we do it, and why was this IPO so successful? The answer to the first question requires a description of the promoter and principal shareholder of Metal1 Mining Corporation, Metallgesellschaft AG. This West Germany company was founded over 100 years ago in Frankfurt as a trading house for non-ferrous metals. It has developed into one of the world's leading firms in the non-ferrous metals industry. The company's worldwide activities in all areas of that business include mining, smelting and refining, the trading of ore, base and precious metals, the production of semi-fabricated and finished metal products, and the provision of engineering, construction and transportation services. Metallgesellschaft AG has also diversified into many other areas, the most significant of which are manufacturing, the production of chemicals, the development and application of technical and chemical processes, the planning and construction of industrial plants, and activities associated with finance, insurance, shipping and freight forwarding, and the provision of barter and countertrade services. The company maintains a network of more than 100 offices around the world; it employs some 25,000 people in its worldwide activities. [Selected financial data, as of September 30, 1987: (MetaUgesellschafl AG) Working Capital DM 8%.6 million CDNS 672.8 million Long Term Debt DM 568.0 million CDNS 426.2 million Sales DM 14.9 billion CDNS 11.2 billion Net Income DM 87.7 million CDN$ 65.8 million Market Capitalization at April 27, 1987: (Metallgesellschafi AG) Outstanding Shares ~,6oo,o0o DM 1,875 million CDNS 1,407 million] For the fiscal year ended September 30, 1987, Metallgesellschaft AG had, on a consolidated basis, net sales of DM13.3 billion, net income of DM100 million and total assets of about DM7.0 billion. Metallgesellschaft AG established the American Metal Company, a predecessor of AMAX Inc. one of the largest ventures undertaken by Metallgesellschaft AG then was the acquisition, through the American Metal Company, of a majority share in the Mexican Penoles mine, a large lead and silver deposit. METALLGESELLSCHAFT AG Figure 1 depicts an overview of Metallgesellschaft AG before and at the time the initial public offering of Metall Mining Corporation's shares took place. It shows that mining was far from the centre of Metallgesellschaft's activities. Therefore, it could not expect to receive an extraordinary amount of board attention. Thus, mining investments not only had to compare well with other mining opportunities, but were in fierce competition with projects from other divisions. In addition, mining was sub-divided into two separate departments -- domestic and international. These two departments had different management styles and diverging interests which resulted in a minimum co-operation between them. The domestic mining department was primarily interested in the survival of the local mines. These mines were characterized by rising operating costs and declining ore grades. It took a special commitment and continued ingenuity to develop and adjust to local conditions, and modern mining and processing technology, in order to remain competitive, or at least survive within the international mining industry. Local management

Jan 1, 1990

By J. F. Gormley

Drill pipe, and the connections used to join the pipe together, have had a long history of development and improvement. With the growing use of high tensile-strength pipe, the rotary shouldered connections used to join the lengths of drill pipe have become more critical. Fatigue-type failures of rotary-shouldered connections, or tool joints, have become a cause of much conern to operators and manufacturers. Most fatigue tests on tool joints have been made on the basis of bending moment applied vs number of cycles, rather than on the basis of stress vs cycles. A desire to learn more about the nature of stress in a tool joint due to bending caused a rather intensive experimental study to determine what actually happens to cause fatigue failure. It was known that a tool joint with insufficient make-up torque was subject to early fatigue failure. Therefore, the establishment of the relationship between make-up torque and allowable bending moment would enable a testing engineer to better correlate the results of various tests. The problem of calculating the stress in a tool joint due to an applied bending moment was complicated by: the effect of unknown stress concentrations; the applicability of the well known formula S = Mc/I; and the question of whether to use the combined cross section of the pin and box in calculating the moment of inertia I. TEST EQUIPMENT The test equipment consisted of the following. 1. A lathe modified to act as a fatigue machine for full-size tool joint or drill-collar specimens. 2. An adapter plate bolted to the headstock of the lathe and into which a short adapter was screwed. 3. Tool-joint pins on sections of drill collars bucked into the adapter. 4. A hydraulic load cylinder which rested on the bed of the lathe and applied bending moments to the joints. 5. Paper-backed strain gauges (FAP-12-12, 1/8-in. gauge length and A-5-1, 1/2-in. gauge length). 6. Eastman 910 contact cement for bonding gauges to joint and Epoxylite 222 waterproofing. 7. A 12-position switchbox, SR-4 bridge balancing unit connected to an SR-4 strain indicator to read the gauge output. 8. A four-channel Sanborn recorder, Model 150, was used as the readout instrument for part of the testing. The fatigue machine was well suited as a loading device. Because of the long lever arm available, the change of moment with distance was small; consequently, the vertical shear stress was small, less than 300 psi. Some difficulty was experienced with the hydraulic load cylinder at high bending moments due to leakage. The strain gauge equipment was simple and quite reliable. A 41/2-in. extra hole (E. H.) joint with "as machined" threads and shoulders and a 2 7/8-in. internal flush (I. F.) joint with copper-plated threads and shoulders were selected for testing because of their common usage in the field. In addition, the 4 1/2-in. E. H. was suitable because it had an inside diameter large enough to permit the insertion and accurate positioning of strain gauges without using special jigs, while the 2 7/8-in. I. F. joint required much lower bending loads to cause separation of the shoulders of the joint when made up to the recommended torque. The joints were made to standard API specifications, except for very small bevels on the box and pin shoulders and cylindrical stress-relief grooves added to the pins. Larger bevels would have

By Ulrich Paschedag

The WESTFALIA group of companies developer and manufactures underground mining machinery for complete high-performance longwalls. WESTFALIA uses a state of the art electrohydraulic system as the most important component for the realisation of today's fully automated plow or shearer longwall. The shield control unit (SCU) allows maximum custom designed software flexiblity as well as maximum hardware reliability. The master control unit (MCU) monitors shield support data as well as the plow/shearer position. By using an industry standard PC in an explosion-proof box with an intransically safe keyboard nearly unlimited software capabilities can be obtained with inexpensive hardware. Among various other modes of operation this MCU allows the monitoring and recording of data which can be transmitted to a surface computer. Production and operational adjustments can be made by the mine management based on the MCU information. Statistical analysis of the distribution of roof pressure under various conditions is also possible. The WESTFALIA automation system PM-4 gives the operator maximum flexibility and helps the mine management to run their longwall more efficiently and safely.

Jan 1, 1994

By L. Ekstrom, J. P. Dismukes

The homogeneity and microstrcture of zone-leveled Ge-Si alloys haw been investigated by sellera1 physical techniques and by metallography as a function of growth rate in the range 3 x 10 1x10 cm-sec', and as a system of alloy composition throughout the system. The temperature gradient at the solid-liquid interface was about 50 deg-cm-' Cellular or dendritic structures char-acteristic of constitutional supercooling were ob-served except at very slow growth rates, which ranged from about 2 x 10 cm -sec for Ge 1 sio alloy to about 2 X 10'5 cm-sec'1 for Ge .sSio.s alloy. Using a simple model similiar to that employed for dilute solid the dependence upon compo-sition over the entire system of the critical growth rate for the onset of constiutional supercooling was calculated, and was .found to he in good agreement with the experimental results. THE recent discovery of the low thermal conductivity of Ge-Si alloys' at high temperatures has revealed that these alloys have high efficiencies for thermoelectric-power generation.', Therefore, a reliable method was needed for the preparation of homogeneous samples required for definitive measurements throughout this alloy system. Due to the low diffusion rates in the solid alloys, the segregated samples obtained by quenching a melt are not readily homogenized by annealing.475 However. isothermal solidification from a melt of constant composition can produce uniform material. Of the available semiconductor crystal-growth procedures, the zone-leveling technique6 applied to a complete solid-solution alloy system by Wang and Alexander' and by others provides a simple method of doing this. In the present work, the homogeneity and microstructure of zone-leveled alloys have been correlated with growth conditions, and the conditions for preparing homogeneous Ge-Si alloys have been established. This has provided insight into the solidification process of alloy semiconductors. EXPERIMENTAL PROCEDURE Sample Preparation. The Ge-Si alloy phase diagram4 shown in Fig. l(a) consists of a complete series of solid solutions. The zone-leveling technique used to prepare most of the samples consists of moving a zone of liquidus composition (C1) through charge material of the corresponding solidus composition (C,), as is illustrated in Figs. l(b) and l(c). To prepare the charge materials, high-purity germanium and silicon were pulverized in a steel hammer mill, cleaned magnetically, and melted together to make uniform chill castings. The zone leveling was carried out in a resistance-heated furnace similar to that of Mitrenin et al.' shown in Fig. 2. However, a few specimens of high silicon content were prepared by the Czochralski technique. The growth rate ranged from 3.5 x X6 to 1.2 X 10~3 cm-sec-'. Temperature gradients in the solid and in the melt were determined by recording the temperature as the molten zone passed over a Pt-Pt 13 pct Rh thermocouple contained in a small

Jan 1, 1965

By William F. Butler, Mo-Hung Che

DEVELOPMENT OF MONEY AND MONEY STANDARDS This chapter is concerned with the rise, and then the decline and fall, of gold and silver as monetary metals. As a first step in tracing the history of this process, it is necessary to consider the nature of money, and the manner in which different forms of money have developed over the centuries. The origins of money go back into deepest antiquity. Once men ceased to be pure nomads and entered into even a rudimentary form of society such as clans or tribes, money had to be invented The first step was barter as farmers or hunters swapped their surplus products for things produced by artisans such as shoes, clothing, and simple tools. But such barter trading is inconvenient even in primative societies It is difficult to match up buyer and seller at any point in time There are problems in arriving at viable and acceptable terms of exchange. The accumulation of savings-wealth-is complicated. No one can be sure that a pile of furs, or wheat, or certainly fish or game can be used in the future to trade for other goods or services. So even prehistoric man saw the need for money. There was a need first for something to serve as a medium of exchange This was an essential first step in the process of specialization-or the division of labor. A farmer, a hunter, or a shoemaker could only devote his full efforts to his trade if he could be sure that he could exchange his surplus production for the other things he needed for existence. This required a medium of exchange-a form of money which would be broadly acceptable. Money was needed for two other reasons Some system of market prices was essential to facilitate the exchange of goods and services. This required some form of common denominator-some standard of value-to govern the exchange process. And there was also need for something to serve as a store of value, a place to put any excess production (savings) with the assurance that it can be used in the future to acquire a general range of goods and services. As a result, money, in one form or another, developed at a very early state in civilization. Yet the centuries have been marked by a search for a form of money which will possess in full measure all of the attributes in money-a reliable and universally acceptable medium of exchange, standard of value, and store of value. -A wide variety of things have been used as money at one time or another: shells, beads, stones, feather, metals, and even the teeth of sharks and dogs. Some of these things were obviously of little or no practical value. They were used because people had confidence in their continued acceptance as a medium of exchange. As the world evolved and as trading ex-

Jan 1, 1976