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By A. W. Bethune, L. M. Pidgeon

The equilibrium vapor pressure of zinc has been determined over the systems: ZnS(s) + Fe(s) = FeS(s) + Zn (vapor) and ZnS(s) + 2Cu(s) = Cu2S(s) + Zn (vapor) by reacting the components in an evacuated tube containing a thin copper fiber, and allowing equilibrium to be established with respect to the brass formed and the zinc in the vapor phase. The composition of the brass formed was determined and equilibrium vapor pressure values obtained from existing data. Between 850' and 1000°C, values for the first reaction ranged from 8 to 58 mm Hg; for the second reaction from 1.8 to 22 mm Hg. THE direct reduction of metallic sulphides may be indicated by an equation of the form MS + X = XS + M [1] where X is some suitable reducing agent. In the case where M is a metal of relatively high volatility, the use of vacuum will displace the equilibrium to the right at comparatively low temperatures in the face of the usually unfavorable thermochemistry. For this technique to be feasible, MS, X, and XS, must of course be nonvolatile compared to M. In this regard, zinc becomes an obvious metal both from the point of view of its volatility and the fact that most commercial ore deposits of this metal occur as the sulphide, and its direct reduction would avoid the expensive roasting process necessary prior to present day reduction methods. Two reducing agents are of interest, namely copper and iron, with the former having the added attraction of being relatively easily regenerated by oxidation in the copper converter. The possibility of these reactions has been considered before. Imbert1 patented a process whereby zinc sulphide was reduced by either copper or iron. The process as described took place at atmospheric pressure and, at the high temperatures required, the system was molten, resulting in the formation of a matte with the consequent reduction in the activities of the reactants. Peterson2 did further experimental work on these reactions and, although promising results were obtained on a small scale, attempts to increase the size of the furnace led to excessive "blue powder" formation. The early workers failed to realize the large reduction in temperature afforded by the use of vacuum and its desirable results. More recently, the direct reduction of zinc sulphide by iron has been the subject of a thermody-namic investigation by Kelley,3 and Gross and War-rington' have studied the kinetics of the reaction in the temperature range 900" to 1000°C, their experiments being conducted using vacuum and indicating that the reaction would proceed practically to completion in 1 to 3 hr, depending on the temperature. A qualitative examination of the system ZnS-Cu carried out at this University indicated that 98 pct of the theoretical zinc in the charge could be recovered in 1 hr at 1000°C when operating under reduced pressure. The purpose of this research program was to study the equilibrium of the two reactions. During the investigation, reference to the experimental work of Schenk5 was found but, due to lack of detail in the report, it was felt that it would be desirable to continue the equilibrium measurements. Selection of Method The measurement of vapor pressure of metals presents obvious problems resulting from the high temperatures which must be employed. In the present case, the production of the "reaction pressure" introduces a further difficulty since a chemical reaction must proceed before any metal vapor pressure is produced, resulting in depletion of the re-

Jan 1, 1954

By Allan E. Martin, Harold M. Feder, Irving Johnson

The cadmium-uranium system was studied by thermal, metallographic, X-7-ay and sampling techniques; special emphasis was placed on the establishment of the liquidus lines, The single inter metallic phase, identified as the compound UCd11 melts peritectically at 473°C to form a-umnium and melt containing 2.5 wt pct uranium. The cadmium-rich eutectic (0.07 wt pct uranium) freezes at 320.6°C. Solid solubilities in uraizium and cadmium appear to be negligible. Between 473°C and 600°C the liquidus line is retograde. NO publication relating to the cadmium-uranium phase diagram was found in the literature. The establishment of this diagram was of considerable interest to us because of a possible application of the system to the pyrometallurgical reprocessing of nuclear fuels. Analysis of liquid samples, metallographic examination, thermal analysis, and X-ray diffraction analysis were used to establish the phase diagram from about 300° to 670°C. Particular emphasis was placed on the establishment of the liquidus lines. The same system was concurrently studied in this laboratory by the galvanic cell method.' Both studies benefited from a continual interchange of information. MATERIALS AND EXPERIMENTAL PROCEDURES Stick cadmium (99.95 pct Cd, American Smelting and Refining Co.) contained 140 ppm lead as the major impurity. Reactor grade uranium (99.9 pct U, National Lead Co.) was most often used in the form of 20-meshspheres. This form was particularly suitable because it does not oxidize as readily as finer powder. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The liquid sampling technique is described elsewhere2 alumina crucibles (Morganite Triangle RR), tantalum stirring rods, tantalum thermocouple protecthecadmiumtion tubes, Vycor or Pyrex sampling tubes, and grades 60 or 80 porous graphite filters were used. Uranium dissolves in liquid cadmium rather slowly. In order to achieve saturation of the melts it was necessary to modify the procedure of Ref. 2 by the use of more vigorous stirring and longer holding periods (at least 3 hr) at each sampling temperature. The samples were analyzed for uranium by spectro-photometry (dibenzoyl methane method) or by polar- ography. The analyses are estimated to be accurate to 2 pct. Thermal analysis was performed on alloys contained in Morganite alumina crucibles in helium atmospheres. Standard techniques were employed; heating and cooling rates were about 1°C per min. For the determination of the peritectic temperature, Cd-10 pct U charges were first held for at least 50 hr at temperatures in the range 435° to 460°C to form substantial amounts of the intermediate phase. For the determination of the effect of cadmium on the a-p transformation temperature of uranium, charges of Cd-25 pct U (-140+100 mesh uranium spheres) were first held near the transformation temperature, with stirring, to promote solution of cadmium in the solid uranium. The holding times and temperatures for these treatments were 18 hr at 680°C for the cooling run and 28 hr at 630°C for the heating run. Alloy specimens for X-ray diffraction and metallographic examination of the intermediate phase were prepared in sealed, helium-filled Vycor or Pyrex tubes. Ingots from solubility runs and thermal analysis experiments also were examined metallographically. Crystals of the intermediate phase were recovered from certain cadmium-rich alloys by selective dissolution of the matrix in 20 pct ammonium nitrate solution at room temperature. Temperatures were measured with calibrated Pt/Pt-10 pct Rh thermocouples to an estimated accuracy of 0.3°C. However, the depression of the freezing point of cadmium at the eutectic is estimated to be accurate to 0.05°C because a special calibration of the thermocouple was made in place in the equipment with pure cadmium just prior to the measurement. EXPERIMENTAL RESULTS The results of this study were used to construct the cadmium-uranium phase diagram shown in Fig. 1. This diagram is relatively simple; it is characterized by a single intermediate phase, 6 (UCd11), which decomposes peritectically, and which forms a eutectic system with cadmium. The solid solubilities in the terminal phases appear to be negligible. An unusual feature of the diagram is the retrograde slope of the liquidus line above the peritectic temperature. The Liquidus Lines. The liquidus lines above and below the peritectic temperature are based on three separate solubility experiments. The data are shown in Fig. 1 and are given in Table I. It is apparent from the figure that the solubility data obtained by the approach to saturation from higher temperatures fall on substantially the same lines as those obtained

Jan 1, 1962

By R. A. Fitch, J. D. Griffith

A performance calculation method was used in conjunction with experimental studies to develop means of predicting and interpreting miscible floods and to explore possible methods. of improving their efficiency. The calculation method is based upon the division of reservoirs into multiple independent zones or strata. Comparison was made with some experimental floods and with a field project to obtain some measure of the applicability of the method. Two aspects of miscible flooding were considered: (I) the displacement of a miscible front through a reservoir, and (2) the distribution and utilization of the solvent volume injected to maintain miscibility. Calculations and experihental observations indicate that alternate gas-water injection behind a miscible front significantly improves miscible flood performance, both within a single stratum and in a multistrata reservoir. Calculations were made on the extent to which miscibiliry is maintained by a given solvent volume in a stratified reservoir. Two alternate criteria for determining the optimum volume of solvent for injection are discussed. The preinjection of a small volume of water ahead of the solvent is suggested as a method of obtaining more efficient utilization of solvent. Calculations and experiments were made to investigate the effects of water preinjection. INTRODUCTION Miscible fluid displacement as a possible means of recovering oil has been the subject of extensive research and numerous field tests over the past several years. This work has brought out both favorable and unfavorable features of the miscible recovery methods. Many tests have shown that a miscible fluid can displace all of the oil contacted, leaving no high residual oil saturation, as is characteristic of immiscible displacements. The miscible methods have proven dificult to control, however, as evidenced by early breakthrough of the displacing fluid and poor sweep efficiency in several field projects. It became apparent early in the investigation of miscible displacement that the development of improved techniques and better methods of control would be required to extend the range of applicability to any significant portion of our petroleum reservoirs. The purpose of this study was to consider the problem of designing miscible floods to obtain better performance. A performance calculation was used in conjunction with experimental studies to develop means of predicting and interpreting miscible floods and to explore possible methods of improving their efficiency. Two aspects of miscible floods were considered separately in this study and the results are presented in two parts. The first part concerns the manner in which the miscible front is displaced through the reservoir. In these calculations the condition of miscibility between the reservoir oil and the displacing fluid is assumed. In the second portion the distribution and utilization of the preinjected solvent in maintaining rniscibility is considered. This portion dealing with solvent utilization applies only to the enriched gas or LPG slug processes. CALCULATION METHOD AND EXPERIMENTAL STUDIES COMPUTATIONAL MODEL The calculations for expected reservoir performance are based upon the multi-strata concept of reservoir properties. The method assumes multiple, independent strata (no crossflow between strata) and explicitly includes variations in patterns, injectivity, areal sweep and displacement efficiency. Lateral variation in permeability within the strata (for example, directional permeability) may be considered in the calculations, provided the variations are similar in all strata. The calculations based on this model furnish the rates of injection and rates of production of both oil and the displacing fluid for the composite system of strata. To carry out calculations on the mathematical model described, information is required on the performance of the displacement process under consideration in a single stratum element of the pattern to be used. In particular, for a given pattern and displacement process, data are required relating injectivity and composition of the produced stream to the volume of fluid injected. Data on the variations in areal sweep must also be available if it is desired to track the areal sweeps in the multi-strata model. These data may be obtained from experimental work such as model studies or other suitable methods. This representation of reservoir properties is, of course, an approximation and may be inappropriate in some cases. But the representation is not an arbitrary one since most oil reservoirs are essentially successive layers of sediment with the net producing pay zone often comprising but a fraction of the gross formation thickness. The fact that permeabilities measured in the vertical direction are frequently but a fraction of the horizontal permeability adds some evidence to the validity of this model. This type cal-

Jan 1, 1965

By D. E. Thomas

Oxidation rate constants were determined for Cu-Pd and Cu-Pt alloys as a function of alloy composition and temperature. Reaction products were identified. Relationship between oxidation rate constants and diffusion constants in the reaction zones is discussed. THE mechanism of oxidation of alloys is consider--'¦ ably more complex and not so well understood as that of pure metals. The oxidation of a one-phase binary alloy of which one component is a noble metal should logically be the simplest case of alloy oxidation, for in this case one is concerned presumably only with the oxidation of the base metal and the diffusion process by which it reaches the reaction site. This had led a number of investigators to study such systems. Probably the earliest work was that of Tammann and Rienacker' on the tarnishing of Cu-Au alloys at temperatures up to 300°C. These alloys oxidize according to the logarithmic law, that is, the film thickness is proportional to the logarithm of the time. The rate of film formation was found to decrease with increasing gold content. Raub and Engel² investigated the oxidation of Au-Cu, Cu-Pd, Au-Ag-Cu, Au-Pd-Cu, and Ag-Pd-Cu alloys at 750°C in air. These alloy systems form a continuous series of solid solutions at the temperature of oxidation with the exception of those containing silver. Au-Cu alloys oxidize parabolically, the rate constant decreasing slowly with increasing gold content up to about 15 atomic pct* Au, and more rapidly thereafter. An alloy with 14 pct Cu forms only a very thin layer of CuO on the surface and probably also a subscale.† Alloys containing more than 14 pct Cu have scales consisting of CuO and subscales of Cu,O embedded in nearly pure gold. The Cu-Pd alloys obey the parabolic law except for slight deviations for alloys containing 53 and 84 pct Cu. The overall oxidation rate decreases rather smoothly with increasing palladium content. A scale consisting of a thin layer of CuO and a thick layer of Cu²O and a subscale of Cu²O embedded in nearly pure palladium was observed for alloys containing 84, 53, and 30 pct Cu. An alloy with 19 pct Cu formed only a subscale of CuO embedded in nearly pure palladium, and an 8 pct Cu alloy formed only a thin film which was presumed to be PdO. The ternary alloys considered by Raub and Engel oxidized in much the same way as did the binaries. Wagner and Grunewald³ found that Ni-Au alloys, oxidized at 900°C in oxygen, formed a scale of NiO and a subscale containing NiO and gold. The overall oxidation rate increases with increasing gold content, passes through a maximum and then decreases to zero for pure gold. The fact that gold increases the oxidation rate was attributed to "pores" in the scale. Kubaschewski' investigated the air oxidation of alloys of platinum or gold with up to 10 pct Cu or Ni at temperatures in the range 300" to 1550°C. Parabolic behavior was noted for all alloys except Au-Ni, with rates decreasing in the order Au-Cu, Au-Ni, Pt-Ni, Pt-Cu. The diffusion coefficients for the latter three systems are known, and they decrease in the same order. However, activation energies for the oxidation of these alloys do not agree with the activation energies for diffusion in the respective alloy systems. Kubaschewski and Goldbeck7 nvestigated the oxidation of Ni-Pt alloys in air at temperatures of 600"

Jan 1, 1952

By G. D. Just

INTRODUCTION Large scale underground mining involves the bulk handling of fragmented material. The cost and efficiency of the mining systems is there- fore significantly influenced by material flow characteristics. Flow problems may occur in the form of ore pass blockages which interrupt the free flow at extraction openings. The costs of such delays can be readily assessed and compared to the costs incurred in reducing blockages by improved fragmentation or larger ore passes. In practice the problem is more complex than this statement suggests because it is generally un- economic to design for zero ore blockages. Another major flow problem occurs in the form of relative movement of ore and waste as the fragmented material is extracted. This produces waste dilution in the recovered ore and influences total ore recovery. This flow problem is much more complex than the ore block- age phenomena. Many questions concerning the precise flow characteristics remain unanswered because of the variability of size distributions, particle shapes, material properties and the total extraction layout and design. Model studies can provide a visual and quantitative illustration of probable flow characteristics but full scale data collection is necessary to evaluate the precision of such information. The methods and types of data obtained must be carefully selected to recover the maximum volume of useful information for operational control and future design. It is essential that honest precision levels are assigned to the data and any subsequent analyses. Grade control data may give misleading short term information on flow characteristics because of the difficulty in knowing the true grade of the mass of material before extraction commences. However, in the long term control of extraction grades is vital to the profitable operation of the mining system. The most efficient extraction design and operational schedule can only be determined after all of the facts and variables are known. This is usually only possible after the orebody has been completely extracted. However, if design and operational personnel have a full appreciation of the nature and variability of material flow under different conditions the best possible results should be achieved. The most significant features of material flow are out- lined in this paper in order to provide mine planning and mine management personnel with some of the necessary information relating to material flow. Available facts and reliable figures from selected publications are noted in association with unbiased and hopefully accurate opinions of the relevance of the data to mine design and mine system control. Possible future developments and profitable areas for research into material flow problems are also detailed. MATERIAL FLOW AND MINING METHODS The effects of material flow on the design and operation of an integrated underground ore handling system is one factor which is common to most mining methods. Analysis of the system as detailed by Just, 1980, permits the identification of unit process objectives. For example, a typical underground ore handling system as illustrated in Figure 1, involves the following unit operations:- (i) Gravity flow of ore in stope (ii) Ore extraction at base of stope (iii) Ore haulage on the production level (iv) Dumping of ore into ore pass system (v) Gravity flow of ore in the ore pass (vi) Underground crushing of ore (vii) Haulage of crushed ore to shaft (viii) Hoisting of ore to the surface. Average flow rates in each of these unit operations can be misleading due to variability in incremental capacity caused by flow blockages and machine delays. Thus to effectively analyse the probable performance of the system, it is necessary to have a measure of the flow loading and haulage rate variability. Mechanical equipment performance specifications can be used to provide such information for loading, haulage and crushing; however, in the case of the gravity flow of material field measurements are required to relate the probability of "hang-ups" to the degree of fragmentation. Factors affecting the frequency of flow stoppages are, size, distribution and cohesiveness of broken material and the geometry and size of the flow channel. Ore pass channel design is relatively simple since regular cross-sectional shapes are used

Jan 1, 1981

By T. E. Scott, D. H. Sherman, C. V. Owen

Mechanical properties and optical metallographic characteristics of vanadium containing 53 ppm (wt) H were investigated from, 77° to 298°K. A sharp ductile to brittle transition induced by the presence of hydrogen was observed between 238° and 223°K and a mar-tensitically formed hydride appeared at 200°K. While there appears to be a subtle relationship between the hydride formation and the ductile-brittle transition, it was concluded that the hydride per se was not sufficietzt to cause the severe em brittletnent. On the basis of the metallographic experiments and the results of a Petch analysis it is suggested that the mechanism of the embrittlement involves a reduction of the true surface energy, or cohesion, of the uanadiunz. THAT hydrogen can severely embrittle vanadium is well-documented;'-5 however, the mechanism by which hydrogen induces the observed embrittlement has not been established. It is not known whether the embrittlement of vanadium is caused by the formation of vanadium hydride or by a more subtle role of hydrogen. Until very recently6>' the solid solubility of hydrogen in vanadium at temperatures in the,range of the embrittlement was not known to a useful accuracy. In general, a severe embrittlement of the type produced by the presence of hydrogen in vanadium can be caused by changes in either of two properties of a metal. Either the yield stress of the metal is raised to the extent that plastic deformation at the tip of a crack cannot occur or the cohesive properties of the metal are reduced, at least locally, to the point at which cleavage is the natural response to applied loads. Of course a combination of these is possible. It is not known which of these properties of vanadium is influenced most by the addition of hydrogen. The purpose of this investigation was to determine the role of hydrogen in the embrittlement of vanadium. Accordingly, the solubility of hydrogen in vanadium in the temperature range where embrittlement is most severe was determined, the appearance of vanadium hydride was examined in relation to the initial ductile to brittle transition temperature, and an attempt was made to evaluate the effect of hydrogen on the yield stress and cohesive properties of vanadium. MATERIAL AND PROCEDURES Sample Preparation. The vanadium used in this investigation was prepared by the iodide refining process described by Carlson and owen.' Three ingots, 3 in. diam by 6 in. long, were cold-swaged to 0.096 in. diam, cut into short lengths, and then arc-melted under purified argon into one ingot. This process was repeated to insure a uniform composition in the final ingot. Chemical analysis of the metal is given in Table I. On the basis of work of Loria et a/ .' the following sequence of treatments was performed in order to obtain a uniform equiaxed ultimate grain structure: a) cold swage q-in.-diam ingot to 0.230 in. diam; b) anneal 6 hr at 1000°C in vacuum; c) by cold swaging reduce 81 pct in area in three steps: 0.230 to 0.187 in. diam, 0.187 to 0.150 in. diam, 0.150 to 0.096 in. diam. This sequence provided the desired grain structure after subsequent annealing treatments. Because annealing in evacuated quartz capsules resulted in contamination by oxygen, all anneals in this investigation were performed in a 304 stainless-steel chamber under a dynamic vacuum of 10- I Torr with the vanadium wrapped in tantalum foil. Prior to all annealing treatments the wires were electropolished for 1 min at 16°C in an 80 pct methanol-20 pct sul-furic acid electrolyte at 12.5 v. Following the final reduction the 0.096-in.-diam wire was cut into 2-in. lengths. A 1-in. gage section was reduced to 0.090 in. diam by electropolishing as above. Five different grain sizes were obtained by annealing the 2-in. samples at different temperatures for 8 hr to insure uniform grain size and residual hydrogen removal. The annealing temperatures used and the resulting grain sizes are given in Table 11. The final step in sample preparation was to charge half of the specimens of each grain size with hydro-

Jan 1, 1969

By Vard H. Johnson

IN 1943 the U. S. Bureau of Mines undertook drilling in an effort to develop new reserves of coking coal in an area near Paonia, Colo., as a part of an attempt to alleviate the shortage of known coking coal of good quality in the western United States. Geologic mapping of the area was undertaken by the U. S. Geological Survey with the purpose of first furnishing guidance in location of drillholes and later aiding in interpreting the results of the drilling. The drilling program was under the general supervision of A. L. Toenges of the U. S. Bureau of Mines. J. J. Dowd and R. G. Travis were in charge of the work in the field. Geologic mapping was started by D. A. Andrews of the Geological Survey in the summer of 1943 and was continued from the spring of 1944 to 1949 by the writer. The first few holes drilled failed to locate coking coal, but in the summer of 1944 coking coal was discovered by drilling 6 miles east of Somerset, Colo., the site of present mining. In the succeeding years, 1945 to 1948, 100 to 150 million tons of coal suitable for coking were blocked out by drilling. The ensuing discussion of the geologic controls on the distribution of coking coal in the area is based on the geologic mapping as well as the drilling done in the Paonia area, more complete descriptions of which have appeared or are in process of publication."' In order that the possible geologic controls affecting the present distribution of coking coal may be considered, it is necessary to discuss briefly the indicators of coking quality coals. Coking Coal Coal that cokes has the property of softening to form a pastelike mass at high temperatures under reducing conditions in the coke oven. This softening is accompanied by the release of the volatile constituents as bubbles of gas. After release of the contained gases and upon cooling, a hard gray coherent but spongelike mass remains that is referred to as coke. This substance varies greatly in physical properties and, to be suitable for industrial use, must be sufficiently dense and strong to withstand the crushing pressure of heavy furnace loads. Western coals have a generally high volatile content and therefore form a satisfactory coke only when they attain a rather high fluidity during the process of heating arid distillation in the coke oven. When this high degree of fluidity is developed, the volatile constituents escape and leave a finely porous coke. On the other hand, when the degree of fluidity is low the product is an excessively porous and therefore physically weak mass that is called char." Small quantities of oxygen present in coal are believed to decrease the fluidity of the material during the coking process and to favor the development of char rather than coke. In consequence, coal chemists have for some time considered the possibility of developing an index to coking qualities by inspection of chemical analyses of coals.' A formula has now been developed that does permit a rough preliminary estimate of the cokability of coal on the basis of the analysis on an ash and moisture-free basis. Coals may be eliminated as possible coking fuels if the oxygen content is greater than 11 pct. Similarly the ratio of hydrogen to oxygen must be greater than 0.5 and the ratio of fixed carbon to volatile constituents must be greater than 1.3. If the coal, on the basis of these limiting factors, appears to have possible coking qualities, the following formula permits determination of the coking index: a+b+c+d Coking index = -------- 5 a equals 22/oxygen content on ash and moisture-free basis, b equals two times the hydrogen content divided by oxygen content on moisture and ash-free basis, c equals fixed carbon/l.3 x volatile matter, and d equals the heating value on moist, ash-free basis/13,600. Coking indices higher than 1.0 suggest that the coal will coke, and indices above' 1.1 indicate good coking tendencies. Although generally usable, this formula 'is not completely satisfactory because the percentage of oxygen shown in ultimate analyses is derived only by difference; i.e., by subtracting the sum of the percentages of the constituents determined analytically from 100 pct. Although the coking index indicates the coking tendencies of coal, it is necessary to make physical tests of coke before its industrial value can be determined. The U. S. Bureau of Mines has developed a standard procedure for determining the approximate strength of coke that would be formed from a given coal. In this test one part of ground coal, mixed with 15 parts of carborundum, is baked to form a standard briquette. The weight, in kilograms, necessary to crush the briquette is termed the agglutinating index. This test determines the relative fluidity attained in the coking process by measuring the cementing strength of the coal in the briquette. A

Jan 1, 1953

By E. P. Burtchaell

A method is presented for evaluating the effect of gravity drive upon the reservoir performance of a high relief pool. Conventional forms of reservoir analysis do not consider the alterations in the basic material balance data caused by gravity segregation of reservoir fluids. A procedure is outlined for structurally weighting physical and chemical data for use in the material balance equation. It is demonstrated how actual pool performance data can be utilized to evaluate the future reservoir performance of a gravity drive pool. INTRODUCTION Conventional reservoir engineering. procedure is inadequate for the analysis of an oil pool which has considerable structural relief, steep dips, and good permeability development. In, pools of this type, gravity drainage has an important part in the movement of oil to the wells and the effects of gravity on the overall pool performance should be included in any analysis of reservoir behavior. Many engineers have the opinion that the force of gravity in the movement of oil is not important until the later life of a pool.' Probably the basis for this belief is that gravitational effects may not be readily discernible until a pool is nearing depletion. This would be especially true for pools not having a high degree of structural relief and permeability development. Actually the effects of gravitational forces are at a maximum when the pool pressure is high, for during this period the hydrostatic head of the oil column is at a maximum and the viscosity of the oil is at a minimum. Oil recoveries from pools having favorable gravity drive characteristics may equal or even exceed recoveries which might be expected from water displacement. Field evidence indicates that in some reservoirs gravity drive has resulted in recoveries greater than that which could have been expected from gas expansion or water drive.'.3 Unfortunately, the possible effects of gravity drive on pool performance have been underestimated and other reasons have been sought to explain the high recoveries obtained. There are unquestionably many reservoirs to which the principles of gravity drainage can be effectively applied. It is the purpose of this paper to illustrate one method whereby gravity drive is included in the reservoir analysis of an oil pool. A hypothetical pool, typical of many California reservoirs, is used as an example. As used in this paper, "gravity drive" is defined as the overall effect of gravitational influences on the recovery of petroleum from the reservoir; "gravitational segregation" as the gravity separation of oil and gas within the reservoir; and "gravity drainage" as the downward movement of oil as caused by the force of gravity. SAND VOLUME DATA Fig. 1 presents a structural contour map of the pool under study. Maximum closure is 1950 feet with dips on the south flank approaching 45". The original gas-oil interface was set at -5200 feet. Average thickness of the producing sand was 200 feet. For use in subsequent calculations ill this paper, the pool was subdivided into 100-foot vertical increments and the sand-volume content of each increment was obtained. If the gross sand thickness is small, under 100 feet, the sand-volume content can be obtained by superimposing an isopachous map upon a structural contour map and planimetering the average thickness of each 100-foot increment. For sand thicknesses over 100 feet, one approacli would be to construct a sufficient number of cross-sections of the pool from which the weighted sand-volume of each 100-foot increment could be obtained. Variations in the sand body with depth, as determined by core data, can also be included in the above process. Table I presents a summary of sand-volume calculations, core data, and the original distribution of reservoir hydrocarbons in the pool. Fig. 2 illustrates the structural distribution of the sand-volume content. A total of 171,398 acre-feet is contained within the productive limits of the pool. Assuming an average porosity of 25% and an interstitial water content of 20%, the original hydrocarbon content was computed to be 227,075,000 barrels. DEPTH-PRESSURE DATA The determination of the initial vertical pressure arrangement in the pool is necessary for PVT and material balance calculations. Whenever sufficient data are available, a plot of pressure versus subsea depth of measurement should be made. From this plot a representative fluid pressure gradient can be established. Lacking sufficient initial pressure data, an initial pressure gradient may he estimated or calculated from avail-

Jan 1, 1949

By David C. Russell

The Department of the Interior used to be a quiet, noncontroversial, almost boring agency. It, after all is the fifth oldest of the Departments, and as an old line Federal agency it has studiously performed its preservation and resource management functions in a caretaker mode--though some would say more "undertaker" than "caretaker"--locking up the body and soul of America piece-by-piece. Yes, quiet, serene. That is until Jim Watt showed up. And we have all seen that version of Mt. Vesuvius which resulted--only it was the environmentalists who blew their tops. Ronald Reagan chose Jim Watt as Secretary of this fine old agency to prove that one-third of our Nation's land and over a billion acres on the Outer Continental Shelf can work for this Nation. At the foundation of President Reagan's charge to Secretary Watt is a belief in the tenets of the free enterprise system, and in the individual freedoms upon which this country was founded. There are those who don't share this belief in democracy and free enterprise, and those who believe this 205 year experiment called the United States of America will fail. Nikita Krushchev said "we will bury you"--obviously he didn't agree with our system. An Italian sociologist, Franco Ferrorotti, said bureaucratic stagnation will kill capitalism. Certainly we have all felt the ravages of bloated bureaucracies. Perhaps one indicator in the United States is the Federal Register, that daily compilation of Government's largesse. In 1970, 20,000 pages of the Federal Register were published. A decade later, in 1980, that volume had quadrupled to 80,000 pages. The Federal bureaucracy can stagnate from excessive budgets as well. The Interior Department spent $60 million on administering Federal coal leasing in 1981. That's nearly two bits a ton for every ton of coal leased in 1981. You wouldn't stay in business very long if your administrative overhead on inventory was that outrageous. But the pessimism of our critics is apparent from more than red tape and bloated budgets. For decades America has been fasting--consuming too little of America's wealth of minerals, subsisting instead on a diet heavily reliant upon mid-east oil, with little emphasis or concern for inventorying and developing domestic energy and mineral resources. Economics--yes. But short-term, short-sighted economics. Excessively dependent upon foreign imports, of oil, cobalt, chrome and other strategic minerals, the U.S. measures its time before another embargo--or fallen Shah, or Soviet manipulation, or Saudi shift, or, as we witnessed in Egypt, assassination--an untimely loss to mankind and efforts to bring peace to the troubled mid-east. These disruptions, in addition to their tragic human tolls, impair the free world's security. Huge chunks of the United States have been locked away in dozens of single land use categories in the name of conservation, with only the foggiest idea of what resources might be denied the American people-and this at a time of unacceptable levels of energy and strategic mineral imports. More than half and perhaps two-thirds of all Government-owned lands are totally withdrawn from or severely restricted to development under the mining and leasing laws. We must continue to rid Government of the overly zealous restraints which have been keeping us from drawing upon that which can help restore our economy and national security. When we assumed responsibility, the United States was dependent on foreign sources for about 40 percent of its oil. In 1981, our oil import bill was approximately $83 billion--nearly 17 times what it was in 1972. Our reliance on foreign sources for essential minerals is even more disturbing. We must look to other countries--some unfriendly, some unstable--for 22 of 36 strategically critical minerals. Yet the energy resources on federal lands which are owned by the American people could meet our needs for centuries if properly managed. Eighty-five percent of the crude oil yet to be discovered in America is likely to come from public lands, as will 40 percent of the natural gas, 35 percent of the coal, 80 percent of the oil shale, nearly all of the tar sands, and substantial portions of uranium and geothermal energy. Our vast hardrock-mineral wealth includes untapped deposits of essential elements we now import, such as chromium, copper, platinum, and cobalt. The obvious question is, if these abundant resources can help to revitalize our economic strength and to preserve our national security, why aren't we using them to better advantage? To a large extent, the answer can be found in past decisions to restrict public access to the federal estate, thus deferring to us or our successors the tough decisions that flow from Congress' mandate to provide for environmentally responsible development of America's energy and mineral treasures. Here is the legacy this Administration inherited: In January 1981, 7 years after the onset of the Mideast oil embargo: ---Less than 15 percent of federal onshore lands were under lease for oil and gas development; ---No oil and gas leases had been issued in Alaska for 15 years;

Jan 1, 1982

By Jerry L. Straalsund, D. Bruce Masson

A dew-point technique was used to determine the thermodynamic activity of zinc at 430°C in a series of e phase Ag-Zn alloys. The composition of the alloys ranged from 72 to 88 at. pct Zn. This range included the composition at which Massalski and King3 found a reversal in the composition variation of the crystallo-graphic c/a ratio, which they attributed to an overlap of the Fermi surface across the (002) faces of the Brillouin zone. The data is presented in a graph in which RT In yz,, where yz, is the activity coefficient of zinc, is shown as a function of atomic percent zinc. This curve has an unmistakable change in slope at the same composition that Massalski and King observed the beginning of the reversal in the c/a ratio. This change in slope of the thermodynamic data is also attributed to a Brillouin zone overlap. Equations are presented to demonstrate that the thermodynamic activity can be related to the density of states of the conduction electrons, and that the observed phenomena are consistent with this model. It is also demonstrated that the contribution of the density of states can be related to the excess stability, a phenomenological parameter recently shown by Darkeen" to be significant in the interpretation of thermodynamic data of metallic phases. The data seem to indicate that zone overlap has caused a spinodal point, and the resulting misci-bility gap, in the phase diagram. THE problem of developing an adequate thermodynamic model of solid solutions has proven to be difficult, and is still only partially solved. The main approach has been to develop a statistical model, such as that of an ideal solution, regular solution, and so forth, to which can be attached corrections for electronic, vibrational, magnetic, ordering, or other contributions. Such corrective terms are usually derived on an ad hoc basis, and it is difficult to predict in advance what their relative importance will be. This problem has been discussed in general terms by Oriani and Alcock,' who have reviewed several thermodynamic models and a few empirical correlations. The measurements described in the present paper were made to demonstrate in a special case the importance of one such corrective term, the contribu- tion of the energy of the conduction electrons of an alloy. It was our premise that the contribution of the energy of the conduction electrons to the thermodynamic activity of the alloy components could be detected; further, that such an effect would be observed at alloy compositions where other phenomena, also ascribed to the energy and density of states of the conduction electrons, are observed. The idea of the importance of the conduction electrons is hardly new. Hume-Rothery and his adherents have developed the well-known theory of alloy phases in which the sequence of phase fields in binary equilibrium diagrams, especially those involving the noble metals with the IIB, IIIB, and IVB subgroups, can be correlated by replacing the composition variable with the ratio of conduction electrons to atoms, e/a. Jones and others have developed a physical explanation for this correlation, in which they consider the solubility limits of phase fields to be restricted by an intersection between the Fermi surface and a Brillouin zone. The general features of the model are also quite well-known—presumably zone intersection causes the density of states to decrease at critical alloy compositions. The attendant increase in energy of conduction electrons in the original crystal structure allows an alternate structure to become more stable as the concentration of polyvalent solute is increased. In spite of the wide acceptance of these ideas on phase stability, there is only indirect* evidence, such as the variations in lattice parameter recorded extensively by Massalskizy3 and others, that Brillouin zone interactions occur. There are few experimental measurements, other than the correlations of the phase sequence, that substantiate the premise that the energy of conduction electrons affects the solubility limits of alloy phases. Much thermodynamic data of alloys has been found to be consistent with the theory; yet there is a lack of detailed data at compositions where zone intersection and overlap are thought to occur. One would expect that the energy of the conduction electrons would make a measurable contribution to the thermodynamic properties of alloys at compositions near zone intersection and overlap if the theory of Hume-Rothery and Jones is correct. This conclusion cannot be avoided, because the phase boundaries are determined by the requirement that the chemical potential of the components be equal in both phases at equilibrium. An electronic effect large enough to alter the stability of a phase should also affect the thermodynamic activity by a measurable amount.

Jan 1, 1969

By Aureal T. Cross

THIS paper is a review of the published literature on research in coal geology, principally exclusive of resource studies, which appeared or became available during 1950 and the latter part of 1949. This report is not to be construed as being complete. The papers referred to in the bibliography are those among many more, which were read either in full or in abstract. Undoubtedly other papers were published which either escaped the author's notice or were not available to him. Those which were seen in abstract only (about one fourth of those listed) were not available in time for the inclusion of more than a notice. An outline of all papers listed in the bibliography has been arranged by subjects and reasonable subdivisions with some papers cited under more than one subject. Most papers are indexed according to the principal subject of discussion or research only as to an unusual or noteworthy section of the entire report. There will likely be some disagreement as to the quality or merit of some of the papers selected and the specialist may be supercritical of the outline or organization of papers in his field. It may be that attention has occasionally been drawn to papers reporting old information or conclusions of questionable value. Conferences and Meetings One of the best indications of the growing interest in coal geology problems in the United States is the increasing number of times this field has been the focus of attention at conferences and meetings. Notable among these are the joint meeting of the Society of Economic Geologists and the Geological Society of America at El Paso, November 1949, at which the principal thesis was concerned with low rank carbonaceous fuel deposits, especially of western United States. Among the papers given which are already available were those presented by Barghoorn,'" Parry? Roe? and Parks."' At the annual meeting of the Botanical Society of America in New York, December 1949, a joint meeting of the Paleobotanical and Microbiological Sections was held for which a symposium on Microbiology in Relation to the Geologic Accumulation of Organic Complexes was organized. Publication of the six papers presented by Ralph G. H. Siu, Elso S. Barghoorn, Irving Breger, Claude E. ZoBell, James M. Schopf, and A. C. Thayson is anticipated. At the regular meetings of the Paleobotanical Section at the same time, several other papers of interest reported on coal ball studies, partial coalification of petrified wood, and floras. In Chicago, April 1950, a symposium on Applied Paleobotany was held by the Society of Economic Paleontologists and Mineralogists in conjunction with the American Association of Petroleum Geologists. The five papers presented at this meeting dealt with the use of Paleozoic plant microfossils for stratigraphic work, J. M. Schopf, Devonian-Missis-sippian fossils of the black shales, Aureal T. Cross, Mesozoic plants of stratigraphic value, Th. Just, plant microfossils of the Tertiary, L. R. Wilson, and studies of the Brandon lignite, Elso S. Barghoorn. Early publication of these in the Journal of Paleontology is expected. The Nova Scotia Research Foundation and the Nova Scotia Dept. of Mines sponsored an excellent 3-day conference in June 1950, which dealt with several aspects of coal geology. Papers on coal classification, P. A. Hacquenbard, structure and sedimentation problems in Nova Scotia, T. B. Haites, new techniques of thermal analysis, W. L. White-head, geochemical investigations of Nova Scotia coals, Irving Breger, the role of fossil plant spores in coal correlation and the stratigraphy of the coal-bearing strata of the Appalachian Region, Aureal T. Cross, were given. Some discussions of these papers by those in attendance were recorded, and the entire proceedings is being prepared for publication. In September 1950, an unusual 3-day field conference was held by the Ohio and West Virginia Geological Surveys under the sponsorship of the Coal Geology Committee. This study of the stratigraphy, sedimentation, and nomenclature of the Upper Pennsylvanian and Permian coal-bearing strata of southeastern Ohio, southwestern Pennsylvania, and northern West Virginia was augmented by two discussions on associated rocks (clays and shales) and stratigraphic nomenclature at Wheeling and Morgantown, West Va. An extensive guidebook was prepared, and transcriptions of the Morgantown meeting were made. As a follow-up of the September field conference, a round-table discussion was held on this general topic at a special open meeting of the Coal Research Committee in conjunction with the November meeting of the Geological Society in Washington. Short prepared statements to invite discussion were given on each of several topics by L. M. Cline, Carl 0.

Jan 1, 1953

By T. L. Joseph

It is a distinct privilege to participate in this meeting convened to honor the memory of Henry Marion Howe, a distinguished scientist and metallurgist. Many have added to our rapidly growing fund of metallurgical knowledge but few have made the unique contribution of formulating basic concepts essential to an over-all comprehensive view of the subject of metallography. Of those previously selected to deliver this lecture, several have added a personal touch to their discourse because they were able to refer to their associations with Dr. Howe. It was not my good fortune to know him or to enjoy his inspiring influence. Like most of you, my contact has been with his published works, which are outstanding in that they provide lucid, detailed expositions of the nature and behavior of metals and alloys. His deep understanding and clarity of expression have greatly accelerated our progress in metallography and in the use of metals. The degree to which a man's thinking, experimentation and writing contribute toward an understanding of basic laws and phenomena determines whether his life's work is of transitory or permanent value. This occasion appropriately recognizes the fundamental importance of Dr. Howe's pioneer work in the field of metallurgy.. On two former occasions, gray iron was selected as a subject for discussion. The fact that the production of pig iron has not been discussed before does not reflect any lack of interest on the part of Dr. Howe or former lecturers in the process that underlies the production of steel. Although Dr. Howe's work in his later years centered around metallography, his earlier publications show a considerable interest in the production of iron and steel. He recognized that in the ascending spiral of metallurgical advancement we are not winding a single thread but are weaving a complex fabric. Specific evidence of his interest in the production of pig iron may be found in his book' on The Metallography of Cast Iron and Steel. In explaining why blast furnaces have been in constant use for about 600 years, he says: "The process is economical because it utilizes with extraordinary completeness the calorific power of the coke due to the thorough transfer of heat from the gaseous products of combustion to the charge." This emphasis on heat transfer, overlooked in many more extended and more recent discussions of the blast-furnace process, illustrates Professor Howe's ability to see the essentials. Other distinct advantages of the blast furnace, such as the removal of- much of the sulphur and practically all of the oxygen, were mentioned. It was also stated that although the blastfurnace process is complex in nature, its outward form is comparatively simple, thus permitting large-scale production at small labor costs. All who contemplate the production of metallic iron from its ores by any other process might well consider the

Jan 1, 1947

By Frederic L. Kadey

Perlite, as a volcanic glass, has been recognized since the Third Century, B.C. (Langford, 1978). The precise details of discovery often become lost in antiquity, and the variations among the stories pertaining to the more recent discovery of perlite as a material of commerce are no exception. Credit in the United States is given to a dentist who, while experimenting with tooth enamels about 1941, discovered that perlite-the rock-intumesced when subjected to heat. At about the same time it is reported that the chief geologist of Silver and Barytes Ores Mining Co. attempted to put out a picnic bonfire on the shores of Milos Island, Greece by throwing beach sand on it. The ensuing pyrotechnic display immediately conjured up in that man's mind the possibility of a new use for the volcanic rock that constituted most of the island. Very little was done with this discovery either here or abroad until after World War II. Today the name perlite is applied to both the hydrated volcanic glass, generally of rhyolitic composition, and to the lightweight aggregate that is produced from the expansion of the glass after it has been crushed and sized. Petrologically, it is defined as a glassy rhyolite that has a pearly luster and concentric, onionskin parting. Occurrences of perlite are restricted to several Tertiary to Quaternary age rhyolitic belts that trend in a generally north-south direction around the world. Commercially suitable deposits generally occur as domes of several hundred feet in height, although glassy zones in welded ash-flow tuffs and others associated with dikes and sills also have been reported. Mining is by ripping and blasting from open pits. Because of weight considerations, perlite usually is shipped to the local market area for subsequent expanding. In the United States, New Mexico leads in production with Arizona, California, Nevada, Idaho, and Colorado following in approximately that order. The principal use for expanded perlite is as a lightweight insulating aggregate in cryogenics, in plaster, concrete, and in loose fill insulation. Expanded perlite is also used in horticultural applications, and after subsequent milling and classification, as a filter aid. The United States is the world's largest producer and consumer of perlite. Table 1 shows the world production of perlite and Table 2 shows the perlite mined, processed, expanded, and sold or used by producers in the United States. Geology Composition and Morphology Any discussion of perlite must take into consideration its dual nomenclature, for it is known by the same name as both the naturally occurring rock and, after processing and expansion, as the lightweight aggregate of commercial significance. In its naturally occurring form, perlite is a rhyolitic glass that contains from 2 to 5% combined water. While perlite also can occur as andesitic or dacitic glass, these latter types are of negligible commercial significance. Table 3 lists the chemical composition of a few typical perlites (Anderson, et al., 1956; Langford, 1979). What sets perlite of commercial significance apart from other volcanic glasses is the fact that under the proper conditions of preparation-crushing and sizing-it will, when rapidly introduced into a flame of sufficient temperature, expand or "pop." All of the elements of composition contribute to the expansibility of the rock. The role of the combined water, however, is the most significant because it is believed not only to produce a fluxing effect in the softening of the highly siliceous glass prior to expansion, but it is also responsible for the explosive force of expansion through volatilization during heating. The current theory of the origin of the water in perlite is now less con-

Jan 1, 1983

By Samuel H. Dolbear

THE value of a mine is basically dependent on its capacity to yield profits. Since the ore must be mined, treated, and sold, some of it in various future years. there is a risk involved as to future costs, selling price, and working conditions. It cannot be expected that the economic condition existing at the time of valuation will continue unchanged for long periods in the future. During the past 20 years, mineral production in the United States has been conducted under a changing economy in many respects more exacting than that applied to other businesses. There have been increased production incentives, technical aid, exploration of privately owned mineral deposits by government at federal expense, and liberal loans for development and equipment, with risk partially assumed by government.. Some of these benefits have been counterbalanced by price ceilings, consumption controls, and stimulation of competition from foreign producers who have been offered the same advantages extended to American operators. For the present, mines will operate under a government policy directed toward reducing federal aid and control. The tenure of this change will depend upon future elections and the status of foreign relations. War and threat of war are now of the most vital significance to the mineral industries. Other factors which influence cost of production, markets, and price of mine output might be classified as Acts of God or Acts of Government. In some countries expropriation and the difficulty of exporting earnings or investment returns are risks that must be considered by foreign capital. Recognizing that this retards American investment in foreign countries, the Mutual Security Agency offers insurance against such expropriation and guarantees the convertibility of capital and profits. Since it is impossible to predict with certainty either cost of production or selling prices of metals for long periods, some assumptions must be made as to profits in the future. The basic assumption must be that the price of the company's product will vary in proportion to changes in operating cost. There is often a lag in this reaction, however, for prices of minerals are generally more sensitive to declines and less sensitive to increases than are costs. This reflects in part the resistance of labor to downward wage revision and a corresponding alertness in realizing its share of price advances. Some labor contracts include automatic adjustments to metal prices. Notwithstanding the complexity of the, problems involved and the difficulty of weighing their effect on value, such risks may be appraised with reasonable accuracy and a rate of earnings adopted that is compatible with the risk. It is, of course, possible to revert to a yardstick of value such as the commodity dollar, which has been advocated from time to time, but while revaluation in 1933 disturbed public confidence, the theoretical gold dollar continues to be the standard of greatest stability. Its gain or loss in purchasing power is reflected ultimately in cost of production and selling price of the mine product. At present 35 dollars are allocated to one ounce of gold. Measurement of Risk In the application of the Hoskold and most other formulae, a yearly dividend rate commensurate with the risk involved is set aside out of annual earnings. If the risk is great, this rate may be 15 to 25 pct of the amount invested. The remainder is placed in a sinking fund invested in safe securities such as high grade bonds or conservative equities, and the interest or dividends from these securities are added to the sinking fund. The sum of these sinking fund payments and the compounded interest at the end of the mine life is taken as the value of the mine. Admittedly the decision as to the size of the risk rate is the most difficult element in valuation and one requiring the most exacting consideration. It is necessary to look years ahead in an effort to determine future costs, market prices, demand, competition which may develop, including that of substitutes, and other influences common to the mine and to the region in which it is situated. Another phase of risk is the enactment of unfavorable legislation, taxes, and what appears to be an alarming spread of nationalization and expropriation. Capital is sometimes borrowed from the government to finance strategic production. Such loans may be collectable only out of production and involve no liability otherwise. Valuation in these cases must recognize the effect of such a reduction in liability. Offsetting some of these risks are the possibilities of mechanization and other cost-reducing discoveries, improvements in mining and treatment methods, new uses for minerals and metals, and normal growth of markets. In this paper, the terms risk rate, dividend rate, and speculative rate are synonymous. Safe rate and redemption rate are also used interchangeably. These alternatives are used here because they are commonly found in the literature on mine valuation. In Michigan, the State Tax Commission has long employed a risk rate of 6 pct in its valuation of iron mines. There the outline of reserves is well established and operating costs and conditions are based on adequate experience. The following comment on rates appears in the report of the Minnesota Interior commission on Iron Ore Taxation submitted to the Minnesota Legislature of 1941.1 Most engineers agree that 7 percent for the specu-lative rate is "an absolute minimum". C. K. Leith in

Jan 1, 1954

By J. Ruben Velasco, Roland B. Mulchay

CANANEA has long been recognized as a remarkable field for geologic study. The copper deposits and rocks of the district have been described by many geologists and engineers, but only the most general correlations have been made between Can-anea sedimentary rocks and other known sedimentary sections in the southwestern United States and northern Mexico. The present paper describes the Cananea sediments in greater detail than has been done before and attempts to fit the Cananea sedimentary section more closely into the geologic time table. The lack of well-preserved fossils has made it difficult to date the sediments accurately in geologic time, but it is possible to make tentative correlations between the Cananea sediments and the southeastern Arizona sections, based largely upon lithology and general position in the geologic column. It appears that sedimentation at Cananea and Bisbee may have been closely similar during Paleozoic time. Even such generalized correlations, however, may be subject to considerable modification in the future. The present study has led to the recognition of other problems of age and mineralization relationships in the Cananea district. Cananea is located in the north-central part of the state of Sonora, Mexico, at an elevation of 5270 ft. It is about 135 miles northeast of Hermosillo, the state capital, and 25 miles south of the international boundary. By road Cananea is 40 miles from the twin towns of Naco, Ariz., and Naco, Sonora, and about 50 miles from Bisbee, Ariz. It is served by the Nogales-Naco branch of the railroad, F.C. Pacifico, and is connected with Chihuahua and Mexico City by the Aeronaves airline. The headwaters of three rivers flowing to the Gulf of California are located in the Cananea Mountains: the San Pedro River, flowing to the north; the Sonora River, flowing south and west; and the Mag-dalena River, flowing west. Elenita Mountain, the highest point in the district, has an elevation of 8140 ft. The Cananea Mountains extend in a series of north-south to northwest-southeast spurs and ridges and are surrounded by gently sloping gravel plains. The mineralized area, lying across the southern and central parts of the range, is about 6 miles long and at most 2 miles wide. Elevations at the mines vary from 5300 ft at Cananea-Duluth mine at the southeast end of the district to between 6000 and 7000 ft at the west end of the mineralized area at Puertecitos-Elenita mines. Principal production has been from the intensely mineralized and altered area of Capote Basin in the central part of the district and the immediately surrounding area to the southeast. The district has produced over 2 billion lb of copper, substantial molybdenum, and minor amounts of lead, zinc, silver, and gold. Total production through 1949 is estimated at more than $300 million. In 1900 large-scale development was started at Cananea by W. C. Greene. Until World War II only high-grade ores were exploited; low-grade ores were extracted after the installation of a large concentrator in the early 1940's, and subsequent operations have been based upon mining and processing ores containing less than 1.0 pct copper from open-pit and underground workings. Mining and concentration of such low-grade ores, however, are made possible only by continued high copper prices, and active exploration for high-grade orebodies has been continued throughout the important mineralized areas. General Geology Study of the involved rock pattern at Cananea has indicated a complex geologic history for the district. Widespread alteration and mineralization have masked many of the salient features and have led to widely varying geologic interpretations over the years. Further work will probably disclose new information which will modify current beliefs. At Cananea a conformable series of sediments of probable Paleozoic age was deposited on an unknown basement. Following Paleozoic time there was an extended period of erosion common to many districts in the southwestern U. S., and there is no present evidence of marine sedimentation at Cananea after the Paleozoic. The eroded surface was eventually covered with a great thickness of extrusive volcanic rocks. The entire series of sediments and volcanic rocks was later intruded by a variety of deep-seated igneous rocks. These included the Cananea granite, the Cuitaca granodiorite, the El Torre syenite, the Tinaja diorite, the Campana diabase and gabbro and the Colorada rhyolite quartz porphyry. Faulting of early age, probably prior to the deposition of the volcanic rocks, may have been responsible for the present position of some of the intrusive rock masses. In the Capote mine on the third and fourth levels the northwest-striking Rick-etts fault zone, with apparent offset of about 800 ft, has been sealed by a dike-like mass of Cananea granite which gradually increases in size with depth. In lower levels of the mine the granite forms a large southeast-plunging mass generally following the course of the Ricketts zone. The granite is not known southeast of the Capote-Oversight mine areas and the Ricketts fault does not appear in the vol-canic~ southeast of Capote Basin, but several plugs of Colorada quartz porphyry cut the volcanics along the assumed general southeast trend of the Ricketts zone. These porphyritic intrusives may be the up-

Jan 1, 1955

By E. A. Ernst, N. F. Carpenter

The benefits derived from an acidizing treatment are a function of the penetration achieved by the acid before complete spending. Additional penetration may be achieved by (1) controlling acid leak-08 into formation pores in the channel faces, and (2) retarding the reaction rate of the acid. A recently developed chemical additive consists of a synthetic polymeric material which absorbs hydrochloric-acid solutions, when suspended therein, swelling up to 40 times its original volume. These swollen particles have the ability to deform and seal-08 formation pores, providing fluid-loss control. In addition, they provide a diffusion barrier between the fracture face and the acid solution, prolonging the spending time of the acid. Field applications of this new technique have shown promising results. A method of conducting acid fluid-loss tests, using carbonate cores, is believed to provide fluid-loss data that are more representative of formation conditions than the conventional filter-paper determinations. INTRODUCTION The concept of oilwell acidizing has changed since its first commercial application, 30 years ago. Originally, it was visualized that the acid penetrated thousands of tiny pores and flow channels in the matrix rock, enlarging them by dissolving the carbonate walls. The resultant permeability increase was assumed to be the responsible factor in increasing production from the well. Recent laboratory studies,' however, have shown that this does not provide the complete picture. Although this type of individual pore penetration by the acid does take place during acid "soaks", designed to overcome "skin effect" due to mud invasion in the immediate vicinity of the wellbore, many years of experience have shown that considerable pressure is required to attain any appreciable injection rate into the fine capillary pores of the rock. During most acidizing treatments, the bottom-hole pressure build-up due to the restriction of flow into the formation exceeds the "breakdown" pressure of the rock so that a fracture is induced. In most cases, such fractures open up along natural, incipient fissures and zones of weakness in the rock and, therefore, tend to follow the natural stress pattern of the rock—whether it be horizontal, vertical or inclined. Because of the comparatively greater permeability of the channel in relation to that of the matrix, the bulk of the acid volume is diverted into the newly opened fracture. Here it quickly penetrates the formation, opening and ex- tending the fracture in much the same manner as a conventional fracturing fluid. Unlike the fracturing fluid, however, most acidizing solutions contain no propping agent; thus, the open fracture will again close when the injection pressure is relieved. Laboratory studies2 have shown that in many cases the etching of the fracture faces, resulting from the reaction between the acidizing solution and the carbonate rock, is nonuniform due to the heterogeneity of the rock structure. As a result, the two fracture faces no longer match when pressure is released, and support pillars and intermediate voids remain, forming a high-conductivity channel for well fluids. Unfortunately, this is not true over the entire area of the fracture, but only over that portion of the fracture where the rock has been partially dissolved by the acid. The acid solution spends as its travels away from the wellbore; once it has completely spent, even though it may provide additional mechanical fracture extension, no additional benefit due to etching of fracture faces can be expected. Studies of acid reaction rates under formation conditions,3 observing the effect of different variables upon spending time, have shown that the reaction was often so rapid that very little penetration of the formation occurred before the acid was spent. Study was undertaken to devise methods of increasing the penetration of the acid before spending, so as to provide greater benefit from the acidizing treatment by etching a greater portion of the fracture faces. Several techniques were devised to accomplish this purpose. First, chemical additives were developed which were designed to retard the reaction rate of the acid, causing it to penetrate a greater distance from the wellbore before finally becoming spent. Another method was to increase the injection rate of the acid. However, it was found that the resultant increased shear tended to accelerate the reaction rate of the acid, partially offsetting the benefits of the higher injection rate insofar as achieving increased penetration before spending was concerned.' Another approach to the problem of achieving increased penetration was the development of fluid-loss additives for acid solutions, which would minimize the volume of acid lost into formation pores in the fracture faces and provide maximum fracture extension for the volume of acid injected during the treatment. The use of fluid-loss additives is now considered the most effective method of providing maximum fracturing-fluid efficiency.~ Unfortunately, this latter technique does not solve the problem of rapid reaction rate, with consequent limitation of the fracture area benefited by reaction with unspent acid. A newly developed acid additive overcomes many of these limitations by providing the dual benefits of fluid-loss control and mechanical retardation of acid reaction

By David R. Maneval, W. E. Foreman, J. Richard Lucas

INTRODUCTION The objective of this chapter is to inform the industry, as well as the public, of the challenges in dealing with the problems associated with the contamination of air and water from coal preparation plants. The need for an informed industry is most important. It is hoped that some contribution may be given to a more efficient and economical approach to the problems of plant waste contaminants at individual plants. The problem has many facets, and consideration to specific area should begin early before any significant problems develop at a given plant. It is then possible to have a reasoned approach before the pressures of an emergency environment force hasty and incomplete solutions. It will be necessary to anticipate these problems in the design of new preparation plants and advance consideration should be given to all the problems concerned with contaminants. The first part of the chapter will concern itself mainly with the contamination aspects of fine-coal cleaning and "black-water" disposal. Also attention will be given to the nature and formation of water from coal-mine drainage systems and the treatment of these waters for industrial use. Some attention will be devoted to the cost of installing and operating the various beneficiation systems for the removal of suspended solids. The second part of the chapter will analyze the problems of air contaminants from coal preparation plants. The nature and the effects of these contaminants and their potential for air pollution will be examined. One of the most critical is the measurement and analysis of these contaminants. As a result of identifying and determining the extent of the problem, better control can be planned. One of the most serious contaminants in air involves the element sulfur, and its elimination as a source of air pollution is one of the most challenging areas in coal preparation today. The last part of the chapter will emphasize the long-range problem of refuse disposal and control. Minimum operating and maintenance costs are functions of the proper selection and geometry of refuse disposal areas. Disposal procedures are varied but must be rigidly pursued or difficulties will result. Maintenance of refuse areas, including monitoring of burning refuse, is critical. It should be recognized that fine-solid refuse disposal systems must be carefully designed to minimize contamination. WATER CONTAMINANTS FROM PREPARATION PLANTS Pollution Aspects of Fine-Coal Cleaning and "Black-Water" Disposal The effluents from coal washeries and waters draining from plant-site surfaces inevitably contain fine coal and coal refuse materials in suspen-

Jan 1, 1968

By J. J. Frawley, W. J. Childs, W. R. Maurer

The object of this investigation was to determine the growth habit of bismuth and bisrrtuth alloy dendrites as a function of supercooling. To do this, techniques were developed to increase the amount of supercooling in bismuth and bismuth alloys. For pure bismuth, the growth habit was dependent on the amount of supercooling. At low amounts of supercooling, about 10" C, prismatic dendrites were obtained. With increased supercooling, about 20 C, a hopper growth habit was observed. In many cases where hopper growth had occurred, the hopper dendrites were twinned during the growth process. This twinned surface enable prismatic dendrites to nucleate and grow by a twin plane mechanism. When the amount of supercooling was increased to about 25 °C, the growth habit was a triplanar growth. With still greater supercooling, about 3s°C, a branched growth habit occurred. The exposed planes on the prismatic, hopper,, triplane, and branched dendrites have been determined. The growth habit of the dendrites which grew along the crucible wall was found to have the (111) as the exposed plane, with <211> growth direction. It is apparent that dendritic growth of a metal is dependent on its purity and the solidification variables present. One of the solidification variables is the degree of supercooling. Supercooling, although often observed, has not been studied extensively until recent years. For dendritic growth to occur in a pure metal, the metal must be thermally supercooled. After the dendrites grow into the supercooled melt, the heat of solidification raises the temperature of the specimen to the melting point of the material and the remaining liquid will solidify at this temperature. Decanting is the removal of this remaining liquid before complete solidification. This removal of the remaining liquid after recalescence had occurred is a great aid in the study of dendritic growth. In this investigation, decanting was accomplished by a vacuum-decanting technique . Other investigators1-5 have studied the growth characteristics of various low-melting-temperature pure metals and alloys as a function of supercooling. However, large degrees of supercooling were not included. For their study of dendritic growth of lead, Weinberg and chalmersl employed a decanting technique which was achieved by pouring off the remaining liquid, exposing the solid/liquid interface. This method was employed later by Weinberg and Chalmers2 for the investigation of tin and zinc dendrites. The method for obtaining a solid/liquid interface was improved by Chalmers and Elbaum. They employed a triggered spring which was attached to the solidifying section of the specimen. Upon activation, the spring jerked the solid interface away from the liquid melt. In the study of growth from the supercooled state, a metal of low melting point which exhibited a high degree of supercooling was desired. Bismuth gave very consistent supercooling when a stannous chloride flux was employed. The maximum supercooling obtained was 91°C, with an average supercooling of between 65" and 75°C. The consistency of supercooling greater than 50°C was very high. The use of vacuum to aid in the rapid decanting of molten metal has proven to be very successful in this investigation. The vacuum gives a rapid decantation, usually leaving the solidified metal structure sharply defined. The purpose of this investigation was to study the effects of supercooling and the effects of alloy additions on the growth habit of bismuth dendrites. The structure of bismuth has been variously defined as face-centered rhombohedral, primitive rhombohedral, and hexagonal. However, bismuth has only one plane with threefold symmetry, the (111) plane, and the crystal-lographic structure is considered a 3kn structure. MATERIALS The bismuth which was employed in this investigation was obtained from the American Smelting and Refining Co. of South Plainfield, N. J. The accompanying spectrographic analysis data indicated the bismuth to be 99.999+ pct pure. The tin was obtained from the Vulcan Materials Co., Vulcan Detinning Division, Sewaren, N. J. It was classified as "extra pure". Nominal analysis was 99.999+pct. In order to prevent contamination of the bismuth melt from the atmosphere, an anhydrous stannous chloride (Fisher certified reagent grade) was added to each melt. The fluxing action obtained from the use of the chloride provided a large amount of supercooling in the specimen. APPARATUS A 30-kw, 10,000-cps motor-generator set, connected to a 6+-in.-diam air induction coil, was employed to melt and superheat the specimens. The temperatures were recorded by means of a chromel-alumel thermocouple and a potentiometric recorder. The thermocouples were 0.003 in. in diam, and were encapsulated with Pyrex glass to prevent the thermocouple from acting as a nucleating agent and also from contaminating the melt. Fig. 1 illustrates the vacuum-decanting apparatus when a liquid flux was employed. A standard 30-ml Pyrex beaker was placed on top of an asbestos insulating block. A 5-mm-ID Pyrex tube with aA-in. spacer tip attached to its end was used for the decanting tube. The spacer tip contributed significantly to a successful decanting operation. The tip located the opening of the decanting tube about -^ in. from the bottom of the

Jan 1, 1969

By T. L. Joseph

It is a distinct privilege to participate in this meeting convened to honor the memory of Henry Marion Howe, a distinguished scientist and metallurgist. Many have added to our rapidly growing fund of metallurgical knowledge but few have made the unique contribution of formulating basic concepts essential to an over-all comprehensive view of the subject of metallography. Of those previously selected to deliver this lecture, several have added a personal touch to their discourse because they were able to refer to their associations with Dr. Howe. It was not my good fortune to know him or to enjoy his inspiring influence. Like most of you, my contact has been with his published works, which are outstanding in that they provide lucid, detailed expositions of the nature and behavior of metals and alloys. His deep understanding and clarity of expression have greatly accelerated our progress in metallography and in the use of metals. The degree to which a man&apos;s thinking, experimentation and writing contribute toward an understanding of basic laws and phenomena determines whether his life&apos;s work is of transitory or permanent value. This occasion appropriately recognizes the fundamental importance of Dr. Howe&apos;s pioneer work in the field of metallurgy.. On two former occasions, gray iron was selected as a subject for discussion. The fact that the production of pig iron has not been discussed before does not reflect any lack of interest on the part of Dr. Howe or former lecturers in the process that underlies the production of steel. Although Dr. Howe&apos;s work in his later years centered around metallography, his earlier publications show a considerable interest in the production of iron and steel. He recognized that in the ascending spiral of metallurgical advancement we are not winding a single thread but are weaving a complex fabric. Specific evidence of his interest in the production of pig iron may be found in his book&apos; on The Metallography of Cast Iron and Steel. In explaining why blast furnaces have been in constant use for about 600 years, he says: "The process is economical because it utilizes with extraordinary completeness the calorific power of the coke due to the thorough transfer of heat from the gaseous products of combustion to the charge." This emphasis on heat transfer, overlooked in many more extended and more recent discussions of the blast-furnace process, illustrates Professor Howe&apos;s ability to see the essentials. Other distinct advantages of the blast furnace, such as the removal of- much of the sulphur and practically all of the oxygen, were mentioned. It was also stated that although the blastfurnace process is complex in nature, its outward form is comparatively simple, thus permitting large-scale production at small labor costs. All who contemplate the production of metallic iron from its ores by any other process might well consider the

Jan 1, 1947

By W. J. Slatosky

W. 0. Philbrook (Cairiegie Institute of Technologyogv—Mr. Slatosky has presented an interesting and constructive paper that represents another step along the way of converting steelmaking from an art to a science. I am confident that his computer will be practical and successful and that with a very few months of experience it will provide a significantly better degree of control than his record of 65 pct of heats within range obtained with the slide-rule calculator . A paper such as this, with a lot of symbols and condensed mathematics, is difficult to comprehend quickly. Since I have had an opportunity to study it carefully, perhaps my evaluation of its validity and accomplishments will save time for others. Mr. Slatosky has correctly used standard principles of stoichiometry and heat balances, which are available to anybody, but he has also brought to them two original contributions: 1) He has developed from operating data some empirical relations for predicting the final FeO content of the slag (at 0.5 pct C end-point) as a function of slag basicity, lance height, and scrap, ore, and scale in the charge. This improves the accuracy of prediction of temperature or scrap requirement compared with assuming an arbitrary, constant FeO content at the end of each heat. There is no assurance yet that exactly the same relations will hold for other furnaces or practices, but similar correlations can be expected. 2) He has combined calculations that are ordinarily carried out laboriously as a number of individual steps into a single, simple linear equation that can readily be fed into a machine. This involved a tremendous amount of painstaking detail work as well as the imagination to see the possibility and work out the steps. While his particular Eqs. [3] and [6] are valid only for the furnace design, charge weight, and blowing time used at Aliquippa Works, only a few numerical values have to be changed to adapt it for other conditions. In order to arrive at a useable solution, Mr. Slatosky had to make some basic assumptions about the process that are similar to those used by others. He neglected variation in some process variables and assumed an arbitrary average value for waste gas analysis and temperature for want of more exact information at the present time. All of these judgments are clearly stated. In addition, some thermody-namic data presently available are not adequate for the job, notably in relation to heats of formation and sensible heat in slag, and some expedient has to be adopted to get around the difficulty. Other people might prefer slightly different judgments about these details and hence obtain somewhat different numerical solutions. This is not of serious importance, however, because the errors accumulate in the "heat loss" term and are largely self-compensating for a constant heat time. Although the extended Eq. l(a) in Appendix I was set up as a rate equation originally, for convenience in using an analogue computer as stated in the paper, the time dependence was removed by later mathematical manipulations and assumptions about the process. The final result is an integration of element and energy balances from initial to final states; this procedure is as legitimate here as in any other form of heat-balance calculation. The formal handling of stoichiometry and thermochemistry appears to be correct, and it is assumed that any arithmetical errors would have come to light in applying the calculations to furnace practice. Mr. Slatosky&apos;s approach is not necessarily unique, in that other people might start with apparently different equations or prefer another form of final equation for another type of computer. However, he has presented an accomplished result that appears to be a theoretically sound and practically useful way of applying scientific principles and rapid computation for better control of steelmaking. His success will undoubtedly encourage himself and others to improve on the mathematical model and its use as better informatioq becomes available. John F. Elliott (Massachusetts Institute of Teck-t2ology)-The last comment by Mr. Richards that a calculator is quite unnecessary for an L-D operation ?-equi??es a rebuttal. The L-D furnace is a very high capacity process which places a premium on close control. When one is making steel at rates between 100 and 200 tons per hr, one cannot afford the luxury of an extra 5 or 10 min at the end of a heat correcting for an error that should never have been made in the first place. Mr. Slatosky&apos;s paper is a very sound application of the simple principles of stoichiometry and the energy balance. It is a satisfactory and valuable start, but only the start of the development of methods of control for this process. An analysis of the process shows that it should be very suitable to control by a computer. This is especially the case when various grades of steel are to be made. In fact, it would seem that the organizations who are planning new and bigger installations of L-D vessels should consider carefully the advantages that would stem from computer control of a vessel with the operator present to do little more

Jan 1, 1962