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By J. R. Long, A. H. Roberson, T. R. Graham, R. S. Dean

EXPERIMENTAL work on the properties of high-purity alloys of the copper-manganese-zinc system has necessarily required extensive metallographic work to determine the equilibrium conditions in this system. Previous work on these alloys is fragmentary and, unfortunately, based on alloys made with impure grades of manganese, thus introducing significant amounts of iron, silicon, aluminum and carbon. Since these elements are known to affect equilibrium conditions, it became desirable to re-examine these alloys made from the pure metals. The alpha solid solution field was of particular interest and, therefore, was chosen for the initial work, which was outlined to determine the composition limits of this field. PREVIOUS WORK Heusler1 conducted an extensive survey of the liquid-solid regions of this system and also made an estimate of the solid-phase boundaries at 340°C. The pertinent part of his diagram is given in Fig. I, but it is of limited usefulness, since it applied to a single temperature only and is based on impure alloys under admittedly nonequilibrium conditions. Bauer and Hansen,2 likewise working with impure alloys, have determined the phase boundaries for alphabeta brasses containing small amounts of manganese and indicate an increase in the extent of the alpha field with increasing manganese. This is not in accordance with Heusler or with data obtained on pure alloys.3 They also described a third constituent precipitating in the alpha plus beta field below 350° to 400°C. but did not identify this constituent. Guillet4 and Heike and Ledibur5 have also noted this precipitate Each of these investigators recognized that impurities present in the manganese could and did have an effect on the structure and properties of their alloys. Corson6 in particular pointed out the hardening effects of silicon, aluminum, and carbon in copper-manganese alloys and Heusler reported that his alloys containing more than 25 per cent manganese were extremely brittle. In all probability this brittleness was due to the impurities present. This early work, therefore, should be taken as a general guide for preliminary studies only, and high-purity alloys may be expected to produce different results. The work of the Bureau of Mines laboratories with electrolytic manganese has been briefly summarized by Dean7 but includes only a short section on this system. Later work3 outlined a limited portion of the alpha field in the neighborhood of 65 per cent copper, 10 per cent manganese, and 25 per cent zinc. The present work was under-

Jan 1, 1945

By J. E. House, C. J. Lewis

In the solvent extraction process, also referred to as liquid-liquid extraction, the clarified uranium-pregnant sulfuric acid leach solution is contacted with an organic extractant dispersed in kerosene; the uranium enters the organic phase and associates itself with the organic extractants. Simultaneously an-ions or cations, as the case may be, leave the organic extractant phase and enter the aqueous phase. The two phases are then allowed to separate by virtue of their immiscibility. Based on the data available, a generalized procedure for the recovery of molybdenum from the sodium carbonate scrub liquor of acid leach uranium mills using secondary and tertiary amine extractants is presented, as is another generalized procedure for the recovery of molybdenum from the bleed stream of alkaline leach uranium mill circuits. Such economic appraisal as can be made at this stage of the development is also indicated. Molybdenum occurs in most uranium ores. Whether the uranium is solubilized by the acid leach route or by the alkaline leach process, some of the molybdenum present in the ore is solubilized along with the uranium. Molybdenum in uranium mill pregant solutions may cause processing difficulties, among which may be mentioned the poisoning of resins, the precipitation of organo-molybdenum complexes, or the build-up of molybdenum in recycle streams. While the uranium milling industry has been successful in applying measures to overcome the problems arising from the presence of molybdenum in the circuits, such measures nevertheless add to the cost of producing uranium yellow cake concentrate. Table I shows the analysis of typical uranium pregnant leach solutions. Uranium recovery by solvent extraction is presently practiced only in conjunction with acid leach circuits, and it may be noted that of about 16,000 tons of uranium ore daily processed by sulfuric acid leach, more than half of this tonnage follows the solvent extraction route. Uranium mills leaching ore with sodium carbonate-sodium bicarbonate solution (the so-called alkaline leach circuit) do not use solvent extraction. In this case the uranium pregnant solution is sufficiently pure to permit the direct precipitation of uranium concentrate with subsequent recycle of the alkaline leach solution. While solvent extraction procedures may be developed which are economically attractive for the alkaline leach uranium process, this has so far not been the case. The earlier uranium mill solvent extraction circuits used organo-phosphate extraction reagents, among which di-2-ethylhexyl phosphoric acid was popular. It should be borne in mind that uranium in its sulfuric acid leach solution exists in an equilibrium involving uranium in both anion and cation forms: uo + 2S0 = [uo2(so4)2] For this reason uranium may be extracted by either cation extractors or anion extractors and this is likewise true of molybdenum. However, the organo-phosphate extractants also load ferric iron which is usually present in the uranium acid leach solution. For this reason, it is necessary to reduce this solution substantially to the ferrous state ahead of solvent extraction using organo-phosphate reagents. The amines, being anion extractors, selectively reject iron and thus render the iron reduction step unnecessary. In the solvent extraction process, also referred to as liquid-liquid extraction, the clarified uranium-

Jan 1, 1961

By H. J. Gerritsen

From presently available components a portable, rugged, reliable apparatus can be built which will be able to detect methane concentrations of 0.1% and lower in air. Sensitivity and design considerations of the apparatus are given. Ways to build even simpler and cheaper apparatus in the future are indicated. Traditionally the problem of detecting and monitoring the presence of dangerous gases present in small concentrations in air has been a difficult one. Whether canaries,' or sophisticated chemical or thermal conductivity methods are used, they seem to be either slow, cumbersome, or otherwise not completely satis factory. A seemingly natural way of gas detection is to measure the strength of absorption undergone by light of a wavelength that the gas to be detected absorbs. This method has been difficult to apply in view of the low power output over a narrow wavelength range in the infrared from traditional glow bar light sources. Besides, the apparatus to select such a narrow band of wavelengths is quite costly and complex. The use of a laser solves these problems simultaneously. Although a variety of lasers are available to detect a variety of gases (such as carbon monoxide or methane) whose early detection would be desirable, this paper deals exclusively with the use of lasers for methane detection. ABSORPTION SPECTRUM OF METHANE IN AIR The absorption spectrum of pure methane is very well known.2-4 There are four fundamental vibrations, all occurring in the infrared of which only two absorb strongly. They occur at 3.3 µ and 7.7 µ. The absorption spectrum is quite complicated due to the fact that the methane molecule can rotate in a variety of rotational quantum states. These rotational states are furthermore split by anharmonic forces such as the Coriolis force.4 When methane is present in air at atmospheric pressure, much of the very fine structure due to the anharmonic force is washed out since the pressure broadening is of the same magnitude as the splitting due to anharmonicity. For most of the spectrum at 3.3 µ, the rotational lines are typically separated by 0.01µ while the individual linewidth is 0.0001 µ. It is thus very important that the laser emit at a wavelength that coincides with one of these rotational lines. Before elaborating on the point that such a laser exists and how it performs, it is necessary for later discussion to point out that in the

Jan 1, 1967

By James C. M. Li, J. Weertman

James C. M. Li (United States Steel Covp.)—The author has discovered a single analytical relation between the minimum, or the steady-state, creep rate and the applied stress confirming a statement made earlier by orn" that such relation should exist and should reduce to the power law at low-stress levels and to the exponential law at high-stress levels. However, as pointed out by the author, all the available theories of creep are not adequate to explain such a single relation. Inspired by such a statement, I have made a suggestion concerning a possible explanation13 of the new relation. This is based on the concept that the rate-controlling step is the cooperative motion of a short dislocation segment. The nature of and the reason for the cooperation have been discussed13 as well as the reason why the motion of the dislocation could be controlled by the mobility of the short segments. A natural short segment has been proposed13 to be the node formed at the intersection of two dislocations. The reason why the node may contain only a few atoms has not been discussed and the application of the proposed model to all the metals and alloys reported in this paper has not been attempted. It seems appropriate to include these in this discussion. The model was partly inspired by the substructure recently observed in the electron microscope on creep specimens. One such example is shown in Fig. 48 in Darken's Campbell Memorial Lecture. The substructure is a collection of dislocation intersections and irregular networks. No pileups have ever been observed in such specimens. A closer look at the network indicates that one set of dislocations is more straight than the other set sug- gesting that the other set may be mobile in the plane of the net. Since, for the network to survive the creep deformation, some dislocation reaction has to take place at the intersection of the two sets of dislocations, the mobile dislocation, even if it can slip in the plane of the net, will have difficulty in moving at these intersections. To illustrate, an idealized network is shown in Fig. 9. The thin lines represent the set of dislocations which are mobile and can slip in the plane of the net except at the nodes which are formed at the intersection of the two sets of dislocations. The other set of dislocations, represented by the thick lines, may have a Burgers vector which is not parallel to the plane of the net, and therefore may be immobile. Because of this nonparallel Burgers vector, the Burgers vector of the node, which is avectorial sum of the Burgers vectors of the two sets of dislocations, will also be nonparallel to the plane of the net. Therefore, the node cannot slip in the plane of the net and the set of mobile dislocations will have to drag the node along as indicated in Fig. 9. Now the problem is how many atoms could be involved in the nodes. Exact calculation of the length of the node is a difficult task especially since the length should be a steady-state length and not an equilibrium length. An estimate of the equilibrium length can be made by balancing the line tension of all the dislocations. The results would be a small fraction of the length 1 between nodes as shown in Fig. 10. In some instances such a calculation shows that the node will not be formed. But, since the calculation is only approximate, it does not rule out the possibility of the formation of a short node. In other instances the equilibrium length of the node is an appreciable fraction of I. Such a node would

Jan 1, 1963

By K. Leutwyler, H. L. Bigelow

Jan 1, 1966

By S. G. Gibbs, A. B. Neely

Jan 1, 1967

By Daniel T. Brian, O&apos

Exploration targets and results in the mining industry are commonly summarized in terms of tonnage and grade. Business appraisals require, as additional information, the expected profit or loss implied by the physical summay. The early incorporation of knowledge gained through financial analysis computations can provide a means for economically resolving many common exploration and development problems. Examples of such applications from the activities of exploration planning, reconnaissance, land acquisition, and development planning are presented. While prospecting for mineral deposits, geologists are frequently asked what they hope to find or have found. The response is usually descriptive, such as "50 million tons of 1% copper," and the economic implications are deferred until a capital investment decision is required. At that time, a financial analysis integrating the four analysis components is completed. These components are: 1) Tonnage and Average grade above cutoff grade 2) Capital and operating costs 3) Product value 4) Appropriate profit or loss accounting Close examination of these components reveals that there is no intrinsic reason for avoiding financial analyses at earlier stages in exploration, as long as the uncertainty of the estimate is realized. Tonnage and average grades are commonly estimated at early stages in exploration. For this component, the appropriate cutoff is the major uncertainty. Capital and operating costs are difficult to estimate before detailed quantitative information is available, but estimates useful for the types of applications pertinent to earlier exploration stages are possible. Product value estimates may or may not be difficult, depending on the pricing structure of the particular commodity. A simplified accounting procedure usually may be adopted without introducing any significant loss of validity. This paper describe some of the financial analysis applications which are pertinent during mineral exploration and deposit development. These applications lend additional insight during exploration planning, land acquisition, physical exploration, and development. The examples are oriented toward a hypothetical management investment policy which is based on a single criterion, a minimum 15% discounted cash flow rate of return. In reality, managements use multiple criteria. This simplification is convenient for purposes of presentation and does not invalidate the examples. Computers are useful, but not a requirement, for the applications described. The use of computers provides the results on a more timely basis at costs lower than equivalent manual computations. UNDERLYING PRINCIPLES AND ANALYSIS METHODS Data estimates are subject to uncertainty. The analyst may choose to assess this uncertainty by using one of two principles. Each principle has some advantages. The principle most commonly employed is "assumed certainty." Each financial analysis is based on one set of selected data, which may represent the average estimates, minimum expected conditions, etc. The critical data is identified by making successive calculations, varying the values used. Such studies, called sensitivity analyses, isolate the economic effect of various uncertainties, and guide the allocation of future efforts toward improving the overall accuracy of the analysis. A second principle, "assumed risk," examines the interactive effect of the current uncertainties by qualitatively assigning probability distributions to each data element. These probability distributions indicate the currently appraised chance that a given numerical value will prove to be true. The corresponding procedure, risk analysis, consists of processing many individual financial analyses, each analysis being based on randomly selected numerical values from the probabilistic distributions. The result is a numerical presentation of the uncertainty, but care must be exercised in the interpretation of results. The advantage of this procedure is the direct measurement of economic uncertainty caused by the interaction of uncertain estimates. Kennecott Copper Corp. has developed computer systems for accomplishing sensitivity and risk analyses.

Jan 1, 1970

By K. P. Fournier

This report describes work on the problem of predicting oil recovery from a reservoir into which water is injected at a temperature higher than the reservoir temperature, taking into account effects of vis cosity-ratio reduction, heat loss and thermal expansion. It includes the derivation of the equations involved, the finite difference equations used to solve the partial differential equation which models the system, and the results obtained using the IBM 1620 and 7090-1401 computers. Figures and tables show present results of this study of recovery as a function of reservoir thickness and injection rate. For a possible reservoir hot water flood in which 1,000 BWPD at 250F are injected, an additional 5 per cent recovery of oil in place in a swept 1,000-ft-radius reservoir is predicted after injection of one pore volume of water. INTRODUCTION The problem of predicting oil recovery from the injection of hot water has been discussed by several researchers. l-6,19 In no case has the problem of predicting heat losses been rigorously incorporated into the recovery and displacement calculation problem. Willman et al. describe an approximate method of such treatment. 1 The calculation of heat losses in a reservoir and the corresponding temperature distribution while injecting a hot fluid has been attempted by several authors.7'8 In this report a method is presented to numerically predict the oil displacement by hot water in a radial system, taking into account the heat losses to adjacent strata, changes in viscosity ratio with temperature and the thermal-expansion effect for both oil and water. DERIVATION OF BASIC EQUATIONS We start with the familiar Buckley-Leverettg equation for a radial system:* This is sometimes referred to as the Lagrangian form of the displacement equation. If the injection water is at some temperature Ti which is above reservoir temperature TR, then lw, the flowing fraction which is water, is a function of both water saturation and fluid temperature at any given time and position in the reservoir. The temperature dependence of lw results from the temperature dependence of the viscosity ratio µo/µm of which lw is a function. Thus:

Jan 1, 1966

By A. M. Keenan, R. H. Carpenter

Geologic faults have always been a plague to the mining industry, and have often reduced a mining venture from a profitable to a marginal operation, and even at times have forced companies to liquidation or bankruptcy. The use of geology as an economic tool in coal mining is not generally recognized, particularly in coal deposits which are horizontal or essentially flat-lying, in which faulting might not be prevalent. However in pitching coal seams, the existence of faults is considered an inherent challenge, as the inclination of the seam or seams per se, is a product of geologic disturbance. The problems of faults are a constant challenge to the management of the Thompson Creek Coal and Coke Corp. in their operations in Pitkin County, Colorado, where high grade medium volatile coking coal is mined. The background for this paper has been provided by the experiences of these operations, in overcoming the effects of faults in mining, and resolving the fault structures. The properties of the Thompson Creek Coal and Coke Corp. are located in central Colorado, 13 miles southwest of Carbondale, Colorado, a tow] on the main highway between Glenwood Springs and Aspen, Fig. 1. The elevation at the mine portals is approximately 8000 feet: there is a relief of some 2.000 feet to the adjacent ridges rising away from the [nine portals. 'The entire present production of these properties totaling 180.000 tons of clean coal per year is trucked to the railhead at Carbondale, Colorado, from whence it is shipped to the Geneva Steel Plant at Provo, Utah. The properties were initially opened in September 1952. A total of 125 men are currently employed with the production conting from the Number 1 and 3 Mines, and development workings of the Number 2 and 5 Mines respectively. While the No. 2 Vine was opened in 1953 prior to No, 3 Mine, the encountering of faults without sufficient development work accomplished to sustain production, necessitated the diversion of manpower to the other [nines for economic considerations. GEOLOGY '1-he productive coal seams occur in the Mesaverde formation of Late Cretaceous age which outcrop along the eastern edge of the Piance Creek Basin from the Grand Hogback, a part of the southwestern flank of the White River Uplift north of Glenwood Springs, southward through the 'Thompson Creek area and the

Jan 1, 1961

By J. E. House, J. L. Drobnick, R. R. Swanson, D. W. Agers

The paper describes an improved process for the recovery, purification, and concentration of copper values from acidic dump leach liquors. The process employs a new liquid ion exchange material (LIX® 64 reagent) capable of separating copper values from iron and other impurities common to dump leach liquors in the typical pH range of 1.4-3.0. Properties and performance of the reagent are discussed. Design scale-up information for both pilot plants and commercial installations, including preliminary economics, are presented. Economic considerations include the production of electrolytic copper from the purified copper aqueous concentrate. INTRODUCTION Since the commercial acceptance of the liquid ion exchange process in the mineral processing industry, it has been predicted that a wide selection of chemical reagents to efficiently and economically separate many metals in solution under a wide range of conditions would be commercially available. Several years ago, General Mills began a basic research and development program to determine if it were possible to develop a reagent to extract economically metallic ion from existing process streams. Progress toward reaching this objective was reported in late 1963, when development of quantities of LIX -63 reagent, a highly selective reagent for the extraction of copper, was introduced. The properties of this reagent are described in a previous paper.' The development work with this reagent indicated that perhaps the largest potential application for a copper extractant, the treatment of acidic dump leach liquors, would not be economically possible with LIX-63 because of limitations of the reagent to extract copper below a pH of 3.0. The relatively small pH adjustment required with LIX-63 would result in a significant processing cost and the undesirable precipitation of ferric hydroxide from the liquor. This pointed to the need for another copper extractant which would extract copper from dump leach liquors without pH adjustment. General Mills was successful in synthesizing a molecule which does not have the pH limitation of the LIX-63, yet possesses the selectivity-solubility properties required of a metallic extractant. The resulting LIX-64 reagent broadens the pH range from which copper can be effectively extracted and separated from other metallic impurities. Of special significance is the fact that the reagent, LIX-64 was developed by combining the technical requirements of a specific problem in hydro-metallurgy with theoretical organic and physical chemical principles.

Jan 1, 1967

By J. F. Butler, H. W. Paxton

The vapor pressures of manganese in equilibrium with several alloys in the iron-manganese-carbon system between 1200° and 1275°K have been measured using the Knudsen effusion technique in conjunction with a vacuum microbalance. The effect of orifice area of the effusion cell upon the measured pressure has been determined. The binary iron-manganese system shows small negative departures from ideality, and the system of mixed carbides, (Fe, Mn)7C3, in equilibrium with graphite behaves ideally. THIS work is a continuation of the investigations in which the Knudsen effusion method has been used to determine thermodynamic activities in systems and at temperatures of interest to metallurgists. In a previous publication,' the free energy of formation of Mn7C3 was determined and some preliminary work on the solution behavior of this carbide with the hypothetical "Fe7C3" was reported. The present work deals with this latter topic and also includes data on the binary ir-on-manganese system. EXPERIMENTAL METHOD The Knudsen effusion method was used to measure the vapor pressure of manganese in both the alloy and carbide sections of this investigation. This dynamic method of vapor pressure measurement presents a problem when studying solid alloy systems in which one of the components has a much larger vapor pressure than the others. Over-all depletion of the alloy in the most volatile component will occur during evaporation so that the pressure of that component will decrease. Even more serious than the over-all concentration change is the surface depletion of volatile component in the alloy brought about by the slow rate of diffusion of this component from the interior to the surface of the solid particle. Since knowledge of this surface composition is necessary in order to relate it to the activity determined through the measurements, changes in surface composition from the analyzed bulk composition are to be avoided in dynamic vapor pressure studies of solid alloys. The system under investigation in this study presents the problem of surface depletion of manganese since its pressure at 1230°K is 105greater than iron and 1020 greater than carbon. Since the existence of a volatile manganese carbide had been ruled out previously,' the high manganese pressure relative to iron and carbon insured that the only species leaving the effusion cell was manganese. Therefore, the effusing species required no analysis so that the manganese pressure was determined directly from the weight loss of the effusion cell. In order to detect small weight losses near the beginning of effusion, a vacuum microbalance was used to weigh the cell continually. These initial weight loss data allowed the rate of manganese effusion to be determined before the surface of the alloy became depleted in manganese. The apparatus used in this investigation is shown in Fig. 1. Temperature was measured using chro-

Jan 1, 1962

By Frank E. Woolley, Robert D. Pehlke

Jan 1, 1965

By Lawrence H. Van Vlack, Alfred S. Keh

The distribution of sulfur in iron was found to be dependent upon the time and temperature of the treatment as well as the chemical composition of the sulfide. With higher temperatures, the sulfide phase spreads more extensively between the iron grains. A complete network, however, does not form until approximately 1300°C (2372°F), ot which temperature the dihedral angle approaches zero. Silicon has little effect on this change. Aluminum, oxygen, and manganese all modify the temperature of sulfide network formation to a higher value. The microstructures which result and have significance in relation to hot-shortness are discussed. SULFIDE inclusions in steel were recognized by metallurgists before the turn of the century. Considerable attention has been paid to them, and numerous studies have been made on the working properties of steel as affected by them. It has been suggested that ho t-shortness of steel is due to the presence of an enveloping liquid sulfide film at the grain boundaries of the steel in the range of the hot-working temperatures. However, several facts have been observed in commercial steels which do not seem to be completely consistent with this explanation: 1) the frequent absence of continuous films of sulfide as observed under the microscope, 2) the absence of hot-shortness in some high sulfur and resulfurized steels, and 3) the limitation of hot-shortness to a definite temperature range. The role that manganese plays in steel to eliminate hot-shortness is well known, but the theory behind it is still under question. Moreover, the effect of de-oxidizers such as aluminum and silicon, and the effect of oxygen are still not clearly known. In this study, the effect of heat treatments and of additions of manganese, aluminum, silicon, and oxygen upon the distribution of sulfide inclusions in iron was investigated. Both the as-cast and the heat treated structures were studied, using microscopic and autoradiographic techniques. Part of the results were interpreted in terms of Smith's' concept of microstructure. Review of Literature Metallurgists used to consider sulfide inclusions as suspended particles. It was Wohrman' who first pointed out that sulfide inclusions are soluble in liquid iron. Many observed facts may be understood on the basis of this concept of solubility. Wohrman found that small castings contain small inclusions. and larger castings contain larger ones. Also, inclusion sizes are smaller near the chilled surface. For the same size ingot, the average inclusion size in a given heat of steel depends upon the rate of solidification. That is, with slow solidification, enough time for precipitation and agglomeration of these

Jan 1, 1957

By W. H. Yarroll Discussion by W. A. Griffith

W. A. Griffith (Head, Research Department, Phelps Dodge Corp., Morenci, Ariz.) - It is gratifying to see the increasingly common use of classical statistical procedures by metallurgical researchers. Mr. Yarroll has given excellent illustrations of the utility of multiple correlation analysis of complex metallurgical data. Our experience in applying these procedures to historical plant operating data has differed, however, from that which he suggests. The uninitiated frequently assume that the volumi-

Jan 1, 1969

By J. L. Green

Virginia-Carolina Chemical Corp., in its Florida Operations, uses both roller mills and ball mills in dry grinding of phosphate rock. The roller mills have been in operation since 1954 in the Mining Department. The ball mills were installed and put in operation in 1960 in the Harding Concentrate Superphosphate Plant. The roller mills in the Mining Department are used to grind phosphate rock for outside customers. This involves short notice orders of varying grinds, grades and types of rock. The ball mills grind phosphate rock for use in V-C's own phosphoric acid and concentrated superphosphate plant. These mills grind generally two types of rock for one grind. In 1959, a 10% speed-up was made in the operating speed of the roller mills. This paper deals with the operational gains and resulting cost savings which evolved from this speed-up, and compares the present operations of the roller mills and of the ball mills in grinding phosphate rock. In January 1959 it was decided to determine the feasibility of reducing the grinding cost on the roller mills, per ton of rock ground, by speeding up the mill 10%. At this time, one mill was completely reconditioned so it would be in top condition. Extensive tests were then run both before and after the mill speed-up to determine the resultant cost savings. These tests showed that, due to this 10% speed-up, the mill capacity was increased approximately 20% and grinding power costs per ton were reduced approximately 10%. Table I shows the results of these tests. Each test run actually represents several of the same type rock and grind, averaged together. Each test run lasted approximately three hours. The validity of these runs has been confirmed by subsequent operation in grinding over 1,000,000 tons of phosphate rock. Accurate records have been kept on power consumption and repairs as well as tons produced. Two types of feed rock were used for the tests — pebble phosphate rock and flotation phosphate concentrate rock. The pebble phosphate rock size is approximately 80-90% plus 20 mesh. The flotation concentrate phosphate rock size is approximately 15% plus 20 mesh and 95% plus 100 mesh. The same two types of rock feed were used for all the test runs. Test Nos. 1, 2, and 3 were run at the original mill speed of 85.5 rpm on the vertical shaft. Test No. 1 was run with a feed of high grade flotation concentrates; the desired fineness attempted was 70% passing 200 mesh. Tests No. 2 and No. 3 were run with a feed of low grade pebble. Test No. 2 was run for a desired fineness of 70% passing 200 mesh. Test No. 3 was run for desired fineness of 50% passing 200 mesh.

Jan 1, 1963

By Henry M. Howe

(Cleveland Meeting, October, 1912.) Manuscript received Aug. 20, 1912. PROFESSOR RUFF'S most illuminating paper' describing his extremely valuable investigation of the carbon-iron equilibrium diagram assigns definite temperatures to certain very important lines in the diagram, viz.: the eutectic temperature EB (Fig. 1) and the " near-eutectic " temperature E'B', but without indicating clearly enough the reasoning which warrants these assignments. These temperatures are of such primary importance that it is well to indicate the apparent gaps in the reasoning, in the hope that they may be filled in. In his diagram, Fig. 1, the point X and the lines B'D'HI represent the experimental results reached by Ruff and Goecke; 2 AB, AEB, and SE represent the liquidus, the solidus, and the solubility of the carbon in solid austenite in the absence of graphite according to Gutowsky,3 AB being also in accordance with Spiecker's data;4 ,S'E' the solubility of carbon in solid austenite in the presence of graphite according to Ruer and Iljin; 5 GS the line A3 after Goerens and Meyer;6 I and EBC the true eutectic line as inferred by Prof. Ruff from Gutowsky's data. B'D' is the carbon content found in cast-iron which had apparently saturated itself with carbon in the presence of the graphite of the enclosing graphite crucibles in which the determinations were made. From its straightness and its sharp inflection near 6.67 per cent. of carbon, the carbon content of * Professor of Metallurgy in Columbia University. 1 Metallurgie, vol. viii., pp. 456 to 464 and 497 to 508 (1911). 2 Idem, vol. viii., pp. 417 to 421 (1911). 3 Idem, vol. vi., pp. 731 to 743 (1909). 4 Idem, vol. vi., p. 524 (Wüst) (1909). 5 Idem, vol. viii., pp. 97 to 101 (1911). 6 Idem, vol. vii., pp. 307 to 312 (1910).

Nov 1, 1912

By H. T. Kennedy, J. E. Little

An empirical equation for the prediction of the viscosity of several pure paraffin hydrocarbons and nitrogen is presented. It involves temperature, pressure and six constants of the material, and it applies reliably to both liquids and gases. The equation is similar in form to van der Waal's equation of state. For the paraffin hydrocarbons methane through r-hexane and nitrogen, an average absolute deviation of 1.9 percent was obtained on 1,006 data points described in the literature by 14 authors. When this equation is extended to complex, liquid hydrocarbon mixtures, a correlation was obtained with an average absolute deviation of 9.9 percent. INTRODUCTION Equations describing the flow of gas and liquid through porous media contain the viscosity coefficient of the fluid. If other pertinent variables remain constant, the volume rate of flow is inversely proportional to this coefficient. In dealing with condensate fluids and volatile oils, however, the compositional effects resulting from changing pressure materially affect the viscosity. The effect of compositional changes also may be significant in certain secondary recovery or pressure maintenance processes, notably miscible displacement or gas injection. Early attempts to describe the performance of reservoirs utilized a volumetric material balance method wherein gas and liquid in the reservoir were identified as produced gas and liquid at the surface. This method of analysis proved adequate for reservoirs at moderate temperature and pressure that contained gas with moderately low amounts of condensable materials. The volumetric material balance procedures for "black oil" reservoirs leave much to be desired when applied to condensate and volatile oil reservoirs because phase behavior and compositional changes are relatively more important in these cases. The alternative is a compositional material balance, which in turn, requires a correlation of properties of the reservoir fluid with composition. This paper supplies this correlation in regard to viscosity, for reservoir crude oils. REVIEW OF LITERATURE The literature contains many empirical equations describing the effects of composition, temperature and pressure on the viscosities of pure liquids and binary liquid mixtures. However, the applicability of a majority of these equations is limited to very low pressures and to a small number of systems. Most of them, when applied to complex hydrocarbon systems, are of little value. The lack of utility of the majority of equations results from the fact that they were developed to show the separate effect of temperature, pressure or composition on viscosity, but not to predict the viscosity as a function of all three variables. And with the few exceptions noted below, they were developed to apply to much simpler systems than hydrocarbon mixtures. Eakin1 developed an equation for the viscosity of pure light hydrocarbons applicable in the gas, liquid and dense fluid regions, and in its most general form is written as µ - µo =A(ebP - e-cpk) The pure component viscosity at atmospheric pressure and temperature T, µo, was calculated using the Sutherland equation: µo = BT3/2/T + S The constants in Eakin's equation permitted the term e-CPk to become quite small at high densities (above 0.215 gm/cc), and the general equation would simplify to

Jan 1, 1969

By L. L. Seigle

Free energies, heats, and entropies of mixing of solid Fe-Au alloys have been measured by the galvanic cell method between 800° and 900°C. A positive deviation from Raoult's law and a large excess entropy of mixing were observed, both attributable to lattice distortion caused by the disparity in component atom sizes. Since the terminal solid solutortiontions are not regular, thermodynamic properties computed from the location of the mis-cibility gap do not agree well with measured quantities. The electromotive force data suggest some changes in the existing Fe-Au phase diagram. ALTHOUGH a considerable amount of information has been accumulated about the thermodynamic properties of metal solid solutions which exhibit negative deviation from Raoult's law, particularly those in which ordering occurs, relatively few experimental measurements have been made on solutions with positive deviation. This is due to the infrequency of broad homogeneous regions suitable for experimental measurement in solutions of this type, since any marked positive deviations from ideality lead to restricted solubility and the formation of miscibility gaps. Thermodynamic data reported in the literature for such systems have usually been calculated from the location of the miscibility gap boundaries under the assumption that the entropies of mixing are ideal, i.e., the terminal solutions are regular.' One of the few binary systems with both positive deviation and a wide homogeneous range in the solid is the Ni-Au system. A recent investigation of solid Ni-Au alloys' revealed that the entropies of mixing were much larger than ideal and consequently thermal data computed from the phase boundaries assuming regular solutions were seriously in error. Theoretical considerations put forward by Zener indicated that high entropy values should generally be associated with systems possessing a miscibility gap in the solid, when this is due to differences in the size of component atoms. These facts suggest that the regular solution assumption is a poor approximation for many solid solutions with positive deviation and that reliable thermodynamic data generally cannot be obtained by conventional methods from the location of miscibility gap boundaries. The Fe-Au system, Fig. 1, resembles the Ni-Au system in certain respects. The presence of a miscibility gap in the solid indicates a large positive deviation from ideality, but there is nevertheless an extensive single phase region suitable for experimental measurement. The following investigation of solid Fe-Au alloys was carried out in order to obtain additional data on the thermodynamic properties of metal solid solutions with positive deviation from Raoult's law and to further compare thermodynamic data computed from miscibility gap boundaries with those measured experimentally. Experimental Method The thermodynamic properties were derived from measurements of the potential developed between pure solid iron and Fe-Au alloys in a high temperature galvanic cell. The experimental apparatus and technique were the same as those used for the Ni-Au alloys and described in a previous report.' Cell electrodes were 1/16 in. diam rods swaged from chill-cast ingots and annealed for one week at 850°C. The alloys were prepared by melting fine gold granules under argon with pure iron obtained from the National Research Co. The cell electrolyte was

Jan 1, 1957

By E. Douglas, D. N. Collins, J. R. Stevens

E. Douglas (Dept. of Scientific and lndustrial Re-search, Warren Spring Laboratory, Hertfordshire, England) — The authors are to be congratulated on the considerable improvements they have made in tailoring efficiency and selectivity terms which are generally superior to the alternative forms in current use. However, I feel that their efficiency expression is limited to lower-grade feeds; its accuracy reduces as the feed grade increases. For example, its application to such processes as the beneficiation of glass sands, refractories and clays will invoIve considerable inaccuracies. The reason for this lies in the direct use of recovery, which, with high-grade feeds, biases their empirical expression, R(1 - c/h). With a 90% grade feed, the recovery weighting for the slightest degree of beneficiation, over a zero efficiency sampling operation, will be 90+%+ I disagree with their second basic requirement which states that there can be no fundamental basis for any single quantifying expression. A formula giving a comprehensive representation of concentra- tion efficiency can be derived fundamentally accord-to the procedure outlined in the literature. '' This formula, called the Basic Efficiency formula, is

Jan 1, 1963

By J. Douglas, W. T. Ford, G. E. Henderson, I. F. Roebuck

An implicit numerical method is presented for simulating the differential and algebraic relations governing one-dimensional three-phase flow in porous media. The method is based upon compositional representation of the hydrocarbon system. Variable physical properties and water-oil capillary forces are included in the formulation; however, the effect of gravity is ignored. The effects of changing composition and mass transfer are considered through the use of known phase behavior concepts and correlations. The differential and algebraic equations and the numeric approximations to these equations are presented, and the computing algorithm is discussed in detail. This method is used to simulate a single-phase, two hydrocarbon-component gas displacement laboratory experiment. The method is also applied in simulating a solution gas drive and a gas injection problem using a reservoir oil represented as a nine-component mixture. For comparative purposes, the latter two problems also are examined with a one-dimensional volumetric model. The results of the simulation of the laboratory experiment demonstrate the relevance of this method to problems wherein the effects of mass transfer significantly enter the displacement process. The comparison of the results of the volumetric and compositional methods applied to a reservoir system illustrates not only the advantages and benefits derived from examining the hydrocarbon system composition, but also the necessity of this approach in application to a general reservoir problem. INTRODUCTION The advent of large memory, high-speed digital computers enabled reservoir engineers and mathematicians to pool their knowledge in the development of sophisticated techniques for the prediction of oil and gas reservoir performance. These techniques have progressed from volumetric and trend analysis calculations to the development of "mathematical models", or reservoir simulators. These latter models, in general, utilize finite difference approximations to the rather complex partial differential equations that mathematically describe the physics and thermodynamics of fluid flow in porous media. Many forms of this "model" type are available today, and much of the recent literature has been devoted to either improving known methods or developing new techniques for use in these prediction methods. The more advanced techniques in use at this time consist of the solution of differential and algebraic relations that describe a reservoir geometry in one, two or three dimensions and that incorporate reservoir hydrocarbon and water fluid systems that obey specified physical laws, having properties that might easily be measured in the laboratory. This type of model utilizes formation volume factors and other volumetric data, expressed directly as functions of pressure, to represent the reservoir fluid system. Experience gained with this type of simulator, commonly known as a "beta-factor model", has indicated that the approach has many outstanding defects, most of them due to the assumption that those properties measured in the laboratory completely describe the behavior of the fluid system throughout the life of the project under study. The effects of varying hydrocarbon composition and mass transfer between the phases of this hydrocarbon system must, by definition, be ignored. These defects, which may often be ignored in

Jan 1, 1970