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By C. F. Weinaug, R. W. Farley, J. F. Wolfe

A rapid, accurate method for predicting the dew points of gas condensate systems and their subsequent normal and retrograde phase behavior with pressure decline has been developed. The method predicts dewpoint pressure, volume percent liquid, condensate content of produced gas, and the liquid and gas compositions at pressures below the dewpoint pressure. Use of a modified form of the BWR equation of state, which was established by regression calculations on experimental data from several gas condensates, provides depletion behavior predictions that are significantly improved over predictions using K-values based on convergence pressures and Standing's correlation for density. INTRODUCTION Prediction of complex hydrocarbon-mixture thermodynamics is fundamental to reservoir and gas process engineering. In particular, accurate descriptions of phase behavior are needed to plan production operations for gas-condensate reservoirs. Although analysis of reservoir behavior during producing and cycling operations can be made for simple reservoir models, extensions of these studies to more complex reservoir systems are still difficult, both with regard to numerical techniques and the phase behavior of the fluids. This report presents a mathematical method for handling the complex phase relationships encountered in retrograde condensates; it represents an advance in reservoir behavior technology in that it will aid the development of closed-form mathematical representations of total production systems. A typical phase diagram for a complex hydrocarbon mixture is shown in Fig. 1. When the reservoir temperature T, is higher than the critical temperature Tc, and lower than the critical-condensation temperature Tct' the mixture is a gas condensate. Decreasing the pressure on a condensate while maintaining nearly constant temperature will result in two phases forming at the dew point. Further decrease in pressure will cause additional liquids to be formed. This phenomenon is called retrograde condensation. As pressure continues to decrease, normal phase behavior regions are encountered (liquid vaporizes as the pressure decreases) until the low-pressure dew point is encountered. When a gas-condensate reservoir is produced, gas is withdrawn and the volume of fluids in the reservoir remains nearly constant as the pressure declines. Heavier components tend to accumulate in the liquid phase as a result of retrograde condensation, while lighter components tend to concentrate in the vapor phase. Thus, as the gas is produced the composition of the gas and the condensate

Jan 1, 1970

By J. L. Lytton

The flow-stress recovery of high-purity aluminurn following a 10 pct tensile prestrain was studied in terms of a fractional flow-stress recovery parameter fr. The flow-stress recovery behavior was related to the dislocation arrangements using transmissiort electron rnicvoscopy. During recovery at 120° and 160°C, nearly stable strength levels were attained, the strength level for 120°C recovery being greater than that for 160°C. This stabilization of flow stress was related to the formation of meta-stable dislocation networks bounding nearly perfect cells. Both network formation and the annealing of dislocation loops were found to be recovery mechanisms, and the stronger metastable strength level joy 120°C recovery was related to a smaller average cell size. Analysis of the networks was consistent with the reaction of sets of dislocations with a/2 (110) Burgers vector to give product Burgers DURING isothermal annealing of cold-worked metals, a degree of softening occurs without re-crystallization, and the processes responsible for this change are termed recovery processes. During recovery annealing, the dislocations generated during cold work become rearranged into low-energy configurations, and as much as 50 pct of the stored energy is released."' The relationship between this rearrangement of dislocations and mechanical behavior is of considerable importance, since the dislocation substructures formed during recovery provide a significant degree of low-temperature strength3j4 and can favorably alter the course of primary creep at high temperatures.4 The purpose of the present study was to relate the flow-stress recovery behavior of high-purity aluminum to the substructural modifications that occur. Electron transmission microscopy was therefore employed for direct observation of dislocation substructures at various stages of recovery following 10 pct prestrain. Several investigators5-' have proposed that dislocations can become rearranged or lost during the preparation of thin foils. It was found early in the present study that the dislocation structures in the thicker regions of the foils changed in a systematic way during the course of recovery. Therefore, it is unlikely that substantial losses or rearrangements occurred during thinning. This point will be discussed in more detail later. The results of various investigators indicate that recovery processes in fcc metals can result in release of 50 pct or more of the total energy stored in the as-prestrained metal, this percentage decreasing with increasing prestrain.' Alloying elements or impurities tend to increase this percentage. The release of stored energy of fcc metals during recovery appears to occur by 1) annealing of point defects if the deformation occurred at sufficiently low temperaturesg and 2) rearrangement of dislocations into low-energy Configurations.1,2In bcc metals, the annealing of dislocation loops has also been observed during recovery after prestrain,10-12 and it has been proposed that this is a recovery mechanism for unidirectionally strained fcc metals.' The density of dislocations in bcc metals has not been observed to decrease appreciably during recovery,10 although the formation of regular dislocation networks has been observed. has shown that the formation of such networks can result in elimination of long-range stresses and can lead to significant release of stored energy without dislocation annihilation. It might thus be expected that network formation is a significant recovery mechanism in fcc metals, although extensive network formation has apparently not been reported in controlled recovery experiments. The formation of sub-boundaries in aluminum has been observed by various investigators13'17 during recovery studies of aluminum, but the structure of these boundaries was not resolved. In this regard, it is significant to note that Bailey and Hirsch,' using transmission electron microscopy, detected no network or sub-boundary formation during recovery of 99.99 pct Ag. Furthermore, Clarebrough et al.2 found no such rearrangements during recovery of copper. EXPERIMENTAL PROCEDURE The high-purity aluminum used in this investigation was obtained in the form of 0.125-in.-thick sheet. Spectrographic analysis revealed that the sheet was 99.995 pct A1 with the following weight-percent impurities: 0.001 Cu, 0.002 Fe, 0.001 Si, and 0.0004 Mg. The as-received sheet was in the heavily cold-rolled condition. The as-received sheet was cold-rolled at room temperature to 0.040-in.-thick sheet in the longitudinal direction, which was the original rolling

Jan 1, 1965

By D. E. Stephenson. Discussion by R. G. K. Morrison, L. Obert

R. G. K. Morrison (Chairman, Dept. of Mining Engineering and Applied Geophysics, McGill University, Montreal, Que., Canada) - The discing of drill core has been a recognized pressure phenomenon for many years but only recently has an interest been taken in the mechanism involved. The work of Jaeger and Cook is referred to in the text. The authors have now advanced the study to establish, within certain loading limitations, a direct relationship between axial and radial stress at failure. This is an important contribution. In mines generally, where pressure conditions result in the spalling of openings, the faces of drifts and crosscuts, on scaling, usually show a concavity with respect to the opening very similar to the face of the drill hole after the separation of the stub. The same holds for shaft sinks. This suggests a similarity between the mechanism of the discing of core and that of the spalling of an opening, under pressure, to develop a more stable outline. The latter, commonly regarded as shear, is the most conspicuous type of failure observed in

Jan 1, 1967

[Chairman ZAY JEFFRIES, Vice-chairman S. SKOWRONSKI, Chairman WILLIAM M, CORSE, Secretary Executive Committee J. R. FREEMAN, JR., Local Section G. E. JOHNSON R. S. ARCHER, Non-ferrous Data Sheets P. D. MERICA EDGAR C. BAIN, Journal Committee L. W. SPRING SAM TOUR, Papers Committee F. L. WOLF H. C. JENNISON, Membership Committee Local Section Committee J. R. FREEMAN, JR., Chairman R. J. ANDERSON, Cincinnati R L. DOWDELL, Minneapolis R. S. WILLIAMS, Boston G. H. CLAMER, Philadelphia W. A. SCHEUCH, Chicago R. F, Woon, New York Papers Committee S. SKOWRONSKI, Chairman F. H. DIx, JR.-Aluminum E. R. DARBY-Bronze C. S. WITH ERELL-Copper H. A. BEDWORTH-Brass W. K. FRANK-BRONZE F. W. HARRIS-Copper R. L. SUHL-Nickel H. M. ST. JOHN--Foundry Metallurgy R. S. DEAN-Theoretical Metallurgy]

Jan 1, 1928

By Rudolph Emmel

THE mines operated by the South American Development Co. are located in the Zaruma mining district of southwestern Ecuador. They are near the old mining town of Zaruma, which is the only important city in the canton of the same name. The district is situated in the upper end of a valley lying between two spurs of the Cordillera, one of which may be considered the Coast Range and the other an intermediate range. The mining camp proper, known as Portovelo, and the plant are 2.4 km. south of Zaruma, on the north bank of the Amarillo River, a tributary of the Tumbes River, which flows southwestward through Peru to the Pacific. Portovelo is difficult of access; it is reached from Guayaquil by means of river steamers and muleback. Embarking at Guayaquil, the route is down the Guayas River, across the Jambeli Canal, and up the Santa Rosa River to Santa Rosa, a distance of 177 km. From Santa Rosa, the road or trail follows the Santa Rosa River, then across the summit of the Coast Range into Portovelo, a distance of 74 km.-a two-day trip on muleback. The mining property of the South American Development Co. comprises 297 lode claims and 142 placer claims. The combined lode claims cover an area, roughly rectangular in shape, 9000 m. long from north to south by 4000 m. wide; the northern edge of the rectangle is about 3000 m. north of the central plaza of Zaruma. Mineral lands in Ecuador are held by virtue of an annual tax per claim paid to the central government, no surface rights being included.

Jan 1, 1925

By Robert M. Funk, James E. Lawver

The development of a laboratory and pilot-scale high-tension electrostatic flowsheet for the production of iron-ore super concentrates having silica contents in the range of 0.1% is presented, A variety of hematite and magnetite ores were tested with this flowsheet, and the pertinent metallurgical data are given. The applications and limitations of this process are brought out in terms of both practical and theoretical considerations. There have been many new developments in the past few years that have required mineral beneficiation engineers to consider new techniques for iron-ore concentration. Developments in iron powder metallurgy, and particularly the making of sheet metal directly from high-purity iron-ore concentrates, and the concept of using metallized pellets as a substitute for scrap in electric-furnace steelmaking have created demands for what is commonly referred to as iron-ore superconcen-trates. In most cases, specifications for superconcentrates are that they contain less than 0.1% total gangue, with some applications requiring less than 0.05% gangue. To produce these concentrates, new and modified processes are being developed, and the three methods receiving attention as the primary concentrating methods are: 1) Magnetic separation in which dry rotor-type equipment is used for magnetite and the high-intensity magnets are used for hematite. 2) Amine flotation. 3) "High-tension" electrostatic separation (or, elec-trodynamic concentration). This paper examines the high-tension electrostatic process in terms of its limitations and abilities for the production of iron-ore superconcentrates. A technically effective and simple flowsheet was developed through laboratory and 5 and 100-ton pilot-plant studies for the production of concentrates containing from 0.02 to 0.20% SiO, with iron recoveries between 85 and 90%. The process is also shown to be economically feasible. Laboratory Test Program Separation Characteristics: The suitability of the electrostatic high-tension method for iron-ore supercon-centration stems from the fundamental mechanism governing the process, i.e., particles are separated on the basis of differences in electrical conductivities. This conductivity is a characteristic property of minerals, and if the difference between the conductivities of two min- erals is great enough, then their separation can be performed by a high-tension machine. As shown in Figs. 1 and 2, the critical factor is the time necessary for the particle charge density, which is established by a corona discharge field, to decay to a level such that the centrifugal force acting on the particle exceeds its electrostatic, or image, force. At this point, the particle can leave the rotor at some trajectory and fall into an appropriate product receptacle. This decay time is directly proportional to electrical conductivity, and the process variables, such as feed rate, rotor speed, electrode configuration, and rotor composition, are selected to optimize the ability of the separator to resolve different conductivities. Table 1 lists the measured conductivities for some of the iron and gangue minerals used in developing the flowsheet. These results were obtained by using the conductivity cell described by Lawver and Wright.' The discharge curve of most minerals that lend themselves to super concentration by high-tension is so fast that the

Jan 1, 1971

By E. F. Adkins, R. W. Douglas

The variation of the spectral emissivity of osmium and ruthenium with temperature can be expressed by the following relations: DURING a study of the sintering characteristics of osmium and ruthenium, discrepancies in the previously accepted melting points of the metals were noted. The melting temperatures had not been measured at the time of the work, but were estimated in the literature as 2700°C for osmium and 2450°C for ruthenium.' A recent investigation by Baird2 has shown the melting temperatures of osmium and ruthenium are 3000" and 2250° C, respectively. In the present work, osmium bars sintered at temperatures as high as 2900° C showed no evidence of melting, whereas ruthenium showed definite evidence of melting at temperatures as low as 2250°C. In view of the apparent discrepancies, the melting temperatures of both metals were determined. The spectral emissivities of both metals were determined as an aid to studies of the sintering characteristics of these metals. MATERIALS AND PROCEDURES The materials used in these studies were metal powders supplied by Englehard Industries, Inc., through the courtesy of The International Nickel Co. Analytical data from three laboratories, although not in complete agreement as to the purity of the material or the major impurity elements, indicated that the maximum impurity levels were 0.5 and 1.0 wt pct in osmium and ruthenium, respectively. The metal powders were pressed to 1/4 by 1/4 by 6-in. bars at 20Tsi using carbon tetrachloride as a lubricant. The pressed bars were presintered 1 hr at 1200°C after heating 1 hr at 400°C. The presintered densities of the several bars of the metals ranged from 65 to 80 pct of ideal density. Specimens were self-resistance heated in a vacuum sintering bell. Temperatures were measured with an L&N, disappearing filament optical pyrometer. True temperatures were read at the base of an 0.30-in.-diam, 0.150-in. deep hole drilled into the center of a presintered bar. Apparent temperatures were read from the surface of the bar adjacent to the hole. MELTING POINT DETERMINATION The melting temperature of the metals was determined as the temperature at which a slight additional increase in current through the specimen resulted in a reduced temperature at the base of the hole. The apparent reduction in temperature is a result of the liquid metal filling the hole, thus altering the black-body conditions. The melting points of osmium and ruthenium, based on three deter-

Jan 1, 1962

Jan 1, 1967

By J. C. Detweiler

THE Jacksonville plant of Humphreys Gold Corp., operating under leases from National Lead Co. and Rutile Mining Co. of Florida, recovers rutile, ilmenite, zircon, and monazite from an ancient beach deposit containing about 2.5 pct of these minerals in combination. The location of the plant is unique, being situated about ten miles from the center of Jacksonville, Fla., surrounded by a thriving suburb. Two four-lane highways pass within 1 ½ miles of the plant. An expressway now under construction will pass over the tailing pile, within 500 ft of the mine office. The elevation at the plant site is approximately 50 ft above sea level. This is one of two mines producing titanium minerals and zircon in Florida. Another mine is also operated by Humphreys at Starke, about 50 miles southeast of Jacksonville. The Jacksonville deposit extends about six miles in a north-south direction, averaging approximately one half mile wide and twenty ft thick. Values begin at the surface over most of its length and ter-

Jan 1, 1952

By A. S. Argon, G. East

From their study of the anisotropy of grain boundary mobility in aluminum, the authors conclude that tilt boundaries have a higher mobility than twist boundaries because the atomic misfit at the pure-twist boundary is relatively small compared to the misfit at a tilt boundary for a given amount of misorientation. If this is true, then one would expect a twist boundary to have a lower grain boundary energy than the corresponding tilt boundary. Fig. 6, taken from the work of Gjostein and Rhines,10 shows that this is indeed the case for [001]-cu tilt and twist boundaries in the high-angle region, thus lending support to the authors' conclusion.

Jan 1, 1968

By A. W. Asman

The problem of balanced design in a belt conveyor has been under constant study. Increased use of this method of transport in recent years has stimulated investigations. Conveyor belt, power transmission and other machinery should be adequate to perform the required service. All components of the belt conveyor should work as an efficient unit moving its load continuously between terminals. As part of a long term research project on belt conveyors, Hewitt-Robins established in 1954 a 2-year grant at Pennsylvania State University. Under terms of the grant, certain fundamental phenomena were to be studied. This work evolved a new concept in belt conveyor power determination based on the principle of belt tension. The Penn State contract furnished the foundation for later more detailed studies. From these most recent investigations, more specific factors were defined. In the final analysis, all of the data collected has been worthwhile in belt conveyor design. Units now operate over long distances at speeds of over 800 fpm. Long high lifts are commonplace. Where vertical or inclined shafts were the rule, belt conveyors receive first consideration. Although belt conveyors have moved forward rapidly, the future will see a tremendous gain in their use. The ideal test belt conveyor would be several thousand feet in length and have a maximum tension of at least 70,000 lb., Also, this conveyor should be horizontai and have a variable feed rate of more than one material. Data from such a field belt conveyor combined with laboratory information would permit accurate analysis. Since this type of conveyor was not available, many field locations were visited: An alternate would have been to erect a closed circuit system in the laboratory. Either method had limitations and the first was selected as having the best possibilities. Manufacturers of conveyor belting and machinery basically have been using the same horsepower formula. As more information became available from field installations, factors in the basic formula were modified. Practically all conveyors are designed today by adding together the horsepowers required to move the empty belt, move the load horizontally, and elevate the load. In selecting size of drive motor, the first two elements are relatively unimportant if the last is large. However, it is the combination of

Jan 1, 1961

By F. W. Bowdish

Analysis of data on the equilibrium exchange of sodium ions from salt solutions for calcium ions, from various fractions of an oxidized calcareous iron ore from Lorraine, France, strongly suggests that the calcium may be attached to the solid by only one of its bonds. Nearly equal values were found for the equilibrium expression from data covering concentration ranges of 1000 fold for the salt and 235 fold for the ion-exchangeable calcium. Differences indicated between the exchangeable calcium contents of the slime and the sandy portions of the ore, as well as the equilibrium relationship itself, are of importance in the flotation of the ore. During an experimental program on the flotation of oxidized calcareous iron ores from Lorraine, France, ion-exchangeable calcium was found in the ore. Because this source of calcium ions, if not controlled, could thwart all efforts at flotation, an extensive study was made of the phenomenon. The part of that study reported here was to obtain data on the equilibrium established between ore solids and solutions of sodium chloride, and to analyze the data to try to understand better the physical chemistry of the exchange. The ore contains oolites of goethite and quartz grains embedded in a matrix consisting of calcite and a brown cement believed to be the residue from oxidation of the silicate minerals found in fresh unoxidized ore. When ground, a substantial fraction of the ore becomes a fine slime in which is concentrated more than half of the alumina content of the ore. It is believed that the alumina occurs as unidentified clay minerals with which most of the ion-exchange capacity of the ore is associated. A preliminary experiment on the exchange of ions from the ore for sodium ions from solutions of NaCl showed that calcium was about ten times as abundant as magnesium in the exchange solutions. Thus calcium was the predominant ion in causing difficulties with flotation, and it was the only one for which data was obtained in this study. It is believed that the omission of magnesium ion exchange from consideration does not invalidate the results. It is possible, however, that inclusion of magnesium in the analyses and calculations or its prior elimination from the samples would have improved the consistency of the results. EXPERIMENTAL Data about the equilibrium exchange of sodium from solutions for calcium from the solids were obtained using two different samples of material. The solids

Jan 1, 1963

By K. C. Mills, E. T. Turkdogan

A number of investigators1 6 have noted the presence of a liquid miscibility gap in the Fe-Sn binary system. However, the first attempt to measure the

Jan 1, 1964

By William P. Blake

We are so familiar with water in its liquid and its solid form, that we seldom think of it as a mineral, and still less as a mineral product of any considerable industrial importance, though in the form of ice it is mined and stored up in enormous quantities yearly. The industry is peculiarly American, and in no other country has the business of cutting and storing ice been so well systematized and perfected. The interest has grown steadily from year to year, until it has attained large proportions, the annual production being counted in millions of tons, requiring, in the aggregate, a large investment of capital in all the Northern States. It gives employment, also, to thousands of men and horses, in the depth of winter, when farming work cannot be carried on. Ice is not only a luxury, but a necessity, in our climate, and is indispensable in many manufacturing operations: and finds constantly increasing applications and uses. As the industry has grown, so the necessity for suitable implements and tools has grown with it, and it has become necessary to systematize and cheapen the methods of handling such a large amount of material with rapidity and economy. As the industry is properly a branch of mining, and as our mining literature does not, to my knowledge, contain any description of the methods and appliances used in it, it seems desirable to place a brief description on record in our Transactions, and I therefore offer to the Institute the following outline description, based partly upon observations for several years past of the methods and processes employed, and partly upon the information obtained from prominent ice-miners and from the manufacturers of ice-tools. My acknowledgments are particularly due to the firm of W. T. Wood & Co., of Arlington, Massachusetts, for much information in detail, and also to the Knickerbocker Ice Company, of Philadelphia. The wood-cut blocks used in the illustration of this paper, have been kindly lent by both of these firms. The sequence of operations in getting ice is as follows : 1. Wetting down a light snow. 2. Scraping off an excess of snow, if present. 3. Marking out the field. 4. Ploughing and cross-ploughing. 5. Cutting the channel and detaching large floes.

Jan 1, 1883

By William I. Busenbark, Elmer C. Newman

At Bingham Canyon, the world's largest open-pit copper mine, annual grease consumption is in the neighborhood of 109 000 kg (240,000 lb), all of which was 544 (120-16) purchased, warehoused, and distributed in 54-kg (120-1b) and 180-kg (400-1b) drums. While perhaps a menial and mundane chore, grease distribution shows on the ledger as a significant expense item. To improve labor and cost performance, Kennecott maintenance engineers undertook a study to find the most direct method for moving multi purpose grease (MPG) from the refinery to the point of final consumption. What they found was a direct vendor system for hulk grease so simple and flexible that long-established drum distribution is being phased out in favor of the newer method throughout 75% of the operation.

Jan 9, 1977

By M. G. Driessen, H. E. Criner

Possible applications of cyclone thickeners for: (1) clarification of the washery water and, (2) recovery of fine coal from the plant bleed. The paper shows: (1) that it is possible to remove all particles including the very finest, from the circulating water, thus obtaining a closed water system and, (2) that reduction of the ash content of the solids of the plant bleed is feasible by means of cyclone thickeners. Performance data for different size cyclones is given in the form of graphs.

Jan 1, 1950

By H. J. Modi, D. W. Fuerstenau

pH effectively regulates the flotation of corundum through its control of the surface charge. Since collector ions function as counter ions in the double layer, the collector must be anionic when corundum is positively charged and cationic when it is negatively charged. Even a long-chained xanthate will float positively charged corundum. Association of the hydrocarbon chains of the adsorbed collector ions gives rise to increased adsorption and increased rate of flotation. Because of this phenomenon, neutral organic molecules aid flotation although the unionized collector cannot promote flotation independently. Na2SO4 was found to depress the flotation of corundum with animic collectors through ionic competition whereas the same salt activates corundum for flotation with cationic collectors. A close connection between ion association, electrokinetic behavior, and floatability is suggested. As part of the increasing interest in the physical chemistry of flotation, strong experimental evidence has been obtained which indicates that organic ions are adsorbed as counter ions by non-metallic oxide minerals mainly because of the electrical forces which exist at interfaces(1-3). Thus flotation of such minerals without activation should then be appreciable only when the mineral and the collector are oppositely charged. Since only limited work has been reported on the effect of surface charge upon flotation behavior(3) this general hypothesis on the flotation of insoluble oxide minerals has not been tested thoroughly. Investigating the flotation of a mineral for which extensive electrokinetic data exist yields a way to test this hypothesis more extensively. The electrokinetic behavior of corundum in solutions containing both organic and inorganic electrolytes has been studied quite thoroughly' Electro-kinetic measurements have shown that in the case of corundum, simply by controlling pH the solid surface can be charged either positively or negatively. For this reason corundum was chosen for study. The object of this paper is to present a study of the flotation of corundum and to explain the results in the light of our knowledge of adsorption mechanisms gained from streaming potential investigations. This paper is concerned mainly with the effect of surface charge on flotation with anionic and cationic collectors, but in addition such flotation phenomena as collector hydrolysis, Van der Waals attraction between hydrocarbon chains, ionic competition, and activation are discussed. While the present paper is confined to a reporting of the data obtained and some of the more immediate conclusions, it will be seen that the results, in combination with those on other systems, do promise a

Jan 1, 1961

By Gilbert Soler

PRODUCERS of alloy steels recognize the importance of chemical composition in rela-tion to the hot-working properties and the typical surface defects found in their prod-uct. Each analysis of steel has its own peculiar characteristics. Under conditions of standard mill practice each analysis is susceptible to certain types of defects. Mill practice must be varied to obtain the best combination of surface and internal quality in the product. Chemical composition influences the cast structure and crystallization character-istics of the ingot. It also determines the rate of heating and cooling, the plastic hot-working range, and the phase structure of the steel at various temperatures as well as the tendency toward scale formation and decarburization, This paper endeavors to emphasize the manner in which chemical composition affects the various properties of steel, and to indicate the relative impor-tance of these factors in relation to the hot-working properties and surface charac-teristics of killed steel. The influence of chemical composition may be outlined as follows: I. Effect on the cast structure of steel, including: A. State of deoxidation, and type of inclusions. B. Gas content of steel. C. Freezing point and melting point of steel.

Jan 1, 1940

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 M. R. TECK, N. Rudd, L. K. Thomas, D. L. Katz

The authors are to be congratulated for presenting the first comprehensive paper on the theory and practice of threshold pressure determination in connection with underground gas storage. It is of particular value since most previous experimental work on this subject has been proprietary to the commercial laboratories engaged in such testing and to their clients. This dlscussion is presented in amplification of the subject paper, not in criticism, and is based upon our experience with approximately 5,000 threshold pressure determinations. Our comments are directed primarily to the experimental procedures as described by Thomas et al. It should be noted that, while clay mineral-rich lithologies are the most common caprock materials, the samples used (Table 1) include low permeability sandstones and carbonates, but do not include shales or other formations in which clav minerals exert a dominant effect. While our experience on samples analogous to those investigated by the authors generally confirms their findings, we have found that even more rigorous experimental conditions must be imposed where clay minerals are the controlling factor. These additional conditions result from the well-known molecular character of the clay minerals themselves in which water is interlaminated with, and bonded to, silicate sheets, thus becoming an essential component of the molecule. In many clay minerals the character of the intersheet bonding, and thus the dimension of the lattice, is strongly affected by variations in the identity and concentration of cations present in the intersilicate water. On a supermolecular scale, adsorbed water films on particle or "flakes" of shale provide much of the cohesive force necessary to maintain mechanical strength. The thickness of these films is variable and inversely proportional to intergranular pressure within the dimensional limits involved in caprock investigation. The thickness of the intersilicate water layers may also be subject to pressure under some conditions. These considerations are reflected in several necessary modifications of the experimental procedures described by the authors. Two of these are, in our judgment and experience, of such importance that they cast real doubt on the validity of data obtained on argillaceous materials without their application. The very careful resaturation procedures proposed by the authors should give good results in connection with the relatively "inert" lithologies used in their experiments. Our experience suggests, however, that they would create more problems than they would eliminate if applied to argillaceous materials. 1. Drying of the sample at the temperature and for the duration indicated by the authors not only will dessicate the sample with consequent shrinkage cracking, parting along bedding planes, and even total disassociation in the case of fissile shales, but it may also alter the character of the clay minerals themselves — in some cases irreversibly. 2. Prolonged evacuation to 2 microns Hg further dessicates the sample and is even more effective in reducing the intersilicate water content. 3. Resaturation with water differing in pH or chemical content from that existing originally in the sample also serves to alter the nature of the sample, particularly its structure and strength. 4. Our experience has been that, even with the thorough precautions proposed by the authors, complete resaturation of very fine grained materials is rarely obtained. Yet our experience confirms the

Jan 1, 1969