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By D. G. F. Hedley, D. F. Coates, K. Barron

INTRODUCTION Preceding papers presented in this symposium have considered the influence of various parameters, such as geologic structure, groundwater, etc., on the stability of rock slopes and have given some analyses and guide lines for slope design. To carry out such analyses it is necessary to put numbers to these parameters; where possible, this is best done on the basis of in- situ observation and measurement. Since none of the design analyses can be considered exact and since conditions vary during excavation, it is also desirable to monitor the behaviour of the slopes as the excavation proceeds. In this manner a feedback of information on the actual excavation conditions can allow a continuous reassessment of the design parameters to be made and can give early warning of incipient failures. The purpose of instrumenting rock slopes is thus to provide information which fits into one of two categories: (a) To give basic data to assist on-site assessment and design of the rock excavation. (b) To provide data for the control and assessment of safety during excavation. The purpose of this paper is to review briefly some of the instruments and measuring techniques available for gathering this data and to indicate where such data may prove useful. This is not a comprehensive review of all available instrumentation but, rather, is a survey of some of the instruments and techniques with which the authors have had some experience and which have proven useful. STRUCTURAL ASSESSMENT Whilst most structural assessment of a site is done on the basis of geologic mapping and core examination, there exists some instrumentation which can, in particular circumstances, assist in this assessment. Seismic instruments can be used to determine the geometry of formations and to give an indication of the relative competency of rocks. These instruments operate using seismic reflection or refraction techniques and, although mainly confined to shallow sub-surface exploration, can be useful in distinguishing between soil/ bedrock contacts and, in some cases, the extent of weathered surface rock.

Jan 1, 1971

By R. Buehl

ALTHOUGH the main features of the transformations occurring in 18-8 have been published already,1-4 certain conclusions merit questioning and discussion. The questions may be summarized as follows: PERCENT REDUCTION BY COLD ROLLING FIG. 1.-VARIATION OF FERRITIC INDUCTION AND PERCENTAGE OF FERRITE WITH COLD REDUCTION. Composition of Alloy: C, 0.08; Mn, 0.40; Si, 0.24; P, 0.014; Cr, 18.13; Ni, 8.94. 1. If ferrite is formed by cold-working austenite, what happens to the carbon with which the ferrite and austenite are both pre-sumably supersaturated? 2. What is the nature of the alpha-ferrite formed at grain boundaries by chromium-carbide precipitation at these boundaries?

Jan 1, 1939

By R. W. Raymond

In my former paper (Bans., xii., 410) I quoted the ruling of Judge Hallett, of Colorado, in the "Iron-Smuggler" case, tried before him in June, 1882. Under his charge, the jury in that case found for the defendants, practically declaring that the deposit on the outcrop of which the Iron Silver Mining Company's claim was located was not a " lode," or else that the portion of it within that claim was not the apex. The case was appealed, and the decision of the Supreme Court, given in February, 1886, is reported in 116 U. S. Reports, p. 529. It simply declares that there is nothing in the charge of Judge Hallett to warrant the setting aside the verdict. The definition of a legal lode given in that case, and quoted in my paper at the page above-named, is perhaps the best of several which Judge Hallet has pronounced. That is to say, his earlier definition, that " a lode or vein is a body of mineral, or mineral-bearing rock, within defined boundaries in the general mass of the mountain," is here accompanied with further explanations, which relieve it from the requirement on one hand, that the body shall be continuously ore-bearing if it he only well-defined, and, on the other hand, that the boundaries shall be well-defined if the ore-bearing body be proved to exist. So far as this particular case is concerned, the approval of this ruling by the Supreme Court merely prevents any re-hearing as to the face. Undoubtedly, the evidence was conflicting; and the jury chose to believe, for the purpose of that occasion, the " experts " who

Jan 1, 1887

By W. J. Joslin

The frontal-advance equation can determine how the fluid withdrawal rate and subsurface operating pressure influence oil recovery from pressure-maintained reservoirs having characteristics favorable for efficient vertical segregation. For effective vertical segregation in formations having low dip angles, the requirements are: thick, massive sands, low viscosity oil and high vertical permeability with few discontinuous shale members. This approach has been successfully applied to the LL-370, which is a massive Eocene sandstone reservoir containing crude with an average gravity of 26" APT, a dip of only 3" and vertical permeability of ½ darcy. The average gas cap saturation was calculated for various rates of vertical gas-oil contact movement corresponding to a wide range of reservoir producing rates. This method also evaluated the effect of different pressure maintenance levels on oil recovery. Applicability of this procedure for calculating the present oil saturation in the LL-370 gas cap has been substantiated from field performance, where the oil saturation was computed by comparing oil recovery with the gas cap volume vacated. INTRODUCTION During the natural depletion history of the LL-370 reservoir, located in Lake Maracaibo, Venezuela, excellent vertical segregation resulted in the formation of a thin gas zone over a substantial portion of the oil-productive area. Subsequently, gas injection forced this thin gas-saturated zone slowly downward, reducing the oil saturation in the gas cap to a low value. The oil recovery has been raised considerably above earlier predictions where vertical segregation effects were under-estimated. In order to determine the maximum efficient producing rate and optimum operating pressure for this reservoir, a vertical gas frontal-advance analysis has been made through application of the fractional flow equation. LL-370 RESERVOIR CHARACTERISTICS The reservoir consists of a truncated monocline of massive. highly-permeable Eocene sandstone, called the B-b formation, covering an area of more than 13,500 acres. The original oil in place was 2.17 billion STB. Internal non-sealing faults subdivide the structure into four blocks called the B-6-x.6, 10, 11 and 13, which are effectively bounded by major faulting on the flanks, an unconformity updip to the west, and an immobile aquifer to the southeast. The producing formation occurs at an average depth of 5,250 ft subsea and has a closure of more than 1,500 ft. A typical producing section has a net oil sand thickness of 170 ft. Scattered throughout the section are a few randomly-positioned shale lenses which increase in thickness and areal extent downdip. The reservoir rock and fluid properties vary with depth. The permeability and produced oil gravity are 1600 md and 28" API at the top, compared to 300 md and 18° API at the water-oil contact. The productivity of updip wells is, therefore, much higher than the reservoir average. The reservoir oil was originally saturated at the crest, grading to a slight degree of undersaturation at the water-oil contact. There was no original gas cap; and material balance and the field performance indicate no water influx. Except for the northern B-6-x.6 block, the fluid and rock properties have already been published.' Average LL-370 reservoir properties are shown in Table 1. RESERVOIR PERFORMANCE UNDER NATURAL DEPLETION Fig. 1 shows production performance from 1939 to date. Early development was gradual, with 30 wells pro-

Jan 1, 1965

By F. W. Maclennan

ORE production from the property of the Miami Copper Co. began early in 1911. Until 1925 this ore came from the so-called high-grade orebodies, which contained a little over 2 per cent. copper. This ore was mined by the following methods. 1. Top slicing after mining the peaks by square setting, which produced 4,524,347 tons, including ore from square setting. 2. Shrinkage stoping with sublevel caving of the pillars, which produced 2,230,577 tons. 3. Undercut caving with hand tramming, which, produced 15,427,672 tons. Estimating December tonnage, the total ore mined to the end of 1929 will amount to slightly more than 43,000,000 tons. The first method was described by E. G. Deane1 and the second by D. B. Scott,1 and the third, together with a general, description of the mine, by J. H. Hensley, Jr.1 The geology of the district has been worked out by. Dr. F. L. Ransome.2

Jan 1, 1930

By C. A. Heiland

THE investigations described were made on a portion of Clear Creek basin near Golden, Colo. (A portion of the area under survey is shown in Fig. 1. The photograph was taken in the vicinity of station No. 2 of Line II.) Three principal purposes were in the minds of the investigators: 1. To repeat with modern, more sensitive and more reliable instruments magnetometric placer investigations previously made. 2. To disprove the recently advanced theory that deposits of the glacial period have no pronounced magnetic effects. 3. To develop in detail the theory of the magnetic effects produced by placer deposits. Six years ago, the first magnetic observations were published, which proved that it is possible to locate gold-bearing channels with relatively crude instruments.1 Two years ago, K. C. Laylander published results obtained with similar instruments.2 The measurements of the latter were discussed by the senior author of this paper.3 At that time, however, the material available for such a discussion was somewhat scarce and not made with the most modern magnetic instruments, although very brilliant results were obtained. Therefore, the senior author felt that magnetic investigations should be made on very clear geologic conditions with the most modern instruments.

Jan 1, 1928

By R. L. Slobod, C. Gatlin

This .study defines the basic mechanism of the mis-cible displacerrzent of oil and writer from porous Medici by various water-driven alcohol .slugs. Three distinct alcohol slug processes were .studied. Considerable data concerning the quanity of alcohol required for oil recovery were also obtained. All data were obtained in a 1-in. diameter, 100-ft long, unconsolidated core. The porosity of this system was 35 per cent. and the permeability was approxitrlately 4 darcies. Total core pore volume wax 5,716 cc. All displacements were conducted at a constant injection rate of 5 to 6 cc//min, which corresponds to a frontal advance of 5 ro 6 ft/hr. The first portion of this paper is concerned with 111 use of one alcohol—isopropyl—a\. the slug material. Isopropyl alcohol (IPA) is completely miscible with both oil rind water; however, miscibility of the threc-component systems, oil-water-IPA, requires a relutively. high concentration of IPA. Hence, the displocement is not of the misoible type unless the IPA concentration is maintained above some critical value. A slug of IPA equal to only 13.5 per cent of the pore volume was jound to be sufficient to obtain complete recover?, of residua1 naphtha. In later studies two distinct process variations were developed. The firsr of these utilized methyl alcohol (MA) and IPA as slug materials. It was shown that methyl alcohol may he substituted for IPA at the front and rear of the slug with no loss of oil recovery. A .slug of 4 per cent MA-4 per cent IPA-4 per cent MA was sufficient for complere oil recovery. Because MA is considerably cheaper than IPA, this represents an important step toward economic application. A .second process variation used normal butyl alcohol (nBA) and MA as the composite slug, the nBA segnzent being injected first. This technique requires the smallest total slug size (approximately 10 per cent) of all processes studied. The high cost of nBA, however, precludes commercial application. It is possible that this basic process, subject to changes of alcohol type, may lead to a commrercicil process. INTRODUCTION Within the last 10 years, considerable study has been devoted to the general mechanics of miscible phase dis- placements in porous media. These studies have. in general, dealt with two-component displacernent. All reported field trials to date have been modified gas drives of one type or another. These utilize either lean gas at high pressure, rich gas at lower pressure or an LPG slug. The irreducible water content of the reservoir remains immobile during these processes. Although these techniques hold great promise. certain drawbacks do exist. Poor areal sweep efficiency, inherent in any displacement having a highly unfavorable mobility ratio, is one disadvantage. Furthermore, the miscibility of all processes which use gas is dependent on pressure. These pressure limitations may prohibit application to shallow reservoirs. There are also many areas where large quantities of LPG and natural gas are not readily available. These factors emphasize the need for improved techniques. The alcohol slug process is also a miscible-phase displacement process. It differs from the previously mentioned two-component techniques, however, in that both the reservoir oil and water are displaced by the slug. This behavior is a consequence of the miscibility of certain oil-water-alcohol systems. In the simplest case, a relatively small volume (slug) of an alcohol (such as isopropyl) is injected into the system. Water is then used to drive the slug through the medium. Thus. three components—-alcohol. oil and connate water-—exist at the front side of the slug. Miscibility is obtained at some alcohol concentration, this being dependent on the solubility of the particular system. Miscibility is maintained within the slug until the alcohol concentration falls below that value required to maintain miscibility. When miscibility is lost, the process reverts to a water flood. Certain inherent benefits of this technique are apparent. High pressures are not necessary to obtain miscibility in these liquid systems. Furthermore, water is a more desirable driving agent than gas because of the improved mobility ratio and the attendant improvement in areal sweep efficiency. The main disadvantage is, of course, the relatively high cost of alcohols. The use of an alcohol slug to recover reservoir oil is not a new idea." ' However, this process has received only limited study, presumably due to the lack of industrial interest caused by the seemingly prohibitive cost of alcohols. The main purpose of this study was to investigate the mechanism of the displacement of oil and water by various alcohol slugs and to develop process modifications aimed toward possible commercial application.

By Donald D. Carr, Lawrence F. Rooney

Perhaps no other mineral commodity in this volume has as many uses as limestone and dolomite. These carbonate rocks are the basic building blocks of the construction industry, the material from which aggregate, cement, lime, and building stone are made. Carbonate rocks, and their derived products, are used as fluxes, glass raw material, refractories, fillers, abrasives, soil conditioners, ingredients in a host of chemical processes, and much more. Although the use of limestone and dolomite goes back before recorded history, new uses and products are continually being found. Carbonate rocks form about 15% of the earth's sedimentary crust and are widely available for exploitation. Found extensively on all continents, they are quarried and mined from formations that range in age from Precambrian to Recent. Reserves of carbonate rock are large and will last indefinitely, although high-purity deposits may be absent or have limited availability in certain areas. Limestone and dolomite are so useful and so abundant that in 1981 about 644 million tons were produced in the United States. In fact, about 75% of all stone quarried or mined in the United States was carbonate rock. Sand and gravel was the only mineral commodity produced in greater quantity. In this chapter we have sought to provide the general reader an overview of carbonate rocks, their composition, distribution, production, and uses, with emphasis on developments since 1960. In doing so we borrowed extensively from our report on the applied geology of limestone and dolomite (Rooney and Carr, 1971). The literature on the limestone and dolomite resources of the United States and Canada is so vast and diverse that one can easily become mired down in print. We tried to list those references that are easily accessible and that provide the economic geologist with a starting point for more intensive study. The table listing selected references on limestone and dolomite resources in Canada and the United States reflects our attempt to be selective rather than exhaustive and to direct the reader to the best sources of detailed information. Geology Mineralogy The principal carbonate rocks used by industry are limestone and dolomite. Limestones are sedimentary rocks composed mostly of the mineral calcite (CaCO3) and dolomites are sedimentary rocks composed mostly of the mineral dolomite (CaCO3 • MgCO3). Aragonite (CaCO3), which has the same chemical composition as calcite but a different crystal structure, is economically important only in modern deposits, such as oyster shells and oolites. Aragonite is metastable and alters to calcite in time. Some other carbonate minerals, notably siderite (FeCO3), ankerite (Ca2MgFe (CO3)4), and magnesite (MgCO3), are commonly found associated with limestones and dolomites but generally in minor amounts. Because of their similar physical properties, the carbonate minerals are not easily distinguished one from the other. Specific gravity,

Jan 1, 1983

By A. Lubinski

In drilling operations, attention generally is given to hole angles rather than to changes of angle, in spite of the fact that the latter are responsible for drilling and production troubles. The paper presents means for specifying maximum permissible changes of hole angle to insure a trouble-free hole, using a minimum amount of surveys. It is expected that the paper will result in a decrease of drilling costs, not only by avoiding troubles, but also by removing the fear of such troubles. SUMMARY, CONCLUSIONS AND RECOMMENDATIONS Excessive dog-legs result in such troubles as fatigue failures of drill pipe, fatigue failures of drill-collar connections, worn tool joints and drill pipe, key seats, grooved casing, etc. Most of these detrimental effects greatly increase with the amount of tension to which drill pipe is subjected in the dog-leg. Therefore, the closer a dog-leg is to the total anticipated depth, the greater becomes its acceptable severity. Very large collar-to-hole clearances will cause fatigue of drill-collar connections and shorten their life, even in very mild dog-legs. Another finding regarding fatiguing of collar connections in dog-legs is that rotating with the bit off bottom sometimes may be worse than drilling with the full weight of drill collars on the bit, mainly in highly inclined holes when the inclination decreases with depth in the dog-leg. Means are given for specifying maximum dog-legs compatible with trouble-free holes. An inexpensive technique proposed is to take inclinometer or directional surveys far apart; then, if an excessive dog-leg is detected in some interval, intermediate close-spaced surveys are run in this interval. The application of the findings should result in a decrease of drilling costs, not only by avoiding troubles, but mainly by removing the fear of such troubles. The result would be much more frequent drilling with heavy weights on bit, regardless of hole deviation. Because of errors inherent to their use, presently available surveys are not very suitable for detecting dog-legs. There is a need for instruments especially adapted to dog-leg surveys. Crooked hole drilling rules should fall into two distinct categories—(1) those whose purpose is to bottom the hole as desired, and (2) those whose purpose is to insure a trouble-free hole. Three kinds of first-category rules in usage today are as follows. 1. A means to bottom the hole as desired is to prevent the bottom of the hole from being horizontally too far from the surface location; this may be achieved by keeping the hole inclination below some maximum permissible value such as, for instance, 5. 2. Another means to achieve the same goal is to limit the rate at which the inclination is allowed to increase with depth. A frequently used rate is 1/1,000 ft. In other words, a maximum deviation of l° is allowed at 1,000 ft, 2 at 2,000 ft, 3 at 3,000 ft, etc. 3. Whenever application of the first two means precludes carrying the full weight on bit required for most economical drilling, then the best course is to take advantage of the natural tendency of the hole to drift updip, displace the surface location accordingly and impose a target area within which the hole should be bottomed. This method has already been successfully applied,'.' and its usage probably will become more frequent in the future. Means for calculating the amount of necessary surface location displacement are avail-able.3'5'6 If in high-dip formations the full weight on bit should result in unreasonably great deviations, the situation could be remedied by increasing the size of collars and (if needed) the size of both hole and collars,351 or in some cases by using several stabilizers. Rules which would fall into the second category (i.e., rules whose purpose is to insure a trouble-free hole) are seldom specified today. It is vaguely believed that following Rules 1 and 2 of the first category will automatically prevent troubles. Actually, this is not true. If at some depth the only specified rule is that the hole inclination must be less than 4", the hole may be lost if the deviation suddenly drops from 4 to 2, or if the direction of the drift changes, etc. Rule 3 of the first category is generally used in conjunction with a rule belonging to the second category, namely, that the hole curvature' (dog-leg severity) must not exceed the arbitrarily chosen value of 1½ /100 ft. Moreover, when using this rule, the industry is not clear over what depth intervals the hole curvature should be measured. All this results in a frequent fear

By G. W. Jarman

The purpose of this paper is to present briefly a description of some of the special methods of separation or concentration, either singly or in combination with others, and to give certain operating data and examples. Explanation of the usual methods of large-production mill treatment, such as flotation or wet tabling, or of chemically treating industrial minerals, is not included in the scope of this paper, although one of these methods might be, in certain instances, augmented by one or more of the special methods that will be enumerated herein. Description of these special methods will be centered on magnetic separators, electrostatic separators and air flotation or air tables. Magnetic Sepaeatohs In general, separation is achieved by exerting upon a particle some kind of force opposed to gravity, either directly or at an angle. For example, in the Wetherill or cross-belt type of magnetic separator some particles are lifted vertically from the others because they have been exposed to a force to which they respond more readily than particles of lesser magnetic susceptibility. Of course, there is a limitation to this vertical rise, for the particle must be of a high enough susceptibility to receive a magnetic force greater than the 980 dynes per gram of gravitational urge. To overcome this limitation, the induction type of magnetic separator was developed, so that it is only necessary to instill, say, 30 to 60 dynes per gram instead of the 080, to cause a deflection away from the vertical in falling, and that deflection can be used advantageously when falling by inserting a dividing knife-edge. The induction magnetic separator (Fig. 1) has become a fairly well known method of concentrating and purifying. For example, abrasive grain was among the materials that did not respond to the previously best known type of magnetic separator, such as the Wetherill type, and the development of the induction magnetic separator in the plant of a

Jan 1, 1942

By G. W. Jarman

The purpose of this paper is to present briefly a description of some of the special methods of separation or concentration, either singly or in combination with others, and to give certain operating data and examples. Explanation of the usual methods of large-production mill treatment, such as flotation or wet tabling, or of chemically treating industrial minerals, is not included in the scope of this paper, although one of these methods might be, in certain instances, augmented by one or more of the special methods that will be enumerated herein. Description of these special methods will be centered on magnetic separators, electrostatic separators and air flotation or air tables. Magnetic Sepaeatohs In general, separation is achieved by exerting upon a particle some kind of force opposed to gravity, either directly or at an angle. For example, in the Wetherill or cross-belt type of magnetic separator some particles are lifted vertically from the others because they have been exposed to a force to which they respond more readily than particles of lesser magnetic susceptibility. Of course, there is a limitation to this vertical rise, for the particle must be of a high enough susceptibility to receive a magnetic force greater than the 980 dynes per gram of gravitational urge. To overcome this limitation, the induction type of magnetic separator was developed, so that it is only necessary to instill, say, 30 to 60 dynes per gram instead of the 080, to cause a deflection away from the vertical in falling, and that deflection can be used advantageously when falling by inserting a dividing knife-edge. The induction magnetic separator (Fig. 1) has become a fairly well known method of concentrating and purifying. For example, abrasive grain was among the materials that did not respond to the previously best known type of magnetic separator, such as the Wetherill type, and the development of the induction magnetic separator in the plant of a

Jan 1, 1942

By H. R. Hanley

THE characteristics of alloyed anodes and their influence on the products of electrolysis and power consumption have been noted previously in the literature.1 This paper presents data in continuation of the subject given in an earlier paper by the authors.2 As noted in the authors' previous paper, the objectives of this work are the reduction in the cell voltage and the purity of the cathode product resulting from the use of alloyed lead anodes. The fundamental facts developed in the previous paper were: (1) that the presence of a small amount of calcium lowers the anode potential approximately 50 per cent. below that of pure lead; and (2) that thallium when present to the extent of 4 per cent. rendered the anode practically stable, thereby lowering the contamination of the cathode by lead to a very insignificant amount. The specific features determined in this recent work are as follows: 1. The lowest limit of calcium in the lead which will still give maximum lowering of the anode potential. 2. The characteristics of the thallium-calcium-lead anode. 3. The characteristics of the silver-calcium-lead anode. 4. The characteristics of the thallium-silver-calcium-lead anode. It was determined that 0.1 per cent. calcium in the anode was sufficient to lower the anode potential approximately 50 per cent. Table 1 shows the characteristics of alloyed anodes tested. The anode composed of 0.1 per cent. calcium, 4 per cent. thallium, and 95.9 per cent.

Jan 1, 1931

By J. W. Wolfe

The Benedict-Webb-Rmbin equation of state was used in digital computer programs to make rapid determinations of natural gas equilibrium phase compositions. Mixture components were the nine hydrocarbons, methane through heptane. Comparative tests were made with data from field separators, plant exchangers and literature sources. For most tests made, the B-W-R equations predrcted component K-vallles, mixture enthalpies and phase aensities within tile accuracy of available correlations for rune-component mixtures: significant deviations were noted when mixtures contained components heavier than heptune. INTRODUCTION Rapid, accurate methods for calculating the properties of hydrocarbon mixtures are needed for predicting the behavior of natural gas processes. For example, because of the common use of two-phase separation methods in gas proccssing, calculations must be made for the density and composition of equilibrium vapor and liquid phases. In addition, predictions must often be made for the temperature and pressure changes associated with the flow of single- and two-phase natural gas fluids through heat exchangers, chokes and turbines. The complex nature of non-ideal mixtures makes rigorous calculations for these natural gas properties difficult and time-consuming. Natural gas properties have conventionally been determined with generalized data correlations. These correlations, such as the K-values presented in the NGAA Equilibrium Ratio Data Book, are usually based on some average property of the mixture and have proven to give satisfactory estimates for the properties of most oil and gas systems. Digital computers, however, have not only increased the utility of these correlations, but also have made practical the use of equations of state for calculating the properties of natural gases. Potentially, if basic pure component data are available, all the desired thermodynamic properties of mixtures can be derived from a single equation of state describing the mixture. Currently. the best equation of state for describing the behavior of pure, light hydrocarbons over single-and two-phase regions, both below and above critical pressure, is that of Benedict. Webb and Rubin.' The equation contains eight constants which are determined by empirically fitting the equation to pure-component PVT data. Benedict and his co-workers presented the clevelopment of their equation as early as 1940.2 The B-W-R equation is a modification of the Beattie-Bridgeman equation of state and gives better PVT predictions than the Beattie equation at densities above the critical density. Benedict et al. made the equation applicable to mixtures by relating the mixture constants to composition and the constants for pure compounds. These authors, in a serics of articles in 1951,' showed the accuracy of the B-W-R equation when applied to light hydrocarbons and their simple mixtures, and demonstrated the equation's utility for making vapor-liquid equilibria calculations. Since its inception, the B-W-R equation has been the subject of many papers. Numerous additions and modifications have been proposed,'-',"'-':' the purpose of most being to improve the equation's ability to predict PVT properties of specific mixture systems. In 1959, Opfell, Pings and Sage summarized much of the work on the B-W-R equation in their book on equations of state." Since natural gases are primarily mixtures of light hydrocarbons, the B-W-R equation is a natural choice for an equation of state to compute both phase equilibria and thermodynamic properties of natural gases. Consequent-

Jan 1, 1967

By C. Land, R. Hultgren

Heat contents of four Cr-Ni alloys were determined in a diphenyl ethev calorimeter. Aside from ferromagnetic effects, Kopp's law of additivity of heat capacities is approximately fol-lowed, in disagreement with earlier results of A. W. Foster. In 1934 Foster1 reported heat-capacity measurements of dilute solutions of chromium in nickel, primarily as a study of the effect of alloying on the ferromagnetic Curie temperature. He found that, apart from the Curie temperature effect, the general level of heat capacities was reduced 10 pct by the addition of 1 pct Cr; 20 pct by the addition of 2 pct Cr. His measurements of pure nickel essentially agreed with accepted values. These results indicate that small amounts of dissolved chromium cause an increase in the Debye temperature of nickel, presupposing a change of frequency of interatomic bonding vibrations which is much larger than should be expected. If Foster's results were verified, therefore, they would have important implications for bonding theory. The only other heat-capacity measurements in this system seem to be those of Taylor and Hinton,' who studied anomalies which they attributed to super-lattice formation at 25 at. pct Cr. At temperatures above the anomaly, Taylor and Hinton found heat capacities at this composition were quite normal, approximately obeying Kopp's law of additivity. EXPERIMENTAL WORK In order to verify or disprove the remarkable results of Foster, the heat contents of four dilute solid solutions of chromiunn in nickel were measured in a diphenyl ether calorimeter. This instrument, described elsewhere,, operates on the principle of the Bunsen ice calorimeter, but uses diphenyl ether as the working substance. Diphenyl ether melts at the convenient temperature of 26.S°C and supplies a more sensitive measure of heat than ice. The hot sample, in an atmosphere of argon, is dropped from a furnace at a measured temperature into a chamber which is surrounded by a mixture of solid and liquid diphenyl ether. The heat from the hot specimen melts some of the solid without chang- ing the temperature of the calorimeter. The amount of solid melted, and therefore the number of calories released by the specimen, is measured from the increase of volume of the mixture, which pushes mercury down a graduated capillary tube. The apparatus has been standardized against the known heat content of pure platinum. Heat loss during the dropping of the specimen was estimated by comparing the heat content of an empty platinum capsule with a solid platinum ball of the same radius and degree of polish of the surface. Repeated tests demonstrate the precision of measurement to be closer than *0.3 pct. Smoothed experimental results are listed in Table I. The tabulated values for pure nickel are taken from kelley, several measurements were made which agreed closely with this tabulation. For chromium, however, no similar agreement was found. The values tabulated were taken from a thorough study of chromium with the diphenyl ether calorimeter which will be published elsewhere.= Suitable plots of the data showed the expected ferromagnetic anomalies in the low-chromium alloys, while the 11 pct alloy shows no ferromagnetic anomaly, but a different, small anomaly below 900°K. This is perhaps the same anomaly found in CrNi, which was once attributed to superlattice formation,' but is probably due to some other cause, such as antifer-

Jan 1, 1960

By K. A. Jackson, G. A. Chadwick, A. Klugert

The diffusion field ahead of a lamellar interfnce is analyzed using an electrical analog. A self-consistent solution is obtained for the shape of the interfnce and the diffusion field by an iterative process. The solutions presented here are for a 50-50 eutectoid or eutectic, The shape of the interface is found to he independent of growth velocity and lamellar spacing, and to depend on the relative values of interfacial free energies at the phase houndaries . The mode of growth of lamellar eutectics and eutectoids has been a subject of much interest for many years.1-4 Mehl and Hagel 1 have shown photomicrographs taken by Tardif when he attempted to determine experimentally the shape of an advancing pearlite interface; the results are completely ambiguous. Brandt' and schei13 have made approximate calculations of the composition ahead of a lamellar growth front. The shape of the advancing front and the composition distribution ahead of the front are difficult to calculate because one depends on the other. It is the purpose of the present paper to describe a method by which this calculation has been done. Lamellar-eutectic growth usually occurs under conditions where the growth is fairly rapid, and the interface temperature is close to the eutectic temperature. The growth rate is usually determined by heat flow. Eutectoid growth, on the other hand, can best be studied by quenching to some temperature, and allowing growth to proceed isother-mally. In both cases the growth is believed to be controlled by diffusion* rather than by the atomic kinetics of the transformation. This being the case, a single treatment of the diffusion equation will apply to both cases, provided the region of the interface in a eutectic may be considered to be isothermal. If a part of the interface could appreciably change its thermodynamic driving force by advancing ahead of or lagging behind the mean interface, then the two cases would not be similar. Eutectics normally grow in temperature gradients of the or-der of a few degrees per centimeter. The normal eutectic spacing is the order of a few microns. Part of the interface would have to extend many lamellar spacings ahead of the mean interface before it experienced sensibly different conditions. The interface temperature is usually a few tenths of a degree below the eutectic temperature so that temperature differences of the order of one-thousandths of a degree (a displacement of one lamellar spacing) would be unimportant. Protrusions large compared to the mean spacing do occur when one phase only grows into a eutectic liquid. This is usually a dendritic type of growth, and easily distinguishable from the lamellar mode of growth. A single treatment of lamellar growth will apply equally well to both eutectic and eutectoid decomposition. At the interface, which as shown above is essentially isothermal, the difference between the equilibrium eutectic temperature Teu and the actual interface temperature Ti, can be divided into two parts: 1) the composition varies across the interface, so that the local equilibrium temperature is not Teu; and 2) the interface is curved, so that the local equilibrium temperature is depressed according to the Gibbs-Thompson relationship. This undercooling can be written as Teu-Ti =?T = mAC(x) + a/r(x) [1] where ?C(X) is the departure of the composition at a point x on the interface from the eutectic composition, see Fig. 1, r(x) is the local radius of curvature at a point x on the interface, m is the slope of the liquidus line on the phase diagram, and a is a constant given by where s is the interfacial free energy, TE is the equilibrium temperature, and L is the latent heat of fusion. The calculations in this paper will be made only for the case where the phase diagram is symmetric, that is, the eutectic occurs at 50 pct, the liquidi have the same magnitude slope m at the eutectic temperature, and C,, the amount of B rejected when unit volume of a freezes, see Fig. 2(a), is the same for both phases. As shown in Fig. 2(b), the composition ahead of the a phase will be rich in B, the composition ahead of the ß phase will be rich in A. The composition at the phase boundary is the eutectic composition. The difference between the local liquidus temperature and the actual tempera-

Jan 1, 1964

By Van H. Manning

In substance, the international aspects of the petroleum industry, as these relate to the United States, are as follows: The domestic production is not keeping pace with the domestic demands; our best engineering talent warns us of the imminence of a decreased production by our oil wells, although more oil is needed; and the only practical source whence this increasing demand can be supplied for some time to come will be the foreign fields. Other nations have given thought to the future and, in recent years, have shown a tendency to adopt strong nationalistic policies regarding their petroleum resources, policies that hinder or prevent the exploitation of these resources by other nationals. In consequence, we find that, facing a probable shortage of the domestic supply, our nationals are excluded from foreign fields; and this in spite of the fact that foreign nationals have been permitted to enter into and exploit our own oil resources on an equality with American citizens and without hindrance or restrictions. This country has supplied the larger part of the petroleum consumed by the world and yet, with a failing supply imminent, it finds that those countries that, have been drawing upon our resources to supply their needs are showing a tendency to exclude us from their resources. In this way we shall be transferred from a position of dominence to one of dependence; and only by sufferance of those countries that are now seeking financial or political control of petroleum supplies, shall we be able to obtain the oil we will need. Impoetance of Petroleum Petroleum has become, during recent years, one of the essentials of our social and industrial life. All civilized countries recognize that the world is dependent on petroleum as on nothing else except textiles: foodstuffs, coal, and iron. Today, the tendency is toward an ever-increasing consumption of petroleum and its products as new and more efficient uses are found for them. The utilization of petroleum is extending more and more into the structure of our civilization. Consequently,

Jan 1, 1921

By Harlowe Hardinge

THE sound made by ball, pebble and rod mills has long been used by the operator as the "telltale " of their operation. The nature of this sound depends upon local conditions and the type of mill used. By experience an operator can tell whether the mill is running properly or not. Some operators are able to detect the difference in sound much better than others and get better results running the same mill under the same conditions. The automatic operation of a mill using sound as the fundamental means for maintaining control presents many problems. The satisfactory solution of these problems requires, for given operating conditions, a greater average output, with improved product for subsequent processing, than can be obtained by manual control. RELATION OF SOUND TO USEFUL GRINDING ENERGY Experience has taught us that there is a difference in character as well as in intensity of sound between a mill grinding wet and one grinding dry, in open or closed circuit, to obtain a coarse or fine product, on the same material, to say nothing of the effect with a variety of different materials. Broadly speaking, a wet-grinding mill operates best at a lower sound level than the same mill grinding dry, with other conditions the same. Several reasons for this variation in sound intensity under these conditions can be advanced, but the important point is that there is a difference, based upon practical results. Since these reasons may be more or less involved, and may be subject to much discussion, only one will be considered here. It is apparent that two balls hitting together or a ball striking the lining, if there is no intervening material, will produce the maximum sound. If a complete cushion of material is placed between the balls or ball and liner, so that the energy is dissipated without doing useful work, the balls will be unable to create enough pressure or force to fracture the particles, and the sound will be at a minimum. At some point in between-that is, where there is sufficient material between the balls or ball and liner so that the ball will fracture the particles without mashing them unduly-the sound

Jan 1, 1939

By C. A. Hartnagel

The production of petroleum in New York state in 1942 amounted to 5,410,000 bbl. This represents an increase over each of the four preceding years, and, with the exception of 1937, is the largest production since the peak of over six million barrels in 1882, shortly after the discovery of oil in Allegany County. The oil industry in New York is virtually stabilized and there has been little or no exploration for new sources of supply in recent years. The boundaries of the present fields were established more than 30 years ago and since then no additional reserves have been found. Deep drilling for natural gas during the past 10 years both within and without the oil fields has failed to find oil in quantity below the present producing sands of Devonian age. Oil Since 1882, the New York fields have produced approximately 140 million barrels of oil. Of this amount, 65 million was produced up to the year 1919 by ordinary pumping methods; that is, without flooding by water or the use of other secondary-recovery methods. In the year 1919, when a law was passed making the use of water-flooding methods legal, the oil production, of the state amounted to only 851,000 bbl. In the 23 years since 1919, there have been produced in the state 75 million barrels, or 10 million more than in the previous 37 years, which included the period of flush production. Price.—On March 26, the price of crude oil was raised from $2.75 to $3.00 per barrel, hut this increase had little or no effect on the number of wells drilled. In the Allegany field, which accounts for three fourths of the state's oil production, 1259 wells were completed in 1942, 7 less than in 1941. The smaller number of wells drilled was not only due to the shortage of labor but also was caused by the fact that in water-flooding territory a definite program for drilling wells is followed, and the flush period of an oil well is not usually reached in time to profit by any given price increase. Daily Production.—All of the oil wells in New York state, some 21,000 in number, are small producers. The average daily oil production is 7/10 bbl. per well. Under good flooding conditions, a maximum production of 5 to 8 bbl, a day is reached about one year after the flood begins to act on the well. In 5 years the daily production usually is less than one barrel. Although most of the oil in New York is produced by flooding, an estimated 2500 old wells produce without flooding. Some of these produce as little as 1/20 bbl. a day and are pumped only at intervals. The small producing Wells are mostly on lands leased to the larger oil companies and later will be included in a flooding program. At present, they are pumped only because the owners of the land insist on the royalty. Government Aid Needed.—Because of its good lubricating qualities, New York oil is one of those for which there is an insistent and growing demand, but even at its present price of $3.00 per barrel, many of the operators are producing at a loss.

Jan 1, 1943

By C. A. Hartnagel

The production of petroleum in New York state in 1942 amounted to 5,410,000 bbl. This represents an increase over each of the four preceding years, and, with the exception of 1937, is the largest production since the peak of over six million barrels in 1882, shortly after the discovery of oil in Allegany County. The oil industry in New York is virtually stabilized and there has been little or no exploration for new sources of supply in recent years. The boundaries of the present fields were established more than 30 years ago and since then no additional reserves have been found. Deep drilling for natural gas during the past 10 years both within and without the oil fields has failed to find oil in quantity below the present producing sands of Devonian age. Oil Since 1882, the New York fields have produced approximately 140 million barrels of oil. Of this amount, 65 million was produced up to the year 1919 by ordinary pumping methods; that is, without flooding by water or the use of other secondary-recovery methods. In the year 1919, when a law was passed making the use of water-flooding methods legal, the oil production, of the state amounted to only 851,000 bbl. In the 23 years since 1919, there have been produced in the state 75 million barrels, or 10 million more than in the previous 37 years, which included the period of flush production. Price.—On March 26, the price of crude oil was raised from $2.75 to $3.00 per barrel, hut this increase had little or no effect on the number of wells drilled. In the Allegany field, which accounts for three fourths of the state's oil production, 1259 wells were completed in 1942, 7 less than in 1941. The smaller number of wells drilled was not only due to the shortage of labor but also was caused by the fact that in water-flooding territory a definite program for drilling wells is followed, and the flush period of an oil well is not usually reached in time to profit by any given price increase. Daily Production.—All of the oil wells in New York state, some 21,000 in number, are small producers. The average daily oil production is 7/10 bbl. per well. Under good flooding conditions, a maximum production of 5 to 8 bbl, a day is reached about one year after the flood begins to act on the well. In 5 years the daily production usually is less than one barrel. Although most of the oil in New York is produced by flooding, an estimated 2500 old wells produce without flooding. Some of these produce as little as 1/20 bbl. a day and are pumped only at intervals. The small producing Wells are mostly on lands leased to the larger oil companies and later will be included in a flooding program. At present, they are pumped only because the owners of the land insist on the royalty. Government Aid Needed.—Because of its good lubricating qualities, New York oil is one of those for which there is an insistent and growing demand, but even at its present price of $3.00 per barrel, many of the operators are producing at a loss.

Jan 1, 1943

By D. A. Elgillani, M. C. Fuerstenau

With either sulfonate or oleate as collector, quartz responds to flotation with moderate additions of calcium only at moderately high pH, where some portion of the activator has hydrolyzed to caOH+ . Calculations of the concentrations of various ionic and precipitated species of calcium and collectors suggest that the products of [(CaOH+) (RSO3)] and [(CaOH+)(01-)] determine whether flotation is obtained under specific conditions. Ion products on the order of 10-12 were calculated for both the sulfonate and oleate systems. The activating effect of calcium ion in nonmetallic flotation systems is of considerable interest because of the normal presence of calcium in natural water. As a result, this phenomenon has received quite some attention in the past. Kraeber and Boppel1 showed that quartz could be activated by calcium above pH 10 with sulfonate as collector. The feasibility of selectively separating quartz from hematite with calcium activation at relatively high pH was demonstrated by Clemmer, Clemmons, Rampacek, Williams, and stacy.2 Cooke and Digre3 showed with a bubble pick-up method that the minimum quantity of calcium ion required as activator for complete pick-up of particles occurs at pH 11.5 for an addition of 20 mg per liter sodium oleate. They also showed that larger additions of calcium (10-fold increase per unit decrease of pH) must be added for complete bubble pick-up as the pH is reduced. Schuhmann and Prakash,4 using a vacuum flotation technique, found that quartz could be floated with moderate additions of calcium chloride and oleic acid at neutral pH, providing the metal ion was present in stoichiometric excess over the quantity needed to form the normal soap with oleic acid. They also reported that calcium will function as an activator only in basic media. More recently, Eigeles and volova5 have shown that essentially complete flotation of quartz is obtained with 6 x 10-4 mole per liter calcium chloride and 1.7 x 10-5 mole per liter sodium oleate at pH 11.6. while no flotation is obtained at about pH 10.9 and below. The importance of adsorption of activator and collector at the air-liquid interface is also demonstrated in these systems. The important role that metal ion hydrolysis assumes in quartz activation systems was also demonstrated recently.6-8 A detailed investigation of metal activation in sulfonate flotation of quartz was undertaken in one system7 and yielded a number of interesting and important observations. Quantification of the data of this system7 to the extent desired was not possible, though, because certain species could neither be ignored nor accounted for accurately. These difficulties can be circumvented when calcium is involved as activator. This detailed analysis was undertaken to obtain a more quantitative explanation of calcium and metal ion activation in quartz flotation. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate9 mol wt 450, and pure potassium oleate were used as collectors. All other reagents used were reagent grade in quality, i.e., n-amyl alcohol as frother, KOH for pH adjustment, and calcium chloride. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. The experimental equipment and procedure were the same as that described previously.6,10 EXPERIMENTAL RESULTS As the presence of precipitates was noted in all of the systems to which ca++ and collector were added, experiments were undertaken to determine the solubility products of calcium sulfonate and calcium oleate using a nephelometer. With this technique, collector is titrated into a known solution, which in this case was 5 x 10-5 mole per liter CaCl2 at pH 5.5. Upon precipitation of the calcium-col lector salt, e.g., calcium oleate, light is scattered and detected

Jan 1, 1967