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By O. C. Ralston

THE use of copper sulfate for improving the flotation behavior of sphalerite is probably at least 15 years old. The original discovery of its activating influence is somewhat obscure. The story goes that in the mill at Mascot, Tenn., its favorable action was discovered by accident, early in 1914, as follows: The original laboratory test work on a sphalerite ore gave favorable flotation results, but after a mill had been built the flotation concentration of the ore was very unsatisfactory. In diagnosing the probable reasons, one fact pointed out was that the laboratory test machine had been constructed of bronze whereas the commercial machine allowed pulp to come in contact only with wood and iron. A plate of sheet copper was hung in the flotation machine and results immediately improved. At first fanciful explanations of electrolytic and electrostatic behavior were given credence, but when the copper plate was removed and a small amount of copper sulfate substituted in the pulp an even more favorable result was obtained. Toward the end of 1914 copper sulfate was also adopted in the acid flotation circuit of the Butte and Superior Copper Co. Just who is responsible for the original discovery the present writers do not know: It seems strange that in that era of flotation litigation this discovery was not patented. While for pragmatic purposes it may be sufficient to know that the mere addition of copper compounds to a flotation pulp is sufficient to activate the flotation of the sphalerite, for scientific purposes it is quite desirable to know more about how the action takes place. It is the purpose of this paper to present certain evidence dealing with the mechanism of the beneficial effect. The description of the effect as activation in contradistinction to depression is now common in both the English and German languages. It makes no assumptions as to whether the zinc sulfide surfaces have been filmed with copper compounds. In fact, the principal differences of opinion expressed in the literature deal with whether there is an actual formation of CuS (or even Cu2S) on the surface of the sphalerite.

Jan 1, 1929

By A. U. Seybolt, C. H. Mathewson

As is well known, many questions affecting the properties and uses of a metal cannot be answered without careful consideration of the state of purity realized in the various operations of preparation, refining, or special treatment that have brought the product to its final state. The occurrence of an impurity in minute quantity offers no guarantee that its effect will be inconsiderable because dissolved substances often modify the properties of a metal quite out of proportion to their concentration. In such cases the determination of solid solubility must be accepted as a problem of considerable difficulty, requiring the use of especially purified materials and methods not ordinarily used in the metallurgical laboratory. This aspect of the equilibrium between metals and their oxides is especially important and a search for fundamental data reveals little except conflicting opinion even concerning the systems of common occurrence and interest. Rhines and Mathewson1 in 1934 studied the solubility of oxygen in solid copper by annealing to equilibrium in air and gave reasons for the failure of other methods, notably the ordinary procedure of heat-treatment followed by microscopic examination, to yield reliable results. In this paper, a similar study has been made of the solubility of oxygen in cobalt. The simple theory of this method is outlined below.

Jan 1, 1935

By J. P. Heller

The purpose of this discussion is to comment briefly on one of the points raised in the paper. The topic is that referred to in the Conclusion 2, in which the authors note a "disproportionate increase in mixing rate" as they proceed from a displacement performed at viscosity ratio 0.998 to one at 1.002. The recovery curve of this displacement, Fig.2A, shows a quite noticeable difference between the two runs in which displaced and displacing liquids were interchanged. This difference is ascribed by the authors to the change in viscosity ratio between the two experiments. This interpretation of the experimental results must certainly be based on rather precise measurements of the fluid viscosities or, at least, of the ratio of their viscosities. The ordinary Ostwald viscometer, employed in the usual way, is only just able to distinguish between liquids whose viscosities differ by two or three parts per thousand. The experimental refinements which then must have been necessary to measure with any precision a viscosity ratio of 1.002 would be worthy of mention. Indeed, one would have expected the authors to devote at least a paragraph to the display of this technique. For the same reason - to emphasize that the details of such unusually critical experimental work should be reported and discussed in the literature — I would have liked to see some comment by the authors on the requirements for temperature control during both the viscosity measurements and the displacement experiments. The temperature coefficient of viscosity of Soltrol C at room temperature has been measured in this laboratory at about - 1.9%/1°C. How much did the coefficients for the fluid mixtures used in the experiment differ from this and from each other Even if the two fluids were identical in this respect, it would appear that a temperature difference of .l°C between them in the flow system would produce a viscosity con- trast equal to that imposed by their composition. Reference to the experimental solutions of these problems would render Conclusion 2 more credible. Published theoretical work on the stability problem contains no indication of such extreme sensitivity to the viscosity ratio in the immediate neighborhood of unity. On the contrary, perturbation calculations such as those made by Chuoke1 and Perrine2 lead to initial finger growth rates proportional to the first power of the viscosity difference. The later instability growth calculated by Scheidegger,3 using the assumption of zero pressure gradient perpendicular to the average flow, is also simply proportional to the viscosity difference. The conflict regarding the sensitivity of the dependence of instability growth or mixing rate on the viscosity contrast needs explicit recognition in the literature. In particular, it would seem that the experimental work reported here should be supported by a more detailed description of the viscosity controls. Further discussion of possible alternative interpretations of the data would also be in order. For instance, is it possible that the unconsolidstted bead pack used changed its characteristics between the runs (due, perhaps, to the handling and inverting involved in the injection of the front) Or, are the data points of Fig. 2A averages from several runs performed in a series in which the two liquids alternated as displaced and displacing fluids? To summarize, it seems to me that the relationship asserted by Conclusion 2 in the paper needs the support of more detailed experimental evidence. REFERENCES 1. Chouke, R. L., van Mews, P. and van der Poel, C.: "The Instability of Slow Immiscible Viscous Liquid-Liquid Displacements in Porous Media", Trans., AIME (1959) Vol. 216, 188.

By A. C. Dorenfeld

Ores of the Mammoth mining district, some 45 miles northeast of Tucson, Arizona, are treated by Mammoth-St. Anthony, Ltd. The ores now treated come from a complex system of veins and faults, comprising three mines, in close proximity: The Mohawk, Mammoth and Collins. The ore treated in the past was oxide ore, which contains economic amounts of gold, silver, lead, molybdenum, and vanadium (as wulfenite and vanadanite). The lead-zinc sulphide ore has never been treated before. The Ore The sulphide ore contains galena, sphalerite, marmatite, pyrite and some chal-copyrite, covellite, chalcocite and bornite, as well as small amounts of gold and silver. The value of the ore is principally in the lead and zinc content. The lead-zinc sulphides are substantially liberated at a minus 65-mesh grind. However, a large part of the chalcopyrite and other copper minerals is not freed, but remains as pin points on the sphalerite. Economically, the copper is unimportant. The gangue is a rhyolite granite, with very little limestone. There is no molybdenum or vanadikm in the sulphide ore. History of Sulphide Treatment Test work on samples of the sulphide ore was conducted by several equipment companies, the Arizona Bureau of Mines and the company's laboratory. Results of this test work indicated that for some reason, which at the time could not be explained, recoveries would be only about 65 per cent lead and 50 per cent zinc. Notwithstanding this, because of the nation's need for metals, the management built a 150-ton treatment plant. The mill was started in June 1942. During December 1942, using the standard method of treating lead-zinc ore, the monthly results were as shown in Table I. These results were poor. Too much lead was in the zinc concentrate, and too much zinc in the lead concentrate. It should be noted here. that prior to December attempts were made to depress the sphalerite with large and varied amounts of cyanide, zinc sulphate, and sodium sulphite with poor results.

Jan 1, 1947

By A. C. Dorenfeld

Ores of the Mammoth mining district, some 45 miles northeast of Tucson, Arizona, are treated by Mammoth-St. Anthony, Ltd. The ores now treated come from a complex system of veins and faults, comprising three mines, in close proximity: The Mohawk, Mammoth and Collins. The ore treated in the past was oxide ore, which contains economic amounts of gold, silver, lead, molybdenum, and vanadium (as wulfenite and vanadanite). The lead-zinc sulphide ore has never been treated before. The Ore The sulphide ore contains galena, sphalerite, marmatite, pyrite and some chal-copyrite, covellite, chalcocite and bornite, as well as small amounts of gold and silver. The value of the ore is principally in the lead and zinc content. The lead-zinc sulphides are substantially liberated at a minus 65-mesh grind. However, a large part of the chalcopyrite and other copper minerals is not freed, but remains as pin points on the sphalerite. Economically, the copper is unimportant. The gangue is a rhyolite granite, with very little limestone. There is no molybdenum or vanadikm in the sulphide ore. History of Sulphide Treatment Test work on samples of the sulphide ore was conducted by several equipment companies, the Arizona Bureau of Mines and the company's laboratory. Results of this test work indicated that for some reason, which at the time could not be explained, recoveries would be only about 65 per cent lead and 50 per cent zinc. Notwithstanding this, because of the nation's need for metals, the management built a 150-ton treatment plant. The mill was started in June 1942. During December 1942, using the standard method of treating lead-zinc ore, the monthly results were as shown in Table I. These results were poor. Too much lead was in the zinc concentrate, and too much zinc in the lead concentrate. It should be noted here. that prior to December attempts were made to depress the sphalerite with large and varied amounts of cyanide, zinc sulphate, and sodium sulphite with poor results.

Jan 1, 1947

By P. A. Witherspoon, S. P. Neuman

Evaluating the permeability of a caprock overlying a potential gas storage reservoir is a very critical problem. Pumping water from the reservoir can be used as an evaluation tool in analyzing this problem. Fluid level changes that occur in the aquifer us well as in the caprock can be measured with appropriately placed wells. If the leakage of water from the caprock into the aquifer is considerable, the effects will be apparent in the aquifer. If the leakage is slight, however, it will not be possible to detect it with certainty from observations in the aquifer alone. Fluid level measurements in the caprock must be relied upon. and improved methods of analyzing such effects have been developed which are based on a theoretical analysis of fluid flow through a caprock of infinite thickness. An example applying these methods to field data is discussed. INTRODUCTION One of the most critical problems in evaluating an aquifer gas storage project is determining the tightness of the caprock overlying the formation to be used as the storage reservoir. A formation that has previously held oil or gas obviously has a suitable caprock, but an aquifer that contains only water gives no such assurance. A number of aquifer projects in the United States have been troubled by gas leaking out of the intended storage zone, and the ensuing difficulties have led to the development of new evaluation methods. One of these new methods is pump testing wherein water is removed from the aquifer at some controlled rate prior to injection of gas. This fluid withdrawal causes a pressure drop to move out through the aquifer for considerable distances in a matter of days or weeks. Depending on the properties of the caprock, a pressure transient can also pass upward (as well as downward) through the caprock layers adjacent to the aquifer. Thus, if the operator has placed observation wells at appropriate distances from the pumping well, the rapidity with which the pressure transients reach different points in the system can be used to investigate the fluid transport properties of both the aquifer and its caprock. The usefulness of pump testing has been recognized by groundwater hydrologists for many years as a means of determining the potential yield and properties of aquifers used in water supply They have introduced the term "leaky aquifer" for a system in which an aquifer is overlain (or underlain) by semipermeable caprock layers. The ease with which water leaks into the aquifer during pumping can, of course, be very beneficial in bringing additional water to the pumped well. Hydrologists have therefore devoted considerable attention to this prob-lem. From the gas storage standpoint, however, the tighter the caprock layers that overlie the intended storage reservoir, the better are the conditions for minimizing or eliminating any vertical migration of gas. Thus, after a suitable geologic structure has been found, the emphasis in aquifer storage projects is in determining that the caprock is tight. Attention has recently been focused on the use of pump testing as one approach to solving this problem.23,24 This paper presents a further development on evaluating the permeability of a slightly leaky caprock when the caprock is of infinite thickness. From the practical standpoint, this means that the caprock layers are thick enough that pressure transients do not reach the outer boundaries of the system during the pumping test. In a subsequent paper, an analysis of the case where the caprock is of finite thickness will be presented. PREVIOUS WORK ON LEAKY AQUIFERS Jacob" developed a partial differential equation describing the flow of water in an aquifer of permeability k that is overlain by a leaky caprock of permeability k'. Fig. 1 shows a schematic cross-section of the system under consideration. One of his principle assumptions was that if k > > k', the direction of flow is essentially vertical in the caprock and horizontal in the aquifer. Neuman19 confirmed the validity of Jacob's assumption using a mathematical model. Another assumption was that a permeable source layer overlies the caprock (Fig. 1) and is able to maintain a constant hydraulic head at the upper boundary of the caprock. By neglecting the effects of compressibility within the caprock, Jacob1* developed a solution for a bounded circular aquifer. Later, Hantush and Jacobx5 used the same assumptions to solve the case of an infinite radial aquifer that is pumped at a constant rate. Their solution may be expressed in di-mensionless parameters by

By Jaakko Kajamaa

Neutron diffraction was applied to determine sheet textures by the transmission method. Cold-rolled and recrystallized copper sheets were investigated. The amount of cube texture was determined for three compositions, in which the phosphorus content was, respectively, 0, 0.005, and 0.03 wt pct. The heat treatment was in every case 8 sec at 650°C. In the two latter cases the cube texture was prevented. In addition a comparison with the X-ray diffraction transmission method was made with the 96 pct cold-rolled copper sheet. Outer parts of both (111) pole figures can be considered to be rather identical. This is seen from the fact that the intensity ratio ITD/120" was 0.45 for neutron diffraction and 0.40 for X-ray diffraction. Differences between the methods were discussed in detail. Features peculiar to neutron and X-ray diffraction in texture studies were listed and compared. In this work neutron diffraction was applied to determine sheet textures. Specifically, it was desired to ascertain whether this method can be used to reveal differences when compared to other methods. In addition, the amount of the cube texture in copper sheets was determined as a function of phosphorus content. Previous applications of neutron diffraction to texture problems include the following: nickel wires,' wire of some bcc metals,' and uranium bars.3 In the neutron diffraction technique the greatest difference is in the sample—its method of production and its volume. A sample needs no treatment and its volume is roughly 105 times larger than the volume of an X-ray diffraction sample. The cold-rolled sheet was investigated both by neutron diffraction and by X-ray diffraction, because it is expected that, due to large number of defects, possible differences in the results of the two methods would be revealed. It is a well-known fact that X-ray lines show broadening when cold-worked. Analysis has shown that this is based chiefly on small crystalline size, micro-stresses, and/or faults.4'5 Neutrons are sensitive to the above-mentioned disturbing factors as well, but circumstances in diffraction are different from the X-ray case. Because the sample represents a larger volume, the result is an average over that volume. In addition, it can be assumed that the sample has preserved its original structure, because it needs no special preparation. The particular limitation of neutrons is the relatively low neutron intensity available from nuclear reactors. This decreases the resolution as compared to the X-ray diffraction methods. Furthermore, absorption mainly reduces diffracted X-ray intensity, while multiple scattering effects, i.e., secondary extinction, disturb neutron diffraction. SO neutrons and X-rays behave in a different way when interacting with matter. As in other structural investigations, one can utilize this difference in texture studies as well. One cold-rolled and three recrystallization textures in copper sheets were investigated by neutron diffraction. The samples were produced at the Outokumpu copper factory to the specifications shown in Table I. The paper is divided into five parts. The first deals with the theory of the measurement. In the second, experimental procedures are described. Results are presented in the third part. Both cold-rolled and re-crystallized samples are studied. Discussion is in the fourth part, and finally in the fifth part some conclusions are drawn. 1) THEORETICAL CONSIDERATIONS Properties peculiar to neutron diffraction are the following: a) the scattering length varies greatly between one element and another; b) many of the elements do not absorb neutrons appreciably. In this connection it is of primary interest to know the interaction of neutrons with lattice imperfections. As with X-rays this problem leads to diffraction analysis of deformed and recrystallized metals. From the physical point of view the main difference is that neutrons are scattered by nuclei (magnetic scattering is not considered here), whereas X-rays are scattered by electrons. The features peculiar to neutron and X-ray diffraction methods in texture studies are listed in Table 11. Pole figures are an important tool in performing structural analysis of deformed or recrystallized metal. Present texture research technology requires pole figures which are as precise as possible. The choice between these two methods depends on the technical information which is required. The X-ray diffraction transmission technique may give results which are not necessarily representative of the average physical state of the sample. Although foil samples normally contain enough crystallites for diffraction, they may not necessarily represent the whole structure. An example of this problem is the frequently observed difference between the "surface" and the "inside" texture of a sample. The production of foil samples may disturb the original structure of the parent material. The selection and orientation of the foil from the sample is quite arbitrary. Normally, a highly deformed piece of metal has several texture components. Different components are deformed in a slightly different manner. This is a re-

Jan 1, 1969

By C. F. Rust

Experimental evidence is presented showing that reproducible formation resistivity factor measurements and resistivity index determinations on reservoir core samples map be made utilizing either the two- or four-electrode methods. Equipment is described which permits the application of either technique to the core specimen without loss of time and with a minimum amount of effort. Since electrical resistivity measurements on reservoir rocks are important not only in electric log interpretations, but also in the study of fundamental rock parameters, it was considered desirable to compare the applicability of both techniques of resistivity measurement. INTRODUCTION The techniques employed in the measurement of electrical resistivity on reservoir rocks, as practiced in the petroleum industry, may be reduced to two fundamental methods: one utilizing two electrodes only, usually referred to as the two-electrode method; the other using two additional electrodes and commonly known as the four-electrode method. In the former, the core sample whose resistivity is to be measured is mounted between two electrodes, usually metal discs, which serve to pass a current of known magnitude through the saniple. The potential drop across the sample, measured between these same two electrodes, and the core dimensions furnish the necessary data to compute he resistivity of the sample. In the four-electrode technique the end plates, again usually ol metal, still serve as current electrodes. Additional probes or electrodes dispersed along the sample are utilized to measure the potential drop. Both methods are used in practice1,2 and it is the purpose of this paper to compare the two techniques as applied to the determination of formation reiistivity factors and the resistivity index exponent n, in Archie's empirical equation I = p/po = Sw 11. To evaluate the two techniques it is desirable to point out the experimental precautions which must be taken to insure reliable results. It is evident from the electrode arrangements of the two- and the four-electrode methods that, for a given sample, the volume of sample included by the four-electrode method is less than the volume included by the two-electrode method. One of the prime difficulties associated with the two-electrode method is the possible occurrence of an abnormally high resistance between the electrodes and the brine-saturated sample, which results in erroneous resistivity values for the core sample itself. Attempts to alleviate this difficulty meet varying degrees of success. Methods used in the past employ such absorbent materials as brine-saturated Kleenex: chamois, or felt. A technique described by Morgan, Wyllie, and Fulton,1 appears to be more satisfactory. Their method consists of spraying or painting the end areas of a core sample with conductive silver paint. This technique reduces contact resistances between the porous medium and the electrodes to a value which is generally negligible as compared to the resistance of the sample itself. In the four-electrode method these requirements are not as stringent since separate probes are used to measure the potential difference acrozs a portion of the sample. In this case, contact resistance occurring at the current electrode; are of no consequence. and those appearing at the potential

Jan 1, 1952

By F. C. Holman

It is desired in these notes to record a vein-phenomenon certainly unique in the writer's limited experience, and, as it seems to him, sufficiently rare to be worthy of mention. In the little mining camp of Forbestown, situated in the Sierra Nevada of California, it was announced one day, when the miners of the Cold Banks mine came off shift, that "washed gravel" had been struck on the 265-foot level. To those acquainted with that section and the character of the mine (a gold-bearing quartz-vein) this was a somewhat startling announcement; for, prolific as the State is, we are not in the habit of mixing up promiscuously our vein- and placer-deposits. However, the statement proved to have some foundation. The mine is located at an altitude of about 2700 feet, on the brink of one of the great canyons of erosion characteristic of the drainage of this range. A lateral ravine cuts the vein at right angles, thus making its general strike approximately parallel to the canyon at this point, and with a variable dip of from 20 to 40 degrees towards the canyon. The strong, well-defined vein, often 20 feet wide and more, presents nothing to distinguish it particularly from scores of others in the State, unless if be considered peculiar in the highly crystalline character of its quartz and the nature of the enclosing country-rock, which is metamorphic in the extreme, very hard, devoid of lamination, and in bedding so obscure that it might easily pass—at least on superficial examination—for one of the basic eruptives. Near by in the district can be found a series of slates common to the gold-belt of this range, and within the limit of the company's property is an intrusion of an acid eruptive. On an adjoining claim a granite shows itself. The mine is opened through an inclined shaft sunk on the vein. The ore carries both free gold and sulphurets, the greater part of its value

Jan 1, 1896

By K. M. Weigert

The position of the three-phase field between the alpha and the beta phases was established. The exact location differs from previous assumptions. The extremely high strength and hardness values were found near the phase boundaries of the ternary compositions. IN 1929, UenoL investigated vertical sections of the Ag-Cu-Zn diagram at constant silver and zinc values. From the evaluation of cooling curves and microscopic studies, he concluded that there was no evidence of a three-phase field in the solid state between the a and ,8 fields. The failure to find evidence for this field was due to the fact that it exists only in a very narrow range of compositions and requires special methods of heat treatment to establish phase equilibrium. In a later publication on the same subject Keinert2 rearranged Ueno's diagrams to conform with the basic phase rules. The existence of a three-phase field was postulated in the solid state between the a phases and the homogeneous ,9 phase between the Cu-Zn and the Ag-Zn binary border systems. The approximate location was based on a few microscopic observations of the structure and it was pointed out that the exact position could be determined only by a larger number of experiments. In the twenty years following these investigations alloys of Ag-Cu-Zn have become of general interest due to various technical applications, principally for brazing. In the course of an overall investigation of the physical properties of ternary Ag-Cu-Zn alloys the author found extremely high values of hardness and strength in alloys of compositions between the a and the yS fields. The exact location of the intermediate phase fields was established by the evaluation of more than a hundred cooling curves and microscopic mountings. Experimental Procedures Preparation of Test Samples: At the beginning of the investigation samples were chillcast into Vi in. diameter iron molds to determine hardness, strength, and the mechanism of primary crystallization. These

Jan 1, 1955

By Jacques B. Wertz

Among the parameters to be considered in the continuous search for new base-metal deposits, there often is a stratigraphic controlling factor that seems instrumental in the localization of ore. In British Columbia, for instance, the Upper Triassic as well as Lower Jurassic volcanics mixed with sediments are a useful indication in the search for copper while, in some parts of Australia, rhyolite bodies seem to be the favorable indicator, and this always within the geosynclinal environment. In Arizona, this stratigraphic factor becomes highly significant and it will be shown here that a large number of ore deposits are to be located around the flanks of ancient calcareous basins or depressions, preferentially corresponding to a certain optimum thickness as revealed by isopachs. The Martin limestone, of Devonian age, is already known for its basal O'Carroll bed which coincides with mineralization at places, and this is a relatively minor control. However, several limestone basins outlined by isopachs are in reality of greater importance as they localize mining districts. Indeed, most mines are found to coincide with a specific thickness of limestone while occurring simultaneously close to major, regional fracture intersections. The regional fractures in question were interpolated and extrapolated from known, important fault expressions, integrating quite well with the existing geology and further confirmed by minor criteria such as contacts, igneous plugs, axes of elongation of batholiths, dikes, etc. Although elements of subjectivity remain, this grid of fractures can be used quite successfully as a working hypothesis in the search for ore. Results of the present study which superposes major structural

Jan 1, 1971

By H. H. Einstein

Swelling ground is one of the most feared problems in tunneling. Although usually not causing sudden failures during construction, the very large and longlasting deformations give contractors and designers the impression of facing an inevitable phenomenon against which there is no technical defense. Examples are concrete liners up to 1 m (3 ft) thickness that have been cracked or crushed, tunnel inverts that are heaving at 0.1 m (0.3 ft) per week during construction and continue to heave during decades. This paper summarizes essential components of design construction procedures where tunnels in swelling rock can be built to perform satisfactorily. It is important to point out that design and construction cannot and should not be separated. The way the tunnel will be built has to be an integral part of the design. Swelling can be defined as time dependent volume increase and is distinguished from squeezing, another time dependent phenomenon occurring in tunneling. Squeezing involves exceeding the shearing resistance while swelling usually does not. Swelling of rock masses can occur as swelling of the intact rock, swelling of wall rock, of gouge and of filler in the discontinuities of a rock mass, and as a combination of the above. Swelling mechanisms have been discussed elsewhere (ISRM 1983).

Jan 1, 1984

By John C. Calhoun, Frank T. Bethel

Glass beads have been surface treated with Dri-film to render them oil wet by n-octane to varying degrees, and capillary desaturation curves have been determined by the restored state method. The desaturation curves show a regularity of increasing displacement pressures as the oil wetness increases. This has been used to compute apparent contact angles between n-octane and water on glass. The family of desaturation curves also shows a regular crossover, such that the residual wetting liquid saturation values are in reverse order to the displacement pressures. A semi-logarithmic variation is shown between the apparent contact angle and the residual saturation. The desaturation data are interpreted to mean that the wetting liquid ceases to be a continuous phase within individual pores before the capillary pressure can be raised sufficiently to force out the wetting phase completely. The saturation of wetting liquid at which this break in liquid continuity occurs is higher as the oil wetness decreases. INTRODUCTION The petroleum industry has for some time been using measurements of capillary pressures on porous media for research correlations and engineering calculations. It has been generally recognized that the capillary desaturation curve reflects the character and arrangement of the pores within the media and the distribution of fluids within the pores. Methods have been proposed for computing pore size distributions, tortuosity factors. and relative permeabilities from capillary desaturation data.' There is little doubt that the interactions between porous rocks and their contained fluids resulting from surface forces play a dominant role in determining the magnitude and direction of capillary pressure measurements. There have been attempts to introduce as variables two quantities — inter-facial tension and contact angle — generally used to char- acterize surface forces, but in spile of the wide interest in these quantities as important variables, few definite conclusions have been drawn concerning their qualitative or quantitative significance. INTERFACIAL TENSION The interfacial tension appears in a capillary pressure function given by Leverett for correlating capillary desaturation type curves. Use of the interfacial tension in this function seems to be justified by other experiments reported. Apparently, interfacial tensions have little bearing on wetting phase residual by desaturation. CONTACT ANGLE The contact angle was utilized as a variable by Bartell and co-workers"." in tests on displacement pressures, later recognized as the initial point of capillary desaturation. Although Leverett did not include contact angle in his original formulation of the capillary pressure function, later workers suggested its addition. Few reports are available to show variation of residual liquid with contact angle as a result of capillary desaturation.' The problems attendant to measuring contact angle within a porous medium are great. As a consequence of the lack of a concrete approach to a measurement. the workers in this area of research have adopted the general expression of "wettability" to indicate the relative position of two liquids saturating a porous body. It has been shown that gross measurements on porous systems, including capillary desatura-tions, are sensitive to wettability. Attempts at giving a scale to wettability in terms of contact angle through capillary desaturation curves have been made and these apparently are steps in the right direction. In these attempts presence of many other variables precludes attainment of exactness. Also, as a result of other variables, it has been impossible to correlate changes in apparent contact angle with changes in other physical measurements of the systems in question. The present work is an attempt to eliminate as many variables as possible in measuring capillary desaturations resulting from changes in contact angle within a porous medium.

Jan 1, 1953

A GREAT and incomparable speculation is whether the discovery of A compounding the powder used for guns came to its first inventor from the demons or by chance. With this invention he certainly far surpassed all men of every age from the creation of the world up to that day when it was announced by him-men so very learned, indeed like angels and of divine intellect, powerful in every knowledge and power. These had not only revived-arts and sciences and discovered new ones with their intellects, but they had information about all natural

Jan 1, 1942

By A. Kenneth Schellinger

THE terms surface tension .and surface energy are well known when applied to liquids and are generally described by referring to the excess energy of the air: liquid interface as a result of unsaturated molecular forces surrounding the surface molecules of the liquid due to the presence of the air phase on one side. Such unbalanced forces produce the familiar water droplet of spherical form and are generally summed up as a surface tension measured in dynes per centimeter which can be shown mathematically to be equal numerically to a corresponding surface energy expressed in ergs per square centimeter. A specific surface energy, however, is best thought of as the energy necessary to produce one unit of new surface on a substance. Hence, in producing a bubble in a flotation cell the impeller must supply surface energy corresponding to the air: liquid interfacial area on the interior of the bubble. Inasmuch as it is relatively easy to extend or contract the surface of a liquid, there are a number of successful methods for liquid surface tension, or energy, measurement based upon surface deformation. This happy state of affairs does not, however, extend to solids, which are considered to possess surface energies for the same reasons as do liquids, i.e. because of unsaturated ionic bonds at the solid gas interface. As in the case of the flotation cell producing surface on liquids as new bubbles, it takes energy to produce new surface on solids as new particles. As every mill man knows, this surface is produced on mineral solids in a grinding mill by the action of a tumbling mass of iron balls. But here so much energy usually is wasted by the inefficient action of these balls that a large amount of heat is generated, and the surface energy production may be easily confused with the energy necessary to produce this ineffective heat. The tumbling balls and fracturing minerals ultimately take their energy from a rather large electric motor. It has been variously estimated that from 10 to 20 pct" only of this energy from the motor does not appear as heat and may be presumed to appear as surface energy on the minerals present.. Such a production of new surface on the mineral phases is accompanied, of course, by a size reduction that is inevitable as more and more mineral interior molecules become surface molecules by the fracture exposure. This size reduction of mineral particles, although the most obvious feature and perhaps the sole object of the milling operation, is from this energy viewpoint the outward manifestation of the production of surface energy only. Measurement of the characteristic surface energies of pure minerals and their various mixtures in ores would be a step towards understanding of the energetics of the commercial grinding operation. In addition, the characteristic surface energy of a mineral is probably a physical property specific for that mineral, and therefore, from a scientific standpoint, should be measured. It is interesting to note that, in contrast to the large body of work on the surface tensions of liquid systems and biological systems, the field of solid surface energies has been neglected. Prior to. 1920 it is difficult to find more than one or two references to work on solid surface energies in Chemical Abstracts. Since 1920 such references number somewhat less than 100, while those on liquid systems are numbered in the thousands. Much of this apparent neglect of the field of solid surface energies (the term is intended to be somewhat inclusive at this point and refers both to the solid: gas, and the solid: liquid interface) is because of the lack of a reliable method of measurement rather than any lack of scientific curiosity. It was, and still is, difficult to produce new surface on a solid without the simultaneous production of interior changes in the same solid which may consume part of the energy used. The extension in the surface area can be measured, but the interior crystal-

Jan 1, 1952

By Harry Roeser

Short cuts for determining the constants of oil decline curves, with the method of least squares as a starting point, are presented and applications made to practical examples. The nature of the raw data does not justify rigid adherence to the orthodox theory but does lend justification to convenient methods of approximation within reasonable limits. If the conventional form y = kxn were changed to y = k(x + c)', methods of determining the curves would be simplified and greater uniformity in calculated results would probably follow. As A result of the publication, several years ago, of some articles on determining the constants of empirical formulas, the determining the constant's of types of curves used for estimating the production decline of oil wells was brought to the writer for study. Methods requiring a minimum of time and labor and a maximum of rigor were sought, as it appeared that the nature of the data from which such curves are computed and the relative uncertainty of occurrence of the events predicted from them did not justify close adherence to the theory on which the solution of such problems is ordinarily based. The technical deficiencies of the solutions presented in this paper, from the standpoint of the method of least squares, are readily apparent to those familiar with that method, but their presentation in detail here is irrelevant to the subject matter. However, it is the author's conviction, after a rather exhaustive study of the problem, that the value of the solutions lose little by the approximate application of the conventional theory. It must be understood by those who use these formulas that the solutions herein given, and the formulas based on them, are merely facilities to aid the valuation engineer in forecasting future events. It is assumed, also, that before application is made of them, prescient judgment based on the circumstances in each case, shows that the forecast has some probability of realization. On this basis only will these formulas be found useful.

Jan 6, 1924

R. F. MCELVENNY.- Over 20 years ago I went back East on a little tour of copper companies to see how copper was handled and fabricated, and I met a Mr. Bassett who took me through the Waterbury branche of the American Brass Co. I have not seen this gentleman for 20 years, but I have a letter from him that I would like to read to you. 'The American Brass Co. Waterbury, Conn. May 19, 1930. To the-Salt Lake City Conference on Reverberatory Smelting Practice: Through the courtesy of Mr. Scott Turner, Director of the U. S. Bureau of Mines, Mr. G. L. Oldright has been temporarily released from his regular duties to act as your secretary. We have asked him and Mr. McElvenny to make the necessary preliminary arrangements and to present to you at the opening session the greetings of the officers and' directors of the Institute. I am very glad that it has been possible for you to come together under the auspices of the Institute and that the acceptance of our invitation has been so very unanimous. Such an acceptance of the invitation to this meeting indicates your interest in getting together for an exchange of technical data and ideas. We anticipate that this meeting will be of real service to the smelting industry through your open discussion and exchange of ideas, and we sincerely hope that you will form an organization which will arrange for future meetings of a similar nature. While it probably may not be desirable to. distribute the minutes of this conference except to the members who take part in it, we hope that later the Institute publications may be enriched by such matter as you think it desirable to have published; and also, that some of you may be able to offer technical papers for the Institute publications. I hope that you will find a permanent organization desirable and trust that it will be possible for you to form such an organization so that conferences may be regularly called. We hope that you can make use of the Institute organization and that we can be of real service to your industry. With best wishes for your success in this undertaking, I am Most cordially yours, W. H. Bassett, President.

Jan 1, 1930

By J. Geertsma

In order to obtain a better insight into the pressure-volume relationship of reservoir rocks a theory of pore and rock bulk volume variations is presented. The theory is independent of the shape of the pores but is restricted to isotropic porous media built up of continuous homogeneous matrix material. The main conclusion obtained from this theory is that only three elastic constants and three viscous constants are required for describing pore and rock bulk volume variations if the porosity is explicitly introduced into the treatment. In addition, reasonable approximations are introduced for various types of reservoir rock, e.g., sandstones, limestones, and shales, which lead to further simplifications of the basic formulas. In consequence there is then a further reduction in the number of deformation constants which have to be determined experimentally. It is shown how measurements of these remaining deformation constants can be performed most conveniently. Finally the application of the theory to reservoir studies is discussed and the translation of experimental results obtained in the laboratory into reservoir behavior is considered. INTRODUCTION The decline of fluid pressure in connection with the withdrawal of fluid from an underground reservoir gives rise to a change in volume of both reservoir fluids and reservoir rock. The volume variation of the reservoir rock results in a decrease of both the pore volume and the total volume of the fluid-filled formation. Whereas the variation in volume of the reservoir fluids with pressure is usually known from PVT analysis, that in the volume of the porous medium is rarely measured, as it is considered of minor importance in reservoir engineering. Nevertheless, certain experimental results' suggest that in a number of cases the neglection of the variation in pore volume may introduce errors into material balance calculations of reservoirs producing above the bubble point. Only a few experimental results on the compressibility of porous rocks have been published. The compressibility of pure quartz and of calcite can be found in a paper by Adams and Williamson'. Botset and Reed' carried out some experiments on the compressibility of loose sands, while Carpenter and Spencer' measured the compressibility of a number of consolidated sandstones, which data were supplemented by Hughes and Cooke5. Hall' finally reported a number of experiments designed to study the influence of the porosity on the compressibility of oil-bearing formations, from which it appeared that, particularly in the low porosity range, the compressibility of the pore volume is important enough to be taken into account. Difficulties, however, arise in applying these experimental results to field cases. This is partly due to the fragmentary nature of the published data. Yet even if more complete data were available, the need for a theoretical background would be strongly felt. Such a background can be partially found in studies carried out by Biot,6,7 who published a theory of elastic deformations of porous materials and their influence on fluid displacement within the pores, by Lubinski8, who studied the stress distribution in an elastic porous medium neglecting pore compressibility, and by Gass-mann" who mathematically analysed the elasticity of packings of spheres. The contributions of Biot intro-duce a number of deformation constants which are impractical for reservoir rocks from an aspect of experi-mental determination. The theory developed by dass-mann is correct but difficult to read. It appeared, how-

Jan 1, 1958

By E. L. Bruce

Gold occurs in many mineral deposits in the rocks of the Canadian Shield. It is present in the ores of many base metals and a considerable quantity is recovered as a by-product from the production of copper at Noranda, of nickel and copper at Sudbury and of copper and zinc at Flinflon. But the greater part of the gold production of Canada is from deposits in which gold is the only metal of value. No gold is obtained from placer deposits within the borders of the Canadian Shield. A brief review of the geological relations of some of the gold deposits of the Canadian Shield will be presented in an attempt to explain certain associations. Only those which are being worked for their gold content will be considered and descriptions will be confined to representative types of deposits, chiefly those of major importance; a few others, differing in certain features from those of the older and larger mines, will be included in order to illustrate the general conditions in which gold occurs in these ancient rocks. Brief summaries will be given of the geological relations of the Beattie and Siscoe mines of northern Quebec, of the mines of the Porcupine and Kirkland Lake areas of northeastern Ontario and of the Howey, Central Patricia and Little Long Lac mines of northwestern Ontario. Genetic relations to igneous rocks of granitic composition, outcropping in the vicinity, have been assumed for many of these deposits. Undoubtedly the ore minerals have been derived from igneous sources and, for some occurrences, there is evidence suggestive of genetic relationship between the ore bodies and neighbouring intrusive rocks. During the past few years, however, many investigators have expressed doubt of the genetic relationship of certain ore bodies to igneous masses near which they occur. As will be seen from .references in the following descriptions the importance of the structural conditions in localizing deposition has been realized. This is pointed out for Canadian pre-Cambrian gold deposits by E. T. Dougherty, who also refers to the

Jan 1, 1937

By C. R. Boyd

The region to which I have the pleasure of calling your attention, though limited in area, is remarkable for the quantity and purity of its mineral deposits, and in these respects it would be difficult to find its equal anywhere. IRON ORES. The red and brown hematites, pipe ore, and semi-magnetites, from which is made in charcoal furnaces the highest quality of iron for car-wheels, extend through the counties of Giles, Montgomery, Pulaski, Wythe, Smyth, Washington, Bland, Tazewell, Russell, Scott, Lee, Floyd, Carroll, and Grayson, Virginia, and run over into Ashe County, North Carolina. One locality of semi-magnetite, in the centre of the great Giles County basin, has in sight, by actual measurement, 50,000 tons of ore, which, according to Prof. Fesquet, contains 69.74 per cent. of iron and no phosphorus. In the great brown-ore belt, which passes through the counties of Montgomery, Pulaski, Wythe, Smyth, and Washington, there is an extraordinary deposit of more than a million tons. A small section of this very long vein, on Cripple Creek, in the County of Wythe, yields an ore which, analyzed by Mr. James Aumann, gave the following results: Metallic iron,........58.15 Water,.........12 96 Alumina,........2.32 Silica,.........1.09 Phosphorus,.. none. At one point towards the western end of Red Land Mountain, in Pulaski County, New River section, I measured a body of ore in this belt which will yield, to a depth of 150 feet, over 8,000,000 tons, and the deposit extends far below the 150 feet measured at the upper part. Again, at Rich Hill, near the mouth of Reed Island Creek, these veins show extraordinary surface development, giving an ore of very great purity. At numerous places, also, in the counties of Giles, Bland, Tazewell, Russell, Scott, Wise, and Lee, these brown and red iron ores are exposed in such vast quantities as to baffle both description and measurement. That of Chestnut Flat, in Giles County, back or west of the Angel's Rest Mountain, is an easily reducible ore, blood-red when crushed, of which there are fully 300,000 tons in sight. Its analysis is as follows :

Jan 1, 1880