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By M. E. Hassan, J. C. Calhoun, R. F. Nielson

An apparatus was constructed for the measurement of inter-facial tensions over a range of temperatures and pressures. This apparatus utilized the pendent drop method, and resembles in construction similar apparatus recently described in the literature and in use in some petroleum research laboratories. The interfacial tensions of benzene, propane, n-pentane, n-hexane. n-octane. and iso-octane against water were measured at temperatures ranging from 26" to 82" C and at pressures ranging from 1 to 204 atm. Values of interfacial tensions for the henzene-water system and their variations with temperature and pressure are generally in good agreement with value? of previous investigations. The data in all cases showed a slight decrease of interfacial tension with pressure at constant temperature in the range studied. The effect of pressure became less as the pressure was increased, with an indication of a reversal of the effect at higher pressures. There was a decrease of interfacial tension with temperature at constant pressure in all cases, as would normally be expected. This rate of decrease became greater the higher the temperature. A general equation is presented for the interfacial tensions as a function of presPurp and temperature over the range studied, and the constants calculated for each system. A definite trend was found in the effect of molecular weight on the interfacial tension at a given temperature and pressure, for the homologous series from propane to n-octane. Data for n-decane from the literature fitted well into this trend. INTRODUCTION It has been recognized for many years that surface forces play an active part in the production history of an oil reservoir as well as in determining the amount of unrecoverable oil. The magnitudes of these forces are governed by the values of the interfacial tensions. These vary greatly with composition, pressure, and temperature. The effect of composition is greater than that of pressure and temperature over the ranges normally encountered. In fact, because of the variety of compounds present in a crude, no attempt has yet been made to correlate crude composition with its surface tension or with its interfacial tension against water. The amount of dissolved methane greatly affects the surface properties of an oil, and there are "surface-active" compounds in crudes which have a much greater effect on boundary tensions than do equal amounts of hydrocarbons. The purpose of the present work was partly to contribute data that would eventually be used in correlations applicable

Jan 1, 1953

By B. E. Fernow

MINING interests in the Western mountains are very seriously affected by the danger to property and life from destructive snowslides and avalanches. This is a danger which the miner has largely brought upon himself by an improvident stripping of the timber from the mountain slopes, and, therefore, he might be expected to take an interest in the reforestation of the areas thus devastated. A canvass was lately undertaken by the writer to ascertain approximately the extent of the damage suffered from this source, but the difficulty of obtaining reliable data has proved too great to permit, as yet, even an approximation. So much, however, is certain : that the loss of life is considerable, and that much property is destroyed almost every winter. True, neither the number of avalanches, nor their destructiveness, nor the amount of loss compares with what Switzerland experiences. This is due not only to the greater precipitousness of the Alps and to different climatic conditions, but also to the fact that in Switzerland a larger number of settlements is exposed to these dangers. A very complete and interesting official report on the very numerous and destructive avalanches occurring in Switzerland during the season of 1887-1888 has just been published as a contribution to the inquiry, whether and how these dangers can be averted. Peculiar weather-conditions, in addition to heavy falls of snow, were the reasons for the frequency of the phenomenon during that winter. This report records 1094 avalauches, by which 850 houses were destroyed or severely damaged; 84 persons and 752 cattle were buried; traffic on railroads and on highways was greatly interrupted, and the damage to personal property alone was valued at over $100,000. One of these snow-masses covered about half an acre, with a cone 250 feet in height. During the same year in Tyrol the number of avalanches was 3647. Of these 1355 run over permanent beds; that is, they recur annually, so that they are

Jan 1, 1890

By H. B. Aaron

DIFFRACTION micrography provides a useful tool for studying complex strain fields. Newkirk1 observed an X-ray diffraction effect due to strain interactions at the intersection of slip lines in LiF and attributed this effect to a reduction of primary extinction due to strain-gradients. It is the object of the current study to correlate the observations and rationalize the appearance of the strain fields around intersecting slip planes in x-ray extinction contrast studies by a semiempirical method. Fig. 1 shows typical strain patterns observed by Newkirk on (200) reflections in LiF using chromium radiation and a variation of the Berg-Barrett (B-B) technique. In other reflections (e.g., {220}) the strain patterns are absent. If one defines a vector 3 along the striations from the more to the less dense portion, and a vector v in the direction of the X-ray beam parallel to the reflecting plane, such that both 3 and v lie in the reflecting plane of the crystal, Fig. 1, then the positions of the striations on (200) reflections appear to be confined such that where is the angle between v and 3, Fig. 1. It will be seen later that 3 is the projection of Sb on the reflecting planes. In some instances the strain effects are observed only above the slip plane, Fig. l(C), in others only below, Fig. l(D). Where the strains appear to be both above and below the slip line, Fig. l(E), one sees that there are actually two slip lines present, Fig. 1(F) and (G). Furthermore, the strain patterns are observed in the vicinity of the intersection of emergent edge dislocations (diagonal lines on the micrograph) with emergent screw dislocations (horizontal lines on the micrograph), e.g., Fig. l(HJ) and (MN), but not in the vicinity of the intersection of two emergent edge dislocation arrays, Fig. l(HJ) and (KL). However, in the latter case the contrast of the dislocation array itself is reduced along (KL) and increased along (HJ). Line (AB) in Fig. 1 is the edge of the crystal, and the material to the left of (AB) is the side of the sample. Any empirical correlation will have to include most, if not all of the aforementioned observations. Lang2 and Newkirk1 determined that the condition for contrast is given by g-b#0 [2] where b is the Burgers' vector and g the diffraction vector (normal to the reflecting planes). If one assumes that the direction of the observed strain fields is given by the vector sum of the slip vectors (Sb1) of the intersecting slip planes, then Eq. [2] may be generalized to g-S#0 [3]

Jan 1, 1963

By Samuel L. Hoyt

Cemented tungsten carbide, a product of a branch of metallurgy which has never possessed more than a relatively minor interest and importance, has recently commanded the attention of engineers, industrialists, financiers and men of business. New methods, new opportunities, new goals, never before considered, have suddenly been brought within the scope of practical realization. It is these results that attract the interest of the world, but we, as engineers and metallurgists, will have equal interest in the product itself and in that branch of metallurgy from which it comes. It seems appropriate, therefore, to speak today on Hard Metal Carbides and Cemented Tungsten Carbide, as the latter represents one of the outstanding developments of recent date in non-ferrous metallurgy. We are interested in the hard metal carbides as a group of related metallic substances and in cemented tungsten carbide as the leading representative of the metallurgy of this group. The literature of this general field is limited, and, bearing this in mind, it seems advisable to attempt to cover the field broadly and to correlate the subject matter, rather than to present a detailed account of any one of its phases. Our annual lecture lends itself admirably to this plan. The quickened interest in cemented tungsten carbide, once its potentialities were recognized, the many sides to the problem of developing the manufacture and use of this new product, and the desire to economize as much as possible in the time of development, have brought many into this work, both in this country and abroad, notably the Osram Lamp Co. and Friedrich Krupp in Germany and the General Electric Co. in this country. It would be presuming too much to attempt to speak too broadly of the present state of the art and science of the hard metal carbides and my remarks arc guided largely by the work done in the General Electric Co., and by our associates in the Carboloy Co. Even here the activities of many in these two groups have centered around the utilization of cemented tungsten carbide, which is outside the scope of this talk. To those whose work is represented in this lecture, it is my pleasant duty to acknowledge their assistance and advice. To Dr. Zay

Jan 1, 1930

By M. R. J. Wyllie

The relationship between the electromotive force (E.M.F.) across a shale barrier and the concentrations of sodium chloride solutions on either side has been investigated. It is shown that the action of a shale barrier is analogous to a glass membrane separating two acid solutions of different hydrogen ion concentrations. The shale behaves as a sodium electrode and is responsive to the activities of the sodium ions in the two solutions in such a way that the potential can be calculated by means of the Nernst equation. This conclusion is confirmed by laboratory experiments. In a borehole the total E.M.F. of a shale cell is the algebraic sum of the ~otential across the shale and a boundary potential. The relationship between total E.M.F. and the resistivity ratio of two sodium chloride solutions is indicated for a number of formation temperatures. The E.M.F. thus predicted is then compared with the .elf potential read from an electric log and good agreement is demonstrated. Based on both the self potential and resistivity curves of the electrical log. a method is given for calculating connate water content in a bed having in-tergranular porosity and containing both connate water and hydrocarbons. INTRODUCTION The first paper on electrical well logging by C. and M. Schlumberger and E. G. Leonardon in 1934' attributed the self potential curve principally to streaming potentials, i.e. to electroki-netic effects. Almost immediately great difficulties were encountered in reconciling many of the curves they obtained with this interpretation. and a ~econd paper' by the same authors soon appeared. In this second paper self potentials were attributed to the combined effects of streaming potentials and electrochemical potentials, the electrochemical potential being considered the result mainly of the interaction of fluids of differing salt concentrations, i.e. a boundary potential, and partly of potentials set up at the faces of impermeable materials. Some experiments involving a gray clay for the impermeable material were quated. The Schlumbergers and Leonardon deduced from the equation for a simple boundary ~otential that the electrochemical potential, as opposed to the electrokinetic potential, could be expressed in the form E=Klog- .......1 pe where K is a constant, pm the mud resistivity. p, the resistivity of the connate water in a porous bed. However, no general expression for the constant K was obtained. Although the literature between 1934 and 1943 contains a number of quotations of their results, the valuable work of the Schlumbergers and Leonardon was not extended so that the electrochemical potential has been generally attributed wholly to boundary potentials between the mud in the borehole and the connate waters in porous formations. Unfortunately, however, the fundamental premise of all these papers, that a boundary potential can give rise to current flow in a borehole, is thermodynamically untenable. As will be shown. the fact that the electrochemical potential can be fairly accurately express as E = K log pm/pc, a form in which a boundary potential may also be written, is partly fortuitous. The boundary potential is indeed an integral part of the expression for the electrochemical potential in a horehole, but in magnitude it represents only about 20% of the total potential. In 1943 an important step in the elucidation of electrochemical potentials was made by Mounce and Rust3 who showed that if a wall of shale separated two compartments which contained saline solutions of different concentrations, and if the two solutions were themselves brought into contact in the pores of a porous inert membrane (such as unglazed porcelain) a current flowed through the shale and saline solutions. The direction of positive current was from the shale into the more dilute solution. The paper of Mounce and Rust, while repeating some of the observations of the Schlumbergers and Leonardon, seems to be the first to show that the shale was the seat of a genuine electrochemical effect capable of causing current flow. In the same paper Mounce and Rust pointed out the similarity between the fundamental conditions of their experiment and the conditions which existed when a bed of shale in the ground was simultaneously in contact with a porous sand containing saline connate water and mud fluid of salinity different from that of the water in the sand. Since it is now generally recognized that the S.P. curve measures ohmic potential changes in the mud fluid in the well bore resulting from changes in current flow, it is apparent that currents having their origin in the electrochemical interaction of mud filtrate and connate waters with shale beds are a very important portion of the total S.P. The work of Mounce and Rusta and others appears to indicate that, in general, the electrochemical portion of a particular kick on a S.P. curve far exceeds any electrokinetic potentials resulting either from streaming potentials or Dorn effects. The Dorn effect, or sedimentation potential. arises when small particles are allowed to fall through certain fluids under the influence of gravity. a difference of potential being observe? between two electrodes placed at different levels in the stream of falling particles. The Dorn effect is unlikely to affect seriously the S.P. curve as now measured. A successful analysis of the electrochemical aspects of the S.P. log should

Jan 1, 1949

By M. R. J. Wyllie

The relationship between the electromotive force (E.M.F.) across a shale barrier and the concentrations of sodium chloride solutions on either side has been investigated. It is shown that the action of a shale barrier is analogous to a glass membrane separating two acid solutions of different hydrogen ion concentrations. The shale behaves as a sodium electrode and is responsive to the activities of the sodium ions in the two solutions in such a way that the potential can be calculated by means of the Nernst equation. This conclusion is confirmed by laboratory experiments. In a borehole the total E.M.F. of a shale cell is the algebraic sum of the ~otential across the shale and a boundary potential. The relationship between total E.M.F. and the resistivity ratio of two sodium chloride solutions is indicated for a number of formation temperatures. The E.M.F. thus predicted is then compared with the .elf potential read from an electric log and good agreement is demonstrated. Based on both the self potential and resistivity curves of the electrical log. a method is given for calculating connate water content in a bed having in-tergranular porosity and containing both connate water and hydrocarbons. INTRODUCTION The first paper on electrical well logging by C. and M. Schlumberger and E. G. Leonardon in 1934' attributed the self potential curve principally to streaming potentials, i.e. to electroki-netic effects. Almost immediately great difficulties were encountered in reconciling many of the curves they obtained with this interpretation. and a ~econd paper' by the same authors soon appeared. In this second paper self potentials were attributed to the combined effects of streaming potentials and electrochemical potentials, the electrochemical potential being considered the result mainly of the interaction of fluids of differing salt concentrations, i.e. a boundary potential, and partly of potentials set up at the faces of impermeable materials. Some experiments involving a gray clay for the impermeable material were quated. The Schlumbergers and Leonardon deduced from the equation for a simple boundary ~otential that the electrochemical potential, as opposed to the electrokinetic potential, could be expressed in the form E=Klog- .......1 pe where K is a constant, pm the mud resistivity. p, the resistivity of the connate water in a porous bed. However, no general expression for the constant K was obtained. Although the literature between 1934 and 1943 contains a number of quotations of their results, the valuable work of the Schlumbergers and Leonardon was not extended so that the electrochemical potential has been generally attributed wholly to boundary potentials between the mud in the borehole and the connate waters in porous formations. Unfortunately, however, the fundamental premise of all these papers, that a boundary potential can give rise to current flow in a borehole, is thermodynamically untenable. As will be shown. the fact that the electrochemical potential can be fairly accurately express as E = K log pm/pc, a form in which a boundary potential may also be written, is partly fortuitous. The boundary potential is indeed an integral part of the expression for the electrochemical potential in a horehole, but in magnitude it represents only about 20% of the total potential. In 1943 an important step in the elucidation of electrochemical potentials was made by Mounce and Rust3 who showed that if a wall of shale separated two compartments which contained saline solutions of different concentrations, and if the two solutions were themselves brought into contact in the pores of a porous inert membrane (such as unglazed porcelain) a current flowed through the shale and saline solutions. The direction of positive current was from the shale into the more dilute solution. The paper of Mounce and Rust, while repeating some of the observations of the Schlumbergers and Leonardon, seems to be the first to show that the shale was the seat of a genuine electrochemical effect capable of causing current flow. In the same paper Mounce and Rust pointed out the similarity between the fundamental conditions of their experiment and the conditions which existed when a bed of shale in the ground was simultaneously in contact with a porous sand containing saline connate water and mud fluid of salinity different from that of the water in the sand. Since it is now generally recognized that the S.P. curve measures ohmic potential changes in the mud fluid in the well bore resulting from changes in current flow, it is apparent that currents having their origin in the electrochemical interaction of mud filtrate and connate waters with shale beds are a very important portion of the total S.P. The work of Mounce and Rusta and others appears to indicate that, in general, the electrochemical portion of a particular kick on a S.P. curve far exceeds any electrokinetic potentials resulting either from streaming potentials or Dorn effects. The Dorn effect, or sedimentation potential. arises when small particles are allowed to fall through certain fluids under the influence of gravity. a difference of potential being observe? between two electrodes placed at different levels in the stream of falling particles. The Dorn effect is unlikely to affect seriously the S.P. curve as now measured. A successful analysis of the electrochemical aspects of the S.P. log should

Jan 1, 1949

By L. C. Skinner

THE Coal Hydrogenation Demonstration Plant at Louisiana, Missouri, was completed early in the year 1949. It has operated more or less continuously since completion except for the time required for making necessary inspections, repairs, and alterations between runs. Operations have included a short vapor-phase run on North Dakota lignite-tar distillate oil in 1949, followed in 1950 by four comparatively short exploratory liquid-phase runs and one vapor-phase run on Rock Springs [ ]

Jan 1, 1953

By P. A. Boeck

(San Francisco Meeting, September, 1915) THE thermal insulation of high-temperature equipment for industrial purposes is a subject that has not received from engineers and designers the attention its importance deserves. This may be attributed to a number of causes: In the first place, heat flow is a rather difficult factor to measure under the working conditions of an industrial furnace, and until the comparatively recent introduction into certain operations of the heat balance sheet, with a systematic attempt to account for the discrepancies in the totals, the various causes of heat losses and the reasons for their existence were not brought to light. Moreover, such rapid advancement and radical changes in the design of equipment, especially in metallurgical lines, have occurred that practice has apparently outdistanced the theory of design. In the modern tendency toward greatly increased size of units, effort has seemingly been made to utilize the heat of fuel gases without proper. attention having been paid to conserving heat energy and confining it strictly to the points of maximum activity. The systematic study of the thermal properties of structural materials, which is being carried out by various government bureaus and also by a number of technical societies, is forming the basis for more intelligent and consistent work in the economically important subject of prevention of fuel waste.

Jan 8, 1915

By A. H. Smallbone, R. Lathe

Considerable efforts have been expended to apply multiple regression techniques to quantitative determinations in x-ray fluorescence analysis. Multiple regression has been shown to be an effective method for correlating x-ray fluorescence intensities to elemental concentrations. Although many other techniques have been devised to solve the problem of matrix effects in x-ray fluorescence analysis, there are few as efficient in terms of storage requirement or ease of programming for digital computers as the multiple regression method. In the case of ore slurry, it has the additional advantage of allowing a unified approach to the problems of slurry density correction and matrix effect corrections. The data used in the present work were obtained with an on-stream x-ray analyzer capable of analyzing 15 slurry streams for as many as nine elements simultaneously. One of its fixed monochromators was set to accept scattered radiation at a discretely selected wavelength as a means of monitoring the slurry's pulp density. The data were reduced to obtain the correlation equations and a computer program combining slurry density with matrix corrections was written in FORTRAN IV to calculate concentrations.

Jan 8, 1969

By John A. Gann

The following investigation constitutes a brief réumé of the more important binary magnesium alloys from the standpoint of metallo-graphic technique, and the effect of heat treatment on structure and properties. The comparative newness of the subject justifies this procedure as a preface to a more detailed study of each individual series of alloys. The work was started with the idea of practical application in the industry rather than as a theoretical investigation. The alloy compositions studied were selected as those most likely to show whether heat treatment would produce beneficial results. Furthermore, it was considered satisfactory to use commercial 99.9 per cent. magnesium, the best commercial grade of alloying ingredients, and to limit the time of heat treatment at the expense of incomplete equilibrium. These facts must be kept in mind when examining the results obtained, and the conclusions drawn. Preparation of Alloys All melts were made in an oil-fired cast-steel pot, approximately 12 in. dia, by 12 in. deep. Approximately 15 lb. of flux and 50 lb. of magnesium were melted and the calculated amount of alloying metal was added. After thorough alloying and puddling, the metal was chill cast in a graphite mold with four 1/2 by 1/2 by 4 in. bars fed from a common sprue and runner. The next higher composition alloy in a given series was made by adding the calculated amount of metal to the heel from the preceding cast. The pot was thoroughly cleaned after each series and new flux then introduced, thus avoiding possible contamination from earlier melts. The percentage compositions given in Table 1 are the calculated values. While not all alloys were analyzed, enough were checked to indicate that the reported compositions are correct to a few tenths of one per cent. A more detailed description of the foundry methods employed has been given in a previous paper. 1

Jan 1, 1929

By John A. Gann

The following investigation constitutes a brief réumé of the more important binary magnesium alloys from the standpoint of metallo-graphic technique, and the effect of heat treatment on structure and properties. The comparative newness of the subject justifies this procedure as a preface to a more detailed study of each individual series of alloys. The work was started with the idea of practical application in the industry rather than as a theoretical investigation. The alloy compositions studied were selected as those most likely to show whether heat treatment would produce beneficial results. Furthermore, it was considered satisfactory to use commercial 99.9 per cent. magnesium, the best commercial grade of alloying ingredients, and to limit the time of heat treatment at the expense of incomplete equilibrium. These facts must be kept in mind when examining the results obtained, and the conclusions drawn. Preparation of Alloys All melts were made in an oil-fired cast-steel pot, approximately 12 in. dia, by 12 in. deep. Approximately 15 lb. of flux and 50 lb. of magnesium were melted and the calculated amount of alloying metal was added. After thorough alloying and puddling, the metal was chill cast in a graphite mold with four 1/2 by 1/2 by 4 in. bars fed from a common sprue and runner. The next higher composition alloy in a given series was made by adding the calculated amount of metal to the heel from the preceding cast. The pot was thoroughly cleaned after each series and new flux then introduced, thus avoiding possible contamination from earlier melts. The percentage compositions given in Table 1 are the calculated values. While not all alloys were analyzed, enough were checked to indicate that the reported compositions are correct to a few tenths of one per cent. A more detailed description of the foundry methods employed has been given in a previous paper. 1

Jan 1, 1929

By G. J. Borbely, E. A. Devuyst, V. A. Ettel

Introduction Of the techniques reported for cyanide removal from effluents, alkaline chlorination is the most common (Fisher and Wasser, 1969; Reidt, 1969). Shortcomings with this technique are the high reagent costs, chlorine contamination, and potential formation of cyanogen chloride. Chemical oxidation methods are also not suitable to remove cyanide from effluents containing sulphides in suspension, such as flotation tailings. An inexpensive method for removing cyanide, combined cyanide and related species from waste waters has been developed in Inco laboratories. The method is based on the use of sulfur dioxide (or a sulfite), lime, and air as the reagents. The decomposition reactions of cyanide, combined cyanide, and related species are catalyzed by copper in solution. Complete removal of cyanide species, most of which are oxidized to cyanate, is obtained by treating copper containing cyanide effluents with sulfur dioxide-air mistures while maintaining the pH between 6 and 10 with addition of lime. The new approach can also be applied to selective destruction of cyanide and combined cyanide in effluents containing sulphides in suspension, such as pyrrhotite. Again, a sufficient amount of dissolved copper must be present or added. Metals and precious metals present in the effluents are recovered as hydroxides by adjusting the pH of the treated effluents to about 9-10. Using the new method, the anionic species are removed in the following order: Free CN- > Complex CN- > Thiocyanate The above removal sequence is unusual as oxidants such as chlorine and ozone oxidize thiocyanate preferentially over the combined cyanide.

Jan 1, 1985

By S. C. Schaeker, A. W. Schlechten, A. H. Larson

PARRAVANO and Malquori' studied the equilibrium of H2S-Hz with molybdenum and its lowest sulfide which they believed to be MoS2. Mc Cabe' has shown that its composition is actually Mo2S3 and determined its dissociation pressure by means of Knud-sen effusion measurements. Stubbles and Richard- son3 have recently studied the equilibrium of gas mixtures of H2S-HZ with the two-phase solid mixtures of Mo-MozS3 and Mo2S3-MoS2. The latter investigators found that M02s3 deviated slightly from the stoichiometric composition, but they did not determine the homogeneous region of the disulfide phase. Morimoto and Kullerud, studied the Mo-S system by quenching, microscope, and X-ray methods and concluded that the disulfide is stoichiometric. The present investigation was concerned with the measurement of the sulfur vapor pressure variation with composition at 1100°C in the homogeneous region of "MoS2". These measurements were made by reacting: 1) molybdenum powder (99.97 pct Moj with sulfur vapor, and 2) MoS1.g9 (formed by reaction of Mo + H2S) with sulfur vapor in a quartz capsule. Conditions were controlled to form an equilibrated phase within the homogeneous region of the disulfide. The quartz capsule was sealed off initially under a vacuum and the residual gases were gettered by titanium powder contained in one end of the capsule. A mixture of Mo + S or MOS,., + S was in the other end. The section containing the titanium powder was heated for 24 hr at 700°C and then removed by flame sealing. The end of the capsule containing the charge was then heated to 1100°C. The other end of the capsule was maintained at a temperature which would produce the desired sulfur pressure in the capsule (liquid sulfur distilled from the charge mixture was retained in this end). After equilibration, the capsule was removed from the heating assembly and rapidly air-cooled. It is assumed that equality existed between the total sulfur pressures (PT) in the two ends of the capsule and not between the partial pressures of the different molecular species (S, SZ, Three separately controlled heating elements were used to maintain the proper temperature gradient over the length (approximately 12 in.) of the capsule. A thermocouple-Wheelco "Capacitrol" system was used for temperature control of the two end heating elements within 2"C. The center heating element was controlled directly by a " Power -stat". Separate controlling and measuring thermocouples were used for both end heating elements. Pt-Pt(l0 pct Rh) thermocouples were used for 1100°C and Chromel-Alumel thermocouples were used for lower-temperature control and measurement of the assembly. Silver foil was wrapped around the end of the capsule containing the liquid sulfur to insure a constant temperature zone. The thermal gradient over the entire length of the capsule was measured to: 1) ascertain that the length of the constant temperature zone of the liquid-sulfur end and the sulfide end was sufficient, and 2) ascertain that the liquid-sulfur zone was the zone of lowest temperature. The data obtained in this investigation are shown in Fig. 1 and Table I. The total sulfur pressure (PT) and p(S2) were calculated from the data of Braune et UZ.~ The compositions of the equilibrated disul-

Jan 1, 1964

By S. C. Geol, C. H. Page

INTRODUCTION Mining at Mindola Mine, Rokana Division of Nchanga Consolidated Copper Mines Limited is the deepest on the Zambian Copperbelt. Mining extends to 1150 metre depth so far and the present plans extend to 1500 metres, although reserves exist below this level. Mindola Mine is the major producer of copper/cobalt ore at Rokana Division and produces approximately 200,000 tonnes of copper/cobalt ore per month. A standard open stoping method is the only method used for mining with minor variations in positioning drilling drives and other development, figure 1. The standard main haulage interval is 75m but in flat dipping areas the full stope height is split into two or three panels. In 1970 severe mining problems were experienced when mining deeper than 850111 below surface. The main problems included: - Heavy support requirements in drilling drives near stope face. - Premature closure of blast holes necessitating pre-charging of the holes with explosives immediately after drilling and well before the day of blasting. - Severe bumping and spitting due to rock movements on drive surfaces and remotely within the rock mass under high stress. - Low mining efficiency due to dilution from the waste hangingwall. - These stress related factors also caused some premature detonations of precharged but unprimed blast holes which became a serious safety hazard. A number of alternatives have been considered to overcome these problems. A search for leas sensitive explosives to avoid the premature detonation problem has been partially successful, however, the need for a method of reducing stress levels at the mining face is still considered essential as the mine goes deeper. This paper describes experiments with Regional Support Pillars as a method of reducing stresses at the mining face.

Jan 1, 1981

By H. E. Kramm

(New York Meeting, February, 1919.) DURING the summer of 1911, I had the opportunity to study in detail the geological conditions of what is known in northern California as " Harrison gulch," in Shasta county. Though the district, as a whole, that is, the western part of Shasta and the eastern part of Trinity county, has contributed during the last 15 years a considerable share of the gold-production credited to Shasta county, very little is known of its geology, perhaps because the country is covered with a dense growth of brush which makes exploration and prospecting extremely difficult. Topographically the district presents a succession of ridges trending approximately N-S.; and alternating with deep narrow canyons. The drainage is partly into . the Sacramento, partly into the Trinity river. Climatic conditions in summer time are almost ideal. It is true, the thermometer may climb to 115°, but the air is dry and the heat is bearable, especially as the nights are always cool. It seldom rains during the summer months, and creeks and springs dry out towards the end of the summer. The winter is severe, lasting from November to April, and usually a thick layer of snow covers the mountains. By reason of the character of its gold-deposits, the region is known to miners as "the pocket country." It contains a series ?of eruptive rocks intruded into slates, cherts, limestones, and conglomerates. Dikes, laccoliths, and batholiths are frequent. In a day's ride it is possible to find all the common igneous rocks from the very acid to the very basic. Serpentines are especially abundant.. The sedimentary rocks are, as rule, broken and shattered as well as folded, and show the effects of intense metamorphism. ? Pocket-hunters " speak of the contact of diabase and slate as the ? pocket-contact." Some rich gold-pockets, however, have also been found in the diabase.

Jul 1, 1912

By R. P. Rothwell

AT this our first meeting I beg to call the attention of the members of our Institute to what is certainly a question of the greatest possible importance to the industries we represent; and more particularly to the welfare of the coal and iron trades : I refer to the enormous waste of coal in mining and in its preparation for market, as now practised in our anthracite coal-fields. It is a fact which many of you can certify to, that we are wasting fully one-ha f of all the coal in the veins we are now working, and there are cases, which might be mentioned where this proportion, immense as it is, has been greatly exceeded. The popular belief that our deposits of anthracite coal are "practically inexhaustible," is very far from being founded on facts. On the contrary, supposing the present rate of increase in the production to be maintained, it is probable that a maximum yield for our coal-fields would be attained in about fifteen years ; there are in fact some of our smaller basins where the principal veins are nearly exhausted and the production has already attained its maximum. There are others, again, where the depth attained-and it must be borne in mind that we commenced working at the surface outcrop-moderate though it is (scarcely ever reaching eight hundred feet), has so increased the cost of mining as to imperil the capital invested, and though it requires but little foresight to predict the time when the difficulties of mining will be very considerably increased by reason of the greater depth, greater quantity of water, fire-damp, and other fruitful sources of cost, yet, ignoring these recognized facts, we continue to waste more than one-half of the coal where it is obtained with the least danger, expense, and trouble, that is, near the surface-either above water-level or at a moderate depth below it. The inspection of almost any accurate mine map will satisfy you that, on an average, we leave fully one-third. of the coal in the ground as pillars to support the roof; in some places more than one-third thus remains, while it is very rare that less than one-quarter is left. In almost every case this coal is absolutely lost, for it will very rarely pay to reopen gangways and lay roads to it after that portion of the mine has been abandoned. Is it necessary in all cases to support the roof, and where it is, may not some artificial

Jan 1, 1873

By A. S. Emanuel

A correlation has been developed for calculating the phase behavior of, gas-condensate systems at reservoir conditions. The correlation is based on the principle of corresponding states and has been coded for an IBM 7094. Experimental K-values were determined for several gas-condensate systems at reservoir conditions to evaluate various semi-empirical parameters of the correlation. The approximate range of application of the correlation is 150 to 300F and 1,500 to 6,000 psi. INTRODUCTION The rapid development of digital computers during the past several years has made feasible the calculation of hydrocarbon phase behavior by methods based on rigorous thermodynamic principles. Good correlationsl have been developed for low to moderate pressures, but these techniques have not yet been extended successfully to reservoir fluids at high pressures. Consequently, the determination of phase behavior of oil and gas systems at reservoir conditions is still based almost entirely on generalized data correlations or on experimental studies of the fluid in question. While these methods have been used successfully many times, they do have inherent limitations that restrict their applicability. Generalized correlations, such as the NGShlA K-charts, are limited to the range of pressure, temperature and components for which the data were determined. The accuracy of these correlations is often questionable because the effect of total system composition is not well defined. Experimental studies offer a reliable method for determining phase behavior, but usually the studies are costly and time consuming. Recently, Leland and co-workers presented a new approach to calculating phase behavior from the principles of corresponding states.6-8 Corresponding states methods determine the thermodynamics properties of a given system by comparison with a reference substance whose properties are known. The accuracy of this approach depends on close chemical and structural similarity between the reference substance and the system in question and between components within the system itself. For high accuracy, it is usually necessary to correct for chemical and structural dissimilarities. In principle, however, the corresponding states method should be no less accurate at high pressures than at low pressures, provided reference substance properties are known. This paper describes an empirical modification of the basic correlation proposed by Leland, et al.6 for the specific purpose of calculating the phase behavior of gas-condensate fluids at reservoir conditions. The modified correlation, which has been programmed for an IBM 7094, may be used for either approximate or precise determination of fluid behavior depending on the amount of analytical and, experimental data available for the system. BASIC THEORY The basic theory of the corresponding states phase equilibria correlation was first published by Leland, Chappelear and Gamson.6 Subsequently, Leland, Chappelear and Leach published methods for improving the accuracy of the original theory.7-9 The aim of the correlation is to calculate the K-value of each component of a given system as a function of pressure, temperature, and over-all composition, where Once the K-values are known, the phase behavior may be determined directly by an appropriate flash calculation. The basic equation for calculating component K-values was taken from the work of Joffe. 4 For any component i of a mixture, the K-value is given by

Jan 1, 1969

By William M. Shepard

The Tintic mining districts of central Utah com- prise one of the major silver-lead producing areas in the United States. Ore valued at nearly $450 million has been produced from these districts since the initial discoveries, in 1869, of veins cutting the Silver City monzonite stock. Subsequent production from the famous manto-type "ore runs", which characterize the Main Tintic district, was followed during the past 40 years by discovery of the blind orebodies of the East Tintic district, including the famous Tintic Standard mine and the most recent discovery, the Burgin mine, currently being brought to full production by Kennecott Copper. The occurrence of blind orebodies of exceptional size and grade in both the Main and East Tintic districts has made this area a field laboratory of major importance for the study of geochemical dispersion halos and alteration features associated with known ore, and has led to the discovery of additional concealed orebodies. The larger share of the basic data-gathering and interpretation has been done by members of the U.S. Geological Survey who have been studying the Tintic mining areas since before the turn of the century. These studies have been supplemented and expanded by the geological staffs of the local operating mining companies, by exploration geologists and by students.

Jan 4, 1966

By Charles A. Ashburner

' I. Natural-Gas Explorations. The rapid development of the natural-gas* industry in Western Pennsylvania, and the great economy which results from its use, both for manufacturing and domestic purposes, has led to an inquiry as to the occurrence of this gaseous mineral in all thickly populated and large manufacturing centers of the United States. Natural-gas springs are to be found in almost every State in the Union, and in many States gas has been obtained in wells sunk either for water, oil, or gas, or in search of solid mineral deposits. The occurrence of natural gas is, however, not dependent upon mere chance, as is popularly supposed, but upon the existence of special geological phenomena; this fact is now recognized by professional men and by many practical men concerned either in the exploration for or in the use of this gas. The desire among our leading manufacturers, to emulate Pittsburgh, has led to the sinking of many wells in many localities, in search of natural gas. Some of these wells are now being located and drilled under the direction of professional experts, but many more have been, and are still being located by "quack " explorers, who often depend upon spiritualistic communications, or the diviningrod, or by intelligent persons, who are ignorant, however, of the geological and physical conditions under which gas has already been found. My attention has recently been directed to a number of these exploring operations where holes have been drilled, and, after failing

Jan 1, 1887

By R. F. Krueger, L. C. Vogel, P. W. Fischer

Previous studies have shown that the permeabilities of sandstone cores are markedly reduced following exposure to drilling fluid and subsequent clean-up with oil at high-pressure gradients. Laboratory experiments reported in this paper indicate that permeability damage from drilling mud or water can be substantially avoided through use of an initial low-pressure gradient followed by gradually increasing gradients during clean-up by reverse oil flow. On the other hand, attempts to improve the permeability of damaged Berea and oil formation cores with high-rate oil backflush (simulated well stimulation) and low-rate clean-up gave erratic results. Essentfully complete permeability repair was achieved in most of the fresh water-damaged cores from Miocene and Pliocene oil-producing formations; only minor improvement was noted generally in tests with both water-and mud-damaged Berea sandstone. Field well stimulation treatments using high-rate back-flush resulted in long-term productivity improvement when production was brought in at gradually increasing production rates and then restricted to a steady value less than the maximum possible rate. Wellbore plugging at high production rates correlated with increasing solids content in the produced oil. Observations and results from these tests agree with current concepts that formation damage in water-sensitive rocks results from movement and bridging of formation fines, rather than from clay swelling alone. INTRODUCTION Many laboratory studies1-g have shown that the permeabilities of sandstone cores are often markedly reduced following exposure to fresh water or water-base drilling mud filtrate. However, work with cores in the restored state has demonstrated that, although permeabilities to water may be very low for sandstones containing hy-dratable clays, flow of oil can often restore a substantial portion of the effective permeabilities to oi1.Neverthe- less, water invasion into water-sensitive sandstone cores results in varying degrees of permanent reduction in permeability to oil.24' Based on field data, Wade's statistical study" of well completion effectiveness also indicated a correlation between productivity damage and water invasion during completion. Similar damage can result from fluid invasion during workover. Nowak and Krueger' and Bertness4 observed in their early work (1951-53) that formation damage in water-sensitive sandstones was associated not only with swelling of expandable clays but also with movement of dispersed particles. Subsequent work by Monaghan et al." (1959), Atwood'' (19641, Mungan" (1965) and Gray and Rex'" (1965) has led to general acceptance of the hypothesis that permeability damage in water-sensitive formations is caused by migration of finely dispersed minerals and bridging in "brush heap" arrangements at pore constructions. In laboratory studies, Monaghan et al.' found the use of chemicals to be of only minor value for repairing formation damage. Atwood? however, was successful in substantially repairing damage in a number of low-permeability cores using an n-hexanol flush. In the field, except for treatments with acids, the use of chemical washes to reduce wellbore damage has had limited and sporadic success and generally is unpredictable. A statistical analysis of stimulation treatments in silt-blocked wells has shown that physical manipulation of wash materials is more important than chemical composition." The recent work reported on formation damage in water-sensitive sands brings to mind the results of some unpublished exploratory work done in 1954 in connection with drilling fluid studies.' This laboratory work and subsequent field stimulation treatments indicated a beneficial effect of controlled pressure drawdown and the associated production rate on formation clean-up. This paper reports the results of this work and more recent supplemental experiments on the clean-up of water-sensitive sandstones damaged by water or filtrate invasion. PERMEABILITY RECOVERY AFTER DAMAGE BY DRILLING MUD APPARATUS AND TEST SAMPLES A drilling mud circulating system was used to expose cores to simulated wellbore conditions. The mud flow system is the same as that described by Krueger and Voge17 except that no provision was made for scraping