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By L. E. Wilsey, W. G. Bearden

This paper presents results of analysis of the effect of fracturing on initial flow rates and on ultimate recoveries from low capacity oil formations. This analysis shows that even in formations of permeability as low as 0.1 md, large fracture treatments can yield oil recoveries and production rates approaching those of high permeability formations. Field production information is shown which supports the analytical work. INTRODUCTION Often hydrocarbon bearing formations are discovered which, while they are known to contain large quantities of oil, will not produce at commercially attractive rates without special well stimulation. Attempts to solve this problem led to the development of such techniques as underreaming, shooting, acidizing, and recently hydraulic fracturing. These methods of stimulation have been highly successful in many fields. All of these treatments, however, affect only the pay section near the well bore and therefore owe their success to circumventing and overcoming local permeability reduction about the well bore. It has been the belief that in treating wells to stimulate production in which there is no permeability reduction near the well, the maximum possible production rate increase would be of the order of two or fourfold. Hence, it has been concluded that fracture treatment of uniformly low capacity (permeability times thickness) formations could meet with but limited success. It is the purpose of this paper to show that the use of fracture treatments much larger than usually used can yield commercially attractive producing rates and high recoveries even in formations of permeability less than 0.1 of a md. PROCEDURE In order to illustrate the effects of fracturing, an analytical study of some hypothetical systems was made in which one factor at a time was varied to show what is important in recovering oil from fractured wells. It was assumed that a horizontal fracture of relatively high fluid-carrying capacity extended from a well bore. The presence of such a fracture will cause a marked influence on the flow pattern and pressure distribution in the formations, with the net effect being to reduce tremendously the resistance to flow into the well bore. A diagram of the resulting flow pattern and pressure distribution is illustrated in Fig. 1. Immediately after production commences, the principal flow of fluid is vertically from the formation flanking the fracture, into the fracture, and then into the well. After sufficient oil and gas have been produced to lower the pressure in the formation adjacent the fracture, oil and gas will begin to flow in a radial manner into the fracture from the formations beyond the end of the fracture. In calculating the performance under such conditions. the material balance or conservation of matter equation and equations of flow were solved simultaneously by a stepwise method of calculation. Flow rates were found by determining the pressure distribution, as illustrated

Jan 1, 1955

By K. A. Jackson, J. D. Hunt

The discussion by Tammann and Botschwar of the transition from eutectie grouth to denrdritic plus eu-tectic growth is reviewed and applied to metallic eutectic systems. Using expevimental data on the geowth rate of the Pb-Sn eutectic, and an extrapolalion of dendritic growth rate in tin and Sn-Pb alloys , qlcantitatice prerlictiotls of the extent of the eutectic region in tin-vich Sn-Pb alloys are made. There are no experimenta1 measuvements available for detailed comparison with these predictions. EUTECTIC structures form over a small range of compositions. The theory of lamellar growth presented by Jackson and Hunt' indicates that it is in principle possible to have eutectic growth over almost the complete range of compositions between the two solidus lines. This does not occur in practice. Alloys far from the eutectic composition grow dendritically followed by a eutectic as shown in Fig. I. The transition from a eutectic to a dendritic plus eutectic interface cannot be predicted from constitutional undercooling arguments because constitutional undercooling always exists ahead of the eutectic interface.' Reasonable predictions can, however, be made using arguments originally put forward by Tammanl. and Botschwar.3 These and later workers'"*6 carried out extensive experimental investigations of the extent of the eutectic range in organic materials. They concluded that the structure formed, eutectic or dendrites plus eutectic, depended on which structure grew faster at the given undercooling. This is, of course, equivalent to the structure which grows with the smallest undercooling at a given growth rate. In this paper, we will discuss these ideas briefly and then apply them to predict quantitatively the range of eutectic growth in tin-rich Pb-Sn alloys. The temperature dependence of the growth rates of dendrites and eutectic for a typical metal alloy of eutectic composition is shown schematically in Fig. 2(a). The growth rate for the eutectic increases more rapidly with undercooling than those of the dendrites because of the short diffusion path maintained in the eutectic, see Fig. 1. For an alloy off the eutectic composition on the A-rich side, the growth rates shift as shown in Fig. 2(b). The liquidus temperature of the a phase increases, that of the 3 phase decreases, and the temperature of zero growth rate for the eutectic does not change. The curves, particularly the dendritic ones, change shape as well, but for our purposes the principal effects occur because of the change in liquidus temperatures.3-6 In an isothermal system, only a dendrites will grow above TE, Fig. 2(b). If the temperature is below TE, and both phases have nucleated, a dendrites will grow ahead of the eutectic at

Jan 1, 1968

By H. H. Reamer, B. H. Sage

Attempts have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-turesl-6 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.t and the temperatures are in the neighbor-hood of 250°F. was investigated. Method The objective of this program was to determine the volumetric behavior of ma-terial as it existed in the reservoir as a function of pressure, temperature and com-position. Strictly speaking, this cannot be accomplished in any simple fashion. How- ever, the variations in composition that are encountered within a producing reservoir may be approximated roughly by means of mixtures made up of two arbitrarily chosen constituents. Experience indicates that the liquid and gas phases from a high-pressure gas trap afford a simple source of material for this purpose. Throughout this discus-sion the samples of the gas phase and liquid phase from the production trap will be called the "trap-gas sample" and the "trap-liquid sample," respectively. The volumetric behavior of both of the trap samples was determined throughout the temperature interval between 100" and 250°F. at pressures up to 5000 lb. per sq. in. In addition, the behavior of eight different mixtures containing varying proportions of the two trap samples was studied throughout the same temperature and pressure intervals. The experimental results yielded information concerning the specific volume of the material as a function of pressure, temperature and the relative quantity of the trap samples. The relative amount of each of the paraffin hydrocarbons of lower molecular weight than n-hexane was determined for each of the trap samples. In addition, the specific weight, viscosity and average molecular weight of the hexanes-and-heavier fraction of the trap-liquid sample were determined as well as similar information for each of five fractions separated from this material by distillation. From these data the weight fractions of each of the components from methane through pentane were determined for the trap samples and eight systematically chosen mixtures. Materials The gas and liquid samples were obtained from the production trap of a well in the Rio Bravo field in California during the fall of 1939. Information concerning the condi- 70

Jan 1, 1941

By T. W. Lippert

In these opening remarks, I will endeavor to give a background of continuous casting of metals. Only passing attention will be given to the different processes to be described by the authors whose papers are on the program, as they are far more familiar than I am with their subject matter. Suffice to say that over the past several years the brass, copper, aluminum and magnesium industries have shifted practically completely from conventional static molds to continuous casting machines. The Aluminum Company of America alone has more than 60 continuous machines in operation. The product as continuously cast is superior metallurgically, less scrap loss is involved, costs are generally lower, and the equipment requires little floor space. A continuous machine, operating as it does with deadly constancy, is a ravenous consumer of molten metal, and in most plants one or two machines are well able to handle large banks of melting and refining furnaces. In steel, interest in continuous casting is today more serious than ever before in history, and there is every reason to believe that continuous machines may secure a minor place in the ferrous industry, particularly for tool and alloy analyses. In the past, steel has been commercially cast continuously, and today many tons of steel are being turned out in this manner. It has been said that the cradle of every science is surrounded by dead theorists— and certainly there are innumerable examples of this in the metals industries. An excellent illustration, for instance, is the continuous rolling of metal, a tantalizing objective that for decades on end exhausted . the efforts of a long line of famous, infamous and unknown inventors. Finally, in 1922, John B. Tytus, of the American Rolling Mill Co., brought forth what now seems such an obviously simple scheme— a concave roll face, each stand of progressivcly less concavity. And out of this one change in design sprang today's wide continuous mill rolling steel sheet Ioo in. wide at 2000 ft. per minute. Another excellent example is the con- . tinuous casting of liquid metal into an intermediate form, preferably one requiring little subsequent breakdown. First, the casting of liquid metal alone was fascinating enough. Then someone passed the cast metal directly into a rolling mill, and shortly thereafter this continuously rolled strip was passed directly into a stamping machine. This leitmotiv of a continuous flow of metal from the liquid phase to a consumer end product, fast and inexpensive, and all housed within a small space, was enough to drive some 200 or so inventors into frenzy over the past hundred years. All the ideas, however, like mayflies, had only their brief afternoon of existence. They were born and they died on paper, as constant exemplification of that great void that always exists between mental production and commercial production.

Jan 1, 1945

By Lester C. Uren

THIS paper reviews the industrial trends and changes in educational concepts that have led to the development of the modern petroleum engineering curriculum. A trend toward emphasis on engineering fundamentals is noted. While most universities are committed to the traditional four-year engineering program, it is agreed that more than four years is necessary for academic preparation of the petroleum engineer in all phases of his profession. The author proposes a coordinated program of undergraduate and graduate training that will permit of adherence to the general pattern of the present four-year engineering course, with provision for extension of the program into specialized graduate courses of professional character. In the latter, emphasis may vary with the interests and objectives of the individual student. A specific undergraduate curriculum is proposed in which upward of 80 per cent of the available time is devoted to engineering fundamentals. A broad survey of the professional field is afforded in courses grouped in the third and fourth undergraduate years, but detailed treatment of the professional aspects of petroleum engineering is reserved for the graduate program. INTRODUCTION Of necessity, engineering curricula must ever be changing to reflect the new techniques, the changing concepts that are presented as the engineering industries develop and unfold. Particularly is this true of the younger engineering curricula representing comparatively new and rapidly changing industries such as the petroleum industry. Institutions that planned their petroleum engineering curricula a decade or two ago now find that the petroleum industry has become vastly more technical in its requirements. Entirely new methods and techniques have come into vogue and must be given place in the curriculum, and some of these are of a character that demands changing emphasis in the fundamental preparatory subjects. College and university faculties cannot complacently assume that curricula in this field that were considered appropriate 10 or 20 years ago still reflect the needs of the industry that they are designed to serve. If they do, their graduates will be poorly equipped to meet the requirements imposed upon them by a rapidly changing industry. Perhaps it is not too much to expect academic authorities to anticipate the trends of industry and equip their graduates with what they will need to attain leadership 10 or 20 years after graduation. Whether or not this desirable objective is possible, there is no excuse for allowing curricula to fall behind the current needs of industry. DURATION OF CURRICULUM The majority of our engineering schools and colleges still adhere to the four-year curricula and there appears to be a definite - sentiment among many engineers engaged in industry that work should be so planned that the engineering student may secure the essential academic preparation for his profession in a terminal four-year program. Yet, in recent years, it has become increasingly apparent that four years of

Jan 1, 1941

By R. S. Handy

Does hand-sorting of mill feed pay? The fact that the practice is so general would seem to indicate that there must be good reasons for following it; yet, to my mind, the advantage in many cases is doubtful enough to invite a thorough discussion of the subject, in an effort to determine under what conditions hand-sorting does pay. A typical sorting plant in the Cœur d'Alene district handles about 800 tons of mine-run ore per day. The material is run over a grizzly with about 4-in. opening; the oversize is crushed to about 4-in. size and joins the undersize, and the whole product is washed and screened on trommels with about 11/2-in. openings. The oversize from these trommels is spread on a belt and the waste and first-class ore are sorted out by hand, the residue being further crushed, and passes, together with the trommel undersize, into the mill feed bins. About 50 tons of shipping ore and 150 tons of waste are sorted out per day, leaving about 600 tons of mill feed. To sort out this material requires 20 ore sorters and five bosses and repairmen. The normal cost of hand-sorting is about 16 c. per ton of run-of-mine ore, or 65 c. per ton of material sorted out. I believe that straight crushing and milling of the run-of-mine ore, in this case, is not only cheaper, but is metallurgi-cally more economical and efficient than hand-sorting followed by milling of the residue. At one of the Bunker Hill rock-houses, 1250 tons of run-of-mine ore are reduced to pass 30-mm., or about 11/4-in., opening in six hours, requiring five men. The equipment and the power consumed are not greatly different from that required in a sorting plant of the same capacity, and the normal cost of thus preparing the feed for milling is under 3 c. per ton of mine product. The relative cheapness of this method as against hand-sorting is thus clearly established, the saving being about 13 c. per ton. If there is any virtue in, hand-sorting, then, it must lie in the metallurgical results achieved. Possibly the favor that hand-sorting has found is due to a misconception as to what happens to the clean shipping ore if it is sent to the mill. If a mill makes, say, an 80 per cent. recovery on its feed, the hand-sorting advocate may assume that if the hand-sorted product be sent to the mill, 20 per cent. of the metals contained in it will be lost. This, I believe,

Jan 1, 1920

By Blake M. Loring

RECENTLY the S-curves for 30 to 40 alloy steels have been published.1,2 These steels show individual characteristics, which make each additional S-curve of great interest. There are important differences in the mechanism of the transformation process, the type of transformation product, and the influence of alloying elements. Steels of the same general alloy composition may possess such variable characteristics with regard to the length of time of isothermal transformation that an S-curve for each heat of steel may be desirable. In the present work the isothermal transformation of a steel having the following composition and grain size was studied: 0.20 percent carbon; 0.21 manganese; 0.026 phosphorus; 0.017 sulphur; 0.056 silicon; 1.45 chromium; 3.25 nickel; austenite grain size, 7. The progress of the isothermal transformation was followed by several different methods, including hardness measurements, dilatometer observations, and examinations of the microstructure. It was not expected that these methods would be in precise agreement.3 Accordingly, the changes in microstructure and hardness were given additional weight in determining the initial stage of transformation and the dilatometer measurements were relied on in estimating the completion of the process. The beginning of transformation was indicated by I per cent of transformation products and the end of transformation by about 99 per cent. The reproducibility of the various methods in the ranges of highest sensitivity was checked by several observations at each time and temperature. The steel used in this investigation was annealed for 24 hr. at 925°C. Macroetching revealed no serious segregation. The specimens for the metallographic and hardness investigations were 1 1/4 by 1/2 by 1/8 in. Wires attached to the samples were used for handling, instead of tongs, to avoid chilling. The specimens were heated at 845°C. for 1/2 hr. and quenched into constant-temperature salt baths held at various temperatures from 205° to 650°C. The time required to transfer the specimens was found to be about x 1 1/2 sec., and nearly 5 sec. more was required for them to come to the temperature of the bath. After various lengths of time in the constant-temperature baths the specimens were quenched in water at 21°C. The specimens were cut in half for the metallographic examination, to provide a surface free from decarburization. To determine the beginning and end of the transformation the percentage of transformation determined metallographically and by hardness was plotted against time. A planimeter was used in the metallographic determination. The hardness and metallographic determinations made at room temperature were confirmed reasonably well by dilatometer measurements taken during the process of transformation at the various temperatures. Two dilatometers were used to

Jan 1, 1941

By J. D. Runkie, A. G. Lyle, G. A. Gillies

Tar evaluation of data obtained by selective flotation from even a simple ore is a very difficult process, and when the ore tested is complex the process becomes extremely difficult and cumbersome The authors, in the course of an investigation into the selective behavior of various flotation reagents on nonmetallic minerals§ were confronted with an aggravated form of this difficulty, owing to the large mass of data that had accumulated over a period of years They finally devised a method whereby the results of the various flotation tests could be correlated and interpreted by means of graphs representing recoveries and rejections of the component minerals in the ore This method of graphical analysis proved so useful in nonmetallic flotation that it was afterwards applied to sulphide flotation, where it yielded equally satisfactory results Since this method of analysis leads to very definite conclusions as to the effect of changes in reagents and flotation procedure, it is felt that a wider application of the method might assist the industry by reducing the amount of test work required, and possibly increase the accuracy of the final analysis GRAPHS In Fig I, four curves are plotted on the same graph with cumulative percentages as ordinates and cumulative weights as abscissas In this instance the four curves are named, respectively the barite-recovery curve, the limestone-rejection curve, the silica-rejection curve, and the summation curve In these tests barite was the mineral concentrated, therefore a barite concentrate was produced Definitions Before explaining the curves in detail it might be advisable to define several new terms, such as "percentage rejection," "summation index," and "summation curve," as well as the word "test," which has been used in a special sense. A "test" will include all the operations performed upon a batch of ore from the time it is placed in the rod mill until the last product has been assayed Thus a test may be a comparatively simple procedure producing only one concentrate and a tailing, or it may be a very complicated procedure producing five or more concentrates of a specific mineral as well as a tailing The number of concentrates produced will depend entirely upon whether the collector was added to the pulp in the flotation cell in one lot or was added in five or more portions Percentage Rejection-The ability of a selective flotation collector to reject an undesired mineral is just as important as its ability to collect the desired mineral The percentage rejection curves shown on the graphs give this factor due consideration and its value is calculated as follows Suppose a concentrate contains 5 per cent of an undesired mineral This indicates

Jan 1, 1942

By T. J. Nowak

The heat flow processes determining the injection and shut-in temperature logs in a water injection well have been analyzed and the theoretical basis for determining the water injectivity profiles from the temperature logs has been presented. Both the injection and the subsequent shut-in logs are necessary to resolve the injection interval into relative water intake strata; the former, to provide an accurate estimation of the thicknesses of the strata, and the latter to indicate the major and minor intake rates into the strata. A procedure is described for estimating the injectivity profile from the temperature logs and is applied to several temperature logs. For a water injection well, a comparison is made of the injectivity profiles obtained from the core analysis, the spinner survey, and the temperature logs. INTRODUCTION In secondary recovery of oil by water flooding, the injectivity profile is needed to obtain diagnostic evaluation of water intake distribution over the injection interval. If the distribution is unfavorable among the various strata, corrective measures can be taken to provide better control. Numerous methods have been developed for determining the injectivity profile from water velocity measurements in well bores. Often, dependence is placed upon core analyses and/or electric logs for estimating the relative water intakes over the injection interval. In many cases, the temperature log method described herein will give results more diagnostic than those obtained through use of the other available methods inasmuch as it is based upon the study of temperature disturbances in and around the well bore as a function of water flow in the well bore and in the formation. This method is the result of analyses of a number of temperature surveys made in water injection wells to determine the point of entry of the water into the formation. The material in this paper is presented in two sections: the first deals with the theoretical study of temperature survey data, and the second deals with the field application. PART I — THEORETICAL TREATMENT OF TEMPERATURE LOG DATA Before discussing the various aspects of heat flow relative to temperature log data, the phenomena that give rise to well bore temperatures — namely, the indigenous formation temperature and the associated rates of heat flow — will be considered. Geothermal Gradient The geothermal gradient is defined as the increment of depth at which the indigenous subsurface temperature increases by l°. It is caused by the continuous flow of heat outward from the interior of the earth. The flow of heat is an equilibrium process between the heat sources, the thermal conductivities of the formations, and the mean surface temperature. Therefore, there is no accumulation of heat energy in the path of heat transmission, and the geothermal gradient for a given formation will depend upon its thermal conductivity.

Jan 1, 1953

By Tell Ertl

THE Piceance Creek Basin in northwestern Colorado is believed to contain the richest large deposit of oil shale in North America. The major portion, about 1650 sq miles, is bounded by the White River on the north, the Grand Hogback, which runs from Meeker to Rifle, on the east, the Colorado River to the south, and the drainage basin of Salt and Douglas Creeks on the west. The Basin is a plateau 7000 to 9000 ft high, composed of 3000 ft of the Green River series of Eocene age and surrounded by a steep escarpment of 1000 to 3000 ft. From the escarpment the beds dip gently toward the center. Although oil shale is found in all members of the Green River series, the rich thick beds are found chiefly in the Parachute Creek member. This is normally capped by 100 to 200 ft of the Evacuation Creek, the youngest member of the Green River series. Actually the Piceance Creek Basin oil shale is not a shale, nor does it contain oil. It is magnesium marlstone holding solid organic matter capable of being broken down by heat into gases, some of which can be condensed into oil. The marlstone is resilient nonporous rock, difficult to sample by pick or hammer and moil. Many companies and individuals prospected the Colorado oil shale shortly after the first World War,1 see Fig. 1, but because of the discovery of large quantities of petroleum in the late 1920's in California, Oklahoma, and East Texas, interest in oil shale development waned and did not revive until World War II. In 1944 the writer, employed by the Bureau of Mines, prospected the high grade oil shale in numerous places along the southern outcrop of the Piceance Creek Basin. Several channel samples about 100 ft in length were cut, see Fig. 2. An eightman crew needed a week to cut a satisfactory channel 80 ft long in the cliff face. The Phillips Petroleum Co., the Union Oil Co. of California and others also prospected the oil shale outcrop. In 1945 the Bureau of Mines initiated a core drilling program for the purpose of obtaining accurate samples from the Piceance Creek Basin. The U. S. Geological Survey set up a program for the geological study of the Basin that is still going on.2 Until the end of 1951 a total of 31 holes was drilled for core with diamond drills, and, in addition, cuttings through the oil shale have been obtained from 4 gas wells drilled by standard rotary oil well rigs. The Bureau of Mines drilled 12 of the holes, the Union Oil Company of California 8, the Standard Oil Company of California 6, the Sun Oil Company 3,

Jan 1, 1952

By H. Becke, D. Stolnitz, D. Flatley, W. Kern

Zinc difhsions in gallium arsenide having surface concentrations as low as 5 x 10'' atoms per cu cm have been attained. A multiple-difhsion sequence is employed during which zinc enters the gallium arsenide from a silicon dioxide film in a solid-to-solid diffusion step. The technique is illustrated for the case of a zinc surface concentration of -1 x 1017 atoms per cu cm and a junction depth of 1.2 p. Radiotracer measurements of -0.1-p layers of gallium arsenide are used to delineate the resulting profile. A diffusion coefficient for zinc in pyrolytically deposited silicon dioxide is reported. ZINC is frequently used as an acceptor impurity in gallium arsenide. As examples, p-n junctions are formed using zinc-diffused layers in solar cells, lasers, and varactor diodes. For these purposes surface concentrations of 10'' to over loz0 zinc atoms per cu cm are desired and readily obtained from a vapor source. Diffusion of zinc into gallium arsenide to yield surface concentrations of about 1017 atoms per cu cm, however, is more difficult. For instance, oldstein' reports that large changes in the vapor density of zinc produce only small changes in surface concentration. Such low surface concentrations are necessary in forming the diffused base of a gallium arsenide double-diffused n-p-n transistor in order to obtain an adequate emitter efficiency. An alternative approach to zinc diffusion which can provide reduction in surface concentration of several orders of magnitude is the introduction of the diffusant from a solid source. This can be conveniently accomplished by using oxide films of the type generally employed for selective diffusion masking. Such oxides also serve to prevent the dissociation of the gallium arsenide surface at the high temperatures of diffusion. DIFFUSION PROCEDURE Fig. 1 illustrates the diffusion sequence which is employed for obtaining zinc surface concentrations in the range from 5 x lom to 1 X 10" atoms per cu cm. The description of technique will be given for the instance of -1 x 1017, which is typically utilized in double-diffused gallium arsenide transistor investigations at this laboratory. Tin- or germanium-doped gallium arsenide wafers drawn from crystals grown by horizontal Bridgman or Czochralski techniques are used, with bulk concentrations ranging from 1 to 3 X 10" carrier atoms per cu cm. Each wafer is chemically polished on the (iii) arsenic face using a mixture of five parts concentrated sul-furic acid, one part water, and one part 30 pct hydrogen peroxide at room temperature, followed by rinsing in deionized and quartz-distilled water. Pyrolytic silicon dioxide was chosen as the oxide coating because of the high quality of the films obtainable, the ease of their preparation, and the excellent control over film thickness and uniformity.

Jan 1, 1964

By J. O. Mack, J. B. Russell

In recent years, solders containing 20 per cent tin with no bismuth or cadmium have been developed by a few companies, and personnel have been properly instructed in their use. In addition, since the tin shortage, a number of solders containing less than 10 per cent Sn, and some with no tin, are being used in special applications; however, a solder of this type has yet to be developed that is satisfactory for general use. Table i.—Composition Ranges Prescribed for a Commercial Substitute Solder Element Per Cent Tin............................ 18.0-20.0 Bismuth (maximum)a............ 0. 80 Silver.......................... O. 10-1. 25 Bismuth plus silver (minimum).... 0. 85 Antimony (maximum)............ o. 50 copper (maximum),,,,,,,,..,,,, 0. I3 Other elements, each (maximum)6 0.03 Lead........................... balance a When silver is present in excess of I per cent, the Bi content shall be 0.50 per cent or over. b Total not to exceed 0.10 per cent. The Purpose of this investigation was to develop an alloy containing a maximum of 15 per cent tin, with no cadmium or bismuth, having solder properties equivalent to or better than those of substitute solders now specified containing 18 to 20 per cent tin (Table I), or even approaching the properties of the standard 40 to 60 tin-lead solder. The wartime restriction of bismuth and cadmium, elements that have beneficial effects on fluidity, solidification range and strength, makes it increasingly difficult to develop a general-purpose solder containing a maximum of 15 per cent tin. In the course of this investigation, 11 elements were used in various combinations with the basic I5-85 tin-lead alloy. These elements were antimony, silver, copper, indium, thallium, lithium, calcium, barium, potassium, sodium and arsenic. In all, 116 low-tin solders were investigated, with the idea of developing a solder that will give satisfactory working properties, specifically in regard to "wetting" of copper, brass and iron, solidification range, capillarity and shear strength of a soldered joint. The relative importance of these various properties plays an important role in the search for substitute solders, since it is almost impossible to retain all of the desired qualities of a high-tin solder and still make drastic changes in the alloy composition. Because of the expected uses of a general-purpose solder, it is necessary that it have properties, especially in regard to wet-tability, that will enable it to be used on the metals in common use. Basic Considerations The maximum liquidus temperature of a solder is determined by the particular application involved and the temperature that can be obtained by the source of heat. If a soldering iron is used, it must not only

Jan 1, 1945

By A. G. Lyle, J. D. Runkle, G. A. Gillies

THE evaluation of data obtained by selective flotation from even a simple ore is a very difficult process, and when the ore tested is complex the process becomes extremely difficult and cumbersome. The authors, in the course of an investigation into the selective behavior of various flotation reagents on nonmetallic minerals§ were confronted with an aggravated form of this difficulty, owing to the large mass of data that had accumulated over a period of years. They finally devised a method whereby the results of the various flotation tests could be correlated and interpreted by means of graphs representing recoveries and rejections of the component minerals in the ore. This method of graphical analysis proved so useful in nonmetallic flotation that it was afterwards applied to sulphide flotation, where it yielded equally satisfactory results. Since this method of analysis leads to very definite conclusions as to the effect of changes in reagents and flotation procedure, it is felt that a wider application of the method might assist the industry by reducing the amount of test work required, and possibly increase the accuracy of the final analysis. GRAPHS In Fig. I, four curves are plotted on the same graph with cumulative percentages as ordinates and cumulative weights as abscissas. In this instance the four curves are named, respectively: the barite-recovery curve, the limestone-rejection curve, the silica-rejection curve, and the summation curve. In these tests barite was the mineral concentrated, therefore a barite concentrate was produced. Definitions Before explaining the curves in detail it might be advisable to define several new terms, such as "percentage rejection," "summation index," and "summation curve," as well as the word "test," which has been used in a special sense. A "test" will include all the operations performed upon a batch of ore from the time it is placed in the rod mill until the last product has been assayed. Thus a test may be a comparatively simple procedure producing only one concentrate and a tailing, or it may be a very complicated procedure producing five or more concentrates of a specific mineral as well as a tailing. The number of concentrates produced will depend entirely upon whether the collector was added to the pulp in the flotation cell in one lot or was added in five or more portions. Percentage Rejection.-The ability of a selective flotation collector to reject an undesired mineral is just as important as its ability to collect the desired mineral. The percentage rejection curves shown on the graphs give this factor due consideration and its value is calculated as follows: Suppose a concentrate contains 5 per cent of an undesired mineral. This indicates

Jan 1, 1942

By A. L. Marshall, F. J Norton

The object of this investigation was to make a comprehensive study of the degassing of molybdenum in order to determine how rigorous a treatment was necessary to completely remove sorbed gases from molybdenum electrodes in vacuum tubes. Some work has also been done with tungsten, nickel, iron and carbon. As a logical development of this work it has been shown that the gas is present throughout the body of the metal and a study has been made of the solubility of nitrogen in molybdenum and tungsten and the rate, of diffusion of nitrogen through molybdenum has been calculated. Tests were made on molybdenum from all the commercial sources and no difference was discovered in the nature of the gases present, the amounts or the ease of removal. The reason for this was apparent when a study was made of the manner in which gases are absorbed by gas-free molybdenum. It is necessary to heat molybdenum to 1760°C. in a vacuum of the order of 0.001 micron for a time which varies lineally with the thickness, in order to obtain a condition in which no further gas is evolved by the sample. A sample so degassed can be handled and subsequently assembled in a tube and then degassed readily. The gases obtained from molybdenum are carbon monoxide and nitrogen, the nitrogen being the more difficult to remove. Apparatus and Technique The apparatus is shown in Figs. I and 2. It consisted of two units, a degassing system and an analytical system. Each had a bake-out oven, as shown surrounding the systems in the sketches. The system , will be traced, starting from the sample in the degassing system. A water-cooled quartz chamber surrounded the sample. The high-frequency coil, which heated the sample, extended only around this chamber and was cooled by an air blast. High-frequency power of 1800-meter wave length was obtained from a self-rectifying oscillator circuit with a maximum power input of 20 kw. A graded seal connected the quartz to the rest of the apparatus, which was of hard glass. The temperature of the molybdenum sample was observed by an optical pyrometer through an optical window about 40 cm. distant from the sample. Since the object viewed under these conditions was not a black body, true temperature was not observed, but the so-called "brightness temperature." The correction of this to true temperature is discussed in a later section. The apparatus was taken apart just above the graded seal; the quartz chamber was slipped off, washed with nitric acid, water and alcohol, and dried by an air stream. The old sample was removed by unscrewing the lower nut, and the new

Jan 1, 1944

By C. R. Dodson, D. Goodwill, E. H. Mayer

The paper summarizes the historical background of the pressure-volume-temperature analyses of reservoir fluids, the errors involved in both the sampling and testing of reservoir fluids, the type of information required of a PVT determination, and the field conditions that limit the application of any one analysis. Particular emphasis is placed on the necessity for approximating as closely as possible the liberation sequence occurring in the producing formation, flow string, and surface separators. A combined differential and flash or "composite" liberation is suggested as the best means of approximating this liberation sequence. HISTORICAL BACKGROUND Petroleum reservoir engineering commonly is considered to be one of the newest fields of petroleum science, yet much work of a theoretical and intuitive nature was done many years before the modern techniques of reservoir analyses were developed. The period 1910-1924 saw considerable work in the field of reservoir behavior done by the U. S. Bureau of Mines. This work:.' although entirely theoretical, pointed out the importance of gas in the recovery of oil from the reservoir. The statement by J. 0. Lewis that 20 per cent or less of the oil originally in place in a pool was recovered from the ground under uncurtailed production conditions caused some operators to re-examine and modify their production methods. However, though these works showed methods of production that have subsequently resulted in greater oil recoveries, they in general went unnoticed, even though there was a fear that the nation's petroleum resources were being exhausted. The period 1924-1933 saw the industry take considerably more interest in reservoir behavior because of an unfounded fear of its inability to replace oil reserves, the possibility of government regulation, and the energy of one man, Henry L. Doherty. Doherty aroused heated discussions in the industry concerning conservation. To prove or disprove his theories the first experimental work on the reservoir behavior of petroleum was undertaken. The papers of Dow and Calkin,' Beecher and Parkhurst," and Mills and Heitheckere are classics although their experimental procedures were crude. These papers proved that the properties of petroleum in the reservoir are quite dissimilar to the properties measured at the well head. Gas dissolved in the oil phase was recognized as having considerable importance as had been predicted by the earlier theorists. Slightly later Miller and his co-workers assembled the first text correlating all the known data on the reservoir behavior of petroleum and used, these data to show the economic value of conservation. Quantitative application of pressure-volume-temperature analyses of reservoir fluids was given in the paper of Coleman, Wilde, and Moore"; this work showed that with sufficient laboratory and production data prediction of reservoir behavior was possible. The refined sampling and labora-

Jan 1, 1953

By Foster Fraas

That variations in the humidity of the air and in the moisture content of a mixture of broken solids being separated electrostatically cause trouble is not new.' Much of the reputation for unreliability commonly ascribed to the electrostatic separation processes is probably due to this one factor alone. Some operators dry thoroughly before separating; and while this is good in many instances, there are others in which it is not the remedy for trouble. Some mixtures behave best in very dry air and with the mixtures fed to the separator while hot to reduce the adsorbed water content. On the other hand, an overdried mixture on coming to equilibrium with more humid air, has been known to take up moisture selectively on one family of particles, as of coal in the presence of slate and clay, and give sharper electrostatic separation. From these observations it is concluded that there is a permissible moisture content for a particle and also for the atmosphere surrounding it, if in equilibrium, at which the particle will have a conductivity or cntact potential2-4 that is ideal for electrostatic separation. This permissible moisture content varies between a wide range of limits for the different materials that are are and with the kind of electrostatic separating process used. Water can be present as a result of adsorption and condensation from the atmosphere, as an accumulation before or during mining, or as a residue from a previous process step. The water may exist as a liquid film or as an adsorbed layer of vapor. If the water exceeds permissible limits it must be removed. Its state determines the method. Drying by evaporation is necessary for adsorbed water, for part of the liquid-film water (that is, up to several percent of the dry weight), and for free water in the internal structure. Large water contents may be removed by drainage Or filtration. At just what point mechanical removal should cease and drying by evaporation begin depends upon the method of mechanical removal and its cost. Particles can also be separated according to their differences in dielectric constant when suspended in a liquid of intermediate dielectric constant. Recovery of this liquid presents a a problem' Permissible Moisture The adsorbed moisture on the outer surface of minerals can be quickly removed or replaced. Accordingly, in speaking of adsorbed moisture contents, either that of the solid or that of the surrounding air may be considered, the two values being connected by a distribution coefficient which varies with the temperature. However, such a condition does not necessarily exist in processes where an initially dry material is suddenly introduced into an atmosphere having a partial pressure of water vapor or where a moist material is suddenly introduced into a dry atmosphere. Here the resultant differences in the

Jan 1, 1949

By Frank C. Appleyard

Gypsum, the dihydrate form of calcium sulfate, has a history of usefulness to man dating back several thousand years, and a worldwide industry has been built on the mining and processing of this versatile industrial mineral. However, anhydrite, the other principal calcium sulfate mineral has very limited use, so much so that separate statistics for it are not always kept, but are usually included with those for gypsum. Although often found in close association, the two minerals have important chemical differences in that anhydrite is the anhydrous form of calcium sulfate (CaSO,) whereas gypsum is the dihydrate (CAS0;2H20). These two molecules of combined water result in significant differences in hardness, density, and solubility of the two minerals. However, of most importance is the difference in thermal properties wherein gypsum, upon the application of a modest amount of heat, can be converted to the hemihydrate of calcium sulfate (CaS0;Vi H,O) or plaster of paris, an intermediate product upon which is based over 90% of the value of all calcium sulfate end products. Anhydrite, on the other hand, is inert at these temperatures and its uses have been limited to only those few cases where calcium sulfate in the anhydrous form may have an advantage. The earliest known use of gypsum plaster dates back some 5000 years to the time of the Pharaohs of Egypt who had discovered that gypsum rock, when exposed to fire, broke down into a powder which when mixed with water would form a putty that could be "plastered" on a rough mud brick or stone wall to make a smooth finish. It was used down through the centuries in a limited way for ornamental purposes, but did not achieve wide acceptance because of its quick (25 to 30 min) setting or hardening time which made it difficult to use. The first real understanding of gypsum chemistry was developed in France about 1755, and the gradual growth of its present utilization dates from that time. In the United States, the first utilization of gypsum was to grind it to a fine material for use as a soil conditioner at about the time of the Revolutionary War, and the term "land plaster" for ground gypsum has remained in use. Another cementituous material-lime or calcium oxide-had become the usual plastering material, but by about 1870 a method for retarding the set of gypsum plaster was discovered and it has today almost completely replaced lime as a plastering material. In recent years, gypsum products sold in the United States have reached a total valuation of approximately $500 million per year as illustrated in [Table 1].

Jan 1, 1975

By Foster Fraas

INTRODUCTION THAT variations in the humidity of the air and in the moisture content of a mixture of broken solids being separated electrostatically cause trouble is not new.1 Much of the reputation for unreliability commonly ascribed to the electrostatic separation processes is probably due to this one factor alone. Some operators dry thoroughly before separating; and while this is good in many instances, there are others in which it is not the remedy for trouble. Some mixtures behave best in very dry air and with the mixtures fed to the separator while hot to reduce the adsorbed water content. On the other hand, an overdried mixture on coming to equilibrium with more humid air, has been known to take up moisture selectively on one family of particles, as of coal in the presence of slate and clay, and give sharper electrostatic separation. From these observations it is concluded that there is a permissible moisture content for a particle and also for the atmosphere surrounding it, if in equilibrium, at which the particle will have a conductivity or contact potential2-4 that is ideal for electrostatic separation. This permissible moisture content varies between a wide range of limits for the different materials that are separated and with the kind of electrostatic separating process used. Water can be present as a result of adsorption and condensation from the atmosphere, as an accumulation before or during mining, or as a residue from a previous process step. The water may exist as a liquid film or as an adsorbed layer of vapor. If the water exceeds permissible limits it must be removed. Its state determines the method. Drying by evaporation is necessary for adsorbed water, for part of the liquid-film water (that is, up to several percent of the dry weight), and for free water in the internal structure. Large water contents may be removed by drainage or filtration. At just what point mechanical removal should cease and drying by evaporation begin depends upon the method of mechanical removal and its cost. Particles can also be separated according to their differences in dielectric constant when suspended in a liquid of intermediate dielectric constant. Recovery of this liquid presents a similar problem. PERMISSIBLE MOISTURE The adsorbed moisture on the outer surface of minerals can be quickly removed or replaced. Accordingly, in speaking of adsorbed moisture contents, either that of the solid or that of the surrounding air may be considered, the two values being connected by a distribution coefficient which varies with the temperature. However, such a condition does not necessarily exist in processes where an initially dry material is suddenly introduced into an atmosphere having a partial pressure of water vapor or where a moist material is suddenly introduced into a dry atmosphere. Here the resultant differences in the

Jan 1, 1947

By A. L. Marshall, F. J. Norton

The object of this investigation was to make a comprehensive study of the degassing of molybdenum in order to determine how rigorous a treatment was necessary to completely remove sorbed gases from molybdenum electrodes in vacuum tubes. Some work has also been done with tungsten, nickel, iron and carbon. As a logical development of this work it has been shown that the gas is present throughout the body of the metal and a study has been made of the solubility of nitrogen in molybdenum and tungsten and the rate, of diffusion of nitrogen through molybdenum has been calculated. Tests were made on molybdenum from all the commercial sources and no difference was discovered in the nature of the gases present, the amounts or the ease of removal. The reason for this was apparent when a study was made of the manner in which gases are absorbed by gas-free molybdenum. It is necessary to heat molybdenum to 1760°C. in a vacuum of the order of 0.001 micron for a time which varies lineally with the thickness, in order to obtain a condition in which no further gas is evolved by the sample. A sample so degassed can be handled and subsequently assembled in a tube and then degassed readily. The gases obtained from molybdenum are carbon monoxide and nitrogen, the nitrogen being the more difficult to remove. Apparatus and Technique The apparatus is shown in Figs. I and 2. It consisted of two units, a degassing system and an analytical system. Each had a bake-out oven, as shown surrounding the systems in the sketches. The system , will be traced, starting from the sample in the degassing system. A water-cooled quartz chamber surrounded the sample. The high-frequency coil, which heated the sample, extended only around this chamber and was cooled by an air blast. High-frequency power of 1800-meter wave length was obtained from a self-rectifying oscillator circuit with a maximum power input of 20 kw. A graded seal connected the quartz to the rest of the apparatus, which was of hard glass. The temperature of the molybdenum sample was observed by an optical pyrometer through an optical window about 40 cm. distant from the sample. Since the object viewed under these conditions was not a black body, true temperature was not observed, but the so-called "brightness temperature." The correction of this to true temperature is discussed in a later section. The apparatus was taken apart just above the graded seal; the quartz chamber was slipped off, washed with nitric acid, water and alcohol, and dried by an air stream. The old sample was removed by unscrewing the lower nut, and the new

Jan 1, 1944

By G. A. Croes, N. Schwarz

The dimensionless groups, to which the variables that govern the displacement of oil from reservoirs by liquids can be combined, are derived. Three types of displacement are considered, viz. cold-water drive, hot-water drive and solvent injection. The derivation of the dimerzsionless groups is carried out by means of the relevant basic equations (in-spectional analysis). The resulting sets of groups are afterwards completed by means of dimensional analysis. The form of the groups is given in such a way that they can be adapted to suit the various boundary conditions that are encountered in practice. The physical meaning of the groups is discussed. They have all been brought together on a chart, from which their mutual relation and their corresporzdence to related dimensionless groups in common use in other engineering sciences can be read off. The limitations of dimensionally scaled model experiments as a useful tool for studying liquid flow in porous media, as occurring in oil reservoirs, are discussed. The use of models to study fluid mechanics has an appeal for everyone endowed with natural curiosity. What active boy has not played with ship and airplane models, or crude models of dam and drainage systems Even in the most advanced technical engineering, such models play a fundamental and indispensable role. "And yet in few departments of the physical sciences is there a wider gap between theory and practice, between scientific knowledge and the state of art, than in the use of models to study hydrodynamic phenomena." Garrett Birkhoff1 INTRODUCTION Laboratory displacement experiments are extensively used to investigate, directly or indirectly, the production behavior of petroleum reservoirs. Such experiments are representative of the reservoirs as a whole, if they are carried out with models that are "properly scaled." The performance of oil reservoirs is governed by the values of a number of variables, which can be combined to dimensionless groups. Two general methods are available for the derivation of these groups. In the first of these, dimensional analysis, combination of the variables is done essentially by trial and error. Its only premise is knowledge of the complete set of relevant variables. In the second method, inspectional analysis, the dimensional homogeneity of the equations describing the behavior of the system to be studied is used. The resulting dimensionless groups can be divided into: (a) independent (variable) groups, such as dimensionless length, time, etc.; (b) dependent groups, giving the dimensionless form of the variables, such as recovery and pressure, that can, at least in principle, be measured during an experiment; (c) similarity groups, which are independent constant groups, such as ratio of length to height of the reservoir and ratio of

Jan 1, 1957