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By Frank Foote, E. R. Jette

In recent years the constitution of the high-silver aluminum-silver alloys has been extensively investigated. Hansenl has reviewed the literature to 1935. More recently, Obinata and Hagiya,2 Hofmann and Volk,3 Taziri4 and Tishchenko5 have confirmed the general features of the phase diagram in the region around 25 atomic per cent aluminum. In this paper we present the results of high-precision measurements of lattice constants of the silver-rich alpha solid solution in the homogeneous range and the neighboring two-phase regions. These results are used to establish the nature of the solid solution, the identity of directly measured densities with those calculated from lattice constants and the homogeneity limits of the alpha solid solution with respect to three different neighboring phases. A study of the earlier investigations indicated that the last two subjects in particular required new and accurate data. Experimental Procedure Preparation of the Alloys.—The alloys were made from high-purity silver and aluminum. The silver was "Proof Silver," 99.999 per cent pure, supplied by the U. S. Metals Refining Co. The aluminum was 99.97 per cent pure (contained Si, 0.009 per cent; Fe, 0.0016 per cent; Cu, 0.004 per cent) and was supplied by the Aluminum Company of America. The lattice constants of these two materials have been reported by Jette and Foote.6 Weighed amounts of the two metals were placed in alundum crucibles and melted in vacuo in a high-frequency induction furnace. The melts were allowed to cool in the crucible, the ingots thus obtained weighed about 10 grams. These ingots were then filed clean, hamered, again cleaned and given a homogenizing anneal in vacuo of from 6 to 15 days at temperatures ranging from 500" to 695°C. The ingots were air-cooled from the annealing temperature. Lattice-constant Measurements.—Carefully prepared filings for X-ray analysis were sealed into evacuated quartz or Pyrex tubes and annealed for various periods of time at suitable temperatures. The furnaces used were vertical, rapid-quenching furnaces, the samples being quenched by crushing the sample tube under water by means of a heavy plunger. The general X-ray technique has been previously described6 The cameras were of the symmetrical, back-reflection, focussing type. Ka, radiation from a cobait-nickel alloy target was used. The wave-length values were taken from the second edition of Siegbaum's book.7 A correction for the index of refraction was applied and the lattice constants were calculated by the method of Cohen.8, 6 The lattice constants were calculated to a common temperature of 25°C., using the value of the linear expansion coefficient of pure silver as 18.9 X 10-6. Presumably the expansion coefficient for

Jan 1, 1941

By Tell Ertl, Ernest E. Burgh

INTRODUCTION THE Bureau of Mines is operating an oil-shale mine 10 miles west of Rifle, Colo., as part of its Synthetic Liquid Fuels program. The purpose of operating this mine is twofold: First, to supply oil shale to an experimental processing plant; and second, to develop practices and select methods for mining oil shale on a commercial scale at the lowest practicable cost. The second purpose-that of finding out how to mine oil shale most cheaply-entails considerable mining research. Since the drilling of oil shale probably will be one of the major items of the mining cost, factors that influence drilling speeds were investigated. One phase of the drilling program was the development of a successful hard-surfaced rock-drill bit1 that can be used for drilling long holes in oil shale without changing bits. During that phase, drilling speeds were measured and drill cuttings were collected for assay and for screen sizing. When the cuttings from the individual tests were compared, a definite relationship was shown to exist between the drilling speed and the coarseness of the drill cuttings. PROCEDURE Measurement of Drilling Speeds All drilling in the tests was done with a Model UMB-D-99W Gardner-Denver wagon drill. Round-lugged drill steel, 1 ¼ in. in diameter was used in 6, 12, and 18 ft lengths with 2 1/8 -in. Timken H-type bits hard-faced with acetylene tube borium. The tests were made in the lower adit of the Bureau of Mines oil-shale mine; the grade of the oil shale drilled ranged from 18.6 to 42.7 gal per ton. During the experiments air pressure varied between 75 and 90 psi while water pressure remained fairly constant at 75 psi. All holes were drilled almost horizontally. Each drill hole was thoroughly cleaned of cuttings after being collared. The advance of the drill along the carriage was measured and recorded as the drilling speed in inches per minute. Method of Collecting Cuttings To facilitate the collection of cuttings, each drill hole was collared in a smooth, vertical portion of the oil-shale breast (Fig 1). A galvanized-steel sheet was fastened to the breast below the area in which the hole was to be drilled. The cuttings washed out of the drill hole by the drilling water were guided by the steel sheet into a wooden box. The cuttings that remained in the drill hole after the drill was withdrawn were scraped out and placed in the same box as the cuttings washed out of the hole. After the cuttings from a 1-min. drilling interval were collected, they were placed in flat metal pans. The fines were allowed to settle and the clear water was decanted. The cuttings then were dried in the sun.

Jan 1, 1947

By C. M. Romanowitz, H. A. Sawin

Placer dredging as we know it today, especially gold dredging, is an industry about 40 years old, dating from the beginning of this century, when a few mining men in California saw the possibilities in adapting earlier dredging methods to California placer fields in and immediately adjacent to streams. At first it was thought that dredges must be operated in existing stream beds, but experience soon pointed the way to dredging alluvial deposits of old stream beds, operating on landlocked dredging ponds. Within the first five or six years of modern dredging, experience was gained so rapidly that dredges to dig 60 ft. below water level were *designed and built. This depth was believed by many operators to be the maximum at which successful dredging could be carried on. Alluvial deposits of gold, suitable for dredging, were readily handled by equipment available and developed early in the industry's history. Much of the gravel was easily dug and if deposits were cemented, contained large boulders, or for some other reason could not be handled by a dredge, the ground was abandoned in favor of other deposits that could be handled easily. Many failures, adversely affecting the dredging industry, resulted from attempts at that time to extend the scope of placer dredging with equipment not suited to the formation being dredged. Dredging ground suited to early equipment was exhausted eventually, but many supposedly undredgeable alluvial fields containing gold in commercial quantities were found and became known to dredgemen. Improved equipment was needed to work deposits known to exist at great depths or associated with unusual obstructions. Operating companies looked to dredge manufacturers and metallurgists, particularly manganese-steel foundries, for improved designs and materials. Experience developed in California has spread throughout the world, and dredges of improved types have been adapted to the mining of platinum and tin as well as gold. Space will not permit a description of all the improvements in dredging since the early days, but a few of the recent developments are worthy of note, because they make possible the dredging of placer deposits of great depth, those having hard, irregular bedrock or containing large boulders in great quantities, and compacted or cemented gravel deposits. Deep Dredging At Hammonton, calif., yuba consolidated Gold Fields has, within= the past two years, built its dredge No. 20. The company has operated continuously in that field since 1904, digging successively at maximum depths of 60 ft., 80 ft., 112 ft., and now 124 ft. below water level. The first dredges were equipped with buckets of 6 and 7½-cu. ft. capacity; six dredges operating in the field today have 18-cu. ft. buckets, digging now 65 to 124 ft. below water level. Some ground near Hammonton has been dug for the third time, owing to the devel-

Jan 1, 1943

By J. H. Brophy, J. Wulff, H. W. Hayden

The mickel-activated sintering of tungsten occurs in two stages of densification. A kinetic analysis of the second stage has been based on an appropriate model of the process. As in the first stage, the rate-controlling mechanism for the second stage is also the solution of tungsten in the nickel carrier phase. The transition from the relatively rapid first-stage results from the spherozdization of pores and the initiation of grain growth. Finer grain size due to higher-nickel content leads to more rapid and higher degrees of densification 1 HE sintering of tungsten is accelerated by small additions of nickel, cobalt, and iron.' Experimental evidence in detail has shown that nickel-coated, hydrogen-reduced tungsten powder may be sintered to more than 90 pet of theoretical density at l100o C.2, 3 Simultaneously, a kinetic analysis of the process showed that it took place in two distinct stages. In the first stage, nickel evidently served as a carrier phase through which tungsten atoms could move. This stage was kinetically similar to the "solution-precipitation" step postulated when the carrier phase is a liquid,4 although in the Ni-W case, there is no evidence of the existence of a liquid phase either in equilibrium phase relationships or in microstruc-tures at the temperatures under consideration. It has been shown that this stage corresponds to a process which is rate controlled by a phase boundary reaction.3 More recent evidence has been presented5 showing that after the initial rapid stage of sintering, densification continues in the final stage but at a slower rate, although no mechanism for this stage of densification was defined. An analysis of later stages of densification in solid state sintering has been presented,6 but it is not directly applicable in the present case of activated or carrier phase sintering. It is the purpose of this investigation to study the final stage of nickel activated tungsten sintering in greater detail The effect of varying nickel content has been examined, and a possible kinetic mechanism defined. EXPERIMENTAL PROCEDURE AND RESULTS Commercial hydrogen-reduced tungsten powder from Wah-Chmg Corp., having a nominal particle size of1 µ and a B.E.T. specific surface area of 5500 sq. cm per g was mixed with aqueous solutions of hydrated nickel nitrate in proportions sufficient to produce nominal compositions of 0.25, 1, 3, and 5 wt pet Ni. This solution was then evaporated to dry-ness at approximately 150" C for 15 hr. Following evaporation, the resulting powder cake was broken with a mortar and pestle and reduced in hydrogen at 800oC for 1 hr. Following reduction, the powder

Jan 1, 1962

By R. A. Pallanch

Probably one of the most perplexing problems with which a mill operator contends is the proper evaluation of his mill results. True, he accurately determines his recoveries of metals and grades of products monthly, weekly, and often daily. These figures do not of themselves directly translate to mill economics. When one figure is unusually good there may be an offsetting circumstance. The advantage of high lead or zinc concentrate grade may be offset by poorer recovery; high lead recovery may be offset by poorer zinc recovery, or vice versa; and so on. Besides, grades or recoveries may not of themselves mean more than a reflection of the grade and character of the ore during the period under study. What the operator sorely needs is some one measuring stick that tells him when he has achieved his greatest return, regardless of grades or recoveries—for if he knows his methods and practices are yielding the optimum return he need no longer concern himself with the assays of products and tailings, or the corresponding distribution of metal values. At first blush it would appear that the obvious answer to this is the actual money return to the mill. Paradoxical as it may seem, however, money return does not make a dependable yardstick any more than do grades and recoveries, as ore condi- tions would vary enough to bring about greater money return during periods when the actual metallurgical work is not as good. The mill operator, of course, should always aim for the greatest return on the ore, once it is in the mill bins, with proper attention always to mill treatment cost. The need of a proper yardstick becomes more imperative with the increasing complexity of the problem. In the case of a simple, single-product operation on a fairly uniform ore, in which only one metal is of significant importance, the need is not great, as grade and recovery pretty well tell their own story. At the other extreme is the operation that makes three or four separate marketable products from a complex mixture of heterogeneous ores that vary tremendously in individual metal contents and ratios, degree of oxidation, and other characteristics, and in which gold, silver, copper, lead and zinc are all significant values. Economic Recovery The first attempt at obtaining a proper single yardstick for a fairly complex ore with which I am familiar is the use of the ''Economic Recovery" term at the lead-zinc flotation mill of the Sunnyside Mining and Milling Co., Eureka, Colorado. This method had been applied there early in Sunnyside flotation-mill history (not later than 1920) and credit for the innovation I believe belongs to Messrs. Kuryla and Marquand. The term "Economic Re-

Jan 1, 1949

By Simon D. Strauss

INTRODUCTION The changes in ownership, management, and operation of the non-fuel minerals industry since the Second World War have been dramatic. World-leading enterprises have lost their identity; host countries have taken over operations from multi-national firms; marketing practices have been drastically altered - and yet the world industry is supplying minerals on a scale far greater than had been anticipated in projections made at mid-century. The world's known mineral resources have been enormously expanded, despite the doom sayers who for decades have been predicting that depletion of non-renewable resources would impose limits to growth. PALEY REPORT One can set the stage by reviewing how the minerals outlook was regarded in a thoughtful and comprehensive analysis made in the years 1950 and 1951. During the War years, President Harry Truman of the United States had come to appreciate the decisive role played by minerals resources through his chairmanship as a U.S Senator of a committee that investigated the procurement and allocation of natural resources. In 1950, in the Cold War era that resulted in actual military conflict in Korea, he appointed a prestigious five-man commission to study the problems of Materials Policy over the following quarter century. Their findings, published in five impressive volumes in early 1952, became known as the Paley report. The text was prepared by expert scientists and economists who spent 18 months assembling statistics, making projections of future demand, and interviewing leaders in industry, academia, and government. [ ] The Commission had correctly foreseen that aluminum would replace copper as the largest volume non-ferrous metal, but it had fallen short of reality by a wide margin indeed for all three materials. Even though the Commission's expectations for growth proved to be extremely understated, it had concluded its report with grave foreboding about the effect of its estimates of demand in relation to supply, as follows: "Consumption of almost all materials is expanding at compound rates and is thus pressing harder and harder against resources which, whatever else they may be doing, are not similarly expanding. This materials problem is thus not the kind of 'shortage' problem, local and transient, which in the past has found its solution in price changes which have brought supply and demand back into balance. The terms of the materials problem we face today are larger and more pervasive." With respect to some minerals, the Paley Report expressed scepticism that, in fact, supplies would be forthcoming regardless of price. Because the Paley demand forecasts understated the actual growth in demand for virtually every mineral, one could logically have expected frequent and protracted shortages in the years since 1950.

Jan 1, 1985

By E. C. Babson

In order to explore the possibility of predicting reservoir performance from laboratory data, behavior of a hypothetical low-permeability reservoir has been estimated by applying data and methods currently available in the literature. A method of calculating decline in productivity index is discussed, and recoveries by internal gas drive, external gas drive and water drive are estimated. Introduction During the life of a producing oil property an operator is faced with many perplexing problems. Any attempt to determine proper well spacing, optimum rate of production, or the desirability of pressure maintenance requires the evaluation not only of a host of economic and practical operating factors but also of the future performance of the reservoir. Although in some cases economic or operating con-siderations may be of primary importance in planning a development or production program, the anticipated effect on ultimate recovery is more likely to be the decisive factor. The soundest basis for evaluating reservoir performance is past experience with oil fields, but pertinent data are difficult to obtain or apply under conditions normally encountered in California fields. Many of these fields are characterized by thick sections of alternating sands and shales complicated by faulting and rapidly changing lithologic conditions. Further compli- cations are introduced by haphazard development and production practices resulting from competitive conditions, changing demand for oil, and insufficient knowledge of structural conditions during early development. Even in the rare cases where development has been systematic and adequate, production policy has usually been controlled by economic and competitive factors rather than a desire to obtain information for use in future operations. In other words, comparable reservoirs in which development and production practices have been systematically varied are seldom found. In the light of these conditions, conclusions based on experiences usually lack the certainty required for decisions involving large sums of money. Some other method of attacking these problems is needed to supplement and orient field experience. Progress in laboratory investigations of the flow of oil, gas, and water through sands has been so rapid in recent years that these data may furnish such a supplementary approach in the near future. In order to explore this possibility the author has attempted to predict the behavior of one type of reservoir by applying published data and methods. Basic Data and Assumptions Calculations outlined in this paper are dependent upon a detailed knowledge of the properties of oil, gas, and water present in the reservoir and the portion of the total pore space originally filled by each. It is also necessary to know how the permeability of the sand to oil, gas, and water varies with the saturations of these fluids 20

Jan 1, 1944

By J. D. Milburn, H. J. Hill

In quantitative interpretation of electrical logs the presence of clay minerals introduces an additional variable which further complicates an already complex problern. Although recognizing the difficulties introduced as a result of the heterogeneity of natural sediments and despite the present incomplete state of knowledge regarding electrochemical behavior of shales, dissemirzated clay minerals and concentrated electrolytes, it was felt that useful empirical correlations might be obtained from experimental investigation. Six typical sandstone formations, having a wide variety of petrophysical properties, were selected for the study. Approximately 45 samples from each formation were selected to satisfactorily represent the range of pore size distribution within the particular formation, As a matter of general interest, four limestone formations were also included in the investigation. Previously proposed equations relating to resistivity, SP and interrelationship of the two phenomena have, where possible, been tested with data obtained in this investigation. These equations do not satisfactorily describe experimental behavior of samples through all degrees of shaliness or throughout the range of brine solution resistivities normally encountered in logging practice. An empirical equation has been developed which quantitatively relates formation resistivity factor to satirrnting solution resistivity, porosity, and "effective clay content." This relation is indicated to be uniformly applicable to clean or shaly reservoir rocks. It is shown that both the SP and resistivity phenomena of shaly samples are related to the sample cation exchange capacity per unit pore volume. The independent chemical determination of this parameter is thus a means of determining the "effective clay content" of samples. Some implications regarding theory and electric log interpretation of shaly sands are discussed. INTRODUCTION The use of electrical resistivity logs as a means for estimating formation porosity is based upon the original work of Archie1. It was shown by empirical methods that the resistivity of a rock, when 100 per cent saturated with brine solution, could be related to rock porosity through the equation, F = Ro/ RW = f-m.......(1) where F, the formation resistivity factor, is defined as the ratio of the resistivity of the 100 per cent water saturated rock, Ro, to the saturating solution resistivity, Rw; f is the ratio of pore volume to bulk volume; and m is the slope of the average line when the data are plotted on log-log paper. This relation was established for relatively shale-free formations containing water having high salt concentrations, and under these conditions F may be considered constant for a given rock sample. Applications of Eq. 1 to interpretation of logs of shale-free formations has been quite successful when satisfactory formation water resistivity data could be obtained. The most readily available means of estimating formation water resistivity is the self-potential log. Conventional methods of SP log interpretation involve correct.

Jan 1, 1957

By E. P. Abrahamson II

The effect of transitiorz element bitzary solid solution additions upon the recrystallization temperature of columbium has been investigated. The elements Mn, Fe, Co, Ni, W, Re, and 0s OWY the yecystallization tempel-aturye, while Ti, V, CY, zr, Mo, Ru, Rh, Pd, Hf, Ta, W, Ir, and Pt mise it. A correlation is kloted between the rate of chatzge of recyystallization tewaperature with atomic hercent solute and the free atom electron configuration of the solute element. The work of Abrahamson and Grant1 has indicated a correlation between the free atom ground-state electron configuration and the change in brittle-ductile transition temperature per atomic percent solute in chromium base alloys. A similar correlation was observed for the change in the recrystallization temperature of iron base alloys by Abrahamson and Blakeney and Abrahamson. It was also observed that the limit of rapid change in recrystallization temperature also Correlated with the electronic configuration of the free solute atom. A further study by Abrahamson4 established the generality of the phenomenon by yielding similar results for vanadium base dilute alloys. It has been inferred that a peri- odicity might be expected with changes in the free atom electron configuration of the solvent element. This study is the third set of transition base metal systems to be studied. It is the object of this and further studies on transitional metal systems to detect any systematic variations in the observed correlation which might contribute to the understanding of the electron interactions which are evidently exhibiting themselves. PROCEDURE All alloys were made using 99.9 pct Cb with 0.030 Ta, 0.016 0, 0.0025 H, 0.003 Mo, 0.021 Fe, 0.005 C, and 0.002 N. The solute elements were 99.9 pct pure. According to the published binary phase diagrams5 and metallographic examinations at X750, all additions were in solid solution. The alloys were arc melted and remelted 6 times in the form of cubic 400-g buttons under an argon atmosphere. They were then hot forged at 1200oC to 0.6-in. diameter, annealed for 3 hr at 1200o under argon, and furnace cooled. The specimens were then machined to 0.400 -in. diameter. Grain size was checked and found to remain essentially constant at 150 i 30 grains per sq mm. The specimens were then cold swaged to 0.187-in. diameter, yielding 46 i 1 pct cold work. All alloys were chemically analyzed for the major solute. Analyses of random samples indicated that the impurity content remained at the values of the starting material. Tungsten contamination was held to 0.007 pet.

Jan 1, 1962

By R. Schuhmann, O. W. Moles

at temperatures of 1150°, 1250°, and 1350°C for liquid copper sulphides ranging in composition from saturation with Cu to about 21.5 pct S. From the experimental data, activities of Cu, S, and Cu2S in the melts were calculated. Also, the results furnish a new determination of the location of the curve showing the compositions of Cu-saturoted sulphide melts in the CU-S constitution diagram. THE "white metal" made as an intermediate L product in converting copper matte to blister copper is a matte approximating Cu2S in composition. It has long been known that liquid Cu-S mattes can exist at a given temperature over an appreciable composition range, with S:Cu ratios ranging up from a lower limit corresponding to equilibrium of the matte with a liquid Cu phase. The Cu-saturated matte has somewhat less S than Cu2S, although previous measurements of the compositions of Cu-saturated mattes are not in good agreement.'" As the S:Cu ratio approaches and slightly exceeds that for Cu2S, the partial pressure of sulphur gas over the liquid matte rapidly approaches atmospheric pressure,5 so that Cu-S melts with much more S than Cu2S can be made and handled only in pressure apparatus. Accordingly, the liquid copper sulphides of interest in copper smelting and readily studied experimentally fall in a relatively narrow composi- tion range about Cu2S. The freezing points of Cu-S mattes show a maximum of 1129°C near the composition Cu, dropping to 1105oC for Cu-saturated mattes having less S and dropping under 1100°C for higher S mattes.' Estimates of the sulphur pressure and other thermodynamic properties of liquid Cu,S were made by Kelley; based on extrapolations from equilibrium measurements on solid Cu,S. More recently, Cox and coworkers' studied equilibria in the reaction: Cu,S + H, e 2Cu + H,S over the temperature range 700" to 1250°C. They measured equilibrium H2S:H2 ratios presumably with both the sulphide and the metal phase present, so that their data above the melting point of Cu,S should measure the S pressure of Cu-saturated sulphide melts. The sulphur pressures of liquid copper sulphides of several S:Cu ratios at their freezing points can be estimated from data given by Posnjak, Allen, and Merwin." However, beyond these few data, no systematic study seems to have been made of the relations of sulphur pressure and other chemical properties of liquid copper sulphides to composition and temperature. The measurements of the sulphur pressures of liquid copper sulphides reported in this paper represent a first step in the quantitative study of the chemistry of mattes. Similar work is planned on

Jan 1, 1952

By C. Richard Tinsley

INTRODUCTION Project financing has been defined by various authors in this book. It is founded on reliance upon the project's own future cash flows and secondarily on the collateral value of the asset base developed. It is chiefly provided by the banking community who, after an assessment of the risks involved (See Chapter 9) analyse the company's presentation (See Chapter 10) in order to structure a financing package often at a leverage of up to 80% debt. This paper describes the various support and structuring techniques used to delimit and abate the risk components perceived from the banks' experience on project development especially for the period before cash flow is generated (pre completion). ADVANTAGES The advantages of project financing extend beyond the offloading of risks to banks. Among the advantages are the following: 1. Longer loan maturity than conventional, unsecured financing; 2. Loan disbursement and repayment tailored to specific mine; 3. Ability of a joint venture without a "track record" to raise financing; 4. Obtain financing where further direct borrowing (corporate credit) limited by existing indentures; 5. Possibility of arranging finance off-balance sheets; 6. Leverage return on equity; 7. Obtain tax savings with certain project financing structures; and 8. Obtain flexible loan repayment conditions. It can also be said that from the point of view of the company, project financing has certain disadvantages which can be summarised as follows: 1. Perceived higher cost (risk premium) compared with straight corporate credit; 2. More documentation; and 3. Need to negotiate risk-sharing aspects. The main attraction of project financing is the ability to pass certain risks on to the lenders within a flexibly funded transaction. (For a more detailed description of the specific risks see the author's paper at the beginning of Chapter 9. The same risk system is followed here.) The typical project financing has corporate support prior to completion and will usually carefully control the resultant cashflow after completion to ensure the bank does not unnecessarily assume further risks of an equity nature. WITHIN THE COMPANY'S CONTROL Operating Risk This is broken into three interrelated segments for ease of description. Technical Component: This must be specifically addressed if new technology or unproven adaptations are to be used. The banks will have scrutinized the sampling and bulk testing work, perhaps grilling the geological, mineral processing, metallurgical, and mining engineering staff or consultants directly. A number of supports are available such as: TECHNOLOGY GUARANTEE: Either the company itself or the process developer will guarantee that the technology will work for a period of, say, six months to two years after startup. If not, then financial penalties will apply although these are rarely sufficient to repay the loan. Many process developers are weak financially and may have little substance to back such a guarantee.

Jan 1, 1985

By John Wulff, J. H. Hollomon

THE opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was redeposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufliciently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion .4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May,6 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to alpha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. "I hey believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They (lid not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,8 in another publication, suggested that the commonly found gray or black arsenical film may act to: (1) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led hint to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed (luring the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (AS208)

Jan 1, 1942

By I. Havenaar

Various methods have been proposed in the literature to calculate the pressure losses in drill-pipe and bit-nozzles, i.e., those parts of the mud-circuit where the largest pressure-losses occur. Very few data, however, are available to check the validity of these proposals. Presented in this paper are the results of pumping experiments with clay-water drilling fluids of different specific gravities and different laminar flow-properties (differential viscosity and Bingham yield value), using pipes of different diameters. In addition, a series of measurements on bit-nozzles is discussed. Two main conclusions may be drawn from this work for the flow through pipes. 1. In the laminar flow region pressure losses can be calculated from the differential viscosity and Bingham yield value of the mud. 2. In the turbulent flow region pressure losses can be calculated with good approximation from a viscosity term which is determined by the volume fraction of the dispersed phase. Calculations making use of laminar flow properties may lead to erroneous results. The effect of temperature on the pressure losses in the case of turbulent flow can be calculated from the change in viscosity of the dispersing medium, i.e., water. The main conclusions determined for the flow through bit-nozzles are that for flow conditions prevailing in the field, the pressure-drops in bit-nozzles are independent of the laminar flow properties of the mud. They are solely determined by the density of the mud and the geometry of the nozzle. INTRODUCTION The last decades have witnessed a steady increase in the depth of oil wells. This is illustrated by the increase in the drilling depth record in the USA from 8,046 ft in 1927 to 21,482 ft in 1953. This increasing depth, together with the experience that high rates of mud circulation and high fluid velocities in the bit-nozzles enhance the rate of drilling, has emphasized the importance of selecting suitable mud-pumps when starting the drilling of a deep borehole. For such a selection it is necessary to be able to calculate the pumping pressures necessary to obtain the required circulation rates. The main part of the pressure-losses in the mud circuit occur in the drill pipe and the bit-nozzles. Various methods have been proposed in the literature to calculate the pressure-losses in the drill pipe1,2,3,4. These methods do not all lead to the same results, and at the time this investigation was started insufficient basic data were available to check their validity. Moreover, to our knowledge, no data are available at all on the effect, if any, of the flow-properties of the mud on the pressure-losses in bit-nozzles.

Jan 1, 1955

By E. C. Babson

In order to explore the possibility of predicting reservoir performance from laboratory data, behavior of a hypothetical low-permeability reservoir has been estimated by applying data and methods currently available in the literature. A method of calculating decline in productivity index is discussed, and recoveries by internal gas drive, external gas drive and water drive are estimated. Introduction During the life of a producing oil property an operator is faced with many perplexing problems. Any attempt to determine proper well spacing, optimum rate of production, or the desirability of pressure maintenance requires the evaluation not only of a host of economic and practical operating factors but also of the future performance of the reservoir. Although in some cases economic or operating con-siderations may be of primary importance in planning a development or production program, the anticipated effect on ultimate recovery is more likely to be the decisive factor. The soundest basis for evaluating reservoir performance is past experience with oil fields, but pertinent data are difficult to obtain or apply under conditions normally encountered in California fields. Many of these fields are characterized by thick sections of alternating sands and shales complicated by faulting and rapidly changing lithologic conditions. Further compli- cations are introduced by haphazard development and production practices resulting from competitive conditions, changing demand for oil, and insufficient knowledge of structural conditions during early development. Even in the rare cases where development has been systematic and adequate, production policy has usually been controlled by economic and competitive factors rather than a desire to obtain information for use in future operations. In other words, comparable reservoirs in which development and production practices have been systematically varied are seldom found. In the light of these conditions, conclusions based on experiences usually lack the certainty required for decisions involving large sums of money. Some other method of attacking these problems is needed to supplement and orient field experience. Progress in laboratory investigations of the flow of oil, gas, and water through sands has been so rapid in recent years that these data may furnish such a supplementary approach in the near future. In order to explore this possibility the author has attempted to predict the behavior of one type of reservoir by applying published data and methods. Basic Data and Assumptions Calculations outlined in this paper are dependent upon a detailed knowledge of the properties of oil, gas, and water present in the reservoir and the portion of the total pore space originally filled by each. It is also necessary to know how the permeability of the sand to oil, gas, and water varies with the saturations of these fluids 20

Jan 1, 1944

By C. S. Matthews, H. C. Lefkovits

The performance of depletion-type reservoirs at the stage in which the gas is at such low pressure that gravity is essentially the sole driving force has been investigated both theoretically and by use of scaled models. A simple theory is developed which completely explains the scaled model experiments. It also agrees with some field data. When the range of production rates to be considered is less than 25, the theory predicts that the production rate decline curve for homogeneous reservoirs in which there is a free surface will be of the hyperbolic type with n = 2: The theory gives a physical significance to the parameter y. INTRODUCTION This investigation was undertaken to determine a method for prediction of performance of reservoirs where gravity is the sole driving agent. Depletion-type reservoirs fall into this category after the pressure has fallen to some low value. Some examples of this type are found at Healdton ('Oklahoma), Oklahoma City (Oklahoma), Midway-Sunset (California), and East Coalinga (California). Generally the production rate per unit thickness is quite low in such reservoirs, with the conse- quence that this stage is sometimes called the stripper stage. However, per well production rates may be of the order of 50 B/D because of the considerable sand thickness open in some of the reservoirs. In the past, predictions of behavior of such reservoirs have been based on empirical extrapolation of the rate of production to the economic limit. Difficulties arise when new wells are drilled in the field or when production is artificially curtailed, since in such cases the decline rate of individual wells or leases changes and no clear trend can be detected. It was hoped that the present study would lead to improved methods for evaluation of such reservoirs. The study was initiated by building a scaled model for a particular field and by running a number of experiments on this model. Later a simple theory was developed which explained the laboratory results completely. The theory led, as shown below, to a hyperbolic-type decline equation which had been used previously' in a completely empirical manner. THEORY The General Case The problem to be treated here is the following: We are given a homogeneous cylindrical porous reservoir with exterior radius r, wellbore radius r., and height h,, containing, from the bottom up to a height hit oil, some gas, and interstitial water (see Fig. 1 A). The portion of the reservoir between K, and h, is filled with gas at low pressure, with residual oil, and with interstitial water. If at a time t = 0, the level of the oil in the wellbore is lowered to a height h,, what is the production rate from the reservoir at a time to The configuration within the reservoir at some instant

Jan 1, 1957

A LARGE attendance at the annual dinner of the Institute, to be held this year on Tuesday eve-ning of convention week, is already assured. Presentation of the Douglas, Hunt and Saunders medals will attract unusual attention since not only in Blaylock, Mathews and Hoover the Institute will be honoring men who have made notable contributions to the advance-ment of their profession, but as to one of them each person as he passes down the reception line will be won-dering whether in renewing acquaintance with our past-president and present Secretary of Commerce, he is not greeting the next president of the United States. Elsewhere in this issue accounts of the professional careers of these three men appear as also of the two younger men, Charles H. Herty, Jr., and P. H. Royster, who are to receive the Robert W. Hunt and the J. E. Johnson awards. Institute honors go for technical achievement, but the Institute will be proud and happy if the nation should later confirm its own judgment by placing larger responsibilities on one of its members. The medals are to be presented at the annual dinner following the President's reception and preceding the dance. There will be no. other speeches and since the occasion falls on Carnival Night a particularly gay evening is anticipated. The event will be at the Wal-dorf as usual, and members are urged to return prompt-ly the reservation cards sent them by mail. Other entertainment features will include a Smoker, Monday evening at 8.15, held at Mecca Temple and in charge of a new committee with Fred Kay of the Petro-leum Division as chairman. He promises that vocal music will not be allowed to interrupt conversation. Lunch will be served each day on the Fifth Floor of the Engineering Societies Building, and ten special luncheons and dinners have been arranged for particu-lar committees and groups as shown by the detailed program. The Woman's Auxiliary has laid out a gen-erous program including luncheons, teas, a theater party on the night the men folks go to the Smoker, visits to museums and, not the least important, a round of the leading shops. The Excursion Committee is arranging for an excur-sion sure to be of interest. The American Smelting and Refining Co. has opened its great Perth Amboy plant to the Institute, and on Thursday, Feb. 23, a party will be taken to it by bus traveling through the Holland Tunnel en route. Full opportunity will be afforded those interested to see the workings of the ventilation system of that great public work. If a sufficient number indicate interest, arrangements will be made for group excursions to other plants in the vicinity of the city.

Jan 2, 1928

By G. R. Countryman, G. H. Thomas, I. Fatt

Miscible displacement in both thewetting and non-wetting phase has been studied in two-phase systems. Experimental data show that dispersion is a function of saturation and cannot be predicted from dispersion theory developed for single-phase miscible displacement. Some of the effect of saturation on dispersion is a result of the development of dead-end pores or a dendritic pore structure in multiphase systems. The presence of dead-end pores or dendritic structure is confirmed by pressure transient studies. INTRODUCTION Displacement by flooding with a miscible liquid is a possible means for recovering the estimated two-thirds of the oil that remains behind after primary production. The immense economic importance of a process that can recover such large quantities of oil has led to extensive laboratory studies of miscible displacement. As usual in production research, most laboratory studies of miscible displacement have not attemped to reproduce all of the conditions existing in a petroleum reservoir. In the early stages of investigation the need has been for information on the broad, basic principles of the phenomena involved in miscible displacement. The effects of overburden pressure, reservoir temperature, and wettability have been considered of secondary importance. However, one property of a petroleum reservoir which is expected to be of major importance and yet has been omitted from many laboratory studies is the presence of interstitial water. Two possible effects of interstitial water on the displacement mechanism in the hydrocarbon phase immediately come to mind. First, from the general1y accepted theory that capillarity governs the distribution of oil and water in porous rock one would expect that for water-wet rock the water will be in the small pores and oil in the large pores. A miscible displacement of oil carried out in the presence of water is operating in a pore size distribution shown in Fig. lb, whereas if the same test had been performed with only one phase present the pore size distribution is as shown in Fig. la. Although there is not yet a theory of miscible displacement which explains in detail the effect of pore size distribution, one would expect the differences between Figs. la and lb to influence the displacement efficiency. A second factor which may make a multiphase system different from a single-phase system is the presence in the multiphase system of dead-end pores or dendritic structure. Experiments of various kinds on reservoir rock have led to the belief that all pores in the network structure of a porous rock take part in conducting fluid during single phase fluid flow.1,2 There are then no dead-end pores and no fingers or dendritic structures containing stagnant fluid. In a multiphase system, however, the second phase may

By K. K. Rao, M. E. Nicholson

IN a recent paper on the solubility of carbon in Ni-Cu alloys,' Nicholson reported that the carbon solubility appeared to be limited by the electronic structure of the alloys and that the solubility was propor- tional to the density of states at the Fermi surface of the "3d" band. In order to determine whether or not this relationship is a general one, the study has been extended to other systems. One of these is the CO-Ni system. This system was chosen for study because 1) it is adjacent to Ni-Cu system in the periodic table, 2) the alloys of cobalt and nickel do not form stable carbides at 1000°C, and 3) the system exhibits no pronounced change (less than 1 pct) in lattice parameter from cobalt to nickel,' see Fig. 1. The alloys were prepared from -200-mesh 99.92 pct Ni furnished by the International Nickel Co. and spectroscopically pure -200-mesh cobalt sponge obtained from Johns on-Matthey and Co. The powders were weighed, mixed, and pressed using a pressure of 40,000 psi. The samples were sintered for 24 hr at 900° C in dry hydrogen and then cold rolled to a thickness of 0.010 in. (Samples containing more than 70 wt pct Co had to be annealed after cold reductions of about 20 pct to avoid cracking.) The alloys were carburized at 1000°C in an alun-durn boat containing Acheson AUC powdered graphite in an atmosphere of carbon monoxide cylinder gas which had been passed through Ascarite to remove carbon dioxide. After carburizing for either 12 or 24 hr the samples were moved to a cool zone of the furnace to cool. Cooling required about 5 min. The samples were filed to remove about 0.005 in. from the surface and then analyzed using a conventional combustion-gravimetric analytic method. The results of this investigation are shown in the lower portion of Fig. 1 and Tabulated in Table I. The nickel percentages for these alloys were determined from the weights of the powders from which the alloys were made. The solubility of carbon in pure cobalt at 1000°C (fcc) is 0.25 wt pct. This is somewhat less than the 0.33 wt pct measured by Boecker.3 From his data, it would appear Boecker's samples were supersaturated before the equilibrating treatment and that a 20-min treatment was not long enough to achieve equilibrium. Since in the present investigation the 12 and 24 treatments produced essentially equal carbon contents, our figure is presumed to represent more nearly the equilibrium value. The solubility of carbon in nickel of 0.19 wt pct agrees quite well with the value of 0.21 wt pct

Jan 1, 1963

By John Wulff, J. H. Hollomon

THE opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was redeposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufficiently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion.4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May,6 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to alpha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. They believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They did not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,8 in another publication, suggested that the commonly found gray or black arsenical film may act to: (I) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led him to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed during the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (As203),

Jan 1, 1942

By C. A. Heiland, Tripp R. M., Dart Wantland

This paper serves to illustrate the application of geophysics to a virtually abandoned mine properly, an application that led to the discovery of an ore body and thus afforded an Opportunity to cOmpare subsequent geologic findings with geophysical data. The work herein described represents, however: more than mere ''case history." It demonstrates that it is possible to obtain satisfactory results by simple means and relatively inexpericnced personnel. The geophysical surveys were made by students as a part of their field assignments in the course of their regular training, and were supervised by Dart Wantland, J. E. Hawkins and R. Maurice 'Tripp. In the course of several seasons an appreciable amount of material was accumulated, which gave graduate students an opportunity for special studies. In this connection, the contributions by L. Massé, R. C. Hyslop, and J. E. Hawkins deserve special mention. The property owners cooperated wholeheartedly in the work, and special thanks are due messrs. J. F. Johnson and S. E. Zelenkov, of the American Smelting and Refining Co., for their interest and for permission to utilize the results of their development work for this publication. Location and Geology The Malachite mine is situated on the northcrn slope of Bear Creek Canyon, 4 miles northeast of Evergreen, I½ miles northwest of Idledale, and 4% miles west northwest of Morrison, in Jefferson County, Colorado. The location (Fig. I) is north of the center of set. 30, T. 45, R. 70 W., at an elevation of about 7500 ft, above sea level, Near the mine the terrain slopes rather uniformly southward at an angle of about 180 pigs. 3 and 7). The geology of the Malachite mine area has been described by J, underhill,' W, Lindgren,2 and J. Boyd.3,4 A map showing surface outcrops and mine workings appears in Fig, 2. the Malachite mine is in an amphibolite belt enclosed in gneisses and schists of the Idaho-Springs formation (probably early Algonkian age). The highly contorted beds are nearly vertical and strike slightly north of west. A series of granite-pegmatite dikes have been intruded almost at right angles into the gneisses and schists and doubtedless are postmineral. While most of the formations are exposed at the surface, a part of the 'lope is covered by slide rock and float, and in the eastern portion by alluvium and creek fill. A quartz-diorite dike cuts through the amphibolite schists at a small angle with nearly vertical dip. The copper sulphides, developed in this dike by magmatic segregation, occur in lenticular form. As far as the mine workings have revealed, the ore lenses are often discontinuous in depth and

Jan 1, 1946