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By Frederick Rhines

PURE copper that has been allowed to oxidize at an elevated tempera-ture in the air is found to be covered with two distinguishable layers of oxide scale. The outer of these, which is very thin, is composed of cupric oxide, while the inner layer, comprising the bulk of the scale, is made up chiefly of cuprous oxide (Fig. 1a). If a small quantity of an alloying element, such as silicon, is present in the copper, silica particles are found disseminated through the cuprous oxide, deposited most abundantly near the metal surface, and, in addition, silica particles occur to a limited depth within the copper itself (Fig. 1b). It is this inner layer, composed of oxide particles precipitated in a matrix of metallic copper that is known as the "subscale" or the zone of internal oxidation. Under a low oxygen pressure it is possible to produce the subscale without the formation of external layers of copper oxides, thus leaving the metal surface bright and apparently clean while oxidation has occurred, in fact, to a considerable depth within the metal (Fig. 2). Although little is yet known in a detailed way of the mechanism of internal oxidation, the general nature of the process is evident. By virtue of the considerable solubility of oxygen in copper,1 it is possible to bring the alloying element in contact with oxygen within the metallic solid solution. If the oxide of the alloying element is more stable than cuprous oxide, the foreign oxide may form and, since most oxides are relatively insoluble in copper, it will not long remain in solution, but will separate as a precipitate. As the metallic solute is exhausted in the zone of precipitation, oxygen that is constantly being supplied at the surface diffuses farther into the alloy and thus produces an ever-thickening shell of subscale. The distribution of the reacting elements in the subscale and adjoining zones must be somewhat as indicated in Fig. 3. The conditions requisite to internal oxidation to be anticipated are thus: (1) a solubility of oxygen in the alloy, (2) the ability of oxygen to diffuse at an appreciable rate into the alloy, (3) the possibility of the

Jan 1, 1940

By F. C. Newton

RefineRs of lead by the Parkes process have always been solicitous of recovering the zinc used in the desilverization, and justly so, as the loss in zinc constitutes one of the heavy costs in this method of refining. Part of this loss is due to the absorption of zinc by lead, and in the present state of knowledge is not recoverable as metallic zinc. The remainder of the zinc, which finds its way into the precious-metal-bearing crust, is recoverable and naturally engages the operators' most exacting attention. Careful elimination of the impurities in base bullion has enabled the refiner to produce a zinc crust better adapted to retorting, which reflects favorably in the zinc recovery;- and to produce a richer crust, thereby lowering the zineking cost, as the increased efficiency of the zinc results in less of it being in circulation. It is obvious that if the ratio of concentration be increased, a lessening of the amount of crust formed will ensue, throwing less work on the retorts and diminishing the amount of retort metal sent to the cupels, thus making an actual money saving in all these operations. In the effort to obtain a rich crust, the metallurgist has increased the heat to a considerable degree, upon the assumption that at the higher temperature the zinc-dver alloy could be squeezed free from the adhering lead. A further possibility for improvement suggested itself in the freezing-point curve of Prof. H. C. Carpenter, upon zinc and silver. Study of this curve disclosed the existence of a definite chemical compound, Zn3Ag2, with a freezing point of 665" C., a promising compound for practical application. In the experiment undertaken it was endeavored to force this compound into the crust, hoping thereby to obtain a higher concentration than formerly. It was recognized that in bringing a large kettle of lead to such a heat, more fuel would be used, the life of the kettle would perhaps be shorter, and other disadvantages would be experienced. AS a commercial operation, the project would have to stand on its own feet,

Jan 1, 1915

By John Birkinbine

The favor with which the members of the Institute received Mr. Fernow's paper upon the use of charbon roux in the manufacture of iron has encouraged me to present this paper, in the hope of having the discussion upon the manufacture and use of the oldest and undoubtedly the best fuel for producing pig iron continued. Owing to the advances made in employing anthracite coal, bituminous coal, or coke, or mixtures of them, we are apt to forget how much of our present development is due to the pioneers in iron manufacture and the fuel which they employed in the production of pig iron. In Mr. Swank's last compilation of the iron and steel works of the United States, the furnace capacity of the country is given as 5,868,000 tons, of which 1,000,000 tons can be made in the 264 charcoal furnaces. In other words, over one-third of the furnaces now in existence use charcoal for fuel, and produce more than onesixth of the iron made. If to this is added the 130,000 tons of blooms and billets turned out by the 122 forges and bloomaries, the importance of the charcoal industries will be appreciated.

Jan 1, 1879

By AIME AIME

INDUSTRIAL Pittsburgh, the center of the coal and iron and steel industry of the world, was host to the Coal Division at its Fall Meeting held there on Oct. 21 and 22 at the William Penn Hotel. The past year has witnessed remarkable progress in new methods of mining and burning of coal and many of the papers on the program discussed these developments. Nearly 100 had registered at the time of the first session on Wednesday morning and this number increased to 168 on Thursday. Owing to the large number of papers on the program, eighteen in all, it was necessary to hold group meetings on Thursday morning, with a capacity attendance at each meeting. . Chairman McAuliffe was on hand early Wednesday morning to open the meeting. George Otis Smith, representing President Lovejoy, came over from Cleveland where he attended the meetings of the Institute of Metals Division. Secretary Parsons arrived later from Cleveland and spent the whole morning with the executive committee of the Division. Doctor Smith, Secretary Parsons, and J. T. Breunich were the official representatives from Institute headquarters.

Jan 1, 1936

By P. G. Winchell, M. Cohen, J. Woodilla

The kinetics of stabilization have been studied with respect to the isothermal component of the martensitic reaction in ivon-nickel alloys. Although the carbun (or nit-vogen) content may be very low in these alloys, it plays an important vole in the stabilization phenomenon. In fact, if these interstitial elements are removed by moist-hydrogen treatment, no evidence of stabilization is found. In the pvesence of 0.007 wt pct C, the activation energy for the stabilization process is comparable to that -for the diffusion of carbon (or nitrogen) in ferrite) rather than in austenitc. This suggests that the interstitial diffiision controlling the stabilization occurs within the martensitic embryos rather than in the matrix of the parent phase. The kinetics furthev indicate that the interstitial atoms tend to diffuse -from the embryos toward the suvroundings, thereby immobilizing the interface. This appears to be the origin of the stabilizing effect -found in these alloys. PHILIBERT' has shown recently that interstitial elements play an important role in the stabilization of martensitic transformations in iron-base alloys. However, determination of the temperature dependence for this stabilization process has produced values (- 11,000 cal per mol) that cannot be readily identified with the activation energy for diffusion of carbon (or nitrogen) in either ferrite or austenite. In the present work, the isothermal mode of the martensitic reaction was employed to derive the activation energy for stabilization, and this was found to agree fairly well with that for diffusion of carbon (or nitrogen) in ferrite. An iron-nickel alloy with 30.8 wt pct Ni and 0.007 wt pct C was used in these experiments, the specimens being in the form of rods 0.074 in. in diam and 2 1/2 in. long. The specimens were sealed in evacuated vycor tubes and austenitized at 1100°C for 1/2 hr prior to quenching in water. A second series of specimens was decarburized (and denitrogenized) prior to the above austenitizing treatment by annealing in moist hydrogen for 182 hr at 1215°C. In order to achieve a "standard" condition in the austenitic state, all the specimens were transformed to martensite by cooling to - 195°C before the final austenitizing. Both the 0.007 pct C and the decarburized series then had an Mi temperature of about - 30°C. The isothermal martensitic transformation was carried out at a reference temperature of -88"C, and was traced by means of electrical resistance measurements. Each resistance value was normalized by dividing by the resistance of the austenitic specimen at O°C, thus giving a resist- ance ratio R. The rate of decrease of the resistance ratio (-dR/dt) provided a measure of the transformation rate. It was found that a plot of R vs log t at the reference temperature resulted in a slightly curved line which could be closely approximated by two straight lines intersecting at a time of 10 min, as shown in Fig. 1. If G = dR/dlogt is the linear slope of either straight segment, the rate of transformation at any given time is: The ratio of G for 1 less than 10 min to that for t greater than 10 min was 1.19 for the 0.007 pct C series and 1.24 for the decarburized series. These ratios made it possible to compute the transformation rate at any time greater than 10 min, knowing the transformation kinetics prior to 10 min. The stabilization treatment was introduced by up-quenching from the reference temperature, usually after 10 min of isothermal transformation: to one of four stabilizing temperatures between 0" and 22"C. After holding for various times, the specimens were down-quenched to the reference temperature for additional isothermal transformation. In this way, it was possible to compare the transformation rate (- dR/dt), immediately after stabilization with the transformation rate (- dR/dt)U in the unstabilized condition. The degree of stabilization was defined as: Ordinarily, Gs and Gu would be measured after the same time of prim isothermal transformation.

Jan 1, 1960

By C. E Shoenfelt, Gail F. Moulton

Proven and developed oil reserves, and productive capacity increased during 1943 in the fieids of the Rocky Mountain region. Oil production during the year was nearly 45 million barrels, or slightly less than in 1942. The rate of production at the start of 1944 was slightly less than at the start of 1943. Pipe-line projects scheduled for completion during 1944 should permit a substantial increase in the rate of production. Wildcat exploration was more extensive in Montana during 1943 than in other states in the region. The results of wildcat drilling were unsatisfactory, although new oil fields were discovered on the Gebo, Little Buffalo Basin and Steamboat Butte structures of Wyoming, the Gage anticline of Montana, and the Clark Lake structure of Colorado. The area of the structures on which the discovery wells were drilled is known to be considerable, but further drilling is required to determine the importance of these fields. The most important increase in proven reserves resulted from the drilling to newly discovered deeper producing formations in the Elk Basin and other fields of the Big Horn Basin area of northern Wyoming. Lack of a market and unfavorable prices for heavy black oils had prevented complete exploration of favorable areas in the Rocky Mountain region for many years. In particular, the effect on further exploitation of the Big Horn Basin area had been quite serious. The increased demands for all oils created by the war and an increase in price in February 1943, combined later with Government approval of construction of pipe lines from the Big Horn Basin area to the Billings and the Casper districts, provided a basis for undertaking a drilling program. The important additions to reserves were made by drilling in previously discovered fields. The newly discovered fields resulted from drilling on favorable structures which had been known for several years. A continuation of the favorable results obtained during 1943 seems possible only if further testing of the newly discovered fields is satisfactory and if drilling on less favorable known structures or geophysical prospects results in the discovery of new fields. The amount of drilling in the Rocky Mountain states of Colorado, Montana and Wyoming, was about the same during 1943 as .in 1942. However, owing to the fact that a number of wells of large potential production were completed in the Elk Basin field, the total initial production of the prodicing wells was- nearly twice as great for 1943 as for 1942. Explorational activity at the end of 1943 seemed to be directed to geophysical methods, which are required to discover structures hidden beneath the rocks of Tertiary age in the Powder River and other large sedimentary basins. It is in

Jan 1, 1944

By C. B. Foraker

THE Magma mine, of the Magma Copper Co., at Superior, Pinal County, Arizona, is 68 miles east of Phoenix and 21 miles west of Miami, Arizona, on highway U. S. 180. TEMPERATURES AND UNDERGROUND WATERS Surface Temperatures.-The average surface dry-bulb temperature at Superior is 72.4º; wet-bulb, 57.4º; with an indicated relative humidity of 38 per cent. The average yearly rainfall from 1921 to 1936, inclusive, was 18.74 in. The maximum condition of the atmosphere is in June, July and August, and the minimum is in January and February. The surface temperatures, of course, influence the temperatures of the down- cast shafts; however, the variation between winter and summer causes a difference of only 2º to 3º in the stopes and working places that are not close to the intake shafts. Average atmospheric conditions are shown in Fig. 1. Rock Temperatures.-Rock temperatures on the deeper levels of the mine are as follows: [ ] There appears to be no difference in rock temperature for any particular horizon of the various formations or in the vein. Water encountered is always the same temperature as the rock from which it flows, and for this reason it is thought that the water is heated by the rock; not the rock by the water. The country rock apparently has been heated by the various intrusions, perhaps the vein itself, and has not yet had time to cool off. The geothermal gradient (Fig. 2) as indicated by the rock temperatures given above is 1 ½ º per 100 feet. Underground Waters.-The underground water varies from 350 to 565 gal. per min., depending on the rainfall. The limestone and other

Jan 1, 1938

THE CHAIRMAN (E. G. SPILSBURY, New York, N. Y.).-The relation of the character of manganese ore to the surrounding rocks was called to my attention very strikingly in a recent investigation in Costa Rica. In the foothills of the main coastal range there is a large deposit of manganese which extends for over 150 miles along the coast. This is in a porphyry district and the occurrences are almost exclusively along the lines of contact between a recent diorite intrusion through the porphyries. Wherever that intrusion appears to have exerted great force, the line of contact is very clear between the porphyries and the diorites. Where the action has been slower and the lifting force of the intrusion more gradual, there has been a zone of fracture of very considerable width. Those ores which occur where the fractured zone has not been very extensive carry a, lower percentage of manganese than where it has been deposited along a wider zone of fracture. In the so-called narrow veins, which are really the predominant ones, the solution carrying the manganese has evidently attacked the silica in the intrusive rock, and the resulting ore is practically a combination of manganese and silica, running froth 20 to 30 per cent. of manganese and from 20 to 40 per cent. of silica: hence those ores are not likely for a long time to become a factor in our manganese supply :for this country. On the other hand, where the disturbance to the porphyritic schist has been more intense; the manganese deposits are not so extensive, but the ore is richer, running from 45 to 51 and 52 per cent. manganese, with a silica content of from 4 to 5 per cent. There seems to be some resemblance in these deposits to those of the Cuyuna range. EDMUND NEWTON, Minneapolis, Minn.-The State Bureau of Mines has been working on the problem of concentrating manganiferous iron ore for two years or more. I should consider hand sorting as the best form of treatment, because it is practised at all of the mines which ship ore for making alloys, but not, however, oil the ore that is being used for pig iron. Hand sorting, assisted by selective mining, is readily applicable to some of this ore because the gangue is practically the original rock and is easily separated. However, it is only in rather limited zones that we find clean patches of rock. Generally the silica exists as a skeleton of the original rock structure, in which the manganese has been precipitated; some of the silica may have been dissolved, but if any of the original rock remains, the silica must be eliminated by ore-dressing processes.

Jan 1, 1918

By Gail F. Moulton, C. E. Shoenfelt

Proven and developed oil reserves, and productive capacity increased during 1943 in the fieids of the Rocky Mountain region. Oil production during the year was nearly 45 million barrels, or slightly less than in 1942. The rate of production at the start of 1944 was slightly less than at the start of 1943. Pipe-line projects scheduled for completion during 1944 should permit a substantial increase in the rate of production. Wildcat exploration was more extensive in Montana during 1943 than in other states in the region. The results of wildcat drilling were unsatisfactory, although new oil fields were discovered on the Gebo, Little Buffalo Basin and Steamboat Butte structures of Wyoming, the Gage anticline of Montana, and the Clark Lake structure of Colorado. The area of the structures on which the discovery wells were drilled is known to be considerable, but further drilling is required to determine the importance of these fields. The most important increase in proven reserves resulted from the drilling to newly discovered deeper producing formations in the Elk Basin and other fields of the Big Horn Basin area of northern Wyoming. Lack of a market and unfavorable prices for heavy black oils had prevented complete exploration of favorable areas in the Rocky Mountain region for many years. In particular, the effect on further exploitation of the Big Horn Basin area had been quite serious. The increased demands for all oils created by the war and an increase in price in February 1943, combined later with Government approval of construction of pipe lines from the Big Horn Basin area to the Billings and the Casper districts, provided a basis for undertaking a drilling program. The important additions to reserves were made by drilling in previously discovered fields. The newly discovered fields resulted from drilling on favorable structures which had been known for several years. A continuation of the favorable results obtained during 1943 seems possible only if further testing of the newly discovered fields is satisfactory and if drilling on less favorable known structures or geophysical prospects results in the discovery of new fields. The amount of drilling in the Rocky Mountain states of Colorado, Montana and Wyoming, was about the same during 1943 as .in 1942. However, owing to the fact that a number of wells of large potential production were completed in the Elk Basin field, the total initial production of the prodicing wells was- nearly twice as great for 1943 as for 1942. Explorational activity at the end of 1943 seemed to be directed to geophysical methods, which are required to discover structures hidden beneath the rocks of Tertiary age in the Powder River and other large sedimentary basins. It is in

Jan 1, 1944

By Charles P. Berkey, Joseph H. Sinclair

This paper describes the results of a visit to the Santa Elena Peninsula, Ecuador, in January and February, 1921. On account of the complicated folding and faulting of the rocks and the peculiar occurrence of petroleum, field work was possible on only a few of the many geological problems and the results here published are only a contribution to the solution of the general problem. We know of nothing published on the geology of the district, except one account, in Spanish and German, by Theodor Wolf. The Santa Elena peninsula, the most important headland of the coast of Ecuador, lies two degrees south of the equator. The chief town, Santa Elena, is about 75 miles west of Guayaquil, the main seaport of Ecuador. The nearest developed oil field is the Zorritos of northern Peru, 120 miles south across the Gulf of Guayaquil. If newspaper reports are true, viz. that the Anglo-Ecuadorian Oilfields, Ltd., has recently brought in a 700-bbl. well on the coast of the peninsula near Ancon, the district may become important in the production of petroleum. At the time of our visit, the best way to reach the peninsula was by a steamer of the Pacific Steam Navigation Go., southward from Panama and northward from Guayaquil. About once a week, one of these steamers anchored 1/2 mile off shore near the village of Salinas, an important cable station. An alternative route, in the dry season, is by automobile from Guayaquil. In February, 1921, a railway bed had been graded part way between Guayaquil and Salinas, but this was detcriorating rapidly because of lack of funds to continue construction or to keep in repair that portion already completed.

Jan 1, 1923

By Charles P. Berkey, Joseph H. Sinclair

This paper describes the results of a visit to the Santa Elena Peninsula, Ecuador, in January and February, 1921. On account of the complicated folding and faulting of the rocks and the peculiar occurrence of petroleum, field work was possible on only a few of the many geological problems and the results here published are only a contribution to the solution of the general problem. We know of nothing published on the geology of the district, except one account, in Spanish and German, by Theodor Wolf. The Santa Elena peninsula, the most important headland of the coast of Ecuador, lies two degrees south of the equator. The chief town, Santa Elena, is about 75 miles west of Guayaquil, the main seaport of Ecuador. The nearest developed oil field is the Zorritos of northern Peru, 120 miles south across the Gulf of Guayaquil. If newspaper reports are true, viz. that the Anglo-Ecuadorian Oilfields, Ltd., has recently brought in a 700-bbl. well on the coast of the peninsula near Ancon, the district may become important in the production of petroleum. At the time of our visit, the best way to reach the peninsula was by a steamer of the Pacific Steam Navigation Go., southward from Panama and northward from Guayaquil. About once a week, one of these steamers anchored 1/2 mile off shore near the village of Salinas, an important cable station. An alternative route, in the dry season, is by automobile from Guayaquil. In February, 1921, a railway bed had been graded part way between Guayaquil and Salinas, but this was detcriorating rapidly because of lack of funds to continue construction or to keep in repair that portion already completed.

Jan 1, 1923

By David W. Brunton

I. INTRODUCTION. THE list of our past-Presidents comprises the names of runny who, in their official addresses, have sketched the current progress of the arts and professions with which they were familiar. Such addresses are, in my judgment., highly useful, setting forth the results of our own work as a. society, and recalling to our minds the particular lines in which discussion would prove most fruitful. . Following this course with some hesitation, I venture to offer an outline of the recent improvements and the present situation in minim and metallurgy in the Western United States. The wonderful advances in mechanics, chemistry, and electricity have all combined to aid these arts to such an extent that. progress during the last decade has undeniably been more rapid than ever before in the history of the profession.. In all mining countries improved transportation-facilities, in many instances called into existence by the traffic created by the mines themselves, have done much- to enlarge the. field of operations by the reduction of freight-, operating- and living-expenses, thereby bringing lower-grade properties into the producing class. Under normal' conditions, as the age of a district in¬creases, all these differentt factors should combine to off-set. the augmented costs attendant on deep mining, and greatly tend to prolong the profitable life of the mines. The more recent and important improvements in our Western mining-practice which have contributed most toward the advancement of the art may be briefly summarized as follows; but, before beginning this portion of ray address, I wish to thank most heartily the many engineering friends who have so

Sep 1, 1909

By J. G. Richardson

The performance of laboratory water floods is compared with the flooding behavior calculated by the Buckley-Leverett techniques from steady-state relative permeability-saturation relations. Both the steady-state and unsteady-state experiments were conducted on the same sand-packed column. Relative permeabilities were calculated by the Welge technique from the unsteady-state waterflooding displacement experiments and compared with those measured by steady-state techniques. An evaluation of the various calculation procedures was made. It was demonstrated that steady-state relative permeabilities could be used to calczcJate waterflood performance. INTRODUCTION To calculate the waterflooding behavior of a given reservoir, relative permeability-saturation relations of the reservoir rock are required. These relative permeabilities are commonly measured on core samples by steady-state experiments such as the Penn State technique.' The relative permeabilities obtained in steady-state experiments are calculated from oil and gas flow rates and pressure drops measured under conditions of equilibrium distribution of oil and water in the pore spaces with slow approach to equilibrium. On the other hand, in water floods the water saturation at a given point changes rapidly with time as the flood front passes. Extensive research2 has shown that the steady-state relative permeabilities to oil and water are independent of the rate of flow and the fluid viscosities. Research has also demonstrated that the waterflooding performance of homogeneous sands uniformly contacted by water is independent of rate when capillary pressure gradients, which are important in short laboratory columns, are made negligible. However, there is little experimental data in the literature comparing relative permeabilities calculated from steady-state flow experiments with those calculated from flooding experiments. In this paper, the production data of two water floods and the relative permeabilities calculated from a series of steady-state experiments on an unconsolidated sand column are presented along with the comparisons calculated by the Buckley-Leverett and by the Welge techniques. The purpose of this study was to determine if steady-state relative permeabilities could be used to predict the waterflooding performance. This study also permitted an evaluation of the Buckley-Leverett and Welge calculation procedures and allowed an insight into the nature of microscopic displacement of oil by water. EXPERIMENTAL APPARATUS AND PROCEDURE The apparatus used in this investigation was a Lucite column 1 ft long and 11/2 in. in diameter. A drawing of the apparatus is shown in Fig. 1. Six pressure taps were evenly spaced along the top of the column to measure the oil pressures. Three pressure taps fitted with small porous disks were spaced along the side of the column to measure water pressure. Water was admitted to the inflow face of the sand through a porous disk while oil was admitted through a hole in the porous disk and distributed to the face of the sand by grooves machined in the porous disk. Retainer screens of 325-mesh stainless steel were cemented over the inlet and outlet ports and the pressure taps to prevent loss of sand. The column was packed with a clean dry sand all of which was finer than 200 mesh. Next, the sand was saturated with a solution of 150,000 ppm sodium chloride solution. The column was weighed dry and water-saturated to obtain data for the calculation of the pore volume. A 151-cp oil was then injected into

Jan 1, 1958

By Jay Carpenter

THIS paper deals with only one step in the treatment of ore at the West End mill; not because the other steps are repetitions of practice in other mills, but because in this particular step there is in use the Trent agitator. This device, although it has apparently failed in many mills, is here giving excellent service and has proved to be well adapted for making a thorough replacement of pregnant solution with a minimum amount of barren solution. The strong and weak points of this agitator, its present simple construction, and its use as a thickener for agitator or battery pulp are features of interest; but perhaps the point of greatest interest to the metallurgist in this day of continuous decantation is its use in a series of tanks for slime treatment by the replacement method. The agitating department of the West End mill consists of six redwood tanks, 24 ft. in diameter, 18 ft. high, each equipped with aTrent agitator, a centrifugal pump, and a motor. The pulp is transferred by a pump from the top of a flat-bottomed tank to a set of arms and nozzles in the bottom of the tank, at just sufficient pressure to cause the arms to revolve. The streams from the many nozzles keep the bottom of the tank clean, and these streams, coupled with the effect of the revolving mechanism and the ascending current, keep the pulp in constant motion and of constant gravity. .These agitating tanks hold 90 tons of dry slime and 202 tons of solution with a 1.24 pulp, our ore having a specific gravity of 2.7. This capacity is about 10 per cent. in excess of the standard 15 by 45 ft. Pachuca tank. The tanks are connected in one series for continuous agitation, the pulp for each agitator being drawn by its pump through a branch suction from near the top of the preceding tank and. delivered to the bottom of the tank by the agitator arms along with the regular pulp of that agitator. This method works automatically, since the flow through the branch suction varies directly with the difference in head of the two tanks. The chance for new pulp to pass out quickly is, therefore, much less than in many other systems of continuous agitation, since the new

Jan 8, 1915

By R. A. Greenkorn, R. C. Smith

Hele-Shaw cells are used to model creeping flow through porous media (where Darcy&apos;s law is valid). The effects of inertia on flow about obstructions in a Hele-Shaw cell can be calculated by a perturbation method if one can determine a solution to Laplace&apos;s equation. Results of a computer solution for flow about circular, square and elliptical obstructions are presented. These results show that or a modified Reynolds number of less than I, the inertia terms are small; and for values of less than 3, the average streamline predicts the ideal flow. Therefore, the analogy might be used for studying flow in porous media up to a modified Reynolds number of at least 3. INTRODUCTION The nature of fluid flow in porous media is of interest in the fields of soil mechanics, ground water flow, petroleum production, filtration and flow in packed beds. Because it is very difficult to study the phenomenological behavior of flow in porous media, homologs and analogs are used to study flow characteristics. A Hele-Shaw model, made of two closely spaced plates - usually glass — is often used as an analogy to two-dimensional flow in porous media. Hele-Shaw2 showed experimentally that the streamline configuration for creeping flow around an obstacle located between two closely spaced parallel plates is the same as for two-dimensional, ideal flow about the same obstacle. Stokes7 verified these observations mathematically. The usual equation of motion for flow in porous media is Darcy&apos;s law. The form of the mathematical statement of Darcy&apos;s law is identical, within a multiplicative constant, to the expression for the average velocity over the plate gap in the plane of a Hele-Shaw model. These models may be used to describe flow in both homogeneous and heterogeneous porous media. In the mathematical proof of the Hele-Shaw analogy it is assumed that the convective terms in the Navier-Stokes equations are negligible and that the equations of motion degenerate to Laplace&apos;s equation, with pressure the dependent variable. Whenever a Hele-Shaw model is used as an analogy to flow in porous media, .the validity of this assumption is in question. Riegels5 showed that if convection is not neglected, the velocity distribution around a cylindrical obstruction in the flow field depends on a Reynolds number, the plate spacing, and a dimension characteristic of the obstacle. Riegels&apos; solution, a perturbation solution, uses the boundary condition that the flow rate into the obstacle averaged over the plate gap at any point on the obstacle is zero. The method requires that a solution to Poisson&apos;s equation for the perturbation pressure be found. Riegels evaluated this solution for the case of the cylindrical obstruction. His method may be simplified by eliminating the need for solving Poisson&apos;s equation for the perturbation pressure. Instead, an analytic expression for the perturbation pressure gradient is obtained (valid for arbitrary shapes) and used to eliminate pressure from the equations for the perturbation velocities. The results show, for symmetrical shapes, that if NRe < 1, the convective acceleration terms are small, and that the average velocities represent ideal flow up to at least NRe = 3, where: L is a characteristic dimension of the obstacle perpendicular to flow, b is the plate spacing, u is viscosity, v, is velocity of approach and p is density. THEORY* Incompressible fluid flow through a Hele-Shaw model and a porous medium are analogous because the equations for the average velocity components in two-dimensional flow are identical if:

Jan 1, 1970

By C. R. Criss, R. J. McCormick

ThiS paper .summarizes the development and perform. ance of the Coldwater Oil field, Isabella County, Mich. Production is obtained at a depth of 3750 ft from a dolomite reservoir, which is probably both Rogers City and Dundee. There appears to be no persistent barrier to vertical fluid movement between the Rogers City and Dundee, and both formations are believed to have a common original oil-water contact. No we1ls are open to production at the level of the Dundee. The discovery of the field in 1944 was followed by the drilling of 81 producing wells and nine dry holes. By the end of 1952, the field had produced 12,763,000 bbl of oil, at which time 69 active wells were producing 3600 B/D oil and 21,000 B/D water. The reservoir has an effective natural water drive, and bottom-hole pressure has declined 75 psi from an original pressure of 1453 psi. Oil is undersaturated at reservoir conditions with a solution GOR of 512 cu ft/bbl and a saturation pressure of 1190 psi. INTRODUCTION Although the Coldwater Field is now in its ninth year of production, it ranks seventh in cumulative recovery, and second in current daily oil production in the State. Following complete development of the field in 1946, it has consistently contributed approximately 11 per cent of Michigan&apos;s daily production. Coldwater appears to have a greater pay thickness than most fields producing from the Rogers City forma- tion in the west central part of the Michigan basin. Except as influenced by the extent of closure and the thickness of the oil column, reservoir performance is believed to be representative of Rogers City fields in this part of the basin. For this reason, it is felt that the following presentation of factual data for the field will be of general interest. HISTORY AND DEVELOPMENT Discovery of the Coldwater field during Aug., 1944, followed favorable subsurface geological correlations and core tests drilled to a shallow stratigraphic marker horizon. The field is located in the west central part of the Michigan Basin in Coldwater Township (T16N-R6W), Isabella County. It is 60 miles west-northwest of Bay City, and near the geographic center of the southern peninsula of Michigan. The discovery well flowed 200 bbl of oil the first 24 hours from the Rogers City dolomite at a depth of approximately 3750 ft. Field production is principally from the Rogers City with a minor amount assumed to come from the underlying Dundee dolomite, although none of the wells are open to production at the level of the Dundee. Both the Rogers City and Dundee formations belong to the Devonian system (See Geologic Column-Fig. I.) In addition to Rogers City-Dundee oil production, sweet gas is produced from the Michigan Stray sand of the Mississippian system at a depth of 1400 ft. The gas reservoir has approximately the same areal extent as the underlying oil reservoir. Although gas production is an important feature of the Coldwater field, this report is concerned only with the oil reservoir. The productive area is approximately 3200 acres. The pool is developed on a 40 acre spacing pattern with wells drilled in the center of the north half of 40 acre tracts, except for a few off-pattern wells drilled along

Jan 1, 1955

By F. H. Buttner, E. R. Funk, H. Udin

Gold wires, 5 mil in diam, are found to creep viscously up to approximately 5.5x106 dynes per sq cm around 1300°K. Beyond this point, an additional slip mechanism appears. The average coefficient in the viscous range at these temperatures is 18.9 ± 7x10 12 poises. This observation and other visual observations made during the experiments agree with Herring&apos;s predictions. EARLY creep studies by Chalmers on single crystals of tin produced some of the first experimental evidence to suggest that metals deform viscously under very light stresses. That is to say, over a small initial stress range up to 150 g per sq mm, the single crystals of tin elongated at a rate proportional to the stress. The proportionality constant between strain rate and stress is by definition the coefficient of viscosity. Chalmers named this range of proportionality the microcreep range. One of the first theoretical attempts to explain the microcreep phenomenon was given by Kauzman,&apos; who applied Eyring&apos;sQ eneral statistical mechanical theory of shear rates to creep data then available. From the rate theory, he deduced the general hyperbolic sine law for shear rate on the assumption that the distortion of the reaction path due to stress is negligible and that the system is an infinite continuum. In order to fit the available data to the equation, it was necessary to assume that creep occurs by shear of rather large blocks of material, rather than by an atomistic shear process as in diffusion. The size of the shear units was shown to increase with increasing temperatures and lower stress, or lower strain rates. In applying the hyperbolic sine law equation to the microcreep data of tin, it was shown by Kauzman that the unit shear blocks became quite small, which suggested to him that microcreep might be a self-diffusion process. Making this an assumption, Kauz- man reworked the rate theory and arrived at an equation where the shear rate is proportional to the stress. In the form of viscosity coefficient, the equation is: o- _ \LkT V = 2qAlA where u is the stress; S, the shear rate; X, the distance in shear direction moved by flow units relative to one another in the unit process; L, the distance between layers of units of flow; T, the absolute temperature; k, Boltzmann&apos;s constant; qAL, a constant proportional to the size of flow units; and kT A, the diffusion coefficient = ------kTe-Q/RT = K X2 h Kauzman applied the expression to molten lead with a fair degree of success, the calculated viscosity being low by a factor of four. For solid lead the result is 5000 times too high. Taking q = 1, and X = dA = L = 21 = nearest neighbor distance, Udin, Shaler and Wulff8 found the equation low by a factor of lo7 for solid copper. On the basis of the discrepancy in lead, Kauzman indicated that microcreep is probably not a simple diffusion process of molecular shear units, but one involving preferential diffusion paths, or even that diffusion in solids does not involve shear at all. Cottrell and Jaswon4 treat the microcreep phenomenon on the basis of slow moving dislocations and apply it to Chalmers&apos; data on tin with fair success. Nabarro Suggested a microcreep model in which mass movement in the direction of pull is effected by the diffusion of holes. The tension on the crystal effectively creates a greater hole concentration at regions near the crystal surfaces perpendicular to

Jan 1, 1953

By N. S. Stoloff, R. G. Davies

A study has been made of the efject oj different dislocation-precipitate interactions upon the temperature dependence of the flow stress of aged Ni-14 at. pct A1 alloy. It is observed that when the dislocations bow between widely spaced (-20004 coherent Ni3Al particles the flow stress decreases with increasing temperature in the normal way. However, when the dislocations cut closely spaced (-5004 particles the flow stress is independent of temperature from -100 to 600°C, due to a balance between softening of the matrix and an increase in strength of the particles with increasing temperature. The retention of strength at high tempera-tures of commercial nickel-base alloys, which are strengthened by the precipitation of a phase based upon Ni3Al, is thought to be due to the unusual strength properties of Ni3Al. The flow stress of Ni3Al increases continuous1y from -196"C to a maximum at -600"C. It is concluded from a series of thermal-mechanical tests that the sevenfold increase in flow stress over this temperature interval is due to a lattice effect and is not diffusion-controlled. The flow stress of precipitation- or dispersion-hardened materials depends on the resistance to dislocation motion within the matrix and the extra energy required for dislocations to bow between or to cut particles. If the dislocations bow between the particles or if the strength of the cut particles is constant with temperature, then the flow stress of the precipitation-hardened alloy must decrease with increasing temperature due at least to the decrease in elastic modulus of the material. There will be softening also from thermally activated cross-slip or climb, offering an additional degree of freedom for dislocations to avoid particles. For example, in the case of nickel containing a dispersion of thoria,&apos; which most probably deforms by dislocations bowing between particles, the flow stress decreases by about 50 pct between 25" and 650°C. In A1-Cu alloys2 aged to produce the 8" precipitate, dislocations cut the particles, and the flow stress decreases by about 20 pct between -269" and 25°C. However, many commercial high-temperature nickel-base alloys, for example Inconel-X and Udimet-700, exhibit little or no decrease in flow stress with increasing temperature up to about 700°C. A characteristic feature of these alloys is that they are strengthened by the precipitation of a phase based upon Ni3A1. Guard and westbrook4 and flinn&apos; have shown that Ni3Al (and alloys in which a third element such as molybdenum or iron is substituted for part of the aluminum) is unusual in that the hardness and flow stress increase with temperature to a maximum at about 600°C. For the flow stress of a precipitation-hardened alloy to be independent of temperature we propose that the particles must be cut by dislocations moving through the matrix and that the strength of the particle must increase with increasing temperature. Theories of precipitation hardening do not take into account the flow stress of the dispersed particles that are cut during deformation; the only dissipative process usually considered7 is the creation of interface within the particle and between the precipitate and matrix. The purpose of the present investigation has been to study in detail the temperature dependence of the flow stress of a nickel-base alloy strengthened by the precipitation of Ni3Al in two structural conditions such that when deformation occurs it does so by dislocations a) bowing between the particles and b) cutting the particles, respectively. A simple binary Ni-14 at. pct A1 alloy was chosen because considerable information is already available for this system concerning phase equilibria and precipitation reactions and rates.&apos; Dislocation-precipitate interactions in the binary alloy should be similar to those in the more complex commercial alloys. In addition, the mechanical and physical properties of NisAl were studied in detail in the hope of elucidating the mechanism by which the strength increases with increasing temperature up to 600°C. EXPERIMENTAL PROCEDURE For the study of the effect of precipitation of Ni3A1 upon the temperature dependence of the flow stress, an alloy containing 14 at. pct A1 was utilized; a Ni-8 at. pct A1 solid-solution alloy was employed as a comparison material. Vacuum-cast ingots were hot-rolled at 1000°C and cylindrical compression samples, 0.20 in. diam by 0.40 in. high, were prepared from the 1/4-in.-diam rod. Specimens were recrystallized and solution-treated at 1000°C for 1/2 hr and then water-quenched. A preliminary study revealed that, when the Ni-14 at. pct A1 alloy was aged for 1 hr at 700°C, significant precipitation hardening was obtained, and that the structure was free from grain boundary discontinuous precipitation; an overaged condition was produced by annealing the aged specimens at 850°C for 1 hr. To circumvent the difficulties involved in the hot rolling and swaging of Ni3A1, compression samples,

Jan 1, 1965

By D. H. Desy, L. C. Fincher

The magnesium-rich end of the Mg-Ti phase diagram was investigated. The liquidus, solidus, and solvus boundaries to 1 pct Ti were established. All alloys were prepared by saturating molten magnesium with titanium in a consumable titanium crucible under inert gas maintained at 230 psig. The liquidus of the Mg- Ti system was determined by analysis of dip samples taken from 700° to 1300°C under equilibrium conditions in a pressurized inert atmosphere furnace and by analysis of small ingots rapidly poured and quenched from 1400° to 1500°C. The solubility of titanium in magnesium ranged from 0.018 wt pet Ti at 700°C (0.012 wt pet at 650°C by extrapolation) to 1.035 wt pet Ti at 1500°C. The solidus for compositions ranging from 0.03 to 1.00 wt pet Ti was determined to be 650° ± 1°C by thermal analysis. The titanium solid solubility values ranged from 0.08 wt pet at 350°C to 0.19 wt pet by extrapolation to 650°C. The freezing reaction is peritectic. No intermetallic compounds were found in the system; the phase in equilibrium with molten magnesium saturated with titanium was found to be titanium with magnesium in solid solution. Solid titanium will dissolve at least 1.32 wt pct Mg. PREVIOUS investigations of the Mg-Ti system have shown considerable disagreement on the solubility of titanium in liquid magnesium. Furthermore, the solid solubility of titanium in magnesium has not been well established. Liquidus curves for previous work and for the present investigation are shown in Fig. 1. Aust and Pidgeon1 used a dip-sampling method on molten magnesium held in equilibrium with solid titanium under a protective atmosphere to determine the solubility and found that it ranged from 0.0025 wt pet Ti at 651°C to 0.015 wt pet Ti at 850°C. Eisenreich2 introduced titanium into molten magnesium by means of TiCL4 adsorbed on BaCl2. Ingots were then cast at various temperatures. Making the assumption that only the titanium dissolved in magnesium at the time of casting was soluble in H2SO4, Eisenreich determined the solubility of titanium in molten magnesium to range from 0.003 wt pet at 655°C to 0.115 wt pet at 800°C. Eisenreich also determined the solid solubility of titanium in magnesium to be 0.015 wt pet at room temperature and 0.045 wt pet at 500°C. Since the solid solubility just below the freezing temperature for the bulk of the alloy was much larger than the liquid solubility just above the freezing temperature, Eisenreich concluded that the freezing reaction was peritectic. Obinata et al.3 equilibrated molten magnesium with titanium in hermetically sealed titanium containers which were then furnace-cooled. The titanium content of the magnesium was then determined and found to range from 0.170 wt pet at 700°C to 0.85 wt pet at 1200°C. No intermetallic compound was found in the system. The Armour Research Foundation4 determined two points on the solvus by electrical resistivity methods: 0.00057 wt pet at 200°C and 0.0008 wt pet at 300°C. At higher temperatures, data were meaningless with no trends observable. The authors of this report believed that the lack of significant data at the higher temperatures was due to variations in specimen geometry, although there was no positive evidence to verify this supposition. The present investigation was undertaken to clarify the uncertainty in both the liquidus and solvus of the magnesium-rich end of the Mg-Ti system. EQUIPMENT AND MATERIALS The equipment used in this investigation, with some modifications, was essentially that used by Crosby and Fowler5 in their determination of part of the Mg-Zr phase diagram. The equipment, as modified for this work, is shown in Fig. 2. It consists of a sealed furnace chamber which can be pressurized with inert gas so that melts can be made above the boiling point of magnesium at atmospheric pressure. Melts are made by induction heating in a titanium crucible which, after diffusion of sufficient magnesium into the walls of the crucible to saturate the titanium at the sampling temperature, comprises the solid phase in equilibrium with the molten magnesium. Dip samples may be taken with the sampling tube, or the entire furnace may be tilted so that ingots may be poured into a mold in the side chamber. The principal difference from the earlier apparatus is in the thermocouple, which in the present equipment is enclosed in a protection tube and immersed directly in the melt. The tips of both the thermocouple protection tube and the sampling tube, which dip into the melt, are made of high-purity titanium. The 4 1/2-in.-long titanium tip of the sampling tube is threaded into a steel tube, O in Fig. 2, which extends through the top of the furnace. To determine whether the temperature at the tip of

Jan 1, 1969

By E. E. Brownson

This paper will be confined to the treatment of methods as applied in the laboratory of the Boston and Montana Reduction Department of the Anaconda Copper Mining Co. at Great Falls, Mont. As the electrolytic plant of this company operates at a current density of approximately 35 to 40 amperes per square foot when running up to capacity, the arsenic and antimony content of the anodes delivered to the plant is of considerable importance as bearing on the purity of the refined cathodes turned out. Owing to the rather high relative percentage of antimony, it has always been the custom to determine antimony as well as arsenic in all forms of copper. Thus, anodes have been analyzed in which the antimony was about equal to the arsenic, although the average shows about 2 parts of arsenic to 1 of antimony. In the refined copper the relative proportions of the two impurities vary considerably, but probably in the average are about equal. In this latter case, the percentage of the two is SO small that ordinarily no attempt is made to separate them, the report of analysis showing percentage of As and Sb combined. Although rapid and exceedingly accurate determinations of arsenic may be made by means of various distillation schemes, the determination of antimony, either by itself or together with arsenic, has always been more or less cumbersome and has required a considerable amount of time. By the methods, details of which follow, the determination of arseluic and antimony, either separated as in the case of anodes or together in case of refined copper, is accomplished in 24 hr. from the time the sample is received by the chemist. As to the accuracy of the results obtained, it can be quite positively stated that in this respect these methods are very satisfactory, much more so than any heretofore employed in our work, and when the rapidity of determination is considered, the results are very accurate.

Jan 1, 1914