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By S. S. Shen, M. J. Pool, P. J. Spencer

Heats of solution of silver and copper in dilute Ag-Cu-Sn alloys at 720°K have been determined using a liquid metal-solution calorieter. Values of the se2f-interaction coefficient n AgAghave been calculated at constant copper concentrations and n Cu Cuhas been determined at constant silver contents. The reliability of the experimental data is shown by the very good agreement between nCujAg and ij &$; these interaction coefficients have experimental values of -9100 and - 9590 cal per g-atom, respectively. Certain solution models are shown to be inadequate for prediction of solute interaction coefficients in dilute Ag-Cu-Sn alloys. In a previous publication' the results of a thermody-namic study of dilute Ag-Au-Sn alloys were presented. The present work represents the continuation of a program to investigate dilute alloys of the noble metals with tin and in particular is concerned with solute interactions in the Ag-Cu-Sn system. By determination of the magnitude and sign of the various interaction coefficients in dilute alloys it is possible to gain some understanding of the different types of solute-solute and so lute-solvent bonding changes that occur as the solute concentrations are varied. Hence systematic studies of alloys with similar physical characteristics as regards size, structure, electronegativity, and so forth, of their components can contribute a great deal to present theoretical knowledge of solutions. The recent definition of an enthalpy interaction coefficient, 11, by Lupis and Elliott2 is of particular value in calorimetric studies such as the present one: where j and i are solutes and s is the solvent; Si is the relative partial molar enthalpy of component i and x represents the mole fraction of solute or solvent. Values of ?Hi can be obtained directly by solution calorimetry and data for n are thus easily determined, often with a high degree of accuracy. ?Hi is related to the relative partial molar enthalpy at infinite dilution, ?Hi and to the enthalpy interaction coefficients by the expression: ?Hi?Hi + X;nz+ ... [2] The aim of the present work was to determine the self-interaction coefficients n AgAgand 178: in alloys of different compositions and also to establish values for n Agcg| and ncuAg. Since it is a thermodynamic requirement (resulting from the Maxwell-type relationships which can be applied to partial molar properties) that nAgcu and ncuAg should be equal, a further aim of this study was to demonstrate the agreement between experiment and theory. EXPERIMENTAL A description of the liquid metal-solution calorimeter used in this research has already been published,3 and no further details of its construction and operation will therefore be given here. Copper supplied by the American Smelting and Refining Co. was indicated by them as being 99.999 pct pure, and the silver obtained from A. D. Mackay, Inc., was also quoted as being 99.999 pct pure. A solvent bath consisting of between 70 and 80 g of 99.99 pct pure Sn was used for each series of experimental drops. Its weight was accurately determined and the appropriate amounts of copper or silver were added to give alloys of the desired composition. Approximately 0.00125 g-atom additions were used for determinations of the heat of solution of silver in the bath, while, for copper, specimens consisting of approximately 0.0015 g-atom were used. The heat capacity of the bath was determined at regular intervals during a series of drops using tin or tungsten calibration samples. The heats of solution of silver and copper in pure tin were first determined as a function of their concentration in order to establish the self-interaction coefficients 7AgAg and ncucu Alloys containing a constant 0.01, 0.02, 0.03, and 0.04 mole fraction of copper were then used to study 17:: in alloys of different copper content, while alloys of the same mole fractions of silver were used to determine equivalent data for 178: at constant silver concentrations. The composition of the bath was held at the desired copper or silver concentration by making calculated additions of the appropriate solute throughout the experiment. From the limiting values of ?HAg in the constant copper content alloys it was possible to study ?HAg as a function of xCu and hence to determine 42:. A similar analysis of the re, values permitted calculation of nAgcu. Heat content and heat capacity data from Hultgren et al* were used to calculate heat of solution values from the measured heat effects at the experimental temperature of 720°K. RESULTS AND DISCUSSION Determinations of ?HAg. A preliminary investigation of the heat of solution of silver in pure tin at 720°K was first made in order to establish the value of nAgAg before additions of copper were made and also to compare the value of ?HOAg(l) with that obtained in the previous study of Ag-Au-Sn alloys.' Then the heat of solution of silver in Cu-Sn alloys was investigated as a func-

Jan 1, 1970

By N. H. Fisher

Geographical Distribution 'he most important known deposits in Australia of what are commonly referred to as the beach-sand minerals are along the most easterly part of the Australian coast, between Southport, 17 miles north of the Queensland-New South Wales border, and Ballina, 50 miles south of the border, and most of the production has come from this area (Fig I). Smaller deposits are known to occur farther to the south at intervals for several hundred miles, and beaches have been worked at Yamba, 96 miles south and Woolgoolga, 150 miles south of the border and at Swansea, 60 miles north of Sydney. Important deposits have been shown to exist on north Stradbroke Island and others have been located farther to the north, as far as Tin Can Bay at the south end of Frazer Island. (Fig 2). Table I gives the list of operators with the location of their deposits and workings, their approximate maximum monthly capacity expressed in tons of heavy mineral produced by their concentrating plants before separation into individual mineral concentrates, their methods of mining and concentrating the minerals, and the products obtained. This table applies as of June 1948, but all the operators are remodeling or improving their plants and plant practices will be modified accordingly. In addition, active boring campaigns have been carried out by Alluvial Gold, Ltd., of Sydney, in the Cudgen-Cudgera area, and by Zinc Corporation Ltd., of Melbourne, on Stradbroke Island, and in other places. Physiography Submergence of the order of 100 to 200 ft at the close of the Pleistocene period left the pre-existing hills as promontories and the valleys as deep inlets. Wave action has built bay-bars and sandspits in a northerly direction from the headlands, and lakes and marshes have formed between these bars and the initial post-submergence coast line. These lakes and swamps have been or are being filled in by river-borne sediments or wind-blown sand. Beasley1 has presented evidence that suggests a recent emergence of the coast line of about 10 ft. The evidence for this belief is the presence of a black sand seam 1/3 mile inland and 17 ft above sea level (Fig 3), and although it is not entirely certain that this seam is of beach formation and owes nothing to windblown concentration, other evidence supports the suggestion of recent emergence. Such emergence would undoubtedly aid the formation of bars and sandspits and the easterly progress of the beach front, leaving a series of parallel dunes (Fig 4). This belt of north-south coastal dunes ranges up to 56 mile in width and as many as 15 lines of dune have been counted (Fig 3). The foredune is generally the highest, upto 25 ft high, and there is in many places a flat platform in front of the dune known as the berm. The dunes behind the foredune are lower and less well defined

Jan 1, 1949

By J. Husson, R. Iffly, M. Gondouin

A systematic variation of well deliverability, as reflected from isochronal back-pressure tests performed at regular intervals, has been observed in some gas condensate wells producing at high rates. The same effects have been obtained using a numerical model of gas and condensate flow which takes into account secondary gasoline deposited in the pore space as a result of pressure reduction, and non - Darcy flow of gas in the vicinity of the wells. Matching calculated values with previous test results has been possible, and future predictions have been obtained. An application of this method to the Hassi Er R'Mel gas-condensate field in Algeria is tentatively shown. INTRODUCTION Flow capacity of gas wells is generally derived from an analysis of back-pressure tests. The empirical equation q = C (?p2)n used by Rawlins and Schellhardtl can be derived rigorously assuming that steady-state radial flow of a dry gas of constant viscosity and compressibility is established during each flow period of the well tests. Furthermore, when Darcy's law applies in the entire flow region, the theory predicts that the exponent n is equal to 1. In low-permeability reservoirs, it was soon discovered that the time required to reach a stabilized flow often exceeded the duration of the flow periods normally available for testing wells. Consequently, transient gas flow had to be considered instead of the steady-state assumption previously used. This led to the isochronal testing procedure established by Cullender2 which has largely replaced conventional back-pressure testing. For dry gas fields, this method yields definite values of C and n equivalent to those of the empirical equation. These values should remain constant for each well as long as the permeability of the formation and the characteristics of the gas (viscosity and compressibility) do not change appreciably. This is the case when reservoir pressure remains -close to the original value and when the formation near the wellbore remains free of plugging. Under those conditions, stabilized flow potential curves of gas wells can be established from a single sequence of isochronal flow and shut-in periods. An analysis of a pressure build-up following a longer production period provides additional data on the transmissivity (k h/ u) of the reservoir, and eventually on the 'drainage radius rd of the well, which can be related to the value of C so that future performance of the well can be predicted using the concepts developed by A. Houpeurt.3 At high flow rates, Darcy's law no longer applies in the vicinity of the wellbore, and inertial effects in the high velocity gas flow introduce additional pressure drops. As a consequence, exponent n of the backpressure tests becomes smaller than 1, and a slight curvature of the log-log plot of ?p2 vs q can be predicted when going from very low to high rates of flow (Elenbaas and Katz).5 The effects of variations of viscosity and compressibility with pressure on the radial flow of dry gas in an infinite reservoir were taken into account by Jenkins and Aronofsky.7 Numerical solutions of the transient flow of an ideal gas in finite radial reservoirs were presented by Bruce, Peaceman, Rachford and Rice.8 In the case of gas condensate wells, however, the presence of gasoline in the pore space as soon as reservoir pressure is reduced below the dewpoint pressure further complicates the interpretation of flow tests so that the prediction of stabilized well performance becomes very difficult. Field observation shows that both C and n derived from isochronal tests vary in time, even when reservoir pressure has not changed appreciably. Such a variation cannot be attributed to any change of the gas characteristics, and must result from the effect of a gasoline saturation on the gas flow.

By S. C. Suboleski, C. B. Manula

In a high risk venture such as mining where capital is committed and contracts are signed on a minimum of information, decisions are based primarily on production forecasts derived through consideration of such factors as management-labor relations, mining practice, variations in physical conditions, and the equipment applied. Among these factors, the physical conditions offer the least opportunity for control, and, due to the wide range of mining conditions experienced, little effort has been made to develop objective methods for measuring their effects on mine output. This paper's aim is to demonstrate a method for assessing these relationships that can be applied under a wide range of conditions both in new mines and in working sections where there is a need to determine the impact of proposed operational modifications. Using empirical data from active underground mines, a mathematical model was developed to derive a set of regression equations for predicting production as a function of mining conditions.

Jan 1, 1982

By J. Weertman

The paper of Gifkins and Snowden considers the interesting but difficult problem of determining the stress dependence of secondary (steady-state) creep at low stresses. These authors have concluded that at stresses below 250 psi (2 x 107 dynes per sq cm) the secondary creep rate of lead is proportional to the stress (viscous creep) and is not proportional to the stress raised to about a fifth power. The experimental data considered by them were obtained on tests conducted at room temperature and at 50°C. The lowest stress employed was 50 psi (3.5 X 106 dynes per sq cm). The authors pointed out the main difficulty in determining the stress dependence of creep at low stresses. The creep tests must be run for very long lengths of time. However they made no estimates of when an experimental creep rate determination must be rejected because it does not represent a true steady-state or minimum creep rate. In order to be certain that a creep curve is within the steady-state region, the total creep strain should be of the order of 0.1 to 0.2. For a creep test of a year's duration this requirement implies that a secondary creep rate smaller than about 10-3 per hr cannot be measured reliably. The corresponding creep rate for a 10-year test is 10-6 per hr. The creep rates of the tests that were considered by the authors to prove the existence of viscous creep were of the order of or less than 10-6 per hr. One can conclude reasonably that this data does not prove unambiguously that large strain steady-state creep rate of lead is proportional to the stress in the stress range of 50 to 250 psi (3.5 x 106 to 2 X 107 dynes per sq cm). Another technique can be used to obtain the stress dependence at low stress levels. The creep rate is a very sensitive function of temperature. The creep rate can be increased by very large amounts merely by increasing the temperature. We carried out steady-state creep tests on lead single crystals25 at temperatures up to 320°C. We were able to obtain creep rate data down to stresses as low as 35 psi (2.5 x 10' dynes per sq cm). Our smallest creep rate was 8 x 10-5 per hr. Thus we obtained large strain, steady-state creep rates to even lower stresses than were considered by Gifkins and Snowden. No evidence was seen for viscous creep. The creep rate was proportional to the stress raised to about a 4.5 power down to the lowest stresses. Since there is no reason to believe that changing the temperature should change the stress dependence of steady-state creep, we feel that large strain viscous creep does not occur in the stress range quoted by the authors for lead single crystals or large-grain polycrystalline samples of lead. This conclusion does not imply that viscous creep may nat occur in a lower stress range or in the same stress range for fine grain material or at creep strains very much smaller than 0.1. Support by the U.S. Office of Naval Research is acknowledged. Authors' Reply R. C. Gifkins and K. U. Snowden We thank Dr. Weertman for his discussion and although, as we hope to show, we do not agree with his reservations, we do concur in stressing the importance of ensuring that creep rates are reliably obtained. Dr. Weertman appears to be content to accept n = 1 for low stresses with fine-grained material but not for single crystals. We believe our results show that the former result cannot be accepted without also accepting the latter. We will also show that the probable errors in our minimum creep rates are insufficient to alter our conclusions, that the criterion proposed by Dr. Weertman is arbitrarily restrictive and his alternative experimental approach possibly invalid. 1) A principal result of our Fig. 1(a) is that n = 1 for polycrystalline specimens at room temperature and 50°C for stresses below -250 psi. There was evidence that crystal slip and grain boundary sliding contributed approximately equaily to the overall strain in this low-stress regime. This implies that either a) grain boundary sliding controls slip within the grains or b) both grain boundary sliding and crystal slip independently occur according to mechanisms which give n = 1. Alternative a does not seem acceptable, so we were forced to consider b. This led us to reexamine work on bicrystals by Strutt and Gifkins and plot curves Fig. l(b). Previously Strutt et al. (loc. cit.), had merged these points with others using the Zener-Holloman parameter and thus, we now believe, had been led to overlook the behavior where n = 1. Curves C and D in Fig. l(b) did appear to confirm the hypotheses that n = 1 for crystal slip at these low stresses and the sliding curve F was similarly of the expected form. It was comparatively easy to find a quantitative theory to account for n = 1 for sliding and the similarity of curves C and D to curve F (all obtained from the same set of specimens) led us to feel that the single-crystal curves were valid. 2) We believe the secondary creep rates for both the polycrystalline and single-crystal specimens to be in error by factors c2. In Fig. 6 creep curves for polycrystalline specimens of lead(1) and lead(II) are reproduced as curves a and b, respectively, and curve c is for a single crystal at 100 psi. It is clear that, although the attainment of secondary creep rate takes 2 years for a and 150 days for b, thereafter the curve is linear for periods of 7 and -1 year, respectively. The single crystal has a linear portion commencing after 20 and extending to 90 days. Creep extension was measured directly using a traveling microscope reading to 0.01 mm on gage lengths marked on the specimens; the gage lengths

Jan 1, 1968

By Lee Hillard Meltzer, Ralph E. Davis

INTRODUCTION During the past few years emphasis has been placed upon methods of estimating the future expectancy of gas production from natural gas fields. Before technical methods were applied, the production expectancy over future years was based upon the knowledge of gas well behavior, learned through long experience and embedded in the "know-how" of men long in the gas producing business. It is doubtful that a technical study of future expectancy of a gas field or a group of fields was ever prepared for the preliminary planning of a natural gas pipe line system built prior to about five years ago. The decline in well production capacity was naturally recognized by all familiar with the business since its earliest beginnings more than 75 years ago. In 1953, the Bureau of Mines published Monograph Number 7, "Back-Pressure Data on Natural Gas Wells and Their Application to Production Practices," which gave to the industry the first technical analysis of the decline in production of individual gas wells. This method affords a means of estimating the future production in relation to decline in reservoir pressure. The demand for technical determination of expectancy of future gas productivity from fields or a group of fields led technical men to the application of the knowledge of well behavior to the problems. The decline in a well's ability to produce as pressures declined could be estimated by the use of the curve known as the "back-pressure potential curve" as developed by the Bureau of Mines. A field containing few, or even numerous, wells could be analyzed on the basis of the sum of potentials of all wells. In most studies of this nature, the problem is to estimate the rate of production that can be expected, not only from present wells but also, from wells that will in the future have to be drilled into the reservoir being studied. The "back-pressure potential" method requires that the following data be known or estimated: (1) Proved gas reserves. (2) Current shut-in pressures and rate at which shut-in pressures change with production. (3) Back pressure potential data on wells in the source of supply. (4) Ultimate number of wells which will supply gas, and their potential. (5) Limitations on productivity such as line pressures against which the wells will produce, friction drop in the producing string, and so forth. It is evident that the resulting estimate of gas available in each year for a future of say, 20 years, contains many uncertainties. While the method may have considerable merit for a field that is fully developed, it cannot be completely dependable in fields that are only partially developed. In such cases, some of the data upon which it is based can only be estimated or assumed. In the study of this problem during the past few years, a method has been developed which we believe has great merit, especially when applied to fields subject to substantial future drilling, and when applied to the study of fields which, on the average, appear to have characteristics similar, in general, to the average of the fields used in the development of the "yardstick" outlined herein. From an analysis of the production history of 49 reservoirs which are depleted, or nearly depleted, a curve has been constructed which shows the average performance of the reservoirs during the declining stages of production. When properly applied, this "average performance curve" can be used to determine the stage of depletion at which a reservoir or group of reservoirs will no longer be able to yield a given percentage of the original reserves. "AVAILABILITY" AND "AVAILABILITY STUDIES" The rate at which. a reservoir will yield its gas depends basically upon physical factors, such as the thickness and permeability of the sand, the effect of water drive, if any, and other conditions, and upon economic factors, such as the number of wells drilled. Within the ranges set by the physical conditions, a rate of delivery tends finally to become established. The rate (or range of rates) represents a balance between the interests of the operator, who desires the maximum return from his property and of the pipe line owner, who desires to maintain a firm supply for his market. This balance, which is influenced by the terms of the contract, determines the capacity which will be developed by the operator, and the time and rate at which the decline in production is permitted to occur. Thus the "availability" of gas

Jan 1, 1953

By D. L. Garthwaite, F. M. Stewart, F. K. Krebill

Pressure has been maintained in the Elk Basin Ten-deep reservoir since the initiation of inert gas injection in Sept., 1949. Oil is being produced under conditions favorable for gravity drainage, including high angle of dip, appreciable structural closure, and fairly good per~neability. Results being obtained are high per cent recovery of oil-in-place, sustained field productivity, reduced operating problems, and recovery of plant products. The high recovery has been calculated by alpplication of the gravity drainage theory described in an earlier AIME paper.' It is also confirmed from field performance by comparing nil recovery to date with gas cap spuce voided. GENERAL INFORMATION The Elk Basin field lies in Park County, Wyo., and Carbon County, Mont., approximately 50 miles east of Yellowstone Park. Located at the northern end of the Big Horn Basin. the field is situated on an elongated asymmetrical anticline (Fig. 1). The pressure maintenance project covered by this paper involves the Embar-Tensleep reservoir in this multi-pay field. Discovered in Nov., 1942, it has a proved productive area of over 6,300 acres. It consists of the 210-ft thick Tensleep sandstone of Pennsylvanian Age overlain by 40 ft of Embar dolomite of Permian Age. The two formations apparently are in communication with each other and are produced as a common source of supply. As 98 per cent of the reserves are contained in the Tensleep sandFtone, in this paper the Embar-Tensleep reservoir will he called simply the Tensleep. The reservoir is found at an average depth of 4,900 it, is approximately 7 miles long and 2 miles wide, and has a maximum oil productive closure of 2,330 ft. The strata dip an average of 21" on the west flank and 45" on the east. There are presently 132 Tensleep wells in the field drilled on 40-acre spacing; of these, 17 are shut in because of high gas-oil ratio (GOR) and eight are gas injection wells. Rock characteristics and related information for the pay section follow: Porosity, avg 10.7 per cent Permeability (air) from cores, avg 118 mds Permeability from PI'S 91 mds Connate water, avg 8 per cent Initial pressure (-400 ft) 2,234 psia Pressure April 1954 (-400 ft) 1.327 psia At high structural positions much of the better sandstone has connate water content of only 2 to 5 per cent as indicated by the coring of wells with oil in nearby Tensleep fields. In special imbibition tests, samples readily imbibed oil but repelled water. In tests on crushed samples, the sand grains rapidly settled in oil and carbon tetrachloride but formed a stable unsinking floc in water. This information indicates that the Tensleep sand is preferentially oil wet. The oil produced averages 29' API gravity and has a high sulfur content. Extensive sampling and testing have established the fact that characteristics of reservoir oil in this field vary greatly with structure, see Fig. 2. Additional detail on the variation of oil characteristics with structure at Elk Basin may be found in Reference 2. At original reservoir pressure the oil was undersatu-rated with gas, the bubble point being 1,250 psi at the crest but only 500 psi at the lowest elevation sampled. As noted on Fig. 2, other fluid properties—reservoir volume factor. solution ratio, gravity, viscosity, and hydrogen sulfide content—likewise vary greatly. These variations complicate mathematical analysis, for it is necessary to average these characteristics in order to enter them into reservoir engineering expressions. To further complicate analysis, sand-face pressure also varies greatly because of the increase in fluid head down structure. As an approximation, average properties under initial conditions may be read from Fig. 2 at the -450-ft elevation.

Jan 1, 1956

By H. Hu

Observations were made on the recrystallization of a 70 pct cdd-rolled silicon-iron crystal with an initial orientation of (113) [332]. Its polygonization and recrystallization characteristics were studied. Results indicated that re crystallization tendency of the deformed crystal is much weakened by the polygonization of the matrix. Complete recrystallization in such specimens is achieved by the growth of recrystallized grains of sufficient size and of the right orientations in relation to the matrix. Evidence was also furnished which suggests that the difference in the re-crystallization tendency is a result of the difference in the severity of lattice bending rather than the difference in orientation of the deformation texture. DUNN and Koh1,2 have made an extensive study on the rolling and annealing textures in silicon-iron crystals. Their results indicated that the recrystallization tendency can be widely different in crystals with different orientations. A particularly interesting example of their results was a crystal with an initial orientation of (113) [332], which developed a deformation texture of (001) [110] after 70 pct cold-rolling. Recrystallization in this crystal took long time anneals at high temperatures. Other crystals having different orientations recrystallized very rapidly. Wiener and corcoran3 have observed the retention of the (100) [011] deformation texture in a low-temperature annealed specimen of a commercial silicon-iron alloy, corresponding to areas of light-etching low-angle boundaries in the annealed struc-

Jan 1, 1960

By George Stanley Scott

Many requests for information as to the possibility of washing coals to some predetermined percentage of ash or sulfur have suggested that the producers aim to satisfy some degree of purity set by the user of the fuel, rather than to attain the greatest economic benefit to all concerned. This paper is written to show that the highest economic purity of washed coal can be determined from washability studies of the raw coal, costs of mining and washing coal, and data on the effect of ash and sulfur on the value of the coal for the particular use for which it is intended. Coke fob Blast-fuenace Use For purposes of illustration, we take the case of coal washed for coke to be used in the iron blast furnace. The method outlined can be made general in its application by substituting for the figures used here the actual operating figures for the particular case under consideration. In general, it costs the blast-furnace operation from 8 to 25 c. per ton of pig iron to slag out each 1 per cent. of ash introduced into the blast furnace by the coke. This figure depends on which one per cent. of ash is removed, and decreases with decrease in ash. When blast furnaces and coal mines are considered as a whole, the figure decreases to zero and then becomes negative, on account of low recovery of washed coal. Various figures1 have been given by different investigators. These figures necessarily differ, not only on account of the differences in operating costs but on account of the difference in the respective fuels as well. For the purpose of this paper, which, as explained, is to point out a method of attacking a certain problem, the figures used in the exposition of the method are of secondary importance. It is apparent that no universally applicable figures can be used, because there are none. Each plant has its own coal,2 its own operating cost, and its own conditions.

Jan 1, 1930

By L. L. McDaniel

During the past few years a nuinber of improvements in smelting and power equipment have been made at the Douglas smelter of the Phelps Dodge Corporation at Douglas, Ariz. In the summer of 1935 work was started on the first unit of a new reverberatory waste-heat boiler plant which ultimately was to furnish steam for a modern high-pressure power pIant. A second reverberatory waste-heat boiler unit

Jan 1, 1944

By G. W. P. Rengstorff, L. E. Olds

PREVIOUS research has shown that cast molyb-denum has good ductility at room temperature if the metal is sufficiently pure. In practice, however, it is very difficult to reduce the impurity content of molybdenum to a few parts per million—the maximum content of impurities allowable to obtain reasonable ductility in coarse-grained molybdenum. Also, subsequent fabrication may reintroduce enough impurity to damage ductility greatly, unless extreme precautions are taken to protect the metal during working. The major impurities which embrittle molybdenum are oxygen, nitrogen and, to a lesser degree, carbon. It is reasonable to assume that the harmful effects of such impurities might be neutralized by small amounts of alloying additions. The desired alloying elements would be those which might fonn stable metal oxides or nitrides that would not be harmful to ductility, or thosewhich might increase the tolerance of molybdenum for oxygen and nitro-

Jan 1, 1958

By L. H. Morris, M. Mordecai

The emission of firedamp from the strata surrounding active workings of longwall coal faces normally follows a cyclic pattern associated with the mining operations being carried out on the face. Mining a coal seam disturbs the uniform distribution of overburden weight such that the working is enveloped by a region of high stress, both above and below the seam, advancing with the coal face. There is a decrease in stress as the strata is relaxed following the passage of the face (1). The paper describes experimental results obtained during the initial investigations of a study intended to examine the permeability of samples of coal measure strata under various triaxial stress conditions. Several investigators have studied the effect of stress on the permeability of rock, usually in the field of oil reservoir engineering. Two general lines of approach are evident. One used by among others Fatt and Davies (2), McLatchie et a1 (31, Brace et al (4) and Gunther (5) was to subject a rock sample to hydrostatic pressure. Gas or water would be passed through a sealed core mounted inside a high pressure hydraulic bomb. The second approach, favoured by Wilhelmi and Somerton (6) and also by Gray et a1 (7) was to employ a so-called 'triaxial' state of stress. Here radial confining pressure and axial stress are applied independently. The permeability is measured in the direction of the axial load. With the exception of Gunther who tested coals and Brace et a1 who tested a granite, the rocks used have been sandstones with permeabilities generally appreciably higher than British coal measure rocks.

Jan 1, 1971

By H. R. Banks

Pondering the action of a ball mill employed to carry on comminution from the product of fine crushing to the point where flotation, cyanidation or other concentrating methods are applicable, one wonders where this machine had its origin. When Henry Wadsworth Longfellow reiterated the observation of that older poet Von Logau, and wrote "Tho' the mills of God grind slowly, yet they grind exceeding small," he probably visualized the type of mill that was employed in medieval times for the production of flour, and can therefore not be considered as having gained admittance to the fraternity of millmen, on behalf of either poet. He does, however, make it quite clear that the efficiency of even these Mills of Destiny was low, and to that extent voices a characteristic of fine-grinding equipment that has been the bugbear of all metallurgical engineers. Principle of Ball Mill The principle of the ball mill probably is traceable to the action along the coast line of oceans or lakes, or in the mountain streams. Wave action on rocks and pebbles, close to the shore line, gives the potential energy to the grinding media, which, in their rolling and tossing, break down the sands, and the resultant "pulp" carried out from the shore is classified and settles out in sizes ranging downward to extremely he mesh. Surely, these are the real mills of God. If we allow our minds to dwell on the total tonnage that has been handled in this way, adding to the sands and clays at present in existence those enormous tonnages of metamorphosed sedimentaries we sense the vast quantity of rock that has been so reduced. Is it not likely, therefore, that the answer to the beginnings of pebble milling, and eventually ball milling, came through the perception of this natural mill by one of our engineering forebears? Methods of Grinding The relatively low return of mechanical input to a ball mill, in terms of useful work accomplished, has always intrigued me immensely. The potential energy absorbed by a ball raised to a high point in its path is apparently released with a very small return in useful work. Is the ball mill the most desirable means of he grinding, or is there some other method through which we can recover a reasonable amount of the energy input in terms of useful work? Some years ago, on his retirement, H. W. Hardinge was questioned as to his thoughts on the trend of fine-grinding equipment. As I recall, his prophecy at that time was that the most likely field for improvement in grinding media would be toward a charge of flat disks with some mechanical scheme to cause them to slide over each other. Undoubtedly, Mr. Hardinge went through the usual experience of the muller and bucking board, the customary introduction of the budding millman to his calling. I have often wondered, but have never got beyond the wondering stage, as to the

Jan 1, 1947

By H. R. Banks

Pondering the action of a ball mill employed to carry on comminution from the product of fine crushing to the point where flotation, cyanidation or other concentrating methods are applicable, one wonders where this machine had its origin. When Henry Wadsworth Longfellow reiterated the observation of that older poet Von Logau, and wrote "Tho' the mills of God grind slowly, yet they grind exceeding small," he probably visualized the type of mill that was employed in medieval times for the production of flour, and can therefore not be considered as having gained admittance to the fraternity of millmen, on behalf of either poet. He does, however, make it quite clear that the efficiency of even these Mills of Destiny was low, and to that extent voices a characteristic of fine-grinding equipment that has been the bugbear of all metallurgical engineers. Principle of Ball Mill The principle of the ball mill probably is traceable to the action along the coast line of oceans or lakes, or in the mountain streams. Wave action on rocks and pebbles, close to the shore line, gives the potential energy to the grinding media, which, in their rolling and tossing, break down the sands, and the resultant "pulp" carried out from the shore is classified and settles out in sizes ranging downward to extremely he mesh. Surely, these are the real mills of God. If we allow our minds to dwell on the total tonnage that has been handled in this way, adding to the sands and clays at present in existence those enormous tonnages of metamorphosed sedimentaries we sense the vast quantity of rock that has been so reduced. Is it not likely, therefore, that the answer to the beginnings of pebble milling, and eventually ball milling, came through the perception of this natural mill by one of our engineering forebears? Methods of Grinding The relatively low return of mechanical input to a ball mill, in terms of useful work accomplished, has always intrigued me immensely. The potential energy absorbed by a ball raised to a high point in its path is apparently released with a very small return in useful work. Is the ball mill the most desirable means of he grinding, or is there some other method through which we can recover a reasonable amount of the energy input in terms of useful work? Some years ago, on his retirement, H. W. Hardinge was questioned as to his thoughts on the trend of fine-grinding equipment. As I recall, his prophecy at that time was that the most likely field for improvement in grinding media would be toward a charge of flat disks with some mechanical scheme to cause them to slide over each other. Undoubtedly, Mr. Hardinge went through the usual experience of the muller and bucking board, the customary introduction of the budding millman to his calling. I have often wondered, but have never got beyond the wondering stage, as to the

Jan 1, 1947

By J.W. Halley

The effects of tin on steel have become increasingly important because of the necessity of using poorly detinned scrap, tin cans, and terne plate, in the open hearth. Since a tin can contains about 1.5 per cent tin, it would be possible to have up to 0.75 per cent tin in steel made with a 50 per cent scrap charge. In order to use tin-containing scrap, it is necessary to know the effect of tin on various grades of steel. The following investigation is by no means comprehensive but covers a number of steels in which tin content is important. Published Work A number of investigations of the effects of tin on rolling quality and physical properties have been published. It has been found that tin increases strength and hardness and reduces ductility and notched impact resistance. The decrease' in ductility and notched impact resistance becomes more marked as the carbon decreases. McKimml found no change in Olsen ductility, Kockwell hardness, yield strength, tensile strength or elongation in cold-reduced strip containing up to 0.124 per cent tin. A tin content of 0.1j per cent gave difficulties in rolling and increased the hardness but 0.21 per cent tin showed no change in properties from material containing very little tin. No explanation of this contradiction is offered. Andrew and Peile2 investigated steels containing 0.10 to 0.25 per cent carbon and up to 0.63 per cent tin. They found an increase in tensile strength of from 100 to 200 lb. per sq. in. for each 0.01 per cent tin on normalized samples. The elongation and reduction of area were decreased and the notched impact resistance was reduced markedly. Quenched and drawn samples did not show embrittling if water-quenched from the draw temperature of 1148°F. (620°C.). They could find no evidence of tin under the microscope. Whitely and Braithwaite3 investigated the effect of tin on rail steel containing 0.55 to 0.60 per cent carbon. They found that 0.08 per cent tin caused a marked decrease in elongation, notched impact resistance and the degree of bend. The tensile strength was increased in some tests and not in others. Bolsover and Barraclough4 investigated the effect of tin up to 0. 50 per cent on a 0.35 per cent carbon steel and on several alloy steels with from 0.30 to 0.40 per cent carbon. They found a comparatively uniform decrease in notched impact resistance with increasing tin on quenched and drawn samples. If the samples were quenched from the drawing temperature or reheated to the drawing temperature and quenched, the embrittling was much less severe. Steels containing molybdenum suffered much less embrittlement than other steels. Experimental WoRk Effect of Tin on Low-carbon Rimmed Steel Increasing quantities of tin were added to four ingots of a heat of the following ladle analysis: carbon, 0.08 per cent; manganese, 0.39; phosphorus, 0.009; sulphur, 0.025.

Jan 1, 1943

By J. W. Halley

The effects of tin on steel have become increasingly important because of the necessity of using poorly detinned scrap, tin cans, and terne plate, in the open hearth. Since a tin can contains about 1.5 per cent tin, it would be possible to have up to 0.75 per cent tin in steel made with a 50 per cent scrap charge. In order to use tin-containing scrap, it is necessary to know the effect of tin on various grades of steel. The following investigation is by no means comprehensive but covers a number of steels in which tin content is important. Published Work A number of investigations of the effects of tin on rolling quality and physical properties have been published. It has been found that tin increases strength and hardness and reduces ductility and notched impact resistance. The decrease' in ductility and notched impact resistance becomes more marked as the carbon decreases. McKimml found no change in Olsen ductility, Kockwell hardness, yield strength, tensile strength or elongation in cold-reduced strip containing up to 0.124 per cent tin. A tin content of 0.1j per cent gave difficulties in rolling and increased the hardness but 0.21 per cent tin showed no change in properties from material containing very little tin. No explanation of this contradiction is offered. Andrew and Peile2 investigated steels containing 0.10 to 0.25 per cent carbon and up to 0.63 per cent tin. They found an increase in tensile strength of from 100 to 200 lb. per sq. in. for each 0.01 per cent tin on normalized samples. The elongation and reduction of area were decreased and the notched impact resistance was reduced markedly. Quenched and drawn samples did not show embrittling if water-quenched from the draw temperature of 1148°F. (620°C.). They could find no evidence of tin under the microscope. Whitely and Braithwaite3 investigated the effect of tin on rail steel containing 0.55 to 0.60 per cent carbon. They found that 0.08 per cent tin caused a marked decrease in elongation, notched impact resistance and the degree of bend. The tensile strength was increased in some tests and not in others. Bolsover and Barraclough4 investigated the effect of tin up to 0. 50 per cent on a 0.35 per cent carbon steel and on several alloy steels with from 0.30 to 0.40 per cent carbon. They found a comparatively uniform decrease in notched impact resistance with increasing tin on quenched and drawn samples. If the samples were quenched from the drawing temperature or reheated to the drawing temperature and quenched, the embrittling was much less severe. Steels containing molybdenum suffered much less embrittlement than other steels. Experimental WoRk Effect of Tin on Low-carbon Rimmed Steel Increasing quantities of tin were added to four ingots of a heat of the following ladle analysis: carbon, 0.08 per cent; manganese, 0.39; phosphorus, 0.009; sulphur, 0.025.

Jan 1, 1943

By I. Fatt

Networks of resistors are used as analog computers to obtain relative permeability and resistivity index curves for networks of tubes. These curves have all of the characteristics of those obtained on porous media and, therefore demonstrate the validity of the network of tubes model. INTRODUCTION In paper I' of this series the network model was shown to give information on the structure of porous media that could not be obtained from the bundle of tubes model. The agreement between the capillary pressure characteristics of a network of tubes and those of typical porous media does not prove the validity of the network made. The bundle of tubes model, although it gives less information, also shows this agreement. In this paper the flow properties of a network of tubes are shown to be in agreement with flow properties of porous media. The flow properties of the bundle of tubes model are not in adequate agreement with those of porous media. The dynamic properties of porous media, such as fluid permeability and electrical conductivity, have been found experimentally to be more sensitive functions of structure and pore size distribution than are the static properties such as porosity and capillary pressure characteristics. The network model can, therefore, be best tested by comparing the dynamic properties of a network of tubes with the observed properties of porous media. All static and dynamic properties of a completely valid model must agree with the observed properties. The most commonly measured sensitive dynamic properties are the relative fluid permeability and the relative electrical resistivity. Experimental measurements of these dynamic properties on sandstone, sintered glass, sintered alumina, and soil are reported in the petroleum and soil science literature. These properties were chosen, therefore, for the test of the network model. In the network model, relative permeability is the permeability of the network when some of the tubes are not conducting fluid, relative to the permeability when all tubes are conducting fluid. Similarly, the relative resistivity is the electrical resistivity of the network of tubes when some of the tubes are filled with a nonconductor. relative to the resistivity when all tubes are filled with the electrical conducting fluid. Single Size Tube Network The simplest porous medium is one in which all pores are of the same size. Such media can be approached by packing beds or columns of uniform size particles of sand, glass, or metal. The model of such medium in this study is a network of single size tubes. The network form, the ß factor, is usually not known for real porous media. If the validity of the network model can be established, then the study of the flow properties

Jan 1, 1957

By E. B. Hunt, T. M. Geffen, C. R. Stewart, V. J. Berry

Laboratory data .show that the gas-oil ratio performance of non-uniform porosity limestones produced by solution gas drive is sensitive to producing rate and to fluid properties. Nan-uniform porosity limestones are those for which laboratcry solution and external gas drive tests yield considerably different relative permeability ratio characterislics. The oil recovery performance by solution gas drive depends directly on the number of gas bubbles formed. Laboratory rates of pressure decline, which are 100 to 10,000 times greater than normal field rates. cause the formation of an unusually large number of gas bubbles. This results in abnormally high oil recovery efficiencies. Since it is impractical to reproduce the number of bubbles formed under field conditions, laboratory solution gas drive data on non-uniform porosity limestones are therefore not directly applicable to field operations. However, certain laboratory data can be used to make a conservative estimate of field performance. The concepts presented in this paper indicate the possibility that increased field oil recoveries may he obtained from non-uniform porosity limestones by rap- idly reducing reservoir pressure for a short interval of time. It has yet to be established that significant improvements in oil recovery from such reservoirs can he realized by varying the pressure decline rate within limits possible in the field. However, the possibility that recovery may be increased in this manner warrants further study. INTRODUCTION Limestone reservoir rocks can be divided into two general classes according to the nature of their pore space. One class has a comparatively uniform pore system composed mainly of voids between grains of the rock (intergranular type porosity). The other class, in addition to having intergranular porosity, has a secondary pore system composed of combinations of solution cavities, fractures, etc., and is considered to have non-uniform porosity. It has been shown in a previous publication' that the laboratory measured gas-oil flow behavior of uniform type porosity limestones is essentially the same for a test simulating a field solution gas drive as for one simulating an external gas drive. For non-uniform porosity type limestones a significant difference in gas-oil flow behavior was found. More efficient behavior was

Jan 1, 1955

By C. H. Li, S. H. Bendel, J. A. Sartell

Small additions of Mg to a 62 Cu-38 Ni alloy reduce the oxidation yates drastically between 500° and 850°C. Metallographic examination of the oxide scale disclosed a continuous network, identified by X-ray diffraction as (Ni, Mg)O solid solutions, located along the former alloy grain boundaries. This network acts as a barrier to diffusion. It is thought to result from the segregation of mg to the alloy grain boundaries. Oxidation occurs preferentially in these regions because of the presence of this more active element. To substantiate these ideas, homogenized alloys ulere oxidized. No oxide network was produced and oxidation rates were the same as for the parent 62 Cu-38 Ni alloy. An interesting aspect of the oxidation of the 62 Cu-38 Ni alloy previously described by the present authors, is the relationship between oxidation kinetics and changes in the microstructure of the oxide.' The oxide scale on these alloys consists of two layers: a thin layer of CuO outside a much thicker layer of Cu20 in which particles of NiO are dispersed. In addition, immediately beneath the oxide-metal interface there is an internally oxidized zone in which NiO particles are dispersed in a copper-rich alloy matrix. Experimental observations on the growth of the individual layers under isothermal conditions have led to the conclusion that the rate-determining step in the oxidation of this alloy is the diffusion of anions through the Cu20 layer. It has been found that this diffusion rate is increased by the recrystallization of the outer CuO layer. Willardson and Gorton have reported that the addition of magnesium to the 62 Cu-38 Ni alloy causes a decrease in the oxidation rate.2 The present investigation was undertaken in order to determine the mechanism by which magnesium additions improve the oxidation resistance of the 62 Cu-38 Ni alloy. EXPERIMENTAL PROCEDURE Fifty-gram ingots of Cu-Ni alloys were prepared by vacuum melting materials of 99.999+ pct purity. These ingots were then remelted in a He atmos- phere and magnesium added in the form of a previously prepared and analyzed Cu-Mg master alloy. This procedure was necessitated by the high reactivity of pure magnesium at high temperatures. The proportion of the alloying elements was adjusted so as to obtain alloys with the desired magnesium content while maintaining a Cu-Ni ratio of 62 :38 by weight. (All alloy compositions will be given in weight percent.) Since it was considered desirable to study the oxidation of only single-phase, solid-solution alloys, it was necessary first to determine the approximate limit of solid solubility of magnesium in the 62 Cu-38 Ni alloy. A series of melts with various magnesium contents was made, homogenized by annealing for 48 hr at 975OC, then cooled in the furnace. Metallographic samples were prepared, etched in a potassium dichromate solution and examined at XI500 for the presence of a second phase. The alloys were then chemically analyzed and it was found that the approximate limit of solid solubility of magnesium in the 62 Cu-38 Ni alloy was 1 pct Mg. The ingots containing less than 1 pct Mg (0.19, 0.29, 0.58, and 0.87 pct Mg) were cold-rolled down to thicknesses suitable for oxidation experiments and specimens for gravimetric studies were cut to dimensions of 3.0 by 1.5 by 0.05 cm, specimens for inert marker studies, 0.6 by 0.6 by 0.17 cm. These were heat-treated in a protective atmosphere at a temperature (975" C) well above the oxidation temperatures and furnace-cooled to insure structural stability of the alloy during oxidation. Immediately prior to oxidation, the specimens were chemically cleaned by immersion for 1 min in a solution of 2 parts nitric acid, 1 part acetic

Jan 1, 1961

By Ionel I. Gardescu

In connection with some of the experiments carried out by the writer on the behavior of gas and oil in a sand reservoir,' an interesting phenomenon was observed which may throw some new light on the problem of recovery of oil from a natural reservoir. The experiments are intended to show the effect of the surface area of the occluded gas masses, originally present in a reservoir, on the further evolution of gas from the oil and its consequent effect upon the rate of production of oil. The apparatus used in the experimental work is shown in Fig. 1. It consists primarily of a sand reservoir R and a displacement chamber D, which is used to induce small variations in volume. The reservoir and displacement chamber form a unit, and a lowering of the plunger D is equivalent to increasing the volume occupied by the oil and gas in the reservoir. The reservoir was first filled with dead oil and maintained under pressure until it was ascertained that most of the free gas had gone into solution. The volume of free gas present in the reservoir was computed from the coefficient of compressibility of the fluids by means of the displacement chamber D, reading to 0.005 c.c. and a special gage J reading to 0.02 lb. per sq. in. The oil was saturated with gas under pressure in reservoir S by circulating the oil for a long period of time through the gear pump B. Subsequently, the saturated oil was circulated through the sand reservoir following the circuit S6, B, S6, R4, the sand reservoir R, R1, R², F4, F1, back to reservoir S. In the following experiments the sand reservoir R was filled with gas-saturated oil at a pressure of 415Ib. per sq. in. with no free gas present. This was ascertained by closing off all the outlet valves and determining the coefficient of compressibility of the system by means of the displacement chamber D. Much difficulty was encountered in eliminating all of the free gas masses from the oil reservoir. The dead oil originally present in the

Jan 1, 1932