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By F. I. Stalkup

Vapor-liquid phase equilibrium experiments have been conducted in a static equilibrium cell on mixtures of a light, 45 API stock- tank gravity reservoir fluid and a rich hydrocarbon gas containing approximately 55 mole per cent of intermediate hydrocarbons. Both apressure-vs-composition study of the gas and a simulated reservoir fluid, and a multiple-batch contact simulation of the condensing-gas-drive oil recovery process were performed. In the latter experiments equilibrium gas and liquid compositions were analyzed. Also, conventional, "condensing-gas-drive", long-tube displacement experiments of the reservoir fluid and gases of various richness were performed. The results of these experiments could not be satisfactorily interpreted by the conventional pseudo-ternary-diagram representation of multicom-ponent phase behavior. The results seem to be explained better by considering a bubble-point surface and a dew - point surface joined in a plait-point locus. Portions of the plait-point locus cannot be "seen" directly by the rich hydrocarbon gas because of curvature of the dew-point surface. In such a system, continuous injection of the rich gas over stationary reservoir fluid might form a zone of contiguously miscible compositions from pure rich gas to pure reservoir fluid by: (1) saturating the reservoir fluid with injected gas to the bubble-point surface; (2) creating by mass transfer with fresh injected gas a path of contiguously miscible compositions along the bubble - point surface to the plait-point locus; and (3) creating by mass transfer with additional injected gas a path of gas compositions along the dew-point surface up to the point where direct miscibility results between dew-point fluid and the injected rich gas. INTRODUCTION The use of the pseudo-ternary-phase diagram to illustrate miscible displacement phase behavior has been discussed by several authors.5,7 Such a representation of phase behavior is not rigorous, but the ternary diagram nevertheless gives a qualitative picture of what actually occurs in a miscible displacement process. Fig. 1 is a typical illustration of miscible displacement phase behavior by a ternary diagram. The multicomponent hydrocarbon system is divided into three pseudo-components: a light fraction containing methane and nitrogen, an intermediate fraction containing ethane through hexanes plus carbon dioxide, and a heavy fraction containing heptane and heavier components. A two-phase region is bounded by a dew-point curve and a bubble-point curve, which are joined at the critical point. The concept deduced from such a representation for miscible displacement by a condensing-gas-drive process is as follows: a rich gas G, which lies to the right of the limiting tie line through the critical point C, is injected into the reservoir and contacts reservoir fluid L, saturating the reservoir fluid to give bubble-point fluid L1 and equilibrium dew-point gas GI. Continued injection of rich gas changes the composition of the saturated liquid L1 through a series of liquid compositions lying along the bubble-point curve, until the critical composition C is reached, at which point direct miscibility with the rich gas is achieved. Some equilibrium gas with compositions lying along the dew-point curve from G1 to C is also formed in this process. Thus, continuous injection of rich gas forms a

Jan 1, 1966

By William G. Pariseau, H. Douglas Dahl

Recent subsidence legislation indicates that mining engineers would be welt advised to be able to predict and control surface damage caused by mine subsidence. To date, such an ability is practically nonexistent. Model analysis is suggested as one of the alternative paths available which might yield fruitful results. Similitude requirements developed for a self-loaded body in static or quasi-static equilibrium indicate that complete similitude without centrifuging is an impracticability. However, a pilot experimental study which used a simplifying assumption to correctly model mine subsidence has produced results in qualitative agreement with field observations. The purpose of this paper is to present a discussion of the various approaches that can be taken in the study of mine subsidence phenomena. Particular attention is focused upon the rational selection and use of laboratory models. Broadly interpreted, mine subsidence is the deformation of the rock mass enclosing a mine. Depending upon a number of factors, the movement of the subsiding rock mass may disrupt gas and water lines or other buried utilities, damage surface structures such as buildings and bridges, dislocate streams, roads, and rail lines, aggravate acid mine drainage and fire problems, and generally mar the landscape. It is clearly a problem that no mine manager can safely ignore. It is also a problem that will grow with the general population increase. In the following discussion, a summary review of past and present approaches to subsidence studies is given. The possibilities of duplicating subsidence phenomena in laboratory models are examined, and an analysis of a particular type of model is presented. Some preliminary results obtained from a model of the particular type analyzed are then discussed. REVIEW OF PREVIOUS WORK Historically, subsidence investigations have been empirical studies in the field and laboratory or theoretical analyses of mathematically idealized media. Empirical and theoretical work in the United States has generally lagged behind investigations abroad. In the United States, field studies are mostly pre-World War 11. These are summarized in the Mining Engineer's Handbook. ' Field studies in Europe are more recent and more extensive. Those made in Great Britain are summarized in the Subsidence Engineers Handbook2 and represent observations made at 157 different collieries. Such studies by themselves are of limited usefulness as are all empirical studies. One can never be certain that conditions at one mine will be similar enough to those at another to warrant the drawing of like conclusions. European subsidence formulas rely heavily upon the "angle of draw" and "critical area" concepts. The angle of draw is defined as the angle between a vertical line through the face, and another line extending from the face to the surface at the point where movement is zero. The critical area is defined in relation to the least extraction necessary to produce maximum subsidence. Fig. 1 illustrates the angle of draw and critical area concepts. First and second "limits of influence" are also shown. The angle of draw and associated critical area concept are obviously not well defined, being dependent upon the accuracy of the surface survey. In Great Britain, the angle of draw has increased through the years from about 26 to 35°. In the United States, zero and negative angles of draw have been reported. In the authors' opinion, these purely geometrical concepts represent an oversimplification of subsidence phenomena and their use, in the United States at least, should be discouraged. Empirical observations of laboratory models containing layers of earth, sand, clay, and plaster were made by Fayol (cited by Peele) as early as 1885. An outgrowth of his work was the "dome theory," a verbal description of what is assumed to occur in subsiding rock masses. The dome theory has since fallen into disrepute. Theoretical analyses worthy of the name treat a subsiding rock mass as a deformable body. In these analyses, the actual rock mass is replaced by an idealized material that deforms according to a simple stress-strain relationship. The stress equations of equilibrium expressing the Newtonian laws of mechanical action and the geometry of strain furnish additional equations that must be satisfied. A loading criterion-generally understood, and in some cases stated explicitly-completes the theory.

Jan 1, 1969

By William Y. Holland, Roger M. Cook

In view of the increasingly widespread deterioration of concrete structures as the result of the interaction of the alkalies sodium and potassium released by hydration of portland cement and susceptible rocks and minerals in aggregates, it is believed that a paper summarizing the geographic distribution of these aggregates will be of interest to producers and users of concrete, concrete products, and concrete-making materials. THIS paper reviews the problem of alkali-aggre-gate reaction in concrete and describes the geologic and geographic occurrence and distribution of alkali-reactive sand and gravel in western United States. It includes no discussion of crushed stone or synthetic aggregates. Most deposits of sand and gravel are accumulations of particles of rocks and minerals from a variety of sources, and it is not unusual for at least one or two varieties of the rocks to contain some form of reactive material. Examination by petro-graphic methods of many sands and gravels, as well as manufactured aggregates, has shown that a comparatively high proportion of the deposits does contain, in greater or lesser degree, rocks and minerals known to be deleteriously reactive with the alkalies of cement. Fortunately the amount of reactive materials is commonly less than that necessary to cause deleterious effects in concrete. As investigation of unsound concrete structures progresses, it becomes evident that the alkali-aggre-gate reaction is even more widespread than supposed, Figs. 1 and 2. Even though some parts of the country appear at present to be immune, further investigations will probably show that the effects of alkali-aggregate reaction can be seen in many structures in these areas, although only on a small scale in most of them. Many concrete structures will, of course, have lived their useful life before disintegration from this cause is serious, and in others the alkali-aggregate reaction may never become significant even though the microscopic evidence of reaction is present. The alkali-aggregate reaction first was reported to be a cause of deterioration of concrete in 1940 when Stanton1 described expansion of concrete pavements in California. Similar expansion and deterioration of concrete was recognized during succeeding years in concrete structures located in many parts of the country, but particularly in the western states. A number of concrete laboratories2 became interested in the problem. It was soon determined that only certain combinations of aggregate and cement caused the alkali-aggregate reaction to take place, and moreover that the reaction progresses only in the presence of water. Further research proved that cements containing more than 0.60 pct total alkalies (pct Na,O + 0.658 x pct K2O), when used with aggregates containing appreciable amounts of reactive ingredients, caused the reaction to take place, usually with subsequent deterioration of the concrete. During the last few years this limitation has been adhered to in both government and private construction as the maximum allowable alkali content of cement to be used with aggregates of known alkali reactivity. Because of this limitation, it appears that deleterious reaction either has been reduced or eliminated in many recently built structures in which it probably would otherwise have occurred. Recent tests have shown that the degree of expansion obtained with any particular cement-aggre-gate combination depends not only on the alkali content of the cement but also upon the relation of this alkali content to the amount and degree of reactivity of reactive constituents in the aggregate.' In laboratory mortar bars, opal and cements with alkali content of as low as 0.2 pct (as equivalent of Na2O) have produced deleterious expansion as the result of alkali-aggregate reaction. These experiments demonstrate that aggregates containing even 0.1 pct of opal are deleteriously reactive. It was soon determined that alkali-silica gels were formed by the interaction of the alkalies of the cement and the reactive aggregate, Figs. 3 and 4. Osmotic or swelling pressures produced by the continued hydration of these gels cause expansion of the concrete with resulting cracking, warping, and dislocation. Evidence of the alkali-aggregate reaction can be seen by a petrographic study of the deteriorated concrete. Among the first structures studied by this method was Parker Dam on the Colorado River, California-Arizona. In the concrete from this dam pebbles of rhyolite, andesite, siliceous limestone, and chalcedonic chert were found to be reactive.

Jan 1, 1954

By B. H. Kear, H. G. F. Wilsdorf

After a few percent strain, dislocations in disordered Cu3Au are arranged in groups in ulell-defined slip planes, which contrasts with the more or less random distribution of dislocations in the corresponding ordered alloy. Unusually long and straigkt dislocation segments observed in the ordered alloy are interpreted in terms of cross slip of screw dislocations from their slip planes into cube planes. It is proposed that cross slip, and also dislocation reactions of the Lomer type, play an important role in work hardening of the ordered alloy. ACCORDING to to dislocations in the disordered lattice are only partial dislocations in the corresponding super lattice, so that in the super-lattice dislocations must occur as pairs, with each pair connected by a ribbon of antiphase boundary. Recently, striking confirmation of the theory was obtained by Marcinkowski, Brown, and Fisher3j4 in a study of dislocation configurations in thin foils of the Cu3Au alloy by transmission electron microscopy. In the present investigation, the observations made by these workers have largely been confirmed. Moreover, it has been found that dislocations in the plastically deformed ordered alloys are often unusually long and straight. This paper is mainly concerned with these new observations. A tentative explanation is offered in terms of cross slip of dislocations in the ordered alloys. PREPARATION OF SPECIMENS An alloy close to the stoichiometric composition Cu3Au was prepared by melting together high-purity copper and gold (99.995 pct) under vacuum in a graphite mold. The resulting ingot was rolled down and cut into strips 1 1/2 by 1/8 by 0.005 in. in thickness. All strips were annealed at 900°C for 3 hr and cooled to 500'~. A few of the strips were quenched from ~OO'C, while the remainder were slowly cooled in the temperature range 400" to 150°C at intervals of a few degrees every 24 hr to produce a high degree of order. After this annealing treatment the average grain size of the material was about 0.1 mm. Material in different states of order was obtained by reannealing fully ordered material at temperatures below the critical temperature: followed by quenching. The equilibrium degree of order attained at a particular reannealing temperature was obtained from the paper by Keating and warren.' A simple hand-operated tensile jig was used to give the strips the required amounts of plastic strain. Following straining, a number of specimens were cut from each strip by means of an electrolytic cutting device.= Finally, each specimen was thinned electrolytically using the polishing procedure described by Bakish and Robertson,7 and these thin sections were examined in the Philips EM-100B electron microscope operating at 100 kv. EXPERIMENTAL OBSERVATIONS Antiphase boundaries. The average domain size in the ordered alloys was found by direct observation to be about 0.25 p. Also, it was observed that the grown-in configuration of antiphase boundaries was changed little by plastic deformation, at least up to 6 pct strain. Fig. 1 shows an electron micrograph of a thin foil of partially ordered alloy (S - 0.8) after 3 pct strain. The micrograph shows a few dislocation pairs and a somewhat crystallo-graphic network of antiphase boundaries. The normal to this foil was found by diffraction analysis to be approximately 11121, with principal directions in

Jan 1, 1962

By Raymond D. Sloan

Dropping from third position among the oil-producing states of the nation in 1942, Oklahoma ranked fourth in 1943 with a total output of 121,431,ooo bbl., a decline of 11.9 per cent from the previous year's total of 137,792,000 bbl. Production ranged from a maximum of 346,900 bbl. daily in February to a low of 322,800 bbl. daily in October, and at the close of the year was averaging 330,000 bbl. daily from 52,096 wells, or an average of 6.3 bbl. per well. The state's well, average at the close of 1942 amounted to 6.7 bbl. At the turn of the year, it appeared reasonable to assume that Oklahoma's producing rate would continue its downward trend during 1944 unless reversed by greater than normal discoveries. To Jan. I, 1944, Oklahoma has produced 5,188,466,-ooo bbl. of crude oil. Development and Exploration A total of 1287 wells was drilled in 1943, representing an increase of 77 wells, or 6.4 per cent over the preceding year's total of 1210. Of the wells completed, 587 (45.6 per cent) were oil wells with an average initial production of 319 bbl.; 127 (9.9 per cent) were gas wells with an average initial of 8,639,000 cu. ft.; and 573 (44.5 per cent) were dry. A total of 333 wildcats was drilled (25.9 per cent of all wells), an increase of 13 (4.1 per cent) over the 1942 total of 320. Of the*wildcats drilled, 46 (13.8 per cent) were oil wells with an average initial production of 235 bbl.; 27 (8.1 per cent) were gas wells with an average initial of 8,249,-ooo cu. ft.; and 260 (78.1 per cent) were recorded as failures. Reconditioning of wells throughout the state led to a total recompletion of 230 wells. Of these, 131 were oil wells with a combined initial production of 8360 bbl., 31 were gas wells with a total initial of 211,950,000 cu. ft., and 68 were abandoned. The 46 successful wildcats opened 33 new producing areas, one of which produced from three separate horizons, and led to the development of production in new horizons in 11 old pools. While none of the 1943 discoveries have as yet developed into what might be termed major pools, the West Moore pool, in Cleveland County, and the West Edmond pool, in Oklahoma County, are the two outstanding new areas opened to production. The West Moore pool, sec. 29, 10 N., 3 W., discovered in December 1943, was completed for an initial production of 248 bbl. of oil in 3 hr. through small tubing chokes in the second Wilcox sand from 8787 to 8800 ft. One well was drilling in this area at the close of the year. The West Edmond pool, an April discovery in sec. 32, 14 N 4 W., is producing from the Hunton lime at a depth of approximately 6950 ft., the world's deepest Hunton lime pool. To the end of the year, 15 oil wells had been completed, with no gas wells and no failures. Accumulated production to Jan. I, 1944, amounted to 474,300 bbl. of 41" gravity oil. There were 29 active operations in the field at the end of the year. The West Edmond and West Moore pool discoveries established the first commercial production west of the Granite Ridge,

Jan 1, 1944

By Raymond D. Sloan

Dropping from third position among the oil-producing states of the nation in 1942, Oklahoma ranked fourth in 1943 with a total output of 121,431,ooo bbl., a decline of 11.9 per cent from the previous year's total of 137,792,000 bbl. Production ranged from a maximum of 346,900 bbl. daily in February to a low of 322,800 bbl. daily in October, and at the close of the year was averaging 330,000 bbl. daily from 52,096 wells, or an average of 6.3 bbl. per well. The state's well, average at the close of 1942 amounted to 6.7 bbl. At the turn of the year, it appeared reasonable to assume that Oklahoma's producing rate would continue its downward trend during 1944 unless reversed by greater than normal discoveries. To Jan. I, 1944, Oklahoma has produced 5,188,466,-ooo bbl. of crude oil. Development and Exploration A total of 1287 wells was drilled in 1943, representing an increase of 77 wells, or 6.4 per cent over the preceding year's total of 1210. Of the wells completed, 587 (45.6 per cent) were oil wells with an average initial production of 319 bbl.; 127 (9.9 per cent) were gas wells with an average initial of 8,639,000 cu. ft.; and 573 (44.5 per cent) were dry. A total of 333 wildcats was drilled (25.9 per cent of all wells), an increase of 13 (4.1 per cent) over the 1942 total of 320. Of the*wildcats drilled, 46 (13.8 per cent) were oil wells with an average initial production of 235 bbl.; 27 (8.1 per cent) were gas wells with an average initial of 8,249,-ooo cu. ft.; and 260 (78.1 per cent) were recorded as failures. Reconditioning of wells throughout the state led to a total recompletion of 230 wells. Of these, 131 were oil wells with a combined initial production of 8360 bbl., 31 were gas wells with a total initial of 211,950,000 cu. ft., and 68 were abandoned. The 46 successful wildcats opened 33 new producing areas, one of which produced from three separate horizons, and led to the development of production in new horizons in 11 old pools. While none of the 1943 discoveries have as yet developed into what might be termed major pools, the West Moore pool, in Cleveland County, and the West Edmond pool, in Oklahoma County, are the two outstanding new areas opened to production. The West Moore pool, sec. 29, 10 N., 3 W., discovered in December 1943, was completed for an initial production of 248 bbl. of oil in 3 hr. through small tubing chokes in the second Wilcox sand from 8787 to 8800 ft. One well was drilling in this area at the close of the year. The West Edmond pool, an April discovery in sec. 32, 14 N 4 W., is producing from the Hunton lime at a depth of approximately 6950 ft., the world's deepest Hunton lime pool. To the end of the year, 15 oil wells had been completed, with no gas wells and no failures. Accumulated production to Jan. I, 1944, amounted to 474,300 bbl. of 41" gravity oil. There were 29 active operations in the field at the end of the year. The West Edmond and West Moore pool discoveries established the first commercial production west of the Granite Ridge,

Jan 1, 1944

By C. Bezemer, I. Havenaar

An investigation was carried out on the dynamic liltration behavior of drilling fluids. In a set-up consisting of a porous pipe through which the drilling mud was circulated, dynamic liltration rates and cake thicknesses were determined as a function of flow rate and filtration time. Eventually, a state of equilibrium was reached; i.e., both cake thickness and filtration rate attained constant values. Concurrently, dynamic filtration tests were carried out in a simple dynamic filter apparatus where mud flow was similar to that in a rotational vismmeter. In both arrangements the relation between equilibrium liltration data and rate of shear at the cake surlace was studied. Filter pipe and dynamic filter apparatus were lound to give identical relations. It was therelore concluded that the latter apparatus, which is suitable lor routine measurements on small amounts of mud, could be used to determine the dynamic liltration behavior of mud under borehole flow conditions. Some data are presented on the effect of filtration pressure and temperature on equilibrium filtration rate and cake thickness. INTRODUCTION In oil well drilling, the drilling fluid used generally forms a mud cake on the permeable sections of the borehole wall while filtrate is lost into the formation. As to the conditions under which this filtration process takes place, a distinction should be made between static mud filtration (mud is not circulating) and dynamic mud filtration (mud is circulating). In recent years several investigatorsl-5 have studied the process of dynamic mud filtration about which little had previously been known. This type of filtration is the subject of this paper which confirms several findings of previous investigators. It differs from already published works, however, in the following respects. 1. It contains a description of a simple laboratory apparatus developed for dynamic filtration measurements on small amounts of mud. 2. The effect of rate of shear at the cake surface on dynamic filtration has been studied. As a result of this study, dynamic filtration data pertaining to the borehole conditions of mud flow can be found from laboratory tests. 3. Some data are presented on the effect of filtration pressure and temperature on dynamic filtration. The work was limited to a small number of muds. No attempt was made to compare data on API filtrare loss with dynamic filtration rates. Previous workers have clearly shown that no correlation exists between static and dynamic filtration rates. EXPERIMENTAL ARRANGEMENT To establish whether the effect of mud flow conditions on dynamic filtrations is governed by the rate of shear at the cake surface, two different types of mud flow were used. In this connection the experiments were partially conducted by means of a porous pipe through which mud was circulated, partly in a dynamic filter apparatus which somewhat resembles a rotational viscometer. In both cases the flow conditions of the mud were well defined, thus making it possible to-calculate rates of shear at the cake surface. The filter pipe was 200 cm long with an internal diameter of 3 cm. Its perforated wall was covered on the inside with filter cloth on which the mud cake could form. Mud was pumped through the pipe at linear rates varying from 20 to 186 cm/sec. The required filtration pressure was obtained by means of a lack-pressure valve downstream of the filter pipe. In this arrangement the type of flow existing in the borehole is reasonably well simulated. The dynamic filter apparatus (Figs. I. and 2) consists mainly of two concentric cylinders with a clearance of about 0.5 cm. The outer cylinder (rotor) can be rotated at rates up to 1,000 rpm. The outer surface of the inner cylinder (radius about 2.5 cm) is covered with filter cloth or paper supported by copper gauze. The two cylinders are mounted inside a pressure

Jan 1, 1967

By James Pollock

SUMMARY THE possibility of colloidal deposition of cinnabar has been neglected. In opalite deposits cinnabar exists in particles within or near the colloidal size range. Colloidal processes have been admitted to be operative in hot springs and low-temperature deposits similar to most cinnabar deposits. Mercuric sulphide sols are stable to elevated temperature and pressure, and in nature probably are chiefly affected by the electrolytes in solution, dilution of colloid, and presence of protective colloids as silica. The stability of mercuric sulphide sols to electrolyte is measured, and shown to be greatly increased by dilution and by the protective action of silica. Mercuric sulphide sols follow the Schulze-Hardy valency rule, therefore the precipitating power of complex mixtures of electrolytes can be computed roughly. The stability of mercuric sulphide sols is shown to be greater than the equivalent precipitating power of the electrolytes in a hot spring depositing mercuric sulphide. It is concluded that finely divided or earthy types of cinnabar are colloidally deposited. POSSIBILITY OF COLLODIAL DEPOSITION While colloidal solution has been suggested as a means of transport for a number of minerals, such as the sulphides of antimony, arsenic, and iron, it has been neglected in connection with mercury. This is surprising because there exists positive evidence that cinnabar is present in certain deposits in particles of colloidal or near colloidal size. Colloidal transport could result from either the rapid dilution or neutralization of alkaline sulphide solution bearing mercury coming in contact with deep ground waters, or from colloidal solution near the original source and subsequent flow to the point of deposition unchanged. That the dilution of a mercuric alkaline sulphide solution will precipitate mercury sulphide in colloidal form has been demonstrated a number of times and is easily confirmed. The dilution hydrolyzes the alkaline sulphide Na2S to the corresponding hydroxide and hydrosulphide NaOH and NaHS, and the diminution of the concentration of alkaline sulphide reduces the solubility. It is not the contention of this writer that colloidal deposition is the mode of transport of mercuric sulphide in all mercury deposits, but that the stability of a mercuric sulphide sol, as demonstrated below, in waters that are similar to those that have deposited mercuric sulphide necessitates consideration of this possibility in many deposits, especially those of the hot-spring and so-called opalite type. EVIDENCE OF COLLOIDAL DEPOSITION Ross1 has shown that most deposits of quicksilver are formed at low temperatures and pressures, and probably by solutions that have relatively simple chemical compositions. In most cases the solutions are probably similar to those observed in hot springs, and in two instances-at Steamboat Springs, Nevada, and Sulphur Bank, California-hot springs have been reported by Becker as actually depositing cinnabar.2 Opalite deposits were believed by early investigators to be surface phenomena

Jan 1, 1944

By H. H. Hasler

THE mining and removal of coal from two or more beds, either simultaneously or consecutively, in vertically adjacent areas have always been matters of concern to mine operators from both operating and recovery points of view. However, with the progressive introduction and use of electrical and mechanical facilities, such problems assume even greater proportions. In this paper typical cases occuring in Cambia County, Pa., are given and procedures whereby such problems may be .greatly reduced, if not entirely eliminated, are suggested. Throughout a considerable portion of the Central Pennsylvania bituminous coal region, particularly in Cambria County (Fig. I), the portion of the region to which references in this paper are made, large areas are encountered where two or more beds of coal occur and have been mined extensively since the earliest days of mining in the county. Generally, operations were commenced in one bed of coal on a property, following which, as conditions appeared to warrant, operations were commenced in another bed or beds on the same property, in some instances by the same operator. Operating results by no means have been uniformly successful, as the following review of some typical cases indicates, partly because of lack of experience in earlier cases and in certain later cases to disregard for the experiences of earlier operators. It is suggested that repetitions of such failures may be reduced largely, if not eliminated entirely, by adherence to a few basic principles founded upon past experiences. Geology and Stratigraphy The geology, stratigraphy, and relief of almost all of Cambria County have been studied and reported at length by the U. S. Geological Survey in its Johnstown, Ebensburg and Barnesboro-Patton Folios and other publications, by the Pennsylvania Geological Survey and by various individuals. All exposed rocks occurring within the boundaries of the county are of sedimentary origin, consisting of alternate beds of sandstone, slate, shale, fireclay, coal, limestone, etc., and all have been classified by the U. S. Geological Survey as extending from the upper strata of the Catskill formation, Devonian system, to and including, in a few hilltop areas, the lower strata of the Monongahela formation, Carboniferous system. Included within that range is the Allegheny formation, Pennsylvania series, which embraces all of the commercially important beds of coal that occur in the county, viz., the A, or Brookville, to the E, or Upper Freeport, both inclusive, shown in Fig. 2. The measures are traversed by a series of anticlines and synclines, extending in a northeasterly and southwesterly direction, which form broad, gently sloping basins (flat to 15 pct pitch, exceptionally to 25 pct). However, the topography of the surface is such that long lines of outcrops of all beds of coal overlying bed B, and to a limited extent bed B also, occur over large areas, a factor which contributed to the early and extensive development of mining activities in the county. Earliest mining developments of commercial importance were made in B, C', D, and E beds of coal, and it is in these beds that the principal mining operations are being conducted. To a limited extent, mining operations also have been conducted in local areas in the A, B rider and C beds. Coal beds being mined today range in thickness from approximately 28 to 60 in. Intervals between the respective beds of coal are variable but conform somewhat to the following general averages: A to B, 60 to 100 ft.; B to C, 50 ft.; C to C', 70 ft.; C' to D, 45 ft.; and D to E, 45 ft. The following are typical mining cases obserced over a period of years in various parts of the county.

Jan 1, 1952

By James Pollock

The possibility of colloidal deposition of cinnabar has been neglected. In opalite deposits cinnabar exists in particles within or near the colloidal size range. Colloidal processes have been admitted to be operative in hot springs and low-temperature deposits similar to most cinnabar deposits. Mercuric sulphide sols are stable to elevated temperature and pressure, and in nature probably are chiefly affected by the electrolytes in solution, dilution of colloid, and presence of protective colloids as silica. The stability of mercuric sulphide sols to electrolyte is measured, and shown to be greatly increased by dilution and by the protective action of silica. Mercuric sulphide sols follow the Schulze-Hardy valency rule, therefore the precipitating power of complex mixtures of electrolytes can be computed roughly. The stability of mercuric sulphide sols is shown to be greater than the equivalent precipitating power of the electrolytes in a hot spring depositing mercuric sulphide. It is concluded that finely divided or earthy types of cinnabar are colloidally deposited. Possibility of Collodial Deposition While colloidal solution has been suggested as a means of transport for a number of minerals, such as the sulphides of antimony, arsenic, and iron, it has been neglected in connection with mercury. This is surprising because there exists positive evidence that cinnabar is present in certain deposits in particles of colloidal or near colloidal size. Colloidal transport could result from either the rapid dilution or neutralization of alkaline sulphide solution bearing mercury coming in contact with deep ground waters, or from colloidal solution near the original source and subsequent flow to the point of deposition unchanged. That the dilution of a mercuric alkaline sulphide solution will precipitate mercury sulphide in colloidal form has been demonstrated a number of times and is easily confirmed. The dilution hydrolyzes the alkaline sulphide Na2S to the corresponding hydroxide and hydrosulphide NaOH and NaHS, and the diminution of the concentration of alkaline sulphide reduces the solubility. It is not the contention of this writer that colloidal deposition is the mode of transport of mercuric sulphide in all mercury deposits, but that the stability of a mercuric sulphide sol, as demonstrated below, in waters that are similar to those that have deposited mercuric sulphide necessitates consideration of this possibility in many deposits, especially those of the hot-spring and so-called opalite type. Evidence of Colloidal Deposition Ross1 has shown that most deposits of quicksilver are formed at low temperatures and pressures, and probably by solutions that have relatively simple chemical compositions. In most cases the solutions are probably similar to those observed in hot springs, and in two instances—at Steamboat Springs, Nevada, and Sulphur Bank, California—hot springs have been reported by Becker as actually depositing cinnabar.2 Opalite deposits were believed by early investigators to be surface phenomena

Jan 1, 1949

By James Pollock

The possibility of colloidal deposition of cinnabar has been neglected. In opalite deposits cinnabar exists in particles within or near the colloidal size range. Colloidal processes have been admitted to be operative in hot springs and low-temperature deposits similar to most cinnabar deposits. Mercuric sulphide sols are stable to elevated temperature and pressure, and in nature probably are chiefly affected by the electrolytes in solution, dilution of colloid, and presence of protective colloids as silica. The stability of mercuric sulphide sols to electrolyte is measured, and shown to be greatly increased by dilution and by the protective action of silica. Mercuric sulphide sols follow the Schulze-Hardy valency rule, therefore the precipitating power of complex mixtures of electrolytes can be computed roughly. The stability of mercuric sulphide sols is shown to be greater than the equivalent precipitating power of the electrolytes in a hot spring depositing mercuric sulphide. It is concluded that finely divided or earthy types of cinnabar are colloidally deposited. Possibility of Collodial Deposition While colloidal solution has been suggested as a means of transport for a number of minerals, such as the sulphides of antimony, arsenic, and iron, it has been neglected in connection with mercury. This is surprising because there exists positive evidence that cinnabar is present in certain deposits in particles of colloidal or near colloidal size. Colloidal transport could result from either the rapid dilution or neutralization of alkaline sulphide solution bearing mercury coming in contact with deep ground waters, or from colloidal solution near the original source and subsequent flow to the point of deposition unchanged. That the dilution of a mercuric alkaline sulphide solution will precipitate mercury sulphide in colloidal form has been demonstrated a number of times and is easily confirmed. The dilution hydrolyzes the alkaline sulphide Na2S to the corresponding hydroxide and hydrosulphide NaOH and NaHS, and the diminution of the concentration of alkaline sulphide reduces the solubility. It is not the contention of this writer that colloidal deposition is the mode of transport of mercuric sulphide in all mercury deposits, but that the stability of a mercuric sulphide sol, as demonstrated below, in waters that are similar to those that have deposited mercuric sulphide necessitates consideration of this possibility in many deposits, especially those of the hot-spring and so-called opalite type. Evidence of Colloidal Deposition Ross1 has shown that most deposits of quicksilver are formed at low temperatures and pressures, and probably by solutions that have relatively simple chemical compositions. In most cases the solutions are probably similar to those observed in hot springs, and in two instances—at Steamboat Springs, Nevada, and Sulphur Bank, California—hot springs have been reported by Becker as actually depositing cinnabar.2 Opalite deposits were believed by early investigators to be surface phenomena

Jan 1, 1949

By D. F. Kaufman, V. V. Damiano, G. J. London, L. R. Aronin

Beryllium bicrystals were Prepared by a seeding and floating zone-melting technique from high-purity beryllium single-crystal material. The starting material was given six floating zone purification passes prior to producing the bicrystals. Symmetric, asymmetric, and antisymmetric bicrystals were tested in tension. Included were bicrystals with boundaries both parallel and perpendicular to the tension axis. Modified symmetric bicrystals were also examined in detail. In these cases, the angles made by the slip planes with the boundary were not equal. Failure by (0001) cleavage, (1180) cleavage, and boundary separation were all observed depending on the orientation of these cleavage planes and the boundary with respect to the tension axis. Failure occurred on whichever system experienced the greatest normal stress. The origin of the fractures observed and the operative dislocation mechanisms were investigated by frac-tography and transmission electron microscopy. The results indicate that low-angle boundaries form in close proximity to the bicrystal boundary and act as sites for crack nucleation. It has been concluded that, although macroscopic compatibility was satisfied in many of the bicrystals examined, the bicrysta1 boundary was effective in Producing "early" failure by local bend plane formation as plastic deformation proceeded, followed by cleavage initiation and crack propagation. SINGLE crystals of high-purity beryllium oriented with the basal plane inclined 45 deg to the tension axis exhibit a critical resolved shear stress of about 300 psi and 200 pct extension by slipping only on the basal plane before failure by cleavage on that plane. Single crystals, oriented with the basal plane parallel to the tension axis, deform by prism slip at a critical resolved shear stress of 9000 psi and exhibit an extension of over 100 pct before failure in a ductile manner.' In contrast to the behavior of single crystals, poly-crystalline beryllium deformed in tension or bending exhibits little or no ductility at room temperature. Beryllium's lack of ductility at room temperature has been attributed to its lack of a sufficient number of independent slip systems. Beryllium has only four independent slip modes at room temperature and according to the Taylor2 and von Mises3 criteria at least five independent shear modes are necessary to completely satisfy the strain compatibility conditions at all the boundaries in a random polycrystalline sample. Studies of beryllium bicrystals thus appear to provide a convenient way in which to determine whether the condition of strain compatibility is a necessary and sufficient condition to prevent failure and whether obviously incompatible boundary conditions result in boundary separation. Bicrystal studies, although not providing all of the constraints encountered in polycrystalline samples, do allow one to select very specific orientation relation-

Jan 1, 1969

By C. R. Johnson, R. A. Greenkorn, R. E. Haring

Three confined five-spot miscible displacements at unity, favorable, and unfavorable mobility ratios were conducted in a shallow, water-saturated sandstone of Pennsylvan-ian age near Chandler, Okla. These studies, plus associated laboratory experiments, were designed to measure miscible displacement performance in a controlled natural system, using known scaling criteria to develop an approach to modeling the heterogeneous field system. We have concluded from these studies that: (I) displacement efficiency in the field is a pronounced function of mobility ratio, indicating that miscible fingering observed in simple laboratory models occurs in the field: (2) field displacements can be quantitatively predicted by scaled laboratory models if the degree and location of field permeability variations are preserved in the models: and (3) arbitrary simplifications of heterogeneity will not necessarily predict observed displacement efficiency, and the simpler the model, the more optimistic the prediction. INTRODUCTION Many processes to achieve miscible displacement of reservoir oil by injected fluids have been conceived and field tested by the oil industry. Among the better known are high-pressure gas, enriched gas, and LPG banks. The simplest form of miscible displacement—one fluid miscibly displacing another fluid of different viscosity but the same density—has been studied extensively in homogeneous laboratory models. Observations of unstable fingering have been made which explain the significant decrease in displacement efficiency as the mobility ratio (ratio of displacing fluid mobility to displaced fluid mobility) increases. General industry experience with field tests of miscible displacement projects, mostly LPG banks, has been premature solvent breakthrough and lower than predicted production rate increases. These results have been attributed to either unstable fingering, unusual or unexpected permeability stratification, or both. Miscible displacement data in a controlled natural system have never been reported, however. Also, it has not been shown that properly designed and constructed laboratory models quantitatively predict field-scale behavior. The purpose of the combined field and laboratory ex- periments reported in this paper is twofold. The first was to measure miscible displacement performance at different mobility ratios in natural rock approaching field size under precise, controlled conditions. The second purpose was to utilize known scaling criteria plus several approaches to heterogeneity to model the field. Comparison of model and actual field results should then determine whether or not the laboratory phenomena (manifested by miscible displacement efficiency) are exhibited in large, natural rock systems. We carried out our program by first locating a shallow, water-saturated reservoir whose rock properties were representative of oil-bearing reservoirs. Detailed reservoir description by core analysis and interference testing showed the field site to be heterogeneous. A sequence of controlled, aqueous-phase miscible displacements was conducted at unity, favorable and unfavorable mobility ratios. A central, confined pattern was used to obtain the displacement data. A laboratory program using sand-packed models was conducted to determine the modeling criteria necessary to simulate field behavior of miscible displacement in a heterogeneous system. SCALING THEORY The detailed derivations and descriptions of the scaling laws that apply to laboratory models of reservoirs are adequately described elsewhere, so the following discussion will be restricted to facets of importance in this study. For a displacement in which one liquid miscibly displaces another, the following dimensionless groups are required to have the same numerical value in the model as in the field: The model also must be geometrically similar to the field, be spatially oriented the same as the field (same dip angle), and have the same initial and boundary conditions as the field (same initial fluid saturations and same injection-production well arrangement). When these conditions are satisfied, the theory predicts that at dny dimensionless time (pore volumes of produced fluids) the dimen-sionless flow potential and dimensionless fluid concentrations will be identical at all dimensionless spatial locations within the model and the field. If this prediction is correct, then the local dimensionless velocities must be identical, thus the instantaneous fraction of displaced fluid produced and the cumulative recovery expressed as fraction of original fluids in place must be identical at all dimensionless times. The theory outlined above has been obtained by either dimensional analysis or inspectional analysis of differential

Jan 1, 1966

Harry HaRkness Stoek, whose sudden death on March 1,1923, was a great shock to his friends in all park of the country, was a man of remarkable personal characteristics and mental ability. Through an acquaintance with him of nearly 35 years, during 12 yeam of which I was intimately associated with him both in business and socially, I learned to appreciate his many high qualities, his strict adherence to high professional and social ideals, and his lovable traits of character. In this appreciation I was joined by every one who was thrown in close personal contact with him. He was a conscientious student, not given to hasty judgments, but when he formed an opinion he was positive in upholding it. At the same time, he was most courteous and kindly in combatting that which he believed was erroneous. In fact, I never knew a person of his attainments more modest, forceful and kindly, or one who had a keener sense of clean humor. In his private life,he was a devoted husband and father, a consistent communicant and worker in the Episcopal Church, and was charitable in all things. In fact, his whole life was marked by helpfulness to others and a determined and successful effort to "make the world better by his having lived in it." Doctor Stoek was born in Washington, D. C., Jan. 16, 1866. His early education was obtained in the public schools of that city and he graduated from the Central High School in the first class to graduate from a high school in Washington. He entered Lehigh University in 1883, graduated in 1887 with the degree of Bachelor of Science, and after a year of post-graduate study in mining and metallurgy he received the degree of Engineer of Mines. During the summer vacation in 1885, he served as an assistant in the Department of Mineralogy in the National Museum at Washington, and during the summer of 1887 acted as U. S. Government inspector of dredging on the Tharnes River, Connecticut. From June, 1888, to January, 1900, he was assistant engineer for the Susquehanna Coal Co., at Wilkes-Barre, Pa. From January, 1890, to June, 1893, he was Instructor in Mining, Metallurgy and Geology at Lehigh University, and had charge of all courses in mining and metdlurgical design, and the visits of students to mines and metallurgical

Jan 1, 1923

Harry HaRkness Stoek, whose sudden death on March 1,1923, was a great shock to his friends in all park of the country, was a man of remarkable personal characteristics and mental ability. Through an acquaintance with him of nearly 35 years, during 12 yeam of which I was intimately associated with him both in business and socially, I learned to appreciate his many high qualities, his strict adherence to high professional and social ideals, and his lovable traits of character. In this appreciation I was joined by every one who was thrown in close personal contact with him. He was a conscientious student, not given to hasty judgments, but when he formed an opinion he was positive in upholding it. At the same time, he was most courteous and kindly in combatting that which he believed was erroneous. In fact, I never knew a person of his attainments more modest, forceful and kindly, or one who had a keener sense of clean humor. In his private life,he was a devoted husband and father, a consistent communicant and worker in the Episcopal Church, and was charitable in all things. In fact, his whole life was marked by helpfulness to others and a determined and successful effort to "make the world better by his having lived in it." Doctor Stoek was born in Washington, D. C., Jan. 16, 1866. His early education was obtained in the public schools of that city and he graduated from the Central High School in the first class to graduate from a high school in Washington. He entered Lehigh University in 1883, graduated in 1887 with the degree of Bachelor of Science, and after a year of post-graduate study in mining and metallurgy he received the degree of Engineer of Mines. During the summer vacation in 1885, he served as an assistant in the Department of Mineralogy in the National Museum at Washington, and during the summer of 1887 acted as U. S. Government inspector of dredging on the Tharnes River, Connecticut. From June, 1888, to January, 1900, he was assistant engineer for the Susquehanna Coal Co., at Wilkes-Barre, Pa. From January, 1890, to June, 1893, he was Instructor in Mining, Metallurgy and Geology at Lehigh University, and had charge of all courses in mining and metdlurgical design, and the visits of students to mines and metallurgical

Jan 1, 1923

By A. M. Gaudin

IT is only in recent years that substantial progress has been made in developing a physico-chemical picture of the solid state. The molecular concept, so useful in dealing with gases, was naturally carried over to the field of crystalline solids; it has resulted in the firm implanting of erroneous concepts that only now are being eradicated successfully. Two simply written and effective books on the subject are Crystal Chemistry by Stillwell1 and An Introduction to Crystal Chemistry by Evans.' A more complete treatment of the subject is available in a book by Wells.' The monograph by Hückel4 also touches on a subject most easily perceived by reference to the brief introduction by Bragg,5 that master of the field. These texts make it clear that while some solids are built of molecules, many are built of ions, others of atoms connected in the form of giant molecules, and still others of cations and electrons. The various lattices in which these entities are systematically arranged, the joint use of several of these entities, and the transitional character of some of the bonds make for the great variety of crystalline solids. The purpose of this paper is to point out a most important corollary of present views on the structure of solids. In this connection the classification of solids in Table I is helpful. Atomic crystals are those formed by the noble gases, e.g., helium and argon. They are soft, sublime at very low temperature, of very low specific gravities, and not encountered in ores. Molecular crystals are uncommon among inorganic materials, common among organic materials. Typical examples from both inorganic and organic fields are sulphur, iodine, naphthalene, benzene, and carbon tetrachloride. These crystals are soft and have low specific gravities; where the molecules are small, the sublimation temperature is low. Filament and sheet crystals are rare. They are typified by elemental selenium and elemental arsenic, respectively. Graphite and molybdenite come near being sheet crystals. These crystals are soft in some directions, tough in others, sublime at various temperatures. Diamantine crystals, typified by diamond, are very few in number, stable at high temperatures, and extremely hard. Ionic crystals are common. Most salts, acids, and alkalies belong in the two classes of ionic crystals; examples are rock salt, fluorite, calcite, and angle-site. The salts, acids, and alkalies that do not belong in these classes are more properly regarded as transitional between ionic crystals, framework crystals, and diamantine crystals, e.g., ice and quartz. Fiber crystals are relatively uncommon mineral-ogically speaking, but common in the fields of living processes. Examples are asbestos, silk, cellulose, and wool. Many fiber crystals are so little known even now that their crystallinity may be doubted. Layer crystals, among the more interesting and useful of solids, include a wide variety of substances

Jan 1, 1956

By I. H. Silberberg, R. L. Reed, O. K. Kimbler

interfacial films have frequently been observed at interfaces between certain crude oils and water. Several investigators have postulated that the presence of these films should influence the efficiency of oil recovery in water drive or waterflood operations. They may also influence the stability of emulsions which are sometimes a problem in petroleum production, and may be a factor in the fonation of paraffin deposits in oil well tubing and flow lines. This paper presents a technique with which a modified Langmuir film balance may be used to study the compressibility and collapse pressure of these natural interfacial films. Experimental data are presented for several nude oil-water systems. Data developed are used to infer the phase state of the film as a function of such variables as rate of reduction of interfacial area, ionic composition of the subtrate and pH of the subtrate. A film of known physical characteristics is shown to have a sinnificant effect on oil recovery from an unconsolidated sand pack. Possible applications of these results to petroleum production are discussed. INTRODUCTION The use of water to displace petroleum from reservoir rocks is of major importance both as a primary and a secondary recovery process. As water invades the rock, oil is completely displaced from some pores and left as a discontinuous phase in other pores. The manner in which water moves from pore to pore is strongly influenced by capillary forces. In view of the complexity of reservoir fluid systems, there can be little doubt that complicated interactions take place at both the liquid-solid and oil-water interfaces. One of the more interesting, and least understood, of the phenomena which take place at the oil-water interface is the formation of interfacial films. These films are believed to result from the adsorption of high molecular weight polar molecules at the interface.l.2 Presence of such molecules may cause a striking alteration in interfacial tension. When the oil-water interfacial area of certain crudes is rapidly reduced, a thin region (film) about the interface assumes the appearance of a solid membrane, and striations, wrinkles and gross distortions may occur. If such a film is solid, it should greatly alter the interfacial tension normally assumed to exist between the oil and water phases. If the membrane is continuous, a solid phase would separate the oil and water. Interfacial films between crude oil and water were observed in 1949 by Bartell and Niederhausers who commented upon the apparent rigidity of the films and their possible importance in the petroleum industry. Morrell and Egloff4 had earlier attributed the extreme stability of emulsions of sea water in fuel oil to very stable asphaltic films. Numerous investigators have observed rigid films in the course of crude oil-water interfacial tension determinations by the pendent drop method. Several investigators5,6,2 have separated inter-facially active materials from crudes and attempted to characterize them chemically. Reisberg and Doscher,2 using Ventura crude, showed the interfacial tension against water (as measured by the pendent drop method) to be affected by aging, contraction and expansion of the interface, and the pH of the water. These investigators attributed the adhesion of oil to a water-wetted surface and the distortions of flow paths in glass capillaries to the presence of rigid films. Dodd7 has studied the interfacial viscosity of adsorbed films and found them to be non-Newtonian in behavior. Craighead and Harvey8 reported a series of displacements in tubes packed with 60 mesh glass beads. They interpreted the results as indicating an effect of stearic acid films on waterflood recovery and imply that natural films may produce similar results.

Jan 1, 1967

By R. C. Amero

FULLERS earth is a general name applied to claylike minerals that have high natural ad-sorptive powers. They are usually distinguished from ordinary clays by a higher content of combined moisture and a lower apparent density. The definition is based on the ancient use of the material for fulling, or cleansing woolen cloth of oil and grease; a more modern definition should mention the ability to decolorize oil and should differentiate between fullers earth, which is naturally active, and certain bentonites which only develop decolorizing power after being leached with strong mineral acids. The distinction between fullers earth and activable bentonite is not a sharp one, since all types of intermediate clays can be found that are more or less naturally active, yet more or less responsive to acid treatment. The differences seem to depend somewhat on the amount of leaching that has been effected by natural ground waters. Physical Properties The principal mineral constituent of activable bentonite is montmorillonite, a hydrous aluminum silicate to which the following formula is generally assigned: Al,Si,O,, (OH), • 12H,O Fullers earth, as well as bentonite, is usually composed of some variety of montmorillonite, but in the United States the largest tonnage of fullers earth is mined from deposits of attapulgite. Attapul- gite is a clay mineral composed of monoclinic crystals of colloidal size, having a fibrous shape similar to that of asbestos. A sectional model of the attapulgite "molecule" is shown in Fig. 1. A single unit is about 18.0 A wide and 12.9 A high. The length of the molecule is variable, but this same molecular pattern is repeated to form needlework crystals, rather than flakes, as is characteristic of the montmorillonite crystals. Attapulgite has been assigned the following formula,' although actually, the magnesia has been largely replaced by alumina: (0%) . (OH), • Mg, . Si, • Olp . 4H20. The fibrous nature of the mineral is clearly shown in the electron micrograph, Fig. 2. Although the deposits contain 5 to 30 pct quartz and carbonate minerals, impurities in the commercial products are held at a low level, principally by selective mining on the basis of oil decolorizing efficiency. The particle size distribution of this fullers earth has been estimated from settling rates, using sodium citrate as a dispersing agent.' Since Stokes' law only applies to spherical particles, the equivalent particle diameter calculated below is probably more nearly an index of diameter rather than length of the needlelike crystals: Eqnivalent Arbitrary Particle Distribution, Size Diameter Pci Classil3catian 0.05 mm 0.80 0.80 pct sand 0.05-0.02 mm 10.96 0.02-0.01 mm 9.65 42.10 pct silt 0.01-0.005 mm 11.40 0.005-0.002 mm 10.09 2-0.5 micron 10.61 0.5-0.2 micron 29.09 56.58 pct clay 0.2-0.05 micron 14.86 0.05 micron 1.96 The differential thermal analysis shown in Fig. 3 is unique and supports the theory that this is a distinct mineral species.' ~ Other general properties of the mineral as shown in Table I.

Jan 1, 1952

By P. L. Raffo, T. E. Mitchell

Single crystals of Ta-Re alloys have been deformed in tension and compression as a function of solute concentration and temperature. The temperature dependence of the yield stress is decreased by alloying. At low temperatures there is a minimum in the yield stress (at about 2 at. pct) as a function of concentration. Three-stage hardening was not observed in the alloys. Linear hardening rates, where observed, were characteristic of stage II in pure tantalum. At low temperatures and high concentrations, work softening was often prominent at high strains. Electron microscopy revealed that dislocations are mostly of screw orientation, although heavily jogged and cusped, and often occurring in dipole pairs. The alloys become more prone to cleavage with increasing rhenium content, due mostly to an increasing yield stress rather than a change in cleavage strength. Alloying apparently decreases the Peierls stress of bcc metals at low temperatures by facilitating kink nucleation at solule atoms on screw dislocations. Higher solute concentrations further increase the yield stress. Quantitative calculations and comparisons with other bcc alloy systems are made to show that the predominant hardening mechanism is due to the interaction of dislocations with misfitting solute atoms close to their slip planes. The interaction is so localized that the core dilatation of dislocations could be important. CONSIDERABLE interest has arisen in recent years concerning the mechanical properties of unalloyed bcc metal single crystals.'-7 These and similar studies on polycrystalline materials have resulted in a considerable understanding of the macroscopic yielding characteristics8, 9 and the process of work hardening.'' This latter advance is due in a large part to the increased use of transmission electron microscopy in P I RAFFO junior Membar AlMF is Metallyureist Iewis such studies and the general observance of three stages of work hardening in the shear stress-shear strain curves. The properties of substitutional alloy single crystals of bcc metals have not been determined in as much detail as in the pure metals. Insufficient systematic studies have been made on the effect of alloying on the magnitude and temperature dependence of the yield stress or the stress-strain curves. The alloy systems which have been studied to some extent have been Ta-W,11, 12 Ta-Mo," Ta-Nb,12'14 Mo-Re,15 W-Re,16 and alloys of iron with nickel,17 platinum,17 vanadium,18 and aluminum.18 A large body of data exists on Fe-Si alloys, but these have mainly been a result of the experimental convenience of using this material in place of unalloyed iron, rather than a comprehensive study of the mechanical properties of the alloy system per se. The present authors have previously reported additional data on the properties of Ta-Re, Ta-W, and Ta-Mo alloy single crystals.1g Some of the data on Ta-Re alloys will be described later in this paper. Briefly, single crystals of Ta-Re (1.2 to 10.6 pct), Ta-W (6.2 and 10.2 pct), and Ta-Mo (2.9 and 9.0 pct) were grown by the floating zone method in vacuum. Compression tests were performed in the temperature range 77" to 623°K. Slip was found to occur in Ta-Re alloys at 77' and 298°K on the (~ll)[lil] system and slip lines were coarser and straighter than in unalloyed tantalum. No three-stage hardening was observed in any of the alloy systems and the curves were nearly parabolic. At temperatures above 175°K the yield stress* increased monotonically with in- creasing composition while at 77" and 175°K the yield stress initially passed through a minimum after which it began to increase again for concentrations greater than about 2 pct Re. Similar minima were observed in Ta-Mo alloys and to a lesser extent in Ta-W alloys. The minimum was interpreted as being a result of a

Jan 1, 1969

By E. Hein, R. A. Dodd

The fatigue softening of prior strain-hardened poly crystalline copper has been determined by measuring changes inflow stress resulting from fatigue treatments. Tensile fatigue does not soften the metal, while the softening due to reversed stress fatigue depends on the extent to which fully reversed stressing is approached. True tensile fatigue is shown to be possible only in the case of long wire specimens. Annealing following fatiguing of strain-hardened metal shows that tensile fatigue is very effective in modifying normal recovery and recrys-tallization. OBSERVATIONS by Ludwik and Scheu,' Kenyon,' Polakowski and Palchoudhuri, Kemsley, and Broom and Ham,596 have shown beyond doubt that strain-hardened metals are softened by reversed-stress fatigue. To some extent the softening might be associated with a rearrangement of dislocations, but the results of Broom and Ham5 on the temperature dependency of the fatigue hardening of annealed copper, and those of McCammon and Rosenberg7 on the partial recovery at 100'C of fatigue-hardened copper suggest that point defects may be involved. Since lattice vacancies are the only species of point defect present in appreciable quantities in thermody-namic equilibrium, most attention has been accorded them in the various theories advanced to explain hardening and softening effects resulting from fatigue. Precise mechanisms remain uncertain, and while some effects may be due to single vacancies, defects arising from vacancy clusters may also contribute to the changes in properties. All types of plastic deformation result in point-defect formation, one frequently invoked formation mechanism involving the nonconservative motion of jogs formed by the intersection of, for example, mixed dislocations. But since fatigue deformation is thought to be a particularly effective way of forming point defects, additional mechanisms peculiar to fatigue must be sought. One possibility is that jogged loops contract during the unloading cycle to give rows of vacancies. A local high-vacancy concentration could conceivably promote polygonization and recovery by climb, and, therefore, could explain the fatigue softening of strain-hardened metals under appropriate conditions of temperature. Conversely, the experiments by Broom and Ham6 on the fatigue hardening of copper single crystals involving subsequent tensile testing of previously fatigued specimens, resulted in the observation of distinctly lowered yield points. This could be due to vacancy atmospheres associated with dislocations, possibly augmented by jogs on dislocations. In addition to the yield-point phenomenon, a post-yield hardening was observed, with a temperature-dependence resembling the friction-hardening of irradiated metals,9 this again suggesting a point-defect mechanism. An important development in this field has been the observation,10 by transmission electron microscopy, of high concentrations of prismatic loops in fatigued aluminum. By analogy with quenched aluminum filmso11 it seems certain that these loops originate in the collapse of vacancy clusters formed during deformation. Metals, such as copper, having a relatively low-stacking fault energy would tend to produce Frank sessile loops (in practice tetrahedral defects with stacking faults on all (111) planes) rather than the glissile prismatic loops observed in aluminum. The manner in which these various defects affect the different aspects of fatigue behavior has not yet been fully investigated. The present work was designed principally to indicate whether tensile fatigue gives rise to hardening and softening effects similar to those associated with reversed stress fatigue, and with the hope of providing additional information on the contribution of point defects to fatigue deformation. Despite the uncertain ty often associated with the interpretation of resistivity data, i.e., the relative contribution of stacking faults and other defects, such measurements are conveniently employed to study point defect pheno-

Jan 1, 1962