Search Documents

By O. R. Wagner, R. O. Leach, H. W. Wood, C. F. Harpke

PAN AMERICAN PETROLEUM CORP.TULSA, OKLA. CASPER, WYO A field test has been made in which additional oil recovery was obtained from a previously-waterflooded "oil-wet" sandstone reservoir. This recovery improvement was accomplished by adjusting the reservoir wettability through chemical treatment of the flood water. The test was made in the Muddy sand of the West Harrisburg Unit, Neb. The chemical used, sodium hydroxide, was injected as a slug of dilute caustic solution through a water-injection well. The natural wettability of the reservoir and the chemical requirements for reversing wettability were determined in the laboratory from contact-angle studies using field water and oil samples. Laboratory flood tests with a synthetic system had shown that reversing the wettability of an oil-wet consolidated core would lead to improved oil recovery. The field performance indicates that the mechanism by which increased oil retovery is obtained in the field is the same as that observed in the lahoratory. Laboratory studies indicate that higher ultimate recoveries and decreascd water-injection requirements result when the adjusting agent is added early in the life of the flood. However, a previously waterflooded area was intentiorzally chosen for the field test so that unambiguous conclusions could be made about the effects of chemical injection on wettability and the extent of oil-recovery improvernent afforded by wettability reversal. Forces existing at the fluid-solid and fluid-fluid interfaces in a porous medium have an important effect on oil recovery during a water flood. Modifying these interfacial forces in the reservoir to improve oil recovery has been the object of much research. Several papers' ' have discussed the use of surfactants to lower the water-oil interfacial tension. This paper describes work concerned with improving oil recovery by modifying the forces at the fluid-solid interfaces— that is, by changing the preferential wettability. An earlier paper: presented evidence to show that some reservoir systems could be changed from preferentially oil-wet to preferentially water-wet by the action of simple chemicals added to the water to increase waterflood oil recovery. The process was attractive for further study because it used only inexpensive chemicals and because it called for a gross "wettability reversal" rather than for a precise adjustment. The present paper is an extension of the earlier work. Laboratory flow tests were made using treated water and oil in a consolidated core to determine the amount of additional oil recovery and the producing performance which might be expected from reversing the wettability of an oil-wet reservoir during a flood. A contact-anglc study using water and oil from the Muddy "J" sand of the Harrisburg field, Banner County, Neb., indicated the reservoir to be preferentially oil-wet and susceptible to wettability reversal through chemical injection. Based on these studies, a field trial of wettability-reversal water flooding was initiated. in the Harrisburg field. The primary purpose of the trial was to determine if wettability-reversal flooding would improve oil recovery in an actual field situation. The field trial was also an important test of the laboratory tecnique used to determine the effect on oil recovery of certain wettability manipulation, as well as a test of the contract-angle method of determining reservoir wetra-bility. The paper is presented in two parts. The first part covers the laboratory experiments leading up to the field trial, and the second part covers the field trial. PART I—LABORATORY STUDY The laboratory experiments consisted of displacement tests using an idealized fluid system and of a contact-angle study with crude and water from the Muddy "J" sand of the West Harrisburg Unit, Banner County, Neb. The displacement tests were designed to determine the effects of a particular wettability manipulation, oil-wet to water-wet, on oil displacement in a water flood. The contact-angle measurements were made to determine the natural wettability of the reservoir and to determine if beneficial wetting changes could be brought about by a chemical addition to the flood water. PROCEDURE DISPLACEMENT TESTS The displacement tests were perfornled in a consolidated sandstone core using a refined oil and water. The wetting properties of this system could

By V. T. Stringfield, H. H. Cooper

ONE of the earliest investigations of ground water in Florida was made in 1513 when Ponce de Leon arrived at St. Augustine in search of the Fountain of Youth. The history of the development of the water resources of the State shows that the large artesian reservoir that underlies Florida was discovered in the latter part of the last century. Part of that history is given by L. C. Johnson' who states that the first successful artesian well in Florida was drilled at St. Augustine between 1880 and 1882. After the City of Jacksonville failed to obtain a flow of artesian water at a depth of nearly 400 ft and abandoned the drilling, R. N. Ellis, City Engineer, and L. C. Johnson, using Johnson's knowledge of the geologic structure of the artesian reservoir, estimated correctly that artesian water could be obtained at a depth of about 500 ft. Thus began the development of the large artesian system in the northeastern part of the State. In 1908, the Florida Geological Survey issued its first report on the ground water of central Florida. More recent reports give the results of investigations that have been in progress in cooperation between the Florida Geological Survey and the U. S. Geological Survey since 1930. As a result, the ground-water geology and hydrology of Florida are now so well known that ground-water problems such as confronted early investigators no longer exist. However, new problems arise and new discoveries are made as the demand for more ground water increases with the development of the State. Water-Bearing Formations Descriptions of the geologic formations and a map showing their distribution at the surface are given in a recent report by Cooke.' The geologic formations that yield the ground-water supplies in Florida represent only a small part (about 1000 ft) of the total thickness of the sedimentary rocks (more than 15,000 ft) that underlie Florida. The water-bearing rocks that yield fresh water include more than two dozen formations that range in age from Eocene to recent. The Eocene formations, which consist chiefly of limestone, are the oldest and the deepest of the formations in Florida that yield fresh water to wells. In 1944, on the basis of a study of the foraminifera, the Applins -ivided the limestone of Eocene age into six formations, which are as follows, from top to bottom: Age or group Formation Jackson Ocala limestone icAvon Park limestone Claiborne -j Tallahassee limestone aLake City limestone Wilcox Salt Mountain limestone xOldsmar limestone The Ocala limestone and the underlying formations of Claiborne age, along with some of the overlying limestone of Oligocene and Miocene age, constitute the principal source of water in Florida and southeastern Georgia and generally may be regarded as forming one artesian aquifer or water-bearing unit. This aquifer is referred to in this paper as the Floridan aquifer, a name proposed by Parker.' In part of Seminole County alone more than 1000 flowing wells yield water from the Floridan aquifer. A yield of 6500 gpm, or about 9.5 million gal per day, by natural flow from a well penetrating the aquifer at Jacksonville, Florida, was observed in 1942. A yield of about 7000 gpm by natural flow was reported for a well 1390 ft deep at St. Augustine in 1887. The largest yield reported from a pumped well penetrating the aquifer is 7500 gpm, or about 10.5 million gal per day. The aquifer is also the source of some of the large springs, such as Silver Springs, whose discharge, according to measurements made by the U. S. Geological Survey, has ranged from 526 to 1350 sec-ft, or from 340 to 872 million gal per day. The top of the Ocala limestone, as represented by contours in Fig. 1, indicates in a general way the geologic structure of the formations that comprise the Floridan aquifer. The Ocala is at or near the surface in the areas represented by shading in the northwestern part of the peninsula and also in an area in western Florida adjacent to Alabama and

Jan 1, 1952

By J. P. Hirth, A. H. Clauer

A simple graphical method is presented for the determination of climb forces on dislocations exerted by uniaxial stresses. In conjunction with standard stereographic projections, the technique is applicable for any crystal system. Climb forces on glide dislocations in bcc crystals are determined as an application. In connection with a study1 of elevated temperature creep of molybdenum single crystals, a detailed analysis of the climb force on a dislocation was necessary. In general, such forces can be calculated for an arbitrary dislocation segment from the Peach-Koehler equation2 (or one of its variants3"6) where Fk are the components of the force per unit length of dislocation line, ?i of the unit sense vector tangent to the line, ojl of the stress tensor, bl of the dislocation Burgers vector, and is the Einstein permutation operator with components ?123 = ?231 = ?321 = —?132 = — ?321 = —?—213 = unity, and all other components zero. It is understood in the suffix notation of Eq. [I.] that repeated indices are to be summed over 1, 2, and 3. For the most general coordinate system, the matrix manipulations required to solve Eq. [I] are fairly complex. However, a simplification can be achieved by specifying a coordinate system based on the dislocation in question. The pertinent system involves cartesian coordinates xi, x;, xi, with attendant unit vectors e'i; ei being parallel to the Burgers vector b, and e'3; being parallel to the climb directions (b x ?), i.e., normal to the slip plane. In this coordnate system b = (bi, 0, 0) and ? = (?'1,?'2, 0). Hence, Eq. [I] yields for the climb force per unit length F3 = ?'2s'11b'1—?'1s'12b'1 [2] The first term on the right side of Eq. [2] is the climb force on the edge component of the dislocation, while the second is the (cross-slip) force normal to the glide plane acting on the screw component. Thus, the problem of determining the climb force reduces to that of resolving the stress components —il and s'12 in the xi coordinate system. Several authors7- l0 have shown, for the glide case, that such stress resolution can be performed most readily by graphical methods. Therefore, we present a similar method for the climb case. Of the suggested methods, we follow that of Hartley and Hirth,9 which can be performed directly with a standard stereographic projection for the crystal system in question. We treat the case of simple tension, or compression, this being the most common creep test in which climb is important. A set of cartesian coordinates (x1, x2, x3) is fixed with x3 parallel to the specimen axis. This set is connected to the x'i set by the factors defined in Table I. A perspective view of the coordinate systems relating them to the glide ellipse, is given in Fig. 1, while a stereographic projection of the coordinate systems is presented in Fig. 2. The transformation matrix connecting the xi and xi coordinates is x'i =aijXj [3] where an a11 a13 aij = a21 a22 a23 a31 a23 [4] s The corresponding transformation for the stresses is i [5] The only nonzero component of okl for the simple tension case is s33,. Hence, using Eqs. [4] and 151, we find that Eq. [2] becomes F3 = b'1s33 sin2 cos ?[cos ? sin a - sin ? cos a] [6] = m1b'1s033 sin a- rn2b's33 cos a where sin a = 5: and cos a = ?i, with a the angle measured from b to ?, i.e., a polar angle in the x1, x2 plane. The same equation with a sign change applies for compression. A graphical plot of the "Schmid" factor m1, relating to the climb force on the edge component, is presented in the stereographic projection of Fig. 3. In this projection the glide plane normal points toward the top of the page and the glide direction points normal to the plane of the page. To use the graph, one

Jan 1, 1970

By K. G. Davis, P. Fryzuk

The diffusivity of silver in liquid tin has been determined, using the capillavy-reservoir technique, over the temperature range 250° to 500°C. The new value, D = 2.5 x 10'* exp(-2480/ RT) sq cm per sec, differs from that obtained by other workers in an earlier investigation. The analysis of data from the capillary-reservoir technique is discussed. In a recent investigation of the solidification of dilute alloys, values for the diffusion constant of silver in liquid tin were required in the analysis of the formation of impurity substructures. AS a result, measurements were made of the diffusion constants in the temperature range 250° to 500°C (melting point of tin 232°C), for the alloy concentrations used in the solidification experiments and at higher concentrations, to verify previous determinations.I)2 The capillary-reservoir method was adopted, using experimental procedures similar to those followed by Ma and Swalin,1 with the main exception that radioactive silver was used in the present investigation to facilitate solute-concentration measurements. EXPERIMENTAL PROCEDURE a) 100 ppm Samples. Glass capillary tubes of 2 mm inside diameter and approximately 5 cm- long were sealed at one end, evacuated, and filled with tin of 99.999 pct purity. The region of shrinkage near the mouth was cut off, and the tubes were then placed in a graphite holder and immersed, with the open end up, in an unstirred bath of alloy containing 100 ppm Ag 110, where they remained for periods of up to 30 hr. On removal from the bath they were cooled by an air blower. The bath was kept under a small positive pressure of argon, and the temperature controlled to within +1°C. A 10-hr diffusion period was used in the majority of the tests, scatter on runs of less than 5 hr being rather large. The procedure outlined above was chosen in preference to putting alloy in the capillary and pure tin in the bath, in order to avoid segregation when the tubes filled with alloy were first solidified. To minimize segregation when the diffusion period was complete and the capillaries again solidified, the earlier samples were held in thin-walled silica tubes which could be cooled very rapidly. Later tests were made in precision-bore Pyrex tubes, to eliminate effects caused by variations in the capillary diameter. No consistent differences in diffusivity as measured in the two types of tube were detected. After removal from the glass tubing, the samples were sectioned into 2.5 mm lengths and counted for y activity, using a scintillation counter with fixed geometry. Samples were also drawn directly from the bath and counted, so that values for C/C,, the ratio of the weight of Ag 110 in the sample to that in the bath, could be obtained. b) 5000 ppm Alloy. To check for possible effects of concentration, the silver content of the bath was increased to 5000 ppm. Complete mixing was found to have taken place in the capillary after a 10-hr period at 300°C. It appears that the greater density of the alloy was sufficient for buoyancy forces to cause instability in the alloy-tin interface, leading to rapid convective mixing. For the 5000 ppm alloy, therefore, the bath was of pure tin and the capillary tube was filled with alloy. With this arrangement, values of D consistent with those for the 100 ppm alloy were obtained, Fig. 1. CALCULATIONS OF DIFFUSIVITY The terminology used applies to a capillary of pure tin immersed in a bath of alloy. 1) Error-Function Method. under the present experimental conditions, the rod of liquid tin into which silver is penetrating may be considered semi-infinite. Assuming the concentration at the mouth of the tube to remain constant at Co, the concentration C at distance x from the mouth of the tube at time / is given by3 Plots of the inverse error function of (1 -C/Co) vs .v gave straight lines passing through the origin with slope 1/2-, x being corrected for shrinkage both on solidification and while cooling to the melting point (total correction about 6 pct at 500°C). Values for log D obtained in this manner are shown in Fig. 1. A least-squares fit to the relation D = Do exp(-Q/RT)

Jan 1, 1965

By W. W. Stephens, W. J. Kroll, H. P. Holmes

THE only two methods for producing commercial quantities of malleable zirconium, up to now, have been using magnesium reduction of the anhydrous chloride under a neutral gas, and using purification of raw zirconium by the iodide dissociation method on a hot filament. The purity of the metal obtained by the latter process is about the same as that resulting from the chloride reduction, with the exception of the oxygen content, which may be about 0.05 pct lower in the iodide metal. Even traces of oxygen have a strong hardening effect on zirconium. Since, in the iodide process, the impurities, Si, Al, Fe, Ni, and Mg in the raw zirconium used, are carried over, it would appear uneconomical to use this method of refining solely to eliminate the traces of oxygen, unless very soft metal is desired. One important step to improve the iodide method, namely, dissociating pure iodide made from carbide and recycling the iodine, which would change this refining process into a method for extracting zirconium from the ore, has not yet been made. The Bureau of Mines, by using the chloride reduction, wanted to produce quantities of a reasonably pure and malleable metal at low cost for large-scale industrial use. This aim has been achieved, and a pilot plant permitting production of 600 lb of malleable zirconium per week will be described (fig. 1). Briefly, the Bureau of Mines process consists of reducing purified gaseous anhydrous zirconium chloride with fused magnesium under a noble-gas atmosphere. The reaction product, magnesium chloride, and any excess magnesium metal present are removed from the sponge zirconium in the next step by fusion and evaporation in a good vacuum at about 925°C. In this process, care is taken to keep air out of contact with the hot metal, which otherwise would contaminate the product with oxygen and nitrogen. Both these impurities embrittle zirconium even when present in an amount as low as 0.1 pct. A number of previous reports1-3 describe the method and the various improvements that finally led to a workable process. The major steps made were the production of large quantities of carbide, which is the raw material for producing the chloride, its chlorination with reasonable efficiencies, and the elimination of iron trichloride contained in the raw chloride, as well as that of the zirconium oxide which is always present in this product. The physical nature of the anhydrous chloride, which sublimes at 331°C at atmospheric pressure and melts at 420°C under a pressure of 25 atm, made it necessary to provide a special safety device on the purification and reduction vessels in the form of a lead-alloy seal, permitting escape of excess gases if pressure tended to build up. The main difficulties encountered in the reduction and in the following step, salt separation in a vacuum at elevated temperature, were caused by the material from which the reaction pot was constructed—iron. This metal reacts with zirconium at about 940°C with formation of a eutectic. The last step, salt separation by evaporation of the magnesium and magnesium chloride in a vacuum, is quite unconventional and has not been used before on such a scale. It is only due to the improved construction of high-vacuum pumps, especially oil-diffusion pumps, that such a method could be used. The various steps of the Bureau of Mines process, as described in the general outline above, may be summarized as follows: (1) production of the carbide, (2) chlorination of the carbide, (3) purification of the raw chloride, (4) reduction of the pure chloride with fused magnesium, (5) separation of excess magnesium and magnesium chloride in vacuum at elevated temperature, and (6) melting of the sponge obtained. Production of Carbide The arc furnace, described in a previous report,' was improved both to reduce the graphite consumption caused by the burning of the bottom plates and to concentrate the heat in order to obtain better power efficiency. This was achieved by providing the bottom with graphite plates entirely embedded in refractory bricks, the contact with the current being made with three water-cooled copper plugs. Figs. 2 and 3 show the arrangement. The crucible, made

Jan 1, 1951

By J. W. Downey, S. T. Zegler

A study has been made of the occurrence of Phases having the Cr30-type structure in ternary alloys having the general composition where B cept for iron and copper all the B components are known to form binary compounds having the type structure. The occurrence of the struc-ture type in the ternary alloys was investigated using optical and X-ray metallography. The results indicate that iron can replace virtually none of the cobalt in at 900°C, but substitutes for nickel in up to the approximate composition tually insoluble in V3Ni and 2) and exhibit complete solubility. At 100 nickel can be substituted for cobalt in VSCo up to the composition solubility; and 3) in the system , two solid solutions having the type structure occur. At the same temperature, 1000°C, V3Si exhibits limited solubility for V3Co but is completely mis-cible with V3Ga. Lattice parameters have been determined for all the binary and ternary phases. The solid solutions are discussed in terms of the atomic size and electronic factors which are thought to influence the occurrence of Cr30-type phases. The binary compounds V3Co and V3Ni were found to form peritectoidally from o phases and a vanadium, the former compound at a temperature between 1000" and 1050°C, the latter between 800°and 900°C. The substitutions of nickel and rhodium for cobalt in V3Co were determined not to raise the superconducting transition of VSCo to a temperature as high as 2°K. The occurrence and stability of binary intermediate phases having the Cr30- or A15-type structure (space group o;, Pm3n) have been discussed in several recent papers . Vanadium forms the struc -ture at or near V3B stoichiometry with all the mem -bers of the cobalt and nickel groups in the periodic table and also with Au, Ga, Si, Ge, Sn, P, As, and Sb. This paper describes a survey of the occurrence of the CrsO-type structure in ternary alloys having the general composition V3(B, B') where B and B' are Fe, Co, Ni, Cu, Rh, Ir, Si, and Ga. The purpose of the survey was to clarify the connection between the position of the B partner in the periodic table and its CrsO-type phase-forming tenden~y.~,~ The survey is part of a broader program concerned with the influence of B-partner substitutions on the superconducting transition temperatures of CrsO-type compounds. The transition temperatures, Tc, of some of the ternary Cr,O-type phases found in the survey are also discussed in this paper. EXPERIMENTAL PROCEDURE The alloys were prepared by arc-melting in an A-He atmosphere and were in the form of buttons, weighing approximately 3 g. The metals used in their preparation were received from commercial sources and were in all cases 99.9+ pct pure. The vanadium was spectrochemically pure except for 800 ppm of Si, 200 ppm of Fe, and 200 ppm of Al. For study of each pseudobinary system at least seven alloys were prepared having the general compositions case of alloys containing gallium, melting losses were small, usually less than 0.3 pct of the total weight of the metals charged for melting. Melting losses were somewhat greater for gallium alloys, ranging in general from 0.9 to 5.0 pct. Ternary V-Si-Ga alloys were chemically analyzed and the results are given in Table I. The analyses show most alloys to be within 2 at. pct of the intended composition. Throughout the balance of the paper the intended compositions are used in discussing the alloys. The cast buttons were annealed within evacuated quartz capsules for times ranging from 3 to 6 weeks at temperatures between 800" and 1000°C and water-quenched. The phases present in the annealed and quenched alloys were identified by optical and X-ray metallography. X-ray diffraction photograms were made with powders prepared from the bulk specimens, by the use of a 114.6-mm-diam powder camera with copper irradiation. The lattice parameter of CrsO-type phases and their standard errors

Jan 1, 1963

By A. K. Mukherjee, J. E. Dorn, J. D. Mole

Investigations were carried out on the effect of polyslip on the strain hardening of aluminum single crystals. The orientations investigated were those lor which the tensile axis was in the [001], [111], [112], and [012] directions plus another for which the Schmid angles for {111}(110) slip were 1 deg. The experimental data were analyzed on a model based on the intersection of dislocations with particular emphasis on the effect of polyslip on the activation volume for inter-section. It is shown that the rate of strain hardening inreases for those orientations wherein attractive dislocation intersections occur and that those orientations which produce the greater number of such intersections exhibit the greater strain hardening. Good correlation of the data is obtained with the concept that attractive junctions, as proposed by Saada, Play an important role in accounting for the rate of strain hardening. EXISTING concepts on the nature and cause of strain hardening in fcc metals have been deduced principally from experiments on the deformation of single crystals under single slip. The effect of crystal orientation on the shapes of the stress-strain curves for single slip have been summarized by seegerl and more recently by Clarebrough and Hargreaves.2 Tensile specimens whose axes fall near the center of the [001]-[011] line of the standard triangle of the stereographic projection exhibit the longest range of easy glide (Stage I) and the lowest rates of linear hardening (Stage 11) whereas specimens whose axes lie near fie [001]-[111] line of the standard triangle have limited or no easy-glide range and exhibit somewhat higher linear strain-hardening rates. Specimens whose axes lie near the [001] or the [ill] poles do not exhibit easy glide and have the highest rates of linear hardening. Kocks3 has shown that the highest rates of linear hardening Occur under Polyslip when the tensile axis coincides with the [111] or the [ 001] pole. Since the rate of strain hardening is sensitive to specimen orientation and the incidence of polyslip, these relationships might help to discriminate between various dislocation models for strain hardening in fcc metals. Previous attempts to analyze the effect of orientation on strain hardening,1"3 however, did not provide a unique answer to this problem. Consequently the present investigation was undertaken wherein additional data, particularly that for the effect of polyslip on the activation volume for intersection, was also determined in order to provide more complete information on the details of strain hardening. Whereas analyses of these data reveal that several recommended models for strain hardening are at variance with the facts, good correlation of the data is obtained with the concept that attractive junctions4 play an important role in accounting for the rate of strain hardening. I) EXPERIMENTAL APPROACH seegerl demonstrated that slip in fcc crystals at low temperatures is dependent on thermally activated intersection of glide dislocations with forest dislocations. This has been confirmed by tests on single crystals of aluminum by Mitra, Osborne and Dorn5 and on polycrystalline aluminum by Mitra and Darn.' Thus in accord with Seeger's theory, the shear strain rate, ?, below a critical temperature, T, is where .V is the number of points of contact per unit volume between forest dislocations and glide dislocations, A is the area swept out per successful intersection, b is the Burgers vector, v is the frequency of vibration of the segment of the glide dislocation undertaking intersection, U is the activation energy for intersection, k is Boltzmann's constant, and T is the absolute temperature. For aluminum, which has an extremely high staeking-fault energy, the constriction energy is negligibly small and therefore the activation energy decreases practically linearly with the stress according to as will be recomfirmed later, where Uo is jog energy at the absolute zero, G and Go are the shear moduli at the test temperature T and O°K, respectively, L is the spacing of the forest dislocations, t is the applied shear stress for slip, and tGo is the stress field that must be surmounted athermally.

Jan 1, 1965

By Kenneth A. Moon

An exact statistical treatment of a one-dimensional model is used as a basis for evoluating the reliability of certain simplified expressions for the activity of the solute in interstitial solutions, including one obtained from the exact expression by setting the repulsive interaction equal to infinity. The latter approximation is found to be satisfactory at low and moderate concentration if the repulsive interaction is large, even though not infinite. A similar expression (identical if the co-odination number is two) is derived from the quasichemical expression of Lacher, and is recommended as the best available expression for the excess configurational entropy of interstitial solutions with excluded sites. Some reasonable models are discussed, and the nature of the saturated solutions is determined by inspection. Some of the models reduce to the one -dimensional case. An analysis is given of the excess partial entropy of hydrogen in V-H; Nb-H; and To-H solutions. MOST treatments of the statistical thermodynamics of interstitial solid solutions have followed the classic paper1 of Lacher in making the simplifying assumption that the configurational entropy of the solution is ideal. However, it is becoming increasingly apparent that there are many interstitial solutions with very large so lute-solute repulsions, and for these the assumption of ideal entropy is not valid or useful. It is important to realize that with substitutional solutions large repulsions between the component atoms must lead to phase separation, whereas in interstitial solutions the free energy of the solution is not drastically increased by large solute-solute repulsions until intrinsic saturation is reached at the concentration where further solute would be forced to enter a site in which it would experience the repulsive effect of one or more solute atoms already present. In the limiting case of an infinitely large repulsive interaction, the excess free energy would be attributable entirely to excess entropy, the enthalpy of mixing being zero. AS will be shown below, even if the repulsions are less than infinite, a treatment based on an assumption of infinite repulsions may be very satisfactory up to moderately high concentrations of the interstitial component. Often in solutions where large repulsive interactions exist, there are also small interactions — often attractive—between solute atoms in configurations other than that corresponding to the large repulsion. In such cases the excess free energy will consist of an excess entropy term attributable to the large repulsive interactions, and an enthalpy term corresponding to the other small interactions. Nomenclature to differentiate succinctly between important cases would be a convenience. In this paper the nomenclature shown in Table I will be used. In Table I, and in the preceeding discussion, excess quantities are defined in terms of standard states which are pure solid solvent and pure (possibly hypothetical) solid saturated phase of the structure in question. In practice, it is more convenient to choose the interstitial element as a component, and its conventional standard state. This will add a composition-independent term to the excess entropy and the enthalpy. The earliest paper known to the present author which treats the thermodynamics of athermal interstitial solutions was given by schei12 in 1951, but the statistical derivations in that paper are open to criticism. Speiser and Spretnak were the first to give a correct statistical treatment,3 limited, however, to concentrations sufficiently low that the number of empty sites excluded from occupancy by more than one filled site is negligible. The purpose of the present paper is to extend the statistical treatment to more concentrated solutions, and to examine the magnitude of the errors introduced by assuming that the repulsive interactions are infinite when in fact they must be finite. THE QUASICHEMICAL APPROXIMATION Fortunately, a standard method already exists for taking into account the effect of large interactions upon the entropy of mixing. This is the quasi-chemical method, in which the probability of existence of a given pair of solute atoms in a certain proximate configuration is assumed to be proportional to exp(-w/kT), where w is the energy increase of the solution when the two atoms are moved from isolated locations in the solution to the configuration in question. A quasichemical treatment of interstitial solutions was given in 1937 in a widely neglected paper by Lacher.4 The result comes out

Jan 1, 1963

"The Garfield plant of the American Smelting & Refining Company is situated about seventeen miles west of Salt Lake City, on the Los Angeles & Salt Lake Railroad, and has freight service by the Denver & Rio Grande Western, Western Pacific and Bingham & Garfield Railways.The site lies between the picturesque Great Salt Lake, with its mountain islands, and the northern point of the Oquirrh Range, which forms the western boundary of the Salt Lake Valley.The location includes several hundred acres of land rising from the southern shore of the lake, selected on account of its adaptability to the economical handling of materials by gravity methods.The smelter is a custom smelter, treating copper ores and concentrates produced in Utah and adjoining states.The ores treated consist mainly of oxides from the Tintic and Park City Districts, sulphides from Bingham District, and concentrates from the mills of the Utah Copper Company, from mills in California, and copper precipitates from the Ohio Copper Company. The last product comes from low grade ores of Bingham Canyon.The following figures represent approximately the daily consumption of materials:Ores and Concentrates…2,700 tonsLime sand…100 ""Coal…350 ""Oil for Roasters…240 Bbls."

Jan 1, 1925

By AIME AIME

The following changes of address of members have been received at the Secretary's office during the period of Jan. 1 to Mar. 15, 1907. This list therefore supplements the annual list of members corrected to Jan. 1, 1907, and brings it up to the date of Mar. 15, 1907. The names of members who have accepted election during January and February, 1907 (new members), are printed in italics. The large number of changes of address since Jan. 1, 1907, shows the importance of publishing these changes as frequently as possible, and the Bi-Monthly Bulletin has been selected as the means to present this information to the members of the Institute. By a simple method of cutting out these names and addresses and pasting them directly over the corresponding names in the annual list of members, the record can be kept practically up to date, and the value of the list correspondingly increased. For this purpose the changes of address have been printed only on one side of the page. The names of new members, being in italics, are readily distinguished from the others, and can be pasted in approximate alphabetical order on the margins of the pages.

Mar 1, 1907

By Jon J. Connor, Richard J. Ebens

The trace element geochemistry of the cherty clay-rich carbonate residuum cover in much of southern Missouri and adjacent parts of Arkansas was investigated during the earl 1970's as part of a statewide geochemical survey of Missouri.1-8 The study was environmentally oriented and focused on the character of the "natural" geochemical environment of the state. A great deal of effort was made to collect samples that would represent the geochemical variability of the near-surface environment in an unbiased way. In general, this was accomplished by use of randomization procedures in both collection and analysis. Most of the sampling sites were selected randomly to prevent personal bias from entering into sample selection. In the laboratory, samples were analyzed in a randomized sequence to circumvent the effects of any systematic bias that may have entered into the laboratory procedures. Several residuum samples contained 1000 parts per million (ppm) or more of lead, zinc, and barium. All these samples were collected in Washington County in or near the barite district. The frequency distributions shown in [Fig. 1] indicate just how unusual the residuum in Washington County is with regard to these three metals and copper. The shaded parts of the histograms represent the samples from Washington County. The histograms are based on analyses of 141 samples from 38 localities scattered over the subcrop of the Cambrian and Ordovician formations of southern Missouri and northern Arkansas. Eight localities were selected randomly from over each of four bedrock units-Bonneterre dolomite; Potosi and Erninence dolomites; Roubidoux formation; and the Jefferson City, Powell, and Cotter dolomites. Six localities were selected randomly from over the Gasconade dolomite. The geochemical "background" for these elements in residuum is defined by samples from outside of Washington County (unshaded part of the histogram); lognormal distribution curves have been fitted to the corresponding parts of each histogram. Clearly, these lognormal models (curves) describe well the background distributions of zinc, barium, and copper. The background histogram of lead concentrations is notably skewed to the right compared to the model. Lognormal distribution curves were also fitted to the data on lead, copper, and zinc in the residuum of Washington County. No model was fitted for barium in Washington County because of the distinct bimodality in the data. All samples containing more than 1000 ppm were collected in the barite mining district and obviously reflect the elevated levels of barium in the district. The frequency distributions for Washington County are clearly anomalous with respect to the background data, those for lead, zinc, and barium being exceptionally so. The models for anomalous lead, zinc, and copper seem to fit reasonably well, although the scatters in the lead and zinc anomalies are considerably larger than the scatters in the corresponding background data. The copper anomaly, although probably real, is greatly subdued compared to that of lead and zinc. Also, it has a scatter similar to that of the copper background, rather than being enhanced like the scatters of the lead and zinc anomalies. On the basis of techniques described by Miesch,4 the chemical abundance of copper, lead, and zinc in residuum in

Jan 1, 1980

By Robert J. Linney

IN the latter part of the year 1943, it was decided to experiment with diamond-drill blast holes in the Old Bed magnetite mine at the Mineville mines of the Republic Steel Corporation, in sections of the ore body where vertical dimensions were large and where development for sublevel bench stopes had already been done. Other possibilities of application for this drilling method were in the reclamation of old floors and pillars in the pitching folds of the Lower Old Bed ore body and in the reclamation of large vertical pillars in the " 21 " Bonanza-Joker ore body. The cross sections and views of the two ore bodies will show the conditions to which the diamond-drill method has been applied. The Lower Old Bed magnetite ore body is lenticular and dips approximately 30° toward the southwest and strikes generally southeast and northwest. An intensely folded structure, which pitches generally on an axis approximately at right angles to the strike, is continuous from the uppermost old workings down to the present bottom of the mine, and probably continues with depth. On successively lower levels this folded structure becomes greater in vertical dimensions and the two folds are closer together in a horizontal dimension. As shown in Fig. 1, this folded structure gives to parts of the ore body considerable vertical dimensions, which provide areas that were developed for sublevel bench stoping above a slushing drift, as shown in Fig. 2. It was in one of these previously developed sublevel bench stopes, No. 26 on the 1185-ft. level, that the diamond-drill blast-hole method was applied for mining the upper sublevel. The lower sublevel was underhand-bench-drilled to the finger raises of the scram drift below. The roof of this stoping area began to break and spall on the lower sublevel, causing the roof to become inclined. Along the hanging wall of the stope this reached an elevation about half way between the two sublevels. A smooth schistose seam in the hanging wall causes the ore to break away freely. Therefore, if bench mining had been carried on in the upper sublevel, a dangerous condition of poorly supported benches would have resulted. When the drillers were slashing across the sublevel to footwall and hanging wall to make a bench, spalling roof of the opening below would probably have carried away part of the bench, and would have left a dangerous place in which to continue underhand benching. A 6 by 8-ft. raise had been driven between the lower stope and the upper sublevel about 200 ft. from a manway. It was decided to use this raise for a starting cut and to arrange holes as shown in Fig. 3, so that a slot would be opened across the ore body between the footwall and hanging wall. This slot would then be used for the purpose of breaking into the ore; by blasting vertical rings of holes drilled at right angles to the axis of the pitching folds as nearly as possible. Layouts of this slot drilling and the rings adjacent are

Jan 1, 1945

By Robert J. Linney

In the latter part of the year 1943, it was decided to experiment with diamond-drill blast holes in the Old Bed magnetite mine at the Mineville mines of the Republic Steel Corporation, in sections of the ore body where vertical dimensions were large and where development for sublevel bench stopes had already been done. Other possibilities of application for this drilling method were in the reclamation of old floors and pillars in the pitching folds of the Lower Old Bed ore body and in the reclamation of large vertical pillars in the "21" Bonanza-Joker ore body. The cross sections and views of the two ore bodies will show the conditions to which the diamond-drill method has been applied. The Lower Old Bed magnetite ore body is lenticular and dips approximately 30° toward the southwest and strikes generally southeast and northwest. An intensely folded structure, which pitches generally on an axis approximately at right angles to the strike, is continuous from the uppermost old workings down to the present bottom of the mine, and probably continues with depth. On successively lower levels this folded structure becomes greater in vertical dimensions and the two folds are closer together in a horizontal dimension. As shown in Fig. I, this folded structure gives to parts of the ore body considerable vertical dimensions, which provide areas that were developed for sublevel bench stoping above a slushing drift, as shown in Fig. 2. It was in one of these previously devel-oped sublevel bench stopes, No. 26 on the 1185-ft. level, that the diamond-drill blast-hole method was applied for mining the upper sublevel. The lower sublevel was underhand-bench-drilled to the finger raises of the scram drift below. The roof of this stoping area began to break and spall on the lower sublevel, causing the roof to become inclined. Along the hanging wall of the stope this reached an elevation about half way between the two sublevels. A smooth schistose seam in the hanging wall causes the ore to break away freely. Therefore, if bench mining had been carried on in the upper sublevel, a dangerous condition of poorly supported benches would have resulted. When the drillers were slashing across the sublevel te footwall and hanging wall to make a bench, spdlling roof of the opening below would probably have carried away part of the bench, and would have left a dangerous place in which to continue underhand benching. A 6 by 8-ft. raise had been driven between the lower stope and the upper sublevel about 200 ft. from a manway. It was decided to use this raise for a starting cut and to arrange holes as shown in Fig 3, so that a slot would be opened across the ore body between the footwall and hanging wall. This slot would then be used for the purpose of breaking into the ore, by blasting vertical rings of holes drilled at right angles to the axis of the pitching folds as nearly as possible. Layouts of this slot drilling and the rings adjacent are

Jan 1, 1946

By B. L. Sackett

In a general way, the situation in copper smelting is quite similar to that of lead smelting. In other words, the introduction and successful flotation of copper ores has tended to decrease greatly the tonnage to be handled by the smelter and therefore has resulted in curtailed smelter operation. However, copper production has increased rather than decreased. The general effect of flotation has been to decrease the number of furnaces operating, but it has also increased to a considerable extent the difficulties in handling the material, just as was outlined in the case of lead smelting. In copper smelting, the flotation concentrates must be roasted and prepared for the reverberatory furnace. Handling Flotation Concentrates The handling of copper flotation concentrate, which is more or less wet and mucky, is more difficult than was the handling of the old gravity concentrate. Also, the roasting of the concentrate and the handling of the calcine produced is more difficult. That is mainly because the material is extremely fine and the tendency to higher dust losses is greatly increased. The draft in the roasting furnaces must be kept as low as possible, and the feeding of the calcine into the reverberatory furnace must be done carefully, so that dust losses may be kept at a minimum. Transition Stages oF Concentration and Smelting The general process through which the copper smelter has gone as a result of flotation has been somewhat as follows: In the relatively old days, when copper ores of low grade were first treated, a large number of furnaces were required, and naturally comparatively poor recoveries were made. Also, the profits on low-grade ores were small and the handling of those ores was possible only because of the large tonnages. Then came gravity concentration, which was a great improvement but which only incompletely removed the gangue material, the insoluble and the iron, from the copper ore, and made comparatively poor copper recoveries. This still left a considerable amount of insoluble and iron, as well as the copper itself, to be treated at the smelter.

Jan 1, 1928

By A. M. Nicholas

WHEN attempting to lift mill pulp containing a considerable percentage of wolframite, in an ordinary bucket elevator, difficulty was encountered from the tendency of the tungsten minerals to settle, on account of their high specific gravity. Lifts not exceeding 20 ft. (6m.) could be accomplished without particular difficulty, because there was insufficient time for consolidation of the heavy minerals in the bottom of the bucket; but with higher lifts, the heavy tungsten minerals would settle so solidly that when the bucket turned over at the top of the elevator the contents could be only partially dumped. In this case it ,was necessary to lift the material a distance of 34 ft. (10m.); hence some means had to be adopted to prevent settling, at least to such an extent that the material could be dumped from the buckets. To reduce the carrying time to a sufficient extent would have required a belt speed of 475 ft. (144.7m.) per minute, which was not feasible. It was decided to try, by vibrating the belt about midway of its span, to keel) the material sufficiently agitated during elevation to prevent settling. Underneath the rising side of the belt was placed a 12-in. (30.48-cm.) idler pulley, 18 ft.-(5.5 in.) up in the total lift of 34 ft. The idler pulley was set eccentric by 3/4 in. (19 mm.) and it was hoped that the vibration thus imparted to the belt, running at a speed of 280 ft. (85 m.) per minute, would prevent settling in the buckets. It was found that the pressure of the belt on the idler, due to the small inclination of the elevator, was not sufficient to overcome sliding on the idler, and the agitation was insufficient to accomplish the desired purpose. The idler was then connected to the drive shaft of the elevator through an intermediate pulley, gearing down to a speed of 20 r.p.m., so that a positive vibration was imparted to the belt; this imparted enough motion to the belt to prevent settling and the contents of buckets clumped satisfactorily.

Jan 2, 1918

By Enrique Touceda

As in the case of steel and the non-ferrous alloys in general, the use of the microscope in connection with the manufacture of malleable cast iron has proved of inestimable value to the industry. Had its use not been invoked, many facts either would not be known at all or, if suspected, would be confined to the realms of conjecture. No fairer statement could be made than that the start of real progress in the industry was coincident with the application of metallography to the product, though the full significance of this statement can hardly be appreciated except by those who not only are conversant with conditions as they existed at the time referred to, but are familiar with the character of works' practice at the present time.. A few years ago, about the only test made to ascertain the physical properties of the product, except in the case of certain plants, was the bending of a casting to destruction, not only with the object of discovering whether or not the metal was ductile, but for the purpose of inspecting the fracture. The characteristics of the fracture, if correctly interpreted, were known to be of value in locating the trouble in castings that were inferior. In general, it was found that if a casting of medium or heavy section would bend through a wide angle before failure took place, the fracture in the majority of cases would have a black velvety appearance; while if it was held at different angles to the direction of the rays of light, it would show a change of color and an iridescent sheen. But an inferior air-furnace heat or anneal might yield castings which, if thin and consequently largely decarburized, could be bent double on themselves and still not possess the fracture described. If, on the other hand, a casting broke short, its fracture might have one of a great many different color and structural peculiarities. Depending on the cause of the trouble, such castings might have any of the fracture characteristics, of which the following is but a partial list.

Jan 1, 1922

By C. V. Milikan

Allocation of allowed production in a prorated field by the use of bottom-hole pressures is a method which is sound in theory. Thus far it has had limited application because the experience in correlating bottom-hole pressures with the depletion of wells or fields is not sufficient to interpret all the pressure changes. With additional data and more general knowledge of bottom-hole pressures their use in proration will probably become common. Bottom-hole pressure is the pressure at or near the bottom of a well. It is usually determined at the face of the producing horizon. Bottom-hole pressure measured while the well is producing, may be called the bottom-hole producing pressure or bottom-hole flowing pressure. If the well has been shut in or shut down long enough for the pressure in the producing horizon within the drainage area of the well to equalize, it may be called the reservoir pressure. The allowable production from a prorated field may be allocated to the individual wells or leases by three methods: 1. Bottom-hole producing or flowing pressures. (a) The potential capacity of a well to produce. (b) A uniform differential pressure while producing at the allowed rate. 2. Reservoir pressures. 3. A combination of bottom-hole producing pressures and reservoir pressures. In most prorated fields the allowed production is allocated to the individual wells or leases in proportion to their individual potentials. This method is based on the theory that there is a direct relationship between the permeability and the porosity of the reservoir. More directly stated it means that there is a direct relationship between the amount of oil in the reservoir and the rate at which it will move through the reservoir. While in general this relationship is true, it may vary considerably in different wells. Furthermore, in many wells the capacity of the reservoir to deliver oil to the well is greater than the capacity of the flow string to deliver oil to the surface. It is especially true where the potential is determined by flowing through tubing or by pumping.

Jan 1, 1933

By W. J. Hillenbrand

The soda-ash method for eliminating arsenic from a molten copper bath has been described previously in some detail.' Briefly, the process consists in blowing powdered sodium carbonate under the surface of the partially oxidized melt and in removing the slag formed, which will contain a certain proportion of the arsenic formerly in the bath. Sodium carbonate melts readily at the temperature of molten copper, and when molten it dissolves arsenic oxide rather rapidly. In the process, sodium arsenate is formed which is removed along with the excess of molten soda ash. In order that arsenic may be eliminated in this way, it must first be oxidized to the pentavalent condition. This, however, is easily accomplished by blowing air into the molten copper until a fair excess of cuprous oxide is present. The manner in which soda ash is introduced into the furnace has a considerable effect upon the efficiency of the process. In the earliest attempts at arsenic removal, soda ash—often in combination with slaked lime, for sodium carbonate is not the only solvent that will remove arsenic—was thrown upon the surface of the bath, was allowed to melt, and was removed after it had dissolved a sufficient amount of arsenic. At present powdered soda ash is generally blown in under the surface of the melt with the aid of compressed air. Melting immediately as it comes into contact with the molten copper, it can react with considerably more of the bath than by the former method, and thus can remove arsenic more rapidly and more completely. Since the resulting slag is removed at once, its very destructive effect upon the furnace refractories is minimized. The effectiveness of the soda-ash method may be gathered from the results of the following test. A 900-lb. charge of copper was melted in a small, oil-fired reverberatory furnace, and sufficient metallic arsenic was added to the bath to bring the concentration of that element to about 0.5 per cent. Air was blown into the melt until its oxygen content was just under 1 per cent by weight. The bath was then sampled and soda ash was blown in under the surface in 5-lb. batches. After each addition

Jan 1, 1934

By Enrique Touceda

As in the case of steel and the non-ferrous alloys in general, the use of the microscope in connection with the manufacture of malleable cast iron has proved of inestimable value to the industry. Had its use not been invoked, many facts either would not be known at all or, if suspected, would be confined to the realms of conjecture. No fairer statement could be made than that the start of real progress in the industry was coincident with the application of metallography to the product, though the full significance of this statement can hardly be appreciated except by those who not only are conversant with conditions as they existed at the time referred to, but are familiar with the character of works' practice at the present time.. A few years ago, about the only test made to ascertain the physical properties of the product, except in the case of certain plants, was the bending of a casting to destruction, not only with the object of discovering whether or not the metal was ductile, but for the purpose of inspecting the fracture. The characteristics of the fracture, if correctly interpreted, were known to be of value in locating the trouble in castings that were inferior. In general, it was found that if a casting of medium or heavy section would bend through a wide angle before failure took place, the fracture in the majority of cases would have a black velvety appearance; while if it was held at different angles to the direction of the rays of light, it would show a change of color and an iridescent sheen. But an inferior air-furnace heat or anneal might yield castings which, if thin and consequently largely decarburized, could be bent double on themselves and still not possess the fracture described. If, on the other hand, a casting broke short, its fracture might have one of a great many different color and structural peculiarities. Depending on the cause of the trouble, such castings might have any of the fracture characteristics, of which the following is but a partial list.

Jan 1, 1922

G. B. WATERHOUSE,* Buffalo, N. -Y. (written discussion?).-One of the most essential features of rail manufacture is the production of rails that will give good service and be free from failures. To this end rails are made to careful specifications and their manufacture is controlled by rigid inspection on the part of both the producing mill and the railroad or its representative, such as the Hunt special inspection referred to in the paper. Captain Hunt refers to the crescent-shape base failures and describes them as ruptures in the rail flanges extending from the outside inward toward the web. This is hardly correct and may be misleading. It has been shown, over and over again, that the base breaks originating in seams invariably start at the center of the rail base; and run longitudi-nally in varying lengths from 3 to 12 in. and sometimes longer. Most of them are from 5 to 8 in. long and then curve outward to the edge of the flange. The split at the center of the base may exist for an indefinite time and not be discovered until the break shows on top of the flange or the piece of flange breaks off. The. stresses that cause the break are explained in two ways: (1) by the eccentric bearing of the rail base, that is taking contact at one side or edge and bringing excessive strain at the center of the base which starts fracture in any seam that may he present at that point; (2) the split may be due to cross strain in the base where this member is thrown into. compression, as happens where a pair of trucks are on opposite sides of the cross tie or rail-base hearing, and the head is put in tension. A careful study of "split base breaks" shows that fully 95 per cent. occur on the tie bearing, which is further evidence that the above de-scribed causes for the initial break are probably correct. These split base breaks are almost invariably progressive, but always start at the center of the rail-base running longitudinally.

Jan 12, 1919