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By F. H. Callaway, W. O. Keller

The various theories as to the well spacing-recovery relationship are reviewed in considerable detail and these theories analyzed in terms of their consistency with modern reservoir engineering concepts. It is concluded that the well spacing problem must be analyzed in terms of recovery efficiency and that a positive answer to the relation between well density and recovery efficiency is not available from direct comparisons of the production histories of wells and fields. The results of an engineering analysis designed to permit approximate calculation of recovery efficiencies as a function of well spacing in a depletion type reservoir from basic reservoir data is presented. Results of this type analysis indicate that the effect of well spacing on recovery efficiency in depletion type reservoirs can be expected to be very small. Limitations of this approach are pointed out, particularly with respect to its application in lenticular reservoirs. Testing techniques are outlined which should indicate whether or not a reservoir is continuous between wells and whether or not satisfactory drainage is being obtained with present spacings. A mass of data of this type indicates continuity to exist in most fields. INTRODUCTION The purpose of this paper is to review critically the engineering aspects of the well spacing problem, both from the standpoint of certain concepts and from the standpoint of reservoir mechanics. The well spacing problem is primarily an economic problem in which the optimum well density for a particular field is that density which will yield the greatest oil recovery consistent with justifiable development costs. The well spacing answer in terms of economic conditions, however, is extremely sensitive to the variation in recovery efficiency with well density. The variation in recovery efficiency with 'References given at end of paper. Manuscript received at the office of the Petroleum Branch October 2, 1949. Paper presented at the Petroleum Branch Meeting in San Antonio. Texas, October 5-7. 1949. well density is properly an engineering problem. Different opinions as to the correct answer to this engineering problem is the basis for most of the wide difference in opinion among various members of the industry as to optimum well spacing. This paper will be confined to the engineering problem of the relation between well density and ultimate oil recovery; economic considerations necessary for the evaluation of optimum well density for any particular field will not be discussed. The paper can be logically divided into two parts. The first part deals with a critical examination of the background and logic of the Cutler Rule and of similar studies by other authors and of related well spacing concepts. It is indicated that the variations in recoveries with well density* observed by Cutler and. others can be logically attributed to regional migration. Theoretical justification of the Cutler type relation wherein observed variations in recovery with well density in the same field is attributed to variations in recovery effiiency, in terms of energy relations, is refuted. The second part consists of a review of concepts of reservoir mechanics with regard to the well density-recovery relation. It is indicated that little variation of recovery efficiency with well density can be expected in a depletion type reservoir, unless lenticular conditions prevent communication between wells. The significance of field test data with regard to the existence or non-existence of lenticular conditions is pointed out. THE CUTLER RULE The first published article concerning the engineering aspects of the well spacing problem to receive wide attention was the work of W. W. Cutler' of the U. S. Bureau of Mines, published in 1924. In a study of decline curves from a large *The expression "well density" as utilized herein refers to the number of acres attributed to each well in a uniform well pattern, and is expressed in acres per well. The term "well spacing" Is utilized to denote the average distance between adjacent wells in a uniform well pattern. †Although the Cutler rule is treated critically in this discussion the authors intend no personal criticism of W. W. Cutler or of his hark The currently accepted concepts of reservoir mechanics were no": existent at the time of Cutler's work, as were even the moat basic tools (such as the bottom hole pressure bomb) for observing reservoir behavior.

Jan 1, 1950

By H. Leslie Bullock

From aluminum to zirconium, the quantitative preponderance of quartz as a gangue material is well recognized. lf this material is to be efficiently removed, its variations must be understood. Variations with temperature are especially important. Too little attention has been given to the thermal polarization of quartz. Under closely controlled conditions, electrostatic upgrading is very reliable. For efficient separation, contact charges must be fostered and charges due to radiation, surface coatings, or thermal polarization avoided. This paper lists thermal transition points of quartz and shows their effect on actual separations. Simple separation tests with all factors except temperature held constant are recommended for determining transition points. With silica making up more than 27% of the earth's crust, its oxides comprising more than 59% of all igneous rocks, and quartz accounting for most of the main free oxides, the mining engineer is in constant contact with quartz, which may occur as a valuable mineral to be purified or, far more frequently, as a gangue material to be removed as completely and economically as possible. As a means of effecting such purification or removal, dry beneficiation is becoming more and more desirable owing to local water scarcities, wet waste disposal problems, or freezing conditions. One method that has been gaining particularly rapid acceptance is electrostatic beneficiation, or the separation of dry free-flowing materials by means of opposite surface charges, differences in potential, or differences in conductivity. Electrostatic beneficiation dates back to the 1870's, but only in recent years have newly developed methods and apparatus and a growing knowledge of solid-state physics widened the field for its economical application. Because the term "electrostatic beneficiation" has been rather loosely used in the literature, it has come to include both electrostatic and electrodynamic procedures. Attracting type separators, however, in which oper- ation is based on differences of surface charge or potential, are truly electrostatic, because the separation occurs in a substantially static field set up between oppositely charged surfaces. Separations with this type of equipment may occur at potentials as low as 1000 v and seldom require potentials as high as 30,000 v. In the new contact charge dielectric separators1 the variation in charge is produced by continuous contact and separation of the particles in the moving feed stream and these charges are fostered by the use of non-conducting support and feed surfaces and by handling the feed in the form of streams of appreciable depth. This favors uniformity of feed and allows higher production rates. The distinctive surface charge differences are set up on the separation of the particles according to Coehn's Law,2 which states that equal and opposite charges are generated on the separation of any two materials in contact and that the substance having the highest dielectric constant will be positively charged. The basic contact charge concept is reliable, but all electrical charges are transient and modified by the electrical conditions of the surroundings. Pyro-electric, photoelectric and radiant effects may modify or totally destroy the contact charges necessary for efficient separation, or contact with conducting surfaces may neutralize them. Such hostile conditions must be carefully guarded against, since they have led to many costly failures in the past. The most consistent difference in surface charges to insure good separation is produced by repeated uniform contact and separation of particles in the moving stream. The thickness of the feed stream possible with this method reduces the effect of contact with the supporting surfaces, but as some contact is inevitable, the best results may be assured by having the dielectric constants of the supporting surfaces between the dielectric constants of the substances to be separated. In general, the hard smooth surface of quartz makes it an ideal substance for electrostatic separation from most minerals. For instance, with calcite, starting with a feed containing 1.9% acid insolubles, one can produce a concentrate containing 0.30% acid insolubles with a tailings containing 21.7% acid insolubles and a yield of 92.8%. The color can be held at 92 or above and the tint at 1.7 or lower. Working with specularite iron ore, laboratory work has given a concentrate of 68.8% Fe., with an iron unit recovery of 96.7%. Excellent results are also in pros-

Jan 1, 1969

By N. J. Grant, R. Nordheim

An extensive study was made of the aging characteristics of alloys based on the 80 pct Ni-20 pct Cr composition hardened with aluminum and/or titanium, each up to 4 pct. Aging was followed by means of hardness and hot electrical resistance measurements as well as by X-ray and microscopy. Stress rupture tests at 1500°F were utilized as a check on the predicted behavior. THE titanium and aluminum hardened Ni-Cr alloys, exemplified by Nimonic 80 and Inconel X, constitute one of the more important groups of alloys developed to meet the demand for materials retaining their strength at elevated temperatures. For service in the temperature range 1200" to 1500°F, these alloys offer high creep resistance. With increasing service temperature, however, the strength of the simpler Ni-Cr base alloys falls off rapidly so that above 1500°F there is a significant loss of strength. The present investigation was undertaken with the hope that a better understanding of the factors controlling the precipitation hardening of these alloys would make it possible to increase the useful service temperature range. Primarily this investigation involved the study of the effects of titanium and aluminum on the hardening and the subsequent softening at elevated temperatures. The titanium and aluminum contents were each varied between 0 and 4 pct by weight at a constant nickel to chromium weight ratio of about 4:1. (Except when otherwise stated, all compositions are expressed on a weight basis.) The major part of the investigation was confined to alloys with less than 0.06 pct C. Recently several papers dealing with the identity of the microconstituents in the titanium and aluminum hardened Ni-Cr alloys have been published. Using X-ray analysis of the residues from anodic dissolution, Rosenbauml was only able to identify carbides and nitrides in Nimonic 80 and Inconel X. However, since Rosenbaum worked with alloys in the hot rolled rather than in the aged condition, his results are inconclusive. Recently Hignett' reported that the hardening of Nimonic 80 was due to the controlled precipitation of Ni,(TiAl) having the cubic Ni3A1 structure. Taylor and Floydv-" published the results of an investigation of the nickel-rich corner of the Ni-Cr-Ti, Ni-Cr-Al, and Ni-Ti-A1 systems. In the Ni-Ti and the Ni-A1 systems the hexagonal Ni,Ti phase, 7, and the cubic Ni3A1 phase, -y', respectively, exist in equilibrium with the nickel-rich solid solution. The interatomic distances in the basal plane of Ni,Ti and the octahedral planes of the matrix are almost equal, thus explaining the Wid-manstaetten type structure formed when Ni,Ti precipitates from solid solution. When Ni:,Al precipitates from solid solution, it appears usually in globular form, often dispersed along rows corresponding to definite crystallographic directions. The 7 and phases are also the only intermetallic compounds which occur in the nickel ternary alloys with up to 25 pct Cr and 10 pct Ti or Al. Taylor and Floyd found that Ni,Ti takes practically no nickel, chromium, or aluminum into solution. Nial, on the other hand, dissolves a considerable amount of chromium and titanium and some nickel. Up to three out of every five aluminum atoms could be replaced by titanium in Ni,Al. This substitution caused a slight increase (less than 1 pct) in the lattice parameter. With respect to the effect of variation in the titanium and aluminum contents on the high temperature strength of Nimonic 80 type alloys, Pfeil, Allen, and Conway" reported that an 80 pct Ni-20 pct Cr alloy containing 0.20 to 0.30 pct A1 had the highest creep resistance when the titanium content was kept between 1.65 and 2.75 pct. Experimental Procedure The materials used for this investigation were electrolytic nickel, electrolytic or low carbon chromium, sponge titanium and 2s aluminum. The alloys were melted in an indirect carbon arc furnace under

Jan 1, 1955

By J. W. Leomrd, B. A. Donahue

Results of research are presented examining the extent to which the analytical characteristics of the relatively distinct coal bands from a variety of coal seams can be related to each other. This paper dis-cusses an approach for developing a practical coal petrographic quality control program based on conventional analyses, most of which is part of the standard A.S.T.M. procedure. The work is a final follow-up to Part I of this series which was prepared by the authors as an approach to applying conventional coal petrography to single coal seams. Recent published work by the authors entitled Petrography for Coal Mining and Coal Prepration: Part I dealt with interrelating various chemical and physical properties of coal1 measured using conventional analyses made on distinct petrographic bands taken from single coal seams. Since most coal production facilities process coal from a single coal seam or from very closely related coal seams in the same area,2 emphasis on interrelating the properties within a single seam appeared appropriate. The distinct petrographic bands were analyzed on the assumption that such differentiated data would be more representative of a heterogeneous coal seam than the single analytical value commonly used to characterize each property of an entire seam.34 Effort was directed at demonstrating the extent to which the interrelated chemical and physical properties 5,6 could be developed into nomographs or petrographic standardization graphs. Thus, one analysis, determined on a series of petrographic fractions separated from a single sample, was used to estimate numerous other properties in each fraction by referring to the previously established petrographic standardization graphs. This conventional approach to coal petrography was undertaken as a suggested feasible means by which a few coal analyses could be employed to develope a more penetrating knowledge of the properties of coal from any given seam in order to monitor more extensively its performance at the point of utilization. Such procedures can support development of the type of in- formation commonly sought through automated testing and through the use of computers.7 The broad knowledge which can be developed through these procedures is intended for application in the generation of an analytical profile or broad characterization of coal. These estimates were not intended as replacements for individual coal analytical tests. In this expanded second part of the research program, distinct petrographic bands from nine coal seams in the Central Appalachian Region were physically and chemically analyzed to elucidate the extent to which this concept of conventional petrography could be broadened for application to numerous coal seams. In presenting this second phase of work, the relationships developed are presented individually and not in a connecting series of nomographs or petrographic standardization graphs as in the previous work, thus leaving open the combinations of possibilities to individual interpretation and application. MATERIAL AND EXPERIMENTAL WORK Nine coal seams, representing a wide range of rank, from the Central Appalachian coal fields were used in this study. The distinct petrographic bands from the Kittanning, Pond Creek, Jawbone, Tiller, Poca-hontas No. 3, No. 2 Gas, Eagle, Winifrede, and Pittsburgh coal seams were separated by carefully removing a portion of each band at the face of the seam. The following were determined: ash, sulfur, free swelling index, heating value, bulk specific gravity, volatile matter, Hardgrove Grindability Index, and Gieseler Plastometer measurements. Determinations, where procedures were available, were carried out using ASTM standard procedures.8 Bulk specific gravity was determined using a kerosene volume displacement procedure modified from a method applied by Headlee and McClelland of the West Virginia Geological survey,9 Those bands with a bulk specific gravity greater than 1.60, which is generally above the practical specific gravity cleaning range of bituminous coals, were excluded and no analyses were performed. Much of the initial organization of this second phase of work was developed through the extensive use of a computerized statistical monitoring program (see Ref. 4). However, in order to achieve the closest possible interpretation of results, the final organization of data proceeded mainly from exhaustive trial

Jan 1, 1968

By Barry D. Lichter, Pierre Sommelet

High-temperature heat contents of InSb, GaSb, and AlSb were measured over the temperature range 400" to 1450°K using a diphenyl ether drop calorimeter. Smoothed ualues of the thermal properties, H$ - H:9s, have been derived and are tabulated at even temperature intervals. The heats of fusion of the three compounds were determined as, respectively, 5707 *100, 7780 * 100, and 9800 5 3011 cal per g-atorn at the determined melting points of 797" l°, 985" * , and 1330" * 5°K. The calculated entropies of fusion are, respectively, 7.16 0.12, 7.90 * 0.11, and 7.37 * 0.23 cal per deg per g-atotn. The heat capacities increase substantially on tnelting in contrast to the behauior of structurally related germanium and silicon. Deriations from the Kopp-Neumann rule are negative for solid compounds and positive for the liquid phases. Previously obsevrrd "post melting" in InSb is confirmed. The high-temperature thermal properties of 111-V compounds are presently not well-established, despite the technical importance of these semiconducting cbmpounds. Uncertainties in available heats of fusion and heat contents have seriously hampered thermo-chemical evaluations' and thermodynamic analyses of phase equilibria2"" in these systems. This paper reports results of high-temperature heat content investigations of InSb, GaSb, and AlSb measured in the range 400" to 1450°K employing a diphenyl ether drop calorimeter. Similar measurements for InAs and GaAs will be reported in a following publication.~ EXPERIMENTAL PROCEDURES Samples. High-purity samples of the compounds InSb and GaSb were supplied in the form of crushed crystal fragments by Dr. Carl Thurmond of the Bell Telephone Laboratories and in the form of single crystals by Dr. A. Strauss of the M.I.T. Lincoln Laboratory. Single-crystal samples of semiconductor-grade AlSb were supplied by Dr. W. P. Allred of the Bell and Howell Research Center. Chemical analyses indicated that all compounds were stoichiometric to *0.1 at. pct, which is within the experimental uncertainties of the analyses. Samples were crushed, weighed, and encapsulated in evacuated, thin-walled, fused silica capsules. The capsules were nearly identical in external shape, 2 cm by 2 cm diam, but varied in weight due to differences in wall thickness. One sample of AlSb was contained in a thin-walled, high-purity alumina cup encapsulated in silica and used for heat content determinations of liquid AlSb. The capsule materials showed no visual evidence of reaction with any of the compounds. The sample and capsule weights are given in Table I. Calorimeter. A Bunsen-type calorimeter, similar in design to a previously described instrument6 but employing diphenyl ether (C6H5)'0 as the calorimetric substance, was used for measurements of heat contents above 300.0°K, the melting point of diphenyl ether. Heat input to the calorimeter caused isothermal melting of diphenyl ether, and the resulting increase in volume was measured by displacement of mercury from the calorimeter into a 200 cm horizontal, calibrated capillary, 1.25 * 0.01 mm diam, or into a weighed beaker. The advantages of diphenyl ether over water have been previously pointed out7 and include: i) an increase by a factor of 3.5 in sensitivity as measured by the ratio of the volume change to the enthalpy change on fusion, ii) the smaller required extrapolation from the melting point to the standard temperature of 298.17"K, and iii) the positive volume change on fusion of diphenyl ether in contrast to the contraction which occurs on fusion of ice. Diphenyl ether was purified by fractional crystallization to 99.95 mol pct as determined from the melting point depression with fraction crystallized. During assembly of the calorimeter, the ether was repeatedly outgassed under high vacuum to remove dissolved air. The calorimeter receiving vessel consisted of an 8-in.-long by 1:-in.-diam copper tube with twelve horizontal 3-in.-diam radiator "fins" for dissipating heat to the surrounding mantle of diphenyl ether. Before forming the mantle the chamber surrounding the receiving vessel contained 3300 cu cm of liquid diphenyl ether above 250 cu cm of mercury which was

Jan 1, 1970

By E. R. Buchanan, R. E. Reed-Hill

Cylindrical magnesium single crystals were deformed in torsion. The axis of torsion was the basal pole. Five crystals were deformed to different strains between 0.08 and 1.03 and then sectioned in order to determine their dislocation densities using the transmission electron microscope. The work hardening rate of all specimens was at least an order of magnitude higher than that normally associated with easy glide in a tension test and comparable to that obserzed in stage B of a tension test. The correspondence between stage B in a tension test and the initial stages of a torsion test is believed to result from the fact that in both cases deformation occurs in a structure containing roughly equivalent densities of the dislocations associated with the three basal slip vectors. THERE are three basic ways of changing the shape of a crystal using slip dislocations. The crystal can be sheared along a slip direction in a slip plane; it can be bent about an axis in the slip plane normal to the slip direction; and, if the slip plane contains multiple slip directions, it can be twisted or rotated about the slip plane normal. Of the three processes, generally known as translational, flexural, and rotational slip, only rotational slip has not been extensively investigated. The object of the present research was to obtain basic information about this phase of crystalline plasticity. This paper is concerned with some aspects of the stress-strain curves obtained by twisting magnesium crystals about their basal poles. Magnesium was selected for four reasons. One, its recovery rate at room temperature is relatively low. Two, single crystals may be easily grown. Three, at room temperature the critical resolved shear stress for basal slip is about two orders of magnitude lower than that for nonbasal slip, so that rotational slip might be expected to occur primarily by basal slip. Finally, relationships between flow stress, shear strain, and dislocation density have been determined for tensile deformation of magnesium crystals,' thereby providing a basis of comparison for the torsional results. EXPERIMENTAL PROCEDURES Crystals were grown from 0.5 in. diam extruded sublimed magnesium rod furnished by the Dow Chemical Co. who reported that it contained in weight percent less than 0.0003 Al, 0.01 Ca, 0.01 Cu, 0.0012 Fe, 0.001 Mn, 0.0005 Ni, 0.003 Pb, 0.001 Si, 0.01 Sn, and 0.02 Zn, with the balance magnesium. All crystals were grown in a dried argon atmosphere using Jill-son's2 modified Bridgman technique. Two different methods were used to obtain crystals with the basal plane normal to the specimen axis. These included direct growth from seeds of the proper orientation, and spark machining (trepanning) of 0.5 in. diam cylinders from larger (1.5 in. diam) randomly grown crystals. The crystals thus produced were polished in a 20 pct HC1 water solution and then etched in a 1 pct HC1 water solution to develop etch pits lying in rows parallel to the basal plane trace. The crystals were then revolved about their axes on the stage of a low-powered microscope. Torsion specimens were prepared only from those crystals whose axes were normal to the rows of etch pits. It is estimated that this simple orientation method was accurate to about 51 deg. 1.625 in. long cylinders were next cut from these selected crystals and then acid machined in a 20 pct HC1 water solution into torsion specimens with a 1 in. long by 0.30 in. diam reduced gage section. Following this, they were annealed in air at 400°C and furnace cooled to room temperature. The specimens were given a final polish in a 10 pct HC1 water solution, rinsed in ethanol, dried, and cemented into brass grips with an epoxy resin. In addition to the torsion specimens, several tensile specimens with their basal planes at 45 deg to the stress axis were also prepared with similar dimensions except that the gage sections were increased to 4 in. in length. The torsion specimens were tested in the apparatus

Jan 1, 1970

By W. M. Robertson

The kinetics of grain boundary groove formation on copper surfaces immersed in liquid lead have been studied over the temperature range of 400° to 900°C. The groove widths were Proportional to the cube root of the annealing time, indicating that the diffusion of copper through the saturated liquid-lead solution is the mechanism by which grooves form. The rate constant for the process can be calculated by a theory due to Mullins. Using published data for the solubility of copper in liquid lead, for the interfacial energy of the solid copper-liquid lead interface, and for the diffusion coefficient of copper in liquid lead, the calculated rate constants almost exactly reproduce the measured values over the entire temperature range. The decay of scratches placed on copper surfaces has also been studied. The rate constant for scratch decay agrees with that for grain boundary groove growth, though scratch decay is sensitive to convection currents in the liquid. The interaction of solid and liquid metals has been studied extensively and has been found to be rather complex. Many of the studies have been complicated by a host of competing effects, including temperature gradients, concentration gradients, the formation of one or more intermetallic phases, natural or forced convection, and the presence in both the solid and liquid of considerable amounts of impurities and alloying elements. Recently theories have been developed of changes in surface profiles driven by capillary forces,' which allow the interaction of the solid and liquid to be analyzed quite directly. The present paper reports a study of the formation of grain boundary grooves on pure copper immersed in liquid lead, which allows the theory to be checked quantitatively. The Cu-Pb equilibrium diagram is quite simple: there are no intermetallic compounds, copper is just slightly soluble in liquid lead, and lead is almost completely insoluble in solid copper.2 The Cu-Pb system has been studied extensively,3-9 and all of the quantities—interfacial energy, diffusion coefficients, and equilibrium solubilities-necessary to calculate the rate of groove growth by a volume-diffusion mechanism are known. The kinetics of grain boundary grooving and scratch smoothing have been studied on the noble metals and the iron group metals in a reducing atmosphere or in vacuum.10 The main interest of these studies has been the determination of surface-diffusion coefficients at metal-gas interfaces using the theories developed by Mullins.1 The present paper uses similar methods for the study of diffusion processes at the interface between two condensed phases. There has been one previous study" of the kinetics of groove growth in a solid-liquid system, which, however, was troubled by the fact that neither interface energies nor diffusion coefficients were known in the Ni-S system studied. THEORY The theory of grain boundary groove growth has been developed by Mullins for the cases of volume diffusion," surface diffusion," and a combination of the two processes.14 He has also analyzed the kinetics of the flattening of a scratched surface by these processes.l5,l6 Several assumptions and approximations were used in the derivations of the surface profile shapes. The applicability of these assumptions and approximations to the present system will be considered in the discussion. At the intersection of a grain boundary with an initially flat interface the equilibrium between the interfacial energy and the grain boundary energy establishes an equilibrium groove angle. This induces curvatures in the interface. The chemical potential of material at a curved interface is higher than at a flat interface, so that material moves away from the region of the grain boundary. Mullins' calculations indicated that the groove profile would be similar to that shown schematically in Fig. 1. Small humps form above the level of the original flat surface. For a volume-diffusion mechanism the separation, w, of these humps at a time, t, is given by and where co is the equilibrium concentration of the solid in the liquid, y, the solid-liquid interfacial free energy, O the volume occupied by a solute atom in the liquid, D the diffusion coefficient of the solid in the liquid, and kT has its usual meaning. For a surface-diffusion mechanism the groove width is proportional to the fourth root of the time. For grooves forming by a combined surface and volume-diffusion mechanism the exponent of the

Jan 1, 1965

By P. Greenfield, P. A. Beck

The phase is a hard and extremely brittle material with a tetragonal crystal structure, containing 30 atoms per unit cell' It occurs in many binary and ternary alloys of the transition elements. The existence of twelve a phases has been reported in binary alloys of metals from the group vanadium, chromium, molybdenum, and tungsten with metals from the group manganese, iron, cobalt, and nickel. It is a characteristic fact that the composition of the o- phases in the various binary systems is not the same. Rather, there is a gradual shift in composition, for instance in the series of chromium a phases, approximately as follows: CrMn,, FeCr, Cr3Co,. In recent years several ideas have been put forward to account for this variability of composition. SullyZ proposed that a was a type of electron compound, characterized by 1.7 electrons per atom in excess of the number required to fill the Pauling atomic orbitals. These excess electrons were supposed to just fill the first Brillouin zone of the u structure. However, later work indicated that the phase is ferromagnetic at low temperatures, so that a- is unlikely to be a full zone compound.~ Another proposal,* which is also based on the structure of the transition elements advanced by Pauling, and in fact leads to essentially the same a compositions as Sully's theory, suggests that the u phase is characterized by a constant number of electron vacancies per atom. The electron vacancy numbers N,. used were originally the same as those in the Pauling theory, but were later modified empirically vn order to bring about better agreement with data for the p phase in certain ternary systems. For alloys, N,, was calculated on the assumption of simple additivity from the electron vacancy numbers of the components, as follows: N,. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2 (Fe) + 1.71 (Co) + 1.6 (Ni). On this basis a reasonably constant value of N, = 3.4 was obtained for all of the binary u phases and a fairly constant value of N,, = 3.1 for the various p phases. More recently, Bloom and Granta pointed out that a similar correlation with the total number of 3d and 4s electrons per atom is also fairly well fulfilled and concluded that no reference need be made to the Pauling theory. This proposal does not lead to the same binary a compositions as the one described above, so that the relative merits of the two proposals may be determined on the basis of direct comparison with experimental composition data. The purpose of the present paper is to provide such a comparison. Since the experimental data for the composition ranges of several of the known u phases were rather incomplete, it was decided to carry out new experimental determinations for many of the binary systems. Experimental Procedure The alloys were prepared by induction melting in recrystallized alumina crucibles, either in vacuum or in helium atmospheres. Some aluminum was picked up from the crucibles in the alloys of high vanadium content, but this was minimized by keeping the alloys in the molten state for as short a time as possible. The maximum aluminum impurity was 0.13 wt pct by chemical analysis, in an alloy containing over 50 wt pct V. In general, the as-melted compositions agreed accurately with those obtained by chemical analysis. In the case of manganese, however, losses inevitably occurred; consequently all manganese alloys were analyzed. Specimens of all alloys were annealed at temperatures ranging from 1000" to 1300°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. All manganese alloys were sealed in quartz tubes under vacuum before annealing. The specimens were held at temperature for between four and eight days before being quenched into cold water. Alloys were prepared for microscopic examination by mechanical polishing, usually followed by electrolytic etching. X-ray diffraction specimens were prepared by crushing the homogenized alloys, and by reanneal-ing the obtained powders in evacuated quartz tubes for a few hours at the temperature of the lump anneal. X-ray diffraction patterns were made with unfiltered chromium radiation, using an asymmetrical focusing camera of high dispersion. Using microscopic and X-ray techniques jointly, the accuracy

Jan 1, 1955

By C. Gatlin, N. E. Garner

Results of impulsive wedge penetration tests on two synthetic, plastically deforming rocks are presented. Basic data obtained were force-time, displacement-time, and force-displacement curves for the impacts, plus the crater geometry. Wedge geometry and blow frequency were varied over a considerable range. The synthetic rocks consisted of wax-sand mixtures; two waxes of diflerent ductilities were used to provide variable "rock" characteristics. Conventional triaxial tests showed that these synthetic rocks exhibited force-deformation curves and Mohr envelopes quite similar to real rocks, except that strengths were much lower. Measured forces from static penetration tests agreed closely with theoretical values; however, dynamic force values were much higher than the static. These latter disparities are attributed to the viscous nature of the waxes. Thus the utility of these or similar rock models must depend on the scaling of rock viscosity, which is as yet unknown for impulsive loadings at elevated stress states. It appears, however, that some macroscopic, static phenomena may be studied with wax-sand rock models. INTRODUCTION The resistance of solid materials to indentation or perforation by projectiles or other penetrators has been studied by workers in many areas. Despite these efforts no universally accepted laws or formulas are available for describing experimental observations. In the metals field the force-deformation behavior of impacting bodies is often analyzed by the Hertz law for elastic collisions, the Meyer law if plastic deformations occur, or some combination of both.' The similarities of these expressions to empirical drilling formulas of the oil industry are apparent. Beginning with the basic contributions of Simon and co-workers at Battelle,' a number of experimental papers concerning the reaction of rocks to vertical impact have appeared in the U. S. mining and petroleum literature.'-' Most published data have, to date, been obtained at atmospheric pressure, although some early high pressure information was reported by Payne and Chippendale.8 Maurer" has recently utilized available brittle impact data to develop a drilling rate equation based on the experimentally observed proportionality between crater volume and blow energy. His result agreed with earlier efforts by both Somerton, who used dimensional analysis, and Outmans, who used plasticity theory. It has long been known that rocks exhibit different modes of failure depending on the state of stress. The literature in this area is considerable; however, papers by Bredthauer, Handin and Hager,13 nd Robinson", are adequate to illustrate the point. Since rocks flow plastically at certain triaxial stress conditions, the mathematical theory of plasticity has been used to analyze the rock drilling problem. Cheatham'" has altered the wedge identation solution of Randtl to rocks, and has developed useful equations for penetrator forces under a variety of conditions. Outmans" has utilized Hill's solution in a similar manner to develop a drilling rate equation. Both Cheatham and Outmans used the linear Mohr-Coulomb rule to relate rock strength and confining pressure. The actual stress at the hole bottom is not easily ascertained, although photoelastic studies by Galle and Wil-hoit," plus the analytical treatment of Cheatham and wilhoiti8 provide some insight. Consequently it is not clear to what extent the highly idealized rheological model of a perfectly plastic solid can be realistically applied to the rock drilling problem. This paper is the first report on a long range experimental study of crater formation in rocks at elevated stress states. The data presented here are from the first phase of the project. Data obtained from impulsive wedge impacts on two synthetic, plastically deforming rocks are presented. MODEL ROCKS Geologists have long been faced with modelling the behavior of the earth and, as a consequence, have studied scaling problems in some detail.' In general, their main problem is handling the wide disparity between laboratory and geologic time. In our studies the time effects (blow velocity or rate of loading, blow duration, etc.) were essentiafly the same for both. model and prototype, as were were geometry and tooth penetration. Thus application of available scaling laws suggests that Similarity is obtained if the stress-strain curves of model and prototype are similar." For this reason Hubbert and Willis''

By R. E. Miner, J. K. Jackson, T. L. Wilson

A study has been made of the transformation kintetics and morphology in gas-quenched Fe-5 pct Ni alloys. Massive ferrite or nlurtensite was found to form at temperatures in agreement with earlier results. Surface Preparation appeared to have the greatest effect in determining the type of transformation Product formed. Grain size change, subgrain morphology, and dislocation densities of massive ferrite were essen-tinlly invariant functions of cooling rate. The mar-tens~tic structures were typical of transformation in austenite grains of the order of the sample thickness. BY introducing the idea of a massive transformation in dilute iron-base alloys, Gilbert and Owen in 1962 served to stimulate a closer inspection of phase transformations in ferrous systems.' A wealth of literature has followed concerned with the morphology,2-5 transformation mode,2'3'6-8 and thermodynamics of transformations.2,5,9 interesting controversies have resulted from the experimental observations; closer attention has been paid to the definition of massive transformations and still to be resolved is the Ms temperature of pure iron. The purpose of this note is to report some observations made in a detailed kinetic and metallographic examination of the transformations that occur in gas quenched Fe-5 pct Ni. The results are pertinent to the Ms extrapolations that have been made for pure iron and the observed substructure of massively transformed alloys. PROCEDURE The material used in this investigation was cast as a 5 lb vacuum induction melted, carbon deoxidized heat. The ingot was hot worked to a strip 0.10 in. thick, decarburized, and cold rolled to final thickness. Specimens were punched to sample shape and decarburized in wet hydrogen at 600°C. The chemistry of test specimens is indicated in Table I. Samples 1 by $ in., by thickness were resistance heated and rapidly cooled in an apparatus as illustrated in Fig. 1. Similar helium quenching apparatuses have been described previously;2,6'10 the distinguishing feature of this apparatus is the nozzle geometry. Twin nozzles with three convergent-divergent, sonic ports were mounted perpendicular to the specimen for quenching purposes. The specimen temperature was monitored with an intrinsic 3 mil chromel-alumel thermocouple spot welded to the specimen and con- nected to an oscilloscope. A single switch stopped the current flow through the specimen, opened a gas flow solenoid valve, and initiated an oscilloscope sweep. Cooling rates were read directly from a photograph of the oscilloscope trace and the quenching rates quoted later were made at a point immediately prior to transformation on the trace. All quenching studies were conducted either under a vacuum of 10"-5 torr or a helium atmosphere. The sample geometry was chosen large enough to permit optical and electron microscopy to be performed on samples. The samples were electropolished for both types of examination in a perchloric-acetic solution. Electron microscopy was conducted on a HU 11A microscope operated at 100 kv. Dislocation densities were determined at the same general operating reflection (110) on foils thick enough to produce Kikuchi patterns. RESULTS AND DISCUSSION Transformation Temperature Observations and OD-tical Microscopy. The quenching results of this study are illustrated in Fig. -2(a). Samples which were treated in the as-decarburized condition transformed in a manner similar to that reported previously—a decrease in transformation temperature occurred as the quenching rate increased until a plateau region was reached. Within the scatter of the results obtained here, there was no break in the transformation temperature-quenching rate plot. This suggests no change in transformation mode. Further metallographic examination confirmed this observation. A martensitic transformation was obtained for similarly treated samples except that the surface was first electropolished. The Ms temperature was approximately 85°C below the plateau determined for the unpolished samples and cooling rates as slow as 2000°C per sec were adequate for producing marten-site. The transformation temperatures are in gen- / STRIP SAMPLE / COPPER I SAX/-/}' / CONNECTOR-----A f, SON|C poRTS AC LEADS 3j ]j"I rofe[ \ Mf/yinK/iKj''^ THERMOCOUPLE X-(^—iie"s*c? ' LEADS 1 INCH Fig. 1-—Schematic scction of gas quenching apparatus

Jan 1, 1970

By B. C. Raynes

IN the early part of 1952, under the auspices of the U. S. Atomic Energy Commission, Horizons Inc. undertook an investigation dealing with the preparation of high purity thorium metal in order to develop an economically competitive production process for this metal based on a recovery of the metal by a fused salt electrolysis, since a survey of the literature of thorium chemistry indicated that electrolytic methods had not received much attention, despite the consideration that electrochemical production methods often offer attractive commercial potentialities. Thorium metal has been prepared by methods which fall into four general categories: 1) reduction of halides or double halides; 2) reduction of the oxide; 3) thermal decomposition of halides; and 4) electrolytic methods. Some of the important results obtained by various investigators since about 1900 in recorded attempts to prepare pure thorium metal are summarized in Table I. A bibliography of pertinent literature is included in this paper. Thorium is strongly electropositive and possesses a great affinity for oxygen and nitrogen. As a result the prospects for the production of high purity thorium from aqueous media or oxygen bearing compounds are remote. The most promising and profitable area of investigation for production of thorium metal lies in fused salt electrolysis. Thorium has been produced previously by this technique from halide salts in fused alkali chloride eutectic mixtures. Until recently, however, the lack of known large uses for thorium has inhibited the investigation of these methods. The basic problem in an investigation into fused salt production methods for thorium is to develop a suitable fused salt system for the economic preparation of thorium. The first portion of the work in these laboratories was a small scale investigation of the electrolysis of potassium thorium fluoride, KThF5, under a variety of conditions. High purity thorium was prepared in this manner, but the process did not appear to offer the simplest and most attractive continuous commercial operation. The work reported here relates to an all-chloride system employing thorium chloride as the cell feed. ThCL4 was produced as an anhydrous material stabilized in molten sodium chloride. This product, further diluted in NaCl, was subjected to electrolysis. The electrolytic process has been studied in cells capable of holding up to 50 lb total salt charge. Ductile, pure thorium metal has been reproducibly obtained in this operation. Considerable experimentation was carried out in the preparation of ThCL as a cell feed free from moisture, oxides, and other impurities. Thorium was cathodically deposited as a coarsely crystalline powder interspersed with residual bath salts. Aqueous procedures for separating and recovering the metal were developed. The thorium metal powder obtained has been evaluated with respect to its hardness, chemical purity, and certain other physical properties. Preparation of ThC1,—Thorium chloride, and the chlorides of some other metals (aluminum, beryllium, tantalum, zirconium, etc.) cannot be obtained from aqueous solution by direct heating and evaporation. Evaporation and heating of a solution of thorium chloride yields a hydrated salt or partially hydrated salt, and finally Tho,. Anhydrous thorium chloride is obtained by forming a hydrated ammonium chloride complex salt in acidified water solution, dehydrating this compound, and finally decomposing the double salt and subliming the ammonium chloride component. Various methods for the preparation of anhydrous thorium chloride, in accordance with this concept, were investigated as indicated in Table I1 from hydrated thorium chloride (ThCl, . 3H2O), and from thorium oxycarbonate (ThOCO,). In the method found most satisfactory for this work, thorium oxycarbonate was dissolved in an excess of concentrated HC1 to give a clear yellow solution. At least 2 mol NH,Cl were added to the solution per mol of contained thorium. Ammonium thorium chloride hydrate was crystallized from solution by cooling and saturation with HC1. The resultant complex, (NH,Cl),ThCl;xH,O, was dehydrated by evaporation at 130° to 150°C and thoroughly dried at about 250°C. The dried ammanium thorium chloride was then mixed with sodium chloride in proportions to form NaThCL or to produce a ThCL4-NaCl mixture with a given thorium content. The ammonium chloride was sublimed off at temperatures above 500°C in an inert atmosphere furnace to give an anhydrous chloride source electrolyte, essentially free of Tho, and of NKC1.

Jan 1, 1958

By J. F. Martin, J. E. Friedline, L. M. Melnick, G. E. Pellissier

A method has been developed for determining gases in steel in which the gases are extracted by vacuum fusion and analyzed by mass spectrometry. This method is especially applicable for determining small amounts of oxygen and nitrogen. The lower limit of detection for both oxygen and nitrogen is 0.0001 pct with an average deviation of about 0.0001 pct for oxygen and 0.00008 pct for nitrogen. Hydrogen analyses by this method are in good agreement with analyses by vacuum tin-fusion. A complete analysis of all gases extracted from a steel sample can be accomplished in 40 min. It has long been known that certain of the gaseous elements exert particular effects on the physical and mechanical properties of steel. With the recent advent of new experimental steelmaking practices it is now possible to obtain steels with extremely low contents of such elements as oxygen and nitrogen. Present methods for determining these two gases are of insufficient sensitivity as applied to steels made by these newer practices, and therefore a new technique was considered necessary. A review of the literature showed that the conventional vacuum-fusion method1 was the procedure most suitable for modification to obtain a sensitive method for determining the gaseous elements present in steel simultaneously. However, for trace amounts of gases it is impractical to increase the sample size because of the physical limitations of the apparatus and the increased degassing time which would be necessary. Also, when only one of the desired gases is present in trace amounts, quantitative separation by conventional vacuum fusion is almost impossible. Since small analytical mass spectrometers are now commercially available, it was decided to use this instrument in conjunction with conventional vacuum fusion for both qualitative examination and quantitative determinations of the gaseous elements in steel. This technique has already been used with success for the analysis of copper and lanthanum.2"4 APPARATUS A vacuum-fusion unit was first designed and built, Fig. 1. This unit was designed especially for the determination of small amounts of nitrogen and/or oxygen in steel since an acceptable method (vacuum tin-fusion)5 was already in use for the determination of hydrogen in steel. The vacuum system was con- structed of Pyrex glass throughout. Mercury check valves were used in place of stopcocks in the high-vacuum section of the system. Ferromagnetic samples are normally introduced into the vacuum system through a mercury lift. In case of a break in the lift, the mercury is prevented from entering the furnace by a self-locking, mercury safety check valve, Fig. 2. This check valve, developed at our laboratory, is a modified T/S ball-and-socket joint placed in the sample inlet system between the mercury and the furnace. A sudden entry of mercury or air pushes this valve into the closed position, completely blocking the top of the mercury lift. The check valve is held in the closed position by the vacuum of the apparatus. A separate entrance tube also was placed in the system, so that samples which would amalgamate with mercury, or which are nonmagnetic, could be introduced into the furnace. A slightly modified Guldner-Beach furnace is used in this system.8 The optical flat was connected to the system by a ground-glass joint to facilitate cleaning, a quartz delivery tube was substituted for Pyrex, and the crucible was used uncovered. Fusion takes place in a high-purity graphite crucible insulated by — 200-mesh high-purity graphite powder. The crucible set (crucible and funnel) is suspended in a quartz crucible. The furnace envelope and the sample inlet system are exhausted by 2 single-stage, mercury-diffusion pumps in series. The first of these is a high-speed pump, which will work only with a very low backing pressure. This pump is used to exhaust the gases from the furnace as rapidly as possible. The second mercury-diffusion pump is used as a backing pump for the first; the capacity of this pump is much lower. However, it will work efficiently against a back pressure of 3 mm of mercury. To assure positive pumping, a modified Naughton and Uhlig condenser7 is used. With the use of proper valving the second pump is also used as a circulation pump in the catalyst system.

Jan 1, 1959

By M. Bevis, E. O. Fearon, P. C. Rowlands

Fe-Ni and Fe-Ni-C martensite specimens have been deformed in compression at room temperature and the habit planes of operative deformation twins determined by two-surface optical trace analysis. The full orientations of the martensite crystals were determined from divergent X-ray beam diffraction patterns. The experimental results are in excelled agreement with predicted twinning modes. In particular, the habit planes of some deformation twins in bcc martensites are consistent with a "Type XI compound'' twinning mode with Kl, Kz, 71, 77~ elements given by {5, 8, 11) {ioi}, (33) (ill) Tetragonal derivatives of this mode are operative in bct martensites. UnUSUAL deformation twinning modes have been reported by Richman' to occur in Fe-Ni-C martensites with bcc and bct structures. The twin habit planes were determined by single-surface trace analysis (pole locus method) and the remaining twinning elements were determined from the geometry of twin-twin intersections. The indices assigned to the observed habit planes are (3 101, "(089)" and "{0, 1,13)" or "{1,2,7} ", and only in the first case do the twinning elements correspond to a predicted twinning mode. This is mode 1.4 in the paper by Bevis et al. The results presented in Ref. 2 indicate that previously unpublished bcc and bct modes should be operative in preference to the (130) mode and anomalous modes reported by Richman. In view of these results and the uncertainties involved in determining habit planes from single-surface trace analysis and twinning elements from twin-twin intersections5 a two-surface trace analysis of deformation twins in Fe-Ni and Fe-Ni-C martensites has been carried out. EXPERIMENTAL PROCEDURES Two alloys with compositions Fe-23 pct Ni-0.6 pct C and Fe-30.4 pct Ni were prepared from 4N pure materials by induction melting under a vacuum of 10"5 mm Hg. The alloys were homogenized at 1350'~ for 5 days. Both of these alloys are austenitic at room temperature with M, temperature - — 50"C. The aus-tenite grain size of the Fe-Ni-C alloy was approximately 300 to 400 p. The Fe-Ni alloy was remelted in a vertical tube furnace and the melt lowered slowly from the hot zone of the furnace to produce s ingle -crystal austenite specimens. Specimens approximately 10 by 5 by 5 mm were cut from the ingots and quenched to various temperatures below the Ms temperature. The specimens were elec-tropolished in a 10 pct perchloric acetic electrolyte before being deformed in compression at room temperature. Martensite plates which exhibited profuse deformation twinning were selected for analysis and the specimen polished on a second surface such that the two surfaces which contained the martensite plate enclosed an obtuse angle of approximately 145 deg. The specimens were then electropolished to reveal the traces of the deformation twins on both surfaces. The full orientations of the martensite crystals were determined using a divergent X-ray beam technique (Kossel line technique) employing an AEI SEM2 electron probe microanalyzer. Details of this technique which include a detailed description of the Kossel camera attachment to the microanalyzer used in the present experiments have been discussed elsewhere.3 Only additional details relevant to this investigation are discussed here. The specimens were mounted with one surface normal to the incident electron beam as illustrated schematically in Fig. 1. The martensite plates to be analyzed were located using the normal scanning equipment of the microanalyzer. The position of the electron beam and hence the position of the source of divergent X-rays generated within the crystal could be located to within 1 p. Exposure times of approximately 8 to 10 min were required for back-reflection Kossel patterns and it was found that useful diffraction patterns could be obtained consistently from heavily deformed martensite plates. A reference line (carbon contamination mark) produced on the two surfaces of the specimen by scanning the electron beam in a direction having a known relationship with the reference !ine in the X-ray camera enabled the full orientation of the crystals to be determined. Martensite plates with widths as small as 8 p could be oriented using this procedure. The Kossel line patterns were interpreted using the charts developed by Rowlands and ~evis~ as generally

Jan 1, 1969

By N. J. Grant, D. Carne, J. B. Seabrook

IT is unnecessary to review much of the literature on hydrogen embrittlement of steel since several excellent reviews and bibliographies exist.1-3 Hot acid pickling and cathodic charging have been known to cause hydrogen embrittlement of steel and have been used as laboratory methods to charge steels with hydrogen.4-8 Experimental Procedure The problem of prime concern in all instances, except in the work of Sims and coworkers,10 is that at no time was there a definite known hydrogen value reported which could be related to a particular value of the degree of embrittlement. It was the purpose of this research to determine the relationship between hydrogen content and degree of em-brittlement quantitatively. The 1020 stock used for the specimens was hot-rolled 7/16 in. diam rod of the following analysis: 0.19 pct C, 0.40 pct Mn, 0.012 pct P, 0.036 pct S' Vacuum-fusion analyses for nitrogen and oxygen gave 0.014 pct O2 and 0.0011 pct N2. Cathodic charging was used to cause embrittle-ment. The advantages of this method were that no quenching was necessary, the impregnation was reasonably controllable, and representative samples for analysis could be prepared simultaneously with the charging of the tensile bars. Analyses for hydrogen were made in a vacuum-fusion type of apparatus which extracted gas from the samples by fusion in a molten tin-iron bath' This apparatus, which has recently been described in detail elsewhere, will not be discussed here.". " Consecutive samples can be analyzed every 15 min with an accuracy of 0'03 ppm. A A from an electrolytic or pickling bath can be charged for analysis in about 3 min, and analysis completed in 15 min. Samples of as-received 1020 stock were analyzed and found to contain a negligible amount of hydrogen (0.06 ppm). Preliminary pickling and electrolytic charging gave highly variable results. Cold-worked samples showed higher values but ranged from 0.6 to 6.0 ppm of hydrogen. Charging at 90°C gave higher values of charged hydrogen, but troublesome films on many of the specimens resulted. It was not until a few drops of a catalytic poison, prepared from 2 g of yellow phosphorus dissolved in 40 ml of carbon disulphide,8 was added to the electrolytic cell that fairly consistent high values of hydrogen could be charged into the as-received 1020 steel at room temperature. The cell used is sketched in fig. 1. The anode and fixture for the tensile specimens were fastened to the cell cover as shown, and the specimen was screwed in place, centrally located with respect to the anode. At first, anodes of lead and graphite were tried, but they contaminated the electrolyte and gave a slight deposit on the specimen. Later, a platinum wire was used in the form of a uniform helix. A current of 2 amp, corresponding to about 0.5 amp per sq in. of cathode, was used for most specimens. The electrolyte was 4 pct H2SO4 solution. Fig. 1 shows the form of the special tensile bar, the main portion of which was an ordinary 1/4 in. diam, 1 in. gauge length test bar, except that two to four small cylinders of stock were left attached by small links to the bottom end of the tensile bar for the purpose of providing samples for hydrogen analysis. Thus the bars and samples were charged with hydrogen simultaneously and an analysis could be made while the bar was being tested mechanically. Experiments were performed to determine how representative the test cylinders were of the middle of the test bar proper. While the bar center was being analyzed, the small cylinder was stored in dry ice, since it had been shown that such storage prevents loss of hydrogen for many hours.12 The results of these checks are shown in table 1. The checks are very good (0.3 ppm) and indicate that it is permissible to use the small end cylinders to establish the hydrogen content of the tensile test bar proper-

Jan 1, 1951

By R. A. Breitrick, J. N. Swinderman, J. J. Cooper, H. L. Bauer Jr.

The Robinson Mining District, near Ely, Nev., is one of the major porphyry copper districts in the world. Within the district is an eight mile long east-trending zone of altered porphyry, metamorphosed sedimentary rocks, and sulphide mineralization surrounded by Paleozoic limestone, dolomite, shale and sandstone, Tertiary volcanics, and Quaternary alluvium. Six major disseminated ore deposits have been exploited in this zone. About 20% of the district production has come from disseminated ore in metamorphosed sedimentary rocks found adjacent to altered quartz-monzonite porphyry. The following brief statements summarize some of the relations between porphyry alteration, metamor-phism, and mineralization: 1) Disseminated copper ore does not occur in unaltered porphyry or in m-metamorphosed sedimentary rocks. 2) Sedimentary rocks have been only weakly metamorphosed where intruded by unaltered porphyry. 3) Intensely metamorphosed sedimentary rocks are found only adjacent to altered porphyry. 4) Many hydrothermal minerals are common to both altered porphyry and adjacent metamorphosed sediments. 5) Disseminated ore is found in altered porphyry and adjacent metamorphosed sedimentary rocks. 6) In general, there is a direct correlation between grade of ore in porphyry and copper content in the adjacent rocks. 7) Chemical changes in the altered porphyry and metamorphosed rocks appear to be related. The foregoing relations support a hypothesis that the porphyry alteration, the metamorphism of the sedimentary rocks, and the ore deposition were all part of a continuous hydrothermal process which probably closely attended the porphyry intrusion. The Robinson Mining District, most often referred to as the Ruth or Ely District, is located in eastern Nev. and is one of the major porphyry copper districts of the world. Production from 1908 through 1962 was nearly 250 million tons of ore averaging a little over one percent copper with a total metal value of nearly one billion dollars. The ore has been produced from six major disseminated-type deposits with the Liberty Pit deposit accounting for 70% of the total district production. Less than one million tons of base metal and gold ores have been produced from the replacement-type deposits of the district. Approximately 20% of the district production has come from underground mining operations; the pit ore has been mined with shovels and removed by train haulage, truck-train haulage combinations, truck haulage, and presently by a combination truck-skip system. Many of the ore deposits formerly worked by underground methods have been and are being exploited by open pit methods. (See Fig. I.) Two co.'s have accounted for virtually the entire production from the district. In 1958 Kennecott Copper Corp. acquired the district assets of Consolidated Coppermines Corp. and is now the sole ore producer in the district. Present operations are confined to the Liberty Pit where 22,500 tons of ore averaging a little less than 0.8% copper is mined per day. Cutoff grade is 0.4% copper, and the stripping ratio is three to one. The ore is hauled by rail 23 miles to the McGill Reduction Plant where it is concentrated to about 20% copper. Molybdenite is recovered as a by-product in the mill. The copper concentrates are smelted in McGill, and the blister copper is shipped for refining to Balt. where gold, silver, platinum and palladium are recovered. The Robinson Mining District has been well known as a porphyry copper district for the past fifty years, but many geologists are unaware of the fact that a large portion of the production has come from disseminated ore found in metamorphosed sedimentary rocks. The scope of this paper describes the occurrences of disseminated ore in the various metamorphosed sedimentary rocks, and presents evidence for the hypothesis that these ores are genetically, spacially, and coevally related to the disseminated ore in the porphyry rocks. Publication of this paper was granted by the management of Kennecott Copper Corp. A. H. James suggested and encouraged the writing of the manuscript. Special mineralogical and spectrographic analyses were performed by the Kennecott Research Center. The deposits of the district have been studied by many geologists since the turn of the century, and

Jan 1, 1964

By C. G. Dunn, P. K. Koh

Microstructure, magnetic torque, and texture data before and after grain growth were obtained on two 3.25 pet Si-Fe specimens having initially the same cold-rolled textures and the same primary recrystallization textures. The latter textures consisted of four components, two only of which were strong; the strong components were near (120) [001] and (320) [001]. The textures of the two specimens obtained by grain growth were different. In one specimen the two weak components were converted into strong components by a secondary recrystallization process; in the other specimen the primary recrystallization texture was retained by a normal grain-growth process. The difference in behavior of the two specimens was interpreted in terms of a difference in the relative grain sizes between weak and strong components; i.e., in terms of a geometrical factor that would alter the early growth rates of grains belonging to the two weak components of the texture. Specifically the growth rate was considered as the product of two terms: a driving force and a boundary mobility. The texture changes observed are considered to favor the oriented-nucleation growth-selectivity theory more than the oriented-growth theory. WHEN primary recrystallization and grain-growth textures form as a result of annealing deformed metals or alloys, the fundamental processes involved are nucleation and growth. Knowledge, therefore, about nuclei and the factors influencing their growth is required not only for the understanding of texture development but also for its control. In the oriented-growth theory of texture formation1, 2, 3 the problem of nuclei is generally disposed of by the assumption that nuclei are available in all orientations; the theory then has to explain the final texture from the initial texture and the way boundary mobility depends on orientation. In the oriented nucleation theory of texture formation"' nuclei are considered to be present only in certain orientations but the importance of growth selectivity is still recognized. For example, the mobility of boundaries of approximately the same orientation and of the coherent type in twins is believed to be low while that of high-angle boundaries, in general, is high. Because of this the theory may be described as an oriented-nucleation growth-selectivity theory. The main feature of the oriented-nucleation theory, however, is the importance given to nuclei; i.e., how they form in specific orientations and how they grow. In the present investigation two cold-rolled single crystals were used to study the effects of growth after primary recrystallization. The cold-rolled textures and the primary recrystallization textures were determined from portions of these specimens and reported earlier.",' The two cold-rolled crystals were in the (111) [112] stable end orientation, the recrystallization textures were nearly identical and consisted of two strong components, designated M and M', which were near (120) [00l] and (320) [00l], respectively, and also some specific weak components near (111) [110] and (111) [110]. It is well recognized that a single strong component in the primary recrystallization texture may be needed for secondary recrystallization3, 5, 8 but unfortunately when this is the case the amount of material left in deviating orientation may be too small either for growth or for positive identification. The present samples proved to be almost ideal for the study of minor components and their influence on texture changes produced by growth after primary recrystallization. The results obtained are interpreted in terms of present knowledge of grain-growth processes. Experimental Procedure Two lots of silicon-iron alloy of essentially the same composition, namely, 3.25 pet Si, 0.004 C, 0.009 P, 0.010 S, 0.035 Mn, 0.070 Ni, 0.090 Cu, 0.009 Sn, with traces of A1 and Cr and the balance Fe, were converted into single crystals 0.025 in. thick and 1.25 in. wide. The orientations were predetermined by the method of reorienting a seed crystal as described elsewhere.3 pecimen 1 from one lot had the (335) [556] orientation while specimen 2 from the second lot had the (111) [112] orientation.* Both crystals were cold rolled to a reduction in thickness of 70 pet while widening approximately 20 pet. Samples of each were selected for determining 1) the cold-rolled texture, 2) the time required at

Jan 1, 1959

By B. H. Sage, W. N. Lacey

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949

By H. H. Podgurski, F. N. Davis

In silver alloys containing less than 0.2 wt pet Cu. the reaction 9 + 1/2 0, = CuO(s) was found to proceed to equilibrium between 700o and 808oC. From measurements of the equilibrium dissociation pressures of the CuO at several temperatures, the differential heat of solution and the activity coeflicients for copper in silver were calculated. These values were found to be in reasonable agreement with those calculated from data appearing in the literature. A metastable "copper oxide" with an atom ratio of oxygen to copper as high as 1.7 was formed by internal oxidation at 300°C of these same dilute Ag-Cu alloys. No anomalous behavior was noted in the temperature dependence of oxygen solubility in silver. The solubility minima between 300" and 800°C reported several years ago can be accounted for, at least in part, by reactions with trace impurities, such as copper. Cold-worked siloer exhibits an enhanced permeability to oxygen. THIS investigation was undertaken because of our interest in interactions between solute and lattice defects in metals. The reason for the choice of the O-Ag system for study is the anomaly in the solubility of oxygen in silver reported by Steacie and Johnson1 in 1926, specifically that isobars between 100 and 800 Torr show solubility minima at 400°C. It was also claimed that the copper impurity in the silver was not responsible for the minima. Recently, Eichenauer and Müller2 proposed that surface adsorption might have been responsible for this solubility anomaly, but no adsorption isotherms are available to check the pressure and temperature dependence observed at the low temperatures. Surface-tension measurements on silver made by Buttner, Funk, and udin3 suggest that a considerable fraction of a monolayer of oxygen exists on silver at 922°C and at an oxygen pressure of 150 Torr. To account for the pressure sensitivity reported by Steacie and Johnson1 at 300°C, the oxygen bound to the surface at 922°C cannot be considered relevant; the existence of a surface layer at 300°C characterized by a lower energy of binding would be required to explain the effect. All of our attempts to detect an interaction of this type with surface sites have failed. In this investigation we have not been able to associate the dissolution of oxygen in silver with a dislocation interaction. Evidently, severely cold-worked silver does not contain a sufficient number of trapping -sites for oxygen. Indeed, our work shows that oxidation of trace impurities in the silver was probably responsible for Steacie and Johnson's results. In addition, we have been able to establish the nature of the reaction with copper impurity in silver by thermodynamic considerations. EXPERIMENTAL PROCEDURE Measurements of both the internal oxidation rates and the solubility were made volumetric ally in a system equipped with a gas burette, a mercury manometer, a McLeod Gage, and a mass spectrometer. The silver and the silver-alloy samples were protected from contamination by mercury vapor from our pressure gages by suitably placed refrigerated (-78°C) traps. Silica reaction vessels were employed for experiments performed above 500°C. Spectroscopically pure gases were used in this investigation. The highest-purity silver used in the solubility measurements was 99.999 pet. By chemical analysis 2 ppm of Cu were found in this silver. The two Ag-Cu alloys used in this research were made up to 0.14 and 0.15 wt pet Cu starting with 99.999 pet Ag. An unexpected source of error was discovered in the course of the work. At temperatures near 800°C silver distilled from the hot silica reaction tubes into cooler regions of our system. Although the weight loss of silver from the sample was not important in itself, oxygen was being consumed by the silver distilled into the cooler part of the system to form a stable oxide phase from which the oxygen was not recovered. In a separate experiment conducted to determine the necessary correction, losses between 0.2 and 0.3 cu cm (stp) of 0, in 24 hr were measured at 810°C. On the assumption that the flux of silver from the vessel to form Ag2O de-

Jan 1, 1964

By W. N. Lacey, B. H. Sage

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949

By H. Dykstra

Calculated wellbore pressures were obtained for parameters of radilcs ratio and permeability. In all cases bur two, after-production was allowed to occur for one day. The calculated pressure build-up data were compared with actual pressure build-up data from a condensate well. The paper discusses the comparison, gives reasons for, inability to match calculated (2nd actual data, and presents conc1usions derived from the comparison. INTRODUCTION Considerable information has been published on the decline in wellbore pressure for oil and gas fields resulting from production of fluids. Considerable information also has been published on pressure build-up for oil fields, but relatively little has been published for gas and condensate fields. Perrine' summarized the equations derived for pressure build-up in oil wells and showed how the different methods could be applied. On the other hand, very little theoretical information has been published on pressure build-up in gas or gas-condensate wells.2-4 Tracy,' by pointing out the similarity between the equation describing oil wellbore pressure decline and the equation describing gas wellbore pressure decline, showed how methods of pressure build-up analysis could be applied to a gas well. In analyzing pressure build-up data for gas or gas-condensate wells, it would be very desirable to compare actual pressure build-up data with calculated pressure build-up data. Such a comparison would lead to a better feeling for the quantitative picture of gas-well build-up curves and would help to establish a degree of confidence in a given build-up curve. This paper discusses the comparison and presents conclusions made from it. Calculated wellbore pressures are given for parameters of radius ratio and permeability. In all cases but two, after-production was allowed to occur for one day. The work was done in an attempt to evaluate the reserves of a gas-condensate field. As will be discussed later, it was not possible to make an evaluation. METHOD OF CALCULATION The method used for solving the depletion and pressure build-up behavior for a gas-condensate well was that developed by West, Garvin and Sheldon.5 or the IBM 704 computer program used, it was assumed that liquid condensing out of solution would have only a minor effect on the flow behavior. Therefore, the field was treated as having single-phase flow, with the gas saturation S, remaining constant at unity minus the connate-water saturation Sw. As will be discussed later, this may not have been a good assumption. It also was assumed that oil production could be considered as equivalent gas production by using a conversion factor based on an analysis of the liquid produced. An outer boundary condition of no-flow was assumed. BASIC DATA The data required for the study were reservoir properties, fluid properties and production data. Reservoir properties included the following: thickness h, 179 ft; porosity, 0.194; connate-water saturation, 0.43; gas saturation, 0.57; permeabilities k, 1.0, 0.5, 0.25 and 0.15 md; radius ratios re/rw, 800, 1,000 and 2,000; wellbore radius rw, 5 in.; initial reservoir pressure P, 6,529 psia; and reservoir temperature, 272°F. The selection of permeabilities was based on core-analysis data showing an average air permeability of about 2 md. With a relatively high connate-water saturation, the average effective gas permeability would be about one-half, or less, of the air permeability. The selection of radius ratios was based partly on the observed rapid decline in wellbore pressure during production and partly on the fact that the well was believed to be located in a relatively small fault block. Reservoir fluid properties were obtained from a reservoir fluid study on a recombined sample of gas and condensate. Gas formation-volume factors were calculated from pressure-volume measurements made at reservoir temperature. Gas viscosities were calculated by the method of Carr, et al,G from an analysis of the re-combined sample. These data are shown as a function of pressure in Table 1. The production schedule from the gas-condensate