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By H. I. Aaronson, W. L. Winterbottom, G. M. Pound

On the basis of a statistical thermodynamic treatment of the data of smithz2 on the activity of carbon in austenite, a Darken and smith23 deduced that the interaction energy, wy, between carbon atoms occupying nearest-neighboring interstitial sites is repulsive. Aaronson, Domian, and pound 24 (ADP) have applied two different statistical thermodynamic analyses to the same data. One analysis, a composite of the treatments of Darken and Smith,23 Speiser and Spret-nak," and Kaufman, Radcliffe, and Cohen,26 primarily takes account of the positional entropic effects of wy in dilute solutions. The other, due to Lacher 27 and Fowler and Guggenheim," is also applicable to more concentrated solid solutions. The equations which both analyses produce for a,, can be rearranged so that, when In a,, is plotted against the appropriate function of the carbon content of the austenite, the plot will have a slope of unity when the correct value of wy is employed. Since no other constant need be simultaneously evaluated in order to make this determination, ascertaining the most probable value of wy from Smith's data on the bases of these analyses was an elementary problem in least-squares statistics. ADP demonstrated that the wy's obtained from both analyses vary with temperature in a statistically significant manner. McLellan, Gerrard, Horowitz, and sprague 29 (MGHS), on the other hand, have recently made a new statistical thermodynamic study of a,, and have concluded from this study that wy is independent of temperature. The equation which they derived for a,, is: where 0 = ratio of the mole fraction of carbon atoms to that of iron atoms, z = number of sites from which occupancy is excluded by the presence of a carbon atom and the repulsive character of its interaction with nearest-neighboring carbon atoms (z = zb in Ref. 24), and x = a geometric parameter taking account of overlapping of the exclusion shells of nearby carbon atoms. z is 1 when wy = 0 and 13 when wy = Q. For a given value of z there is a definite value of X . In the absence of an equation connecting z and X, MGHS computed geometrically the value of x at several integral values of z; x increases from 0.47 to 8.67 as z is increased from 2 to 5. MGHS fitted Eq. [I] to the a,, data of Ellis, Davidson, and Bodsworth30 at 925° and 1050°C and to the data of smithz2 at 1000°C. Confining z to integral values in the range 4 to 6, and also somewhat restricting AG, the values of z, X, and AG were sought which would minimize the average root mean square percent deviation, D, of the calculated a,, values from those obtained experimentally. Finding that D was almost always smallest when z = 5, they concluded that z is independent of temperature. Since:23, 26 where R = gas constant and T = absolute temperature, and w,, was considered to be similarly invariant, this statement cannot be strictly true. The temperature range employed, however, was small and the interval between the values of z tested was sufficiently large so that the results could still be consistent with a constant The statistical treatment of the a,, data applied by MGHS is clearly quite approximate. Since more than three values of a,, are available at each temperature, z, and X, and AG have actually been over deter mined, rather than underdetermined as their treatment implies. In order to make more complete and exact use of the a,, data, we shall employ the Legendre Method of Least Squares, as described by Whittaker and Robinson. This technique permits conversion of the overdetermined system of equations produced by the substitution into Eq. [I] of the available pairs of a,, and 0 data at a given temperature into an even determined system. Solution of the latter system yields the most probable value of each of the three constants. This procedure will allow a statistically rigorous test to be made of the conclusion drawn by MGHS in respect of the temperature dependence of In order to obtain linear iiequations of conditions" from Eq. [I], the exact values of the three unknown constants are replaced by G/RT = =/RT + y, where z, i, and aG are estimated values of the constants. This allows the conditional equations to be written in the form:'l where fi -f6, i, =/RT) = the right-hand side of Eq. [I] for a given pair of ayi and values. When applied to Eq. [I], these relationships become: The i equations of condition are reduced to three "normal equations" in the manner discussed by Whittaker and Robinson. The normal equations are then solved for a, ß, and y. Both of these operations are most conveniently performed by means of the computer technique of Winterbottom and Gjostein.32 This technique was used iteratively until the value of 0 (the most sensitive of the three correction factors) became 10.01. (Until they became small, a, 8, and y

Jan 1, 1969

By William Cochran

The mineral waste disposal system at the Grace Mine, Morgantown, Pa., was designed to minimize environmental effects while allowing much of the waste from the iron mine, mill, and concentrator to be utilized. Standard cost estimating procedures were used by the Bureau of Mines to determine waste disposal costs. Mill tailings and rock waste disposal costs were estimated at $0.151 and $0.276 per ton, respectively, for the 1965-67 production period. Total waste disposal cost was reduced about $0.015 per ton by utilizing part of the waste as aggregate. The net average cost for disposal of all mineral waste was $0.189 per ton.

Jan 1, 1969

By L. Cichowicz, K. K. Millheim

The constant-rate drawdown test performance for a low-permeability, verticany fractured gas well was investigated. A series of gar wells were tested by flowing each well at constant rate until the data could be analyzed using con-ventional radial flow theory. Each well was then shut in to build up. After a sufficient buildup was obtained, another flow Iest commenced but at a higher flow rate than Ihe first test. Again, the well was shut in when radial fiow was obtained. his procedure was repeated for three to four different flow rates. Two wells in the San Juan basin were tested using this procedure. Both wellere fractured after completion, cleaned up and then shut in until flow testing commenced. Test designs of both wells permitted investigation of the most realistic values of egective permeability, wellbore radius and turbulence factor. Also, being able to determine the eflective fracture flow area and vertical fraclure efficiency was inherent with this testing approach. It was observed that fractures in both wells influenced the Pressure behavior for approximately Is to 40 hours (depending on the flow rate) before radial flow was evident. After this time, drawdown data were analyzed using radial pow theory. When a low-permeability gas well has vertitally oriented, induced fractures, the early flow geometry ic. essentially linear. It will be shown how to determine when a flow test has been conducted long enough so lha' the most representative values of effective permeahiiity. wellbore radius and turbulence factw can be calculated. From the linear pressure data, valuable information about The fracture treatment, such as the effective flow area and vertical fracture efficiency, can be determined for vertically froctured wells. Introduction During tests on gas wells in the Sari Juan basin7 initial transient behavior lasted for many days because of the low permeability of some porous media. As a result, stabilized flow performance could not be obtained. If these wells received some type of stimulation treatment, early pressure behavior deviated from conventional theoretical radial Row. When conventional radial flow theory was used to analyze these low-permeability fractured gas wells, larger values of flow capacity and absolute open flow potentials (AOF) sometimes resulted. Wells were assigned open flow poten- tials that proved to be 3 to 10 times higher than the well would sustain over a longer period of production. In some cases where the wells had flowed for longer periods of time during a constant-rate drawdown test, it was noticed that the effective flow capacity appeared to be decreasing with time until a certain value was reached. The early nonradial pressure behavior can be explained If linear flow is assumed. Rusell and Truitt mathematic. ally investigated the vertically fractured well in a bounded area. They showed that early flow behavior was essentially linear and, for x,/x. approximately less than 0.10 radial flow was obtained after short periods of time. Then realistic values of effective permeability and skin could be determined. Scotta experimentaliy studied the vertically fractured well with a heat flow analog. He showed that earb flow was linear, Both studies indicate that, for small values of x,/x,, linear flow approaches radial flow if the well is tested long enough, To help prove this concept of early linear flow caused by induced vertical fractures, two low-permeability gas wells were tested. Both wells received large fracture treatments prior to testing. A vertical fracture was indicated from the analysis of fracture treatments, As anticipated, tests of both wells indicated early linear flow that was later followed by a period of radial flow, Data collected from each well were analyzed. From the well tests, plus other information on each well, the effective permeability, wellbore radius and turbulence factor were calculated. Effective fracture flow areas calculated from test analyses for each well proved to be approximately one-fourth the created area calculated from classic hydraulic fracturing theory: other fractured wells that were tested but not presented in this paper also indicated that the effective fracture flow area was one-fourth to one-third the created area predicted from hydraulic fracturing theory. The vertical fracturing efficiency was estimated from the calculated values of effective wellbore radius and fracture flow area. For the two wells tested, calculated fracture lengths x, were 112 and 105 ft, and the vertical fracturing efficiencies E, were 122 and 183 percent. Development of Flow Model Agnew' showed that most induced fractures below 1,500 ft are vertical. Anderson and Stah15 indicated that most of the fractures they studied were vertical. Thc model proposed for early flow in most vertically fractured gas wells is shown by Fig. 1. This model should approximate early flow behavior until radial flow is reached, at which time a radial model with an effective wellbore radius of 0.5 they will

Jan 1, 1969

By Roland W. Merwin

The Bureau of Mines has studied the possibility of using the heap leaching process for treating the gold ores in the sedimentary beds of northeastern Nevada. This paper summarizes all available information on the technical and economic feasibility of heap leaching oxidized ores from these beds, past industry application of vat leaching, results of recent Bureau of Mines and industry tests on heap leaching ores from this region, and requirements for planning the proper application of heap leaching. Preliminary tests on representative samples of ores from the region show that a satisfactory recovery of gold can be obtained by heap leaching the ores with cyanide at a relatively coarse size. Significant deposits of gold ore occur in sedimentary beds of various locations over an extended area 40 miles wide and 200 miles long in northeastern Nevada. The area is centered 40 miles west of and runs parallel to the leading edge of the Roberts Mountain thrust fault system, a prominent geologic feature in the area. The general locations of past and present gold mining operations are shown in figure 1. (slide 1)

Jan 1, 1969

By F. Ames Smith

Offshore oil and gas production operations have moved from water depths of about 50 feet in 1948 to the present record depth of 340 feet. Although mobile drilling rigs are widely used for exploratory drilling, most development drilling and production operations have been conducted above water from the decks of fixed, bottom-founded platforms. Increasing water depths have caused problems associated with design and construction of these platforms and with laying of pipelines, but not so much with other activities. After a platform is installed, drilling, production, and maintenance operations are similar to those onshore and are relatively unaffected by water depth. Events of 1968 indicate that offshore production may soon extend into much deeper water. These events include leasing of Santa Barbara Channel acreage in water depths over 1500 feet, and the successful drilling of a wildcat well in 1300 feet. Designs have been developed for platforms suitable for installation in water over 600 feet deep, and studies suggest they may be used in some areas to water depths of 800 to 1000 feet. Buoyant towers can probably support above-surface platforms in water 1000 feet and deeper. Although the cost of either of these platforms will be high, once installed they will permit relatively low-cost development drilling and production operations compared with estimates for subsea production systems. In some cases, savings in development drilling costs alone could pay out the platform investment.

Jan 1, 1969

By N. F. Schulz, H. A. Lex

Representative samples of typical manganiferous iron ores from the Cuyuna Range, Minn., were reduced to the metallic iron state at temperatures just short of fusion with an excess of coke in the manner prescribed by the R-N Direct Reduction Process. The magnetic separation characteristics of the reduced ores were determined at several grinds by means of the Davis magnetic tube concentrator. The efficiency of metallic iron concentration by magnetic separation was a direct function of the degree of metallization of the ore sample and of the degree of liberation at-tained in grinding. Some improvement of liberation characteristics was observed if a small amount of sodium chloride was present in the ore during reduction. Despite the extremely fine-grained structure of the crude ores, iron concentrates containing more than 90% Fe at iron unit recoveries of 90% or more were obtained from well-metallized samples of three of the four ores tested. The rejection of manganese to the tailings corresponding to such separations varied from 80% to 95%. The manganiferous iron ores of the Cuyuna Range in Minnesota constitute a major potential source of manganese in the United States provided that a technically and economically feasible process can be devised for its recovery. The iron and manganese of these ores occur chiefly as oxides or carbonates in the form of very small, irregular, discrete grains embedded in a matrix of quartz or other siliceous gangue. The present investigation was undertaken as a sequel to an earlier one conducted jointly by the U.S. Bureau of Mines and the R-N Corp. Those results indicated that the R-N Direct Reduction Process might be a means for recovering both a metallic iron concentrate and a marketable manganese by-product from Cuyuna manganiferous iron ores.' The R-N Process is one of many proposed schemes for the treatment of crude iron ores involving the di- rect reduction of the iron content to metallic iron followed by physical extraction of the iron. In general, it consists of the following stepsz2 1) Iron oxide in crushed natural ores or iron concentrates is about 95% reduced to metallic iron at elevated temperatures but without fusion in a rotary kiln in the presence of a solid carbonaceous fuel (usually coke), limestone, and combustible gases. 2) The kiln product, consisting of metallized ore, excess coke, lime, and coke ash is cooled. The excess coke is recovered and recycled to the kiln feed. 3) The metallized ore is ground for liberation and magnetically separated to yield a metallic iron concentrate. 4) The metallic iron concentrate is agglomerated by a briquetting process. The reduction kiln temperatures must be high enough for the desirable chemical reactions to proceed at practical rates without causing fusion of any of the ore constituents. The time of exposure of the ore to the reducing conditions must be ample for 90% to 95% metallization of the iron oxides present. If more than 95% of the iron is metallized, however, difficulties may arise in the briquetting step, presumably because of accompanying higher carbon content of the metallic iron. Although not always necessary, powdered limestone or dolomite may be added at some time during reduction to aid in eliminating sulfur and phosphorus from the final product.3,4 Other additives, notably sodium chloride, when present during reduction, result in improved liberation characteristics of the metallic iron from certain reduced ores.'v6 Under the reducing conditions normally employed, P(co + H2)= 1 atmosphere, and 1830' to 2150°F (1000° to 1170°C), the R-N Process is claimed to be adaptable to a wide variety of low, medium, and high grade iron and manganiferous iron ores. The manganese oxides and carbonates are reduced mostly to nonmagnetic MnO which is rejected to the nonmagnetic tailings. Manganese-bearing pyroxenes of the original ore, however, may be rejected poorly, if at all, apparently because these minerals occur within the iron lattice or are entrapped in the metal particles.7 The investigation was limited to studies of the Cuyuna ores listed in Table I, which were reduced to the metallic iron state under various conditions

Jan 1, 1969

By John E. Kelley

The Bureau of Mines conducted a study to determine the feasibility of joining refractory metal compounds to each other and to oxide ceramics by a vacuum hot press-diffusion bonding method. Very satisfactory joins were made of ZrC to ZrB2, ZrN to ZrB2, ZrC to ZrN, and of ZrC, ZrN, and ZrB2 to Al203. Each of these join assemblies contained a mixture layer comprising 50 weight-percent each of the two end compounds. The mixture layer, sandwiched between each end compound, enhanced bonding and smoothed out the thermal expansion gradient between the two end members. Strength and thermal shock tests showed that the join areas of the ZrC, ZrN, and ZrB2 joins were stronger and more shock resistant than the parent materials. Also included in the joining tests was one each of TiC to TiB2, TiC to TiN, TiB2 to TIN, and TiC to ZrB2 joins. Each of these was well bonded, showing that the vacuum-hot-press method can be used for a variety of systems.

Jan 1, 1969

By Ernest A. Kaarsberg

This paper presents the results of studies of the elasticity of some isotropic and anisotropic rock samples based on longitudinal- and shear-wave pulse velocity measurements. Experimental evidence from velocity measurements on isotropic steel samples is also presented to show, within error limits, that any two of the elastic constants required to completely describe the elasticity of an isotropic solid can be obtained from any two of the following four velocity measurements: longitudinal "rod,' "plate," extended medium (infinite medium equivalent), or shear wave. Measurements of three of these velocities in an approximately isotropic basaltic rock sample are used to illustrate this application to this type of rock. For the anisotropic study, a suite of Colorado oil shale samples is used. These rocks exhibited transverse isotropy. The five elastic constants required to completely specify this type of anisotropy are obtained from longitudinal- and shear-wave pulse velocity measurements made in directions parallel, perpen-dicular, and at 45° to the bedding plane. Density, velocity, and elastic modulus relationships among these shales are also given. Duvall 1 has described a method for determining the elastic constants of isotropic and, in two cases, anisotropic rock samples. This method is based on ultrasonic pulse techniques and on resonance-frequency measurements of rock samples in the shape of rods (diamond drill cores). Rock samples, however, are not always available in rod form. When this is the case, other methods can be used to study their

Jan 1, 1969

By Craig S. Hartley

Expressions are obtained for the energy changes associated with the reaction of (a& (111) slip dislocations on intersecting (110)planes in anisotropic bcc metals. An energy criterion for assessing the likelihood of dissociation of the products of such reactions is also presented. It is found that the "burrier reactions" which form a(100) dislocations at the intersection of two active {110) slip planes are more energetically favorable in metals which exhibit a high value of Zener's anisotropy factor, A, than those which have a low value. The results are presented in a form which permits the stacking fault energy to be obtained from a measurement of the separation between par-tials in a dissociated configuration. However, until accurate calculations or measurements of the stacking fault energies involved are available, it is not possible to assess the physical importance of dissociated dislocations. In a recent paper,' the energy changes associated with several types of reactions between two slip dislocations, (a/2)(111){110), in bcc structures were calculated.* Isotropic elasticity and the approxima- tion v = -3- were employed. The purpose of this work is to present calculations of the energy changes for many of the same reactions using anisotropic elasticity. The problem of dissociation of a(100) and a(110) dislocations is also considered, and maximum fault energies for which dissociation will be energetically favorable are calculated for several bcc metals. Two general types of reactions are considered; those for which the reactant (a/2)(111) dislocations have long-range attractive forces and those for which the reverse is true. An example of the former is: (a/2)[lll] + (a/2)[lll]-a[l00] while the latter are typified by: (a/2)[lll] + (a/2)[111] -a[011] Only reactants lying in different slip planes are considered; therefore, the products must lie along (111) or (100) directions, which are the intersection of two {llO} planes. It will be assumed that the reactants and products are infinitely long parallel dislocations, since in this case the energy change associated with the reactions is a maximum.' THEORY The self-energy per unit length of a straight mixed dislocation in an anisotropic medium can be written? where b is the Burgers vector, K is an appropriate combination of the single-crystal elastic constants, and R and ro are, respectively, outer and inner cut-off radii of the elastic solution. The energy given by Eq. [I] does not account for any variation of the core energy with orientation. This could be manifested by an orientation dependence of the core radius or, equivalently, the Peierls width, of the dislocation. However, the energy contribution due to this source is expected to be small, and current models of the dislocation core are not sufficiently accurate to justify such a refinement. It has already been shown that for the isotropic case the energy contributions due to nonzero tractions across the cores of the reactants and products exactly cancel one another in the reaction.' Accordingly, it will be assumed that this contribution to the total energy change in the anisotropic case is small. In the subsequent discussion it is also assumed that the core radii of the reactant and product dislocation are the same and that, where stacking faults are formed, the faulted region is bounded by the centers of the partials. Consequently only changes in elastic energy due to the reactions will be considered. When the dislocation is parallel to either the (111) or the (100) directions, K may be written:375 K = (Ke sin2 a + Ks cos2 a) [2] where K, and Ks are the combination of elastic constants corresponding to an edge and screw dislocation lying along the same direction as the mixed dislocation, and a is the angle between the direction tangent to the dislocation line and the Burgers vector. Eq. [2] should not be confused with the isotropic approximation to the variation in energy with line Orientation.6 It should be noted that the essentially isotropic expression for K is a result of the characteristic symmetry of the (111) and (100) directions and is not, in general, valid for other dislocation directions in anisotropic cubic metals. The energy* change for a reaction in which the re- actant and product dislocations are parallel perfect dislocations can be written: where Ep and E, refer to the self-energies of the products and reactants, respectively. For dislocations parallel to (100) and (111) directions, Eq. [3] becomes:

Jan 1, 1969

By K. E. Gray, G. M. Myers

In previous publications,5 results of single-blow bit tooth impacts on saturated rocks at various stress states were reported. This paper extends these earlier works to include study of bit impact tests on salt water-saturated Berea and Bandera sandstone samples under conditions of elevated confining and pore pressure. During the tests dynamic filtration and deposition of a mud cake were occurring due to the presence of drilling mud in the borehole and a borebole-to-formation pressure differential. Results indicate that saturation of these sandstones with salt water tends to make them weaker than when saturated with nonreactive fluids. Plastic failure often occurs even when extremely high fluid-loss muds are present in the borehole. The failure mode tends toward plasticity with decreasing fluid loss. Brittle failure of sandstones in mud-filled holes is apparently relatively rare. Depending on the stress level, and the associated failure mode, withdrawal of the bit tooth induces a tensile force that seems rather important relative to the quantity of rock removed by vertical tooth impact. INTRODUCTION A vast majority of the oil wells drilled today involve the use of colloidal muds having a measurable mud filtrate loss. It is known from field experience that reduction of the water loss of a mud generally results in a reduction of the penetration rate. This paper describes an investigation of crater formation at simulated bottom-hole pressure conditions for drilling fluids having different water losses. The literature on single bit tooth impact (cratering) at atmospheric conditions is extensive, but only a limited amount of work has been performed at the stress conditions similar to that found in oil wells. Spherical penetrator cratering tests on rocks at hydrostatic pressure were performed by Payne and Chippenda1e.1 Chisel impact studies on limestone with independently varying overburden and borehole pressure and atmospheric pore pressure were reported by Garner, et al.2 Gnirk and Cheatham3 performed "static" penetrator tests on dry rocks at equal overburden and borehole pressures. Podio and Gray4 studied the effect of pore fluid viscosity at atmospheric pore and borehole pressures and varying overburden pressures. Their results illustrated the importance of fluid saturation of the rock. Yang and Gray5 reported single tooth impact tests on saturated rocks at elevated borehole, pore and confining pressures, but with equal pore and borehole pressures. For the work reported in Refs. 4 and 5, filtration across the hole bottom purposely was avoided. Maurer6 has investigated the effect of independently varying pore and borehole pressures at elevated overburden pressures by using a zero water-loss mud in the borehole. His tests were carried out under conditions that allowed independent control of overburden, pore and borehole pressures, but without control of filtration at the hole bottom. EXPERIMENTAL APPARATUS AND PROCEDURE APPARATUS The single blow chisel impact apparatus used by Garner,2 as modified for this study, is shown in Fig. 1. A cross section of the pressure vessel is shown in Fig. 2. Several pieces of auxiliary equipment were added to the original apparatus in order that the borehole and pore pressure could be applied in a manner analogous to the actual bottom-hole situation. The pore-pressure system included a filtrate volume-measuring transducer and had sufficient surge capacity to allow filtrate to be injected into the sample without significant changes in pore pressure at points remote to the borehole. The borehole-pressure system contained a cross connection to the pore-pressure system so that both systems could be pressured simultaneously. The borehole-pore pressure differential was applied rapidly by the use of a quick and full-opening valve. The operation of this valve triggered two industrial

Jan 1, 1969

By W. F. MacIsaac

"The large low-grade Copper Mountain deposit is located in the northern portion of the Gaspé Cooper Mines property. It is approximately 1 mile north of the Needle Mountain deposit. The orebody outlined to date lies in the top 1,000 feet of the Grande Greve formation. Chalcopyrite occurs in association with pyrite and quartz in small veinlets and numerous fractures. The deposit is immediately adjacent and parallel to a quartz-feldspar dyke and may be associated with a nearby porphyry stock. Stratigraphy, alteration and structure appear to have played an important role in ore deposition."

Jan 1, 1969

By J. B. Dorsey, T. W. Brinkley

Performance of a high-pressure, vaporizing gas-drive project in a volatile oil reservoir is discussed. The project has been in operation for over 8 years. Present recovery from the over-all displaced portion of the reservoir is 40 percent, and an ultimate recovery of 60 percent is indicated. Calculations reflect an over-all displacement volume of 50 percent for the entire reservoir; therefore, ultimate oil recovery will be 30 percent of the entire reservoir oil originally in place. Laboratory vaporization tests conducted prior to project initiation also are presented and discussed, along with an analytical method of determining stock-tank oil production and gar injection requirements related to over-all volumetric displacement efficiency from these data. Introduction The Shoats Creek field is located in Beauregard Parish, La., in the extreme western part of the state (Fig. 1). Discovered in 1956, the field is productive in three Cockfield sand zones, ranging in depth from 8,000 to 9.000 ft. The upper two zones, 1st and 2nd Cockfield, are condensate-bearing gas reservoirs. The lowest zone, the 5th Cockfield, is a volatile-oil reservoir. Laboratory work conducted on crude oil from the 5th Cockfield zone shortly after field discovery demonstrated that, when contacted with dry gas, signidcant volumes of the oil could be vaporized at reservoir temperature and at an appropriately high reservoir pressure. Further study led to the conclusion that early initiation of a crude vaporization project in the 5th Cockfield zone would be superior economically to other methods of reservoir depletion. Consequently, the zone was unitized and gas injection operations started late in 1958. This paper discusses laboratory work performed in conjunction with the project, and project performance to the present. History of Development The 5th Cockfield zone in Shoats Creek is composed of a thin, very shaly, low-permeability sandstone. Oil accumulation is controlled by a structural trap bounded by faults along the north and west and by a water contact on the southern boundary (Fig. 2). The zone covers a productive area of 1,550 acres at an average depth of 9,000 ft. The net sand section is thin, having a maximum thickness of 10 ft and an average thickness of 5.5 ft (Fig. 3). Average reservoir rock properties, as determined from core analysis are presented in Table 1. Shaliness of the zone is illustrated by the typical electric log of the 5th Cockfield section in Fig. 4. Because of the thinness and poor quality of the sand, the 5th Cockfield was developed on a wide spacing. Eleven completions were made in the zone between 1956 and 1961 for an average density of 140 productive acres per completion, with the majority of wells being dually completed in the 2nd and 5th Cockfield. Average initial potential for producers in the 5th Cockfield was 130 BOPD. Oil from the 5th Cockfield has a stock-tank gravity of 50.5" API; with a bubble-point pressure of 3,515 psia, the oil was highly undersaturated at the original reservoir pressure of 4,675 psia. Pertinent properties of the oil as determined in the laboratory are presented in Table 2. Because of the volatile nature of the crude, laboratory studies of its susceptibility to vaporization, as well as a vapor-liquid phase study, were conducted in addition to a standard PVT analysis. The vaporization study was conducted in a visual cell; a stepwise illustration of this work and laboratory measurements are presented in Fig. 5. Field

Jan 1, 1969

By James A. Hartlage

Work on the design of Kelex 100 was initiated several years ago at the Research Laboratories of Ashland Chemical Company. The effort was specifically directed toward the synthesis of an organic molecule which would strongly and selectively chelate copper ions in acidic solutions and form an oil soluble complex which would be stable in contact with an aqueous phase having a pH of approximately one. This publication describes efforts to establish data which could be used to estimate the economic utility of the new reagent. For helping to accomplish these ends, the author wishes to acknowledge the assistance of Mr. A. V. Henrickson of Hazen Research, Inc. for gathering a portion of the data presented here and to thank the copper companies who supplied leach solutions for studies described in this paper.

Jan 1, 1969

By Clarence O. Babcock

Model pillars of limestone, marble, sandstone, and granite, with length-to-diameter ratios of 3, 2, 1, 0.5, and 0.25 (0.286 for granite), were broken in axial compression to determine to what extent an increase in end constraint increased compressive strength. Radial end constraints of 13 to 23 percent of the average axial stress in the pillar, produced by solid steel rings bonded with epoxy to the ends of dogbone-shaped specimens, increased compressive strength somewhat above that of cylindrical pillars without ring constraint. However, when the results were compared with those obtained by other investigators for straight specimens of several rock types taken collectively, with L/D ratios greater than 0.5, the resulting strengths were not significantly different. Thus, the amount of end constraint produced by the solid steel rings was about the same as that produced by the friction from the steel end plates. In other tests a radial prestress of 3,000 psi or 5,000 psi was applied prior to axial loading by adjustable hardened steel rings to increase the constraint above that obtained for the solid rings. The average radial constraint stress, expressed as a percentage of the average axial pillar stress at failure for the 3,000 psi prestress, was 54.3 percent for limestone, 40.3 percent for marble, 44.7 percent for sandstone, and 23.4 percent for granite. The average radial constraint stress, expressed as a percentage of the average axial pillar stress at failure for the 5,000 psi prestress, was 74.2 percent for limestone, 51.2 percent for marble, 61.6 percent for sandstone, and 29.7 percent for granite. These constraints increased the compressive strength significantly above the strength of straight specimens and solid-ring constrained specimens. These results suggest that large horizontal stresses in orebodies mined by the room and pillar method should increase the strength of the pillars and allow an increase in ore recovery by a reduction of pillar size when major structural defects are absent.

Jan 1, 1969

By L. J. M. Smits

A theoretical equation is developed describing membrane potentials of shaly sands as a function of the cation-exchange capacity per unit pore volume of the rock and saturating water salinity. This equation is based on the same simple physical model as that employed earlier7 describing the electrical conductivity of shaly sands. Experiments conducted with NaCl solutions showed that the equation is obeyed, except in the case of saturated salt solutions where minor deviations were observed. A possible explanation is given for this discrepancy. As the clay content and the porosity of shales may vary appreciably, shale membrane potentials also vary. It was found that membrane potentials of shales can be calculated accurately with the aid of the same theory. Consequently, changes in membrane potentials can be accounted for by simple measurement of cation-exchange capacities per unit pore volume of both shales and shaly sands. Charts are given to facilitate interpretation of the electrochemical part of the SP in terms of cation-exchange capacities and the salinities of mud filtrate and formation water. INTRODUCTION A spontaneous potential (SP) log is a record of the way in which the electrical potential of a sonde varies as it passes down a borehole. Such variations frequently reflect rock texture, e.g., permeable beds intercalated in an impermeable series often are indicated by a sharp change in potential. Nowadays it is recognized that SP logs may be interpreted in terms of formation-water salinity and formation shaliness. The four sources of the SP are illustrated in Fig. 1. El and E4 represent streaming potentials generated by the flow of mud filtrate through mud cake opposite permeable formations and through shale, respectively. An extensive review of the literature on the evaluation of these streaming potentials is given by Lynchl and will not be discussed here. The remaining part of the SP generally is called the electrochemical potential, which is divided into two parts: a membrane potential across the shale (E3, Fig. 1) and a membrane potential in the permeable sand at the diffusion boundary between formation water and mud filtrate (E2, Fig. 1). It was found by wyllie2 that the membrane potential across the shale, E3, is the most important contribution to the electrochemical potential, the shale acting as a semi permeable membrane. When the sand is clean it does not influence the diffusion process, so E2 equals the value of the so-called liquid-liquid junction potential observed when the two solutions diffuse freely into each other. When the sand contains clay, however, this interferes with the diffusion process and affects the diffusion potential generated. The greater the proportion of clay, the stronger this effect will be. Wyllie,3 Doll4 and Poupon et al.5 took this effect into account theoretically, starting from a physical

Jan 1, 1969

By Ralph B. Adair

The Bureau of Mines conducted laboratory and continuous pilot plant flotation tests to determine the feasibility of recovering commercial-grade mica from an Alabama graphitic-mica schist. Preconcentration of the ground ore on a Humphrey's spiral was employed to reject the heavy minerals and part of the quartz in a product virtually free of mica. The acid-cationic mica flotation process recovered over 89 percent of the mica in a product containing 98.7 percent mica. Grinding of the mica concentrate in a fluid energy mill produced a product with a bulk density of 12 lb per cubic foot.

Jan 1, 1969

By N. N. Breyer, W. R. Warke, S. Dinda

A model for the low-temperature peak, LTP, in fcc metals is presented. In high stacking fault energy metals, e.g., aluminum and nickel, it is proposed that a reversible dislocation glide and climb process might give rise to the observed high relaxation strengths and activation energies equivalent to volume self-diffusion values. In low stacking fault energy metals such as copper, gold, and silver, dislocation climb is energetically unfavorable at T < 0.5 Tm and the relaxation process is therefore mainly one of reversible glide. This model is used to explain the effect of a change in grain size and impurities on the LTP. THE low-temperature grain boundary damping peak, LTP, in spectroscopically pure aluminum,&apos; copper,17&apos; gold,2 nickel,3 and silver4 has recently been the subject of a detailed investigation by our laboratory. The main results are summarized in Table I. An empirical relationship was found between the peak relaxation strength, AE, and the width of the dissociated dislocation, do,* given by: do = µa2/24p? (Ref. 5) [I] where p is the shear modulus, y is the stacking fault energy,6-8 and a is the lattice parameter, Table 11. 4E is plotted against do in Fig. 1. Two regions are apparent: region (a)! which contains all but one of the metals, where AE decreases linearly with increasing do, i.e,, AE 1/do; and region (b), where ?E is approximately independent of do. A similar trend is observed when the ratio Qp/QL is plotted as a function of do, Fig. 2. (Qp and Ql are the activation energies for the peak and for lattice diffusion, respectively). In the past, when Qp and QL were found to be comparable, the relaxation peak was explained in terms of grain boundary sliding.10 The equivalence of Q, and Qb. the activation energy for grain boundary diffusion, prompted the suggestion that it was a consequence of reversible grain boundary migration on an atomic scale." A new model for the LTP, which is based on the experimental relationships in Figs. 1 and 2, is presented. In region (a) it is suggested that stress relaxation occurs through the reversible glide and climb of grain boundary dislocations; in region (b) only reversible glide can take place. The resultant effect on the grain boundary might be sliding or "a bowing out", but, since the total distance moved will be 50A, the atomic movements are considered of primary im- portance. It must be emphasized that this is only a qualitative model, but at the moment it appears the most likely way to explain the widely varying, but re-

Jan 1, 1969

By John G. Holmes

The generation of low cost power is but one phase of the TVA program for regional development. During the 36 years since TVA began, growth in its generation of electric power has necessitated a shift from a predominantly hydroelectric power system to a combination steam and hydroelectric system. The addition of steam-electric power plants to TVA&apos;s generating system was necessitated by the rapid increase in the traditional and defense demands for electric power in the 80,000-square-mile area served by TVA, the need to firm up the hydroelectric power, and the fact that all available sites for sizeable hydroelectric projects had been developed. At present TVA owns and operates 40 power plants--29 hydroelectric and 11 steam-electric plants. The total generating capacity of the hydroelectric plants is 3,105,430 kw, and the capacity of the steam plants is 13,951,135 kw. This provides a total generating capacity of 17,056,565 kw for the plants operated by TVA. Individual capacity of the 112 hydroelectric units ranges from 10,000 to 67,500 kw, and the individual capacity of the steam-electric units now in operation ranges from 60,000 to 950,000 kw. In addition to this generating capacity, TVA distributes the power from 6 U. S. Army Corps of Engineers hydroelectric plants on the Cumberland River. These plants contribute an additional 725,000 kw. Also, under an agreement with the Aluminum Company of America, TVA directs the stream flows and generation of their 423,715-kw system on Tennessee River tributaries and shares with Alcoa in the increased generation resulting from this coordinated operation.

Jan 1, 1969

By D. W. McGlashan

Zeta potential changes were determined as a function of pH, metal ion, and surfactant concentrations. Prom the analysis of data, flotation experiments were carried out to correlate float-ability with the differences in zeta potential. Cassiterite in water bears a negative zeta potential, The zeta potential of cassiterite is sensitive to pH changes; the electric double layer arises from the preferential adsorption of H+ and OH- ions and subsequent ionization of the hydroxylated surface. It is suspected that hydronium-ion concentration may cause reversal in the sign of the zeta potential. The ZPC was found to occur at pH 3.4. Metallic ions and the hydrated ions thereof affect the zeta potential of cassiterite in differing degrees of intensity. Without prior activation, sulfonated surfactants do not change the zeta potential of cassiterite. Sodium alkyl aryl sulfonate is especially active on lead-activated cassiterite and ferric-activated cassiteriten Microcalorimetric fiests confimed the activity of ions on cassiterite and showed the hydrated character of cassiterite smfaces. Close correlation between zeta potential and microflotation results was achieved.

Jan 1, 1969

By T. H. Ramsey, Richard Shield

A process has been developed for fabricating thin-film resistors that are compatible with integrated circuits. Films are produced by evaporation of single refractory metals using an electron beam heating source. Resistor paths are then made using standard photoresist etching techniques. A low-temperature coefficient of resistance is obtained by control of nucleation during deposition of the film. One application of the process has been the development of a discrete resistor used for current setting in linear integrated circuits. Multiple thin-film resistors were formed on oxidized silicon substrates using molybdenum metal as a source. An evaporated protective layer of SiO2 over the resistor prevents resistance changes which might occur during subsequent high-temperature processing. Properties of a typical resistor are as follows: R = 15.7 ohm per sq, tolerance surface dimensions = 0.028 by 0.028 in., stable after 4000 hr at 0. 75 w without heat sink. THIN-FILM resistors have been investigated for many years with a large selection of usable resistors resulting from a wide variety of materials. Many of the processes necessitate a high degree of complexity but in nearly all cases the conclusions have been that the materials used in each case were acceptable provided the deposition process was reproducible and could be controlled sufficiently to give the required tolerances. It is our opinion that simplicity is still the key to thin-film resistor fabrication. In this regard, the single metal is obviously the simplest process to control, provided all the necessary properties can be obtained. The idea is not original in this laboratory by any means. Others have taken this approach.&apos; It has been demonstrated that a fairly wide range of resistivities can be obtained by careful control of deposition parameters for any given metal, and by selection of several single metals a very broad range of stable resistors can be obtained. The transition from one metal to the next is made when a film becomes too thin for adequate process control or long-term stability. A great deal of emphasis is once again being placed on the thin-film resistor. Although they have been thoroughly studied in the past, new applications have been found that require the properties obtainable only from thin-film resistors. Integrated circuits, in general, are advancing toward higher speeds and radiation environments which require replacement of the present diffused resistors. Linear circuits in particular are requiring high-power, high-precision resistors for the more advanced applications. The particular requirements of some linear circuits are such that a discrete resistor is required. The resistor described in this paper was developed as a 15.7-ohm precision discrete resistor for use in a current regulating circuit requiring a +2 pct end of life overall tolerance, a dissipation of 750 mw, and the ability to operate over a fairly broad temperature range (i.e., a low temperature coefficient of resistance, TCR). State-of-the-art integrated circuit and silicon processing technology lends itself well to the fabrication of thin-film resistors. Not only is the resistor thin film well-suited to integration on individual circuits, but the oxidized silicon surface provides one of

Jan 1, 1969