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By F. W. Rols-Hausen, F. W. Jessen

It is the purpose of this paper to present data on brines occurring in the Frio formation of the Texas Gulf Coast, and to show how their composition varies, (1) with depth below the surface, (2) with depth below the top of the formation, and (3) along the approximate strike. The brines vary in chloride content from 3,180 to 73,000 p.p.m., though the average salinity of the salt waters is shown to vary with total depth; the concentration being 35,000 to 40,000 p.p.m. at 3500 to 5500 ft., slightly less than 50,000 p.p.m. chloride at 5500 to 6500 ft. and average 38,000 to 40,000 below 6500 feet. From the analyses available, it appears that the highest concentration of salts occurs in the upper 300 ft. of the formation, while lower salinity is found with increasing depth below this point. The salt waters from wells in Starr County show less concentration of dissolved salts than in any other group of wells farther north along the strike. In all, 116 analyses from 63 fields and 14 wildcats, from depths ranging from 1300 to 11,400 ft. below the surface and from z to 3240 ft. below the top of the Frio, are recorded. Introduction Brines have been studied for many Years in an attempt to solve some of the geologic and production problems associated with the production of oil and gas. One practical application of study of . water analyses is the correlation of waters occurring above, in, or below the producing sand in the same field or throughout the same formation. The Frio formation, the series of sands and shales occurring below the Marginulina zone and above the Vicksburg, is one of the major oil and gas-producing formations in the Texas Gulf Coast. Fossils are rare or absent in the upper Frio throughout most of the area. When available, cuttings and cores, and electric logs were used to determine the top of the Frio. A change in lithology was used to determine this point in most of the wells, and fossils were used in some of the deep wells. It is realized that a change in lithology is not perfect for correlation purposes over long distances and some of the trends may be influenced by the inability to differentiate between the nonfossiliferous Marginulina zone and the Frio. It underlies virtually all the area shown on the accompanying map (Fig. I). Although it is not productive in the updip facies, it has been explored to a limited degree below I2,000 ft. Further more, toward the coast line future drilling to deeper depths should encounter this formation. Although thousands of wells have penetrated or drilled entirely through the formation, very few water samples have been secured from the many sands occurring in this formation and analyzed. Previous Investigation No previous published study has been made of the chemical composition and concentration of waters from the Frio formation. However, one water analysis

Jan 1, 1944

By B. M. Larsen, T. E. Brower

In two previous paperslJ dealing with the carbon-oxygcn reaction, and the simultaneous content of each, in liquid steel in the furnace, we have made use of the quantity A[O], defined as the excess oxygen beyond what would be in equilibrium with carbon then present if the pressure of carbon monoxide were I atm.; that is, if [C] X [O] is taken as 0.00222, A[O] = [O] - 0.0022[C] where [O] is the percentage of oxygen by weight as measured by the method described earlier.3 This quantity ?[O] proves to be substantially independent of carbon content over the range 0.08 to I,z per cent, as well as of the basicity of the slag, and is nearly always within the limits o.o15 to o.oz5 per cent when the bath is boiling normally and is in what we have termed a steady state, Apparently it must be at least about 0.014 per cent before boiling occurs; but this threshold value seems to depend upon the ease of bubble formation at the metal-hearth interface, hence upon the condition of the surface of the hearth. In any case, ~(01, on the average, changes considerably following any disturbance of the bath, as by addition of ore. The present paper deals with the average changes in A[O] level following addition of spiegel or crop ends, or after procedures to promote stirring, or by tapping of the steel from the furnace. The observations were made on a large number of commercial heats, and consequently are subject to the influence of various disturbing factors; the results have the compensating merit of showing the consistency obtainable under the limitations imposed by practical operation. Variability of Excess Oxygen in Normal Open-hearth Operation The preceding genera' statements refer to the average value of A[0] particularly in heats that are boiling actively; on individual heats, which are less active, there may be a variable time lag between the disturbance and its effect, which complicates the interpretation of what is going on. For instance, if in the normal refining process boiling is sluggish, the slag usually is gaining Oxygen from the gas phase above it, Or from added Ore$ faster than it is losing oxygen to the metal; Yet when the bath starts to boil vigorously, the opposite condition may prevail for Some time. The consequence of this lag is a variation of A[o], the interpretation of which in a sing1e heat may not be immediately obvious. This condition is illustrated in Figs. I and 2. In Fig. 1, A[0] at the beginning of the test period was near the lower limit of its usual range (dashed lines) in the steady state as a consequence of the lime boil, which had ended about as indicated. The bath is now cold, carbon drop is slow, and the first small orc feed causes only a small rise in A[O]; as the temperature rises and as lime dissolves in the slag, and the bath becomes more active, the

Jan 1, 1948

By H. C. Vacher, C. J. Newton

EXTENSIVE investigations in the field of residual strain measurement by X-ray diffraction have been made by Bollenrath, Hauk, and Osswald,1 by Smith and Wood,2'3 by Greenough; by Rosenthal and Norton." and many others. Since X-ray strain measuremeits apply only to those crystals of the test body which are of the proper condition and orientation to diffract and since the residual strains revealed may be accompanied by either body or tex-tural stresses, there has been considerable disagreement among investigators with respect to the validity of conclusions in this field. Although the experi-mentors have employed a variety of loading schemes, surface preparations, and X-ray wave lengths, the observations almost invariably have been made only on the outer surfaces of the specimens. The present note is not to be construed as an exposition of a new method of stress analysis by X-ray strain measurements on sections but as a presentation of some results which point to interesting possibilities for further experiments with sections. The two test rods used in this study were of ingot iron annealed at 910°C. The initial length of the gage section was 2 in. and the diameter was 0.415 in. Cross-sections were cut from the ends of the annealed rods to provide strain-free material. The tensile rod was axially loaded the desired amount in a commercial testing machine. A 1 in. portion of the gage length was cut from the other rod and was subjected to compression in the same machine. Details of this plastic straining of each rod are given in the upper half of Table I. A half-cylinder piece about 1/4 in. long was obtained by making a short longitudinal plane cut containing the axis of the rod near the center of the gage length. From adjacent material a disk about 1/8 in. thick was cut to provide the cross-section specimen. Later another section was cut from this same region with an angle of 30" between the normal to its surface and the axis of the test rod. A cross-section and a longitudinal section were cut from the compression rod in a similar manner. All of these as well as the strain-free cross-sections were mounted in Bakelite and used as specimens for the following X-ray strain measurements. During the course of the study, it became apparent that the condition of the surface of a specimen was a highly critical factor. One of the annealed strain-free specimens as a control was subjected to about 24 hr of polishing with fine alumina, interrupted about every 2 hr for etching with 1 pct nital. Its lattice parameter was determined at intervals from measurements on back-reflection X-ray diffraction patterns, which were calibrated with diffraction from tungsten powder. The parameter gradually approached the value found in the literature for strain-free iron and remained there, within the limits of the experimental error. This determined a long polishing and etching procedure which was adopted for all the specimens and which gave X-ray results from the surfaces believed to be representative of each specimen as a whole. A large number of back-reflection patterns were made with cobalt and chromium radiation, all at normal incidence. Except for some preliminary stationary exposures made to monitor the removal of cold work from the surfaces, each exposure was made with the specimen slowly translating and the film slowly rotating. In appropriate cases a thin layer of a standard metal powder, tungsten with cobalt radiation and silver with chromium, was dusted over a film of vaseline on the surface of the specimen to serve to calibrate the X-ray patterns. After the preliminary work, four films were made,

Jan 1, 1956

By M. A. Dayananda, R. E. Grace, P. F. Kirsch

Ternary diffusion experiments were carried out at 750°C with vapor-solid diffusion couples in single-phase copper-rich Cu-Zn-Sn alloys. The Philibert-Guy method was used to calculate intrinsic diffusion coefficients at compositions corresponding to the plane of inert markers imbedded in the diffusion couples. Inter diffusion coefficients were determined at common composition points of intersecting diffusion paths. Intevdiffusion coefficients were also obtained at compositions corresponding to maxima in the tin concentration pvofiles Relations between the interdiffusion coefficients and the expansion of vapor-solid diffusion couples are described in detail. Such relations permit the calculation of constant interdiffusion coefficients in binary couples from expansion data directly. In ternary couples expansion data provide an additional constraint on the interdiffusion coefficzents. ThE phenomenological analysis of diffusion in ternary solid solutions has been developed extensively, and various approaches taken in the determination of diffusion coefficients have been reviewed recently by Guy et al.' Finite,' semi-infinite,3 and infinite4 diffusion couples have been used in studies of ternary diffusion, but most of the work has been done with infinite diffusion couples. Semi-infinite diffusion couples3 (vapor-solid couples) have been used to determine both intrinsic and interdiffusion coefficients in the Cu-Zn-Mn system, in which two diffusing species, zinc and manganese, were supplied from the vapor phase. If only one component has a sufficiently high vapor pressure to be supplied from a vapor source, vapor-solid diffusion couples may still be used. In this case the boundary conditions at the gas/solid interface may be governed by partial equilibria rather than by virtually complete equilibrium between the phases. In the present work diffusion measurements were carried out at 750°C with vapor-solid couples of Cu-Zn-Sn alloys. Only zinc was transported between the vapor source and the diffusion disks, because the vapor pressures of both copper and tin are at least 108 lower than that of zinc. Both intrinsic and interdiffusion measurements were made at several compositions. A secondary objective was to relate expansion of the diffusion couples with the interdiffusion process. Such measurements for binary couples yield average values of the interdiffusion coefficients over composition increments. In ternary diffusion couples ex- pansion data provide an additional constraint on the interdiffusion coefficients. COMPOSITION-DEPENDENT INTRINSIC AND INTERDIFFUSION COEFFICIENTS As shown by Philibert and GUy5 the determination of intrinsic diffusion coefficients in a ternary system requires two independent diffusion couples containing marker planes with identical composition. In the case of vapor-solid couples such a requirement torresponds to two couples set up with the same vapor source exposed to two diffusion disks of different composition. Inert markers placed initially on the disk surfaces become imbedded during diffusion. If the pair of couples exhibits appreciable marker burial with marker planes of virtually the same composition, the intrinsic diffusion coefficient may be evaluated at the composition of the marker planes. Fig. 1 is a schematic diagram of the concentration of of a Cu-Zn-Sn ternary vapor-solid couple after diffusion of zinc from a vapor source into a binary Cu-Sn alloy. The areas, Ai correspond to the cumulative intrinsic fluxes of the three diffusing species across the marker plane:5 where Ji is the intrinsic flux of component i, t is the diffusion time, and D3i are the intrinsic diffusion coefficients. For the determination of interdiffusion coefficients a pair of diffusion couples with intersecting diffusion paths is needed. At the composition point of intersection (C1, C2) the coefficients are evaluated from the equation:3

Jan 1, 1969

By L. O. Bacon, D. O. Wyble

THERE has been considerable speculation among mining geologists and mining men in general as to the relative merits of gravity methods in iron-ore exploration. Most of the investigations which have been carried out in recent years have been done by mining companies, and few if any of the results have been published. Three gravity surveys have been made in the Iron River-Crystal Falls area,' " one by the U. S. Bureau of Mines, with inconclusive results, and the other two by Radar Exploration Co. for the Cleveland-Cliffs and the M. A. Hanna companies, with results not known to the writers. Both the last-mentioned surveys were detailed investigations, the stations being spaced as close as 10 ft along traverses,' and were made to determine the feasibility of locating iron ore by gravitational methods. Because of the presence of a large body of ore already extensively drilled, Dr. Harold L. James of the U. S. Geological Survey, Iron River, Mich., suggested that a further test of gravitational methods of exploration be made in the Round Lake area of Iron County, see Figs. 1 and 2. This survey indicated a considerable regional gradient and led to a study of the surrounding gravity field and its relation to the major structural features of the syncline within which the iron formation lies. The southwestern part of Iron County presents a series of hills and hollows elongated in a roughly north-south direction. The bedrock topography is of pre-glacial origin. Relief is moderate; a maximum elevation difference of approximately 350 ft was observed during the survey. Major drainage is dendritic with the larger streams: the Brule to the south, the Paint to the north, and the Iron in the central part. Hills are thickly grown with hard- woods, and lowland areas, not under cultivation, are usually covered by second-growth softwoods. The area covered in this paper includes the southern half of Iron County, Mich., with a deep synclinal basin occupying the central part of the area, and the southeast corner of Gogebic County, immediately to the west of Iron County. The upper Huronian iron formation, slates, and graywackes which form the synclinal basin rest upon a greenstone basement. The basin has not been completely outlined by exposures, drill records or other means, as outcrops are scarce and the thick mantle of glacial drift makes geological investigations extremely difficult. Glacial drift varies in depth up to 300 ft or more. The drift is usually thickest under the hills and is thinnest in the depressions and along drainage courses where most of the bedrock exposures occur. The area over which gravity investigations were made is almost, entirely covered by glacial material. Bedrock of the basin consists of a complexly folded series of iron formation, slates, and graywackes. One of the series of slates has a high magnetic susceptibility due to the fine-grained magnetite it contains. This formation can be detected readily. by magnetic methods and provides a marker horizon which can be easily followed. The magnetic slates are stratigraphically above the iron formation, and much of the geological interpretation of the area is based upon the magnetic anomalies they produce.

Jan 1, 1953

By E. E. Gardner, P. A. Schumann

A description of a new four-point probe configuration which permits measurement of epitaxial layer resistivity is given. An analytic solution to the potential distribution due to a point current source on a multilayered structure is briefly described. Typical solutions for this probe configuration are presented. Probe spacing, layer thickness, substrate resistivity, and substrate thickness enter into the calculation. Correction factors for typical cases are given. A brief description of the construction of a probe which can achieve a small spacing of 15 is presented. The prohe is constructed so that all points are adjustable by micrometers and the probe spacing and configuration can be easily altered. Measurements of layer resistivity with the four-point probe are compared with those taken with the three-Point probe and diode-capacitance techniques. TWO techniques of obtaining profiles of N/N+ epitaxial structures are given. The reproducihility of the probe spacing and resistivity measurement is discussed. The effects upon the resistivity measurement of errors in the measurement of the lager thickness, substrate resistil)itv, and substrate thickness are presented. SINCE its introduction by valdes' in 1954, the four-point probe has been the most widely used tool for determining semiconductor resistivity. Its usefulness ranges from the evaluation of bulk semiconductor ingots to the characterization of impurity profiles in diffused structures. In general the four points, two current probes and two potential probes, are placed on one surface of the material being tested either in an in-line array or in a square array. Numerous correction factors1 8 have been worked out for these configurations which are dictated by the finite geometry of the sample being tested. One method of evaluating thin wafers has been proposed which has two probesg on each side of the wafer. Further modifications have added a fifth'' and a sixth" probe. One paper1' has discussed the accuracy of the four-point probe and the precautions necessary in its use. With the exception of the method where two points are placed on opposite sides of the wafer, the four-point probe is restricted to evaluation of wafers with a homogeneous resistivity or to the case where an isolating junction exists between the substrate and the layer (epitaxial or diffused) being evaluated. Due to the relative resistivities and thickness, the resistance of the epitaxial layer is much greater than that of the substrate, and consequently a majority of the current flows through the substrate. The potential distribution at relatively large distances from the current sources is determined by the substrate resistance, and hence the AV/I value is a measure of the substrate resistivity and not that of the epitaxial-layer resistivity. In the immediate vicinity of a current source the potential distribution is determined by the layer resistivity among other factors. Consequently, if the potential probe is placed very close to the current source, then with appropriate correction factors it is possible to determine the layer resistivity. This was the theoretical basis for using two closely spaced probes on opposite sides of an epitaxial wafer. However, due to mechanical problems, it is desirable to place the four probes on the same side of the wafer. This paper discusses the potential distribution in

Jan 1, 1965

By Strathmore R. B. Cooke, Emert W. Lindroos, Norman F. Schulz

DURING the course of an investigation of the effects of various starch products on hematite and quartz in regard to their separation by flotation, it was found that whereas most starches flocculated suspensions of hematite in water, they did not flocculate similar suspensions of quartz. However, a derivative of whole corn starch containing approximately one tenth aminoethyl group (-—CH,CH2NH2) per glucose unit proved to be an exception. This aminoethyl starch was a very good flocculant for both hematite and quartz, and also possessed the property of depressing both minerals in cationic flotation tests. In view of the widespread use of starch as a flocculating agent of solids in tailing water, pulps, and for coal slimes, ore and various other purposes in sulphide and nonsulphide flotation, attention is called to the effective surface activity of aminoethyl starch in flocculating suspensions of the two minerals investigated. Test Materials The starch products employed included Globe Pearl starch No. 144 and fresh aminoethyl starch, both supplied by the Corn Products Refining Co. Dr. A. L. Elder" has kindly furnished a description The minerals used in the various tests are listed in Table I. Their specific surfaces were determined by the air permeability method, which gave results reproducible to within plus or minus 3 pct. Surface areas obtained by krypton adsorption were greater than the air permeability values by a factor of 2.0 for quartz and 62.4 for hematite. Starch Adsorption on Mineral Surfaces Starch adsorption data were obtained by agitating for 1 hr measured volumes of neutral starch solutions of known concentrations with weighed quantities of finely divided mineral of measured specific surface. The mineral then was separated from the pulp liquor by centrifugation and the residual starch content determined by chemical analysis. The analytical procedure consisted of oxidizing the starch with an excess of dichromate in acid medium at elevated temperature and titrating the excess dichromate by the ferrous ammonium sulphate—potassium permanganate method. Analytical results were reproducible to within less than 1 pct. Adsorption data obtained in unbuffered solutions near the neutral point are plotted in Fig. 1. The adsorption on either mineral was far greater for the aminoethyl starch than for the Pearl starch. Flocculation The degree of flocculation was determined for a given pulp by measuring the time required for the supernatant liquid to reach a certain degree of clarity. This was accomplished by passing a standard light beam through the pulp, contained in a glass settling tube, and measuring the time required after agitation ceased for the intensity of the transmitted beam to reach a predetermined value. Starch reagent was added to each pulp in small uniform increments, and the settling time was determined after each such addition. Increase in pulp liquor volume due to the added starch reagent was ignored in these tests. Pulps were maintained at or near neutrality. of the preparation of the aminoethyl starch: "Three hundred and sixty grams of powdered unmodified corn starch was slurried in 3 liters of water and stirred during gelatinization. Eighty-six grams of ethylenimine was added slowly during reflux which was continued for 4 hr. The yellow solution set to a gel upon cooling. This was broken up and neutralized with HC1. The thick paste was dried on hot rolls. Adsorbed polyethylenimine and salts were removed from the yellowish products by washing first with acidified aqueous '60 per cent' alcohol. The white product contained nitrogen corresponding to about one aminoethoxy group per ten glucose residues." Only laboratory samples of this starch derivative have been prepared. The starch reagents for use in flocculation, flotation, and adsorption tests were made up by dispersing the appropriate quantities of air-dry starch in cold water, adding boiling water, and heating for 30 min at 120°C under pressure. When used ip adsorption tests, the starch solutions first were cleared of insoluble matter by centrifugation.

Jan 1, 1953

By R. W. Olson, A. L. Benham

Viscous fingering was studied as it occurred in an open Hele-Shaw model (1 ft x 4 ft x 1/16 in.); it was also studied in the same model packed with 80-mesh glass beads during miscible displacements under unfavorable viscosity ratio conditions. It was determined that the lengths of 20 elements of the front were distributed normally around the average position of the combined elements under all conditions. Represented by the normal distribution, the length of the viscous fingers grew linearly with the distance traveled from the point of finger formation, increased with displacement velocity, and increased with increasing mobility ratio. Results obtained during the first few inches of displacement were of little or no use in predicting finger growth and/or finger length throughout the 4-ft model since the point of finger initiation cannot be predicted and would often occur several inches from the point of injection with either positive or apparent negative coordinates. The fingering occurring during a miscible slug displacement was much greater than would be predicted based upon the actual mobility ratios between in-place fluid and slug and between slug and following fluid, using the results described above for miscible displacement in the absence of a slug. Many of the experiments in the packed model showed that the rate of growth of the viscous fingers was diminishing toward the end of the displacement in the 4-ft long model, indicating that microscopic mixing, such as diffusion or dispersion, was decreasing the viscous fingering effect. INTRODUCTION Viscous fingering is a manifestation of a finger-shaped interface between displaced and displacing fluids occurring during typical miscible displacement projects for oil recovery. Its cause may be traced to the instability of a viscous fluid being displaced by a more mobile fluid. Viscous fingering takes on important significance in the miscible slug process 1.2 where it may be a dominant factor in determining minimum slug size. Experimental1-3 and theoretical4-7 studies of viscous fingering have been made by other investi- gators. However, an exhaustive study of the variables affecting viscous fingering had not been made. The present study was undertaken in an effort to determine the effects of some of the more obvious variables—such as mobility ratio, displacement velocity, distance displaced, and packing—upon viscous finger length and growth in a small laboratory model. It does not necessarily follow that conclusions reached by studying the results of this model study may be applied to the field. Future studies would have to evaluate the effect of model size on extension of these results. EQUIPMENT AND EXPERIMENTAL PROCEDURES A flow diagram for the equipment used in this study is shown in Fig. 1. Basically, it consisted of (1) a constant-rate pump for the injection of displacing fluid into (2) a model made up of two flat transparent plates spaced a small distance apart and (3) provisions for the production of fluid into a calibrated graduate. The displacing fluid contained a dye which allowed visual observation of finger spacing and length. The pump performed at rates from 2.5 cc/hr to 480 cc/hr, while pumping a light mineral oil into a bladder in a closed glass container holding the displacing fluid. The model was made up of two plates of 1-in. Plexiglass with dimensions 1-ft wide by 4-ft long. These were spaced 1/16 in. apart so that the internal model dimensions were 1-ft wide x 4-ft long x 1/16

By J. H. Hollomon, J. C. Fisher

THE fundamental problem concerning the fracture of both crystalline and noncrystalline solids is the divergence between the actual and the theoretically computed fracture stresses; the stress required for fracture, computed from the forces between atoms, is many times that actually observed with commercially available materials. Computations have been made1, 2 indicating that the theoretical fracture stress should be from 100 to 1000 times that actually observed. There are other incidental problems that have arisen, perhaps the most important of which is the problem of size effect often observed in the measurement of the fracture stress of non-metallic solids, such as glass. Another effect concerns the relation between deformation and the stress required for fracture. Experiments recently made with pearlitic steels indicate that the tensile fracture stress increases with increasing tensile deformation and decreases with increasing prior compressive deformation. This marked anisotropy of the effect of deformation on the fracture stress is in contrast with the essential isotropy of the flow stress. Early experiments on rock salt crystals by Joffé, et a13 have illustrated the effect of tensile strain in increasing the tensile stress required for fracture. A consistent theory must be constructed that will explain not only the divergence of the measured fracture stress from the theoretical value, the size effect, and the effect of deformation; but will also explain and predict the effects of combined stress, of temperature, of strain rate, and of metallurgical structure. With respect to this last variable, it has now been relatively well established that the carbide particle is the element of structure controlling the fracture of steels. In steels carbide particles vary in shape from plates to spheroids. It has been found that not only does the magnitude of the fracture stress depend upon the size and shape of these particles, but also its dependence upon strain is affected by changes in shape and size of the particles. The precipitate resulting from the age hardening of duralumin also modifies the fracture stress of this alloy. Nonmetallic inclusions greatly lower the fracture stress of all metals. The magnitude of the lowering depends on the size and shape of the included particles. In glass, the major source of the low fracture stress has been fairly conclusively demonstrated by Griffith4 to arise from real flaws or cracks present in the material. He showed that the stress concentration at the end of a defect was of sufficient magnitude to raise the stress at this location to a value comparable with the theoretical strength of the material. If the cracks were reduced in size, Griffith showed that the observed fracture strength increased by virtue of the decrease in stress concentration. He also pointed out that cracks disposed perpendicularly to the applied tensile stress would be more effective in lowering the fracture

Jan 1, 1947

By Anna H. Connard

SUMMARY The discussion focusses on developments in the debt/equity swap market since the Marte project was negotiated in early 1988. It emphasises carrying forward the recent market trends to anticipate the breadth and scope of debt/equity conversions for mine development in the 1990s. Secondary market prices of LDC paper, conversion values and political influences in the host countries and the use of near debt and commodity-based instruments as components of mine financing in debt/equity deals will be placed in the perspective of recent trends and expectations for the future. THE MARTE PROJECT The Marte mine is a gold porphyry deposit in Chile's high Atacama, for which financing was put together at the beginning of 1988. The Marte project was financed by a combination of common equity and loans. It was unusual that the equity infusions were made under different programs. Some of the international equity was infused with fresh funds via DL 600. Other common foreign equity was provided through the conversion of Chilean bank debt under Chapter XIX. On the loan side,. export credits for the import component of machinery and equipment were sought. Local bank financing was negotiated for the remainder of ' the project's anticipated cost. The debt conversion market in Chile was at its apex in terms of interest, activity and government support when the mine financing was arranged. The price of Chilean paper in the secondary market hovered about 62 to 66 cents per U.S. dollar of face value. Meanwhile, the Chilean government was negotiating conversion redemptions significantly closer to full face value. The government differentiated between debt paper exchanged for corporate investors who had sourced that paper in the secondary market, and debt paper held by bank investors who would incur a transaction loss in the conversion. The use of a combined DL 600lChapter XIX equity financing created different yield calculation bases for the various investors. Chapter XIX prevents remittance of profits before year 5 and capital repatriation before year 11. Investors choosing this vehicle have either for a corporate policy in the target project not to declare dividends until repatriation is allowed, or they have to seek uses for the peso liquidity that would be generated through dividend declarations in the early years. However, DL 600 investors face no such waiting period on dividends, nor do they have restrictions imposed on cashing out of the investment before the 11th year. Therefore, any equity structure with components of both investment mechanisms will have inherent differences in cost basis and future income flows for the various participants. This equity imbalance is defensible if the investment motivations of the parties are analyzed: a mining investor using fresh funds looks for a hurdle return on equity calculated at conservative commodity prices, with as much flexibility to reap upside benefits as possible; a mining investor choosing to invest through a debt conversion mechanism will realize a modest short term gain on the conversion, reducing his effective cost basis, but sacrificing some return because of the waiting period on repatriation of dividends. INVESTMENT OBJECTIVES A bank investor exchanging his own paper for an equity participation in a mining project realizes a conversion loss on the transaction. He seeks a risk adjusted acceptable hurdle rate of return to recoup that loss over time. Motivation for the bank investor to take that loss may be derived partly from a strategy to diversify its existing portfolio by internal policy and externally regulated guidelines. The bank will compare yields on its loan portfolio to that country with anticipated dividend flows discounted back at a risk adjusted rate. It will analyze the project with return objectives of yield enhancement over time and with

Jan 1, 1990

By W. D. Robertson, E. Scala

Electrical resistivity of a number of pure liquid metals and alloys has been measured as a function of temperature and composition. The data show a close correspondence between the liquid and solid states with respect to thermal, structural, and compositional relationships. STUDY of diffuse scattering of X-rays by liquid metals1 has demonstrated that some degree of order persists above the melting point and that the atomic constitution of liquids is more analogous to the solid state than to a gas. Consideration of the change in various thermodynamic properties that accompanies transformation from solid to liquid leads to the same general conclusion.² evertheless, specific knowledge of the constitution of the liquid state is limited when compared with that of the solid and gaseous states owing, in part, to the difficulty of interpreting the X-ray data and in part to the indirect character of deductions based on thermodynamic data. Of the structure-sensitive physical properties, electrical resistivity of liquid metals is perhaps the most easily interpretable, particularly when comparison is made with the solid state. According to the available data, most of which was obtained prior to 1914, cubic metals exhibit a normal linear and positive temperature dependence in the liquid state and the data have been accepted without question. The divalent metals, zinc and cadmium, are apparently exceptional in that resistivity is not linear with temperature and it passes through a minimum. Mercury also exhibits a nonlinear temperature dependence but the slope is always positive. Important comparisons with magnesium could not be made at the time the following work was undertaken because the necessary experimental data were not available. Data on liquid solutions are very limited and are largely from a single source."-" Based on Bornemann's work, Norbury7 pointed out that the resistivity of liquid copper alloys appeared to be dependent on the valence of the solute and that the increase due to the solute was of the same order as in the solid state. However, large extrapolations were involved and no quantitative relationship was developed. Therefore, before proceeding with additional deductions regarding the resistivity of liquid metals and interpretation in terms of structure, it appeared necessary to verify and extend the previous work with particular emphasis on divalent metals and the effect of alloying elements of different valence in dilute liquid solutions. The present work includes: 1—A determination of the resistivity of high purity liquid magnesium, tin, indium, copper, zinc, and cadmium as a function of temperature. 2—The effect of 1 atom pct of copper, cadmium, aluminum, tin, antimony, and

Jan 1, 1954

By H. A. Deans

A three-parameter mathematical model for one-dimensional flow in porous media is developed. The objective of the model is to predict accurately the longitudinal dispersion associated with the flow of either gases or liquids over a wide range of Reynolds number. A qualitative analysis of the model parameters is given. Published experimental pulse-response curves are compared with results predicted by the model. Several general types of problems are given for which the model can be used. INTRODUCTION The problem of multicomponent single-phase flow through porous media is encountered in the study of petroleum reservoirs, gas chromatographic and ion-exchange columns, industrial fixed-bed con-tacters and elsewhere. These particular examples span the wide range of flow conditions possible; Reynolds numbers of less than l0-4 are not unusual in oil-production problems, while values in excess of 103 are common in large fixed-bed operations. The study of flow-dependent transport phenomena is complicated both by the changes in the character of the flow over this range, and by the irregularity of the flow boundaries inherent to porous media. Dispersion is one of the important phenomena known to depend fundamentally on flow conditions as well as on fluid and medium properties. As used in this paper, the term "dispersion" refers to the observed mixing of fluid elements of different composition which occurs in flow systems. The actual mechanism may be one or more of a number listed below. Only dispersion in the direction of the mean flow (referred to as axial or longitudinal dispersion, or mixing) is considered here, although lateral dispersion arises as part of certain coupled mechanisms. MECHANISMS FOR LONGITUDINAL DISPERSION A number of distinct mechanisms are known3,5,7,8 to contribute to the phenomenon of longitudinal dispersion. The more important of these are as follows. 1. Molecular diffusion in the flow direction. 2. Turbulent (cell) mixing. 3. Lateral transport processes coupled with velocity and/or residence time distributions, including: (a) "Taylor" diffusion caused by the interaction of velocity profiles in individual voids with lateral molecular diffusion; (b) separation and remixing or interdiffusion of streams having different velocities around particles; and (c) the couplipg of gross velocity profiles, caused by viscous instability or inhomogeneous porosity, with lateral dispersion. 4. Finite mass-transfer rate between a porous matrix and the flowing phase, and finite diffusion rate inside elements of the porous matrix. It is a well documented fact that these mechanisms, whether acting individually or in combinations, produce essentially similar integral effects. The observed dispersion can be described approximately by solutions of the diffusion equation with a properly chosen dispersion coefficient. Necessary conditions for equivalence between dispersion and diffusion are discussed by Klinkenberg and Sjenitzer.7 Apparently these conditions are not satisfied exactly in many real systems. "Best fit" solutions of the diffusion equation often depart appreciably from measured breakthrough curves for the usual pulse- or step-forced experimental systems. In particular, pulse response curves usually show some degree of asymmetry and "tailing" which cannot be reproduced by the one-parameter diffusion model. The three-parameter model proposed herein attempts to produce these effects in a realistic manner. Asymmetry and tailing are predicted for certain sets of parameter values, while for other sets the new model agrees with the diffusion model. VELOCITY DEPENDENCE OF DISPERSION Molecular diffusion apparently controls at sufficiently low Reynolds number in both gas and liquid systems.*l3 At Re > 20, turbulent cell mixing is dominant for gases flowing at low pressure; the data of McHenry and Wilhelm8 show that the mixing cell is approximately 1 particle diameter long in random sphere packs. on the other hand, the data

By Ö. Valla, A. Muan, K. Grjotheim

The solid miscibility gap between CaO and "FeO" in the system CaO-"FeO" in contact with metallic iron gradually closes as MnO is added as a third component. On the liquidus surface of the system CaO-"FeO"-MnO, this situation gives rise to a boundary curve which originates in the bounding system CaO-''FeO", proceeds a short distance into the composition triangle of the ternary system, and then vanishes. A new approach has been used to follow the course of this boundary curve. It is shown that the curve vanishes at a much lower temperature and at much lower MnO contents than has been inferred previously. The oxides CaO, "FeO", and MnO together with SiO2 are the major components of the slag phase formed in the basic oxygen process. Hence, the system CaO-"Fe0"-MnO is of considerable technological interest. In addition, the system is theoretically interesting. The three oxides above all have sodium chloride structure. The size differences among the cations are such that in the bounding "binary"* systems CaO-MnO and "FeO"-MnO complete solid-solution series are formed,1,2 whereas in the system CaO-"FeO" there is only limited mutual solubility in the solid state,3 see Fig. 1. Hence, a solid miscibility gap exists in a part of the "ternary"* system Ca0-"Fe0"-Mn0, and a liquidus boundary curve originates at the peritectic point, point a in the insert in Fig. 1, in the system CaO-"FeO", extends a certain distance into the ternary system, and then vanishes. Very little quantitative information on the system Ca0-"Fe0"-Mn0 is available in previous literature. Fischer and Feischer4 sketched isothermal sections at 1600° and 1700°C, and estimated that the vanishing boundary curve extends to approximately 1650°C and a composition of 42 wt pct MnO. The work to be described in the following was aimed at locating experimentally the "vanishing" liquidus boundary curve, determining its end point, and deriving representative isothermal sections below and above the temperature of the end point of this curve. EXPERIMENTAL METHODS The phase relations were determined by the well-known quenching method. (For a description of this method as applied to oxide systems, see the original paper of Shepherd, Rankin, and wright.5) Prereacted oxide mixtures of desired compositions were contained in iron crucibles and heated in a vertical tube furnace in an atmosphere of purified nitrogen. After equilibrium was judged to have been attained, the samples were quenched to room temperature, the phases present were identified by microscopic and X-ray examination, and total iron oxide contents were determined by chemical analysis. "Fisher Certified" reagents (MnCO3, CaCO3, Fe2O3, and Fe) served as starting materials. The calcium carbonate and ferric oxide were heated in air at 400° and 800°C, respectively, for 24 hr prior to use. Manganese oxide was prepared by decomposing the carbonate in a graphite crucible in hydrogen atmosphere at 1000°C. The product was ground under acetone to -100 mesh. The iron powder was used directly without any preparation. Dicalcium ferrite was used as a starting material for some mixtures. It was made by mixing some of the above prepared CaCO3 and Fe2O3 in proportions corresponding to the formula 2CaO. Fe2O3. This mixture was then fired in air for

Jan 1, 1969

By B. K. Larkin, H. K. van Poollen, H. C. Bixel

A detailed treatment is given of the transient pressure behavior of a well located near a linear discontinuity. On either side of the discontinuity, the values of permeability, viscosity, compressibility, and porosity are uniform, but may be different from those on the other side of the discontinuity. These results generalize previously published works which assumed the permeability ratio for media on different sides of the discontinuity was zero, one, or infinity. One application of this material would be to facilitate detection of facies changes or fluid-fluid contacts by transient testing. Solutions, presented graphically, show pressure decline for constant rate fluid production. The range of variables examined includes dimensionless time from 0.1 to 100, rnohility ratio from 0.001 to 1000 and specific compressibility ratio from 0.001 to 1000. For dimensionless tinze less than 0.4, the pressure behavior is essentially that of a well in an infinite reservoir. Thus, reservoir properties near the well may be estimated in the usual manner. Using an overlay technique to match an experimental curve with one of the theoretical curves, it is possible to estimate the distance to a discontinuity by substituting the actual time t and the corresponding dimensionless time , at which a match occurs into the equation where is the diffusivity near the well, and may be estimated from data taken at early time. Because of both the complexity of the solutions and limited computer facilities, well interference problems were not examined extensively. However, it was found that well interference may be masked by the discontinuity in some cases. By superposition of the results of constant rate fluid production, the problenz of pressure buildup may be treated. Such results show that for early shut-in times correct values for the transnzissibility are obtained from conventional semilog plotting. However, erroneous values of the static reservoir pressure are obtained unless data at large shut-in times are taken. INTRODUCTION Transient well testing has yielded estimates of such reservoir parameters as static reservoir pressure, permeability. porosity, and well bore effects. In most tests, it was assumed that the reservoirs were homogeneous and iso-tropic. Anisotropic media' and radial discontinuities were considered.'.' Various studies have been made on multiple-layer reservoirs." ' Linear discontinuities have been described for problems of one-dimensional flow.' In the present paper, a mathematical treatment is given for a well located near a linear discontinuity in an otherwise infinite medium (see Fig. 1). An actual reservoir analogy would be a well in a relatively thin reservoir near a fluid-fluid contact, or a well located in a reservoir exhibiting a sudden change in rock and formation characteristics, such as thickness, porosity, or permeability. A sudden change in porosity or permeability may be caused by clay fill or other types of facies changes. Sudden thickness changes niay be the result of such geological formations as buried shore lines and channel deposits. In otherwise uniform formations, a linear discontinuity may be caused by fluid-fluid interfaces such as oil-water contacts. 3s-oil contacts, or gas-water contacts.

By D. Turnbull, R. E. Cech

THE supercooling behavior of pure liquid metal droplets has been described.' The solidification behavior of small droplets of Cu-Ni alloys as a function of composition is described herein. The Cu-Ni system is of interest for such an investigation because the components are miscible in all proportions in both the liquid and solid state and the phase diagram of the system, Fig. 1, is a type often encountered in metal systems. It was noted by Van Riemsdyk2 and others that the nature of the "blick" of gold droplets during assaying is not perceptibly affected by the content of the platinum group metals that are soluble in both liquid and solid gold. With the exception of these very qualitative observations there appear to have been no prior investigations of the supercooling of alloy droplets. A series of nine alloys varying in composition by 10 pct (nominal weight) steps was made using certified OFHC copper, 99.996 pct purity, obtained from the American Brass Co., and electrolytic nickel pellets, 99.92 pct purity, obtained from the International Nickel Co. The alloys were melted and cast in vacuo in a high frequency induction furnace. Segregation was minimized by chill casting into 1-in. diam steel molds. Each alloy rod was homogenized at a temperature 50°C lower than the solidus for 100 hr in dry hydrogen. Samples for solidification experiments and chemical analysis were machined from the same portion of each rod and at a depth of in. from the rod surface. A Car-boloy tool was used in taking turnings to minimize contamination of sample by the cutting tool. As a check, a number of samples for microscopic observation were chipped from the ingot with a fragment of pyrex glass. The resultant data in all cases agreed, within experimental error, with the data obtained from machined turnings. A number of small particles, 30 to 50 micron diam, of a Cu-Ni alloy were placed in a quartz vial 1/32 in. diam x % in. long. This was inserted into a platinum ribbon heater and mounted in a high temperature microscope stage. The general procedure followed in inserting samples into the stage and measuring the temperature of melting and solidification was the same as described in an earlier paper.' A chromel-alumel thermocouple was used to study alloys of 88.93 pct Cu, 80.62 pct Cu, and 72.27 pct Cu. A platinum-10 pct rhodium thermocouple was used for the remainder of the alloys. Procedure The assembled high temperature microscope stage was first evacuated and the sample given a 2 min in situ treatment at 900 °C in dry hydrogen to remove surface oxides which might otherwise catalyze crystal nucleation. After this treatment the atmosphere was changed to purified helium and melting and solidification were observed microscopically. It was not possible to determine the solidus with certainty. However, the liquidus temperature was measured very accurately since the surface of the particle changed in appearance from coarse and uneven to smooth, mirror-like within a few degrees. The visually determined liquidus temperature was checked by finding the highest temperature to which the particle could be heated such that it did not supercool upon lowering the temperature. This temperature which checked within experimental error with that found by observing surface change was assumed to be characteristic of the thermody-namic liquidus. In order to minimize the effect of selective evaporation of copper from the alloy, samples were changed frequently and the droplets were heated no more than 50 °C in excess of the liquidus temperature T,. When the latter conditions were fulfilled, T, values were reproducible. After melting, the temperature was decreased slowly until the particles solidified. The sudden release of heat of fusion on solidification caused the

Jan 1, 1952

By A. William Johnson

It was pointed out in an earlier paper1 that our understanding of the atomic mechanism by which diffusion occurs in metallic alloys is scarcely in an advanced state. This unsatisfactory condition is the result not of any lack of interest, but of the difficulty of designing experiments that .will yield suitable data. The diffusion coefficient of an alloy, measured in the usual way, is simply a number specifying the rate of homogenization of a nonhomo-geneous metal; this number, of itself, can furnish neither the rate at which the individual atoms move nor information as to the mechanism by which they move. It does not necessarily follow, however, that such information cannot be obtained, even if the path to be followed is still not clear. Much success has been attained in the study of diffusion in ionic crystals. A number of experiments, for which there are few counterparts in connection with metals, yield information often indicating a detailed mechanism by which diffusion probably occurs. From such work, quite acceptable theories of lattice imperfections have been developed by Wagner, Schottky, Frenkel, Jost and others.2 It is postulated that real crystals of stoichiometric composition contain, in equilibrium, certain imperfections of which the most importarlt types are: (I) vacant cation sites, with an equal number of interstitial ions; (2) vacant anion sites, with an equal number of interstitial ions; (3) equal numbers of anions and cations in interstitial positions; (4) equal numbers of vacant anion and cation sites. The classification of a particular crystal according to this scheme then follows from studies of the variation of electrical conductivity with pressure of the electronegative component surrounding the crystal, with ion size, and with temperature; other physical phenomena, such as the Hall effect, have aided in establishing the classification. The relative mobility of the anion and cation may be determined by chemical analysis of the salt at the electrodes following electrolysis. With such information, and knowing that one ion never occupies the lattice site normally belonging to an ion of opposite sign, it is usually possible to ascertain the diffusion mechanism. It is clear that the same experiments are not applicable to metal crystals, and substitute experiments that yield as much information have not yet been devised. Much can be learned, however, about the mobilities of the two* kinds of atoms in alloys by the use of radioactive metals as indicators. Only one such experiment has been performed in the past. In 1933, Seith and Keil,3 in an effort to explain the great difference between the rate of diffusion of gold in lead and of lead in lead, measured the rate of diffusion of radioactive lead in 3 gold-lead

Jan 1, 1942

By George C. Lipsey

FOR many years the mining of coal and other minerals occurring in sedimentary formation has been planned according to information obtained by diamond drilling. Placer mines have used churn drills for sampling and estimating deposits, and some metal mines have used the method either wholly or in part. The diamond drill method, therefore, although not entirely new, has come into more prominence in the last few years. Several large-scale developments now being planned or in the production stage have used this method in varying degree. This paper will describe the operations of the Howe Sound Exploration Co., Ltd. at Snow Lake, Manitoba, where a gold mine was developed and equipped for mining and milling wholly on the basis of diamond drilling results. The property has been in operation nearly 3 years, so that results can be compared with the estimates and assumptions made from the diamond drilling. In developing the subject it is necessary to outline as briefly as possible the normal method of mining, from discovery to production stage. Table I sets forth these various stages, the methods of financing, the percentage of total cost, and the relative time interval required for each section of the work. The plan presented in this table cannot be applied to all mining developments, but it gives a basis on which to work. In Stages 2 and 3 the investment is moderate, and if the property does not respond favorably the options or interests can be terminated. Stage 4 represents a sizeable investment, and it is more difficult to drop the property after this part of the operation is completed. Stages 2, 3, and 4 may be repeated several times by different groups or companies before Stage 5 is reached, but when Stage 5 has been started the total capital investment must be provided and there can be no turning back. It will be noted that there is a total of 116 units of investment in the overall cost if one company proceeds with Stages 2, 3, 4, and 5 in order. Stage 4, however, consumes time which is important when markets are being considered. Bringing a property into production when metal prices are low is much more difficult than when the prices are high, and if this stage can be set aside production is attained more quickly. When Stage 4 is eliminated the total becomes 86 units of cost for Stages 2, 3, and 5, but an adjustment of 14 units must be added to Stage 5. These 14 units represent the useable value of Stage 4. Thus Stage 4 represents an investment of 30 units if carried on before Stage 5, but 14 units if included with Stage 5. This is accounted for by the fact that development work can be accomplished more cheaply under Stage 5, since everything that is done is planned on a production basis with permanent services. Stage 4 must of necessity be governed by expenditures, and a great many temporary services, including housing and power plants, must be provided. The prospect shaft is a small one, and drifts,

Jan 1, 1952

S. Tandanand, Twin Cities Mining Research Center, U. S. Bureau of Mines As an addition to the fine reviews on drilling presented in the foregoing papers, we feel it would be appropriate to mention briefly some work in this area by the U. S. Bureau of Mines. The Bureau has had under way for several years at its Twin Cities Mining Research Center studies directed toward a better understanding of basic drilling mechanisms. The work includes drillability investigations with diamond rotary, and with percussive drilling systems, as well as fundamental studies of rock behavior under drill bit types of loading. Results of our work to date have contributed the following to the state of the art. MECHANISM OF ROCK FAILURE-Rock fragmentation through use of mechanical energy systems, including drilling systems, consists of two major components-machine and rock. The two components are related to each other by their functional behavior and their resultant motion which the components mutually influence. Forces in the systems are transmitted directly to the bit which in turn induces stresses in the rock. When the induced stresses exceed the strength of the rock, the rock fails resulting in penetration. Rock strength is a function of the forces applied to the rock. Stresses under a drill bit, regardless of bit configurations, are essentially compressive, resulting in a condition where the rock has the highest resistance to failure. The ratio of principal stresses induced under drill bits is an indication of the mode of failure in the rocks. Initially, compressive stresses under the drill bit cause rock to undergo inelastic deformation. The impression observed at the first stage of crater formation under the drill bit shows that rock is no longer elastic. Associated subsurface failure at this stage precedes total rupture which subsequently appears at the rock surface. Thus, explanation of crater formation, by applying theory of elasticity alone, is likely to be over-simplified. ENERGY VERSUS VOLUME OF ROCK REMOVED-Experimental results show that energy per unit volume of rock removed is constant for a particular rock and bit type. Rock offers a definite resistance to penetration, depending on the method of the energy application; this may be defined as the drilling strength of a rock. Energy consumption in a drilling system may be divided into two components: 1) Energy required to move the machine parts; and 2) energy consumption in breaking rock. Component 1 is dependent on the type of the machine. Component 2 is dependent on the strength properties of rock and the efficiency of the bit in rock cutting. The sum of the energy required in both components determines the total energy required in breaking rock. Our work in this area has included consideration of both diamond and percussive drilling systems. PENETRATION RATE-For a drilling rate expression to be useful in predicting field performance, it should include the operating characteristics of the drilling machine. Eq. 37, for example, is simply a statement of the fact that the drilling rate is determined by the power output of the machine (2pNT) and the power requirements to break the rock in the hole (AER). In order to predict the performance of a particular drill and the effect, for example, of the rotary speed, on the drilling rate, R, Eq. 37 must be modified to include the

Jan 1, 1967

By G. C. Wallick, J. S. Aronofsky

This paper presents an experimental verification of numerical solutions of the differential equation describing the transient flow of an ideal gas through a porous material including gas slip effects. Several experiments previously proposed by one of the authors are described together with the correlation of the experimental results with the numerical solutions. Excellent agreement is shown between experiment and theory, thus demonstrating the validity of both the basic assumption made in the derivation of the differential equation and of the numerical solutions of the differential equation. INTRODUCTION In a recent paper,' one of the authors has discussed a numerical solution of the differential equation describing the unsteady flow of an ideal gas through a porous material. This paper was primarily concerned with the effect of gas slip on the flow behavior. In steady state measurements, Klinkenberg2 and others have observed that the apparent gas permeability Kn of a porous material may be expressed as a linear function of the reciprocal average pressure 1/P of the form, ka = b + m/P........(1) where the intercept b is a constant for a given porous material and the slope m is a constant for a given porous material-gas combination. Aronofsky1 assumed that Equation (1) could be used to describe transient flow if P was replaced by the average pressure in an infinitesimal volume element. A number of numerical solutions of the resultant differential equation were presented and specific flow experiments were proposed as a means of testing the numerical solutions. The purpose of the present paper is to describe the results of several of these experiments and the correlation of the experimental data with the results of the numerical analysis. Reference should be made to the previous paper' for details of the mathematical and numerical analysis. EXPERIMENTAL PROCEDURE A simplified schematic drawing of the experimental apparatus is shown in Fig. 1. An 8.89 cm diameter limestone core of length L = 14.82 cm was mounted in a conventional rubber sleeve permeameter cell. The external sleeve pressure in this cell was maintained equal to 500 psig during all experimental tests, thus permitting only longitudinal flow through the core. One end of the core, X = L, was connected to an adjustable cavity of volume V as well as a pressure gauge or manometer. The other end of the core, X = 0, was connected to a Nullmatic pressure regulator which was in turn connected to a nitrogen cylinder or vacuum pump. In each experiment, the core and adjacent dead volume were charged with nitrogen to a uniform gas pressure P1. The pressure at X = 0 was then suddenly raised or lowered to a constant pressure P, and the resulting pressure buildup or pressure decline at X — L was recorded as a function of the time. The porosity + and the permeability constants m and b were determined using the transient method which was suggested by the results of the numerical analysis and which was described in the earlier paper.' The following average values for these constants were obtained as a result of 19 separate evaluations: 171 -0.259 2 0.005 md-atm; b = 0.374 5 0.008 md; and F = 0.098 ± 0.005*. It should be noted that in order that transient phenomena will be slow enough to be observed conveniently, it is desirable to use a porous material of very low permeability, e.g., less than I md. Moreover, it is in this low permeability range that the gas slip effects are most significant. Thus, such a low permeability sample is very suitable for use in an experimental verification of the numerical solutions previously described.

Jan 1, 1955

By T. R. Ingraham

The thermal decomposition of cupric sulfate and of cupric oxysulfate has been examined by deter-mining the equilibrium gas pressure generated over each pure compound. The equilibrium data have been used to calculate the thermodynamic properties of both compounds, and the results have been combined with previously published data to establish a predominance-volume diagram for the Cu-S-O system over the normal range of roasting temperature and gas composition used in the treatment of copper minerals. Copper oxysulfate recrystal-lizes at 1100°K with an apparently irreversible en-dothermic heat requirement of 2.9 * 0.3 kcal per mole. WHEN mixed sulfide minerals containing copper are roasted, either of two procedures may be followed, depending on the nature of the other metals. In the first procedure, the roasting is controlled to produce a maximum amount of water-soluble copper sulfate which may be removed selectively from the water-insoluble compounds of the other metals. In the second, control is directed toward the production of water-soluble sulfates of the other metals and an insoluble salt of copper. Effective control of either of these processes would be enhanced by knowledge of the thermal stability of cupric sulfate and of cupric oxysulfate. In this paper, established data for the thermal stability of cuprous and cupric sulfide and of cuprous and cupric oxide will be combined with new data for the therma1 stability of cupric sulfate and cupric oxysulfate, to designate the volumes of stability of the significant compounds in the Cu-S-O system in the temperature range 750° to 950°K. EXPERIMENTAL Materials, Apparatus, and Procedure. The copper source material used in all experiments was Fisher Certified Reagent Grade "anhydrous" cupric sulfate, for which the following analysis was supplied by the manufacturer: chloride, 0.002 pct; alkalies and earths, 0.2 pct; insoluble, 0.002 pct; iron, 0.020 pct. Cupric oxysulfate was prepared from the normal sulfate by two procedures. In the first, equimolar quantities of cupric oxide (prepared by decomposition of the sulfate) and cupric sulfate were ground together and heated under vacuum in a sealed silica vessel at 800°C. This procedure was subject to failure because of explosion of the silica vessels due to the pressure of the final traces of water released from the sulfate on the initiation of its decomposition. The second procedure involved roasting the cupric sulfate, with frequent rabbling, in a muffle furnace at 725°C for a period of 48 hr. This produced an excellent product, which was confirmed as copper oxysulfate by X-ray and chemical analyses. The experimental technique used was that of measuring the total pressure exerted by the sulfur trioxide, sulfur dioxide, and oxygen produced by the following reactions: 2 CuS04 = cuo • CuSO4 + SO3 [1] cuo . CuSO4 = 2 cuo + SO3 [2] SO3= SO2 + 1/2 O2 [3] The apparatus used in the experiments has been described previously.1-3 Its main feature of a U-tube mercury manometer in which the mercury is protected from corrosion by enclosure in a flexible Pyrex bellows. Before beginning a run, the interior of the apparatus, including the bellows-manometer and all connecting tubing, was thoroughly washed with hydrochloric acid and distilled water to remove any

Jan 1, 1965