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By W. A. Boyer

MINE hoisting ropes can be loaded to capacity only when the strength of each component is exactly known. Characteristic curves provide this information. When load and rate of acceleration are specified for an individual rope, the characteristic curve assumes a predetermined shape. The factor of safety, is the value drived by dividing the breaking strength of the rope by the total stress on the rope where it goes over the sheave wheel. Total stress is made up of the weight of skip and cage, weight of ore, weight of rope between sheave and rope clevise or attachment, friction load, and acceleration force. Bending stresses are neglected in this discussion, as sheaves and drum di- ameters are assumed to be large enough to reduce these stresses to a negligible value. Fig. 1 gives a family of characteristic curves for 13/8-in. improved plow steel hoisting ropes of 6 x 19 or 6x21 construction with hemp core. The curves will hold for all rope sizes of this specified quality when they are subjected to an acceleration rate of 1.608 ft per sec2. As acceleration rates of most deep shaft hoists are close to this value, this family of curves is presented as a standard. Deviation is slight for other rope sizes. Note that for 0, which is the most important, the deviation is within the width of the line on the graph. In a comparison of values for ropes of 5/8-in. and 21/4-in. diam the deviation ranges from a maximum 1.2 pct at 0 ft to 0.6 of 1 pct at 5000 ft. The value of 5.55 is the same for all ropes at 2500 ft. The tabulated columns to the left of the curves are values of total connected load for each size of rope from 5/8-in. to 21/4-in. diam inclusive. With each of these connected loads the safety factor characteristic curve for the rope will be as indicated.

Jan 1, 1957

By E. A. Holbrook

LOCAL yearly taxes levied on bituminous coal lands in Pennsylvania have become a cost of first importance to the coal industry of the State. In Pennsylvania there is no State tax on real estate, but local taxation of real estate furnishes the greater part of the revenue necessary for the small governmental unit, as counties, townships, boroughs, and local school, road, and poor districts. Coal in place in the ground, whether or not title thereto has been severed from ownership of the surface, is assessed as real estate and on its supposed sale or market value. There are eight classes of counties in Pennsylvania, based on population; in populous counties of the first, second and third class, assessments are made by a county board appointed by the county commissioners and are fairly uniform throughout the county. In counties of the fourth to the eighth classes inclusive, property assessments are made by property assessors elected by and for each township within a county. In these counties the board of county commissioners acts as a board of equalization and review to hear appeals. In most counties, therefore, where there is a large unmined reserve of coal, assessments on that coal vary for each township, irrespective of the fact that the coal bed is continuous under many townships.

Jan 1, 1933

By C. R. Dale

The need for instruments to measure the movement of fluids and gas in wells has been recognized by engineers for many years. Information regarding flow in the producing interval has a direct bearing on completion practices in new wells and also provides information on the production characteristics of the well. Many hours of engineering time are spent in planning and completing wells but knowledge as to whether or not the original planning has produced the desired results has not always been complete. Many questions such as the following often arise: Why is it that two wells are completed under supposedly identical conditions, yet one well is a good one and the other is a poor one? Are the sands that look the best on the electric log contributing to the production? These and many other conditions in the producing well need to be under- stood in order to develop more efficient production practices and to improve on methods of completing new wells. It is the purpose of this paper to briefly describe one type of instrument, outline the methods of running the equipment and show the results of surveys made under various conditions. With an understanding of the use of this type of survey its importance can be evaluated in relation to the problems encountered by the operator. DESCRIPTION OF INSTRUMENT The instrument is a velocity recorder employing a clock-controlled 16mm film for recording the rpm of an extremely sensitive rotor which is rotated by the flow of fluids or gas in a well. The helical-vaned rotor and shaft, weighing one-half of one ounce are an integral unit exposed to the well fluids and are the only moving parts not enclosed in the fluid-tight housing. No packing or fluid seal of these parts is necessary and the shaft is mounted top and bottom on special jeweled bearings. Fig. A is the lower part of the instrument showing rotor and shaft with the protecting housing sleeve removed. The rpm of the rotor is recorded on the moving film by a combination electrical and optical system. The record is a series of dashes on the film, each dash and space representing twenty (20) revolutions of the rotor. (Film record of survey made in California well showing station recordings at various depths.) As the movement of the film is controlled by the clock the number of dashes and spaces in one minute of film travel represents the rpm of the rotor. The range of the instrument is from 0 to 2,500 rprn. The barrel or housing is 1-11/16 in. OD and seven feet long. Various types of expanding fluid traps are attached to the lower end of the instrument to direct the flow through the 1 in. orifice containing the rotor. The fluid trap for upward flow is shown in Figs. B and C. This assembly consists of eight arms with light spring

Jan 1, 1949

By C. R. Dale

The need for instruments to measure the movement of fluids and gas in wells has been recognized by engineers for many years. Information regarding flow in the producing interval has a direct bearing on completion practices in new wells and also provides information on the production characteristics of the well. Many hours of engineering time are spent in planning and completing wells but knowledge as to whether or not the original planning has produced the desired results has not always been complete. Many questions such as the following often arise: Why is it that two wells are completed under supposedly identical conditions, yet one well is a good one and the other is a poor one? Are the sands that look the best on the electric log contributing to the production? These and many other conditions in the producing well need to be under- stood in order to develop more efficient production practices and to improve on methods of completing new wells. It is the purpose of this paper to briefly describe one type of instrument, outline the methods of running the equipment and show the results of surveys made under various conditions. With an understanding of the use of this type of survey its importance can be evaluated in relation to the problems encountered by the operator. DESCRIPTION OF INSTRUMENT The instrument is a velocity recorder employing a clock-controlled 16mm film for recording the rpm of an extremely sensitive rotor which is rotated by the flow of fluids or gas in a well. The helical-vaned rotor and shaft, weighing one-half of one ounce are an integral unit exposed to the well fluids and are the only moving parts not enclosed in the fluid-tight housing. No packing or fluid seal of these parts is necessary and the shaft is mounted top and bottom on special jeweled bearings. Fig. A is the lower part of the instrument showing rotor and shaft with the protecting housing sleeve removed. The rpm of the rotor is recorded on the moving film by a combination electrical and optical system. The record is a series of dashes on the film, each dash and space representing twenty (20) revolutions of the rotor. (Film record of survey made in California well showing station recordings at various depths.) As the movement of the film is controlled by the clock the number of dashes and spaces in one minute of film travel represents the rpm of the rotor. The range of the instrument is from 0 to 2,500 rprn. The barrel or housing is 1-11/16 in. OD and seven feet long. Various types of expanding fluid traps are attached to the lower end of the instrument to direct the flow through the 1 in. orifice containing the rotor. The fluid trap for upward flow is shown in Figs. B and C. This assembly consists of eight arms with light spring

Jan 1, 1949

By Lloyd Jones

THE strip industry made rapid strides in regard to both width and gage until about 1922, when the maximum width was about 20 in. In the hot mills, strips of thin gages in wide widths could be pro-duced, but only at a sacrifice of length of coil, con-siderable increase in power, and decreased tonnage out-put on the min. Hot mills, like the Bray sheet mill and the modern strip and skelp mills, demonstrated that . wider strip could readily be rolled, if such a product was desired. The strip manufacturers were really limited in width, not by the hot strip, but by the cold rolling of wide strip. This factor was roll pressure. The diameter of rolls increased as the width of strip increased. For cold rolling strip 20 in. wide, cold rolls were approximately 20 in. diameter. As the rolls became larger, the arc of contact between the rolls and the strip increased approximately, according to the formula, b=\/Rd where b = the width of contact R = roll radius d = total reduction Now the crushing strength of cold steel of low carbon varies from 70,000 to 100,000 lb. per sq. in. With each succeeding pass the crushing strength increases and may approach 250,000 lb., according to the total reduction. The total reduction in cold rolling of low-carbon steel will range from 40 to 70 per cent of the original thickness, usually in about three or four passes. On this basis, assuming a reduction of 20 per cent in one pass, the crushing strength of steel assumed at 120,000 lb., we have a total pressure between rolls, which (assuming that the rolls do not deform) equals: Roll Strip Strip Diameter, Width, Thickness, In. In. In. Pounds 10 10 0.100 380,000 20 20 0.100 1,080,000 30 36 0.100 2,375,000 42 50 0.100 3,900,000 These figures are approximate, but you will note that in increasing the width five times, or 50 in., the total pressure between the rolls increased approximately ten times. In other words, the pressure per inch of width increased from 38,000 to 78,000 lb. for the same per-centage of reduction.

Jan 3, 1928

By M. E. Wadsworth, J. S. Cho

The kinetics of silicate adsorption from aqueous colloidal (SO2 . nH2O) silicate sols on thoria (ThO 2) surfaces were determined at 100, 150 and 200°C in an autoclave system. The amount of chemisorbed silica on the thoria surface was determined by means of infrared spectroscopy. First order kinetics were observed in all cases with the anomalous result that the first order rate constant was found to vary with the initial amount of silica added to the system. These results have been correlated quantitatively by means of a strain model of adsorption involving two types of surface silicate bonding, both of which may be readily observed in the infrared spectrum. Initial adsorption occurs rapidly to produce one type of surface silicate followed by a slow transition to a second type of surface bonding, the latter transition representing the slow step in the adsorption process. Initial interest in silicate adsorption on thoria arose from the dispersive effect silica has on finely divided thoria in aqueous suspensions. Spaepen et al studied the equilibrium adsorption of silica on thoria and noted increased adsorption up to approximately 215°C with a notable decrease in adsorption at temperatures above 215°C. Similar results were observed by Cho and Wadsworth2 who identified two types of surface silica by infrared spectroscopy. At temperatures of 100°C and above, rapid initial adsorption occurred producing a surface species with maximum infrared absorbance at 9.4 After extended periods of time, the 9.4 species converted to a more strongly bonded surface silicate with maximum infrared absorbance at 10.3. The latter was very strongly bonded and difficult to remove by desorption in hot distilled water, while the 9.4 species could be removed more readily by similar treatment. The 9.4 and 10.3-p species were distinguishable from free unadsorbed silica which had maximum infrared absorbance at 9.1 The kinetics of the formation of the strongly chemisorbed silica (10.3) on thoria as determined by infrared examination are presented in this study. EXPERIMENTAL PROCEDURE As a source of silicate, Ludox SM (16.36% SiO2) or Ludox HS (30.25% SO2), DU Pont colloidal silica in aqueous suspensions, was added directly to a thoria slurry made up of one liter of distilled water and one gram of thoria. The thoria used was designated D-16-650 and was received from the Chemical Technology Div. of Union Carbide Nuclear Co. It was prepared by firing thorium oxalate at 650°C. The D-16 thoria had a surface area of 32.4 ± 0.6 sq m per g as determined by nitrogen adsorption.* This thoria 'Determined by Unlon Carbide Nuclear Co., ORNL. had a total adsorption capacity for silicate of approximately 19.4 mg of silica per gram of thoria.1 This amounts to approximately one SiO2 molecule for every surface thoria site. In all cases in this study.

Jan 1, 1963

By E. Miller, K. Komarek, W. Johnson

The activity of aluminum in solid Cr-A1 alloys has been measured by an isopiestic technique between Cr-A1890' and 1126" and 13 and 80 at. pct Al. The integral free energy of mixing has a minimum value of —5600 cal per g-atom at 59 at. pct Al. The maximum solid solubility of aluminum in chromium was determined to be 43 at. pct Al, and the composition limits of the compounds CrA14, Cr4A19, and Cr5Al, at 1000"~ were found to be 79 to 80, 66 to 70, and 59 to 63 at. pct Al, respectively. The thermodynamic properties of the Cr-A1 system have been investigated as part of a thermodynamic study of aluminum-transition metal systems.172 Little information is available on the equilibrium properties of the Cr-A1 system. The heats of formation of solid Cr-A1 alloys have been determined by Kubaschewski and Haymer at 600" and low-temperature specific heat data have also been obtained.~ More extensive work has been performed on the phase diagram, and a compilation has been provided by Hansen and Anderko,~ their phase diagram at elevated temperatures being essentially based on the work of Bradley and LU.~ The high-temperature portion of the phase diagram shows an intermediate phase CrA14 decomposing peritectically at 1018°C and existing at 82 at. pct A1 at 1000°C. They also identified the compounds with solubility limits of 72 to 75 at. pct A1 at 1000°C, and Cr5A1,, existing at 61 at. pct A1 at 1000°C. The maximum solid solubility of aluminum in chromium at 1000°C was found to be 46 at. pct Al. These elevated-temperature data were obtained by examination of quenched samples and were considered as less precise than the lower-temperature data. Koester, Wachtel, and Grube7 have revised the phase diagram as a result of their magnetic susceptibility and X-ray study. The results of this work differ appreciably from those of Bradley and Lu at temperatures above 800°C. The CrA1, compound is given as existing between 79 and 81 at. pct A1 at 1000°C, and they do not indicate the presence of a CrA13 phase reported by Bradley and Lu. They also report the compound Cr4Alg as having solubility limits of 66 to 70 at. pct A1 at 1000°C, while Bradley and Lu show this compound stable only up to 870°C. Koester et al. state that the high-temperature modification of the compound Cr5A18 is stable down to 1125"C, and not 980°C as stated by Bradley and Lu, and that the low-temperature modification of Cr5Al, has a range of homogeneity of 58 to 63 at. pct A1 at 1000°C. They also report that the maximum solid solubility of aluminum in chromium is 43 at. pct A1 at 1000°C. APPARATUS AND EXPERIMENTAL PROCEDURE An isopiestic method was employed which has been successfully applied to the determination of aluminum activities in solid ~e-All and Ni-Al alloys. Alloy specimens were held at different positions in a temperature gradient and were equilibrated with aluminum vapor from an aluminum reservoir kept at the temperature minimum of an impressed thermal gradient in a closed alumina system. Diffusion of aluminum into the specimens occurred until equilibrium was reached, at which the partial pressure of aluminum in each of the specimens was given by the vapor pressure of the pure aluminum reservoir. The activity of aluminum referred to liquid aluminum as the standard state in a given equilibrated sample at temperature T could therefore be expressed by: vapor pressure of pure aluminum at _ the temperature of the reservoir Vapor pressure of pure liquid aluminum, at specimen temperature T Since both the temperature of the aluminum reservoir and the specimen temperatures were determined experimentally, and the vapor pressure of pure aluminum is known as a function of temperature,' the activity of aluminum in a given aluminum alloy of known composition could be calculated. Initial runs were made with samples consisting of pure chromium chips placed in alumina crucibles. These runs exhibited large inconsistencies, indicating that equilibrium was not attained. High aluminum content Cr-A1 alloy powders were therefore substituted for the pure chromium specimens. The starting composition of the alloys was adjusted through experimentation until the concentration change necessary to attain equilibrium was small. In this manner, consistent results were obtained in reasonable times. SPECIMEN PREPARATION Alloy specimens were prepared from chromium of 99.997 pct minimum metallic purity: with 0.028 to 0.038 pct H, 0.0002 pct N, and 0.27 to 0.46 pct 0 (Aviquipo, Inc.). The aluminum had a purity of 99.99+ pct and the following impurities: 0.003 pct Cu; 0.002 pct S; 0.002 pct Fe; 0.001 pct Pb; 0.001 pct Ga (Aluminum Corp. of America). Alloy powders were prepared from weighed mixtures of chromium and aluminum by double-arc melt-

Jan 1, 1969

By A. A. Venghiattis

A rational approach to the selection of the appropriate perforator to use in each specific zone of an oil well is presented. The criteria presently in use for this choice bear little resemblance with actual down-hole condilions. These environmental conditions affect the elastic properties of rocks. One of these elastic properties, acoustic velocity, is suggested as the leading parameter to adopt for the choice of a perforator because, being currently measured in the natural location of the formation, it takes into account all of the effects of compaction, saturation, temperature, etc., which are overlooked in the laboratory. Equations and curves in relation with this suggestion are given to allow the prediction of the depth of perforation of bullets and shaped charges when an acoustic log has been run in the zone to be perforated. INTRODUCTION When an oil company has to decide on the perforator to choose for a completion job, I wonder if it is really understood that, to date, there is no rational way of selecting the right perforator on the basis of what it will do down-hole. This situation stems from the fact that the many varieties of existing perforators, bullets or shaped charges, are promoted on the basis of their performance in the laboratory, but very little is said on how this performance will be affected by subsurface conditions such as the combination of high overburden pressure and high temperature, for example. The purpose of this paper is to show the limitations of the existing ways of evaluating the performance of perforators, to show that performances obtained in laboratories cannot be extended to down-hole conditions because the elastic properties of rocks are affected by these conditions and, finally, to suggest and justify the use of the acoustic velocity of rocks, as the parameter to utilize for the anticipation of the performance of a perforator in true down-hole environment. EVALUATING THE PERFORMANCE OF A PERFORATOR It is natural, of course, to judge the performance of a perforator from the size of the hole it makes in a predetermined target. Considering that the ultimate target for an oilwell perforator is the oil-bearing formation preceded in most cases by a layer of cement and by the wall of a steel casing, the difficulties begin with the choice of an adequate experimental target material. For obvious reasons of convenience, the first choice that came to the mind of perforator designers was mild steel. This is a reasonable choice for the comparison of two perforators in first approximation. Mild steel is commercially available in a rather consistent state and quality, and is comparatively inexpensive. The trouble with mild steel is that it represents a yardstick very much contracted; minute variations in depth of penetration or hole diameter and shape may be significant though difficult to measure. The penetration of projectiles in steel being a function of the Brinell hardness of the steel (Gabeaud, O'Neill, Grun-wood, Poboril, et al), it is often difficult to decide whether to attribute a small difference in penetration to a variation on the target hardness or to an actual variation on the efficiency of the projectile. Another target material which has been widely used for testing the efficiency of bullets or shaped charges in an effort to represent a formation—a mineral target as opposed to an all-steel target—is cement cast in steel containers. This type of target, although offering a larger scale for measuring penetrations, proved so unreliable because of its poor repeatability that it had to be abandoned by most designers. The drawbacks of these target materials, and particularly their complete lack of similarity with an oil-bearing formation, became so evident that a more realistic target arrangement was sought until a tacit agreement was reached between customers and designers of oilwell perforators on a testing target of the type shown on Fig. 1. This became almost a necessity about seven years ago because of the introduction of a new parameter in the evaluation of the efficiency of a perforator, the well flow index (WFI). The WFI is the ratio (under predetermined and constant conditions of ambiance, pressure and temperature) of the permeability to a ceitain grade of kerosene of the target core (usually Berea sandstone) after verforation. to its vermeabilitv before perforation. The value of this index ;or the present state if the perforation technique varies from 0 to 2.5, the good perforators presently available rating somewhere around 2.0 and the poor ones around 0.8, There is no doubt that, to date, the WFI type of test is by far the most significant one for comparing perforators. It is obvious that a demonstration of a perforator

By B. Fazan, O. D. Sherby, J. E. Dorn

McLean's technique was employed to determine the effect of temperature on the contribution of grain boundary shearing to the total creep strain in pure aluminum over the range of 610° to 747°K. The contribution of grain boundary shearing at the same stress was found to depend upon a temperature-compensated time, where the activation energy AH was practically identical with that for total high temperature creep. SEVERAL outstanding investigations by McLeanl-' have demonstrated that the total creep strain in polycrystalline aluminum at 473°K arises from microscopically detectable slip, subgrain tilting, and grain boundary shearing. Whereas microscopically detectable slip arises from dislocations that move out of the grains, subgrain tilting is due to entrapment of dislocations of like sign in subgrain bound-arles. Consequently, creep in polycrystalline aggregates appears to be the resultant of two mechanisms, namely, migration of dislocations and grain boundary shearing. This suggests that an appropriate law for creep should contain two additive terms ?1 = ?d + ?yb where the total creep strain, ?1, depends on the sums of the creep strains arising from motion of dislocations, ?d, and from grain boundary shearing, ?yb. But extensive investigations5 over wide ranges of alloys, grain sizes, temperatures, and stresses have shown that the total creep strain is quite accurately dependent on the single term functional relationship ?1 = f (?), s = constant where s is the stress (constant),* ? = te-?H/RT, t is the time under stress, AH is the activation energy, R is gas constant, and T is absolute temperature. Since Eq. 2 was found to be valid over those ranges where appreciable grain boundary shearing is observed, it appears probable that the activation energy for grain boundary shearing might be identical with the activation energy for migration of dislocations. Thus, under a given stress, it could be thought that where fd and fgb represent the appropriate functions for each mechanism of creep. The primary objective of this investigation was to obtain a direct check on the accuracy of this hypothesis. Experimental Procedure and Results Rolled aluminum sheet (99.987 pct Al), 0.100 in. thick, was used in this investigation. Creep specimens having a 0.25 in. wide, 3 in. long gage section were so machined that their axes were in the rolling direction. All specimens were annealed for 9 hr at 894°K before testing to produce a mean grain diameter of about 0.1 in. One face of each specimen was polished electrolytically in 10 pct HBF4. In order to permit accurate measurements of grain boundary shearing, the polished surface was lightly scribed with a ruling machine accurate to ±0.0001 in. to give a uniform grid of lines which were 0.01 in. apart. Although it was thought that surface working might modify the creep behavior in the vicinity of the scribed grid lines, this technique nonetheless was employed because such local differences in creep properties should not modify seriously the fractions of the total creep strain due to grain boundary shearing or to migration of dislocations. All creep tests were conducted under constant load with an initial stress of 250 psi. The specimen tem-

Jan 1, 1955

By S. I. Liu

THE effects of strain histories, consisting of several prestrains in opposite directions, on the flow and fracturing characteristics of metals determined in a final test have been investigated previously.'" Such strain histories vary from a single prestrain in tension or compression to the number of strain cycles leading to fatigue failure.' Between these two limits, various strain histories could be visualized and some can be attained readily. One such example is a strain history consisting of a first prestrain in tension of various magnitudes and a second prestrain in compression also of various mag-nitude. In this investigation the strain history was extended to the combination of these two limits, i.e., a single prestrain in tension or compression followed by balanced strain cycles of a selected magnitude e, = k0.12. It was found in this case that only compressive initial prestrains could be investigated with sufficient accuracy.* Such strain histories can be considered also as (low cycle) fatigue tests of a metal subjected to various amounts of cold working. It appears from previous publications that cold working within a wide range of reductions usually raises the un-notched fatigue strength of many metals.'-' This effect, however, has been found to be inconsistent and sometimes reversed for other metals?.7 Furthermore, Ludwik reports that the yield strength of cold-worked specimens may be reduced by cyclic strains, while that of materials without cold work is generally increased in the initial cycles." " In addition to the above tests, a study was made of the effect of intermediate re-solution heat treatment on low cycle fatigue behavior. Such anneals should eliminate the strain hardening induced by the cyclic strains. As far as their effect on the fracture characteristics is concerned, a few previous tests seemed to indicate that the damage resulting from cyclic strains is retained only partially after heat treatment." A further investigation was made in which one specimen was subjected to repeated unbalanced tension cycles in which the strain interval was approximately $ 0.013. This repetition of plastic tension damages the material slightly. This result appears to confirm Ludwik's observations." " Commercial 3/4-in. rod of the aluminum alloy 24ST4 was selected for this investigation. The material was subjected to the following treatments before machining: 1—Re-solution treatment at 920" ± 10°F for 45 min, 2—water quench at room temperature, and 3—aging for four days at room tem-perature.? The treated material then was machined to desired specimen contour and tested. A coolant was used during machining to minimize any artificial aging effects of heating during machining. In some cases the 24ST4 specimens were reheat treated after having been strained. In these cases, the heat treatment was the same as the re-solution heat treatment described above. Procedure As shown in Fig. 1, threaded end specimens with a minimum diameter of 0.266 in. and a contour radius of 2 in. were used for prestraining to an axial compressive strain ranging from 6, = —0.10 to E, = —0.48. For large prestrains, two consecutive corn-

Jan 1, 1952

By M. J. Pool, P. J. Spencer

Using liquid tin as the solvent metal, the heats of solution of silver and gold in dilute Ag-Au-Sn alloys have been determined at 723°K by solution calorimetry. From the values obtained, the various enthalpy interaction coefficients in the liquid solutions have been calculated. The self-interaction coefficients Au and Ag values of 2413 and -6322 cal per g-atom in binary Au-Sn and Ag-Sn alloys, respectively. For an alloy containing 0.04 mole fraction Ag, Au is equal to 2443 cal per g-atom, and in an alloy containing 0.04 mole fraction Au, Ag has a value of —8883 cal per g-atom. Ag Au has been determined as —2650 cal per g-atom. ADDITION of a second solute to a dilute binary alloy may cause striking changes in the thermodynamic characteristics of the alloy. As yet, such influences cannot be reliably predicted and it is only by accumulation and critical assessment of data that definite patterns can be established. Solute interactions in dilute solutions were first treated mathematically by Wagner,1 who derived expressions for the Gibbs energy interaction coefficients. For an alloy consisting of. two dilute solutes, i and j, in a solvent s, these coefficients are given by: where yi is the activity coefficient of component i and x represents the mole fraction of solute or solvent. Other interaction coefficients have since been established in terms of the various partial molar thermodynamic properties of an alloy; the definitions of these are summarized in a recent paper by Lupis and Elliott.2 Mathematical and experimental studies of such coefficients have received much attention recently, providing a very useful theoretical background to an understanding of the nature of solute interactions taking place in dilute solutions. One of the definitions to arise from such work has been the extension of Wagner's treatment by Lupis and Elliott4 to include an enthalpy interaction coefficient, defined as. where ?Hi is the relative partial molar enthalpy of component i. ?Hi is related to the relative partial molar enthalpy at infinite dilution, ?Hio, and to the enthalpy interaction coefficients by the expression: Values of ?Hi can often be obtained with a high degree of accuracy by calorimetry, and, if the composition of the alloy is carefully controlled by making calculated solute additions throughout a series of measurements, application of Eq. [2] will enable reliable enthalpy interaction coefficients to be determined. Partial heats of solution must be investigated as a function of solute concentrations down to xi = 0, and, since ? values are obtained from the slope of mi plotted against x, great care must be taken to obtain precise data. The data for binary systems which are presently available often require extrapolation of ?Hi values from compositions as great as xi = 0.05 or even 0.1 to obtain limiting heats of solution. Reliable enthalpy interaction coefficients are thus impossible to obtain from published data for most of the alloy systems already investigated. The aim of the present work was to determine values of Au, Ag, Ag, and Au in the limit xsn -1 for the relatively simple Ag-Au-Sn system and from these results to gain some insight into the possible influence

Jan 1, 1969

By A. S. Malicsi, R. J. Lipp, I. Iwasaki

A loch-grade copper-nickel deposit, with an estimated 4.6 Gt (5 billion st) and average analyses of 0.6% copper, 0.2% nickel, occurs in northeastern Minnesota. In addition to copper, nickel, cobalt, and precious metals, the Duluth gabbro contains magnetite, ilmenite, olivine, plagioclase, and biotite. It u estimated that flotation tailings that would be produced by a concentrator of optimal size to sustain a smelter would amount to 20 Mt/a (22 million stpy). The flotation tailings, having already been ground, warrant a closer examination for recovery and use of potential byproducts. Residual sulfide minerals and fibrous minerals may also be isolated and treated separately for useful purposes or for disposal in an environmentally acceptable manner. Two flowsheets were developed; one involving preconcentration by low- and high-intensity magnetic separation and another involving preconcentration by gravity concentration. Concentration methods for recovering and purifying individual byproduct minerals were investigated. From their chemical, physical, and mineralogical characteristics, the potential areas of application and marketabilities of each product fraction were surveyed.

Jan 1, 1985

By Jacques B. Wertz

Among the parameters to be considered in the continuous search for new base-metal deposits, there often is a stratigraphic controlling factor that seems instrumental in the localization of ore. In British Columbia, for instance, the Upper Triassic as well as Lower Jurassic volcanics mixed with sediments are a useful indication in the search for copper while, in some parts of Australia, rhyolite bodies seem to be the favorable indicator, and this always within the geosynclinal environment. In Arizona, this stratigraphic factor becomes highly significant and it will be shown here that a large number of ore deposits are to be located around the flanks of ancient calcareous basins or depressions, preferentially corresponding to a certain optimum thickness as revealed by isopachs. The Martin limestone, of Devonian age, is already known for its basal O'Carroll bed which coincides with mineralization at places, and this is a relatively minor control. However, several limestone basins outlined by isopachs are in reality of greater importance as they localize mining districts. Indeed, most mines are found to coincide with a specific thickness of limestone while occurring simultaneously close to major, regional fracture intersections. The regional fractures in question were interpolated and extrapolated from known, important fault expressions, integrating quite well with the existing geology and further confirmed by minor criteria such as contacts, igneous plugs, axes of elongation of batholiths, dikes, etc. Although elements of subjectivity remain, this grid of fractures can be used quite successfully as a working hypothesis in the search for ore. Results of the present study which superposes major structural

Jan 1, 1971

Discussion of the paper of Edward Keller, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 80, August, 1913, pp. 2093 to 2115. GEORGE L. HEATH, Hubbell, Mich.:-In the admirable paper quoted, is mentioned the date when the 5-g. assay was first proposed is a standard for refined metal. The author omitted, however, to mention a later paper,1 which contains a proposal for the use of a single " stock solution " of mixed acids, which has been adopted by the American Brass Co. and others. The suggestion is made that such a scheme would save time and manipulation with converter metal. Unless the low current of 0.5 ampere and the large excess of nitric acid, recommended by Mr. Keller, have been proved necessary to hold up antimony-and selenium, the use of the mixed solution which we have adopted will permit the use of 1 ampere of current per square decimeter of cathode surface, until the solutions have become colorless. At this point, we wash the covers and reduce to 0.5 ampere to prevent oxidation or contamination. The ordinary split electrodes have been used. With strong current, at least, the use of an excess of nitric acid tends to the neutralization of the solution before the end of the period, from the formation of too much ammonia., and this is detrimental. Antimony deposits more easily than arsenic, and tends to drag the latter dorm with it. There must, be some such explanation for the fact. that we have made hundreds of deposits of pure cathodes from Lake material containing no antimony, but as. high as 0.5 per cent. of arsenic. By placing an assay beaker in the Frary solenoid, or rotary device, a cathode deposit with less than 0.01 per cent. of impurity is easily obtained in one operation from 3 g. of whitneyite, carrying from 7 to 10 per cent. of arsenic. In such a case, it is necessary to test several times for end point and remove the plate as soon as no brown tint appears (at once) when hydrogen sulphide water is added to the test portion on the spot plate. Edward Keller's proportion,, of solvent figure out as 14 cc. of strong nitric to 11.4 cc. of sulphuric acid (1.84).

Jan 11, 1913

By H. J. Tschirner, L. P. Davidson, R. K. Carpenter

HE electrolytic zinc plant of the American Zinc Co. of Illinois, at Monsanto, was expanded in 1943 to a capacity of 100 tons of slab zinc daily. This capacity was not attained because of inability of the leaching plant to deliver an adequate amount of solution for electrolysis. Changing the leaching method so that the acid was added to the roasted zinc material reversed the usual procedure and made it possible to attain the desired capacity. The conditions which prevented satisfactory work before this change and the difficulties which arose in reversing the usual leaching procedure are described. The "reverse" leach operation as now practiced is carried out as follows: All the calcine to be leached is fed continuously to a slurry mixing tank. About one third of the acid to be used is fed to the tank with the calcine. The slurry is discharged continuously to a Dorr duplex classifier in closed circuit with a Hardinge mill. The classifier overflow is pumped to any of six leaching tanks where the leach is completed. A finished leach is discharged through Allen-Sherman-Hoff pumps to Dorr thickeners, from which the overflow goes to the zinc dust purification and the underflow to vacuum filters. This change in leaching procedure from the usual one of adding calcine to a large amount of acid made it possible to provide an adequate amount of purified solution to the electrolyzing division and at the same time filter and dry all the residue produced. Operating savings in reagents and better metallurgical recoveries were also important benefits. The original flowsheet of the leaching plant provided leaching, sedimentation of the insoluble residue, and purification of the neutral zinc sulphate solution with zinc dust. The thickened residue was filtered and washed. The purification cake of excess zinc dust, precipitated copper and cadmium, and any insoluble residue was filtered off on plate-and-frame duplex classifier. Settlement in the thickeners was inadequate and the suspended solids in the thickener overflow gave rise to filtration difficulties after the zinc dust purification. Further, the filtration and washing of the leach residue was poor, and it became necessary to pump a large amount of unwashed or poorly washed residue to storage ponds outside the plant building. Two causes of the poor settling and filtration were determined: Soluble silica and ferrous iron in the calcine treated. The latter was a result of poor roasting and with more experience ceased to be a major problem. The silica was a normal constituent of the feed and the working out of the problem became a matter of controlling its solubility. The obvious method to render the silica insoluble was by intensive roasting. This, however, met with total failure as such roasting resulted in silicates, probably zinc, soluble in the 13 pct acid used for leaching. Attempts were made to coagulate the fine gelatinous slime with addition agents. Glue, lime, starch, beef-blood serum and others were tried without success. All the suggested tried-and-tested means of operating the thickeners gave no consistently good results. Variations in leaching time, in addition of calcine to the leaching tanks, "conditioning" of the pulp by prolonged agitation, immediate discharge of the leach upon completion to avoid breaking up flocs were all tried and given up as ineffective. Byron Marquis, of Singmaster and Breyer, worked with the plant staff on a beaker scale until a leaching procedure was developed which gave consistent results and a promise of overcoming the difficulties which had plagued the plant operation. It was suggested that the difference in solubility of silicates and zinc oxide in sulphuric acid could be made use of in a leaching method where the acidity was controlled carefully. Such control is possible when acid is added to a slurry of calcine. This process reverses the normal procedure of adding calcine to a vessel of acid, hence the term "reverse leach" was applied. In this way, the overall acid concentration can be kept very low. In the tests made, it did not exceed 0.05 g per liter free sulphuric acid. Numerous advantages were realized when no silicates were taken into solution and later precipitated as a bulky gel. The gel had made reasonable thickening and filtration of the leach pulp and practical drying of the residue impossible. When the gel was eliminated, thickening rates were increased as much as five times. The volume of residue after thickening represented about 10 pct of the total leach pulp and had been as high as 95 pct when the gel was present. The thickened pulp was filterable and the filtered cake was dried readily after washing. The zinc extraction from the calcine was slightly lower. This was more than compensated for by the increase in zinc recovered in solution from zinc which had been trapped in the gelatinous residue. The amount of copper recovered was lower. However, the amounts of other impurities, such as arsenic, antimony, and germanium, taken into solution were lower. This was particularly true of antimony. Since the inception of reverse leaching, no concentrates have failed to yield solutions free of antimony even when present in the calcine to the extent of 0.2 to 0.3 pct. Oxidation of ferrous iron is a problem of reverse leaching. Ferrous hydrate does not precipitate at pH 5.3 to 5.4 where a leach is finished. The usual oxida-

Jan 1, 1952

By Donald L. Katz

The compressing of gas into a partially depleted gas drive oil reservoir to bring the contents to a single phase miscible with gas is proposed as a process worthy of serious study. The compressed gas and vaporized oil would be recovered by cycling. This paper explores the Possibility of recovering oil from reservoirs of 6,000 ft or more by this method. INTRODUCTION Many new methods for increasing the recovery of oil from reservoirs are under consideration in the various research laboratories. One method which should be considered for recovering oil From partially depleted gas drive fields is to compress gas into the reservoir until the contents become a single phase miscible with more gas. Natural gas then may be cycled through the reservoir to recover the oil. This procedure ideally will eliminate the capillary effects of the liquid ill the porous media and should permit recoveries similar to those obtained in cycling operations, probably of the order of 80 per cent. This paper explores the information now available for the prediction of the performance of such a project and discusses the problems likely to be encountered in recovering oil by cycling. For many years dry natural gas has been passed through oil reservoirs to recover natural gasoline which would vaporize from the oil. Recently a process of recovering more of the high boiling hydrocarbons has been described by employing high pressures at which the heavier hydrocarbons have a higher volatility. Nevertheless. this reported method does not eliminate the differential nature of the vaporization process and capillary forces are still present in the reservoir. The process under discussion in this paper would minimize differential vaporization and would remove capillary forces which are responsible for low oil recoveries. Higher gas pressures are required to accomplish this removal of the miniscus, but it does not follow that more gas is required for oil recovery. The process is limited to reservoirs deep enough to permit the use of the required pressure — Probabably 6,000 it and deeper. DESCRIPTION OF THE PROCESS Briefly, the process is to compress natural gas into an oil reservoir which is partially depleted so that it has an oil saturation in the range of 40 to 60 per cent of the hydrocarbon pore space. The injected gas will pass through the channels formerly carrying gas to the wells to build up the pressure and dissolve in the oil phase. This injection will continue without production from the field until the reservoir reaches a single phase. If one were to select unique conditions such that the gas composition, the reservoir oil composition and the Per cent saturation would bring the mixture in the reservoir to the critical temperature and pressure simultaneously the phase behavior accompanying injection is shown by Fig. 1. The oil-gas mixture in the depleted reservoir has a critical temperature at C,. Addition of natural gas to the mixture will give a new critical temperature for each addition. Mixture No. 3 is shown to have its critical temperature at the reservoir temperature and reservoir pressure at P: the critical pressure. Under ideal behavior, the entire reservoir would be at iti critical temperature and pressure and the entire hydrocarbon content would be at a single phase. If the reservoir content were a binary system of methane and a heavy constituent. it would be miscible with more methane. However, for complex mixtures the critical locus does not confine the two phase region, and the dew point curves of Fig. 1 occur above the critical locus. If fluid which was injected into the rezervoir at the critical point were of the

Jan 1, 1952

By Henry R. Linden

The demand for natural gas continues to increase at higher than anticipated rates, partly because of its widening price advantage over most other fossil fuels when the cost of air-pollution control is included. However, there are clear indications that the natural gas supply from the conliguous 48 states and continental shelves will not keep up with this rapid growth in demand indefinitely. Projections are presented which define the extent of potential deficiencies from the 1970's to the year 2000. Among the sources of supplemental gas - imported pipeline natural gas from Canada and Mexico, tanker import of liquefied natural gas, and synthetic pipeline gas from coal and oil shale -by far the most abundant at potentially competitive costs is pipeline gas from coal. The state of development and relative economics of the various coal gasification processes are reviewed. It is shown that synthetic pipeline gas could become a very substantial market for bituminous coal and lignite at current mine-mouth prices - 60-70 million tons of coal for each trillion cubic feet of synthetic pipeline gas produced. This corresponds to only slightly more than the current annual increase in gas demand. Although annual discoveries (gross additions to proved reserves) of natural gas in the United States are still on a general upward trend from the current level of 22 trillion cu ft annually, most forecasters do not expect this to increase substantially in the foreseeable future. For example, the updated (to include 1966 and 1967 data) mathematical model of natural gas discovery and production in the U.S. developed by the Institute of Gas Technology (IGT)' projects that discoveries will level out at about 25 trillion cu ft annually in the late 1970's and during the 1980's and then decline to about 21 trillion cu ft by the year 2000 (Fig. 1). This adds up to a new supply for the period 1968-2000 of about 790 trillion cu ft. Experts who usually reflect the producers' viewpoint, such as Radford L. Schantz of Foster Associates,* are relatively more pessimistic. In contrast, a forecast just made by the U.S. Dept. of the Interior is much more optimistic.3 It assumes an increase in gas discoveries of 2.2% per year over the period 1965-80, reaching about 30 trillion cu ft in 1980. If this rate of increase were extended to the year 2000, annual discoveries would reach 46 trillion cu ft at that time, for a total over the period 1968-2000 of about 1100 trillion cu ft. To these forecasts of new gas discoveries must be added proved reserves of roughly 290 trillion cu ft,4 bringing total U.S. supplies for the rest of the century to nearly 1100 trillion cu ft (IGT) and possibly as high as 1400 trillion cu ft (U.S. Dept. of the Interior). This is approximately the same range as that of two estimates of total remaining recoverable natural gas supply: Potential Gas Committee, 980 trillion cu ft5 and IGT, 1450 trillion cu ft.6 Only the 1965 estimate by the U.S. Geological Survey7 suggests that economically recoverable natural gas supplies will not be exhausted around the end of the century. These forecasts are, naturally, based on the assumption that changes in technological, economic, and regulatory environment as they affect the gas industry will be of an evolutionary, not revolutionary, nature. The various forecasts of potential natural gas supply must now be compared to forecasts of natural gas demand (Table I). The general consensus is that the recent Future Requirements Committee projection to 1990' (extended to the year 2000 by the most recent U.S. Bureau of Mines (USBM) projection9) represents the minimum gas requirements (Table 11). They add up to a total of 1030 trillion cu ft for the period 1968-2000. Even this minimum anticipated gas demand exceeds the total remaining supply estimate by the Potential Gas Committee and would nearly exhaust the proved reserves plus new discoveries projected by IGT. The supply situation would appear much tighter if the demand projections of the Texas Eastern Transmission Gorp.10 and the American Gas Assn.(A.GA.)'' were used (Table I). Yet, these higher forecasts probably do not include the effects of such new markets as gas fuel cells, use of liquefied natural gas as a transport fuel, etc. They also may not fully reflect the impact of air quality control on the fuel market. Obviously, the probable discrepancy between projected supply and demand can only be accommodated in four ways. 1) Rapid increase in exploration and drilling activity to provide new supplies in the amount projected by the optimistic U.S. Dept. of the Interior forecast, coupled with an increase in net pipeline imports from Canada and Mexico from the present 0.5 trillion cu ft per year

Jan 1, 1970

By R. G. Knickerbocker, W. H. Yarroll, P. E. Churchward, J. W. Hunter, J. H. Jacobs

THE present paper records a chapter in the history of the development of an electrolytic manganese industry in the United States.1 A relatively large pilot plant at Boulder City, Nev., for the production of electrolytic manganese was conceived as part of the national defense program to make this country independent of foreign importation of manganese ore. The first authorization, in November 1940, however, was for a plant of only several hundred pounds capacity. Improvements in process and subsequent additions to some sections authorized by subsequent appropriations have enabled the plant to produce as much as 2000 lb. of manganese a day for substantial periods of time. Since in pilot-plant operation frequent changes are made in the flowsheet, the electrolytic manganese plant was constructed so that equipment could be rearranged with a minimum of expense and time. Several different kinds of the various types of equipment were installed for many of the operations, so that the one most suitable for the process might be chosen. Pilot-plant operations were begun in November 1941 and have been continuous except for brief shutdowns for installation of new equipment. More than one-half million pounds of manganese have been produced. The improvements in process, selection of equipment, and operational procedure developed are recorded here. DEVELOPMENT OF THE PROCESS The work of early investigators on the electrolysis of manganese solutions has been reviewed by Shelton.2 Until the method of continuous production of manganese by electrolysis was perfected by Shelton2-4 and coworkers, no practical procedure had been devised. The method as originally developed by the Bureau of Mines will be described here only briefly. The manganese dioxide ore was reduced in a rotating kiln-type furnace at 650°C. in an atmosphere of "city" gas. The calcine was leached with spent electrolyte and enough sulphuric acid to produce a neutral leach solution containing 25 grams manganese per liter as manganese sulphate and 200 grams per liter of ammonium sulphate. Arsenic was removed from the solution by the addition of 0.05 gram iron per liter as ferrous sulphate followed by oxidation

Jan 1, 1944

By Adolf Gurlt

It has long been known that minute quantities of foreign substances, when alloyed with steel, are capable of materially altering its physical properties. Thus, half a century ago, Faraday and Stodart, in England, discovered in the famous Indian steel, known as " wootz," small quantities of aluminum, from 0.0728 to 0.693 per cent., and attributed its extraordinarily good quality to the presence of such minute quantities of that metal. Since aluminum is now produced by electrolytic means on a large scale and at low cost, its addition to cast-steel has been frequently recommended of late. Chromium was alloyed with steel fifty years ago by the celebrated French metallurgist, Berthier, of Paris, and has recently been successfully applied to the same purpose by Holtzer, of Terre-Noire. In 1860 titanium was alloyed with crucible steel by Robert Mushet, of Coleford, the alloy containing up to 0.50 per cent. of titanium, which was extracted from Norwegian ilmenite. The titanium-steel was much vaunted by him for its excellent qualities. Rhodium, a very rare metal of the platinum series, was maintained by Berthier to improve steel materially in strength and hardness. Manganese has always been held by Sheffield steel-melters to provide steel with excellent qualities, and this influence was quite recently investigated by H. M. Howe and L. Campredon. Nickel was tried as an addition by Berthier, not to speak of gold, silver and platinum ; and nickel-steel has recently been brought into prominence by J. Riley and others, who recommend it for its great strength and toughness, particularly as material for armor-plates.

Jan 1, 1894

By William H. Baer, George M. Carlton, Blake M. Loring

IT is a well known fact that age-hardening alloys remain in a supersaturated, or partially supersaturated, condition only for limited periods of time at temperatures below the solvus. In order to develop optimum properties by subjecting the quenched alloy to precipitation or age-hardening treatment at a specified temperature, it is necessary that the cooling rate be sufficiently high to maintain the required degree of supersaturation of the solid solution. In practical applications the size and shape of the specimens obviously have considerable influence on the rate of cooling and there is need for more information on the effects of various rates of cooling. Cooling rates of quenched aluminum alloys generally have been established by the type of quenching medium, the temperature of the medium and the dimensions of the specimen.1,2,3 Except for the work of Roth3 little quantitative information is available on the measurement of cooling rates of aluminum alloys and the significance of the influence of various cooling rates upon the mechanical properties. The purpose of the present investigation was to study the use of the Jominy test for aluminum alloys (Table I). EXPERIMENTAL PROCEDURE The material for this investigation consisted of extruded rods 1 ¼ to 1 ½ in. in diam. The chemical compositions were as follows: [ ] The modified L-type Jominy specimen with dimensions shown in Fig I was selected as the most convenient means for obtaining a wide range of cooling rates. The standard Jominy specimen was not satisfactory because its cooling rate was not sufficiently high. The four flat surfaces machined at right angles along the length of the L-type specimen to a depth of 0-015 in. facilitated the hardness measurements. The specimens were machined from the extruded stock with no intermediate forging. New specimens were used for each aging experiment. The specimens were given solution treatments of 2 hr duration at recommended temperatures in a Hoskins furnace (Table 2). The temperature of the furnace was maintained constant to ±3°C. No protective atmosphere was necessary because the thin film of oxide that formed on the surface of the specimens had no effect on the hardness measurements.

Jan 1, 1948