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By G. S. Upadhyaya, A. D. McQuillan

HERE would appear to be a simple relationship between the group number in the periodic table of the early transition metals and the maximum amount of hydrogen which they can absorb.' Thus group IIIA metals (Sc, Y, and La) yield a trihydride in which the metal atoms are on a fcc lattice and the hydrogen atoms occupy both tetrahedral and octahedral interstices. Group IVA metals (Ti, Zr, Hf) form dihy-drides in which the metal atoms are on either a fct or cubic lattice, but in which only the tetrahedral interstices are occupied by hydrogen atoms. In group VA (V, Nb, Ta) the hydrogen-saturated metal attains a composition slightly below that of a monohydride under normal conditions. Finally the metals of group VIA (Cr, Mo, W) do not dissolve appreciable quantities of hydrogen. The manner in which hydrogen solubility disappears on alloying a group VA metal with one from group VIA has previously been investigated.2 It is necessary, in order to obtain a general picture of the reactions of alloys of the early transition metals with hydrogen, to examine a system containing metals from groups IVA and VA in which there must be a change from a fcc to a bee hydride phase. The system chosen for investigation was the pseudobinary system between titanium hydride and niobium hydride. Metallic alloys were prepared by melting iodide-prepared titanium with zone-refined niobium in an argon-atmosphere are-furnace. To ensure homogeneity each alloy was cold-swaged and then heated at 1250°C in a high-vacuum furnace until metallo-graphic examination confirmed its complete homogeneity. Small weighed specimens of the alloys were charged with hydrogen using gaseous hydrogen generated by heating titanium hydride. The apparatus has been described elsewhere.3 Throughout the charging process the hydrogen pressure was kept at about 1 atm while the specimen, initially at 800 °C, was slowly cooled to 150°C over a period of days. The total amount of hydrogen absorbed by each specimen and the room-temperature crystal structure of the hydride powders were determined. The X-ray investigation indicates that the fee hydride phase arises from alloys extending in composition from titanium to 67 at. pct Nb. After a two-phase field lying between 67 and 74 at. pct Nb in which the fee and bee hydrides coexist, all alloys richer in niobium yield a distorted bee hydride. Data derived from parameter measurements are presented in Fig. 1. The atomic volume per metal atom has been plotted against the composition of the initial metallic alloy in order to facilitate comparison of the effects of hydrogen addition in the two phases of different crystal structure. The amount of hydrogen absorbed by each alloy at saturation in terms of the hydrogen to metal ratio and alloy composition is given in Fig. 2. Over the whole range of the fee hydride phase the hydrogen content remains constant, while in the distorted body-centred hydride phase, the hydrogen content increases with increasing titanium content reaching a hydrogen/metal ratio of 1.4 at the boundary of the two-phase region. It seems likely, therefore, that the maximum hydrogen content of the fee hydrides is limited to a hydrogen/metal ratio of 2 because hydrogen atoms

Jan 1, 1962

By T. A. Wilson

THE plastic deformation of slender single crystals of zinc has been described in some detail in the paper by Mark, Polanyi and Schmid,1 which has become a classic, and also by one of the present authors in a somewhat shorter account.2 The study of single-crystal zinc is termed classical because zinc single crystals offer, perhaps, the best material yet available for the study of atomic behavior during deformation and the effect known as "strengthening" in metals. A considerable amount of additional work has also been clone on single-crystal zinc, but as it 'is not closely related to the present paper it will not be considered. Throughout all the former work, the mechanism of plastic deformation first described by Mark, Polanyi and Schmid has been assumed to hold. This may be said to offer the strongest confirmation of its correctness. Even so, the picture of the process has never been as completely portrayed as is desirable. The first object of the present paper is to describe work that has been done in this field, and which is even yet being carried on, in the hope that a more complete picture may be obtained. Mathewson and Phillips3 have recently described a new mechanism of the deformation of zinc based on their study of large rectangular crystals. One of their conclusions was that deformation produced twinning with a rotation of some of the basal planes into positions 94° removed from their original position; a position almost the same as that of the prismatic planes before twinning. A second conclusion was that fracture occurred along these basal planes in their new position, and, therefore that fractures previously regarded as prismatic were in reality basal. Such findings are of great significance and they raise a question as to the generality of such behavior. Professor Mathewson's opinion is that even the slender cylindrical single crystals behave in the same manner as his large rectangular crystals when strained by simple tension.

Jan 1, 1927

By M. Nicholas, D. M. Poole

The diameters of sessile drops have been found to increase linearly with time in five reacting binary metal systems. The spreading rates of the drops are markedly dependent on temperature and on prior alloying of the solid with the lower melting point metal, hut are independent of the drop volume, wetting atruosphere , solid-surface roughness, and prior alloying of the drop with the substrate metal. A mechanism has been suggested that relates the linear-spreading rate to lateral diffusion of the liquid-metal atoms into the solid at the drop edge. An Arrhenius- type equation has been derived that describes the temperature dependence 0) the spreading rate, and although the agreement between the actual and the predicted pre-exponen-tial terms is poor that between the activation energies is excellent and the variation in the spreading rate of copper on Ni-Cu alloys produced by different extents of alloying can be predicted with considerable accuracy. CHEMICAL interactions frequently change the wetting behavior of solid-liquid systems causing, for example, "secondary spreading1 of sessile drops beyond the size defined by the surface and interfacial tensions of the unreacted components. The kinetics of the contact-angle decreases associated with this spreading are similar for many systems, but few studies have been made with the objective of determining whether the similarities are a reflection of a common mechanism. Some workers2,3 have assumed the secondary spreading is controlled by changes in the liquid surface and liquid-solid interfacial tensions and hence by the composition of the liquid, and contact-angle changes measured by the vertical-plate technique have been used to follow the course of liquid-solid chemical reactions.4 Other processes that have been invoked to explain these time-dependent changes in specific systems include the removal of adsorbed gas from the liquid-solid interface.5 penetration of containment layers on the solid Surface,6 interdiffusion,1,7 reori-entation of the solid surface into a wettable configuration: vapor-phase transport of the liquid onto the solid in advance of the drop,9 and, from vertical-plate studies. capillary flow between oxide layers and the solid surface.10 One of the reasons for the profuseness of these suggestions may be the complexity of the contact-angle change kinetics. However, in an analysis of secondary spreading gold and copper on UC,11 it was found that the diameter of the contact area between the sessile drop and the solid surface showed a simple linear increase with time although contact-angle changes were more complex. To check whether the linearity was merely fortuitous! additional exploratory work was conducted with four reacting metal-metal systems: Au on Ni. Cu on Ni, Cu on Fe, and Ag on Au. Linear spreading was observed in every case even though the kinetics of the contact-angle changes were complex. A further detailed study of the kinetics of linear spreading of five reacting metal-metal systems has been made with the object of determining the mechanism involved. The influence of variables such as temperature, drop volume. and the initial composition of the drop on the linear-spreading rate has been measured and compared with those predicted by a number of possible mechanisms. The systems employed in this study (Cu and Au on Ni and Pt, and Ag on Au) were selected because of the availability of potentially relevant chemical and physical property data. the simplicity of their phase diagrams at the wetting temperatures, and the ease of experimentation. EXPERIMENTAL TECHNIQUES The purities of the metals used in the study were: copper, 99.9 pct; gold. 99.96 pct; nickel, 99.2 pct; platinum 99.99 pct; and silver, 99.999 pct. The wetting tests were performed in a split tantalum tube vacuum resistance furnace of a conventional design. The furnace element was held vertically and was 1 $ in. in diam and 6 in, long. Viewing ports were provided in the water-cooled chamber to enable the specimens to be observed in both the horizontal and vertical planes. The temperature in the hot zone of the furnace could be held at 1500" i 5°C for an indefinite time. The surfaces of the solid-plaque metals were ground flat on Microcut paper and both the sessile drop and substrate metals were ultrasonically cleaned in methyl alcohol prior to their insertion in the furnace. After loading, the furnace was pumped down to a pressure of 2 x 10-5 mm of mercury and degassed for 30 min at 900° to 950°C. The temperature was then increased at more than 100°C per min to that used in the wetting test. The vacuum at the wetting temperature was better than 5 x 10-5 mm of mercury. Dewetting and retraction of the drop on cooling did not occur and the contact-area diameters, therefore, were measured after solidification with a vernier traveling microscope. The diameters quoted later are arithmetic means of ten measurements. The standard error of the mean never exceeded 3 pct and was often less than 1 pct.

Jan 1, 1967

By Arthur Phillips, E. N. Skinner

DURING the course of an experimental program concerned with the hydrogen embrittlement of copper containing oxygen in concentrations within the solubility limits it became necessary to make a critical appraisal of the literature dealing with the solubility relationships of oxygen and solid copper. The latest determinations, and perhaps the only data obtained on "spectroscopically" pure copper, are those of Rhines and Mathewson1 who reported that the solid solubility increases from 0.007 per cent oxygen at 600°C. to about 0.015 per cent at 1050°C. Hanson, Marryat and Ford2 had previously placed the solubility limit at less than 0.009 per cent oxygen at 1000°C. and Allen and Street3 had suggested, on the basis of an unpublished research by T. Hewitt, not over 0.005 per cent oxygen at 500°C. In the introductory stages of the investigation indirect evidence accumulated to suggest that the solubility limits were significantly lower than those previously reported. For this reason it was deemed essential to clarify this point before proceeding with a program intended to establish a quantitative relationship between hydrogen embrittlement and oxygen concentrations positively known to be within the solid solution range. Furthermore, the increasing production and the highly selective applications of the commercial "oxygen-free" coppers inevitably direct attention to the practical necessity for exact knowledge regarding the effects of minute concentrations of the elements ordinarily found in the high-purity coppers now available. Of these elements oxygen occupies a unique position, not only by virtue of its specific effects on copper but more particularly in view of its important reactive tendencies toward the other impurities with which it is associated. Rhines and Mathewson considered several methods for measuring the solubility of oxygen and finally adopted the simple plan of saturating the specimens, obtained from redeposited cathode copper, by heating at the desired temperature in air. After the removal of surface oxide by mechanical and chemical means, the oxygen content was determined in the underlying metal. In general, this process of saturation, with a few modifications, was followed by the present writers. Although the procedure is direct and has obvious advantages, its effectiveness, unfortunately, is reduced by an excessive scaling of the copper, particularly at the higher temperatures. After saturation treatments above 900°C. the writers found that the specimens, necessarily rather thin in the original condition, consisted largely of scale and yielded too little metal for a satisfactory analytical sample. Furthermore, great difficulty was experienced in effecting complete removal of the scale. Needless to say, it is necessary to exercise extraordinary care in the preparation of the surface of the analytical sample in order to eliminate submicroscopic fragments of cuprous oxide which ordinarily are lodged in the crevasses and

Jan 1, 1941

By C. E. Abbott

THE Birmingham district, Alabama, is distinctive in the proximity to one another of its deposits of iron ore, coal and flux. These three basic requisites for the making of iron and steel are found within a radius of 10 miles. Both dolomite and limestone are produced, the former for blast-furnace flux and the latter for basic open-hearth operations. The Tennessee Coal, Iron and Railroad Co., a subsidiary of the United States Steel Corporation, operates a limestone mine at Muscoda, near Bessemer, 12 miles southwest of Birmingham, served by its own railroad transportation system. The mine has a capacity of 130 tons per hour. Average analyses of a recent month's production are as follows: Fe2O3 Si02 A12O3 CAC03 MGCO Lump, per cent 0.51 0.22 98.63 0.14 Crushed and washed, percent 0.70 0.26 98.36 0.18 Lump stone, 2 1/2 to 7 1/2 in., is used in open-hearth operations at Fairfield Steel Works. Fine crushed and washed stone, 1 ¼ to 0.063 in., is calcined at the, lime-burning plant and used for lime charges at the Ensley open hearths.

Jan 1, 1936

By Jack Washburn

The c axis indentations in zinc crystals were shown to undergo 100 pct strain recovery on heating. The mode of deformation and the details of the polygonization and collapse of indentations were found to be consistent with a number of predictions of dislocation theory. IT has been observed that indentations of the type made by Jillson in zinc crystals can, under certain conditions, be macle to shrink in size and even completely disappear on heating the crystal, Fig. 1. The details of the process are interesting in that they afford a simple experimental illustration of several predictions of dislocation theory. The indentations were made as shown in Fig. 2 by dropping a 0.2 g indenter with a hemispherical point on a cleavage face of a. zinc crystal. Such indentations can be made through relatively great thicknesses in the c-axis direction. The material close to the struck surface, where mechanical twinning and complex distortion occurred, was removed by cleavage. The remaining crystal, which was about 1 cm thick, contained a dent that was accurately round and almost the same size on both top and bottom surfaces. The indentation had the form of a flat cone of half angle approximately 89°, having a rounded apex and a rounded intersection with the unde-formed part of the crystal. The mode of deformation was primarily slip on the three equivalent systems in the basal plane. Six types of dislocation loop (plus and minus in each of the three directions) as shown in Fig. 3 are required by the geometry of the indentation. The maximum shear strain in the radial direction amounted to approximately 2.5 pct. Slip was distributed in the usual, microscopically nonuniform, manner among the possible parallel slip planes. When an indentation was made close to a (2110) surface, three separate sets of interpenetrating slip bands appeared as shown schematically in Fig. 3. A small biaxial tension strain in the plane of (0001) is also a geometrical necessity for the formation of an indentation. If the sides of the dent are tilted l° with respect to the undeformed surrounding crystal, and the surround-

Jan 1, 1957

By Blamey Stevens

My previous paper is entitled, The Laws of Igneous Ernanation Pressure. The present paper lays no claim to the exactitude and completeness of a law, since it is of a provisional nature and may be disregarded when experiments have established a basis for more exact reasoning. The general physical states in which aqueous emanations may occur are first considered. The possible physical couditions under which the mineral elements may occur in emanations are then discussed, and a classification of deposits, dependent on emanation, is proposed. A system of scientific experimental investigation is outlined, and it is shown that the physical and chemical properties of emanation may be exactly determined thereby. The investigation is urged as feasible and simple, and not necessarily requiring large and costly apparatus. It is the only step necessary to make possible the formulation of a complete set of laws of igneous emanation. Process of Emanation. In a rising column, magma ranges in temperature from 900° to 1,200°C. Exhalation must begin at some fairly great depth. What this depth may be we can only surmise, since no experimental evidence is available. Exhalation, however, continues as the magma flows upward, until at another level the occluded gases have all escaped. This depth is probably upward of 5,000 ft. (See Fig. 1.) All exhalations must come from between these two levels. As the whole emanation is the sum of the exhalations and residues, the residues must come from below the uppermost level. They will be most abundant when coming from those parts of the intrusion which have solidified below the lower level.

Jan 1, 1913

By R. A. Morse, C. R. Holmgren

The production of oil by water flooding can be substantially increased by the maintenance of free gas saturation in the reservoir during the flooding operation. This effect is accomplished by the alteration of oil relative permeability characteristics and the occupation by gas of pore space that would otherwise be filled with residual oil. The amount of reduction In residual oil can be calculated from appropriate water-oil relative permeability characteristics. This paper presents experimental data in support of the foregoing conclusions and an example of the calculations. The microscopic pore saturation concepts of the mechanism are discussed. A method of practical application to field floods is presented together with discussion of certain limitations. INTRODUCTION The presence of free gas has been reported by a number of investigators to significantly affect the oil recovery which can be obtained from sandstone flow systems by water flooding.1,2,3,4,5 The effect of gas, noted in every instance, has been to cause lower residual oil saturations than could be obtained by water flooding the same systems in the absence of free gas. The degree of improvement in recovery has been observed to vary widely, depending on the systems used and the conditions of the tests. The increased oil recovery obtained because of the presence of gas during a water flood has been variously attributed to changes in physical characteristics of the oil, selective plugging action of the gas, inclusion of oil mist in the free gas phase, and the additional sweeping or driving action of the free gas. All but the first of these suggestions imply changes in the displacement mechanism. The change in viscosity and inter-facial tension of the oil phase, within the pressure range used for all the experimental work, is certainly not sufficient to account for the differences in residual oil saturation noted dess there is a drastic change in the displacement process. One other effect which logically seems capable of causing differences in residual oil saturation of the magnitude noted in the experimental work is that of simple replacement. In a water-wet system containing oil, water, and gas, it is to be expected that the gas will exist inside the oil. This is the position of minimum free surface energy, since the gas-oil interfacial tension will be less than the gas-water interfacial tension. There is no apparent reason to expect that the existence of free gas within the oil phase should alter the saturation at which the non-wetting phase (now oil and gas) should become discontinuous and hence trapped so as to be unrecoverable by direct displacement by water. If this is the situation, then trapping of a certain percentage of gas saturation during water flood should result, at infinite water-oil ratio, in a like reduction of oil saturation below that attainable by flooding in the absence of free gas. It is visualized that the gas will exist as bubbles inside the discontinuous residual oil as illustrated in Fig. 1, with the size of the oil bubbles being substantially unchanged due to the presence of the gas. As a practical matter, it can be anticipated that the presence of a free gas saturation inside the oil phase will reduce the relative permeability to oil which will exist at any particular water saturation. This reduction will be caused by two factors — -the addition of the gas-oil interface, and the reduction of area available for oil flow in the pores containing gas. This reduction in oil permeability at any particular water saturation will result in water breakthrough at a lower water satu-

Jan 1, 1951

By R. A. Morse, C. R. Holmgren

The production of oil by water flooding can be substantially increased by the maintenance of free gas saturation in the reservoir during the flooding operation. This effect is accomplished by the alteration of oil relative permeability characteristics and the occupation by gas of pore space that would otherwise be filled with residual oil. The amount of reduction In residual oil can be calculated from appropriate water-oil relative permeability characteristics. This paper presents experimental data in support of the foregoing conclusions and an example of the calculations. The microscopic pore saturation concepts of the mechanism are discussed. A method of practical application to field floods is presented together with discussion of certain limitations. INTRODUCTION The presence of free gas has been reported by a number of investigators to significantly affect the oil recovery which can be obtained from sandstone flow systems by water flooding.1,2,3,4,5 The effect of gas, noted in every instance, has been to cause lower residual oil saturations than could be obtained by water flooding the same systems in the absence of free gas. The degree of improvement in recovery has been observed to vary widely, depending on the systems used and the conditions of the tests. The increased oil recovery obtained because of the presence of gas during a water flood has been variously attributed to changes in physical characteristics of the oil, selective plugging action of the gas, inclusion of oil mist in the free gas phase, and the additional sweeping or driving action of the free gas. All but the first of these suggestions imply changes in the displacement mechanism. The change in viscosity and inter-facial tension of the oil phase, within the pressure range used for all the experimental work, is certainly not sufficient to account for the differences in residual oil saturation noted dess there is a drastic change in the displacement process. One other effect which logically seems capable of causing differences in residual oil saturation of the magnitude noted in the experimental work is that of simple replacement. In a water-wet system containing oil, water, and gas, it is to be expected that the gas will exist inside the oil. This is the position of minimum free surface energy, since the gas-oil interfacial tension will be less than the gas-water interfacial tension. There is no apparent reason to expect that the existence of free gas within the oil phase should alter the saturation at which the non-wetting phase (now oil and gas) should become discontinuous and hence trapped so as to be unrecoverable by direct displacement by water. If this is the situation, then trapping of a certain percentage of gas saturation during water flood should result, at infinite water-oil ratio, in a like reduction of oil saturation below that attainable by flooding in the absence of free gas. It is visualized that the gas will exist as bubbles inside the discontinuous residual oil as illustrated in Fig. 1, with the size of the oil bubbles being substantially unchanged due to the presence of the gas. As a practical matter, it can be anticipated that the presence of a free gas saturation inside the oil phase will reduce the relative permeability to oil which will exist at any particular water saturation. This reduction will be caused by two factors — -the addition of the gas-oil interface, and the reduction of area available for oil flow in the pores containing gas. This reduction in oil permeability at any particular water saturation will result in water breakthrough at a lower water satu-

Jan 1, 1951

By Eric S. Cheney

Sulfur isotopes are best used in conjunction with other geological studies to determine the origin of known deposits; concept-oriented exploration programs can then be developed to find similar deposits. Geochemical processes are capable of causing different S '41S" ratios in the minerals and fluids participating in natural reactions. Because the magnitude of the resultant isotopic difference is inversely proportional to temperature, sulfur isotopic studies can be used to determine the source of the sulfur in high temperature deposits. The narrow spread of sulfur isotopic values from ores related to cupolas of felsic intrusions suggests that the sulfur in the ore-forming fluids was derived from a fairly uniform source (such as the intrusions) rather than by heated ground water from the adjacent country rocks. However, geologic and isotopic evidence suggest that the sulfur of many nickel sulfide ores may have been derived from the country rocks rather than the associated mafic igneous rocks. This sulfurization hypothesis implies that mafic intrusions in sulfur-rich country rocks should be prime exploration targets. Sulfur isotopic analyses of sulfides in the mafic rocks may indicate whether sulfurization has occurred. In equilibrium geochemical reactions S" is concentrated in the minerals with the greater bonding strengths. Thus the isotopic compositions of coprecipitated sulfides that have not undergone exsolution may be used as geothermometers and to distinguish multiple periods of mineralization, post-ore metamorphism, etc. The sulfur isotopic compositions of coexisting sulfides at Butte, Mont., indicate that the copper minerals did not originate by simple replacement of pyrite. Geologic and isotopic evidence suggest that the mineralogical and isotopic zoning at Butte formed almost isothermally during the geochemical evolution of the ore-forming fluids upward and outward from the Central zone. Unidirectional reactions cause enrichment of S" in the products. At low temperatures the isotopic effects of bacterial and inorganic reactions are difficult to distinguish. Anaerobic sulfate-reducing bacteria apparently were responsible for the sulfur of Gulf Coast salt domes and for diagenetic pyrite in sandstone-type uranium deposits. Sulfur (and carbon) isotopic data suggest that the roll ore bodies of sandstone-type uranium deposits originated by limited inorganic oxidation of diagenetic pyrite rather than by bacterial activity. Accordingly roll ore bodies should be most numerous and thickest against those portions of the sandstone aquifer that contain pre-ore pyrite.

Jan 1, 1975

By H. J. Ramey

As fluids move through a wellbore, there is transfer of heat between fluids and the earth due to the diflerence between fluid and geothermal temperatures. This type of heat transmission is involved in drilling and in all producing operations. In certain cases, quantitative knowledge of wellbore heat transmission is very important. This paper presents an approximate solution to the wellbore heat-transmission problem involved in injection of hot or cold fluids. The solution permits estimation of the temperature of fluids, tubing and casing as a function of depth and time. The result is expressed in simple algebraic form suitable for slide-rule calculation. The solution assumes that heat transfer in the wellbore is steady-state, while heat transfer to the earth will be unsteady radial conduction. Allowance is made for heat resistances in the wellbore. The method used may be applied to derivation of other heat problems such as flow through multiple strings in a wellbore. Comparisons of computed and field results are presented to establish the usefulness of the solution. INTRODUCTION During the past few years, considerable interest has been generated in hot-fluid-injection oil-recovery methods. These methods depend upon application of heat to a reservoir by means of a heat-transfer medium heated at the surface. Clearly, heat losses between the surface and the injection interval could be extremely important to this process. Not quite so obvious is the fact that every injection and production operation is accompanied by transmission of heal between wellbore fluids and the earth. Previously, the interpretation of temperature logs',' has been the main purpose of wellbore heat studies. The only papers dealing specifically with long-time injection operations are those of Moss and White3 and Lesem, et al.' The purpose of the present study is to investigate wellbore heat transmission to provide engineering methods useful in both production and injection operations, and basic techniques useful in all wellbore heat-transmission problems. The approach is similar to that of Moss and White:' DEVELOPMENT The transient heat-transmission problem under consideration is as follows. Let us consider the injection of a fluid down the tubing in a well which is cased to the top of the injection interval. Assuming fluid is injected at known rates and surface temperatures, determine the temperature of the injected fluid as a function of depth anti time. Consideration of the heat transferred from the injected fluid to the formation leads to the following equations. For liquid, Eqs. 1, 1A and 2 are developed in the Appendix. These equations were developed under the assumption that physical and thermal properties of the earth and wellbore fluids do not vary with temperature, that heat will transfer radially in the earth and that heat transmission in the wellbore is rapid compared to heat flow in the formation and. thus, can be represented by steady-state solutions. Special cases of this development have been presented by Nowakl and Moss and White.3 Both references are recommended for excellent background material. Nowak' presents very useful information concerning the effect of a shut-in period on subsequent temperatures. Since one purpose of this paper is to present methods which may be used to derive approximate solutions for heat-transmission problems associated to those specifically considered here, a brief discussion of associated heat problems is also presented in the Appendix. Analysis of the derivation presented in the Appendix will indicate that many terms can be re-defined to modify the solution for application to other problems. Before Eqs. 1, 1A and 2 can be used, it is necessary to consider the significance of the over-all heat-transfer coefficient U and the time function f(t). Thorough discussions of the concept of the over-all heat-transfer coefficient may be found in many references on heat transmission. See McAdams5 or Jakob," for example. Briefly, the over-all coefficient U considers the net- resistance to heat flow offered by fluid inside the tubing, the tubing wall, fluids or solids in the annulus, and the casing wall. The effect of radiant heat transfer from the tubing to the casing and resistance to heat flow caused by scale or wax on the tubing or casing may also be included in the over-all coefficient. According to McAdams, on page 136 of Ref. 5>

By J. F. Myers, R. J. Tower

"There is nothing new under the sun." All over the world, mineral-dressing engineers are working at their problems, no two of which are alike. Each encounters equipment and process problems. Many devise simple ways and means of overcoming their difficulties. Many of these problems are quite common in the industry, yet, since no one human being seems capable of thinking of everything, these problems at some plants often are looked upon as necessary evils. The purpose of this symposium is to gather together, from competent engineers, devices and practices that have been useful to them. Most of the ideas contributed are not new, yet there is no plant operator, old timer or youngster, who will not find some idea herein that will give him a suggestion for improving his operation. Space does not permit a complete elaboration on all of the contributions offered. Each item is summarized, but this will be ample for those skilled in the art of mineral dressing. A list of contributors appears at the end of the paper, and the superior number at the end of each item identifies its source. General Equipment A signal light to show that a steel bin, containing relatively line, moist ore, is full, can be made by suspending a copper rod in the bin to a sufficient depth to ensure ample contact with the ore. One wire of a 32-volt circuit should be attached to the rod and one to the side of the bin. Sufficient current will flow to make the signal light burn. A 110-volt circuit could be used, but 32 volts ensures safety.10 Fig I shows a circular bin for crushed ore. It is a concrete structure footed on the ground, using no supporting columns. Tailing from the sink-float was used for aggregate. Cross conveyors for discharging ore are not required, nor is a tripper for filling. Segregation is minimized by drawing from different gates. An exhaust fan on top of the bin eliminates condensation due to temperature of the ore.21 A beam with an adjustable point of suspension near the center permits rigging rolls for removal in a very few minutes. This makes unnecessary the lacing of the cable through the hub bolts on one side, around the shaft on the other, and the trouble of balancing the load.8 The ratchet handle on a Symons crusher may be replaced by a drum with a cable wound on it. When the cable is pulled by a crane or hoist it causes the drum to revolve and thus screws or unscrews the bowl. This reduces handwork and materially shortens the time required for the job.' TO Spread ore feed from an apron feeder over a belt conveyor, place a heavy steel bar about midway between the top

Jan 1, 1949

By Henry A. Wentworth

Electrostatic separation of ores in its present form is generally known as the Huff process, from the name of Charles H. Huff, of Boston, Mass., through whose constant and persistent labors (with the invention of Clinton E. Dolbear as a basis) the successful commercial process embracing separative machinery and the various electrifying devices has been developed step by step, and the finances for the long period of development provided, and the method finally established and recognized throughout the world as an important and successful addition to the ore-dressing department of metallurgy. The permanent field-success of electrostatic separation began in 1908 with a 20-ton Huff experimental mill built specially for the purpose by the American Zinc, Lead & Smelting Go., in Platterille, Wis., a plant which was a success from the start and was gradually increased in capacity as the market-conditions warranted to 100 tons of concentrates per day. Much credit is due to the above-mentioned company for its initial

Jan 1, 1913

By V. J. Berry, J. D. Pendergrass

Well pressure transient tests provide a means for directly obtaining information about formation pressure and reservoir flow capacity. Such tests have also been proposed for determining presence and location of faults or other reservoir closures and for measuring oil in place. For mathematical convenience, most theoretical studies have considered the reservoirs to be homogeneous. Definitive information is not yet available to show whether the actual presence of nonuniformities will make pressure transient behavior different from that of a uniform reservoir. The conclusions reached from actual transient tests are questionable, therefore, insofar as they rely on the original assumption of homogeneity. One type of nonuniformity commonly assumed to exist is that of stratification. In most reservoirs the strata are thought to be in vertical communication. Equations for the transient flow of a single-phase, compressible fluid in a one-well, bounded, circular reservoir have been solved for several situations involving crossflow between multiple strata of various thicknesses and permeabilities. The results show that except for the very early flow period, which usually is too short to be analyzed, the transient performance observed at the well is substantially identical with that of a homogeneous reservoir having the same dimensions and having the same steady-state flow capacity. Thus, stratification does not adversely affect interpretation of well transient tests. This conclusion holds for all commonly encountered combinations of reservoir thickness and external radius. Deviations are observed for unusually thick reservoirs whose outer radii are relatively small. The results of these studies also show that the presence and the amount of stratification cannot be simply diagnosed from reservoir pressure transient data when there is crossflow between strata. INTRODUCTION The last decade has brought wide acceptance of the transient well pressure test for determining reservoir parameters. Following the original work of Hurst and van Everdingen,1 the mathematical theory was thoroughly explored. Numerous authors have suggested how to determine static reservoir pressure, permeability-thickness product, original oil in place and reservoir limits for different reservoir geometry. The same mathematical techniques have been used to predict the transient performance of a reservoir over a long period of time. Most of the theoretical work has been for homogeneous, isotropic systems. Some results have also been presented for a homogeneous, anisotropic reservoir.2 Petroleum reservoirs are not homogeneous. The deposition process seems to favor creation of a stratified formation. This concept is sufficiently well accepted so that the most natural extension of the transient flow theory beyond the homogeneous case is to a stratified formation. Results for a stratified reservoir with no vertical communication between layers can be obtained from the results for a homogeneous reservoir. Lefkovitz, et a1,3 have given a thorough treatment of the two-layer case. Two recent papers4,5 have treated the case of a two-layered reservoir with vertical communication or crossflow, between layers. Russell and Prats4 find that, after a relatively short time, the two-layered reservoir with crossflow exhibits a simple exponential pressure decline. From this time forward, the behavior is not distinguishable from the behavior of a homogeneous reservoir having the same steady-state flow capacity. The results of Katz and Tek 5 are equivalent. Russell and Prats4 also speculate that a multi-layered reservoir with crossflow will behave as a homogeneous system after long enough production time "... providing the contrast in kh between layers is not too great". They also suggest that, at intermediate times, "... the relative positions of the layers with respect to each other will have a great influence on the production behavior and on the time at which the previously mentioned large-time approximation might be valid". Katz and Tek5 remark upon the mathematical difficulty of treating a reservoir having many layers or strata. If relative position of the layers is also

By E. T. Turkdogan, P. Grieveson

Experimental results are given for the rate 0.f solution of nitrogen in y iron in the temperature range 1000° to 1200°C. It is shown that, when purified reacting gas is used, the rate-controlling process is the diffusion of nitrogen into the iron. The difhsiuity of nitrogen in y iron is calculated from the results and the equation logD = —(8800/T) — 0.04 is recommended to represent the temperature dependence of the diffusivity. In some experiments using unpurified nitrogen, solution rates are found to be slower than those attributable to a solely solid-state diffusion process. Indications are that in the presence of impurities in the gas, e.g., H,O, chemisorption of nitrogen at the surface is hindered and becomes a rate-controlling process for the transfer of nitrogen across the gas -metal interface. ALTHOUGH the solubility of nitrogen in y iron at known nitrogen activities has been well-established,'-a the kinetics of the solution of nitrogen in iron are not known. The work of Darken, Smith, and Filer' indicates that at temperatures below about 1300°C the rate of solution of nitrogen in y iron is controlled by a chemical reaction at the metal surface, while at temperatures above about 1300°C the rate-controlling process is the diffusion of nitrogen in the metal. Fast and verrijps studied the denitro-genization of y iron using wet hydrogen at 950°C and their results clearly indicate that the rate of nitrogen removal is controlled by diffusion of nitrogen in the metal. In Part I of this series of papers, the kinetics of the solution of nitrogen in y iron are discussed in the light of the present experimental work. EXPERIMENTAL Apparatus. The reaction chamber consisted of a platinum wire-wound resistance furnace with a re-crystallized alumina reaction tube. The temoerature of the furnace, which was automatically controlled to approximately 1°C, was measured with a Pt/Pt-13 pct Rh thermocouple and a potentiometer. The temperature distribution in the working zone of the furnace was determined using a calibrated Pt/Pt-13 pct Rh thermocouple and the hot zone was found to be approximately 3 in. long with a temperature variation of * 3°C. A series of experiments was also carried out at 1000°C and pressures above atmospheric using a pressure vessel which was similar in construction to that described elsewhere.1° Materials. Ferrovac E grade iron used in all ex-

Jan 1, 1964

By D. K. Deardorff, Haruo Kato

D. K. Deardorff and Haruo Kato (U. S. Bureau of Mines)—We wish to refute the 1875" 20°C value that Giessen, et al., report as the transformation temperature of hafnium. Although these authors state that their work along this line will be reported later, we can't leave their value undiscussed, for we believe it to be 125°C too high. Our value of 1750° 20°C, which the authors mention, has been substantiated in our laboratories by the use of three other methods. The first method of substantiation was by heating and cooling curves using a hafnium/tungsten thermocouple, the couple having first been calibrated against a t/Pt-10 pct Rh couple. The second method was by quenching and metallography of dilute Hf-Ta alloys. The third cussion, it may be pointed out that the observations of Rogers referred to large unidirectional strains where the internal cracks or voids appeared only after a strain of 32 pct or more. On the contrary the internal fissures observed, as a result of fatigue cycling, occurred for a total extension of some 5 pct and furthermore followed the directions of the slip zones. Finally, it is not our contention, as implied in Dr. Alden's last paragraph, that the tensile stress is an important factor in crack propagation. Indeed, in connection with the reference to the companion report, special note is made of the fact that "Deformation was apparently concentrated in grains which have a slip plane nearly perpendicular to the specimen axis and thus near the plane of maximum applied shear." This dependence of the growth of fissures on the orientation of the slip planes with respect to the direction of maximum applied shear is clearly shown in work on the torsional cycling of single crystals which has been submitted for publication. method was by heating and cooling curves with W/W-26 pct Re thermocouple. Counting the original resistometric method, four different methods have yielded 1750" 20°C as the transformation temperature of hafnium. All our work on determination of the hafnium transformation temperature has shown that the specimen under test must be quickly heated to and through the transformation temperature if the lowest possible transformation value is to be determined; otherwise a higher value not representative of pure hafnium will result. Speed was emphasized in all methods. In our resistometric work the corresponding voltage, amperage, and temperature readings were taken quickly and the transformation temperature was usually reached within 5 min total heating time. In the thermal analysis work involving Hf/W or W/W-26 pct Re thermocouples the transformation temperature was attained within three minutes total heating time, this time being less because the two variables were

Jan 1, 1963

By J. Downie, H. A. Kendall, G. H. F. Gardner

Some cases of the motion of two miscible fluids in uniform linear models are discussed. There is no bulk flow through the models, and the convection currents are caused solely by density gradients. Horizontal, vertical and inclined positions of the models are treated separately. Analytical formulas for the motion of a narrow transition zone between the fluids are obtained and compared with measurements, and the limitations are discussed. Observations of the ultimate stabilizing effect of diffusion on the motion me compared with the theory. It is shown that fluid motion in an inclined model with a constant rate of bulk flow can be directly deduced from the cases discussed, provided the viscosity ratio is small. INTRODUCTION In some reservoirs, convection currents caused by variations in the fluid densities may be significant. For practical purposes it may be desirable either to minimize the effect, particularly in miscible displacement, or to maximize the effect as in some schemes for the production of heavy crude oils by combustion. Experiments by Craig, et al,l have shown the effectiveness of gravity in reducing the efficiency of a miscible displacement when the mixed zone between the displacing and displaced fluids is narrow compared with the height of the system. The presence of a board transition zone from one fluid to the other has been shown by Perkins, et al,2 to nullify considerably the influence of a difference in density. Indeed, the theoretical discussion given by Perrine3 has shown that when the transition zone exceeds a certain critical length the efficiency approaches 100 per cent. Many additional results 495 have been published on miscible and immiscible displacements which show the importance of density difference and also mobility ratio. The aim of the present paper is to discuss some cases of gravity segregation of miscible fluids in linear models such as are often used in the laboratory to evaluate recovery processes, and to supply additional experimental evidence in support of the conclusions. An attempt is made to calculate simply the magnitude of the fluid motion caused by density pdients and mobility ratios, and to quantify the modifications in the fluid motion produced by the combined effect of molecular and convective dispersion. However, it should be pointed out that the uniform permeability of the models and the use of only a single pair of fluids (whereas several pairs of fluids may be employed in a recovery scheme) severely restricts direct conclusions about natural reservoirs. For conciseness, the motion generated by density gradients is emphasized for the case of no bulk flow through the models. This is not a drastic limitation because, as shown in Appendix A, a fluid motion with a constant bulk flow through any linear model is equivalent to a fluid motion with no bulk flow in the same model inclined at a different angle to the horizontal, provided only that the density is a linear function of the viscosity of the fluid mixture. HORIZONTAL MODEL In this case the model is assumed to have a rectangular cross-section with a horizontal breadth b, vertical height and a great length L. Throughout.the paper it will be assumed that x-axis points along the length, the y-axis along the width and the z-axis along the height. Thus, in the present case the x, y plane is horizontal. Initially, the transition zone between the fluids is assumed to be thin and parallel to the y, z plane. An example of this situation in a practical problem arises in a scheme for using air for cushion gas in the storage of fuel gas in aquifers. 6 With the passage of time the denser fluid sinks and spreads along the bottom of the model while the lighter fluid rises. The interface extends from the top plane of the model to the bottom. Experiments have shown that for practical purposes this interface may be treated as a plane surface at all times. The surface is significantly curved, however, for viscosity ratios greater than about 10. Other complications arise with large viscosity ratios because of the nonlinear dependence of the viscosity on the composition of the mixture, so that the simple results given here are restricted to fairly low viscosity ratios.

By D. W. Fuerstenau, G. D. Gumtz

Use of the discretized batch-grinding model for the simulation of locked-cycle grinding tests from batch-grinding data is illustrated. The simulated results were compared with actual locked-cycle experimental data for the dry grinding of dolomite. To illustrate the utility of this simulation method, a number of relationships between operating and performance parameters were generated, including relations between batch grinding and the Bond test, the production rate and the circulating load, and the production rate and the product size. A large amount of testing is done each year in the mineral industry for use with grinding unit cperations, and much of the experimental test data is obtained by the tedious locked-cycle testing procedure. In addition to being experimentally complex and requiring large amounts of sample, the very nature of the locked-cycle experiment yields results that cannot readily be interpreted. The attempts that have been made to model comminution systems during the last few years may provide a better and simpler way to obtain and analyze grinding test data; these models involve elements of both fitting to "model equations" and deterministic representations.1-1 The traditional engineering design techniques for comminution systems have relied mainly upon large amounts of industrial operating data that have been correlated with locked-cycle grinding data.',' Bond's empirical mill-design procedure involving locked cycle testing remains the most generally available method to this day. The purpose of the present paper is to show how much more useful data can be obtained from a simple batch-grinding experiment that provides information which subsequently can be utilized with population balance models of the grinding process to simulate locked-cycle behavior. These simulation results can, of course, be used in Bond's general design scheme. However, the combination of batch-grinding tests and the population balance model allows many more conditions to be considered than do single laboratory tests under specific locked-cycle conditions. The use of these simulation techniques for prediction of locked-cycle behavior represents one of the first practical applications for the simulation method in comminution.

Jan 1, 1971

By L. G. Evans, C. Rampacek, G. A. Freeman

A large aggregate tonnage of oxidized and mixed oxide-sulfide copper ore of the southwestern U.S. is not amenable to conventional flotation concentration or sulfuric acid leach treatment. Most of the ores contain chrysocolla as the principal oxide copper mineral, for which no successful commercial flotation method has yet been developed. Acid leaching some ores is not feasible since they contain substantial quantities of calcite and other acid-consuming constituents. Other ores decrepitate during leaching or contain excessive slime and clay minerals which cause plugging of the ore beds.

Jan 10, 1961

By Robert J. Brison

On the basis of experience accumulated during the completion of some 150 gold/silver process development projects, general guidelines are presented for developing the most cost effective process for a specific project. Steps involved in process development for lode ore deposits generally include a review of pertinent background information on the ore deposit, sample procurement and preparation, sample characterization, study of concentration possibilities, investigation of leaching and metal recovery methods, economic evaluation of alternative processes, optimization of the selected process, a pilot plant program if warranted, and finally, process design and feasibility studies. Each of these steps is discussed, with emphasis on the relation between technology and economics.

Jan 1, 1984