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By John Chipman, Minu N. Dastur

This paper presents equilibrium data on the reaction of water vapor with vanadium dissolved in liquid iron at 1600°C. The thermo-dynamic behavior of vanadium and oxygen when present together in the melt is discussed. A deoxidation diagram is presented which shows the concentrations and activities of vanadium and oxygen in equilibrium with V209 or FeV2O4. STUDIES of the chemical behavior of oxygen dissolved in pure liquid iron1-3 have served to determine with a fair degree of accuracy the thermody-namic properties of this binary solution. The practical problems of steelmaking, however, involve not the simple binary but ternary and more complex solutions. Only a beginning has been made toward understanding the behavior of such systems. The silicon-manganese-oxygen relationship was studied long ago by Korber and Oelsen4 and more recently by Hilty and Crafts." The carbon-oxygen reaction was investigated by Vacher and Hamilton6 and by Marshall and Chipman.7 A number of deoxidizing reactions have been studied empirica1lys'10 with the object of determining the appropriate "deoxidation constants." The work of Chen and Chipman" afforded a clear-cut view of the effect of the alloy element, chromium, on the thermodynamic activity of oxygen in liquid ternary solutions. These investigators determined the oxygen content of experimental melts which had been brought into equilibrium with a controlled atmosphere of hydrogen and water vapor and were able to show that the presence of chromium decreases the activity coefficient of oxygen. They determined also the conditions under which the two deoxidation products, Cr2O3 and FeCr2O4, were formed and showed that the activity of residual oxygen is considerably less than its percentage. It was the object of this investigation to apply a similar method to the study of molten alloys of iron, vanadium, and oxygen. Vanadium was once considered a moderately potent deoxidizer, but this is now known to be erroneous, in the light of its behavior in steelmaking practice. Its reaction with oxygen retains a certain amount of practical interest in that a high percentage of one element places a limit on the amount of the other that can be retained. As a deoxidizer it will be shown that vanadium lies between chromium and silicon. Experimental Method The apparatus was that used by the authors3 in their study of the equilibrium in the reaction: H2(g) +O = H2O(g);K,= [1] PII., ao Crucibles of Norton alundum or of pure alumina were used. The latter were made in this laboratory and were of high strength and low porosity. Under conditions of use they imparted no significant amount of aluminum (less than 0.01 pct) to the bath. Temperature measurements were made with the optical equipment and calibration chart of Dastur and Gokcen.= The charge was made up of calculated amounts of ferrovanadium (20 pct V) and clean electrolytic iron totaling approximately 70 g. The first few heats were made in alumina crucibles with an insufficient amount of vanadium so that no oxide of vanadium would be precipitated under the particular gas composition. All the heats were made at 1600 °C under a high preheat and with four parts of argon to one part of hydrogen in the gas mixture to prevent thermal diffusion. The rate of gas flow was maintained constant at 250 to 300 ml per min of hydrogen. The time for each heat was three quarters of an hour after the melt had melted and attained the required temperature (1600°C). The water-vapor content of the entrant gas mixture was gradually raised in succeeding heats, keeping the vanadium content of the melt constant. This was controlled by manipulation of saturator temperature. A point was reached when for a given H2O:H2 ratio some of the dissolved vanadium was oxidized and appeared as a thin, bright oxide film on top of the melt. By raising the temperature of the melt it was possible to dissolve the oxide film which reappeared as soon as it was cooled down to 1600°C. The temperature readings taken on the oxide film were consistently higher by 80" to 85 °C as observed by the optical pyrometer. The heat was allowed to come to equilibrium under a partial covering of this oxide film. At the end of the run the power and preheater were shut off and the crucible containing the melt was lowered down into the cooler region in the furnace. This method of quenching proved quite

Jan 1, 1952

By GLENVILTE A. COLLINS

(Presented at a Meeting of the Spokane Local Section of the Institute, Feb. 17, 1912, and accepted for publication in the Bulletin. ) WHILE I am not at the present time engaged in active mine-management, my duties permit of extensive study and examination of many mines, mills, and reduction-works in various places throughout the United States. Being much interested in efficiency-work in general, and an ardent reader of writings on this subject by Frederick W. Taylor and others, as applied to manufacturing-plants, and having served my apprenticeship from mucking to the engineering design of ore-dressing and underground plants, I hope that this paper will lead others to investigate the field more fully, to the improvement of general mine- and mill-operations, as well as the advancement, intellectually, physically, and financially, of the employee and his relations with the employer. If a man who is prepared to look closely and observe broadly starts in Canada and zig-zags from camp to camp to southern Mexico, taking time casually to inspect mines, mills, and smelters, he will be pitifully impressed by the great difference in customs, and the general waste of labor, time, and money throughout the country. He will so seldom observe a dollar's worth of results given in exchange for a dollar spent that he will form a poor opinion of operating-efficiency and management. This highly-scientific department, requiring an amount of skill and executive ability equaled in few, if any, of the professions, certainly falls short of the standard established in our greater manufacturing industries. It is easily said that this is due to the diversity of conditions in mining, milling, and smelting. But on second view it must be admitted that there is room for tremendous improvements in nearly every mining-organization. The proposal of such improvements is often met by the argument that any mine

Sep 1, 1912

By Carle R. Hayward

LEAD ore smelting plants have been operating in general at reduced capacities and secondary lead has assumed relatively more importance during the last year. Present smelting practice results in a large amount of dross, often over 25 per -cent, from blast-furnace lead. This is usually treated at a fairly high temperature in a reverberatory furnace to remove part of the lead and produce a matte-speiss product which is shipped to a copper plant. Few smelters are satisfied with this 'treatment. The fume losses are high and the matte-speiss contains considerable lead. It would seem that a fruitful field for research was open here.

Jan 1, 1934

By I. F. Jackson, H. L. Hartman

Hard-metal inserts have received considerable attention in the mining industry recently for a variety of excavating and penetrating purposes. Their use in percussive drilling and in coal cutting machines is well known, but attempts to utilize them in cutting materials such as dimension stone have been discouraging because of excessive tool wear and failure. Particular attention is given to those properties of hard-metal inserts that affect their resistance to wear. A consideration of the actual wear mechanism shows the importance of correct mounting of the inserts and of the selection of suitably powered driving motor so as to achieve minimum tool wear and maximum tool life. Comparisons are made between the performances of types of hard-metal inserts, relating their inherent properties with results obtained in laboratory tests. As part of a broad program to improve the quarrying and processing of industrial minerals, The Pennsylvania State University has been investigating the machinability of slate under laboratory and field conditions. It should be emphasized that the results of the research presented in this paper are also applicable to other natural structural materials, and particularly to the more workable ones such as limestone and sandstone. Improvements which accrue in cutting and sawing should prove of benefit to all the dimension stone industry. Further, it may be pointed out that the results reported here are applicable to rotary drilling (with drag bits) as well as to cutting and sawing of rock. INVESTIGATIONS IN RELATED FIELDS The investigation was initiated with an extensive survey of available literature related to metal cutting and to rotary drilling. The following similar features between metal cutting and slate cutting became evident: 1) Hard-metal inserts are widely used as a cutting tool in both cases. 2) The forces acting on the tool may be resolved into normal and tangential components. 3) Rate of penetration and tool wear are important criteria in each case. On the other hand, important differences also exist: 1) Most metals, exhibit plastic behavior, while slate (and most rock) is a brittle material under normal conditions. 2) In metal cutting the component of force acting parallel to the surface of the workpiece is considerably greater than the force holding the tool against the workpiece. 111 slate cutting, this situation is reversed. Similarities between drag-bit rotary drilling and slate cutting are as follows: 1) In both casts, a tool, usually of the hard-metal insert type, is used to penetrate a brittle material. 2) The drilling forces and related variables, such as rotation speed, are similar. 3) Chip formation in each case is essentially the same. 4) The shape of the tool is similar in rotary drilling and slate cutting. Important differences are also apparent: 1) The objective of drilling is to produce a directed hole, while in cutting it is to form a kerf. In core drilling, however, a kerf is also produced. 2) The horizonta1 component of force in rotary drilling decreases from the center to the outside of the tool, whereas in slate cutting the component is almost uniformly distributed across the width of the tool. 3) The power absorbed in the drill rod is greater in rotary drilling. 4) The clogging action of chips, if excessive power is applied to the tool and if flushing is insufficient, is more serious in rotary drilling. Because of the striking similarities between metal cutting and slate cutting, and between rotary drilling and slate cutting, it was considered that the findings of investigators in those fields would serve as a guide for experimental studies of slate cutting. The following is thus devoted to a discussion of those aspects of metal cutting and rotary drilling pertinent to the present investigations.

Jan 1, 1962

By L. H. Reiss, J. Groult, L. Montadert

Many fields, where the reservoir is composed of sandy layers, show great complexity because of the lack of continuity which results from a particular type of seditnentation. This complexity may be a factor of prime importance in studying reservoir drainage, especially in the displacement of oil by water or gas. This paper describes work done to study this heterogeneity and its influence in the exploitation of the fields of the lower Devonian sandy shale in the Fort Polignac Basin in Algeria. Two lines of research were followed. 1. On the border of the hasin, a detailed sedimentological study established rules for the distribution of the sandy zones, which furnished hypotheses necessary for devising a geologic model of the reservoir. A certain number of sandy zones were recognized and characterized by their sedimentation. 2. In the interior of the basin, production logs deterrnined the productivity profile. Study of these point data led to a description of the distribution of oil and gas phases in the reservoir so that the continuity of different zones between the wells could be deduced. These techniques were applied to the study of the lower Devonian sandy shale reservoir of Zarzaitine. The sedimentological study guiding the correlation work, with the aid of the conventional static data (logs and cores), led to the establishment of a useful geologic model of the reservoir. Production logs, thanks to the contribution of dynamic elements, permitted corrobora-tion of the model. In particular, the logs confirmed separation, as proposed by the sedimenfological study, of two comparable sandy groups by revealing the continuity of a thin impermeable layer, invisible on conventional logs. INTRODUCTION The heterogeneity of sandstone reservoirs considerably influences the distribution of fluids, as well as their displacement in the reservoir. Rational development of a field and maximum recovery of hydrocarbons are closely tied to an exact and precise knowledge of the intern architecture. We will try to show how it is possible I refine the knowledge of the reservoir by seeking qui different and varied sources of information. Productic geology, the group of techniques which leads to idei concerning reservoir architecture and its geometric descris tion, furnishes the framework of this undertaking. Of these techniques. those used so far are qui varied. Descriptive as well as quantitative, the technique partake as much of classical geology as of reservo science. They include (1) geologic studies of the enti basin, especially a stratigraphic and sedimentologic study of the reservoir member at its outcrop, detail1 observations of cores taken from wells and, finall oriented cores; (2) interpretation of geophysical dat (3) interpretation of electric logs, nuclear and sonic lo and dipmeters: (4) petrophysical study of the reserve on samples taken from wells; (5) reservoir dynamics (stu of the production history and, in particular, interpretati of production logs); and (6) analysis of the fluids a thermodynamic studies. This incomplete list could also include (1) study the migration of the fluids, (2) geochemistry (chemi characterization of the oils), (3) regional hydrodynamii and (4) injection and detection of tracers. If most of these techniques are classic, attention i nevertheless be called to applying two of the techniql in conjunction: the study of the reservoir member its outcrop and the study of dynamic distribution fluid phases in the reservoir through use of product logs, used in the study of the sandy shale reservoirs the lower Devonian of the Fort Polignac Basin, Alge in particular, their application to the study of the 2 zaitine field where they have led to a new and satisfact model of the reservoir will be described. THE ZARZAITlNE FIELD Situated in the interior of the Fort Polignac 8 about 150 kilometers (km) north of the lower Devol outcrop, the Zarzaitine Devonian oil field was discovc On Ian. 28, 19'' (Figs. 1 and l8). It is in the fern a monocline truncated by two perpendicular fault: great throw, with a downthrown section to the north\: Erosion at the top of the structure has caused one of it to disappear. It is a reservoir with a gas cap an m coefficient on the order of 1:5, open to the aql On the northeast, with the oil zone covering an Of 106 sq km and with initial oil reserves of 222 mi

Jan 1, 1967

By P. E. Rider, K. A. Gschneidner, O. D. McMasters

The solid solubilities for thirteen rare-earth metals in gold were determined by using the X-ray parametric method. Solubilities ranged from 0.1 at. pct for lanthanum in gold up to 8.8 at. pct for scandium in gold. The solubilities from lanthanum to gadolinium were very small and essentially constant, but a sharp increase occurred from gadolinium to scandium. The large solubilities for the heavy rare-earth metals were not expected because of the large size and electrochemical differences between rare-earth atoms and the gold atom. Contributions from first- and second-order elasticity theory plus an electronic contribution were found to reasonably account for a more favorable size factor. Electron transfer from the rare-earth metal to the gold Is thought to occur such that the resultant rare-earth and gold electronegativities are favorable for solid-solution formation. It was also found that this mutual adjustment of size and electronegutivity does not occur if the pure-metal size factors are greater than a critical value of 25 pet. The eutectic temperatures for ten systems were determined and these remained fairly constant at approximately 809 "C for the lighter lanthanide metal-gold systems until the Er-Au system was reached, at which Point the eutectic temperature successively increased reaching a maximum of 1040°C in the Sc-Au system. This rise was correlated to the size factor becoming more favorable for solid-solution formation at erbium. The valence state of ytterbium was found to change from two in the pure metal to three when ytterbium is dissolved in the gold matrix. RECENT results1 reported concerning the solubility of holmium in copper, silver, and gold, showed that the solubility of holmium in gold was quite large, 4.0 at. pct, compared with 1.6 in silver and 0.02 in copper. The small solubilities of holmium in silver and copper are quite reasonable in view of the large size difference (22.2 and 38.2 pct, respectively), large electronegativity difference (0.59 for both systems), and possible unfavorable valency factor (assuming one for silver and copper and three for holmium). The large solubility in gold, however, is unexpected because these same factors are also unfavorable for holmium and gold (22.5 pct size difference and 0.69 electronegativity difference), and because the light rare-earth metals, lanthanum, cerium, and praseodymium, have negligible solid solubilities in gold.2 In view of this unexpected behavior, it was felt that a study of the solid solubilities of most of the rare-earth metals in gold would be desirable to better understand the factors involved in the formation of solid solutions. Of the rare-earth metals added to gold in this study, only ytterbium is divalent in the pure metallic state (the other rare-earth metals are all trivalent) and many of its physical properties (such as the metallic radius, electronegativity, and so forth) are much different from those of the normal trivalent rare-earth metals.' The properties of ytterbium are such that one would expect solid-solution formation to be less favorable for ytterbium in gold than for any of the normal trivalent rare-earth metals. But chemically ytterbium is known to possess a stable trivalent state, and it is quite possible that ytterbium may alloy as a trivalent metal under certain conditions rather than as a divalent metal. Because of the dual valency nature and because so little is known about the alloying behavior of ytterbium, the gold-rich ytterbium-gold alloys are of special interest. EXPERIMENTAL PROCEDURE Materials. The gold used in this investigation had a purity of 99.99 pct with respect to nongaseous impurities. In general the rare-earth metals were prepared by reduction of the corresponding fluoride by calcium metal.3 The impurity contents of the metals used in this study are given in Table I. Preparation of Alloys. Two- or 3-g alloy samples were prepared by arc melting. The samples, with the exception of some of the Er-Au alloys, had weight losses of 0.5 pct or less. All alloy concentrations noted in this paper are nominal compositions. After arc melting, the alloys were wrapped in tantalum foil, sealed off in quartz tubing under a partial atmosphere of argon, homogenized for approximately 200 hr at 780°C, and then quenched in cold water. X-Ray Methods. The X-ray parametric method was used in determining the solubility of the rare-earth metals in gold. filings were sealed in small tantalum tubes by welding under a helium atmosphere. The tantalum tubes were then sealed in quartz tubing under a partial argon atmosphere, and annealed for times ranging from 1/2 to 3 hr (the length of time was inversely proportional to the an-

Jan 1, 1965

By Leon McCulloch

WIIen clean iron and metallic zinc dust, protected from the air, arc heated below the melting point of zinc, the iron takes on a coating that has excellent protective value. This coating is a brittle alloy of zinc and iron, and the process is called sherardizing. Although the zinc particlcs are covered with oxide and cannot touch the iron, an extremcly small amount of the zinc vaporizes and the vapor, reaching the iron, alloys with it. Other zinc then vaporizes to replace that which has been removed from the atmosphere. This process continues indefinitely at a decreasing rate, for the coating already formed permits zinc to diffuse through it to combine with the iron beneath. In this way, the coating grows outward from the surface of the iron, as the bark grows from a tree. The method of growth was clcarly seen while sherardizing small cubes of cast iron, at about 450" C., in a srnall glass-stoppcrcd bottle enclosed in a rotating drum. The dust contained about 3 per cent. iron, which prevented caking, and coatings % in. thick were grown in a few hours. After a heavy layer had been formed, the cubes mere again treated for a shorter time. The layer last formed was seen to lie next to the iron, instead of at the outer surface, showing that the growth was from the surface of the iron outward. The coatings split at the edges and corners, leaving the iron exposed there. Flakes of graphite from the iron were lifted upward and embedded in the coatings. The composition of sherardized coatings varies from the outer surface inward, as would be expected from the mode of growth. That is, the iron content increases slowly at first, then more rapidly as the iron is approached. At the surface the least amount of iron possible is 6 per cent., as the experiments described below have shown. A study was made of the effect of iron in zinc dust on the proccss and on the resulting coatings. Glass bulbs, holding the small pieces to be sherardized, together with enough zinc dust to make them two-thirds full, were heated in a small, rotating electrically heated and controlled furnacc. The bulbs had 6-in. (15 cm.) necks, of 96-in. (9.Fj mm.) tubing, plugged

Jan 1, 1923

By Leon McCulloch

WIIen clean iron and metallic zinc dust, protected from the air, arc heated below the melting point of zinc, the iron takes on a coating that has excellent protective value. This coating is a brittle alloy of zinc and iron, and the process is called sherardizing. Although the zinc particlcs are covered with oxide and cannot touch the iron, an extremcly small amount of the zinc vaporizes and the vapor, reaching the iron, alloys with it. Other zinc then vaporizes to replace that which has been removed from the atmosphere. This process continues indefinitely at a decreasing rate, for the coating already formed permits zinc to diffuse through it to combine with the iron beneath. In this way, the coating grows outward from the surface of the iron, as the bark grows from a tree. The method of growth was clcarly seen while sherardizing small cubes of cast iron, at about 450" C., in a srnall glass-stoppcrcd bottle enclosed in a rotating drum. The dust contained about 3 per cent. iron, which prevented caking, and coatings % in. thick were grown in a few hours. After a heavy layer had been formed, the cubes mere again treated for a shorter time. The layer last formed was seen to lie next to the iron, instead of at the outer surface, showing that the growth was from the surface of the iron outward. The coatings split at the edges and corners, leaving the iron exposed there. Flakes of graphite from the iron were lifted upward and embedded in the coatings. The composition of sherardized coatings varies from the outer surface inward, as would be expected from the mode of growth. That is, the iron content increases slowly at first, then more rapidly as the iron is approached. At the surface the least amount of iron possible is 6 per cent., as the experiments described below have shown. A study was made of the effect of iron in zinc dust on the proccss and on the resulting coatings. Glass bulbs, holding the small pieces to be sherardized, together with enough zinc dust to make them two-thirds full, were heated in a small, rotating electrically heated and controlled furnacc. The bulbs had 6-in. (15 cm.) necks, of 96-in. (9.Fj mm.) tubing, plugged

Jan 1, 1923

By A. Schild

The effect of heating a producing well on the rate of oil recovery has been analyzed in the simple case of a well producing oil by a radial drive and in the steady state. Differences of production rates with and without borehole heating have been calculated and plotted; these measure some of the benefits of the thermal recovery process. A striking feature is that the production increase tends rapidly to a constant value for large production rates. Some concrete examples, including a rough comparison with field data. are discussed. Heating requirements have been calculated and plotted on the assumption that the heaters used are 100 per cent efficient. Heating has been thought of as applying only to low volume wells producing heavy oils. However, the calculations suggest that the thermal process considered might be profitable even for some wells producing large quantities of light oil, especially in unconsolidated formations where fracturing is not possible. In the case of wells producing other fluids with the oil or of wells producing partly or wholly by gravity drainage, the theory developed does not apply in detail. It can be expected, however, that any general qualitative be-havior will remain valid. Under normal temperature conditions, high viscosity emulsions sometimes form around the wellbore, lowering the permeability in the vicinity of the well and impeding the production of oil. Borehole heating often prevents such emulsification. This important effect is not easily amenable to mathematical analysis and has not been included in the theory presented here. It should therefore be kept in mind that the benefits due to borehole heating may in fact exceed the values given by the following calculations. INTRODUCTION The recovery of viscous, low gravity oils can often be stimulated by applying heat to the production zone. The higher temperature lowers the viscosity of the oil, increasing its mobility, and therefore its rate of production. One thermal method of recovery 1,2,3,4. consists in operating a heater inside a producing well and, at the same time, producing oil from the well. In this paper a simple theoretical model is analyzed to study the effect of such heating on the recovery of oil. The reservoir mechanics of the process is the only aspect of the problem which is considered here. The details of the heating system are ignored, and it is simply assumed that the heater raises the temperature in the immediate vicinity of the producing well to a pre-assigned temperature T w. Although heating requirements are calculated, these refer only to the heat supplied to the formation and to the oil being produced; they do not include heat losses due to the inefficiency of the heater. A short outline of the theory follows: The heat supplied to the producing well flows out into the formation by means of thermal conduction. At the same time, the flow of oil carries heat by convection from the formation towards the producing well. After sufficient time has elapsed, a steady-state is reached where the temperature, the velocity of the oil, etc., no longer vary with time but are functions of position only. In the steady state the temperature decays like an inverse power from the high value Tw at the wellbore to the original reservoir temperature T. at some distance away from the well. The effect of the high temperature and low oil viscosity near the producing well is the same as if the oil were produced at reservoir temperature To but through a producing well of a larger radius. From this point of view, the energy and money being expended to provide heat

Jan 1, 1958

By Thomas C. Wilder

ALTHOUGH there is an abundance of thermodynamic information available in the literature today, no experimental data on the standard molar properties of formation of zinc oxide have ever been reported for the temperature range 419.5" to 908°C. This is the temperature range for which zinc metal is a liquid. so that the formation reaction is: Data have been reported for Reaction [I] where zinc is a solid or a gas. Maier. Parks, and nderson' measured the electromotive force of the cell: in order to obtain the free energy of the reaction: over a limited temperature range. With the known properties of H2O, those of ZnO were calculated. These workers found that t;j of ZnO is -75,930 ± 150 cal per gfw and Mtf is-83,000 300 cal per gfw at 25°C. akolkin made similar measurements to obtain ilF7 and AH; of -75,870 and -82,540 cal per dw respectively at the same temperature. Truesdale and arirlg and Kitchener and 1gnatowicz4 measured the equilibrium of the reactions: respectively, in order to determine Ff of ZnO from the known values of CO, CO2, and H/X The thermodynamic properties of ZnO, presumably taken from the above investigations, are tabulated by Kubaschewski and vans' and Wicks and Block" The latter reference also gives values for the range where zinc is a liquid. These numbers are probably acquired from the known extremities of the range plus Cp data of the components. In the present work the electromotive force of the cell: was measured in order to calculate the properties of ZnO from the well known values of NiO for the temperature range where zinc is a liquid. In Cell [B] the cathode reaction is: and at the anode: The overall reaction is: for which the free energy change is: where is the electromotive force in volts of cell [B] after correction for the Pt-Ta thermocouple. The standard molar free energy of formation of NiO is very well known as a function of temperature. Kiukkola and agner's data are used in most tabulations. The error is probably less than I00 cal per gfw, The latter authors were the first to use solid mixed oxide electrolytes in galvanic cells. Their work with NiO and other oxides was performed with cells similar to Cell [B] using a variety of reference electrodes of fixed oxygen potential. There may be a small composition range for which either NiO, ZnO or both exist. If nonstoichiometry does exist for these oxides, then the properties described herein are those for the metal saturated compositions. The simple cell design was the same as described elsewheres except that the molten metal electrode was about 125 g of pure zinc including a small (0.25 to 0.50 g) amount of ZnO. The mixture of pure nickel and NiO powders making up the reference electrode was contained in a tube of the ZrOl + CaO electrolyte which was immersed in the molten zinc. A platinum contact was made to the reference electrode; tantalum to the zinc. A refractory cement plug was necessary at the open end of the electrolyte tube in order to prevent zinc vapor from contaminating the reference electrode. Experimental details such as the vessel containing the cell, furnace, temperature control and measurement, and electromotive force determinations of the cell have all been outlined previously. The temperature was varied randomly in the range between the freezing and boiling points of zinc. After each temperature change, time was allowed for the drift at the new temperature to be less than +;"c whereupon a series of three cell readings was taken at least 10

Jan 1, 1970

By John M. Tinsley, Calvin D. Saunders, H. K. van Poollen

In the past few years much con-sideration has been given to the evaluation of the effect of hydraulic fracturing on the productivity of wells. Generally, these studies included the evaluation of fracturing materials, fracture extension and formation damage due to the use of various fracturing fluids. Only little consideration has been given to the characteristics, and in particular the flow capacity, of the fracture itself and its effect on well productivity. This paper presents the results of laboratory investigations pointed toward fie evaluation of the efficiency of various fracrures with special emphasis on the flow capacity of these fractures. Data presented in this paper are the results of both an electrical model study and physical testing. Under consideration are (I) effect of overflush, (2) premature production of well after treatment, (3) "tailing-in" with coarse sand near the end of the treatment, (4) effect of propping agent size and concentration, (5) reduction in effective frac-ture permeability caused by formation caused by formation fines, silt and clays, and (6) effect of various fluids on formation strength and competency. The results of this investigation indicate that the flow capacity of a fracture is affected by any or all of the various parameters mentioned above. The authors believe that a better understanding arid utilization of these factors should result in more efficient formation fracturing. INTRODUCTION Hydraulic fracturing has become almost a standard practice of many companies for stimulating production from old and new wells. Although most companies utilize this service, techniques of application vary widely between companies and areas. Probably too often when a well in an area responds favorably to a particular technique all future wells in the same area are treated in a similar manner. Possibly a modification of the technique would result in a further production increase. Variables, of which many are extremely difficult to evaluate from field results, hamper the selection of procedure changes. Attempts are being made by a number of organizations to analyze statistically treating techniques from production data. This is a very worthy and necessary approach but very possibly laboratory investigations may aid in evaluating some of the variables which tend to affect the results of a fracturing treatment. Some of the factors cannot be studied from practical field experience and only laboratory tests can show the possibilities which might exist. One of the factors which appears to be of major concern today is the flow capacity of the created fracture and how it can be changed. Papers on this general subject have been primarily concerned with the size of propping agent and the extent of fracture. Papers have also been written on the possible permeability damage to formations by fracturing fluids. In addition, it might be possible that another type of flow restriction is prevalent. This would be a restriction of flow through a sand-packed frac- ture caused by foreign materials integrating within the propping agent. This paper presents preliminary data obtained in an attempt to evaluate the effect of some factors affecting flow through sand-packed fractures. No attempt is being made to offer a fracturing technique adaptable to all areas and conditions, but to furnish data tending to show the possible effects which might be caused by variations in procedures and materials. PROPPING AGENT PERMEABLLITIES A hydraulically induced fracture containing sand as a propping agent may theoretically be classified as a packed-sand system. The flow of fluids through such packed systems has been the subject of much research. Although there have been numerous methods proposed for the evaluation of such systems, most writers agree on the general properties affecting their flow capacity or permeability. These properties include porosity, particle size, sphericity and the roughness of the particle. In some methods of evaluation . the particle size and sphericity terms are combined to produce an equation which is a function of the surface area of the particles. In this study the permeability of various fracturing sands was both measured and calculated. The apparatus for the permeability measurements consisted of a 52-in. Lucite tube with a 2.5-in. ID. A screen and drain plug were fitted in the bottom of this tube to retain and hold the sand in place while allowing fluid flow. Two pressure taps consisting of thin, highly perforated

By W. H. Brandt

ThEre has been much progress in the last two decades in understanding the hardenability of steel. Roughly, the progress has been along two lines, which may be designated as empirical and fundamental. This empirical work has progressed to the point where steels may be manufactured to the desired characteristics quite closely and heat-treatment and application problems can be approached with considerable confidcnce. Particularly noteworthy among the empirical work is that of Grossmann,12. who has given formulas for calculating hardenability as a function of composition, and the establishment of the isothermal transformation curve by Davenport and Bain.13 The latter does not fall entirely in the class of an empirical study, for while it provides a means of presenting a tremendous amount of empirical data in the form of a single curve, it also outlines clearly the problems that face the fundamental investigator. The isothermal transformation curve shows clearly that the phenomena occurring in the neighborhood of the knee of the curve are those that limit the hardenability of steel. Above the knee of the curve, the product of decomposition of austenite is lamellar pearlite and fundamental progress has consisted chiefly of a detailed study of structure and formation of pearlite, largely at the hands of Mehl and his collaborators.'-5 They have shown that formation of pearlite proceeds by a process of nuclea-tion and growth and they measured both the nucleation and growth rate. However, there is still a wide gap between our empirical knowledge and fundamental knowledge, owing largely to the fact that there is no satisfactory theory of nucleation rate or of growth rate. This paper is being written in an attempt to Hl in a small part of the gap. A method was prcsented recently1' for calculating the velocity of edgewise growth of pearlite using an expression for the carbon concentration that satisfies the diffusion equation. The edgewise velocity of pearlite growth in a plain carbon eu-tectoid steel was calculated, using linear extrapolations of the ferrite and comentite solubilities. While the results are in fairly good agreement with the experimental facts, the calculated velocity of edgewise growth is smaller at 600°C. than G, the radial growth velocity of pearlite nodules, whereas one would expect it to be larger. In this paper the calculation will be repeated using a new extrapolation for the ferrite solubility, which gives better agreement between G and T', the calculated velocity of edgewise growth. A calculation will also be made of the effect of carbon content on velocity of edgewise growth, and the problems of calculating the effects of other alloying elements on growth rates will be discussed. It will be assumed that the mechanism of pearlite growth, established by Mehl and

Jan 1, 1947

By W. H. Brandt

ThEre has been much progress in the last two decades in understanding the hardenability of steel. Roughly, the progress has been along two lines, which may be designated as empirical and fundamental. This empirical work has progressed to the point where steels may be manufactured to the desired characteristics quite closely and heat-treatment and application problems can be approached with considerable confidcnce. Particularly noteworthy among the empirical work is that of Grossmann,12. who has given formulas for calculating hardenability as a function of composition, and the establishment of the isothermal transformation curve by Davenport and Bain.13 The latter does not fall entirely in the class of an empirical study, for while it provides a means of presenting a tremendous amount of empirical data in the form of a single curve, it also outlines clearly the problems that face the fundamental investigator. The isothermal transformation curve shows clearly that the phenomena occurring in the neighborhood of the knee of the curve are those that limit the hardenability of steel. Above the knee of the curve, the product of decomposition of austenite is lamellar pearlite and fundamental progress has consisted chiefly of a detailed study of structure and formation of pearlite, largely at the hands of Mehl and his collaborators.'-5 They have shown that formation of pearlite proceeds by a process of nuclea-tion and growth and they measured both the nucleation and growth rate. However, there is still a wide gap between our empirical knowledge and fundamental knowledge, owing largely to the fact that there is no satisfactory theory of nucleation rate or of growth rate. This paper is being written in an attempt to Hl in a small part of the gap. A method was prcsented recently1' for calculating the velocity of edgewise growth of pearlite using an expression for the carbon concentration that satisfies the diffusion equation. The edgewise velocity of pearlite growth in a plain carbon eu-tectoid steel was calculated, using linear extrapolations of the ferrite and comentite solubilities. While the results are in fairly good agreement with the experimental facts, the calculated velocity of edgewise growth is smaller at 600°C. than G, the radial growth velocity of pearlite nodules, whereas one would expect it to be larger. In this paper the calculation will be repeated using a new extrapolation for the ferrite solubility, which gives better agreement between G and T', the calculated velocity of edgewise growth. A calculation will also be made of the effect of carbon content on velocity of edgewise growth, and the problems of calculating the effects of other alloying elements on growth rates will be discussed. It will be assumed that the mechanism of pearlite growth, established by Mehl and

Jan 1, 1947

By N. S. Stoloff, J. N. Mushovic

Age hardening response of a Mg-Th-Zr alloy has been studied at temperatures in the range 60° to 450°C. Transmission microscopy revealed clustering of thorium atoms at low aging temperatures, supporting a previous report of GP zone formation. Peak strengthening, which is observed at 325°C, is due to the formation of a coherent, ordered, DO19 type superlattice structure, of Hobable composition Mg3Th, as plates parallel to the matrix prism planes. These plates later reveal a Laves phase structure of composition Mg2Th. The equilibrium Mg4Th phase begins to precipitate in two different forms at an early stage, competitively with the Mg2Th plates. RECENT work on the Mg-Th system indicated that, unlike most magnesium-base alloys, complex precipitation phenomena may be occurring. The partial phase diagram of the Mg-Th system indicates that an equilibrium phase, Mg5Th, is the sole intermediate phase.' sturkey,' however, has reported, using X-ray and electron diffraction techniques, that a metastable fcc Laves phase, Mg2Th, precedes the formation of the equilibrium compound, which he identified as closer in composition to Mg4Th. Murakami et al.3 reported that the equilibrium phase precipitates preferentially on grain boundaries and dislocations in a Mg-1.7 wt pct Th alloy; Kent and Kelly4 aged a more dilute alloy, Mg-0.5 wt pct Th, for 4 days at 220°C and found similar results. In addition, they reported that a platelike phase with a structure close to that of the magnesium matrix forms perpendicular to the basal plane and is probably ordered. Research on a Mg-4 wt pct Th alloy by electrical resistance measurements and transmission electron microscopy has suggested that GP zones may form at low aging temperatures.3 However, the electron micrographs purporting to show this phenomenon were not conclusive. In view of the fragmentary evidence concerning the nature of the precipitation processes in the various Mg-Th alloys, an aging study was undertaken to clarify the characteristics of the various precipitates which form and to correlate the mechanical properties of the system with the direct precipitate-dislocation interactions. The latter results are presented elsewhere.' The purpose of this paper is, therefore, to discuss the precipitation sequence in this system. EXPERIMENTAL PROCEDURE Sheet stock (0.060 and 0.010 in. thick) of a commercial Mg-3.93 wt pct Th-0.42 wt pct Zr alloy (designated HK3lA) similar to that studied by sturkey2 was supplied through the courtesy of Dr. S. L. Couling of Dow Metal Products Co. Zirconium does not enter into any precipitation reactions,' but is present primarily as a grain refiner. The alloy was chill cast, warm rolled to 0.090 in. thick stock, and then finally reduced by a combination of hot and cold rolling. The alloy chemistry is given in Table I. This material was solution treated at 580°C for 4 hr in a dry CO2 atmosphere, and then water quenched. Material in this condition was fairly clear of precipitate particles and was fully recrystallized. Aging at temperatures less than 200°C was accomplished by immersing the alloy in a silicone oil bath; for higher temperatures, aging was done in a salt pot. Age hardening treatments were conducted at 60°, 80°, 105°, 135°, 160°, 250°, 325°, 350°, and 450°C for times ranging from 5 min to 400 hr. Hardness tests were performed on chemically polished 0.060-in.-thick blanks of solution treated material which were aged at the various temperatures for increasing lengths of time. For aging temperatures above 150°C the Rockwell Superficial 30T scale was employed, while samples hardened at temperatures below 150°C were monitored with the 45T scale. Each data point consists of at least three separate readings. Yield stresses also were measured at room temperature on both 0.060 and 0.010 in. sheet specimens aged at 325°C. The aged foils were thinned by the window method in a solution of 80 pct absolute alcohol and 20 pct concentrated perchloric acid (70 pct) maintained at 0°C. A stainless steel cathode was used and the applied voltage was 10 to 15 v. Thinned samples were rinsed in distilled water and pure methanol. After the me-thanol rinse the thin foils were quickly dried between filter paper. Foils prepared by the above method were examined in a Hitachi HU11B electron microscope operating at 100 kv. RESULTS A) Hardness. The hardness data are depicted in Figs. 1 and 2. Peak strengthening occurs at 325°C after aging about 6 min, see Fig. 1. Significant strengthening is achieved also at 350°C, but aging at 450°C produces only softening. The stepped curve at 250°C indicates that a complicated precipitation process may be occurring at that temperature. Fig. 2 suggests that at least two hardening mechanisms exist since the lowest temperature hardness peaks are displaced to the left of the peaks obtained at 135° and 105°C. A great deal of scatter is observed at long times in all cases due to magnesium surface degradation caused by the silicone oil bath. B) Identification of the Strengthening Precipitates. The structure formed atlowagingtemperatures (c10O°C) was not clearly resolvable by transmission microscopy. The only bright-field evidence for a change in structure was a mottled appearance which could be observed at extinction contours, as shown in Fig. 3(a), and the disappearance of this effect when dislocations produced under the influence of the electron beam passed through the matrix, as noted in

Jan 1, 1970

By S. W. Parr, T. E. Layng

The low-temperature carbonization of coal involves the carrying out of the coking process under conditions wherein neither the coal mass nor any of the passageways through which the volatile products pass are heated above 700" or 800" C. For convenience in this discussion, the single number 750" will be used to designate the maximum range. This temperature is not selected arbitrarily; it is the result of certain natural conditions that are inherent in the substances involved. Two of these conditions arc sufficiently pronounced to suggest a line of demarcation at this point as follows: (1) Below 750°, all the heavy hydrocarbons are expelled, which means that, at these lower temperatures, the illuminants, the gases of high calorific value, and the condensible oils are discharged; above 750") there are given off the lean, non-illuminating gases consisting for the most part of hydrogen and marsh gas and having no condensible constituents present. (2) Below 750") there is substantially no secondary decomposition; above 750") the volatile products are readily decomposed, forming tars, naphthalene, free carbon, etc. It is not intended to maintain that no secondary decompositions occur below 750". Many recent studies have demonstrated the practicability, especially in the presence of catalytic substances, of cracking certain of the hydrocarbon compounds; but at these lower temperatures the step is a moderate one, as, for- example, from xylene to toluene or from toluene to an anthracene. These changes are moderate in amount. Not only do the reactions proceed slowly but they are subjected to the decomposing . conditions for only a short time. This is evident when it is recalled that at these initial temperatures the decomposition of the coal is very rapid and, if anywhere near a neutral pressure is maintained, the movement of the evolved gases is lively and reduces, correspondingly, the time for the retention of the gases in the passageways where these milder decomposing conditions exist. It is acknowledged that the maintenance of these temperature conditions at the present time has only an ideal and not a practical status. Actual operations under these conditions, as a? industrial accomplish-

Jan 1, 1920

By B. F. Zwick

No new fields have been discovered in Ecuador during 1945, though Shell. Company of Ecuador's Vuano No. 1, near Arajuno in the Oriente concession, which was reported to have drilled to .5281 ft., tested a small, noncommercial quantity of 13° gravity oil. In the upper section, the well tested large flows of fresh water and has been abandoned. Shell is preparing to move to another location.

Jan 1, 1946

By I. R. Kramer

Studies of the effect of size of the specimen on the change of slopes of Stages I and 11 by surface removal showed that the change of Stage I was independent of size with respect to the polishing rate; however, the change in the slope of Stage 11 with polishing rate increased directly in proportion to the surface area. The removal of the surface during the test affected the plastic deformation characteristics of gold, aluminum, and zinc single crystals and polycrystalline aluminum. The apparent activation energy of aluminum was found to be decreased markedly by removing the surface during the deformation process. In previous papers1-3 it was shown that the surface played an important role in the plastic deformation of metals. By removing the surface layers of a crystal of aluminum by electrolytic polishing during tensile deformation, it was found that the slopes of Stages I, II, and III were decreased and the extents of Stages I and II were increased when the rate of metal removal was increased. By removing a sufficient amount of the surface layer after a specimen had been deformed into the Stage I region, upon reloading, the flow stress was the same as the original critical resolved shear stress and the extent of Stage I was the same as if the specimen had not been deformed previously. The slope of Stage I was decreased 50 pct and that of Stage 11 decreased 25 pct when the rate of metal removal was 50 X 10"5 ipm. These data show that in Stage I the work hardening is controlled almost entirely by the surface conditions, while in Stages 11 and III both surface conditions and internal obstacles to dislocation motion are important. It appears that during the egress of dislocations from the crystal, a fraction of them becomes stuck or trapped in the surface regions and a layer of a high dislocation concentration is formed. This layer would not only impede the motion of dislocations, but would provide a barrier against which dislocations may pile up. In this case, there will be a stress, opposite to that of the applied stress, imposed on the dislocation source and dislocations moving in the region beyond this layer. It has been found convenient to refer to this layer as a "debris" layer. The "debris" layer may be similar to the dislocation tangle observed by thin-film electron microscope techniques.4 Reported in this paper are the results of studies on the effects of removing the surface during plastic deformation on aluminum crystals of various sizes. The effects of the surface on the yield point behavior of gold and high-purity aluminum crystals as well as the creep behavior were also determined. The effects of surface removal on polycrystalline aluminum (1100-0 and 7075-T6) are also reported. EXPERIMENTAL PROCEDURE For those portions of the investigation involving creep and tensile specimens, single crystals, having a 3-in. gage length and a nominal 1/8-in. sq cross section, were prepared by a modified Bridgman technique using a multiple-cavity graphite mold. The single crystals were prepared from materials which had initial purities of 99.997, 99.999, 99.999, and 99.999 pct for Al, Cu, Zn, and Au, respectively. The aluminum specimens for the size effect studies were prepared through the use of a three-tier mold in which crystals having a cross section of 1/8, 1/4, and 1/2 in. were grown from a common seed. The mold design was arranged so that one 1/2-in. crystal, two 1/4-in. crystals, and four 1/8-in, crystals of the same orientation could be cast. With this technique, it was possible to obtain only one set of crystals with the same orientation. Because of this limitation, it was not possible to determine both the changes of extent and slope of the various stages since a large number of crystals of the same orientation would have been required. Instead, only the change of slope as a function of the rate of metal removal was studied by abruptly altering the current density of the electrolytic polishing bath at various strains within the regions of Stages I and 11. The experimental techniques used for the tensile studies were essentially the same as those used previously.1,3 The specimens were deformed in a 200-lb Instron tensile machine, usually at a rate of 10-5 sec-5. A methyl alcohol-nitric acid solution was used as the polishing bath for aluminum. The temperature was maintained constant within ±0.l°C by means of a water bath. The tensile machine was

Jan 1, 1963

By Walter C. Lawson

THE primary objective in laying track in panel sections is to reduce the number of track laborers required. This is possible because the work is mechanized. Moreover, because the work is mechanized and each of the operations needs only a few men, and each is self-contained, the work can be carried on at night as well as in daylight; therefore, the method provides a means of preparing tracks on more than one shift. The laying of tracks in open pits and quarries in panel sections is not new but new methods have been made possible by the introduction of new types of equipment. The purpose of this paper is to describe the methods that are followed in' the Morenci open pit. GENERAL MINING OPERATIONS Full-scale ore production at Morenci is about 50,000 tons daily. The normal yearly output of ore and waste is 32,000,000 tons, of which 30,000,000 tons is handled by rail haulage. This requires the building of approximately 47 miles of loading and other temporary tracks during a 12 months' period (Fig I). Broken ore and waste, is loaded., into 90-ton capacity dump cars with 5-cu-yd full-revolving electric shovels. Shovel banks are uniformly 50 ft high:. They are blasted- with churn drill holes, and the broken material from a blast is loaded out with two shovel cuts, the first one being called (locally) the "splatter" cut and the second one the "clean-up" or "face-up" cut. When a shovel is making its clean-up cut, the loading track is about 70 ft from the toe of the bank and, under normal conditions, a bank is blasted against it without removing the track. It is thus evident that each track is used for two shovel cuts before relocation is necessary, inasmuch as a single position serves for both the clean-up cut prior to blasting and for the splatter cut following the blast. The normal advance of a solid bench by a single blast is 40 ft (Fig 2). PREPARATION OF PANEL GRADE In preparation of panel grades bulldozers and rooters are used for the bulk of the work and an auto-patrol road grader for the final stage. At Morenci, bulldozers have always been used for track-grade preparation, but before the introduction of the other two types of equipment grades were uneven and irregular at best, and always necessitated a big gang of track laborers to hand-block under the ties with rocks after a track was laid into place. High blocking also made poor track because of instability and caused frequent derailments. Under these conditions derailments were generally bad as re-railing became difficult. Much track was torn up and many ties broken in the process. The inadequacy of the hand-blocked track, together with the inefficiency of hand blocking, constantly pointed to the desirability of reducing the amount of labor required, so various means were tried to improve conditions, such as wood

Jan 1, 1947

By F. Julius Fohs

With portions of two coal basins within its borders and a few scattered fields already developed, the question arises: What is the future of Kentucky as an oil-producing State? Is the long list of failures due to lack of commercial pools, or unintelligent prospecting? A study of its beds and irregularities of structure points not only to a large waste of development money on unpromising areas, but also to the presence of a few structures well worthy of development. The surface rocks of Kentucky show in succession more than 4,000 ft. of Paleozoic sediments and more than 2,000 ft. of Cretaceous, Tertiary, and more recent deposits. Folding and erosion have brought these beds to the surface, where they have been observed and studied in detail by my associate, James H. Gardner, myself, and others. This has given opportunity to observe the beds offering suitable reservoirs and having the proper impermeable covering; also the mapping of outcrops and outcrop lines, taken in conjunction with available well records, indicates that certain areas are worth testing, and with even greater definiteness shows areas which should be excluded, as devoid of possibilities. West of the Tennessee River, Cretaceous, Tertiary, and Quaternary sediments occur so that all trace of ancient folding is obliterated, the sediments overlapping unconformably Mississippian rocks. This area embraces 2,000 square miles, or one-twentieth of the area of the State, the Paleozoic rocks covering the remainder. Since there is nothing upon which to base the location of tests for oil and gas in the Cretaceous-Tertiary beds of Kentucky, the Paleozoic area will be chiefly considered. The distribution of Paleozoic rocks in Kentucky is centered about the north-northeast striking Cincinnati geanticline, bringing to the surface on the Jessamine dome the oldest rocks exposed in the.State, those of the Devonian, Silurian, and Ordovician systems. On either flank of this great earth-arch are the Mississippian rocks, sloping gradually beneath the coal-measure basins to the west and to the east. West of the western coal basin, and. between it and the Cretaceous-Tertiary rocks further west, is a high area of Mississippian rocks. Crossing the State

Jan 1, 1915

By E. E. White

I DISAGREE with Mr. Brinsmade on several points, and I will discuss his remarks under the same six topics which he has used. 1. Rate of Interest Earned by Sinking-Fund.-I believe Mr. Brinsmade is confused in his ideas as to the effect of new gold on the interest earned on money. The flood of gold which he mentions certainly should not operate, to increase interest rates, but since it replaces and adds to liquid capital should reduce interest rates and counteract the destruction of liquid capital which he mentions. Furthermore, it is doubtful if the destruction of capital since 1897 by wars and catastrophes has been any greater in proportion than in similar periods before 1897. With regard to savings banks, I would say that only 3 per cent. is allowed on deposits through a large part of the West. As to bonds, they can be bought to yield any rate. of interest desired up to 6 per cent., but, a 5 per. cent. bond is not as safe as a 4 per cent. bond, nor a 4 per cent. bond as safe as a 3 per cent. government security. I do not understand why Mr. Brinsmade says that Mr. Denny's quoted opinion of a 3 per cent. rate is evidently based on English conditions before the Boer War. Certainly there is no reference to the Boer war or to English conditions in Mr. Denny's article. M. Howard Burnham, in his admirable work on mine valuation, says': ". For instance, redemption is taken at 3 per cent., because even 4 per cent. represents a greater risk, as is indicated by the purchase of Government paper to bear only 3 per cent., the great desideratum of the .latter being security." . Again, Mr. Burnham says:2 "The tables are calculated on the assumption that the dividends shall accumulate at 3 per cent. only, as in accordance with the general idea set out elsewhere, a rate greater than 3 per cent. involves appreciable risk with which it were inaccurate to saddle the sinking-fund if risks are to be segregated, this being the basis of all the writer's calculations."

Jan 6, 1914