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By Edward Martinez

The reactions occurring in the copper segregation process were studied by heating mixtures of chryso-colla, salt, and a reducing agent. The techniques used in this investigation were differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). The initial chloridizing of the oxide copper occurs below 500°C and cupric chloride may be the compound formed. Volatilization and reduction of the copper chloride take place above 550°C, although these reactions do occur to some extent below 550°C. A difference in the distribution of the metallic copper in the reducing agent was found when sodium chloride was used compared to magnesium or calcium chloride. Segregation was obtained with mixtures of cupric oxide, salt, and charcoal with no quartz or silicate present. Preliminary tests indicate that segregation may occur even in the absence of water vapor. The DTA and TGA techniques were found to be of great value in studying these reactions. The copper segregation process is a method for treating oxide copper ores. The ore is heated, most commonly in a kiln, with a reducing agent and a halide salt, generally sodium chloride, to approximately 700°-750°C and held for 30 to 60 min. The addition of the salt results in the migration and reduction of the oxide copper to metallic copper on the surface of the reducing agent rather than in the original mineral structure. The metallic copper can then be recovered by a subsequent leaching or flotation step.1-4 Experimental work in 1923 on oxide copper ores from the Sagasca mines in Chile led to the discovery of the reduction process. It was found that during the reduction of the copper mineral with coal, at about 700°C, the copper migrated to the surface of the coal instead of remaining disseminated in the ore. The unusual behavior of the copper, which caused it to migrate from the ore particles to the coal, was traced to the presence of a small quantity of sodium chloride occurring in the ore. Further experiments with oxide copper ores proved that the presence of a halide, either occurring naturally or admixed with the ore, caused the copper to migrate from the ore particles and to segregate in the charge. The ratio of salt to reducing agent may vary somewhat, but in general 0.5% to 1.5% sodium chloride and 0.5% to 1.0% coal or coke have been mixed with the ore. Less than stoichiometric amounts of salt are required to convert all the oxide copper to a chloride, so that a cycle of reactions appears to be occurring. Several investigations reported in the literature have proposed reactions to explain the mechanism of the process.5-10 There appears to be general agreement that water is necessary for the reactions to occur; that once the sodium chloride reacts with silica or silicates in the ore, the hydrochloric acid formed will convert the cupric oxide in the mineral structure to cuprous chloride. However, there appears to be a conflict of opinion on the reactions involved in the reduction of the cuprous chloride to metallic copper on the surface of the carbon. Rey has indicated that salt, water vapor, and

Jan 1, 1968

By H. H. Spain, R. C. Rumble, H. E. Stamm

This paper presents a reservoir analyzer study of the performance of the Woodbine formation in the East Texas basin. The study was made possible by the compilation of available information on the configuration. thickness and the pressure drawdown of the formation. The investigation was made of the pressure variations in the basin incident to production from the several Woodbine reservoirs. In addition, the apparent compressibility of Woodbine water was evaluated so that the potential water yield of the formation could be determined. The distribution of permeability of the Woodbine sand and the interference between producing areas were also investigated. In conjunction with this basic study of the Woodbine sand, an acceptable match of the production-pressure relationship in the East Texas Field was established on the analyzer. INTRODUCTION When production is taken from a reservoir contiguous to an aquifer, the resultant pressure gradient causes a water influx into the reservoir. For some years it has been the practice to predict the performance of water drive reservoirs with mathematical equations that relate the water influx into reservoirs to their pressure behavior. A rigorous solution of these equations is quite complex: hence, the conventional method requires the simplifying assumptions that the formation have constant thickness, permeability and poiosity, and that it have a known and regular shape. It is necessary to use performance records of the reservoir in question to determine the equation constants that make the results of the mathematical calculations duplicate the reservoir history. The values of the constants determined in this manner sometimes differ so greatly from theoretical or measured values that the constants appear unreasonable. The equation constants comprise such factors as the thickness, porosity and permeability of the formation, and the viscosity and compressibility of water. Usually the thickness, porosity and viscosity are known within a reasonable degree of certainty. whereas the formation permeability and the water compressibility are known with considerably less certainty. Hence. permeability and compressibility values are arbitrarily selected that will make the mathematical equations duplicate the reservoir behavior. In many reservoir studies the value of the compressibility of water thus selected has exceeded the reported value by a factor of from severalfold to manyfold. Whether this excessive value results from the inadequacy of the mathematical approach to take into account the shape irregularities and the heterogeneities of the aquifer, or is due to some type of formation compaction and decrease of porosity has not been established. Because of the significance of the potential water yield of formations with reference not only to oil reservoirs but to water resources as well, it is very important that a representative value for the effective water compressibility be determined. One of the best known examples of a field for which it has been possible in the past to predict the future reservoir pressure is the East Texas Field. Until about 1943 it was possible by means of mathematical equations to duplicate past pressure behavior and to predict with a high degree of accuracy the reservoir pressure of the field. Since 1943, however, the calculated pressures have deviated progressively from the observed pressures to such a degree that in recent years, it has

Jan 1, 1951

By W. C. Ellis, E. S. Greiner

Metallic titanium has been prepared in small quantities since the beginning of the century. Hunter1 reported in 1910 that he obtained a malleable product of 99.9 pct purity by the reduction of the tetrachloride by sodium in a closed container. Later Van Arke12 and Fast prepared small quantities of malleable titanium by thermal decomposition of titanium iodide. Another method for producing malleable titanium from tetrachloride was reported by Kr0ll4 who used magnesium as the reducing agent. More recently Dean, Long, Wartman, and Anderson5 working at the U.S. Bureau of Mines have reported the preparation of the metal on a pilot plant scale by the reduction of titanium tetrachloride by magnesium in an atmosphere of helium. Their product, which is malleable, was used in the present investigation. Early in 1948 after the work of this paper was completed Campbell, Jaffee, Blocher, Gurland, and Gonser6 described the strength and working characteristics of pure titanium which was prepared by the iodide method on a scale producing 300 to 600 g per run, in the form of 0.3- to 0.4-in. diam rods. Their product is characterized by low hardness and large capacity for cold work which they attribute to a high degree of purity with respect to oxygen, nitrogen, and carbon. Titanium has a melting point of about 1725 C," it may be classed as a light metal since the specific gravity is 4.5 g per cc-I. The crystal structure is close-packed hexagonal from room temperature to 885°C. Above this temperature the structure is reported7 as body-centered cubic. The change in crystal structure has been associated with discontinuities in specific heat,8 electric resistanceg and theimoelec-tric force10 at temperatures near 890°C. It is reportedll that annealed titanium has a tensile strength of 78,700 psi which can be increased by cold-work to 123,000 psi. In the present investigation, the lattice constants at room temperature, the thermal expansivity between 30 and 800°C, as well as the electrical resistivity and thermoelectric force against platinum between — zoo and I000 C have been determined. Materials For the measurements, two series of specimens were prepared from titanium furnished by the U. S. Bureau of Mines. The first was made from an annealed sintered compact, 0.38 in. thick. Sections of the compact were cold-swaged with intermediate anneals in vacuum to the sizes used. Sizes over 0.25-in. diam were annealed at I000°C and smaller sizes at 800°C. Specimens originating from the sintered compact are designated in this paper as A. The second series of specimens was made from a rod of titanium, 0.19 in. in diam, which was cold-swaged with the necessary intermediate anneals to the required sizes. This series of specimens is designated B. The impurities in the specimens of titanium, determined by chemical analysis, are given in Table 1. Oxygen and nitrogen which Were not determined by analysis, are probably present although in small quantities in view of the ductility of the material.

Jan 1, 1949

By Arthur F. Taggart

RECENT jig practice has shown such marked departures from the pronouncements of the textbooks, particularly as to particle size recovered and size range of feed, as to make it desirable to reexamine the mechanism of jig action. This paper presents the results of such a study. The general conclusions of the paper are: I. A jig bed is a bi-functioned as well as bi-parted body. The upper layer comprises a plastic stream moving slowly in a substantially horizontal direction from feed lip to tail board. It serves to rough out tailing and light middling and to pick up heavy middling and lift it out of the jig box. The lower layer acts as the ultimate separating means by absorbing concentrate and rejecting heavy middling. 2. The separating function of the lower layer is performed in three definitely different ways, depending upon the relative sizes of the grains presented to it and those composing it. EXPERIMENTAL The experimental work consisted of close and long-continued visual observations of operating beds in a plunger jig, eccentric driven, and in determinations of the settling rates of various metal spheres through a quartz bed under various conditions of operation. Falling velocities were measured by an ingenious method devised by A. C. Dorenfeld, a student in the Mining Department at Columbia. Spheres of different metallic alloys, Y8-in. diameter, were cast with a short piece of fine copper wire frozen in to serve for suspension. A short piece of black cotton thread was looped to the top of the wire to serve as an indicator. The set-up for a test is shown in Fig. I. The thread should be boiled, if necessary, to make it freely water absorbent. The piece of clean plate glass D is supported rigidly at the proper height in a vertical position. The white scale E is similarly supported behind the glass. At the beginning of a test, D is filmed with water by holding it (best with clean rubber finger cots) under running tap water. It is then clamped in approximate position and C, already wet, is laid across it and drawn straight and vertical with the upper end at or near the top of D, and the ball A slightly above the top of the expanded bed. The water film holds the string to the glass. For a test the string is released, its upper end position noted just after the top of the ball becomes submerged, when the corresponding time is read, and thereafter simultaneous readings of position and time are taken as desired. Results of the visual studies of the bed are given at the pertinent places in the following discussion. Results of the settling tests are summarized in Figs. 2 and 3. DEFINITIONS The name bed as used herein refers to the entire mixture of solids and water filling the jig box. A layer is a stratum of a bed composed of particles of substantially the same specific gravities. A granular product is long-range when it approximates a crushed or ground product limited as to upper size only; a shorlrange product is one closely sized. A bed is loaded when operating with continuous feed

Jan 1, 1943

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

For some years we have been carrying on a rather comprehensive investigation of the occurrence of oxygen in liquid open-hearth steel. This investigation was interrupted by the war emergency and is therefore incomplete, with many questions still answered only partially, if at all; yet it seemed worth while to present a report of progress on this difficult field of research, if for no other reason than to promote discussion and further investigation of this important problem. The significance of such studies depends in large measure upon the accuracy of measurements of oxygen content in liquid steel while it is still in the furnace or as it flows into the ladle, or thence into the mold and there is, as we shall show, good reason for believing that the main source of uncertainty is in the sampling, not in the analytical method as such. The difficulty arises from the fact that any method of sampling is of itself apt to alter the amount of oxygen in solution in the liquid steel, because this oxygen is in a readily reactive condition. On the one hand, being usually present at a concentration appreciably in excess of that corresponding to equilibrium with the carbon then present, it may decrease rapidly in percentage by reaction with carbon and evolution of CO, especially if the liquid metal is in any way shaken or brought in contact with a cooler solid surface. On the other hand, it may increase rapidly by ab- sorption of oxygen from a slag, a furnace atmosphere, or from air. These circumstances, which are inherent in the problem, as well as our conclusion that, despite the considerable amount of careful work already done, there is still no method of sampling liquid steel acceptable as an unquestioned standard, ed us to undertake systematic comparisons of oxygen content of large numbers of samples taken: (I) by a single method at different positions and levels in the bath; (2) at the same place by different sampling methods; and (3) from bath, tapping stream and pouring stream. The different sampling methods yield somewhat different values and there is as yet no way to tell with certainty which is the most accurate. But the general reproducibility and consistency of the results give us some confidence in certain inferences we draw from them: namely, that the "spoon" method of sampling, properly carried out, gives somewhat more consistent results than the "bomb" method, as it has usually been practiced; that, in the bomb method, an aluminum cap is preferable to a steel cap; that the oxygen content of liquid steel in a finished heat is substantially the same all over the bath at the same level, and tends to decrease at lower levels further from the slag interface; also that it tends to decrease, and to decrease erratically, from furnace bath to tapping stream entering the ladle. Accordingly it seemed desirable to report these observations in detail as a first step, so that the reader may judge their significance as a contribution towards solution of the main problem, which is to find a means of pre-2

Jan 1, 1945

By Bernt Ellingsaeter, Terkel Rosenqvist

IN the silicothermic reduction of magnesia, burned dolomite is treated with high grade ferrosilicon in an evacuated steel retort at temperatures between 1150° and 1200°C. The following reaction is assumed to occur MgO + CaO + 1/2 Si (Fe) - Mg(g) +- & Ca,SiO, + Fe with the equilibrium constant on the basis of thermodynamic data for the substances involved and assuming unit activity for all solid constituents, Kubaschewski and Evans' calculated the magnesium pressure as a function of temperature logp,, (mmHg) = 15.06-1.61 T- log T- 13,16O/T. Pidgeon and King," who measured the magnesium pressure by means of a flow method, found values about three times the calculated ones. This may be caused by uncertainties in the thermodynamic data, but may also be caused by the formation of other reaction products, such as Ca,SiO,, which is known to be the stable silicate in equilibrium with lime. Whatever the exact reaction may be, it is evident that as long as all other factors are maintained constant the magnesium pressure will vary with the silicon activity, viz: p,, = &,. (p,,) ", where (p,,)" is the magnesium pressure by the reduction with silicon of unit activity. In the present investigation, p,,, was therefore measured for various grades of ferrosilicon and their silicon activities were calculated. The experimental method was similar to that used by Pidgeon and King. Briquettes of burned dolomite and Fe-Si alloys were placed in a 1 in. heat resistant steel tube and were heated to 1200°C. By means of a flow of purified hydrogen, the magnesium vapor was swept into a condenser filled with steel wool. From the amounts of hydrogen used and magnesium condensed the magnesium partial pressure was calculated. First a tube of 28 pct Cr steel, and later a tube of Kanthal D (a ferrous alloy with 22.6 pct Cr, 2 pct Co, and 4.5 pct Al), was used as a heat resistant tube. The latter tube showed the best heat resistance. The dolomite used had the following composition: 43.6 pct MgO, 55.5 pct CaO, 0.2 pct K,O + NalO, 0.2 pct Fe,O,, and 0.3 pct insoluble. The ferrosilicons were prepared from 98 pct Si of technical grade (0.7 pct Al, 0.3 pct Ca, and 1 pct Fe) by melting with various amounts of electrolytic iron of high purity. The alloys thus obtained were analyzed on their iron and silicon contents, which added up to between 99 and 100 pct. The amounts of reactants were chosen so that there would always be an excess of the oxides, and the average decrease in silicon content during the experiments would be about 1 pct. Most of the reaction occurred in the part of the reaction mixture facing the gas flow. The change in the silicon concentration in the part facing the condenser was, therefore, negligible. To facilitate the reaction, about 1 pct fluorspar was added to the briquette mixture. Fluorspar does not enter the reaction, but is known to act as a

Jan 1, 1957

By A. J. de Witte

INTRODUCTION The importance of determining dips of subsurface formations in wells, especially in wildcat wells, is self-evident and need not be enlarged upon. Various dipmeter instruments have been described in technical literature1,2,3,4 over the years. The introduction of the continuous dip-meters3,4 has made the earlier types obsolete. Continuous dipmeter logs are run by at least two different major service companies. Included as part of the service are a limited number of dip calculations—usually 10—made at different levels from the log. Very frequently this is the total result of a dip survey. It is believed that dipmeter surveys would be of considerably more advantage if geologists and engineers were able to make their own calculations from the original records. Determination of dips from the dipmeter record starts with the correlation of three log curves taken at different sides of the borehole. It cannot be over-emphasized that the quality of the results hinges primarily on this correlation. Nobody should be better qualified to correlate logs than a subsurface geologist or field engineer. The next requirement is to have an easy yet accurate way of computing the dip from the correlated points. Service companies use a mechanical device for this purpose. Directions for a graphical method were given in a recent article by B. 0. Prescotts. This paper describes a different graphical technique which, in our experience, is simpler, faster and at least as accurate. The entire manipulation is carried out on the stereonet in a number of easy moves. The paper is divided into two parts. This first part contains the introductory sections and full explanation of the geometry involved. The second part reviews the reading of data from an actual field log and summarizes the practical rules for computation of dips, the whole process being illustrated by an example. Following the outlined procedure, one could calculate a good many levels in a relatively short time, thus being able in particular to check suspected anomalies such as fault zones or unconformities in as close detail as the log will permit. GENERAL EXPOSITION OF THE METHOD Prnciple of the Dipmeter The position of a plane in space is defined by the location of three points, not on a straight line. Referring to Fig. I, if a borehole traverses a bedding plane, we can determine the strike and dip of the bed by finding three points which are not in line along this plane. Such points as A, B, and C are obtained with the dipmeter. The device consists of three electrodes (or caliper arms)1, 2, and 3 spaced at 120 angles, as schematically indicated, whose readings are separately recorded (Curves 1, 11, 111, to the right). When electrode 1 passes the boundary of the bed, Curve I will kick, etc. From these curves, we know the relative distances of points A, B, C, measured along the axis of the hole. If A is at zero, then B and C are at levels d1 and d2 up the hole,

Jan 1, 1957

By G. H. Lair, B. J. Langford, S. H. Rockwood

Volumetric reservoir analysis is dependent upon a firm relationship between porosity, connate water, and net pay. Capillary presswe data on core samples interrelate these three factors. It is shown that other reservoir problems may be resolved: (I) whether water production is indigenous or extraneous to the oil producing interval, (2) an oil-water contact is being approached, and (3) whether the oil-water contact is remotely situated. INTRODUCTION Volumetric analysis of carbonate reservoirs challenges the ingenuity of the reservoir engineer due to an absence of data on the minimum oil-bearing and oil-producing pores of a given reservoir rock. Many studies with this as the ultimate objective are available on the physical characteristics and fluid-flow behaviors of the carbonate reservoir. Some of these publications are: Hassler, Brunner and Deahl's1 study of the role of capillarity in oil production; Jan Law's' and A. C. Bulnes3 statistical treatment of core analysis data; Chalkley's method4,5 or estimating specific surface areas and porosity; Walter Rose's9 report on porosity, reserves, and recovery; Archie's78 tex-tural classification of carbonate rocks; Stewart and Spurlock's9 large core analysis; Purcell'sl0 mercury injection method in studying capillary pressure phenomena; Stewart, Craig, and Morse's" model multiple-phase flow test in investigating the relative permeability effect; and Fatt's12 illumi-nating network model of porous me-dia. The present study shows that the static reservoir parameters of porosity, connate water, and net productive thickness may be interrelated by utilizing a statistical arrangement of mercury capillary pressure data in addition to routine core analysis. This report summarizes the techniques that are followed to obtain these relations which are applicable to carbonate and sandstone reservoirs that do not contain clays. Capillary pressure statistical studies may be extended to include clay-bearing rocks by utilizing water capillary pressure data. POROSITY It is necessary that the laboratory determine the porosity value that includes the pores that are filled with hydrocarbons and water in the reservoir. This is the reservoir's total porosity. When true total porosity values are not available, correlations between porosity and capillary pressure characteristics lose their significance since they cannot be related through oil-base mud core data to the porosity and connate water values found in reservoirs. Methods used to obtain reliable porosity data will not be discussed; however, care should be exercised in selecting samples for measurement. In homogeneously porous formations, small core plugs sampled frequently will furnish adequate information. Where heterogeneity, particularly vugginess, is present, large-core porosity data may be required; in such reservoirs a suite of capillary pressure samples may be selected from small plugs. CAPILLARY PRESSURE Capillary pressure data provide a method for relating two carbonate reservoir parameters, porosity and connate water saturation, which in turn permit delineation of productive rock types necessary for selecting the third parameter, productive thickness. Specific applications of capillary pressure data to petroleum reservoirs were suggested by Archie8 and Pur-cell."' Their work demonstrated that in preferentially water-wet rock, porc

Jan 1, 1958

By R. J. Bethancourt, D. M. Collingwood

The use: of a pilot waterflood is very desirable where all of the pertinent data necessary to initiate a full scale waterflood are not. available. This paper attempts to take a specific case and .show the step by step process of starting with a pilot waterflood and progressing to a full wale flood as results are obtained. INTRODUCTION Many of the older fields of Soutlwest Texas are approaching depletion by primary produrtion methods. As primary protlllc:inp operations on individual properties approach their economic limit. conflicting considerations face management: cm the one hand. plugging and abandonment of wells for equipment salvage; on the other hand, further investment in secondary recovery installtions, equilent, and well workovers in the interests of conservation anal additional oil reserves. In main instances, where primary production by pressure depletion and gas solution drive has been comparatively good, there still exists the possibility of an economic secondary recovery by waterflood. This is not necessarily true to the same degrre of all such fields. nor all portions of large fields. To properly evaluate the economics of a prospective water-11ot1cI requires a considerable amount of precise geological. statitical. and physical data Such information on the older field.; is often very limited. and in the case of the property discussed in this paper was considered inadequate to justify investment in an overall waterflood. Primary production was estimated at :39 per cent of the original oil in place, yet sand conditions of permeability and homogeneity, and position in the field appeared to be favorable for a limited margin of profit from a carefully controlled waterflood. Thus a pilot waterflood, with its minimum initial financial risk, followed by extension as favorable results were obtained, seemed to be the answer for the Sun Oil Co L. Wiederkehr lease in the Nortl Government Wells Field, Duval County. Texas DESCRIPTION OF RESERVOIR Approxinately 8,200 wells have been drilled in Duval County. As of March 1, 1952, there were 3,350 producing oil wells in 92 different fields, with very few flowing wells (Fig. 1.) Sun Oil Co. operates the I.. Wiederkehr lease located in the North Government Wells Field in Duval Countv. 85 mile. west of Corpus Chriti and 100 miles south of San Antonio. The lease has been subjected in part to a controlled five spot waterflood. The North Government Wells Field is roughly 7 miles long and 3 miles wide, with numerous overlapping producing zones. The L. Wiederkehr lease of 3.085 acres. Has seven producing zones from 700 to 7.500 ft. The lease is in the northern section of the field where it is widest, and has 710 acres productive from the North Government Wells .and. (Fig. 2.) The North Government Wells sand, Jackson group. Eocene age, at an average depth of 2.250 ft (minus 1.750 subsea). has a thickness range of 25 ft on the east side of the L. Wiederkehr lease to 4 ft on the west side. It has a slight overall dip to the North and East of some 33 ft to the mile.

Jan 1, 1953

By Edward E. Hicke, Charles A. Stickels

The dihedral angle of liquid-lead inclusions in solid nickel has been measured as a function of temperature from 371 to 816 C at zero pressure. and as a function of pressure up to 50,000 psi at 317 and 593 C. Thermodynamic expressions are derived for the temperature and pressure coefficients of interfacial tensions in this system. A method is presented for obtaining relative tempmature and pressure coefficients from dihedral-angle data, and the resulting values are used in conjunction with the thermodynamic relations to calculate excess properties of the solid-liquid interface. Defining the position of the solid-liquid interface by the condition that the excess concentration of lead is zero, the excess concentration of nickel and the excess entropy at the solid-liquid interface are: where y(593) is the interfacial tension of the nickel grain boundary saturated with lead at 593C and zero pressure. These values are considered reliable to within a factor of two. While similar calculations are not possible for the nickel grain boundary, it is shown that the expwimental results imply that the excess concentration of nickel at the boundary and the excess entropy of the boundary are negative. THE temperature and composition dependencies of interfacial tensions in metal systems have been reported by several authors in the last 15 years.'-' No measurements of the effect of pressure on inter- facial tensions in metals have been reported, although measurements made on nonmetallic gas/liquid and liquid/liquid systems suggest that a measurable effect should exist.6-l2 The purpose of these experiments was to determine the influence of temperature and hydrostatic pressure on dihedral angles in the Pb-Ni system. The equilibrium dihedral angle is expressed as a ratio of interfacial tensions by2: where 8 is the dihedral angle, yGB is the Ni-Ni grain boundary tension, and SL is the solid Ni-liquid Pb interfacial tension. Three sets of ex- periments were run to determine: a) the effect of temperature from 371" to 816°C on the dihedral angle at zero pressure; b) the effect of pressure up to 50,000 psi on the dihedral angle at 371° and 593°C. THERMODYNAMICS The properties of interfaces of most direct concern are the interfacial tension, excess concentrations of various components at the interface and the excess entropy of the interface, S°. These quantities are defined following Gibbs. Consider an interface separating phases a and 0. Construct two surfaces C, and C such that all properties of phase a remain uniform up to C, and all properties of phase 0 remain uniform up to C. The region between C, and Cp is the interfacial region. Let a "dividing surface", D, be constructed in the interfacial region such that it passes through all points "similarly situated with respect to the condition of the adjacent matter."l3 Surface D divides the interfacial region into a portion a' adjacent to phase adjacent to phase . Let a closed curve, C, enclose an area A in D. Erect normal lines to D along C; these lines and the surfaces C,, Cp, and D then enclose volumes V and V' in the two halves of the portion of the

Jan 1, 1964

By Donald Jaffe, Michael B. Bever

The solidification of Al-Zn alloys (2 to 70 pct Zn was investigated at different rates of solidification. The resulting structures were studied; the amounts of nonequilibrium eutectic were measured and compared with the amounts calculated on the assumption of no diffusion in the solid. The compositions of the cored primary constituent were investigated by quantitative autoradiography after activation of the zinc by neutron irradiation. These compositions were also determined from microhardness values. IN a recent investigation of the soltdification of aluminum-rich AI-Cu alloys,' the amounts of non-equilibrium eutectic were measured and compared with the amounts calculated on the assumption of no diffusion in the solid. The compositions of the cored primary constituent were investigated by quantitative autoradiography. The work reported here extends the investigation of nonequilibrium solidification to the Al-Zn system in the range from 2 to 70 pct Zn. In addition to autoradiography, microhard-ness values were used to determine compositions on a micro scale. Solidification Experiments The alloys contained approximately 2. 6, 12, 20, 30, 50, and 70 wt pct Zn and the balance aluminum. According to published diagrams the eutectic reaction occurs at 382°C between the eutectic liquid (95 pct Zn), a (82.8 pet Zn), and $ 498.9 pct Zn). Solid-state reactions at lower temperatures (due to the miscibility gap between 350" and 275"C, the eutectoid at 275'C, and the precipitation from supcrsaturated a) did not affect this investigation. Even if they occurred to any appreciable extent, they did not alter the evidence pertaining to the solidification structures. The alloys had to be of high purity to avoid radioact~ve contamination during activation. The aluminum analyzed 0.015 pct Si, 0.009 pct Fe, less than 0.004 pct Cu, and less than 0.006 pct Mg with traces of sodium and titanium; the zinc was reported to be at least 99.99 pct pure with traces of iron and magnesium. The alloys were prepared under argon in an induction-heated, bottom-pouring furnace, and poured into a coated steel mold, which could be preheated to temperatures up to 700°C in order to control the rate of solidification. The pouring temperatures ranged from about 40" above the liquidus for 2 pct Zn alloys to about 130°C above the liquidus for 70 pct Zn alloys. As soon as the melt entered the mold, the readings of a thermocouple placed % in. above the bottom of the mold were recorded by a recording potentiometer. Cooling at the rate induced by the initial temperature of the mold was continued to a temperature 100°C below the liquidus; the mold with its contents was then quenched in icy brine. Quenching from a fixed interval below the liquidus was used to provide a standardized procedure, since the solidus and liquidus temperatures and the interval between them vary greatly over the composition range investigated. The temperatures from which the samples were quenched were below the equilibrium solidus, but under nonequilibrium conditions some liquid was still present. This residual liquid solidified during the quench. The samples measured 314 in. diam and 11, in. height. Drillings for chemical analysis were taken

Jan 1, 1957

By M. P. Tixier, K. S. Kunz

A method for the interpretation of temperature curves recorded in gas producing wells is described. One essen-tial feature of the method is a simple graphical construction which conveniently reflects the amount of gas flowing from a given producing formation. This method, applied in conjunction with the Induction Log and radioactivity logs, is valuable to determine the points of entry of gas and to estimate the over-all thickness of the producing zones and their respective contributions to the total production. The method in particular is helpful in evaluating the effect of fracturing operations. An outstanding result of the application of the method is to bring to the light the relative importance of sand-shale interfaces in the production of gas. The paper is illustrated with field examp1es. INTRODUCTION The electrical logging tools involving conventional systems are not applied in wells which do not contain water base mud (empty holes, or wells filled with oil base mud), because of the absence of electrical connection between the electrodes and the surrounding formations. It is, therefore, common practice in this case to use other methods which do not require the presence of a conductive fluid in the borehole: resistivity log with scratcher electrodes, Induction Log, radioactivity logs, temperature log. . . . Such conditions are encountered in some regions, as the San Juan Basin, N. Mex., where a technique of drilling gas wells, using gas as a drilling fluid, has been introduced in the last two years. By the middle of 1953, an appropriate method for the logging of these wells was devised on the basis of field tests and of theoretical studies. It is the purpose of the present paper to give a description of this method. In these wells the logging operations are performed during the process of gas production, so that the temperatures in the boreholes are strongly affected by the cooling due to the expansion of the gas. On the other hand, a special thermometer, with a high sensivity and a short time constant, has been recently made available, which has enabled much more detailed and accurate recordings of the borehole temperatures than with the conventional instruments. As a result of these two circumstances, the temperature log constitutes the essential element of the method, in making possible the detection of the gas producing zones, the definition of their boundaries, and the estimation of the respective contributions of each separate zone to the total production. The method also involves the radioactivity and Induction Logs, as auxiliary documents. These logs in the present instance are helpful in the determination of the reservoirs. However, the information they give in this respect is limited. This comes from the fact that, due to the absence of the MicroLog and/or MicroLaterolog and of the SP log, the estimation of formation factors and connate water salinities is somewhat conjectural. Furthermore, little help is obtained from the Neutron log for the evaluation of porosity and of formation factor because the variations of gas saturation affect the Neutron log in a way similar to the variations of porosity. It should be said also that even an exact knowledge of the gas saturation of the reservoir beds would not

Jan 1, 1956

By J. W. Martin, L. K. Singhal

Grain boundary M23CB precipitates have been shown to form by a process involving the migration of an austenite grain boundary, and each plate of precipitate is in parallel orientation with one of the austenite grains constituting the boundary. The carbide distribution and morphology appear to be sensitive to grain boundary mis orientation. Some areas of austenite grain bowzdary permit the development of an array of M,C, particles, some of which are in parallel orientation with one grain and some with the other grain constituting the boundary. Massive carbide at grain boundary triple points is also shown to be in parallel orientation with one constituent grain. PREFERENTIAL precipitation during aging of carbides of the type (Fe,Cr)23C6, usually written MZ3C6, in grain boundaries of quenched austenitic stainless steels has been widely recognized. M23C6 has a complex cubic crystal structure' which contains ninety-two metal atoms and twenty-four carbon atoms per unit cell. Less energy is involved in forming grain boundary precipitates than in the formation of intragranular precipitates, and the process is further enhanced by the accelerated diffusion rates in the boundaries and by the probability of segregation of chromium atoms and carbon atoms to the region of the grain boundaries during prior solution heat treatment in order to reduce lattice strain. Early electron micrographic studies2, 3 involving either extraction replica or normal replica techniques established the geometric or dendritic form of the carbide particles, although this approach led to dis- pute as to whether the particles grew within the plane of the boundary or grew into the matrix.4-6 More recent thin-foil studies' have claimed to identify a discontinuous precipitation process involving M23C6 at grain boundaries, and the object of the present work was to attempt to clarify the situation using modern electron micrographic and diffraction techniques. 1) EXPERIMENTAL 1.1) Material. The steel selected for this work had a base composition of 24 pct Ni-25 pct Cr-3 pct Ti and contained about 0.04 pct C. The full analysis if given in Table I. This alloy was in the form of strip which had been hot- and cold-rolled to a thickness of 0.6 mm. 1.2) Heat Treatment. Specimens 4 cm long by 1 cm wide were solution-heat-treated for 3 hr in argon at 1150°C, followed by water-quenching. Specimens were subsequently aged in vacuo at 750°C for periods up to 500 hr. 1.3) Preparation of Electron Microscope Specimens. The heat-treated strips were cut bv spark machining into discs of 3 mm diam and 0.6 mm thickness. he-discs were dished on both sides using an electrolytic jet of 15 pct HCl electrolyte at 80 v. Final electro-polishing of the discs was carried out using 10 pct perchloric acid, 20 pct glycerol, and 70 pct ethanol at 10 v. The current density was kept below 300 ma. cm"2 by cooling the electrolyte to 0" to 5°C. As soon as a small hole appeared, the electropolishing was stopped and the specimen was quickly washed with ethanol.

Jan 1, 1969

By R. Maddin, A. Lawley

Single crystal Mo-Re alloys (99.99+ purity), grown by electron bombardment floating zone heating, were deformed in tension at temperatures from -196° to +200°C. At -196oC, Mo-6 pet Re and Mo-20 pct Re alloys deform by slip on systems of the type (101) [1ll]. Above-78oC, the operative slip system is of the type (112) [111], (101) [1ll], or (211) [1ll], depending upon orientation. Mo-39 pct Re alloys deform by twinning and slip at all test temperatures with a (112) [111] type twinning system. Critical resolved shear stress for slip and twinning is calculated as a function of composition and temperature, and the mechanical properties compared with those of less Pure polycrystalline alloys. HEXAGONAL close-packed rhenium, c/a = 1.615, is highly soluble in molybdenum. The bee molybdenum-rich solid solution extends to approximately 42 at. pet Re* at 2500°C,' Fig. 1. Recent work on polycrystalline alloys has shown conclusively that the addition of rhenium to molybdenum improves both the fabricability and the low-temperature ductility.2"5 Similar behavior is observed for W-Re and Cr-Re alloys.5 Initially, Geach and Hughes2 found that the Mo-30 pct Re alloy could be cold rolled to approximately 90 pct reduction before the onset of cracking. The remarkable effect of the rhenium was later confirmed by Jaffee et al. 3-5 with an optimum condition of maximum strength combined with maximum ductility at the Mo-35 pet composition. At higher rhenium contents, the ductility was severely impaired due apparently to the presence of brittle tetragonal s phase, Fig. 1. In the Mo-35 pet Re alloy, at least 110 ppm (parts per million) oxygen could be tolerated before cold workability was reduced. By comparison, the corresponding tolerance figure in unalloyed molybdenum is ~ 10 ppm. The effect of rhenium was considered in terms of: 1) a reduction in oxygen solubility in the lattice; 2) a redistribution of intergranular oxide from grain boundary films to isolated spheres; and 3) the promotion of twinning as a further mode of plastic deformation. Paradoxically, twinning is often associated with brittle fracture in iron and the silicon irons.6'7 Work to date has been restricted to are-melted and powder metallurgy polycrystalline material of ~ 99.9 pet purity. The present investigation was initiated for the purpose of determining the mode and crystallography of plastic deformation of a series of bee Mo-Re alloy single crystals over a wide temperature range from -196o to +200°C. Using high-purity zone-melted material (~ 99.99 + pet purity), the specific role of rhenium in the molybdenum lattice may be understood more fully since effects due to grain boundaries and oxide redistribution will be absent. At the same time, the study provides a comparison of single and polycrystalline deformation behavior. EXPERIMENTAL TECHNIQUES A) Preparation and Purity of Single Crystals. Alloys in the form of either are-cast and swaged or sintered and ground bar, 0.120 in. diam, were obtained from the Chase Brass and Copper Co. Alloy single crystals ~ 8-in. long were grown from the

Jan 1, 1962

By R. S. Hooper

In attempting to describe recent mining developments at the Bunker Hill mine, it may be well to recall first the old days of hand mining when holes were laboriously drilled by hand to a maximum depth of three feet, and were shot one or two at a time, in order that the miner could take advantage of every slip, crack or bedding plane, and so save as much drilling as possible. Broken muck, of course, was loaded by hand shoveling into wheelbarrows or small cars, and heading advances or stope tonnages were governed by the number of men that could find room to work in any given place. The first big improvement over these old methods was the introduction of the reciprocating type of air-powered rock drill. This innovation, crude as it was, enabled the miners to set up a machine and drill a complete round of holes in one shift; but broken muck was still loaded by hand, and the size and rate of advance in headings were limited by time required to remove the broken rock. The next improvement of consequence was the appearance of the hammer-type rock drill, which greatly increased drilling speed over the reciprocating type, and made possible the completion of a full cycle in one shift, by the use of crossbars in headings, and permitted drilling and mucking to be carried on at the same time. Rock drills continued to improve as time passed, and finally the smaller and more efficient mucking machines appeared on the scene, and it became possible to muck out a round of broken rock and have a clean setup for one or more drill columns and machines. A complete cycle of mucking, drilling, and blasting was completed in one shift with an average advance of five feet. These conditions prevailed for several years, but as the mine grew deeper, the distances to transport the workers grew longer, and this fact together with the shortening of the working day, soon presented the problem of attempting to complete a cycle of operations in a shift of only six hours at the working faces. Anticipating this condition, the operating heads at the Bunker Hill had started an intensive study of more and better mechanization, and over a period of comparatively few years have adopted and placed in service methods and machines that make it possible for a three-man crew to consistently advance headings seven by nine feet in cross section, at the rate of eight feet, and more, per shift, doing all the mucking, switching, drilling and loading. These improvements consist of the following major items: I. The development of a light, flexible, easily transported jumbo equipped with pneumatic columns (Fig I), that has decreased the "setting up" and "tearing down" time an average of 11/2 hr per shift, Or 25 PCt of the available working time. These jumbos were developed at the Bunker Hill mine by members of the staff and consist of two pneumatic columns attached to a suitable carriage. They fold

Jan 1, 1949

By B. L. Landrum, P. B. Crawford

Theoretical and potentiometric model studies have been made of the effect of non-uniform lateral permeabilities on pattern sweep efficiency and production capacity in waterflood and gas-cycling programs. It is shown that a diflerence in directional permeability by a factor of three may result in a sweep efficiency of only 43 per cent for a five-spot pattern or a sweep of either 79 or 38 per cent for a direct line-drive square pattern, depending on the direction of the line-drive flood. Changes in the pattern conductivity varied from about 0.8 to 1.34 over this same permeability variation, depending on the pattern used. It is suggested that measurements be made to determine the possible magnitude and extent of the directional permeability phenomenon early in the field developinent and certainly prior to the initiation of any fluid-injection progmm. INTRODUCTION Irregularities in reservoir sand properties long have been a major difficulty to anyone attempting to explicitly describe the field characteristics of oil production. In particular, it is well known that vertical and lateral permeabilities often differ appreciably; however, the existence of large regions with lateral permeabflity variation is not widely recognized. A number of years ago, extensive studies were conducted by the Secondary Recovery Research Labcratory of the Pennsylvania Grade Crude Oil Association, primarily on the Bradford field. Johnson and Hughes' reported a permeability trend in the northeast-southwest direction. They indicated that flow in the preferred direction may be 25 to 30 per cent greater in that direction than in the northwest-southeast direction. They also reported that similar effects may be found in other nearby fields. The origin of the permeability variation has been discussed by Griffith Hutchinson' described the results of labora- tory tests on limestone cores, pointing out that per-ferential directional permeabilities were significant in one-half of 10 formations studied and that the average permeability ratio was 16:1. Barfield, Jordan and Moore analyzed the fluid-injection displacement performance in the Spraberry and reported that the effective ratio of permeability parallel to the major axis to the permeability perpendicular to this axis was 144:l and that it inclined along an angle of about 30". To prevent the reduction of sweep efficiency which would normally result from flooding or cycling in such reservoirs, well spacing could be varied from the customary square to a diamond-shaped pattern. Johnson and Hughes' presented a method for determining the desired shape. Another method will be discussed in detail in the next section. It is the purpose of this paper to investigate quantitatively the effect of directional permeability upon the sweep efficiency and production capacity of the five-spot and line-drive well patterns. Information currently in the literature will be applied to this particular problem and augmented by a potentiometric model study. It is stressed that the effects herein discussed may or may not be of great importance because field data on this phenomenon are far too scant to form such an opinion. It is suggested that, if conditions similar to those found by Johnson and Hughes frequently exist (as may well be the case), more consideration cdrtainly should be given to this problem.

By W. M. Phillips

Processing kaolin clays from the sedimentary deposits of Georgia and South Carolina is described in this article. While the major processing steps are touched on briefly, emphasis is given to the dewater-ing of the clay-water slurries (slips) formed in the processing of kaolin clays. The dewatering steps discussed include gravity settling, centrifugal dewatering, vacuum filtration and thermal drying. Particular attention is given to vacuum filtration and the variables affecting filtration of these kaolin clays. Kaolin consists essentially of the mineral kaolinite, which is a hydrated aluminum silicate (Al2O3 . 2SiO,). Commercial deposits of kaolin occur in several areas of the U. S., but approximately 90% of the kaolin produced in this country comes from Georgia and South Carolina. These deposits are of sedimentary nature and occur in a geological fall line in the Tuscaloosa formation at elevations between 300 and 450 ft above sea level. Over two million tons of kaolin clays are used by industry in the U. S. each year. A big percentage of this tonnage is used in the paper industry for coatings in making glossy and high quality grades of printing papers. In addition, large tonnages are used as pigments; as fillers for rubber, plastic and fertilizers; and in ceramics. Properties of kaolin that make it widely used in the above applications are its particle size fineness, natural whiteness, chemical stability and non-abrasiveness. In addition to these desirable properties, it is relatively inexpensive. The finer coating grades of clays range in price from $15 to $28 per ton while the coarser filler grades sell within a range of $7 to $13.50 per ton. Pure kaolin particles are small hexagonal flat platelets. Above the 2-p size, the particles usually consist of stacks of plates, while below the 2-p particle size they occur as individual flat, hexagonal plates. Since these individual platelet particles provide the most desirable coating and flow characteristics, major importance is given to particle size fractions of 2 p and smaller. Generally, coating grade clays are those with all particles smaller than 15 p and at least 70% of the particles less than 2p. These coating grades also have 50% or more of the particles smaller than 1 µ in size. The extremely fine grades of coating clay currently being produced approach the range of 100% smaller than 2p. The filler grades of kaolin have 100% of the particles passing 325 mesh but have less than 70% of their particles below the 2-p range. Fig. 1 is a schematic representation of the major processing steps involved in preparing kaolin clays for marketing. MINING All kaolin mining is open pit. The ratio of overburden to clay will average 3:1, but this ratio can, of course, be much higher depending upon the grade of the clay and the size of the deposit. Most of the commercially mineable deposits occur from 20 to 120 ft below the ground surface. Both draglines and pans are used in removing the overburden and mining the clay deposit itself. After mining, the most common method of transporting the clay to the processing plant is by blunging or re pulp-

Jan 1, 1963

By A. C. Stoddard

Early in the present century, prospect-ing was active in the area of the present Miami district. There were plenty of blue and green copper outcroppings, but very little ore of a grade that would stand shipping costs had been uncovered. Late in the first decade of the century, tunnels were driven into the north and south slopes of the Inspiration ridge, and two of them exposed disseminated copper sulphide ore. This was the original discovery of such ore on the ground of what eventually became the Inspiration Division of the consolidated company. By 1910 exploration of the ground area was well along and by 1911 underground development had been started. In the next few years a large tonnage of disseminated copper ore had been proven— sufficient to justify the expenditure of several million dollars in mine development and for mine equipment plus large sums for treatment plants. The mine and treatment plants were placed in production July 1, 1915. To Jan. I, 1945, there had been produced from the mines of the Inspiration Consoli-dated Copper Co., more than 106,000,000 tons of ore. Nearly all of this tonnage had been recovered by block caving. GeologIcal and EconomIc FActors Block caving is a mining system based on the fact that if a mass of rock has a sufficient number of fractures and planes of weakness the mass will disintegrate if the support of an area of sufficient size is taken away—that is, "undercut." If the material that caves away from the bottom of a block is drawn off the spalling is progressive. There is a limit to the speed of this spalling or caving action, which varies with the structure of the rock being caved. If the rock is drawn at a rate faster than the caving rate, and if this drawing is continued too long, a void may be created that could make a very dangerous condition if the area should drop as a block and force the air below the uncaved rock out through the raises and drifts. This can be a very destructive force. On the other hand, if the broken material is not drawn fast enough the swell of the material in place to broken material would pack the mass until it was almost solid again and could not be drawn without much blasting, or perhaps even partially undercutting again. Geologically therefore it would seem that any rock with seams and fractures would cave; but for block caving there should be enough seams and fractures in a limited area so that such an area will cave and produce a product that can be drawn safely, rapidly enough and at a cost justified by the value of the product being drawn. At the Inspiration the disseminated ores occur in two formations, the Pinal schist and the Schultze granite. There is no material difference in the grade of the ore formed in the schist and in the granite. The chief copper minerals are chalcocite, malachite, azurite and chrysocolla. Other copper minerals occur in limited quantity.

Jan 1, 1946

By W. N. Lacey, R. H. Olds, B. H. Sage

Samules of liquid and gas were obtained from the primary separator of a well in the Paloma field. The volumetric properties of the samples and of six systematically chosen mixtures of the samples were experimentally determined at 100°, 190°, and 250°F. at pressures up to 5000 lb. per sq. inch. From these data the influence ,of pressure and temperature upon the composition and specific volume of the bubble-point liquid and of the retrograde dew-point gas was established, The formation volumes and gas-oil ratios of the rnixtures investigated were calculated on the basis of the plant-product oil, which is defined as the isobutane and less volatile portion of each mixture. The results are presented in graphical and tabular form. The volumetric behavior of the mixture corresponding to that produced by the well at the time of sampling was determined for 235ºF., the reported reservoir temperature, by graphical interpolation of the experimental data with respect to composition and temperature. The results indicate that the well-production mixture probably existed as a gas at its retrograde dew point under the conditions of temperature and pressure believed to prevail in the producing zone at the time of sampling. The effect upon the phase behavim occasioned by the omission from the well-production mixture of certain components of intermediate molecular weight was investigated. In the first case, all of the isobutane and 11-butane, and substantially all of the iso-pentane, were removed from the mixture of trap samples corresponding to the well production. In the second case, all the propane, isobutane and n-butane, and substantially all of the isopentane, were removed. Both modifications led to considerable increases in the retrograde dew-point Pressure at 235ºF.; an increase of 558 lb. Per sq. in. above that of the unmodified well-production mixture in the first case, and an increase of 1208 lb. Per sq. in. in the second. It was concluded that the material? remaining after the removal of certain components of intermediate molecular weight could not be injected back into the reservoir in the saqe proportion in which they were produced without entailing appreciable loss of liquid material through condensation within the formation. Introduction Under the usual conditions of production practice, petroleum arrives at the surface of the earth in a physical state considerably different from that in which it existed in the underground reservoir. The relative rates of production and the properties of oil and gas measured at surface conditions do not constitute, in general, even a qualitative description of the fluids existing in the reservoir. The estimation of reserves and the attainment of optimum efficiency with regard to rate, quantity, and cost of production require accurate data concerning the physical properties of petroleum throughout large changes in pressure and temperature. Many schemes have been devised for predicting the behavior of propane, as it is encountered in nature? but the experimental work upon which these predictions are based has not, for the most part, been extended to the higher pressures that occur in practice, nor do these methods permit, as yet, the estima-

Jan 1, 1945

By R. S. Hooper

IN attempting to describe recent mining developments at the Bunker Hill mine, it may be well to recall first the old days of hand mining when holes were laboriously drilled by hand to a maximum depth of three feet, and were shot one or two at a time, in order that the miner could take advantage of every slip, crack or bedding plane, and so save as much drilling as possible. Broken muck, of course, was loaded by hand shoveling into wheelbarrows or small cars, and heading advances or stope ton¬nages were governed by the number of men that could find room to work in any given place. The first big improvement over these old methods was the introduction of the reciprocating type of air-powered rock drill. This innovation, crude as it was, enabled the miners to set up a machine and drill a complete round of holes in one shift; but broken muck was still loaded by hand, and the size and rate of advance in headings were limited by time required to remove the broken rock. The next improvement of consequence was the appearance of the hammer-type rock drill, which greatly increased drilling speed over the reciprocating type, and made possible the completion of a full cycle in one shift, by the use of crossbars in headings, and permitted drilling and mucking to be carried on at the same time. Rock drills continued to improve as time passed, and finally the smaller and more efficient mucking machines appeared on the scene, and it became possible to muck out a round of broken rock and have a clean setup for one or more drill columns and machines. A complete cycle of mucking, drilling, and blasting was completed in one shift with an average advance of five feet. These conditions prevailed for several years, but as the mine grew deeper, the distances to transport the workers grew longer, and this fact together with the shortening of the working day, soon presented the problem of attempting to complete a cycle of operations in a shift of only six hours at the working faces. Anticipating this condition, the operating heads at the Bunker Hill had started an intensive study of more and better mechanization, and over a period of comparatively few years have adopted and placed in service methods and machines that make it possible for a three-man crew to consistently advance headings seven by nine feet in cross section, at the rate of eight feet, and more, per shift, doing all the mucking, switching, drilling and loading. These improvements consist of the following major items: I. The development of a light, flexible, easily transported jumbo equipped with pneumatic columns (Fig I), that has decreased the "setting up" and "tearing down" time an average of 1 1/2 hr per shift, or 25 pct of the available working time. These jumbos were developed at the Bunker Hill mine by members of the staff and consist of two pneumatic columns attached to a suitable carriage. They fold

Jan 1, 1947