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By H. J. Ramey

The wellbore acts as a storage tank during drawdown and build-up testing and causes the sand-face flow rate to approach the constant surface flow rate as a function of time. This effect is compounded if non-Darcy flow (turbulent flow) exists near a gas wellbore. Non-Darcy flow can be interpreted as a flow-rate dependent skin effect. A method for determining the non-Darcy flow constant using this concept and the usual skin effect equation is described. Field tests of this method have identified several cases where non-Darcy flow was severe enough that gas wells in a fractured region appeared to be moderately damaged. The combination of wellbore storage and non-Darcy flow can result in erroneous estimates of formation flow capacity for short-time gas well tests. Fortunately, the presence of the wellbore storage eflect permits a new analysis which can provide a reasonable estimate of formation flow capacity and the non-Darcy flow constant from a single short-time test. The basis of the Gladfelter, Tracy and Wilsey correction for wellbore storage in pressure build-up was investigated. Results led to extension of the method to drawdown testing. If non-Darcy flow is not important, the method can be used to correct short-time gas well drawdown or build-up data. A method for estimation of the duration of wellbore storage effects was developed. INTRODUCTION In 1953, van Everdingen and Hurst generalized results published in their previous paper3 concerning wellbore storage effects to include a "skin effect", or a region of altered permeability adjacent to the wellbore. Later, Gladfelter. Tracy and Wilsey4 presented a method for correcting observed oilwell pressure build-up data for wellbore storage in the presence of a skin effect. The method depended upon measuring the change in the fluid storage in the wellbore by measuring the rise in liquid level. To the author's knowledge, application of the Gladfelter, Tracy and Wilsey storage correction to gas-well build-up has not been discussed in the literature. It is, however, a rather obvious application. Gas storage in the wellbore is a conlpressibility effect and can be estimated easily from the measured wellbore pressure as a function of time. Several approaches to the wellbore storage problem have been suggested. As summarized by Matthews, it is possible to minimize annulus storage volume by using a packer, and to obtain a near sand-face shut-in by use of down-hole tubing plug devices. Matthews and Perrine have suggested criteiia for determining the time when storage effects become negligible. In 1962, Swift and Kiel' presented a method for determination of the effect of non-Darcy flow (often called turbulent flow) upon gas-well behavior. This paper provided a theoretical basis for peculiar gas-well behavior described previously by Smith. Recently, Carter, Miller and Riley observed disagreement among flow capacity k,,h data determined from gas-well drawdown tests conducted at different flow rates for short periods of time (less than six hours flowing time). In the original preprint of their paper, Carter et al. proposed that the discrepancy in flow capacity was possibly a result of wellbore storage effects. Results of an analytical study of unloading of the wellbore and non-Darcy flow were recorded by carter.14 In the final text of their paper, Carter et al.!' stated that they no longer believed wellbore storage was the reason for discrepancy in their kgh estimates. In view of the preceding, this study was performed to establish the importance of non-Darcy flow and well-bore storage for gas-well testing. In the course of the study. a reinspection of the previous work by van Everdingen' and Hurst' was made, and the basis for the Gladfelter, Tracy and Wilsey' wellbore storage correction was investigated and extended to flow testing. WELLBORE STORAGE THEORY As has been shown by Aronofsky and Jenkins,11-12 Matthews," and others, flow of gas can often be approximated by an equivalent liquid flow system. The following developnlent will use liquid flow nomenclature to simplify the presentation. Application to gas-well cases will be illustrated later. First, we will use the van Everdingen-HursP treatment of wellbore storage in transient flow to establish (1) the duration of wellbore storage effects, and (2) a method to correct flow data for wellbore storage. DURATION OF WELLHORE STORAGE EFFECTS When an oil well is opened to flow. the bottom-hole pressure drops and causes a resulting drop in the liquid level in the annulus. If V. represents the annular volume in cu ft/ft of depth, and p represents the average density of the fluid in the wellbore, the volume of fluid at reservoir conditions produced from the annulus per unit bottom-hole pressure drop is approximately: res bbl-- (V, cu ft/ft) (144 sqin./sq ft) psi -(5.615 cu ft/bbl)(pIb/cuft) ........(I)

Jan 1, 1966

By E. B. Olds, B. P. Burt

The mines of the Consolidated Gopper-mines Corporation are at Kimberly, in the Robinson mining district, White Pine County, Nevada. The blanket-like ore body is a disseminated copper deposit occurring in monzonite porphyry and, in general, is thoroughly fractured, altered, and soft. Contained in the porphyry ores of the extreme westerly end of the ore body are pendants of hard garnetized limestone. A younger monzonite porphyry underlies the ore-bearing porphyry, which in turn rests on limestone and shale. Block caving is the standard method of mining. Because of the undulating top and bottom contours of the ore body, the main haulage level was selected and driven at an elevation calculated to be the most economic depth below the major tonnage sections of ore. Fig. I shows a general section of the Emma Nevada ore body taken through its long axis, which lies roughly in an east-west direction. Mine openings in either type of porphyry require heavy timbering and constant maintenance and repair, particularly in horizons at or near the ore body contact. Where the ore lies close to the haulage level, slusher hoists and scrapers are used to transport horizontally the ore to the main haulage drift (Fig. 2). For the extraction of high-lying ores, a system of branch raises is used; and the ore is mined by gravity. Slushing methods are used also on the high-lying ore-body fringes. Slusher drifts are often driven from the fringe branch raises that have already served their purpose, in order to minimize the cost of the preparatory work in mining the thinner portions of the ore body (Figs. 3 and 4). When a block of ore is developed and undercut, it is economical to mine it as rapidly as the ore will cave efficiently; and this procedure often presents safety problems because of men with equipment working in a relatively congested area. The single-track main haulage drift is about 11/2 miles long, and lateral haulage drifts are driven under the ore body at intervals determined by the height of the ore body above the haulage level. In order to minimize repair and maintenance, the

Jan 1, 1949

By Robert B. Bossler, Parke A. Dickey

The presence of connate water in oil sands is of far greater practical significance in secondary oil-recovery operations than it is in primary operations. The percentage saturations of oil, water, and gas in a depleted field determine whether it will be economically possible to recover oil by secondary methods, and whether water-flooding or gas-driving, or either, will be successful. It is suggested that economic recovery of oil by secondary water-flooding can occur only when a rich bank of oil is formed by the encroachingm water. If the sand has a greater effective permeability to water than it has to oil before flooding, a bank will not be formed, and water-flooding will not be successful, although gas-driving may be. Published results of laboratory work indicate that the effective permeability of a sand to oil and water depends primarily on the saturation of the sand by these phases. They also indicate that a small difference in relative saturation produces a large difference in effective permeability to the phase in question. There thus exists a critical range of saturations, wherein a small change in oil and water content of the sands will make water-flooding possible or impossible. In gas-drive operations the water saturation is less critical but no less important. The presence of connate water in a sand increases the proportion of the residual oil that may be recovered by gas drive. Sands containing oil saturations too low and water saturations too high to make water-flooding possible can often be subjected to gas drive with economic recovery of oil. The results of laboratory work on test samples that do not contain water cannot be applied to normal field operations. More tests on cores containing water as well as oil are desirable, and the improvement of coring technique is necessary. However, sufficient data are already available to enable an operator to use core data intelligently in estimating the chances of a secondary oil-recovery program. Introduction In recent years laboratory work has led to a much better understanding of the principles of oil-reservoir performance. The general principles of the expulsion of oil from sandstone by gas or water were developed by geologists of the Second Geological Survey of Pennsylvania in the 1870lsl but only recently has the mechanism of gas or water drive been intensively investigated. Most published articles have large the facts established in the labora tory to the primary production of oil from flush fields- This Paper is not based on any new observations, but is an attempt to apply some of the conclusions obtained in the laboratory and described in the literature to the recovery of oil from depleted pools by secondary methods. One of the most important factors that determine whether or not a secondary-recovery operation is economically successful is the ratio of injected fluid to oil recovered. This ratio may be expressed as the over-all or cumulative gas-oil ratio if gas is the driving medium, or water-oil ratio if water is the driving medium. Recent theoretical and experimental work has shown that the relative amounts of

Jan 1, 1944

By Parke A. Dickey, Robert B. Bossler

The presence of connate water in oil sands is of far greater practical significance in secondary oil-recovery operations than it is in primary operations. The percentage saturations of oil, water, and gas in a depleted field determine whether it will be economically possible to recover oil by secondary methods, and whether water-flooding or gas-driving, or either, will be successful. It is suggested that economic recovery of oil by secondary water-flooding can occur only when a rich bank of oil is formed by the encroachingm water. If the sand has a greater effective permeability to water than it has to oil before flooding, a bank will not be formed, and water-flooding will not be successful, although gas-driving may be. Published results of laboratory work indicate that the effective permeability of a sand to oil and water depends primarily on the saturation of the sand by these phases. They also indicate that a small difference in relative saturation produces a large difference in effective permeability to the phase in question. There thus exists a critical range of saturations, wherein a small change in oil and water content of the sands will make water-flooding possible or impossible. In gas-drive operations the water saturation is less critical but no less important. The presence of connate water in a sand increases the proportion of the residual oil that may be recovered by gas drive. Sands containing oil saturations too low and water saturations too high to make water-flooding possible can often be subjected to gas drive with economic recovery of oil. The results of laboratory work on test samples that do not contain water cannot be applied to normal field operations. More tests on cores containing water as well as oil are desirable, and the improvement of coring technique is necessary. However, sufficient data are already available to enable an operator to use core data intelligently in estimating the chances of a secondary oil-recovery program. Introduction In recent years laboratory work has led to a much better understanding of the principles of oil-reservoir performance. The general principles of the expulsion of oil from sandstone by gas or water were developed by geologists of the Second Geological Survey of Pennsylvania in the 1870lsl but only recently has the mechanism of gas or water drive been intensively investigated. Most published articles have large the facts established in the labora tory to the primary production of oil from flush fields- This Paper is not based on any new observations, but is an attempt to apply some of the conclusions obtained in the laboratory and described in the literature to the recovery of oil from depleted pools by secondary methods. One of the most important factors that determine whether or not a secondary-recovery operation is economically successful is the ratio of injected fluid to oil recovered. This ratio may be expressed as the over-all or cumulative gas-oil ratio if gas is the driving medium, or water-oil ratio if water is the driving medium. Recent theoretical and experimental work has shown that the relative amounts of

Jan 1, 1944

By W. M. Peirce

Commencing in 1922, each year a lecture has been presented to the Institute of Metals Division at this February meeting. The range of subjects has been very- broad. Some speakers have dealt with the most advanced work in the very heart of the science of physical metallurgy. Others have stimulated our imaginations by discussing the most recent progress in related fields of science. Others have told us of the latest art, which is at any moment of greater practical importance than the latest science, of metals. I feel that this broad precedent in the choice of subjects will justify my choosing to talk about some of the prosaic details of how, during the last generation, industry has effectively organized research to accelerate progress in our own and all other fields of science and related art. A number of years ago I visited one of this country's well-known research laboratories and had the pleasure of chatting for a few minutes with its equally well-known director. Being particularly interested at the time in the organization problems connected with industrial research, I broached that subject. My host stated in effect that he didn't believe in organized research. He was, of course, resorting to a rhetorical hyperbole. to pain: out the danger of overorganization which can so easily drift into regimentation and destroy individual initiative. Actually nearly all of us, much as we cherish our personal freedom of action, believe in organization because the history of progress in every field of human activity has been a history of men learning to work together, to cooperate, to create an efficient division of labor. We use organization to achieve this coordination. At the same time our form of organization must not stifle individual initiative or it will prove a deterrent rather than an aid to accomplishment. Research, too, must be organized for greatest achievement but especial skill and care are perhaps needed to avoid stifling the initiative of the individual workers. I have, of course, followed with keen interest and much benefit the vast amount . that has been said and written on this subject in the past twenty years but I still find new stimulation in discussions with my good friends working in this field. It is my hope that this discussion may serve a like purpose. It would be ungracious not to make due acknowledgment to the many able contributors to this particular phase of human progress, but their very number and the great volume of their writing makes it impossible to trace to any one individual a particular significant and valuable idea. I shall content myself therefore with this general acknowledgment and with acknowledgment of the specific debt that every research man owes to those who have so ably kept before the public, and in particular before industrial executives, the place of research in the modern scheme of things' Because of the legitimate publicity thus given to research, the day is past when any

Jan 1, 1944

By L. J. Dijkstra, R. J. Sladek

IN earlier work the effect of manganese on the general behavior of nitrogen in iron was the subject of a careful examination by Fast.' Part of the investigation was made, in collaboration with one of the present authors (L.J.D.), by using the internal friction method. This technique, which has been described elsewhere,' showed some significant changes in the properties of Fe-N alloys by the addition of a small amount of manganese namely: 1—Under standard conditions the maximum of the nitrogen peak in pure iron appears around 20 °C and the half width is about 27 °C. By addition of 0.5 atomic pct Mn a general broadening of the internal friction peak occurs. The half width is increased by about 9°C. Moreover, a shift of the maximum of about 5°C toward a higher temperature takes place, Fig. 2. 2—The precipitation of nitrogen from the supersaturated solution, measured, e.g., at 200 °C, was inhibited by the addition of the amount of manganese given in effect 1. The broadening of the nitrogen peak was confirmed in more recent work3 on samples which were prepared from Westinghouse Puron iron. The effect of manganese on the rate of precipitation, however, was much less striking than in the earlier work' based on Philips high purity iron. Theory To explain the first change in properties just referred to, effect 1, the following two assumptions were made:' First, every manganese atom in sub-stitutional solid solution creates around it six interstices located between an iron and a manganese atom, as is evident from Fig. 1. These interstices, conveniently called Fe-Mn interstices, have for nitrogen a free energy level which is AG* lower than the normal Fe-Fe interstices between two iron atoms. For such low concentrations of manganese as 0.5 atomic pct, the possibility that two manganese atoms will be nearest neighbors can be disregarded. Second, it is assumed that in addition to the normal relaxation time TFe at least one new relaxation time, Mn, Fe, enters in the phenomena which is associated with the elementary diffusion jumps between a Fe-Mn interstice and an adjacent Fe-Fe interstice. Fig. 1 gives schematically the free energy for a nitrogen atom as a function of its position along the line ABC. A tentative analysis of the nitrogen peak in a 0.5 pct Fe-Mn alloy based on these assumptions has been made in Fig. 2. The dotted curve with a maximum at 22°C is caused by jumps between Fe-Fe interstices, the dotted curve with maximum at 32°C by jumps between an Fe-Mn and an Fe-Fe interstice. The two effects added together give the dash-dot internal friction curve for the alloy. In the following these two components will be referred to as the normal peak at 22°C and the abnormal one. (The small secondary peak at

Jan 1, 1954

By W. M. Peirce

Commencing in 1922, each year a lecture has been presented to the Institute of Metals Division at this February meeting. The range of subjects has been very- broad. Some speakers have dealt with the most advanced work in the very heart of the science of physical metallurgy. Others have stimulated our imaginations by discussing the most recent progress in related fields of science. Others have told us of the latest art, which is at any moment of greater practical importance than the latest science, of metals. I feel that this broad precedent in the choice of subjects will justify my choosing to talk about some of the prosaic details of how, during the last generation, industry has effectively organized research to accelerate progress in our own and all other fields of science and related art. A number of years ago I visited one of this country's well-known research laboratories and had the pleasure of chatting for a few minutes with its equally well-known director. Being particularly interested at the time in the organization problems connected with industrial research, I broached that subject. My host stated in effect that he didn't believe in organized research. He was, of course, resorting to a rhetorical hyperbole. to pain: out the danger of overorganization which can so easily drift into regimentation and destroy individual initiative. Actually nearly all of us, much as we cherish our personal freedom of action, believe in organization because the history of progress in every field of human activity has been a history of men learning to work together, to cooperate, to create an efficient division of labor. We use organization to achieve this coordination. At the same time our form of organization must not stifle individual initiative or it will prove a deterrent rather than an aid to accomplishment. Research, too, must be organized for greatest achievement but especial skill and care are perhaps needed to avoid stifling the initiative of the individual workers. I have, of course, followed with keen interest and much benefit the vast amount . that has been said and written on this subject in the past twenty years but I still find new stimulation in discussions with my good friends working in this field. It is my hope that this discussion may serve a like purpose. It would be ungracious not to make due acknowledgment to the many able contributors to this particular phase of human progress, but their very number and the great volume of their writing makes it impossible to trace to any one individual a particular significant and valuable idea. I shall content myself therefore with this general acknowledgment and with acknowledgment of the specific debt that every research man owes to those who have so ably kept before the public, and in particular before industrial executives, the place of research in the modern scheme of things' Because of the legitimate publicity thus given to research, the day is past when any

Jan 1, 1944

By V. R. Garfias, H. J. Hawley

FoR a number of years the senior author has been interested in the various geologic and engineering problems involved in the development of the petroliferous districts of northeastern Mexico, having in a previous paper* endeavored to present a summarized statement of the information relating to the geology and soil resources of this region. Of the many interesting geologic phenomena, perhaps those which have been the object of most speculation relate to the igneous intrusions which, in places, have a controlling influence on the accumulation of oil in commercial quantibies, a relationship which has been tentatively explained by various observers with as many interestingly different views. The authors of the present paper aim to record, in the course of a general discussion of the various viewpoints, some additional data, and present further tentative conclusions with a view to rounding out an up-to-date summary of the subject. The greater part of the area in question lies in the State of Vera Cruz, only a northwest fraction being in the State of San Luis Potosi. Vera Cruz is bounded on the north by the State of Tamaulipas, the northernmost of the Mexican States along the Gulf. The topography of the States of Tamaulipas and Vera Cruz and of Texas and Louisiana to the north, is controlled by the Gulf coastal plain which in northern Vera Cruz has an average width of about, 60 miles, the transitional topography between that of the rugged Banks of the Sierra and the lowlands of the coast being made up of a series of terraces and irregular hills and valleys. Geology and StRucture The greater part of the mainland of Mexico is made up of Tertiary and later effusive rocks and of sedimentaries of Cretaceous age. The igneous rocks form a belt from 150 to 300 miles wide, spurs of which shirt

Jan 1, 1918

By G. L. Hassler, E. Bruner

An apparatus and method is described whereby the relation between saturation and capillary pressure under decreasing saturation can be quickly determined for small core samples. The initially saturated core is cen-trifuged at increasing rates and the average saturation is measured at each rate with the aid of a stroboscope device. A theory and calculation procedure is given whereby the accelerations and saturation values can be converted into a true curve of capillary pressure versus saturation. The present work differs from previously described use of the centrifuge to obtain capillary-pressure curves of core samples3 in that the core is centrifuged alone, so that the whole range of saturations required by the properties of the sample and the radially varying centrifugal force occurs within the sample. The calculation procedure nevertheless secures correct results from simply obtained values of the average saturation. The apparatus described was developed in connection with studies of capillary pressure and wetting of oil-field rocks, and the paper provides the apparatus background for a previous publication' dealing more fully with the uses and implications of the data in petroleum engineering. The method is applicable, however, to general combinations of immiscible fluids and porous or comminuted solids, and may be useful in other fields. Introduction The importance of capillary phenomena in determining the behavior of liquids in porous media has long been recognized. The concept of capillary Pressure was early formulated, and in recent Years discussions of the application of the laws of capillarity to oil field problems have appeared.l-3 One reason why progress in the application of capillary phenomena to the solution of problems of reservoir mechanics has not been more rapid has been the lack of a, satisfactory technique for measuring the capillary pressures in reservoir rocks. It is the principal purpose of this paper to describe a method by which the relation between capillary pressure and saturation can be determined for small consolidated core samples which have been extracted and resaturated, Capillary Diaphragm Perhaps the most direct way to measure the capillary pressure in a rock is to make piezometric contact with the wetting liquid through a diaphragm of porous material with high displacement pressure saturated with the liquid in question.3-6 The liquid in the diaphragm assumes the pressure of the liquid in the core, which can then be measured with a manometer, while the atmospheric air is prevented by capillarity from entering the diaphragm and affecting the pressure measurements as long as the displacement pressure of the diaphragm is not exceeded. With an apparatus of the type illustrated schematically in Fig. I, the relation between capillary pressure and saturation can be measured for a small core sample by starting with the core saturated 100 per cent, applyillg successively greater suctions

Jan 1, 1945

By S.H. Ash, P.S. Miller

Extensive and diversified resources justify large populations and great industries. To carry on the business of commerce and meet the demands of large populations, the utilization of tunnels in some form for transportation purposes constitutes an important link in modern civilization. The driving of tunnels has been appropriated by the tunneling branch of the heavy-construction industry, and the progressive steps taken by modern tunnel builders were not even dreamed of 50 years ago. Great strides have been made toward more rapid progress in tunneling in the United States during the past I0 years. Tunneling consists of a definite cycle of operations developed from ideas that are crystallized and translated into action programs through various engineering phases that begin with the first preliminary survey and do not end until the job is completed. Once the line of the bore is established and a time set for the completion of the work, the face must advance according to estimates prepared before the work commences. This schedule must be followed in regular sequence from the moment the drills start against a new face of rock until they are ready again to drill the Succdeding face, constituting a round. Mining is largely tunneling carried on under conditions often more inherently hazardous than actual tunnel construction, but for various reasons" tunne1ing is more hazardous than mining in any branch of the mineral industry. On the other hand, obstacles are sometimes encountered in heavy-construction tunneling projects that when met in mining enterprises do not offer comparable tasks to avoid or overcome them. One is the existence of water under high pressures. In mining enterprises, various alternatives offer a solution in driving a tunnel, even to the extent of its discontinuance or the abandonment of the mine, but a "construction" tunnel usually must go forward because some important project depends largely if not entirely upon it. This paper describes an unusual method of driving a water-supply tunnel through rock carrying water under pressures and conditions that did not permit the use of ordinary tunneling methods. The Delaware Aqueduct The new Delaware aqueduct is a Manhattan project of some magnitude; when regular it will contain what probably will be, for some time to come, the longest tunnel in the world. Various features in its construction are currently described in the trade journals of the construction industry, and informative engineering details are given in the Delaware Water Supply News, published twice a month by the Board of Water Supply of the City of New York. Work was begun on this project on March 24, 1937. The tunnel will convey water from reservoirs at the headwaters of the Delaware River to the City of New York.

Jan 1, 1943

By P. S. Miller, S. H. Ash

Extensive and diversified resources justify large populations and great industries. To carry on the business of commerce and meet the demands of large populations, the utilization of tunnels in some form for transportation purposes constitutes an important link in modern civilization. The driving of tunnels has been appropriated by the tunneling branch of the heavy-construction industry, and the progressive steps taken by modern tunnel builders were not even dreamed of 50 years ago. Great strides have been made toward more rapid progress in tunneling in the United States during the past I0 years. Tunneling consists of a definite cycle of operations developed from ideas that are crystallized and translated into action programs through various engineering phases that begin with the first preliminary survey and do not end until the job is completed. Once the line of the bore is established and a time set for the completion of the work, the face must advance according to estimates prepared before the work commences. This schedule must be followed in regular sequence from the moment the drills start against a new face of rock until they are ready again to drill the Succdeding face, constituting a round. Mining is largely tunneling carried on under conditions often more inherently hazardous than actual tunnel construction, but for various reasons" tunne1ing is more hazardous than mining in any branch of the mineral industry. On the other hand, obstacles are sometimes encountered in heavy-construction tunneling projects that when met in mining enterprises do not offer comparable tasks to avoid or overcome them. One is the existence of water under high pressures. In mining enterprises, various alternatives offer a solution in driving a tunnel, even to the extent of its discontinuance or the abandonment of the mine, but a "construction" tunnel usually must go forward because some important project depends largely if not entirely upon it. This paper describes an unusual method of driving a water-supply tunnel through rock carrying water under pressures and conditions that did not permit the use of ordinary tunneling methods. The Delaware Aqueduct The new Delaware aqueduct is a Manhattan project of some magnitude; when regular it will contain what probably will be, for some time to come, the longest tunnel in the world. Various features in its construction are currently described in the trade journals of the construction industry, and informative engineering details are given in the Delaware Water Supply News, published twice a month by the Board of Water Supply of the City of New York. Work was begun on this project on March 24, 1937. The tunnel will convey water from reservoirs at the headwaters of the Delaware River to the City of New York.

Jan 1, 1943

By R. L. Braun, D. L. Leach

Laboratory experiments simulating in-situ copper recovery from primary sulfide ores in sulfuric acid systems pressurized with oxygen are reported. Copper extraction and acid consumption data are correlated with temperature in the range 50 to 150°C and quenched pH in the range 0.25 to 2. Adverse changes in the chemical composition of the leach solution and the formation of gangue-mineral alteration products and secondary sulfides can severely limit the extraction of copper above 90°C. Keeping the pH below the self-buffered value of about 2 and the temperature below about 110°C produces the maximum extraction rates. Forcing the pH too low not only results in excessively high acid consumption but may also limit the extraction of copper at temperatures above 100°C.

Jan 1, 1977

By J. A. Richardson

J. A. RICHARDSON[t]-Mr. Stuckey's account of the geology of the kaolins of North Carolina suggests that they exhibit some features similar to those of the Malay Peninsula. About one half of British Malaya (some 26,000 square miles) is occupied at the surface by igneous rocks, of which granite and its associated derivatives constitute fully 90 pct. The average granite is a biotic variety. It is predominantly potassic but carries, in addition, notable amounts of soda and lime so that albite and albiteoligoclase are generally common constituents of the rock. The minor derivatives from granite "magma" likewise include potassic and sodi-potassic members. Decomposition of the granitic rocks has led to the formation of kaolin in many localities, but, in general, the deposits are rather small and, at present, none is exploited commercially. True primary or residual kaolins (as defined by Stuckey; p. 48 Vol. 173, p. 2 TP 2219) have been developed from feldspar veins, pegmatites and from other granitic differentiates which cut through the larger masses of granite; they are usually small and narrow. Kaolin has been derived from aplite, quartz porphyry, quartz micro-porphyry, felsites and microgranites belonging to a complex known as the Chegar Perah-Pulai intrusion in northwest Pahang and southwest Kelantan. The bulk of the component rocks has been more or less strongly sheared. Kaolin-like end products have been formed from both sheared and nonsheared varieties. Kaolin has been formed also by the complete breakdown of trondjemite flanking the northwestern and western margins of the complex Bukit Ranjut syenite intrusion in northwest Pahang. These trondjemites range in composition from essentially quartz-free albiteplagioclasites to quartz-free microcline rocks; they are, in effect, the syenitic homologues of white sodic and potassic granite-aplites. The granites in Malaya have generally undergone more or less severe surficial weathering leading to the production of a spongy and rather cellular or a soft "mealy" material (sandy clay) down to depths of about 100 ft; in places the granite is strongly decomposed down to 150 ft. There has occurred, therefore, widespread partial kaolinization, but, in general, no extensive deposits of good quality kaolin seem to have been formed by these processes of decay. Frequently, the katamorphic processes of desilicification have advanced beyond the production of kaolin towards the formation of lateritic end products. The more important Malayan kaoiins seem to be confined to the western alluvial plains, particularly in areas either where granite crops out at surface, or where it forms the bedrock of the alluvium. There are numerous excellent examples around Gopeng and elsewhere in the Kinta Valley of Perak. Such kaolins belong to Stuckey's groups of secondary deposits, and, like them, these also may be bedded. Field observations have established the existence of what for want of a better name is referred to by the Malayan Geological Survey as "granite wash." It is believed that granite, undergoing extensive deeply penetrative and probably rather rapid destruction under humid tropical weathering (temperature around 90°F; rainfall about 100 in. per annum; high humidity) "flowed," was moved by "creep" and, in addition, probably slumped in large waterlogged masses of sandy clay from topographic salients onto the adjacent flats. Either during this period of transmigration or later when the sludged granite detritus, after having more or less come to rest, was attacked by flowing water, differential sorting and erosion took place with the result that the resorted debris was moved and later deposited as bedded alluvium. In this way, banded "granite wash" was produced comprising alternating bands of clayey sand (resorted granite sludge) and white

Jan 1, 1947

By A. W. Bethune, L. M. Pidgeon

The equilibrium vapor pressure of zinc has been determined over the systems: ZnS(s) + Fe(s) = FeS(s) + Zn (vapor) and ZnS(s) + 2Cu(s) = Cu2S(s) + Zn (vapor) by reacting the components in an evacuated tube containing a thin copper fiber, and allowing equilibrium to be established with respect to the brass formed and the zinc in the vapor phase. The composition of the brass formed was determined and equilibrium vapor pressure values obtained from existing data. Between 850' and 1000°C, values for the first reaction ranged from 8 to 58 mm Hg; for the second reaction from 1.8 to 22 mm Hg. THE direct reduction of metallic sulphides may be indicated by an equation of the form MS + X = XS + M [1] where X is some suitable reducing agent. In the case where M is a metal of relatively high volatility, the use of vacuum will displace the equilibrium to the right at comparatively low temperatures in the face of the usually unfavorable thermochemistry. For this technique to be feasible, MS, X, and XS, must of course be nonvolatile compared to M. In this regard, zinc becomes an obvious metal both from the point of view of its volatility and the fact that most commercial ore deposits of this metal occur as the sulphide, and its direct reduction would avoid the expensive roasting process necessary prior to present day reduction methods. Two reducing agents are of interest, namely copper and iron, with the former having the added attraction of being relatively easily regenerated by oxidation in the copper converter. The possibility of these reactions has been considered before. Imbert1 patented a process whereby zinc sulphide was reduced by either copper or iron. The process as described took place at atmospheric pressure and, at the high temperatures required, the system was molten, resulting in the formation of a matte with the consequent reduction in the activities of the reactants. Peterson2 did further experimental work on these reactions and, although promising results were obtained on a small scale, attempts to increase the size of the furnace led to excessive "blue powder" formation. The early workers failed to realize the large reduction in temperature afforded by the use of vacuum and its desirable results. More recently, the direct reduction of zinc sulphide by iron has been the subject of a thermody-namic investigation by Kelley,3 and Gross and War-rington' have studied the kinetics of the reaction in the temperature range 900" to 1000°C, their experiments being conducted using vacuum and indicating that the reaction would proceed practically to completion in 1 to 3 hr, depending on the temperature. A qualitative examination of the system ZnS-Cu carried out at this University indicated that 98 pct of the theoretical zinc in the charge could be recovered in 1 hr at 1000°C when operating under reduced pressure. The purpose of this research program was to study the equilibrium of the two reactions. During the investigation, reference to the experimental work of Schenk5 was found but, due to lack of detail in the report, it was felt that it would be desirable to continue the equilibrium measurements. Selection of Method The measurement of vapor pressure of metals presents obvious problems resulting from the high temperatures which must be employed. In the present case, the production of the "reaction pressure" introduces a further difficulty since a chemical reaction must proceed before any metal vapor pressure is produced, resulting in depletion of the re-

Jan 1, 1954

By Klaus Detert

Fifteen and 18 pct Ni maraging steel and several binavy and ternary alloys of the iron-rich corner of the Fe-Co-Ni system have been studied. After annealing in the austenite range, these alloys were deformed slightly by cold rolling and subsequently aged. Compavison of experimental measurements at various processing stages indicates that small degrees of deforn~ation (5 to 10 pct reduction in thickness) do not influence hardness and strength or the aging kinetics. Electrical resistivity and ductility are somewhat redu]ced and the coercive force is substantially lower when compared to identical samples which were not deformed. The results are explained in terms of retained austenite which transforms into martensite with the small amount of deformation. RECENTLY there has been increasing interest in maraging steel for applications in electric power generators requiring a high ratio of power to weight.' Fifteen pct Ni maraging steel has been investigated to evaluate its properties and performance for application as high-strength magnetic rotor steel,' and a thorough investigation of the precipitation and transformation processes in this alloy has been conducted in this laboratory.3 The influence of deformation, which preceded the aging treatment, was also studied. It was found that a small deformation in the order of 5 pct has a rather striking effect in reducing the coercive force. Other interesting effects on the properties caused by such deformation have led to the more detailed studies reported herein. EXPERIMENTAL METHOD The methods used to produce the samples from 15 pct Ni maraging steel have been described elsewhere.3 The general procedure of hot forging and cold rolling to sheet has been followed. The composition is included in Table I which also contains the composition of the 18 pct Ni maraging steel grade 250 studied. More data about the material and the processing of the 18 pct Ni maraging steel have been recently reported.4 The experimental alloys of binary and ternary Fe-Ni-Co alloys were made by levitation melting in an argon atmosphere and casting into rod-shaped ingots 7 mm thick weighing 20 g. From these ingots 25-mm-long rods were machined to study the phase transformation by a dilatometer. These rods were then cold-rolled to strips, 2.4 mm thick. Annealing for austenitizing was done in tube furnaces in an argon or helium atmosphere followed by cooling in the water-cooled portion of the tube. Aging was done in a salt bath containing a neutral blend of Alkali nitrates and nitrites. Vickers hardness was measured using a load of 50 kg for 15 sec. Tensile tests were carried out on a hard beam tensile tester at a strain rate of 5 X lo-' per sec using flat samples with a gage length of 37.5 mm and a cross section of 1.25 by 6.25 mm. Estimated sensitivity was 5 K x strain and 0.35 kg per sq mm stress. Magnetic saturation was determined on small cylindrical samples, 2.5 mm in length and diameter, by measuring the force exerted by the gradient of a magnetic field of 1000 oe per cm in a mean field of 11,500 oe. The measured values could be reproduced within *1 pct. Coercive force was measured by a precision-type magnetic field probe in a magnetic coil as described by Foerster.5 The magnetizing field was 1300 oe. The samples were 5 cm long, 1 cm wide, and 2.4 mm thick. he coercive force was measured to within +0.1 oe. Electrical resistivity was measured by using a potentiometer on flat strips with a gage length of 100 mm and a cross section of 2.5 by 0.5 mm. The accuracy of the measurement was 0.1 pct but the reproducibility of the measured specific resistivity among different samples was in the order of 1 pct. The method used to prepare the samples for electron transmission has been reported elsewhere.3 RESULTS Fig. 1 shows the influence of deformation after annealing on the resistivity, hardness, and coercivity. The samples were annealed for 30 min at 1000"C,

Jan 1, 1968

By Amitava Gangulee, Michael B. Bever

The order-disorder transition in Ag-Mg alloys in the range 17 to 26 at. pct Mg was investigated and some thermodynamic, electrical and mechanical properties of ordered Ag-Mg alloys were measured. A modification of the phase diagram is proposed on the basis of measured transition temperatures. The stability of the ordered structure is analyzed in terms of the quasichemical theory. Kinetic aspects of the order-disorder transition were also investigated. The energies of ordering at 273°K of Ag-Mg alloys were measured by liquid metal solution calorimetry. The electrical resistivities and the tensile Properties of the ordered alloys were measured. The exothermic energy of ordering increased with magnesium concentration up to the composition Ag3Mg; it is discussed in terms of the quasichemical theory. Pronounced order hardening was observed and can be explained by several strengthening mechanisms, which are particularly effective because of a change in crystal structure associated with the ordering transition. IN silver-rich solid solutions containing approximately 17 to 26 at. pct Mg, long- range ordering may occur during appropriate therma1 treatments. Clare-brough and Nicholas1 first detected such long-range order in the solid solution of composition Ag3Mg and suggested that the unit cell of the superlattice contained 256 atoms. x-ray2 and electron diffraction3 investigations confirmed the occurrence of long-range order, but indicated a shifted Ll2-type structure. On the basis of recent X-ray measurements the crystal structure of ordered Ag3Mg has been confirmed as type D023.4 The present paper is concerned with the order-disorder transition in silver-rich Ag-Mg solid solutions and some thermodynamic, electrical, and mechanical properties of the ordered alloys. The effects of short-range order on the properties of silver-rich solid solutions containing up to 26 at. pct Mg are discussed in a concurrent paper.5 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Specimens. Specimens of Ag-Mg alloys containing from 18 to 26 at. pct Mg were prepared in the form of 1.0-mm-diam wires as described in Section 1.1 of Ref. 5. Disordered specimens were prepared by annealing at 773°K for 1 hr and quenching into iced brine. Ordered specimens were prepared by annealing at 773°K for 1 hr and slowly cooling to room temperature over a period of 15 days. The specimens were stored at 78°K. 1.2) Resistivity Measurements. Electrical resistivi- ties were measured by a potentiometric method.' Equilibrium values were obtained at several temperatures. The kinetics of ordering were investigated by following the time-dependent changes of the resistivity of initially disordered specimens during annealing. The specimens were enclosed in copper capsules and immersed in salt pots; the heating up was accelerated by injecting preheated helium into the capsules. 1.3) Calorimetry. The energies of ordering of the alloys were measured in a tin solution calorimeter as the difference between the heat effects of additions of completely ordered and disordered specimens of the same composition. The procedure and the method of calculation have been described.6 Magnesium was used for thermal compensation in most calorimetric runs in order to improve the accuracy.677 1.4) Mechanical Tests. Tensile tests were carried out with wire specimens at room temperature as described in Section 1.5 of Ref. 5. Microhardness measurements were also made.? 2) RESULTS AND DISCUSSION The characteristics of the order-disorder transition of silver-rich Ag-Mg solid solutions will be discussed first. Some thermodynamic, electrical, and mechanical properties of the ordered alloys will then be considered and compared with the corresponding properties of dis-disordered alloys. 2.1) The Order-Disorder Transition. 2.1.1) Thermodynamic and Structural Aspects. The transition temperatures Tt were determined from discontinuities in the slope of the equilibrium resistivity vs temperature curves. Normalized curves for three compositions are shown in Fig. 1. The transition temperature increases with the magnesium concentration and reaches a maximum at the stoichiometric composition Ag3Mg. The transition temperature of the alloy Ag3Mg was measured as 665° ± 2°K and compares with published values of 660°,1 663°,8 and 66°k.3 In the slopes of the resistivity vs temperature curves of alloys containing 22.2 and 22.5 at. pct Mg, discontinuities were observed at two temperatures. Such upper and lower discontinuities indicate a two-phase field. A modified form of the published phase diagram9 is shown in Fig. 2. A two-phase field was found only on the low-magnesium side of the composition Ag3Mg. On the high-magnesium side, the existence of a two-phase field could not be established because of insufficient resolution, but such a field must be present. This part of the phase diagram can be made complete by a eutec-toid-type reaction a = (a' + ß). The existence of a boundary between the two-phase fields (a + ß) and (a' + ß) is also in accord with published lattice parameters.3 The crystal structure of ordered Ag3Mg (type Do23)

Jan 1, 1969

By J. E. Coyne, L. E. Tanner, J. E. Boyd

In recent investigations of the isothermal transformations of the retained 0 phase in a titanium alloy having 13 pct V, 11 pct Cr, and 3 to 4 pct Al, there have been indications that the w transition phase is the initial decomposition product at temperatures below about 950°C (510 c).' This metastable phase, found in a number of titanium-base alloys rich in stabilizing elements and known to have an adverse effect on their ductility and toughness, is not easily observed by the usual experimental techniques. Since wis coherent with the /3 matrix,495 distinct interphase boundaries are not revealed metallographically. However, in some cases, an etching effect (i-e., a "mottled" /3 surface) poorly resolved by light microscopy has been found to correspond with the presence of w.6 X-ray diffraction examination has generally been the most suc- cessful means for identifying this phase and crys-tallographic determinations have been made.4'5 Dynamic elastic modulus7 and electrical resistivity measurementse have also aided in the identification of w. In the current study, the electron microscope was utilized to examine microstructures in aged Ti-13V-11Cr-3A1 that were unresolvable by light microscopy techniques. Using negative parlodion replicas (shadowed with chromium at 27 1/2 deg) examination was made of various transformation

Jan 1, 1962

By Derek J. Fray, John Chipman

THE solubility of graphite in y-iron has been determined by several workers'12 with reasonable agreement. With the increasing use of more complex steels, it is necessary to understand more fully the thermodynamics of the austenite phase. The activity of carbon in a number of alloys is known but the maximum solu- bility of graphite has only been measured by Sohnchen and piwowarsky3 for Fe-Ni and Fe-Si alloys. Recently, Chipman and Brush reviewed the published data on the activity of carbon in binary and ternary austenite and also obtained expressions for calculating the solubility of graphite in Fe-Ni, Fe-Co, and Fe-Si alloys. On comparing the theoretically derived solubilities with the limited results of Sahnchen and Piwowarsky, it was found that the agreement for Fe-C-Si was excellent but there was considerable discrepancy for Fe-C-Ni and no data for Fe-C-Co. It was therefore decided to measure the solubility of graphite in a series of Fe-Ni and Fe-Co alloys. The alloy samples were made up by induction melting a high-purity master alloy under an inert atmosphere in an alumina crucible and drawing the molten metal into four-bore alumina tubes. Using this technique, it was possible to form alloy rods approximately 2 in. long and 1/18 in. in diam. Sixteen lengths of fine rod could be made without solidifying the master alloy. These were then allowed to cool under the inert atmosphere before being sectioned. The samples were packed in a graphite crucible with spectroscopic graphite powder, together with a piece of pure iron foil. Dry hydrogen, which had been saturated with isopropyl alcohol at room temperature, was passed over the crucible at 1000°C for 72 hr. At the end of the 72 hr argon displaced hydrogen in the reaction tube and the crucible was quickly pushed to the water-cooled end. The samples were thoroughly cleaned of the adhering graphite and analyzed. The pure iron samples always contained 1.5 0.02 pct C, which compares favorably with the data of smith2 and

Jan 1, 1970

By Reginald Williams

THE amount or value of the precious metals consumed in dentistry is probably amazing to most people. It falls very little short of that which is consumed in jewelry. Inasmuch as the ultimate destination is in the human mouth, dental alloys enjoy some importance because life and health depend upon restorations made with them. Prosthetic dentistry has made wonderful progress in the last few years. The manufacturers who supply the metals also deserve commendation. This industry which deals with metals to go-into people's mouths is comparatively new. There is no literature on the subject, and little or no precedent by which to be guided. It was only by close cooperation with the dentist or prosthetic technician that desirable physical properties were produced, as-nearly as possible, in the metals which were available and permissible. It is true that there were and still are conflicting opinions among the dentists as to the physical properties they require. Sometimes they request the impossible, such as alloys which are exceedingly stiff and springy, yet will bend or adjust easily. Even in this latter instance, progress has been made by supplying methods of heat-treatment whereby metals may be softened or hardened at will. (Figs. 1 and 2.) The demands made upon manufacturers are extremely varied. They must supply metals of tensile strengths ranging from approximately 30,000 to 100,000 lb. per sq. in. and over. The latter metals must be workable and in many instances capable of extreme deformation. They must not be affected by mouth conditions, nor should they oxidize greatly when molten, at red heat, or during a soldering operation. In addition to physical, specifications, color demands must also be met. The firm of which I have the most, knowledge manufacturers 11,553 standard stock articles of precious metals, taking into consideration formulas, finenesses, grades, colors, gages, lengths, sizes and weights. If special demands are taken into consideration, the number would be in excess of 25,000. Wrought metals are manufactured in a great many alloys of different sizes and shapes, such as plate, bar, rod, wire, sheet, strip, mesh and foil. There are also other products of importance.

Jan 1, 1928

By R. M. Asimow

Both smith1 and wells2 have shown that the dif-fusivity of carbon in austenite increases rapidly with increasing carbon concentration. Smith has shown, in addition, that part but not all of this increase can be attributed to the concentration dependence of the activity coefficient of carbon in austenite. From the work of Eshelby', it is known that, because of the image displacements, there is a uniform dilatation of the material in a body containing random centers of dilatation. It is thus tempting to explain the enhanced diffusivity as resulting from this apparent negative pressure caused by the interstitial carbon atoms.* That is, the activation free energy for diffusion is not directly a function of concentration if we consider that the alloy is subjected to a concentration-dependent pressure. To proceed with a quantitative solution, it is necessary to determine the activation volume AV for the diffusion process. An exact calculation of AV is quite a difficult problem and does not appear to have been solved as yet. A simpler procedure is to use the semiempirical, macroscopic theory of seyes' which relates the activation free energy AG to AV. Keyes has shown that for many types of diffusion processes the following relationship is valid Where p is the Gruneisen constant and x the compressibility. This relationship is based on the assumption that AG can be identified with strain-energy terms. In general there will also be contributions to AG due to a change in the energy of the valence electrons of the metal; thus the relation must be considered largely empirical. Surprisingly, for self-diffusion where it is well-known that the electronic contribution is quite important,' the Keyes relation works quite well for many systems. For interstitial diffusion where it might be expected that the relationship is on a firmer theoretical basis, the limited experimental data available is not in particularly good agreement as can be seen from Table I. However, it must be remembered that besides the uncertain basis of the Keyes formula there is considerable uncertainty in some of the experimental values of AV. The only real justification for using the Keyes formula in the present analysis is that it gives a result which satisfactorily solves the problem at hand and, further, there are no more reliable procedures for calculating AV available. The coefficient 3 in Eq. [I] is determined such that the room-temperature value for x is to be used. The activation entropy AS is estimated as 8.95 x 10"3 kcal per OK mole using the values in Table I1 and the Zener" relation AS = PAHIT, where p is a dimensionless thermal coefficient of Young's modulus which is to be evaluated at low values of T/T,, aH is the activation enthalpy, and T, is the melting temperature of the alloy. The resulting value of AG at 1000°C is 25.6 kcal per mole. The Gruneisen constant (p = 3cup/XC,), where p is the density, is evaluated from the room-temperature data in Table I1 after calculating C, from the relation. A value of p = 8.32 g per cu cm based on the value of a. in Table I is used. The result is C, = 5.0 x lo6 erg per g, H = 2.32, and AV = 3.41 cu cm per mole at 1000°C and infinite carbon dilution. It is assumed that the activation volume is not a function of carbon concentration. The theory could be refined to consider AV a function of concentration, but due to the uncertainties in the parameters there seems little justification for this. Carbon dissolved in austenite forms a nonideal solid solution, so that in writing an equation for. the diffusivity of carbon it is necessary to take into account the change in activity coefficient with concentration. The resulting equation is16

Jan 1, 1964