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By O. R. Wagner, R. O. Leach, H. W. Wood, C. F. Harpke

PAN AMERICAN PETROLEUM CORP.TULSA, OKLA. CASPER, WYO A field test has been made in which additional oil recovery was obtained from a previously-waterflooded "oil-wet" sandstone reservoir. This recovery improvement was accomplished by adjusting the reservoir wettability through chemical treatment of the flood water. The test was made in the Muddy sand of the West Harrisburg Unit, Neb. The chemical used, sodium hydroxide, was injected as a slug of dilute caustic solution through a water-injection well. The natural wettability of the reservoir and the chemical requirements for reversing wettability were determined in the laboratory from contact-angle studies using field water and oil samples. Laboratory flood tests with a synthetic system had shown that reversing the wettability of an oil-wet consolidated core would lead to improved oil recovery. The field performance indicates that the mechanism by which increased oil retovery is obtained in the field is the same as that observed in the lahoratory. Laboratory studies indicate that higher ultimate recoveries and decreascd water-injection requirements result when the adjusting agent is added early in the life of the flood. However, a previously waterflooded area was intentiorzally chosen for the field test so that unambiguous conclusions could be made about the effects of chemical injection on wettability and the extent of oil-recovery improvernent afforded by wettability reversal. Forces existing at the fluid-solid and fluid-fluid interfaces in a porous medium have an important effect on oil recovery during a water flood. Modifying these interfacial forces in the reservoir to improve oil recovery has been the object of much research. Several papers' ' have discussed the use of surfactants to lower the water-oil interfacial tension. This paper describes work concerned with improving oil recovery by modifying the forces at the fluid-solid interfaces— that is, by changing the preferential wettability. An earlier paper: presented evidence to show that some reservoir systems could be changed from preferentially oil-wet to preferentially water-wet by the action of simple chemicals added to the water to increase waterflood oil recovery. The process was attractive for further study because it used only inexpensive chemicals and because it called for a gross "wettability reversal" rather than for a precise adjustment. The present paper is an extension of the earlier work. Laboratory flow tests were made using treated water and oil in a consolidated core to determine the amount of additional oil recovery and the producing performance which might be expected from reversing the wettability of an oil-wet reservoir during a flood. A contact-anglc study using water and oil from the Muddy "J" sand of the Harrisburg field, Banner County, Neb., indicated the reservoir to be preferentially oil-wet and susceptible to wettability reversal through chemical injection. Based on these studies, a field trial of wettability-reversal water flooding was initiated. in the Harrisburg field. The primary purpose of the trial was to determine if wettability-reversal flooding would improve oil recovery in an actual field situation. The field trial was also an important test of the laboratory tecnique used to determine the effect on oil recovery of certain wettability manipulation, as well as a test of the contract-angle method of determining reservoir wetra-bility. The paper is presented in two parts. The first part covers the laboratory experiments leading up to the field trial, and the second part covers the field trial. PART I—LABORATORY STUDY The laboratory experiments consisted of displacement tests using an idealized fluid system and of a contact-angle study with crude and water from the Muddy "J" sand of the West Harrisburg Unit, Banner County, Neb. The displacement tests were designed to determine the effects of a particular wettability manipulation, oil-wet to water-wet, on oil displacement in a water flood. The contact-angle measurements were made to determine the natural wettability of the reservoir and to determine if beneficial wetting changes could be brought about by a chemical addition to the flood water. PROCEDURE DISPLACEMENT TESTS The displacement tests were perfornled in a consolidated sandstone core using a refined oil and water. The wetting properties of this system could

By K. C. Ten Brink, Allen D. Garrison

A rrevious paper1 reviewed some of the properties of clays and shales and presented some data on the nature of the gelling phenomenon. It included a brief discussion of origin of clays and shales, their composition, structure, retention of water, ionization, base exchange, and the nature of the gelling of water suspensions. Other publications of the Institute2-8 have discussed the properties of clays and their relations to drilling-fluid behavior and control. It is the purpose of this article to present some new data obtained and arranged in a different manner and making possible a better understanding of the chemical reactions involved in the control of drilling-fluid characteristics during the normal drilling operations. Experimental Procedure The difficulties involved in the measurements of the flow characteristics of plastic fluids are too familiar to recite. The possible applications of some of the well-known instruments to this problem have been adequately discussed by Hobson9 and he has given an excellent bibliography. Although there are many viscosimeters of varied design, none of them appear to fulfill the most obvious demands of accuracy in the measurement of clay or shale suspensions. Since the fluid characteristics are dependent on the rate of flow of the fluid, and the viscosity usually falls off very rapidly as the rate is increased, it is clear that the first requirement is that the instrument shall be capable of a wide variety of speeds. The viscosity of the fluid at any fixed and constant rate of flow is also a function of time, so that the second demand is that the instrument shall be capable of a constant and continuous motion for a prolonged period of time.

Jan 1, 1940

By K. C. Ten Brink, Allen D. Garrison

A rrevious paper1 reviewed some of the properties of clays and shales and presented some data on the nature of the gelling phenomenon. It included a brief discussion of origin of clays and shales, their composition, structure, retention of water, ionization, base exchange, and the nature of the gelling of water suspensions. Other publications of the Institute2-8 have discussed the properties of clays and their relations to drilling-fluid behavior and control. It is the purpose of this article to present some new data obtained and arranged in a different manner and making possible a better understanding of the chemical reactions involved in the control of drilling-fluid characteristics during the normal drilling operations. Experimental Procedure The difficulties involved in the measurements of the flow characteristics of plastic fluids are too familiar to recite. The possible applications of some of the well-known instruments to this problem have been adequately discussed by Hobson9 and he has given an excellent bibliography. Although there are many viscosimeters of varied design, none of them appear to fulfill the most obvious demands of accuracy in the measurement of clay or shale suspensions. Since the fluid characteristics are dependent on the rate of flow of the fluid, and the viscosity usually falls off very rapidly as the rate is increased, it is clear that the first requirement is that the instrument shall be capable of a wide variety of speeds. The viscosity of the fluid at any fixed and constant rate of flow is also a function of time, so that the second demand is that the instrument shall be capable of a constant and continuous motion for a prolonged period of time.

Jan 1, 1940

By R. W. Raymond

(Cleveland Meeting, October, 1912.) UNDER the names of Conservation, Social Justice, the New Nationalism, and Progressive Democracy, many earnest reformers are calling for a new system of Federal government to replace the one which they ascribe to our fathers, and declare to have been outgrown. They are proposing the lease by the United States of certain natural resources on the public domain, for the profit of the U. S. Treasury, instead of the sale of such resources to private citizens or associations of citizens. In the present paper, I shall try to show that this notion is neither new nor good. It is clear that the United States is owner, as well as sovereign, of public lands acquired through conquest or purchase from other nations, as it was owner of the public lands expressly ceded to it by the original thirteen States. Its policy with regard to such lands involves, therefore, two entirely distinct questions: What shall it do as owner ? and, What shall it do as sovereign ? The latter question, it must be confessed, has played but a small part in our history. All the prerogatives of sovereignty which were not explicitly conferred upon the Federal government by the original States were retained by them. The ownership or control of precious or other metals or minerals in the earth, for instance, was thus reserved to the several sovereign States. New York, South Carolina, and other States have passed laws on this subject, without regard to Federal authority. As new States have been successively admitted to the Union, the tacitly accepted theory has been,. that they thereby acquired all the reserved rights of the original States. These newer States largely outnumber the first. thirteen; and it is inconceivable that they would submit to any deprivation of sovereignty based on historical grounds. One of them-Texas-came into the Union by its own voluntary

Oct 1, 1912

By N. S. Kenny, A. A. Burr

THE purpose of this note is to present evidence that vacancies, which have been produced by quenching from a high temperature, alter the rate of strain-hardening of an hep single crystal. The majority of investigations of the effects of quenched-in vacancies on the yield stress of metals have been made using fee samples in the form of thin wires. However, there is an inherent disadvantage in using such wires to study the effects of vacancies on the rate of strain-hardening of metals because fee wires begin stage II slip either immediately upon yielding or very shortly thereafter. When stage II slip occurs, very rapid strain hardening also occurs, masking the effects of vacancies on the rate of hardening. In this investigation single crystals of magnesium hep were studied since magnesium has only one slip plane at low temperatures and has, therefore, an extensive easy glide region. In addition, the effect of both static and dynamic recovery on the rate of hardening were eliminated by testing in liquid nitrogen. Both forms of recovery occur in hep metals by dislocation climb, which is a diffusion controlled mechanism and is negligible at liquid nitrogen temperatures. Finally, the dependence of the strain-hardening rate on the crystal orientation was eliminated by using the equations of Schmid and Boas.' Variations in the strain-hardening rate could, therefore, be attributed to the presence of vacancies. Single crystals in the form of rods approximately 5 mm in diam and 6 cm long were grown by a modified Bridgman technique from commercial high-purity magnesium (99.97 pet) supplied by the Dow Chemical

Jan 1, 1962

By Tell Ertl

THE Piceance Creek Basin in northwestern Colorado is believed to contain the richest large deposit of oil shale in North America. The major portion, about 1650 sq miles, is bounded by the White River on the north, the Grand Hogback, which runs from Meeker to Rifle, on the east, the Colorado River to the south, and the drainage basin of Salt and Douglas Creeks on the west. The Basin is a plateau 7000 to 9000 ft high, composed of 3000 ft of the Green River series of Eocene age and surrounded by a steep escarpment of 1000 to 3000 ft. From the escarpment the beds dip gently toward the center. Although oil shale is found in all members of the Green River series, the rich thick beds are found chiefly in the Parachute Creek member. This is normally capped by 100 to 200 ft of the Evacuation Creek, the youngest member of the Green River series. Actually the Piceance Creek Basin oil shale is not a shale, nor does it contain oil. It is magnesium marlstone holding solid organic matter capable of being broken down by heat into gases, some of which can be condensed into oil. The marlstone is resilient nonporous rock, difficult to sample by pick or hammer and moil. Many companies and individuals prospected the Colorado oil shale shortly after the first World War,' see Fig. 1, but because of the discovery of large quantities of petroleum in the late 1920's in Cali- fornia, Oklahoma, and East Texas, interest in oil shale development waned and did not revive until World War 11. In 1944 the writer, employed by the Bureau of Mines, prospected the high grade oil shale in numerous places along the southern outcrop of the Piceance Creek Basin. Several channel samples about 100 ft in length were cut, see Fig. 2. An eight-man crew needed a week to cut a satisfactory channel 80 ft long in the cliff face. The Phillips Petroleum Co., the Union Oil Co. of California and others also prospected the oil shale outcrop. In 1945 the Bureau of Mines initiated a core drilling program for the purpose of obtaining accurate samples from the Piceance Creek Basin. The U. S. Geological Survey set up a program for the geological study of the Basin that is still going on." Until the end of 1951 a total of 31 holes was drilled for core with diamond drills, and, in addition, cuttings through the oil shale have been obtained from 4 gas wells drilled by standard rotary oil well rigs. The Bureau of Mines drilled 12 of the holes, the Union Oil Company of California 8, the Standard Oil Company of California 6, the Sun Oil Company 3,

Jan 1, 1953

By Tell Ertl

THE Piceance Creek Basin in northwestern Colorado is believed to contain the richest large deposit of oil shale in North America. The major portion, about 1650 sq miles, is bounded by the White River on the north, the Grand Hogback, which runs from Meeker to Rifle, on the east, the Colorado River to the south, and the drainage basin of Salt and Douglas Creeks on the west. The Basin is a plateau 7000 to 9000 ft high, composed of 3000 ft of the Green River series of Eocene age and surrounded by a steep escarpment of 1000 to 3000 ft. From the escarpment the beds dip gently toward the center. Although oil shale is found in all members of the Green River series, the rich thick beds are found chiefly in the Parachute Creek member. This is normally capped by 100 to 200 ft of the Evacuation Creek, the youngest member of the Green River series. Actually the Piceance Creek Basin oil shale is not a shale, nor does it contain oil. It is magnesium marlstone holding solid organic matter capable of being broken down by heat into gases, some of which can be condensed into oil. The marlstone is resilient nonporous rock, difficult to sample by pick or hammer and moil. Many companies and individuals prospected the Colorado oil shale shortly after the first World War,' see Fig. 1, but because of the discovery of large quantities of petroleum in the late 1920's in Cali- fornia, Oklahoma, and East Texas, interest in oil shale development waned and did not revive until World War 11. In 1944 the writer, employed by the Bureau of Mines, prospected the high grade oil shale in numerous places along the southern outcrop of the Piceance Creek Basin. Several channel samples about 100 ft in length were cut, see Fig. 2. An eight-man crew needed a week to cut a satisfactory channel 80 ft long in the cliff face. The Phillips Petroleum Co., the Union Oil Co. of California and others also prospected the oil shale outcrop. In 1945 the Bureau of Mines initiated a core drilling program for the purpose of obtaining accurate samples from the Piceance Creek Basin. The U. S. Geological Survey set up a program for the geological study of the Basin that is still going on." Until the end of 1951 a total of 31 holes was drilled for core with diamond drills, and, in addition, cuttings through the oil shale have been obtained from 4 gas wells drilled by standard rotary oil well rigs. The Bureau of Mines drilled 12 of the holes, the Union Oil Company of California 8, the Standard Oil Company of California 6, the Sun Oil Company 3,

Jan 1, 1953

By A. U. Seybolt

RECENTLY, cases of coexisting ordered and disordered phase equilibria have been reported among face-centered cubic metals,1"3 but not on body-centered cubic systems.4 McQueen and Kuczynski5 showed a single line as the boundary between ordered solid solution of Fe3Al type and corresponding disordered solution in the Fe-A1 phase diagram based mainly on dilatometric and magnetic measurements. Such a single line would indicate a second or higher order transition. or an absence of coexisting order and disorder. The writer found previously a two-phase equilibrium region at 800°C consisting of ordered and disordered solid solutions of Fe3Si in a matrix of approximately 1-6 wt pct Si (Fe3Si is of 14.3 wt pct Si). A similar two-phase region of ordered and disordered Fe3Al solid solutions might be expected if the similarity between Fe3Si and Fe3Si structures hold true. In the present investigation, a wire of 22 at. pct Al, balance Fe and 0.0513 cm in diameter was subjected to electrical resistivity measurement in vacuum as a function of temperature between 300 and 800°C, see Fig. 1. There was excellent agreement between data taken on heating and on cooling: no hysteresis was observed. The Curie temperature was determined to be 640 °C which agrees with the finding by McQueen and Kuczynski.5 But in addition, there were two transitional points in the resistance-temperature plot at 510oC and 400 "C. The former is thought to be a connection with the transition from disordered state to a coexisting order and disordered equilibrium state; while the latter, from such coexisting state to ordered state. Fig. 2 shows a phase diagram where the suggested two-phase region lies between dotted lines. The solid lines are those of McQueen and Kuczynski.5 Since these authors found only a single-phase boundary between ordered and disordered Fe3 Al, it would seem likely that the dilatometric method used by these authors was not sufficiently sensitive to resolve the ordering reaction into the two-phase boundaries. In addition, their phase diagram conflicts with the statement they make on P. 1 of their paper: "The sharpness of the peaks indicates that ordering to Fe3A1 is a first order reaction." The suggestion of coexisting order plus disorder in Fe3A1 must be considered tentative until confirmed by high-temperature X-ray examination. If

Jan 1, 1961

By Homer S. Frankhouser

Materials may be dredged, processed, stored and loaded for shipment at a single site in water depths ranging from 250 to 1200 ft. Solution mining may also be accomplished in deep sea situations. And, open air subsea mines with direct surface access may be developed and worked under the ocean floor. These concepts for deep sea mining are the results of extensive testing of individual components of the proposed systems by Dravo Ocean Structures, Inc., a subsidiary of Dravo Corp. A basic structure in these systems is the articulated platform. The platform consists of a gravity- type base and a buoyant cylindrical column which is constructed at an onshore location, towed to the offshore site and installed in a matter of days without use of heavy equipment. The base is also buoyant for towing purposes. This allows for gradual flooding to the point of negative buoyancy for positioning and anchoring to the ocean floor.

Jan 1, 1971

By J. B. Scuffham, G. I. Warwick, J. B. Lott

The development of solvent extraction processes over recent years has led to their application on an increasing scale in metal extraction plants. The author's company has recently been awarded a contract for the design of the world's largest solvent extraction plant based on pump-mix mixer-settlers. The plant is designed to extract copper from a leach liquor and has an aqueous throughput of 12,000 imperial gpm. The design is based largely upon data obtained from the company's own research laboratories, where work has been undertaken on mixer impeller design, baffle design. settler area, organic entrainment recovery, etc. Investigations have been conducted into the effects of mixer impeller speed, recirculation rates, phase continuity, phase ratio, etc., on extraction efficiency, settler area, and organic entrainment losses. The implications of the results of this work on the design of a large plant using pump-mix mixer-settlers are discussed and the techniques used in overcoming certain scaling problem are outlined.

Jan 1, 1973

By Ralph Sweetser

AT the joint session of Blast Furnace and Open Hearth Committees, April 7, 1937, at Birmingham, the subject of the quality of basic open-hearth pig iron was so well presented and discussed from so many different viewpoints that it was the general opinion that progress had been made and that such meetings were conducive to the advancement of the art of making pig iron of the right quality for the open-hearth man to produce the most satisfactory quality of steel. It was agreed that there is a decided differentiation between the chemical analysis of pig iron and the "quality" of pig iron. Paul J. McKim said that open-hearth furnace operators frequently make refer-ence to certain types of iron as "bad iron," "dirty iron," "cold metal,' etc., claiming that when using these irons, although they are within specified chemical analysis, it is impossible to produce quality steel. Mr. McKim gave a list of the suggested causes of those "certain types" of bad irons that have a thoroughly respectable analysis but a thoroughly disreputable character. Another open-hearth man, P. A. Maclsaac, of Nova Scotia, said that: The effects of iron flint is below standard in analysis or in that mysterious property called quality, are well known to all open-hearth operators. It has been shown that iron of this type results in the production of steels on which the rejections of finished product, run high. What is to be done about it? I would say that the burden of producing high-quality iron should be placed squarely on the shoulders of the blast-furnace man, even as that of making good steel is shouldered by the open-hearth luau. It is the purpose of this paper to bring out into the open this 'mysteri-ous property called quality"; that is, in those "certain types" of basic pig iron that make it impossible to produce quality steels; and at the same time to point the way for the blast-furnace man to be able to shoulder the burden that Mr. MacIsaac and all other open-hearth men and foundry-men have placed upon him.

Jan 1, 1938

By B., Hoyaux

A first requirement for assessing the safety of a rock slope, either artificial or natural, particularly if the rock behaves in an elastic-brittle manner, is a proper knowledge of the distribution of stresses within the slope and their development with time and advancement of workings.

Jan 1, 1972

By D. H. Baldwin, R. E. Reed-Hill

WITH the polarized-light microscope, the basal-plane trace may be located on hcp crystal surfaces to an accuracy of approximately 1 deg. This determination can also be made on very small crystalline areas, approaching a micron in width. Measured basal-plane trace distributions on selected specimen surfaces can yield1,2 valuable texture information. However, the polarized-light microscope is probably best suited to orienting

Jan 1, 1965

By D. R. Wieland, A. N. Barron, A. R. Hendrickson

A definite relationship has been found between the reactivity of flowing hydrochloric acid and its shear rate in a carbonate fracture. Both flow velocity and fracture width affect the acid reaction rate. Laboratory studies were conducted on acid reactivity at different flow velocities through horizontal-linear fractures, using 15 per cent hydrochloric acid at 80' F and approximately 1,100 psi. Fracture width varied from 0.02 to 0.20 in. These data provide a new basis from which the spending time and penetration of the acid can be estimated. Equations were derived expressing the relationship between injection rate, fracture width, acid concentration, time and fracture height, for linear and radial fracture systems. Because the penetration of the acid before spending is closely related to the extent of productivity increase resulting from an acidizing treatment, these data provide a valuable insight into some of the controlling factors that must be taken into consideration during treatment preplanning. INTRODUCTION Acidizing of carbonate reservoirs to improve production characteristics has been widely practiced since 1932. Originally, it was assumed that the acid uniformly penetrated natural formation pores and flow channels, enlarging them and thereby increasing their flow capacity. Little consideration was given to the reaction rate of the acid, or how far it would penetrate away from the wellbore into the formation, before spending. It has been shown recently' that, unless fractures are present in the rock, very little penetration is attained before spending, and the benefits of the acidizing treatment are largely confined to the immediate vicinity of the well-bore. Therefore, acid treatments may be classified into two categories: (1) matrix acidizing, in which the acid flows through multiple: formation pores; and (2) fracture acidizing, in which the bulk of the acid travels through fractures in the rock, whether natural or induced. When acidizing treatments are conducted at pressures of sufficient magnitude to open and extend such fractures, it is often desirable to inject a propping agent to hold the fracture open after the treating pressure has been released, thus providing a highly conductive flow channel through the rock. In some cases where acid attack produces surface irregularities, the resulting flow passages can be sufficient to provide high conductivity without use of a propping agent. During injection, the acid dissolves the carbonate rock with which it comes in contact until it is spent. Deeper penetration of the spent acid into the formation produces no appreciable benefit (if no propping agent is used) because the unetched fracture faces will rejoin when treating pressures are released and the fracture will "heal", with negligible resultant conductivity. The spending time of the acid thus becomes important in determining how far from the wellbore the improved-conductivity zone extends. The spending time of acid after injection into carbonate rock depends on the rate at which the acid reacts with the rock. This in turn is controlled by a number of factors, as previously reported. 2-4 These include temperature, pressure, acid concentration, rock composition, injection rate and the area-volume relationship between the acid solution volume and the surface area of the formation flow channels through which it penetrates. Thus, in matrix acidizing, where an extremely large area is exposed to the acid, spending is rapid. In contrast, spending time is prolonged in open fractures, where the area-volume ratio is much lower. Thus, greatest penetration of the acid before spending will be achieved in acid-fracturing treatments where fractures are held open by hydraulic pressure. Perkins and Kern5 have presented equations for fracture-width determinations which, for hard formations such as limestone or dolomite, indicate that high injection rates and viscous fluids are required to create wide fractures. Increasing the injection rate will, in itself, produce faster reaction rates. Because this type of reaction can be considered to be first-order diffusion-controlled, '-' the rate of movement of fluid past the rock surface affects the thickness of the diffusion layer, in turn affecting the reaction rate. Staudt, et al,10 report the results of tests in which a rotating marble cylinder was immersed in acid, and the weight loss at different speeds determined. Such test conditions, however, are not truly indicative of the situation in a formation during an acid-fracturing treatment. This paper reports reaction-rate data obtained under

By Walter S. White

The Michigan native-copper district has produced about 5,400,000 tons of copper since mining began in 1845. The copper occurs primarily as open-space fillings and replacements in amygdaloidal flow tops and conglomerate beds of the Portage Lake Lava Series, of middle Keweenawan age. Secondary minerals with which the copper is associated include microcline, chlorite, epidote, pumpellyite, prehnite, quartz, and calcite; zeolites, other than laumontite, are not abundant. A zonal pattern of the secondary minerals transects bedding and suggests regional metamorphism mainly to the grade of the prehnite-pumpellyite graywacke facies of Coombs. Most of the major copper deposits are near the upper limit of abundant quartz in this zonal pattern. The distribution of copper in both amygdaloid and conglomerate deposits is controlled partly by primary permeability of the rocks and partly by later tectonic fracturing that was concentrated in the mechanically weak flow tops and sedimentary beds. Ore shoots and deposits are therefore controlled partly by primary structural features, such as areas of thick and thin fragmental amygdaloid or the boundaries of conglomerate lenses, and partly by regional structure: a number of ore deposits are in synclinal downwarps. The copper-bearing solutions that formed the deposits were ascending. They may have come from a large concealed intrusive, or may have been driven out of the porous tops of lava flows when the rocks were compacted and metamorphosed at great depth in the central part of the Lake Superior syncline. The second hypothesis seems more consistent with the widespread distribution of the copper, its relation to mineral zoning that represents truly regional metamorphism, its native state, and the likelihood that copper deposition was later than most or all of Keweenawan volcanism.

Jan 1, 1968

By R. D. Pehlke, J. V. Gluck

The limiting activity coefficient of zinc in a "binary " solvent has been described for several dilute ternary solutions by combining literature data from recent interaction studies in the terminal regions with thermodynamic data for the central regions. Results are discussed in terms of the Alcock and Richardson random solution model. The observed behavior agrees semiquantitatively with predictions using the model. RECENT efforts in the thermodynamics of dilute ternary liquid metallic solutions have been mainly concerned with the interactions between two dilute solutes, that is, the terminal region at an apex of the composition diagram.'-' A more general case is that of the behavior of a dilute solute over the full range of a ternary system, or, more specifically, the limiting activity of solute i as projected to the k-j binary side of the i-j-k composition triangle. An implication of this is that the interaction between i and j at the k apex should connect in some way to the interaction between i and k at the j apex. A model to characterize various types of expected behavior has been discussed by Alcock and Richardson.9,10 Such behavior can range from a simple linear relation for In yi over the 1-k binary to more complex curved relations which depend on various assumptions regarding the heat of solution in the j-k binary system and the presence or absence of clustering with solute i. Quantitative data to assess these concepts have been limited primarily to the cases of nonmetallic interstitial solutes in ferrous solutions. Alcock, Richardson, and various coworkers9-13 have discussed the behavior of oxygen, sulfur, silicon, or hydrogen in dilute solution over the range of iron + metal systems; however, the only data considered by them for substitutional nonferrous metallic solutions were the results of Elliott and Chipman concerning the activity of cadmium in the Pb + Sn, Pb + Bi, and Pb + Sb systems.9 These data were limited and did not cover the terminal regions in detail. An opportunity to extend the Alcock and Richardson considerations to the dilute solution of zinc in various "binary" solvents has been afforded by combining results of several of the recent investigations of ter-minal-region interactions with previous data from the literature for the same more concentrated solutions. RESULTS AND DISCUSSION The results of the analysis are shown in Figs. 1 to 5 where the log activity coefficient, (In yZn)xzn--o, is plotted vs the composition of the "binary" solvent. In these plots the end points are the values for In yzn in the appropriate binary solution with Bi, Pb, Sn, Cd, or In at the indicated temperature—usually 550°C (823°K). For the terminal regions the slopes were drawn using the first-order interaction parameters taken from various studies reported in the literature. The data points shown in the central regions were obtained by the short extrapolation to infinite dilution of the logarithm of the activity coefficient calculated from thermodynamic studies reported in the literature for the same systems. The sources of the data are indicated on each figure. Second-order effects were not considered. Reasonably smooth curves can be drawn to connect the central region with the terminal regions for the Zn-Pb + Bi system, Fig. 1, the Zn-Pb + Zn system, Fig. 1, and the Zn-Bi + Cd and Zn-Bi + Sn systems, Fig. 2. As shown in Fig. 2, where central region data are available from two independent investigations, the agreement is quite good. The Zn-Pb + Cd system does not appear to be as well behaved as the previous four, Fig. 3; however, this type of behavior has also been

Jan 1, 1970

By E. S. Wheeler

The rapid increase in the use of monel metal and malleable nickel in the form of sheet, rod and tube has resulted in a similar increase in the demand for these metals in the form of castings. These castings range in size from small valves and pipe fittings weighing a few ounces to large centrifugal pumps, gate valves and marine propellers, some of the last weighing as much as 24,000 lb. A group of such castings is shown in Fig. 1. A large nickel agitator is shown in Fig. 2. Monel metal castings are widely used in accessories for steam power plants and in a variety of chemical plant equipment where the corrosion resistance, high strength and toughness characteristic of this metal render it particularly valuable. Nickel castings find extensive use in the construction of corrosion-resistant apparatus, and are often used in conjunction with wrought nickel sheet and tube in the fabrication of equipment for handling a variety of chemical and food products, particularly dairy products. In response to this demand for castings, numerous foundries have undertaken the production of castings of these metals and have met with varying degrees of success. The successful production of castings of monel metal and nickel requires careful attention to molding practice, proper melting equipment

Jan 1, 1930

By Enrique Hauser

Discussion of the paper of ENRIQUE HAUSER, presented at the New York meeting, February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 521 to 534. GEORGE A. BURRELL, Pittsburgh, Pa. Mr. Hauser determined the influence of inert gases on the properties of fire-damp mixtures, and one might take some issue with his work on the effect of hydrogen, on those mixtures. It is valuable information to have, but as far as the practical application of it goes, it is not of much significance, because one does not find it in mines, at least not in any appreciable amount. The same Fig. 1.-APPARATUS FUR DETECTING COMBUSTIBLE GASES IN AIR. thing can be said of ethylene. Ethylene is formed in considerable quantities as a product of heat reaction, but normally, in the coal mines, as a result of a great many analyses we have made at the Bureau of Mines, we cannot say that ethylene is a combustible gas found in the fire-damp in coal mines.

Jan 5, 1916

By A. M. Tweedy, Felix A. Vogel

Since the publication of Prof. J. W. Richards's paper on The Schumacher Briquetting Process,' this process has been in operation on a practical scale in two plants in the United States, and a few notes on the results obtained may be of interest. An experimental plant, consisting of a toggle press and a hydraulic press, was installed at Johnstown, Pa., together with the necessary bins and other equipment, and an attempt was made to briquette a mixture of Mahoning fines and blast-furnace flue dust, in a ratio of 7 parts of ore to 3 parts of dust. The results were unsatisfactory, in that the briquettes made were not hard enough to stand the severe handling to which they were subjected in the various transferences necessary between the press and the furnace. The trouble was due to several causes: First, the mechanical arrangement of the plant, which did not lend itself to a proper hardening and loading of the briquettes into the cars. Second, the irrrgular composition of the flue dust, as to both its lime and its fine coke contents. Third, the variability of the moisture content of the ore, and its viscosity when wet. Fourth, the ratio of fine ore to flue dust; that is, it was attempted to bind in too large a quantity of fine ore for the small amount of flue dust used. The first trouble could be overcome, and has been improved upon in the plant as it stands to-day. The second trouble was important, because of the small amount of dust used as a binder, and might have been easily removed by mixing the flue dust of the different furnaces, which, however, was never done. The third difficulty was more serious, but could have been partly solved, had it been possible to meet this along with the fourth difficulty, by decreasing the percentage of ore in the briquettes. It was proposed to do this, but it seems that the problem at the works in question is, primarily, to prepare Mahoning fines for reduction in the blast furnace, and only secondarily to use up the flue dust, and a solution along this line did not seem to be interesting.

Jan 1, 1914

By N. E. Rogen, N. J. Grant

WHILE direct measurements of the growth of precipitate particles during aging is of fundamental value, few such measurements have been made. Direct measurements by means of optical or electron-microscopy and X-ray techniques are preferred, however, many of the aging studies have been based on indirect methods such as electrical resistivity and hardness. Because of the minute size of most precipitate particles (less than 1000A) the light microscope is of limited use while electron microscopy is subject to slowness, etching problems and consequent resolution problems. It is fortunate that alloys of the Nimonic type, based on Ni-Cr-Ti-Al, lend themselves to accurate and relatively easy particle size measurements. With proper balance of titanium and aluminum, the only aging precipitate is the gamma prime (r') Ni3,(Al, Ti)2 phase and this phase is the basis of the high-temperature strength of these allos.3-6 The Ni3(Al, Ti) phase is a face-centered-cubic, ordered structure with nickel atoms occupying the cube faces. Titanium atoms can replace three out of every five aluminum atoms and when substituting do so preferentially.2 Electron microscopy has shown that during aging of most of the commercial alloys of this type, precipitate particles are unusually uniform in size and distribution, and that the volume of (r') phase is large (20 pct).4,7 The aim of this investigation was to measure the growth of (y') phase during aging. In so doing, it was hoped that a clearer understanding of the aging process would be attained. X-ray line broadening was used as the measure of precipitate particle size. This technique was selected because it can measure and average the diameter of thousands of particles in one operation. The variations in hardness and matrix lattice parameter with aging were also studied and related to the particle size. EXPERIMENTAL PROCEDURE An alloy of the following composition was studied: Cr Ti A1 C Ni Wt pct 20.71 2.98 1.43 0.04 bal. At. pct 22.06 3.47 2.95 0.18 bal. The alloy, a 15- lb vacuum melt, was forged to 1/2-in. diam at a temperature of 1900" to 2200°F; was solution heat treated for 4 hr at 2000°F and water quenched; and was then aged in various ways. The ASTM grain size was 4 to 5. No (7') phase could be detected by X-ray analysis after solution treatment and electrolytic extraction. Aging was performed on 2-in. long specimens at 1400°, 1500°, and 1600°F for increasing times. One-half inch sections were removed after each time increment and were then electropolished in a solution of H3P04 saturated with chromium trioxide at a potential of 30 v and rectified with a tantalum electrode. Rockwell hardness measurements were taken using one side of the polished specimen. Matrix lattice parameter determinations were made on the other side using filtered chromium radiation references with the position of the (220) line of a silicon standard. To enable the precipitate particles of the (y') phase to be measured using X-ray line broadening techniques, it is first necessary to separate and concentrate this phase by electrolytic extraction. Extraction is necessary because the difference between matrix and precipitate lattice parameters is only approximately 0.5 pct and intensities of.the (y') phase lines are very weak relative to those of the matrix. The extraction techniques employed have been described before and found to produce a reasonably quantitative separation.398 A water solution of 15 pct H3Po4 is used at a current density of 0.5 amp per sq in. at 6 v. The precipitate particles are separated from the liquor by centrifuging and decanting and are then washed, dried and repowdered. A plot of the X-ray intensity vs diffraction angle for the (111) line of the precipitate particles was used as a measure of particle size. The intensity curve approximated the shape of Gaussian distribution function and its breadth was measured at the half height. The (220) line of a silicon standard was used to correct the measured line breadth for instrumental and other broadening errors. The Scherrer formula was used to calculate particle

Jan 1, 1961