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By J. A. Hren, G. Thomas

A high-temperature stage has been used to study precipitation and dissolution in thin foils of Al-20pct Ag alloy directly in the electron microscope. The results show that the aging characteristics are similar to those observed for bulk materials, and in addition, direct evidence is presented for clustering at the solid solution temperature. The limit of solubility of G. P. zones is-350°C. The heterogeneous precipitation, the growth and dissolution of ?&apos;have been studied in detail. Growth of ?&apos; parallel to the basal planes, occurs by continuous motion of inter -facial partial dislocations. Growth stops at intersecting particles due to formation of sessile a/6 <110> interfacial dislocations. Growth normal to the habit plane occurs by the spontaneous nucleation of partial dislocations on alternate (111) planes and the thickening rate is --10-3= times the lengthening rate. The precipitates dissolve in layers and the final product is a whole a/2 <110> dislocation . The nucleation -growth -dissolution processes are thus completely reversible. Kinetic data obtained from the dissolution rates of ?&apos;particles enable the diffusion coefficient to be determined and the activation energy is found to be 37.5(±4) kcal mol-1, which is that expected for dzffusion of silver in aluminum. The velocity of the interfacial dislocations is thus dependent solely on the rate of diffusion of silver atoms. RECENTLY it was demonstrated that a high-temperature stage could be effectively used in the electron microscope to follow directly the processes of precipitation and dissolution in thin foils of A1-4 pct Cu alloy.&apos; These experiments also provided kinetic data which enabled the diffusion coefficient to be estimated. This new development of electron metallography opens up many fruitful areas of research and it was decided to investigate the aging behavior in thin foils of A1-20 pct Ag alloy, particularly the mechanism of heterogeneous precipitation (i.e., precipitation on lattice defects). This system was chosen because the aging characteristics of bulk specimens are now well known,2"7 and because we wished to obtain more details of the role played by partial dislocations and stacking faults in the nucleation growth and dissolution of the hcp ?&apos; phase. This is of interest for the general case of fcc-- hcp transformations. Part of the A1-Ag phase diagram is shown in Fig. 1. The use of a high-temperature stage also enables a study to be made of the clustering process (formation of G. P. zones) and to determine the structure of the solid solution prior to the usual quenching and aging procedures. It is also possible to obtain kinetic data from measurements of the rates of dissolution of precipitate particles. Unlike the results of previous experiments on A1-4 pct CU 1 where much of the initial precipitation occurred on the foil surfaces, the results on the A1-20 pct A1 alloy were identical to those reported for bulk specimens6,7 and no surface precipitation was ever observed. Thus, it was possible to follow the aging sequence: G.P. zones — ?&apos; — ? directly in the thin foils. This paper is concerned with the formation and dissolution of zones and the ?&apos; phase, and no attempt has been made so far to follow the mode of discontinuous precipitation of ?. I) EXPERIMENTAL DETAILS The high-purity A1-20 pct Ag alloy was prepared by the Aluminum Co. of America in the form of 0.001-in.-thick sheets. These were cold rolled with intermediate anneals to a thickness of 0.0004 in.,

Jan 1, 1963

By W. D. Robertson, E. G. Grenier, V. F. Nole

The electrical, mechanical, and corrosion cracking properties of an age-hardenable Cu-Ni-Si alloy have been studied over a range of time, temperature, and deformation states for the purpose of determining the relationship between the properties and the structural state. The precifitate has been identi3ed as and the sites of preferred precipitation have been located by electron microscope studies of the structures developed by various combinations of heat treatment and plastic deformation. An extreme form of deformation banding has been observed in the aged alloy that results in high strain concentration in bands lying parallel to {111} planes. These bands are the structural paths along which transcrys-talline cracks propagate in the deformed alloy. The observations provide a basis for a general mechanism of transgranu-lar corrosion cracking of face-centered cubic alloys in terms of stacking fault probability. AMONG the age-hardening copper alloys the copper-nickel-silicon (Silnic Bronze) type is outstanding in exhibiting a high strength combined with a considerable capacity for cold working, a relatively high conductivity, and a low to negligible susceptibility to stress corrosion cracking. It is not a new alloy and it has been the subject of a number of investigations,1-5 which were made primarily to establish practical composition and heat treatment limits. The structural characteristics of the aging processes in this alloy have not previously been studied in detail. This particular investigation was undertaken to explore, in detail, and over a wide range of conditions, the properties obtainable by various combinations of working and heat treatment and to correlate structural changes with the observed mechanical, electrical and corrosion properties. MATERIAL AND PROCESSING Eight different commercial heats of the alloy were made and used in the investigation. The range of composition among the eight heats is shown in Table I. Billets, 8 by 24 in., were cast into water-cooled molds, extruded to 1.687-in. rod, and quenched in water after extrusion. Extruded material was rod rolled to 0.750 in., annealed at 1450° F for 2.5 hr, and quenched in water. Subsequent working operations were performed by tandem rolling to various sizes depending on the degree of reduction required. Final cold-working operations were performed by drawing to a uniform size of 0.187 in. diam and straightening by a roller straightening machine (Lewis). The combinations of heat treatment, working and aging that were investigated are summarized in Table 11; the various treatments were performed in the order given in each row of the table, and they will be subsequently identified by the symbols shown in the first column. SOLUTION TREATMENT All material investigated in the cold-worked condition, or cold worked prior to aging, was solution

Jan 1, 1962

By F. M. Stewart

A paper by Hurst and van Ever-dingen in 1949 led to the practical solution of many nonsteady-state flow problems.&apos; Subsequently, applications of this material have been discussed by several authors. The purpose of this note is to outline a simplified direct procedure for water-influx pressure predictions for pressures above the bubble point. The prcposed procedure is unique in that after the "time-conversion factor" and the "influx constant" are obtained, predictions are made without trial and error. The elimination of trial and error is made possible by expressing certain PVT characteristics as explicit functions of pressure. The procedure is applicable to fields producing at pressures above the bubble point and under radial water drive from an infinite aquifer. In the usual applications it is required to predict (1) withdrawals given future pressure history or (2) reservoir pressure, given future withdrawals or production. The theory, assumptions and conditions under which the nonsteady-state solutions hold are covered in the references and are not repeated. The simplified direct procedure outlined here has been developed from published solutions for the so-called "pressure case". A similar direct procedure for the same special conditions has been developed for the "rate case"; however, in this instance the procedure is lengthy and offers no advantage over the trial-and-error solution. Consequently, this paper covers only the procedure based on the pressure case. DISCUSSION Under the pressure case prediction of withdrawals from a water-drive field, given the future pressure history, involves the use of a nonsteady-state water-influx term together with the material balance equation. The solution of a particular problem requires the following steps: (1) division of past pressure and production data into equal time intervals; (2) computation of cumulative water influx vs pressure drop for each time interval of past history using the material balance equation; (3) determination of the best values for the "time-conversion factor" and the "influx constant" by equating the nonsteady-state influx term with the influx computed in Step 2 (this requires a trial-and-error procedure); (4) prediction of influx for a given pressure drop using the influx term and the computed factors from Step 3; and (5) calculation of fluids produced using the predicted influx in the material balance equation. A forecast of the water-oil ratio or water production rate is required to complete the calculation. It is assumed that a reliable estimate of original oil in place is available, as well as the production and pressure history, and data on reservoir fluid characteristics. If the original oil in place is unknown, it may be computed simultaneously with the tinie-conversion influx factors2,3. However, the oil in place so computed may be considerably in error3; consequently, it is usually preferable to use oil in place estimated from pore-volume data unless there is considerable doubt as to its accuracy. The Material Balance Equation Above the Bubble Point Above the bubble point the simpli-

By Robert Thomas

DURING the past 20 years the advantages of reinforced concrete as a substitute for timbering in so-called permanent mine openings have been fully recognized, and its use has become almost general practice in the larger mines. The term "permanent mine openings" is used advisedly and is assumed to embrace such openings as ventilation shafts, material shafts and main hoisting shafts, with their adjacent stations, ore pockets, etc. In the concreting of such openings, the actual cost as compared with that of timbering has been of secondary consideration, the support of large openings, elimination of fire hazards, and prevention of inter-ruptions to production being the primary objectives. The ultimate economy, however, of lining such openings with concrete when they are to remain in use during the entire life of the mine, and especially when they are in bad ground, will seldom be questioned. During this 20-year period there have appeared in engineering publi-cations a number of interesting articles on the use of concrete in mines, nearly always describing some specific project of major proportions, such as the concreting of ore pockets, large stations or main hoisting shafts. Such articles are unquestionably of interest, since the projects require considerable engineering thought, not only in the method of excavating large openings, but in their engineering design as well. Concreting of main hoisting shafts, particularly when this is done with the least possible interruption to production, provides some interesting problems. The concreting of haulage drifts of the dimensions commonly found in mines, on the other hand, soon develops into a routine operation, there-fore it is with some hesitancy that the author attempts to prepare an article on this subject. The writer can recall only one article on the concreting of mine haulageways, although several articles have been written concerning the concreting of tunnels considerably larger in dimensions than those required in general mine practice.

Jan 1, 1936

By B. Woyski

MANY writers, in discussing defects caused by oxidation and gassing of bronzes and red brasses advocate substantially the same cure for both. But from its nature, oxidation cannot take place if there is an excess of fuel in the furnace, while the gases absorbed by some alloys are products of incomplete combustion of the fuel. Hence the metal can be either oxidized or gassed, but it is doubtful whether these actions can take place simultaneously. Oxidation can be easily overcome by the use of deoxidizers or it may be avoided by protecting the molten metal with suitable fluxes. Absorption of gases is more difficult to overcome. The regulation of the air and fuel, so as to produce complete combustion, and the protection of the bath by mineral fluxes are the most important factors. Gas expulsion, resulting in gas holes, porosity, unsoundness, and swollen or cauliflower-headed risers, is said to have several causes. One writer&apos; lists the most common causes in the order of their importance, as follows: Superheated metal, dirty or slaggy furnace conditions, using metals low in quality or those previously subjected to bad melting practice, poor grade of fuel, use of newly lined or damp ladles, indiscriminate mixing of scrap or illogical combinations of metal. Superheating the metal usually occurs when the heat is ready to be poured but for some reason must be held in the furnace. In this case, a careful furnace tender tries to avoid overheating the metal by keeping a mild fire; that is, a reducing fire which, unfortunately, results in gassing the metal. A dirty, slaggy furnace may result in gassing the metal by retarding the heating and prolonging the time necessary to bring the metal to the proper temperature, thereby increasing the chances of gassing in uncertain furnace atmosphere.

Jan 5, 1922

By R. W. Hertzberg, F. D. Lemkey, J. A. Ford

The effect oj unidirectional solidification upon the microstructural, crystallographic and mechanical characteristics of high -purity A1-A13Ni eutectic a1loy specimens has been investigated. varying the growth rate caused the morphology of the Al3Ni phase to gradually change from platelets to rods. In addition, the effect of increasing the rate of planar liquid-solid interlace movement is to decrease the Al3Ni rod diameter and inter-rod spacing. The platelets and rods grow approxinlately parallel to each other and are aligned in a faulted substructure. A single unique crystallographic relationship hetween the A1 and ASNi phases was found and may he descrihed as : interface {001} Al3Ni {331} Al and growth direction <010>Al3Ni || <110> Al The platelet interlace and the aligned rows of rods are both uniquely defined by the above statements. Alignment of the Al3Ni phase by unidirectional solidification has given rise to a threefold increase in strength over that exhibited by specimens with an as-cast microstructure. These results illustrate the possible use of this eutectic alloy as a zohisker -reinforced structure. It has been demonstrated by Winegard et al.,1 Kraft and Albrighht,2 Chilton and winegard,3 Chad-wick,4 Yue,5 Tiller,6 and others that a planar liquid-solid interface may be established in binary eutectic alloys by proper control of heat flow during the solidification process. The unidirectional movement of such an interface results in a eutectic mi-crostructure consisting of an essentially parallel array of the two phases over an entire ingot. Two dominant phase micromorphologies have been produced using this technique: that of substantially parallel alternating lamellae of each phase or long thin parallel rods of one phase imbedded in a continuous matrix of the other phase. While not all eutectics can be controlled in this manner, it has been shown that a "normal" eutectic may, under properly controlled conditions of purity, liquid and solid thermal gradients, and solidification rate, be forced to solidify with essentially parallel phase particles. Kraft and Albright2 have demonstrated that, when the growth rate is too rapid or when the thermal gradient in the liquid at the growing interface is too low, a layer of constitutionally supercooled liquid, formed by impurity build-up, will stabilize a cellular rather than a planar interface. The unidirectional movement of the cellular interface forms the macrostructure of eutectic colonies.7 Chilton,3 Chadwick,4 and Tiller,&apos; studying eutectics of zone-refined Pb-Sn, A1-CuAl2, Zn-Sn, and Cd-Zn systems, noted that in the absence of impurities a planar interface is stabilized even when rapidly solidified. Although it is generally agreed that impurities break down a planar interface to form the eutectic-colony macrostructure, at present the origin of the varying micromorphologies (i.c., plates or rods) in a given normal eutectic alloy is not completely understood. Tiller8 has predicted that the micromor-phology produced may be dependent on solidification rate (i.e., at fast rates a rodlike structure is preferred whereas at slow rates a lamellar structure should form), and also suggested that rod formation may be favored at large phase-volume ratios. yue5 has experimentally verified Tiller&apos;s prediction in the eutectic Mg-Mg17Al12 by observing a lamellae-to-rod transition with increasing growth rate where the phase-volume ratio was approximately 2.3:1. However, Hunt and chilton9 more recently unidirec-tionally solidified over a wide range of growth velocities six different eutectic systems with phase-volume ratios between 12:l and 2.7:1 and observed no lamellae-to-rod transition. chadwickl0 has proposed that the change in micromorphology in some eutectic alloys is due entirely to the presence of impurities and further states that the lamellar structure is the characteristic structure of pure eutectic alloys even when the phase-volume ratio is as great as 12:l. Kraft11,12 has shown that the parallel lamellae in certain eutectic alloys assume a unique crystallographic relationship during unidirectional growth. This preferred crystallography may be developed

Jan 1, 1965

By W. H. Bassett, J. C. Bradley

Beads of metal frequently appear at the ends of cast-copper wire bars and on the sides of wedge cakes near the top. These are richer in cuprous-oxide than the rest of the casting. A micrographical study of these exudations has been made. 11 is suggested that the materical is forced through the surface while the copper is solidifying. If not eliminated in process of manufacture, it shows on the finished polished sheet copper in patches differing in color from the main body of the shad. Figures 1 to 4 show the copper exudations, at different magnifications, as they appear on the ends of cast wire bars, and on the sides, usually near the top, of wedge cakes. Sometimes the exudations are in fine "drops;" at other times, large masses of the material are found. Microscopic examination of the copper exudation indicates that it is high in oxide and of eutectic proportions. Because of the difficulty of securing a suitable sample, the protuberances have not been analyzed chemically; but the spectroscope shows no indication that there are any more metallic impurities present than in the balance of the copper. The lowest copper plus silver content of the coppers studied for this paper was 99.914 per cent.; the highest, 99.966 per cent.; so the oxygen content of the whole casting would be well under 0.07 per cent. Structure of Protuberances The segregation of oxide between grains in the interior of the cast bar, not far from the "set," is shown in Figs. 5 and 6. In general, the amount of cuprous oxide begins to increase at a point about 0.01 in. below the normal surface of the casting, i. e., the base of the drop; but it does not attain maximum concentration in the main body of the metal. Vertical sections, Figs. 7 to 12, show that there is a definite line of large cuprous-oxide globules at the base of the drops. Horizontal sections at this place show that these large globules lie in a thin billowy

Jan 1, 1926

By K. H. Hiller

A rotational viscometer has been designed which perrnits the measurement of the rheological properties of drilling muds and other non-Newtonian fluids under conditions equivalent to those in a deep borehole (350F, 10,000 psi). The important mechanical features of this instrument are described, and its design criteria are discussed. The flow equations for the novel configuration of the viscometer are derived and the calibration procedures are described. The data and their interpretation, resulting from measurement of the flow properties and static gel strengths of homoionic montmorillonite suspensiom at high temperatures and pressures, are presented. Data are also presented for the flow behavier of typical drilling fluids at high temperatures and pressures. The pressure losses in the drill pipe and the annulus depend critically upon the flow parameters of the drilling fluid. This work demonstrates the need to measure these parameters under bottom-hole conditions in order to obtain a reliable estimate of the pressure losses in the mud system. INTRODUCTION The rheological properties of drilling fluids are affected by temperature and pressure, but the extent of these effects on the dynamic flow properties is not well known. Measurements of changes of the flow properties of clay-water drilling muds with temperature have been reported by Srini-Vasan and Gatlin.1 The temperatures reported did not exceed 200F, a limitation imposed by the apparatus used by these authors. The rheological properties of clay suspensions were measured at temperatures up to 100C by Gurdzhinian.&apos; Neither the nature of the exchange ions in the clay suspensions nor the degree of purity were defined in his work, nor were the measurements extended to currently used drilling fluids. The lack of systematic measurements of dynamic flow properties at high temperatures and pressures seems the more surprising since during the last decade the importance of the control of the hydraulic properties of drilling fluids has come to be widely recognized. Very good mathematical treatments of the friction losses in drill pipe and annulus have been developed.3 4 These treatments are based on the assumption that drilling fluids behave as Bingham plastic fluids. Quite often this assumption is justified, while in other cases a power law equation pro- duces better fit than the Bingham model does. For convenience in applying viscometer data to pressure-drop calculations, the Bingham plastic flow equation is preferable and, therefore, has been applied to the data reported in this paper, although other equations may fit these data more accurately. In a Bingham plastic fluid the relationship between the shearing stress 7 and the rate of shear D is given by the following equation: where is the plastic viscosity and 4 the yield point. If 4 = 0, the equation for simple Newtonian flow, 7 = pD, is obtained. Two empirical constants are required for the description of laminar flow of a Bingham plastic fluid, and calculations of the flow behavior at high temperatures and pressures cannot be better than is permitted by the accuracy with which these constants are known. For this reason a high-pressure, high-temperature rhe-ometer has been designed to measure the plastic viscosity the yield point +, and the static gel strength S, at pressures up to 10,000 psi and temperatures up to 350F. The important features of its design will be described. The results of measurements on homoionic clay slurries will be discussed insofar as they are relevant to an understanding of the general flow behavior of clay-water drilling fluids. The results of measurements on some typical drilling fluids will be presented also, and their practical implications will be briefly discussed. DESCRIPTION OF EQUIPMENT MECHANICAL FEATURES A viscometer designed to measure the plastic viscosity, yield point and gel strength of non-Newtonian fluids must permit the measurement of the shearing stress t at any given rate of shear D. This is possible only if t and D are approximately uniform throughout the entire sheared sample. A Couette apparatus is the most convenient method of realizing this condition, as has been pointed out by Grodde." The "high-pressure, high-temperature rheometer" described in this paper is basically a rotational Couette viscometer that is immersed in a cell in which pressure and temperature can be controlled over the range of interest. Fig. 1 shows schematically the important features of the pressure cell and associated equipment. The heart of the instrument is the rotating cup. It is shown more clearly in Fie. 2. which revresents the lower one-third of the pressure cell (below the input drive shaft shown in Fig. 1), and it is shown in detail in Fig. 3. For measurements of dynamic flow properties, the rotating cup is driven by a 1/2-hp electric motor, which operates through a Vickers

THE slag performs two useful functions. in open-hearth steel-making. First, it is the means of disposal of all the impurities, save carbon, which are removed from the charge materials in refining the steel, so it must be suited to receiving and retaining as much as possible of undesirable elements with minimum loss of iron and useful alloying elements. Second, the slag serves as a buffer between the flame and the bath and transfers oxygen to the metal at a measured pace contrasted with the violent and difficultly controlled oxidation of the bessemer process. At the same time, the slag is a thermal insulator that limits the rate at which heat can be delivered to the metal from the flame, and a heavy slag blanket thereby serves as a brake on production rates. It has been said with justification that the secret of good steel- making is to make a good slag and the steel will take care of itself. In a broad sense, the subject of slag control includes not only the adjustment of the composition of the slag but also of its relative weight in terms of percentage of the metal-bath weight. The slag is made up essentially of: (1) oxides formed by oxidation of silicon, manganese, phosphorus, and iron in the charge, (2) SO2, MnO, MgO, and other oxides charged as such or introduced incidentally with ores or fluxes or by refractory erosion, and (3) lime charged or fed to the heat to neutralize the "acidic" oxides present (SiO2 and P2O5). Obviously, if practically perfect control were possible over the composition of the charge as well as over the oxidation process during the melting period, both slag weight and composition would be very nearly predetermined, and the control problem would be solved. Unfortunately, only a somewhat imperfect control over these factors is possible, so the operator must begin during the lime boil and continue through the refining period to discover and correct departures from the normal pattern of slag development. To do this as the heat progresses, the first helper must be able to make quick estimates of the composition and physical state of develop-

Jan 1, 1951

By E. G. De Coriolis

The development of huge production facilities and of new or improved processes for manufacturing magnesium from its raw sources has been an outstanding achievement of this war. Furthermore, at least one new method has reached a stage of pilot production that offers promise. Its potentialities seem to indicate that a reduction in cost and simplification or elimination of problems incident to the use of at least one of the present processes are quite within the realm of possibility. Although magnesium of very high purity (99.9 per cent and higher) is obtained, and the rate of recovery reasonable (60 to 70 per cent). the ferrosilicon reduction process is open to a serious objection, which at the time its use was proposed was thought to be sufficient to raise some doubts as to its success, at least on a high production basis. The temperature range at which the reaction is carried out—namely, 2100" to 2150°F.—is very close to the failure temperature of the material of which the retort is made. It is so close that for a time it was assumed it might make commercial use of the process an impossibility. However, at the time under discussion, the demand for magnesium was so great that it was felt by those who had to go ahead and produce this essential metal that the emergency warranted their taking a chance on this process. Subsequent developments have fully justified the soundness of their decision. Fortunately for the war effort, when the plants were put into operation it was discovered that although the retorts did collapse in rather short periods of time, as predicted, they could be blown back into operable shape by application of high-pressure air. This practical method of operation so relieved the situation that the problem disappeared. Nevertheless, if the process had not been successful, or the production of magnesium by the electrolytic process had not been able to keep pace with demands, our war program would have been seriously impaired. Fireless Cooker&apos;&apos; Process For this reason a program was set up and assigned for the development of a new method that had been suggested to the War Production Board in 1941. It is believed justifiable in terming the method "new" for several reasons: (I) while utilizing the same (ferrosilicon) process as the Pidgeon, hence involving similar reactions, the type of retort or furnace is essentially different, (2) the method of operation, reaction temperatures, etc., differ materially, and, most important of all, (3) the problems to be overcome in making the process successful were not and could not have been anticipated by anything previously known about the Pidgcon process. As will be shown later, the briquetting process, the condenser, the furnace lining

Jan 1, 1949

By J. A. B. Forster

W. G. WOOLF*—The paper has a wealth of data that take careful, detailed study. As has been indicated the highlights can be only touched in the paper. The design and the arrangement of the rabble teeth as well as some of the other details of operation show a very careful study and a scientific approach to the problem which in most plants using hearth roasters are matters of trial and error with empirical conclusions and, perhaps too often, just arbitrary supervisory preferences which may be erroneous. Here the problem has been approached from a scientific angle which think well merits careful study. The ability to treat the tonnages they get through these furnaces think is made easier by reason of the high sulphide sulphur in the resulting calcines which the balance of the plant—the leaching and so on—can cope with. As indicated by Mr. Weldon in his dis- cussion earlier this morning, in most zinc plants an attempt is made to have as low a sulphide sulphur content in the roaster calcine as possible. But in the operation of the Risdon plants, they are able to cope with sulphide sulphur content up to 5 pct which is far beyond the amount of sulphide sulphur that can be handled elsewhere. I think the autogenous roasting is made easier because driving out the last percentages of sulphide sulphur brings on the necessity for extraneous heat, and that is further exemplified because even at Risdon the author shows the desirability of using some oil to better the operation, particularly for uniformity of roasting results and to obtain more regularity of furnace operation. A. A. CENTER*—Regarding the hard crusts in the beds of the furnace and autogenous roasting, the paper speaks of the former being due, at least to a considerable extent, to lead sulphide in the crusts. I wonder if the author has considered the hard crusts as being due in large part to zinc sulphate. While I was developing large zinc operations we ran into hard crusts which had to be dug up. I took several lumps which were so hard they showed the marks of the rabble teeth very plainly and kept them in my office for some weeks. A visitor came along one day, and as he was having similar troubles, I told him what we were doing about ours. I started to pick up one of these lumps and to my amazement the thing crumbled in my hands whereas originally it had been so hard it wore the rabbles down very rapidly in the furnace. I sent the sample to the laboratory and found that it analyzed very high in water-soluble zinc and sulphate-sulphur. The crumbling of the lumps was evidently due to the anhydrous zinc sulphate gradually taking on moisture from the air and forming crystalline zinc sulphate seven parts water. The increase in volume would, of course, result in disintegration of the lumps. As to getting a high tonnage in the autogenous roast, that is partly because of finishing at about 5 pct sulphide sulphur. It is a real job to get down to, say, ½ pct sulphide sulphur, which is what is usually desired, and still put through a good tonnage.

Jan 1, 1950

By W. W. Whitaker, C. W. Manry, R. H. McLean

In an eccentric annulus, cement may favor the widest side and bypass slower-moving mud in the narrowest side. Tendency of the cement to bypass mud is a function of the geometry of the annulus, the density and flow properties of the mud and cement and the rate of flow. Bypassing can be prevented if the pressure gradient protluced from circulation of the cement and buoyant forces exceeds the pressure gradient necessary to drive the mud through the narrowest side of the annulus at the same velocity as the cement. In the absence of buoyant forces, one requirement for this balance is maintenance of the yield strength of the cement greater than the yield strength of the mud multiplied by the maximum distance from the casing to the wall of the borehole and divided by the minimum distance. If the yield strength of the cement is below this value, bypassing of mud cannot be prevented unless buoyant forces or motion of the casing significantly aid the displacement. INTRODUCTION Successful primary cementing leaves no continuous channels of mud capable of flow during well treatment and production. Prevention of channels requires care. Tep-litz and Hassebroek provide evidence of channels of mud after primary cementing in the field.&apos; Channeling of cement through mud in laboratory experiments has also been reported.&apos;-&apos; Recommendations for improving the displacement of mud include (1) centralizing the casing in the borehole,&apos;-" 2) attaching centralizers and scratchers to the casing and moving it during displacement,18 "3) thinning the isolating the cement by plugs while it is circulated down the casing,%( (5 establishing turbulence in the cement," and (6) holding the cement slurry at least 2 lb/gal heavier than the mud and circulating the cement slurry at a very low rate of flow.&apos; Although much has been written about the above parameters, the relative importance of each has not been well defined. In this investigation, the mechanics of mud displacement are described through results from analytical models and experiments. The model chosen — a single string of casing eccentric in a round, smooth-walled, impermeable borehole — is analagous to casing centralized in a borehole which is not round and to placing more than one string of casing in a borehole. In each, some paths for flow are more restricted than others. A fluid flowing in the borehole may seek the least restricted, or most open, path. This tendency for uneven flow can lead to channeling of cement through mud unless preventive measures are taken. The analytical models describe channeling and give means of balancing the flow. Experimental data test the analytical models and illustrate effects of motion of the casing, differences in density and mud&apos;s tendency to gel. Results are encouraging. Piston-like displacement of mud by an equal density cement slurry is possible through proper balance of the flow properties of the mud and cement slurries to the eccentricity of the annulus. The more eccentric the annulus, the thicker must be the cement relative to the mud. If proper balance is not achieved. bypassing of mud by cement cannot be prevented without assistance from motion of the casing or buoyant forces. Increasing the rate of flow can help to start all mud flowing but cannot prevent channeling of cement through slower moving mud in an eccentric annulus. Thinning the cement slurry tends to increase channeling although the extent of turbulence in the annulus may be increased. Description of flow in an eccentric annulus begins in the next section. It is assumed that (1) the casing is eccentric and is stationary, (2) the mud and cement slurries have the same density and (3) the gel structure of the mud has been broken and the mud and cement follow the Bingham flow model. Effects related to these restrictions will be discussed. FLOW PATTERNS SlNGLE FLUID IN ANNULUS Flow of a single fluid through an eccentric annulus is illustrated in Fig. 1. Part A shows laminar flow of a Newtonian fluid. This distribution of flow was calculated by Piercy, Hooper and Winney.&apos; In fully developed turbulent flow, the velocity distribution around the annulus is less distorted, but the flow still favors the widest part of the annulus Parts B, C and D of Fig. 1 are a qualitative representation of the flow of a Bingham fluid. The yield strength of the fluid increases the severity of bypassing compared to Newtonian flow. At a very low rate of flow, all flow is confined to that portion of the annulus which has the minimum perimeter-to-area ratio. The fluid shears on the perimeter of that area when the pressure gradient multiplied by the area just exceeds the yield stress of the fluid multiplied by the perimeter. Whether or not the minimum perimeter-to-area region encompasses all of the annulus or only a part (as shown in Part B) depends on the geometry of the annulus. If only a part begins to flow, increasing the rate of flow increases the area flowing until finally there is flow throughout the annulus.

Application of Kutter&apos;s Formula to Gases Discussion of paper by F.-ERNEST BRACKETT, presented at the Pittsburgh Meeting and issued, as Pamphlet No. 1578-A-F, with MINING AND METALLURGY, June. 1926. C. S. WITHERELL, New York, N. Y..(written discussion).-There is no reason to doubt that the relationship between the rate of, flow and. the impelling force of all fluids can be expressed by a general typical equation that takes cognizance of all relevant factors such as density, viscosity (or its reciprocal, mobility) and nature of channel-walls. Most fluids that are commonly conveyed by flow in confined channels are so highly mobile that they may be considered non-viscous, hence for these fluids the factor of viscosity does not need to appear in the equation. Water is the outstanding example of this class of fluids and its dynamic behavior has been so thoroughly investigated that proven formulas pertaining thereto, be they rational or empirical, would naturally serve as prototypes for the other non-viscous fluids. As non-viscous fluids can be classed all gases and vapors, most unsaturated aqueous solutions, gasoline, alcohol, etc. Viscous fluids comprise those that have a sluggish flow such as most oils, tar, molasses, etc., the&apos; high viscosity of which is due to shearing resistance between molecules, a force that must betaken into account in figuring the flow of fluids of this class.

Jan 10, 1926

By A. H. Larson, L. G. Twidwell

The influence which Au, Ag, Sb, Bi, Sn, and Cu have, both individually and collectively, on the activity coefficient of sulfur in liquid lead at 600"C zuas studied by circulating a H2S-Hz gas wlixture over a specific lead alloy until equilibrium was attained. Subsequently, the H2S concentration in the equilibrium gas mixture and sulfur concentration in the condensed phase were deterruined. The elements gold, silver, and antinzony (above 8 at. pct) increased the activity coefficient of sulfur. Bismuth had no apparent effect. Tin (above 3 at. pct) and copper decreased the coefficient. The influence of an individual element, i, on sulfur is best reported as the interaction parameter, riS, which is defined as The values o these first-order interaction zus are: ESzu = —55.0. These interaction parameters are used to predict the activity coefficient of sulfur in six fouv-component alloys and one seven-component alloy. Comparisons are made with direct experimental determinations. INTERACTIONS in dilute solution have been studied by many investigators. Most of the experimental work has been confined to solute-solvent interactions in simple binary systems and solute-solute interactions in ternary systems. Dealy and pehlke"~ have summarized the available literature on activity coefficients at infinite dilution in nonferrous binary alloys and have calculated from published data the values for interaction parameters in dilute nonferrous alloys. Interaction parameters are a convenient means of summarizing the effect of one solute species on another in a given solvent. Only a few investigators have studied interactions of the nonmetallic element sulfur in a metallic solvent. They are as follows: Rosenqvist,~ sulfur in silver; Rosenqvist and Cox,4 sulfur in steel; chipman, sulfur in alloy steels; Alcock and Richardson,% ulfur in copper alloys; Cheng and Alcock,&apos; sulfur in iron, cobalt, and nickel; Cheng and ~lcock,&apos; sulfur in lead and tin. The only reported work on the Pb-S system in the dilute-solution region is that of Cheng and Alcock.&apos; Their investigation involved a study of the solubility of sulfur in liquid lead over the temperature range 500" to 680°C. The results may be summarized by the following relationship: S (dissolved in lead) + Pb(1) = PbS(s) log at. %S = -3388/T + 3.511 Experimentally, it was found that Henry&apos;s law was valid up to the solubility limit of sulfur in lead, i.e., at 600°C up to 0.43 pct. Their investigation did not include the study of sulfur in lead alloys. More accurate calculations could be made in smelting and refining systems if activity coefficients of solute species could be accurately predicted in complex solutions. One of the objectives of this study was to compare the experimental data with the values calculated from the equations derived from models for dilute solutions proposed by wagner9 and Alcock and Richardson. A temperature of 600°C was chosen as the experimental temperature to attain reasonable reaction rates and to minimize volatilization of the condensed phase. EXPERIMENTAL Materials. The Pb, Au, Ag, Sb, Bi, Sn, and Cu used for preparation of the alloys were American Smelting and Refining Co. research-grade materials. All were 99.999+ pct purity except the antimony and tin which were 99.99+ pct. The initial alloys prepared for this study consisted of twenty-one binary alloys, eleven ternary alloys, and one six-component alloy. The constituent elements were mixed for each desired alloy and were placed in a crucible machined from spectrographically pure graphite. The crucible was placed in a vycor tube which was evacuated with a vacuum pump and gettered by titanium sponge at 800°C for 8 to 12 hr. After the gettering was completed, the chamber containing the titanium was sealed and removed. The remaining sample chamber was placed in a tube furnace at 800°C for 2 hr and quenched in cold water. The final operation consisted of homogenization of the alloy for 1 to 2 weeks at a temperature just below the solidus for the individual system. The resulting master alloys were sectioned into small pieces and a random choice made for individual equilibrations. Cobalt sulfide (Cogs8) used to control the gas atmosphere in the circulation system was prepared by passing dried HzS for 24 hr over a Co-S mixture heated to 700°C in a tube furnace. This material was then mixed with cobalt metal to give a two-phase mixture which, when heated in hydrogen to a particular temperature, produced a desired H2S/H2 gas atmosphere in the circulation system. A Cu2S-Cu mixture also used in this study was prepared in a comparable manner. Apparatus for Equilibrium Measurements. The experimental technique of this study required apparatus

Jan 1, 1967

By W. J. Sharwood

(San Francisco Meeting, September, 1915) CUPELLATION is well known to be one of the most effective methods of separating silver and gold from base metals and other impurities, as well as one of the most accurate means for their estimation. In the latter application it consists in absorbing in some porous medium the fused lead. oxide formed by the oxidation of the lead "bath," which carries with it the oxides of other base metals present. It has long been recognized that small amounts of both silver and gold were removed and absorbed together with the base metals, as well as being to some slight extent volatilized, and in work of the highest accuracy a correction is made for the "cupellation loss." Thus. in the assay of bullion this is done by means of "proofs" of like composition, which are manipulated throughout in precisely the same manner as the assay pieces, and are assumed to lose or gain like amounts. In the case of certain very rich ores and commercial products the loss is adjusted by assaying the cupel itself and recovering the precious metal absorbed, but this doubles the labor and does not remedy the loss by volatilization. Arbitrary tables have been drawn up by various authorities with the object of enabling a correction to be applied without the use of a check. These have been of very limited practical use owing to the fact that a number of factors affect the losses sustained. For a fixed amount of precious metal the loss varies with the amount of lead used, with the nature and amount of the impurities, with the porosity of the cupel, with the air supply, and above all with the temperature at which cupellation is carried on. Pure silver loses relatively much more than gold, but the loss in either is diminished by au addition of the other metal. The concentration of precious metal in the litharge increases as the concentration in the lead increases, but little work has been published connecting the two. If all other conditions remain the same the actual total loss increases, but the percentage loss diminishes, with an increase in the weight of precious metal treated.

Jan 8, 1915

By Bradley Stoughton, Henry M. Howe

This paper presents an experimental verification of some of the predictions made by one of us1 concerning the influence of certain conditions of casting upon the size and position of the pipe, and the position of the segregate, in steel ingots. The predictions which we have been able to verify are the following: A. That the pipe is shortened and the segregate raised: 1. By slow casting; 2. By casting with the large end up instead of down; 3. By retarding the cooling of the top, e.g., by means of a sinking-head. B. That the pipe is shortened by slow cooling. C. That the pipe and segregate lie in the last-freezing part. Our procedure was to cast ingots of wax (commercially pure stearic acid) containing a little bright green copper oleate (usually 1.5 per cent.) under varying conditions; to saw each ingot open along a longitudinal plane passing through its axis; and to examine the longitudinal section thus laid bare. In order to make the segregate or enriched part more distinct in color from the impoverished part, a very little red cerasine was added. An experiment which will be described later showed that the cerasine itself does not segregate markedly, if at all. Hence we may assume that the strong contrasts between the green and red shown in so many of our ingots are due, not to segregation of cerasine, but to that of the green oleate, in the wax which in itself is uniformly reddened with cerasine.

Jan 1, 1908

By C. S. Sivil

To modern civilization the platinum metals are of inestimable value. Their distinctive properties, both physical and chemical, render them indispensable in an age in which the processes of the laboratory are becoming an essential part of the daily life of the world. Generally, their function, though vital to particular processes, is not spectacular, and so remains unknown to all except the operators. EARLY METHODS OF MANUFACTURE The properties of platinum were recognized as of prime importance for scientific work at. a very early date, probably between 1750 and 1760. The difficulty of making articles from it seemed almost insurmountable, because no means of attaining the temperature necessary to melt it were known at that time. It is true that solid platinum could be obtained by fusing the metal with a more volatile metal such as arsenic, which was subsequently driven off by baking, but such a method, at its best, would give only a very brittle product, which was totally unsuitable for the purposes for which it was intended. Little, if any, progress could be made until it was discovered that platinum sponge, heated to white heat and hammered in an iron or clay mold, would metallize and retain the shape of the mold. This was a process that could not be wholly satisfactory but from it developed the method of pressing the sponge in a mold and forging it at white heat into wire or sheet. At present a somewhat similar process must be used for fabricating articles of tungsten, molybdenum and other metals of high fusing point, as with these metals we face today the same problems that the scientists of the eighteenth century encountered with platinum, but possibly the next significant advance in the metallurgy of these metals will be the devising of means to melt and cast them.

Jan 1, 1931

By Maurice B. Dusseault, Edo Nyland

Numerous consistent seismic signals are being generated in a pilot fireflood in a 750 m deep high permeability unconsolidated channel sand in Eastern Alberta. The pilot has a central air injection well, eight production wells on artificial lift, and two internally placed observation wells. Surface seismometers and a 12-hydrophone downhole string were deployed to detect seismics signals. Date were collected for 22 hours employing signal-triggered event detectors recording on cassette tapes. Monitoring during twelve hours of steady air injection at 625m3/s yielded a clear event frequency of about 50 events/h. The events were mostly clear compressional wave arrivals originating in the vicinity of the firefront. Stopping air injection caused a gradual drop in event frequency, and the rate was reestablished when air injection was reinitiated. Spectral frequency analysis and knowledge of material properties indicate that the events are shears of a stick-slip nature associated with the strain-weakening behavior of the over-compacted reservoir sands. The event amplitude indicates small-scale shearing, and different amplitudes suggest that planes re-shear with lower energy release levels. The triggering mechanism for shear rupture is high shear stress created by thermal expansion in the area of highest ther- mal gradient. Other enhanced recovery techniques may also produce useful signals for process control. In particular, steam flooding, hydraulic fracturing, and high-pressure injection operations likely generate mappable microseismic events which can be applied directly to production/ injection strategy.

Jan 1, 1982

By A. S. Yue

The movphology of the Mg-32 wt pct Al eutectic has been studied as a function of freezing- rate and temperature gradient. At slow freezing rates a lamellar eutectic was formed; whereas, a rod-like eutectic was generated at fast rates. The inter-lamellar spacing increased as the freezing rate decreased in aggreement with theoretical predictions. Lamellar faults, morphologically similar to edge dislocation models in crystals, were responsible for the subgrain structures in the eutectic mixture. A linear increase in fault density with freezing rate was observed. Fault concentl-ations of the order of 10 per sq cm for a range of freezing rates from 0.6 to -3.0 x 10 cm per sec were estimated. The transformation from lamella?, to rod-like morphologies was determined experimentally to be dependent on the freezing rate and independent of the temperature gradient. Moreover, the number of rods formed per- unit cross-sectional area increased exponentiallv with increasing freezing rote. BRADY&apos; and portevin2 classified eutectic structures into lamellar, rod-like, and globular according to the morphology of the solid phases present. Although this classification is quite descriptive, very little has been reported on the details of the mechanism by which the eutectic structures are formed. Recent work by Winegard, Majka, Thall, and chalmers3 and by chalmers4 on lamellar eutectic solidification suggest that the maximum thickness of the lamellae decreases with increasing rate of solidification due to inadequate time for lateral diffusion. scheilS and Tiller&apos; have shown theoretically that the lamellar widths indeed depend on the solidification rate. However, there has been no experimental evidence to support the theory. Chilten and winegard7 have studied the interface morphology of a eutectic alloy of zone-refined lead and tin. They found that the lamellar width decreased as the freezing rate increased in agreement with the theoretical predictions of scheils and Tiller.&apos; More recently, Kraft and Albright&apos; have investigated the microstructures of the A1-CuA12 eutectic as a function of growth variables. They observed lamellar faults present in the lamellar eutectic, similar to edge dislocation models in crystals. Furthermore, Kraft and Albright reported that they could not designate which extra lamellar was responsible for the formation of a lamellar fault even under electron microscopic magnification. In this paper, the morphology of the Mg-A1 eutectic structure is described. The effects of freez- ing rate on the interlamellar spacing and on the lamellar fault density are presented in detail. The transformation from lamellar to rod-like eutectics is discussed in terms of the freezing rate and the temperature gradient. EXPERIMENTAL PROCEDURE The experimental details of alloy preparation, the decanting mechanism and the determinations of the freezing rate and the temperature gradient have been reported elsewhere. Measurements of plate-edge angles were made with a microscope. The true angles used to determine the interlamellar spacings were determined by a two surface analysis technique.&apos;&apos; Since the decanted interface structure does not represent the true eutectic morphology on the solid,g all measurements were made from an area in the solidified bar behind the interface. Measurements of the apparent interlamellar spacings between the two phases of the eutectic were made on a photographic negative by means of a calibrated magnifier. Each value listed in Table I represents the average of thirty measurements on one negative. In general, these measurements are approximately equal with an error of less than pct. The average rod diameter for each specimen was also measured on a magnified photomicrograph. Each value of the diameter represents the average of fifty measurements. RESULTS AND DISCUSSION The experimental observations and their discussion to be presented here are restricted to the morphology of the eutectic structure and to the effects of the freezing rate and the temperature gradient on the solidification of eutectics. INTERLAMELLAR SPACING It has been shown previouslyg that the micro-structure of the decanted interface and the longitudinal section of the Mg-A1 eutectic is characterized by the presence of both lamellar and rod-like morphologies. The lamellae become more regular as the freezing rate is decreased. A three-dimensional photomicrograph representing a perfect lamellar morphology is illustrated in Fig. 1. The lamellae of the top and longitudinal sections of the specimen are regularly spaced while those in the transverse section are not quite straight and parallel. Their parallelism is slightly distorted because fault lines producing a discontinuity are present. A method for calculating the interlamellar spacings A, is described in Appendix 1. The true

Jan 1, 1962

By J. E. Elliott, K. O. Miller

Solubility studies were carried out to establish the phase distributions for various Fe-Ni-Pb-C alloys at temperatures where the metallic components exist as liquid solutions. Temperature us composition diagrams for the Ni-Pb, Fe-Pb, Fe-Ni-Pb, and Ni-Pb-C systems are derived by employing various approximations in conjunction with the data. Results are summarized for 1550°C in a quaternary phase diagram of the Fe-Ni-Pb-C system. BECAUSE surprisingly little information has been published on the phase diagrams of the Ni-Pb, Fe-Pb, Fe-Pb-Ni, and Fe-Ni-Pb-C systems, a study of these systems was undertaken to ascertain the important phase relationships in the temperature range of 1300" to 1550°C. Measurements were also made on the carbon-saturated systems in the hope that they would assist in the interpretation of the systems without carbon. This paper reports the results obtained from the simple equilibration of the various liquid and solid phases. EXPERIMENTAL PROCEDURE The experimental technique involved holding appropriati quantities of the metals in an alumina crucible, or in a graphite crucible when saturation of the melt with carbon was desired, for sufficient time at the desired temperature to ensure equilibrium. Then a sample of each liquid phase presen was drawn into a small-bore silica tube. This sample was withdrawn quickly from the furnace, cooled, and sent to the chemical laboratory for analysis. The cell assembly used is shown in Fig. 1. Durin the work on the Fe-Pb-Ni system, it was placed in a furnace wound with 20 pct Rh-80 pct Pt wire. This furnace eventually failed and subsequent studies were carried out between 1350" and 1475°C in a tube furnace heated by silicon-carbide resistance elements. A protective atmosphere of argon with approximately 10 pct hydrogen was supplied to the cell assembly at a gage pressure of 1 in. of water. Hydrogen was passed over palladized alumina and then anhydrous calcium chloride for purification. Argon was purified of oxygen and water vapor by passing it over copper gauze at 550°C and then through a calcium chloride drying column. The gases were mixed and redried before they entered the equilibration cell. Temperature was measured by calibrated Pt/Pt-10 pct Rh thermocouples and a Rubicon Type B potentiometer. The thermocouples were standardized against the melting points of pure nickel

Jan 1, 1961