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By W. E. Stiles

A method is presented for predicting the performance of water flooding operations in depleted, or nearly depleted, petroleum reservoirs. The method makes use of permeability variations and the vertical distribution of productive capacity. From these two parameters can be calculated the produced water cut versus the oil recovery. Derivations of the mathematical analogy is shown and sample calculations and curves of prediction are presented. Comparison is made of the predicted and actual performance of a typical 5-spot in an Illinois water flood. INTRODUCTION The use of water as a flooding medium in both depleted and "flush" oil reservoirs is gaining greater recognition and acceptance. Many of the shallower fields, depleted by primary production, have been and are being subjected to water injection in order to obtain some part of the large volume of oil remaining after primary production. Some of the earlier water flood installation proved highly discouraging and the value of water flooding was often questioned. Many of these earlier floods were haphazardly selected and developed as little was known of the physical characteristics and contents of the producing formations. The prior evaluation of the flood performance was impossible. During the past decade the development of the required reservoir engineering tools-—core analysis, reservoir fluid analysis, electric logs, fluid flow formulae, etc.—has allowed the engineer to construct and apply the methods which are presently being used to evaluate the economic and mechanical susceptibility of a reservoir to flooding. This discussion will present a method for taking into account the effect of permeability variations in predicting the performance of water floods in depleted reservoirs. PERMEABILITY AND CAPACITY DISTRIBUTION It is generally agreed by most investigators that in a single phase system fluid will flow in a porous and permeable medium in proportion to the permeability of the medium. Producing formations are usually highly irregular in permeability, both vertically and horizontally. However, zones of higher or lower permeability are often found to exhibit lateral continuity. Thus, while structurally comparable stringers in adjacent wells may differ several fold in permeability values, they usually bear resemblance as being part of a general continuous higher or lower permeability section. It is generally agreed that where such stratification of permeability exists, injected water sweeps first the zones of higher permeability, and it is in these zones that "break-through" first occurs in the producing well. It is a basic assurnption of the presently described method that penetration of a water front follows the individual permeability variations as if such variations were continuous from input to producing well. This is admittedly not rigorously true, but can be justified as making possible a simplifying mathematical approach to an otherwise extremely complicated three dimensional flow problem. As a basis for study of the lateral flow of fluids in formations of irregular permeability, the irregularities may be conveniently represented by a permeability distribution curve and a capacity distribution curve. In obtaining these curves, the permeability values, regardless of their structural position in the formation, are rearranged in order of decreasing permeability. If these permeability values so arranged are plotted against the cumulative thickness, a permeability distribu- tion curve is obtained. This curve may then be likened to a "smoothed" permeability profile of the formation. In making comparison between different distribution curves it is convenient to state the permeabilities in terms of the ratio of the actual permeability values to the average permeability of the formation. These ratios termed "dimensionless permeabilities", are used in this paper rather than the permeabilities in terms of millidarcys. The capacity distribution curve is a lot of the cumulative capacity (starting with the highest permeabilities) versus the cumulative thickness. The capacity and thickness are given as fractions of the total capacity and thickness. Mathematically, the capacity distribution is the intergration of the permeability distribution curve. In practice it is convenient to first obtain the capacity distribution curve and derive from it a smoothed dimen-sionaless permeability curve. The method of obtaining the capacity distribution curve is illustrated in the successive column of Table 1, in which capacity and thickness are derived as fractions of their respective totals. If only a small number of permeability values are available, it is generally desirable to smooth the resultant curve. This has been done to give the capacity distribution curve shown in Figure 1. The differentiation of the capacity distribution curve to obtain the permeability distribution curve is shown in Table 2. Here, the capacity values are read from the smoothed curve at intervals of cumulative thickness, and the increments of capacity are divided by the increments of thickness to obtain the dimensionless permeability, K. Due to this stepwise procedure of calculation these premeability values must be plotted at the midpoints of the successive increments of thickness. The curve so obtained from these data is shown in Figure 1. The total area under the K' curve is equal to unity.

Jan 1, 1949

SEC 1 The membership of the Institute shall comprise seven classes, namely 1 Members, 2 Honorary Members, 3 Senior Members, 4 Associates, 5 Junior Members, 6 Rocky Mountain Members, 7 Junior Foreign Affiliates All shall be equally entitled to the privileges of membership, excepting that no member of any class whose residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote SEC 2 Members A person to be eligible for election or transfer into the class of Member must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields This shall not apply to Rocky Mountain Members SEC 3 Honorary Members Each candidate for Honorary Membership must be recommended by the Committee on Honorary Memberships and must be elected by ballot at a meeting of the Board of Directors by the unanimous vote of the Directors present, provided, however, that the number of Honorary Members shall at no time exceed twenty Such election shall automatically act as a transfer of such member from any other class of membership to which he may belong SEC 4 Senior Members The Directors may, at the special request of any Member or Associate who has reached the age of seventy years and who has paid

Jan 1, 1952

By S. E. Bretherton

This title introduces the subject I wish to describe to my fellow members, very few of whom, I 'hope, have ever had as much trouble with the smelting of ore containing much zinc, either in the lead blast furnace or the matting furnace, as circumstances have forced upon me: First, for several years in Leadville, Colo., after the sulphide ores containing zinc had been developed with greater depth and were sold to the intereats with which I was connected for smelt-ing in the blast furnace for the recovery of the lead, silver, and gold; then, in New Mexico and Arizona, where the principal source of ore supply for our custom smelter was from miners who sent most of their product in the form of concentrates, which we briquetted and smelted in the blast furnace, producing a matte containing copper, silver, and gold, for which we were paid; together with some zinc and lead, which was penalized if in excess of a maximum base set by the refinery to which we sold our copper matte; last, but not least, my experience in Shasta county, Gal., where for the sake of recovering $13 per ton value in copper, silver, and gold, I have smelted ore containing as high as 40 per cent. zinc (the last 18,951 tons smelted averaged 15 3/10 per cent. zinc) which we not only lost, but which it cost us money to lose. After such an experience, and knowing that, instead of being worth only $13 per ton, such 15 per cent. zinc ore should be worth about $30, including zinc at the present market value, the question of recovering the zinc in a profitable manner from such ore became very interesting to me. During several years' time I sent samples, of from 5 to 1,200 lb. each, to be tested by the different best-known zinc-recovery plants, and experimented with several processes proposed by others for the treatment of such ore, with but little encouragement, until I

Jan 1, 1914

By William B. Plank

IN this paper are presented the results of a complete statistical survey of the enrolment, courses and degrees, and the employment situation of recent graduates in all of the 46 institutions in the United States, including Alaska, and four of the six schools in Canada that grant degrees in mineral technology. The data were collected by the writer by means of a questionnaire in December, 1933, to which all the institutions, except one, replied. Included also are data of a similar study made by the writer in May, 1933, for the S. P. E. E. summer session of mining and metallurgical teachers at the University of Wisconsin and published in the Journal of Engineering Education for December. 1933. Some of the data of a paper of the writer's entitled, "The Trend of Mineral Engineering Student Enrolment in the United States," read at the A. I. M. E. meeting on Feb. 16. 1931, are given for comparison. Acknowledgment is made to all the administrative officers of the institutions who took the time from their busy lives to supply the in- formation asked for. Their fine cooperation has alone made possible these two surveys with a completeness of detail never before attempted

Jan 1, 1934

By R. R. Unterberger

Three different physical techniques have been used to see through or probe into rocks, so miners might know what is ahead or overhead. These are radar, sonar, and a unique type of sonar called nonlinear sonar. Five radar systems have been developed. The highest frequency used is 4300 MHz for detecting small fractures at close range. This gives the best resolution. For longest range (over 2000 m, or 6560 ft) we use the 30 MHz radar for finding faults ahead of mining or ranging to salt dome flanks. Two types of salt, dome and bedded, are recognized. Radar works well in dry (dome) salt, but not in bedded salt which contains small amounts of water. The dipole moment of water absorbs energy from the radar. Thus was born the 30 MHz radar system and sonar probing systems. These can probe to 100 m (328 ft) even into wet salt. All probing systems measure data in time, which are converted to distance by measuring the time of travel of radar or sonar through salt pillars of known thickness. Ranges of probing in salt are from less than 1 m (3.3 ft) to more than 2000 m (6560 ft). Uses of radar and sonar probing in mines include mapping the top of salt above a mine; mapping salt dome flanks; finding impurities in salt such as anhydrite, sandstone, or potash stringers; locating old boreholes in salt pillars; locating fractures in salt; and finding faults or water zones ahead of mining.

Jan 1, 1985

By Howard Martens, Pol Duwez

IN two papers published in 1949, alloys of chromium with the refractory metals tungsten, molybdenum, tantalum, and columbium were investigated in view of their possible use as high temperature resisting materials. For the Cr-Ta system, a partial phase diagram was presented and the only intermediate phase was identified at Ta2Cr3. A phase of the same composition was also observed in the Cb-Cr system. The X-ray diffraction data presented in these papers, however, were insufficient for crystal structure determination. It is shown in the present study that the only intermediate phase in both the Ta-Cr and the Cb-Cr systems corresponds to the ideal stoichiometric ratio TaCr2, or CbCr2. Both structures are cubic, MgCu, type. At high temperature, however, TaCr2 has a hexagonal MgZn, type structure, which can be retained at room temperature by fast cooling. The alloys were prepared by melting in a helium arc furnace on a water-cooled plate. The design of the furnace was essentially the same as that described in ref. 3. Some alloys were also obtained by sintering compacts made of the mixed powders pressed at 80,000 psi. The sintering was carried on for 4 hr at 1375°C. The tantalum and columbium powders were supplied by Fansteel Metallurgical Corp., North Chicago, 111. The tantalum powder was the reagent grade, with a particle size smaller than 400 mesh and a total impurity content less than 0.1 pct. The columbium powder was smaller than 325 mesh and contained approximately 0.1 pct C and traces of Fe, Ti, and Zr. The electrolytic chromium powder from Charles Hardy, Inc., New York, was smaller than 300 mesh and contained about 0.1 pct Na, 0.05 pct Ca, and traces of Cu, Al, Mg, Si, and Co. Powder diffraction patterns were obtained with a 14.32 cm camera, using copper Ka radiation filtered through nickel foil. The powder pattern of the TaCr2 alloy obtained by sintering at 1375'C was different from that obtained on the same alloy rapidly cooled from the melt. Contrary to this result, the powder pattern of CbCr2 was the same, whether the alloy was made by sintering at 1375°C or by melting, and was similar to that of the TaCr, sintered. It was also found that the structure of the TaCr2 specimen obtained by melting was retained after heating for 4 hr at 1590°C, but transformed into the structure found in the sintered specimen after heating for 4 hr at 1375°C. Hence, the structural change of TaCr2, appears to be a reversible polymorphic transformation. CbCr2 and ToCr2 Structure, Low Temperature Form By using large scale Hull-Davey charts, the powder pattern of CbCr, and of the low temperature form of TaCr2 were readily interpreted on the basis of a face-centered cubic lattice with a parameter of approximately 6.95 kX. The indices of the reflections together with the values of sin' 0 are given in Tables I and 11. From this list of observed reflections, it appears that the (200), (600), (024), (046), and (028) reflections are missing. The lack of (h00) reflections for h 4n indicates a four-fold screw axis. The missing (Okl) spectra for k + 1 An indicate the existence of a diamond glide d. The combination of these symmetry elements can be found in the O— Fd3m space group, which is therefore the most probable one. After having determined the approximate density of TaCr, by the immersion method, the number of molecules per unit cell was calculated and found to be nearly eight. This information, added to the fact that the most probable space group is O leads to the consideration of a structure of the MgCu2 type, in which the atoms have the following positions: 8 magnesium in a and 16 copper in d. On the basis of this structure, intensities were computed by means of the usual formula: 1 cos'20 I a sin2 cos where F is the structure factor; 8, the Bragg angle: and p, the multiplicity factor. As shown in Tables I

Jan 1, 1953

Jan 1, 1962

By John Wulff, J. H. Hollomon

THE opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was redeposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufliciently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion .4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May,6 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to alpha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. "I hey believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They (lid not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,8 in another publication, suggested that the commonly found gray or black arsenical film may act to: (1) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led hint to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed (luring the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (AS208)

Jan 1, 1942

By H. C. Boynton, Albert Sauveur

In the course of some experiments conducted in the Metallographical Laboratory of Harvard University, some interesting facts were brought to light which appear to be worth recording in advance of a more elaborate and exhaustive paper which the authors hope to present to the Institute in the near future. Fig. 1 shows, under a magnification of 100 diameters, the microstructure of the cross-section of a steel bar 1/2-inch square, containing 0.52 per cent. carbon, heated to 1100 degrees C. and cooled slowly with the furnace. Fig. 2 illustrates the structure of the same steel, heated to the same temperature but cooled more rapidly in the air. Both samples were cut from the same bar and heated side by side in the furnace. When a temperature of 1100 degrees C. had been reached, one sample was taken out of the furnace and allowed to cool in the air, while the other was cooled with the furnace. The only difference, therefore, in the treatment of both samples will be found in their respective rate of cooling. This variation in the rate of cooling resulted, as shown

Jan 1, 1904

The following is an incomplete list of members and guests who called at Institute headquarters during the period Oct. 10, 1918 to Nov. 10, 1918. J. Carson Adkerson, Virginia. George H. Parsons, Hayden, Ariz. Andrew B. Armstrong, Connecticut. W. E. Pomeroy, New York. Courtenay DeKalb, San Francisco. Ezra C. Rider, Bisbee, Ariz. Clifford G. Dennis, San Francisco. H. W. Seaman, Chicago, Ill. Rudolph Emmel, Boston, Mass. William Allen Smith, Northampton. Emil Gathmann, Baltimore Md. R. K. Stockwell, Salt Lake City, Utah. Ernest S. Geary, Denver, Colo. W. G. Swart, Duluth, Minn. W. E. Hopper, Washington, D. C. Kirby Thomas, New York. W. Spencer Hutchinson, Boston, Mass. - Warren D. Thompson, Harvard Club. E. W. Kohl, Jr., Philadelphia, Pa. H. Vincent Wallace, Los Angeles, Cal. E. C. Nighman, Butte, Mont. Paul T. Benson, formerly with the Tacoma smelter, has resigned his position there to accept one with the Great Metals Mining and Milling Co. at Nespelem, Wash. Prof. Edward E. Bugbee, of the Mining Department of the Massachusetts Institute of Technology, has been granted a leave of absence to accept the position of Assistant Director of Education for the S.A.T.C. of five southern states with headquarters at Raleigh, N. C.

Jan 12, 1918

By Michael Tenenbaum

Selected characteristics of nonmetallic phases were determined in low-carbon sheet steels which had been produced by various refining; deoxidizing, and casting procedures. The results showed little influence of the refining process on the quantity, distribution, size, and character of the nonmetallic phases. The quantity of inclusions was governed by the deoxidation procedures. While the mode of casting influenced the internal structure and the pattern of inclusion distribution, it had little effect on the quantity of nonmetallics. The vast majority of inclusions were under 30 µ in diam, and there was little change in size distribution during hot and cold rolling. The composition and structure of the inclusions were expained an the basis of known equilibrium phase diagrams for the appropriate systems. Additional work is needed to explain some of the observations of this paper. HENRY Marion Howe's contributions to the metallurgical profession include his many writings, the wisdom that he imparted to his students, and the inspiration that he gave to the many scholars, teachers, and industrialists who knew him personally. It was Professor Howe's intimate colleague, Albert Sauveur,1 who, in the first Howe Memorial Lecture, could have been speaking for the metallurgist of our generation as well as his own when he wrote, "...how many of us on the point of going astray were called back to the right path by Howe's guiding torch?" More than a quarter of a century later, Francis Foley,2 one of the last in the Howe Lecture series who worked directly with the great man, delivered the ultimate tribute, "...truth, in its time is so hard to identify." While Professor Howe strove to be right, "he was content if he provoked the reader to take the next step along the path to greater knowledge." Like so many of my predecessors, I sought guidance for this lecture by referring to Professor Howe's two classic texts, Metallurgy of steel,3 and Metallography of Steel and Cast Iron: the former book interpreting the facts as he saw them near the start of his career, and the latter—published 26 years later—pointing to many fertile fields for metallurgical investigation. Those of us who harvest the fruits of Henry Marion Howe's contributions to the metallurgical profession now look with wonder at the tremendous legacy he has provided. It is rewarding to study his writings and to recognize the anticipation of such aspects of modern ferrous metallurgy as: 1) Direct reduction 2) Steelmaking reactions 3) The approaches and benefits of degassing 4) Solidification mechanisms 5) Habits and behavior of nonmetallic inclusions 6) Recrystallization phenomena 7) Slip and slip propagation 8) Dislocations 9) Discontinuous deformation 10) Microscopic and macroscopic segregation

Jan 1, 1970

By J. L. Stokes, L. J. Demer

It has recently been shown' that epitaxial films of silicon carbide deposited on silicon single crystals possess desirable properties for semiconductor applications. There is one apparent disadvantage to such a system, however; since epitaxial deposition is a high-temperature process, it can result in plastic deformation of the silicon substrate. The accompanying Berg-Barrett X-ray diffraction photographs reveal plastic deformation in two silicon semiconductor crystals which occurred when the crystals were coated with an epitaxial layer of silicon carbide at 1150°C. Due to differences in thermal expansion between the silicon substrate and the epitaxial silicon carbide, the silicon was subjected to stresses while still in the plastic temperature range. Both crystals shown were 0.7 in. in diam and 0.0055 in. thick. The crystals were sliced from a larger crystal so that their polar axes were parallel to the [ill] direction. After cutting, the crystals were polished with diamond paste, and etched in HC1 vapor to remove surface damage re- sulting from the cutting and polishing operations. This provided clean, damage-free surfaces on which to deposit the silicon carbide. Figs. l(a) and l(b) are reflection and transmission photographs, respectively, of the same crystal. A smaller portion of the crystal is shown in the transmission geometry, because a vertical slit was

Jan 1, 1965

By J. F. Crouch

INTRODUCTION Roll front uranium has unique geologic characteristics (L,) which require specialized mining procedures. Roll front uranium occurs in arkosic sandstones with the ore zone typically less than 100 feet in thickness with up to 400 feet of overburden. The areal extent of ore is often a few thousand acres. Within the ore zone, ore grade material occurs in C and S shaped rolls, which are a few feet in width and height but may run laterally for several hundred feet. Since the total mine plan may include mining all ore, a roll front uranium mine may cover a few thousand acres. For both economic and environmental reasons, a roll front deposit is mined as a series of phases or sub-pits (3, 4) as illustrated in Figure 1. A typical sub-pit is 400 to 500 feet across. Sub-pit 1 is stripped initially and the overburden is spoiled on the surface. Depending on haul distance and overburden characteristics, stripping is done with trucks and shovels (or front-end loaders) or scrapers. When ore is encountered in sub-pit 1, mining begins, and the stripping equipment is moved to sub-pit 2, with sub-pit 2 overburden also being spoiled on the surface. When ore is encountered in sub- pit 2, sub-pit 1 mining should ideally be complete so the mining equipment can move to sub-pit 2 and sub-pit 3 overburden can be spoiled in the mined out sub-pit 1 area. Ore is mined selectively in a series of 12 to 24 inch cuts by a 2-1/2 yard backhoe on the basis of radiometric probing. For effective drainage, ditches must be maintained on the boundary of sub-pits, and mining lifts are kept as level as possible, with the orebody slightly elevated as part of general good mining practice. Waste removal in the ore zone is done by self- loading scrapers near the orebodies and by push-pull or push loaded scrapers away from the orebodies. Each self-loading scraper cut is

Jan 1, 1983

By M. van Swaay, C. E. Birchenall

Palladium has a large capacity for the dissolution or occlusion of hydrogen; the gas also diffuses very rapidly through the metal. Palladium thimbles are widely used in the laboratory for purification of hydrogen by diffusion. The use of palladium filters could be extended to several large-scale applications if greater stability of the permeation process could be attained. In this paper a number of aspects contributing toward this goal are discussed, and new data on solubility and diffusivity are given. Palladium sheets of 0.005, 0.010, or 0.020 in. thickness were prepared by three procedures: casting and rolling, sintering palladium powder, and sintering palladium powder to which 0.1 pct thorium oxide had been added. Half-inch diam circular specimens were cut and clamped in a stainless steel holder provided with knife edges to seal the palladium sheet with soft copper gaskets. The seals were tested for leaks at l0-5 mm Hg. No difficulties from this source were encountered even after many temperature cycles in the system. The holder was silver-soldered to Kovar-glass seals and attached to the system through glass ball joints. Each joint was sealed with Apiezon wax and was adjacent to a cold trap. In several experiments the holders were fused directly into the system, eliminating the ball joints, to show that the wax did not affect the filter. Three filter holders were supported in holes in a stainless steel cylinder, which also acted as a temperature equalizing block inside the resistance wound furnace. The measuring thermocouple was inserted in one of the holders. A potentiometric controller with control thermocouple on the furnace heater winding maintained ± 0.2oC. Electrolytic hydrogen was purified and stored as shown in the flow diagram, Fig. 1. It could be admitted to either or both sides of the palladium specimens. Only a mechanical pump was used, for even high pumping speeds would not bring the pressure on the off-gas side of the filter below 10 to 50p Hg owing to the rapid hydrogen flow through the filters. A series of steady-state permeability studies allowed identification of several conditions of permeability loss. A constant fore pressure was maintained while the low-pressure face was pumped. After enough time had elapsed for a steady flow to be established the pump was cut off, and the rate of pressure increase in a thermostated bulb was measured to determine the flow rate. The time delay method of Daynes1,9 was adopted since it offered the possibility of determining solubilities and diffusivities. For each measurement both sides of the filter were evacuated for 15 min, which gave about 10-4mm Hg residual pressure. Hydrogen was admitted to one side or the other of the filter at a fixed pressure. The pressure on the off-gas side was observed as a function of time. A

Jan 1, 1961

By Evans B. Mayo

As a result of studies distributed over the earth- including ocean basins as well as continents- some tectonists recognize four dominant structural trends: 1) northwest; 2) northeast; 3) nearly east- west, or equatorial; and 4) nearly north-south, or meridional. Baker' proposed a theory to account for these trends and Sonder5 called their world-wide arrangement the regmatic shear pattern. Moody and Hill6 proposed a much more complicated shear network which, although fascinating and perhaps ultimately useful, will not be followed here. In a recent review of deformation within the Cordillera, Wisser7 mentioned the four fundamental directions. The fact that many geologists deny the existence of the regmatic shear pattern implies that the fundamental structures are far from obvious. It may mean, also, that some geologists are not accustomed to examine regional and world maps analytically. The maps require much study, and certain features, should be isolated on overlays. Even so, with the present limited knowledge, uncertainties remain. The following analysis is a qualitative experiment, subject to change as information accumulates, and should be supplemented by the western sheet of the Tectonic Map of the United States.8

Jan 11, 1958

By R. W. Balluffi, R. Resnick

NUMEROUS investigations of chemical diffusion in a brass have been made and the results are collected in several places.1-3 This work has been mainly concerned with the determination of the chemical diffusivity as a function of composition and temperature. In 1947 Smigelskas and Kirken-dall&apos; showed that zinc and copper diffuse at different rates in face-centered-cubic brass, and since then, a number of efforts have been made to determine the intrinsic diffusivities of zinc and copper in this alloy.1, 5-9 Horne and Mehl8 in particular have recently determined the intrinsic diffusivities as functions of temperature and composition using sandwich-type couples and inert markers. Inman et al." also have determined the intrinsic diffusivities in homogeneous alloys using tracer techniques. When the present work was started, no information of this type was available. Consequently, measurements of the intrinsic diffusivities were made as a function of temperature at a constant composition of 28 atomic pct Zn with vapor-solid diffusion couples where the zinc was diffused into the diffusion couple from the vapor phase. The application of these couples to the study of diffusion in a: brass has been described previously.0,7 The temperature dependence of the intrinsic diffusivities was found to follow the relation D, = A, exp(-Hi/RT) and the values of Hzn, and Hcu, were found to be closely the same. It is emphasized, however, that the chemical dif-fusivity (D = N1D2 + N2D1) is a composite diffusivity and does not necessarily follow this exponential form. It is usually found to do so within experimental error for substitutional alloys because the heats of activation of the intrinsic diffusivities generally are not greatly different.&apos;" Also, at the onset of this work, there was no information available concerning possible unequal diffusion rates of individual components and the existence of a Kirkendall effect in alloys with other than face-centered-cubic structures. Since then, two reports indicating a Kirkendall effect in body-centered-cubic ß brass have appeared. Landergren and Mehl" have published a note describing Kirkendall diffusion experiments with sandwich-type couples. Inman et a1.9 also find a Kirkendall effect in this alloy using the tracer technique. In the present work, several aspects of the Kirkendall effect in ß brass were further investigated using vapor-solid couples. Two different couples were used, one in which the zinc was diffused into the specimen from the vapor phase and the other in which the zinc was diffused out of the specimen into the vapor phase. Briefly, the existence of a Kirkendall effect is confirmed and it is found that Dzn/Dcu = 3 at about the 46 atomic pct composition in this alloy at 600°, 700°, and 800°C. As a result of the unequal diffusion rates of zinc and copper, volume changes occur and subgrain formation is observed in the diffusion zone. In addition, significant porosity is produced by the precipitation of supersaturated vacancies. Diffusion in this alloy is therefore outwardly similar to diffusion in a brass where these effects are also observed, a Brass Experimental Methods—The use of vapor-solid couples in studying diffusion in a brass has been described in previous articles.6,7 The method briefly consists of sealing a copper specimen with Kirkendall markers initially placed on its surface in an evacuated quartz capsule along with a large zinc source of fine a brass chips and then diffusing the zinc into the specimen through the vapor phase. The zinc concentration at the specimen surface rises rapidly enough to a value near that of the a brass source so that the surface concentration may be regarded as constant during diffusion. Under these boundary conditions, values of the chemical diffu-sivity may be obtained by applying the Boltzmann-Matano analysis to the concentration penetration curve, and the intrinsic diffusivities may be obtained from Darken&apos;s5 equations when the velocity of marker movement is known. The diffusion specimens were made from OFHC copper in the form of disks 3.2 cm diam and 0.5 cm thick with faces surface-ground parallel to within +0.001 cm. Markers in the form of fine alumina particles <0.0002 cm diam were placed on the specimen surface. These specimens were then sealed in quartz capsules along with enough a brass chips of a 30.0 atomic pct Zn composition to keep the source concentration from decreasing by more than 0.3 atomic pct Zn as a result of the loss of zinc to the specimen during diffusion. The quartz capsules which were initially evacuated to a pressure of

Jan 1, 1956

By A. S. Venkatadri, H. B. Bell

The equilibrium sulfur distribution between molten iron and Ca0-Mg0-Al203 slags containing iron oxide was investigated at 1550°C. The results were used to derive the iron oxide activities at low iron oxide concentrations in the slag by combining the sulfide capacity data obtained from gas-slag work with the free energies of both the sulfur solution in iron and the iron oxide formation in slag. The derived ferrous oxide activities were compared with values based on Tem-kin&apos;s kin&apos;s and Flood&apos;s ionic models. One difficulty in using these models is that the nature of the aluminate ion in slag is uncertain. Nevertheless, such indirect methods, in particular, those described in the present paper, are of value because of the difficulty of measuring small amounts of oxygen in liquid iron in equilibrium with slag. It is shown that these methods confirm the consistency of thermodynamics data on liquid iron and slags. It is well established that decreasing the iron oxide activity in the slag increases the desulfurization of molten iron at constant slag basicity. This effect is most pronounced at the very low iron oxide activities, characteristic of blast furnace slags. Yet a precise quantitative determination of the significance of low iron oxide contents in slag in blast furnace desulfuri-zation is not possible for the following reasons: a) difficulty of separation of iron "shots" from the slag, and b) errors in chemical analysis of small amounts of iron oxide in slags. In view of these obstacles, one must resort to indirect methods of calculating iron oxide activities. EXPERIMENTAL TECHNIQUE The apparatus for providing the sulfur equilibrium data has been described previously1 and was similar to that used by ell&apos; in connection with the study of slag-metal manganese equilibrium. The procedure consisted of: a) melting about 50 g of Armco iron in a magnesia crucible in a platinum furnace, b) adding a mixture of about 15 g of lime-alumina slag and varying amounts of Fe2O3 and CaS, and c) maintaining the temperature at 1550°C for more than an hour in an atmosphere of argon to enable the sulfur equilibrium to be attained. Several melts were made using lime-alumina slags with basic composition 55, 50, and 45 pct lime. During the experiment the temperature was controlled manually using a Pt/10 pet Rh-Pt thermocouple. After the experiment, the Power was shut off and the flow rate of argon was increased to freeze the melt as quickly as possible. The analysis of sulfur in the metal was carried out by the oxygen combustion method3 using uniform drillings from the top and bottom of the metal button. After crushing and grinding and removal of any iron particles with the aid of a hand magnet, the slag was analyzed for sulfur by the CO2 combustion method.4 The E.D.T.A. method was employed for the analysis of lime5,6 and magnesia,= the ceric sulfate method7 for the analysis of slag iron oxide, and the perchloric acid dehydration method5 for the analysis of silica. The remaining amount was taken to be Al2O3 precipitation with ammonium hydroxide in several preliminary melts had confirmed the propriety of using this simple procedure. RESULTS The activity of iron oxide in binary, ternary, and more complex slags has been the object of numerous investigations, and the two experimental methods for its determination are: 1) Equilibrating the metal with the slag in question and measuring the oxygen content of the metal. The ferrous oxide activity is then given by aFeO L%OJSat where [%0]sat is the oxygen content of the metal in equilibrium with pure iron oxide slag. This method was used by Chipman et al.8,9 2) Equilibrating the slag in iron crucibles with known partial pressures of H2/H2O or CO/CO2 mix-tures.10-12 This method is limited to temperatures between 1265" and 1500°C. The very low oxygen content of the melts in this investigation made it impossible to derive the ferrous oxide activity by the first of these methods. Therefore, the iron oxide activities were computed by means of: Sulfide capacity data from the gas-slag work" Temkin&apos;s concept14 Flood&apos;s approach15 a FeO from Sulfide Capacity. The method of calculating the aFeO involves the sulfide capacity of the slag (c,), the sulfur distribution coefficient (Ls), the free energy of dissolution of sulfur in iron, and the free energy of formation of iron oxide in the slag. Bell and Kalyanram13 have investigated the sulfur absorption characteristics of lime-alumina slags containing magnesia by the Carter-Macfarlane method16 (based on comparing the sulfide capacity of the slag in question with that of a standard slag of unit lime activity) and have derived lime activity values. The relation between sulfide capacity and their lime activity a&apos;CaO is given by: Cs= 3—: Xa&apos;CaO at 1500°C

Jan 1, 1970

Jan 1, 1968

By C. D. Thurmond

Jan 1, 1968

Jan 1, 1968