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By M. Cross

INTRODUCTION The development of refining processes involving gas injection into liquid metals has seen the evolution of a variety of designs [I]. During the last few years or so the top, bottom and side blown processes have, essentially, been combined to produce a series of mixed gas blowing schemes (eg. the LBE [2,3] and LD-OB processes [4,5]). Although, a variety of mixed gas blowing processes have been carefully engineered and recorded operational experience now attests to their effectiveness, optimising their design and operational performance is another matter. Detailed process analysis of such operations is impeded by the complex nature of the physical and chemical processes involved: . fluid flow behaviour of the liquid metal and injected gases, . chemical reactions in the vessel, . mass and heat transfer within the fluid phases in the vessel, . influence of the geometry (eg. location of the tuyeres, etc.), . monitoring the operational performance. By and large, design and operating parameters evolve from a combination of laboratory scale experiments, pilot plant work and, of course, practical engineering experience. Conventionally, the gas-liquid system used to model the industrial process is air-water, for a number of valid reasons including – . visual demonstration plus geometric and (to some extent) dynamic similarity, . the fact that the system demonstrates, at least, qualitatively many of the complex features of gas injection - interaction between the gas and the liquid - the nature of the gas flow behaviour - qualitative indications of mass transfer rates Important experimental contributions to the understanding of gas liquid systems include the work of Brimacombe [6], Wraith [7], T.Robertson [8], D.Robertson [9], Guthrie [10] and Szekely [11] (these references provide starting points to identify the major published work in this area). Although air-water systems have been instrumental in providing a great deal of qualitative insight into the fluid flow behaviour of the processes, reliable quantitative predictions are more problematic. A number of workers (notably Brimacombe and colleagues [6, 12])have demonstrated that different gas-liquid systems can lead to wide variations in behaviour. Other limitations of physical modelling include the assumptions of isothermal flow, scale- up of turbulent flow behaviour and the inability to directly include the effects of chemical reactions. The above limitations in physical modelling, therefore, yield a natural role for mathematical modelling provided that it can be made comprehensive enough whilst remaining cost-effective. The major physical processes involved in gas injection systems may be summarised as . behaviour of the gas envelope structure in moving through the liquid metal . the global movement of the liquid metal . momentum interaction between the liquid metal and the injected gas . heat transfer and mass exchange via the chemical react ions. The behaviour of gas envelopes forming at a tuyere and then moving through the liquid has been investigated thoroughly by a large number of workers. Such models are generally based upon simple physic- al concepts derived from visual observation. An early model by Davidson and Schuler (DS), based upon a force balance between the liquid inertia and a combination of the bouyancy and momentum forces on the envelope, has proved to be a useful tool in predicting bubble volumes at detachment [13]. The DS model has been successfully modified in a number of ways [14-17] to cope with heat transfer and reactive transfer rates, etc. Furthermore, the basic ideas summarised above have also been confirmed on industrial converters by both Guthrie [I8] and Brimacombe [19]. Models have also been developed to predict the behaviour of the "chemical" component of some gas-liquid systems. However, one thing is clear; all gas-liquid reactive systems are governed by the degree to which effective mixing occurs. As such, the processes are dominated by the behaviour of the heat and mass exchange of the two phase fluid flow system. It is the pattern of movement of the turbulent liquid metal plus its interaction with the injected gas which must be predicted reliably, if sufficiently comprehensive comp-

Jan 1, 1984

By D. R. Mitchell

MEETING for the thirteenth time in New York as part of the five-ring circus known as the Annual Meeting A.I.M.E., the Coal Division experienced a wartime boom in attendance. Technical sessions were crowded and whereas 65 seats were set up for the annual luncheon meeting of the Division over 100 members showed up, many of whom had to be fed elsewhere. Possibly the Coal Division should adopt "13" as its lucky number. Discussions at technical sessions, formal and informal, were lively. Those papers containing material directly concerned with the war, or containing information that might be usable for war industries, were enthusiastically received. Some criticism was made in regard to the present method of handling discussions and it was suggested that better success would be had in getting discussions in the record by the use of hired reporters. This is being considered by the executive committee of the Coal Division.

Jan 1, 1943

By Cyrus Garnsey

NECESSITY FOR PRICE FIXING DURING the latter part of 1916 and the early months of 1917, clue to war activities, there was a threatened shortage of coal which resulted in panic among consumers and a rush to obtain coal at once at any price. As a result of this insistent demand for immediate delivery, prices were bid up by the consumers to unprecedented heights; spot coal which had previously been selling at from $1.50 to 82 per ton was bid up to $5, $6, and, in exceptional cases, as high as $7.50 or more per ton. Then when the April, 1917, contract period arrived, contracts could be made only at prices ranging from $3 up to $5 and $6 per ton for the year's delivery. This condition caused such a demoralization of the business, and so much complaint, that some action to regulate prices was considered essential by the National Administration. LANE-PEABODY AGREEMENT In May, 1917, a committee under the chairmanship of F. S. Peabody, of Chicago, was appointed by the Council of National Defense, through Mr. Lane, to consider the whole question of bituminous coal. This committee, with the Secretary of the Interior, Mr. Lane, after numerous meetings and long negotiations with the operators throughout the country, announced on June 29 an agreement between the Committee and the producers, fixing a tentative maximum price for bituminous coal throughout the country at $3 per net ton f.o.b. mines, to which was added 25 c. for selling commission to wholesalers. This plan was based on the idea of fixing a maximum price, high enough to greatly-stimulate production, with the expectation that the laws of supply and demand would, with ample production, operate to maintain fair and just prices for coal throughout the country.

Jan 9, 1918

By Rex B. McLellan, W. A. Oates, William W. Dunn

Vapor transport experiments have been carried out in order to determine the saturation solubility of carbon in cobalt and nickel with respect to graphite over a large temperature range. Some of the uncertainty existing in the thermodynamics of these systems has been removed and accurate estimates of the heat and entropy of solution of carbon in nickel and cobalt have been deduced. The relatitle partial entropies of carbon are considered to be predominantly vibrational in origin. ALTHOUGH the thermodynamic properties of solid solutions of carbon in cobalt and in nickel have been investigated previously, the results of these investigations show a marked lack of agreement amongst themselves. In this investigation simple vapor transport experiments have been undertaken in order to measure the temperature variation of the saturation solubility of carbon in nickel and cobalt with the object of removing to some degree the uncertainties in the thermodynamics of these systems. In the case of the C-Co system, early measurements of the saturation solubility of graphite in Co show results at the same temperature differing by almost an order of magnitude.1-5 Recently Schenck, Frohberg, and Jaspert6 measured the equilibrium between CH4-H2 mixtures and C-Co solid solutions at five temperatures ranging from 850° to 1050°C. Their values of the activity of carbon in the solid solution, deduced from a knowledge of the chemical potential of carbon atoms in the gas, varies linearly with composition at each temperature and the authors concluded that the solutions were Henryan. The saturation solubilities deduced from Schenck, Frohberg, and Jaspert's measurements are in good agreement with the solubility determined at 1000°C by Rao and Nicholson7 and the value at 1000°C deduced from the measurements of smith8 on the equilibrium between CO/CO2 mixtures and C-Co solutions. The object of this investigation was to check the results of Schenck, Frohberg, and Jaspert and also to extend the range of solubility data to higher temperatures. In the case of the C-Ni system, there is fairly good agreement between the values given by schaefer9 for the saturation solubility of carbon C, in nickel, the value given at 1000°C by Rao and Nicholson,7 and that deduced from Smith's8 measurements of the equilibrium between C-Ni solutions and CO/CO2 mixtures at 1000°C. The values of C, deduced from Schenck, Frohberg, and Jaspert's6 measurements of the carbon activity in nickel are also in fairly good agreement. However, there is a large discrepancy between the above set of measurements and those of Lander, Kern, and Beach," who measured the carbon solubility of nickel in equilibrium with graphite by depositing an excess of graphite on the surface of Ni-foils from a gaseous mixture and subsequently diffusing in the carbon. These results are considerably higher than those mentioned above. The determinations6 of carbon activity a, in nickel from the CH4-H2 equilibrium showed that at all the temperatures investigated, the ac-values varied linearly with concentration up to about a, = 0.6 and then began to increase with concentration much more rapidly. On the basis of auxiliary experiments in which C-Ni solutions were equilibrated with graphite, Schenck, Frohberg, and Jaspert concluded that their CH4-H2 solid equilibrations at high values of a, were spurious and a, behaved linearly with composition up to the saturation limit (a, = 1). The short linear extrapolations of Schenck, Frohberg, and Jaspert's a, data yield values of C, in good agreement with those of Lander, Kern, and Beach." The solubility data for nickel discussed here is presented in Fig. 1 in the form of plots of ln[Cc/(l - 2cc)] vs 1/T. The discrepancies mentioned are clearly seen. In this investigation a vapor transport method is used to measure C, over as wide a temperature range

Jan 1, 1969

The following is an incomplete list of members and guests who called at Institute headquarters during the period Sept. 10, 19188 to Oct. 10, 1918. Thomas J. Adams, Rahway, N. J. A. N. Mackay, London, England. Henry M. Ami, Washington, D. C. A. W. MacNichol, San Francisco, Cal. Chester Atkinson, Peru, South America. Ernest Marquardt, Casper, Wyo. Bennett R. Bates, Berkeley, Cal. Lieut. S. A. Mewhirter, Denver, Colo. Robert S. Botsford, Petrograd, Russia. William A. Nelson, Nashville, Tenn. Juan Felix Brandes, Santa Barbara, Cal. Robert W. Olinger, Bahia, Brazil, So. G. A. Collins, Seattle, Wash. Amer. C. V. Corless, Coniston, Ont., Canada. G. Preumont, La Paz, Bolivia, So. Amer. F. T. Eddingfield, Washington, D. C. William H. Rettie, Yonkers, N. Y. C. Mason Farnham, Barre Plains, Mass. . Julius Segall, Minneapolis, Minn. F. N. Flynn, Trail, B. C., Canada. Robert Y. Seip, Franklin, N. J. Duncan D. Forbes, Humboldt, Ariz. H. M. Schleicher, Boston, Mass. Alexandre Gouvy, Paris, France. Chester Steinem, Ft. Monroe, Va. Henry G. Granger, Cartagena, Colombia, A. L. Sweetser, Pittsburgh, Pa. So. Amer. . H: E. Treichler, Creighton Mine, Ont., E. Harms, El Paso, Tex. Canada. Alfred G. Heggem, Tulsa, Okla. Frank A. W. Tullock, Yumbo, Colombia, H. B. Henegar, Mascot Tenn. So. Amer. A. M. Kivari, Denver, Edward I. Williams, Ft. Monroe, Va. T. M. Kniffin, Brookline, Mass. Alfred W. G. Wilson, Ottawa, Canada. Charles Lehman, London, England. Donald H. McLaughlin, Camp Meade,Md. C. E. Addams, who recently resigned as general manager for the Arizona Hercules Copper Co., has leased the Ray silver-lead property three miles from Ray, Ariz. Bennett R. Bates has resigned his position as general superintendent of the Cubo Mining & Milling Co., in order that he may take the examination for an officer of engineers.

Jan 11, 1918

By WILFRED SYKES

THE story of the rolling of strip steel is not limited to any one plant or individual or group of individuals. It is a story with many ramifications. First of all, it should be understood that the strip mills we are considering are continuous mills, in that the steel passes directly from one mill to the other in a more or less straight line. Continuous mills are not new; in fact, they have been used for many years in the rolling of a few simple shapes. They were, however, driven by one motor through jackshafts, and as a result the speed of each roll stand had a fixed relation to that of every other stand in the series. This in turn fixed the reduction that could be made in each stand. The mill could produce simple things, but was not satisfactory for the production of the variety of strip now required. It was, therefore, necessary to get away from the restrictions of that kind of drive. To accomplish this, the designer could either separate

Jan 1, 1936

By J. W. Freeman, J. P. Rowe, R. F. Decker

HEAT-to-heat variations in properties of an alloy of constant nominal chemical composition have been a perplexing problem to the metallurgist. These heat-to-heat differences have been especially baffling in high-temperature metallurgy. In order to establish fundamental reasons for these heat-to-heat variations, the National Advisory Committee for Aeronautics has sponsored and financially assisted an extended research program on heat-resistant alloys at the University of Michigan. As part of the program to find the contribution of processing variables, Frey, Freeman, and white' studied effects of heat treating on nickel-base alloys and Ewing and reeman' investigated effects of hot-working practice on N155 alloy. To extend the program to the study of effects of melting practice on high-temperature properties, a 55 Ni-20 Cr-15 Co-4 Mo-3 Ti-3 pct A1 composition was selected for experimentation. The objective of this program was to establish the melting-practice variables which influenced the hot-working characteristics and creep-rupture properties and, at the same time, establish the metallurgical mechanisms for the effects. During the course of the investigation of practices using vacuum melting, it became increasingly evident through chemical analyses supplied by industrial concerns that a major variable was melt reaction with the crucible. This paper is devoted to the results of this phase of the melting-practice study. EXPERIMENTAL PROCEDURES Experimental 10-lb heats were induction melted in the University of Michigan vacuum-melting unit with the melting practices outlined in Table I. Aim analysis for the basic alloy, in wt pct, for all heats was as follows: Cr Co Mo Ti Al 20.0 15.0 4.0 3.1 3.1 Mn Si C Ni 0.12 0.12 0.08-0.15 Bal. Small amounts of boron and zirconium were added to certain heats as listed in Table I. These additions

Jan 1, 1959

By Paul T. Benson

MOST important of the various departments of a custom smelter, so far as the financial welfare of the plant and the confidence of shippers are concerned, is that responsible for correct weights, accurate moisture sampling, and the obtaining of control samples that are strictly representative of the lot of ore from which they come. Treatment rate schedules are based on the metal content of ores received, reduced to dry weight. These rates must be low enough to keep the ship- per from taking his business else- where and still must allow the smelter a profit. Assay results, likewise, must satisfy the shipper, but if they show too high a metal content for the ore they represent, the smelter will actually lose money. It is always considered, and constant checks through umpire assays prove, that laboratory results are closely correct, so the bur- den of the plant profit and loss and the satisfaction of the shipper rest squarely upon the sampling department.

Jan 1, 1936

By J. D. Ridge

The geologic setting and mineral relationships of seven European massive sulfide deposits that more or less conform to the bedding of the largely noncal-careous sedimentary rocks and/or bedded volcanics in which they are found are considered here. These orebodies consist largely of massive beds or lenses of sulfides usually surrounded by halos of disseminated sulfides and distorted by tectonic activity. The formations containing these deposits have been metamorphosed in varying degrees at times subsequent to their lithification. The ore-forming process is thought to be essentially volcanic, with the ore constituents being brought to the shallow-water site of deposition through tectonic fissures from magma chambers at depth as gases or relatively concentrated hydrother-mal solutions. Certain European ore deposits of base metal sulfide have previously been considered to be of hydro-thermal or magmatic origin, but today a number of European mining geologists consider them to be syngenetically produced. In an effort to provide American geologists with some idea of the reasons behind this change in thought, the geological settings of seven of these deposits have been studied. These are: Ldkken, Meggen, Rammelsberg, Ergani-Maden, Outokumpu, Boliden and Roros. These deposits lie in bedded rocks that have undergone metamorphism from causes not universally agreed upon; most of the formations were originally shales, and may have been intercalated with limey and occasionally quartzitic beds, volcanic tuff, agglomerate, extrusive lavas and usually basic intrusives. Deposits of the conformable type, however, are not confined to these rock types but may be in calcareous and associated igneous rocks or almost entirely in volcanics. These deposits may be closely associated in space with igneous rocks that, again, are usually basic types. Although the ages of the enclosing rocks range from mid-Precambrian (Boliden and Outokumpu) to Eocene (Ergani-Maden), the bulk of them are Paleozoic, with two (Meggen, and eammelsberg) being upper middle Devonian and two (LØkken and RØros) being Cambro-Ordovician. Geographically, two are in West Germany, four in Scandanavia and one in Turkey. Of the seven deposits, six are mined for copper, with three of these also producing zinc, and two lead; one is mined for zinc and minor lead. In the discussions of the seven conformable deposits that follow, I have attempted to present as uniform a treatment as their varying characters will permit. For each deposit, I have considered the stratigraphy of the area, its major structural characteristics, the form of the orebodies, their mineral content, and the origin of the ore. In the last of these subdivisions, I have presented only the viewpoint of those who believe the ores to have been formed by syngenetic processes, processes that went on at the same time as those which produced the beds that enclose the ores but that are not, in the deposits in question, thought to have been sedimentary in the strict sense of the term. The materials of which these orebodies are composed, it is suggested, did actually collect by falling through sea water to the floor of that portion of the sea in which they accumulated. The ore constituents, however, are believed by a considerable number of European geologists to have been added to the sea water from intratelluric sources, probably igneous magma chambers, as exhalations — hydrothermal solutions or volcanic gases. The effect of the encounter with sea water on these ejected gases or water-rich vapors was to precipitate their potentially solid constituents with great rapidity; they were deposited so quickly, in fact, that the amounj of normally accumulated mechanical or chemical sediment deposited over the same period of time was essentially negligible. The ores formed in this manner, however, are generally interbedded with normal sediments or with lava flows, or with any combination of these two types of rock-forming materials. Such departures as these deposits may have from their original mineral content and attitude are thought to be directly related to the degree of dynamic or static metamorphism that they may have undergone after their accumulation. I have not attempted here to present alternate hypotheses to that of so-called exhalative sedimentation although, of course, such exist and, in my

Jan 1, 1963

By C. S. Harloff, Frank R. Corwin

THE Nichols Copper Co., associated with the Phelps Dodge Corp. and the Calumet & Arizona Mining Co., has constructed at El Paso, Tex., and is now operating a copper refinery with a yearly capacity of 100,000 tons of anodes. Transportation facilities were perhaps the most important of the considerations that led to the selection of this site. The rapid industrial development of the Middle and Far West has increased the consumption of copper there. The advantage of local refining as against shipping the copper to the Atlantic sea- board is apparent. Copper refined in the Southwest is equally competitive for export shipment, either from the Gulf or the Pacific Coast ports. The tonnage of copper produced in the Southwest not only justifies the construction of this plant, but may warrant considerable expansion in years to come.

Jan 1, 1930

By F. C. Stanford

THE work of an engineer is to direct natural forces so that they bring about the results that he wishes to secure. Heretofore he has concerned himself chiefly with physical forces and inanimate objects, until he has secured a truly marvelous degree of control over them. The great problem of the present age is to secure a like degree of knowledge and control of the human factor. Progress has already been made along this line, but, it is only a beginning. Wilhelm Ostwald says that scientific knowledge enables a man to be a true prophet; but it must be remembered that a good many people do not seem to be able to maintain a high average in prophecy. In short, the average of knowledge is not equal to the average needs of the present time, but continually fails to keep pace with it. It has been aptly said that the really essential need of the period is for more brains; if we only had sufficient knowledge and sagacity we could not only solve all difficulties, but prevent them from arising. This generalization holds good for an industrial organization. The most vital need of the management is for more brains. The logical course for an engineer in charge of an industrial organization is, therefore, to direct whatever forces may be at his command toward the development, training, and guiding of all the brains in his organization. This is easier said than clone, for it involves the carrying on toward two objectives, the maximum of productive work, and the development of the individuals who perform it. This is essentially like the rebuilding and enlarging of a plant, keeping it in full operation the while. On the other hand, if the aim is merely for maximum production from an organization, without offering opportunity for development, the final outcome will necessarily be like that f a plant that is driven at full capacity without stopping for repairs or improvements; it eventually becomes so run down that either a complete rebuilding is necessary or else it has to be abandoned.

Jan 2, 1918

By H. Kahata, I. Iwasaki, Y. Takahasi

A combined process of segregation roasting-flota-tion or magnetic separation was developed to recover nickel from lateritic iron ores and oxidized nickel ores. An ore was mixed with a halide, such as sodium or calcium chloride, and a solid reductant, and roasted, whereby the nickel content was segregated out as discrete metallic particles. Either by magnetic separation, or by flotation using a sulfhydryl collector together with a heavy metal salt as an activator, the metallic nickel could be concentrated, Effects of such variables as the types and amounts of the halide and solid reductant addition and of the roasting conditions were extensively investigated. The concentration results on several types of ores from Japan, the Philippines, and New Caledonia are presented. Laterite is a residual product of rock decay in tropical and subtropical regions, and consists mainly of hydrated oxides of iron and alumina. Those derived from serpentine sometimes become enriched in nickel, cobalt, and chromium contents. Oxidized nickel ores are of the similar origin, but their nickel as well as silica contents are higher due to gamierite-type silicates. Apparently, nickel enrichment is more pronounced in the transition region between the surface layer of iron laterite and the underlying serpentine. Iron laterites often contain over 50% iron, and their reserve is reported to exceed 22 billion tons, corresponding approximately to 20% of the world iron ore reserve.1 It is readily apparent, therefore, why the iron laterites have attracted much attention of the steel industry as a potential source of iron ores. Numerous attempts to remove nickel and chromium as byproducts, have been reported in literature.' Worldwide discoveries of high-grade iron ore deposits in recent years have inevitably lessened the interests in iron laterites. However, in view of the tremendous potential for their gross value and supplies of nickel, cobalt, chromium, and alumina along with iron, the problem remains as a challenge. Much of the chromium in laterites is present in the form of relatively coarse particles of chromite, and various classification methods have successfully been applied for its removal.2,3 The nickel, however, is intimately associated with limonite, and ordinary concentration techniques are totally ineffective. Much attention has, therefore, been given to hydro-metallurgical or pyrometallurgical means. Yet, all the known processes appear to have limitations either economically or for the use of products as iron raw materials due to a high residual content of nickel. Some attempts have been made to pre-roast laterites or oxidized nickel ores, particularly with sulfidizing agents, and to remove nickel either by magnetic separation,' or by flotation.4 It is apparent that any such concentration process would require grain growth of nickel during roasting for effective separation. Oxidized copper ores are reported to be concentrated by the segregation roasting-flotation process,5 in which the ores are roasted with a chloridizing agent and a carbonaceous reductant in order to promote the growth of metallic copper through repeated cycles of copper chloride volatilization and its reduction on the solid reductant surfaces. Examination of a vapor pressure-temperature diagram of various metal chlorides indicates that a separation of nickel from iron may be effected by a similar process. In fact, the segregation roasting of laterites was reported to increase the extraction of nickel by the ammonia leach process, as compared to the ordinary reduction roasting.6 In the present article some of the preliminary experimental results of the segregation roasting, followed by either flotation or magnetic separation, on laterites and oxidized nickel ores are reported. The effects of various parameters in the roasting as well as in the concentration steps are discussed. MATERIALS AND METHODS An oxidized nickel ore from Thio, New Caledonia, and three laterites from Homonhon, the Philippines, Wakasa and Miyagawa, Japan, were selected for the

Jan 1, 1967

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

By M. F. Burr, F. V. Lenel, G. S. Ansell

The mechanism of materials transport was studied in a model experiment in which a silver sphere was sintered to a silver plate under an applied external stress near 800° C. For this purpose the rate of growth of the neck between the sphere and the plate which is proportional to the strain rate of the creep process involved in a neck growth was determined by measuring the change in electrical resistance of the away. This rate of neck growth will depend upon the magnitude of the applied external stress. By measuring the rate just before and just after a change in the external load and therefore the applied stress, the relationship between strain rate and stress can be derived. For material transport by slip in a pure metal it is expected that the strain rate should be proportional to the 4.5th power of the stress, while for transport by diffusional flow the strain rate should be proportional to the first power of the stress. It was found that for stresses above 5 X 10' dynes per sq cm (70 psi) the exponent in the stvain rate-stress relationship was near 4.5 while for a stress of 0.7 x 108 dynes per sq cm (10 psi) an exponent of 1.8 was determined indicating that under the conditions of the experiment the transport mechanism for creep in silver shifts from diffusional flow to slip in the region of 0.7 x 106 dynes per sq cm (10 psi). The importance of these findings for an understanding of the mechanism of material transport in conventional sintering (without an external load) is pointed out. In a paper by Early et al.,' the mechanism of material transport during sintering was treated as a creep process. It was pointed out that two possible types of creep processes could operate during sintering. In one of these material transport takes place by vacancy diffusion due to a gradient in chemical potential. The vacancy sinks in this diffusion process may be either grain boundaries, as in Herring-Nabarro microcreep, or regions beneath a surface of small radius of curvature. The diffusive transport may be by volume, grain boundary, or surface diffusion. In the other mechanism, creep takes place by slip, i.e., dislocation motion with its rate generally controlled by dislocation climb. One method of distinguishing between these two modes of materials transport is to investigate the creep rate, i.e., the rate of material transport as a function of stress. For material transport by vacancy diffusion, the creep rate is proportional to the stress.' For creep by slip, controlled by dislocation climb, the creep rate is proportional to a power of the stress. For pure metals this power is 4.5;374 for dispersion-strengthened material a fourth power relationship can be derived.5 This difference in the stress dependence of the strain rate is illustrated schematically in Fig. 1, in which the logarithm of strain rate is plotted vs the logarithm of the stress for material transport in a pure metal by vacancy flux and by dislocation climb. The stress range in which the two types of material transport overlap would be expected to be relatively small. In the experiments described by Early and coworkers compacts pressed from spherical copper powder were sintered isothermally under an applied axial external load in a dilatometer. During sintering the magnitude of the applied external load was changed and the rate of axial shrinkage of the compact before and after the load change determined. In order to find the stress dependence of the strain rate the magnitude of the stress acting on the neck area between the spherical particles before and after the load change had to be calculated. This stress is the resultant of the stresses due both to the externally applied load and to surface tension. The stress due to surface tension is a function of the geometry of the powder compacts. It can be determined, at least for simple geometrical arrays,'76 but it is difficult to obtain exact values of the stresses for actual powder compacts when only average values of particle diameters and of neck diameters between particles are available. The calculation of stress and the strain rate-stress relationship is therefore only very approximate.

Jan 1, 1968

By L. L. Melton, W. T. Malone

Fluid mechanics research conducted with non-Newtonian fluid systems now permits prediction of the behavior of these fluid systems in both laminar and turbulent modes of flow through circular pipes. Present work concerns non-Newtonian fluid systems currently used in the hydraulic fracturing process. During fracturing treatments, an unsteady-state condition may frequently be encountered arising from. the reaction rate of a chemical additive. This condition must be evaluated in order to predict the actual behavior of a particular fluid during field application. Design and operation of the apparatus used to determine fluid-flow behavior permit obtaining data under such non-equilibrium conditions. This paper shows methods used to obtain rheology measurements, develop hydraulic relationships and evaluate chemical reactions producing unsteady-state conditions. Engineering application of this research is illustrated by employing measured rheological values and developed hydraulic retationships to produce frictional pressure loss (psi/100 ft) us flow rate (bbl/min) charts of common tubing and casing sizes for an example fracturing fluid. How these charts and chemical reaction rate information are then combined to predict actual turbulent hydraulic behavior during unsteady-state field conditions is also discussed INTRODUCTION Many fluids used in hydraulic fracturing contain chemical additives which impart non-Newtonian fluid properties that may drastically alter their hydraulic behavior. Equally drastic alteration in wellhead pressure, injection rate and hydraulic horsepower requirement may result from these fluid properties. Prior research conducted to relate non-Newtonian fluid properties with hydraulic behavior has not as yet produced a universal relationship, particularly for the turbulent flow region. which of the many Possible non-Newtonian fluid properties is responsible has not been conclusively established. A systematic description, suggested by Metzner, of the many possible non-Newtonian fluid properties exhibited by real-fluid behavior, and a current discussion of theoretical and applied aspects of non-Newtonian fluid technoloy can be found in Handbook of Fluid Dynamics. f Little or no research has previously been attempted with fluids exhibiting time - dependent properties. Addition of chemicals during a fracturing treatment is often accomplished by continuously mixing and displacing the fluid. This produces a time-dependent effect or unsteady-state condition while the fluid is progressing through surface and wellbore conductors. This condition is due to solution or chemical reaction of the additive. Considerable departure from conventional methods of obtaining and interpreting data was found necessary to consider these conditions. Therefore methods were developed to obtain hydraulic behavior information under these complex, unsteady-state conditions. Relationships presented in this paper to predict hydraulic behavior of non-Newtonian fluids in circular pipes were obtained by constructing and operating a small pipeline apparatus in the manner of a pilot-plant study. These relationships are suggested as scaleup equations and are not proposed as fundamental rheological parameters. While perhaps deficient from a fundamental research viewpoint, a pilot-plant study does permit the determination and convenient evaluation of variables pertinent to a process. A pilot-plant study can result in a valid engineering application procedure even when fundamental relationships are still undefined. An excellent series of articles by Bowen has appeared in the chemical engineering literature.2-8 These give a thorough review of proposed hydraulic relationships and their limitations for non-Newtonian fluid behavior in circular pipes. A graphical method is presented to scale up data for a fluid exhibiting an anomalous hydrau1ic behavior in the turbulent flow region. Considerable assistance has been obtained from these articles to interpret the anomalous behavior noted during this investigation. These articles also provided assurance that a pilot plant is a practical approach to evaluate the hydraulic behavior of non-Newtonian fracturing fluids. _____________

Jan 1, 1965

By Richard L. Ash

7.3-1. Introduction. All phases of mining competent materials are affected directly by the results achieved from primary blasts. It is imperative that their design suit each particular set of mining conditions. In general, the round design must provide an adequate tonnage of material, properly placed with suitable fragmentation, to ensure that loading, haulage, and subsequent disposal or processing are accomplished at the lowest possible cost. Blasting rounds are designed by the proper application of cratering relationships developed for the single, concentric, confined explosive charge. Blasting for surface mining and most open-cut heavy construction, however, is characterized by the use of rounds, composed of a number of explosive charges with relatively long lengths, which are placed in benches with specific finite dimensions. Therefore, modifications must be made to the classical, single point-charge cratering concepts. It is the purpose of this discussion to outline the basic principles, significant variables, and procedures for their integration in the design of rounds that are applicable to conditions characteristic of surface mining. Because relatively insensitive blasting agents will be used in most instances, particular attention must be given to priming, control of confinement, and selection of charge diameters that ensure complete explosive-reaction execution. 7.3-2. General Considerations. The primary requisites for any blasting round are that it ensure optimum results for existing operating conditions, possess adequate flexibility, and be relatively simple to employ. It is important that the relative arrangement of blastholes within a round be properly balanced to take advantage of the energy released by the explosives and the specific properties of the materials being blasted. There are also environ- mental and operational factors peculiar to each mine that will limit the choice of blasting patterns.

Jan 1, 1968

By C. O. Rison

HIGH explosives, particularly nitroglycerin, have been used in torpedoes for the purpose of shooting oil and gas wells for more than 60 years. The early history of the oil industry in Pennsylvania is not clear as to who actually torpedoed the first well, although in 1865 the Roberts Torpedo Co. procured a patent covering the process. Gunpowder was first used, although nitroglycerin was substituted shortly afterwards. Wells are shot for the purpose of increasing the flow of oil and gas A shot-hole in the producing horizon, with its contributory fissures and fractures, increases the area of and stimulates drainage into the hole. The shot-hole also acts as a collecting basin from which the oil is pumped. As a rule, hard or close-grained sands or limes are shot, other more or less porous and soft formations usually do not require shooting. and might be injured by blasting. Shooting is also resorted to in mechanical trouble such as straightening crooked holes, sidetracking pipe or tools, and for severing frozen strings of casing or drill pipe. Explosives arc also used sometimes to extinguish oil or gas-well fires although that work, which involves unusual conditions and methods, does not properly come within the classification of oil-well shooting. Some Factors to Be Considered in Shooting Wells Although nitroglycerin has been used extensively for more than half a century in shooting oil and gas wells, there is still a great deal of uncertainty as to the proper method of shooting or the amount of explosive required to produce best results in a particular formation. The possibility of shooting unproductive or cavey formations above or below the productive horizons, shooting into lower water, destroying casing seats, and the splitting or collapsing of casing strings, are factors that require consideration. The engineering departments of a number of the larger oil companies are making a study of methods of shooting, and the amounts of liquid nitroglycerin or other explosives required in shooting various productive

Jan 1, 1929

By F. J. Plecity, J. T. Michalak, W. C. Leslie

Isothermal recrystallization and grain growth in zone- and vacuum-melted irons and Fe-Mn alloys, up to 0.60 pct Mn, were studied in the range 480° to 650° C, after 60 pct cold reduction. In initial stages, rate of grain growth and rate of recrystallization of iron decrease with time. The recrystallization is typical of a growth-controlled process, and rate of growth is determined by the extent of recovery. Mn decreases rates of growth and of recrystallizatzon. The recrystallization process changes at about 0.30 pct Mn and nucleation may become time-depetzdet~t. In recent years, considerable effort has been expended in determining the effects of solute elements on recrystallization and boundary migration in fcc metals. The results have indicated that the effects produced by single solute additions are dependent upon both the element added and its concentration.'-' In contrast, there have been very few attempts to determine the characteristics of recrystallization and boundary migration in high-purity bcc metals, especially after heavy deformation, and the effects thereon of single solute elements.9-11 This study was undertaken to determine the recrystallization characteristics of various "high-purity" irons and the effects of manganese additions at two levels of base purity. It was hoped that the information obtained would improve our understanding of the recrystallization of pure metals and aid in formulating a theory for the effect of solute elements. The interest was not entirely academic, for the annealing of low-carbon steels, which is of very great commercial importance, is but poorly understood. MATERIALS The compositions of the irons and iron-manganese alloys used are listed in Table I. The zone-melted iron and Fe-Mn alloys were made by Battelle Memorial Institute. Iron S-1 was arc-melted in a water-cooled steel mold in an argon atmosphere. The ingot was forged into a bar, then given two horizontal zone-refining passes in an alumina boat. Iron V-4 was treated in a similar manner, but was not zone-refined. The iron for the zone-melted Fe-Mn alloys was induction melted in vacuum in MgO crucibles and cast into alumina molds. The ingots were forged into bars, machined to shape, and a groove milled down one side of each. The best available electrolytic Mn was placed in the grooves, and the bars were zone melted. The vacuum-melted Fe-Mn alloys were induction melted in this Laboratory in MgO crucibles and poured into cast-iron molds. Iron V-5 was purchased from National Research Corp. in the form of a small vacuum-cast ingot. The low-carbon steel was made by induction melting in air at the U.S. Steel Corp. Applied Research Laboratory. The history of the materials prior to the final cold reduction differed; these details are given in the Appendix. The penultimate grain size of the principal materials was kept in the range ASTM 2 to 4, except for the low-carbon steel. PROCEDURES The cold work prior to the final recrystallization anneal was kept constant at 60 pct. It is known that rolling procedure can influence the kinetics of recrystallization of ironI2; therefore, all specimens were rolled in one direction only, between clean,

Jan 1, 1962

By A. F. Melcher

The present paper is a progress report on an investigation of the physical factors of oil and gas and especially of their sands,' such as pore space, size of pores or permeability, retentivity, viscosity of the oil, temperature, pressure, thickness and area of the pay sand, water relations, and capillarity. The purpose is to determine as many of these physical factors as possible, and to ascertain the relations existing, directly or indirectly, between these physical factors and the production of oil and gas. As yet only pore space2 and size of grains of pay sands have been investigated, although an apparatus has been designed to determine the permeability of a sand to oil, water, or gas under definite drops of pressure between the entrance face and exit face of the sample. Messrs. E. W. Shaw, R. Van A. Mills, D. Dale Condit, G. B. Richardson, G. C. Matson, and C. H. Wegemann collected the samples upon which the physical determinations were made. Acknowledgment is made to my colleagues of the United States Geological Survey for many suggestions and criticisms; to Mr. Mills for the production data given of the oil wells from which some of the samples were collected; to Mr. A. W. McCoy of the Empire Gas and Fuel Co., Bartlesville, Okla., for many ideas. Determining Pore Space of Oil and Gas Sands In selecting a method for the determination of pore space, two objects were kept in mind: First, the method must not only be sufficiently

Jan 1, 1921

By Irving B. Cadoff, Stojan M. Zalar

AgInTe2, CuInTe2, and all Proportions of CuxAg1-xInTe, forMed homogeneous single phase alloys after direct solidification from the nielt. X-ray analysis indicated a zinc-blel~de strzccture typical of the chalcopyrite compounds, and the electrical resistivity and Sccbeck coefficient values were in the semiconducting range. AuInTe, and AuxA4g,-, InTe, formed by what appeared to be a peritectic reaction (the thermal analysis curves showing more than one arrest) and were conseyue~ztly polyphase. Substitution of copper into AgIrzTe, resulted in a continuous transition in the room tenzperature Seebeck coefficient from the negative AgIzTe, to the positive CuInTe,. A zero coefficient was obtained at about Cuo.55 Ago.45 InTe, . The temperatzire variation was similar to that observed for the stoichiometric compounds, that zs, tendency towards "p" concEuction at elevated temperatures. The thernzoelectric figure of merit for the compo~uzds, as determined by the Putley -Harmnn method were in the range 10- to 10-7 "K-l; the thermal conductivities in the order of 0.15 cal per sec-cm-oK. INCREASED interest in semiconducting intermetallic substances is expanding much of recent research from simple binary compounds into polyatomic systems and solid solutions. Ternary compounds A' represent a covalent extension of the binary semiconductors Within the a tin isoelec-tronic series, Ag-Cd-In-Sn-Sb-Te-I, divalent cadmium atoms in CdTe are being substituted for by monovalent silver and trivalent indium atoms to form the compound AgInTe, . By cross-substitution with elements of other isoelectronic series, a great number of ternary compounds A 'B"'c? is possible. In all of them, however, a necessary though not sufficient condition for the covalent, semiconducting bond—that there be four sharing orbital electrons per atom—must be fulfilled. In AgInTe,, each silver or indium atom is tetrahedrally surrounded by four tellurium atoms, while each tellurium atom is co-valently bound to two silver and two indium atoms. Synthetic chalcopyrites A'B"'c~ were first recognized as potential semiconduct&rs by Goodman and Douglas.' Austin, Goodman, and Pengelly discuss preparation difficulties and some electronic measurements on AgInS, , AgInSe, CuInSe, , AgInTe, , and CuInTe,. Chalcopyrites A B c2v are mentioned in papers attempting to classify and predict semiconducting behavior of intermetallic compounds; on the basis of saturated tetrahedral sp3 bonds,3 by specific selection criteria,' and by crystallographic considerations."

Jan 1, 1962