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By B. H. Caudle, A. B. Dyes, R. A. Erickson

The study of the influence of fluid mobilities on the sweepout pattern resulting from the injection of gas or water has been extended to cover the production period which follows breakthrough of the injected material. Mobility ratios over the range common in field operations (0.1 to 17) were studied for several pattern floods (five-spot, staggered, and direct line drive). The experimental data required for these studies were obtained by the use of the x-ray shadowgraph technique using miscible oil phases of different viscosities in porous plate mode1s of a reservoir element. From the shadowgraph pictures obtained before and after breakthrough of the injected fluid, flowing ratios at the producing well and cumulative volumes injected were calculated. The method for applying such data in predicting field behavior is illustrated for a water flood of a five-spot. For this case a range of mobility ratios of 0.5 to 5.0 results in: (I) nearly complete (95 to 100 per cent) sweepout pattern efficiencies at abandonment conditions, (2) production after breakthrough being responsible for as much as one-third of the total recovery at the lower mobility ratios, and (3) a twofold variation in the operating life of the reservoir. In determining the merits of a secondary recovery operation, the fraction of the reservoir which is ultimately to be swept by the injected fluid is of major importance. Because of its significance a large amount of research has been applied to the study of areal sweepout efficiency. Muskat, Wyckoff and Botset1,2 have presented the classic analysis of the pattern efficiency at breakthrough for several injection patterns in which the mobility of the fluids ahead of the injected phase front was equal to the mobility of the fluids behind the front. Aronofsky3 as extended this analysis of recovery at breakthrough through numerical computations and by the stepwise use of the potentiometric model to include the effect of different fluid mobilities ahead of and behind the invasion front on the line drive performance. Fay and Prats' have also employed numerical computations to show the influence of one other condition of fluid mobilities on the five spot flood. In a previous paper' a new method of attack on this problem which employed x-ray and porous plates was described. At that time experimental results were also presented which described the effect of fluid mobilities on the reservoir area contacted by the injected fluid at breakthrough for the five spot and direct line drive patterns. Most of the literature pertaining to sweepout pattern efficiency has emphasized the pattern which is obtained at breakthrough of the injected phase. The increase in the sweepout pattern which occurs after breakthrough

Jan 1, 1955

By J. A. Pusateri, M. A. Orehoski, N. R. Arant

Plant studies on commercial-size ingots and laboratory experiments with induction furnace heats have demonstrated that the major source of ingot cracks is associated with two conditions arising during top-pouring practice: 1—solidification during pouring, and 2—turbulence created by the impact of the stream. Methods of controlling the two factors were effective in eliminating or significantly reducing ingot cracks. BECAUSE the process of removing surface defects from hot-rolled product is so costly, the steel industry is striving constantly to develop methods of preventing, or at least decreasing, the occurrence of surface defects. Investigations have revealed steel-making and processing variables related to major surface defects, and controlling these variables has led to improvements in surface quality. However, the fundamental causes of major surface defects, such as ingot cracks, have not been determined; consequently such defects persist. At the Research and Development Laboratory of the United States Steel Corp. in Pittsburgh, a seam research program was initiated to determine the fundamental causes of certain major defects. As a part of the program, ingot cracks in killed, finegrained C1020 steel were selected for study. A cost survey indicated that, of the steels produced in sizable tonnages, carbon steels in the range of 0.18 to 0.23 pct C content require the most conditioning. Since this is particularly true of C1020, any im-provement of surface quality that might be effected from the study would be beneficial. Also, since the frequency of ingot cracks is exceedingly high for this grade, the steel would provide an excellent opportunity for a thorough study of the ingot-crack-ing problem. Why steels in this carbon range tend to exhibit more ingot cracks than do other steels was not considered in the investigation; the mechanism of ingot-crack formation was of paramount importance. Also, only the top-pouring practice was considered in the investigation, because this pouring procedure is used more extensively than others. In this study, ingot cracks are defined. as deep surface defects that sometimes are observed in an ingot prior to rolling but usually are observed during the initial stages of rolling on the primary mills. These defects may occur at any angle to the rolling direction but are most prominent in the transverse or nearly transverse direction. The appearance of ingot cracks on the rolled product varies with respect to their angle of formation and with the extent of rolling after their first occurrence. Ingot cracks are also termed "deep seams," "arrowheads," "irregular cracks," and "transverse cracks." Fig. 1 shows ingot cracks in a rolled bloom. This report summarizes: l—the exploratory investigation of commercial-size ingots; 2—the labor-atory investigations related to determining the source of ingot cracks and developing corrective methods; and 3—the plant evaluations of laboratory methods of decreasing ingot cracks. Exploration of lngot Cracks in Commercial Ingots Materials and Experimental Work: At the Du-quesne Works of the United States Steel Corp., five heats of killed, fine-grained C1020 steel were selected for the exploratory phase of the seam-research program. The heats were made by open-hearth practices that are considered most conducive to good surface quality. They were top-poured into 22x25 in. big-end-up hot-topped molds. One as-cast ingot and four other ingots rolled to the following cross-sectional sizes were set aside from each heat: 16x20 in.; 9 1/2x10 in.; 5x5 in.; and 2x2 in. The processing of the heats, from the time of charging in the open hearth furnaces to the end of the rolling operation on the primary mill, was observed carefully and recorded. The cast ingot and the four rolled ingots from each heat were examined for surface defects. The cast ingots were split longitudinally near the vertical center plane to expose the ingot structure beneath badly cracked regions. Also, a series of transverse sections was cut at about 1 in. intervals in a badly cracked area of one ingot. All sections were ground, polished, examined by sulphur printing and deep etching, and photographed. The rolled ingots

Jan 1, 1955

By M. C. Udy, F. W. Boulger

AN incomplete phase diagram for the U-Ti systern was determined earlier 1 and more recently, a tentative diagram was presented for the uranium-rich end of the system.' In the present re-examination of the whole system of U-Ti alloys, high purity materials were used. Melting stock for the alloys was high purity uranium, containing about 0.09 pct C as the only appreciable impurity, and high purity iodide-process titanium purchased from New Jersey Zinc Co. Both metals were cold rolled to about 1/6 in. thickness, sheared to about I/' in. squares, and cleaned by pickling. The alloys were arc melted under a helium atmosphere in a water-cooled copper crucible. A thoriated-tungsten electrode was used. The furnace chamber was evacuated, then flushed with helium, prior to each melting. It was finally filled with stagnant helium at one atmosphere pressure. Each alloy was remelted three times after the original melting, to insure homogeneity. The alloy button was turned bottom side up before each re-melting operation. Some 22 alloys were examined. Their compositions were spaced at appropriate intervals between 100 pct Ti and 100 pct U. Analyses were made on chips taken after fabrication. The major contaminant was carbon, which varied from 0.03 to 0.08 pct. It appeared in the microstructure as titanium carbide. Alloy compositions were calculated to a carbon-free basis for consideration on the diagram. Tungsten and copper, possible contaminants from the melting operation, were generally less than 100 parts per million each. Fabrication All alloys were forged and rolled to bars approximately V8 in. square. They were clad either in SAE 1020 steel or in a 5 pct Cr-3 pct Al-Ti-base alloy, depending on the fabrication temperature. A temperature of 1800°F (980°C) was used for alloys near the compound composition. This necessitated using the titanium-base alloy, since iron reacts with titanium at this temperature, producing a low melting alloy. Other alloys were fabricated at 1450°F (790°C), using steel jackets. No iron-titanium reaction occurred at this temperature. The jackets were welded in place in an argon atmosphere. Those alloys sheathed in steel were declad and then reclad between rolling and forging operations. On the other hand, those clad with the titanium alloy were cut to a roughly rectangular shape prior to clading and were then carried through both the forging and rolling operations without opening. Those alloys near the compound composition were found to be cracked when the clading was removed. The cracked materials had been plastically deformed, however, and at least some of the cracking had OCcurred during cooling. Heat Treatment The rolled bars, after being declad and shaped to remove surface contamination, were all given an homogenizing treatment of 160 hr at 2000°F. (Samples were taken for analysis following the declading and shaping operations.) All were heat treated at the same time in one furnace, but each was sealed in a purified argon atmosphere in an individual Vycor glass tube. Argon pressure was such that it was approximately atmospheric at temperature. One end of each tube contained titanium chips and this end was heated to 1200°F (650°C) for 10 min prior to the heat treatment. This purged the atmosphere of residual reactive gases. The balance of the tube was warmed during the purge to liberate adsorbed moisture and gases, which also reacted with the hot chips. The bars were furnace cooled from the homogenization treatment. Specimens of each alloy were water quenched after 2 hr heating at 1000°, 1200°, 1400°, 1600°, 1800°, and 2000°F (540°, 650°, 760°, 870°, 980°, and 1095°C). In addition, some were treated at intermediate temperatures of 1300°, 1500°, and 1700°F (705", 815", and 925°C) and at 2150°F (1175°C). Specimens, about '/s in. cubes, were cut from the bars, sealed in individual Vycor tubes, and heat treated as described. All specimens heat treated at the same temperature were processed together. Samples were quenched by breaking the Vycor tube rapidly under water. Metallographic Examination Specimens were mounted in bakelite and ground wet on 180 grit paper held on a 1750 rpm disk. They were then ground wet by hand, using 240, 400, and 600 grit papers. The rough grinding was continued long enough to get well below the surface. Specimens were mounted separately because of the variation in the rate of etching between alloys. The specimens were polished with rouge on a 4 in., 1725 rpm wheel covered with Miracloth. Alloys on the titanium side of the compound composition were etched with a solution of 2 pct hydrofluoric acid in water saturated with oxalic acid. A few crystals of ferric nitrate were added as a bright -ener. Specimens were immersed 5 sec, polished to remove the etch, then re-etched. With the higher titanium alloys, it was often necessary to start the etch on the polishing wheel, because of the formation of a passive film. In some instances, a plain 2 pct hydrofluoric etch was satisfactory. For the alloys on the uranium side of the compound, a distinction between the compound and the uranium phase developed after standing a short time in air. This could be hastened by the application of heat, such as obtained by placing the specimen on a radiator. A deep etch was necessary to develop details in the uranium-rich phase, such as the Widmanstaetten pattern sometimes obtained by quenching y uranium. A 2 pct hydrofluoric acid solution was used for this deep etching.

Jan 1, 1955

By George B. Clark

Many basic engineering principles of all four phases of mining operations, namely, prospecting, exploration, development, and exploitation, can be analyzed better in terms of quantitative geology. Geological data from both field and laboratory will also complement scientific methods now being developed. THE geological data emphasized so successfully in prospecting for new deposits, that is, structural controls, strength of solutions, and type of mineralization, are basically those required for successful exploitation. In the mining of newly discovered deposits the most economical methods should be employed as early as possible to keep the overall cost per unit produced at a minimum and to permit maximum extraction of valuable minerals. A crucial question is: How can geological data be translated into useful quantitative results which will aid in achieving this end? H. E. McKinistry' has suggested that a solution may be reached in one of two ways: 1—the usual approach, use of judgment based on experience; or 2—mathematical calculations and tests on models, both subject to certain limitations. He also suggests that in addition to better use of geology more case data and theoretical data are needed on which to base sound judgment. Further research, therefore, is necessary. Perhaps in this field the emphasis should be on more specialization in mining methods and ground movement by men with thorough training in physics, engineering, geology, and underground mining. These specialists would be equipped to point out the most economical and scientific methods of exploitation. Selection of a stoping method is governed by the amount and type of support a deposit will require in the process of being mined, or by the possibility of employing the structure of the deposit to advantage in mining the ore by a caving method. In addition to these factors there are others which almost invariably influence the choice of an economical method of mining:' 1—strength of ore and wall rocks; 2—shape, horizontal area, volume, and regularity of the boundaries of the orebody, and thickness, dip and/or pitch of the deposit and individual ore shoots; 3—grade, distribution of minerals, and continuity of the ore within the boundaries of the deposit; 4—depth below surface and nature of the capping or overburden: and 5—position of the de- posit relative to surface improvements, drainage, and other mine openings. In the final analysis it is usually necessary to disregard the less important of these factors to satisfy the requirements of the more important. Because of the variation of geological conditions throughout and surrounding the deposit, no mining method will be everywhere ideally applicable to the conditions encountered in one ore deposit. The immediate problem is to interpret the above physical characteristics of deposits in terms of geological characteristics. Very few quantitative geological data are available on the factors related to a choice of mining methods. However, there are many descriptive data in mining and geological literature which collectively show how important an effect details of geology have upon all phases of mining operations. The following categories of basic mining methods were investigated to establish the geological factors that have affected their successful application: 1— open stopes with pillars; 2—sublevel stoping; 3— shrinkage stoping; 4—cut-and-fill stoping; 5— square-set mining; 6—top slicing and sublevel caving; and 7—block caving. It should be noted that the first five of these methods are listed in the order of increasing support requirements. Mines were selected as examples only where geological descriptions were complete enough to warrant their use. A study of the geological factors involved in mining operations led to a choice of the following classifications, employed in Table I: 1—structural type of orebody; 2—dimensions (geometry); 3— country rock (type); 4—faulting, folding, and fracturing; 5—alteration of ore and rock; 6—type of mineralization; and 7—geological factors determining mining method (summary). Of these factors only one yielded results that can be defined from available data in a quantitative manner, i.e., dimensions of the deposit. These are the most reliable guides that can be used in selection of suitable mining methods. They are, in general, the properties of geologic structure most difficult to evaluate by studies of models, pho-toelastic studies, and other laboratory methods, all of which are at present more limited in their applications than the geologic method. Application of geology has proved a reliable guide in other phases

Jan 1, 1955

By H. H. Hausner, S. Storchheim, J. L. Zambrow

The solid state bonding of aluminum to nickel was studied as a function of temperature, pressure, and time at pressure. The initial results indicated that as the reaction conditions were varied, marked changes in tensile strength occurred. Plots of the log penetration coefficient vs the reciprocal of absolute temperature for various isobars were straight lines displaced from each other. THE techniques of bonding different metals to A each other include brazing, welding, welding by application of a molten phase, and solid state welding without any molten phase present. This last technique, the pressing of metals either at room temperature or at some temperature below the melting point of the metals to be joined, seems to offer interesting possibilities for bonding purposes. However, this technique has not been completely investigated, and very little is known about the diffusion phenomena which occur during solid state welding. Some previous work on the effect of pressure on diffusion1 was inconclusive. This paper is concerned with an investigation regarding the effect that the processing variables, such as pressure, temperature, and time at pressure, have in solid state bonding. The tests were made with aluminum and nickel and special emphasis was given to the strength of the bond between these two metals and to the intermetallic penetration rate during the bonding process. It seems that the effect of pressure on the intermetallic penetration is of particular importance for practical purposes and this effect was therefore studied in detail. Procedure Apparatus: The means of solid state bonding used for this study was that of the hot-pressing technique. This method requires the equipment pictured in Fig. 1 and involved the following procedure. The two metals to be bonded were placed in an aquadag lubricated 18-4-1 tool steel die, 16 in. high by 1.440 in. ID, between punches of 1.366 in. diameter made of the same material. A thermocouple

Jan 1, 1955

LIMA (PERU) Established May, 1952 (Official year begins in June) Luncheon meetings third Wednesday monthly Ernesto A Baertl, Chairman Arthur C Hall, Chairman-elect Raymond R Beard, 1st Vice-Chairman Edgardo Portaro, 2nd Vice-Chairman Walter E King, Secretary-Treasurer Av Santa Cruz 331 San Isidro, Lima, Peru Alberto E Brazzini, Asst Treasurer Daniel M Rodriguez, Asst Secretary Robert P Koenig, '56, Section Delegate Arthur C Hall, Alternate Section Delegate

Jan 1, 1955

By R. C. Mahon

THE importance of ground water control in glacial drift overlying mines is widely recognized. Adequate handling of the problem results in considerable saving in overall pumping costs, as the cost of pumping the larger quantity of water under low heads from surface wells is more than offset by the decrease in the quantity of water to be pumped from the mine under high heads. Eliminating or partly reducing seepage of water through the ledge reduces moisture content of the ore, a factor especially important in iron ore mines, where a reduction of 1 pct in moisture effects a very material saving. An important though indeterminate saving is also brought about by the elimination of water in the working places underground. The Homer and Wauseca mines of Hanna Coal & Iron Co. at Iron River, Mich., cover 480 acres. When these mines were started it was possible to operate on only one 40-acre tract, as the depth of water over the remainder of the property was too great to permit operation. Although the average depth of the ground water over the area being mined at that time was less than 50 ft it was necessary to pump 1200 gpm from the mine, the greater part from a depth of 750 ft. The slate footwall and graywacke hanging wall are almost impervious, and it was apparent that seepage into the mine was mainly through the iron formation in which the orebodies were located. Analysis of the water in the iron formation showed it to be of the same character as that in the glacial drift, while the water in both walls was heavily mineralized, also indicating that the water passed much more freely through the iron formation. The first attempt to take off the water above the ledge was by means of drainage drifts driven 15 to 20 ft below the ledge, Fig. 1. Various schemes were used to get the water into these drifts: 1—Holes 15 to 20 ft long were drilled from the back of the drifts to the ledge, but these were difficult to drill and blocked easily. 2—Sections of the drifts were blasted down. This gave a large flow for a time but eventually almost total blockup occurred. 3—Raises 4x4 ft were driven above the drifts to within 8 ft of the

Jan 1, 1955

By D. L. Everhart

The search for new deposits raises two important questions: Where did the metallic ions that formed the orebodies come from? What processes and geologic factors were involved in ore replacement? A review of the wide geological variety of recent uranium discoveries tells how these questions are being answered. SOONER or later intelligent exploration for uranium leads to these questions: Where did the metallic ions that formed the orebodies come from? What processes and geologic factors were involved in ore replacement? These matters, of course, make a big difference in how best to look for orebodies. Before these questions are discussed it might be well to point out other factors bearing on the subject. The whole business of uranium exploration is only a little over ten years old, participation by the public is only about six years old, and real interest and activity by more than a few large mining companies has arisen only in the past two or three years. Throughout this short period, uranium exploration has been affected by the unique influences of necessary security measures and by division of the overall job into individual projects by a large number of specialists in diverse fields. This has meant that a normal interchange of information on the nature of uranium deposits has really only just begun. Compared to the vast amount of published studies on iron, copper, lead, zinc, and gold deposits over the past 50 to 75 years, current knowledge of uranium deposits is in its infancy and much of the pertinent information is still scattered about in a number of unpublished sources. The volume of reports on all phases of uranium exploration is now beginning to mount at a remarkable rate, and geologists with widely varying specialized backgrounds in uranium geology are engaging in spirited debates over the origin of uranium and the relative importance of geologic controls of various deposits. One of the most interesting features of known uranium deposits of the world is the wide variation, see Table I, in character and geologic environment. It should be noted that many types became prominent during 1953. The davidite-bearing veins of Radium Hill, South Australia, are almost unique, although the same mineral occurs in a different kind of deposit in Mozambique. Recent studies indicate that brannerite disseminated in the granite near Cracker's Well, South Australia, may soon constitute uranium ore. Basalt has been added to the list of favorable host rocks in the Northern Territory of Australia. Basalt is also the host of the pitchblende veins of the Martin Lake deposit, Beaverlodge district, Saskatchewan. The truly remarkable rich and extensive Steen deposit near Moab, Utah, is of the uraninite-vanadium oxide type. Secondary hydrous uranium arsenates and phosphates constitute the uranium minerals in the disseminated deposits of the Wind River Basin, Wyo., a new district discovered in the summer of 1953. Uranium minerals in shales adjacent to fractures were newly reported in New Mexico and several other parts of the world during the year. The well-known important uraninite dissemination in the Rand conglomerates of South Africa has a counterpart, as discovered in the summer of 1953, in the Mississagi quartzite and conglomerate of the Blind River district, Ontario. Gunnar deposit of the Lake Athabaska district, Saskatchewan, consists of uraninite in both granite and sedimentary gneiss beneath a granite cap, and large new orebody of the Eldorado Co. in the same general area follows a preferred stratigraphic horizon in schists. Uranium is, generally speaking, a very soluble and ubiquitous element. It occurs in at least two valency states and for this reason is not easily tied down in natural solutions. As Gruner' has pointed out, it is probable that uranium starts in the hexava-lent state in nearly all solutions instrumental in its transfer. It is believed that under oxidizing conditions the uranium moves in solution as the uranyl ion, UO. In solutions ranging in pH from 1 to 5, the uranyl ion is most commonly in association with

Jan 1, 1955

Jan 1, 1955

By J. B. Newkirk, A. H. Geisler

The alloy Cu4Pd has a disordered face-centered-cubic structure when quenched from temperatures between 478ºC and the melting point (about 1100°C). Below 478ºC an ordered phase is stable. The results of a Debye-Scherrer X-ray analysis indicate that the ordered phase has a tetragonal unit cell described by the space group C24h — P42/mt with 2 Cu in 2a, 2 Cu in 2f, 4 Cu in 4j (x = 0.2, y = 0.6), 4Pd in 4j (x = 0.4, y = 0.2), and 8 Cu in 8k (x = 0.1, y = 0.3). The orientation relationship between the face-centered-cubic phase and the ordered tetragonal phase is given by: [100],,. // [130]al,. COO1Ia.d.//COO1I,,.. • The behavior of Cu,Pd is typical of ordering alloys except that the transformation is very sluggish. The increase in hardness and the microstructural and X-ray diffraction effects are interpreted in terms of coherency strains caused by the ordering. AN anomalous construction in the Cu-Pd phase diagram (Fig. 1) was reported in 1939 and has been allowed to stand without further published attention since that time. The odd figuration about the composition 10 to 27 atomic pct Pd is derived mostly from the work of Jones and Sykes.1 Evidently several features of this binary system require further study if the constitutional forms are to be well understood. The present paper includes a study of one of these features, that is, the crystal structure of a single ordered alloy containing nominally 20 atomic pct Pd. This choice of composition was suggested by the work of Harker and associates who determined the structure of Ni4Mo2 and Ni4W.3 The nature of the ordering process in Cu4Pd was studied also by observing the hardness, microstructure, and Debye-Scherrer patterns of specimens which had been aged at various temperatures after quenching from an initial disordering treatment. Experimental Methods A 20 gram ingot of Cu4Pd was made by melting spectrographically standardized copper from Johnson, Matthey, and Co., and commercially pure (99.5 + ) palladium in an argon-filled quartz tube. Chemical analysis showed that the ingot contained 80.0 atomic pct Cu. The ingot was rolled about 60 pct to a strip 0.060 in. thick and was homogenized for 16 hr at 950°C in low pressure argon. Rods cut from the rolled strip were worked into wire 0.015 in. in diameter, and specimens for hardness and microscopic examination were cut from the remaining strip. All specimens, with the exception of some of the wire, were given an initial disordering treatment by heating for 16 hr at 950°C, followed by water quenching. A 10 cm length of as-drawn wire was water quenched after being held in a temperature-gradient furnace4 for 89 days. Room-temperature Debye-Scherrer photograms were then made at points along the wire to determine the temperature below which the ordered phase was stable. Although the accuracy of temperature determination in the gradient was only about ±10 °C, the temperature gradient was sufficiently gradual that the sensitivity was much better and locations which had differed by as little as 1°C could be distinguished. An analysis of the crystal structure of the well ordered alloy was made by X-ray diffraction using a specimen cut from this wire. The change of Debye-Scherrer pattern as ordering progressed was studied by using isothermally aged samples of initially disordered wires. The wires were sealed under low-pressure argon in small quartz tubes for heat treatment. After the aging treatment, the tubes were quenched in water and photograms were made at room temperature in a 10 cm diam camera using filtered Cu kX. (A = 1.540511) Hardness was measured on a Vickers hardness tester using a 10 kg load and 2/3 in. objective lens. Reported values are the average of at least three impressions made on flat specimens 0.060 in. thick. After the hardness of a heat-treated sample had been measured, it was resealed in low-pressure argon and returned to the furnace for continued aging at the same temperature. In this way, two samples served for all aging times at each temperature. Hardness specimens which had been aged 500 hr or more were used for metallographic examination after the final aging treatment. A dilute potassium-dichromate etching solution was used.

Jan 1, 1955

By W. M. Baldwin, J. T. Brown

The effect of hydrogen on the ductility, c, of SAE 1020 steel at strain rates, i, from 0.05 in. per in. per rnin to 19,000 in. per in. per rnin and at temperature, T, from +150° to —320°F was determined. The ductility surface of the embrittled steel reveals two domains: one in which and the other in which The usual "explanations" of hydrogen embrittlement are in accord with the first of these domains only. THE purpose of this investigation was a fuller A characterization of this of the investigation effects of varying temperature and strain rate on the fracture strain of hydrogen-charged steel. To be sure, it is known that low and high temperatures remove the embrittlement that hydrogen confers upon steels at room temperature,1 * see Fig. la and b, and that high strain rates have a similar effect,'-' see Fig. 2a, b, and c. However, the general effect of these two testing conditions on the fracture ductility of hydrogen-charged steels is not known, i.e., the three-dimensional graphical representation of fracture ductility as a function of temperature and strain rate is not known—only two traverses of the graph are available. The need for such a graph is not pedantic. To demonstrate this point, Fig. 3a, b, and c shows three of many three-dimensional graphs, all possible on the basis of the two traverses at hand. The important point (as will be developed in the Discussion) is that each of them would indicate a different basic mechanism for hydrogen embrittlement. It will be noted that the four types of ductility surfaces in Fig. 3a, b, and c may be characterized as follows: Material and Procedure Tensile tests were made at various temperatures and strain rates on a commercial grade of % in. round SAE 1020 steel in both a virgin state and as charged with hydrogen. The steel was spheroidized at 1250°F for 168 hr to give the unembrittled steel the lowest possible transition temperature. The steel was charged cathodically with hydrogen as follows: The specimen was attached to a 6 in. steel wire, degreased for 5 min in trichlorethylene, rinsed with water, and fixed in a plastic top in the center of a cylindrical platinum mesh anode. The assembly was placed in a 1000 milliliter beaker containing an electrolyte of 900 milliliters of 4 pct sulphuric acid and 10 milliliters of poison (2 grams of yellow phosphorous dissolved in 40 milliliters of carbon disulphide). A current density of 1 amp per sq in. was used which developed a 4 v drop across the two electrodes. All electrolysis was carried on at room temperature. Temperatures for tensile tests were obtained by immersing the specimens in baths of water (+70° to + 150°F), mixtures of liquid nitrogen and isopen-tane (+70° to —24O°F), and boiling nitrogen (-240" to-320°F). Specimens were tested in tension at strain rates of 0.05, 10, 100, 5000, and 19,000 in. per in. per min. The 0.05 and 10 in. per in. per rnin strain rates were obtained on a 10,000 lb Riehle tensile testing machine, the 100 in. per in. per rnin rate on a hydraulic-type draw bench with a special fixture, and the 500 and 19,000 in. per in. per rnin rates on a drop hammer. The fracture ductility of hydrogen-charged steel at room temperature and normal testing strain rates (-0.05 in. per in. per min) is a function of electro-lyzing time, dropping to a value that remains constant after a critical time.'* Under the conditions of • The hydrogen content of the steel continues to increase with charging time even after the ductility has leveled off to its saturated value.' this research the saturated loss in ductility occurred at approximately 30 min, see Fig. 4, and a 60 min charging time was taken as standard for all subsequent tests. After charging the steel with hydrogen, the surface was covered with blisters. These have been described by Seabrook, Grant, and Carney.' The original diameter of the specimen was not reduced by acid attack, even after 91 hr. Results The ductility of both uncharged and charged specimens is given as a function of strain rate in Fig. 5, and as a function of temperature at four different strain rates in Fig. 6. These results are assembled into a three-dimensional graph in Fig. 7. It is seen that the locus of the minima in the ductility curves of the charged steels divides the ductility surface into two domains. At temperatures below the minima,

Jan 1, 1955

By E. R. Morgan

A series of manganese-rich ferromagnetic alloys has been studied. The alloys are based upon an interstitial solution of carbon in manganese. In each of the systems investigated, the ferromagnetic phase was found to be face-centered-cubic in structure. This magnetic phase is based upon the composition (Mn, X)4C; where X is a metallic element which has both a positive size factor with respect to manganese and a high positive valence. Typical elements of this type are aluminum, indium, and tin. Preliminary magnetic measurements indicate that the effective magnetic moment of manganese in the alloys is at least 1.0 Bohr magneton per atom. It is emphasized that the critical atomic separation beyond which ferromagnetism can occur will be governed by the electronic configuration of the manganese atoms. Lattice parameter measurements show that the ferromagnetic condition in the present alloys is associated with an increased atomic separation of only 3 to 6 pct compared with a hypothetical face-centered-cubic lattice of pure manganese. MANGANESE which is paramagnetic and not ferromagnetic in the pure state can become ferromagnetic if suitably alloyed. Under favorable conditions manganese can have an effective ferromagnetic moment of the order of 3.41,2 or even 4.0 compared with a moment of 2.2 Bohr magnetons for iron. The incidence of ferromagnetism is believed to be controlled by the degree of atomic separation.4,5 This is consistent with the fact that the atomic separation, when considered in terms of the ratio of the atomic diameter R to the diameter r of the 3d-shell, is larger in the ferromagnetic metals. The values of R/r calculated by Slater,' for metals of the iron group are given in Table I, and Slater has suggested that the critical ratio of R/r is 1.5. Consideration of the criterion of atomic separation alone would suggest that there are three classes of possible ferromagnetic manganese alloys: 1— Ordered structures, of either solution or compound types, such that manganese atoms are not near neighbors; 2—Structures in which the separation of near-neighbor manganese atoms is sufficiently increased by the presence of suitable solute atoms; and 3—Dilute solutions of manganese. Typical ferro- magnetic alloys of types 1 and 2 are the Heusler alloys and Mn4N, respectively. There are no recognized ferromagnetic alloys of type 3. In view of the proximity of the ratio R/r for manganese to the critical ratio of 1.5, the present work was concentrated on manganese-rich alloys rather than on ferromagnetic alloys of low manganese content, several examples of which are already known. Calculation of the distance of closest approach of manganese atoms in each of its allotropic forms, Table 11, indicates that the high temperature ? phase provides the most suitable basis for ferromagnetic alloys of high manganese content. However the high temperature forms of pure manganese cannot be retained on quenching, although a face-centered-tetragonal form apparently can be produced by electrodeposition. Since the critical separation which must be exceeded in order to obtain ferromagnetism is dependent upon the number of electrons in the d-shell, no exact critical value of R/r can be assumed. Not only will this separation vary from one pure metal to another, but it will also vary with the valency of the given type of atom when it is in an alloy. Raynor8 has shown that metals of the iron group probably

Jan 1, 1955

By P. Payson

EMBRITTLEMENT of hard-tempered martensite (500°F embrittlement) appears to be coincident with the beginning of the third stage of tempering. During the first stage, primary martensite of steels containing over 0.25 pct C decomposes to a mixture of c carbide and martensite of appreciably constant carbon content close to 0.25 pct.' During the third stage of tempering, cementite forms. In steels with

Jan 1, 1955

By H. C. Brown

SINCE 1934 the steel industry has been utilizing the spectrograph for supplementing wet chemical analysis in the production control of electric and open hearth furnaces. This means of control made great strides during the war years because of the general acceptance of the spectrograph and the increased emphasis that was placed on rapid control methods. However, in the post war era, with the demand still on increased production, it became apparent that a still more rapid and economical means of production control was needed. Since the spectrograph had been used mostly in the analysis of low alloying and residual elements, it also became apparent that equipment was needed to extend the spectrographic technique to the analysis of the high alloying elements in stainless steel. For these reasons, companies manufacturing spectrographic equipment were prompted to start development work on direct reading instruments. In June 1949, the Applied Research Laboratories of Glendale, Calif., announced that a direct method of spectrochemical analysis for stainless type steels had been developed. This paper will describe the use of the Applied Research Laboratories Production Control Quantometer in the quantitative control of stainless, silicon, and plain carbon steels being made at the Butler Pennsylvania Div. of the Armco Steel Corp. The Armco Butler Div. has one 70-ton electric furnace and six 150-ton open hearth furnaces. The electric furnace is employed in the making of all types of stainless steel and the open hearth furnaces are used for the production of silicon, wheel, and plain carbon steels. The ARL quantometer was purchased primarily for the purpose of controlling the steelmaking in the electric furnace, but its use has been extended for the analysis of final tests (ladle tests) on a number of different types of stainless, silicon, and plain carbon steels. Because of this additional work by the quantometer, substantial savings in manpower and time have been realized by the laboratory. In the analysis of a set of preliminary tests from the stainless steel furnace, approximately 40 min in laboratory time are saved due to quantometric analyses. Despite the fact that more specialty grades of stainless steel are being made in the electric furnace, the average tons per hour have been increased since the quantometer was put into operation. Specialty grades require more furnace time than regular commodity grades of stainless steel. The installation of the ARL production control quantometer was completed on March 13, 1952. By May 1, 1952, the instrument was calibrated for nickel, chromium, manganese, silicon, and molybdenum, which are the elements necessary for the production control of the stainless steel furnace. Within the following month, training of personnel on the quantometer was achieved and a study of the accuracy of the instrument showed that the results obtained were sufficiently accurate for control purposes. Therefore, on June 11, 1952, the quantometer was placed on production control for all types of stainless steels. Starting September 11, 1952, the instrument was gradually placed on ladle analysis (final tests) as the analytical curves were refined and additional curves were drawn. The quantometer has been relatively free of breakdowns since placing it on production control. The samples from only one stainless steel heat have had to be analyzed by wet chemistry because of instrument trouble. The previously existing heat-time record was also bettered by 15 min on a commodity grade of 18-8 stainless steel. Scope of Control In general, the quantometer determines all elements necessary for the production control of all types of stainless steel heats and for the ladle analysis of various types of stainless steel heats. It is also used in reporting final results for silicon, manganese, chromium, nickel, molybdenum, tin, copper, and aluminum on all silicon steel grades and manganese, chromium, nickel, molybdenum, tin, and copper on several plain carbon steel grades. Table I shows the elements and the concentration ranges of these elements in the various types of stainless, silicon, and plain carbon steel that are determined on the quantometer. A study of the results obtained on ladle test samples of stainless steel types 410, 430, 430 Ti, 446, 301, 302, 304, 304L, 305, and 17-7 PH will be discussed. Also included in the study are the results obtained on ladle test samples of a number of silicon steels. Apparatus In order to take full advantage of the potentials of the production control quantometer, the unit has been placed in an air-conditioned room with relative humidity control. The temperature is maintained at 73'22°F and the humidity at 45&5 pct. The air conditioning serves as a precaution to minimize the amount of adjustment and calibration needed during operation. It also reduces contaminating fumes and dust and thereby lessens the necessity for maintenance on the equipment. The quantometer is composed of three units: the high precision multisource unit, the 1.5 meter vertical spectrometer, and the console. The source unit supplies excitation conditions varying from spark-like discharges to arc-like discharges. The voltage to the source unit is supplied by a motor-generator

Jan 1, 1955

By J. H. Wernick

IN a study of the rate of decomposition of %-in. cubes of limestone, dolomitic limestone, and dolomite in a sweeping nitrogen atmosphere, Joseph, Beatty, and Bitsianes' found that the zone of calcination advanced at substantially a constant rate at a given temperature. The purpose of this paper is to show that their data indicate at least two processes occurring when the above carbonates decompose. It is suggested that there are two processes occurring consecutively, one the limiting process in a given temperature range and the other the limiting process over another temperature range. The data of Joseph and co-workers have been extended by use of the Arrhenius equation, Eq. 1, a relation beween the velocity constant k of a reaction and the absolute temperature T. d In k A ' dT Rr2 A is the activation energy in calories per mol (additional energy that must be added for an average molecule to react), and R is equal to 1.986 cal

Jan 1, 1955

By F. D. Rosi

The slip and twinning behavior in extended titanium crystals were studied in some detail. The formation and appearance of coarse kink bands are discussed. Their crystallographic geometry was determined by X-ray analysis. A phenomenological interpretation of the complexities in kink band development is also presented. The critical resolved shear stress, coefficient of shear hardening, and plane of fracture were determined for several crystals extended at room temperature. THE slip and twinning elements observed in the room-temperature deformation of titanium were enumerated in a previous paper1 in which considerations were advanced regarding the nature and selection of these elements and their effect on the known mechanical properties of this metal. The present study concerns the crystallographic, microscopic, and mechanical aspects of flow in relation to the slip and twinning elements, and includes a prediction of slip systems, nature of slip and twin markings, inhomogeneities of plastic flow, and stress-strain characteristics. Unless otherwise noted, arc-melted titanium sponge (99.77 pct) was used in these experiments. The method of production of crystals, their dimensions, and the surface preparation for micrographic examination have been reported.&apos; For obtaining stress-strain characteristics, only those crystals which traversed the entire width of the specimen and were at least 8 mm in length were used. Tensile deformation of the crystals was performed with conventional grips for sheet specimens and a constant-stress loading beam, designed after the method of Andrade and Chalmers.&apos; The specimens were loaded by allowing sand to flow from a reservoir into a bucket suspended from the longer end of a balanced 6:1 lever arm at a rate controlled to load the specimen approximately 2 kg per min. Strain measurements were made using the Baldwin SR-4, bonded, resistance-wire strain gage, Type A-8, which permitted a reading accuracy of 2 microinches per inch. The formulas used in the evaluation of shear stress and shear strain, as in deriving the coefficient of shear hardening, are given by Schmid and Boasv n terms of the original orientation and change in length of the crystal. For calculating the critical resolved shear stress, the standard equation was used. The crystallographic nature of the unpredictable slip observed in a number of specimens was determined by the single-surface X-ray method of analysis as described in ref. 1. Experimental Results Prediction of Slip System: It was reported&apos; that room temperature slip in titanium takes place predominantly on {10i0} and in a <1120> direction, giving three potential slip systems. Hence, it should be possible to predict the operative primary system in the manner used by Taylor and Elam&apos; for alu- minum (i.e., the one with the greatest component of shear stress in the direction of slip). The stereo-graphic construction in Fig. 1 shows that this is true. In all cases, slip was found to occur initially on the (0110) plane and, in a number of cases, in the [21f0] direction. (The direction of slip was not determined for all orientations.) It follows that duplex slip can be expected when two slip systems are geometrically equally favorable for slip, as demonstrated in Fig. 2. In both crystals slip took place simultaneously on the (1700) and (olio) prismatic planes, as indicated by Fig. 2a and b. In the case of crystal B the movement of the specimen axis with increasing extension was toward the (10i0) direction, which represents the stable end orientation resulting from alternate slip on the [2ii0] and [1120] directions. This is analogous to the duplex slip process in face-centered cubic metals." Unpredictable Slip: In a number of crystals whose orientations were well within the operation of a single slip system, secondary slip occurred on planes not predicted by the criterion of maximum shear stress. Examples are shown in Fig. 3. In addition to

Jan 1, 1955

By Harold Vagtborg

Equilibrium vaporization ratios were obtained for light hydrocarbons, nitrogen, carbon dioxide, and hydrogen sulfide in a reservoir fluid containing 35 mole per cent hydrogen sulfide. The data cover the range from 700 to 2500 psia at 154°F. The results of this study are compared with results obtained by other investigators on systems containing less hydrogen sulfide. When large amounts of hydrogen sulfide are present, the equilibrium vaporization ratios for ethane and heavier hydrocarbons are greater than the ratios for systems containing little or no hydrogen sulfide. Large amounts of hydrogen sulfide have the reverse effect on the ratios for methane. Routine PVT studies were performed on the reservoir fluid including flash and differential liberations of the dissolved gas. The pressure-volume relationships of the saturated fluid were also determined. It is shown that the use of published correlations on physical properties of reservoir .fluids can lead to gross errors when applied to systems containing large amounts of hydrogen sulfide. INTRODUCTION Equilibrium vaporization ratios for various components in naturally occurring crude oil and condensate systems have been reported in the literature.1,2,3,4 Recently, several papers have been published with emphasis on non-hydrocarbon components such as nitro- gen, carbon dioxide and hydrogen sulfide.5,6,7,8,9 The increased discovery of reservoir fluids having high concentrations of these non-hydrocarbon components, particularly hydrogen sulfide, has created a need for a further study of their phase behavior. Equilibrium vaporization ratios are known to vary with pressure, temperature, and overall composition of the system.&apos;" It was anticipated that ratios for systems containing large amounts of hydrogen sulfide would differ from the ratios for systems containing small amounts of hydrogen sulfide. Therefore, the present work was undertaken in order to obtain reliable equilibrium vaporization ratios for the reservoir-fluid in question. PROCEDURE The procedure followed was evolved after considerable experimentation on methods of handling the very sour crude. It was found that drying agents (e.g. CaCl2 and CaSO4) absorbed an appreciable amount of hydrogen sulfide from the gas used to prepare the recombined samples. The concentration of hydrogen sulfide dropped as much as 10 mole per cent in a single pass through a 3-ft drying tube. It was also found that when undried gas was agitated with mercury in the PVT cell, a black scum, believed to be mercuric sulfide, was formed and the hydrogen sulfide content of the gas dropped several mole per cent. Because composition changes during a run could not be tolerated, separation of the mercury and sour fluid was necessary. In order to effect this separation, a stainless steel piston, equipped with Teflon O-rings, was placed in the PVT cell between the mercury and the sour fluid. This piston had to be constructed in three parts because

Jan 1, 1955

By J. O. McCaldin, P. Duwez

ALLOTROPIC transformations between 1000° and 1900°C have recently been reported for several metallic elements. Since the proposed transformations are based on limited evidence, it was decided to examine the elements in question as well as some refractory metals by thermal analysis with a photoelectric technique similar to that described by Hug-gins, Roll, and Udin.1 In this method, a lead sulphide cell was used to detect thermal radiation from an electric-resistance heated strip specimen. A thermocouple spot welded to the specimen was used to calibrate the temperature of the system under steady temperature conditions, and recording was accomplished with a cathode ray oscilloscope. In the method used by the present authors, the temperature calibration was omitted and the cathode ray oscilloscope was replaced by a recording galvanometer. This technique, in which electric current passing through the specimen heats it, will be referred to henceforth as Method 1. Another arrangement was required for those cases where the specimen could not be formed into a wire or strip suitable for resistance heating. In such cases the specimen was a sintered compact heated by thermal radiation from a hot tungsten strip, Fig. 1. The specimen was insulated from the heating strip with a thin layer of thoria powder or suspended on 0.004 in. tungsten wires. The take-up spring had just sufficient tension to prevent buckling of the heating strip due to thermal expansion. This technique will be called Method 2. Both methods were tested with specimens of iron and titanium and the well known allotropic transformations, a toy and ? to 8 in iron and a to in titanium, were very clearly detected. Fig. 2 shows one of the records obtained for titanium. For this particular experiment, the iodide titanium specimen was a square rod 0.080 in. on an edge and 3 in. long.

Jan 1, 1955

By Leendert de Witte

Conventional resistivity logs consisting of a short normal, a long normal, and one or more long lateral curves do not give data that allow a complete quantitative interpretation in beds thinner than 20 ft. Reservoir rocks usually exhibit zones of continuous homogeneity of quite limited thickness where the long lateral curves become useless because of adjacent bed effects and boundary phenomena. If the beds are 12 ft or thicker, the short and long normals may be used for qualitative interpretation, which can be streamlined by the application of simplified departure curves. For beds of a thickness less than twice the long normal spacing, this procedure breaks down. The combination of the limestone curve, the later-olog or guard electrode log, and the microlaterolog permit quantitative interpretation for beds that are at least 10 ft thick, provided the mud resistivity and the hole diameter are known with sufficient accuracy. For beds thinner than 10 ft, combinations of the microlaterolog with short spaced laterologs and pseudo laterologs appear to be promising. Interpretation of these curves again requires the application of simplified departure curves. Resolution of various possible combinations was analyzed using departure curve data calculated on the Whirlwind I computer at the Massachusetts Institute of Technology. A field example is shown using the microlaterolog-microlog combination, and the combination of a 6-in. modified laterolog plus a 6-in. pseudo laterolog. INTRODUCTION For the purpose of quantitative interpretation of resistivity logs in porous formations, we want to obtain two essential quantities from the logs, namely, the true resistivity of the undisturbed formation, Rt, and the resistivity of the part of the formation invaded by mud filtrate, Rt. The apparent resistivities of all conventional logging devices are functions of these two parameters and are also influenced by a third unknown parameter, the diameter of the invaded zone, d. It has been shown&apos; that from the normal curves alone it is impossible to arrive at a unique solution for the three unknowns, Rt, R1, and d1. In very thick homogeneous beds, if invasion is not too deep, we can obtain a fair approximation to Rt from the long lateral curves and then use the two normal curves to find Rt and d1 Even under the most favorable conditions, the resolution of this system is not very good. The short normal does not give a reasonable approximation to R1 unless invasion is very deep (dl>16 hole diameters). For very deep invasion, however, the long laterals no longer approximate Rt. For bed thickness between 20 and 40 ft, the long laterals are affected appreciably by the adjacent beds; and the curves are distorted by boundary anomalies to the extent that they lose their quantitative usefulness in most cases. For the same bed thicknesses, the normal curves still function reasonably well. Although it is impossible to find unique solutions Lor R1 and Rt using the normal curves alone, we can obtain a reasonable approximation for the ratio R1/Rt through the use of simplified departure curves. This fact was brought to our attention by A. J. de Witte, geologist with Continental Oil Co. As the magnitude of Rl/Rt is a major clue to the presence of oil in formations, this method can be used to good advantage for qualitative analysis and will be discussed in somewhat greater detail. With the aid of suitable bed thickness corrections, the analysis of the normal curves may be used for bed thicknesses larger than 12 ft. For thinner beds, the method rapidly loses its resolution; and we have to resort to different types of resistivity logs if we want to attempt to analyze the curves quantitatively. The inadequacy of conventional resistivity curves in thin beds is far more serious than generally realized. Fig. 1 shows a conventional E. S. with a 16-in. and 64-in. normal and a 16-ft lateral through a section of Lansing-Kansas City lime, in comparison to a guard electrode survey through the same section in a neighboring well. The porous zones, which show up as low resistivity breaks on the guard electrode log, are completely masked by adjacent bed effects and boundary anomalies on the conventional curves. Even the short normal shows most of the porous Zones only as Vague deflections and in many cases fails to register Their

Jan 1, 1955

By D. J. Carney, E. C. Rudolphy

Large macroscopic nonmetallic inclusions were related to altered fireclay refractories by chemical and microscopic means. Pouring refractories are discussed as a source of these large inclusions. Nozzles and wells are major contributors. Use of alkali and titania contents as tracers is described. Recommendations are offered to minimize the sources of inclusions from pouring refractories. IN any attempt to improve the cleanliness of plain carbon and alloy steels, consideration must be given not only to the proper deoxidation practice to minimize inclusions, but also to sources of inclusions from pouring refractories. In some cases, the inclusions resulting from deoxidation may be minor in amount, yet a relatively dirty steel may be produced as a result of improper care in the pouring practices for the steel. The number of studies of inclusions resulting from pouring refractories has increased recently and some excellent reports on this subject have already been published.&apos;4 Some of these reports were reviewed briefly in a companion paper by M. P. Fedock.5 Mr. Fedock&apos;s contribution is a fine addition to the studies necessary to improve steel cleanliness for the ultimate benefit of all steel producers and consumers. In the interest of constantly improving cleanliness, the authors have been actively engaged for the past two years in experimentation to determine more closely the sources of inclusions in steel. One phase of this work was associated with efforts to define more closely the sources of macroscopic inclusions which have been experienced on occasional heats. The term "macroscopic inclusions" is defined in general as those inclusions which are visible to the naked eye or at low magnifications of the order of less than X25. These inclusions sometimes can be seen in the macro-etch tests of billets and slabs. This report summarizes a few of the field experiments and laboratory studies conducted at the South Works of the United States Steel Corp., which were made regarding nozzles, wells, and ingot scums, as well as inclusions occurring in steel products. The data in the present study, together with the data of Mr. Fedock concerning ladle erosion, should be of value in regard to future studies of inclusions arising from pouring refractories. The knowledge gained as a result of data collected thus far at South Works has been helpful in improving the cleanliness of the products and in pointing the way toward further improvements. Similarity of Large Inclusions to Refractories and Altered Refractories In the routine inspection of billet etch tests, occasional inclusions visible to the naked eye have been observed. These large inclusions most frequently occur near the top of the ingot and near the billet surface. When such material was encountered, careful examinations were made in an attempt to determine the origin of these inclusions. In a relatively few cases, examination revealed that the material was unaltered fireclay refractory of a type similar to that used for hot-top material, with only the surface of the inclusions having an altered appearance under the microscope. However, the great majority of these inclusions were completely altered-refractory material. The term "altered refractory" is defined

Jan 1, 1955