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By Arthur F. Colombo

The selective flocculation, desliming and flotation process developed by the U.S. Department of the Interior, Bureau of Mines, as part of its goal of maintaining an adequate supply of minerals to meet national economic and strategic needs is described. The application of the selective flocculation and cationic flotation process to three oxidized taconites from the western Mesabi Range in Minnesota is discussed. Data from the operation of a 408-kilogram-per-hour (900 lb/hr) pilot plant employing reclaimed water are summarized for the three types of oxidized taconites.

Jan 1, 1980

By John B. Goddard, David R. Brosnahan

Leaching of uranium in situ from sandstone deposits with ammonium carbonate solution containing dissolved oxygen occurs rapidly compared with the leaching of the bulk of the sulfur present as FeS2. However, because of their high reducing capacity and their relative abundance, the FeS2 minerals consume the bulk of the oxidant. A pressure leach apparatus was constructed that permitted measuring oxygen consumption by FeS2, best described by a first-order reaction. The experimental rate constants for various cores are roughly proportional to their FeS2 contents.

Jan 1, 1983

By John M. Warde, Eileen P. Burke

ORES of manganese and chrome have a high order of strategic importance, both metals are basic to the metallurgy and usefulness of steel, the fabric on which our economy rests. Looking beyond the current recession and short range picture of oversupply in these ores, this review attempts to answer the following questions regarding the longterm outlook for these key commodities: By 1970, what will be the probable demand here and abroad, what are future supply prospects, and what effect is the USSR likely to have on the world market? (See summary forecast on facing page.)

Jan 8, 1958

By Steven T. Mitchell

The introduction of Vertical Crater Retreat (VCR) Stoping at the Homestake Mine in Lead, SD, constitutes a major advance in Homestake Mining Company's efforts to improve productivity and reduce costs through under- ground mine mechanization. The work to date indicates that Vertical Crater Retreat Stoping is one of the safest methods of underground hardrock mining today, and is competitive with all other forms of stoping in terms of cost and productivity. Homestake anticipates that VCR stoping will account for approximately 35% of the total mine production in 1981.

Jan 1, 1981

By James W. Dally, William L. Fourney, Anders Ladegaard Peterson

For the past 3 years, the authors have been conducting research sponsored by the National Science Foundation (RANN) to improve the process of excavation by drilling and blasting. The approach followed has been experimental where the development of stress waves and fractures initiated at the bore hole have been investigated in order to obtain a complete understanding of the dynamic Fracture process. The second step in the approach has been to introduce modifications in the drill and blast procedure which will permit closer control of the fracture process.

Jan 2, 1978

By J. Halpern, D. R. McKay

SOME of the most important hydrometallurgical developments in recent years relate to processes involving the oxidation of sulfide minerals in aque- ous suspension at elevated temperatures by air or oxygen under pressure. Among these is the acid pressure-leach process which has been developed, particularly for the treatment of pyritic uranium ores.1-5 In this process, an aqueous suspension of the ore is digested in an autoclave, in which an overpressure of air or oxygen is maintained, at temperatures above 100°C. Oxidation of the pyrite (FeS,)

Jan 1, 1959

By W. S. Potter

THE proportions of manganese and carbon in manganese steel are familiar to all, because manganese-steel castings have been well known for a decade or more in this country. The same alloy has now become a commercial product in the wrought state, and, as not only rails and bars are rolled daily but a great variety of forged and otherwise fabricated shapes are appearing, it may be interesting to mark the progress and, perhaps, to look a little closely into the nature of this important material of engineering.

Jan 4, 1914

By R. L. Segall

AN unusual thermal etch figure in copper is described and an explanation in terms of twinning is suggested. A flat polycrystalline specimen of OFHC copper cut from a rolled sheet was electro-polished in orthophosphoric acid and annealed at 950°C in a vacuum of approximately 10-3 mm Hg for 2 hr. The specimen was found to be thermally etched, the markings on the surface being consistent with the assumption that they were the traces of the (111) planes which are developed preferentially because they have the lowest free energy. However, on one grain (the grain shown in Fig. 1) the traces formed an almost regular pentagon and at first sight it seemed unlikely that they could all be (111) traces. These traces were studied further because it was thought that they might be a type of growth spiral. A fringe pattern showed that this was not so, the grain being sensibly flat and the only features having steps were the striations and the faint curved line passing out from the center of the pentagons. To obtain some additional information, the specimen was deformed in tension. The effect of the stress was first to cause the appearance of lines running from the centers to the apexes of the pentagons and then to tilt the five segments so formed. At a much greater stress, appreciable slip appeared on the grain; these effects can be seen in Fig. 2. The micrograph was taken at a fairly late stage in the deformation and the tilting is quite marked. The magnification is the same as in Fig. 1, and although some slip can be seen it could be observed better by varying the illumination and using higher magnifications. In each segment of the grain, slip (which takes place on the (111) planes) was parallel to the side of the pentagon in that segment. The marked changes in direction of slip from segment to segment seemed to be incompatible with the presence of a regular array of subgrains. These results suggest that some of the five segments were twins. If this is so, since the twinning plane in copper is the (111) plane, the radial lines must be traces of the (111) planes on the surface. From the symmetry of the striations about the radial lines, these planes must be almost perpendicular to the surface. The angle between <III>directions in face-centered-cubic copper is 70&apos;32&apos;. If, in Fig. 3, OAB (triangle 1) is taken as matrix and OA, OB are (111) planes viewed edge on, then AB is in the correct direction to be the trace of either of the other two (111) planes on the surface. If triangle 2 is the twin (about the (111) plane perpendicular to the surface and containing OB) of triangle 1, then once again it can be shown that all lines are traces of (111) planes. Similarly, triangle 3 is the twin of triangle 2, 4 of 3, and 5 of both 4 and 1. (The sequence is, of course, quite arbitrary.) However, if this were the case there would be a discrepancy of 7&apos;20&apos; to be accounted for. It is suggested that the faint curved line passing outward from the center of the pentagon represents either a low angle boundary or a sixth small twin. The slight step shown by the fringes at this line might be an indication that the former is the case. This explanation does not account for the coincidence of obtaining a grain whose surface must be so close to (110) and obtaining the curious twinning described previously; it would be of interest to find a specific mechanism for this.

Jan 1, 1958

By J. S. Brown, A. G. Guy

With the exception of the work of Tammann and Hartmann,1 no published information has been found on the structural changes produced in eutectic structures as the result of heating following plastic deformation. In part this lack of information may be due to the fact that many eutectic structures contain an intermetallic compound as a prominent phase, and as a consequence have been considered to be unworkable. For example, Tammann and Hartmann were able to obtain useful data only on those alloys that they could greatly reduce in thickness by cold rolling. This restriction placed on the investigation of alloys containing intermetallic compounds has been largely removed by the work of Savitskii2 which showed that large deformations of such alloys can be produced by relatively slow compression at temperatures near the melting range. It was possible, therefore, to carry out the present work on a range of binary eutectics including one composed of two intermetallic compounds. The essential results obtained on the alloy systems studied are illustrated by the Pb-Mg eutectic containing 33.2 pct Mg, Fig 1. The cast structure, Fig la, was obtained by melting together magnesium of 99.8 pct purity and chemically pure test lead, casting into a heated, small steel mold, and furnace cooling in the mold from about the eutectic temperature. The fairly coarse eutectic structure thus obtained was too brittle to work at room temperature without cracking. Fig 16 shows the worked structure obtained by compressing a 1/2-in. cube 70 pct in about 15 sec at 550°F and then water quenching. The pronounced changes in the distribution of the two phases produced by heating the worked alloy at 850°F for 1 hr are shown in Fig lc. Recrystallization of both phases appears to have taken place, and the mechanical properties of the cast alloy must have been significantly changed by the working and heat treatment. Similar results were obtained with the Mg-59.5 pet Bi, Mg-36.4 pet Sn, Mg-65.4 pet Cu, and Bi-40 pet Cd eutectics, only the last of which could be worked at room temperature. Tammann and Hartmann reported a thickening and shortening of the needles of the eutectics which they heated about 10°C below the melting range for 1 hr after drastic cold rolling. They found the following eutectics, given the indicated amounts of reduc- tion, to have a granular structure after heat treatment: Sn-9 pet Zn (98 pet); Cd-82.5 pet Pb (60 pet); and Bi-43.5 pet Pb (90 pet). On the other hand the alloy Al-11.7 pet Si (60 pet) showed no change after heating. Tammann and Hartmann observed a distinct shrinking of the needles in unworked eutectics subjected to heat-treatment. In the present work inappreciable change in the eutectic structure was found on heating undeformed alloys. In summary, it appears that eutectic structures can be recrystallized into a "spheroidized" condition by heating near the eutectic temperature after severe deformation. If the eutectic contains one or more brittle phases the necessary deformation can be accomplished by pressing at high temperatures. It is reasonable to expect that this tendency towards equiaxed grains from the plate- or needle-like eutectic structure should be general since the energy relations and mode of growth in recrystallization are so different from those that hold for eutectic crystallization. References 1. G. Tammann and H. Hartmann: Ztsch. Melallkunde (1937) 29, 141-144. 2. E. M. Savitskii: Doklady Akad. Nauk S.S.S.R. (1940) 62, 349-351. Abstr. in Melal Prog. (July, 1949) 56, 126, 128.

Jan 1, 1950

By M. W. Cox, V. F. Hollister

EXPLORATION for metallic mineral deposits is carried on by those special adaptations of methods which the explorer believes will yield most economically or satisfactorily the particular answer sought. In this project the usual methods of geologic observation, recording, and interpretation, when combined with magnetic geophysical methods and geochemical soil sampling, led to disclosures of appreciable zinc mineralization where none was visible in surface exposure. Since 1945 considerable work has been done with geochemical prospecting methods, chiefly in determining the presence and distribution of various elements existing in minor amounts in rocks, soil, vegetation or waters of mineralized areas. Such work, in which the U. S. Geological Survey has taken the lead, finds a ready place in the field repertoire of the exploration geologist as a supplement, not a substitute, for other methods. The Chollet project was carried out in 1951 by the American Smelting & Refining Co. near its Van Stone mine in northern Stevens County, Wash., in the area shown in Fig. 1. The Van Stone mine is located in the Onion Creek drainage of the Selkirk Mountains, midway between the towns of Colville and Northport, Wash., and some twenty airline miles west of the Metaline mining district. Its zinc-lead orebodies, currently yielding about 1000 tpd of ore, occur as bedding replacement deposits in the middle Cambrian Metaline formation near an intrusive granodiorite contact. The target of exploration at the Chollet prospect was a similar geologic environment along the intrusive contact about 5 miles west of the mine. Geographic Setting The Chollet ground covers a north-facing slope at 3000 to 4000-ft elevation. Second-growth jack pine and tamarack with some hemlock and yellow pine make a thick forest cover. A heavy under-forest of alder, willow, and lesser shrubs occupies the draws, see Fig. 2. Grassy slopes appear at higher elevations. The lower slopes are underlain by a thick blanket of glacial till and alluvium so that outcrops are scarce; however, perhaps 50 pct rock exposure prevails at higher elevations. This part of northern Washington annually receives about 25 in. of precipitation, which largely falls as snow in the winter months. Summers are dry with occasional rainy periods. General Geology The Van Stone mine and the Chollet prospect lie along the southern margin of a westerly extending lobe of the Kaniksu batholith, one of the series of granodioritic masses that are intrusive into Cretaceous and older rocks in northern Washington and southern British Columbia. The margin is composed of complexly deformed Paleozoic sediments ranging in age from the lower Cambrian Maitlen phyllite on the east, through middle Cambrian Metaline formation (limestone and dolomite), to Ordovician Ledbetter slate on the west. In general the formations strike N10 to 50E and dip steeply northwestward, although dip reversals and minor folding occur. This general rock distribution is shown on Fig. 3. In this area the Metaline formation, which is the host rock for mineralization, appears to be of about 4000-ft thickness that can be conveniently divided into the same three units defined by Park and Cannon&apos; for the Metaline area. The basal part consists of 1000 ft of interbedded white limestone, argillaceous limestone, and gray silty argillite. The middle part, approximately 1500 ft thick, consists of fine-grained black, gray, and white dolomite. This unit also contains minor interbedded limestone. The upper part is a gray massive limestone about 1500 ft thick that grades upward into slaty limestone and slate capped locally by a thin black jas-peroidal dolomite which is either the uppermost member of the Metaline formation or the basal member of the overlying Ledbetter (Ordovician)

Jan 1, 1956

By M. Prats

This paper presents a method for obtaining the correct values of the breakthrough sweep efficiency of the staggered line drive, taking into account the proper shape of the breakthrough streamline. Results obtained were different from those previously published, which were obtained by using an inexact shape of the breakrhrough streamline. INTRODUCTION In Section 9.31 of Muskat&apos;s&apos; The Flow of Hotnogeticous Fluids Through Porous Media, it is stated that in a staggered line drive flood "the streamline of highest average velocity [is] the line of centers between input and output wells" (see Fig. I). Muskat used this concept to determine the relationship between the breakthrough sweep efficiency and the geometry of the staggered line drive pattern. Although it is clear from symmetry considerations that the breakthrough streamline passes through the midpoint between input and output wells, it is equally clear, as shown in Fig. 239 of Ref. 1, that the breakthrough streamline is not represented very well by the straight line joining the input and output wells. Therefore, it is desirable to determine the proper relationship between the breakthrough sweep efficiency and the pattern geometry by using the proper shape of the breakthrough streamline. METHOD OF SOLUTION It was found that the effect of the geometry of the staggered line drive on the breakthrough sweep efficiency can be investigated easily by making use of the method developed in Ref. 2. With this method, it can be shown that the general complex potential for the staggered line drive, which can be considered as a rectangular five-spot, is given in the coordinate system of Fig. 1, by O(z) = In cn(z\m) = +(x,y) + i $(x, y) . (1) where z = x + iy, +(x, y) is the potential distribution and $(x, y) is the stream function. The function cn (zm) is a Jacobian elliptic function of parameter m and has simple zeros at z,. = (2n + 1) K + 21iK and simple poles at z, = 2nK + (21 + 1)iK. Thus, the complex potential behaves like a(z) = ln(z - zr.) in the neighborhood of the production wells and behaves like a(z) = - ln(z - Z,) in the neighborhood of the injection wells. Since (z - z1.v) = rll.ei, we note that the potential + has the proper logarithmic behavior near the two wells, while the stream function $ varies with the angle, decreasing clockwise around the production well and increasing clockwise around the injection well. The functions K(m) and K&apos;(tn), related by K(m) = K&apos;(m,), where m + m, = 1, are known as the complete elliptic integrals of the first kind. By use of other properties of the Jacobian elliptic functions, the general stream function distribution for the staggered line drive can be obtained from Eq. 1: From the Jacobian elliptic function values, sn(0lm) = 0 dn(O(m) = cn(0jm) = 1, and f[K&apos;(m)Iml = 03, it follows that the stream function given by Eq. 2 satisfies the proper symmetry conditions near a production well P located at [K(m), 01 and an injection well I located at [0, K&apos; (m)]. That is, the line IOP in Fig. 1 is a streamline with value G (0. 0) = -0. and the straight lines connecting I and P to the point [K(m), K&apos; (m)] is a streamline of value $[K(m), K&apos; (m)] = -7/2. Similar symmetry conditions are obtained near other wells. It should be nuled that for m = m1, = 0.5, Eq. 2 reduces to the stream function distribution of the regular five-spot given in Ref. 7. SHAPE OF THE BREAKTHROUGH STREAMLINE It is apparent, from symmetry considerations, that the breakthrough streamline ($,) passes through the point [K(m)/2, K&apos; (m)/2]. Its value there is so that the shape of the breakthrough streamline $,, is given by

Jan 1, 1957

By Rex W. Woods

The clue history of performance of a highly volatile type oil reservoir which is now greater than 80 per cent depleted is presented. The reservoir is at a depth of approximately 8,200 ft and includes an area greater than 7,500 acres. The reservoir has been exploited by 10 wells which to date have yielded about 10,880,000 bbl of stock tank oil by pressure depletion. Reservoir pressure has declined from an original of 5,000 psi to approximately 1,450 psi. Produced gas/oil ratio has increased from 3,200 to 23,000 cu ft/bbl with a corresponriing increase in APl gravity of the stock tank oil from 440 to 620 . Pressure and fluid data are given for different stages of depletion. INTRODUCTION In papers by Sloan,&apos; and Cook, Spencer and Bo-browski,&apos; properties of highly volatile type reservoir oil were discussed in detail and methods were presented for predicting performance of reservoirs containing this type of fluid. The purpose of this paper is to present performance history of a highly volatile type oil reservoir designated as Reservoir A which has been produced by pressure depletion and field separation without processing of gas GEOLOGY The reterence field which includes Reservoir A is a structural feature north of a trend of major folding along a northeast-southwest axis. In the area of development, the structure has the appearance of a dome with formation dip of three to four degrees, but structural relations between the reference field and the axis of major folding to the south have not been determined. No faulting within the field is evident. Oil and gas productive sands have been found at depths of 7,000 ft to 10,000 ft in a columnar section of Mio-Oligocene age. The sand bodies in the section are lenticular and usually continuity of sand is limited to a small area. Sand A which forms Reservoir A at a depth of 8,200 ft, however, has exceptional continuous development in the reference field. Fig. 1 shows an isopachous map of net oil sand for Reservoir A. Net thickness of oil sand at producing wells ranges from 14 to 34 ft with an average of 22 ft. Pinch-out of sand has been shown by drilling in the southwest part of the field, but extent of the reservoir on the northwest and northeast parts of the field is indicated only by thinning of the sand. The vertical oil column between the highest and lowest producing well in the reservoir is 339 ft. No water-oil contact has been found within the reservoir. As interpreted from the isopachous map, the reservoir includes about 8,900 acres with an average net sand thickness of 12 ft. Because of limited data on extent of the reservoir, the isopachous map permits only an approximation of sand volume in the reservoir. DEVELOPMENT AND PRODUCTION Reservoir A was discovered during 1938 and was developed with eight wells to the end of 1942. One well was completed during 1946 and the tenth well in the reservoir was completed during 1951. Three of the original wells and the last completion have produced from Sand A only. Six wells have produced from Sand A through the casing side of dual completions. Initial producing rates of the original wells ranged from 800 to 1,000 BOPD. Production history for the reservoir is shown in Fig. 2. Production of the reservoir was begun during 1940 and in May, 1952, peak production from seven wells was 5,300 BOPD. At the end of March, 1954. cumulative production was 10.880,000

Jan 1, 1956

By J. R. Kyte, V. O. Naumann, C. C. Mattax

Imbibition and waterflooding tests at reservoir conditions show that conventional tests at room conditions sometimes lead to recovery estimates that are too low. Core samples which are of intermediate wettability at normal test conditions may be strongly water-wet at reservoir conditions. This was found to be true for samples from two of three reservoirs investigated. For the other reservoir, less difference was observed between the wettability of samples at normal test conditions and at reservoir conditions. Samples which became more water-wet at reservoir temperature and pressure also water flooded more efficiently at reservoir conditions. These results show that core analysis tests on intermediate wettability samples should be performed at reservoir conditions to obtain representative data. INTRODUCTION Throughout the oil industry, core analysis tests normally are performed using refined oils and at room temperature and pressure. This procedure has always been subject to question because the possibility is generally recognized that the reservoir environment may influence displacement behavior. Burkhardt, et al,&apos; have performed waterflood tests at reservoir conditions on East Texas cores. They found little difference between results obtained at reservoir conditions and results of conventional flooding tests at room conditions. As they pointed out, however, this situation might not be general since they obtained data on only one rock and crude-oil system. This paper presents data which demonstrate that it is sometimes necessary to perform core analysis tests in a simulated reservoir environment to properly represent the reservoir wettability and displacement characteristics. The work is specifically concerned with reservoirs which were thought to be of intermediate wettability on the basis of conventional test results at room conditions, i.e., core samples imbibed only small amounts of either oil or water and exhibited no decided preferential wettability characteristics. Tests were performed on cores from three such reservoirs to determine their behavior in the reservoir environment. lmbibition and waterflood tests were used to demonstrate the effect of reservoir environment on reservoir rock wettability and displacement characteristics. Results of tests performed at reservoir conditions were compared with results from conventional tests. Imbibition tests were performed on samples from all three reservoirs. Waterflood tests were performed on samples from only one reservoir. Fluid properties for the three reservoirs studied are shown in Table 1. Tests at reservoir conditions were performed using bottom-hole crude oil at reservoir temperature and pressure. The aqueous phase used in these tests was a synthetic brine approximating the reservoir brine composition. Conventional tests were performed at room conditions with refined oils and synthetic reservoir brine. The oil-to-water viscosity ratios were adjusted to the reservoir values. The cores used in all the tests were taken from the reservoirs using either brine alone or a bentonite-car-boxymethylcellulose mud without additives as coring fluids. Previous tests show that these fluids have no significant effect on the wettability of reservoir rock samples.1 The cores were preserved in brine at the wellsite to prevent wettability changes during shipment and storage. Wellsite imbibition tests have been performed on fresh samples from several reservoirs (including Reservoir A) and compared with later laboratory imbibition tests on samples preserved in brine. The comparison showed that the wettability of the preserved cores was the same as that of fresh, surfaced cores at the wellsite.2 IMBIBITION TESTS Conventional imbibition tests were performed on preserved cores using the apparatus and procedures described by Bobek, et al.2 A sketch of the apparatus for imbibition tests at reservoir conditions is shown in Fig. 1. The preserved samples were first centrifuged to expel excess water and then placed in a stainless-steel container which served

By Nicholas J. Grant, Olaf Troili, John Chipman

IN recent studies of the factors which affect the rate of desulphurization and its equilibrium, it became apparent that certain concurrent reactions were operative which had a significant effect on desulphurization. This is emphasized in the experiments of Hatch and Chipman1 and of Grant, Kalling, and Chipman&apos; by the slow approach to a final state of equilibrium which is in marked contrast to the initial rapid transfer of sulphur from metal to slag. Since the removal of sulphur is of such profound importance in iron and steelmaking, it appeared necessary to investigate the reactions responsible for this behavior. It is now known that the presence of iron oxide in the slag interferes seriously with the principal reaction of blast-furnace desulphurization: CaO (slag) +-S + C - CaS (slag) + CO [l] The interfering reaction is most simply expressed as: CaS (slag) + 0 = CaO (slag) +-S 121 and a small concentration of oxygen (or FeO) is sufficient to hold a considerable amount of sulphur in the metal. It has been shown by Grant, Kalling, and Chipman2 that the addition of MnO to blast-furnace slag slows the removal of sulphur from the metal. This effect overshadows the contribution of MnO to basicity and is ascribed to its oxidizing power. It will be shown in this paper that SiO, also has sufficient oxidizing power to interfere with blastfurnace desulphurization. This is, of course, only one of its several effects. Primarily it is an acid and therefore reduces the concentration of excess lime. But when silicon is reduced to the metal the oxygen to which it was previously bonded becomes in part available for reaction 2. The proof of this statement is found in the following experiments. Experimental Procedure and Results Utilizing the same procedure and apparatus described by Grant, Kalling, and Chipman&apos; five additional heats were made using slags IV and 11, the starting compositions of which were: slag IV—40 CaO, 10 MgO, 35 SiO,, 15 A1,0,; and slag 11—50 CaO, 10 MgO, 25 SiO,, 15 Al3O3. An important difference between these heats and those previously reported was that silicon to the extent of 1 to 4 pct was added to the present heats whereas the starting silicon content was formerly about 0.2 pct. Table I shows the slag and metal analyses for heats 82 to 87, and Table I1 shows the silicon addi- tions made to the charge. These additions are based on 400 g of metal and 400 g of slag. All heats had 1.65 400pct S charged before the cold slagadditions. The temperature was maintained at 1525°C. Rate of SiO, Reduction: Fig. 1 shows the silicon content of the metal in contact with slag IV at 1525°C as a function of time. Heat 70 from the work of Grant, afunctionKalling,of and Chipman is included as the lowest starting silicon. It will be noted that eeven with 4 pct Si in the starting metal, there is an increase in silicon content with time. Heat 84 is apparently approaching silicon equilibrium very slowly. Heats 70 and 82 with very much lower slowly.starting silicon show a more rapid initial rise in startingsilicon content but do not reach equilibrium during a long holding period. Fig. 2 shows 3 different initial silicon contents for Fig.2shows3differentheats 73 (from Grant, Kalling, and Chipman) 86 and 87, in contact with slag II, the most basic slag. Heat 73 is increasing in silicon with time, whereas heat 87 with an initial silicon content of 3.7 pct shows a decrease with time. Heat 86 shows a very close approach to equilibrium. The rate of transfer of silicon from slag to equilibrium.metal is very slow in all of those heats, even those which are initially far from equilibrium. ____

Jan 1, 1952

By D. H. Shaffer, W. F. Harris, W. M. Hickam, M. H. Loeffler

Experiments have been performed on the quantitative addition to niobium of enriched isotopes 018 and 017 at the 0.1 - 40 micro-gram level and their subsequent recovery. A measured quantity of molecular oxygen of known isotopic concentration is added to niobium metal by oxidation. Recovery of the enriched isotopes as carbon monoxide is by the vacuum fusion technique. Quantitative determinations of the enriched isotopes are made in standard volumes at constant temperature using accurately calibrated micromanometers and the mass spectrometer as pressure measuring instruments. THE presence of low concentrations of nonmetallic impurities in metals can often adversely affect the physical properties of the metal. The increase in hardness and the embrittlement of refractory metals due to oxygen is well known. In metallurgical studies dealing with the diffusion rates or the effect of oxygen on the physical properties of refractory metals, it is often necessary to add small quantities of oxygen to the metal and later recover the total quantity present. It is desirable, therefore, to establish the accuracy with which microgram quantities of oxygen can be added to niobium and recovered by vacuum fusion. The successful addition of microgram quantities of oxygen to metals by the usual manometric techniques and the subsequent recovery by vacuum fusion is difficult because of the uncertainty in the accurate determination of the quantity of oxygen originally present in the metal and because of the chance of contamination by atmospheric oxygen. In order to minimize these uncertainties earlier workers have added quantities of O16 at levels much higher than the oxygen concentrations that are of interest.&apos;-3 In order to eliminate the uncertainty associated with the O16 additions to metals at low microgram levels, experiments have been performed on the quantitative addition of oxygen highly enriched in O17 and O18 at the 0.1 to 40 pg level to niobium and the subsequent quantitative recovery of the isotopes by vacuum fusion. Since the natural abundance of O17 is 0.04 pct and of 0" is 0.2 pct this enriched oxygen provides a uniqueness from interference not achieved in earlier work.&apos;-= A measured quantity of molecular oxygen of known isotopic concentration is diffused into the metal. Recovery of the isotopes in the form of carbon monoxide is by vacuum fusion. The total quantity of gas is determined in standard volumes at constant tempera- ture using accurately calibrated Consolidated Electrodynamics micromanometers and the mass spectrometer for pressure measurements. The molecular and isotopic composition is determined mass spectrometrically. APPARATUS A schematic of the oxygen addition apparatus is shown in Fig. 1. Take-offs are provided for the attachment of the isotope container and for sample bulbs which are used to transfer samples to the mass spectrometer. Metal valves are used throughout the system including the sample bulbs in order to achieve a vacuum of 10"6 mm Hg. Evacuation is accomplished with a 3-stage oil-diffusion pump backed by a mechanical pump. A liquid nitrogen trap is used to remove condensables and to prevent oil vapor from entering the system. A micromano-meter is used for pressure measurements. The furnace assembly is shown in Fig. 2. It consists of a quartz tube joined to the apparatus through a 40/W joint with Apiezon W low-pressure wax. The furnace cap, also a 40/W pyrex joint, is provided with a pyrex hook. The sample is suspended from this hook with a platinum wire. The total volume of the furnace section is 435 ml. All volumes were determined by expanding a known volume of gas at a known pressure into the evacuated system and re-measuring the pressure. Both the micromanometer used on the oxygen addition system and the micromanometer used on the mass spectrometer were compared to a precision

Jan 1, 1961

By W. Rostoker, H. Nichols

It has been demonstrated in previous work1&apos;2 that wetting of aluminum alloys by liquid mercury can cause fracture to occur with substantial suppression of prior plastic flow. This has been interpreted as the action of a critical liquid species in reducing the cohesive strength of a stressed solid at sites of potential crack nucleation. In this way the critical transverse stress for fracture nucleation is reached at much lower stresses than is normally the case. The stresses for both fracture nucleation and fracture propagation are depressed by the same mechanism. In so doing the plastic-energy component of fracture energy is reduced to a level which is of the same order of magnitude as the surface, interfacial, or cleavage energy. Recent work2 has illustrated the influence of dispersed precipitates, cold work, and combinations of these on brittle fracture associated with plastic strains of the microyield order of magnitude. This has been rationalized in terms of the contribution of internal microstress fields to the stress magnifications at points of obstruction of active slip bands in a stressed metal. The presently reported studies on an Al-4-1/2 pct Mg alloy amplify this subject by introducing thermal-mechanical conditions which can produce strain aging. As amply demonstrated by Phillips, Swain, and borall, the tensile behavior of aluminum alloys containing magnesium reveals a yield-point elongation and successive discontinuous elongations over the whole plastic-strain range. This gives a stepped or serrated character to the stress-strain diagram. The yield-point elongation is not temperature-dependent. On the other hand, the discontinuous extensions in the plastic-strain range are gradually suppressed by lower temperatures of testing. At -78"C, only the yield-point elongation persists. The yield-point elongation itself can be suppressed by rapid quenching to room temperature from an annealing temperature of 500°C. The argument presented by Phillips et 1. and Cottre114 is that the yield-point elongation derives from surmounting at a critical stress the restraint to slip by grain boundaries which have been reinforced by appreciable magnesium-atom segregation. The serrated character of the plastic-strain range is the result of rapid strain aging during the test. This is made possible by the inevitable proximity of magnesium atoms to any dislocation line. In the Al-4-1/2 pct Mg alloy there is one magnesium atom for every twenty-two aluminum atoms and, with a coordination number of 12, a magnesium atom is on the average only about two atomic distances from any given lattice site. Rapid strain aging is therefore a reasonable expectation. A study of mercury embrittlement of the Al-4-1/2 pct Mg alloy (commercial designation 5083) provides an opportunity to relate the interplay of grain size, grain boundary restraint to slip and strain aging in the brittle-fracture process. One lot of commercial sheet material of 0.125-in. thickness was used for all of the tests. The specimen shape and test procedures used were the same as those described in a previous publication.2 A range of grain sizes between 0.0057 and 0.0125 mm was produced by various combinations of plastic prestrain and annealing. The coarsest grain was somewhat elongated in shape. In this case the measurement was taken in the direction transverse to the axis of tension as more meaningful to a brittle-fracture process. In the annealed condition, specimens wetted with mercury failed with zero permanent elongation at stresses slightly below the normal yield point, i.e., stresses at 0.05 to 0.2 pct strain. Since this occurs before yield-point elongation can begin, fracture derives from slip contained within individual grains and restrained from propagating across grain boundaries. No significant difference in wetted fracture stress was observed between specimens which had been water-quenched or furnace-cooled from the annealing temperatures. This signifies that the degree of magnesium segregation at grain boundaries

Jan 1, 1964

By F. Weinberg

In developing a mechanism for the solidification of metals from the melt, it has been proposed that solidification proceeds by the growth of platelets parallel to close packed planes. The evidence for this is based primarily on observations of decanted interfaces of lead1,2 and tin on which platelets 1 to 10 µ thick4 were observed. In recent observations of decanted eutectic alloys, 5,6 it was found that the eutectic structure on the decanted surface was markedly different than that of the bulk material, with the surface structure extending approximately 10 µ behind the interface.&apos; This suggested that, at least for these experiments, a residual liquid layer 10 µ thick had been left on the decanted interface, which solidified subsequent to decanting. If a similar thickness of residual liquid was left on the decanted surfaces in the lead and tin observations referred to above, then it is questionable to what extent the observed platelets can be related to the solid-liquid interface before decanting. The purpose of the present investigation was to measure the thickness of the residual liquid layer on a decanted surface of tin, using relatively standard decanting procedures. The technique used was to add approximately 200 ppm of Tl204 (PI) to the melted portion of a high purity (99.999 pet) bar of tin, which was being progressively melted from one end, and then decant during melting. Since only the melt contained the radioactive tracer, the activity emanating from the decanted surface could be used as a measure of the thickness of the residual liquid layer. Progressive melting was carried out in the same fashion as single crystal growth, namely, in a horizontal graphite boat, in an argon atmosphere, using a moving furnace. The decanting was done in two ways; 1) removing the furnace and suddenly dropping the melt end of the boat, and 2) suddenly jerking the solid away from the liquid by the action of a falling weight (estimated peak acceleration 3 x 105 cm per sq sec), using a split graphite container. In all cases the melt was vigorously agitated by bubbling argon through it. The activity of the decanted surface was measured through an aperture 1.5 cm by 0.5 cm in a lead shield with an Anton tube geiger counter. Assuming that the active layer on the surface had the same concentration of Tl204 as the decanted liquid, the thickness of the layer could be determined from the measured activity of the decanted material, and the relationship between activity and material thickness. The latter was determined by rolling some of the decanted material into foil and measuring the activity of multiple layers of the foil. The activity At of material of thickness t (in mm) was determined to be A, = Ao(1 - e-22.5t) where Ao is the activity of the bulk material. The results of the measurements of the thickness of the residual liquid layer for six decants are given in Table I. The variation in t is attributed to variations in the decanting procedure and the rate of melting, the latter being difficult to control because of the vigorous agitation of the liquid. The rate of melting was in the order of 2 cm per hr, estimated from the position of the solid-liquid interface during melting. The results indicate that a residual liquid layer of the order of 10 µ in thickness is left on the decanted interface in agreement with the observation on eutectic alloys referred to above. If the mixing of the liquid during melting is not complete, as was

Jan 1, 1962

By Denton R. Wieland, Harvey T. Kennedy

The frequency of bubble formation is measured for oils from the East Texas field and the Slaughter field in cores from these fields. East Texas oil was also tested in a Slaughter core. The data checked previous results in that a definite supersatrtration may exist without the formation of bubb1es in periods of observation totaling 158 hours. Measured frequencies varied from zero at supersaturations below 14 psi to 3.1 bubbles/sec/ cu ft of rock at 40 psi supersaturation INTRODUCTION The formation of bubbles is essential in a solution gas-drive reservoir in the displacement of oil. In formations where the basic pore structure consists of fine pores or fractures connected to larger pores or crevices, bubble formation in the fine pores may be the most effective means by which the oil may be displaced, even if secondary methods are applied. The most efficient oil displacement would occur where at least one bubble would form in every pore. As the pressure decreased, the bubbles would expand, due to the gas diffusing into the bubbles, and displace the oil toward the lower pressure area around the wellbore. Kennedy and Olson&apos; have shown that the total number of bubbles formed in a reservoir is primarily dependent upon the rate of pressure drop, the rate of diffusion of gas through oil, and surface area of the rock. The surface tension of the liquid and other characteristics of the rock may also exert an important effect, which would give a different frequency to different rocks and oils and various combinations of different rocks and oils. The purpose of this paper is to present frequency measurements on two rocks and two oils. A hydrocarbon liquid is at equilibrium with gas when it contains the maximum volume of gas in solution that it can have at the prevailing temperature and pressure. If the temperature is maintained constant and the pressure is reduced below the equilibrium pressure, the liquid is supersaturated to the extent of the difference in the two pressures until the gas comes out of solution as a free phase. As shown by previous work, and confirmed in the present investigation, the number of bubbles formed per second increases with an increase in supersaturation. Kennedy and Olson showed that a tenfold increase in the rate of pressure decline resulted in a tenfold increase in the number of bubbles formed per cubic foot of reservoir rock, e.g., for decline rates of 0.1, 1, and 10 psi/day, the number of bubbles formed per cubic foot would be 40, 400, and 4,000, respectively. For another hypothetical system, Stewart, Hunt, and Berry&apos; estimated that for pressure declines of 0.1, 1, and 10 psi/day, the number of bubbles formed would be approximately 10, 100, and 1,000 cu ft of reservoir rock. Their value of bubbles formed is lower than given by Kennedy and Olson; however, the order of magnitude agreed satisfactorily. The rate of diffusion will also affect the number of bubbles formed. If the diffusion coefficient is high, the gas in solution in the oil surrounding a single bubble will tend to diffuse into the bubble rather than forming other bubbles. On the other hand, the formation of more bubbles will tend to occur if the diffusion coefficient is very low. In his thesis dated Aug., 1953, Wood" reports on the frequency of bubble formation in a system consisting of oil and rock from the Rangely field. In the present work, the apparatus of Wood was redesigned to allow greater precision, especially at low supersaturations, where bubble growth is slower, and detection is more difficult.

Jan 1, 1958

By A. J. Sedriks

ALTHOUGH the occurrence of a readily visible tarnish on the stress-corrosion fracture surfaces of titanium alloys tested in oxygenated nitrogen tetrox-ide solutions has been reported,&apos; the possibility that the formation of this tarnish is a requirement for cracking to proceed does not appear to have been considered. It has been proposed that failure occurs in this system as a result of some electrochemical-mechanical process.2 However, recent studies3-6 of the stress-corrosion cracking of a brass in certain ammoniacal solutions, which also cause visible tarnishing, have led to the view that failure occurs by the repeated formation and fracture of a brittle surface film of cuprous oxide. The purpose of this note is to point out the similarities which exist between the tarnish which forms on a brass and that found on titanium alloys failed in nitrogen tetroxide, and to suggest, by analogy, that a similar tarnish-rupture mechanism may be operative in the latter case. The titanium alloy selected for the present study contained 5.2 pct Al, 2.5 pct Sn, 0.025 pct C, 0.16 pct Fe, 0.014 pct N, 0.012 pct H, 0.07 pct 0, and 0.002 pct Mn by weight. Vacuum-annealed alloy strips measuring 4 by 0.25 by 0.04 in. were used to prepare self-stressed test specimens. Each specimen was made from two strips by bending the end portions and spot welding them together to produce curved sections of uniform bending stress. (The exact details of preparing such specimens have been described by Lisagor el al.7) The curvature in the strips determines the ma-magnitude of the outer fiber stress, which in the present specimens was 100,000 psi (yield stress = 120,000 psi). The specimen surface in the spot-welded end regions was shot-peened to induce compressive stresses and thereby eliminate the possibility of stress-corrosion cracking in these regions. The test environment was nitrogen tetroxide, initially containing 99.5 pct N2O4, 0.1 pct H2O, and 0.08 pct C1, through which oxygen had been bubbled for 30 min. During testing the tetroxide was subject to an oxygen pressure of 250 psi. The duration of the test was 96 hr, and during this time stress-corrosion cracks propagated through some 50 pct of the thickness of the specimens. After testing, the tarnish was liberated from the fracture surface by immersion in a methanol-5 pct bromine solution, and then examined by electron dif- fraction and transmission electron microscopy using a JEM-7 electron microscope. The possibility that the bromine solution had affected the structure of the tarnish was investigated by an "in silu" examination of the stress-corrosion fracture surface using a reflection electron diffraction attachment designed for handling bulk specimens. Typical areas of the tarnish liberated by the me-thanol-bromine solution are shown in Fig. 1. Fig. l(a) reveals that the tarnish consists of individual platelets, and from Fig. l(b) it can be seen that the platelets are joined together to form a semicontinuous film, the boundaries of the titanium substrate grains being retained in the tarnish. Electron-diffraction patterns taken from these areas exhibited diffraction spots typical of a monocrystal. The diffraction pattern shown in Fig. 2 was taken from the central area in Fig. l(n). Monocrystal patterns obtained from areas containing numerous individual platelets can only be explained by assuming that their growth is governed by the titanium substrate (i.e., their growth is epitaxial). In other areas, the tarnish had folded over or became mechanically damaged, and these areas gave diffraction patterns consisting of "spotted" rings, enabling interplanar spacings of the tarnish lattice to be determined. These spacings, measured using a

Jan 1, 1968

By E. S. Machlin, C. W. Chen

RECENTLY Chen and Machlin&apos; proposed a mechanism for intercrystalline cracking in metals during high-temperature stressing. According to this mechanism the formation of voids at grain boundaries is primarily responsible for intercrystalline cracking. A model has been provided to demonstrate the initiation of submicroscopic cracks and voids at jogs of grain boundaries where grain boundary sliding is inhibited. Submicroscopic cracks can grow as a result of either further grain boundary sliding or localized tensile stress. In the former case, it is believed that grain boundary sliding produces more voids which link together to produce macroscopic cracks and which may lead to the eventual failure of the metal. Concurrently, Nield and Quarrell2 reported their interesting results obtained in a systematic investigation of intercrystalline cracking in two aluminum alloys under various creep conditions. Their observations are generally in agreement with the above mechanism, especially the conclusion that voids are formed as a direct consequence of grain boundary sliding. On the basis of the volume fraction occupied by voids, they could find no confirmation of vacancy condensation as the mechanism for void growth. Furthermore, an important feature of intercrystalline cracking has been likewise pointed out by them that the majority of cracks are not formed at grain corners. Nield and Quarrel1 meanwhile emphasized the importance of grain boundary migration by designating it as one of two main processes operative in the mechanism of crack formation during creep. The designation seems unnecessary because overemphasis of grain boundary migration only complicates the mechanism of void formation. There are two reasons which militate against the inclusion of grain boundary migration in the mechanism of void formation. In the first place, the formation of intercrystalline voids per se does not require grain boundary migration. Secondly, in addition to grain boundary migration, void formation may be minimized by any other process such as plastic deformation which is capable of relieving localized stresses around jogs. Chang and Grant3 have shown that intercrystalline cracking is prevented in aluminum by lattice bending in high stress regions. The influential role played by grain boundary migration in creep has also been realized in our studies. In several cases, voids did not appear at all in grain boundaries whenever grain boundary migration took place prominently during creep. The purpose of this paper is to discuss the effect of grain boundary migration on the formation of intercrystalline voids and other related rupture properties. Experimental evidence indicates that in an unstable grain structure void formation may be markedly modified by structural changes. The abnormally high ductility and the transcrystalline mode of fracture observed in copper at elevated temperatures reveals that effective grain boundary migration minimizes void formation. Grain boundary migration has long been known as a common high-temperature phenomenon in metals with the grain configuration in a nonequilibrium state. Its effect on ductility and mode of fracture has not been recognized until recently.4 Since the introduction of the term "Equicohesive Temperature," the conventional belief has been that below the equicohesive temperature the ductility of metals increases moderately with decreasing temperature until the ductile-to-brittle transition temperature of fracture is reached. In this temperature range, metals fracture in a ductile mode with a "cup-and-cone" fracture surface. Above the equicohesive temperature, ductility remains invariably low and decreases slightly with increasing temperature. The mode of fracture is strictly brittle and intercrystalline. Typical examples have been shown for a brass and copper in Fig. 1 and 9, respectively, in the paper by Greenwood, Miller, and Suiter.5 The observation in the upper temperature range that ductility of metals is low and insensitive to temperature may be explained in terms of void formation at grain boundaries. It is also in accordance with the findings of McLean6 and Fazen, Sherby, and Dorn7

Jan 1, 1961