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By Walter B. Devereux

Metallic copper is a product of native metallurgy in various parts of Mexico, and by somewhat varied processes. While recently examining copper mines in the State of Jalisko, I had an opportunity of witnessing Mexican copper smelting by a process which I have not seen described, and which is interesting from the fact, that a fine quality of copper is produced from sulphurous ores in three metallurgical operations, and apparently without excessive loss. The process was carried on in buildings which were part of a plant erected by an American more than twenty-five years ago for the purpose of smelting and working copper. After a few years this man met with accidental death, and the works have been but little used since. Located in the centre of a high range of mountains, far from any town or seaport, and inaccessible except over difficult mule trails, these substantial buildings, filled with furnaces and heavy machinery,

Jan 1, 1883

By Robert Maes, Robert de Strycker

The Cu-Sn-As systeM was studied in the region near the Cu-42 and (214-As binary diagrams, where reactions in the solid state appear, resulting from the decomposition of the y(Cu-Sn) phase and from the formation of the 7 phase (Cu,As). The techniques used were microscopic observation, thermal analysis by dilatometry, and X-vay diffraction. The formation of the 7 phase gives rise to a ternavy pevitectoid veaction; the decomposition of the y phase gives rise to five transitional reactions. The temperatures of almost all these reactions could be determined; in the most favorable cases , the accuracy of this determination was of 11.5-C. The 7 phase is stabilized by tin additions, the arsenic atoms being replaced by tin atoms up to 35 pct; this has allowed the preparation of pure j) phase and the confirmation, by extrapolation, of the conrposition of this compound in the Cu-As diagram. In the first part of this work, the solidification reactions in the Cu-Sn-As phase diagram were studied. In the copper corner, the structure of the alloys presented the evidence of reactions in the solid state: on the one hand, all the alloys containing the y phase of the Cu-Sn diagram showed, under the microscope, that this phase had formed different decomposition products after complete solidification; on the other hand, the appearance of the 7 phase of the Cu-As diagram necessitated the introduction of a peritectoid formation reaction. The study of the decomposition of the y phase has been done by preparing about forty alloys that were homogeneous y at high temperature. The formation of the 7 phase has been studied by means of a few alloys with a composition near the homogeneity field of this phase at room temperature. The part of the Cu-Sn phase diagram of interest for this study is represented by Fig. 1, with the phase designation which will be used in the remainder of this paper; it is drawn after Hansen and Anderko.' The Cu-As diagram has already been presented in Part I of this work; the significant features of this study are the existence of the arsenides CusAs and Cu5Asz, and the formation of a compound CUEAS, designated as the 7 phase, by a peritectoid reaction at about 325°C. EXPERIMENTAL METHODS The fundamental technique for the investigation of this part of the Cu-Sn-As constitution diagram was microscopic observation; the greatest part of the observed alloys has also been subjected to thermal analysis by dilatometry; a few selected alloys have then undergone an X-ray analysis by powder diffraction. Alloy Preparation. The alloys were prepared from the same products as in Part I of this study: cathode copper, arsenic with a purity better than 99.5, and tin with a purity of 99.98. The fusion of the ternary alloys was realized from

Jan 1, 1967

By J. T. Norton, N. J. Grant, I. S., Servi

Coarse grained high purity aluminum was tested in creep at temperatures of 400° to 1200°F to develop subgrain structures. Measurements of subgrain size, distribution, and rotation were made from X-ray diffraction patterns. Subgrain size and distribution were checked metallographically and the size was compared with average slip band spacing. The slip family was determined for several specimens. THE interest and research recently evident abroad in the role of subgrain formation and polygon-ization as a contribution to the creep of metals at elevated temperatures is deserving of greater attention in this country. Such metallic subgrains can be defined as macroblocks existing within the grains. The general observation has been that the macro-blocks which belong to the same grain have a maximum difference in orientation of a few degrees. In spite of the considerable amount of work that has been done since Jenkins and Mellorl observed the "division of existing crystals into smaller units when deformation occurs at an annealing temperature," the subject of subgrain formation is only now receiving truly active discussion and investigation. The existence of subgrains has been revealed by metallographic methods, as in the work of Jenkins and Mellor,1 and by X-ray methods, first applied to this problem by Homes.' Hirst3 and Calnan and Burns4 applied the back-reflection Laue technique to the study of coarse grained specimens. Wood et al.5 and Greenough and Smith' examined the ring obtained with a back-reflection camera for the study of fine grained specimens. In addition to the above, the transmission technique was used by Wood.6 A special technique was developed by Guinier and Tennevin8 in order to improve the resolution. Metallographically, the subgrains have been observed directly on the surface of deformed specimens by Wood et al.,3 or have been made evident on repolished surfaces by applying a suitable etching reagent. The latter technique, first suggested by Lacombe and Beaujard,9 was then improved by Wyon and Crussard.10 Subgrains can be formed in single crystals after small amounts of bending followed by heating after this cold work, or during deformation at elevated temperatures. The first phenomenon was analyzed by Cahn11 for the simple case of pure bending followed by annealing. Cahn suggested a mechanism of subgrain formation based on the dislocation theory and called this phenomenon "polygonization." He extended this mechanism to the more complex case of local bending, such as the bending which may occur when a polycrystalline specimen is deformed in tension. Cahn's suggestion was later found quite consistent with the results obtained by Dunn and Daniels." An explanation has been presented recently regarding the formation of subgrains during deformation at elevated temperatures by Chang and Grant.'" In general, there are two schools of thought on the subject. One, according to Wood et al.,5 is that subgrain formation is a mechanism of deformation which is operative under certain conditions in the same way that the slip process is the mechanism of deformation which is operative under other conditions. The boundaries between the subgrains undergo a viscous flow which contributes substantially to the deformation of the material. The second, according to Cahn,13 Wyon and Crussard,10 and Chang and Grant,18 is that subgrain formation is the effect of simultaneous deformation and annealing and is,

Jan 1, 1953

By Henry Rogatz

During the year 1937, there were 663 oil wells drilled in the Texas Panhandle, making a daily initial production of 322,332 bb1.—that is, 191 more oil wells drilled than in the previous year, with an increase in the total daily initial production of 66,283 bbl. The total daily potential of the field as determined by the Texas Railroad Commission in its Schedule of Dec. 17, 1937, was 1,039,982 bbl., or an increase of 205,094 bbl. over the previous year. On Dec. 17, 1937, the daily allowable of 68,578 bbl. was assigned to the entire field. The total amount

Jan 1, 1938

By Paul R. La Pointe

GEOTECHNICAL OBJECTIVES OF UCG PROGRAM Underground coal gasification (UCG) is one of several in situ extraction technologies for utilizing deep, otherwise unmineable coal. This technology involves the injection of air or oxygen into the target coal seam, ignition of the coal and recovery of product gases. Geotechnical characteristics of the coal and enclosing rock strata strongly influence the success of this Process. The flame front follows the coal cleats (Hill, 1979), and cleating and bedding control the manner in which coal collapses into the cavity, thereby affecting recovery efficiency (Ramirez and others, 1982). Moreover, coal seams typically behave as fracture dominated aquifers in which cleat orientations govern subsequent contaminant dispersal. For these reasons, the Anaconda Minerals Co. undertook a detailed study of fracturing within the Wyodak-Anderson Coal in the eastern Powder River Basin (PRB) near its Rocky Hill UCG test site (Fig. 1). STRESS HISTORY AND FRACTURING IN THE POWDER RIVER BASIN Vertical jointing, or cleating, in coals may arise from shrinkage shortly after deposition under low confining pressures, or later in time, soon after burial but after the coalification process is well advanced (Ting, 1977). There is much evidence to support the formation of cleating after coalification (e.g. Hawkes and Mellor, 1970; McCulloch and others, 1974), which suggests that the stress state existing at that time strongly influences cleat formation. McCulloch and others (1974) argue that the typically better developed face cleat forms parallel to the plane containing [ol] and [o2]. Where the relation between cleats and stess has been studied (McCulloch and others, 1974; Stone and Snoeberger, 1977; Ward, 1977; Kulander and Dean, 1978), the highly systematic face cleat strongly parallels the [o1] direction. Stone and Snoeberger (1977) report face and butt cleat measurements of N70E and N29W for the Felix Coals 220 m stratigraphically above the Wyodak at the Hoe Creek UCG site (Fig. 1). Structural trends also indicate the past state of stress in the PRB. Glaze and Keller (1963) suggest that the NE-SW regional compression during the late Permian formed major N-S fold lines and basement magnetic anomalies. Mapel (1959) describes folds having N60W and N30W rends in the northern PRB, as well as a large normal fault trending northeast. Glass (1976) also describes normal faults trending northeast. Similarly, Olive (1957) mapped normal faults

Jan 1, 1984

By E. W. Davis

If the tonnage of merchantable iron ore remaining in the Lake Superior district is divided by the average of the annual shipments for the past 20 years, it will be found that this ore supply will be exhausted in approximately 35 years. This computed exhaustion period would be an indication of the future activities of the iron-mining industry if it were not for the fact that merchantable ore is being manufactured from low-grade ore, of which there is an almost inexhaustible supply in the Lake Superior district. It is true that at present only the simplest of these low-grade ores are being concentrated to any considerable extent, but progress is being made with the treatment of the more complex ores, and now, in addition to 20 washing plants on the Mesabi Range, three plants are equipped with jigs for the treatment of ore that cannot be concentrated simply by washing. The latest addition to the ore-treating plants of the Mesabi Range is a magnetic roasting and concentration plant at Cooley, Minn., in which ore that cannot be concentrated either by washing or by jigging is roasted to the magnetic state and concentrated on magnetic separators. This plant is beginning its third season of operation, and while it is too soon to make definite predictions, there are strong indications that this new process may make commercially possible the manufacture of high-grade, merchantable iron ore from large quantities of low-grade ore now considered worthless. After the iron oxide contained in an ore has been converted to magnetite, almost any desired grade of concentrate can be produced, using magnetic-concentration equipment of the types now in general use for the concentration of the natural magnetites of New York, New Jersey and Pennsylvania. The conversion of hematite (Fe203) to magnetite (Fe3O4) is easily accomplished by heating the ore to a dull red temperature in a reducing atmosphere. The reaction is slightly endothermic, and while it requires 200 B.t.u. to heat to 900' F. one pound of hematite ore containing 45 per cent Fe, it requires only 100 B.t.u. to convert the oxide into magnetite. In the laboratory, using small quantities of ore, this conversion is very simple, but large furnaces suitable for commercial

Jan 1, 1939

By E. W. Davis

If the tonnage of merchantable iron ore remaining in the Lake Superior district is divided by the average of the annual shipments for the past 20 years, it will be found that this ore supply will be exhausted in approximately 35 years. This computed exhaustion period would be an indication of the future activities of the iron-mining industry if it were not for the fact that merchantable ore is being manufactured from low-grade ore, of which there is an almost inexhaustible supply in the Lake Superior district. It is true that at present only the simplest of these low-grade ores are being concentrated to any considerable extent, but progress is being made with the treatment of the more complex ores, and now, in addition to 20 washing plants on the Mesabi Range, three plants are equipped with jigs for the treatment of ore that cannot be concentrated simply by washing. The latest addition to the ore-treating plants of the Mesabi Range is a magnetic roasting and concentration plant at Cooley, Minn., in which ore that cannot be concentrated either by washing or by jigging is roasted to the magnetic state and concentrated on magnetic separators. This plant is beginning its third season of operation, and while it is too soon to make definite predictions, there are strong indications that this new process may make commercially possible the manufacture of high-grade, merchantable iron ore from large quantities of low-grade ore now considered worthless. After the iron oxide contained in an ore has been converted to magnetite, almost any desired grade of concentrate can be produced, using magnetic-concentration equipment of the types now in general use for the concentration of the natural magnetites of New York, New Jersey and Pennsylvania. The conversion of hematite (Fe203) to magnetite (Fe3O4) is easily accomplished by heating the ore to a dull red temperature in a reducing atmosphere. The reaction is slightly endothermic, and while it requires 200 B.t.u. to heat to 900' F. one pound of hematite ore containing 45 per cent Fe, it requires only 100 B.t.u. to convert the oxide into magnetite. In the laboratory, using small quantities of ore, this conversion is very simple, but large furnaces suitable for commercial

Jan 1, 1939

By D. I. Bardos, F. X. Spiegel, R. K. Malik, Paul A. Beck

Study of the occurrence of elongated ß-Mn phase fields and of their direction of extension in fifteen ternary systems indicates that the ß-,mn phases formed by manganese with other transition elements and with either silicon, germanium, or tin may be considered as electron phases. In these phases the alloying behavior of silicon on the one hand and of germanium and tin on the other shows a significant difference . Formally all observations can be satisfactorily described by attributing to germanium and tin an apparent electron concentration of nine electrons per atom. This behavior may be interpreted by assuming that germanium and tin exclude itinerant electvons because of a strong repulsive potential arising fromthe requirement that their wave junctions be orthogonal to those of- the closed d shells of these atoms. The absence of a d shell in silicon allows this atom to admit itinerant d electrons. The following new ternary phases of unknown structure were identified by means of their X-vay difjraction patterns: (Mn,Co,Si)I , (Mn,Co ,Si)Y, (Mn.Co,Si)Q , (Mn ,Ni ,Si)W , and (Mn, Ti ,Si)A. The X-ray data suggest that these phases have large unit cells and that to some extent they may he related structurally to the 0 phase. The a phase and certain other phases formed by transition elements are characterized by their preferred occurrence at a constant electron concentration. AS a result, these "electron phases" have relation to electron concentration. The tendency of the B phase to form elongated phase fields in ternary systems along the directions of constant electron concentration has been previously demonstrated. The occurrence of an elongated 0-Mn phase field in the ternary system Mn-Co-Si was schematically indicated by Cherkashin et al.l0 The present study includes fifteen ternary systems, each containing in addition to manganese a second transition element from the group Ti, V, Cr, Fe, Co, Ni and one of the nontransition elements silicon, germanium, or tin. In each system the boundaries of the B-Mn phase were determined in the 900°, 950°, or 1000°C isothermal section, the temperature being dictated on the one hand by the requirement of sufficient rates of diffusion to approach equilibrium conditions in reasonably short annealing periods and on the other hand by the need to avoid as much as possible the partial melting of alloys during annealing.

Jan 1, 1967

By John W. Cahn, John E. Hilliard

Single crystals of copper and silicon-iron were cold rolled in orientations chosen to produce individually the major components of the poly crystalline deformation texture. The orientation dependence of the recrystallization kinetics was studied relative to the primary recrystallization textures of these specimens. It is not possible to rationalize the poly crystalline re crystallized textures on this basis. The results suggest an important role of the interaction of adjacent crystals during the deformation of aggregates. BRICK and Williamson1 first noted evidence that the recrystallization temperature was different for straight-rolled and cross-rolled copper given comparable reductions. Michalak and Hibbard2 investigated quantitatively the effect of rolling procedure on the kinetics of recrystallization of cold-rolled copper and found that material cold-rolled the same amount by straight-pass, cross-pass, and compression-pass techniques developed different deformation and recrystallization textures, different 1-hr recrystallization temperatures, and different recrystallization kinetics. However, the temperature dependence of the rate of recrystallization was essentially the same for all techniques. Similar results were obtained on iron. Dunn and Koh3 in studying the recrystallization textures of cold-rolled silicon-iron single crystals reported large differences in the annealing temperatures and times required to recrystallize specimens of different orientations cold-rolled the same amount. Liu4 and Liu and Hibbard5 utilized the concept of different recrystallization temperatures for different orientations of cold-rolled crystals to rationalize the difference in recrystallization textures found in various face-centered-cubic metals. Their explanation predicted a significant difference in the recrystallization kinetics of deformed (110) [112] crystals as compared to (358) [352] crystals, and, in fact, Liu4 reported evidence that this difference existed at least qualitatively. Verbraak6 who rolled and recrystallized a series of copper single crystals found that the double (112) [111] rolled orientation is related to recrystallized cube texture formation. The effect of rolling intensity on the relative amount of cube component suggests an important role of recrystallization kinetics. Walter and Hibbard7 while trying to relate the behavior of rolled and recrystallized single crystals of silicon-iron to the behavior of polycrystal-line silicon-iron again noted that differences in recrystallization kinetics were necessary to rationalize their results. The purpose of the present investigation was to obtain quantitative kinetic data on the recrystallization of single crystals of both copper and silicon-iron rolled to initial isolated individual orientations corresponding to those found in the polycrystalline deformation textures. These data might indicate the importance of the deformation orientation, i.e. the range of available nuclei, the deformed matrix orientation into which these nuclei grow, and the orientation dependence of their growth rate during primary recrystallization on this texture. I. COPPER Experimental Procedure—A single crystal of 99.98 pet purity copper, grown by the Bridgman technique, was purchased in the form of a bar 1 1/2

Jan 1, 1962

By Oscar Weiss

STILFONTEIN and surrounding areas gave nega-tive results in all prospecting attempts since about 1904 when Goerz and Co., a forerunner of Union Corporation Ltd., first drilled in the region and on the farm Stilfontein. Subsequent efforts by African and European Investments Co. and Anglo American Corp. from 1934-37 were completely unsuccessful. Holes drilled by these companies on the farms Riet-fontein, Hessie, and Palmietfontein were stopped in the Lower Witwatersrand system without finding payable reefs. The results of gravimeter, ground magnetometer, and aerial magnetometer surveys are presented in the area, in and around the new Stilfontein Gold Mine, in the Klerksdorp District of the Transvaal in the Union of South Africa. The gravimeter and ground magnetic surveys were completed in 1947—48. The gravity anomalies suggested a block of Upper Witwatersrand quartzites faulted-up between denser rocks of dolomite and Ventersdorp lava. Boreholes S.T. 1, 2, and 3 were drilled in 1948 and, after penetrating the dolomite and Ventersdorp lava, entered Upper Witwatersrand quartzites and intersected the Gold Estates Reef and Vaal Reef. Subsequent drilling delineated the suboutcrop of the Vaal Reef and determined the main structure of this horizon. The gold content of the Vaal Reef was highly payable and shaft sinking is now in progress. The Stilfontein Gold Mining Co. has been formed and, up to date, f5,000,000 capital has been raised for plant, shaft sinking, and development. The payable Vaal Reef horizon extends further south from Stilfontein, the reef occurring at increasing depths. It is possible that at least another mine may be established on these deeper horizons. The farm Stilfontein 39 is situated in the Klerksdorp District of the Transvaal. This farm and the surrounding areas have been subjected to repeated programs of prospecting dating back to about 1904, when Goerz and Co., the forerunner of Union Corporation, Ltd., first drilled on the farm and in the surrounding areas. From 1934-37, numerous boreholes were drilled on the neighboring farms, Riet-fontein. Hessie. and Palmietfontein, by African and European Investment Co. and Anglo American Corp. All these efforts were completely unsuccessful, and nobody suspected any possible gold-bearing area on Stilfontein until about 1947, when a gravity traverse run by B. D. Maree on the main road, showed a negative gravity anomaly. During 1947-48, the writer's organization completed gravimeter and magnetic surveys on Stilfontein and Rieffontein. An area of negative gravity anomalies was mapped, and it was suggested that this could be caused by blocks of Upper Witwatersrand quartzites, of the average density of 2.65, faulted up between dolomites and Ventersdorp lavas, the density of both of these rocks being 2.8. Fig. 1 shows the geology of the area as mapped by L. T. Nel of the Geological Survey of South Africa. The boreholes on Stilfontein, with the exception of a single hole of Goerz and Co., were drilled after the completion of the geophysical survey. The grouping of the first boreholes S.T. 1, 2, 3, 4, 5, and 6, clearly shows that these were located in the zone of negative gravity anomalies. Fig. 2 shows the gravity anomaly contours. Fig. 3 shows two sections across the gravity anomaly, together with the corresponding geological sections as obtained from boreholes. The close relation between gravity values and thickness of dolomite plus Ventersdorp lavas is striking. The two latter formations having the same density (2.8), act as one mass as far as gravity effects are concerned. Fig. 4 shows the magnetic anomalies observed on the ground by vertical magnetometers and at 500 ft abbve mean ground level by aerial magnetometer. The latter are anomalies of the total magnetic intensity. The magnetic results show that, on the farm Rietfontein and on the northern half of Stilfontein. Lower Witwatersrand magnetic shales were to be expected at relatively shallow depths. As the strongly

Jan 1, 1952

By John C. Sawyer

A brief review is given to show that catastrophic oxidation of stainless steel in the presence of lead oxide is similar in many respects to catastrophic oxidation as caused by MoO3 and V2O5, Experimental data are presented to show that lead oxide accelerates the normal oxidation process of stainless steel by chemically altering the normally protective oxide film formed on the base metal. Data are given to show that similar reactions occur during oxidation of stainless steel in the presence of MOO3,and V2O5. THE mechanism by which pure metals oxidize at high temperatures has been the subject of intensive research for many years and much has been accomplished towards understanding the processes involved. The mechanisms by which alloys oxidize have also been investigated, but due partly to the fewer number of investigations and partly to the complexity of the oxide systems present, available knowledge is not as extensive as with pure metals. When oxidation processes are further complicated by atmospheres contaminated with sulfide, halide, or oxide vapors, the knowledge of fundamentals becomes meager or altogether lacking. Thus, it is not surprising to find that the catastrophic oxidation of stainless steels in metal oxide vapors of MOO, and V2O5 is not a well understood phenomenon despite the fact that a number of investigations have been undertaken. The literature in dealing with the subject of catastrophic oxidation is primarily concerned with the effects of MOO3 and V2O5, but does mention that other metal oxide vapors, one of which is lead oxide, appear to promote a similar type of accelerated oxidation. While this latter effect is virtually unknown, the deleterious effect of lead oxide is of considerable commercial importance, as it is believed to be one of the fundamental reasons for exhaust-valve failure in gasoline engines. For this reason studies have been in progress for many years attempting to better understand the mechanism involved. Modern exhaust-valve alloys"2containing 20 to 25 pct Cr plus nickel and/or manganese are in effect high-grade austenitic stainless steels exhibiting ex- cellent oxidation resistance in air at exhaust valve operating temperatures of 1100° to 1700°F; yet these same alloys are prone to corrode during engine service because of the conditions attending their operation. These conditions are such that the valves become coated with deposits of complex lead compounds mainly derived from gasoline additives of tetraethyllead, ethylene dibromide, and ethylene dichloride. Literature searches3-7 and discussions with various investigators show that considerable difference of opinion exists as to the nature of the lead-bearing deposits found on the surface of exhaust valves and the atmospheres to which they are subjected; yet, all seem to generally agree that corrosion, a gradual transformation of alloy to nonmetallic products of corrosion, is a consequence of the presence of lead compounds. This majority opinion seems to be substantiated by laboratory engine tests which show that corrosion does not occur to any appreciable extent when lead-free fuels are used. The first observations of catastrophic oxidation reported in the literature were probably made by pfeil,8 but it was Leslie and Fontana9 who undertook the first detailed study of the phenomenon. Their work was chiefly centered on the acceleration of oxidation which took place when stainless steels containing more than 3 pct Mo were heated in air with restricted circulation. These investigators reported that the presence of other oxides near the surface would further accelerate the rapid oxidation which occurred. While they recognized that the effect was attributable to the presence of molybdenum, it was Rathenau and Meijering" who emphasized the fact that the presence of molybdenum in the alloy was incidental to the presence of MOO3 vapor in the atmosphere surrounding the specimens. Evans,11 as well as Cunningham and Brasunas 12 studied similar

Jan 1, 1962

By R. Kerby, T. R. lngraham

The rates of cadmiuln cementation from buffered solutions were studied on both the cylindrical and circular faces of a rotating zinc disk. The activation energies are equivalent on both surfaces, but the rate is more rapid on the cylindrical face. At higher temperatures and at pH values above 6.4, the rate of deposition increases because of an increase in the cathodic area of the deposit. The rate may also be increased by decreasing the thickness of the diffusion layer by rapid stirring. The presence of small amounts of copper, cadmium, lead, iron, or aluminum in the zinc does not affect the cementation rate, but when srnall amounts of copper, cobalt, and arsenic were present in the solution cadmium deposition ceased shortly after it started. Small amounts of copper in solution become cemented with the cadmium to form a coarse deposit of Cd3Cu. When zinc ores containing cadmium are processed for electrolysis, the cadmium appears with the zinc in the leach liquors. Because of the discharge potential of the cadmium ion and the hydrogen overvoltage on metallic cadmium, the cadmium ion must be removed prior to zinc electrolysis to prevent its codeposition. Cadmium is usually removed from acidic zinc sulfate solutions by cementation on zinc. When zinc sheets are used with the appropriate conditions of pH and temperature, a finely divided, high-purity cadmium powder is obtained; it floats to the surface with attached hydrogen bubbles and, after careful washing, may be processed directly to a marketable product.' The reaction on zinc sheets is relatively slow because of the limited amount of exposed cathodic area on the sheets. A much more rapid reaction is obtained when zinc powders are stirred into the solution, but this procedure does have a potential disadvantage: some unreacted zinc may be trapped in the cemented cadmium and thus lower its grade.1 The equilibrium constant at 25°C for the displacement of cadmium by zinc is of the order of lo", which indicates that at equilibrium the displacement would be essentially quantitative and no back reaction need be considered. This indication is not entirely true, however, because in the presence of oxygen any loose cadmium which is out of contact with metallic zinc tends to redissolve after cementation.' The overall effect is much the same as that to be expected if the equilibrium constant were much smaller. Previous experimental work on cementation reac- tions3 is in general agreement that the rates of cementation usually follow first-order kinetics. The metal on which cementation occurs is considered to consist of anodic areas from which metal dissolves and cathodic areas onto which the reactive metal is cemented. For the reaction to continue, the cemented deposit must remain open and porous for the removal of ions. Usually, the deposited metal influences the rate of cementation; when it blocks the pores in the deposit, the rate of cementation will be decreased. Alternatively, when the cemented metal grows as den-drites or as coarse powder the cathodic area is correspondingly increased and the rate of cementation increases,3 Thus, it is only during the initial stages of cementation, prior to the development of deposit effects, that the kinetic behavior of the reaction may be studied without ambiguity. In this paper, experiments will be described for cementation of cadmium from dilute solutions onto the surface of a rapidly spinning zinc cylinder. The effects of ionic concentration, disk rotation speed, temperature, and impurities will be described. APPARATUS AND PROCEDURE The apparatus used for the experiments was described in a previous paper.4 It consisted of a 2-liter vessel in which the contents were protected, against oxidation, by a stream of prepurified nitrogen. The vessel was immersed in a water bath which controlled

Jan 1, 1970

By J. Gordon Parr, D. H. Polonis

RYSTALLOGRAPHIC relationships between martensitic a' (close-packed-hexagonal) and retained fi (body-centered-cubic) have been studied in binary alloys of titanium with manganese, molyb- denum, chromium, and iron.'" In these investigations, the habit planes of the martensitic phase were determined, as well as the orientation relationships between martensitic and parent phases. In each alloy

Jan 1, 1957

By Waldemar Gooskov

IN his well-known work,1 published in 1867, P. Ritter von Rittinger gives the following formula for the velocity of a particle settling in still water: v=C/D(a -1) and for average grains he assigns to the constant C a value of 2.44. As is well known, the value of C depends on the shape of the grains resulting from crushing, and it is obvious that values obtained for coal particles will not only be very different from those for ore particles but will even be characteristic of coal from a certain seam. The only way of finding an accurate value of C, applicable to conditions in Russia, where all coal-washing plants are built on German principles, is to conduct a series of tests of which the results will determine what value of C is to be used. In the investigation outlined in this paper the theories of Prof. Robert H. Richards2 were taken as the basis of the tests; the slimes were removed from the charges to eliminate the trouble of handling them; and to obtain accurate results free from errors inevitably resulting from human observation, photographic apparatus was used and a series of pictures taken which form the basis for constructing a suitable diagram of velocity vs. time.3

Jan 1, 1928

MANY are the salts produced. by Nature in various regions and parts of the world, as Pliny shows in his History. Likewise, many are the differences among things that are salty and from which salt can be extracted, as, for instance, all the lyes from any kind of ashes and the urine of all animals. But because these are not things that give men the useful elements necessary to life, I shall omit speaking of them in detail with the exception of some of the more notable ones, and I shall tell you that I find that men proceed in only two ways in order to have a sufficiency for their needs. One is that of extracting it from the salty waters of the sea itself, or from springs, with a certain technique [34v] adapted to the places, either by congealing or by evaporation; and the other is that of mining it from the earth. The latter salt is clear and beautiful, and it is mined from mountains, already made by Nature in the form of stone without the aid of art. All these salts have more or less efficacy* according to the fineness or coarseness of their earthy elemental mixture, and according to the provinces and places where they are found generated. All are of an earthy

Jan 1, 1942

By E. H. Dix, F. Keller

The use of magnesium as an alloying element in aluminum alloys has been limited, in general, to comparatively small quantities. In duralumin-type, strong aluminum alloys, magnesium is present to the extent of 35 to 3/4 per cent. and various grades of Magnalite and the "Y" alloy of the National Physical Laboratory of England contain up to 1 1/2 per cent. In this country small quantities of aluminum alloy sheet containing 4 per cent. magnesium are produced commercially. All commercial aluminum contains sufficient silicon to convert a portion of the magnesium added to the compound Mg2Si. It is well known that the solubility of both magnesium and magnesium-silicide decrease with decrease in temperature. It is, therefore, impossible to separate the age-hardening effect of the magnesium-silicide from that of magnesium, except by the use of aluminum of such high purity that the silicon content is negligible. The present paper is the fifth l, 2, 3, 4 of a series from the laboratories of the Aluminum Co. of America reporting the results of investigations of the equilibrium relations in aluminum-rich alloys made from the high-purity aluminum manufactured by this company. 5 Previous Investigations A number of investigations have been made of the constitution of the complete aluminum-magnesium system and several determinations made

Jan 1, 1929

By F. Keller, E. H. Dix

The use of magnesium as an alloying element in aluminum alloys has been limited, in general, to comparatively small quantities. In duralumin-type, strong aluminum alloys, magnesium is present to the extent of 35 to 3/4 per cent. and various grades of Magnalite and the "Y" alloy of the National Physical Laboratory of England contain up to 1 1/2 per cent. In this country small quantities of aluminum alloy sheet containing 4 per cent. magnesium are produced commercially. All commercial aluminum contains sufficient silicon to convert a portion of the magnesium added to the compound Mg2Si. It is well known that the solubility of both magnesium and magnesium-silicide decrease with decrease in temperature. It is, therefore, impossible to separate the age-hardening effect of the magnesium-silicide from that of magnesium, except by the use of aluminum of such high purity that the silicon content is negligible. The present paper is the fifth l, 2, 3, 4 of a series from the laboratories of the Aluminum Co. of America reporting the results of investigations of the equilibrium relations in aluminum-rich alloys made from the high-purity aluminum manufactured by this company. 5 Previous Investigations A number of investigations have been made of the constitution of the complete aluminum-magnesium system and several determinations made

Jan 1, 1929

By O. R. Wagner, R. O. Leach, H. W. Wood, C. F. Harpke

PAN AMERICAN PETROLEUM CORP.TULSA, OKLA. CASPER, WYO A field test has been made in which additional oil recovery was obtained from a previously-waterflooded "oil-wet" sandstone reservoir. This recovery improvement was accomplished by adjusting the reservoir wettability through chemical treatment of the flood water. The test was made in the Muddy sand of the West Harrisburg Unit, Neb. The chemical used, sodium hydroxide, was injected as a slug of dilute caustic solution through a water-injection well. The natural wettability of the reservoir and the chemical requirements for reversing wettability were determined in the laboratory from contact-angle studies using field water and oil samples. Laboratory flood tests with a synthetic system had shown that reversing the wettability of an oil-wet consolidated core would lead to improved oil recovery. The field performance indicates that the mechanism by which increased oil retovery is obtained in the field is the same as that observed in the lahoratory. Laboratory studies indicate that higher ultimate recoveries and decreascd water-injection requirements result when the adjusting agent is added early in the life of the flood. However, a previously waterflooded area was intentiorzally chosen for the field test so that unambiguous conclusions could be made about the effects of chemical injection on wettability and the extent of oil-recovery improvernent afforded by wettability reversal. Forces existing at the fluid-solid and fluid-fluid interfaces in a porous medium have an important effect on oil recovery during a water flood. Modifying these interfacial forces in the reservoir to improve oil recovery has been the object of much research. Several papers' ' have discussed the use of surfactants to lower the water-oil interfacial tension. This paper describes work concerned with improving oil recovery by modifying the forces at the fluid-solid interfaces— that is, by changing the preferential wettability. An earlier paper: presented evidence to show that some reservoir systems could be changed from preferentially oil-wet to preferentially water-wet by the action of simple chemicals added to the water to increase waterflood oil recovery. The process was attractive for further study because it used only inexpensive chemicals and because it called for a gross "wettability reversal" rather than for a precise adjustment. The present paper is an extension of the earlier work. Laboratory flow tests were made using treated water and oil in a consolidated core to determine the amount of additional oil recovery and the producing performance which might be expected from reversing the wettability of an oil-wet reservoir during a flood. A contact-anglc study using water and oil from the Muddy "J" sand of the Harrisburg field, Banner County, Neb., indicated the reservoir to be preferentially oil-wet and susceptible to wettability reversal through chemical injection. Based on these studies, a field trial of wettability-reversal water flooding was initiated. in the Harrisburg field. The primary purpose of the trial was to determine if wettability-reversal flooding would improve oil recovery in an actual field situation. The field trial was also an important test of the laboratory tecnique used to determine the effect on oil recovery of certain wettability manipulation, as well as a test of the contract-angle method of determining reservoir wetra-bility. The paper is presented in two parts. The first part covers the laboratory experiments leading up to the field trial, and the second part covers the field trial. PART I—LABORATORY STUDY The laboratory experiments consisted of displacement tests using an idealized fluid system and of a contact-angle study with crude and water from the Muddy "J" sand of the West Harrisburg Unit, Banner County, Neb. The displacement tests were designed to determine the effects of a particular wettability manipulation, oil-wet to water-wet, on oil displacement in a water flood. The contact-angle measurements were made to determine the natural wettability of the reservoir and to determine if beneficial wetting changes could be brought about by a chemical addition to the flood water. PROCEDURE DISPLACEMENT TESTS The displacement tests were perfornled in a consolidated sandstone core using a refined oil and water. The wetting properties of this system could

By Morris Muskat

A general theory has been developed for the effect of permeability stratification on the efficiency of the gas-injection phase of cycling operations. It has been applied to three special types of permeability variation; namely, exponential, probability, and linear. In the case of the exponential permeability distribution the effect of areal pattern sweep efficiency was also taken into account. The exponential permeability distribution can be characterized by the ratio of the maximum to minimum permeability, which has been termed the stratification constant. Curves were calculated for the variation in total wet gas recovery and total gas throughflow, to give that recovery to various abandonment limits of the wet gas content in the produced gas, as a function of the stratification constant. The cumulative wet gas recovery decreases monotonically as the stratification constant increases and is generally higher at the lower values of the wet gas content abandonment limits. The total gas throughflow first rises to a maximum as the stratification increases, and then ultimately declines. The effect of the areal sweep pattern efficiency is relatively minor as compared to that of the stratification constant, except in the region of low values of the latter where the formation is substantially uniform. The probability distribution can be characterized by a "variation" parameter varying from o to I as the formation changes from strict uniformity to extreme variability. The curves of total wet gas recovery and total gas throughflow to different abandonment limits of wet gas content versus the variation parameter have the same general characteristics as for the exponential permeability distribution. In the linear permeability distribution the ratio of maximum to minimum permeability also serves as a stratification constant index defining the distribution. The curves of total wet gas recovery and gas throughflow to fixed abandonment limits versus the stratification constant are similar to those for the exponential permeability distribution. However, for the higher values of the stratification constant the recoveries and throughflows do not asymptotically fall to o as in the latter, but approach constant values determined by the abandonment limit of wet gas content in the produced gas. Introduction It is becoming generally recognized that one of the most important factors determining the economic feasibility of cycling operations is the areal continuity and permeability distribution of the producing formation. While the effects of areal variations in permeability, porosity, thickness, and well pattern on the sweep efficiency can be evaluated by electrical model studies,' those due to permeability stratification require separate treatment. Several studies have been reported2,3 on the' influence of permeability variations on the wet gas recovery by cycling. In these, however, discontinuous permeability variations either have been assumed explicitly, or the analysis has been carried through as if they were discontinuous. While, in fact, the actual permeability profiles will undoubtedly be discontinuous, recent develop-

Jan 1, 1949

By Morris Muskat

It is pointed out that the application of capillary pressure curves obtained by drainage or desaturation processes to the calculation of the fluid distribution in interphase transition zones involves a number of difficulties; namely: (I) the development of very low nonwetting phase saturations appears to be in contradiction with the lack of mobility of such distributions indicated by permeability-saturation curves, (2) dispersed nonwetting phases are thermodynamically unstable, and (3) discontinuous phases should not be subject to hydrostatic equilibrium requirements. While these difficulties could be obviated by assuming that the capillary pressure drainage curve has an initial horizontal segment, they are automatically circumvented by application of the imbibition capillary pressure curve to the lower part of the water-oil transition zone. These generally show zero displacement pressure at only partial wetting-phase saturations. The countercurrent upward flow of oil into the main oil-saturated pay and downward drainage of water also suggests that wetting phase imbibition processes will control the saturation distribution immediately above the water-saturated section. Similar considerations, with a generalized interpretation of the apparent wetting-phase behavior of the oil and gas phases, provides a basis for constructing the curve for fluid distribution in the oil-gas transition zone. In the transition zones so derived, the oil begins with a nonvanishing saturation at the water-oil contact and terminates with a similar saturation at the top of the gas-oil contact. The gas-oil transition zone begins with an equivalent nonvanishing gas saturation. Introduction It has been a common assumption for some years that the nature of the fluid dis- tribution in virgin reservoirs, and in particular that in the transition zones between the oil and water and between the oil and gas sections, can be computed by a simple application of capillary pressure data. The results of such calculations appear to have been first reported by Leverett.' The latter, however, indicated only the numerical values of the parameters used in the computations, without explicitly describing the procedure. Leverett's illustrative calculated transition zones are reproduced in Fig I. Although no critical study of the apparently obvious method of calculation has been published, one cannot proceed very far in the computation without encountering some rather fundamental questions not yet answered in the literature. This paper is not written under the pretense that the whole transition-zone problem has been fully and satisfactorily solved. Its purpose, rather, is to discuss suggestions for its treatment, much of it admittedly hypothetical, and emphasize the nature of the uncertainties arising therein; for the literature, as now available, gives little indication that there are any problems still outstanding. The Transition-zone Equation The basic equation, which presumably gives directly the fluid distribution without recourse to any further consideration, is: Ap = (r1 - r2)gh [1] where r1, y2 are the densities of the two contiguous fluids, h is the height above the "capillary-free" zone of complete saturation with fluid I, g the acceleration of gravity, and Ap is the capillary pressure across the average interface at the height

Jan 1, 1949