Search Documents

By B. Russell, J. R. Tuffley

The stability regions of the normal sulfate and the various basic sulfates of lead in 02-SO2 and PhS-SO2 gas atmospheres were calculated from available thermodynamic data over the temperature range 600o to 1200oC. Roasting experiments were carried out on samples of synthetic lead sulfide at various temperatures and for various roasting times. Compounds in the oxidized surface layers were identified by X-my techniques. The order in which the various reactions occurred was determined by considering the experimental results in conjunction with the thermodynamic calculations. The results of these investigations were applied to the sintering of lead sulfide concentrates, and the extent to which each of the various reactions occurred in a sinter bed was determined. PRODUCTS which may be formed during the roasting of PbS are PbS04, PbSO4. PbO, PbSO4 . 2PbO, PbSO4 . 4PbO, PbO, and Pb.1, 2 The formation of some sulfates has been studied by a number of investigators3-' whose experiments have mostly been confined to the temperature range between 500" and 850°C. Culver, Gray, and spooner3 were able to isolate the reactions which formed PbSO4 and PbSO4. PbO by carefully controlling the compositions of the roasting gases. The kinetics of these reactions were studied within the temperature range 673" to 807°C. Gardner4 and Merrick5 also studied the kinetics of oxidation of PbS. Gardner disregarded the existence of basic sulfates and, as a result, misinterpreted some of his experimental data. Merrick recognized that most of the products of oxidation were mixtures of basic sulfates, but was unable to identify the individual components. Hoschek6 oxidized PbS in air at temperatures up to 800°C. The products were analyzed after roasting had proceeded for some minutes, but no attempt was made to follow the reactions in the initial stages. Consequently, no roasting mechanism was derived. He also showed that PbSO4 and PbSO4 - 4PbO decomposed slowly in air at temperatures in the region of 800°C. The stability regions of sulfates in the temperature range 500" to 850°C have been only partially determined, while practically no information is available for higher temperatures. In the lead sintering process, PbS concentrates are roasted at temperatures within the range 1000o to 1200°C. In order to investigate sulfate formation, it is necessary to determine the effects of temperature and gas composition upon the various oxidation reactions and upon the regions of stability of the various lead sulfates. Kellogg and Basu2 introduced an equilibrium diagram similar to those in Figs. 1 to 3 which provides a convenient medium for represent-

Jan 1, 1964

By D. J. Rose, W. M. Armstrong, A. C. D. Chaklader

The wetiability of single crystals of MgO by specimens of vacuum-cast iron was studied using the sessile drop technique in vacuo at 1550ºC. Formation of FeO at the liquid-vapor interface caused the contact angle (6) to decrease from 117 to 65 deg during the first minute. After cooling, all specimens possessed a peculiar annular interfacial deposit of Fe,O,. Within the annulus the interface showed no sign of chemical attack. Chemical reaction occurred where the iron was alloyed with Ti, V, Cr, Nb(Cb), Ta, cmd Zr. Vnriation of 6 with alloy concentration was studied. Although vanadium md chromium improved the wettability of MgO by iron, the effect of Zr, Ti, Nb, and Ta was indeterminable because the 8 derived from sessile drop considerations was that of the metal against a restrictive peripheral volume of liquid oxide wetting the substrate. INTEREST in the nature of metal-ceramic interactions has been stimulated by progressive development of metal-ceramic combinations. One of the more valuable methods used for bond investigation is the sessile drop technique. Recent attempts to improve wettability through solute additions to the drop have revealed that the solute may a) react with the oxide creating new compounds at the solid-liquid interface, b) adsorb at the interface in a monolayer formation, or c) distribute throughout the drop uniformly causing no wettability variation. This work, part m in a series1,2 of investigations of interface reactions between metals and ceramics, embraces a study of the Fe-MgO system. MgO possesses a large negative free energy of formation (-173 kcal per g mole 0, at 1550ºC) compared to FeO at this temperature (-73 kcal per g mole 02). Hence the electronegativity difference between the drop and substrate allows selection from an extensive group of metal solutes with intermediate electronegativity differences that would, in the absence of chemical reactions, be expected to adsorb pre- ferentially at the solid-liquid interface. However, the high oxygen pressure of MgO in vacuo creates an oxidation environment which influences the solute behavior. Recent studies of the Fe-MgO systemJ74 have been restricted by chemical reactions that obscured observations. In view of the current interest in liquid-phase sintering of metal-ceramic combinations under partial oxidizing conditions,5 a more comprehensive study of the Fe-MgO system seemed beneficial. EXPERIMENTAL PROCEDURE 1) Specimen Preparation. Optical-grade MgO single crystals and Ferrovac vacuum-cast iron were used in all experiments. A spectrographic analysis of the iron indicated 0.008 C, 0.05 V, 0.005 Mo, 0.01 Ti, 0.002 S, 0.01 Cr, 0.001 Mg, 0.01 Si, 0.003 A1 (wt pct). The MgO crystals were cleaved along (100) planes into plates approximately 20 by 20 by 1 mm. Following annealing in vactto at 1100°C for 3 hr, surface irregularities were removed by a chemical etch in phosphoric acid at 100°C. The iron rod was machined into small cylinders approximately 0.250 in. in diam and length and these were carefully cleaned in organic and acidic solutions to remove surface impurities. All specimens were weighed to the nearest 0.1 mg. 2) Apparatus. The apparatus described in detail by previous authors1,2 was modified for this work. A Polaroid Land Camera was incorporated into the optical system so that drop measurements at ten-second intervals after melting were possible with ultra-high-speed self-develop ing film. 3) Procedure. The iron cylinders were placed upright on the MgO plates and positioned in the molybdenum susceptor. After furnace assembly the system was pumped down to a vacuum of 1 µ and flushed with H2 at 800°C. The system was again evacuated to 5 x 10-5 mm of mercury and the temperature raised to 1550°C within 2 min. The molten drops were photographed at appropriate time intervals. TWO min after melting the iron vapor pressure caused gas discharge, or corona, within the tube. The specimens were then slowly cooled to room temperature, sectioned and examined metallographi-cally. X-ray identification of interfacial reaction products was attempted by the powder diffraction technique. Alloying elements (Ti, V, Cr, Zr, Ta, Nb) were added to the iron in various concentrations up

Jan 1, 1963

By G. R. Mansfield

THE third year of Government exploration f or potash by the U. S. Geological Survey and-the U. S. Bureau of Mines under the authorization of the act approved June 25, 1926 (Public 424-69th Cong.) is drawing to a close. The results thus far obtained are thought to be sufficiently interesting and satisfactory to justify the presentation of a brief preliminary account of the work. REVIEW OF EARLIER EXPLORATION The general geologic similarity of the Permian basin of Texas and New Mexico to the potash field of Germany had long ago suggested the possibility of the presence of potash salts somewhere in that basin, but petroleum exploration was then making little headway there and the necessary data could not be obtained. The discovery by Udden in 1912 of potash in brine from the Spur well in Dickens County, Texas, was the first direct evidence of its presence. In 1915-17 the U. S. Geological Survey drilled a test well with standard tools at Cliff side near Amarillo, but failed to find potash. Nevertheless, an observer has been kept in the field, at first in cooperation with the Texas Bureau of Economic Geology but since 1922 by the Survey alone, to `secure data and samples from oil and gas tests. Since the discovery of oil in Reagan County in 1923 exploration by drilling has been rapidly extended to many parts of western Texas and southeastern New Mexico. The identification of the potash-bearing mineral polyhalite was first announced by the Geological Survey in June, 1921, the material having come from cuttings from the Bryant well in Midland County and the Burns well in Dawson County, Texas. Successive discoveries and announcements of similar purport aroused widespread interest in potash exploration, which culminated in the action by Congress already noted.

Jan 1, 1929

By A. E. Blakeslee

Morphological and electrical properties of GaAs epitaxial layers are influenced not only by changes in the nominal substrate orientation but also by small amounts of misorientation from the exact crystal planes. Deviations up to 5 deg from {11IA}, {11IB}, and (100) planes were investigated. Growth rates increase progressively with angle, approximately I u per hr per deg. Size and density of growth pyramids fall off with increasing angle, but other effects that are deleterious to the surface may occur which are heightened by increased misorientation. Carrier concentration decreases and electron mobility consequently increases as the angular offset increases, except in the case of strong compensation, where the mobility trend is reversed. It has long been known that changes in the crystallo-graphic orientation of the substrate may cause pronounced effects on the morphological properties of vapor grown semiconductor films. Reports of orienta-tion-dependent growth rates and surface characteristics are as old as the literature on epitaxy itself. shawl has recently published a comprehensive study of the dependence of growth rate on substrate temperature and orientation in epitaxial GaAs. It is also well-known that misorienting the substrate surface a few degrees away from the nominal low-index crystal-lographic plane often produces a much smoother epitaxial surface. This was reported by Tung2 for silicon, Reisman and Berkenblit3 for germanium, and by Kontrimas and Blakeslee4 for GaAs, and use is commonly made of this fact in the semiconductor industry to help guarantee smooth vapor deposits. The effects of substrate orientation on the carrier concentration and mobility of vapor grown GaAs were first documented by williams5 in 1964 and have been observed by several other authors since then,6,7 but no one has yet reported a careful study of how small changes influence these properties. We have made such a study and have found that sizable differences in growth rate, morphology, carrier concentration, and mobility can indeed be observed for epitaxial films grown on substrates that are oriented by progressive small increments away from the exact crystal plane. EXPERIMENTAL Early in the investigation an arsine synthesis system of conventional design8 was employed to produce growths on {111A}-oriented GaAs substrate crystals. In that early work, pronounced effects on carrier concentration and electron mobility were observed as a function of slight misorientation from this low index plane. That observation led to the more careful study that is reported here. An AsC13 system, differing in major aspect from those commonly in use today9 only in that the reactor is vertical rather than horizontal, was used for the detailed study. The gallium source was at 900°C and the substrates were at 750°C. The flow rate of pal-ladium-diffused H2 through the AsCl3 bubbler was 200 cu cm per min, and the flow rate of bypass H2 was also 200 cu cm per min. The substrates consisted of chro-mium-doped semiinsulating GaAs to facilitate elec-trical evaluation of the overgrowth by means of Hall and conductivity measurements on conventional eight-legged Hall bridges. They were misoriented by 0 to 5 deg from the {111A}, {111B}, and (100) planes, toward the (100) from the {111A} and {111B} and randomly toward the <111A> or <111B> from the {loo). The crystals were oriented for sawing by the Laue back-re-flection technique, which is good only to about ±1/2 deg; but after polishing or sometimes after epitaxial growth the wafers were checked by a diffractometer technique which is accurate to about * 0.1 deg. After lapping, the wafers were polished with NaOCl after the technique of Reisman and Rohr,10 and just before use they were cleaned in NaOC1, thoroughly rinsed with de-ionized water, and blown dry with nitrogen. Each run employed four wafers, each misoriented by differing amounts from one of the three major faces, and at least two runs were made for each orientation. The runs were continued long enough to provide at least a 15-µ or thicker layer. SURFACE MORPHOLOGY The appearance of all the films that were grown in a given run always changed from wafer to wafer as a function of increasing misorientation, but not always in the same regular fashion. At least three different trends were observed. These are more easily seen than described, and reference to the series of photo-

Jan 1, 1970

D. F. HEWETT, Washington, D. C. (communication to the Secretary*).-I am not prepared to discuss the metallurgical use of manganese in the form of alloys. In connection with other work for the U. S. Geological Survey, however, I have been investigating incidentally, for about 5 years, the American as well as other sources of manganese. There are some conclusions that come out of this investigation that may interest those whose greatest interest lies in the use of the alloys. From a geological point of view, most manganese ore deposits may be regarded as concentrated masses of manganese oxides, as there are few masses of the other manganese minerals that are rich enough in manganese and low enough in silica to warrant smelting. The deposits of the Huelva district, in Spain, which are largely manganese carbonate and silicate, are exceptions to this statement. Some deposits of manganese oxides, such as those of Russia and Cuba, are bedded with ancient sediments, and although they are clearly concentrated under unique conditions, the source of the manganese cannot be determined. Probably 60 per cent. of the world&apos;s production of manganese ore, or 95 per cent., if that of Russia be excluded, is derived from the superficial parts of deposits that have undergone weathering and enrichment near the surface. In other words, the situation with the manganese ore supply is such as it would be with regard to copper, if instead of being derived largely from deep zones of deposits of deep-seated origin, such as veins, it were derived solely from the zone of secondary enrichment. Manganese oxide occurs in all rocks but is most abundant in igneous rocks, of which, according to Clarke, it forms an average of 0.10 per cent. It also forms 0.05 per cent, of the average limestone, but only traces are present in shales and sandstones. It is interesting that although many commercially important manganese deposits occur in rocks that are but slightly richer in manganese than the average, the most important deposits occur in rocks of unusual character that are much richer in manganese than the average. Thus, the most important deposits of India and Brazil overlie or occur near masses of rocks that contain excessive amounts of manganese garnet and pyroxene.

Jan 5, 1917

By Pierre R. Hines

These notes are based on observations made while on a recent trip through the West, for the purpose of studying the practical operation of the ball-mill. The writer takes this opportunity to express his thanks for courtesies extended at the many plants visited as well as for the valuable data received: While there are several types of ball-mill on the market, particular attention will here be given to the diaphragm type, as the open-trunnion type, especially the conical mill, has been thoroughly discussed in the Transactions. There is a prevailing impression that the ball-mill is a recent development; however, ball-mills were used extensively in Montana and other western states for crushing ores for concentration as far back as 1808. Its present prominence is due in part to its recent successful application by one of the large copper companies. Without any reference to dry grinding, the first successful ball-mill for wet crushing, which is still in operation, was built 10 years ago.l This mill, designed by Erminio Ferraris for crushing Sardinian ores for concentration, is of more than passing interest. It embodies the peripheral discharge with grates, large forged-steel balls, and the principal features of the modern ball-mill. The results approach present-day practice, the chief differences being that the mechanical construction has been improved in the modern types. Crushing Action of Ball-mill The action of the balls and the principles of crushing have been studied by several investigators.2 Their conclusions are confirmed by results obtained by the writer in experimenting with a small machine built at

Jan 1, 1918

By E. G. De Coriolis

The development of huge production facilities and of new or improved processes for manufacturing magnesium from its raw sources has been an outstanding achievement of this war. Furthermore, at least one new method has reached a stage of pilot production that offers promise. Its potentialities seem to indicate that a reduction in cost and simplification or elimination of problems incident to the use of at least one of the present processes are quite within the realm of possibility. Although magnesium of very high purity (99.9 per cent and higher) is obtained, and the rate of recovery reasonable (60 to 70 per cent). the ferrosilicon reduction process is open to a serious objection, which at the time its use was proposed was thought to be sufficient to raise some doubts as to its success, at least on a high production basis. The temperature range at which the reaction is carried out—namely, 2100" to 2150°F.—is very close to the failure temperature of the material of which the retort is made. It is so close that for a time it was assumed it might make commercial use of the process an impossibility. However, at the time under discussion, the demand for magnesium was so great that it was felt by those who had to go ahead and produce this essential metal that the emergency warranted their taking a chance on this process. Subsequent developments have fully justified the soundness of their decision. Fortunately for the war effort, when the plants were put into operation it was discovered that although the retorts did collapse in rather short periods of time, as predicted, they could be blown back into operable shape by application of high-pressure air. This practical method of operation so relieved the situation that the problem disappeared. Nevertheless, if the process had not been successful, or the production of magnesium by the electrolytic process had not been able to keep pace with demands, our war program would have been seriously impaired. Fireless Cooker&apos;&apos; Process For this reason a program was set up and assigned for the development of a new method that had been suggested to the War Production Board in 1941. It is believed justifiable in terming the method "new" for several reasons: (I) while utilizing the same (ferrosilicon) process as the Pidgeon, hence involving similar reactions, the type of retort or furnace is essentially different, (2) the method of operation, reaction temperatures, etc., differ materially, and, most important of all, (3) the problems to be overcome in making the process successful were not and could not have been anticipated by anything previously known about the Pidgcon process. As will be shown later, the briquetting process, the condenser, the furnace lining

Jan 1, 1949

By M. E. de Morton

Recovery and early recrystallization of heavily deformed, 99.98 pct Cr was investigated by studying metallographic structure. X-ray line sharpening, electrical resistivity, plastic properties, internal friction, and shear modulus. Appreciable recovery of resistivity, internal friction, and shear modulus together with some hardening and relief of internal strains occurred before the visible growth of a textured substructure above 350°C (recrystallization in situ). The complex behavior of shear modulus, internal friction, and its strain amplitude dependence during annealing are discussed qualitatively in terms of the relative mobility of dislocations. BY plastically deforming fully recrystallized 99.98 pct Cr above the brittle to ductile transition temperature, at -350°C. as in wire drawing, chromium can be made very ductile at room temperature. However, this ductility is lost on annealing at high temperatures when recrystallization takes place.&apos; The present investigation was made to determine the general pattern of the changes in a number of physical and mechanical properties during recovery and recrystallization of heavily deformed chromium as part of an effort to elucidate the reasons for lack of ductility in the fully recrystallized condition. PREPARATION OF MATERIAL Wire specimens 0.027 in. in diam were prepared from arc-melted, electrolytic chromium by extruding, hot swaging and finally wire drawing at 300" to 350°C, i.e. above the brittle-to-ductile transition temperature. The total reduction in area of the wire was 98 pct and the last 3 pct of reduction was made at 100" to 150°C before cooling to room temperature. The impurity content of the material is shown in Table I. Internal friction and modulus measurements were made on a single specimen after annealing in situ at successively higher temperatures. For all other measurements, a fresh specimen was used for each temperature and annealing of these specimens was done in evacuated (0.001 mm Hg) and sealed silica tubes for 1 hr at the various temperatures up to 700°C. EXPERIMENTAL METHODS AND RESULTS The occurrence of a. transition in some physical properties of chromium at - 40°C2 imposed limitations on the temperature region where some of the measurements could be made. The reason for this transition in chromium is at present unknown but is probably associated with an antiferromagnetic state observed below - 40°C.* Heavy deformation produces an anomalous decrease in resistivity when measured at temperatures below -40°C4 though a normal increase is observed above this temperature. On the other hand internal friction in heavily deformed chromium5 over the temperature range 40" to 50°C is invariant with temperature. Above and below this range internal friction is strongly temperature dependent, increasing with increasing temperature. A temperature in this range was therefore convenient for both resistivity and internal friction measurements and for consistency the measurements of the mechanical properties were also made at about this temperature. No structural change has, however, been observed in careful X-ray measurements6 between -195" and 50°C, i.e. departure from cubic symmetry was not greater than 3:10,000; X-ray line sharpening measurements were therefore more conveniently made at room temperature.

Jan 1, 1962

By E. G. De Coriolis

THE development of huge production facilities and of new or improved processes for manufacturing magnesium from its raw sources has been an outstanding achievement of this war. Furthermore, at least one new method has reached a stage of pilot production that offers promise. Its potentialities seem to indicate that a reduction in cost and simplification or elimination of problems incident to the use of at least one of the present processes are quite within the realm of possibility. Although magnesium of very high purity (99.9 per cent and higher) is obtained, and the rate of recovery reasonable (60 to 70 per cent), the ferrosilicon reduction process is open to a serious objection, which at the time its use was proposed was thought to be sufficient to raise some doubts as to its success, at least on a high production basis. The temperature range at which the reaction is carried out-namely, 2100° to 2150°F.-is very close to the failure temperature of the material of which the retort is made. It is so close that for a time it was assumed it might make commercial use of the process an impossibility. However, at the time under discussion, the demand for magnesium was so great that it was felt by those who had to go ahead and produce this essential metal that the emergency warranted their taking a chance on this process. Subsequent developments have fully justified the soundness of their decision. Fortunately for the war effort, when the plants were put into operation it was discovered that although the retorts did collapse in rather short periods of time, as predicted, they could be blown back into operable shape by application of high-pressure air. This practical method of operation so relieved the situation that the problem disappeared. Nevertheless, if the process had not been successful, or the production of magnesium by the electrolytic process had not been able to keep pace with demands, our war program would have been seriously impaired. "FIRELESS COOKER" PROCESS For this reason a program was set up and assigned for the development of a new method that had been suggested to the War Production Board in 1941. It is believed justifiable in terming the method "new" for several reasons: (1) while utilizing the same (ferrosilicon) process as the Pidgeon, hence involving similar reactions, the type of retort or furnace is essentially different, (2) the method of operation, reaction temperatures, etc., differ materially, and, most important of all, (3) the problems to be overcome in making the process successful were not and could not have been anticipated by anything previously known about the Pidgeon process. As will be shown later, the briquetting process, the condenser, the furnace lining

Jan 1, 1945

By John Chipman

HE lecture on &apos;Thermodynamic Properties of Blast Furnace Slagso prepared in 1959 and published two years later required revision in one particular before it appeared in print. The activity of SiO, was deter mined through studies of the equilibrium: SiO, (in slag) 2C (graphite) = (in Fe) 2C0 (1 atm) The ratio for each experimental temperature was found from the heat of formation of cris-tobalite, the entropies and heat capacities of the re-actants, by virtue of the third law of thermodynamics. Discrepancies between several kinds of data led to investigations regarding other equilibria involving SiO, on the suspicion that there might be an error in the third-law value of its free energy. In particular the equilibrium: was restudied by Kay and Taylor who Confirmed the earlier results of Baird and Tayloron which their SiO, activities depended. The free energy of Sic was also rechecked4 independently. These and other equilibrium measurements led to the conclusion6 that the free energy of SiO, at high temperatures is in error and requires a correction of about -5 kcal. The exact source of the error is uncertain; it could lie either in the entropy of SiO, or in its heat of formation, but it more probably lies in the latter. Adjustment of this free energy lowers the ratio by a factor of approximately 4. Accordingly it will be necessary to multiply by this factor all of the SiO, activities determined by this method.&apos;,B Referring to the lecture cited, this correction should be applied in Figs. 8, 9, 10, 19, and 20. It applies also to the experimental data of Fig. 13, bringing these as well as those on the ternary system into good agreement with the work of Taylor and associates. At the same time it eliminates the discrepancy shown in Fig. 11, lowering both lines until the upper

Jan 1, 1962

By Alfred V. de Forest

WE are now assembled in this hall for the eighteenth lecture in honor of the memory of our greatest American metallurgist, Henry Marion Howe. Many of his most intimate contemporaries, led, as was fitting, by Professor Sauveur, have described his vital accomplishments in three fields: as a leader in technical industrial development; in theoretical research; and finally as a teacher and source of inspiration for nearly two generations of students. In 1914 Professor Howe had retired from active teaching, but maintained his laboratory at Columbia University under the care of Arthur G. Levy, with whom he published many of the papers that later were incorporated into his last book, "The Metallography of Steel and Cast Iron." My position at the time was that of personal assistant to Professor Campbell-no pay, no duties, but the great privilege of preparing specimens, taking pictures and attending to some of the current consulting work. Whenever possible, I visited Howe&apos;s laboratory to chat with Levy and gather ideas about the wonderful field of metallography-in which I was a rank amateur, rescued by the quiet enthusiasm of Donald Smith of Princeton from an instructorship in civil engineering. Levy let me act as a fly on the wall during the Professor&apos;s occasional visits. Busy as he was, Professor Howe took the time and trouble to encourage my interest, as he had done for hundreds of others. He told me how he went about gathering his own information speculating as to causes, considering experiments, and verifying his conclusions. I ventured to mention some tests I had run on the irregular stretching of wires of different metals. He read the small volume I had prepared of ill-assorted facts and fancies and remarked: "Nobody cares for your theories or the history of your tests. Describe what you found as briefly as possible and perhaps I can help you to publish." Curiously enough, among my discards were some autographically recorded load-versus-electrical-resistance measurements. Taken with inadequate knowledge and equipment, these curves did not reproduce consistently, but if the relationship between strain and resistance had then been explored, the latest type of strain gauge might have been in useful service for the past 25 years. Professor Howe was a gifted teacher, perhaps because he was primarily an ardent and assiduous student. His own eagerness to learn and his willingness to revise and extend his opinions constantly encouraged those of his environment to be diligent and painstaking in the pursuit of knowledge. In honoring his memory, I also wish to bring to mind the kindly, humorous and quiet Levy, and join his name again, as it was for too brief a space in the past, with that of many-sided Henry Marion Howe. FACTORS OF IMPACT STRENGTH The subject chosen for the Howe Memorial Lecture by Dr. Gillett last year

Jan 1, 1941

By A. J. de Witte

INTRODUCTION The importance of determining dips of subsurface formations in wells, especially in wildcat wells, is self-evident and need not be enlarged upon. Various dipmeter instruments have been described in technical literature1,2,3,4 over the years. The introduction of the continuous dip-meters3,4 has made the earlier types obsolete. Continuous dipmeter logs are run by at least two different major service companies. Included as part of the service are a limited number of dip calculations—usually 10—made at different levels from the log. Very frequently this is the total result of a dip survey. It is believed that dipmeter surveys would be of considerably more advantage if geologists and engineers were able to make their own calculations from the original records. Determination of dips from the dipmeter record starts with the correlation of three log curves taken at different sides of the borehole. It cannot be over-emphasized that the quality of the results hinges primarily on this correlation. Nobody should be better qualified to correlate logs than a subsurface geologist or field engineer. The next requirement is to have an easy yet accurate way of computing the dip from the correlated points. Service companies use a mechanical device for this purpose. Directions for a graphical method were given in a recent article by B. 0. Prescotts. This paper describes a different graphical technique which, in our experience, is simpler, faster and at least as accurate. The entire manipulation is carried out on the stereonet in a number of easy moves. The paper is divided into two parts. This first part contains the introductory sections and full explanation of the geometry involved. The second part reviews the reading of data from an actual field log and summarizes the practical rules for computation of dips, the whole process being illustrated by an example. Following the outlined procedure, one could calculate a good many levels in a relatively short time, thus being able in particular to check suspected anomalies such as fault zones or unconformities in as close detail as the log will permit. GENERAL EXPOSITION OF THE METHOD Prnciple of the Dipmeter The position of a plane in space is defined by the location of three points, not on a straight line. Referring to Fig. I, if a borehole traverses a bedding plane, we can determine the strike and dip of the bed by finding three points which are not in line along this plane. Such points as A, B, and C are obtained with the dipmeter. The device consists of three electrodes (or caliper arms)1, 2, and 3 spaced at 120 angles, as schematically indicated, whose readings are separately recorded (Curves 1, 11, 111, to the right). When electrode 1 passes the boundary of the bed, Curve I will kick, etc. From these curves, we know the relative distances of points A, B, C, measured along the axis of the hole. If A is at zero, then B and C are at levels d1 and d2 up the hole,

Jan 1, 1957

By A. J. de Witte

It has been observed that upon invasion of a sand containing oil or gas and connate water by mud filtrate the hydrocarbons are more rapidly flushed by the filtrate than is the connate water.&apos; In time, it appears that the following displacement pattern emerges: oil (or gas) is being swept ahead by connate water which, in turn, is pushed by invading fluid. Eventually the connate water may have "banked up" sufficiently to form a zone of appreciable thickness leading the invading front. In the extreme case, Fig. 1 shows how the situation will develop.&apos; Immediately adjacent to the borehole (radius r) there is a zone, the invaded zone proper, where the connate water has been flushed out completely and which contains only residual oil or gas and mud filtrate. This zone (extending out to a radius ri) grades more or less abruptly into the next (thickness A), which contains only residual hydrocarbon and connate water. Beyond it, again more or less sharply bounded, extends the virgin formation with the original interstitial water saturation Sw. The various saturations are indicated in Fig. 1. The three zones generally will be marked by resistivity contrasts owing to their different fluid contents. As the connate water is usually more saline than the invading fluid, the second zone having a high connate water saturation forms a concentric cylindrical ring or annulus of low resistivity R, around the borehole.&apos;,&apos; It will be referred to as the "low zone." Fig. 1 shows schematically the resistivity profile. It is clear that the phenomenon of a low zone could not occur in invaded water sands. The presence of a low zone, therefore, would be a qualitative indication of a hydrocarbon-bearing formation. Granted that the phenomenon is real, if it were pronounced enough to be detected, one might thereby have a means of locating oil or gas in the ground. This is the aim of the "displacement logging" method.&apos; In any case, the presence of a low resistivity zone will affect the reading of electric logs. Using conventional log interpretation techniques, one must be aware of this and, if necessary, correct for it. Whether correction or detection should be the goal will depend primarily on the magnitude of the effect. The type of log which is likely to be affected most is the induction log. The current pattern of an induction log is concentric with the borehole. Any concentric ring of low resistivity, therefore, will tend to become crowded by current lines. This zone of maximum current density will obscure the relative contributions to the current conduction by other portions of a bed making, for instance, the contribution of the virgin formation less significant and thus detracting from the value or the induction log as an R, reading device. The present note is intended to ascertain the maximum possible effect of a low zone in the extreme case portrayed by Fig. 1 on three commercially available types of induction logs, sc., 5 FF 27, 5 FF 40 and 3 F 60. Type 5 FF 27 or 5 PF 40 is currently run in conjunction with a 16 in. normal and SP log. This combination is gradually replacing the regular electric survey (two normals and one lateral) as a standard log in many areas. On the basis of the scheme of Fig. 1 (sharp boundaries between successive zones), the thickness of the low zone may be computed for various amounts of infiltration measured by the ratio of invaded zone diameter to hole diameter D,/d. Referring to Fig. 1, we can set up a material balance for the water displaced from the invaded zone proper and the water present in the low zone. The volume of connate water displaced from invaded zone upon flushing by mud filtrate is: V1 = e p (r2 - r2) ? Sw . where c = bed thickness ? = porosity Su, = original connate water satu-ration. The volume of water finally accu-mulated in the low zone is: Vz = e p [(r1 -?)2 - r2 4] ? Sw . where SW1 = 1 — Sor = "water" saturation in the invaded and low zones both. The volume of water originally present in the low zone is:

Jan 1, 1958

By P. L. De Bruyn

The behavior of collectors at the mineral-solution interfaces is usually explained in terms of an ionic adsorption process. Through the distribution of collector ions between the solid surface and the co-existing solution phase the mineral is believed to acquire a water-repellent surface coating. Quantitative adsorption studies have been made on simple flotation systems only within the last few years. Such investigations were made possible by the adoption of the radiotracer method of analysis. As a consequence of these studies a new parameter has been added to aid the understanding of the flotation process.

Jan 3, 1955

By P. L. De Bruyn

The adsorption density of dodecylammonium ions at the quartz-solution interface has been Theadsorptiondensitydetermined as a function of collector concentration and pH. A ten thoushasbeenandfold range of amine salt concentration was covered at neutral pH. Experimental results show that over a thousandfold concentration range at neutral pH, the adsorption density (I) is proportional to the square root of collector concentration. Except at high concentrations, I increases with increases with increasing pH, but in general this effect is surprisingly small. . , . . A critical pH curve has been established for the flotation of quartz with dodecylammonium acetate. The conditions along the flotation curve are correlated with the adsorption measurements. THE behavior of collectors at the mineral-solution interfaces is usually explained in terms of an ionic adsorption process. Through the distribution of collector ions between the solid surface and the- co-existing solution phase the mineral is believed to acquire a water-repellent surface coating. Quantitative adsorption studies have been made on simple flotation systems1-4 only within the last few years. Such investigations were made possible by the adoption of the radiotracer method of analysis. As a consequence of these studies a new parameter has been added to aid the understanding of the flotation process. The research investigation to be discussed in this paper was undertaken to obtain a better understanding of the behavior of a cationic-type collector. This objective was approached through the determination of the distribution of dodecylammonium acetate between the quartz-solution interface and the solution as a function of the collector salt concentration and pH. To bring this investigation to focus on the more practical aspect of flotation research, an attempt was also made to correlate the adsorption results with actual flotation tests. Quartz: A —100 mesh ground crystalline quartz was infrasized; the products of the third and fourth cones were mixed together and reserved for experimental purposes. This stock material was cleaned by leaching in boiling concentrated HC1. After leaching the quartz was rinsed with distilled water until the filtrate showed no trace of chloride ian. It was then washed several times and dried. The qwrtz had a specific surface of 1400 cma per g as deterhined by the krypton gas adsorption method. Collector: The distribution of dodecylammonium acetate between the quartz surface and the solution phase was determined by the radiotracer method of analysis with carbon 14 as the tracer element. The radioactive amine salt with C" synthesized into the hydrocarbon chain5 was supplied by Armour and Co. The tracer element was located adjacent to the polar group. The radioactive salt as received had a specific activity of about 0.14 mc per g. When desired, dilution of this activity was effected by addition of non-radioactive dodecylammonium acetate also supplied by Armour and Co. ........ All other inorganic reagents used in this research were of reagent grade. Conductivity water was used for making up all solutions. Adsorption Tests: Two different experimental methods were used. In the first, to be designated as the agitation method, a weighed amount of quartz and a measured volume of amine salt solution were agitated in a 100-ml or 50-ml glass-stoppered pyrex graduated cylinder. The cylinder was filled with solution up to the stopper, since erratic results were obtained when an air space was left over the suspension. Time of agitation varied from 1 to 2 hr. Preliminary tests at different agitation times showed that the amount adsorbed remained constant for all agitation times exceeding 1/2 hr. After this conditioning period, the solids were separated from the solution by filtration through a Buechner fritted-disk funnel. The solution was re-circulated 10 times or more to allow the fused silica disk to come to equilibrium with it. Determinations of the amount of amine adsorbed on the frit itself indicated that this amount was less than 10 pct by weight of the amine acetate abstracted by 10 g of quartz. The funnel with quartz covered by a thin layer of solution was then centrifuged for approximately 5 min, at which time the moisture content of the solids was reduced to about 5 pct by weight. The wet quartz was blown into a tared beaker, re-weighed and allowed to dry at room temperature. A final weighing was then made to determine the moisture content. The second experimental method, similar to the procedure adopted by Gaudinand Bloecher,&apos; will be referred to as the column method. Two liters of solution were passed through a bed of quartz contained in a Buechner funnel attached to a pyrex separatory funnel by means of a ball and socket joint. Preliminary tests showed that increasing the volume of solution above 2 liters does not give a measurable increase in adsorption. From 4 to 4 1/2 hr were required for 2 liters of solution to pass through the column. The moisture content of the quartz was again reduced to a minimum by centrifuging. A slightly modified column apparatus was used for experimenting with alkaline amine solutions. The same basic unit was used, but the underflow from the Buechner funnel was again fed into a Separafory

Jan 1, 1956

By Margaret G. Scroger, Luke L. Y. Chang, Bert Phillips

Using the sealed-system technique, isothermal sections at 1000°, 1400°, and 1700°C for the system Co-W-O hare been determined. The equilibrium data were obtained by microscopic and X-ray diffraction examination of samples winch had been equilibrated in pellet form fit sealed capsules and subsequcelly quenched. The only ternary phase in the system is CoWO, which mells congruentlly at approximately 1280°C. At 1000°C, this ternary phase exists in equilihrinm with all the allows and oxide compounds in the hounding binary systems. At 1400°C, liquid forms in thin oxygen-rick region near the CoWO4 composition and only one phase assemblage in the system (W + WO2 + H&apos;5CV7) contains no In order for tungsten to be used to its full potential as a refractory metal. it is necessary that coatings be developed which will preclude oxidation of the metal. It is true that coatings now in use do protect tungsten for short periods at temperatures near 1700 °C. but no coating has been developed which protects adequately at or above this temperature where the use of tungsten is most required. This situation exists despite the great effort in recent years to develop such coatings. and it has become evident that success in this area can be achieved only after a more fundamental knowledge of the thermochemical and therrnophysical propertics of tungsten oxidation and tungsten -metal oxidation is obtained. In our 1aboratories. a project liclrriel. At 1700°C, tungsten is the ouly solid phase which is stctble, and a large range of compositions melt to two liquids, one metallic and one oxidie. The sealed-system method of etjuilibra lion prevents the determination of the partial pressure of oxygen and the total gas pressure orer the condensed phases at equilibrium. This data is not available and can be obtained only by some other method. We can generalize on these unknowns and indicate that both partial pressure of oxygen and total pressure of the gas phase must increase as compositions change from the W-Co binary toward the oxygen apex and as temperatures increase. has been initiated which is directed at providing some of this fundamental information through a study of metal-tungsten-oxygen reactions and equilibria and the properties of any intermediate phases which result. This paper is based on a part of this program in which the system Co-W-O was studied between 1000° and 1700°C. I) RELEVANT INFORMATION FROM THE LITERATURE A) The Notable Lack of High-Temperature Work on Metal-Tungsten-Oxygen Systems. It should be pointed out that there has been no published report (of which we are aware) which deals with the study of a metal-metal-oxygen system at 1700°C. Also, there has been no report on a complete metal-luugsten-oxgen system at any temperature. As a matter of fact. before this program started. The

Jan 1, 1965

Abramovits, Charles, Student. Case School of Applied Science Cleveland, Ohio. &apos;37 Adams, Benjamin C., Jr Address Wanted. &apos;36 Adams, Ernest C., Student, Univ. of Illinois 908 W. Green St., Urbana, Ill. &apos;35 Adams, George H. 4021 Walnut St., Riverside, Calif. &apos;36 Afshar, Hodji Khan ?A. Box 2072, Norman, Okla. &apos;35 Ahlen, Louis S., Student, Univ. of North Dakota Univ. Sta., Grand Forks, N. D. &apos;37 Ahrenholz, Herman William, Jr., Student, Lehigh Univ Bethlehem, Pa. &apos;35 Alger, Robert P., Student, Missouri School of Mines & Met Rolla, Mo. &apos;36 Alkire, Robert L., Student, Univ. of Pittsburgh Pittsburgh, Pa. &apos;37 Alleman, Virgil C., Student, South Dakota School of Mines Rapid City, S.-D. &apos;37 Allen, C. G., Student, Case School of Applied Science Cleveland, Ohio. &apos;37 Allen, Eugene S., Student, Univ. of California Berkeley, Calif. &apos;37 Allen, George W., Student, Michigan College of Min. & Tech Houghton, Mich. &apos;37 Allen, Harry Berkley, Student, Univ. of California Los Angeles, Calif. &apos;37 Allen, Henry, Jr., Student. Univ. of Arizona Sigma Chi House, Tucson. Ariz. &apos;37 Allen, Paul W., Student, Mass. Inst. of Tech Cambridge, Mass. &apos;35 Allen. R. M.. Jr.. Student. Virginia Polytechnic Inst., "G" Co Blacksburg, Va. &apos;35

Jan 1, 1937

By J. D. Edwards

When Charles Martin Hall invented the electrolytic process for the production of aluminum, one basic requirement was a supply of pure alumina. Now, more than 50 years later, the same requirement still holds, and there are no technical straws in the wind to indicate that this situation is likely to change. Long ago, Aluminum Company of America took a number of steps to see that this country should not face shortages of alumina and aluminum in time of emergency. As one step to this end, the Company developed and used a supply of bauxite in South America in order to conserve dwindling Arkansas reserves. Another, and more a program than a step, was to investigate every type of process that might bear the possibility of utilizing the low-grade ores of aluminum that are more plentiful than bauxite. It is a long story, but the investigation included electric-furnace processes, acid extraction processes and alkaline extraction processes, with or without preliminary furnace and sinter treatments. Some of the processes developed were operated in commercial production. This work has been continuous since the first World War. The turn of the wheel came sooner than was expected when, in 1942, bauxite shipmerits through the caribbean became uncertain and hazardous through the operation of submarines. The tremendous requirements of aluminum for the war effort were consuming high-grade bauxite at an alarming rate and a national search for substitutes began. High-grade bauxites, for technical and economic reasons, have been defined as those containing about 7 per cent or less of silica. While bauxite of this grade was limited in amount in the United States, there was in sight a substantially greater volume of low-grade, high-silica bauxite not amenable to economic treatment by the Bayer process, but richer in alumina than the clays or other available low-grade ores. It was at this point, and after several years of intensive research on this particular phase of the problem, that Aluminum Research Laboratories brought to completion the invention of one of its research staff, which made practical the utilization of large reserves of low-grade bauxite in America. Bayer Process The Bayer process has been almost universally used for the production of alumina from bauxite. This process, in outline, comprises the digestion of hely ground bauxite in a solution of caustic soda (NaOH) under pressure and at an elevated temperature. Alumina in the bauxite goes into solution as sodium alumi-"ate and the impurities—oxides of iron, titanium and silicon—remain undissolved. The undissolved residue, known as "red mud,&apos;&apos; from its color, is separated and run to waste. AluKlinum hydrate (A12O3.3H2O) is precipitated from the solution of sodium aluminate, and the liquor containing the caustic soda and some alumina is returned to the Process for digesting more bauxite. The aluminum hydrate, after washing, is calcined at a high temperature to produce

Jan 1, 1949

By Frederik W. de Klerk

INTRODUCTION During the past 40 years, there has been in the United States of America and other industrialised Western countries a distinct displacement in the procurement of minerals from domestic sources towards an increased dependence on imported minerals. This was caused in part by one or each of the following: a lack of local supply of particular minerals, domestic source depletion or exhaustion and the relative ease and inexpensiveness of obtaining minerals from comparatively unexploited sources in underdeveloped and some developing countries, notably in the Middle East, South America, Southern Africa, and Australasia. Governments of the industrialised nations, concerned about the reliance of their economies on imported raw minerals examined both the degree of reliability and the extent of mineral resources in the countries and regions supplying the essential minerals. This brought a painful awareness of the vulnerability of industrialised countries as a result of the possible interruption of their mineral imports. In this regard, the United States of America may be quoted as a case in point: a report by a House of Representatives Subcommittee on Mines and Mining (Santini Subcommittee)1 revealed that the United States in 1980 was dependent on foreign sources for more than 50 per cent for 24 of the 32 minerals essential for national survival. The Subcommittee also acknowledged that although the United States may develop its own alternative energy sources, there are in many cases no substitutes for the strategic + minerals imported from foreign sources, from countries which are often unstable at best, hostile at worst. This resulted in various policy responses as well as contingency measures, amongst other, renewed emphasis on the utilisation of domestic mineral resources, an intensified search for substitutes of critical minerals and increased stockpiling programmes. Increased attention was devoted to analyses of the political and economic conditions prevailing in the regions from which strategic and other minerals are exported to the industrialised countries, and the formulation of policy measures vis-a-vis those regions. One region which attracted a considerable degree of attention has been Southern Africa, and in particular South Africa.2 The Santini Subcommittee affirmed that while the bulk of the minerals imported by the United States is supplied by a number of source countries, a host of critical[t] minerals vital to the well-being of that country (and this includes all the Western industrialised countries) originates from Southern Africa, a region, deservedly referred to as the "Persian Gulf of Minerals". Apart from the Republic of South Africa the mineral-rich countries concerned are Angola (diamonds, iron ore, oil), Botswana (diamonds, coal), South West Africa/Namibia (diamonds, uranium), Zambia (copper, cobalt), Zaire (industrial diamonds, copper, cobalt) and Zimbabwe (gold, nickel, chromium, asbestos). The Subcommittee however noted that, with the exception of cobalt, the greatest portion of the reserves of the critical minerals listed, lies within the borders of South Africa. SOUTH AFRICA A RELIABLE PURVEYOR OF MINERALS In view of the continual instability and political risk, along with the nationalisation of mineral industries in third world countries, importing industrialised nations have in recent years become more and more concerned about security of long-term supply, and have in consequence begun to diversify their mineral enquiries to areas where the following conditions prevail: • Long-standing record of consistency of supply; • An economic system of private enterprise; • Political stability; • A well integrated infrastructure, with a maintenance of transportation and development costs at realistic levels, and • Attractive investment opportunities, with security of the return of profits.

Jan 1, 1982

By John Griffen

K. F. Tromp (Kerkrade, Holland)—Your assumption that the Dutch State Mines have lead in the development of heavy medium processes—the Barvoys, Loess, Driessen—is not correct. The credit should be given to a Dutch engineer Mr. deVooys, the inventor of the Barvoys process. deVooys started in 1932 in Hiickelhoven, a German but Dutch-owned mine, where he was a director. Several plants on the Continent as well as in Great Britain were erected. The State Mines started their first plant in 1937. They could not get that plant working satisfactorily and built another one. Their process made no headway, and up to 1946 there was only one plant installed, the one at their own pit. Since 1946 they started the cyclone process and only since that time have they been more active, though industrial cyclone washeries are still in their infancy. deVooys sold his patents to the Dutch State Mines in 1946 and this might have given you the impression that the pioneer work had been done by the Dutch State Mines. John Griffen (author&apos;s reply)—I wish to thank Mr. Tromp for giving the correct story on the development of heavy medium processes in Holland.

Jan 1, 1952