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By Samuel L. Hoyt

THIS paper gives a short account of plastic deformation as observed in single crystals of zinc, zinc having been selected for the experiments described herein because the phenomena are comparatively so simple and can be studied throughout such a wide range. It is hoped that the paper will serve to show the type of information which studies of single crystals afford and will contribute toward the solution of the general problem of metallic behavior. PRODUCTION OF ZINC SINGLE CRYSTALS The method of Czochralski,1 as modified by von Gomperz,2 was used to produce the crystals studied. The equipment is shown in Fig. 1. Molten zinc is held in a crucible at a temperature which is not far above its melting point, as measured by a pyrometer. A lava disk floats on ,the melt, and is provided with a central hole about 1 mm. in diameter. A glass tube, drawn into a capillary at the lower end, is suspended from a string which is wound up by an electric drive at the speed desired. At the start, the glass capillary is let down into the melt and the hoist is started.. The capillary brings up a small quantity of molten metal with it to a point just above the lava disk. At this point, a jet of hydrogen cools it and causes it to crystallize, with the result that a small crystal forms. As the hoisting is continued, more molten metal is drawn up, in turn to be solidified by the jet of hydrogen. This additional metal continues the growth of the crystal already formed, and a long, cylindrical crystal results. The speed of hoisting used was generally between 0.1 and 0.5 mm. per sec., and the crystals were from 4 to 6 in. long and about 1 mm. in diameter. By varying the conditions, crystals of quite different orientations were obtained and were used in the study of the phenomena to be described.

Jan 1, 1927

By Henry Lloyd Smyth, J. Ralph Finlay

The most important area of the so-called Keewatin rocks of northern Minnesota is that which runs westerly from Lake Saganaga, near the national boundary, and finally disappears beneath the drift (or has not been farther traced), in the neighborhood of Vermilion Lake. With this belt we have a general acquaintance, extending back some four years. During the past year we have had the opportunity of studying in considerable detail a small part of it, embracing an area of about 12 square miles on the south and east shores of Vermilion Lake. In this paper we desire to record our observations and conclusions, which seem to us important. II.—Literature. Outside the Minnesota Geological Survey, the list of the investigators who have studied the geology of the Vermilion Lake area is not long. Whittlesey, in 1876,* mentioned the occurrence, in the area about Vermilion Lake, of rocks resembling the Canadian Laurentian. Chester,? in 1884, described the iron-ore at Vermilion Lake as occurring in connection with jasper and quartzite, intimately bedded with the country-rock, chiefly sericite schist, and standing in a nearly vertical attitude. The Vermilion iron-bearing rocks, and those of the Mesabi range, he says, are of the same age.

Jan 1, 1896

By Hermann Wedding

It is now fourteen years since we German ironmasters, in considerable number, visited the United States on the occasion of the Philadelphia Exposition, and found the iron metallurgy of this country, as must be frankly confessed, in an advanced stage of development not previously suspected by us. At that time the United States already occupied, as now, the second rank, with Germany in the third, the product of pig-iron for that year being, in Great Britain, 6550, in this country, 2093, and in Germany, 1850 kilotons.* This relative position has not been changed. The present annual product of the three countries is, in round numbers, Great Britain, 8380, the United States, 7790, and Germany, 4530 kilotons. But the proportion of the United States, which was, in 1876, but 15 per cent. of the world's product, has now advanced to 30 per cent. When we left America in 1876, it was not only with gratitude for cordial hospitality and for the liberality with which our professional colleagues here had opened to our inspection whatever was worthy of notice in our special field, but also with the conviction that we had collected a great treasure of new and interesting information which we could utilize for the benefit of our German Fatherland. Particularly the achievements of the never-to-be-forgotten Holley in the field of Bessemer practice, set us an inspiring example for imitation in our own country. As an expression of our thanks in more practical fashion, I attempt in this paper to sketch what we have done in Germany since

Jan 1, 1891

By G. C. McCartney, S. J. Kidder

The Helen Mine, of the Algoma Steel Corporation, in the Michipicoten district, Ontario, Canada, has produced more than 6,240,290 tons of iron ore. Prior to and during World War I, 2,823,369 gross tons of brown ore were shipped, and from 1939 to the end of the 1944 season, 3,416,921 gross tons of siderite ore were produced from open-pit operations. Brief descriptions are given of the nature of the ore, the mining methods employed and the manner of treatment of the ore. Shipment of the finished product, known as Algoma sinter, is made to blast furnaces in both Canada and the United States. The iron-ore bodies—i.e., the oxide ores of the Old Helen and the siderite of the New Helen—are a part of a tabular shaped area of iron formation that extends over a length of more than 100,000 ft. and has a maximum width of 1000 ft. The ores are considered to be a product of introduction of iron-bearing material accompanied by replacement of the rocks already present. It is shown that introduction took place subsequent to the development of the major folded structures. It is believed the iron-bearing material emanated from an igneous source. Introduction The Michipicoten mining district derives its name from the Indian word1 meaning "place of bold promontories" or "region of big places," and anyone who has visited this part of Canada will agree that the district is well named. In 1897, there was active prospecting for gold in the district and the Ontario Bureau of Mines2 opened a recording office at the Hudson's Bay post at Michipicoten River. In the summer of 1897, Ben Boyer, probably searching for gold, discovered an outcrop of brown iron ore at the east end of a small lake, less than 8 miles, in an air line, northeast of the nearest point on Michipicoten Harbour. In the following year, extensive surface exploration and diamond drilling disclosed a commercial body of nonbessemer brown ore, possibly 700 ft. long and 200 ft. wide, of about the following analysis:3 Fe (natural), 57.15 per cent; S, dried at 212°F.. 0.113; SiO2, dried at 212°F., 4.00; P, dried at 212°F., 0.125. The property (Figs. 1-3) was taken over by E. V. Clergue and ultimately was transferred to the Algoma Steel Corporation. The Algoma Central Railway shortly afterward built its line from Michipicoten Harbour to the mine, together with an ore dock at the Harbour. Thus, within three years of its discovery, the mine had adequate shipping facilities and a market for its ore. Production of Brown Ore and Pyrite The first shipment of brown ore was made in July 1930. By 1939, the mine was shipping at the rate of 170,000 long tons

Jan 1, 1949

By S. J. Kidder, G. C. McCartney

The Helen Mine, of the Algoma Steel Corporation, in the Michipicoten district, Ontario, Canada, has produced more than 6,240,290 tons of iron ore. Prior to and during World War I, 2,823,369 gross tons of brown ore were shipped, and from 1939 to the end of the 1944 season, 3,416,921 gross tons of siderite ore were produced from open-pit operations. Brief descriptions are given of the nature of the ore, the mining methods employed and the manner of treatment of the ore. Shipment of the finished product, known as Algoma sinter, is made to blast furnaces in both Canada and the United States. The iron-ore bodies—i.e., the oxide ores of the Old Helen and the siderite of the New Helen—are a part of a tabular shaped area of iron formation that extends over a length of more than 100,000 ft. and has a maximum width of 1000 ft. The ores are considered to be a product of introduction of iron-bearing material accompanied by replacement of the rocks already present. It is shown that introduction took place subsequent to the development of the major folded structures. It is believed the iron-bearing material emanated from an igneous source. Introduction The Michipicoten mining district derives its name from the Indian word1 meaning "place of bold promontories" or "region of big places," and anyone who has visited this part of Canada will agree that the district is well named. In 1897, there was active prospecting for gold in the district and the Ontario Bureau of Mines2 opened a recording office at the Hudson's Bay post at Michipicoten River. In the summer of 1897, Ben Boyer, probably searching for gold, discovered an outcrop of brown iron ore at the east end of a small lake, less than 8 miles, in an air line, northeast of the nearest point on Michipicoten Harbour. In the following year, extensive surface exploration and diamond drilling disclosed a commercial body of nonbessemer brown ore, possibly 700 ft. long and 200 ft. wide, of about the following analysis:3 Fe (natural), 57.15 per cent; S, dried at 212°F.. 0.113; SiO2, dried at 212°F., 4.00; P, dried at 212°F., 0.125. The property (Figs. 1-3) was taken over by E. V. Clergue and ultimately was transferred to the Algoma Steel Corporation. The Algoma Central Railway shortly afterward built its line from Michipicoten Harbour to the mine, together with an ore dock at the Harbour. Thus, within three years of its discovery, the mine had adequate shipping facilities and a market for its ore. Production of Brown Ore and Pyrite The first shipment of brown ore was made in July 1930. By 1939, the mine was shipping at the rate of 170,000 long tons

Jan 1, 1949

By P. G. Shewman, T. L. Wilson

Using published surface-diffusion (D,) data and published sintering equations, it is shouln that surface difusion should dominate the neck-growth stage of intering for all materials in which D, has been measured (six metals and A1as). Also, grain boundary diffusion can be expected to contribute appreciably to shrinkage and possibly to neck growth below some critical temperature of the order of 70 pct 01- the absolute melting temperatuve. In view of the widespread conclusion in previous sintering work that volume diffusion dowzinates neck gvowth, experiments were conducted using spherical copper powders to test this conclusion. Scaling studies on neck growth at 950°and 1020°C clearly demonstrated that suyface diffusion dorninates. Kinetic studies on shrinkage gave more equivocal results that indicated an increasing role of' grain boundary transport at lower temperatures. Five diarszeters from 100 to 300 u were used in the scaling sludy and a temperature range of -650' 10 950 C was covered in the shrinkage studies. All experiments were conducted in dvy hydrogen. In 1949, Kuczynski published his now classic paper on the determination of the transport mechanism in sintering from the time laws of neck growth. In the interim, these laws have been applied to many systems and slightly modified by several authors. Essentially all these authors concluded that, for crystal- line materials, the dominant transport mechanism in neck growth is volume diffusion. This stems from the observation that the neck radius increases about as t"5 and that the activation energy approximates that for lattice diffusion. A related but independent series of studies stems from Mullins' rigorous analysis of the growth of the groove formed where a grain boundary meets a free surface." xperimental work stemming from this analysis has shown that for each crystalline material studied (Au, Ag, Cu, Ni, Fe, Pt, Al2O3) surface diffusion was clearly the dominant transport mechanism for groove widths up to the order 10 to 20 p. The ratio of the quantity of material being carried by lattice diffusion to that carried by surface diffusion increases linearly with the groove width, so surface diffusion is dominant for all widths under 10 to 20 u. The analysis of the relative contributions of surface and volume diffusion to grain boundary grooving, and to neck growth in sintering, shows that they are quite similar. Thus, using the available surface-diffusion data and the approximate equations of Kuczynski, or the more rigorous recent equations of Nichols and Mullins, 3 it can be shown that the small necks between particles must grow almost entirely by surface diffusion. The purpose of this study was to re-examine the basis for the conclusion that the neck-growth stage of sintering proceeds by volume diffusion. Using spherical copper powders, of several different diameters, precise experimental measurements were made of both neck growth and shrinkage. Application of Herring's scaling laws to the neck-growth data clearly indicated that neck growth occurred by surface transport, even though the neck radius increased as or Using the recent analysis of Mullins and Nichols as well as published data on surface diffusion, it is shown that the observed time law, as well as actual rate of neck growth, can be satisfactorily explained by a surface-diffusion mechanism.

Jan 1, 1967

By Richard O. Carlson

Ions of p31 and B 11 were implanted in natural insulating diamond macles. The thin (-0.4µ) layers showed sheet resistances of 107 to 1011 ohm per sq and activation energies of 0.17 to 0.34 ev above room temperature. However, no Hall effect could be measured, indicating that mobilities were less than I to 10 sq cm per (v-sec). Such low mobilities may be due to excessive scattering due to radiation damage in the bombarded layer or to very high concentrations of active compensating impurities. Annealing did not materially change the room -temperature properties, but the temperature was limited to -800°C by surface graphitization, the latter process probably being accelerated by lattice damage in our diamonds arising from the ion bombardment. A weak n-type thermoelectric power was detected after p31 irradiation, but it cannot be presumed that we have made the phosphorus ions active as donors in diamond. The natural diamonds have a high and uncontrolled concentration of impurities and, when coupled with the radiation damage and graphitization problems, would appear to seriously limit the quality of semiconductor that we can presently achieve by ion implantation in diamond. ALTHOUGH diamonds are usually thought of as insulating in terms of their electrical conductivity, it was found about 15 years ago that natural semiconducting diamonds do occur rarely, and these were designated as type IIb diamonds. These p-type semiconducting diamonds were found to be dominated by an impurity level 0.37 ev from the valence band. Evidence today based on correlation of the concentration of acceptor states from Hall effect measurements with the impurity concentrations determined by neutron activation analysis point to aluminum as the dominant acceptor impurity.' The compensating donor is believed to be nitrogen, which has a donor level 1.6 ev above the valence band.' However, only a small fraction of the total nitrogen content in the diamond is electrically active. An infrared absorption band at 7.8 p and ultraviolet absorption near 4 ev have been associated with nitrogen, the former providing a quantitative measure of nitrogen content.3 The nitrogen content is -l020 cm-3 in insulating or type I diamonds, but is less than 10'' in natural semiconducting diamonds. Much of this nitrogen is distributed in platelets oriented in (100) planes and not atomically dispersed in the diamond lattice.4 Semiconducting diamonds have been deliberately formed by incorporating impurities into the graphite charge in the high-pressure apparatus used to form diamonds.5 These manufactured semiconducting diamonds are always p-type, and while some show the 0.37 ev level due to aluminum, most such samples have been ascribed to impurity banding effects.6 The best natural or manufactured semiconducting diamonds have hole mobilities near 1500 sq cm per (v-sec) at room temperature, and those with the 0.37-ev level can be analyzed to reveal an acceptor concentration of 3 to 8 X 1016 cm-3 and a donor concentration 3 to 10 times lower.' NO bulk n-type diamonds have ever been reported, but the electron mobility has been measured as 1900 sq cm per (v-sec) by irradiating a diamond with ultraviolet to excite electrons out of the deep nitrogen donor level or other levels.7 New hope for the formation of n-type diamond has emerged from the ion-implantation method whereby desired impurities are introduced into a crystal lattice by bombardment with a high-energy beam of the impurity ion. It was found in the case of silicon that the usual donors such as phosphorus and arsenic and acceptors such as boron and gallium could be implanted into silicon. Wentorf and arrow' produced semiconducting layers on diamonds by an ionic bombardment in a glow discharge at potentials of about 2 kv. The observed typeness from thermoelectric probing seemed to depend on the atmosphere gas (nitrogen, argon, or hydrogen) rather than on the electrode material, but the nature of the conduction process in the thin damaged surface layer is completely unknown. A Russian group under Vavilov has attempted high-energy ion implantation in natural diamonds using boron and lithium ions9 and later also phosphorus, aluminum, and carbon ions.10 Their papers claim n-type layers from lithium, phosphorus, and carbon implant and a p-type layer from boron and aluminum implant, though the methods of type determination are not described in detail. Under government contract support, the Ion Physics Corp. has studied ion implantation in several semiconductors. While the bulk of their study1' was devoted to the irradiation of silicon, they did carry out a short study on boron and phosphorus implantation into natural diamonds. They did observe surface conducting layers but did not determine the typeness of the layers. For our experiments, phosphorus and boron were chosen as the dopant ions because of their respective donor and acceptor behavior in germanium and silicon. Moreover, they are the lightest mass dopants of the shallow level donors and acceptors from columns 111 and V of the Periodic Table (excluding nitrogen which is already present in diamond), and will have the largest depth penetration into the diamond lattice. EXPERIMENTAL Diamonds. As the target diamonds for our ion implantation study, we chose commercially available macles, which are flat, twinned diamond crystals. By scanning through the stock of a wholesale distributor

Jan 1, 1970

By Carl Lee

CHICAGO in the last week of June fulfilled all its promises to the visiting engineers except one. This holds true with respect to the activities of the Regional Meeting of the A. I. M. E. in particular and of Engineers' Week in general. No one expected to find much of the beautiful in the outward aspects of the Fair-the Century of Progress Exposition, to be more formal; but they expected novelty, color, and startling lighting effects at night, and they were in no sense disappointed. It has been said that the architecture is a portent of the style of the buildings of the future; most who have seen the Fair hope that this forecast will prove inaccurate. As to the exhibits themselves, they are splendid. They are in keeping with the theme of the Exposition-a Century of Progress in science, in engineering, in the industries based upon them. No attempt will be made here even to suggest the exhibits that are most interesting. There are plenty for every one; and any member of the Institute who has the opportunity should by all means visit Chicago before the end of October.

Jan 1, 1933

By J. A. Brierley, Roshan B. Bhappu, D. H. Reynolds, P. H. Johnson

Although the economic importance of recovering copper by leaching of mine work dumps from open-pit operations has been realized for some time, serious attempts to understand and to improve such operations through scientifi research has been made only in recent years. This progress report covers the results of chemical, physical, and biological studies pertaining to the dump-leaching process and discusses salient features and parameters that may be helpful in improving such operations. The dump leaching of low-grade copper ores, as an integral part of the open-pit mining operations in the Southwest, has been practiced for the last 50 years and is increasing in importance as one of the major sources of copper. The recent acceleration in dump leaching can be attributed to: (1) the greater tonnages of low-grade ores mined and dumped at newer mines as well as resulting from increased stripping ratios at the older mines, (2) the relatively small investment required for dump leaching facilities per pound of copper recovered contrasted with expansion of milling facilities to recover equal amounts of the metal by raising tonnage throughout, (3) low labor requirements needed for leaching, and (4) the simple and continuous nature of the process needing little close supervision of trained operators. In the past, the mining companies have not worried about efficiency in dump leaching but have been satisfied with whatever metal recoveries could be made without much effort. However, because of the huge amounts of metal accumulating in the low-grade waste dumps, compared to the relatively small amount recovered annually, an operator today cannot leave dump leaching to chance. What appears to be a simple, empirical process is actually a very complex one involving a large number of critical factors that encompass Several Scientific disciplines, such as physics, chemistry, geology, biology, and hydrology. It is imperative that

Jan 1, 1970

By C. Scala, M. Gondouin

Published laboratory data have established that very significant streaming potentials can exist across mud cakes subjected to pressure differentials such as exist between a mud column and formation fluids. Since shale is similar in kind and in properties to a well-formed mud cake, it appeared possible that streaming potentials might also arise across shales. A practical consequence would be that the streaming potential contribution to the SP would be smaller than might otherwise be assumed since the SP is measured with respect to the "shale bare line". The resultant contribution would be the difference between the streaming potential across the shale and that across the mud cake. In order to investigate this possibility, a laboratory apparatus was devised for measuring streaming potentials under pressure conditions normally encountered in wells. Reported data on streaming potentids across mud cakes were verified. More important, appreciable streaming potentials were found across shale samples. As in the case of mud cakes, the shale potentials varied with the concentration and nature of the impregnating electrolyte. Dependence on pressure was In a different rela-tion than that for mud cakes, possibly because of the lower compressibility of shales. The differences in streaming potentials between the shales md mud cakes were generally small, although they might vary considerably in practice depending on the relative electro-kinetic properties of the particular shale-mud cuke combination. A "poorly eflective" shale with a "very eflec-tive mud cake" would produce the largest negative addition to the electrochemical component of the SP. Results of field experiments with pressurized wells were considered in the light of the laboratory results. INTRODUCTION Field experiments wherein the pressure of the mud column in a borehole was varied have often indicated the presence of a streaming potential, but its magnitude was not easily predictable and its sign sometimes changed from one formation to another in the same well.' In the interpretation of SP logs from standard surveys, nevertheless, the correct value of R,, is very frequently obtained, within the limits of field accuracy, using only the simple electrochemical expression of the SP provided that proper corrections are made for bed thickness, ion activity, etc.' Accordingly, it was apparent that the streaming potential component of the SP in a borehole was considerably more complex than commonly assumed and clarification was indeed necessary The close similarity in nature and constitution of a shale to a well-compacted mud cake suggested that a streaming potential might also exist across shales as pointed out by M. P. Tixier in 1953 and as recently emphasized by Wyllie." e practical consequence would be that the streaming potential across the mud cake would be canceled, at least in part, on electrical logs since the SP is recorded with respect to the shale potential as a base line. This appeared to be a plausible explanation for many of the effects observed but no supporting data were available. In 1955 preliminary experiments at low pressures were conducted in our laboratories which supported the hypothesis of the shale streaming potential and formed the basis for later studies at borehole pressures.* EARLY LOW PRESSURE EXPERIMENTS The early experiments were conducted primarily to determine the possibility of a streaming potential across shales. The shale used was a compact type designated as No. 7 from Reagan County, Tex. (Permian). Cut samples were saturated for over one month in .2 to 2.0-N NaCl solutions. In order to eliminate all electrode polarization effects, a dynamic method was used. A transient pressure of about 1 atm was applied across

By R. Gibala

Internal-friction measurements on hydrogen-charged iron over the temperature range 4° to 300°K are reported. Two relaxation peaks, the hydrogen Snoek peak at 48 °K and the hydrogen cold-work peak in the range 145" to 2200K, are observed at 80 kc per sec. The effects of hydrogen-charging, aging, and deformation on the internal-friction results are determined and are used to show evidence of partitioning of hydrogen between solid solution and dislocations. The hydrogen-dislocation binding energy is estimated from the behaviors of the relaxation tiwzes and relaxation strengths of the Snoek peak and the cold-work peak. Its value is approxi,mately 6400 cal per mole. MANY investigators have demonstrated the usefulness of internal-friction measurements in determining the manner in which interstitial impurities interact with dislocations in bcc metals. Part of this success has resulted from the existence in bcc interstitial alloys of two anelastic relaxation peaks—the Snoek peak' and the cold-work or Koster peak2 (designated hereafter by SP and CWP, respectively). The SP has its origin in the redistribution of interstitials in solid solution among sites made energetically nonequivalent by an applied stress. The rate at which the redistribution occurs, measured by the relaxation time for the process, is related in a simple way to the diffusion rate of the interstitial in the free solution. The relaxation strength is proportional to the concentration of interstitial in solid solution. The CWP appears to have its origin in the relaxation of an interstitial-dislocation complex for which the relaxation time at a given temperature is much longer than that for the SP. The relaxation strength depends strongly on the concentration of interstitial and the amount of deformation at relatively low concentrations and deformations.2-8 From the dependence of the relaxation strength on interstitial concentration, the SP and CWP may serve as measures of the concentrations of interstitials in free solution and bound at dislocations, respectively. Thus their behaviors have been used to investigate interstitial-dislocation interactions in Fe-C, Fe-N, and several refractory metal systems.'-' However, the Fe-H system has not been studied extensively,? even though disputes in recent years over the mechanism of hydrogen embrittlement in steels involve argument over the extent to which lattice hydrogen and hydrogen-dislocation interactions play an important role.?-'' Previous work on Fe-H indicates the internal-friction behavior to be qualitatively consistent with that for other systems. Apparently, both a SP and a CWP are observed in the temperature ranges 30" to 50°K and 100°to 140°K, respectively (at 1 cps). However, there is neither sufficient nor accurate enough information to identify convincingly these peaks with their supposed counterparts in other systems. Nor have there been any attempts to make quantitative use of these peaks to study hydrogen diffusion, aging, or interaction processes. In this paper, an attempt is made to obtain more complete information on internal friction of hydrogen in iron than presently available. Internal-friction measurements in the range 4° to 300°K on hydrogen-charged iron show that the two peaks discussed above are in fact the hydrogen SP and CWP. Several effects of hydrogen charging, aging, and deformation on these peaks are observed and are used to determine the partitioning of hydrogen between solid solution and dislocation sites in iron. EXPERIMENTAL Materials. The starting material for this investigation was a high-purity iron supplied by National Research Corp. as a 1-in.-diam rod. The following analysis was given (inwt pct): C, 0.004; N, 0.0003; 0, 0.007; P, 0.002; S, 0.005; Si, 0.006; Mn, 0.001; Cu, 0.002; Ni, 0.005; Cr, 0.001; Mo, 0.001. After an initial vacuum anneal (-5 XTorr) at 700°C, the rod was cold-

Jan 1, 1968

By E. T. Knight, John D. Gill

IN ITS capacity for service to the public the oil industry is truly gargantuan. But it is only in this respect that the industry is the voracious, many-headed, many-armed and many-handed creature it has been so often painted by those who know it not too intimately and only from the outside. Contrasted sharply with the immensity of the service rendered is the relatively modest share of the national income which has gone to those who provided the tools and the mental and manual labor with which the service was performed. No doubt the relative meagreness of the re- ward was the result of a combination of fortuitous circumstances respecting the nature and accessibility of the industry's raw material and the extensive development and application of the most advanced technology, spurred by an intense competition.

Jan 1, 1940

By H. H. Podgurski, F. N. Davis

In silver alloys containing less than 0.2 wt pet Cu. the reaction 9 + 1/2 0, = CuO(s) was found to proceed to equilibrium between 700o and 808oC. From measurements of the equilibrium dissociation pressures of the CuO at several temperatures, the differential heat of solution and the activity coeflicients for copper in silver were calculated. These values were found to be in reasonable agreement with those calculated from data appearing in the literature. A metastable "copper oxide" with an atom ratio of oxygen to copper as high as 1.7 was formed by internal oxidation at 300°C of these same dilute Ag-Cu alloys. No anomalous behavior was noted in the temperature dependence of oxygen solubility in silver. The solubility minima between 300" and 800°C reported several years ago can be accounted for, at least in part, by reactions with trace impurities, such as copper. Cold-worked siloer exhibits an enhanced permeability to oxygen. THIS investigation was undertaken because of our interest in interactions between solute and lattice defects in metals. The reason for the choice of the O-Ag system for study is the anomaly in the solubility of oxygen in silver reported by Steacie and Johnson1 in 1926, specifically that isobars between 100 and 800 Torr show solubility minima at 400°C. It was also claimed that the copper impurity in the silver was not responsible for the minima. Recently, Eichenauer and Müller2 proposed that surface adsorption might have been responsible for this solubility anomaly, but no adsorption isotherms are available to check the pressure and temperature dependence observed at the low temperatures. Surface-tension measurements on silver made by Buttner, Funk, and udin3 suggest that a considerable fraction of a monolayer of oxygen exists on silver at 922°C and at an oxygen pressure of 150 Torr. To account for the pressure sensitivity reported by Steacie and Johnson1 at 300°C, the oxygen bound to the surface at 922°C cannot be considered relevant; the existence of a surface layer at 300°C characterized by a lower energy of binding would be required to explain the effect. All of our attempts to detect an interaction of this type with surface sites have failed. In this investigation we have not been able to associate the dissolution of oxygen in silver with a dislocation interaction. Evidently, severely cold-worked silver does not contain a sufficient number of trapping -sites for oxygen. Indeed, our work shows that oxidation of trace impurities in the silver was probably responsible for Steacie and Johnson's results. In addition, we have been able to establish the nature of the reaction with copper impurity in silver by thermodynamic considerations. EXPERIMENTAL PROCEDURE Measurements of both the internal oxidation rates and the solubility were made volumetric ally in a system equipped with a gas burette, a mercury manometer, a McLeod Gage, and a mass spectrometer. The silver and the silver-alloy samples were protected from contamination by mercury vapor from our pressure gages by suitably placed refrigerated (-78°C) traps. Silica reaction vessels were employed for experiments performed above 500°C. Spectroscopically pure gases were used in this investigation. The highest-purity silver used in the solubility measurements was 99.999 pet. By chemical analysis 2 ppm of Cu were found in this silver. The two Ag-Cu alloys used in this research were made up to 0.14 and 0.15 wt pet Cu starting with 99.999 pet Ag. An unexpected source of error was discovered in the course of the work. At temperatures near 800°C silver distilled from the hot silica reaction tubes into cooler regions of our system. Although the weight loss of silver from the sample was not important in itself, oxygen was being consumed by the silver distilled into the cooler part of the system to form a stable oxide phase from which the oxygen was not recovered. In a separate experiment conducted to determine the necessary correction, losses between 0.2 and 0.3 cu cm (stp) of 0, in 24 hr were measured at 810°C. On the assumption that the flux of silver from the vessel to form Ag2O de-

Jan 1, 1964

By T. C. Campbell

Copper is extracted from the Chuquicamata oxide ore by a hydro-metallurgical process. The ore is crushed to 3/8-in. sizing, and leached with a sulfuric acid electrolyte. Chlorine is precipitated. and the ferric iron reduced in the enriched electrolyte, after which the copper is recovered by electrolysis with insoluble Chilex and lead-antimony anodes, the spent electrolyte being returned to leaching. Cathodes are melted and refined in market furnaces and cast into commercial wire-bar and cake shapes. Sulfuric acid for the process is supplied by the brochantite in the ore. Water for washing the ore is advanced through the solution system and finally after cutting by electrolysis to from 6 to 16.0 grams per liter is completely stripped by the cuprous chloride method and run to waste. The cuprous chloride so obtained plus that resulting from precipitation of chlorine from strong solution is dissolved in ferrous chloride brine and the copper cemented on scrap iron. The cement so obtained is in part used to reduce ferric iron in electrolyte, and as it is of exceptional purity is also furnace refined and cast into an exceptional quality of fire-refined copper. Fig. 1 is flow sheet of the operation. The reduction plant is composed of seven divisions as follows: (1) crushing, (2) leaching, (3) tailings disposal, (4) dechloridizing, (5) sulfur dioxide treatment, (6) electrolytic tank house, (7) smelting and melting. A brief description of each of these divisions will be given. Crushing Ore that is frequently blocky and up to 5 ft. in section is crushed in four stages to 3/8-in. mesh. The first stage of crushing is called primary and the next three stages are known as secondary crushing. The first stage is accomplished with two 60-in. Superior McCully gyratory breakers by which the ore is broken to 9 in. The second coarse gyratory breakers crush the ore to 3-in. sizing. There are seven No. 10 McCully gyratories in this service, for one of which recently has been substituted a No. 7 cone crusher. The third and fourth stages of crushing are accomplished by fifty 48-in. disk crushers. In the third stage 14 disk crushers break the ore to 1 in., and in the last stage 36 disk crushers turn out the final product of 0.371-in. sizing. Reference to the flow sheets of Figs. 2 and 3

Jan 1, 1934

By S. Chander, D. W. Fuerstenau

The inherently sluggish nature of the reactions involving sulfide minerals, particularly molybdenite, in aqueous solutions under ambient flotation conditions make their investigation complicated and difficult. Since the physicochemical nature of sulfides is known to be controlled by electrochemical reactions, a number of attempts have been made in the past to study sulfide mineral-collector interactions through rest potential and electrode polarization measurements. The purpose of the present investigation was to study the interaction of potassium diethyldithiophosphate (KDTP) with molybdenite. In the present investigation of the interaction of KDTP at the molydenite surface, molybdenite electrode rest potential measurements and electrode polarization behavior were experimentally determined under various solution conditions. The standard reduction potential for the equilibrium between dithiophosphate ions (DTP-) and bis(diethoxythiophosphoryl)disulfide (DTP) [(DTP). + 2e :i7-± 2DTP- (1)] can be evaluated from the electrode rest potential measurements on a platinum electrode in deoxygenated KDTP solutions saturated with freshly prepared (DTP)2. Experimental A platinum wire was used as the electrode for potential measurements. Prior to each measurement the elec-

Jan 1, 1975

By J. E. Dorn, L. A. Shepard

LOW and Gensamer' demonstrated a number of years ago that the yield point phenomenon in mild steels was associated with the presence of fer-rite soluble carbon or nitrogen. More recently the yield phenomenon in body-centered-cubic metals containing interstitials was rationalized by Cottrell' in terms of a simple dislocation model. Interstitial atoms interact with dislocations in two ways; they cause not only local expansions but induce local tetragonality in the lattice. Consequently, interstitial~ interact with the hydrostatic tension and shear components of the stress about dislocations. They tend to migrate toward the expanded regions of edge dislocations and to assume sites that relieve the shear stresses of screw dislocations. Thus, a dislocation saturated with solute atoms constitutes a lower free energy state than that obtained when the dislocation threads through the average composition regions of the matrix. A greater stress will be required to separate the dislocation from its atmosphere than to move the dislocation through the matrix. This factor gives rise to the upper yield stress, which is required to unleash a series of dislocations in a localized region. This local yielding is propagated across the specimen to form a thin band of plastically deformed material known as a Lueder's band, making an angle of about 45" to the stress axis. Once the band has formed, deformation continues at the lower yield stress by the spreading of the Lueder's band in the direction of the applied stress. Undoubtedly the spreading of Lueder's bands at the lower yield stress is accomplished by the high stress concentrations at the band fronts, which serve to induce continued unlocking of new dislocations in advance of the migrating band fronts. Cottrell and Bilby have shown that the dependence of the yield point on temperature can be deduced by assuming that thermal fluctuations aid the stress in unlocking small dislocation loops from their solute atmospheres. Once a loop that exceeds a critical size has been nucleated, the entire locked diqlocation is released and can migrate. Fisher4 simplified this analysis by assuming that the locking forces were short range, so that if the dislocation loop were displaced only one Burgers vector from its atmosphere, it would be unlocked. Applying his model to the special case of delayed yielding under a constant stress of the order of the upper yield strength, he demonstrated that the delay time 7 for yielding should depend on stress and temperature according to where A and B are constants, G is the shear modulus, and u and T are the resolved shear stress and absolute temperature, respectively. Cottrell and Bilby, Fisher, and Fisher and Rogers' have shown that the above deductions are at least in qualitative harmony with the experimental facts. A number of investigators5-0 have shown that the yield point phenomenon can also be induced in sub-stitutional alloys of face-centered-cubic metals. In general such yield points are not as pronounced as those encountered in body-centered-cubic metals containing interstitials. The yield point phenomenon in these materials is usually enhanced by prestrain-ing at low temperatures and aging at intermediate temperatures. Undoubtedly the yield point phenomenon induced by strain aging substitutional alloys also results from locking of dislocations. But the locking of dislocations in substitutional alloys of face-centered-cubic metals differs somewhat from interstitial locking of dislocations in body-centered-cubic metals. Substitutional elements in face-centered-cubic lattices cause only radial displacements of the adjacent lattice points. Consequently, only the edge components of dislocations can be locked by the mechanism suggested by Cottrell. Additional locking, however, can be obtained by the Suzuki mcchanism.10 In face-centered-cubic metals, dislocations exhibit lower energies when they are present in the

Jan 1, 1957

By W. E. Rudolph, R. E. Baylor

DUE to its location in the Atacama Desert, one of the most barren of the earth's surfaces, Chuquicamata's water supply presents unusual problems. Yearly rain-fall averages less than one tenth of an inch at the plant. However, there are summer showers above 12,000 ft in the Cordillera to the east, the resulting run-off flowing through old river valleys buried beneath more recent volcanic formations, to be impounded within sediment-filled basins. This water emerges at springs where the outlets of these basins are blocked by lava flows, and here are formed the small streams which feed the only important river of the region, the Rio Loa. Chuquicamata's water is obtained from these springs and rivulets. [ ] The map above indicates four pipe lines from which potable and industrial water are supplied. Potable water, amounting to 4500 metric tons per day, is conveyed in the Toconce pipe line from springs 59 miles due east of Chuquicamata. This water is used not only for drinking, but also for boilers and other needs requiring high quality. For industrial water at the oxide plant, there are two 12-in. pipe lines from the Rio San Pedro, carrying a total of 17,000 metric tons per day of slightly brackish water. This water is at present used mainly for leaching and for hygienic purposes. Water Source Found For the present and future needs of the sulphide plant, it was calculated that at least 32,000 metric tons per day of make-up water would be required. For this purpose, a pipe line of 44 miles length was constructed to bring in the entire flow of the Arroyo Salado, one of the eastern tributaries of the Loa. The salt content of this water is so high (over 5000 parts per million of solubles, mostly chlorides) that it is highly detrimental to farming, and the Chilean Government had been studying projects to separate these waters from others of the Loa system in order to improve agricultural conditions in the fertile valley of Calama. So it happened that the Government was willing to award rights to the Arroyo Salado waters under agreement whereby the Mining Company removes waters from the Rio Loa system above Calama for all time. The outlet of these waters, after serving their purpose at the new concentrator and leaving the plant in tailing, is the Salar de Talabre, an old salt lake which presents fully ten square miles of surface to serve as an evaporating pan, the outlets having now been blocked by dams. Here the dry climate of Chuquicamata is a favourable factor, evaporation averaging slightly above 1/4 in. per day. The Toconce and San Pedro pipe lines have been functioning from 26 to 34 years, and through the use of special cleaning tools which were developed at the plant, as well as deaeration of the more active Toconce water, these pipes are now maintained at capacities which do not diminish as years go on. Constructing the Dam The Arroyo Salado pipe line design and construction involved certain special and interesting features, and inasmuch as this line and its intake works are solely for the needs of the new sulphide plant, more detailed description is given. The waters are impounded at a gravity dam constructed of concrete to a height of 100 ft above the river bed, keyed into the precipitous Dacite walls of the narrow canyon (barely 6-ft wide at the bottom, only 25-ft width at 50 ft above). A small secondary dam was built 100 ft down stream from the main dam, providing a pool of 15-ft depth to protect the main structure from flood flows over the spill-way during the rainy season. A system of four 36-in. syphons was designed for discharging these flood waters from the lower depths of the lake, in order to avoid eventual sedimentation behind the dam. The lake has a length of 3300 ft, and its water level is controlled by an adjustable spillway permitting draw-down of eighty inches, amounting to 41,000 metric tons of available capacity. This regulation is necessary because of wide fluctuations in stream flow between day and night due to freezing of feeders. During the construction of the dam the entire river flow was handled within a 36-in. pipe line some 2000 ft in length. As the excavations proceeded

Jan 1, 1952

By E. H. Jr. Dix

THE consideration of alloying elements for aluminum has led to a series of investigations of the equilibrium relations between aluminum and those alloying elements. Therefore, the aluminum end of the aluminum-antimony diagram has been studied. The general form of the aluminum-antimony equilibrium diagram has been worked out by Campbell and Mathews1 and by Tammann.2 Campbell and Mathews described principally the beginning of solidification. They found the curve of beginning of solidification to rise gradually from the melting point of pure aluminum to a maximum at about 67 per cent. aluminum. After a slight lowering of the curve at a little greater antimony concentration the curve again rises to a maximum at 18.4 per cent. aluminum, which corresponds to the compound AlSb. The curve then drops to the melting point of pure antimony. Tammann explained the maximum occurring at about 67 per cent. aluminum as the result of the slow formation of the single compound AlSb. The space lattice of the compound AlSb, according to Owen and Preston,3 is face-centered cubic, the antimony atoms being intermeshed with an identical aluminum lattice. Very little, if any, work has been done on aluminum alloys containing small amounts of antimony.

Jan 1, 1930

By W. W. Wirth

RESEARCH looking toward the reduction of the cost of roof support by substitution of longer-life materials for wooden timber is fully justified by the fact that roof support is an important element of all production costs. Permanent or semipermanent roof support will reduce the expense of timber-maintenance crews during steady operations, but even more markedly during idle periods. The management, therefore, is faced with the important problem of timber renewals, which in times of regular operation are frequently obscured by more urgent problems of production. Increased use of timber in the Anthracite Region of Pennsylvania is caused mainly by increased percentage of coal obtained from robbing areas, which requires more timber for safety than develop-ment work, and maintenance of long haulageways through crushed ground despite the fact that less coal is transported over them. The timber reserve in the immediate vicinity of the mines has been depleted to such an extent that it is necessary to secure 70 per cent of the timber requirements from distant sources. Originally, mine timbering in this region was done by largely utilizing round props or legs with round collars. The whole cross section of the tree from which timber was cut was utilized by forming the joints between the legs and the collars with saw and adze, using plank or round saplings for lagging behind the legs and over the collars to prevent material falling between them. The Mine Inspectors' report of 1898 records an important digression from the use of round timber, when two tunnels at the Babylon colliery, near Pittston, Pa., were timbered with 12 by 12-in. square timber sets with mud sills, through quicksand for distances of 425 and 160 ft., respectively. The timbers were lagged with 3-in. plank to control sand.

Jan 1, 1940

By M. C. Flemings, R. Mehrabian, G. E. Nereo

Analytical expressions derived previously are used to describe quantitatively effects on macrosegregation of some solidification and mold design variables. Al-4.5 pct Cu alloy is used as example. It is shown that abrupt changes in heat transfer rate result in solute-rich or solute-poor "bands". Severe solute-rich bands accowzpany "reheating" that can result, for example, from abrupt formation of an air gap at a mold-metal interface. With planar isotherms, solute-poor regions also result from reduction in cross section through which fluid flow to feed shrinkage takes place. It is suggested that the negative "cone" of segregation often found at the base of large ingots results from this reduction in cross section for feeding. Consideration is given to the positive and negative segregation to be expected in laboratory ingots in association with changes in ingot cross section. Under-riser positive segregation is considered and it is concluded this segregation results when vertical temperature gradient is low in the region of the riser; the segregation is accentuated by the temperature gradient reversal which can occur in inadequately insulated risers ("'hot tops"). Finally it is shown for Al-4.5 pct Cu alloy that the assumption of constant k and p in analytic solutions gives calculated results close to those obtained for the case of ziariable k and 0. A basic "local solute redistribution equation" was derived earlier' for calculation of macrosegregation resulting from flow of solute-rich liquid to feed solidification shrinkage, thermal contraction, and/or other contractions occurring during solidification. This expression relates fraction liquid, g~, to liquid composition, CL, at a given position x, y, z, in a solidifying Eq. [I] is for the general case of three-dimensional heat and fluid flow assuming constant solid (but not necessarily liquid) density during solidification, negligible net solute change from diffusion, and no pore formation. In this paper we first demonstrate application of this equation for calculation of macrosegregation in several examples involving one-dimensional heat and fluid flow. Specifically considered are examples in which segregation results from sudden changes in heat flow conditions. Next, Eq. [I] is used to describe segregation in examples where isotherms remain planar but where fluid flow is no longer one-dimensional. Application of this expression illustrates the type of segregation to be expected in unidirectionally solidified ingots of gradually or abruptly varying cross section. For segregation calculations, A1-4.5 pct Cu alloy is employed with constant k and p Vz = 0.172, 4 = 0.055), eutectic composition (CE = 33 pct Cu). In all examples, fraction eutectic is neglected in velocity calculations; this was previously shown to introduce little error.' A linear distribution of fraction liquid in the liquid-solid zone is assumed. In a concluding section it is shown that the assumption employed of constant k and /3 gives results close to those obtained when the actual (variable) values of k and 0 are employed.

Jan 1, 1969