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By A. Phillips, D. H. Killpatrick, V. Kerlins

The tensile failure of two dispersion-strengthened Ni-20 Cr alloys was studied and compared to the fracture of a similar alloy with no dispersoid. The fracture characteristics were studied using electron fruc-tography and transmission electron microscopy. In all three cases, the mode of failure was found to be microvoid coalescence. The failure in the dispersion-strengthened alloys was found to have initiated at the particles. The size of the dimples in the fracto-graphs was found to be related to the spacing of the particles, but not to the total elongation before failure. The elongation before failure was found to be related only to the amount of dispersed phase. These results are compared to those predicted by a theoretical model of ductile failure. THE continually increasing strength requirements for creep-resistant materials capable of long life at service temperatures above 1600"F (875"C) have developed considerable interest in dispersion-strengthened nickel-base alloys. The high yield strength of these alloys results from the presence of a dispersion of fine particles of thoria which act to impede the normal motion of dislocations. Many theories have been presented to explain the role of the dispersion in the strengthening of these alloys. A good review of these theories is presented by Ansell.' The ultimate strength of such alloys is not only related to mechanisms raising the yield strength, but also to the amount of work-hardening which occurs. This work-hardening is determined by the work-hardening rate and the amount of plastic strain before failure. Since fracture limits the amount of plastic strain, a study was undertaken to gain a better understanding of the fracture mechanisms in these alloys. Electron fractography and transmission electron microscopy were used to study the fracture characteristics in two dispersion-strengthened alloys and one similar alloy containing no dispersoid. These results are related to the tensile properties of the dispersion-strengthened alloys at room temperature and at 2000°F (1095°C). The results are also related to a theory for ductile fracture. 1) PROCEDURE Standard tensile specimens were made from 0.020-in. (0.051-cm) sheets of three different Ni-Cr alloys. The alloys had nominal compositions of Ni-20Cr, Ni-20Cr-2Th0,, and Ni-2OCr-4Th0,. All alloys were supplied in an annealed condition. The specimens were fractured in tension at room temperature to determine the effect of the dispersed thoria on the fracture appearance. The tensile properties were determined from the average of a minimum of three ten- sile specimens for each condition tested. The fracture surface of all of the alloys was examined by electron microscopy using standard two-stage plastic-carbon replica techniques. Thin foils of the dispersion-strengthened alloys were used to investigate the size and spacings of the dispersion particles, and to investigate sections of the 2 pct thoria alloy taken from areas of the specimen adjacent to the fracture surface. The thin foils were mechanically ground to 0.010 in. (0.025 cm) and then chemically polished to approximately 0.001 in. (0.003 cm) in a solution of 29 g of ferric chloride and 10 ml hydrochloric acid in a liter of water. The polishing solution was maintained at 150"F (65°C) during the thinning operation. The final thinning of the foil was done electrolytically using a solution of 700 ml ethanol, 100 ml 2-butoxy eth-anol, 120 ml distilled water, and 78 ml perchloric acid (70 pct). The potential was maintained at 15 v and the bath temperature at -20°~ (-29°C) during the thinning operation. The final thickness of the foil was approximately l000A as determined from the width of twins boundaries observed in many of the foils. 2) RESULTS AND DISCUSSION The electron fractographs of the fracture surfaces of the alloys are shown in Figs. 1, 2, and 3. The normal interpretation of this type of fractographz is that, as a result of the difference between elastic and plastic properties of the matrix and the particles or other inhomogeneities in the alloy, microvoids are formed

Jan 1, 1969

By Michael Hoch, Walter C. Wyder

The Cr-Ni system was investigated between 900" and 1400°C and 45 to 100 wt pct Cr. The Cr-Fe system was studied between 1200" and 1385°C and 70 to 100 wt pct Cr. Powdered alloy compacts were produced from high-purity chromium, nickel, and iron poulders. The compacts were sintered in an argon atmosphere and then machined into small, 0.030-in. diam cylindrical specimens. These were then heated by induction in the high-temperature X-ray diJfractwn camem under a helium atmosphere and irradiated with copper Ka radiation. From the results of the high-temperature X-ray diffraction patterns it can be concluded that chromium exists only in the bcc form, and that no eutectoid reaction occurs in the Cr-Ni system in the temperature interval 900" to 1400°C. The X-ray diffraction patterns are in agreement with the Cr-Ni phase diagram of Bechtoldt and Vacher, and Williams. It is possible that chromium undergoes one or more allotropic transformations between room temperature and its melting point. Most of the evidence was gathered from the study of the chromium-rich ends of the Cr-Ni and Cr-Fe binary systems. All the investigations rely heavily on indirect methods: thermal analysis, electrical resistivity, and micro-graphic inspection of quenched samples. In the present work the chromium-rich side of the Cr-Ni and Cr-Fe binary systems is studied, using high-temperature X-ray diffraction techniques. Thus the coexistent structures can be observed directly at temperature. PREVIOUS INVESTIGATIONS ~ansenl shows two possible Cr-Ni phase diagrams 1) a simple eutectic [Liquid =a-Cr(bcc) + y-Ni(fcc)], 2) a eutectic [Liquid+ P-Cr(fcc) + y-Ni(fcc)] and euctectoid [p-Cr(fcc) ==a-Cr(bcc) + yNi(fcc)]. The latter is based on the work of Grant and co-workers.2 Stein and rant'" placed the eutectoid composition at 1215°C and 68 wt pct Cr; their diagram is shown in Fig. l. Similarly, Sully3 also discusses the two proposed diagrams. Price and Grant,4 working on an isothermal section of the Cr-Ni- Fe ternary diagram at 1300°C, made no mention of a ß-chromium phase (fcc). The ß-chromium structure was also reported by Misencik 5 in the Cr-Nb(Cb) system. Williams 6 studied the Cr-Ni system using precipitation techniques. His work included the chromium and nickel solvus lines below 1250°C. He reported no ß structure nor any eutectoid reaction. The solvus lines which he produced were very similar to those of Jette, et al 7 below 1000°C. He concluded that Grant and coworkers2 had misinterpreted their data, and that effects which they had reported were actually due to the rapid and extensive precipitation of the nickel-rich phase. Bechtoldt and vacher8 used sintered powdered alloy compacts in an attempt to find the ß phase. They used metallographic and room-temperature X-ray diffraction techniques and also failed to detect the fcc chromium phase. They attributed the low slope of the chromium solvus at approximately 1150°C as the probable cause of the abundant precipitation obtained. They also stated that the precipitation was the probable cause for the abrupt discontinuities in the thermal analysis and electrical resistivity data which led to the conclusion that a eutectoid reaction existed. Fig. 1 also shows their diagram. Grigor'ev and coworkers9 investigated the polymorphic changes of chromium in the Cr-Ni phase diagram. Using standard microstructural and thermal analysis techniques, they published a phase diagram which contained five polymorphic forms of pure chromium and four eutectoid reactions. They stated that the room-temperature bcc chromium transformed to a fcc structure at 930°C, to bcc at 1300°C, to hcp at 1650oC, and then finally to bcc at 1830°C. The eutectoid reactions were placed at 850°, 960o, 1140°, and 1220°C. Also to be noted was the fact that the uppermost phase, the bcc above 1830°C, was different from the upper phase of Grant and coworkers,2 the fcc above 1840°C. Their eutectoid reactions, temperatures and compositions fall

Jan 1, 1963

By D. A. Stevenson, R. A. Burmeister

Single-phase silver antimony telluride has been prepared by zone-melting techniques using initial compositions of A new phase appears upon prolonged annealing of this material, but the reaction does not appear to be a simple eutectoid decomposition. A complete analysis of the phase equilibria is complicated by the slow kinetics involved. The Hall coefficient, magneto -resistance, electrical resistivity, and Seebeck coefficient are all sensitive to the presence of second phases. The low Hall mobilities measured for single-phase material indicate that the usual band theory is inadequate to explain the observed transport properties in the system. Density anomalies of up to 2.5 pet between measured and theoretical density were observed but are not conclusive evidence for a defect structure. COMPOSITIONS in the Ag-Sb-Te system have been studied previously by several investigators.1"18 The interest in this system arises from potential thermoelectric applications of alloys on the Ag2Te-Sb2Tes vertical section. Although the composition corresponding to the formula AgSbTe, has received most attention, it has been found to consist of more than one phase.7'8 A thorough understanding of the properties of this heterogeneous material has been impeded by both lack of knowledge of the properties of the homogeneous phases comprising it and the problem of analysis of transport properties in an inhomogeneous system. The present work describes the preparation of the homogeneous ternary phase and the corresponding electrical properties of both homogeneous and heterogeneous material. MATERIAL PREPARATION Most specimens for this investigation were prepared by encapsulating the elements in evacuated quartz tubes after which they were melted and homogenized in the liquid state. The ambient temperature was then dropped to 500°C and the resulting ingot zone melted. The growth rate, width of zone, stoichiometry, and number of passes have an effect on the resultant microstructure. Grains several centimeters in length were easily produced by this method. Other solidification techniques were also used, including uniform slow cooling of the entire specimen and rapid freezing. The microstructures of specimens produced by these techniques frequently differed appreciably from similar compositions prepared by zoning. A variety of nonequilibrium microstructures characterized by long needlelike particles resulted from the rapid-freeze method. PHASE EQUILIBRIA The lack of information on phase equilibria is a major difficulty associated with a comprehensive study of the Ag-Sb-Te system. Considerable confusion has resulted from the use of the formula AgSbTe, to identify the cubic ternary intermediate phase even though it has been established that material of this stoichiometry normally contains AgzTe as a second phase.798 In this paper, silver antimony telluride will denote the cubic ternary intermediate phase comprising the major portion of AgSbTe,. The term "single phase" will denote material which consists of only the cubic phase (as evidenced by metallographic examination and X-ray diffraction) and the term heterogeneous will describe multiphase material containing AgzTe, SbzTe3, or other phases in addition to the cubic phase. The single-phase material may actually contain a variety of inhomogeneities—gradual changes in composition on a macroscopic scale, localized fluctuations in composition, clusters or other products of early stages of the precipitation process, and a variety of point and line defects—all of which will not be detected by the present techniques for determining homogeneity. Single-phase material has been prepared from compositions close to 59 mole pct SbzTe3 21 (this notation refers to the location on the Ag,Te-Sb2TeS vertical section). Zone widths of =2 cm and growth rates 51.2 cm per hr were used. The single-phase region at elevated temperatures extends off the vertical section to a composition which can be expressed approximately as Ag,,SbzgTes,.9 The latter two compositions as well as AgSbTe, are represented in the conventional Gibbs triangle in Fig. 1. It is not presently possible to ascribe exact values to the limits of the single-phase region on a given isotherm or vertical section due to the extremely

Jan 1, 1964

By R. A. Thomas, R. L. Solbod

The importance of transverse diffusion on the finger development in a miscible-phase displacement at an adverse mobility ratio of tbree was studied in a porous plate 1/4-in. thick, 3-in. wide and 18-in. long. Fast displacement rates (29 ft/D) and slow rates (1.6 ft/D) were used to determine the effect of residence time on the geometry of the fingers. The shape of the fingers was observed directly by use of the X-ray technique. At fast rates numerous narrow fingers were observed, but at slow rates a single somewhat bulging finger was produced. The amount of material moved transversely by diffusion across the plate was sufficient to modify the finger geometry in the slow-rate run because of the long residence time. These results are in contradiction to some of the postulates in the literature. The composition of the effluent stream, however, was not affected by the flow rate. This result is not inconsistent with the observed change in the shape of the finger in a short model, but it seems likely that a short model does not offer adequate and proper scaling of the reservoir. The model used was probably a valid one for studying the effect of transverse diffusion on the finger geometry, but a longer model would be needed for proper scaling of the effect of the change in the finger shape on the efficiency of displacement as measured by the composition of the effluent stream. INTRODUCTION Fingering can be defined as the uneven advance of the injected phase as it moves into a porous medium displacing the resident phase from the pore spaces of the rock. The use of this term is usually restticted to the situation in which the displacing phase is less viscous or more mobile than the fluid being displaced. Under these conditions, not only are fingers formed, but the length and width of the fingers grow with distance traveled in the porous medium. This subject has become one of great interest to the oil industry because of the present trend toward the use of various forms of miscible-phase displacement to increase oil recovery. Since in nearly all of the known modifications of the miscible-phase displacements an unfavorable mobility ratio exists (the displacing phase has a lower viscosity than that of the crude oil), the conditions are proper for fingering to develop. An appreciable amount of fingering appears to be a severe handicap to these processes for it increases the volume of agent required for the process to be a success, and such an increase puts a severe strain on the economics of the proposed processes. In some cases, such as for a mobility ratio of 200 unfavorable, it has already been demonstrated that the proposed process would not be economic if the fingering in the field were to be of the same magnitude as that observed in the laboratory. A number of aspects of fingering have been studied and reported in the literature. While the phenomenon of fingering cannot be regarded as a completely understood subject, considerable information exists on the effect of the path length and the mobility ratio on the growth of fingers. Less-complete data are available on the effect of the diameter of the flow path on the character and amount of the fingering, and even less agreement in results exists on the effect of rate of flow on the nature of fingering. This paper deals with one aspect of this latter subject. OBJECTIVE The objective of this study was narrowed down to one rather specific feature of the behavior of fingers in miscible-phase displacement in porous media. The variable studied was the effect of rate of flow on the nature and the development of fingers. It should be made clear at this point that, while rate was the apparent variable, the real variable was residence time; that is, at low rates the fluids are present at a given spot in the porous medium for a longer time interval than at fast rates. The purpose of the study, therefore, was to determine the changes which occur in the fingering and the possible benefits which might accrue from a longer residence time during that period when fingers are

By H. T. Sumsion, A. U. Seybolt

The results of an investigation of vanadium-rich V-O solid solutions are presented, indicating the structure and lattice parameters of two solutions, a and ß, and their approximate temperature-composition existence. The a solution is the terminal body-centered cubic one, and contains up to 3.2 atomic pct 0. The ß solution has an ordered body-centered tetragonal structure, is formed at 1270°C, and exists from about 15 to 22 atomic pct 0. From the evidence available, the various phase boundaries have no appreciable temperature dependence. Evidence has been found for a polymorphic transformation in pure vanadium at 1550°C. IN an earlier investigation' dealing with the preparation of pure vanadium by calcium reduction of the oxide, it was found that small amounts of oxygen drastically reduced the ductility of the metal. Because this effect was so marked, it was decided to make a study of the solubility of oxygen in solid vanadium. This report deals principally with this solubility and the nature of the phase relationships in the vanadium-rich region, particularly at temperatures below 1300 °C. However, during the investigation enough data on the V-0 system were obtained to make it appear worthwhile to present a tentative phase diagram up to the composition VO. The only significant prior work found on this system are the contributions of Klemm and Grimm,' and Mathewson et al.3 Klemm and Grimm prepared a wide range of V-O compositions by powder techniques including the compositions VO.l, VO.2, VO.3 and VO4 (9.1, 16.8, 23, and 28.6 atomic pct 0, respectively). The first three compositions were found to consist of a body-centered tetragonal solid solution, while the last also showed lines of VO (NaCl structure). They found that the parameter c, increased and the parameter a, decreased with increasing concentration of oxygen. For their composition VO.27, or about 16.8 atomic pct O, they cite the values a, = 2.948A, c, = 3.53A, and c/a = 1.2. Klemm and Grimm made no attempt to determine the solid solubility limit nor to construct a phase diagram. They did, however, give some data on the homogeneity range of VO, and they proposed a structure for the body-centered tetragonal solid solution; these points will be taken up later. Materials and Preparation of Samples The vanadium used in this investigation was prepared in the laboratory by the method previously mentioned.' A typical analysis is as follows: Fe, 0.007 pct; Si, 0.02; Ca, 0.06; C, 0.224; O2, 0.044; N,, 0.0017; H2, 0.003; and V, 99.34 ±0.3 (assay). The vanadium assay is probably low by about the error given. The impurities total about 0.36 which, if subtracted from 100, gives a purity of about 99.6. At the time material was being prepared for this work no suitable technique was available for melting vanadium without appreciable contamination. The procedure adopted therefore was to cut the calcium-reduced regulii into slices which were then rolled to strip about 0.025 in. thick for oxygen diffusion. Pieces of rolled vanadium of approximately 0.025xY4xl in. and weighing about 0.3 g were suspended in a vertical fused-silica tube which was part of an ordinary gas absorption apparatus. The silica tube was heated by an electric resistance-tube furnace which could be raised around the silica tube or lowered away from it as desired. This apparatus had no novel features which require detailed description. Other than the silica tube and furnace, it consisted of a glass system evacuated by a liquid nitrogen trapped mercury diffusion pump, a mercury-operated gas burette, a McLeod and a Pirani gage, and a mercury manometer. It was also equipped with suitably located stopcocks for isolating various parts of the system; the vacuum ordinarily attained was between 10" and 10-6 mm of mercury. Oxygen generated by decomposing MnO2 was passed through anhydrous magnesium perchlo-rate before introducing it into the gas burette and thence to the absorption chamber.

Jan 1, 1954

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

IT has been demonstrated that inclusion size, distribution, and composition affect the machin-ability of resulphurized steels. Merchant and Zlatinl concluded that large sulphide inclusions aided machining by forming a (lubricating) coating on the tool face. Boulger et al.² and Van Vlack³ noted that the size, distribution, and composition of the inclusions in the steel affected the machinability. Steel specimens containing large globular sulphide inclusions usually exhibited excellent cutting properties, while machinability was adversely affected by the presence of numbers of oxide-type inclusions. Consequently a thorough knowledge of all the factors which affect the inclusions in the final product is desirable. Since almost all the inclusions have their origin in liquid steel, it was necessary to begin a study of inclusions in free-machining steels by studying the inclusions and chemical segregation in the as-cast ingot. Very little information is available on the size, distribution, shape, and composition of inclusions in large, capped, free-machining steel ingots, particularly the B1113 grade. Gregory and Whiteley4 made a general study of the inclusions in a small, high sulphur, free-machining steel ingot. Also, numerous authors have described the solidification and segregation characteristics of the four basic types of steel ingots, namely, rimmed, capped,7 semikilled,7,8 and killed7,9,10 ingots. Most of these studies were made with plain carbon or low alloy, low sulphur steel. It was desirable to study not only the ingot but also the change in size, shape, and number of inclusions on rolling an ingot to a bloom and thence to a billet. This procedure was followed and it is hoped that this study may serve the dual purpose of adding to the general knowledge of ingot solidification as well as contributing to the knowledge of the size, shape, distribution, and composition of inclusions from the ingot to the billet in a high sulphur, free-machining steel. Procedure A 12.000-lb 23x35x75 in. slab ingot of the B1113 grade was cast, sectioned, and studied both macro-scopically and microscopically. An adjacent ingot from the same heat and of the same size was rolled to a 77/8x77/8 in. bloom and thence to a 21/2x21/2 in. billet. These various bloom and billet sections were also sectioned and studied macroscopically and microscopically. Sectioning the Ingot: The ingot herein described was obtained from the United States Steel Corp.'s South Works Bessemer Blow No. 0193, a B1113 mechanically capped heat. The 23x35 in. ingot (No. 2) was teemed according to normal procedures and after stripping and transportation to the rolling mill was not placed in the soaking pit but allowed to air cool in an upright position. When completely solidified, the ingot was cut into sections by means of a powder scarfing torch and further sectioned by saw cutting as indicated in Fig. 1. Cut No. 2 (1x10x12 in.) from sections A through H was cleaned thoroughly, macroetched in a solution of 50-50 water and hot muriatic acid and used to obtain a macrograph of a horizontal section from the surface to slightly beyond the center of the 23-in. ingot dimension. Cuts No. 5 and 3 (lx81/2xl0 in. each) from sections A through H were treated in a similar manner to obtain a macrograph of a horizontal section from the surface to slightly beyond the center of the 35-in. ingot dimension. The composite macrograph of these horizontal ingot sections, which shows a vertical section of the ingot from top to bottom, is shown in Fig. 2. It should be noted that sections No. 2 are normal to sections 5 and 3 in the composite. Drillings for chemical analyses were obtained from selected positions within the above-mentioned ingot sections as noted in Fig. 3. The oxygen content was determined by the vacuum-fusion method. Samples for microscopic examination were cut from

Jan 1, 1954

By Joseph E. Worthington

The present-day Northumberland gold mine is one of the deposits generally characterized as a Carlin-type occurrence. It lies at the crest of the Toquima Range in Nye County near the center of Nevada. Gold mineralization occurs in two modes, in argillaceous and in silicified limestones, and is generally very fine-grained or micron gold. The Northumberland district has had a history that is typical of many western gold districts: minor production prior to World War II and intermittent exploration thereafter until a combination of geological insight, improved economics, and the advent of heap leach technology created the Northumberland gold mine. Nye County, Nevada, was sparsely populated and little explored in the early years of the settlement of the west; the Northumberland district was not established until 1866. Initial interest was in silver and the district operated as a very small producer for the next seventy years. The disseminated gold occurrences in silicified limestones were recognized and Northumberland Mining Co. was organized to develop the property in the late 1930s. Northumberland Mining Co. actually conducted drilling operations (over 200 drill holes) and mined from small open pits in the silicified limestones. They ultimately produced almost 936 kg (33,000 oz) gold before being shut down by War Production Board Order L-208 in 1942. After World War II gold mining activities were essentially nil for over a decade due to the poor economics of gold production. The property was, however, a known gold producer and attracted recurrent exploration attention. About 45 holes were drilled under the direction of Peter Joralemon for private interests between 1959 and 1963. Next Kerr McGee drilled about 25 holes during 1963 and 1964. Some- what later, in 1968, Homestake drilled 20 holes. The property was then acquired by Idaho Mining Co. which drilled about 30 more holes between 1972 and 1974. By this time the Northumberland mine was becoming somewhat shopworn with over 300 holes drilled. Interest in gold prospects was increasing substantially in Nevada, how- ever, due to rising gold prices in late 1974, and several companies were interested in continuing exploration at Northumberland. In 1975 Cyprus Mines Corp. was successful in obtaining a joint venture arrangement with Idaho Mining Co. for further exploration and development of the property. The overall Cyprus exploration program was under the direction of James G. Hansen, Vice President Exploration. The geologist recommending acquisition of Northumberland was Peter E. Chapman who reported to Joseph E. Worthington, Manager of U.S. Exploration for Cyprus. The basis for selection of the Northumberland mine as an exploration target for Cyprus by Chapman was essentially prior knowledge of regional and 16cal geology and of the mine. Exploration for the next few years was directed by Chapman under the supervision of Worthington. During 1975 and 1976 rotary and check core drilling were conducted that indicated that a substantial Carlin-type or disseminated, low-grade gold deposit occurred in two separate bodies. Drilling was based on geologic mapping and rock chip geochemical sampling. Both ore zones were reflected at the surface as gold and arsenic anomalies in rock chips. Heap leach tests attempted in 1977 were aborted by a flash flood, but were completed in 1978. Engineering studies occupied the next couple of years until the property achieved production in the fall of 1981. It is now producing by open-pit mining with gold recovery by heap leaching and cyanide extraction at a rated capacity of approximately 2722 t/d (3000 stpd) ore. Metal recovery has been projected (probably conservatively) at 5 10 kg/a (18,000 oz per year) gold and 1.6 Mg/a (59,000 oz per year) silver. Reserves are reported to be adequate for ten to fifteen years of production. REFERENCES Anon., 1981, "Gold in Nevada," Span Magazine, Vol. 21, No. 3, Standard Oil Co., pp. 6-9. Koschman, A.H. and Bergendahl, M.H., 1968, "Principal Gold- producing Districts of the United States, Professional Paper 610, US Geological Survey, p. 193. Kral, V.E., 195 1, "Minerals Resources of Nye County, Nevada, Bulletin, Vol. 45, No. 3, Geology and Mining Series 50, Nevada University.

Jan 1, 1985

By WALDEMAR T. SCHALLER, EDWARD P. HENDERSON

THE material available for mineralogic study, consisted of drill cores, 2 to 3 in. thick, supplemented by small well cuttings. Such study has added no essential new information regarding the minerals, though the refractive indices, used for determinative purposes, have been determined more accurately than before, permitting the development of a scheme for the rapid identification of these minerals. The essential points brought out by the investigation are two: (1) that certain mineral associations evidently point the way to an understanding of the geologic history and (2) that a definite sequence of mineral formation has taken place so that the original minerals formed have been in part-reacted on producing new compounds and associations; Twenty minerals have been found. The most important are :

Jan 1, 1929

By W. P. Sykes

RECENT investigations of the molybdenum-carbon alloys have been reported by Becker and Ebert1,? Westgren and Phragmén2, T. Takei3, and H. Tutiya4. Takei3 studied the Mo-C system by employing metal-lographic and X-ray methods, and the other publications described the determination of the crystal structure of the molybdenum carbides. In exploring this system by a technique previously applied to the tungsten-carbon series5, the results of Takei were confirmed with two definite exceptions; i.e., first the composition of the eutectic, and second the nature of the carbon-rich intermediate phase. Consequently, a more thorough examination of the molybdenum-carbon constitution was initiated in an effort to correlate the data supplied by the microstructures, diffraction patterns and chemical analyses.

Jan 1, 1935

The North American Coal Corp. Increasing demand for coal, stimulated by the national energy shortage, and complicating and often conflicting, demands by government and ecology groups for better land reclamation methods continued to propel advances in surface mining technology during 1974. To meet current demands for coal (estimated at more than 700 million t for 1975 and 1.5 billion t in 19851, equipment manufacturers and coal operators concentrated on increasing the productivity of all surface mining equipment. The trend towards larger equipment, particularly in overburden removal, loading, and haulage machinery, prevailed during the year, notwithstanding the perennial debate over the economics and practicality of using large, inflexible equipment. Increasingly, the industry called on computers to monitor productivity and help design more efficient production systems

Jan 2, 1975

By D. W. Duncan, A. Bruynesteyn

An ore containing chalcopyrite was microbiologically leached in 6 ft columns at particle sizes ranging from -2 +1 ½ inches, to -3/8 + 3/16 inches. The rate of leaching increased exponentially as the particle size decreased. The controlling factor was the active leaching volume made up of the particle surface area and the depth of penetration of the bacteria and leach liquor into the particle. This volume became an increasingly larger part of the total volume as the particle size decreased. The sample under test leached poorly at larger particle sizes and it was calculated that under commercial conditions, it would produce at best a pregnant solution containing 100 mg/l (0.2 lb/ ton) of copper per 100 ft of dump height.

Jan 1, 1974

By C. H. Mahoney, P. E. LeGrand, A. L. Tarr

MAGNESIUM, it is now generally realized, differs in some important aspects from most other structural metals, not excepting even its close neighbors, the aluminum-base alloys. This is particularly true with respect to the effects of elevated temperatures on the two light metals when in the molten state. Aluminum, on the one hand, should not be raised above its melting point any higher than is absolutely necessary if one is to avoid danger of gas absorption and a tendency toward grain growth in the resultant casting.1 Magnesium alloys, in sharp contrast, actually benefit by being heated to temperatures considerably above their melting point. It is a commonly accepted practice to establish the desired fine grain in the industrial magnesium alloys of the aluminum-bearing group by raising the temperature of the melt after the refining treatment to some 25e C (482°F.) above the melting range. To recall briefly the typical practice for magnesium alloys, the molten metal is refined by fluxing at about 730° C. (1350 F.), and after the melt has been covered with a suitable flux, the temperature is raised to between 870°C. (1600°F.) and 930°C. (I700°F.). It is then cooled as quickly as possible to the casting temperature. This superheating, as it is called, results in a fine-grained cast metal structure which has superior mechanical properties, enhanced amenability to solution heat-treatment, and better machinability than cast metal that has not been superheated. The minimum temperature of superheating varies to some extent with the composition of the alloys to be treated and usually increases with the percentage of magnesium in alloys containing the same constituent metals.2 It should be noted that the grain-refining effect of superheating is markedly apparent only in connection with the alloys containing aluminum as an alloying constituent-the binary alloy containing r.5 per cent manganese, for example, is not refined in grain to any noticeable extent by a superheating effort. While the phenomenon of superheating is well known in the magnesium industry, the mechanism of the process has remained a mystery. During the superheating cycle something occurs that forces a fine grain upon the solidifying metal. The process has been controlled in an empirical manner, and occasionally, especially on large-scale melts, and for no apparent cause, no grain refinement is obtained from a superheating treatment. Only a few papers of importance have been published on the subject. Of these, one of the most helpful is the paper by Achenbach, Nipper and Piwowarski,3 which gives considerable data concerning the effect of superheating on various properties such as fluidity, shrinkage and hot crack formation, as well as grain size, and a discussion without any definite conclusions on the theoretical aspects of superheating. A short article by Murphy, Wells and

Jan 1, 1945

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By Terkel Rosenqvist

Few subjects in iron metallurgy and steelmaking have caused so much discussion and have resulted in so many divergent and partly contradictory statements as the theory of the distribution of sulphur between molten iron and slag. An interesting survey of the different points of view is given by Grant and Chipman.1 Grant and Chipman themselves conclude in their paper that, at least in the open hearth and electric steel furnaces, the governing reaction is a simple distribution like: FeS steel ? FeS alas [Ia] and MnS steel ? MnS alas [Ib] They conclude that no significant reaction takes place according to the more classical scheme: FeS steel + CaO slag ? FeOslag + CaS slag [2a] This is the reaction which is regarded by most investigators as the primary sulphur reaction in the blast furnaces, where it is accompanied by the reaction with carbon: FeO slag + C ? Fe + CO [2b] The writer suggests an alternative to the reactions mentioned above. It is the opinion of the writer that the a priori assumption of defined molecular compounds being present in molten steel as well as in molten slag, has retarded rather than promoted a solution of the sulphur problem. As for the constituents of molten steel, it is taking too much for granted to mention the presence of FeS and MnS. If this infers that the melt contains diatomic molecules, the statement must be made that at least such molecules do not exist in the solid state at room temperature. Solid FeS crystallizes in the nickel-arsenide structure, and MnS (high temperature form) in the sodium-chloride structure. In these structures the sulphur is surrounded by six metal neighbors, and no molecular groups can be isolated. When sulphur is dissolved in molten steel, it is expected to maintain the same coordination number as in the solid state. We know that sulphur in steel has a certain chemical potential and a chemical activity which can be expressed by the reaction: S steel + H2 ? H2S where the activity A. is proportional to the ratio PH2S/Ph2. We know also that this activity is influenced by the presence of other constituents. For instance, there is reason to assume that carbon and silicon increase the sulphur activity and manganese decreases it. However, the exact relationship here is scarcely known, and further investigations are needed. Concerning the molten slags, if anything should be assumed a priori it would be that they are composed of ionic rather than molecular parts. There are indications of this in that solid silicates form ionic structures, and molten slags show high electric conductivity and can be electrolyzed.2 It has been claimed by Taylor and Chipman3 that their activity investigations

Jan 1, 1949

By Terkel Rosenqvist

Few subjects in iron metallurgy and steelmaking have caused so much discussion and have resulted in so many divergent and partly contradictory statements as the theory of the distribution of sulphur between molten iron and slag. An interesting survey of the different points of view is given by Grant and Chipman.1 Grant and Chipman themselves conclude in their paper that, at least in the open hearth and electric steel furnaces, the governing reaction is a simple distribution like: FeS steel ? FeS alas [Ia] and MnS steel ? MnS alas [Ib] They conclude that no significant reaction takes place according to the more classical scheme: FeS steel + CaO slag ? FeOslag + CaS slag [2a] This is the reaction which is regarded by most investigators as the primary sulphur reaction in the blast furnaces, where it is accompanied by the reaction with carbon: FeO slag + C ? Fe + CO [2b] The writer suggests an alternative to the reactions mentioned above. It is the opinion of the writer that the a priori assumption of defined molecular compounds being present in molten steel as well as in molten slag, has retarded rather than promoted a solution of the sulphur problem. As for the constituents of molten steel, it is taking too much for granted to mention the presence of FeS and MnS. If this infers that the melt contains diatomic molecules, the statement must be made that at least such molecules do not exist in the solid state at room temperature. Solid FeS crystallizes in the nickel-arsenide structure, and MnS (high temperature form) in the sodium-chloride structure. In these structures the sulphur is surrounded by six metal neighbors, and no molecular groups can be isolated. When sulphur is dissolved in molten steel, it is expected to maintain the same coordination number as in the solid state. We know that sulphur in steel has a certain chemical potential and a chemical activity which can be expressed by the reaction: S steel + H2 ? H2S where the activity A. is proportional to the ratio PH2S/Ph2. We know also that this activity is influenced by the presence of other constituents. For instance, there is reason to assume that carbon and silicon increase the sulphur activity and manganese decreases it. However, the exact relationship here is scarcely known, and further investigations are needed. Concerning the molten slags, if anything should be assumed a priori it would be that they are composed of ionic rather than molecular parts. There are indications of this in that solid silicates form ionic structures, and molten slags show high electric conductivity and can be electrolyzed.2 It has been claimed by Taylor and Chipman3 that their activity investigations

Jan 1, 1949

By R. W. Gurry

THERMODYNAMIC calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a. better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganeie, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B203 in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1943

By E. C. Houston, H. S. Rankin

Olivine is considered a valuable potential source of metallic magnesium in the chloride electrolytic process. Treatment of olivine with hydrochloric acid can be carried out under conditions that prevent the formation of gelatinous silicic acid, which would inhibit the reaction by forming a covering around the ore particles. It is our hypothesis that the formation of gelatinous silicic acid is avoided by the dehydrating action of the magnesium chloride, which takes up water to form a series of hydrates and leaves the silicic acid in granular condition. Leaching serves to separate the magnesium chloride from the silicic acid and unattacked ore, which can be treated with fresh acid in successive steps until extraction is essentially complete. The leach solution can be i purified by the addition of caustic magnesia and the precipitated impurities removed by decantation or filtration. The resulting magnesium chloride contains: Fe, less than 0.001 Per cent; Mn, 0.012 ; per cent; Ni, none. Chlorination† of olivine has two major defects: (1) a large part of the chlorine goes to form silicon and iron chlorides, (2) the anhydrous magnesium chloride is held by absorption in the finely divided silica. SupplY It is well known that olivine, a silicate of magnesium and iron, is present in large amounts in several localities in the United States. The largest deposits occur in the southeast and on the Pacific Coast.' The southeastern deposits were surveyed by Lewis2 in 1896 and by Hunter3 in the period 1933-1940 It is estimated that high-grade olivine, conveniently located with regard to transportation and power, is present in excess of 230 million tons above local drainage level in western North Carolina and north Georgia. Previous Technical Work In the past few years, olivine has attracted considerable attention in the refractory field. In the chemical processing industry, however, it has long been thought axiomatic that the cost of processing silicates is an economic barrier to their utilization, especially where more reactive minerals, such as carbonates, oxides or salts, are available. This attitude is not entirely justified in connection with olivine. unlike most silicates, olivine is readily attacked by acids, chlorine and other reagents without resorting to fusion to break down the silicate structure. Olivine has been suggested as a raw material for making epsom salt by roasting with pyrites.4 Other processes include acid treatment6 and digestion with calcium chloride.6 Recently a small plant was built near Webster, N. C., for making epsom salt from olivine by treatment with sulphuric acid. This plant is now in commercial operation, producing approximately two tons per day. Olivine is also receiving attention from the fertilizer industry as an inexpensive source of soluble magnesium.

Jan 1, 1942

By H. S. Rankin, E. C. Houston

OLIVINE is considered a valuable potential source of metallic magnesium in the chloride electrolytic process. Treatment of olivine with hydrochloric acid can be carried out under conditions that prevent the formation of gelatinous silicic acid, which would inhibit the reaction by forming a covering around the ore particles. It is our hypothesis that the formation of gelatinous silicic acid is avoided by the dehydrating action of the magnesium chloride, which takes up water to form a series of hydrates and leaves the silicic acid in granular condition. Leaching serves to separate the magnesium chloride from the silicic acid and unattacked ore, which can be treated with fresh acid in successive steps until extraction is essentially complete. The leach solution can be purified by the addition of caustic magnesia and the precipitated impurities removed by decantation or filtration. The resulting magnesium chloride contains: Fe, less than 0.001 per cent; Mn, 0.012 per cent; Ni, none. Chlorinationt of olivine has two major defects: (I) a large part of the chlorine goes to form silicon and iron chlorides, (2) the anhydrous magnesium chloride is held by absorption in the finely divided silica. SUPPLY It is well known that olivine, a silicate of magnesium and iron, is present in large amounts in several localities in the United States. The largest deposits occur in the southeast and on the Pacific Coast.1 The southeastern deposits were surveyed by Lewis2 in 1896 and by Hunter3 in the period 1933-1940. It is estimated that high-grade olivine, conveniently located with regard to transportation and power, is present in excess of 230 million tons above local drainage level in western North Carolina and north Georgia. PREVIOUS TECHNICAL WORK In the past few years, olivine has attracted considerable attention in the refractory field. In the chemical processing industry, however, it has long been thought axiomatic that the cost of processing silicates is an economic barrier to their utilization, especially where more reactive minerals, such as carbonates, oxides or salts, are available. This attitude is not entirely justified in connection with olivine. Unlike most silicates, olivine is readily attacked by acids, chlorine and other reagents without resorting to fusion to break down the silicate structure. Olivine has been suggested as a raw material for making epsom salt by roasting with pyrites.4 Other processes include acid treatments and digestion with calcium chloride.6 Recently a small plant was built near Webster, N. C., for making epsom salt from olivine by treatment with sulphuric acid. This plant is now in commercial operation, producing approximately two tons per day. Olivine is also receiving attention from the fertilizer industry as an inexpensive source of soluble magnesium.

Jan 1, 1942

By H. S. Rankin, E. C. Houston

Olivine is considered a valuable potential source of metallic magnesium in the chloride electrolytic process. Treatment of olivine with hydrochloric acid can be carried out under conditions that prevent the formation of gelatinous silicic acid, which would inhibit the reaction by forming a covering around the ore particles. It is our hypothesis that the formation of gelatinous silicic acid is avoided by the dehydrating action of the magnesium chloride, which takes up water to form a series of hydrates and leaves the silicic acid in granular condition. Leaching serves to separate the magnesium chloride from the silicic acid and unattacked ore, which can be treated with fresh acid in successive steps until extraction is essentially complete. The leach solution can be i purified by the addition of caustic magnesia and the precipitated impurities removed by decantation or filtration. The resulting magnesium chloride contains: Fe, less than 0.001 Per cent; Mn, 0.012 ; per cent; Ni, none. Chlorination† of olivine has two major defects: (1) a large part of the chlorine goes to form silicon and iron chlorides, (2) the anhydrous magnesium chloride is held by absorption in the finely divided silica. SupplY It is well known that olivine, a silicate of magnesium and iron, is present in large amounts in several localities in the United States. The largest deposits occur in the southeast and on the Pacific Coast.' The southeastern deposits were surveyed by Lewis2 in 1896 and by Hunter3 in the period 1933-1940 It is estimated that high-grade olivine, conveniently located with regard to transportation and power, is present in excess of 230 million tons above local drainage level in western North Carolina and north Georgia. Previous Technical Work In the past few years, olivine has attracted considerable attention in the refractory field. In the chemical processing industry, however, it has long been thought axiomatic that the cost of processing silicates is an economic barrier to their utilization, especially where more reactive minerals, such as carbonates, oxides or salts, are available. This attitude is not entirely justified in connection with olivine. unlike most silicates, olivine is readily attacked by acids, chlorine and other reagents without resorting to fusion to break down the silicate structure. Olivine has been suggested as a raw material for making epsom salt by roasting with pyrites.4 Other processes include acid treatment6 and digestion with calcium chloride.6 Recently a small plant was built near Webster, N. C., for making epsom salt from olivine by treatment with sulphuric acid. This plant is now in commercial operation, producing approximately two tons per day. Olivine is also receiving attention from the fertilizer industry as an inexpensive source of soluble magnesium.

Jan 1, 1942