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By K. Harms, T. D. Jones

TO unload large tonnages of lead bullion cast in 100-lb. bars is a problem which has confronted the lead refineries for many years. The bars, on arrival, must be restacked for unloading by truck or hand-charged to charging machines. Selected crews of labor, capable of working at sustained speeds for five- or six-hour periods, are required for this exhausting task. Due to the fatigue involved crew personnel changes rapidly. During the war it became increasingly difficult to maintain crews, especially in critical labor areas, so that the development of casting and shipping ten-ton lead blocks from the smelters to the refineries became a must in our operating program. For many years lead refineries, when making interdepartment or intradepartment transfers, have cast lead blocks weighing five or ten tons which are easily handled by crane by merely attaching the crane hook to a steel anchor embedded in the frozen lead blocks. In previous years, the practice was to use regular smelter slag pots which, due to their rounded shape, produced what were called "buttons" by the refinery personnel. The button-type blocks were unsafe as they rolled and tipped easily and were unsatisfactory for stacking since no piling pattern could be followed. To remedy this situation, flat-bottom molds came into general use and later the bottoms were made concave to prevent slipping.

Jan 1, 1946

By T. F. Archbold, P. G. McCormick

Silica fiber 11arkevs and hardness irzdentatiozs have been used to study the thermal diffusion of racancies in zinc placed in temperature gradients of 460o and 706oK per Cm All markers mored toward the higher temperatures, and the data show that the heat of trarlsport Q is greater than the eizthalpy of z,acancj3 forrjalion E by an amount equal to 3.5 kcal per mole. These results ore not in agreement with those obtained in either of the two previous studies with zinc. The problem is discussed in terms of experimental differences and racancy source and sink efficiencies. THE general interest in thermal-diffusion phenomena over the past several years has prompted a number of marker movement studies using pure metals. In order to understand better the relationships between thermal and mass flow, a general goal of the experiments has been to obtain values for the net enthalpies carried by the diffusing atoms. For self-diffusion by means of the vacancy mechanism, the determination of relative marker positions before and after an anneal in a temperature gradient permits a calculation of a value for (Q - Ef). Q is the transferred enthalpy, and Ef is the enthalpy of vacancy formation in the metal being investigated. The initial experimental study of thermal diffusion in pure metals was accomplished by Shewmon who found essentially no movement of surface-hardness indentation markers in single and bicrystals of zinc held for 20 days in a temperature gradient of 310°C per

Jan 1, 1967

By Edward Wichers

THE purpose of this paper is to set forth the matters of principal interest in connection with work done in the past few years on the purification of the metals of the platinum group, including the study and modification of methods already in the literature and the development of new procedures. For the most part, the results will be given in summary form, reserving the publication of detailed data and directions for a forthcoming paper to be issued by the Bureau of Standards. In recent years increasing interest has been shown in the preparation of the pure platinum metals, both by those concerned with the manufacture of the metals and their alloys for scientific and industrial purposes and those who are engaged in the study of the chemical or physical properties of the elements. The purification of the metals usually has been regarded as a matter so involved and difficult as to require the attention of specialists. It is hoped that this paper will show that any of the metals can be prepared in any desired degree of purity by relatively simple straightforward chemical methods. For the most part, it is thought that the methods given are suitable for small-scale refineries as well as for the laboratory; also, that they will bring the time required for the purification of any of the metals within reasonable limits. The new procedure suggested for purifying platinum should prove to be much shorter than any methods described in the literature.

Jan 1, 1928

By J. B. Newkirk, D. L. Martin, A. H. Geisler, R. Smoluchowski

A FUNDAMENTAL investigation of the mecha-nism of the ordering reaction and of the accompanying changes in properties has been undertaken, since an extensive study of this process could well contribute to the knowledge of phase transitions in alloys. Cobalt-platinum alloys were chosen for the study since they exhibit interesting and unusual permanent magnet properties.1,2. In addition, the ordering reaction in cobalt-platinum alloys is a convenient one to study experimentally because of the high maximum ordering temperature, the large difference in the X-ray scattering power of cobalt and platinum atoms, and the relative ease with which the alloys can be plastically worked into wire and strip. In the early stages of this study, it became apparent that the published phase diagrams&apos;, &apos; of the cobalt-platinum system contained questionable features, in the region of 40 to 60 atomic pct Co, which were considered in another publication by the authors.4 That portion of the research reported elsewhere on the equilibrium states of cobalt-platinum alloys does not confirm the presence of a previously reported, high temperature disordered tetragonal phase and a low temperature body-centered cubic phase. On the other hand, the structure of the ordered phase is face-centered tetragonal with an atomic distribution analogous to that of CuAu.4 This lattice forms from the disordered face-centered cubic phase in such an orientation that the <100> directions are parallel to the <100> direc-tions of the disordered phase. At compositions other than the ideal 50 atomic pct the ordered phase can exist in equilibrium at high temperatures with the disordered phase. A Widmanstatten pattern of plate-like particles of the ordered phase parallel to (110) planes of the disordered matrix is observed when an initially disordered alloy is held at these temperatures. The temperature range of the two-phase region has been determined for three alloys by X-ray diffraction analyses, microscopic examination, and electrical resistivity measurements, and these results are incorporated with some of those of Gebhardt and Köster in the revised phase diagram of fig. 1. The purpose of the investigation reported here was to examine the mechanism of ordering in co-balt-platinum alloys by X-ray diffraction and metal-

Jan 1, 1951

By John J. Croston

The year 1935 witnessed one of the world&apos;s oldest industries—gold mining—attain the stature of a billion dollar business. Preliminary estimates indicate that somewhat over 30,000,000 oz. of gold was produced, the largest output ever recorded and exceeding the previous year by more than 11 per cent. Of this huge total the Witwatersrand field produced about 10,800,000 oz., compared with 10,480,000 oz. in 1934. Russia was apparently the stellar performer, and from incomplete data it appears that between five and five and a half million ounces were produced by the Soviets compared with 4,200,000 last year and 2,814,000 in 1933. The United States nosed Canada out of third place with a production of 3,546,000 oz. against 2,916,000 in 1934, while Canada increased her total from 2,965,000 to 3,291,000 oz. Similarly, gains of lesser magnitude were made in Australia, the Gold Coast and other countries. As a result of great activity in developing outlying areas on the Rand, and the great number of new companies building mills in Canada, Australia, the Gold Coast and the United States, the years 1936 and 1937 should see new high records, as these new producers will more than offset any decline in the older properties. The whole world has become "gold conscious" during the past three years. It has been the subject of innumerable articles by economists and others, but, unfortunately, because of their lack of actual mining knowledge, they have treated the production of gold as a static affair, ignoring geological and technical factors. It is hardly necessary to draw attention to the fact that the world&apos;s gold-mining industry was slowly but steadily shrinking in importance, owing to the gradual depletion of known deposits that were profitable to work at costs existing prior to 1929. The International Geological Congress at Pretoria and the League of Nations Committee drew attention to the estimates of the mining experts of the various governments predicting a steady falling off in world production. On the Rand there

Jan 1, 1937

By E. F. Adkins, R. I. Jaffee, C. T. Sims

The effect of oxide dispersions on mechanical proberties of cobalt and cobalt-base powder-metallurgy alloys was investigated. This study shows that oxide dispersions added to pure cobalt greatly improve the high-temperature creep resistance of the metal. Dispersions in powder-metallurgy .cobalt alloys were muck less effective. COBALT is extremely valuable as an alloy base for certain high-temperature applications. Important examples may be found in the widespread use of cast and workable alloys in aircraft gas-turbine engines. With the increases in cobalt production in recent years, greater use may be made of cobalt-base alloys for high-temperature applications, provided

Jan 1, 1960

By J.B. Pullen

The United Verde mine is in the north central part of Arizona, on the northeasterly slope of the Black Hills, near the town of Jerome. Ore was first discovered in the district about 1875, and the first mining claims were located by M. A. Ruff-ner and associates in 1877. In 1888 the late Scnator William A. Clark secured control of the property and under his ownership it developed into one of the country&apos;s most important copper producers. The property was sold to the Phelps Dodge Corporation in 1935, and since then has been under this Corporation&apos;s management. Except for shutdowns caused by general world-market conditions, production has been continuous from 1890 to date. Geology The mineralized zone ranges in area from approximately 12 acres to less than 5 acres. All mineralization occurs in the pre--Cam-brian intrusives. The first intrusion, according to geologic records, was the quartz porphyry, which later was intruded by augite diorite. Following the diorite intrusion through a series of intrusions of lesser magnitude, a pipelike mass of massive sulphide, quartz and rock was formed. The diorite forms the hanging wall of this mass, and the porphyry the footwall. Between the footwall and the sulphide a band of chlorite schist was formed, probably owing to metamorphic conditions. Commercial ore occurs along the contact of the schist and sulphide extending into the sulphide, sometimes entirely through the schist, and fingering out into the porphyry. The ore deposit was formed by replacement similar to deposits formed in limestone areas. Faulting and deformation occurred in pre-Cambrian times and again in the Tertiary period, removing approximately 2000 ft. from the top of the main United Verde ore body, forming the United Verde Extension ore body, the only other major ore body in the district. Major development work has shown that the sulphide mass extends to the 3300-it. level, and diamond drilling below this level has indicated that the mass might extend below the 3700-ft. level, but in a diminished quantity. While many copper minerals exist in the mine, the chief commercial mineral is chalcopyrite. Aplan and vertical section of the mineralized zone showing the principal geological eatures is shown in Figs. I and 2. General Description and Physical Condition or Mine After over 50 years of active production, ore still exists on almost every level of the mine. This condition is due to many causes —-mine fires, which broke out as early as 1894, caused the abandonment of certain areas; subsidence and ground movements retarded the cleaning up of others. Furthermore, in the early days there was such an abundance of ore that when mining became dificult it was a simple matter to replace the production by going to a deeper level. Several attempts were made to recover the ore in the fire zone, both by glory-holing

Jan 1, 1943

By Warren J. Jackson, John L. P. Campbell

Automatic recording of the radioactivity of the earth&apos;s formations provides a log of relative intensities that, if properly interpreted, can be applied to oil-field engineering. Production, engineering, and geological departments regard the radioactivity log as a forward step in the securing of more conclusive information for successful well completions. Explanations of the technique, together with some of the problems to which radioactivity logging have been applied, are presented in this paper. Introduction Those responsible for the completion of new oil and gas wells, or with planning workover operations on old wells, have followed closely the development of radioactivity well logging because they are interested in reducing the number of unknowns that usually are present in such work. Many operators have made use of the log, or are acquainted with at least one of the applications, but it is unlikely that any one operator is familiar with all of the many applications that are possible. The purpose of this paper is to present a representative example of each of the many applications, wherever the information has been released by an operator, and to illustrate by hypothetical examples other applications, releases for which have not been given. In this way, it is hoped that a better understanding of the scope of this new engineering tool may be obtained. Although the literature contains many references that describe in detail the theory, development, and application of radioactivity well logging, a brief discussion of the technique may be helpful to those who are investigating the subject for the first time. All rocks contain radioactive material in varying concentrations. In general, shales contain relatively more radioactive material than sandstones or limestones. These radioactive materials disintegrate with time into other materials of lower atomic weight, and in that process of disintegration the rocks are emitting many rays, the most penetrating of which is the gamma ray. The intensity of emission of the gamma ray is proportional to the quantities of radioactive materials present. A higher rate of emission would be observed, therefore, opposite a shale than opposite a sandstone or limestone. Since measurable intensities of gamma rays are capable of penetrating as many as five concentric strings of casing, and as the gamma-ray intensity is relative to the formations, the measurements of variations in gamma-ray intensities offer a means of identifying cased-off formations in their proper stratigraphic sequence. The Gamma-ray Curve The measurement of gamma-ray intensities is accomplished by means of an ioniza-tion chamber that consists of a heavy cylinder, about 3 ft. long, that contains two insulated electrodes and is filled with an inert gas under high pressure. Under normal conditions no current will flow through the gas when an electrical potential is set up between the electrodes, but when

Jan 1, 1946

By John L. P. Campbell, Warren J. Jackson

Automatic recording of the radioactivity of the earth&apos;s formations provides a log of relative intensities that, if properly interpreted, can be applied to oil-field engineering. Production, engineering, and geological departments regard the radioactivity log as a forward step in the securing of more conclusive information for successful well completions. Explanations of the technique, together with some of the problems to which radioactivity logging have been applied, are presented in this paper. Introduction Those responsible for the completion of new oil and gas wells, or with planning workover operations on old wells, have followed closely the development of radioactivity well logging because they are interested in reducing the number of unknowns that usually are present in such work. Many operators have made use of the log, or are acquainted with at least one of the applications, but it is unlikely that any one operator is familiar with all of the many applications that are possible. The purpose of this paper is to present a representative example of each of the many applications, wherever the information has been released by an operator, and to illustrate by hypothetical examples other applications, releases for which have not been given. In this way, it is hoped that a better understanding of the scope of this new engineering tool may be obtained. Although the literature contains many references that describe in detail the theory, development, and application of radioactivity well logging, a brief discussion of the technique may be helpful to those who are investigating the subject for the first time. All rocks contain radioactive material in varying concentrations. In general, shales contain relatively more radioactive material than sandstones or limestones. These radioactive materials disintegrate with time into other materials of lower atomic weight, and in that process of disintegration the rocks are emitting many rays, the most penetrating of which is the gamma ray. The intensity of emission of the gamma ray is proportional to the quantities of radioactive materials present. A higher rate of emission would be observed, therefore, opposite a shale than opposite a sandstone or limestone. Since measurable intensities of gamma rays are capable of penetrating as many as five concentric strings of casing, and as the gamma-ray intensity is relative to the formations, the measurements of variations in gamma-ray intensities offer a means of identifying cased-off formations in their proper stratigraphic sequence. The Gamma-ray Curve The measurement of gamma-ray intensities is accomplished by means of an ioniza-tion chamber that consists of a heavy cylinder, about 3 ft. long, that contains two insulated electrodes and is filled with an inert gas under high pressure. Under normal conditions no current will flow through the gas when an electrical potential is set up between the electrodes, but when

Jan 1, 1946

By J. B. Pullen

The United Verde mine is in the north central part of Arizona, on the northeasterly slope of the Black Hills, near the town of Jerome. Ore was first discovered in the district about 1875, and the first mining claims were located by M. A. Ruff-ner and associates in 1877. In 1888 the late Scnator William A. Clark secured control of the property and under his ownership it developed into one of the country&apos;s most important copper producers. The property was sold to the Phelps Dodge Corporation in 1935, and since then has been under this Corporation&apos;s management. Except for shutdowns caused by general world-market conditions, production has been continuous from 1890 to date. Geology The mineralized zone ranges in area from approximately 12 acres to less than 5 acres. All mineralization occurs in the pre--Cam-brian intrusives. The first intrusion, according to geologic records, was the quartz porphyry, which later was intruded by augite diorite. Following the diorite intrusion through a series of intrusions of lesser magnitude, a pipelike mass of massive sulphide, quartz and rock was formed. The diorite forms the hanging wall of this mass, and the porphyry the footwall. Between the footwall and the sulphide a band of chlorite schist was formed, probably owing to metamorphic conditions. Commercial ore occurs along the contact of the schist and sulphide extending into the sulphide, sometimes entirely through the schist, and fingering out into the porphyry. The ore deposit was formed by replacement similar to deposits formed in limestone areas. Faulting and deformation occurred in pre-Cambrian times and again in the Tertiary period, removing approximately 2000 ft. from the top of the main United Verde ore body, forming the United Verde Extension ore body, the only other major ore body in the district. Major development work has shown that the sulphide mass extends to the 3300-it. level, and diamond drilling below this level has indicated that the mass might extend below the 3700-ft. level, but in a diminished quantity. While many copper minerals exist in the mine, the chief commercial mineral is chalcopyrite. Aplan and vertical section of the mineralized zone showing the principal geological eatures is shown in Figs. I and 2. General Description and Physical Condition or Mine After over 50 years of active production, ore still exists on almost every level of the mine. This condition is due to many causes —-mine fires, which broke out as early as 1894, caused the abandonment of certain areas; subsidence and ground movements retarded the cleaning up of others. Furthermore, in the early days there was such an abundance of ore that when mining became dificult it was a simple matter to replace the production by going to a deeper level. Several attempts were made to recover the ore in the fire zone, both by glory-holing

Jan 1, 1943

By Charles W. Goodale

The ores of the Butte district present a variety of combinations, and their treatment by concentration is an interesting study. They may be classified in general as follows: 1. Copper-silver ores, which are produced by the mines of the Anaconda group, and by the Mountain View, Colusa, Silver Bow and Parrot. The high-grade ores from these properties are roasted and then smelted; but a large proportion of the output is low-grade and siliceous, and hence requires concentration. The copper-bearing minerals are chalcocite, bornite, enargite and chalcopyrite, in varying proportions in the different mines, the gangue, which breaks readily into grains, being quartz and feldspar. 2. Silver-copper ores, of which the Gagnon vein is the largest producer. The grade of the ores from this mine is such that nine-tenths of the output requires concentration. The silver- and copper-bearing minerals of this vein are massive wurtzite, sphalerite, bornite, chalcopyrite, pyrite, tetrahedrite, enargite, tennantite and galenite, with a quartz gangue associated with feldspar and small quantities of barite and fluorite. The gangue is very hard and not at all granular. 3. Silver-ores containing a small amount of gold, embracing the product of the Alice, Magna Charta and Moulton claims, on what is known as the Rainbow lode, and that of the Lexington, Blue Bird, Nettie, Burlington and other mines. The gangue is quartz, carrying pyrite, sphalerite, galenite, tetrahedrite and argentite, with manganese in the form of rhodochrosite and rhodonite. Good results on ores of this class cannot be obtained by concentration, because large percentages of the silver-bearing minerals are disseminated through the gangue in such minute grains that even the finest practicable crushing

Jan 1, 1897

By Robert Archer

THE proper material of construction for a given purpose is that material which meets the requirements satisfactorily at the lowest ultimate cost. It is consistent with this principle that most aluminum castings are made of an alloy containing about 8 per cent. copper. This alloy possesses mechanical properties satisfactory for general engineering purposes together with manufacturing characteristics leading to the production of finished castings at low cost. It is to the aluminum industry what gray iron is to the iron and steel industry. Just as some services require "semi-steel," malleable castings or steel castings instead of gray iron, there is a certain and growing demand for aluminum castings of superior strength or ductility, or both. Since the beginning of the industry producers and others have sought to develop alloys or processes by which such castings could be made. Out of these efforts have emerged many alloy compositions and special processes, of which only a few have had sufficient merit to survive. It is the purpose of this paper to describe those which seem to the authors to offer the greatest promise for the production on a commercial scale of aluminum castings of superior mechanical properties, with special reference to heat-treated castings. The suitability of an alloy or process for actual manufacture is affected by so many factors that the problem of appraisal is not a simple one. Since this is such an important part of the whole subject it is proposed to discuss briefly some of the requirements. The final verdict is of course the result of commercial trial and experience. It will therefore, perhaps, be profitable to employ a somewhat historical method of treatment in discussing the subject of alloy development.

Jan 9, 1926

By Benjamin Talbot

(New York Meeting, February 1913.) THE problem of segregation and cavities in steel ingots is a subject which has given and is still giving metallurgists, en¬gineers, and operators matter for serious consideration.. This question has come more into prominence lately in the United States, clue largely to the desire of railroad engineers to secure a better rail than they have obtained in the past, as the service they demand is increasing in severity; and no doubt manufacturers will be able to meet what is required of them. The rails here are as good as those made in other countries, but the conditions of service and the extremes of climate are more severe and consequently more breakages occur. Various reasons have been advanced to explain why rails may not be as good in quality to-clay as in the past. Some engineers consider that modern methods of manufacturing, designed chiefly to obtain large output, tend to reduce the standard of excellence of more deliberate methods. Others think that 4-ton ingots are worse than those of 2 tons. Again, it is .stated that the 100-ton heat in one ladle is too large, and is a :step in the wrong direction in casting. My experience upon the question of the size of the ingot is that in rolling rails of from 85-to 100-lb. sections, the range of ingot is only practically such that the difference in the size does not help in the question of segregation, cavities, or blow-holes.

Jan 4, 1913

By H. K. Birnbaum

The effect of 1ow-temperature stabilization anneals on the structure of the 0 phase Au-Cd alloys and on the diffusionless transformations observed in these alloys was examined by X-yay diffraction techniques. A phase separation in the ß-phase region was proposed to account for the experimenta1 results. The effects of quenching from elevated temperatures on the transformation behavior of these alloys were shown to be consistent with the proposed mechanism. IT has been shown that the high-temperature ß phase (CsCl structure) of the Au-Cd alloy system transforms to a phase having an orthorhombic (D2) ß&apos; structurel1-3 for compositions near 47.5 at. pct Cd and a tetragonal (4/m, m, m) ß" structure* in the vicinity of 50.0 at. pct Cd. Both transformations are diffusionless, crystallographically reversible, and occur on cooling at about 60° and 30°C respectively. The temperature interval from the beginning to the end of the transformation is of the order of 5°C in each case. Although the transformations are normally athermal, some of them have been reported to occur isothermally.= wechsler6,7 has shown that the effects of quenching a 49.0 at. pct Cd alloy from elevated temperatures are consistent with the retention of a nonequilibrium number of lattice vacancies. Annealing of these quench effects results in a broadening of the X-ray reflections.8 After a suitable quench, the 47.5 at. pct Cd alloy transforms to a phase having not the p&apos; orthorhombic structure but another structure which has properties similar to that of the ß" tetragonal structure.5.9 This change in the type of transformation has also been obtained after long anneals in the ß-phase region at about 70oC10 The present investigation was primarily concerned with the structural changes accompanying the above transformation phenomena. The change in transformation product and accompanying physical changes during an anneal in the ß phase have been termed stabilization effects. Experimental Procedure —The results reported in this investigation were obtained with the use of a Norelco diffractometer fitted with a temperature-controlled cryostat. The specimen temperature was controlled to better than ± 0.l°C during the measurements. CrKa radiation monochromated electronically with the use of a scintillation counter and pulse height analyzer was utilized. Specimens containing 47.5 and 50.0 at. pct Cd were prepared by sintering filings obtained from homogenized ingots of the proper alloy composition. (Gold of 99.999 pct purity and cadmium of 99.98 pct purity were used). All heat treatments were carried out with the specimens capsulated in vacuum ( < 10 % mm Hg) or in a He-H gas mixture. The quenching technique used in these experiments was to drop the pyrex capsule which contained the specimen from the annealing furnace into water, the temperature of which was controlled. The pyrex capsule shattered on contacting the water resulting in a relatively rapid quench. After the heat treatment, the specimens were mounted in the diffractometer and were left undisturbed in the diffractometer specimen holder during each sequence of measurements. EXPERIMENTAL RESULTS A) Low-Temperature Annealing—The transformations which were considered "normal" for these alloys were those obtained athermally during furnace cooling at approximately 50°C per hr after an elevated temperature anneal. Under these experimental conditions, the specimens were observed to transform to phases having structures whose diffraction patterns could be indexed as the ß&apos; orthorhombic structure for the 47.5 at. pct Cd and as the 0" tetragonal structure for the 50.0 at. pct Cd alloys. The transformation temperatures on cooling were approximately 60" and 30°C, respectively. Under the "normal" conditions both transformations were observed to go to completion, i.e., the entire volume of the ß phase was transformed to the product phase. In some specimens an extremely weak ß 110 reflection was observed at 20°C indicating that a small amount of retained ß was present. The effect of low-temperature annealing on the nature of the diffusionless transformations was examined for the 47.5 and 50.0 at, pct Cd alloy. The specimens were annealed in evacuated capsules at temperatures in the vicinity of 600°C (as specified in Table I) for 24 hr and were then cooled to 100°C at a rate of 50°C per hr. The specimens were then removed from the capsules and mounted in the diffractometer without allowing the specimen temperature to drop below 80°C. Annealing at the low temperatures was accomplished in the diffractometer by means of the cryostat which was mounted around the specimen. During the low-temperature anneals the lattice parameter, integral breadth of the reflections, and ratios of the integrated intensities of the fundamental and super lattice reflections for the 0 cubic phase were periodically determined. After annealing for the required time, the specimens were slowly cooled in the diffractometer and the diffraction patterns were recorded as a function of temperature. The specimens were cooled until the phase transformations were completed, following which the specimens were heated and diffraction

Jan 1, 1960

By S. Lipson, H. W. Antes, H. Rosenthal

A study was made of the effect of ingot structure on the strength and ductility of high-strength wrought-aluminum alloys. It was found that a fine-cast structure facilitated complete homogenization which, in turn, resulted in significant increases in ductility and strength. A completely homogenized 7075-T6 alloy developed tensile properties of 85,000 psi UTS, 75,000 psi YS, with 40 pct RA. Completely homogenized 7001-T6 alloy tensile properties were 102,000 psi UTS, 99,000 psi YS, with 19 pct Ra. A method was devised for making small ingots having secondary dendrite arm spacing of less than 10 u. This method involved multiple-pass arc melting of commercial rolled plate with a tungsten electvode. This material could be completely homogenized after 3 hr at 900°F; homogenization of the original plate material was not complete after 120 hv at 900°F. Degree of homogeneity was determined by use of metallographic and electron-microprobe analyses. The electron-micro-probe study also showed the preferential segregation of solutes in the microstructure. HIGH-strength aluminum alloys, such as those of the 7000 series, usually freeze by the formation and growth of dendrites. The dendrite arm spacing (DAS) depends on the rate of solidification.&apos; Commercial ingots are usually direct chill-cast to promote more rapid solidification, but, due to the large mass of the ingot, localized solidification times are long and a large DAS results. During solidification, solute elements are rejected by the solid as it forms, causing enrichment of the liquid and ultimately solute-rich interdendritic regions. In order to attain a homogeneous ingot, the segregated solutes must diffuse across the dendrite arms. The larger the DM, the longer the time for complete homogenization. In the case of commercial ingots, the DAS is so large that the time for complete homogenization is prohibitively long and, therefore, second phases or compounds are always present. These un-dissolved phases are carried over to the wrought material during processing, resulting in an impairment of strength and ductility. In addition, the mechanical fibering of the undissolved second phases or compounds during working results in mechanical property anisotropy. If complete homogenization could be attained, higher ductility could be expected. The realization of higher ductility at current strength levels is a desirable objective; however, if higher-strength alloys were wanted, it might be possible to sacrifice some of this ductility by adding more solute elements and produce even higher-strength alloys than are currently available. Further, if complete homogenization leads to more efficient utilization of solute elements, then more dilute alloys should have relatively high strengths with very high ductility. In all instances, it would be expected that the degree of mechanical property anisotropy due to mechanical fibering would be reduced. Therefore, it was the purpose of this investigation to produce cast structures that would facilitate homogenization and to determine the effect of homogenization on the properties of high-strength, wrought-aluminum alloys. MATERIAL CLASSIFICATION Commercial Alloys. In order to illustrate the non-homogeneous condition that exists in commercial high-strength, wrought-aluminum alloys, typical micro-structures of 7001, 7075, and 7178 are shown in Fig. 1. The chemical compositional specifications of these alloys are given in Table I. It can be seen in Fig. 1 that a considerable amount of undissolved second-phase material is present in each of these alloys. The solute elements associated with the undissolved phases were identified by electron microanalyses. Back-scattered electron images and characteristic X-ray images of the three commercial alloys are shown in Figs. 2, 3, and 4. These data indicate that the second phases are regions of high copper and high iron-copper concentrations. The second-phase material also was analyzed for magnesium, zinc, manganese, chromium, and silicon, but no significant enrichment above that of the matrix was found. Therefore, the problem of homogenization resolved itself into one of dissolving the copper-rich and the iron-copper-rich second phases. In order to accomplish this objective, two approaches were made. The first was to reduce the iron as low as possible since this element has a maximum solid solubility of 0.03 pct in aluminum. The second was to produce cast structures with finer DAS to facilitate dissolving the second phases. Commercially Produced High-Purity Alloys. A special high-purity, 2000-lb ingot of 7075 alloy was made by a commercial producer. This alloy contained the following weight percentages of solutes: 5.63 Zn, 2.48 Mg, 1.49 Cu, and 0.21 Cr. All other elements combined were less than 0.02 pct by wt including iron and silicon at less than 0.01 pct each. The ingot was cast and processed into rolled plate using standard commercial techniques. Microstructures of standard commercial 7075 and the special high-purity 7075 are shown in Fig. 5. It can be seen from this figure that the high-purity alloy has less undissolved second-phase material, but a significant amount was still present. The second phase in the high-purity material did not contain iron but it was found to be enriched with copper. The slight effects of the increased purity and de-

Jan 1, 1968

By Richard R. Zupp, David A. Stevenson

An experimental method to determine the carbon activity in various solid solutions was developed. Samples of the solid solutions and an Fe-C reference sample were equilibrated with respect to carbon content by annealing them in a Hz-CHI gas mixture in a closed cell. The carbon content of each sample was determined, and the carbon activity was obtained from the carbon content of&apos; the reference sample and well-established data for the dependence of the carbon activity on the carbon content in Fe-C alloys. The influence of vanadium on the activity of carbon in austenitic Fe-C-V alloys at 1000°C was determined by this technique. A general semiempirical correlation was developed to describe the dependence of the activity coefficient of- carbon on the composition of ternary austenitic iron-base alloys containing interstitial carbon and a substitutional solute. The correlation is particularly useful in predicting the partitioning of- carbon between various alloys. THE influence of substitutional solutes on the activity of interstitial solutes in metallic solid solutions is important in the theory of alloy phases. Solid solutions of particular interest are the fcc austenite phases of ternary Fe-C-Z systems, in which carbon is the interstitial solute and Z represents any substitutional solute. Carbon-activity data are also needed in these solid solutions to solve practical problems; the quantitative treatment of diffusion-controlled transformations&apos; is an examvle. Experimental information is available for ternary austenitic solid solutions containing Mn,2 Si,2 and A16 as the substitutional solute. Because qualitative preliminary studies indicated that vanadium appreciably decreases the carbon activity,14 the present investigation was undertaken to determine the influence of vanadium on the activity of carbon in austenite. Although Flender and ever" measured carbon activity over a range of compositions in the Fe-C-V system, they were primarily interested in determining phase boundaries in the ternary system, so most of their measurements were outside the composition range for stability of single-phase austenite. Petrova and Shvartsman&apos; also made limited measurements of the carbon activity in Fe-C-V alloys. The dependence of the carbon activity on the carbon content of an alloy may be determined by passing COCOz or H2-CH4 gas mixtures of carefully measured composition over the alloys, determining their equilibrium carbon content, and utilizing the relevant equilibrium relationships. smith16 used this technique with both CO-COZ and HZ-CH4 gas mixtures to determine the dependence of carbon activity on carbon content in pure Fe-C alloys. His data, which are in good agreement with those of some previous and subsequent investigators,6&apos;17 but not with those of others,lfl&apos;ao are usually considered to be the most reliable. Although the same method can be applied to Fe-C-Z alloys, it is difficult experimentally, because the appropriate gas mixtures are almost pure CO or Hz. A simpler technique is to simultaneously equilibrate the Fe-C-Z alloys and pure Fe-C alloys with the gas mixtures, and then use Smith&apos;s data to determine the carbon activity in the pure Fe-C alloy. A number of investigators have employed this technique. others Have used the partitioning of carbon at the interface of a diffusion couple prepared from an Fe-C alloy and a Fe-C-Z alloy. In the present study, a closed-cell method was developed by which carbon was selectively transferred via a gas medium between pure Fe-C alloys and Fe-C-V alloys which were not in physical contact. A similar method was developed independently by Heckler and winchel14 and used to study the Fe-C-Ni system. EXPERIMENTAL METHOD A schematic diagram of the experimental arrangement is shown in Fig. 1. In a typical experiment, a 5-g Fe-C sample was placed in one compartment of a quartz cell, and a 5-g Fe-V sample was placed in each of the other compartments. The cell was evacuated, outgassed, backfilled with approximately 125 Torr of hydrogen, and sealed. After being placed in a fur-

Jan 1, 1967

By A. Grant Elliot, H. W. Lavendel

qualitative picture has been developed to describe the oxidation behavior of TaSi2-coated tantalum and CbSi2-coated columbium. These systems have a significantly lower inherent oxidation resistance than MoSi2-coated molybdenum does. This stems primarily from the fact that Ta2O5 and Cb2O5 are nearly as stable thermodynamically as SiO2, whereas MoO2 or Moos are not. Further, diffusion of silicon in the Ta- and Cb-Si system is considerably slower than in the Mo-Si system. These ,factors prohibit the mechanism of selective oxidation of- silicon which accounts for the oxidation resistance 01- MoSi2-coated molybdenum. The silicide can be stabilized by adding suitable Modifiers which increase the thermodynamic stability of the silicate formed during oxidation. Modifiers, such as aluminum, can be inroduced into solid solution in the coating. in controlled amounts through proper selection of the source in the pack cementation process of coating fov~rzatiorz. Addition of aluminum to TaSi2, coatings on tantalum was effective in moderately increasing the oxidation resistance. EXTENSIVE experimental work and analysis have established the nature of the oxidation behavior exhibited by MoSi2- and MoSi2 -coated molybdenum-base alloys, and defined the conditions for maximum protection against oxidation of the substrate.&apos;-* The oxidation resistance of MoSi2 in the temperature-pressure range of 1100°C-PO2 > 10-5 atm to 1900°C— PO2 > 10-1 atm is due to the formation at the surface of a continuous film of SiO2 which results from selective oxidation of silicon. Under the prevailing kinetic conditions, this film is stable toward the molybdenum silicide with which it comes in contact. Initially molybdenum oxidizes also, but it forms volatile species. SiO2, however, nucleates and grows as a condensed phase. Once a continuous film of SiO2 has formed, the oxidation rate falls to that observed for the oxidation of pure silicon indicative of diffusion through the oxide film as the rate-controlling mechanism. This oxidation behavior is of course highly dependent upon temperature and oxygen pressure. Bartlett and Gage13 and Bartlett, McCamont, and Gagelb define precisely this dependence in terms of the oxygen partial pressures and silicon diffusivities required to support a stable SiO2 film. At low temperatures (near 500°C—the "pest" region) silicon diffuses too slowly to be selectively oxidized. Hence, molybdenum and silicon oxidize readily in proportion to their stoi- chiometry. At high temperatures and low pressure, SiOz dissociates to form volatile SiO(g), and a protective film cannot be maintained. Application of the MoSiz/Mo system is limited to temperatures below 1900oC, the eutectic between MoSi, and MO5Si3.5 The oxidation behavior of MoSi2-coated molybdenum is essentially the same as that outlined above with the exception that the MoSi2 is not in equilibrium with the molybdenum substrate. At the temperatures under consideration silicon will diffuse rapidly into the molybdenum eventually converting the coating to MosSi3.4 The rate constant for subsequent decomposition of Mo5Si3 into Mo3Si plus silicon, and/or the diffusivity of silicon through Mo3Si then becomes low enough to allow active oxidation of both molybdenum and silicon with subsequent degradation of the specimen. A stable silica film can be formed but at temperatures and/or oxygen partial pressures higher than those required with MoSi2 present as a source of si1icon.l, 4 Because of the similarity between the silicides of molybdenum and those of columbium and tantalum one would expect similar oxidation behavior for coatings in the respective systems. This is not entirely the case, however, as shown by the experimental results reported herein. Regarding tantalum and columbium disilicide coatings on tantalum and columbium substrates, respectively, the oxygen arriving at the surface of the coating partitions itself nearly equally between the metal and the silicon, and a two-phase oxide layer (Me2O5 plus SiO2) is always formed. The diffusion of silicon in the tantalum and columbium silicides is relatively slow, compared to that in the molybdenum silicides, which further enhances this equipartitioning of oxygen. Thickening of the coating during service by inward diffusion of silicon into the substrate is correspondingly slow, and the effective thickness of the coating at the roots of cracks and defects is only slightly changed providing high probability for premature coating failure. Furthermore, the SiO2 glass that is generated is not thermodynamically stable with respect to the coating. The metal silicide tends to reduce the SiO2 liberating either free silicon or SiO. The situation can be improved by suitably modifying the coating such that the stability of the protective glass which is generated during service is increased. Thus, selective oxidation of silicon and the modifying agent will occur, and the silicide coating will not tend to reduce the oxide layer. Modifying agents can be introduced into the coating by the pack cementation process. Using sources containing the modifier at controlled chemical potentials allows control of the coating composition. Partially substituting aluminum for silicon in TaSi2 coatings by forming a Ta(Si,Al)2 solid solution was effective in moderately increasing the oxidation protection.

Jan 1, 1968

By J. H. Henderson, L. A. Wilson, R. L. Gergins, R. J. Wygal, D. W. Reed

This paper presents a method of predicting the production history of an underground combustion recovery process. A rigorous solution of the thermodynamics and hydrodynamics involved is beyond the scope of this report. However, a practical scheme to appraise combustion recovery performance has been Worked out. By prudent assumptions, regarding the attainment of steady-state conditions, a trial-and-error solution, which satisfies both material balance and three-phase relative permeability requirements has been evolved and tested. As a combustion zone moves through a formation the interstitial water, the water of combustion and a portion of the oil wil1 be vaporized. These vapors will move downstream to a cooler region of the formation where they will condense. Part of the remaining oil will be displaced by the imposed gas drive and what remains behind will be consumed as fuel. The fluids will distribute themselves downstrean? in a manner which will satisfy the three-phase relative permeability characteristics of the formation. Three distinct zones will exist ahead of the combustion zone: (I) a zone termed a water bank which contains three mobile phases, oil, water and gas; (2) a region containing two mobile phases, oil and gas, called the oil bank; and (3) a zone having the fluid saturution distribution which existed prior to combustion. The mobile water will impose a water flood on the oil in the region containing three flowing phases. The process can be visualized as a simultaneous water .flood and combustion-supported gas drive. It is possible to estimate the saturation distributions in the water bank and oil bank as well as the production history for any combustion temperuture if the porosity, three-phase relative permeability characteristics, oil viscosity and initial saturations are known. This has been done for injection pressures ranging from I to 100 atm, oil viscosities of 10 to 1,000 cp and porosities from 20 to 40 per cent. Several of these calculations have been checked in the laboratory, with the result indicating rather good agreement between the predicted and observed production histories. The analytical and experimental techniques are described and the comparison of predicted and observed performance presented. INTRODUCTION Considerable research by the oil industry during the past 10 years has been directed toward the thermal recovery of crude oil. Of all schemes considered, the one receiving the most attention is in situ combustion. This is a process in which part of the oil is actually burned within the reservoir rock. The uniqueness of the process lies in its potential. Theoretically, this potential generates from the following: (1) it may open the door to vast reserves previously not economically producible, (2) it may induce increased production rates where low rates are now realized and (3) it may give high over-all recovery efficiency. The general idea of the process has received considerable attention in the literature &apos;-&apos; and the following brief description is intended for orientation only. In situ combustion can be visualized by considering a linear system, one end of which represents the injection well and the other the producing well. The formation at the inlet end is raised to ignition temperature by placing a gas or electric heater at the face of the formation or by the ignition of thermite, charcoal or similar material. While heating, the water and part of the oil in the heated region is vaporized and moved out into the reservoir by the injection of gas containing oxygen. In addition, part of the oil is displaced as liquid by the imposed gas drive. The oil not displaced is modified to an immobile, coke-like material (hereafter referred to as coke) by the high temperatures existing immediately ahead of the combustion zone. This coke is used as fuel, and the combustion front advances through the formation at a temperature which is probably in excess of 800°F. As the combustion front advancek it will drive ahead all interstitial oil not rendered immobile and all interstitial water plus the water formed by the combustion of hydrogen. As a result the sand behind the combustion zone is freed of all oil and water. Although the general description of the process has been outlined in the literature, there has been no consideration of the behavior of the fluids moving downstream from the combustion front. It is the purpose of this paper to present a technique

By Joseph A. Holmes

Iv all new movements unavoidable misapprehensions arise, which should be cleared away, lest they retard the progress of the movement itself. An impression has gone abroad that the movement for conservation of resources is a new movement. No one knows better than the engineer that this is not the case. Men like Douglas and Raymond and John Fritz and Edison and McDonald, and hosts of others, have preached and practiced conservation as applied to mineral resources throughout a long and useful life-time; and, in general, the work of the engineer and the chemist, both in this and in other countries, has been along the line of continually greater efficiency in the use of all available materials. And the results already accomplished through the efforts of these experts are now saving annually many millions of dollars to the people of the United States in materials and labor. It is true, however, that the need for conservation, that is, for a wiser and more efficient use of the natural resources, has taken on a new life, and is being brought home to the people of the United States in a manner which is awakening public interest and even the public conscience. It is, therefore, both appropriate and fortunate that the engineers, the chemists, and the thinking men of all classes are availing themselves of the present impetus to the movement to emphasize anew the lessons which heretofore they have found it more difficult to impress upon the American public or even upon the captains of industry. Still another of these misapprehensions is to the effect that many of the leaders in the present movement hope to bring about conservation of resources through legislation or execu-

May 1, 1909

By L. O. Bieber, L. H. Martin

DIFFERENT MELTS OF THE same type of nickel and high-nickel alloys, while having almost identical mechanical properties at room temperature, may have widely varying hot malleability. Either the upper limit or burning temperature may vary or a variation in malleability may occur within the temperature limits normally encountered during hot working. Melts which have reduced hot malleability of the latter type, are said to have a "hot short" range. Examination of melting records and chemical analysis of these heats fails in most cases to show the reasons for these variations. In May, 1930, an investigation was started to determine if a quick and accurate method of hot-malleability testing could be developed which would predict the ability of the metal to withstand hot forging and hot rolling by standard mill practices. The results obtained were so satisfactory that from that time on, all melts of nickel and high-nickel alloys produced in the International Nickel Company&apos;s Huntington, W. Va. Works have been tested when hot malleabilty was an important factor. To date, over 63,000 commercial melts of Monelt † nickel, Inconel† and other high-nickel alloys have been tested and the test data compared with processing results. As the result of experience gained in over sixteen years, two standard methods of hot malleability testing have been adopted.

Jan 1, 1948