Search Documents

By G. Townsend Harley

STOPING methods in which shoveling plays an important part are gradually being replaced by other and cheaper methods. But there will always be considerable shoveling done underground in stopes as well as in drifts, tunnels, urinzes, and shafts. At the mines of the PhelpsDodge Corporation at Tyrone, N. M., the cost of shoveling in all stopes in 1917 amounted to 24c. per T. In the top-slice stopes for the same period, it cost 27 c. per T. or 16 per cent, of the total cost of these stopes. The tonnage for shovelers from all stoping was 9.3 T. per man, and for topslicing 8.2 T. per man. These stopes were not unduly hot, and there was not more than the usual amount of timber to interfere with the work of the men. The tonnages obtained per shoveler were considered low; first, because of a poor grade of Mexican labor, many of the men having come in from railroad grading camps; and second, because of a poor spacing of raises, especially in the top-slice stopes, where, in general, they were spaced 25 ft. by 66 ft. (7.6 by 20.1 m.) centers. The average wage per laborer shift was $2.67 during the year. It was thought, however, that even under these conditions the men were not producing the tonnage that they should, so, with the consent of the management, the writer undertook to determine how the general efficiency of the underground shoveling could be improved. No predetermined plan for conducting these experiments was arranged because we had no definite ideas as to the scope of the work or the number of elements into which the investigation would resolve itself, before all of its phases could be determined. We were sure, however, that any work that would thoroughly cover the ground would have to be in the nature of a systematic time study, combined with a course of instruction in correct shoveling methods and adequate and intelligent supervision of the work. Two or three companies in the Southwest have done some work to determine the proper shovel to be used undcrground, but so far as is known the work has been limited to equipping certain parts of their mines with a particular type and size of shovel and thereafter watching the cost and efficiency records. In each case it seems to have been the shovel that held the 21-lb. (9.5-kg.) load that gave the bcst results. Excepting personal communications from these companies, the only data available on scientific shoveling are contained in F. W. Taylor's book, "The Principles of Scientific Management," and D. J. Haucr's article, in The Contractor for March 29, 1918, "A Hundred Hints for Shovelers." This paper discusses and draws conclusions from several thousand time-study readings, taken both on the surface and in the mines for nearly a year. A sufficient number of readings were taken on each factor in the problem for the plotting of curves of the performances and to obtain accurate indices of the work to be expected from this class of labor. The work is not as complete in all of its details as we would like to havc it, because we were forced to stop the work temporarily, owing to the numbcr of men going into the National service and our inability to get others who could make time studies. The results obtained so far, however, have been of such a startling nature that we have decided to submit them at this time, subject to future modification. It is hoped, also, that a free discussion of this paper will lead to a disclosure of any errors that may have becn embodied and offer some valuable suggestions for the conduct of future work.

Jan 1, 1920

By R. F. Burdyn

The inadequate use of centrifugation to economically recover solids from weighted drilling fluids reflects the need for better equipment and techniques for this putpose. Laboratory studies in the development of an improved separator are described in which an operating equation is derived and tested. Results show that the concentric cylinder geometry employed effectively separates bnrite from a suspension and that the operating equation provides a good approxinmtion for scale-up. INTRODUCTION Our current drilling technology frequently requires a high-density drilling fluid obtained by addition of barite. In the course of drilling, formation solids which are too fine to be removed either by screening or settling become suspended in the drilling fluid and gradually the volume of solids in the mud increases. The volume fraction of solids must be limited (if a satisfactory set of rheological parameters are to be maintained). A centrifugal separatorprovidesan economical way of accomplishing this. The barite recovery process can be considered as a separation of two solids. One, the light solids, composed of formation and added solids, has a specific gravity of 2.6 to 2.7; the other, barite, has a specific gravity of 4.2 to 4.3. This density difference, plus the fact that the average light-solids particle size is much smaller than the average barite particle size, permits separation by a centrifuge. In drilling fluids some of the coarse particles of the light-solids-range will settle faster than fine particles of the barite-particle range. As a result a complete separation of the two species is not possible. since the object of the process is not merely recovering the maximum amount of barite but includes as well removing the maximum amount of light solids, an optimum barite recovery efficiency exists. From a practical standpoint this optimum cannot be determined in the field for each drilling fluid system, and in practice the separation is less than optimum, with some sacrifice of barite. Drilling technology has included centrifugal separators for barite recovery for more than a decade. Results have been reported by a number of investigators indicating that the process is practical and economica1. l-4 The decision to use a centrifuge is based on economics in which direct cost savings and the indirect benefits in rig time derived from improvement of the drilling fluid are important factors. One would expect that centrifugal separation of barite from drilling fluids would significantly affect barite consumption; however, this is not the case. The Minerals Yearbook shows an annual domestic barite consumption in the drilling industry of nearly 1 million tons.5 By rough estimate there are perhaps 80 separators presently in field use. Assuming half of these in use at any one time, operating an average of four hours per day, at recovery rates averaging 3,000 Ib of barite per hour, total annual recovery is about 90,000 tons. This is less than 10 per cent of he total barite used. I conservatively estimate that barite consumption in drilling operations can be reduced by 30 per cent through greater utilization of centrifugal separators. To encourage more widespread acceptance of centrifugal separators in the drilling industry, improved equipment and techniques would be very desirable. The present paper, covering theory and results obtained from a laboratory model, is the first in a series on he development of an improved mud separator for field use. THE CONCENTRIC CYLINDER GEOMETRY AS A SEPARATING DEVICE Consider the geometry shown in Fig. 1, consisting of two concentric cylinders separated by an annular space. These are arranged so that the outer cylinder is fixed and the inner one can be rotated about its axis on shafts sealed against the ends of the outer cylinder. If the outer cylinder is fitted with openings at either end, the inner

Jan 1, 1966

By J. A. Herbst, D. W. Fuerstenau

This paper examines the zero order production phenomenon in the context of the size discretized batch grinding model. A restrictive interrelationship between the selection and breakage parameters of the model, which is mathematically sufficient to ensure zero order behavior, is delineated. Based on this interrelationship, a scheme is developed for predicting the values of the selection and breakage parameters for all size fractions from a minimum of experimental data. To test this scheme, dolomite was ground in a laboratory batch ball mill. Successful simulation of the comminution behavior of this system was achieved using the batch grinding model with the parameter values obtained from the proposed scheme. Historically, a preponderance of comminution research has centered on attempts to relate breakage energy to the performance of comminution machines. Concomitantly, grinding data were interpreted almost exclusively in terms of inherently empirical energy-size reduction relationships1-3 or "laws of comminution"4- 6 which were based on highly oversimplified descriptions of the fracture process. In some instances, these relationships provide a crude basis for the correlation of experimental data, but, invariably, this approach is inadequate for meaningful process simulation. The control and optimum design of comminution circuits require a mathematical model capable of depicting the size reduction behavior of every size fraction for grinding conditions of technological importance. Energy-size relationships do not provide this detailed information. For example, an energy-size analysis for batch ball-milled dolomite has recently been completed in the authors' laboratories.7 This analysis provided a satisfactory correlation between the hypothetical size modulus, which characterizes only the finer portion of the size distribution, and the input energy. However, this relation did not constitute an adequate description of the complete system. In general, one of two distinct viewpoints toward simulation has been adopted in recent comminution research. The first approach focuses on the fracture of single mineral specimens, with the essential aim of representing the over-all process in terms of the breakage characteristics of individual particles and the characteristics of the stress field which the particles experience within the particular size reduction device. As illustrated by Harris's review,' the actual incorporation of single-specimen fracture information into a description of the behavior of a multiparticle comminution system has seldom been attempted. The only model to accomplish this incorporation was the one developed by Schönert.8 The Schonert model treats single-passage grinding machines in terms of a distribution of effective loads acting on a particle, a distribution of required particle breakage energies, and the breakage product distribution. However, the use of single-particle fracture behavior to derive models of the size reduction process is at present limited to machines in which the particle residence time is approximately equal to the time required to apply stress. As a result, Schönert's analysis cannot be used to advantage to simulate the complex environment which prevails within a tumbling mill. For multiple-passage systems a second approach to the description of comminution processes has been more fruitful. This approach entails the formulation of a mathematical model which is phenomenological in nature in that it lumps together the entire spectrum of stress-application events which prevail in a system under a given set of operating conditions. The appropriately defined average of these individual events is then considered to characterize the over-all breakage properties of the device. Thus, to analyze the performance of a tumbling mill, the manner in which the particles of a particular size (or size fraction) are stressed need not be distinguished. Instead, a single parameter is assumed to represent the resistance of that size to fracture, given the average grinding environment which exists in the mill. The isolation of such a parameter and a related set of quantities, which constitute the breakage product size distribution for the average event in this size fraction, allows the formulation of physically meaningful descriptive equations capable of yielding precise and detailed information for simulation.

Jan 1, 1969

By L. Valentik

Many attempts have been made during the last 40 years to evaluate the performance of gravity separation equipement, that is, the effectiveness with which light and heavy particles are separated. The most comprehensive treatment of the subject was made by Cerchar at the 1st International Conference on Coal Preparation held in Paris in 1950. The methods suggested by the Conference were accepted and very widely used in the last two decades. This paper discusses an improved method of evaluation in the light of the now-accepted standard presentation. The float-and-sink analysis of the product is presented on a Gaussian distribution curve, resulting in an easier visualization of the inherent difficulties of separation. The ogives of the distribution curve me then plotted, giving a quantitative measure of the deviation from perfect separation as an error distance instead of an error area. Illustrations of the new method are given both for gravel and for coal preparation, but the content is valid and applicable to other types of minerals which are separated by gravity methods. Many attempts had been made during the last forty years to evaluate the performance of heavy-media separation (HMS) equipment, that is, the effectiveness with which floats and sinks are separated.'-' The most comprehensive treatment of the subject was made by Cerchar at the 1st International Conference on Coal Preparation held in Paris. 6 The primary aim was the thorough understanding of the mechanism of separation and the unified presentation of data on gravity separation so that the evaluation and comparison of washery performance could be made from all over the world. No strict overall standardization has been achieved, but after the conference a more or less uniform presentation of performance was accepted, which, during the last two decades, has been very widely used. In this paper, illustration of the old methods and an improved method of evaluation will be given. HEAVY-MEDIA SEPARATION (HMS) PERFORMANCE CRITERIA In the ideal HMS process, all material lower in density than the specific gravity of separation (SGS) would be recovered as floats and all material of higher density would appear as sinks. In order to evaluate the misplaced material, the washery products are tested at the density at which the washing unit is operated. The original type of plot1,7, 8 is shown in Fig 1; this was developed primarily for coal cleaning units. The curve for raw coal represents the cumulative percentages of sink material. The refuse curve is also plotted as a cumulative sink, the percentages being expressed in terms of raw coal. This diagrammatic representation of the results of washing units has the merit of easy visual observance of the degree of separation obtained. The error areas (cross-hatched) are a measure of the amount of misplaced material and therefore they can be used to characterize the quality of separation. The ideal and actual separating performance between floats and sinks can be best seen from the partition curve developed by Tromp,2 where the ordinate is the percentage recovery of the sinks, and the abscissa is the specific gravity (Fig. 2). It can be seen from the shape of the curve that as the SGS is approached, the proportion of material reporting to the improper product increases rapidly. In fact, the SGS can be defined as the density of the material in the feed that is distributed equally between float-and-sink products. When the upper half of the curve is inverted, a shape similar to that of a Gaussian error distribution curve is obtained and therefore the analysis of gravity separation may be carried out by using the law of probability. The shape of the curve in Fig. 2 is determined partly by the density composition of the feed, and partly by the sharpness with which the unit separates floats from the sinks.9, l0

Jan 1, 1970

By H. Biloni, B. Chalmers

Metallographic studies of the segregation of solute in and near the surfaces of chill-cast alloys have shown that, under sufficiently severe conditions, nucleation on the cold mold surface is followed by the formation of a disc of solid of the same composition as the liquid. This disc is surrounded by two concentric rings in which the concentration first decreases and then increases. The discs and rings are surrounded by a region in which arms of low solute concentration separate regions of high concentration. These arms start at the periphery of the outer ring and are initially radial; they make a gradual curved transition from the radial direction to a crystallographic direction. A normal dendritic substrcture is established beyond the position at which the arms have become crystallographically aligned. When the cooling is less severe, the disc becomes less irregular in shape and has a concentration minimum at the center. The term "Predendritic" is proposed for these transitions. A qualitative explanation is outlined for the phenomena observed at the surface and in the equiaxed region of the ingots. It is well-established1-' that the normal mode of solidification for alloys under most conditions is dendritic. A characteristic of dendritic solidification is the growth of rods or plates in specific crys-tallographic directions. The remaining liquid solidifies later, usually with a higher concentration of solute than the original liquid. Very little is known, however, about the transition from a crystal nucleus until the dendritic pattern is established. It is clear that there must be a transition because the nucleus is much smaller than the characteristic spacings found in the "steady-state" structure. And it also seems clear that the initial conditions must be important since the undercooling existing during the nucleation of the grains has a remarkable influence upon the grain size4 and the segregation pattern. The present paper reports a study of the micro-segregation in regions where crystals have nucleated, and the conclusions that can be drawn regarding the early stages of growth, in connection with the details of the solidification process. Aluminum of 99.993 purity, A1-Cu alloys containing 0.5 to 20 wt pct Cu, and Pb-Sn alloys with 5 wt pct Sn were cast and examined metallographically at the as-cast surface, close to the surface, and in the interior after casting. The alloys were cast from controlled temperatures against surfaces at different temperatures ranging from room temperature to approximately the liquidus temperature of the alloy. The surfaces were, in various experiments, graphite, stainless steel, copper, and aluminum. The methods used for metallographic examination were as follows. 1) The Nomarski phase contrast interferometer6 was used to obtain information on the topography of the as-cast surface. 2) The distribution of any solute present in A1 99.993 pct and copper in the A1-Cu alloys was studied by the anodic film technique originated by Lacombe and Mouflard7 and previously applied in the study of the solidification of aluminum by Biloni.8 The electropolished surface of the specimen is anodized under controlled conditions so that the thickness of the oxide film and therefore the interference colors under white light are sensitive to the local composition. This technique was applied to the as-cast surfaces and to metallographically prepared surfaces from the interior. 3) If in Al-Cu alloys, the surface is anodically oxidized for several minutes, instead of seconds as in the color-film technique, the copper segregation is outlined by a different level with respect to the matrix. This method is less sensitive but complementary to that for the color films. 4) The distribution of copper revealed and mapped by the metallographic techniques was confirmed by electron probe. 5) In samples with high concentration of copper, evidence for the copper distribution could be seen optically after electropolishing.

Jan 1, 1965

By N. Jaffee, J. E. Dorn

An activation energy of 27,400 5 1000 cal per mole was obtained for the creep of poly crystaLline aluminum over the temperature range of 273° to 350°K, at strains varying from 0.003 to 0.230. Stresses varied fronz 2250 to 6000 psi, strain rates from 0.1145 x 10-5 to 29.5 x 10~s min.-1. A strain temperature-compensated time correlatzon was oblained indicating that the structure was depedent solely upon the strain at a given stress; X-ray diffraction analyses and tensile tests on precrept specimens verified this. PREVIOUS investigations1 have revealed that the apparent activation energies for creep of high-purity polycrystalline aluminum are insensitive to the applied stress, strain, and strain rate. On the other hand, the apparent activation energy is dependent on the temperature1,2 as shown by the data reproduced in Fig. 1. Each plateau of this curve is associated with a unique rate-controlling dislocation mechanism for thermally activated creep. It is now very well-established that over the high-temperature range, where the activation energy is about 35,500 cal per mole, the creep rate is controlled by the dislocation climb mechanism. 3 Over the intermediate range of temperatures, from about 260° to 370°K, another unique activation energy, namely 28,000 cal per mole, is obtained. Current evidence strongly supports the contention that cross slip is the rate controlling mechanism for creep in this case: 1) Crystal recovery can occur by a number of mechanisms prominent among which are climb and cross slip. Astrom,4 using the Borelius micro-calorimeter, reported rapid crystal recovery of cold-worked polycrystalline A1 at 340° to 370°K giving an activation energy of 28,000 cal per mole and additional recovery at 455° to 478°K giving an activation energy of 3 6,000 cal per mole. Whereas the latter recovery process was clearly associated with the dislocation climb mechanism, the former, 28,000 cal per mole process could have arisen as a result of the cross-slip mechanism. 2) Single crystals of high-purity A1 favorably oriented for octahedral glide exhibit an activation energy for creep of about 3400 cal per mole over the range from 0° to 400°K and that of about 28,O:O cal per mole over the range from 600° to 775°K . Whereas the lower activation energy process is accompanied by the development of sharp slip-band traces, the 28,000 cal per mole process was uniquely characterized by extensive cross slip. 3) Theoretical calculations by Seeger and schoeck6 suggest an apparent activation energy for cross slip in A1 of about 24,000 cal per mole and another theoretical estimate by Friedel 7 gives the observed 28,000 cal per mole as the theoretical activation energy. It is therefore consistent with this evidence to, at least tentatively, ascribe the 28,000 cal per mole creep process in A1 to the operation of cross slip as the rate controlling mechanism. Although creep has been rather well-explored in the dislocation climb range, very little, excepting perhaps the activation energy, is known about creep in the cross slip range. This investigation was undertaken, therefore, to reconfirm the activation energy for creep in polycrystalline A1 in the intermediate temperature range and to study the strain-time relationship for creep at a constant stress in the cross slip region. EXPERIMENTAL PROCEDURE AND TECHNIQUE The three types of high-purity A1 alloy specimens described in Table I were used in this investigation. Specimens were milled from 0.100 in. thick cold-rolled sheets with their tensile axes in the rolling direction following which they were given a recrys-tallization and grain growth heat treatment at temperatures well above those which were subsequently employed in the creep tests.

Jan 1, 1962

By M. A. Grossman

The harden ability of most steels can be predicted within 10 to I5 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In the method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a "pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain size may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter", namely, the diameter of bar, in inches, that will just harden all the way through (absence of un-hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test The data bring out certain features rather clearly. For example: i. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals,,) are known; thus an "incidental,, chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybdenum when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful, as would appear to be common experience; observe that an increase from no manaanese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added "20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the fist small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using I.o per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost 10 per cent in hardenability (in these units); this, however, does not apply to certain It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome-molybdenum and chrome-vanadium steels, un-dissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum Passible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the

Jan 1, 1942

By M. A. Grossman

The harden ability of most steels can be predicted within 10 to I5 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In the method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a "pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain size may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter", namely, the diameter of bar, in inches, that will just harden all the way through (absence of un-hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test The data bring out certain features rather clearly. For example: i. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals,,) are known; thus an "incidental,, chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybdenum when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful, as would appear to be common experience; observe that an increase from no manaanese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added "20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the fist small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using I.o per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost 10 per cent in hardenability (in these units); this, however, does not apply to certain It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome-molybdenum and chrome-vanadium steels, un-dissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum Passible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the

Jan 1, 1942

By J. Brett, S. Friedman

A study of the diffusion of nickel into both fibrous and recrystallized 0.065-in.-diam silica-alumina doped tungsten wire at 1200°C has been conducted. The diffusion profiles were determined by chemical dissolulion of successive circumferential layers and spectro-photometric determination of nickel in the etchant. It was shown that the diffusion of nickel into tungsten is markedly structure-sensitive. No significant amount of nickel could be introduced at 1200°C into tungsten which had first been recrystallized at temperatures of 2300°C, leading to an upper limit estimate for the bulk diffusivity of nickel in tungsten of 10-11 sq cm per sec at 1200°C. However, nickel did diffuse into initially fibrous wires, caused re crystallization, and was alsays present at the advancing recrystallization front. The accumulation of nickel in an initially fibrous region ceases when the recrystallization front arrives. The characteristics of the resulting diffusion profiles are explained in terms of the relation between diffusion processes and micro structural changes. WHILE it is well-known that the presence of nickel and certain other metals causes low-temperature recrystallization of the cold-worked fibrous structure of doped tungsten,''' the character of the phenomenon is not well understood. Recently it was shown that the recrystallization reaction can be induced at low temperatures by the presence of solid nickel on the surface of doped wire, but not by exposure to nickel vapors.3 Once recrystallization was initiated, a continued source of nickel was required for propagation of the recrystallization front. The phenomenon appeared to be a complicated solid-state reaction since, in addition to the change in structure of the tungsten from fibrous to equiaxed grains, diffusion of nickel from the surface into the recrystallized and fibrous structures was occurring with possible chemical reaction between nickel and tungsten at the surface and interaction of nickel with the dopants which ordinarily stabilize the fibrous structure within the wire. The objective of the present work was to study the diffusion of nickel into fibrous and recrystallized tungsten structures in order to clarify the relationship of the diffusion process to nickel-induced recrystallization. Studies of interdiffusion in the Ni-W system4"7 have been principally concerned with the mobility of tungsten in nickel. Information on diffusion of nickel in tungsten is meager, and there seem to be no studies of the mobility of nickel in tungsten which elucidate the structural aspects of the phenomenon. The present experiments were designed to determine the diffusivity of nickel at 1200°C in fibrous tungsten, in large-grained tungsten prerecrystallized at high tem- perature, and in tungsten recrystallized at 1200°C due to the presence of nickel. Although the concentration profiles were determined in these experiments, unexpected changes in boundary conditions or complex diffusion paths complicated the analysis of these profiles so that the interpretation could not be readily expressed in terms of simple diffusivities. EXPERIMENTAL PROCEDURE The experiments were conducted on Sylvania 0.065-in.-diam silica-alumina doped commercial tungsten wire, hereafter designated as ordinary doped wire. A special lot of 0.065-in.-diam silica-alumina doped low-nickel wire was also used. Impurity analyses of the wire are given in Table I. The experimental design is shown in Fig. 1. All heat treatments were conducted in vacuum. Two groups of ordinary doped wire were prepared for diffusion with nickel. One group in the as-received (fibrous) condition was elec-tropolished, nickel-plated, and annealed at 1200°C for 20 and 40 hr, or was exposed to nickel vapor at 1200°C for 20 and 40 hr. The second group was recrystallized to an equiaxed grain structure at 2300°C for 3 hr, electropolished, nickel-plated, or exposed to nickel vapor for anneals at 1200°C for 20 and 40 hr.

Jan 1, 1969

By E. V. Kleber, V. F. Novy, R. C. Vickery

The constitutional diagram has been determined in part for the sgstem Gd-Fe. Seven intermetallic compounds have been found at compositions corresponding to the following Gd-Fe ratios; 2:3, 1.2, 1:3, 2:7, 1:4, 1:5, and 2:17. The GdFe, com-pound has a congruent melting point above 18000C, whereas all of the remaining compounds melt incongruently, A eutectic exists at 13 wt pct Fe at a temperature of 860°C. ALTHOUGH an increasing amount of information is becoming available on the metallurgy of pure rare earth metals, relatively few studies have been made on alloy systems of the rare earths with the transition metals; iron, nickel, and cobalt. Even less data are extant on gadolinium alloys although it could be expected that such alloys might possess interesting structural and magnetic properties. In this paper, we report investigation of the gadolinium-iron alloy system. Studies on systems containing nickel and cobalt will be presented in subsequent papers. Previous data on gadolinium-iron compounds have been reported by Endter and Klemm1 and Jep-son and Duwez.2 Both reports agree on the existence of the GdFe2 phase, which crystallizes with the C-15type structure (face-centered cubic). This is in accord with results of the present work. EXPERIMENTAL The gadolinium metal used was prepared by met-allothermic reduction of high purity gadolinium fluoride. A typical analysis of the metal thus produced indicated the principal impurities to be oxygen, 0.24 pct, and tantalum, 0.2 pct. The iron metal used for alloying was a reagent grade material. Alloys were prepared by arc melting mixtures of the respective metals. Appropriate quantities of the two component metals were carefully weighed, blended and compacted. The compacts were then melted in an arc furnace consisting of a water-cooled copper hearth plate and a water-cooled tungsten-tipped counter electrode contained in a brass vacuum chamber. The furnace was evacuated to an absolute pressure of less than 1 with the leak rate established as being less than 20 per min. The furnace was then back-filled to a pressure of 25 mm of Hg, with a 75 pct He-25 pct Ar mixture. Arc melting at 25 v and 300 amp was maintained for about 30 to 60 sec until the entire visible area of the sample became molten, by which time surface tension had drawn the molten metal pool into a large bead. After allowing the furnace to cool, the alloy button was inverted and the melting process repeated. A series of melts was made covering entire composition ranges from 100 pct Gd to 100 pct Fe. All samples were examined metallographically in the as-melted condition. As the phase diagram became rationalized, and differential thermal analysis had given indications of temperature arrests, annealing was carried out in vacuo or in argon. Generally, compositions containing more than about 60 pct Gd were heat treated at 750°C and alloys containing less than this quantity of gadolinium were annealed at 1000°C. Prolonged annealing times were of the order of 100 to 200 hr. Metallographic examination was repeated on the annealed materials. Although little material loss was noted during alloy preparation, chemical analyses were made on all specimens prepared. The following standard, analytical techniques were used. Samples were dissolved in hydrochloric acid; insoluble material was filtered off, ignited and fused with potassium pyro-sulfate. The cold melt was leached with dilute acid and the solution thus obtained added to the main sample solution. Gadolinium was always determined gravimetri-callv as oxide from oxalate ignition. Iron was removed from an aliquot sample by electrolysis on a mercury cathode at approximately six volts. Gadolinium in the iron-free electrolyte was then precipitated as oxalate which was subsequently ignited to oxide. Iron was determined volumetrically in an aliquot solution by reduction with stannous chloride fol-

Jan 1, 1962

By R. J. Blackwell, J. R. Rayne, J. R. Henderson, W. M. Terry, D. C. Lindley

This paper presents the results of a laboratory investigation of the efficiency of water-solvent mixtures in recovery of oil. These mixtures may have the high displacement efficiencies characteristic of solvent floods and the high sweep efficiencies characteristic of water floods. Thus, the water-solvent process may increase the number of reservoirs in which a miscible-type displacement can be used profitably. The experiments on the use of water-solvent mixtures for recovery of oil were conducted to find the general applicability of the process. These studies demonstrated that, in flowing through sands, water and solvent segregated into a solvent layer on the top and a water layer on the bottom rather than flowing through the sands as a uniform mixture. Calculations based on the simultaneous flow of the water and solvent in layers were used to predict the effective mobility of the mixtures and the optimum operation of the process in steeply dipping, homogeneous reservoirs. As most reservoirs are not suited for the operation of the process under ideal conditions, experimental studies were conducted with sand-packed models scaled to represent more realistic reservoirs. These studies included the effects on recovery of oil of rate of injection, viscosity of oil, variations of permeablity within a formation and variations in water-solvent ratio. For the range of con-ditions studied, higher recoveries of oil were obtained with water-solvent mixtures than with water or practical volumes of solvent alone. INTRODUCTION A group of intriguing—because of their great possibilities—new oil recovery methods at the disposal of the petroleum engineer are the miscible displacement processes. These processes (high-pressure gas drive, en-riched-gas drive and LPG bank driven by methane) displace all of the oil from the portions of the reservoir swept by the injection fluid. The key question confronting the engineer applying one of these techniques to a particular reservoir is, "What fraction of the reservoir can be swept by injection of a practical volume of solvent?"." Intensive laboratory studies have been made during the past several years in seeking answers to the question of the sweep efficiencies which can be expected in solvent floods.' - These studies provided the answer that low-viscosity, low-density solvents channel and by-pass oil in sands with no dip. In horizontal sands, solvent flooding becomes less efficient as the viscosity of the oil increases, the recovery of oil at solvent breakthrough decreases and larger volumes of solvent are required to achieve a given recovery. More efficient displacement of oil by solvent is observed under certain conditions in sands with dip.".' If the permeability and dip of the sand are sufficiently high, gravity segregation of low-density solvent injected updip can prevent channeling. At rates of depletion below a critical rate,"." no channeling occurs. Unfortunately, in many reservoirs, the critical rate is so low that production of oil at rates below this rate is not economically attractive. And at rates over four times the critical rate, channeling is almost as severe in sands with dip as in horizontal sands. These findings pointed out that, for solvent floods to be generally applicable in recovering oil from all types of reservoirs, new methods of improving their sweep efficiencies are needed. Simultaneous injection of water with the miscible fluid was suggested by Caudle and Dyes7 as a method for improving sweep efficiencies. They theorize that water flowing with the solvent would decrease the effective mobility of the solvent and cause it to contact more oil sand. If, indeed, the water and solvent flowed as a uniform mixture, the process should have the advantages of the high displacement efficiencies characteristic of miscible floods and the high sweep efficiencies of water floods. Thus, the method (at least in theory) would greatly increase the number of reservoirs in which miscible-type displacements would be feasible. A research program was conducted to probe the technical feasibility of the water-solvent process. It

By P. F. Gnirk, J. B. Cheatham

Single bit-tooth penetration experiments under static load were conducted on six rocks at confining pressures of O to 5,000 psi using sharp wedge-shaped teeth with included angles ranging from 30 to 120° In general, the force-displacement curves for all rocks exhibit an increasingly nonlinear and discontinuous behavior with decreasing confining pressure. The confining pressure at which a rock exhibits a macroscopic transition from predominantly ductile to predominantly brittle behavior during penetration vmies from about 500 to 1,000 psi for the limestones to greater than 5,000 psi for dolomite. The correlation between calculated values of force per unit penetration based on plasticity theory and experimental values is quite encouraging, even at confining pressures as low as 1,000 psi A qualitative correlation between volume of fragmented rock per unit energy input for a single bit-tooth and drilling rate for microbits appears to exist over a confining pressure range of 0 to 5,000 psi. INTRODUCTION Laboratory experiments utilizing a small-scale drilling apparatus have demonstrated that penetration rates are reduced considerably as a result of increasing the confining pressure from atmospheric to a few thousand psi?-3 This undesirable situation can, in general, be attributed to a combination of decreased efficiency of chip removal at the bottom of the borehole, increased rock-failure strength, and a possible change in the mechanism of chip generation and rock fragmentation with increasing confining pressure. To more fully understand the principles underlying the last circumstance, it is the purpose of this investigation to experimentally study the mechanism of single bit-tooth penetration into dry rock at low confining pressures and, in particular, to establish the confining pressure at which the penetration mechanism may undergo a brittle to ductile transition for various rock types commonly encountered in drilling. Confining pressure as used here refers to the differential pressure between the borehole fluid pressure and the formation-pore fluid pressure. EXPERIMENTAL PROCEDURE Using an experimental apparatus previously described: a single, sharp wedge-shaped tool was forced under a "statically" applied load into an effectively semi-in finite dry rock sample subjected to a prescribed confining pressure. To prevent the invasion of the con fining-pressure fluid into the pores of the rock sample during penetration, the exposed surface of the rock was jacketed with a layer of silicon putty.* Electrical instrumentation incorporated into the apparatus yielded a graphical plot of force on the tool as a function of penetration or displacement of the tool into the rock during an experiment. During the course of the experimentation the following conditions were maintained constant: (1) pore pressure — atmospheric (i.e., the rock was dry); (2) temperature — 75F; (3) rate of loading — essentially static (approximately 0.002 in./sec); (4) bit tooth — a sharp wedge-shaped tool loaded normal to the rock surface; (5) rock surface — smooth and flat; (6) drilling fluid — hydraulic oil; and (7) maximum depth of penetration — approximateiy 0.1 in. In addition, each experiment was performed on a different rock sample so the rock surface is free of a layer of cuttings and of any previous indentation craters. The influence of the corners of a borehole was neglected, since each rock sample was cemented inta a section of aLuminum tubing to simulate a semi-infinite body. Indentation experiments were made on a sandstone, two limestones, a marble, a dolomite and a schist with a 60' bit-tooth over a range of confining pressures from atmospheric to 5,000 psi and at a constant confining pressure of 1,000 psi for a variety of bit-teeth with angles ranging from 30 to

Jan 1, 1966

By L. V. Pirela, S. M. Farouq Ali

Some interest has been expressed recently in the application of solvents in conjunction with a thermal drive, such as a steamflood. At least one field project of this type has been reported. This paper makes the first attempt to provide some of the basic information necessary for choosing a solvent for such an application. Results of displacements conducted at elevated temperatures are also discussed. This paper shows that, in the case of alcohol-hydrocarbon-water or brine ternary systems, the system miscibility may increase, decrease, or both increase and decrease within the same system when the temperature increases. The distribution coefficient was consistently found to increase in favor of the oleic phase with an increase in temperature, which is advantageous from the standpoint of oil recovery. Results of solvent displacements in a sandstone core showed that even a relatively small temperature effect in the favorable direction (increase in miscibility and distribution coefficient) can lead to a 50 percent increase in oil recovery. On the other hand, if the system miscibility decreases with the temperature, even though the distribution coefficient increases, the oil recovery at the higher temperature may not increase. INTRODUCTION Miscible displacement has been the subject of many investigations. Miscible-phase solvent flooding, employing solvents such as alcohols that are miscible with both oil and water, has received considerable attention. Investigations conducted by Gatlin and Slobod,l Taber, Kamath and Reed,2 Holm and Csaszar,3 and Farouq Ali and Stah14 have helped in understanding the mechanism of solvent flooding. While the use of alcohols and similar solvents as oil recovery agents is economically unattractive, these solvents nevertheless provide a means of understanding the mechanistic aspects of important miscible-phase oil recovery processes such as the Maraflood process (discussed by Gogarty5). As shown by Taber et a1.,2 the phase behavior of a solvent-oil-water system is of .utmost importance in determining the efficiency of the oil displacement. This paper makes the first attempt to obtain the ternary phase behavior data for nine alcohol-hydrocarbon-water/brine systems at elevated temperatures. Results of core tests at elevated temperatures are also presented which corroborate the effect of temperature on oil recovery, as judged on the basis of phase-behavior data. The use of solvents at elevated temperatures has been suggested earlier by Farouq Ali.6 At least one field test of this type has been reportedO7 With the widespread use of thermal recovery techniques, it is possible in some situations (especially in steamflooding) that the use of a suitable solvent in conjunction with the heat carrier may be economically feasible. This paper attempts to provide some of the basic information needed for judging such feasibility. LOCATION OF THE PLAIT POINT The phase behavior of a typical ternary system consisting of a solvent, hydrocarbon and brine (or water) can be represented by a triangular diagram such as the one shown in Fig. 1 (for temperature TI). Point Pon the binodal curve represents the plait point, being the limit of tie lines such as Y1 Y2 The compositions of the coexisting oleic and aqueous phases are given by points Y2 and Y1, respectively, for any mixture composition along Y1Y2. The characteristics of ternary diagrams have been discussed by Findlay8 and others. Taber et aL3 have shown that the position of the plait point in a particular ternary system plays the decisive role in determining whether or not theoleic phase would be displaced in a continuous manner during an alcohol displacement. The area above the binodal curve also is important, since it represents

Jan 1, 1969

By L. O. Storey

The McDermitt mine was found as a separate mercury ore-bearing occurrence approximately 305 m (1000 ft) northeasterly and in a different geologic setting from the old Cordero mine, which had been the district's major producer. The following briefly describes the discovery of the new deposit and the Placer Amex lnc. involvement. The Cordero mining property was under lease by Sierra Mineral Management from the owner Fred H. Lenway in February 1971, when the property was brought to the attention of Placer Amex Inc. (known at that time as American Exploration and Mining Co.) by Richard F. Hewlett of Sierra Mineral Management. The property was first examined by Amex geologists in the spring of 1971, who reported favorably on the project. During that year, Sierra Minerals Management had retained Dr. Larry Walters as a consultant. He proceeded to drill test mercury soils anomalies which he had found northeast of the old Cordero mine in an area overlain by recent alluvium and gravel. An area known as the D area was subsequently blocked out and ascribed a tonnage of about 18 1 kt (200,000 st) which occurs in the vicinity of the eastern edge of the currently defined McDermitt ore body. This mineralization was found in flat lying mercury-bearing lakebeds, unlike the steep structurally controlled ore which was mined in the old Cordero mine. It became apparent to Placer Amex that since the chances of much more extensive ore were good in such a geologic environment, additional exploration was warranted. A joint venture was formed in October 1972 by American Exploration and Mining Co. and Sierra Mineral Management to further explore the Cordero property. The project exploration was fully funded and managed by Amex. Sampling began by Placer Amex in the D area where an open trench had exposed the lakebed ore. Visible cinnabar could not account for the high-grade mercury assays taken from the trench, and an unknown mercury mineral was suspected. Subsequent work established the presence of a chlorine-bearing mercury sulfide which may have enriched the lakebeds as a secondary supergene mineral. Early identification of the mercury-bearing mineral corderoite (Hg3Cl2S,) aided in the geologic concepts for the ore occurrence and was helpful in exploring for the expansion of the D area. Corderoite was found occurring with cinnabar in the lakebeds, and in places it is a major contributor. Specimens of the unique ore were given to Dr. Eugene E. Foord and Dr. Pieter Berendsen at Stanford University, who subsequently identified the chemical and crystallographic makeup of the new mineral and described it for the first time as a naturally occurring substance. Metallurgical work on mercury recovery from the newly described mineral was carried out by the Placer Development Ltd. laboratories in Vancouver, and an acceptable recovery system was worked out together with a planned mill design. Step out drilling from the D area by Placer Amex Inc. encountered extensive flat lying lakebed ore. The McDermitt ore body, as subsequently defined by drilling, was found to contain 2.7 Mt (3 million st) of open pittable ore, containing approximately 5 kg/t (10 lb per st) Hg. The ore body gently dips to the north and is found lying mainly in claybeds just above an opalite breccia blanket which overlies the earlier volcanics. Some ore is also found in the opalite breccia. The mine and mill were constructed under an operating joint venture with Placer Amex Inc. and Sterling Mineral Ventures, and production began in June 1975 at the rate of 20,000 flasks per year. The mine is currently in progress.

Jan 1, 1985

By R. I. Jaffee, E. S. Bartlett, D. N. Williams

The oxidation resistance and fabricability of molybdenum powder-metallurgy alloys containing up to 20 wt pct nickel in the form of a fine dispersion were studied. The effects of dispersion distribution and of amount and type (pure nickel or nickel compounds) of additive were considered. A definite improvement in oxidation resistance was observed, but the amount of improvement fell far short of requirements for an oxidation-resistant alloy. Fabricability by hot-rolling was limited. INVESTIGATIONS at Ohio State university1 and Battelle Memorial institute2 have indicated that the attainment of a truly oxidation-resistant molybdenum-base alloy for high-temperature service, with the coincident retention of high-temperature strength and toughness, will be a difficult, if not impossible, feat. Among the most promising alloy systems studied was the molybdenum-nickel system shown in Fig. 1. Alloys in this system show good oxidation resistance at temperatures well above the normal melting point of molybdenum trioxide because of the regenerative formation of protective nickel-molyb-date (NiMoO4) on the surface of the alloy during exposure at high temperatures. Unfortunately, the required alloy content to obtain oxidation resistant molybdenum-nickel alloys far exceeds the limits of the narrow terminal solid-solution boundary, and closely approaches the peri-tectic composition involving the brittle intermetal-lic compound, MoNi. Because of the peritectic reaction, fusion alloys are characteristically brittle, since the MoNi phase, being the last to form, tends to occur as a continuous grain-boundary network around each molybdenum grain. An added problem with this system is that the protective nickel-molybdate layer formed at high temperatures is unstable, undergoing one or more allotropic modifications upon cooling. The volume changes associated with this modification during cooling are such as to cause violent expulsion of the protective molybdate coating from the surface of the piece. This is, of course, quite detrimental in material exposed to cyclic temperature during service. The research reported here resulted from an attempt to overcome the aforementioned problems associated with the molybdenum-nickel alloys primarily by controlling the amount, size, and location of the MoNi phase. By using powder-metallurgy techniques of alloy preparation and sintering the blended molybdenum-nickel powder mixtures at a temperature below the peritectic reaction temperature, molybdenum-nickel alloys with a randomly dispersed MoNi phase were produced. MATERIALS The molybdenum powder used in the preparation of alloys for this study was commercial hydrogen reduced, minus 325-mesh (Tyler) material. Master alloys, by which nickel was added, consisted of elemental carbonyl nickel powder (12 average particle size), an alloy of 50 wt pct Ni-50 wt pct Cr, and compounds of MoNi, Ni,Si, and Ni2B. The nickel-chromium powder was prepared by filing a vacuum-arc-melted ingot, separating impurities magnetically, and screening to minus 200-mesh. The MoNi powder was prepared by pulverizing a hydrogen-sintered powder-metallurgy compact to minus 325-mesh material. Further sizing of this powder for study of effects of dispersion distribution was accomplished by air classification of the minus 325-mesh powder. The Ni2Si and Ni2B powders were prepared by crushing vacuum-sintered powder-metallurgy compacts to minus 200-mesh material. EXPERIMENTAL PROCEDURE Specimen Preparation—The general procedure followed in the preparation of alloys for testing is described as follows: 1) Blending. Either hand-blending of the powders in a ceramic mortar and pestle for X 1/2 or mechanical blending was used. Hand-blending seemed preferable for optimum homogeneity. 2) Compacting. Most of the blended powders were pressed to green compacts at pressures of 15 tons per sq in. in a single-action die, although some were pressed at 80 tons per sq in. A 1 X 11/4 X 1/4-in. green compact was the standard size for oxidation test material, and 7 X 1/2 X 1/4-in. compacts were used for fabricability test specimens. 3) Sintering. All green compacts were sinteredat

Jan 1, 1959

By L. Luini, E. Lee

An exploratory survey of the heat treatment response of commercial titanium alloys (Ti-150A, RC-130B, and MST 3AI-5Cr al-loys) shows a wide range of possible hardness and microstructural characteristics. The hardening is primarily dependent on the solid state transformation of the phase. An age hardening reaction which apparently is associated with ß decomposition and precipitation has been shown. Brittleness and notch sensitivity appear to be characteristic of age hardening to high hardness. Ductility, tensile strengths, and elongations are given. A NUMBER of commercially produced titanium-base alloys have been made available by the titanium metals industry. These alloys were developed to combine the light weight of titanium with increased strength through alloy additions. Usually the properties of these alloys are reported for material in the hot rolled and annealed condition. Since the production of commercial titanium has preceded the investigation of titanium-base alloy systems, the potential of these alloys is not well known. Although heat treatability has been indicated for these alloys, data on the response to heat treatment are quite limited. The heat treatability of titanium is based on the allotropic transformation of the high temperature, body-centered cubic ß structure to the low temperature, hexagonal close-packed a structure at approximately 1625 °F. This transformation in the pure metal is of little practical significance in heat treatment since the high temperature phase is not amenable to controlled transformation. Alloy additions serve to alter the transformation kinetics and permit control of the transformation by heat treatment variables. The effects of different alloys on the allotropic transformation in titanium classify them in two general categories,1 a stabilizing and ß stabilizing elements. The a stabilizers, represented by aluminum and oxygen, raise the temperature limits of the low temperature phase and introduce a two-phase a + ß temperature range. The ß stabilizers, represented by molybdenum and columbium, lower the equilibrium temperature of ß and give rise to an extended temperature range where both a and ß phases are stable. Another type of ß stabilizer, represented by iron, chromium, and manganese, introduces a eutectoid reaction. Some commercial titanium alloys belong to complex multiple element systems. Based upon the phase diagrams of the binary systems, the general effect of commercial compositions is to vary the stability of the high temperature phase and significantly alter its transformation characteristics. Therefore it is expected that the characteristics of alloyed titanium can be altered by heat treatment. The present investigation was undertaken to survey the variations in hardness, microstructure, and mechanical properties as affected by heat treatment variables. Commercial Alloys lnvestigated The commercially available titanium-base alloys selected for this investigation and obtained as 3/4 in. diameter hot rolled and annealed bars are listed in Table I. The producer did not determine the chemical composition of the Ti-150A heats X1052 and L685. The early heats of Ti-150A, prefixed with the letter X, were melted with tungsten-tipped electrodes and cast in approximately 500 lb ingots 12 in. in diameter. The heats prefixed with the letter L were melted under a revised melting practice yielding approximately 1300 lb ingots 16 in. in diameter. The final annealing treatment was at 1200" to 1250°F for 1 hr. The MST-3A1-5Cr alloy was melted in an induction furnace and cast in 7 in. diameter ingots. This practice produces high carbon material and some variation in the amount of carbides was found in different sections of the same bar. The RC-130B alloy was melted with a carbon arc. This alloy showed approximately 2 pct carbides. No large segregation effects were observed.

Jan 1, 1955

By W. M. Albrecht, W. D. Klopp, R. I. Jaffee, B. G. Koehl

Kinetic studies were made of the reactions of tantalum with oxygen, nitrogen, and air at 400o to 1500°C. The tantalum-oxygen reaction is linear from 500° to 1250°C. The tantalum-nitrogen reaction follows a cubic rate law at 400° to 700°C and a parabolic rate law at 800" to 1475°C. The reaction behavior in air is initially parabolic followed by a transition to linear behavior. In the search for high-temperature materials, considerable interest is being shown in the refractory metal, tantalum. It is the third highest melting metal with a melting point of 2996°C. Also, tantalum has excellent ductility, making it one of the most workable refractory metals. In considering high-temperature applications of tantalum, the oxidation kinetics of the metal must be known. Such information also serves as a basis for the development of corrosion resistant tantalum-base alloys. Therefore, this study was made to investigate the reaction of tantalum with air, nitrogen, and oxygen. LITERATURE Several oxides of tantalum have been reported. The pentoxide, Taz05, is the only oxide of tantalum whose identity has been established. A high-temperature modification, aTa2Os, has been reported by several investigators.1-4 A low-temperature phase, ßTa2O5, undergoes an allotropic transformation at 1320o to 1350oC. 5-8 Four other oxides of tantalum have been reported. The oxides TaO2, TaO, and Ta4O have been reported by schonberg.9 A suboxide Ta2O, was observed by Wasilewski 6. However, the presence of oxides lower than Ta2O5 is questioned by Lagergren and Magneli.7 In oxidation studies, vermilyeal0 and Peterson, et al.,12 reported one possible phase intermediate between Ta and Ta2O5. Only Ta2O5 was formed in the tantalum air reaction, as reported by Michae1.l3 Several studies have been made on the kinetics of the tantalum-oxygen reaction. vermilyeal4 investigated the range 50° to 300°C and found that the rate of growth of a thin adherent oxide film could be described by the Cabrera-Mott theory. Gulbransen and Andrew15,18 studied the reaction kinetics of tantalum in oxygen pressure of 1/10 atm at 250° to 450°C. At all temperatures the reaction followed the parabolic rate law for periods up to two hours. The oxidation behavior in the range 500" to 1000°C was found to be linear at oxygen pressures of 0.2 to 600 psi according to Peterson. et al.l1 At very low pressures (1 x 10-3 to 2 X lo-' mm of Hg) Gebhardt and seghezzi17 reported linear oxidation at 800° to 1500°C. The reaction of tantalum with air is similar to the reaction with oxygen. Studies have been made by Waber, et a1.,12 and Michae1.l3 Two nitrides of tantalum, TaN and Ta2N are known. Their structures have been determined by Brauer and Zapp 18,19 The tantalum-nitrogen reaction kinetics have been investigated by Gulbransen and Andrews. 15, 16 The reaction follows the parabolic rate law at 500° to 850°C at a nitrogen pressure of 1/10 ,atm. At the same temperature, the tantalum-nitrogen reaction is much slower than the tantalum-oxygen reaction. EXPERIMENTAL TECHNIQUES Material— The material used in this study was high-purity, electron-beam-melted tantalum obtained from the Temescal Metallurgical Corp. The hardness of the as received ingot was 76 Vhn. The analysis of the material is given in Table I. Methods—Cylindrical specimens of tantalum approximately 0.9 cm in diam and 0.5 cm in length

Jan 1, 1962

By R. G. Schaal

The Magma Mine at Superior, Arizona had an unimpressive beginning as a. worked out silver mine that was purchased in 1910 for $130,000 and then incorporated into the Magma Copper Company which has been continuously mining the deposit since 1915. Copper is the principal metal produced. However, zinc, gold, silver and iron have also contributed to the total metal product. Prior to 1973, the production rate of 1500 tons per day was maintained by hoisting 4 and 5 ton pay-loads at speeds up to 1100 FPM through four small hoisting shafts. The hoists used included 8' and 7' diameter double drum, double clutched doc. and a.c. motor driven geared units built as early as 1917. One old timer that did yoeman's service for many years was an 8' Bollen Pulley with a.c. geared drive that utilized an endless rope system with mechanical grip and release mechanism built into the pulley's throat. Primary power for all of these old production hoists was 25 Hertz. Exploration that was completed in 1967 developed a reserve of 10 Million tons of 5 per cent copper which was sufficient to justify new capital expenditures for enlargement of productive facilities to 3300 tons per day. To reach the new reserves a 22' I.D. concrete lined vertical shaft was sunk to an initial depth of 48431. A 12 ½ diameter adit was bored from the mill side of the mountain to intercept the shaft at a point about 1100' below the collar. This 9200' long adit provides the right-of-way for the mine to mill railway and egress for heavy supplies from rail head as well as a conduit for potable water, electric power, compressed air and mine drainage. Mine operating levels begin 3582' below collar and thereafter have been cut at 100' vertical intervals. Skip loading stations have been installed 4282' and 46821 below collar with an in-shaft skip dump station located 800' below collar. This provides for 4500 tons of storage above the mine to mill train loading station located 1100' below collar. Ore and waste are moved horizontally from stope chutes and drift headings by rail haulage to transfer raises which channel all material to the two mentioned skip loading stations. The 22' diameter shaft crossection is arranged with the two skip compartments on the south side separated from the manway and utility compartments by the cage compartment. The cage counterweight operates in a portion of the southwest quadrant of the shaft. The hoisting plant consists of two conventional Nordberg double drum, single clutch, geared, d.c. motor driven units that are identical except for the drives and automatic controls. The drums are 15' diameter x 105" face with LeBus grooving for 2-1/8" diameter wire rope wound in three layers. Mechanical design emp1o::ed is the same as has been used for the past twenty- five years. One drum is attached to the main shaft by 2 large bolted integral shaft flenge. The loose drum is engaged by a 4-arm positive tooth clutch meshing with radially cut teeth of the clutch ring which is bolted to the drum. The drums are one-piece steel plate weldments having a finished weight of 60 tons each and are mounted upon a 36" diameter shaft that also weighs 60 tons. With the addition of brake rings, clutch, bull gear and rope, the total dead weight adds up to nearly 250 tons that is supported by just three double row spherical roller pillow block bearings. There is no bearing between the drums. All pinion shafts as veil as all head sheave journals are supported in the same type of antifriction bearings.

Jan 1, 1975

By D. Turnbull, R. E. Cech

FISHER, Hollomon, and Turnbull have developed a theory for the nucleation of martensite. They first tested the theory on Fe-C alloys and low alloy steels. The major factor influencing nucleation of martensite was considered to be statistical composition fluctuations occurring in small regions at high temperature and frozen-in on quenching. These local regions of varying size and composition serve as nucleation centers. They become supercritical, one by one, as temperature is progressively lowered, resulting in temperature-dependent or athermal transformation. Fisher next applied nucleation theory to substi-tutional solid solution alloys. Detailed predictions were made for Fe-Ni alloys because of the availability of free energy data on this system. It was shown that composition fluctuations that were significant energy-wise did not occur, and nucleation frequencies could be calculated from average properties of the system. Nucleation was predicted to occur as time-dependent and having the functional relationship to give a C curve of nucleation frequency vs temperature. The analysis further predicted that the nucleation frequency was extremely sensitive to composition. Experimentally, it would be found that the transformation in some compositions is so slow that measurable amounts will not form in a reasonable length of time. With other compositions, only slightly different, the nucleation frequency becomes so great that the material becomes transformed while still distant in temperature from the maximum nucleation frequency. On quenching an alloy of such composition, the observed transformation kinetics would be similar to those found in Fe-C alloys. Cech and Hollomon repeated experiments of Kurdjumov n which the kinetics of transformation were similar to those predicted by Fisher for Fe-Ni alloys. The alloy studied in this investigation contained 73.3 pct Fe, 23.0 pct Ni, and 3.7 pct Mn. Fisher,' using an idealized model for the extent of transformation as a function of the number of martensite crystals per grain of parent phase, derived nucleation frequencies from the transformation curves of Cech and Hollomon. Complicating influences such as coupling effects between grains in the polycrystalline specimens were neglected. Nevertheless, excellent agreement was found between the theoretically and experimentally derived nucleation frequencies. These experiments, however, could not provide a critical test of the theory. Experimental nucleation frequencies could vary widely from those calculated, depending upon the extent of deviation from ideal partitioning and the extent of coupling effects. Further, since the compositions of material theoretically analyzed and experimentally determined were different, the free energy changes involved in the experimental work could only be estimated. Also, the effect of heterogeneities on the transformation kinetics was not considered. For these reasons, it was decided that experiments designed to test the validity of the Fisher analysis must be conducted on binary Fe-Ni alloys, which were the ones considered theoretically by Fisher. The martensite transformation in Fe-Ni alloys has been the subject of considerable study. Machlin and Cohen have shown that transformation proceeds in a manner quite unlike that in any other ferrous alloy system. They found that single crystals would transform to a large extent in a single burst. In large grain polycrystalline specimens, frequently more than one grain and sometimes the whole specimen would transform at the same instant in this manner. Results on filings indicated that different particles would undergo the burst transformation at widely different temperatures. These results support the conclusion that the transformation behavior could not be described by a single nucleation frequency as would be the case if the nucleation were homogeneous. It appeared that further work was necessary to define the factors responsible for burst-type transformation, so that the conditions could be altered to favor homogeneous nucleation of martensite if such could be accomplished. This report summarizes the results of some experiments conducted with powdered Fe-Ni alloys for this purpose and the re-

Jan 1, 1957

By Werner Engelmaier

Constant-strain rotating-bending fatigue tests were conducted on 2024-T3 aluminum alloy constant-strain McAdams-type specimens in ultrahigh vacuum, 10-lo Torr, and in atmospheric air. In the elastic strain range the ratio of vacuum-to-air fatigue life varied from about 10 at a maximum bending stress of 37 ksi to near unity at the endurance limit. After 10 pct of the fatigue life, intergvanular microcracks appeared on the surface which did not appreciably propagate further until the last 5 pct of the fatigue life, where trans-granular cracks propagating first in slip-plane cracking and then in the stress-dominated mode led to failure. No reduction in residual tensile strength resulted from the fatigue of the specimens short of fracture. The mechanism governing the fatigue life operates between the occurrence of the intergranular microcracks and the initiation of the trans granular cracks. MORE than forty years ago, Mc Adam' and Haigh2 published the first systematic studies showing that the fatigue properties of metals were greatly affected by environments. Gough and sopwith3 found in a later study that the fatigue life of metals subject to corrosion can be substantially increased by reducing the atmospheric pressure. This and their later work4'5 was, however, done in a vacuum of only 10~3 Torr. Subsequent studies6-' at a vacuum of 10- Torr showed that water vapor is the primary agent affecting the fatigue properties of aluminum alloys. Only recently was ultrahigh vacuum used for fatigue studied.l Various theories have been put forward to explain this phenomenon. Wadsworth and Hutchings12 postulated that cracks form very early in the test and that the chemical attack by the corrosive components of the atmosphere at the root of the cracks enhances the speed of the crack propagation. They also noted that chemisorbed layers of gas on the fresh crack surfaces prevent cold welding of the crack and make the separation irreversible. Ham and Reichenbach, on the other hand, reported that their specimens showed no cracks after a run in vacuum, even though the runs were long enough to have caused the specimen to fracture in atmospheric air. They also reported that in argon at 0.14 Torr the fatigue life was about 5 times longer than at 7 X lo-' Torr. Jacisinll reported that fatigue tests in dry nitrogen showed results close to those obtained in ultrahigh vacuum. The present experiment was designed to determine the extent to which cumulative fatigue damage, i.e., the accumulation of length of fatigue cracks, reduces the residual static tensile strength of an aluminum alloy in both ultrahigh vacuum and atmospheric air and to obtain fatigue-life data for this aluminum alloy at various strains. It was also hoped that information ex- tracted from these data might support one of the previously mentioned theories. 1) EXPERIMENT Test Specimens. The material tested was commer-cial 2024-T3 aluminum alloy. In addition to aluminum, this alloy contains approximately 4.4 pct Cu, 0.5 pct Fe, 0.5 pct Si, 0.6 pct Mn, 1.5 pct Mg, plus smaller amounts of other elements.13 Some typical mechanical properties of this aluminum alloy are listed in Table I.'~ The material was used in the as-received condition, i.e., solution-treated and cold-worked. Mc Adam-type1' constant-stress specimens and notched fatigue specimens were machined from 4 -in. -diam rods, Fig. 1. The critical section of the McAdam-type samples was polished with a 45-deg spiral motion to a No. 8 microfinish. The notch in the notched specimens was machined on a lathe with a forming

Jan 1, 1969