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By J. M. Toguri, K. Grjotheim

It is known 1,2 that the equilibrium between titanium metal, TiCl2 , and TiCl3, in a solvent of molten metal chlorides, is influenced both by the total amount of dissolved titanium and by the type of solvent. Assuming that the trivalent titanium forms the complex ion Ti111 Cl4, the equilibrium reaction may be expressed by the following equation, (Me) TiIII cl4+ 1/2 Ti = 3/2 TiII cl2+ (Me) Cl The ideal ionic equilibrium constant for this reaction is, Where the N's are the molar ionic fractions in the equilibrium melt, and (Me) the different types of cations present in the equilibrium mixture. The following thermodynamic relation is derived between Kand the concentration of cations in the equilibrium melt, mix The N"S are the equivalent ionic fractions, and so forth are constants corresponding to the standard changes in free energy for reactions in melts where only the cation indicated is present, and f (y1) is a function of the activity coefficients in the equilibrium mixture. When this term vanishes, a simplified linear relationship between In Kideal and the concentration is obtained. The simplified relationship has been applied with satisfactory results to the experimental data of Mellgren and pie,' and Kreye and Kellogg.2 MANY existing methods for the production of light metals involve the reduction of their respective metal halides in the presence of salt melts composed of alkali or alkaline earth chlorides. In such a solution phase, the light-metal halide may undergo stepwise reduction from a higher, to a lower valence, and finally to a zero valent state. In this connection, the disproportionation equilibrium is of great interest. In the case where the higher valence is three and the lower valence is two, the disproportionation equilibrium may be written as follows, 3 Me11 = 2 Me111 + Me [I] If this equilibrium occurs in a salt melt containing a large excess of alkali chlorides, a typical ionic melt is obtained. It is then possible to formulate the cation equilibrium: 2 Me+h' + Me = 3 Me++ [II] Reaction [11] is analogous to a cation exchange reaction. It has been shown thermodynamically that the equilibrium constant for such a reaction in 2

Jan 1, 1960

By G. R. St. Pierre, A. J. Wilhelem

In connection with the reduction of hematite or magnetite to metallic iron, it appeared desirable to study the rate of reduction of each oxide to the next lower oxide under conditions which excluded all other condensed phases. For this purpose, pellets of Fe,O,, Fe,O,, and oFeOo were prepared. A gas train for the preparation of Ar-Hz-H20 mixtures was employed to establish a continuous flow of a controlled atmosphere over a pellet suspended on a balance. In this manner the following individual reduction steps could be studied: For example, pellets of hematite were reduced solely to magnetite by adjusting the gas atmosphere such that it was oxidizing to wustite. In other words, the reaction was complete when the hematite pellet had been totally converted to magnetite. The pellets were prepared from Baker Chemical ferric oxide. The ferric oxide powder was moistened and handrolled. Air sintering at 950°C produced Fe,0, pellets with a density of 3.65 g per cm3. The pellets ranged in size from 0.6 to 1.2 cm diam. The magnetite and

Jan 1, 1962

By Sir Robert Hadfield

SINCE the writer has been intimately connected with the development of manganese steel for many years, some remarks upon the early work with regard to the rolling and forging of this material might he of interest, and particularly as to the question of rails of special quality and of superior wearing qualities. In a paper on Iron Alloys, with Special Deference to Manganese Steel, read before this Institute at the International Engineering Congress in Chicago in 1893,1 the writer mentioned that, about 20 years ago, his firm in Sheffield produced railroad material, such as tires and axles, of forged and rolled manganese steel, thus showing that this product could be manipulated and worked up into the various required forms. The tires illustrated in the paper referred to above formed a particularly difficult class of work to produce in a special steel, but no special obstacles were met with Although there was no difficulty at that time in making and producing manganese steel in various forms, forged, rolled or pressed; nevertheless, on account of its higher expense, sufficient encouragement

Jan 2, 1914

By John Chipman, Wayne L. Worrell

Using recent thermodynamic data for the carbides and oxides of tantalum, columbium, and vanadium, the stable solid phases aboue 1300°K and at 1 atm CO(g) pressure in each M-C-O system have been determined. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures necessary to obtain these metals by carbothermic reduction under reduced pressures. TANTALUM, columbium, and vanadium react with carbon to form the M,C and MC carbide phases. The M,C carbides have narrow homogeneity ranges, but the MC phases possess considerable ranges of homogeneity.' The free energies of formation of the MC carbides were recently measured, and those of MC and M2Ccarbides have been estimated., (The notations MC and MC denote, respectively, the carbide compositions at the carbon-rich and at the metal-rich boundaries of the homogeneous MC phase.) In this paper, these carbide data are combined with thermodynamic data for the oxides to predict the stable phases in the Ta-C-O, Cb-C-O, and V-C-O systems at specified temperatures and oxygen pressures. M-C-O PHASE DIAGRAMS The solid phases in equilibrium above 1300°K for each M-C-0 system are shown in Figs. 1, 2, and 3. Above 1300°K, the vapor would consist entirely of carbon monoxide; and these phase diagrams were obtained by specifying the vapor pressure of CO(g) to be 1 atm. The temperature at which any two solid phases become unstable is specified along the two-phase equilibrium lines in each diagram. To simplify the diagrams, all solid phases in the Ta-C-O and Cb-C-O systems are represented as stoichiometric compounds. However, the homogeneity ranges of VO and VC are indicated, because they form a complete series of solid solutions.3 It also should be noted that the homogeneity range of

Jan 1, 1964

By Herbert H. Kellogg

The chemistry of sulfide roasting is analyzed to show those aspects of performance which Thecan be predicted from considerations of thermodynamic equilibrium. It is concluded that equilibrium calculations can serve as a yardstick for prediction of roaster-gas composition and sulfate formation in the calcine for fluid-bed roasting practice. A method of calculation which combines the equilibrium and stoichiometric factors is outlined, and illustrated by an example from the roasting of Cu-Fe sulfides. ON first examination the roasting of sulfides would not seem to be a process to which equilibrium calculations could be applied to yield results of practical value. The burning of sulfides is an ex-tremely spontaneous reaction, excess air is always used to obtain rapid reaction, and in most traditional roaster designs (hearth roasting) the temperature and gas composition vary widely from point to point in the roaster. These are all conditions which promote a non-equilibrium state in the roasting process. However, the introduction of the fluid-bed roaster1 has brought to roasting practice new conditions of operation, so that equilibrium calculations can be used to predict certain limited aspects of practical operation. The fluid bed is characterized by uniformity of temperature, gas composition, and calcine composition from point to point throughout the bed. These relatively uniform properties of the bed make the meaningful calculation of the equilibrium state of certain reactions in roasting possible. It is the purpose of this paper to analyze roasting from an equilibrium viewpoint, to show where the method may be expected to yield valuable information, where it fails, and to outline methods of calculation. Main Roasting Reaction The reaction MS (s) + 3/2 0, = MO (s) + SO, [I] might well be called the main roasting reaction. It adequately accounts for the well known facts that metal sulfide and air are the main reactants, and metal oxide and SO, the main products. Deviations from this simple stoichiometry will be discussed under side reactions. For all metal sulfides, Reaction 1 is strongly exothermic and the equilibrium position is far to the right. Since the reaction is exothermic, the equilibrium shifts in the right-to-left direction as the temperature is raised. However, at all practical roaster temperatures (between 500" and 1200°C), the amount of this shift is small, and the equilibrium position remains far to the right. The main roasting reaction is essentially irreversible, and the application of equilibrium considerations to this reaction will not be! a fruitful field of investigation. A knowledge of the rate of this reaction. although not the proper subject of this paper, is of great importance to the roasting process. Analysis of the factors which influence this rate shows that: 1) The rate will increase rapidly with increased temperature. 2) The rate will be proportional to the partial pressure of oxygen at the surface of the reacting particle. Because of diffusion effects, the partial pressure of oxygen at the particle surface may be considerably less than in the bulk of the roaster gas. For this reason, intimate contact between gas and solid and high relative velocity between gas and solid, such as can be obtained in a fluid bed or flash roaster, will markedly increase the rate of reaction. 3) The rate will be proportional to the surface area of metal sulfide. Therefore, smaller particle size will permit a more rapid rate per unit of weight. To achieve practical rates of roasting the partial pressure of oxygen in the roaster gases must be maintained at a finite level at all times. Even where the gas-solid contact is very good, as in the fluid-bed roaster, the oxygen content of the gas must not be allowed to drop below some limiting value (perhaps 1 pct), or the rate of the main roasting reaction will become too small for practical operation. Side Reactions in the Gas Phase The gas phase during roasting of metallic sulfides contains the elements oxygen, sulfur, nitrogen, by-

Jan 1, 1957

By Y. Oka, H. Majima

When a rock particle is subjected to an external force, internal stresses and deformations are experienced by the particle. Assuming that the breakage of a rock is mainly due to tensile stresses generated by the action of a pair of concentrated loads, F, directed in compression towards the loading points at the shortest distance, as illustrated in Fig. 1, the stress and deformation experienced by a particle of irregular shape can be determined with the aid of the theory of elasticity. According to the photoelastic experiments made by one of the present authors,' the stress states in a rock particle of irregular shape are quite similar to that of an inscribed sphere of diameter x, as indicated in Fig. 1, but accompanied by the faint stresses, in the vicinity of the particle outside of the inscribed sphere. Therefore, the stress components in an irregularly shaped particle can be estimated by referring to stress components in a sphere. Applying polar spherical coordinates to an elastic spherical body, as shown in Fig. 1, the stress components are all expressed as multiples of F /x2 and more or less influenced by the loading angle and Poisson's number m. In general, the energy w, acting on a rock particle is defined as the product of loading compression F

Jan 1, 1970

By P. K. Leung, S. R. Allada, P. M. Dranchuk, D. Quon

The alternating direction explicit procedure (ADEP) makes use of the boundary conditions to reduce multi-dimensional problems to a series of one-dimensional problems. The method, previously applied to reservoirs containing only an under-saturated oil, has now been extended to cover the case of natural gas reservoirs. l his involves solving a non-linear partial differential equation, application of the procedure is straightforward and no calcuIational problems were encountered. INTRODUCTION There has been a growing interest in formulating mathematical models of petroleum and natural gas reservoirs — models which permit the engineer to examine and evaluate the physical and economic consequences of various alternative production policies. The tremendous reduction in the cost of solving such models in recent years has made possible their use as an almost routine management tool. This reduction is the result not only of improved computer hardware but also of the development of more efficient mathematical techniques. The present paper is concerned with the application of a recently proposed numerical method (ADEP) to two-dimensional gas reservoirs. STATEMENT OF THE PROBLEM Given a two-dimensional Region R, bounded by a closed Curve C (Fig. 1) such that the behavior on Curve C is known, the differential mass balance for each fluid phase in R, neglecting gravitational effects and assuming Darcy's law for fluid transport, can be written as:

Jan 1, 1967

By R. D. Pehlke, J. V. Gluck

AS a portion of a general study of liquid-metal thermodynamics, high-temperature galvanic cells were used to study the effect of added dilute solutes on the activity of zinc in dilute solution with molten bismuth in the range 450° to 650°C. 1,2 The cells were of the type The experimental procedures have been described previously.1 In the course of studies conducted in the bismuth-rich corner of the systems Bi-Zn-Au and Bi-Zn-Cu, marked discontinuities were observed in the electromotive force-temperature relations for a number of the experimental compositions. Above the discontinuity temperatures, the relations, which were linear, exhibited slopes similar to the binary alloy of the same mole fraction zinc, as shown in Figs. I and 2. Below the discontinuity temperatures, the slopes were markedly different, but the relations remained linear. In general, as the amount of the third eletnent was increased, the slope of the lower portion of the relations tended to become less positive. The slopes of electromotive force-temperature relations reflect the entropy of mixing of zinc and, therefore, the occurrence of a discontinuity marks the transition between two different equilibrium situations involving the solution of zinc. A number of other investigators3-5 have used such observations to determine liquidus boundaries in binary alloys. Since the upper portions of the ternary electromotive force-temperature relations of this study had the same slopes as the binary alloys, the discontinuities are interpreted as marking the transition between the single-phase liquid region and the underlying two- and three-phase regions. Reference to the Zn-Bi equilibrium diagram6 confirms that the binary alloys were single-phase liquids at the experimental temperatures. Fig. I shows the electromotive force-temperature relations for the alloys containing Bi-Zn-Au and Fig. 2 shows similar relations for the Bi-Zn-Cu alloys. In the lower portion of each figure, the temperature of the discontinuity is plotted vs the mole fraction of the added solute at the various levels of zinc concentra- tion. Cross-plots from these curves at constant temperature permitted the construction of the partial liquidus surface isotherms shown in Figs. 3 and 4.

Jan 1, 1967

By V. J. Parks, Leonard Obert, A. J. Durelli

The state of stress in the region where core discing initiates has been investigated through the use of three-dimensional photoelastic models and the results of this study have been compared with those of a previous investigation of rock models. This comparison showed that discing initiates at a point of maximum shear stress, but that the magnitude of the shear stress, as determined photoelastically, is much larger than the shear strength of the rock as deter-mined from conventional triaxial testing. Moreover the shear stress required to produce discing is not constant, but depends on the applied stress field. Possible explanations for these effects are included in this article. In both exploration core drilling and overcore drilling to determine the stress in rock, occasional sections of the core obtained are broken into a series of discs.I* This discing phenomenon has been investigated in the laboratory to ascertain the state of stress required to produce it. The objective of the study was to obtain information that would make it possible to approximate the state of stress in subsurface rock from which disced cores are obtained. Referred to as the discing test, this laboratory study was conducted to determine the applied axial and radial loads required to produce discing in cylinders of rock from several sources. The dimensions of these cylinders are given in Fig. 1. Discing was produced by first applying an axial load to the cylinder and then diamond drilling the core along its axis. The radial load was then incrementally increased until discing initiated. The discs fractured or ruptured* on surfaces approximately normal to the axis of the core (planes A, B, C, D, E, Fig. 2). In many instances, the bottommost disc fractured before the drill had advanced past the points F and F', cre- ating a mush room-shaped fracture surface FEF'. Alternatively, it was also found that the same shaped fracture surface could be created by first drilling in an unloaded core to some point, say F and F', and then triaxially loading the core until fracture occurred on the plane FEF'. Jaeger and cook4 produced similar fracture surfaces in specimens subjected only to a radial biaxial load. From these laboratory studies and observations made in the field, it can be inferred that fracture or rupture initiates in the proximity of the lowest point in the kerf area, (at F and F', Fig. 2) and that the fracture or rupture surface progresses inward from this point. The experiments described above, however, do not provide any information as to the state of stress at the point at which fracture or rupture initiates. In the investigation discussed in the following sections, a three-dimensional photoelastic analysis was conducted to determine the stress distribution in the proximity of the kerf area of a triaxially loaded plastic (epoxy) cylinder containing a short section of core.

Jan 1, 1969

By David R. Mitchell, Ernest M. Spokes

There is evidence that study of minerals now considered to have susceptibilities too low for magnetic separation should be continued. Present concepts may be false. INFORMATION on magnetic properties of minerals other than magnetite is scanty and sometimes erroneous. Often there is no information at all. W. R. Crane's table of tractive forces published in 1901 is still the best guide in the field, but Crane's data can be used as a guide only, since he ignored such important factors as impurities in the minerals, size, and packing effect. During the 1930's work by the U. S. Bureau of Mines added greatly to knowledge of the behavior of certain minerals in a magnetic field. The USBM bulletin gave for the first time complete magnetic characteristics for magnetite and fragmentary data for a few other minerals. The work reported here covers a study of the magnetic-susceptibility relationships of the wolframite series of minerals and sphalerites as related to their chemical compositions. Theories are proposed to explain divergences found from commonly accepted beliefs. Gouy Method for Determining Magnetic Susceptibility: The Gouy principle has been adequately described in the literature1-3 and applied in various ways.'- It may be summarized by stating that a body of material (gas, liquid, solid, or powder mixed with gas or liquid) of cylindrical shape changes in apparent weight if suspended with one end in a zone of higher magnetic field strength than is found in that portion of the field surrounding the other end of the cylinder. This may be expressed as K2 - K1 A (H2 - H2) - mg. [1] In determining the susceptibility of mineral specimens by the Gouy method, the mineral is reduced to a fine powder and packed in a glass weighing tube. Precise measurement of the bore and depth of the tube is made unnecessary by a calibration procedure. Using the basic expression of Eq. 1, Hoare"

Jan 1, 1959

By J. Jones-Parra, R. S. Reytor

The porosities of fractured limestone reservoirs can be divided into two broad types in accordance with their effects on fluid distribution and fluid flow. In the coarse porosity, gravity segregation lakes place freely and the resistance to fluid flow is very small. In the fine porosity there is no segregation and a high resistance to flow, and it has relative permeability characteristics similar to tight sandstones. By analyzing the affect of the two porosities it is concluded that in some cases to recover the maximum amount of oil it is necessary to remove large quantities of gas from the reservoir by producing at high gas-oil ratios. In this manner the fine porosity is drained of its oil and the gas-oil contact drops slowly permitting higher production rates from the oil leg. Since this conclusion is contrary to widely accepted principles of conservation, a mathematical model (Fig. I) was constructed to duplicate the conditions desired. The behavior of the model indicates that under certain conditions it is possible to recover more oil by producing at high gas-oil ratios than by production at low gas-oil ratios, and that the rate of production is affected more by gas shut-offs than by the decrease in pressure (Figs. 2, 3, 4 and 5). INTRODUCTION It has been noted that certain limestone reservoirs behave in such a way as to indicate that there are two distinct types of porous spaces available for fluid storage and fluid flow. Regardless of the nature of these porous spaces the distinguishing characteristic is that in one type of porous space there is definite gravity segregation between the oil and the gas; while in the other, the gas evolved tends to remain distributed equally throughout the reservoir. For the sake of simplicity the porosity in which gravity segregation takes place at a fast enough rate to affect the behavior will be called "coarse po- rosity", while that in which this is not so will be termed "fine porosity". The behavior of a reservoir of this type would be different than that of a sandstone reservoir, especially if most of the oil is in the fine porosity. It has been observed that fluid flow to the wells takes place mostly through the coarse porosity. The large fractures which

By R. L. Fullman, J. W. Cahn

A method is derived for obtaining the distribution of sphere diameters and plate thicknesses (or pearlite spacings) from size distribution functions obtained along randomly oriented lines. The method described offers several advantages over existing methods. IT is often of interest to measure not only the average particle size but also the distribution in sizes of particles dispersed in an opaque material, such as an alloy. Particles of a single size will exhibit a range of apparent sizes on the plane of polish. If the sample contains a distribution of particle sizes, the distribution of observed sizes on the plane of polish is related to the distribution of actual particle sizes by an integral equation, For example, a distribution of sphere sizes, N(r),

Jan 1, 1957

By David Schroeder, John Chipman

Jan 1, 1964

By C. Crussard, R. Tamhankar

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers accord-ing to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Gerhurd Derge Carnegie Institute of Technology Schenley Park Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Staff Coordinator, James J. Burke THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Past-President; John Chiprnan, Vice President; T. D. Jones, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. W. Thornton, Chairman; Dennis Carney, John Chip-man, J. C. Fulton, J. H. Hollomon, H. H. Kellogg, A. E. Lee, R. Maddin, J. D. Sullivan, and D. Swan. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: T. B. King, Chairman; S. J. Dickenson, R. P. Hermsdorf, R. Schuhmann, Jr., and P. T. Stroup. Institute of Metals Division: Robert Maddin, Chairman, F. Lincoln Vogel, Jr., Vice-chairman, W. A. Backofen, R. W. Balluffi, J. H. Bechtold, M. B. Bever, R. S. Busk, C. G. Goetzel, Paul Gordon, C. D. Graham, .Jr., Robert F. Hehemonn, R. I. Jaffee, F. E. Jaumot, Jr., Irving R. Kramer, A. J. Lena, Harold Margolin, C. J. McHorgue, Russell A. Meussner, J. B. Newkirk, H. W. Paxton, G. E. Pellissier, I. S. Servi, Alan U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman; T. B. King, F. C. Langenberg, W. 0. Philbrook, and T. 0. Winkler. Published bimonthly by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription $20 per year for non-AIME members in United States and North, South, and Central America; $25, foreign; $5 for AIME members. Single copies, $4.00, single copies foreign, $5.00. The AIME is not responsible for any statement made or opinion expressed in its publications . . . Copyright 1958 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AIME New York ... Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts... Second class postage paid at New Yark, N. Y., and Ann Arbor, Mich. Volume 212, Number 6.

Jan 1, 1959

By J. B. Fletcher

The Miami mine first started operations in 1910. For convenience, the history of the orebody can be divided into the following categories (Fig. 1): 1) 1910 to 1925: 24.4 million tons of high grade ore, mined by top slicing, sublevel caving, etc. 2) 1926 to 1954: 102 million tons of low grade ore, mined by block caving.

Jan 1, 1961

By F. H. Buchella, J. F. Buchanan

The San Manuel copper deposit is located about 45 miles northeast of Tucson. The concentrator, smelter, administration building, and other plant facilities are located about seven miles southeast of the ,nine area at the new town of Sari Manuel as shown on Figure 1 (Sketch).

Jan 1, 1961

By M. R. TECK, N. Rudd, L. K. Thomas, D. L. Katz

The authors are to be congratulated for presenting the first comprehensive paper on the theory and practice of threshold pressure determination in connection with underground gas storage. It is of particular value since most previous experimental work on this subject has been proprietary to the commercial laboratories engaged in such testing and to their clients. This dlscussion is presented in amplification of the subject paper, not in criticism, and is based upon our experience with approximately 5,000 threshold pressure determinations. Our comments are directed primarily to the experimental procedures as described by Thomas et al. It should be noted that, while clay mineral-rich lithologies are the most common caprock materials, the samples used (Table 1) include low permeability sandstones and carbonates, but do not include shales or other formations in which clav minerals exert a dominant effect. While our experience on samples analogous to those investigated by the authors generally confirms their findings, we have found that even more rigorous experimental conditions must be imposed where clay minerals are the controlling factor. These additional conditions result from the well-known molecular character of the clay minerals themselves in which water is interlaminated with, and bonded to, silicate sheets, thus becoming an essential component of the molecule. In many clay minerals the character of the intersheet bonding, and thus the dimension of the lattice, is strongly affected by variations in the identity and concentration of cations present in the intersilicate water. On a supermolecular scale, adsorbed water films on particle or "flakes" of shale provide much of the cohesive force necessary to maintain mechanical strength. The thickness of these films is variable and inversely proportional to intergranular pressure within the dimensional limits involved in caprock investigation. The thickness of the intersilicate water layers may also be subject to pressure under some conditions. These considerations are reflected in several necessary modifications of the experimental procedures described by the authors. Two of these are, in our judgment and experience, of such importance that they cast real doubt on the validity of data obtained on argillaceous materials without their application. The very careful resaturation procedures proposed by the authors should give good results in connection with the relatively "inert" lithologies used in their experiments. Our experience suggests, however, that they would create more problems than they would eliminate if applied to argillaceous materials. 1. Drying of the sample at the temperature and for the duration indicated by the authors not only will dessicate the sample with consequent shrinkage cracking, parting along bedding planes, and even total disassociation in the case of fissile shales, but it may also alter the character of the clay minerals themselves — in some cases irreversibly. 2. Prolonged evacuation to 2 microns Hg further dessicates the sample and is even more effective in reducing the intersilicate water content. 3. Resaturation with water differing in pH or chemical content from that existing originally in the sample also serves to alter the nature of the sample, particularly its structure and strength. 4. Our experience has been that, even with the thorough precautions proposed by the authors, complete resaturation of very fine grained materials is rarely obtained. Yet our experience confirms the

Jan 1, 1969

By Robert Bakish, William D. Robertson

AFTER more than fifty years of investigation and continuing failure in service, a satisfactory mechanism to explain stress corrosion cracking in homogeneous alloys is still lacking. The relative chemical activity of grain boundaries and adjacent grains, inferred from the boundary structure, has been used to explain intergranular cracking in a brass.' This concept is probably correct as a general hypothesis, but it requires much more extensive development in order to explain satisfactorily the observed phenomena. For example, the specific function of the solute in an alloy must be considered, because intergranular failure does not occur in pure metals,' which are structurally similar to homogeneous alloys. Also, in this connection, an inter crystalline fracture path in binary copper alloys can be changed to a transcrystalline path by relatively small ternary additions.' The fracture path in ß brass is predominantly transcrystalline,' in contrast with an inter crystalline path in a brass. Whether the two different fracture paths are the result of a difference in composition, crystal structure, or the state of long range order is unknown and cannot be determined with ß brass, because only the ordered state can be obtained at room temperature. The study of chemical activity at structural sites in the Cu-Zn system is restricted by the formation of opaque films in an ammonia environment in which stress corrosion cracking is generally observed. Furthermore, both components of the alloy are chemically active and the interpretation of observations is therefore relatively complicated. The Cu-Au system is a better choice for the purpose of studying structural factors. In particular, CuAu is very susceptible to cracking in ferric chloride and opaque films are not formed in this solution; it may be obtained in different states of long and short range order; and, finally, only copper is oxidized in dilute ferric chloride, which considerably simplifies the chemical problem. To provide information necessary for a more general explanation of stress corrosion cracking in homogeneous solid solutions, the following structural factors have been investigated in a Cu-Au alloy having a composition corresponding to Cu,Au: 1) the effect of long and short range order; 2) the structural sites from which copper is removed from the annealed and cold worked polycrystalline alloy; and 3) the effect of annealing time and temperature on structural reactions in the cold worked alloy. Experimental Procedure A Cu-Au alloy of nominal Cu3Au composition was cast from cathode copper and high purity gold and fabricated into sheet and wire. Chemical analysis for copper and gold indicated 48.92 wt pct Cu and 51.01 pct Au. Quantitative spectrographic analysis indicated 0.01 pct Ag, 0.002 pct Pd, 0.001 pct Pb, and 0.002 pct Fe, with traces of magnesium, silicon, and zinc. Presumably most of the remaining 0.055 pct corresponds to the limits of analytical precision. Heat treatments of wire and sheet were conducted in argon or vacuum. Wire specimens, 0.064 in. diam, were heated for 1 hr at 850 °C to establish a definite

Jan 1, 1957

By M. F. Trice

PYROPHYLLITE is a hydrous aluminum silicate (A12Si4010(OH)2)1 that occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mobs' scale.1 The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey,2 contain pyro-phyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, "are noticed in but small quantities to the extent they might occur as accessory constitu-ents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 percent and the alumina from 22 to 33 percent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent.

Jan 1, 1940

By J. B. Cheatham, M. D. Biggs

This paper presents a systematic method for determining the forces on a simplified roller bit. The kinematics of an actual roller bit drilling in rock is complex; nevertheless, it is desirable to obtain an accurate analytical model.. As a preliminary study, the roller bit is represented here by a simple two-dimensional bit and the rock by a Coulomb plastic material. Results from previous work, plus additional assumptions, are incorporated into a computer program to determine the forces required to move the bit in a specified manner. Example problems are worked by use of this program. By studying similar drilling problems and by supporting laboratory work, one could eventually obtain an accurate analytical model for drilling by an actual roller bit. This could lead to the compilation of a catalog of results that, in turn, would allow selection of the optimum drill bit for any given situation. INTRODUCTION

Jan 1, 1970