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By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale forma¬tion) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. EXPERIMENTAL PROCEDURE Silver.-The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By Richard R. Zupp, David A. Stevenson

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

Jan 1, 1967

By D. E. Mikkola, G. E. Poquette

X-ray diffraction was used to study the growth of antiphase domains in quenched (or "disordered&apos;? Cu3Au annealed in the range 300" to 385°C. Measurements of the long-range order parameter indicate that a high degree of order is established rapidly at these annealing temperatures. Average domain sizes obtained by Fourier analysis of the superlattice peak profiles show that antiphase domain growth is analogous to classical metallurgical grain growth (i.e.,fol-lows a D2 US kt relation). The activation energy for the growth process, 44 kcal per mole, indicates diffusion control. The anisotropy in the observed effective domain sizes from seven different superlattice peaks can be best accounted for by a configuration involving antiphase domain boundaries on {100 } and (111 ) planes, where the (100) boundary is the low-energy type, {lOO} Type I. The disappearance of the (111) antiphase domain boundary during domain growth is dif-fusion-controlled with an activation energy of 48.5 kcal per mole. On the other hand, the behavior of the parameter representing the amount of (100) Type I boundary indicates that there may be a conversion of the higher-energy boundary types to (100) Type I boundary during the growth process. THE order-disorder transformation in the alloy Cu3Au has been the subject of numerous experimental investigations over the past 40 years, most of which have involved measurements of convenient physical properties such as resistivity and hardness as a function of heat treatment. The interpretation of these data is difficult because measurements of this type have the disadvantage that they yield total changes resulting from several different atomic processes which may be occurring simultaneously. The present study was undertaken to establish by means of X-ray diffraction the kinetic behavior of one of these atomic processes, namely antiphase domain growth. In the completely ordered state Cu3Au has an L12 structure which can be described as an fcc type arrangement of atoms in which the gold atoms occupy the corner sites and copper atoms the face-centered sites. Three other equivalent unit cells can be formed by allowing two gold atoms to occupy opposite face-centered sites and copper atoms to occupy the remaining corner and face-centered sites. These four different unit cells are crystallographically related by a shift of 1/2<110>. Quenching from above the critical temperature (392°C) to room temperature retains the "disordered" structure-a "random" arrangement of copper and gold atoms having the fcc structure. Annealing the disordered alloy below the critical temperature causes ordering to occur through the nucleation and growth of ordered regions at different points throughout the crystal. These small ordered regions, each based on one of the four types of unit cell, grow by consuming the disordered material until they impinge to form a domain structure in which the domains are antiphase by a shift of 4(110). The boundaries between domains are called antiphase domain boundaries (APDB) and they have been found to lie primarily on &apos; {100} planes in highly ordered Cu3Au. Two types of APDB can occur on ( 100) planes. An example of an (001)1/2[110] shear type APDB is shown in Fig. I. Because of the layer of copper atoms separating the domains in this case, there are no near-neighbor violations across the boundary and it has a low surface ener This type of APDB will be referred to as {lOO} Type I. Fig. 2 shows an (001): [011] climb type APDB, (100) Type 11. This type of APDB can be described as resulting from removal of a (200) plane followed by a shift of 1/2<110> to bring the separated regions together. Near-neighbor violations across (100) Type I1 APDB make it a high-energy boundary. There are numerous other possible APDB configurations; however, it is only worth noting that shear type APDB can be produced on the (111) plane by motion of a normal fcc dislocation with Burgers vector 1/2<110> through the ordered structure. A (111); [110] shear type APDB is shown in Fig. 3. Again, because of the near-neighbor violations this type of APDB has a higher energy than the (100) Type I APDB.

Jan 1, 1970

By W. C. Maurer

A study of bit-tooth penetration, or crater forniation. under simulated borehole condirions has been made. Pressure conditions existing when drilling with air, water and mud have been sirnulated for depths of 0 to 20.000 ft. These crater tests showed that a threshold bit-tooth force must he exceeded before a crater is .formed. This thresh old force increased with both tooth dullness and diflerenrial pressure between the borehole and formalion fluids. At low differential pressures, the craters formed in a brittle manner and the cuttings were easily removed. At high differenlial pressures, the cunings were firmly held in the craters and the craters were formed by a pseudoplas-tic mechanism. With constant farce of 6,500 16 applied to the bit reeth, an increase in differential pressure (sitnulated mud drilling) from 0 to 5,000 psi reduced the crater volumes by 90 per cent. A comparable increase in hydrostatic fluid pressure (simulated water drilling) produced only a 50 per cent decrease in volutne while changes in overburden pressure (simulated air drilling) had no detectable effect on crater volume. Crater tests in unconsolidated sand subjected to differential pressure showed that high friction was present in the sand at high pressures. Similar friction belween the cuttings in craters produces the transition from brittle to pseudo plastic craters. INTRODUCTION The number of wells drilled below 15,000 ft increased from 5 in 1950 to 308 in 1964. Associated with these deep wells are low drilling rates and high costs. High bottom-hole pressures produce low drilling rates by increasing rock strength and by creating bottom-hole cleaning problems. This paper describes an experimental investigation of crater formation under bottom-hole conditions simulating air, water and mud drilling. Although numerous investigators have studied bit-tooth penetration (cratering) at atmospheric pressure conditions, only limited work has been done on cratering in rocks subjected to pressures existing in oil wells. Payne and Chippendale2 have studied cratering in rocks subjected to hydrostatic pressure using spherical penetrators. Garner et aLJ conducted crater tests in dry limestone by varying overburden pressure and borehole fluid pressure independently and using atmospheric formation-fluid pressure Gnirk and Cheathem4,5 have studied crater formation in several dry rocks subjected to equal overburden and borehole pressure and atmospheric formotion pressure. Podio and Gray studied the effect of pore fluid viscosity on crater formation using atmospheric borehole and formation-fluid pressurc and varying overburden pressure. Although these studies have provided useful information on crater formation under pressure, they were limited in that the three bottom-hole pressures could not be varied independently and, therefore, that many drilling conditions could not be simulated. The prersure chamber used in this study allowed visual observation of the cratering mechanism and independent control of the borehole, formation and confining pressures. By using different fluids in the chamber, pressure conditions existing in air, water and mud drilling to depths of 20,000 ft were simulated. The mechanisms involved in cratering at these different pressure conditions were studied for teeth of varying dullness and at different loadins rates. High-speed movies (8,000 frames/sec) and closed-circuit television were used to visually study the crater mechanism under pressure. EXPERIMENTAT PROCEDURE PRESSURE CHAMBER The Pressure chamber in Fig. I was used to simulate bottom-hole pressure conditions. This chamber has been pressure-tested to 22,500 psi and is normally operated at pressures up to 15,000 psi. The chamber contains four lucite windows&apos; used for illuminating and observing the crater mechanism under pressurc. A closed-circuit television and a Fastax camera (8,000 frames/sec) have been used in these studies. Cylindrical rock specimens (8-in. diameter X 6-in. long) were subjected to three independently controlled pressures simulating overburden, borehole fluid and formation-fluid pressures. Overburden pressure, which corresponds to the stress induced by the overlying earth mass, was applied by exerting fluid pressure against a rubber sleeve surrounding the rock. Borehole pressure, which is the pressure exerted by the column of mud in the wellbore, was simulated by applying pressure to the fluid overlying the rock in the chamber. Formation pressure was simulated by applying pressure to the water saturating the rock. The borehole and formation pressures were equal except when mud was used in the chamber, in which case the differential pressure between these fluids acted across the mud filter cake.

Jan 1, 1966

By Alexander Field

The hot-rolling properties of a series of high-sulfur steels are described. From a consideration of the sulfur, manganese, and zirconium contents of these steels, it is shown that zirconium reacts with the sulfur content of molten steel in accordance with the equation Zr + 2S = ZrS2. Zirconium disulfide appears in the finished state as gray-colored inclusions, similar to manganese sulfide in plastic behavior and general appearance. Zirconium completes its act of deoxidation before proceeding to combine with sulfur and indirectly increases the effective sulfur-combining power of any manganese which may be present. IN A previous paper,1 the experimental methods used and some of the results obtained in an extensive investigation of steels containing zirconium were described. The present paper considers in greater detail one of the most interesting of these effects, namely, the elimination of "red shortness" and the occurrence in steel of a compound of zirconium and sulfur. A consideration of the actual percentages of zirconium, manganese, and sulfur in numerous steels in the light of behavior during rolling has led to new conclusions of the most practical import regarding the reciprocal relationships of these elements. The microscopic examination of high-sulfur steels containing zirconium has also been productive of interesting results. Before discussing the experimental data in question, it may be stated, briefly, that the reaction between zirconium and sulfur in molten steel may he represented by the simple equation, Zr + 2S = ZrS2, and that the zirconium sulfide thus formed occurs in the finished steel in the form of gray-colored inclusions, closely resembling manganese sulfide and, like the latter, exhibiting plasticity at rolling temperatures. Molten steel containing zirconium retains such a negligibly small amount of oxygen in solution that the foregoing reaction goes to completion.

Jan 2, 1924

By Charles P. Berkey, Joseph H. Sinclair

This paper describes the results of a visit to the Santa Elena Peninsula, Ecuador, in January and February, 1921. On account of the complicated folding and faulting of the rocks and the peculiar occurrence of petroleum, field work was possible on only a few of the many geological problems and the results here published are only a contribution to the solution of the general problem. We know of nothing published on the geology of the district, except one account, in Spanish and German, by Theodor Wolf. The Santa Elena peninsula, the most important headland of the coast of Ecuador, lies two degrees south of the equator. The chief town, Santa Elena, is about 75 miles west of Guayaquil, the main seaport of Ecuador. The nearest developed oil field is the Zorritos of northern Peru, 120 miles south across the Gulf of Guayaquil. If newspaper reports are true, viz. that the Anglo-Ecuadorian Oilfields, Ltd., has recently brought in a 700-bbl. well on the coast of the peninsula near Ancon, the district may become important in the production of petroleum. At the time of our visit, the best way to reach the peninsula was by a steamer of the Pacific Steam Navigation Go., southward from Panama and northward from Guayaquil. About once a week, one of these steamers anchored 1/2 mile off shore near the village of Salinas, an important cable station. An alternative route, in the dry season, is by automobile from Guayaquil. In February, 1921, a railway bed had been graded part way between Guayaquil and Salinas, but this was detcriorating rapidly because of lack of funds to continue construction or to keep in repair that portion already completed.

Jan 1, 1923

By M. P. Tixier

In several log interpretation methods, water saturation is evaluated by use of the ratio of the readings of a short spacing resistivity device and a long spacing resistivity device plus information on the mud filtrate and connate water resistivities, which is often derivable from the SP. These methods are valid over a certain range of conditions, usually specified by moderate invasion and R.. greater than R,. Since these methods involve no explicit evaluation of the formation factor, F, the saturafiion so found may be used in the standard Archie equation to derive a computed formation factor which, as a check, may be compared with the formation factor known from other independent measurements. Discrepancies in the two values of formation factor generally indicate that the ratio method is not within its range of applicability. If the computed F is too low, the corresponding S, is too low; if the computed F is too great, the corresponding S, is too great. By means of this "porosity balance" check, and some knowledge of the probable conditions of invasion, the interpretation can often be improved. The poqosity balance check is discussed for the cases of the Induction-Electrical Log Interpretation Method, the Rocky Mountain Method, and the R.,/R, Method. For the first method, a discussion is also given for the case of shaly sands. INTRODUCTION Al though many logging tools are available to obtain a practical value of porosity, the only logging method reflecting the water saturation is electrical logging. Water saturation is commonly computed from electrical log data by means of the basic Archie formula, Where F is the formation factor, R, the resistivity of the formation water, and R, the true resistivity of the formation. One difficulty in this procedure is a possible error in the evaluation of R, from the logs— for example, in the case of very deep invasion. There is no possibility, inherent in the procedure, which would provide a check of the accuracy of R, and, hence, of the computed saturation. Other approaches have been proposed which are based essentially on the ratio of the readings made with two dzerent devices: one device, with a short radius of investigation, provides a value close to the resistivity of the invaded zone; the second device, with a long radius of investigation, gives a value close to the true resistivity of the bed. By these methods, the determination of saturation is made independently of any direct knowledge of the formation factor. Therefore, if the formation factor (or porosity) is known from other sources (core analysis, neutron log, MicroLog . . .), it becomes possible to take advantage of this additional information in order to check the value of saturation derived from these latter methods. Inasmuch as this proposed check procedure relies on a knowledge of the value of formation factor or porosity, it has been deemed appropriate to call this verification a porosity balance. The purpose of this paper is to discuss the principle and the application of the porosity balance, depending on the method of interpretation being used. Basis of the Method There are in existence three interpretation methods by means of which the water saturation can bc found without a knowledge of the formation factor (or porosity). As just stated, they are based on the fact that the ratio of the two resistivities (one measuring the resistivity close to the hole, the other measuring the resistivity far from the hole) is independent of the formation factor since it affects the two resistivity measurements in the same way. Chronologically, the resistivity ratio methods are: (1) the Rocky Mountain Method, which has been used since 1943 and was explained in a paper in 1949;&apos; (2) the R../R, Method or Shaly Sand Method, presented in 1954, which permits the calculation of the water saturation in both clean and shaly sands2; and (3) the Induction-Electrical Log Method, presented in 1957 for the interpretation of the induction-electrical log combination." Each method requires certain definite conditions in order for the interpretation to be reliable. The porosity balance method will let us know whether these conditions are fulfilled. In clean formations we know that the fundamental Archie relation (Eq. 1) must always be verified. This relation can be rewritten:

By J. Chipman, T. Fuwa

The effects of various elements on the activity coefficient of carbon in liquid iron have been studied by two experimental methods: 1) equilibration with controlled mixtures of CO and CO2; 2) the solubility of graphite in the melt. Activity coefficient of C is increased by Al, Co, Cu, Ni, P, Si, S, and Srz. It is decreased by Cr, Cb, Mn, Mo, W, and V. THE thermodynamic properties of the iron-carbon binary system have now been fairly well established, although some uncertainty remains with respect to the exact location of some of the phase boundaries. The activity of carbon in ferrite and in austenite has been measured in the classic researches of R. P. smith&apos; while similar measurements by Richardson and ~ennis, and by Rist and chipman3 have established the values of the activity of carbon in liquid iron up to 1760°C. On the other hand, our knowledge of the effects of alloying elements on the activity of carbon in dilute solutions is restricted to Smith&apos;s experiments on systems Fe-C-Mn and Fe-C-Si in the austenitic range and to some more recent experiments of schwarzman4 in the a range. In addition there have been a number of determinations of the effects of various elements on the solubility of graphite in liquid iron, and from these the corresponding effect in saturated solution may be obtained. The purpose of the present study was to extend the investigation of the liquid system to include the effects of alloying elements upon the activity coefficient of carbon, principally in dilute solutions. Equilibrium measurements were made on the reaction C + co, = 2 CO (g) The prepared mixture of CO and CO,, diluted with argon, flowed over the surface of the liquid metal which, after several hours&apos; exposure to the gas, was quenched and anqlyzed. As in the earlier experiments, the principal experimental difficulty was in the deposition of carbon on the parts of the furnace at temperatures slightly below that of the metal bath. In order to minimize this difficulty, the ratio (Pco)2 /PCo2 was restricted to values not much higher than 100 atm, and correspondingly the carbon concentration in the metal seldom exceeded 0.30 pct. EXPERIMENTAL METHODS The method and apparatus were essentially the same as used by Rist and Chipman.3 The gaseous mixture consisting of highly purified CO, CO,, and argon, each controlled by a flowmeter, was led into the furnace and passed over the surface of the liquid-iron melt which was heated and stirred by high-frequency induction. One slight modification was made in that a molybdenum susceptor was placed outside the crucible for the sake of uniformity of temperature and to combat the tendency of carbon to precipitate on the crucible wall. Pure alumina crucibles approximately 25 mm ID were used. The charge consisting of about 30 g was made up of electrolytic iron, the alloying element to be added, and enough graphite to supply slightly more or less than the anticipated equilibrium carbon concentration. All metals used were of high purity. Metallic chromium, columbium, and vanadium were from special lots supplied by the Electro Metallurgical Co. Tin, copper, molybdenum, tungsten, cobalt, and nickel were of purest commercial grades. The electrolytic iron, after being cut to the proper size for charging, was prereduced by hydrogen at 850° to 1000°C to remove surface oxidation. The oxygen content of the reduced material was 0.002 pct. This treatment made it easy to control the carbon content of the initial melt. The charge was melted under the gas mixture to be used for the entire run. In some earlier melts the charge was melted under a stream of argon, but in this case some alumina was reduced from the crucible, and the aluminum thus absorbed in the melt was subsequently oxidized with the formation of a solid film of alumina on the surface of the melt. AS another safeguard against film formation, overheating of the bath was carefully avoided. All runs were made at a temperature of 1560°C. Under experimental conditions a charge of pure iron picked up 0.17 pct C in 3 hr and 0.23 pct C in 6 hr under an atmosphere for which the equilibrium concentration of carbon is 0.27. It is clear that the time required to reach equilibrium from an initially carbon-free melt would be very great. For this reason each experiment was started with a melt of known carbon concentration not far above or below the expected equilibrium value, and each melt was held at temperature for a period of at least 5 hr. Under such circumstances it was possible to chart the approach to equilibrium from both high-carbon and low-carbon materials. Temperature was controlled by frequent optical observation and adjustment and the metls were timed in such a way that the final 2 hr occurred during a time when electric power was steady; for example, 2 to 4 pm or after 11 pm. In melts containine volatile metals such as copper, tin, and mangane\e the time of holding was decreased somewhat in

Jan 1, 1960

By J. Lewis, J. Harper, M. F. Ashby

A grain boundary in a metal interacts with second-phase particles, which exert a pinning force (first estimated by Zener) on the boundary opposing its motion. We have computed the shape of boundaries which interact with more or less spherical second-phase particles and have constructed a soap-film model to reproduce the shape of the boundary surface. An important result is that measurement of this shape allows the pressure, or driving force, on the boundary to be measured. We hare applied this technique to grain boundaries in two alloys and hate measured the pinning force exerted by single second-phase jwrticles on the boundaries. It is in good agreement with Zener&apos;s estimate. J\. boundary between two grains, or two bulk phases, interacts with small inclusions or particles of a second phase, whether they are gas or solid. This interaction means that the boundary, forced to migrate by a difference in free energy between the material of the two grains or phases which it separates, exerts a force on a particle which it touches, tending to drag it forward. (The movement of inclusions through metals under the influence of this force, has, in fact, been observed. 1-3) Equally, the particle can be thought of as exerting a pinning force on the boundary, tending to hold it back. Zener (in a celebrated private communication4) first realized that this interaction, and the resulting pinning force, existed. His calculation of its magnitude was crude but adequate: a spherical inclusion of radius r blanks off an area nr2 of the boundary on which it sits; since the boundary has an energy of rMM x per unit area, the blanlung-olf decreases the energy of the system by MM: this energy is returned to the system if the boundary is pulled free from the inclusion— a forward movement of the boundary by a distance r will do this—so that the maximum pinning force is Trrym.M- A similar argument can be made for inter-phase boundaries. The nature of the particle itself did not enter this, or two subsequent treatments.5,6 When it is considered, tic leifthe energyoftheb a) The boundary may enter and pass through the particle if the energy of the boundary is lower within the particle than in the matrix. Fig. l(r/). Certain coherent precipitate particles behave like this. h) More usually, the boundary will bend round the particle, enveloping and bypassing it. Fig. l(b). In doing so, it changes the structure and energy of the interface between the particle and its matrix. This means that the boundary does not touch the particle surface at right angles, as early treatments assumed,5&apos;9 but at some angle a which depends on this change in surface energy of the particle, and can be calculated from the equilibrium of surface tensions. Most precipitate particles and inclusions behave like this. Gas bubbles or liquid drops can be regarded as belonging to either group. The progress of bypassing is conveniently measured by the angle shown in Fig. 1. When the nature of the particle is ignored, its maximum pinning force is exerted when - 45 deg. When it is considered, this critical value of is found to depend on a and thus on the nature of the particle. The maximum pinning force lies between nryMM and 2jtjMM (Appendix 1). not very different from Zener&apos;s result. In reality, a boundary between crystals has a specific energy and tension which varies with the orientation of the boundary. Furthermore, recent experiments7 indicate that such a boundary is not atom-ically smooth, but has steps on it: migration of the boundary corresponds to the sweeping of these steps across the boundary surface, like the Frank model of crystal growth from the vapor. This means that the interaction of a boundary with particles should really be considered in terms of the way in which particles hinder the movement of these steps. To suppose a grain boundary or interphase boundary to be smooth, and to ignore the variation of its energy with orientation, is to liken it to a soap film. The advantage of this soap film approximation, which we have used throughout this paper, is that interaction energies and boundary shapes can be calculated easily. We have done this by numerical computation and by using a soap film model, and have compared the results with grain boundaries in an aluminum-based and a copper-based alloy. It turns out that the shape of the boundary which bulges between particles allows the pressure an it to be calculated; that is, the local driving force an the boundary can be measured. This has allowed us to check the Zener relationship experimentally.

Jan 1, 1970

By A. U. Seybol

Eight binary iron alloys were examined after ion nitriding experiments to determine the behavior of the following elements: Al, Mo, Mn, Si, Ti, V,Cr, and C. Only Al, Cr, Ti, and V additions caused hardening in binary iron alloys. A few steels were examined to see the effect of Cr, Cr + Al, Cr + Ti, and Cr + V. It is suggested that a useful new class of ni-triding grade steels might be those containing about I pct V. The nitriding of steel, first described by Fry1 about 45 years ago, rapidly attained commercial application with very little knowledge of the fundamentals involved. While Fry,&apos; in describing the status of nitriding in 1932, apparently correctly postulated hardening by precipitated nitrides, the details of the nitriding process were not understood, nor has the situation changed much since that time. It is also interesting to note that the compositions of some typical nitriding steels given by Fry at that time have changed little in the intervening years. Currently used nitriding steels owe their surface hardening to either chromium (as in 4340 steel) or aluminum plus chromium as in the Nitralloy grades, where both CrN and AlN appear to contribute to harden ing. Titanium additions have been studied experimentally, but thus far titanium steels have not won wide commercial acceptance. This subject will be expanded later. The orthodox ammonia nitriding process has been reviewed very adequately many times as in Jenkins3 and Case and VanHorn,4 and their is no need to outline the process here. Ion nitriding is not as well-known, although there have been several descriptions5-9 of the process given, sometimes with comparisons with the ammonia process. Most of these papers are primarily concerned with a description of the equipment, or of the physics or electrical engineering aspects of ion nitriding, but Noren and Kindbom9 gave the results of a metallurgical investigation using both processes. In brief, ion nitriding is carried out in a vacuum chamber from which the air is exhausted and replaced by a N2-H2 mixture, typically containing 10 to 20 pct N2, at about 5 to 10 torr pressure. While ammonia gas has also been used in ion nitriding, there is no evidence that ammonia makes any improvement in the ion nitriding process. A few hundred volts dc is applied between the grounded container wall (positive) and an insulated center post supporting the work (negative) to be nitrided. A glow discharge is created in the ionized gas, accelerating positive nitrogen ions to the work. These ions contain enough energy to form the normally unstable Fe4N "white layer", thus establish- ing surface nitrogen solubility characteristic of the a Fe/Fe4N equilibrium. This creates a substantial concentration gradient, driving dissolved nitrogen into the steel. The temperature employed is in the same range (around 500" to 550°C) as in ammonia nitriding, but because of factors which are not understood at present the nitriding time is ordinarily considerably reduced in ion nitriding. Other advantages have been cited,9 but it is not the purpose of the present work to contrast the two processes. The present objective was to examine the behavior of binary iron alloys during ion nitriding with respect to the microstructure, hardness level, and depth, and to examine some of these factors in steels as well. In this way it was hoped to be able to find out something about the individual role of these elements in steels. While all the work was done by ion nitriding, there seems to be no reason why any conclusions reached would not equally apply to ammonia nitriding, excepting only the kinetic aspects of the process. Another objective was an exploration of the critical-ity of the ion nitriding variables: gas composition, pressure, temperature, and time. EQUIPMENT AND MATERIALS The equipment used was substantially as described by Jones and Martin.8 The vacuum tank was about 12 in. in diam by about 18 in. high, and consisted of water-cooled stainless steel, with a single small window at the top for viewing inside. This sat on a heavy mild steel base equipped with the main pumping port, pressure control port, and vacuum gaging. A series of variable resistances was interposed between the glow discharge and a large-capacity -40 amp variable primary transformer feeding a 1000-v transformer, but 600 v were about the maximum ordinarily used. With the small l-in.-round, 4-in.-thick discs used for nitriding, the electrical load was usually about 500 v at 0.8 amp. The specimen temperature was controlled by a stainless-steel sheathed chromel-alumel couple, whose junction was in the steel stool upon which the flat discs were placed. These were ground through 400 Sic paper. Cycling of the temperature controller caused -0.2 amp variation in ion current, providing an ample control band. The binary iron alloys were made from vacuum-melted hydrogen-deoxidized electrolytic iron and alloys of 99.9 pct purity. Cast ll-lb-square tapered ingots were forged and hot-rolled to about 11/4-in.-diam rounds. Discs of 1/4 in. thickness by about 1 in. diam were machined from the rods for nitriding specimens. The following alloys were prepared: 1 pct each of Mn, Mo, Cr, Ti, Al, V, Si, and an Fe-0.8 pct C alloy. EXPERIMENTAL VARIABLES Of the variables total gas pressure, nitrogen partial pressure, temperature, and time, only nitrogen partial pressure was found to be critical to the operation. A critical nitrogen partial pressure was found corre-

Jan 1, 1970

By M. J. Marcinkowski, Gordon E. Lakso

An extensive investigation has been made of the deformation behavior associated with the Fe3Si super-lattice using transmission electron microscopy techniques. Above 243°K the stress-strain curve exhibits three stages. Stage I occurs at a very low stress level and is related to the generation of perfect superlat-tice dislocations. Stage II is characterized by an extremely rapid rate of work hardening and is associated with the Taylor type locking of these superlattice dislocations. Finally Stage III is related to dynamic recovery processes since the work hardening rate is very small. Below 243ºK, only Stage I is observed, but it occurs at a much higher stress level. This latter observation is related to the generation of imperfect dislocations in Stage I with the consequent production of second nearest neighbor antiphase boundaries. The reason for this is that insufficient thermal energy is available at these low temperatures to generate the complete and perfect superlattice dislocations. It has been shown that the fully ordered FeCo alloys, i.e., those possessing the B2 type structure, exhibit three distinct stages of work hardening whereas the corresponding disordered alloys show only one.&apos;" This difference in behavior between the disordered and ordered alloys has been attributed to the fact that dislocations in the former case travel only as ordinary 1/2ao(111) types whereas in the latter case the move through the lattice as coupled 1/2a0(111) dislocations separated by an antiphase boundary (APB), i.e., the so-called superlattice dislocation. Although some preliminary work has been carried out concerning plastic deformation in ordered alloys possessing the DO3 type superlattice,3 no detailed analysis similar to that described in Refs. 1 and 2 has been attempted. Specifically, it has been suggested that the superlattice dislocation in this particular type structure should consist of four ordinary 1/2ao<111> types bound together by first and second nearest-neighbor APB&apos;s. Fe3A1 and Fe3Si are the two classic alloys possessing the DO3 type lattice; however, because of the somewhat higher ordering energies associated with the FesSi alloy, which in turn assures that dislocations will travel through the lattice as perfect superlattice dislocations under at least some conditions, it was chosen for the present investigation. Because of the extreme brittleness of Fe3Si, all deformation was done in compression. Stress-strain curves were obtained using both polycrystalline samples as well as single crystals. In the latter case the crystals were oriented so that deformation could be controlled either by single or double slip. They were then wafered parallel to and at various angles to the operative slip planes. These wafers were in turn examined by transmission electron microscopy (TEM) techniques in order to determine the extent of the interaction from the dislocation configuration contained therein. EXPERIMENTAL PROCEDURE The alloys used in this investigation were arc melted under helium from electrolytic iron of greater than 99.90 wt pct purity and transistor grade silicon of 99.99 wt pct purity. A typical analysis of interstitial impurities showed 120 ppm 0, 15 ppm N, and 65 ppm C Because of the extremely low ductility of the Fe3Si alloys, it was necessary to spark cut 0.230-in. diam polycrystalline cylinders 0.400 in. long from arc-melted fingers using a thin-walled brass tube as a cutting tool. The polycrystalline alloys could not be recrystallized since very little strain was induced in preparation. However they were annealed at 1273°C for 15 min in evacuated vycor capsules to relieve any cooling stresses that may have developed during solidification and then air cooled. The resulting grain size of the alloy was 0.50 mm. According to warlimont4 1273ºC is just within the single phase field where FesSi possesses the DO3 type lattice. In addition because of this high critical ordering tem-ature, air cooling from this temperature was believed sufficient to fully order all of the Fe3Si samples used in the present investigation. For the same reason, no attempt was made to achieve any degree of disorder by quenching. In fact, rapid quenching from 1123°K caused cracking. Such cracking was first suggested by sato5 with respect to the experimental observations of Glaser and Ivanick.6 Single crystal compression specimens were spark cut from single crystal ingots grown in a Bridgman type furnace. The iron and silicon for the crystals was prealloyed by arc-melting two 130-g buttons which were cut into small pieces before remelting in the furnace. This procedure resulted in a long-range inhomogeneity of 0.5 at. pct Si between the top and bottom of the 2-in.-long single crystal ingot, which was assumed to be negligible in the present investigation. The single crystals, after orienting and spark-cutting, were about 0.37 in. by 0.37 in. in cross section and about 0.5 in. long. True stress-strain curves were obtained using an Instron Tensile Testing machine in conjunction with techniques described previously. 1,7 The strain rate was 0.05 in. per in. per min. Prior to testing, the ends of all the compression cylinders were hand polished using a special jig to insure parallelism after which the sides of the samples were electrochemically polished to eliminate stress risers and to facilitate slip line observations. Test temperatures between 77" and 823°K were obtained using various cooling and heating media as described in Ref. 7 while at the upper end of this temperature range, a mixture of equal

Jan 1, 1970

By L. H. Reiss, J. Groult, L. Montadert

Many fields, where the reservoir is composed of sandy layers, show great complexity because of the lack of continuity which results from a particular type of seditnentation. This complexity may be a factor of prime importance in studying reservoir drainage, especially in the displacement of oil by water or gas. This paper describes work done to study this heterogeneity and its influence in the exploitation of the fields of the lower Devonian sandy shale in the Fort Polignac Basin in Algeria. Two lines of research were followed. 1. On the border of the hasin, a detailed sedimentological study established rules for the distribution of the sandy zones, which furnished hypotheses necessary for devising a geologic model of the reservoir. A certain number of sandy zones were recognized and characterized by their sedimentation. 2. In the interior of the basin, production logs deterrnined the productivity profile. Study of these point data led to a description of the distribution of oil and gas phases in the reservoir so that the continuity of different zones between the wells could be deduced. These techniques were applied to the study of the lower Devonian sandy shale reservoir of Zarzaitine. The sedimentological study guiding the correlation work, with the aid of the conventional static data (logs and cores), led to the establishment of a useful geologic model of the reservoir. Production logs, thanks to the contribution of dynamic elements, permitted corrobora-tion of the model. In particular, the logs confirmed separation, as proposed by the sedimenfological study, of two comparable sandy groups by revealing the continuity of a thin impermeable layer, invisible on conventional logs. INTRODUCTION The heterogeneity of sandstone reservoirs considerably influences the distribution of fluids, as well as their displacement in the reservoir. Rational development of a field and maximum recovery of hydrocarbons are closely tied to an exact and precise knowledge of the intern architecture. We will try to show how it is possible I refine the knowledge of the reservoir by seeking qui different and varied sources of information. Productic geology, the group of techniques which leads to idei concerning reservoir architecture and its geometric descris tion, furnishes the framework of this undertaking. Of these techniques. those used so far are qui varied. Descriptive as well as quantitative, the technique partake as much of classical geology as of reservo science. They include (1) geologic studies of the enti basin, especially a stratigraphic and sedimentologic study of the reservoir member at its outcrop, detail1 observations of cores taken from wells and, finall oriented cores; (2) interpretation of geophysical dat (3) interpretation of electric logs, nuclear and sonic lo and dipmeters: (4) petrophysical study of the reserve on samples taken from wells; (5) reservoir dynamics (stu of the production history and, in particular, interpretati of production logs); and (6) analysis of the fluids a thermodynamic studies. This incomplete list could also include (1) study the migration of the fluids, (2) geochemistry (chemi characterization of the oils), (3) regional hydrodynamii and (4) injection and detection of tracers. If most of these techniques are classic, attention i nevertheless be called to applying two of the techniql in conjunction: the study of the reservoir member its outcrop and the study of dynamic distribution fluid phases in the reservoir through use of product logs, used in the study of the sandy shale reservoirs the lower Devonian of the Fort Polignac Basin, Alge in particular, their application to the study of the 2 zaitine field where they have led to a new and satisfact model of the reservoir will be described. THE ZARZAITlNE FIELD Situated in the interior of the Fort Polignac 8 about 150 kilometers (km) north of the lower Devol outcrop, the Zarzaitine Devonian oil field was discovc On Ian. 28, 19&apos;&apos; (Figs. 1 and l8). It is in the fern a monocline truncated by two perpendicular fault: great throw, with a downthrown section to the north\: Erosion at the top of the structure has caused one of it to disappear. It is a reservoir with a gas cap an m coefficient on the order of 1:5, open to the aql On the northeast, with the oil zone covering an Of 106 sq km and with initial oil reserves of 222 mi

Jan 1, 1967

By G. A. Stamboltzis, N. Arbiter, C. C. Harris

Fracture under low-velocity free-fall and double impact and under slow compression have been investigated. The pattern of breakage and the size distribution of resulting fragments of sand-cement and glass spheres have been determined. Photoelasticity methods were used to simulate the stress distributions in free-fall impact in order to explain the observed patterns of breakage. Oblique fracture planes, occurring only in free-fall impact, develop along lines which coincide with the trajectories of maximum compression as determined by mathematical analysis. Breakage efficiencies for different modes of fracture were compared for both types of spheres. For the same specimen and loading system, static loading and low-velocity dynamic loading induce geometrically similar stress fields resulting in reasonably similar fracture patterns and shapes of fragments. This work had its origin in a desire to understand three fundamental processes involved in autogenous comminution: namely; free-fall impact, double impact, and slow compression. To simplify the investigation, it is preferable to reduce the entire multi-stage fracture process to its most elementary form; that is, to study products resulting from a single-stage operation, such as the breakage of a specimen under single fracture conditions. The goal of this research is to study the energy utilization in the single fracture of brittle specimens and to relate the pattern of breakage and the resultant fragment size distribution with the nature of the material, the specimen size, the manner of load application, and the rate of loading. Published works on single fracture have mainly been concerned with tests on large (> 1-in.) irregular mineral pieces, especially coal and coke. These were mainly friability tests employing a single blow on closely sized pieces. More recently, small mineral specimens in the sieve range and glass spheres have been investigated.5-7 Kick8 has reported free-fall and double impact tests with large large cast-iron, cement, and clay spheres. The establishment of a minimum breaking height independent of size in the free-fall impact tests, and the direct proportionality between the minimum work required for fracture and the volume of the specimen in double impact tests were used by Kick as an experimental proof of his classical law of "Proportional Resistances." In the present work, spherical shapes were chosen because of their simple body geometry and consequent impact and stress field symmetry. Because the study involves several physical principles in connection with brittle-fracture, it may be of interest in fields where the strength of materials is of importance. APPARATUS The equipment for the free-fall impact testing is illustrated in Figs. 1 and 2. This consisted of a massive (17 x 17 x 3-in.) hard steel plate onto which specimens were dropped and a specimen release mechanism which could be set at any desired height up to 10 ft above the plate so that the impact velocity could be varied up to about 25 ft per sec. Double impact breakage is characterized by two points of loading situated at opposite poles. For this mode of breakage the apparatus was modified (Figs. 3, 4 and 5) so that a falling mass provided an impact of predetermined magnitude on a specimen resting on the plate. A spring-loaded device operated immediately after fracture to arrest the falling mass and to record its residual kinetic energy. Precautions were taken to avoid secondary breakage. Slow compression tests were performed on a conventional hydraulic testing machine, the specimen being held between two hardened parallel bearing blocks. In the case of glass spheres, carbide bits were used. Photoelasticity studies were performed on two-dimensional models held in a loading frame equipped with a force gauge (Fig. 6). The models were viewed in a polariscope and isochromatic fringe patterns were recorded photographically. SPECIMENS Sand-Cement Spheres: A series of sand-cement spheres were prepared by molding in spherical glass flasks.

Jan 1, 1970

By H. C. Goodrich

AT THE Utah Copper mine, steam shovels were first used, in 1906, for the removal of overburden, and in June, 1907 for the mining of ore. Prior to 1907, the ore came from underground development work and from stoping. The use of the steam shovel gradually increased until 1914; since then all material, both overburden and ore, has been loaded by power shovels operating on the various benches of the mine. During FIG. 1.-SCENE OF UTAH COPPER MINE BEFORE OPEN-PIT MINING WAS BEGUN. these 19 years, there has been a great improvement in open-pit mining; largely in the use of equipment having greater capacity and dependableness. The history of the development of mechanical shovels and related equipment, as affecting the Utah Copper Co., would be interesting and would justify considerable space; but of greater interest at this time is the operation of the equipment now in use. The Utah Copper mine is in a great deposit of copper-bearing monzonite, which occurs as a prominent headland of the Oquirrh range of

Jan 9, 1925

By K. A. Natarajan, I. Iwasaki

Platinum electrodes are not inert as often thought to be. The reactivity of platinum electrodes can explain their erratic behavior in many electrochemical measurements of metallurgical interest, e.g, in flotation systems, streaming potential measurements, contact-angle measurements, and in leaching systems. The anomalous behavior of platinum electrodes in redox potential measurements in aqueous systems was studied through Eh and pH measure ments in water-oxygen, iron-water-oxygen, and manganese-water-oxygen systems. Stability relations between Fe++ and Fe (OH), and between Fe (OH), and Fe (OH), were studied to judge the correspondence between experimental and theoretical equilibrium lines. The practicality of redox potential measurements in estimating ferric-ferrous ratios in aqueous systems was investigated along with their suitability as indicators in leaching operations, e.g., the removal of iron by aeration from manganese leach solutions. Platinum electrodes have often been used in the measurement of dissolved oxygen concentrations and of redox potentials (Eh) in a variety of fields, e.g., analytical chemistry,&apos; corrosion," geology and mineralogy,,&apos;&apos; biology,"&apos; sewage treatment,&apos; * hydrometallurgy,"I" and flotation."la The effectiveness of Eh-pH diagrams, first reported by Pourbaix&apos; in 1949, has contributed much towards the theoretical understanding of numerous problems encountered in the metallurgical industry. Not many references are available in the literature, however, wherein attempts have been made to confirm Eh-pH diagrams from experimental measurements. One reason might be that, in spite of the apparent simplicity of the electrochemical technique, the direct measurement of Eh involves complex practical problems.&apos; Factors such as the purity of the solution, the type of electrodes used, the history of the indicator electrode, and the type of atmosphere (namely, oxidizing, reducing, or inert) do have effects on the measured Eh values. The influence of mixed potentials cannot be underestimated. The poisoning of platinum electrodes by organic and inorganic impurities present in the solution may lead to erratic results. Platinum, commonly thought to be an inert electrode material, is not really so, as attested by a number of previous investigators who advised caution concerning the anomalous behavior of platinum electrodes in various electrochemical measurements.&apos;" In the present article, a few pertinent experiments related to Eh-pH measurements in systems of interest in the metallurgical and water pollution fields are described in an attempt to correlate such information with what is already known, especially in the electrochemical literature. Iron-water and manganese-water systems were selected with a view of studying the correspondence between experimentally observed and theoretically established equilibrium lines. The work included an investigation of the behavior of platinum electrodes with respect to pretreatment and adsorption characteristics, the measurement of dissolved oxygen concentrations and their relation to Eh, the determination of the electrode potential of the ferric-ferrous couple at different pH, and the measurement of oxidation potentials in iron-manganese leaching systems. Experimental Procedure A rotating platinum electrode was used in many of the measurements to study the effect of rotation on measured Eh values. The electrode made by the Pine Instrument Co. consisted of a stainless steel rod with a platinum disk soldered to the end. It was covered with a Teflon insulation along the sides, so that only the circular tip of the electrode was exposed to the solution. Prior to its use, the platinum surface was brightened on a metallurgical polishing wheel with alumina as an abrasive, unless specified otherwise. The electrode was rotated with a Sargent cone-drive motor at 350 rpm. The contact of the electrode with the external circuit was made by filling a notch at the top of the stainless steel shaft with mercury and by dipping a copper wire into the mercury pool. The performance of the rotating platinum electrode was compared with the performances of a Beckman platinum button electrode and a platinum wire electrode. All the potentials were measured with respect to a saturated calomel electrode. A saturated KC1-agar bridge was used to minimize the liquid junction potential. A Beckman Zeromatic pH meter together with a Beck-man electrode switch was used to measure both the Eh and pH. A double-walled, all-Pyrex jar with a capacity of about 1 liter and themostated by circulating water of constant temperature was used for a reaction cell. Four equally spaced ports in the cover provided access for a glass electrode, a salt bridge connecting the saturated calomel electrode, a dispersion tube for bubbling gases into the cell solution, inlet and outlet tubes for passing the desired gases over the solution, and a graduated burette for introducing reagents from outside. The rotating platinum electrode was inserted through an opening in the top-center of the cover, and a positive gas pressure was maintained inside the cell to prevent air from entering into the cell compartment. A magnetic stirrer was used to mix the solution inside. For the determination of dissolved oxygen in the test solutions, the polarographic techniquex was used.

Jan 1, 1971

By Charles Clayton

CAST-STEEL runners, while not interesting from a commercial standpoint, furnish valuable material for microscopic study. Foley1 found not only the usual ingot structure, but zones of Widmannstattian structure, which he explains as due to differential crystallization. The writer, in examining nickel-steel runners, found a type of pro-eutectoid ferrite that is unusual and most probably new. The runner in question was 8.75 cm. (3.5 in.) in diameter and analyzed at its center 2.69 per cent, nickel and 0.350 per cent. carbon and at its edge 2.62 per cent. nickel and 0.359 per cent. carbon. The macrostructure, which is the usual type, is shown in Figs. 1 and 2, which are a cross-section and the longitudinal surface, respectively. Slight segregation of ferrite can be seen near the center of the segment and at other points near the edges of polyhedral grains. Stead&apos;s reagent brings out the dendritic structure within the grains as shown in Figs. 3 and 4. This texture is what would be expected of such a steel. Figs. 5 to 10 show the peculiar swirls of pro-eutectoid ferrite, the finding of which prompted this paper. These swirls, or eddies, if such a term can be applied, occur in all parts of- the runner and in all parts of the individual grains. I he tipper left-hand figure shows this ferrite at a grain boundary; the middle left-hand figure shows the inner portion of a grain; and the lower left-hand figure shows these swirls at the edge of a grain which is also the outer edge of the runner. Straight-lined ferrite associated with swirls is found in the areas of Figs. 11 and 12. The texture of the carbon-bearing constituent of the runner is shown to- some extent in Fig. 12, the pearlite being very fine or sorbitic. Higher magnification does not bring out any new features either in the peculiar ferrite or in the pearlite. Figs. 13 and 14, at 240 diameters, show the curved and straight-lined ferrite.

Jan 3, 1920

By C. Feng, W. E. Krul

A study was made of the development of texture and the anisotropy in plastic flow of Ti-8Al-1Mo-1V alloy. Based on Pole figure determinations, the shifting of texture induced by rolling at approximately 400°C was found to be due primarily to slip rotation for the major Portion of the material. Grain boundary shear is believed to be an important factor. The anisotropy of the textured alloy was examined in terms of the variations of yield stress under tension and the ratio of bi -axial strain increments µp, in the temperature range 25" to 290°C. The results were related to Hill&apos;s theory on plastic anisotropy. The Schmid factors of (1100)[1120], (1101)[1120/, and (1101)[1120] slip systems were analyzed and found to be compatible with the observed anisotropy. Cross-slip between these planes was proposed as a possible deformation mode. In a number of published articles, considerable interest has been directed to the possible achievement of texture hardening in hcp metals. Following Backofen, Hosford, and Burke,&apos; this phenomenon was related to the yield criteria of the material and was expressed in terms of the biaxial strain ratio, r = d?w/d?l. The higher the value of r, the greater is the expected potential for texture hardening under certain loading conditions. For a given material, r varies with direction. Such variation can be traced to the anisotropy in plastic flow and can be explained within the framework of the various modes of deformation. Hatch2 found that a high r value coincides with a texture whereby the (0001) pole is closely aligned with the surface normal for sheet materials, Based on the analysis of the slip on the {1010}, {1011}, and (0001) planes, Lee and Backofen3 and Avery, Hosford, and Backofen4 concluded that the resistance to thinning is reduced by the operation of the (0001) <1120> slip system; with this reasoning they were able to explain the low r values (i.e., r « 1) observed in magnesium alloy sheets in the rolling direction and in commercially pure titanium in the transverse direction. The general equation, dealing with plastic flow in a polycrystalline aggregate has been used to correlate the plastic anisotropy and texture. In this expression, T and s are shear and normal stresses, and dri and d? are shear and normal strain increments, respectively. Assuming that five slip systems are operative within each grain and applying the principle of maximum work,5,6 one can determine the m value among the available systems. On this basis, Hosford7 and Chin, Nesbitt, and Williams&apos; were able to correlate m with yield stress under plane-strain compression, and Svensson9 was able to predict the variation of yield stress in textured aluminum. These workers made their analyses from materials in which slip operation is known to be associated with plastic flow. Questions remain regarding the derivation of Hill&apos;s theory on plastic anisotropy,10,11 since it was formulated on von Mises&apos; yield criterion.&apos;&apos; Its ability to deal with other forms of deformation has been in doubt.13 Others have discussed the validity of Hill&apos;s quadratic equation relating strain and yield stress.14&apos;15 For hcp titanium, deformation by various modes of slip and twinning operations has been reported.16-20 If all possible modes of deformation operate and contribute substantially to the plastic flow, it is difficult to imagine how the quadratic expression can suitably describe the anisotropic plastic flow of titanium alloys. Backofen and Hosford15 considered that Hill&apos;s is a macroscopic theory and implied that the major mode of deformation by slip mechanism will adequately describe anisotropy of the material. In the present investigation, slip operation will be shown to play the major role in the development of sheet texture induced by rolling of a commercial titanium alloy. Although twinning and other modes of deformation may also operate, their operation is believed to be secondary. The anisotropic properties of the sheet, which can be expressed in terms of directional variation of r, µp = -d?w/d?l and the yield stress will be shown to be governed primarily by slip operation. MATERIALS AND EXPERIMENTAL TECHNIQUES The titanium alloy chosen for the present investigation had a nominal composition of 8 wt pct Al, 1 wt pct Mo, 1 wt pct V, and 0.1 wt pct interstitial impurities. Sheets varying between 0.1 and 0.15 in. thickness were used. The alloy was received in a condition which was prepared by rolling at 900°C and annealing at 700°C. Subsequently, the sheets were subjected to further reduction in thickness by rolling at 400°C. A total reduction in thickness of 65 to 70 pct was obtained by a series of quick passes in a rolling mill with intermediate reheating. Further reduction in thickness was not possible due to cracking developed at the edges of the sheets. X-ray measurements were conducted in a Siemens and a Norelco unit to determine the texture of the sheets. Reflection techniques were used exclusively with CuK, radiation and a nickel filter. The loss of X-ray intensity due to geometric defocusing was calibrated with a technique described previously." The (0001), (1010), and (1071) pole figures were plotted from 0 to 80 deg, and to present the texture elements quantitatively, inverse pole figures were constructed following the technique described by Jetter, McHargue, and Williams.22 Tensile experiments were carried out at 25", 175",

Jan 1, 1970

By S. V. Krusiewski, J. W. Gabelman

Regional metallogenic zones and areas of equal paragenetic range have been interpreted from a compiled metallogenic map. of Mexico. Mineralization gradients of the pattern subsequently identified extend inland from coastal zones of high-temperature mineralization, and join in a central longitudinal zone of relatively low-temperature mineralization, apparently leaving no zonal room for lowest temperature deposits. The striking regional zoning pattern can be correlated with regional deformation gradients of similar position and orientation. The gradients represent at least three major orogenic cycles in two structural belts. Paleozoic structural belts existed along each coast with deformation gradients diminishing inland toward a narrow, central peninsular craton. The Mesozoic-Tertiary Mexican (Cordilleran) belt covered the entire country with a gradient oriented toward the Gulf of Mexico. Most ore deposits in this belt are of Tertiary age, although Tertiary mineralization gradients seem to have "inherited" the pattern left by Paleozoic tectonic gradients. Mineralization gradients can be used to identify the regions most favorable for the occurrence of selected metals. A metallogenic province is characterized by particular proportions of various metals, and the relative proportions can vary from province to province; but within any province the same intensity of mineralization would produce similar deposits in different places. Declining intensity of minetalization produces different kinds and sizes of deposits in zones that are concentrically arranged around sites of strongest rock alteration. On a regional basis, districts of similar average intensity of mineralization occur in zones that generally parallel some tectonic grain with the result that tectonic deformation has been designated a principal cause of mineralization. Variations in the type and intensity of deformation would determine the type as well as size of metal deposits. Mexico is especially favorable for such a study be- cause of its great abundance and variety of epi-genetic mineral deposits in various lithologic, structural and tectonic environments. The concept is also useful in recognizing portions of Mexico favorable for the occurrence of specific metals. METALLOTECTONIC ZONING IN MEXICO Theory: In studies of individual districts and groups of districts throughout North and South America, areal zoning of metal deposits generally seemed to respond to the paragenetic sequence of iron, gold, copper, zinc, lead, silver, antimony and arsenic, gold and fluorite. However, the definition of district zones is greatly obscured by contemporaneous or rhythmic deposition of metals, especially in the middle of the paragenetic range, and by the common superimposi-tions of different generations of metals. Zones could usually be distinguished only for groups of metals, such as early precious metals, base-metal sulfides, sulfosalts and late precious metals. The best defined zoning in a district is normally the spatial separation of the greatest volumes of altered and metallized rocks.&apos; Exceptions are districts representing the high- and low-temperature extremes of the mineralization range where the former creates a matrix for the latter. In most districts the total quantity of alteration products is greatly in excess of, and appears to be roughly proportional to, the total quantity of metallization products. Subsequent to the bicomponent nature of each district, the most important mineralogical feature is the great excess of one to several metals or minerals which results in a district identifiable as one of predominantly gold, copper, lead-zinc, fluorite, etc., although a great variety of other elements may be present. The para-genetic range for the abundant elements in any district is only a portion of the entire possible range for all the elements representing the complete process throughout the region. Early during investigations of this type, it became apparent that the consistent bicomponent character of districts allows two methods for studying epi-genetic mineralization patterns. One is to identify and plot altered rock "pipes,"* which are easily recognizable in the landscape by their anomalous

Jan 1, 1969

By Harry M. Mikami, A. Gene Sidler

Chemistry of the evolution of materials in contact with copper converter tuyeres is delineated by means of analyses of periodic punch rod samples taken during a converter cycle. Lining samples from known peripheral and end locations from three converters were investigated chemically and petrographically. One set of eight specimens representative of all lining parts was removed for study before completion of the campaign. Purely surface removal by slag action is minor. Slag filling of interconnecting cracks extending to the hot face results in a "stoping&apos;&apos; action which shapes the hot face contour and is a significant factor. Major wear mechanism is believed to be copper metal slabbbing caused by metal first penetrating joins and invading fractures or impregnating brick structure laterally from the joints. Importance of lining design and joint fit are emphasized. New laboratory tests are indicated. In the copper converter, molten matte, which is essentially a solution of iron and copper sulfides, is blown with air to produce blister copper. During the first stage of the process the FeS component is oxidized to SOz and FeO, the latter combining with a siliceous flux to form a predominantly ferrous silicate slag. Successive increments of matte and flux are charged, blown, and skimmed of slag until sufficient CuzS ("white metal") has accumulated. This white metal is then blown to copper metal in the final or blister-forming stage by the oxidation of sulfur to SOz and the reduction of combined copper to metal. The reactions of both stages are exothermic so provide the required heat. Temperature is controlled by cold scrap copper, flue dusts, smelter reverts, and so forth. Considerable vari- ation in practices occur depending on the type of converter, grades of the matte and flu, and other factors. Lathe and Hodnett&apos;s&apos; survey of world converter practices gives much information on these variations and their effects on the refractories. Principles of converting chemistry are presented by Newton and wilson,&apos; Ruddle,&apos; and schuhmann. Most copper converting occurs within the temperature range 2100" to 2370°F although individual smelters report1 ranges from as low as 1700" to 2240°F to a high of 2200" to 2400°F. Temperature intervals reported from beginning to end of blow varied from 45" to 540°F. Average temperature range was 2030" to 2260°F and the average interval 250°F During the matte-blowing stage varying amounts of magnetite (FeO.Fe,O,) are formed in the slag as suspended crystals and also the liquid portion of the slag will contain, in addition to ferrous silicate, some Fe20s which adds to the potential magnetite formation if the temperature falls. This is a component of the so-called "dissolved magnetite" often referred to in the literature. Although the slag may contain minor amounts of CaO, A1209, MgO, and alkalies, the principal components are Fe0-Fez03-SiO,. The phase equilibria relationships of this system have been elucidated by Muan~ and Schuhmann, et a1.&apos; These data and estimates of converting atmospheres by schuhmann4 are useful tools in studying slag behavior. It would appear that in many cases reported magnetite contents of slags are apparently higher than actually is present at operating temperature. This is probably because much of it is formed during slag solidification. The quaternary systems which have Mg-0,1,0,&apos; and addition to iron oxides and silica are also of interest in considering the reactions of the slags with basic refractories. The formation of magnetite has an important interrelationship throughout the pyrometallurgy of copper (Mossman,&apos; Gronningsater and Drummond," Ruddle,&apos; Elwood and Henderson") but its presence in the converter particularly relates to operating efficiency and lining life in certain instances. Archi-

Jan 1, 1963

By Charles S. Barrett

THIS paper is a progress report covering metallographic applications of the electron microscope that have been made during the past year at Carnegie Institute of Technology. An account is presented of the techniques that have been most satisfactory, the difficulties encountered, the resolution obtained, and the peculiarities that have been noted in the microstructures. About 12m exposures have been made during the year on the instrument, which is an RCA type B2 transmission microscope,1 and a number of these have been selected to illustrate the results obtained. Prints are also included showing the common types of falsities-to borrow a term from the biological field, the "artifacts." In brief, the paper is a record of our attempt to determine the value of the electron microscope in the study of the structure of metals and alloys. n addition to comments on techniques and the quality of photomicrographs obtainable with them, the paper discusses the nature of the etch attack on a few metals, and the possible relation between the fine structure revealed by etching and the mosaic block structure of the grains. Since numerous papers and reviews are available on the subject of imperfection in crystals, the comments here may be very brief; in fact, are restricted almost entirely to points having to do with recent theories relating the strength of metals to imperfections and to spacings of slip lines. SPECIMEN PREPARATION AND PHOTOGRAPHS Mechanical polishing by hand was used throughout this work. Precautions that must be taken in microscopy at high magnification, which have been well explained by Vilella in his book on Metallographic Technique for Steel, are likewise important with the electron microscope. This applies particularly to the need for repeated polishing and etching (each successive polish becoming less severe and each etch lighter), since the final etch should in general be no heavier than is used for oil-immersion optical microscopy and in many instances should be much lighter (compare Figs. 6a and 7a, 6d and 7b). An extremely light etch, of course, is incapable of cutting through a flowed layer of appreciable thickness. Unquestionably it would be very advantageous in each instance to compare the structures obtained by electrolytic polishing with those obtained by mechanical polishing, but difficulties with the electrolytic method have prevented this in the following collection of prints. The choice of etchant is important, of course; for example, picral proved superior to nital for tempered martensite. With the exception of Figs. Ib and IC, the replicas used were of silica, deposited up0n polystyrene and floated from the polystyrene in ethyl bromide according to polystyrene in ethyl bromide according to the method of Heidenreich and Peck.2 The samples were mounted in Bakelite, polished and etched, then the polished Bakelite

Jan 1, 1943