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By Bruce Chalmers, D. C. Larson

Aluminum crystals with longitudinal-axis orientations of (111) . (110), and (100) were deforined in tension and annealed. The conditions of deformation were controlled so that the re crystallization nuclei originated in either the heavily deformed regions at saw cuts {artificial nucleation) or in the lightly deformed matrix (spontaneous nucleation). The artificial-nucleatioln experiments showed that in lightly deformed (110) and (100) crystals low-angle twist boundaries are most mobile, while in (111> crystals and heavily deformed (110) and (100) crystals high-angle tilt boundaries with near (111) rotations are favored. The spontaneous-nucleation experiments showed the existence of preferred orientations in the (111) crystals. The nonrandomness of the grain orientations is quantitatively determined through a comparison with the results which would he obtained from a randowl set of grain ovientations. PREVIOUS recrystallization studies have been performed on single crystals deformed in tension.1 7 The crystals used in these studies usually had random tensile-axis orientations and the extent of deformation was not a primary consideration. The present study concerns the recrystallization of single crystals with tensile-axis orientations of (Ill), (110), and (100). The emphasis of this work is on the influence of the tensile-axis orientation and the degree of deformation on both the nucleation and growth processes. The multiple-slip orientations were chosen because secondary slip or slip intersection promotes nucleation.1,5,8 These crystals recrystallize at lower strains than the crystals which are oriented for single slip. Also, the greatest variation in deformation behavior is exhibited by the multiple-slip orientations. The stress-strain curves for crystals with tensile-axis orientations of (111) are higher than the stress-strain curves for poly-crystals, and the stress-strain curves for crystals with tensile-axis orientations of (100) are lower (at large strains) than the stress-strain curves for the crystals which deform initially in single slip.g The recrystallization nuclei originated in either 1) the homogeneously* deformed matrix of the crys- tals or 2) the heavily and inhomogeneously deformed regions at saw cuts. The nuclei will be referred to hereafter as spontaneous and artificial nuclei, respectively. The two terms do not imply a difference in the nature of the nuclei; they imply simply a difference in the mode of introduction of the nuclei. During spontaneous nucleation very few (always less than ten) grains nucleate, while during artificial nucleation large numbers of grains nucleate. Only a fraction of the artificially nucleated grains penetrate very far into the deformed matrix during annealing. The grains that penetrate the farthest into the deformed matrix will be referred to as the dominant grains. EXPERIMENTAL PROCEDURE The thirty-five crystals used in this investigation were grown from the melt in milled graphite boats at a rate of 1.6 cm per hr. The crystals had dimensions of approximately 6 by 12 by 80 or 6 by 6 by 80 mm and the aluminum was of 99.992 pet purity. The as-grown crystals were annealed at 610°C for 24 hr and furnace-cooled. They were then heavily etched and electropolished in a solution of five parts methanol to one part perchloric acid. The crystal orientations were obtained by back-reflection Laue photographs and were accurate to ±2 deg. The tensile-axis orientations were (loo), (110), and (111). Two of the side faces of the (111) crystals were (110) lanes. The (110) crystals had both {100) and {110) side faces and the (100) crystals had (100) side faces. The crystals were deformed at a strain rate of 0.003 per min. Shear stress and shear strain were obtained by multiplying and dividing the tensile stress and strain, respectively, by the Schmid factor, m. For the (111) crystals m = 0.272 and for the (110) and the (100) crystals m = 0.408. The Schmid factor is effectively constant during deformation for all orientations. The deformed crystals were sawed into 1-in.-long specimens while the crystals were totally enclosed in a graphite boat. The sawing was performed very carefully in order to limit the plastic deformation to the sawed regions. The specimens were electropolished in the solution mentioned above to remove the sawed-end deformation as well as controlled amounts of surface material. A special stainless-steel grip was used to hold the specimens during the electropolishing treatment. The gripping faces were flat, with no teeth, to prevent the introduction of extraneous de-

Jan 1, 1964

By C. K. Ferguson, J. A. Klotz

This paper describes experimental investigations conducted at the California Research Corporation's model oil well. The first part describes filter loss from several drilling muds through bore hole walls during mud circulation and drill string rotation. The effect of mud properties and drill string rotation with mud circulation is described. Filtration from a bore hole full of drilling mud, not circulating, but under pressure for extended time periods, is also discussed. The second part describes filter loss to permeable formations from beneath a drilling bit where filter cuke has no opportunity to develop appreciable thickness. If potential flow theory is applied to predict filtrate invasion from this hole bottom, targe invasions arc calculated. But model well experimentation shows that filtrate invasion from the hole bottom is controlled by mud particles that penetrate the formation ahead of the bit. This experimentation provides data to estimate the effect of mud particle penetration on fluid loss to formation. The third part presents an estimate of mud filtration during drilling of a well. INTRODUCTION As oil wells are drilled by the rotary method, drilling mud circulates up the annulus between drill pine and well wall. Drillers adjust mud density so that the pressure at the bottom of the mud column is several hundred psi greater than the pressure of reservoir fluid. As a result of this pressure difference, the liquid part of the mud filters into the rock around the bore and mud solids deposit as a filter cake on the well wall. For many reasons the petrogleum industry, within the past 20 years, has spent much money and energy to determine the volume of mud filtrate that enters rock around the well bore and dedicated much research effort to reduce this volume. Among the reasons for attempts to determine the volume of mud filtrate and to reduce this volume are the following: 1. If filtrate damages the permeability of oil sand, the resultant damage to oil well productivity will depend on the distance that the filtrate invades the oil sand; reduction of filtrate volume may, therefore, increase well productivity. 2. Filtrate that penetrates shale sections may cause the shale to swell and to slough into the well bore. Uncontrolled sloughing may stick drill pipe. Reduction in filtrate volume may reduce drilling trouble. 3. Electric log resistivity curves are changed by invasion of a mud filtrate; the change depends on the depth to which filtrate invades. Knowledge of this depth is necessary before resistivity logs can be interpreted accurately. For these reasons, specifications the place an upper limit to drilling mud filter loss are now written into almost all drilling programs. These specifications are based on APT Recommended practice 29, Standard Field Procedure for Testing Drilling Fluids,' which describes a static filtration test operated at 100 psi filtration pressure and at ambient temperature. Although this test is adequate for mud control, it cannot be used to compare filtration properties of different muds. Schremp and Johnson' showed, for example, that mud with a low API filter loss does not necessarily have low filter loss at bottom hole temperature and pressure. Also, no information has been available about the effect of bottom hole mechanics (mild circulation, drill string rotation, and bit action) on mud filtration. This paper discusses filtration data measured in the California Research Corporation's model oil well, which models closely oil well bottom hole geometry and hydrodynamic conditions. The filtration processes that

Jan 1, 1955

By H. T. Clark, S. Feigenbaum

The importance of measuring the temperature of molten steel in the open-hearth furnace has been recognized for many years. Poor temperature control may be costly to steelmaking operations and lead to a lowered quality of the steel. Low or excessive temperatures may shorten the life of the furnace, ladles and molds. Rates of reactions in the furnace and efficiencies of deoxidizers are known to change materially with a change in the temperature of the metal and slag. Ladle skulls and mold and stool stickers cause steel to be scrapped instead of being converted into useful products. Finally, the structure, segregation and surface condition of ingots are affected by the teeming temperature. Mill investigations of the effect of bath temperature upon steelmaking operations have been largely qualitative in character, based upon observations by practical melting men. The physical chemist has used the empirical information available and has reached reasonable and useful conclusions with respect to the various melting processes. The introduction of a reliable direct-reading pyrometer will permit accurate quantitative evaluation of the effects of temperature and should furnish a more rational basis for study of the thermochemistry of steelmaking. The problem is not merely one of making a small numbcr of temperature measurements in the open-hearth furnace. This has been done by several methods to a * Assistant Manager, Research and Development, Jones and Laughlin Steel Corporation, Pittsburgh, Pennsylvania. Issued as T.P. 2031 in MEtals Technology, June 1946; also in Open Hearth Proc., 1946. † Open-hearth Metallurgist, Jones and 1aughlin Steel Corporation, Aliquippa. Pennsylvania. degree of precision that was apparently satisfactory. Considerable effort by a number of investigators has been directed rather to the development of an open-hearth bath pyrometer that would be both accurate and practical for routine measurements. To be practical, the pyrometer should be inexpensive to operate; that is, the installation, operating and maintenance costs should be exceeded by the tangible benefits to the open-hearth operator. Temperatures from 2800' to 3100°F. are. encountered in the open-hearth furnace. The surface of the molten metal is covered by several inches of slag, which prevents direct observation of the metal surface for optical or radiation measurements. Both slag and metal are highly reactive at these temperatures and will attack to a greater or lesser extent any material immersed in them. Adequate protectioil of thermocouples, which of necessity must be brought to the temperature of the bath, has generally resulted in a large, heavy assembly made up of brittle materials, unsuited for handling on the open-hearth floor. The life of the equipment was short and maintenance was an important consideration. Earlier Work Any of a number of Physical Properties of liquid steel could conceivably be used a a basis for temperature measurement. Efforts to the present time, however, have been confined largely to measuring either the thermal electromotive force generated between two dissimilar materials immersed in the steel or the intensity of radiation from the surface of the steel. These

Jan 1, 1947

By J. O. Lewis

The operation of gas-condensate fields is comparatively new and involves physical principles with which the industry was not prcviously familiar. It has been necessary to devise methods for testing gas-condensate wells and to correlate laboratory and field data. In this paper new methods are advanced for interpreting well G.P.M.† tests whereby dilution by dry gas can be estimated and information supplied on revaporization of condensates by dry gas. Inaccuracies in well test data are discussed. Changes in flow rates can cause changes in the G.P.M. of the effluent and it may take some time for a well to become stabilized after an important change in flow rate. Retrograde tests as usually conducted cannot be directly compared with field G.P.M. data, because the retrograde tests usually include solution gas in the condensates, which are reported On the cumulative basis whereas field data (G.P.M.) usually report pentaneS PlUS on a rate or instantaneous basis. Introduction Though long known to physicists, the phenomena Of retrograde condensation became known to the oil and gas industry Only in recent years, when deeper drilling disclosed that the behavior of vapors under changing pressures was different in high-pressure reservoirs than under the low-pressure operations with which the industry was familiar. These deep, high-pressure reservoirs in which condensation and vaporization behaved inversely to the accustomed manner became known as "gas-distillate," or preferably "gas-condensate" fields. Partly to prevent precipitation and retention of liquids in the reservoir, but still more to prevent the waste of residue gas, the operation known as "recycling," or preferably "cycling," was instituted, in which the residue gas is reinjected into the reservoir, thus maintaining pressure and driving the wet gas to the producing wells. For lack of field experience to serve as a guide, the industry had to assume that theory and laboratory experiments could accurately forecast retrograde behaviors in operating these gas-condensate fields, but it is obvious that these assumptions should be checked at the first opportunities against actual field experience. To make such checks, it is necessary to accumulate a large quantity of reliable field data, but experience has shown that it is difficult to obtain reliable field data and that the laboratory data as usually presented are not in directly comparable form. The problems of correlation involve the complex phase behavior on the one hand, and a knowledge of field data and a visualization of underground conditions on the other hand. This paper is an approach from field experience, The purposes of this article are to discuss the sources of uncertainty in the data and to present methods of analyzing, interpreting and correlating laboratory and field data. Data mostly from lower Gulf Coast fields are presented, from which some conclusions can be derived, but better data from more sources than those available to the writer will be required before satisfactory answers to many questions can be obtained. This paper is presented to stimulate the analysis and publication of data from other fields, the reexamination of field and laboratory methods, and the taking of more complete and reliable field tests. For these purposes, the writer presents some speculations that otherwise would not be appropriate.

Jan 1, 1947

By D. L. Harris

Chemical upgrading testwork on Stillwater chomite concentrate shows that reduction roasting and leaching (sulfuric acid and/or ferric sulfate) can provide upgraded feed to ferrochromium furnaces for making upgraded ferrochromium. Two-stage reduction smelting in electric arc furnaces can make upgraded ferrochromium also. Sulfating roasts and leaching (acid and/or water) results using gaseous SO2—SO3 or solid ammonium sulfate were not satisfactory for upgrading chromite. Chemical upgrading of domestic Stillwater (Montana) chromite has been considered at various times1'2' to provide a material with higher chromium to iron ratio, more like foreign high grade ore, for the production of standard grade ferrochromium. Physical bene-ficiation of Stillwater chromite ore can provide a ratio, Cr/Fe, no higher than the ratio in the chromite mineral, which is approximately 1.7. For comparison the analyses of a foreign metallurgical grade chromite ore, a high grade electrostatic process Stillwater concentrate and a stockpile concentrate from the Stillwater ore are noted in Table I. Single stage smelting of the high grade foreign ore with a ratio, Cr/Fe, of 3.37 can provide a ferrochromium of over 65 pct chromium content. Similar smelting of the Stillwater concentrate with a ratio of 1.7 can provide a ferrochromium of 50 to 55 pct chromium content.' It has been demonstrated on a pilot plant scale that chemically upgraded Stillwater chromite having a ratio, Cr/Fe, of 3.0 also can be smelted to provide a ferrochromium containing over 65 pct chromium.5 Two major considerations for an upgrading process are the ratio, Cr/Fe, in the product and the chromium recovery. A minimum ratio, Cr/Fe, of 3.0 is required in the product but for economic reasons a higher ratio is desirable for blending purposes as long as the recovery is satisfactory. Data from different kinds of chemical upgrading testwork are presented in this report. Some of the testwork was conducted to make a product which was not intended to be feed for ferrochrome smelting, but the data are considered pertinent to chemical upgrading. Results reported by others are noted also for comparison. WORK REPORTED BY OTHERS The U. S. Bureau of Mines has contributed much to the literature on chemical upgrading of chromite and a summary is given in Table 11. Reduction roasting and acid leaching were reported by Boericke and Bangert,1 by Lloyd and Gorst, et a1,2 and by Boericke3 to demonstrate very good success on a laboratory scale and only fair success in pilot plant tests for Stillwater (Benbow) concentrates. This work included basic studies on thermodynamic properties to explain the reduction and leaching results. Canadian workers, Downes and Morgan,9 have reported experimental success in upgrading a low grade Bird River chromite, similar to Stillwater material by the same process. Russian workers1' have noted results on reduction tests of high grade chromite which may apply to low grade ores and which help in understanding the reduction process. The use of flux additives in the reduction process was an innovation of their work. The Canadian workers9 also reported other kinds of experiments, including autoclave leaching of the chromite in a limited amount of sulfuric acid. An insoluble basic chromium sulfate was formed and separated from soluble iron, magnesium, and aluminum sulfates to provide an upgraded material. U.S. Bureau of Mines workers, Lloyd, Rosenbzum, Home and Davis,' reported on autoclave leaching of Benbow concentrates as a means of obtaining chromium alum for electrolysis. This last work required selective crystallization of alum to separate iron from chromium. Chloridizing roasting of Benbow and Mouat concentrates has been reported by Hunter and Banning6 and others8 to show that the iron chloride could be volatilized from the chromite to provide upgraded residues.

Jan 1, 1964

By Jeffrey L. Thompson, Kenneth A. Gutschick, Robert C. Freas, Robert S. Boynton

Lime, the "versatile chemical," is, generally speaking, a calcined or burned form of limestone commonly known as quicklime, calcium oxide or calcia, or, when water is added, calcium hydroxide or slaked lime. Almost 40 different lime products are available, a fact which has contributed to the rather loose use of the term lime as well as to much confusion and misunderstanding. The term is frequently, albeit erroneously, used to denote almost any kind of calcareous material or finely ground form of limestone or dolomite. Lime is usually made from high-calcium or high-magnesium limestone, generally having a minimum of 97% combined carbonate content. Normally, high-calcium limes contain less than 5% MgO. When the lime is produced from a high-magnesium limestone, the product is referred to as dolomitic lime. Calcination, or the production of lime, has its origins in the earliest days of alchemy, with the general reaction class having been identified in an Arabic text printed in 1000 A.D. It was much later, however, in the mid-1700s to the mid-1800s before this basic reaction became understood from a scientific perspective. The production of lime has been so basic and simple that its underlying scientific principles have over the years received only intermittent investigation. Rather, much of the thought and inquiry has been directed toward the development of kilns. Thus, it has only been in the last 15 to 20 years that lime has received any concentrated scientific investigation relative to the thermodynamics and kinetics of the calcination and hydration reactions. Calcination refers to a broad class of reactions, of which the lime/limestone reaction is just one, wherein a substance is heated to less than its melting point, resulting in a weight gain or weight loss. In the calcination of limestone to produce lime, the basic chemical reaction is as follows: [CaCO3 (limestone) + heat (1000° to 1300°C)= 100 CaO (quicklime) + CO2 T 5644 or CaCO3 • MgCO3 (limestone) 10084 + heat (900°C to 1200°C) CaO • MgO (quicklime) + 2CO2 T 56 4088] While there is nearly universal agreement about the equilibrium conditions related to the limestone/lime reaction above, there have been numerous and varied calcination models developed for the reaction. Recent investigations have resulted in the development of the model shown in Fig. 1. From this model it can be seen that calcination is a function of both temperature and CO2 pressure. It does not, however, provide any indication of the rate at which the reaction takes place. Calcination is strongly time variant with different limestones. In a very broad sense this relates to the fact that the calcination reaction starts on the exterior surface of the limestone and then proceeds toward the center. As the calcination reaction takes place, the CO2 released at the reaction interface must make its way through the lime to the exterior surface. Therefore, because calcination is limited by gas diffusion to the surface of the partially calcined limestone, natural impurities in the stone, differences in crystallinity, grain boundary chemistry, density variations, and imperfections in the atomic lattice all play a significant role in

Jan 1, 1983

By H. T. Clark, S. Feigenbaum

The importance of measuring the temperature of molten steel in the open-hearth furnace has been recognized for many years. Poor temperature control may be costly to steelmaking operations and lead to a lowered quality of the steel. Low or excessive temperatures may shorten the life of the furnace, ladles and molds. Rates of reactions in the furnace and efficiencies of deoxidizers are known to change materially with a change in the temperature of the metal and slag. Ladle skulls and mold and stool stickers cause steel to be scrapped instead of being converted into useful products. Finally, the structure, segregation and surface condition of ingots are affected by the teeming temperature. Mill investigations of the effect of bath temperature upon steelmaking operations have been largely qualitative in character, based upon observations by practical melting men. The physical chemist has used the empirical information available and has reached reasonable and useful conclusions with respect to the various melting processes. The introduction of a reliable direct-reading pyrometer will permit accurate quantitative evaluation of the effects of temperature and should furnish a more rational basis for study of the thermochemistry of steelmaking. The problem is not merely one of making a small numbcr of temperature measurements in the open-hearth furnace. This has been done by several methods to a * Assistant Manager, Research and Development, Jones and Laughlin Steel Corporation, Pittsburgh, Pennsylvania. Issued as T.P. 2031 in MEtals Technology, June 1946; also in Open Hearth Proc., 1946. † Open-hearth Metallurgist, Jones and 1aughlin Steel Corporation, Aliquippa. Pennsylvania. degree of precision that was apparently satisfactory. Considerable effort by a number of investigators has been directed rather to the development of an open-hearth bath pyrometer that would be both accurate and practical for routine measurements. To be practical, the pyrometer should be inexpensive to operate; that is, the installation, operating and maintenance costs should be exceeded by the tangible benefits to the open-hearth operator. Temperatures from 2800' to 3100°F. are. encountered in the open-hearth furnace. The surface of the molten metal is covered by several inches of slag, which prevents direct observation of the metal surface for optical or radiation measurements. Both slag and metal are highly reactive at these temperatures and will attack to a greater or lesser extent any material immersed in them. Adequate protectioil of thermocouples, which of necessity must be brought to the temperature of the bath, has generally resulted in a large, heavy assembly made up of brittle materials, unsuited for handling on the open-hearth floor. The life of the equipment was short and maintenance was an important consideration. Earlier Work Any of a number of Physical Properties of liquid steel could conceivably be used a a basis for temperature measurement. Efforts to the present time, however, have been confined largely to measuring either the thermal electromotive force generated between two dissimilar materials immersed in the steel or the intensity of radiation from the surface of the steel. These

Jan 1, 1947

By T. B. Counselman

PRobably the earliest concentration of iron ore in this country was carried on in the northeastern magnetite areas. Magnetic concentration was relatively simple and gave a concentrate that, after agglomeration, and in spite of beillg high in phosphorus hecause of the dry concentrating methods then in use, was satisfactory blast-furnace feed. Production from the northeastern magnetitc area languished after the discovery and development of the Lake Superior ores, where there was seemingly an unlimited tonnage of high-grade ore, first the Michigan ores, and subsequently the still larger deposits of Minnesota. For years only the higher grade, direct shipping ores of the Lake superior district were mined. Those of Michigan, and of the Vermilion Range in Minnesota, were hard ores and came principally from underground mines. The softer ores of the Mesabi came partly from underground mincs, but mostly from the enormous deposits that could be worked by open-pit methods. The costs of ore from these open-pit deposits, even with the high initial cost of stripping, were so low that the underground mines of the Mesabi could hardly compete. The so-called Old Range ores, of Michigan and of the Vermilion Range of Minnesota, were hard and lumpy, and opened UP the burden in the blast furnace, therefore making possible harder driving with greater output. Also, some of these Ores were of such grade and physical characteristics that they were suitable for charge ore in the open hearth. These ores, therefore, commanded a price premium. and could compete with the softer, finer, but cheaper, Mesabi ores. The big tonnage reserves, however, are on the Mesabi. and it is these big open-pit deposits that contitue- our stock pile of iron ore, from which we are drawing so heavily during this war period. On the western end of the Mesabi the ore was found to be high in silica, and not suitable as furnace feed. As early as 1902, attempts were made to concentrate this so-called wash ore and by 1910 the first washing plant was put into operation. The Process was very simple, consisting essentially of a sizing and washing operation, with scalping screens, logwashers and tables, which later were replaced by classificrs. Ore particles finer than I00 mesh were deliberately wasted, because these fines were undesirable in the furnace. Fortunately, these tailings were impounded, and already are being reworked. Before long some of the low-grade ores began to require more elaborate treatment than the simple washing operation and, tables having been discarded because of their low capacity, in favor of classifiers, jigs were next introduced. These were able to discard coarser pieces of tailing than classifiers. Jigs are in active use today, various improvements having been made in their design and application. Various other machines and methods of concentration have been tried from time to time, and have in turn been discarded for more improved processes., The latest and most important process that has been 38

Jan 1, 1944

By John D. Verhoeven

A technique has been developed for carrying out normal freezing experiments with a current density of 2000 amp per sq cut passing through the solid-liquid interface. The equation relating the effective distribution coefficient to the equilibrium distribution coefficient in electric field-aided solidification, originally developed by Huckc et al.,1 has been modified for the case of concentrated solutions. Preliminary experiments on the Sn-Bi system give qualitative agreement with the equation. The data are analyzed by a slightly novel use of the normal freeze equation which allows one to determine the effective distribution coefficient more easily. Very extensive mixing in the liquid was found at these high current densities and it is postulated that the mixing results from a vertical component of the magnetic Lorentz force generated by the electric current. In the search for techniques of obtaining ultrahigh-purity metals the inefficient but very effective technique of electrotransport has received little attention. Electrotransport is most effective in the liquid state and a natural application, therefore, is to apply an electric field across the liquid zone of a zone-melting experiment. The present investigation was undertaken to study the effect of an electric field upon solidification of metals, so that the usefulness of electrotransport in such solidification experiments as zone melting could be determined. In zone-melting and normal-freezing experiments it is difficult to achieve complete mixing in the liquid in the immediate vicinity of the solidifying interface. Consequently a solute build-up will occur at the interface in the portion of the liquid where complete mixing does not occur (an equilibrium distribution coefficient, ko, less than one, and unidirectional atom motion will be implied throughout). This local solute build-up produces a corresponding rise in the solute concentration in the solid so that the ratio of the solute concentration between the solid and the bulk liquid is larger than the equilibrium distribution coefficient. This ratio is defined as the effective distribution coefficient, k,. The differential equation describing the solidification process may be derived by applying the continuity equation to an expression for the net solute flux at the interface. The solution to this differential equation then allows one to determine the solute distribution in the liquid and the relationship between k0 and ke. One of the most useful solutions to this equation was first derived by Burton, Prim, and Slichter,' in which they assumed that a) the equilibrium distribution of solute was maintained on the plane of the interface, 11) the solute build-up ahead of the interface in the liquid disappeared at a distance 6 from the interface, and c) the solute distribution in the liquid was invariant with time. The following well-known relation between ko and ke was then obtained, where R is the rate of solidification and D the diffusion coefficient of the solute in the liquid. This equation appears to correlate the data from a number of different types of solidification experiments very well. Application of an electric field across the solid-liquid interface can produce an additional flow of solute atoms as a result of the electrotransport. When the polarity of the field is such as to direct the electrotransport flux away from the interface the solute build-up may be diminished, even to the point of producing a solute depletion and a consequent ke smaller than ko. The quantitative description of this process and the resulting form of Eq. [I] was first given by Hucke et al.1* and then inde- where E is the electric-field intensity and U is the differential mobility, i.e., the velocity of the solute atoms with respect to the solvent atoms per unit electric field. Both authors follow the method of Burton, Prim, and Slichter in their derivation, the only difference being the additional electrotransport term in the flux equation. It has been pointed out1,3 that Eq. [2] predicts the possibility of a noticeable increase in the purification of materials by solidification in an electric field. The validity of Eq. 121 has not been checked experimentally and it is possible that other factors' arising from the presence of an electric field across

Jan 1, 1965

By K. Mukherjee

Instantaneous resistance change during martensitic transformation in Fe-30 at. pct Ni alloy has been studied using a low-noise electronic system. The smallest signals recorded in this investigation were of the order of 10 pv. These small signals did not show the initial increase reported by earlier investigators to support a double shear mechanism.&apos; A variety of pulse shapes and sizes was observed during "burst" transformations, and these signals were neither a linear function of the size of martensite plates nor of the volume fraction transformed. Even the smallest signals, presumably from single plates, showed complications resulting from elastic and/or plastic deformation, shock wave propagation, and so forth, which are inherent in the growth process of a martensite plate. The time of formation and interface velocity determined froni this experiment agree very well with the pioneering work of Bunshalz and Mehl.&apos; AN Fe-30 at. pct Ni (c0.005 pct C) alloy was used to study the time of formation of martensite plates. Martensitic transformations, unlike the nucleation and growth processes, are usually characterized by an extremely fast reaction rate. During the transformation, the crystal structure changes and this change is propagated through a finite volume of the parent crystal lattice within a very short time interval. The interface between the two phases probably consists of moving dislocations, and the time of formation of the plate depends on how fast this dislocation interface can move. Knapp and Dehlin~er or Cottrell and Bilby mechanisms, or similar dislocation models, can be used to calculate the time of formation of a martensite plate of a given size. In the past, conventional photographic technique475 as well as electrical resistivity techniques"~-" have been used to measure the time of formation of a martensite plate. The specific resistance of the martensitic phase in Fe-30 at. pct Ni alloy is lower than that of the austenite phase. Therefore if a current is passed through a small austenite sample in series with a large external resistance, then one would observe a voltage change across the sample as martensite is formed. Such dc measurements are shown in Fig. 1. The initial large voltage drop in Fig. 1, at the M, temperature, is due to a "burst" transformation where a large number of plates are formed in a cataclysmic manner within a very short interval of time. Even during the later stages of transformation as shown in Fig. 1, one can observe discontinuous voltage changes due to small bursts. In order to resolve the time scale of such discontinuous stages, the voltage signals are amplified and fed into a highspeed oscilloscope. In this investigation a low-noise amplifier was used for the first stage of amplification. The signal to noise ratio was further improved by the design of a pulse transformer. This transformer was capable of amplifying the signal by a factor of six. Voltage signals were studied over a wide time scale ranging from 2 sec to 0.1 psec. I) EXPERIMENTAL PROCEDURE A) Specimen Preparation. Specimens were cut from induction-melted Fe-30 at. pct Ni (<0.005C) alloy and cold-rolled to 0.2 by 1 mm cross section and an average length of 5 cm. During mechanical shaping, the specimens were strain-annealed at 950°C for 24 hr in vacuum. Finally the finished samples were vacuum-annealed at 1000°C for 6 hr and water-quenched to room temperature. The average grain diameter was 0.02 cm. B) Cooling System. The M, temperature of the alloy was -55°C. Fig. 2 shows the arrangement which was used to cool the specimen at a slow rate. The specimens were mounted inside a i -in.-diam hole in the 2-in.-long section of the copper specimen holder. This cavity was filled with silica gel. A dummy specimen was used under identical conditions for

Jan 1, 1969

By D. J. McAdam

IN a recent survey of the literature, the author has found evidence incompatible with prevalent views regarding the technical cohesive strength and yield strength of metals. Some of the evidence regarding the technical cohesive strength was presented in a previous paper,21 and views were presented that are believed to be in better accord with the evidence. In that paper, it was shown that the technical cohesion limit (contrary to prevalent views) varies with the combination of principal stresses,† and that the influence of plastic deformation on the technical cohesive strength is not in accordance with prevalent views. In this paper, consideration will be given to both the technical cohesion limit and the yield stress as affected by the combination of principal stresses. Evidence will be presented that the variations of the yield stress and the technical cohesion limit with the combination of principal stresses are not in accordance with prevalent views. Consideration will also be given to ductility and work-hardening capacity, which depend on the initial difference between the technical cohesion limit and the yield stress. By the "technical cohesion limit" is meant the mean stress at actual or potential* fracture. An example of a technical cohesion limit is the "true" breaking stress of a tension-test specimen, the breaking load divided by the sectional area at fracture. The cohesion limit thus obtained for a ductile metal, however, has been greatly altered by the plastic deformation. It is important to consider the cohesion limit of the metal prior to this deformation, and the variation of the cohesive strength with plastic deformation. The relation between the cohesion limit and the corresponding flow stress† determines the ductility of a metal and the energy that it will absorb before fracture. In this paper, as in the previous paper,21 tensile stresses will be viewed as positive and compressive stresses as negative. The algebraically greatest principal stress will be designated S1, the least principal stress will be designated S3, and the intermediate principal stress will be designated S2. In the previous paper, attention was confined to stress combinations with two of the principal stresses equal (with the intermediate principal stress S2 equal either to S3 or S1). In this paper, consideration will also be given to the effect of stress combinations with all three principal stresses unequal. In the earlier sections of the paper (pp. 1 to 14), attention will be confined to stress combinations with

Jan 1, 1942

By Allen F. Agnew

Detailed stratigraphic studies in the Wisconsin-Illinois-Iowa district have made it possible to map the folds and faults that controlled the deposition of the zinc-lead ore. Prospecting on the basis of this mapping and prospecting in lower zones that are potentially ore-bearing have led to discoveries of ore. GEOLOGIC studies for the Federal and State governments in the Wisconsin-Illinois-Iowa zinc-lead district were begun in 1835, and subsequent surveys were made in the three states at intervals until 1916, see Table I. The current study of the district, Fig. 1, by the U. S. Geological Survey was begun in 1942 in the hope that a systematic investigation would help increase production of zinc and lead, then in extremely short supply. Major emphasis of the USGS program was on detailed mapping of the geologic structure and ore deposits. Preliminary maps and reports covering localities of intensive mining activity have been published during the course of this study, Fig. 2. By 1950 the objectives of the study by the USGS were revised; 71/2-min quadrangles of relatively unprospected localities as well as intensively mined localities are now being mapped in Wisconsin. Since 1945 the investigation in Wisconsin has been made in cooperation with the Wisconsin Geological and Natural History Survey, and since 1951 the geologic mapping of areas of particular interest in Iowa has been performed in cooperation with the Iowa Geological Survey. At intervals since 1943 the Illinois State Geological Survey has mapped the geologic structure and ore deposits of localities in the Illinois part of the mining district, see Fig. 2. Geology was applied by mining company personnel as early as 1853, but only sporadically, with periods of greater application between 1890 and 1925. Much of the so-called geologic work was in reality mining engineering. Since 1946 the major mining companies in the district have employed geologists who have successfully applied geologic techniques in the search for ore. History of Mining Occurrence of galena in the district was known as early as 1658 or 1659, when French explorers heard of lead mines that were apparently in the vicinity of Dubuque, Iowa. In 1690 a trading post was established near Dubuque to obtain galena. The first significant attempt at mining by white men took place in 1788 when the Indians granted to Julien Dubuque mining rights for 20 miles along the west side of the Mississippi River, including the vicinity of Dubuque, Iowa. By 1805 lead was being mined near Galena, Ill. In 1819 permanent settlement of the region was begun, and most of the important lead-producing areas had been found by 1830, see Fig. 3. Lead production in the Wisconsin-Illinois-Iowa district between 1830 and 1871 far exceeded that of any other district in the U. S.&apos; Smithsonite was first mined in 1859, and sphalerite was mined as early as 1867. After 1873 the production of sphalerite exceeded that of smithsonite. In 1873 annual zinc production from the district first equaled lead production, and from then until 1893 production of zinc and lead was roughly the same. Since 1893 the ratio of zinc to lead mined has generally ranged between 5:l and 20:l. In 1942 the Wisconsin-Illinois-Iowa zinc-lead district ranked 14th among zinc-producing districts of the U. S. From 1946 until February 1953 the dis-

Jan 1, 1956

By D. E. Menzie, D. L. Dauben

This paper discusses the physical parameters involved in the slow flow of high molecular weight polymer solutions in porous media. The interacting effects of polymer properties and porous media properties on flow performance are considered. Experiments were conducted with the polyethylene oxides, with molecular weights ranging from 200,000 to over 5,000,000. Frontal advance velocities ranged from I to 30 ft/day. The porous matrix consisted of a flow cell packed with glass beads. Polymer solutions were characterized by viscosity and normal stress measurements. Under certain conditions, unexpectedly high flow resistance was observed. This behavior was observed to be a function of flow rate, pore size, polymer molecular weight and concentration. The polymer solutions exhibit "dilatant" flow behavior in porour media in contrast with the pseudo-plastic behavior in simple flow systems. A theoretical ex-planation of such behavior is presented. INTRODUCTION The use of polymers in the injected water of a waterflood increases oil displacement efficiency by reducing the mobility (k,/pu) of the driving phase. A reduced driving phase mobility results in improvements in the areal sweep efficiency and in the vertical coverage in stratified reservoirs. This mobility reduction may be achieved by a permeability reduction, a viscosity increase or by a combination of the two. Early attempts at increasing the injected water viscosity were not successful because of the poor economics involved. The use of such materials as glycerin, sugar or glycols to increase water viscosity was not economically feasible. Attempts in using certain naturally occurring polymers were not too successful because of the high polymer losses to the rock. A high molecular weight, partially hydrolyzed polyacry-lamide was introduced 3 years ago as a waterflood additive.&apos;,&apos; Initial work by Pye&apos; indicated that the presence of these polymers in dilute concentrations decreases the water mobility 5 to 20 times more than would be expected from measurements of the solution viscosity. Such an effect would be of obvious economic value since only a small polymer concentration would be required to accomplish a large reduction in water mobility. This research was designed to study the basic flow mech anisms of polymer solutions in porous media. The interacting effects of polymer properties and porous media properties on flow performance are considered. This study indicates some of the conditions under which these interactions can lead to significant mobility effects. is valid only for Newtonian fluids. For polymer solutions and other non-Newtonian fluids the equation must be modified to consider that viscosity is a variable quantity. Modification of the Darcy equation to include non-Newtonian effects has been the subject of several recent investigations."" The modifications generally adopt a rheological model. such as an Ellis or Dower law model. to Dorous media by defining some characteristic channel radius. Most of these studies showed the porous media flow behavior to be predictable from viscometric data. Investigations involving the flow of high molecular weight polyacrylamide solutions through cores have generally encountered the high flow resistances reported previously by Pye. This high flow resistance has generally been attributed to an in-depth permeability reduction, as evidenced by a reduced permeability to water which has displaced polymer solution from the porous media. Marshall and Metzner" report high flow resistances, which they attribute to viscoelastic effects. In this paper, the effects of polymer molecular weight, pore size, flow rate and concentration are considered. The polymers used are the polyethylene oxides known as Poly-ox. This class of polymers was used because of its availability in a wide range of molecular weights and because of its known ability to propagate well through porous media. THEORY PHYSICAL PROPERTIES OF POLYMER SOLUTIONS The polymer molecule dissolves in water by means of hydrogen bonding, but retains some of its own structural identity while in solution. Nonionic polymers, such as polyethylene oxide, are generally considered to have a random coiling configration. This type of molecule has the ability to "sequester" or hold a large volume of solvent within its coils in a manner similar to that of a sponge. The random coil is easily deformed and under an applied stress

By D. Atkinson, C. Bodsworth, I. M. Davidson

A geometric model of interstitial solid solutions, which has been used previously as a basis for the prediction of carbon activities in Fe-C austenite, is shown to serve also for the calculation of nitrogen activities in Fe-N austenite. The model has been developed to enable predictions to be made of the activities of an interstitial element in the presence of two host atom species. The activities calculated via the model are shown to be in satisfactory agreement with the measured values in the austenite phase for carbon in Fe-C-Co, Fe-C-Cr, Fe-C-Ni, Fe-C-~n, Fe-C-Si, and Fe-C-V alloys and for nitrogen in Fe-N-Ni alloys. The effect of the second substitu-tional solute on the logarithm of the activity of the interstitial element is expressed as the product of a constant mad the atomic concentration of that solute. The constants so derived we related to the thermo-dynamic interaction coefficients which describe the effect on the activity coefficient of carbon of an added solute element. In recent years the thermodynamic activities of carbon and nitrogen in the single-phase austenite field have been determined for iron binary alloys and for several iron-base ternary alloys. In order to extend the use of these measurements, it is desirable to be able to predict with reasonable accuracy the activities of the interstitials at compositions and temperatures other than those which have been measured experimentally. In all the systems studied to date, the interstitial elements do not conform to ideal behavior. Hence, the available data cannot be extrapolated or interpolated using the simple thermodynamic concepts of solutions. Several models have, therefore, been formulated for the purpose of predicting the activity of an interstitial element in the presence of one species of host atom. These models can be divided into the geometric1"5 and energetic6-&apos; types. The former group is based on the assumption that at low concentrations the activity of the interstitial species is determined by a composition-dependent configurational entropy term and an excess free-energy term which is temperature-dependent but independent of composition. The purpose of this paper is to show that the treatment, based on a geometric model, can be extended to enable predictions to be made of interstitial activities in the presence of two substitutional host atom species. THE CONFIGURATIONAL ENTROPY OF MIXING ICaufman5 has shown that the configurational entropy, S,, for a binary solution comprising of a host atom species, A, and an interstitial species, I, can be expressed as: where NI is the atom fraction of the interstitial species, R is the gas constant, and (2 - 1) is the number of interstitial sites excluded from occupancy by the strain field around each added interstitial atom. The number of interstitial sites per host atom, p, is unityg for the fcc austenite solutions considered here. The configurational entropy of mixing for a ternary solution comprising two substitutional atom species, A and B, and one interstitial species, I, can be derived similarly. Let the number of atoms per mole of each of these species in the solution be represented by «a, ng, and nI. From geometric considerations, it is improbable that the addition of a few atom percent of a second host atom species will change the type of sites (i.e., octahedral) in which the interstitial atom can be accommodated in the austenite lattice. At higher concentrations (determined largely by the relative atomic radii of the atomic species present and any tendency to nonrandom occupancy of the host lattice sites) other types of interstitial sites may become energetically favorable. Restricting consideration to compositions below this limit, for 1 = 1 the number of suitable interstitial sites is given by (n + nB). However, if each interstitial atom excludes from occupancy (Z - 1) additional sites, the total number of sites available for occupation is reduced to (n + ng)/Z. The number of vacant interstitial sites is given by: The total number of recognizable permutations of the atoms must include the recognizable, different configurations of the A and B atoms on the host lattice. Assuming that these arrangements are purely random, and are not affected by the presence of the interstitial species, the total number of recognizable permutations in the ternary alloy is given by: The configurational entropy is obtained by expanding, using Stirling&apos;s approximation, and collecting like items, as:

Jan 1, 1969

By E. B. Hughes, F. G. Norris

Oxidation is characteristic of all processes for making steel from pig iron. This thought has been aptly expressed by H. W. Graham13 in the recent Howe Memorial Lecture, "The process of steel-making consists of using iron oxide to reduce the carbon content of the pig iron to the desired level." Direct oxidation refers to the reaction that results from introducing oxygen either alone or mixed with other gases directly into the steel bath. In working a heat, oxygen in some form is added to the steel to remove the undesirable constituents as oxides. There are two general methods of supplying this oxygen to the open hearth bath. The method in which the oxygen is added as a compound such as Con or iron ore is designated an indirect method because the steel bath must first decompose the compound to attain oxygen in a usable form. The other method in which oxygen is added to the bath in the elemental or gaseous form, more or less diluted by other gases such as nitrogen, is a direct method because no decomposition is necessary before the oxygen reacts with iron to form FeO which is dissolved in the bath in a usable form. Bubble formation (at least of a macroscopic size) presents no problem in case of direct oxidation because the reacting agent (oxygen) is in the form of bubbles when entering the metal. Regardless of whether oxygen is intro- duced into the bath directly or indirectly, several reactions proceed concurrently. In the presence of the bath of molten iron, FeO is formed either by oxidation of iron by oxygen or reduction of oxides by iron. This FeO dissolved in the molten iron is the source of oxygen for the oxidation of manganese, carbon, silicon, and phosphorus if these are present. The oxidation of carbon from steel is the controlling steelmaking reaction. The introduction of oxygen into the bath, its reaction in the elimination of impurities, and its control by the use of de-oxidizing additions have been subjects of importance since steel was first made by the bessemer process. Direct oxidation is, in a sense, an application of the bessemer principle to the open hearth process. Graham13 states: "The use of oxygen or air jets introduced into the metal bath is essentially an effort to approach in the open hearth the turbulence, rapid interface reaction, and high production rate per hour that exists in the bessemer process." The general subject, "Oxygen in Steel-making," was given new life by the studies of Herty and associates starting about1925. The current interest in elemental oxygen is intimately related to the large scale production of oxygen developed during the war period. Some of the first applications were made during the early summer of 1946 at the Steel Co. of Canada using oxygen with the fuel. Such a use is of considerable interest and importance in contributing to faster heats but is not the subject of the present discussion which deals entirely with the introduction of elemental oxygen directly into the open hearth bath.

Jan 1, 1949

By L. D. Clark, S. S. Saluja

A physical law, governing the rupture of rock by confined explosive charge correspondent to current expressions for determining weight of charge to rupture rock burden, W, was developed in the form Q = cVw3 by two early investigators performing unique experiments with ice. The coefficient C, is found by trial blast. Recent physical tests conducted with rock, synthetic materials and ice to establish the validity of the theory on which it and other related formulae are based indicated: (a) that failure under hydrodynamic impact pressure is by tension rather than shear as was assumed; (b) that the fundamental law of mechanics, enabling the determination of Q = cvw3, modified to the form P = R x Sa x Wb is valid when low velocity explosives are used; (c) that rock breakage under the action of low velocity explosives is entirely due to explosion gas pressure, as was believed; (d) that under the action of high velocity explosive it is due to the joint effects of scabbing and gas pressure; and that further possible modification could make the above equation also applicable to these joint mechanisms. shape could be easily frozen and because large loads would not be required. They found: (a) that the not unfamiliar shearing equation for metals was applicable to ice where P = load in lb; S = periphery of pressure surface, in.; W = burden, in.; K = modulus of rupture by shear in lb per in.2; and (b) that "the form of cavity produced by the application of gradual pressure is similar to that obtained by blasting in rock under similar conditions of free face and pressure surface!" This similarity in crater shapes leads to the conclusion that rock would rupture by shear, as did ice, and its behavior under the force of a blast could be governed by such a relationship as P = S x W x K. Three important interrelated empirical expressions were derived and rock, charging and spacing coefficients C,, C, and e were established and substantiated by trial blasts. In checking the accuracy of the main assumptions, duplication of the ice tests, substituting rock, suggested that K is not constant and that P = K x W x S, though valid for ice, does not necessarily hold for homogeneous limestone.&apos; Conclusions from this later work raised questions making continued investigation desirable because such conclusions do not destroy the practical value of the empirical equations or theory. Further study for the establishment of the relationship between load, burden and periphery of the pressure surface and possible application of these to the mechanism of rock blasting was undertaken by the authors of this paper. MECHANICAL TESTING - EXPERIMENTAL PROCEDURE Certain inconsistencies in the results of the aforementioned tests repeated on three types of limestone suggested these inconsistencies be attributed to rock inhomogeneity. It was also suspected that the loading speed, which could not be held uniform, may have contributed. The earlier work with both rock and ice

Jan 1, 1964

By D. T. Peters, J. C. Bisseliches, J. W. Spretnak

The pain boundary relaxation phenomenon in high-purity copper, 0FHC copper, and a precipitation-hardenable alloy o-fCu-2 uit pct Co has been studied by internal ,friction and elastic aftereffect techniques. The data were analyzed by assuming the broad distribution of relaxation times observed obeys a lognormal distribution law which enables calculation of the relaxation strength. Grain size had no effect on relaxation strength, although the peak width increased with increasing grain size and decreasing temperature. A double grain boundary peak was produced in high-purity copper by annealing to produce secondary recrystallization. The activation energy measured for 99.999 pct Cu is 37.5 * 3 kcal per mol and 46.5 kcal per mole for OFHC copper. A small peak in the Cu-Co alloy at about 220°C at 1 cps was deduced to be the grain boundary peak. Its height increased and its activation energy decreased with increasing aging time. Except for erratic peak positions the observations were consistent with the theory of pain boundary sliding. BEFORE the mechanism of the grain boundary internal friction peak in metals can be satisfactorily explained, the detailed characteristics of the relaxation process must be documented. Of interest are the effect of grain size on relaxation strength, the high-temperature background, and peak width and position. The effect on the grain boundary peak of a precipitate at grain boundaries and of the change in distribution of the particles with aging time must also be explained by any existing or forthcoming theory. The model which has received the most attention was proposed by KG&apos; and zener2 and proposes that the anelastic strain results from sliding of adjacent crystals at grain boundaries. The sliding is limited by the interlocking of grain corners. It follows, according to this model, that the relaxation strength is independent of and the relaxation time is proportional to the grain size. The proportionality between grain size, D, and relaxation time, t, has been confirmed by K&&apos; and Bisseliches . In this case, the internal-friction peaks of various specimens can be superimposed by plotting Q-&apos; as a function of the parameter vD exp H/RT where v is the frequency and H the activation energy. However, the data of Starr et 01.&apos; and Leak6 fit better to a parameter containing D to an exponent near two. A meaningful relationship is not always deducible from the shift of peak temperature with grain size. KG7 demonstrated that a twofold variation in grain size obtained by varying the amount of cold work followed by identical recrystallization anneals will cause a peak shift that is too large to be accounted for even by an exponent of two. Since the decreased grain boundary area existing with a larger grain size is exactly compensated for by an increased sliding distance, the relaxation strength should not decrease with increasing grain size. The height of the internal-friction peak has generally been observed to be rather insensitive to grain size as long as the average grain diameter does not approach the specimen diameter. Exceptions have been reported by Koster, Bangert, and Lang8 for copper, and by Leak6 for iron. The observations for copper could well have been confused by the presence df 0.3 pct0. The possibility that the peaks may simply be increasing in width with increasing grain size and that the relaxation strength, which is proportional to the area under the peak, may remain constant was not examined. his point has been checked in this investigation using high-purity copper. Atomic mechanisms to account for damping by sliding at grain boundaries have been proposed by KG7 and Mott. KG predicts the activation energy to be identical to that for self-diffusion. Mott&apos;s "island" model suggests the activation energy is nL where n is the number of atoms in an island and L is the latent heat of fusion per atom. Other authors have felt that a value equal to the activa-

Jan 1, 1964

By Milton Glicken

THE airborne geophysicist is a busy man these days. In his plane he may have the airborne magnetometer, the airborne scintillation counter, and the airborne electromagnetic surveying system. Each of these is an independent tool, but all require additional auxiliary equipment for locating the aircraft in space: recording altimeters and Shoran or aerial cameras. Now there is still another piece of equipment, the airborne magnetic gradiometer, an accessory to the magnetometer. To understand its uses, consider the function of the magnetometer itself. Aside from detecting magnetic ore, the airborne magnetometer finds greatest use in spotting intrusions of igneous material. Where there is enough contrast in magnetic susceptibility of igneous rock and adjacent formations, it outlines the intrusion. Certain minerals also influence the magnetometer directly, but with the exception of magnetite and possibly one or two others, their effect is weak and can be detected only when there is sufficient ore and the magnetometer flight passes very close to it. An igneous intrusion of infinite depth with vertical sides is represented on a magnetometer record by an anomaly, as in Fig. 1. Amplitude of the high depends on susceptibility contrast of the igneous rock. Generally speaking, the edge of the intrusion lies below the point of inflection of the curve, and this point, where the curvature changes from positive to negative on the magnetometer profile, would be near A in Fig. 1, with a counterpart, of course, on the other side. Location of the contact is one of the principal objects of the survey, but finding the precise point is not always easy, as inspection of the curve near A will show. Mineralization is often found at the contact zones, as at B. Magnetic effects, if detected, may be small, as in B&apos;, and when superimposed on the anomaly due to the instrusion they are very difficult to discern and analyze. Furthermore, if these small fluctuations are to be perceived by the magnetometer the vertical scale should be large. This increases the slopes of the anomaly and makes detection of small deviations and inflection points even more difficult. The airborne magnetic gradiometer was designed to help overcome these difficulties. What it presents is the first derivative of the magnetometer record with respect to time, that is to say, the slope at any point. Fig. 2 represents an actual magnetometer record (solid line) with the corresponding gradiometer record (dashed line) superimposed. Both records read from right to left. Vertical lines on the original magnetometer record are automatic steps designed to keep the pen from going off scale. The slope of any curve is greatest at the point of inflection or point where the curvature changes sign, and this point is a maximum (or minimum) on the gradi- ometer. The chief advantage of the gradiometer is that maxima or minima are much easier to see and to locate precisely; hence an accurate location for the point of inflection can easily be found. Note that points C and D are more sharply defined than C and D&apos;. Similarly the small fluctuations of the original record, so important to the interpreter, are far more clearly shown at E, F, and G, than on the original record at E&apos;, F&apos;, and G&apos;. Though not necessarily highs and lows on the gradiometer, they do show up clearly what would take a painstaking analysis to detect on the original magnetometer record. Will the gradiometer have a particular configuration which indicates an orebody? Not necessarily. The total intensity curve, or original magnetometer record, can display an orebody in various ways, depending on dimensions, orientation, latitude, and composition, as well as on direction, flight height, and instrumental sensitivity of the traverse. Where the total intensity can take on so many different shapes the gradiometer must vary too. It is generally recognized that interpretation of total intensity magnetometer records requires an expert analysis; the gradiometer can be of considerable assistance to the expert but it does not replace him. Mechanism of the gradiometer is simple. A Leeds & Northrup recorder in the aircraft records the magnetic gradient simultaneously with the total intensity, which is on another recorder. Fiducial marks are put on both records simultaneously and the speed of the paper through the recorders is kept the same on both. This makes it possible to place one record over the other for direct comparison. In the laboratory the flights are positioned on a map. Maximum and minimum points on the gradiometer, which can then be posted on the map at their proper locations, may be expected to fall along a trend crossing the direction of flight. Trends should indicate the edge of an intrusion, or some other important features, and when superimposed on the total intensity contour map help greatly to locate the points of inflection, or line of zero curvature.

Jan 1, 1956

By P. R. Gage, R. W. Bartlett

At high temperatues and reduced oxygen pressuves, molybdenum silicicles oxidize to form SiO(g) vathev than a passivating SiO2 film. This is a sevious problem for low-pressure applications of sili-cide-coated rejvactory tnetals. As oxiclalion pvoceeds, the higher oxidntion potential of silicon initially suppresses oxidation of molybdenum and silicon is depleted near the surface. Eventually, silicon depletion causes secondary passivation (SiO2) mid an active to passiue transition in oxidntion behavior at moderately low pressures. At very low pressures, silicon depletion continues until steady-state oxidation of both silicon and rnolyhdenum can proceed at rates propovtional to their initial stoicliiorrzetvies. Ohsel-vations of &apos;oxidatiou-rate belzcriliov at temperatures from 1101° to 1700°C and oxygen pressures from 10-7 to 1 at in were made using thermogravimetn&apos;c, X-ray diffraction, and elect?*on-rtric?ro/,vobe techniqrres. The experimental results are in good agreement with calculated lirnits for the various types of behavior that were based on tlievtnochernicnl atzd dffusion rate data for the Mo-Si system. A protective oxide film normally forms during the oxidation of elemental silicon. However, at elevated temperatures and reduced pressures this film is not present and oxidation is rapid. wagnerl has shown that this behavior occurs because SiO(g) is more stable than SiO2. The behavior of the silicides at high temperatures is similar but more complicated. Molybdenum and several silicide compounds are involved and the chemical activity of silicon, or the equivalent silicon vapor pressure, can vary considerably in these phases. Also, diffusion in the silicides resulting from reactions in which a higher silicide is reduced to a lower silicide, or molybdenum containing dissolved silicon, must be considered. EXPERIMENTAL AND ANALYTICAL METHODS Isothermal oxidation experiments were conducted using hot-pressed MoSi2 and Mo5Si3 wafers. Each experiment was conducted at a fixed oxygen pressure by controlling the flow of oxygen in and out of the furnace chamber. Most of the experiments were conducted in a molybdenum-wound tube furnace. Special construction features, including use of a high-purity dense A12O3 refractory tube, permitted operation in high vacuum to 1500°C. Higher temperatures could be obtained at higher working pressures and with a sacrifice of tube lifetime. Temperature was measured with three Pt 6 pct Rh/Pt 30 pct Rh thermocouples and controlled with a proportional controller. Weight changes were monitored with a quartz spring balance. The few experiments, at higher temperatures and low pressures, were conducted in a cold wall vacuum chamber using induction heating with direct susceptance of the sample. Because of the variable levitation effect of the induction coil on the sample, weight changes could not be monitored continuously in these experiments. All samples representing both experimental methods were weighed before and after oxidiation and examined with a microscope and analyzed by X-ray diffraction. The analytical treatment assumes equilibrium at interfaces and uses existing thermodynamic data. For convenience, equilibria are expressed as chemical potentials or as vapor pressures of the gases involved. The resulting differences in equilibrium vapor pressure between adjacent interfaces and between the surface and external atmosphere drive diffusion processes in the solid and gas boundary film, respectively. These diffusion processes govern the rate of oxidation. A bibliography of the sources of thermochemical data for the reactions pertinent to the Mo-Si-O system is given in Table I. Reactions are listed with the sources of free-energy data referenced. Since all of these reactions involve one or more gas species, usually oxygen, a plot of the product-gas chemical potential, -RT In Pg, vs absolute temperature for each reaction is given in Fig. 1. These curves can be used to determine equilibrium vapor pressures or to compare the stability of different compounds in the various gases: O2, Si, SiO, and Moo3,. The data of Table I and Fig. 1 were used to determine the analytical results presented in this paper. EXPERIMENTAL RESULTS The weight changes for three MoSi, samples oxidized at 1500°C are plotted against time in Fig. 2. The treatments were identical except for the indicated variance of oxygen pressure and each curve represents one of three characteristic types of behavior that were observed. The upper curve is an example of passive oxidation, which is defined as

Jan 1, 1965

By J. D. Hanawalt, C. E. Nelson, J. A. Peloubet

The subject of the salt-water corrosion resistance of magnesium alloys is somewhat like that of the pitting of stainless steels, in that it involves a relatively small. percentage of the applications but receives a much greater proportion of the publicity. Actually magnesium alloys are in use in many exterior applications as well as interior, with no trouble from corrosion. Magnesium and its alloys have a striking stability against atmospheric attack, being far superior to iron. Specimens exposed unprotected to atmospheric weathering for Io Years show only a superficial surface-film formation. The basic nature of magnesium and of its important alloys is that they are also resistant to the attack of salt water even in an unprotected state, giving substantially no loss in weight after one year of alternate immersion in 3 per cent NaCl solution (Fig. 1). This basic behavior is often masked because of the extreme sensitivity of these alloys to certain impurities and combinations of impurities. It is known, and the subject of increasing emphasis, that higher purity leads generally to greater stability for many materials, non-metallic as well as metallic. However, a review of the literature on the corrosion factors in magnesium alloys shows that almost all researchers worked with base metal in which metallic impurities varied in uncontrolled amounts. The major factor, that of metallic impurities, Probably greatly overshadowed the effects of minor ones such as flux inclusions, nonmetallic impurities, porosity, metallographic state, which these researchers presumed to study. In the present investigation the first observation of interest is that whereas magnesium of commercial purity (99.9 per cent pure) has a corrosion rate in alternate immersion in 3 per cent NaCl solution at room temperature of anywhere from 5 to Ioo mg. per sq. cm. per day, the corrosion rate of high.purity magnesium is 0.15 ± 0.05 mg, per sq. cm. per day. The principle followed in the experiments was to add to such base magnesium other elements, singly and in inin in controlled and known amounts and to observe the corrosion behavior of the resulting alloy. These experiments show the existence of what may be called tolerance limits" of magnesium and some of its alloys for certain impurities. The extremely small percentages of impurities involved and the sharpness of the corrosion discontinuities appear to be quite unpredictable, In order to carry on this work, it was necessary to develop an analysis technique suitable to the problem. In some cases it was necessary quantitatively to analyze impurities to less than 0,001 per cent. The experimental data to be presented are based on observation of about 5000 alloy specimens and on more than 50,000 quantitative analyses. while the primary purpose of this paper is to present the experimentally obtained data on corrosion rates as a function of composition, and particularly to demon-

Jan 1, 1942