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By W. Shockley

THIS lecture can best begin with a statement of the chief conclusion: The metallurgical industry will find profit in supporting fundamental research on dislocations. This support should be done both in their own laboratories and in universities. My lecture consists of an exposition of the basis for this conclusion. The experience on which I base it is drawn largely from two fields in solid state physics—one field is transistor electronics and the other is dislocation theory. At present the relationship of solid state physics to technology is different in these two fields. In electronics without question, the physics has led the technology. In metallurgy, on the other hand, the technology in the form of metallurgical art is far ahead of the fundamental science. In transistor electronics, physics has suggested and can still suggest previously unachieved combinations of matter that will have new and useful properties; that is, the physicist can make specific predictions. The physicist can also have some confidence that the predicted devices will actually come into existence in a matter of months or years and that they will live up to the predictions. In metallurgy, the physicist cannot to a comparable degree make predictions and have the same hope that they will lead to something new and valuable. There are a number of reasons for this difference. The first is simply historical. Transistor physics is young. It may be regarded as dating from the announcement of the transistor, in which case it is about four years old, or from the first real control of semiconductors as materials (this was accomplished largely by metallurgists, by the way) in which case it is about ten years old. Metallurgical art, on the other hand, is thousands of years old. There is no doubt that the advance of this art has been and will be hastened by a good fundamental understanding of the quantum theory of atomic phenomena. It, is too much to expect, however, that theory will soon catch up with the lead that practice has gained in a thousand years, and that theory will then point out specific pathways to better materials. It seems more probable that modern atomic theory will serve to interpret and organize information much as thermodynamics has done through phase diagrams. In this lecture, I shall emphasize an important feature common to both solid state electronics and to metallurgy. This common feature is the harmonizing principle that justifies discussing electronics and metallurgy as related topics in solid state physics. In both cases the important properties of the materials arise from imperfections. By imper- fections I mean deviations of the materials from perfect single crystals. The imperfections may be of many forms. From the point of view of utility they may be either good or bad, and a given type may be good or bad depending on circumstances. The technical material of my lecture will be divided into two parts. The first will be chiefly concerned with four types of imperfections in germanium crystals. The control of these imperfections makes possible the fabrication of useful electronic devices. A good example of such control is the junction transistor, which I shall discuss from this viewpoint later. The junction transistor, as some of you may have heard, can be used as an amplifier of electrical signals and in a number of respects surpasses what has hitherto been achieved with vacuum tubes. The second part of my technical material will be concerned with dislocations. For about fifteen years the theoretical physicist has had dislocations in mind as the most important kind of imperfection in metals. He has, however, until recently had experimental material of a highly speculative nature to back up his assertions. I am fortunate in the timing of this lecture to be able to describe some recent results that put dislocations on a far more definite basis than has been the case in the past. In fact there are now some experiments which reveal the characteristic properties of dislocations almost as clearly as experiments in transistor physics reveal the properties of holes and electrons, properties that I shall soon describe. It is this advance in the status of dislocations that emboldened me to make my initial assertion that the metallurgical industry will profit from supporting fundamental research on dislocations. Transistor Electronics In order to discuss imperfections in semiconductors, it is necessary to visualize a reference condition that may be regarded as perfect. In the cases of silicon and germanium, which find application in transistor electronics,' the perfect structure is the diamond structure shown in Fig. I. In this structure, each atom is surrounded by four neighbors with which it forms four covalent or electron-pair bonds. These bonds use all of the four valence electrons possessed by each of the silicon or germanium atoms. The electronic structure of the crystal is thus complete and perfect. A crystal of silicon or germanium with a perfect electron-pair bond structure would be an insulator, In order for electrical conduction to occur, it is necessary for imperfections to arise in the electronic structure. In this lecture, I shall discuss four possible imperfections whose symbols and relationships are indicated in Table I. We shall consider first, as an example, a crystal of silicon containing an arsenic atom as an impurity.

Jan 1, 1953

By A. Lubinski

In drilling operations, attention generally is given to hole angles rather than to changes of angle, in spite of the fact that the latter are responsible for drilling and production troubles. The paper presents means for specifying maximum permissible changes of hole angle to insure a trouble-free hole, using a minimum amount of surveys. It is expected that the paper will result in a decrease of drilling costs, not only by avoiding troubles, but also by removing the fear of such troubles. SUMMARY, CONCLUSIONS AND RECOMMENDATIONS Excessive dog-legs result in such troubles as fatigue failures of drill pipe, fatigue failures of drill-collar connections, worn tool joints and drill pipe, key seats, grooved casing, etc. Most of these detrimental effects greatly increase with the amount of tension to which drill pipe is subjected in the dog-leg. Therefore, the closer a dog-leg is to the total anticipated depth, the greater becomes its acceptable severity. Very large collar-to-hole clearances will cause fatigue of drill-collar connections and shorten their life, even in very mild dog-legs. Another finding regarding fatiguing of collar connections in dog-legs is that rotating with the bit off bottom sometimes may be worse than drilling with the full weight of drill collars on the bit, mainly in highly inclined holes when the inclination decreases with depth in the dog-leg. Means are given for specifying maximum dog-legs compatible with trouble-free holes. An inexpensive technique proposed is to take inclinometer or directional surveys far apart; then, if an excessive dog-leg is detected in some interval, intermediate close-spaced surveys are run in this interval. The application of the findings should result in a decrease of drilling costs, not only by avoiding troubles, but mainly by removing the fear of such troubles. The result would be much more frequent drilling with heavy weights on bit, regardless of hole deviation. Because of errors inherent to their use, presently available surveys are not very suitable for detecting dog-legs. There is a need for instruments especially adapted to dog-leg surveys. Crooked hole drilling rules should fall into two distinct categories—(1) those whose purpose is to bottom the hole as desired, and (2) those whose purpose is to insure a trouble-free hole. Three kinds of first-category rules in usage today are as follows. 1. A means to bottom the hole as desired is to prevent the bottom of the hole from being horizontally too far from the surface location; this may be achieved by keeping the hole inclination below some maximum permissible value such as, for instance, 5. 2. Another means to achieve the same goal is to limit the rate at which the inclination is allowed to increase with depth. A frequently used rate is 1/1,000 ft. In other words, a maximum deviation of l° is allowed at 1,000 ft, 2 at 2,000 ft, 3 at 3,000 ft, etc. 3. Whenever application of the first two means precludes carrying the full weight on bit required for most economical drilling, then the best course is to take advantage of the natural tendency of the hole to drift updip, displace the surface location accordingly and impose a target area within which the hole should be bottomed. This method has already been successfully applied,'.' and its usage probably will become more frequent in the future. Means for calculating the amount of necessary surface location displacement are avail-able.3'5'6 If in high-dip formations the full weight on bit should result in unreasonably great deviations, the situation could be remedied by increasing the size of collars and (if needed) the size of both hole and collars,351 or in some cases by using several stabilizers. Rules which would fall into the second category (i.e., rules whose purpose is to insure a trouble-free hole) are seldom specified today. It is vaguely believed that following Rules 1 and 2 of the first category will automatically prevent troubles. Actually, this is not true. If at some depth the only specified rule is that the hole inclination must be less than 4", the hole may be lost if the deviation suddenly drops from 4 to 2, or if the direction of the drift changes, etc. Rule 3 of the first category is generally used in conjunction with a rule belonging to the second category, namely, that the hole curvature' (dog-leg severity) must not exceed the arbitrarily chosen value of 1½ /100 ft. Moreover, when using this rule, the industry is not clear over what depth intervals the hole curvature should be measured. All this results in a frequent fear

By T. F. Bower, M. C. Flemings, H. D. Brody

A series of experiments are reported which show thai reasonable assumptions for analysis of solute redistribution in solidification of castings and ingols illclr(de: negligible undercooling before nuclcation of solid phases, negligible increase of solute in advance of the tips of growing dendrites, complete diffusion within the Liquid oer distances the order, of dentrite arm spacings, platelike dentrite t/o?$holog?.. Qzmli/ali,e and periment is obtained JOY Al-Cu alloys front measurements of amount of nonequilibrium second phase, minimum solute content at the centers dentrites arms (after solidification), and 3) change in minimum solute content in dentrite arms during solidification. In a previous paper' analyses were given describing solute redistribution in dendritic solidification. The analyses were undertaken primarily to permit prediction of "severity of microsegregation" in a casting or ingot after solidification and cooling to room temperature, but can also be used to predict "local fraction solid' as a function of temperature in the solidifying alloy. Numerical results were given for Al-Cu alloys. The aims of this paper are to examine the validity of some of the assumptions of that analysis, and to compare predictions of the theory with experiments. All experiments reported are on Al-Cu alloys, the bulk on Al-4.5 pct Cu alloy. EXPERIMENTS Experiments conducted were on small ingots, 41/2 in. in diam by about 10 in. high. solidified in a controlled thermal environment (i.e., in a resistance-heated, re-circulating air furnace, whose temperature could be controlled to 1°C). In one series of experiments, the ingots were solidified very slowly (solidification time was varied from 8 to 1000 hr) and at constant rate of heat extraction. In a second series of experiments the ingots were solidified ( 'unidirectionally". Fig. 1 is a sketch of the method of making the two different types of ingots. The unidirectionally solidified ingots were fully columnar, and the slowly solidified ingots had equiaxed structures, Fig. 2. In making the slowly solidified ingots, the mold employed was carbon steel, coated with inert refractory. Typically the mold and its environment were heated to 700°C. The molten alloy was then poured into the mold and the temperature of the system equilibrated above the liquidus. The environment of the mold was next cooled with a controller responding to a differential thermocouple that measured the difference between the temperature of the melt and the temperature of the mold environment. The differential thermocouple consisted of one chromel-alumel junction in the melt connected in opposition with a second junction in the furnace. The potential across the differential thermocouple was input to the controller which acted to keep this potential at a set. constant value; hence the temperature difference between the two junctions was maintained nearly constant. Major resistance to heat flow in the above apparatus was between the metal surface and the furnace atmosphere, not in the metal itself. By maintaining a constant temperature difference between the metal and the furnace atmosphere, the controller maintained an essentially constant rate of heat extraction during solidification, regardless of amount of heat released by the metal per unit temperature change. When the metal temperature dropped just below the eutectic temperature. the ingot was removed from the furnace and water-quenched. The unidirectionally solidified ingots were cast in a similar mold to the foregoing except that provision was made to extract heat through the bottom face of the mold by passing air or water through the mold base, Fig. 1. For these experiments, metal and mold temperature were again equilibrated above the liquidus. Temperature of the mold environment was then held

Jan 1, 1967

By J. E. Berry

AII evaluation is made of the acoustic velocity log for measurement of formation porosity. Plots of field-observer1 velocities vs core-measured porosities of sandstones and limestotnes with inter intergranular porosity show that the velocity log gives a useful measure of porotity, in agreement with published data. A new method of plotting electrical and velocity log data makes it easier to recognize hydrocarbon-water coritnct~ from log darn and to make serni-quantitative estinlates of hydrocarbon saturation. Two examples of this interpretation technique are given. This paper also discusses the various factors that affect acoustic velocity and shows how corrections can be made for some of these factors. INTRODUCTION Although the continuous velocity log was developed primarily as an aid to seismic interpretation, it is finding widespread use for measurement of porosity. The purpose of this paper is to evaluate this use of the log. Results are presented for the velocity-porosity relationship in many sandstones and one limestone. Practical applications of porosity values derived from the velocity log to improve interpretation of electrical surveys are presented. Various parameters which affect velocity in porous media are considered. Porosity, composition, cementa-tion, pressure difference (overburden pressure minus fluid pressure), fluid saturation, and wellability are discussed. Some of the ideas are opinions based on general considerations of well logging problems while others are supported by published data and our own observations. Major conclusions from these studies arc given in the body of the paper and detailed discussions of some of the various factors affecting porosity are given in the Appendix. POROSITY Sandstones The primary factor affecting the velocity of sound in porous media is porosity. Wyllie, et al,1 have reported a time average equation for the relationship between velocity and porosity.* This has found considerable acceptance in the industry. Other relationships between velocity and porosity have been proposed, none of which are entirely satisfactory. It is doubtful that any one relationship will completely describe all situations. We have tried an empirical relationship based on correlating log velocities with core-measured porosities. Measured porosities were averaged over a depth interval equal to the spacing used in recording the velocity logs. The depth range for the information used was from 2,000 to 12,000 ft. Velocity measurements were normalized for the effects of depth and overburden pressure. A detailed discussion of the basis for this normalization is given in the Appendix. The change is usually insignificant and when working with individual formations it can be neglected. All velocity measurements were normalized to a depth of 10,000 ft. The velocity-porosity data for sandstones in Fig. 1 came from 20 wells scattered throughout the Mid-Continent and Gulf Coast areas. The scatter of the data points is attributed to three causes: 1. There is no theoretical basis for expecting an exact velocity vs porosity relationship and it is not possible to correct precisely for the effects of such factors as impurities, grain shape, manner of cementation, etc. Some of these factors are discussed in the Appendix. 2. Porosities measured by core analysis are not necessarily representative of what the velocity log "sees". 3. Inaccuracies appear in the velocity log reading. This is particularly true of velocities from one-receiver logging tools.*" A linear-time curve (time-average equation) is plotted in Fig. 1 along with the best straight line through the points. Velocities used for the linear-time curves were 19,500 ft/sec for the matrix velocity (zero porosity) and 5,500 ft/sec for fluid velocity. For clean sandstones with velocities greater than 10,000 ft/sec, there is little difference between the velocity-porosity and the time-porosity curves. Both curves are well within the scatter of data points. The data points in Fig. 1 were restricted primarily to clean sandstones, using the SP and/or gamma-ray logs as clues to the lithology. Where a lithologic de-

By J. Paone, S. Tandanand

This paper studies the behavior of rock at the initial state of crater formation resulting from stresses created under a drill bit. The purpose of this study is to determine which mechanical properties of rock are important in rock fragmentation by drilling. Although a definite relation between the drilling strength and relevant mechanical properties has not been established, maximum yield strength or hardness of rock is apparently a parameter of drillability of rock. The strengths of rock were considered from the Mohr-Coulomb criterion from which the surface of failure was constructed. The results from previous triaxial tests on Solenhofen limestone were adopted in establishing a limit of failure. Inelastic behavior of Solenhofen limestone was observed under a low velocity impact of a hemispherical bit and under static indentation with a similar bit. Permanent set at low applied loads in the indented area was measured with an interferometric technique. A quantitative determination of strengths of the rock was made under static indentation. The maximum yield strength estimated from the average stress over the contact area for plastic deformation was used as the crushing strength of rock under a drill bit. Much research has been done on energy requirements and mechanisms of energy dissipation to perfect rock fragmentation by a drilling process. But more needs to be done. More needs to be known about the mechanisms of energy dissipation or failure criteria of rocks in the drilling process in order to evaluate the efficiency of energy requirements in specific rock fragmentation. This paper examines some published studies on rock failure and energy dissipation and presents some findings in that phase of research concerned with rock fragmentation by drilling. This work is specifically concerned with rock behavior at an early stage of failure induced by a concentrated load. Consideration is limited to the primary phase of the crater formation under drill bit, i.e., before chipping takes place. Failure Phenomena of Rocks: Failure of rocks can be classified into two types, fracture and plastic flow. Both involve separation of material to form new surfaces with complete or partial loss of cohesion. Fracture is further classified as extension (or cleavage) fracture and shear fracture. Extension fracture involves separation in a plane without shear stress component, while shear fracture involves slippage along a plane as a result of combined stresses. Then, shear fracture inclines to the axes of the principal stresses. Plastic flow occurs under combined stresses, especially at high confining pressure and temperature, and denotes macroscopically irrecoverable deformation of rocks. Flow mechanisms have been classified as in-tergranular failure, intragranular gliding, and re-crystallization of mineral constituents.6 Failure phenomena in rocks are complicated because they include fractures and plastic flow as well as a friction process developed intrinsically as the internal stresses increase. All can occur in one rupture process, depending on the varying stress conditions. Both fracture and plastic flow are encountered in rock drilling. Rock failure under a drill bit as observed in drop tests simulating a single blow of a percussion drill, consists of two types, crushing and chipping. Crushing is considered as a separation of material particles by many fractures resulting from the application of high compressive stresses exceeding the strength of rock at the contact area. Chipping results from subsurface fractures extended to the face surface; this phase is preceded by crushing or surface deformation. The state of stress under the drill bit and the strength of rock create and control these two types of failure. The state of stress under the bit and in the vicinity of the contact area depend on the bit configuration and the magnitude of applied force. The strength of rock, characterized by its ability to resist penetration, depends on its composition and structure. However, the term "strength" quantitatively defined, is still ambiguous and may or may not correspond to the tensile, compressive and shear strength obtained from simple tests. Rock Failure Criterion: Rocks are weak in tension, their tensile strength being many times less than their compressive strength. This characteristic excludes

Jan 1, 1967

By H. G. Doll

A new electrical logging method. called MicroLaterology is described. whereby the resistivity R of the invaded zone close to the wall of the bore hole is measured. This method essentially utilizes a system of concentric circular electrodes iml,edded in an insulating support which is applied to the wall of the hole. A beam of current of very small diameter is focused horizontally into the formations by means of an automatic control device. and then opens widely at short distance from the wall. with this method, R most often can be recorded directly. except when the mud cake is very thick. in which case a correction is easily provided. The basic role of factor R in the quantitative analysis of electrical logs in terms of fluid saturation and of porosity is explained. The paper is illustrated with field examples. INTRODUCTION In electrical logging. the resistivity of that part of the penneable and porous formations which is invaded by mud filtrate is an important factor in the interpretation. Measurements made with the conventional devices — normal. lateral — and also with improved systems as the Laterolog and induction logging' — are very often more or less affected by the presence of the invaded zone. and the knowledge of the resistivity of this zone is useful in the evaluation of the true resistivity of the beds. which itself is a basic element for the determination of fluid saturation. Moreover. the comparison of the resistivity of the invaded zone with the resistivity of the mud filtrate gives valuable indications on the magnitude of the formation resistivity factor — which in turn is necessary for the quantitative interpretation of the logs. both in terms of fluid saturation and of porosity. On the other hand. it is generally admitted that the invaded zone is not a homogeneous medium separated from the uncon-tamirlated part of the bed hy a well defined cylindrical boundary. but that the fluid distribution—filtrate. connate water. hydrocarbon — and hence. the resistivity. in the invaded zone varies progressively with the distance from the wall of the hole. The term "resistivity of the invaded zone" therefore corre-sponds to an average value which is a function of the distribution of the fluids Inasmuch as the law of this distribution is not exactly known, the resistivity of the invaded zone is not a well defined factor. A much better definition is obtained if the medium under consideration is limited to that part of the formation which is within a short distance from the wall of the hole. It seems likely a within a distance of at least two or three in., most of the fluids in in the pores of tile formation have been displaced by the mud filtrate. The connate water has almost certainly been flushed out. and the oil. if any has generally been reduced to a comparatively small amount. The resistivity witliir~ the radial limit of two to three in. is. therefore. prac.tically constant at an). given level: its value. at least when the proportion of conductive solids in the formation is negligible. is chiefly dependent on the resistivity of the filtrate and on the porosity of the formation, and is affected only to a relatively small degree by the presence of the small amount of residual oil. This part of the formation close to the wall of the hole will he designated in the following as the "flushed zone." a-distinguished from the more general term of "invaded zone'. which relates to the part of the formation extending from the wall out to the distance where the formation is completely uncontaminated. The symbol R,, will he used for the resistivity of the flushed zone. (The notation R is related to the radial distance from the hole. If x designates this distance. xo is the initial value of x, i.e., the value corresponding to the region very close to the wall.) The determination of R is difficult, if not impossible. from logs made with the conventional devices. The long normal and the long lateral are. of course. not suited for this purpose because their radii of investigation are by far too large. The short normal. and the limestone sonde—-after correction for the effect of the hole hole — give resistivity values which corre. spond to materials situated within a comparatively short distance from the hole, but this distance is still several time. as great as the thickness of tire flushed zone. The only value which can be obtained with these devices corresponds to an average resistivity of the invaded zone- — and this only provided the invasion is deep enough, since otherwise the meas "red values would also be affected by the uncontaminated region beyond the invaded zone. It should nevertheless be recalled that despite these limitations. the measurements given by the short normal and or the limestone sonde are always very useful for qualitative interpretation. and also in favorable cases for the qantitative analysis of the logs in terms of saturation and porosity. The MicroLog. which was primarily developed for the detection of permeable beds and for an accurate determination of their boundaries. provides a good approach towards the evaluation of R. In the case of hard formation.. however. The

Jan 1, 1953

By I. Cornet

INTRODUCTION WITH the greatly expanding use of magnesium during the war, it appeared necessary to the War Metallurgy Committee that the notch sensitivity of magnesium alloy extrusions be further investigated and the influence of various factors upon notch sensitivity be noted. Accordingly, the National Defense Research Committee of the Office of Scientific Research and Development placed a research contract with the University of California, supervised by the War Metallurgy Committee. The work discussed herein was done under "Restricted" Project NRC-21, reported in Dec. 1943 1; it has been released for publication by the O.S.R.D. SCOPE OF THE INVESTIGATION The notch sensitivity of various magnesium alloy extrusions was determined under axial tension, and also under several conditions of nonaxial tension. Hardness, grain size and other metallographic features were observed; stress-strain data were obtained, and the chemical compositions of the alloys were determined, in order to correlate these quantities with the notch sensitivity. Notch sensitivity under axial tensile load was determined for a few specimens which had been cold worked to various degrees by tensile prestraining. Magnesium alloy extrusions studied included Dowmetal 0, X, J, and M. For comparison, extrusions of aluminum alloy 24S-T, cast bars of aluminum alloy I22-T2, and cast bars of magnesium alloy C were also tested, The specified chemical composition of these alloys is given in Table I. All bars tested were within specification limits of composition. Investigation of the tensile notch sensitivity of various magnesium alloy extrusions, under conditions of axial and eccentric load, showed little or no correlation with stress-strain or other conventional data. Since the many uncontrolled variables present might mask significant relationships, one alloy was selected for intensive study. Magnesium 0 alloy extrusions were subjected to experimental heat treatments, and the changing hardness, tensile strength, microstructure, and notch sensitivity observed. EXPERIMENTAL TECHNIQUES AND PROCEDURES Tensile Testing Bars used for axial loading were machined with 3/8 in.- and with 1/4-in. minimum diam, and included specimens with 6o° V notches (Fig I and 2). Each V-notched specimen was roughed out carefully and then finished with a honed tool. These V-notched bars were sampled frequently, sectioned, polished, and examined at 500 X magnification to control

Jan 1, 1948

By P. Gobin, J. Perez, P. Peguin

The strain-amplitude- dependent part of the internal friction of alluminum after several ther momechanical treatments has been measured in the I-cycle range and at the ambient temperature. The internal friction in the outer layer of the torsional specimen us stress is computed from the experimental data. The curues obtained are analyzed in tevnzs of u coirzbinntion of AH and p, which aye, respectively, due to the vecersible unpinning from weak pills and to the plastic strain. Considerirlg the notion of thermally activated unpinning and repinning, it is shown that in our experimental conditions tlze dislocation lines acl as in the H model of Granato and Liiclze. It is also seen that the internal friction p which appears at higher- strains call be described by a simple expression which is in good agreement with our results. A qualitative interpretatiorz is proposed by combining these new types of intelpnal fviction. We define the internal friction 6 as half the ratio of the dissipated energy aW during one cycle to the maximum supplied strain energy W of a material submitted to a periodic stress. Experiment and theory show that internal friction varies with stress above a critical value.' Below this value the internal friction is strain-amplitude-independent and is often masked by an experimental background; so we shall call it AB. ~bove this critical value, the internal friction is strain-amplitude-dependent. This quantity is usually called aH:' and it can be explained as a thermal unpinning of dislocations.3-6 Furthermore, at higher stresses, a rapid increase of internal friction appears. This phenomenon could be caused by the plastic strain,' so we shall call it Ap. It seems interesting to us to study the influence of several t her momechanical treatments on the curve internal friction 6 vs strain E, in order to study the variation of AH and p with the concentration and the repartition of linear and point defects. In order to try to explain the results obtained, we shall propose and discuss models for H and hp and shall show that we obtain a combination of these two types of internal friction. 1) EXPERIMENTAL PROCEDURE 1) Preparation and Treatment of Specimens. We

Jan 1, 1968

By D. Dever, E. S. Fisher

Measurements of the temperature dependence of the elastic moduli in single crystals of hep ruthenium, rhenium, cobalt, dysprosium, and erbium were carried out for various temperature ranges so as to investigate the correlation, suggested by prior work, between the shear anisotropy ratio, A = C44/C66, and the occurrence of the hcp — bee phase transformation. These measurements confirm the suggestion that A has a positive temperature dependence in that group of hcp metals that undergo thermally induced transfornzations to the bee structure and a negative or zero temperature dependence in the other hcp metals. It appears, from indirect evidence, that the hcp -fee transformation in cobalt is preceded by a highly negative temperature dependence of A. These results indicate that elastic anisotropy is an important factor in determining the temperatures at which martensitic phase transformations occur. Two possible roles for elastic anisotropy are proposed: 1) the shear-modulus ratio within the habit planes must be nearly similar for the two phases and 2) a large anisotropy decreases the stress necessary for the movement of the transfornzation dislocations. FUCHS' calculations of the elastic moduli in the alkali metals have shown that the high shear-anisotropy ratios, c/c', in certain bee metals and alloys are the result of large negative contributions to c' = (c11 - c12)/2 arising from the nearest-neighbor repulsive forces.' On this basis, and following Zener,2 the association between high c/c' ratios and the martensitic phase transformations that occur upon cooling certain bee metals is explained as a unique characteristic of the bee structure. Recent measurements of the elastic moduli in hcp titanium and zirconium show, however, that a high elastic anisotropy also exists in these hcp structures at the temperatures at which they transform to bee upon heating3. If there exists a direct and consistent correlation between the elastic anisotropy in close-packed structures and the occurrence of transformations to the bee phases then there is evidently a need to re-examine the conclusions of Zener theory. Elastic anisotropy may also be the result of the effects of temperature on the stability of the low-temperature close-packed structures or it may play an important role in the mech- anism of the martensitic transformations. The present measurements were aimed at establishing the phenomenological correlation between elastic shear anisotropy in hcp structures and the thermally induced hcp —bee transformations that occur in the majority of the twenty-three hcp metals, as shown in Table I. Prior to the present work the temperature dependence of the anisotropy ratio, A = c44/c66, was known at various temperatures for nine of the metals listed. The data showed a negative temperature dependence of A for cadmium, zinc, magnesium, and cobalt, which do not transform to bee, and a positive temperature dependence of A for thallium, zirconium, titanium, hafnium, and yttrium. The correlation was, however, ambiguous in that these two groups of metals are also separated with respect to the c/a ratios as noted in Table I. There remained the possibility that the temperature dependence of A is a function of c/a and not consistently associated with the transformation. The measurements of the elastic moduli in rhenium and ruthenium, in which hcp —bee transformations do not occur, were needed to help decide this question. The studies of dysprosium and erbium were undertaken to determine whether the correlation holds for the heavy rare earth metals.

Jan 1, 1968

By Gordon H. Geiger, J. Bruce Wagner

Electrical conductavity and therrnoelectvic nzeasuretnents on synthetic hematite slabs with 0.01 to 0.90 at. pet Ti and with 0.30 at. pet Ca were made. Additions of titanium and of calcium both increased the electronic conductivity with titanium yielding greater n-type behavior and calciurn p-type behavior. Reduction studies of hematite to magnetite in CO-CO2 atmospheres between 600° and 900°C initially exhibited linear kinetics. These linear rates were increased by additions of titanium and decreased by calcium. IN recent years many studies have been reported in the literature on the kinetics of the reduction of hematite and magnetite to iron. In addition, Hansen and Josephl and Schenck and Schultz2 have reported studies on the reduction of hematite to magnetite, the first step in total reduction to iron. In order to evaluate the results of the studies of over-all reduction in terms of the actual mechanism of the reaction and to define further the important factors in the rate- controlling mechanism of the magnetic roasting reaction, the following experiments were undertaken. Specimens of undoped hematite and hematite containing titanium or calcium in solution as doping agents were reduced to magnetite in CO-CO2 mixtures. In addition, electrical-conductivity measurements were correlated with the reduction kinetics using concepts of defect solid-state chemistry. EXPERIMENTAL Fisher certified Fe2O3 powder was used to make specimens for both the electrical and kinetic studies (see Table I for analysis). Doping with titanium and calcium was accomplished by adding TiO2 and CaO powders to the Fe2O3 powder. The powders were mixed in a Waring blender for minimum times of 1/2 hr. Satisfactory blending was achieved based on comparison of analyses of individual specimens af- ter reduction. The specimens were formed in a steel die using opposed punches with a rectangular opening 10.0 by 40.0 mm. The Fe2O3-TiO, platelets were pressed cold at 16,000 psi. They were sintered for approximately 16 hr at 1075°C in air, in accordance with information in the literature3, 4 on the time and temperature needed to obtain solution of the titanium in the hematite. The Fe2O3-CaO mixtures were first cold-pressed at 20,000 psi and sintered for 3 hr at 1225°C to insure solution of CaO. This material was then ground to -325 mesh in a 6-in. ball mill and the resulting powder was used to make platelets in the same manner as above. The sintered platelets were usually between 1/16 and 1/8 in. thick. They were ground on a carborundum wheel and polished on 2/0 paper. Typical dimensions of the kinetic-study specimens were 1.6 by 0.8 by 0.05 cm, and a typical weight was 0.3 g. Conductivity and thermoelectric specimens were approximately the same size, but were subjected to further sintering in order to ensure maximum densification. Finally, all specimens were measured to the nearest 0.0005 in. and weighed on a Mettler H-15 balance to the nearest 0.0001 g and the density calculated. The average density of the specimens used for the reduction studies was 4.87 g per cc, or 7.1 pet total porosity. The standard deviation ranged from 0.14 to 0.063 g per cc within a composition group. In the present study, the apparent surface area as measured with a micrometer was taken as the true surface area. The chemical analyses for calcium and for titanium within a group showed maximum variations of 50.04 pet from the average values used in Figs. 9 and 11. In order to suspend the specimen from the balance for the kinetic studies, a hole, 0.03 in. in

Jan 1, 1965

By W. K. Godfrey

The highest compressive strength cement has the highest bond strength in tests in which the cement is subjected to a confining pressure. After perforating, the bond strength is reduced to nearly zero when the pipe is supported by weak cement. Perforating does not affect the bond strength, however, when the pipe is supported by strong cement. Pipe supported by weak cement is damaged by perforating with expendable capsule jets, but is not damaged by perforating with the hollow carrier gun. High strength cements are recommended for oil wells that are to be perforated. Introduction The purpose of this work is to determine the effect of jet perforating on the bonding strength of oilwell cement at simulated down-hole conditions. Bond strength is a good criterion for determining the effectiveness of cement in performing its main function, i.e., that of isolating zones. According to the literature on the subject, the optimum cement strength for perforating is low and should not exceed 2,000 psi compressive strength. This conclusion was based on the appearance of bullet and jet perforations in neat and gel cements largely done in the absence of a confining pressure more than 15 years ago. Discussion Literature A relatively weak cement has been recommended in the literature as having optimum properties for perforating. In 1947, Oliphant and Farris tested bullet perforating of neat cements at various curing times.' Some of the tests were made at down-hole conditions. They reported that the optimum cement strength for perforating was about 2,000 psi compressive strength. Enlarged holes occurred when strength was too low, and the cement shattered and cracked when the strength was too high. In 1951, Morgan and Dumbauld tested bullet and jet perforating of neat and gel cements at surface conditions.' They reported that optimum cement has a compressive strength less than 2,000 psi. In their tests at atmospheric pressure, high strength cement shattered and cracked when perforated. Thus, the optimum cement strength was based on the appearance of neat and gel cement after perforating. In 1953, Clark showed a relation between cement strength and fluid shutoff.' He concluded that a 500 psi compressive strength is required for good fluid shutoff and that maximum bonding ability is developed at approximately 1,000 psi compressive strength. In 1964, Bell and Shore invalidated most of the conclu sions by the previous authors when they demonstrated that atmospheric pressure tests cannot be used to determine casing deformation and damage that will result from perforating under down-hole conditions.' They showed that the higher the hydrostatic pressure, the more restricted will be the expansion of gases generated by the charge. Less casing deformation and damage occurs under down-hole conditions than at atmospheric pressure. In recent work, Bearden et al. reported that jet perforating at surface pressure with the hollow carrier gun caused the cement sheath to shatter and crack.' The perforating, however, did not seriously affect the pressure required to leak past the casing cement bond. Only three cementing mixtures were tested, and presumably they had strengths in excess of 2.000 psi. Bearden et al. also reported that the hydraulic bonding strength increased as the compressive strength increased. Their hydraulic test showed that approximately 1,000 psi pressure is sufficient to break the casing cement bond for a well aged neat Portland cement sheath. Unfortunately, the tests were not run with a confining pressure, so Bearden et al. were merely measuring the strength of their outer 8%-in. casing. In our investigation, we measured the hydraulic bond strength of cement to pipe under a confining pressure and found that the bond strength was not limited to 1,000 psi. Cement Bond The bond strength is a good criterion for measuring the effectiveness of cement in performing its main function, that of preventing interzonal communication of fluids behind the casing. Measuring bond strength after perforating should be a good quantitative method of determining optimum cement properties, and should be a better method than that used by previous investigators,11 ' who simply observed the appearance of the cement after perforating.

Jan 1, 1969

By Paul F. Kerr, Raymond F. Robinson

Uranium mineralization occurs in the footwall of the Sunshine vein from the 2900 to the 3700 level. Veinlets of uraninite associated with pyrite and jasper have been so extensively divided and recemented that units more than a few feet in length are seldom observed. The wall rock is St. Regis quartzite of the Belt series. The age of the uraninite, on the basis of isotopic analyses, is 750 * 50, which agrees with geological data suggesting that phases of the Sunshine mineralization are pre Cambrian. THE Sunshine mine in the Coeur d'Alene district, Idaho, is well known for its silver-bearing veins but prior to the summer of 1949 had not been recognized as a possible source of uranium. At that time, during a geiger counter reconnaissance by T. E. Gillingham, R. F. Robinson, and E. E. Thurlow, high radioactivity was noted and radioactive specimens were collected from the footwall of the Sunshine vein.' The detection led to the identification of uraninite-bearing veins, since explored jointly by the Atomic Energy Commission and the Sunshine Mining Co. After the occurrence was noted, the geology of the uranium deposit was studied by the Sunshine staff, and a laboratory examination of the ores was conducted at Columbia University. Several types of laboratory work were undertaken. Differential thermal curves were made of selected siderite samples and results from many more were secured through the work of Mitcham.2 X-ray diffraction and X-ray fluorescence analyses were employed on uraninite, jasper, and siderite. Chemical analyses were made through the cooperation of the Division of Raw Materials of the Atomic Energy Commission. General Geological Features Several silver-bearing veins cut the overturned north limb of the Big Creek anticline as mapped by Shenon and McConne1,³ while the Osburn fault, a long-recognized regional feature about a mile away, marks the north boundary of the Silver Belt. The Sunshine vein, Fig. 1, has a south dip more or less parallel to the 60" axial plane of the fold and cuts rocks of the Belt. Series, starting with the Wallace formation near the surface, continuing downward through the St. Regis formation, and probably extending into the Revett quartzite which lies below the bottom or 3700-ft level. The limb of the anticline is locally modified by secondary folds, one being prominently exposed in the uranian area along the Jewel1 crosscut near the Sunshine vein. Crumpling of the limb resulted from compression which formed the anticline and probably preceded the faults in which the vein deposits accumulated. Evidence of drag along these faults points to reverse movement in the uranium-bearing area and elsewhere. This is true of major faults in the mine workings, and the majority of faults which can be mapped, as pointed out by Robinson.' The St. Regis formation, as measured in the mine, appears to have an initial thickness of some 2000 ft, but the apparent thickness due to thickening during folding is some 3400 ft. Along the Sunshine vein the purple and green rocks characteristic of the Wallace formation in the nearby Military Gulch section p. 37 of ref. 5) have been completely bleached because of introduced sericite. Hydrothermal solutions acting on the wall rock have substituted for the original color a pale greenish cast, although no pronounced mineralogical change has resulted, as Mitcham has observed.' The silver and the uranium depositions appear to belong to distinct epochs resulting from several periods of emplacement. Likewise, multiple periods of deformation account for the faulting. Uraninite is generally associated with silicification, while silver . mineralization accompanies carbonate veins. Rarely, uraninite may be found in a matrix of siderite. Ordinarily uraninite formed prior to ar-gentian tetrahedrite. Where clusters of veins form a stockwork, uraninite-jasper veins often favor one trend while tetrahedrite-siderite veins favor another. During deformation, brecciation of the St. Regis quartzite provided openings between broken rock fragments for precipitation from vein-forming solutions. Fractures due to major breaks were filled during the first stages of vein formation, while later deformation displaced the first veins and provided new channels along which further mineralizing solutions proceeded. The uraninite veins, as the first formed, have suffered fracturing, displacement, and segmentation. Uranian vein segments uncut by faults and more than a few feet in length are rare or nonexistent. Siderite veins are more massive and often extend without a break for tens and even hundreds of feet. In general they show much less segmentation. While the siderite is usually later, there is an overlap in the periods of deposition, some earlier siderite veins being extensively segmented in much the same way uraninite veins have been broken. Vein silica is more extensively distributed than the uranium and iron mineralization it carries. Along the vein course concentrations of uraninite frequently fade away and barren white quartz continues, the transition often occurring within a few feet along strike or down dip. An example appears on the 3700-ft level where a uraninite vein, see Fig. 2a,

Jan 1, 1954

By P. R. Sperry, M. L. Holzworth, P. A. Beck

The basic work of Z. Jeffries 1,2,3 has long ago established the main features of grain growth in the presence of a dispersed second phase. Working with sintered specimens of initially fine grained tungsten, to which various amounts of thoria had been added, Jeffries found that grain growth was inhibited, that is, practically prevented, up to a certain annealing temperature. When this temperature, which increased with the thoria content, was exceeded, extremely large grains developed abruptly from the fine grained matrix. such a a temperature" was later found by Gross-mann~3,14 in certain types of steel, while ~~i~ showed15 that in other steels grain growth was gradual, without inhibition and abrupt coarsening. Later work demonstrated the connection between coarsening and aluminum additions. The viewpoint that the direct cause of inhibition and coarsening in aluminum killed steels is a fine dispersion of aluminum oxide21 appears to be held quite generally, although some doubts have been voiced even very recently, 20 In steels with Ti additions the titanium carbide phase is considered responsible for the inhibition effects found.20 The coarsening temperature increases with the titanium content. That coarsening may occur, as a result of, certain heat treatments, even in low carboil rimmed sheet steel, was shown by Samuels. He also detected coarsening in a steel ingot of similar composition, after giving it the same heat treatment as that used by him for the sheet material. In this instance the identity of the inhibiting phase has not been determined. However, Tangerding found23 that even the few small carbide particles, which occur in carbonyl iron, have a very marked inhibitive effect. As a result of an oxidizing anneal at 850°C, large grains begin to form at the surface of the carbonyl iron specimen, and gradually grow inward as the subsurface oxidation of the carbide particles progresses and eliminates the obstruction. The carbide particles Can be removed also by annealing in hydrogen, with similar results. But if the oxidizing anneal of 10 hr at 850°C in air is followed between in hydrogen for 75 hr at the Same temperature, grain growth is more hibition usually the whole specimen is transformed into a single crystal (approx. 1.5 cm X 5 cm). The reversed procedure, that is, hydrogen annealing followed by oxidizing annealing leads to smaller grains. Tangerding arrived at the logical conclusion that there must have been in his specimens some additional obstruction to grain growth hibition from a minor impurity, other than carbon. It seems likely that this obstruction was caused by an oxide formed during the oxidizing anneal and gradually reduced rtain the subsequent hydrogen-annealing. Other instances of grain growth inhibition of varying severity, associated with a dispersed second phase, have been described by several authors. Notable examples: lead with 0.06 pet Cu or Ni,24 cartridge brass with 0.12 pct Cr,25 or with up to 0.15

Jan 1, 1949

By L. A. Geoffrion, R. H. Perkins, J. C. Biery

Densities of cerium metal and several lour-melting binary cerium alloys were measured over the range 25° to 800°C. A rolumeter, using NaK as working fluid, was used to obtain the data. The cerium, Ce-Co, Ce-Ni, and Ce-Cu alloys all exhibited an increase in density on melting, while a Ce-Mn alloy expanded on melting. FOR the proper design of a nuclear reactor, the change in density of the fuel with temperature must be known. This is especially important in a system utilizing molten fuel, such as LAMPRE (Los Alamos Molten Plutonium Reactor Experiment), since a relatively large change in density usually occurs during the solid-liquid transition. The fuel for LAMPRE is a Pu-2.5 wt pct Fe alloy with a melting temperature of 410°C. However, limitations in reactor design with this fuel have led to consideration of other plutonium-containing alloys for use in future generations of this type of reactor. Several ternary alloys containing plutonium and cerium as two components have satisfactorily low melting points. The system that at the present time appears to be most acceptable is Pu-Ce-Co; it exhibits little change in melting temperature with wide variation in plutonium concentration. Other alloys that have received some consideration contain nickel, copper, and manganese as the third constituent. The proposed fuel alloys are difficult to handle experimentally in the 25" to 800°C temperature range since they oxidize readily, react with many solvents, and contain a poisonous fissionable material. In addition, in this temperature range the alloys pass through the solid-liquid transition. Several techniques are available for measuring the densities and volume coefficients of expansion of solids or liquids. However, the only apparatus that appears suitable for measuring expansion coefficients over this temperature range and through the phase transition is a volumeter. In a volumeter, the indicating medium must be essentially inert to and insoluble in the material being studied. It must also possess a low vapor pressure over the operating temperature range, and its coefficient of expansion must be accurately known. One material that is satisfactory in nearly all of these respects is the alloy Na-78 wt pct K, which melts at -10°C and has a vapor pressure of 860 mm Hg at 800°C. This relatively high vapor pressure at 800°C requires an overpressure of an inert gas to prevent boiling. While a volumeter is capable of determining accurately the volume coefficients of expansion of materials, it cannot be used for absolute density measurements. Therefore, a density determination at a known temperature must be coupled with the volumeter measurements to give all the desired data. The weight-loss technique using immersion in bromobenzene at room temperature proved to be satisfactory. The preliminary work that was done on this experimental program involved developing and calibrating the equipment, and measuring the densities and volume coefficients of expansion of cerium and some low-melting binary cerium alloys. The complications that are caused with the introduction of plutonium into the system were avoided until the equipment was proved to be satisfactory and until experience was gained in its operation. It is this first phase of the experimental work that is described in this report. DESCRIPTION OF EQUIPMENT AND OPERATING PROCEDURE The NaK volumeter is shown schematically in Fig. 1. Basically, the equipment consists of two weld-sealed stainless-steel containers of nearly identical volume. One container holds a tantalum crucible and the specimen being measured; the other contains a tantalum crucible and a tantalum specimen used as a control reference material. To avoid temperature gradients, the bombs are located in a copper block inside the furnace. Stainless-steel capillaries of equal length and volume connect each stainless-steel container to a glass viewing capillary. The stainless-steel containers, stainless-steel capillaries, and a portion of the glass capillaries are filled with NaK (22 wt pct Na-78 wt pct K). The NaK/gas interface in the glass capillary is viewed with a cathetometer which is accurate to *0.5 mm. The cathetometer readings are used to calculate the volume changes of the samples during a run. This volumeter is basically the same as that described by F. Knight in Plutonium 1960. 2 However, changes in equipment design and operating procedure were made to eliminate some major operating difficulties. These changes are summarized below. 1) In filling the manometer with NaK, gas was frequently entrained in the system. Evacuation of the system before filling failed to eliminate the en-

Jan 1, 1965

By Henry Rawdon

ANY laboratory corrosion test, as judged from the practical point of view, is valuable only to the extent that it foretells what will, in all probability, occur in service. Such a test is most properly to be considered as a "pilot test, " that is, a test which indicates the direction along which action may be expected to occur rather than as a truly quantitative test which would be expected to tell just how and to what extent the action would proceed. It is generally recognized that laboratory corrosion tests should be chosen with particular reference to the character of service expected for any particular type of metal, so far as it can be foreseen. Even when this requirement has been fulfilled, however, the question whether the actual service behavior of the material is in accordance and general agreement with predictions based upon such laboratory tests is always a pertinent one. The information available in the technical literature bearing on the correlation between the service behavior of metals from the corrosion standpoint, and the results obtained with the same metals in laboratory corrosion tests is very meager, indeed. The results which have been obtained in weather-exposure tests of sheet duralumin which form the body of this discussion are presented here for their bearing on this particular phase of the problem of the corrosion resistance of duralumin. Although the exposure tests described have not been completed, in the sense that all of the tests, in the series initially laid down, have been accomplished, still the general trend shown by the results is so clear that a number of definite conclusions at this stage (subject, of course, to possible modification in the light of later results) are believed to be warranted. The tests reported upon here form one phase of the much broader study of this subject which has been under way for several years in which the National Advisory Committee for Aeronautics, the Bureau of Aeronautics of the Navy Department, the Army Air Corps and the Bureau of Standards have cooperated. Without the very helpful cooperation of the manufacturers in furnishing the

Jan 1, 1929

By H. L. Lovell, L. H. E. Weyher

Cyclones have been used successfully in the mineral industries to solve solid-liquid as well as solid-solid separation problems in the processing of fine particles. Substantial information is available about the operation of cyclones as thickeners, classifiers, and concentrators using a dense medium. However, very little is known about the operation of the cyclone as a fine coal concentrator not using dense medium. This application of the cyclone, namely to wash fine coal in water, requires that classification phenomena be minimized in order to arrive at an effective separation of the high density ash and sulfur-bearing mineral particles from the low density coal particles over a wide particle size range. The authors have investigated the role of feed pressure, orifice diameters, and vortex-finder length in the cyclone washing of fine coal (--1/4 in.) in water. The results of this investigation show that cyclone washing of fine coal in water is an effective unit operation particularly capable of reducing the inorganic pyritic sulfur content. The combination of hydrocyclones with complimentary equipment such as Sieve bends, shaking tables, and flotation units appears to be especially promising and may ultimately yield fine coal processing systems that could approximate the high recovery efficiencies of today's coarse coal cleaning circuits. In the future, fine coal beneficiation can be expected to receive even greater research emphasis as a result of increasing sulfur restrictions on all major coal markets. In a previous paper, work, conducted at the Pennsylvania State University, on the hydrocyclone washing of fine coal was discussed.' The initial evaluation based on that wo-rk demonstrated the feasibility of hydrocyclones as fine-coal cleaning devices, and in that previous paper selected test data were presented that showed in principle how product yield and assay respond to variations of the major cyclone operating variables. The present paper reports in greater detail on the findings and presents a comprehensive evaluation of the data as follows: (1) Hydrocyclone throughput rates were related to feed pressure and other variables by regression equations. These equations are compared with other capacity-vs.-pressure drop expressions taken from the literature on classification cyclones. (2) The flow ratio was found to be the most important variable for the separation of the solids. Control of this ratio through various cyclone operating parameters is discussed. (3) The data on the product yield as well as the ash and sulfur assays from the tests were evaluated by means of correlation and multiple regression analyses. Because size-classification phenomena cannot be suppressed completely in hydrocyclone washers, product yield and assay data are regressed against cyclone operating variables separately for different size classes. These equations then reveal how the interactions of the cyclone operating variables vary in terms of the separation for different size classes. (4) Density partitions from additional tests were analyzed by supplementing product-size analyses with sink-float analyses of the separated product size classes. The evaluation of these data show how classification phenomena affect separation by density. The results demonstrate in particular the feasibility of the hydrocyclone washer for removing pyritic sulfur from fine coal. In addition to these specific findings, the investigation points up the value, in general, of using hydrocyclone washers in combination with unit operations such as screening, table concentration, and flotation. In order to make optimum use of the hydrocyclone washers and work out the most effective combination of unit operations, it is important to have careful flowsheet analyses corresponding to the given feed and product requirements. Analyses of this kind are now possible by means of computer simulation of flowsheets and other operation research tools. INTRODUCTION Before proceeding with the detailed treatment and evaluation of our results, it will be useful to review the fundamental aspects of cyclone separators and also restate the experimental procedures and data handling employed in these studies. Review of Cyclone Fundamentals: AS shown in Fig. 1, the basic components of cyclones commonly used

Jan 1, 1970

By H. I. Aaronson, C. Wells

Configurations of ferrite crystals have been found in a plain carbon steel which appear to have resulted from the nucleation of new ferrite crystals at the interphase boundaries of previously formed crystals despite the high carbon concentrations which necessarily develop at these boundaries. This phenomenon has been termed sympathetic nucleation. An attempt has been made to reconcile the occurrence of sympathetic nu-cleation with current nucleation theory. THIS investigation is one of a series on the formation of proeutectoid ferrite from austenite. From the viewpoint of chemical composition, this reaction consists of the nucleation and diffusional growth of crystals of carbon-poor ferrite within a matrix of carbon-rich austenite. The austenite adjacent to the austenite-ferrite boundaries will be greatly enriched in carbon, approximately to the value of the y/(a + y) equilibrium curve or its metastable extrapolation at the temperature of transformation. Those areas of austenite appreciably farther removed from the growing ferrite, on the other hand, will be relatively unaltered in composition, especially at the earlier stages of transformation. Since rates of nucleation are considered to decrease exponentially with decreasing supersaturation,' the frequency with which ferrite nuclei appear at austenite-ferrite boundaries should be negligible in relation to that at which they form in other regions of the austenite. During this investigation, however, many groupings of ferrite crystals have been found which appear to have resulted from the nucleation of ferrite at austenite-ferrite boundaries. This phenomenon has been given the name of sympathetic 71.1tcleation. A number of micrographs of morphological configurations caused by sympathetic nucleation will be presented, after which an explanation for this reaction will be proposed in terms of current nucleation theory. Some of the structures to be considered are composed of bainite, an aggregate of ferrite and carbide, rather than of ferrite. Since ferrite and bainite differ only in that bainite forms under conditions which result in the nucleation of carbides behind the advancing austenite-ferrite boundaries,' it will usually be unnecessary, for the purpose of this paper, to distinguish between the two reaction products. All studies were performed on an electric furnace steel (obtained from the Vanadium Alloy Steel Co.) containing 0.29 pct C, 0.76 pct Mn, 0.25 pct Si, 0.005 pct P, and 0.007 pct S. The alloy was cast as a 150 Ib, 7x7 in. cross section ingot and forged into bars 2x2 in. in cross section. These bars were homogenized for 48 hr at 1250°C in an Endo-Gas atmosphere. The depth to which decarburization penetrated during this heat treatment was determined by chemical and microscopic analyses and the affected metal was removed by machining. Specimens for isothermal transformation studies were cut from the remaining material; most of these specimens were 1/2x1/4X1/16 in., though some with a thickness of 1/32 in. were prepared for use at the shorter reaction times and lower reaction temperatures. Specimens were austenitized for 30 min at 1300°C, isothermally reacted for various times at temperatures ranging from 775" to 475 "C, and then quenched in iced water. The austenite grain sizes within individual specimens ranged from ASTM Nos. 1 through —4. A commercial heat-treating salt which was continuously deoxidized by an immersed graphite crucible served to minimize the loss of carbon during austenitizing; thick covers of powdered graphite and immersed graphite rods effectively prevented decarburization in the lead pots employed for the isothermal reaction treatments. The heat-treated specimens were sectioned and mounted in Bakelite. Following the completion of standard grinding and mechanical polishing procedures, the specimens were electrolytically polished with a Buehler-Waisman apparatus and etched in 2 pct nital. Experimental Results Rules of Evidence for Sympathetic Nucleation—On the basis of observations made on a single plane of polish, one precipitate crystal may be considered to have been sympathetically nucleated at the inter-phase boundary of another precipitate crystal when the following conditions are fulfilled: 1) The sympathetically nucleated crystal is not in contact with a grain boundary or a subboundary in the matrix phase. 2) The shape, size, and location of the crystal at whose boundary sympathetic nucleation occurred (hereafter termed the base crystal) and the crystal formed by sympathetic nucleation substantially pre-clude the possibility that the plane of polish em-ployed may have concealed the fact that both crys-tals actually nucleated at a grain boundary or a sub-boundary in the matrix phase.

Jan 1, 1957

By Paul M. Tyler

Mineral raw materials, because they are essential to our industrial prosperity and military strength, must be made available in substantial quantities regardless of cost. Variations in the cost of procuring minerals, as compared with the cost of obtaining other commodities, and changes in the cost of production of different minerals relative to one another, will naturally influence the quantities of a given mineral item that can be marketed readily. However, in the last analysis, the cost of winning minerals from the ground usually constitutes only a small fraction of the value of the end-use products and services derived from them. The miner's share of the cost of a typewriter, telephone circuit, or even a modem office building, is almost insignificant. Far more important to the ultimate consumer, therefore, than any minor saving in cost is the assurance of ample supplies of the minerals needed to aliment our expanding economy. To create a successful metal mining operation involves (1 ) the discovery and systematic development of a mineral deposit, (2) extraction of the ore, (3) the mechanical and metallurgical processing to eliminate worthless or harmful impurities, and (4) the profitable disposal of the product. The fist step of the technological process belongs chiefly in the realm of the geologist, the second is a mining engineer's job, the third is mainly up to the millmen and extractive metallurgists; whereas the fourth and equally important step poses a commercial problem that has aspects in common with the marketing of other products. Ore finding is far from being an exact science. There is no mathematical criterion for evaluating the efficiency of prospecting and exploration. Lady Luck shares the honors or assumes part of the blame along with the prospector and geologist. Marketing like- wise involves factors that seemingly defy engineering analysis. Although the other steps can be measured with some degree of mathematical accuracy, even they tend to vary so widely in basic principle, as well as in

Jan 1, 1964

By K. L. Komarek, P. F. J. Landler

Synthetic polycrystals of wustite were reduced ilz H2-H2O mixtures over limited roncentration ranges wiltun the wustite. field and the weight changes were continuously followed with a McBain quartz spiral balance. The reduction was. found to be controlled by a combined surface plus solid-state diffusion reaction. The solid-state diffusion had an activation energy of 38 kcal. Self--diflusioities of iron decreased with itzcreasing vacancy concentration. The activation energy of. the surface reaction runs different tor- different samples. The surface reaction-rate constan increased with increasirzg vacancy concentration. THE reduction of the oxides of iron has been studied for many years. Edstroem' has summarized the early work and has provided much information on the reduction of magnetite and hematite by hydrogen and carbon monoxide. More recent summaries are those by smeltzer2 and Themelis and Gauvin.3 Most investigators have reported that the iron metal which forms the outer layer during gaseous reduction is rather porous. According to Kohl and Engel14 the formation of such a porous iron layer depends on the properties of the underlying wiistite layer, on the reaction of the gas with the wustite surface, and on the transport of matter through the wustite layer. McKewan, Quets, Wadsworth, and Lewis, and Knacke 10 have found that, if a porous iron layer is formed, a surface reaction between gas and wustite at the bottom of the pores controls the rate of reaction. Seth and ROSS 11 and Warner 12 have pointed out that the influence of the gaseous pore diffusion through the porous iron layer cannot be neglected. It has further been shown that the wiistite layer formed during reduction is dense and that transport of matter across the layer occurs only by solid-state diffusion of iron ions.13,14 The solid-state diffusion rates observed by Edstroem and Bitsianis 14 and the surface reaction rates observed by Quets eta1.' show that an interaction of the two steps in controlling the reaction rate has to be considered. In this investigation the reduction of wustite was studied with respect to the interaction of the two steps, isolated from any other effects, by reducing wustite within the wustite field from higher to lower oxygen concentrations with H2-H2O gas mixtures. A similar study with CO-CO2 mixtures has been performed by Levin and wagner.15 Fused synthetic wustite polycrystals were reduced in steps of 0.4 wt pct from 24.4 to 23.2 wt pct 0 and over a temperature range from 700" to 1050°C. A few tests were also conducted with reduction steps from 24.4 to 23.6 wt pct 0 and 24.5 to 23.2 wtpct0. The Fe-O phase diagram is shown in Fig. 1 where the composition of the gas phase in equilibrium with the condensed phases is plotted as pct H2 vs the temperature. A careful study of the literature led to the conclusion that the fully drawn equicomposition curves (in wt pct O) in the wustite field used by Edstroem 1,16 and other authors needed some correction. Based on results by Darken and Gurry17 (shown as open circles) and on some of our own data, four corrected curves for 23.2, 23.6, 24.0, and 24.4 wt pct O were calculated (drawn as dashed lines in Fig. 1) which should replace the fully drawn equicomposition curves. MATERIALS AND APPARATUS Materials and Specimen Preparation. Wustite was prepared from iron sulfate (Fisher Scientific Co., New York) which had a purity of over 99.92 pct, with small amounts of manganese, copper, and zinc adding up to 0.03 pct. From the aqueous solution iron oxalate was precipitated and decomposed to magnetite according to Economos. 18 The magnetite powder was pressed into cylinders and sintered in vacuum at 900°C for several hours. The sintered compacts were placed in a platinum crucible of 2.5 cm diam which was fitted into a high-purity alumina crucible and then inserted into the center of the graphite heating element of an electric resistance furnace.lg The furnace was evacuated to below 1 p Hg and the magnetite sample was slowly heated. The evolution of gases during heating deter-

Jan 1, 1967

By W. A. Nagel, R. P. Alger, H. Sherman, J. Tittmann

A sidewall epithermal neutron tool has been developed to substantially reduce environmental effects that have previously complicated neutron log interpretation. Designed for operation in uncased wells, the device provides increased accuracy in both liquid-filled and empty holes. A brief discussion of neutron moderation, diffusion and capture shows that logs using epithermal neutron detection depend on a smaller number of formation-characterizing parameters than those using thermal neutron or capture gamma ray detection. Thus, they come closer to providing an unambiguorls determination of hydrogen content. In this new device a directionally sensitive epithertnal neutron detection system has been incorporated in a side-wall source-detector skid to minimize borehole effects. The effects of variations in borehole size and shape, mud type, temperature and salinity are greatly reduced. Small residual borehole effects are then computationally accounted for in the surface control panel to provide a borehole-corrected neutron log. The log presents a direct recording of neutron-derived porosity on a linear scale. With corrections for borehole effects already applied, this direct recording of porosity simplifies log interpretation. Furthermore, comparison with a linear porosity presentation of a formation density log permits sandstones, limestones and dolomites to be readily identified. Thus, in complex or variable lithology, porosity is determined with greater accuracy and reliability than heretofore. Laboratory data and field results demonstrate the improvements in neutron logging afforded by this new side-wall epithermal neutron logging device. INTRODUCTION The new Sidewall Neutron Porosity (SNP) logging system, designed for use in uncased wells, provides reliability and accuracy never before achieved with neutron logs. The effects of variations in borehole diameter and shape, fluid salinity, mud weight and temperature—parameters that have long complicated neutron log interpretation— are suppressed or corrected for by this sidewall epithermal neutron detection system. Furthermore, to simplify interpretation the SNP log presents a direct recording of computed porosity on a linear scale. The performance improvements achieved by this new system arise primarily from the combination of two im- portant design features. First. though not unique to this new tool, an epithermal neutron detection system is used,',' Epithermal neutron detection substantially reduces the perturbing influences of the thermal neutron absorption properties of rock matrices and water salinity. Second, the neutron detection system is mounted in a directionally sensitive sidewall skid to greatly minimize borehole effects. The purpose of this paper is to explain briefy the advantages offered by the detection of epithermal neutrons, to describe the SNP equipment and the log, to present calibration and correction data and to give examples of interpretation methods made especially convenient by this new system. ADVANTAGES OF EPITHERMAL NEUTRON DETECTION Epithermal neutron detection, of all the neutron methods in current commercial use, provides the simplest determination of formation hydrogen content. Advantages of epithermal neutron detectors, as compared with thermal neutron and gamma ray detectors, are probably best explained by a brief review of the life of a source-emitted neutron. A fast neutron from the source will eventually be cap-tured by the nucleus of an atom. However. before capture is likely to occur, the fast neutron (energy of 100,000 electron volts (ev) or more) will be slowed down until it is in thermal equilibrium with its surroundings. The neutron is then considered to be a "thermal" neutron (average energy of 0.025 ev at 25C). The overwhelming majority of the slowing down thus occurs in reaching epithermal energies (energies just above thermal—0.5 to several ev). After reaching thermal energy. the neutron will "diffuse" through the formation with, on the average, no further energy change until capture. Upon the capture of the thermal neutron, relatively high energy gamma rays arc usually emitted. Hydrogen plays a very important role in the process of slowing down fast neutrons. On the other hand, the absorption effects of water salinity and low concentrations of other strong thermal neutron absorbers—relatively unimportant in the moderation process-—are very important in thermal diffusion, capture and the production of gamma rays. Thus, by detecting only epithermal neutrons with the SNP, spurious effects due to these thermal neutron absorbers are greatly minimized as compared to the effects on tools using thermal neutron or gamma ray detectors. The epithermal neutron detection system affords another important advantage. Log response in various litho-

Jan 1, 1967