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By James R. Holden, Frederick E. Wang

Through both single-crystal and powder X-ray diffraction methods, ten A6B23-type compounds have been confirmed to exist between lanthanides (A) (plus scandium and yttrium) and manganese (B); A = Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu. The formation of a compound of this type is shown to he extremely atomic size-sensitive; hence it can be classified as a "size-factorH compound. The "enveloping effect", a geometrical consideration observed in its crystal structure, is proposed as the reason for the A6B23-type compound being size-sensitive. The approximate ideal geometrical ratio of the radii R/r is 1.31 while experimentally A6B23-type compounds have a radius ratio lying within the range 1.2 to 1.4. FLORIO t al.' characterized the structure of Th6MnZ3 as fcc, space group Fm3m, with 116 atoms in the unit cell. Since then, a number of isotypic binary compounds, and recently Gd n,,' have been confirmed to exist. The fact that strontium and barium form A6Bz3-type compounds with magnesium strongly suggested the possible existence of Ba6Liz3. However, investigation3 showed the compound Ba6LiZ3 to be absent. Since both strontium and barium are group 11-a elements and are therefore "open metals",6 the nonexistence of Ba6LiZ3 can hardly be explained satisfactorily by valence-electron considerations. On the other hand, the consistent atomic-radius ratio, (R/r),* observed for the known A6Bz3-type compounds,3 strongly suggests that the formation of compounds of this type is atomic size-sensitive. Therefore, one is tempted to explain the nonexistence of Ba6LiZ3 entirely on the basis of the atomic-size difference between strontium and barium. However, this approach is not entirely without objection. Atoms are not rigid spheres and are known to vary in size within certain limits.7 Since the atomic-radius difference between strontium and barium (0.07 to 0.09A) is within these limits, it is reasonable to assume that the size difference would have a negligible effect on the formation of Ba6LiZ3. This view is further supported by the fact that the radius ratio, R/r, in other known "size-factor" compounds is observed to range widely—for example, from 1.08 to 1.45 for ABz-type compounds (C15, MgCuz type)' and from 1.37 to 1.58 for AB5-type compounds (D2d, CaZn5 type).g The present investigation was undertaken in order to find a more satisfactory explanation for the non-existence of Ba6LiZ3 and, consequently, a better understanding of the nature of the A6Bz3-type compound. The primary objectives are to confirm the previous conclusion3 that the A6B23-type compound is indeed a "size-factor" compound and subsequently to determine the atomic-radius ratio range in which the A6Bz3-type compound can exist. In order to achieve these objectives, stoichiometric A6Bz3 alloys, where manganese (B) was alloyed with various lanthanide elements (A), were selected for investigation. The atomic-radius ratios of lanthanide elements with manganese range from 1.26 for Lu/~n to 1.46 for Eu/Mn. This radius ratio range includes and exceeds the range of all previously reported A6Bz3-type compounds—1.32 for Th/Mn' through 1.38 for Sr/Li. Furthermore, the atomic-size difference between successive elements of the lanthanide series in order of atomic number) is of the order of 0.01A (europium and ytterbium are exceptions). The series of lanthanon-manganese alloy systems is ideally suited to a precise determination of the limits of allowable atomic-radius ratio for A6Bz3-type compound formation. EXPERIMENTAL PROCEDURE The lanthanide metals, in ingot form, supplied by Michigan Chemical Corp. (St. Louis, Mich.) and Nuclear Corp. of America (Burbank, Calif.), were guaranteed by the suppliers to be at least 99.9 wt pct pure (traces of silicon, calcium, and other minor constituents present on occasion, not to be more than 0.05 wt pct) as shown by spectrographic analysis. Manganese metal, in polycrystalline form, was redistilled from the commercial, chemically pure grade and was analyzed to be at least 99.95 wt pct pure. In all cases, the atom ratio between the two elements in each charge was A (rare-earth meta1):B (manganese) = 6:23 and a constant weight, 3 g, of

Jan 1, 1965

By S M. Roscoe

Relationships of Noranda sulphide deposits to volcanic rocks are reviewed and chemical variations within the volcanic sequence are described. The assemblages of minor elements in the pyrites and pyrrhotites of the Noranda and l\llatagami deposits are similar and are characterized by a high content of cobalt, tin and other elements. Isotopic compositions of lead, other geochronological data and stratigraphically disposed zonal distributions of sulphides and minor elements indicate that the deposits were formed prior to folding and metamorphism. Lead isotope data indicate that the Matagami deposits, and several others, were probably formed about 2.95 x 109 years ago and that the Noranda deposits may be about 50 million years younger. The volcanic sequence at Noranda is younger than the thick sequences bordering it on the east and on the west. The relationships are consistent with the hypothesis that these strata-bound sul1>hide de-posits are coeval with their associated volcanic rocks. T HE writer has been engaged in a metallogenic study of the region between Sault Ste. Marie and Chibougamau. An essential objective of this study is the classification of mineral deposits with regard to their composition, form, geological

Jan 1, 1965

By D. Y. F. Lai, R. J. Borg

Tracer diffusion of Fe59 has been measured in the a-stabilized Fe-1.8 at. pet V alloy from 700° to 1500°C. The activation energies are obtained in both the presence and absence of magnetic order. Furthermore, it is established that diffusion in the alloy is identical to that in pure iron and consequently the values of Do and Q accurately represent the temperature dependence for self-diffusion. The purpose of this investigation is to obtain an accurate estimate of the temperature dependence for self-diffusion in bee iron in both the presence and absence of magnetic order, and, in so doing, to establish the temperature range of the magnetic effect.&apos;" As the temperature interval suitable for diffusion measurements is severely limited in both bee phases of pure iron because of the intervening fee ? phase, the experiments were performed on an a-stabilized alloy containing 1.8 at. pet V. This alloy is bee over the entire range from room temperature to the melting point. Although there have been several independent investigations of self-diffusion of iron in a, iron,1, 3-6 there still exists considerable disagreement regarding the values of Do and Q for the paramagnetic region. The two systematic studies of diffusion in 6 iron6, 7 previously reported are also only in fair agreement; but in view of the extremely small temperature range available for diffusion studies, i.e., 1390o to 1535oC, this is not surprising. It is comparatively easy to obtain accurate values of Do and Q for the a-stabilized alloy inasmuch as measurements can be made over the entire temperature range -700o to 1500°C. However, in order to assume that these same values apply to pure iron requires careful comparison of the data in the a, and 6 regions in both the alloy and pure iron. We have made several measurements in the appropriate temperature ranges and are unable to establish any systematic difference between the diffusion coefficients of iron in pure iron and in the alloy. We therefore conclude that the values obtained for the alloy are truly applicable to pure iron; the complete evidence favoring this conclusion will be discussed later in this paper. EXPERIMENTAL The experimental methods will be given here only in barest detail since they have been thoroughly de- scribed elsewhere.l, 7 The alloy was prepared by induction melting and chill casting under argon. Diffusion samples were machined from the ingot and annealed in hydrogen for several days at 900°C to give an average grain diameter of 1 to 2 mm. The penetration profiles of the tracer were established by a sectioning technique, the residual activity being counted after the removal of each section. The tracer used is Fe59 which emits two high-energy ? rays of 1.098 and 1.289 Mev, respectively; these were detected by a ? scintillation counter equipped with a pulse-height analyzer. For the measurements in the temperature range -700o to 1130°C the samples were vapor-plated with Fe59, encapsulated in quartz under vacuo, and annealed in resistance-heated furnaces which are controlled to ±1°C. The specimens diffused at higher temperatures are prepared as edge-welded couples, the two halves being separated by a thin washer of the alloy to prevent sintering. The diffusion anneal is then carried out by inductive heating under a dynamic vacuum. The temperature is monitored pyrometrically. RESULTS The diffusion coefficients are obtained from the penetration profiles in the usual way using the error-function complement relationship. The results over the entire temperature range are shown in Fig. 1. In the linear region, 900o < t > 1500°C the least mean squares (lms) values of the diffusion coefficients are given by D = 1.39 exp[-(56.5 ± 1) x 103/Rt] cm2/sec [l] The average departure of the measured diffusion coefficients from the values given by Eq. [1]In order to determine whether or not the slope is truly constant over the entire range from 900" to 1500°C, the data are arbitrarily divided into two groups, the first containing values between -900" and 1133°C and the second between -1133o and 1500°C. The lms values for the two groups are given by Eqs. [2] and [3]: D = 0.519 exp[-55.7 x 103 /RT](900° to 1133°C) cm2/sec [2] D = 1.45 exp[-56.7x103/RT] (1133° to 1500=C) cm2/sec [3] Thus, there is no significant difference between the high- and low-temperature segments of the linear region. This not only assures us of the consistency of the values obtained by induction heating as compared to those obtained from the resistance-heated

Jan 1, 1965

By Jr. Norman

Thermoelectric properties of depleted uranium selenides and tellurides were investigated from room temperature to 700 C. Several depleted uranium monoselenides and monotellurides were doped with selected cationic and anionic materials to determine the effect of impurity additions on the thermoelectric properties. The undoped uranium selenides and tellurides were semimetallic conductors exhibiting low Seebeck coefficients and electrical resistivities. Partial or complete degeneracy was in evidence, indicating a charge carrier energy distribution similar to that in a metal. Doping increased the Seebeck coefficients of the uranium monoselenides and monotellurides; however, the corresponding change in the power factor in the figure of merit was small because of the increase in electrical resistivity.

Jan 1, 1965

By P. G. Shewmon

If interfacial equilibrium is maintained at the interface between a growing precipitate and the supersaturated matrix, so that solute diffusion alone determines the growth rate, the precipitate shape should evolve toward that characteristic of the dendrites found in solidification. However, this shape is rarely observed in precipitation reactions proceeding at high temperatures where interfacial equilibrium is usually felt to prevail. Thus some other stabilizing factor must enter, to keep the interface smooth. It is shown that a slow interfacial reaction (low interfacial mobility) will stabilize the interface, while transformation stresses have a IN studying the kinetics of phase transformations such as solidification or proeutectoid precipitation at high temperatures, it is customary to assume that equilibrium exists across the interface and that the rate of the reaction is determined by the rate at which heat and solute diffuse to and from the interface. In the case of precipitation, such an assumption predicts an almost infinite rate of initial growth. It is generally stated that the rate cannot be infinite and that during some initial period the rate must be determined not by solute diffusion but by an interfacial reaction, i.e., transferring atoms across the interface. The duration of this much weaker stabilizing eFfect and impurities tend to enhance instability. It is also concluded that a sets an upper limit on the wavelength of the perturbation that can give instability. Thus initially all flat or smoothly curved particle interfaces will be stable even if their growth is diffusion-controlled. Proeutectoid precipitation in the Fe-C system is considered in some detail and it is shown that the experimental results can only be rationalized if the growth rate of ferrite in steel transformations is determined by a slow interfacial reaction for all hut a few orientations between the two phases. initial period has never been clearly established, but it is generally assumed to be too short to affect any measurable results.&apos; Several authors have pointed out that in the case of interfacial equilibrium any bump in the surface will grow out ahead of the planar interface due to the higher gradient in front of it.2j3 Thus the interface will be unstable with respect to an irregular interface with points (plates) propagating rapidly out ahead of the interface into the supersaturated phase. Recently, Mullins and Sekerka have given equations for the stabilizing effect of surface tenion.~ They found that for particles with a radius of curvature of 1 p or greater the stabilizing effect of surface tension will be completely overcome by a supercooling, or supersaturation, of as little as

Jan 1, 1965

By E. F. Koch, J. L. Walter

oriented crystals of iron and iron with 3, 5, and 6.25 pct Si were rolled to reductions of 10 and 70 to 97 pct at room temperature. Similarly oriented crystals were deformed in tension. Dislocation substructures of the deformed crystals were observed by transmission electron microscopy to determine the effect of silicon on the formation of substructures. Pole figures were obtained to relate orientation changes to substructure. When rolled 10 pct, the iron crystals and the 3 pct Si-Fe crystals formed cells, 1 and 0.2 u in diameter, respecliuely. Cells were absent in the higher-silicon crystals. Extended dislocations and possible stacking faults were observed in the 6.25 pct Si-Fe crystal rolled 10 pct and annealed at 650°C. The stacking-fault energy was estimated to be 20 ergs per sq cm. Rolling to 70 pct resulted in the formation of sub-bands (0.9 µ wide) ill the iron crystals and transition bands (containing 0.2-µ-wide subbands) in the 3 pct Si crystals. No subbands formed in the 5 pct Si-Fe crystal until it was ankzealed. SliP occurred on (112) planes ill tension. The slip traces on the 3 pct Si crystal were wary while those on the 5 pct Si crystal wvere straight. The strain-hardening coefficient for the 5 pct Si crystal was nearly zero. Cells did not form, at least at elongations up to 10 pet. The results suggest that cross slip of iron is restricted by additions of silicon beyond about 3 pct possibly by formation of immobile extended dislocations. IN a previous paper&apos; the authors described the substructures developed in (100)[001]-oriented crystals of 3 pct Si-Fe which were rolled to reductions of 10 to 90 pct at room temperature. At low reductions (10 to 20 pct) cells, approximately 0.2 to 0.3 ja in diameter, were formed. The cell walls consisted mainly of edge dislocations. With increasing reduction (up to 50 pct) the cells were seen to elongate in the rolling direction. In certain regions of the crystal there were significant reorientations which were characterized as rotations about an axis normal to the (100) or rolling plane. These regions were called "transition bands". The regions in which there were no reorientations were called (&apos;deformation bands". At reductions of 60 to 70 pct the elongated cells in the transition bands became sub-bands separated by low-angle tilt boundaries with angles of disorientation of about 2 deg. The elongated cell structure in the deformation band was replaced by a general distribution of dislocations. It was noted that the width of the subbands in the transition bands remained 0.2 to 0.3 µ; i .e., the width of the subbands was the same as the initial cell diameter for reductions up to at least 70 pct. From this, and from considerations of the mechanism of formation of the transition bands,&apos; it was concluded that the subbands evolved directly from the initial cells. In order to check this conclusion, it was decided to examine the relationship between initial cell diameter and width of subbands produced by large rolling reductions. Cell size is known to be dependent upon the temperature of deformation.2,3 However, preliminary experiments with 3 pct Si-Fe crystals indicated that the change in cell size with increasing temperature of deform,ation was not sufficient for the present purpose. On the other hand, cell diameters generally reported for iron deformed at room temperature2&apos;3 range from 1 to 2 p, a factor of 3 to 10 larger than the cells in 3 pct Si-Fe rolled to 10 pct reduction,&apos; indicating the possibility of a marked dependence of substructure (at least in terms of cell size) on the amount of silicon in iron. Thus, the investigation was enlarged to include the study of the effects of varying silicon content on substructure in lightly rolled as well as in heavily rolled crystals of iron and iron with 3, 5, and 6.25 pct Si. The crystals used in this study all had the same orientation, (100)[001], with respect to rolling plane and rolling direction. These were rolled to reductions of from 10 to 97 pct and the substructures determined by electron transmission microscopy in both the rolled state and after annealing. In addition, stress-strain curves were obtained from (100)[001]-oriented crystals of iron and 3 and 5 pct Si-Fe to determine the effect of silicon on tensile properties. The dislocation substructure of the tensile specimens was also determined for Samples pulled to 2 and 10 pct elongation at room temperature for comparison with the substructures produced by rolling. 1) EXPERIMENTAL PROCEDURE Crystals with 3, 5, and 6.25 pct Si were prepared by annealing 0.012-in.-thick sheets of high-purity Si-Fe in purified argon at 1200°C to effect growth

Jan 1, 1965

By G. A. Crowder

Far infrared spectra, most of them in the region 15-200 microns and for both the liquid or solution state and for the vapor state, were obtained for twenty-seven compounds.

Jan 1, 1965

By C. G. Rhodes, D. Kramer

High-field critical transport current density (J) measurements at 4.2 °K as a Junction of applied magnetic field (H) were made on samples of cold-rolled and annealed columbium with H parallel to J. Microscopic examination of the samples revealed a well-defined planar fiber structure produced by the cold rolling. J was found to he lower when fibers are parallel to the direction of magnetic field penetration than when they are perpendicular. This effect may he a consequence of the interaction of flux movement with fiber boundaries. THE severe changes in microstructure brought about by cold working superconductors leads to profound changes in their superconducting behavior. In particular, the ability of a superconductor to carry a transport current with zero resistance (the maximum value of this current density will be called "J" in the presence of large external magnetic fields (to be referred to as "H") is greatly influenced by the microstructure. In the case of columbium, LeBlanc and Little1 and Autler et a1.2 have observed an increase in J due to cold work. LeBlanc and Little also observed an anisotropy in J in cold-rolled columbium strips, which Hake et al.3-6 have shown to depend upon the angle between H (H ? J) and the rolling plane. An increase in J due to cold work has been found in a variety of high-field superconducting alloys3&apos;4&apos;7-9 as has the anisotropy effect.10 First explanations of why cold work raised J invoked the idea that dislocations carried the high-field supercurrents,8,11 since cold working drastically increases the dislocation density and presumably the number of supercurrent paths. However, recent ideas on the nature of high-field superconductivity together with new experimental evidence reveal that the bulk of certain superconductors can remain superconducting in high fields while carrying high transport currents. These later developments have been discussed by Berlin-court and Hake12 and a comprehensive review has been prepared by Berlincourt.13 According to the ideas of Gorter14 and Anderson,15 one would expect that the influence of microstructure on high-field supercurrent density will depend on tine interaction between microstructure and penetrating flux and on the direction of the Lorentz

Jan 1, 1965

By R. H. Moore

The data for diffusion in dilute binary alloys with the Solvents Ag, Cu, Ni, Fe. Al. and Pb hare been correlated as a function of atomic volume. Linear equations of the form: Q = b - a log V are obtained with constants "a" and "b" ciuirac-teristic of each solvent metal. In most cases. 3-d In recent years measurements of diffusion coefficients in solid binary alloys. using small concentrations of radioactive isotopes. have resulted in accumulation of highly reproducible data. Such and 4-d transition elements correlate on separate straight lines from those which serve to correlate the non/ransition elements. The data for the uon-transilion elements diffusing in silver and copper liave been fitted by least-squares analysis. It is concluded that the size and charge effects which determine the magnitude of the activation energy for diffusion are a function of atomic volume. systems represent the simplest possible examples of chemical diffusion since solute interaction effects can be neglected and Kirkendall-like phenomena do not occur. Generally it is found that thc diffusion rate of the solute is within an order of magnitude of the diffusion rate of the solvent. The differences have been attributed to the effect of size and to electrostatic interactions between the solute and solvent atoms.

Jan 1, 1965

By Stephan Stecura

Crystallographic modifications and kinetics of solid-state phase trans-formations were determined for five rare-earth" sesquioxides--La2O3, Nd2O3, Sm2O3, Eu2O3, and Gd2O3. Oxides used for crystal modification studies were prepared by thermal decomposition of the following high-purity salts of the five rare-earth elements--carbonates, chlorides, fluorides, nitrates, oxalates, and sulfates. X-ray diffraction patterns of the cubic and hexagonal oxides were indexed by a graphical method and patterns of the monoclinic oxides by Ito&apos;s method. The kinetics of crystallographic transformation were determined by high-temperature X-ray diffractometry. The kinetic data were interpreted using a shrinking sphere model. All of the transformations followed first order kinetics. Activation energies were calculated by application of the Arrhenius equation. These solid-state phase inversions were concluded to occur by a reconstructive transformation mechanism.

Jan 1, 1965

By R. T. DeHoff, L. J. Buteau, J. Kronsbein

Network topology is introduced and used to describe sinter bodies at various stages of the sintering process. The matrices of incidence, loop-branch. tree-branch, and cut-branch are constructed and their relationship to the three-dimensional void space and the common two-dimensional bounding surface is established. The sintering body is assunzed to remain connected but this is not so with the void space. The topological invariants known as Betti numbers are related to this observed fact and provide parameters which measure the progress of the sintering process. They are extracted from the matrices by means of known algebraic operations. Experimental procedures are given which permit actual construction of the various matrices and determination of the Betti numbers by serial sectioning of the sinter bodies. A sinter body is produced by exposing a large number of metallic particles (0.00001 to 0.3 in. diam) to a temperature that is near but below their melting point. When these particles are maintained at such a temperature for a sufficient length of time, it is found that the interparticle contacts become welded. As time increases, these welds, often referred to as necks, grow. All of the space between the particles constitutes a single connected void; an ultimate consequence of sintering is the breaking up of the void into separated parts. A mathematical apparatus for describing the geometric characteristics of a sinter body at each stage of the process was first proposed by F. N. Rhinesl when he introduced the application of topology to this problem. He described the sinter body in terms of one of its topological invariants, the genus. The most important advantage of a topological description is invariance with respect to continuous deformations. This means that particle sizes and shapes need not be considered, resulting in considerable simplification and generalization of the geometric description. In the case of a sinter body, wherein the internal geometry is particularly complex, the simplification provided by topological concepts is absolutely essential. The important parameters in the Rhines model are the number of particles and the interparticle contacts. The invariant considered called genus is given by Euler&apos;s formula for the connectivity of two-dimensional surface of the sinter body. This surface includes the pore-solid interface. The Euler formula is G = C - P + 1 [1] where C = number of interparticle contacts, P = number of particles, and G = genus of the surface bounding the sinter body. In topology the term genus may be used to mean the number of self re-entrant cuts that can be made on a closed surface without dissecting it into more than one connected surface. Its use is restricted to the surface and does not apply to the three-dimensional volume enclosed or excluded by it. In the case of sintering, the volume enclosed by the surface is defined as the sinter body; the volume excluded will be referred to as the void space. There is an intrinsic reason for using genus as a characteristic number associated with a sinter body. The genus is related to the Gaussian curvature by the integral of the product of the principal curvatures taken over the entire surface of the sinter body, as given by

Jan 1, 1965

By M. J. Pool, J. R. Guadagno

THE relative partial molar heats of solution in liquid tin have been determined for phosphorous, arsenic, and antimony at 750°K. This work was carried out as part of an over-all program to determine the heats of formation of the III-V semiconducting compounds. A differential twin-type liquid tin solution calorimeter was used in the investigation. All three elements are endothermic upon solution in tin. The relative partial molar heats of solution go through a minimum value at arsenic. No concentration dependence of the heat of solution was found in the dilute (0 to 2 at. pct solute) solution range investigated. The measured heat effects and the calculated relative partial molar heats of solution at infinite dilution are listed in Table I along with the relative heat contents of the solutes calculated from the data of kelley.1 All of the values are referred to 750°K even though the calorimeter temperature fluctuated by *1°K during the course of the experiments. In this range of temperature change no variations were found which were outside the experimental error. This would be expected since the partial molar heat of solution is in general a very insensitive function of temperature. The limits of error given in Table I represent the standard deviation from the mean. The reported error estimates only apply to the estimated precision of the data and not the accuracy. Systematic errors could be present which would affect the absolute values given. This is especially true in the case of phosphorous and arsenic where vaporization could occur. If this were true, the experimental values reported here would be too high and the true partial molar heat of solution would be less than that given in Table I. Moreover, the heat-content data could be in error and this would also affect the calculated values. The relative partial molar heat of solution of phosphorous at infinite dilution in liquid tin is given in Table I. This value is based on eight drops at

Jan 1, 1965

By H. Guyod

The response of the Guard Electrode sonde (LL3) and the Laterolog (LL7) can be mathematically computed only for cases that do not represent realistic conditions. A resistance network analogue that simulates a number of typical—although idealized—formations was used instead to obtain, for both devices, a large number of resistivity logs and current distribution maps. From these data, charts were prepared for estimating true resistivities under a number of conditions. Some of these charts and current distribution maps are presented. INTRODUCTION Two main benefits are expected from a resistivity log: (1) obtaining geological information for mapping and other purposes, and (2) obtaining petrophysical data, based on true rock resistivity. The geological information can be derived from any resistivity curve having sufficient vertical detail, but true rock resistivities frequently are difficult to determine with desired accuracy because we do not have sufficient interpretation data. This is particularly true for the records given by the Laterolog tools. The object of this paper is to throw some light on the factors affecting the responses of these tools so that better resistivity data can be obtained from Laterologs. LATEROLOGS Laterolog measuring systems are of two types: the LL3 sonde, frequently called "Guard", and the LL7 sonde. Both measure the resistance between a single exploring electrode placed in the borehole and a faraway return electrode whose influence will be assumed here to be negligible. Although the principles of these tools have already been outlined,1-3 it is desirable to review them briefly in this article. LL3 Fig. 1, left side, represents a long cylindrical, vertical current electrode placed in a medium of uniform resistivity. The current leaving the center section of the electrode flows essentially along horizontal lines, delineating a surface having the shape of a biconcave lens. It is the elec- trical resistance offered to this particular group of current lines that is measured by the Guard tool. This is done in practice by having a long cylindrical electrode consisting of three sections physically and electrically separated by thin insulating washers, as shown in the center of the figure, and keeping the three sections at the same potential. It is obvious, for all practical purposes, that the current and potential distributions about this electrode are the same, as if we had a continuous electrode of same dimensions. Because the three sections are electrically separated, the resistance seen by the center section E can be independently measured. This section will be called the exploring electrbde, or E electrode. Its height generally is from a few inches to 1 ft. The outer sections are the guards G, which are several feet long. The combined length of the three sections is from 10 to 12 ft for the tools currently used in the petroleum industry. Let V denote the potential difference between E and the faraway return electrode, and I be the current flowing between these two electrodes. The resistance (Re) seen by the exploring electrode is VII, and the corresponding apparent resistivity is Ra = k(Re),............(1) where k is the tool calibration factor. The previous description establishes that the Guard tool uses that central portion of the sonde from which, in a uniform medium, the current follows essentially horizontal paths. When the formation being logged is fairly uniform, and when its resistivity is of the same order as

Jan 1, 1965

By Stanley R. Riggs

The rocks exposed in the phosphate district are of Neogene age and consist of clayey quartz and phosphorite sands overlying phosphatic dolomite. The Bone Valley Formation is redefined as a marine phosphorite containing primary phosphorite and abundant terrigenous sediments. It contains a Middle Miocene vertebrate and invertebrate fauna and conformably overlies the Hawthorn Formation containing similar invertebrate fauna. A new, unnamed formation, with Pliocene and Pleistocene fauna and containing reworked phosphorite, overlies the Bone Valley disconformably. Its phosphorite is derived from the subjacent Bone Valley by post-Middle Miocene erosion and deposition in stream channels and marginal marine environments. The Bone Valley contains two main types of primary marine phosphorite. Orthocbemical phosphorite, a direct precipitate of microcrystalline phosphorite (microsphorite), occurs as a cement or binder in thin beds. Allochemical phosphorite consists of clastic phosphorite particles that were originally formed as microsphorite on another part of the shelf. Microsphorite was deposited in a very shallow open marine environment which had an abnormally high phosphorous content caused by upwelling currents. The mechanism of deposition is still in doubt, but organisms probably were a major factor. Soon after deposition, microsphorite was indurated, periodically torn up, and the resulting fragments transported and deposited elsewhere on the shelf. These processes account for a great portion of the clastic phosphorite in the Miocene deposits of Florida. The primary fossil skeletal material is of minor importance.

Jan 1, 1965

By L. Burris, G. A. Bennett, P. A. Nelson

Staznless steels ave rrzuch less seuel-ely attacketl by zinc lapov than by molten zinc systems. To determine the applicubility of stainless steels fov equipment items which would be exposed only to zinc vapor, the corvosion resistance of several stainless steels to zinc vapor was investigated in 500-hr- exposuves at 900° C. Two austenilic stainless steels, Types 304 and 3-17, suffered severe intergranular attack. Loss of nickel from these steels and micro-probe crnalyses indicated the probable formation of low-melting zinc-rich phases. Good vesistance to attack by zinc vapor, as determined by metallo-9-rpaphic excr)rtination and physical testing, Loas exhibited by Type 405 stainless steel, a jevvitic steel. Type 440C stainless steel, a tnartensitic steel, although suffering considevable loss in weight, was not structurally weakened. At Argonne National Laboratory liquid zinc and zinc-rich alloys are being employed as solvent media in pyrometallurgical processes under development for recovering and purifying discharged reactor-fuel materials.&apos; Because of the high solubility of most metals in liquid zinc,&apos; there are few metals which can serve as container materials for liquid zinc at temperatures much above the melting point. The poor corrosion resistance of the common metals and alloys to molten zinc has been discussed by Eldred.3 DeKany, Lavendel, and Burris4 tested some of the less-common alloys of the nonrefractory metals and found that they also have poor resistance to attack by liquid zinc and Zn-Mg solutions. Of the metallic materials, only some of the refractory metals such as tantalum, tungsten, and molybdenum and their alloys have shown resistance to attack by liquid zinc.4-7 In the process-development work at Argonne National Laboratory, tantalum and tungsten vessels have been used to hold liquid-zinc alloys. These vessels are housed in stainless-steel equipment, principally to permit maintenance of an inert atmosphere and operation at various pressures. In this experimental work, it has often been observed that Type 304 stainless steel suffers little attack by zinc vapor at temperatures up to about 800 °C. In contrast, severe attack occurs in areas where zinc condenses as a liquid. The extent of attack by zinc vapor on several stainless steels was investigated because there are possible useful applications of stainless steel for equipment items which would be exposed only to attack by zinc vapor. These applications include, for example, housings around processing equipment as indicated above and vapor lines leading from zinc stillpots or retorts to condensers. EXPERIMENTAL EQUIPMENT AND PROCEDURE The experimental procedure consisted in exposing stainless-steel test coupons to static zinc vapor for 500 hr at a temperature of about 900°C. The apparatus, shown in Fig. 1, consisted of a 12-in.-long closed tantalum tube jacketed in Type 304 stainless steel to prevent oxidation of the tantalum. A Zn-10 wtpct Mg* alloy charge of 293 g in the bottom of the

Jan 1, 1965

By P. W. Bennett, E. M. Elkin

A new technique for the recovery of palladium and platinum and sludge from go12 electrolyte eliminates many of the drawbacks of the zinc-dust cementation process. In the electrolytic refining of gold by the Wohwill method, the electrolyte contains about 100 gpl gold as AuCl, and 100 gpl free hydrochloric acid. Any palladium and platinum contained in impure gold dissolve and accumulate in the electrolyte. When their concentration approaches that of gold, it becomes desirable to discard the electrolyte and to recover the gold and the palladium and platinum. As practiced at Canadian Copper Refiners until recently, discarded electrolyte was treated with sulfur dioxide to precipitate the gold. 2AuCl3 + 6H2O + 3SO2 —2Au + 6HC1 + 3H2SO4 The gold precipitate was filtered off, washed with water, and melted with scrap anodes. The wash water was added to the gold-free filtrate and treated with zinc dust to cement the palladium and platinum. PdCl2 + Zn — Pd + ZnCl2 PtCl4 + 2Zn—Pt + 2ZnCl2 The precipitate was separated and sold as Pd-Pt concentrate, and the barren filtrate and wash water were discarded. The receipts of palladium and platinum at this company were too small to warrant their refining. The process suffered from a number of disadvantages. Handling the gold-free solution was disagreeable, as it was laden with sulfur dioxide even after blowing with air overnight. Subsequent treatment with zinc dust was also troublesome. A large excess of zinc dust was required. Spray, acid mist, and vigorous evolution of hydrogen accompanied the reaction. The Pd-Pt precipitate was grossly contaminated with occluded unreacted zinc and with yellow granules of sulfur, thought to be formed by the reduction of sulfur dioxide and its derivatives. Repeated boiling of the precipitate with hydrochloric acid and washing with water decreased somewhat, but did not eliminate, the zinc. After drying overnight, the precipitate hardened to a clinkerlike mass that was difficult to grind. Grinding, handling, and packing created heavy dusting. Even weighing in an analytical balance generated dust, indicating that the powder was easily charged with static electricity. The total palladium and platinum content of the powder varied from 56 to 72 pct, with an average of 65 pct. The powder dissolved in aqua regia with difficulty, leaving a small amount of insoluble residue. However, the main drawback of the process was the strongly hygroscopic Pd-Pt product. The powder showed a marked though erratic increase in weight and a corresponding decrease in assay on exposure to air, even during the course of laboratory analysis. Such changes were the source of disagreement between Canadian Copper Refiners and the buyers of concentrate. The cause of the change in weight is believed to be hydrogen, liberated by the action of zinc dust on hydrochloric acid. Some of this hydrogen was adsorbed so strongly by the precipitate that it could not be driven off during the drying. On exposure to air it oxidized catalytically, forming water. Experiments soon showed that the entire process of treatment of discarded electrolyte then in use would have to be changed. A small quantity of apparatus was moved into the gold room, and experimentation was held to a minimum compatible with the development of a new process. PALLADIUM AND PLATINUM PRECIPITATION It was thought that zinc could be replaced with a reagent other than a hydrogen-evolving metal. Semiquantitative experiments showed that platinum and palladium could be precipitated completely from the gold-free solutions with such well-known reagents as sodium formate, formic acid, formaldehyde, and paraformaldehyde. Sodium formate was the preferred reagent, since the other three are volatile and somewhat toxic. The gold-free solutions used were those saturated with sulfur dioxide, partly freed of sulfur dioxide by aerating overnight, completely freed by boiling, as well as strongly and weakly acidic, neutral, and alkaline solutions. The reactions are complex and can be represented by these over-all equations: PdC1, + HCOONa — Pd + NaCl + HC1 + Co2 PtCl4 + 2HCOONa — Pt + 2NaCl + 2HC1 + 2CCX, Strongly acidic solutions required as much as five times the theoretical amount of sodium formate as did solutions neutralized to pH 4.5. Increasing the pH decreased the consumption of

Jan 1, 1965

By F. O. Jones

The capabilities of small proportions of divalent cations, such as calcium or magnesium, for controlling clay blocking are reported. Potentially sensitive formations can be exposed to fresh water if at least one-tenth of the salts dissolved in both the native water and invading fresh water are calcium and magnesium salts. Often, even less suffices. The behavior evidently depends upon the cation exchange properties of the clays, which favor adsorption of calcium and magnesium over sodium. Clays having sufficient adsorbed calcium and magnesium resist dispersion by water and consequent blocking of permeability. An allied phenomenon, the dependency of clay blocking on salinity contrast, is also reported. Abrupt change from highly saline to fresh water can cause blocking which may not occur if salinity is lowered slowly. A process related to osmosis is thought responsible for this behavior. Applications of findings to drilling, fracturing and water flooding are discussed. INTRODUCTION Many formations, when exposed to fresh water, can lose permeability through clay effects.&apos;,&apos; For example, drilling-mud filtrate can cause oil permeability decreases, which persist long enough to interfere with drill-stem testing and well completion.3 Ultimate productivity may suffer when clay damage is severe, especially if drawdown pressures are low.&apos; The injection pressures and the time required for water flooding can increase if clay blocking occurs. Earlier work indicates that clay blocking is caused by obstruction of flow channels by clays or other mineral fines dispersed by fresh water.&apos;!" It is well known that increasing salt concentrations in water tends to prevent clay blocking. Also it is well established, although perhaps not as widely known, that the nature of the dissolved solids is also important. If, for instance, formation clays are exposed to calcium chloride solution and then exposed to weaker solutions of calcium chloride or distilled water, considerably less permeability damage results than if the clays had been exposed instead to sodium chloride solutions. The reasons for this behavior are: (1) clays are cation-exchange, or base-exchange, materials similar in this respect to zeolites or exchange resins, and (2) clays in the calcium form do not disperse easily in fresh water, whereas clays in the sodium form do. The base-exchange form of a clay is easily altered by flowing a solution through it. For example, a sodium clay can be changed to a calcium clay simply by passing a calcium chloride solution through the clay bed. There is general agreement that the reason calcium and magnesium clays do not disperse easily in fresh water is because the calcium ions do not ionize easily from the clay surfaces.&apos; Sodium clays, however, are believed to allow the sodium ions to ionize from the clay particle surfaces. In fresh water, this allows the particle to accumulate a net negative electrical charge great enough for the particles to repel one another and, therefore, disperse more easily. The foregoing suggests that, even in the presence of a large excess of sodium, a relatively small ratio of divalent cation, such as calcium or magnesium, might serve to prevent clay dispersion. The divalent ion probably adsorbs to a disproportionately large extent, because of being adsorbed more tightly, with the result that the proportion of divalent cation on the exchange positions of the clay might then be great enough for the clays to resist dispersion. Consequently, an investigation was conducted to find how mixtures of salts in solution influence clay blocking. APPARATUS AND PROCEDURE Water permeability tests were conducted using conventional techniques. The equipment is illustrated schematically in Fig. 1. Flow rates of solutions driven through small core samples at known temperatures and pressures were measured. Regulated compressed air, usually at 10 to 15 psig, was used to drive the solutions. Core samples 0.75 in. in diameter and 1 in. long were used for the most part. Cores were saturated by evacuating and then admitting a de-aerated solution. Tight core samples were first saturated with carbon dioxide gas and then evacuated and saturated with the test solution. After saturation, 140 psig pressure was imposed for several hours. Cores were tested to insure absence of gas saturation by a Boyle&apos;s

Jan 1, 1965

By J. E. Sandor, P. F. Schmidt

A general review of the present knowledge of the semiconductor/oxide interface is given, with emphasis on silicon and germanium. The electrical properties of clean surfaces and the changes that occur upon oxidation are described. A brief disczcssion of the methods and mechanisms of oxidation of silicon is given, and the interaction between the semiconductor substrate and the oxide phase is considered. Physical properties of the oxide film, charge storage effects due to the dielectric, and some device applications of oxide films on semiconductors are discussed. THIS paper will be heavily preoccupied with the elemental semiconductors germanium and silicon. Undoubtedly some injustice is done thereby to other semiconductor-oxide systems, but it is not readily possible to cover all aspects of so vast a field in the present review. In considering the semiconductor/oxide interface, we may start out by discussing briefly an idealized clean semiconductor surface, and may then follow the changes brought about by oxidation, as the oxide is allowed to grow progressively thicker. The references given are not a complete list, but are to be taken as guides to the literature. Tamml suggested in 1933, based upon the study of a one-dimensional asymmetrical potential model, that localized surface states may appear at the surface of a crystalline lattice; it was pointed out by Fowler that these states should occur in pairs. shockley3 examined the origin of such surface states on the basis of a more general one-dimensional model and found that surface states may appear in the forbidden region between the highest filled and the lowest vacant band. This happens when the two bands overlap, as, for instance, the "s" and (&apos;p" bands of the diamond structure. In a three-dimensional model these levels would produce a surface band which is half-filled for diamond, and the number of surface states should be approximately equal to the number of surface atoms. This picture of the surface has been refined by more recent theoretical work, like Handler&apos;s4 and Koutecky and Tomasek&apos;s~ without introducing essential modifications. When these concepts were applied to semiconduc-

Jan 1, 1965

By J. B. Cheatham, J. W. McEver

A laboratory investigation of the behavior of casing subjected to salt loading indicates that it is not economically feasible to design casing for the most severe situations of nonuniform loading. When the annulus is completely filled with cement, casing is subjected to a nearly uniform loading approximately equal to the overburden pressure, and, although the modes of failure may be different, the design of casing to withstand uniform salt pressure can be computed on the same basis as the design of casing to withstand fluid pressure. Failure of casing by nonuniform loading in inadequately cemented washed-out salt sections should be considered a cementing problem rather than a casing design problem. INTRODUCTION Casing failures in salt zones have created an interest in understanding the behavior of casing subjected to salt loading. The designer must know the magnitudes and types of loading to be expected from salt flow and he must be able to calculate the reaction of the casing to these loads. In the laboratory study reported in this paper, short-time experimental measurements of the load required to force steel cylinders into rock salt are used as a basis for computing the salt loading on casing. These results must be considered to be qualitative only since rock salt behaves differently under down-hole and atmospheric conditions and also may vary in strength at different locations. The beneficial effects of (1) cement around casing, (2) a liner cemented inside of casing, and (3) fluid pressure inside of casing in resisting casing failure are considered. ROCK SALT BEHAVIOR UNDER STRESS The effects of such factors as overburden loading, internal fluid pressure, and temperature on the flow of salt around cavities have been studied extensively at The U. of Texas. Brown, et al.1 have concluded that an opening in rock salt can reach a stable equilibrium if the formation stress is less than 3,000 psi and the temperature is less than 300°F. At higher temperatures and pressures an opening in salt can close completely. These results indicate that calculations based upon elastic and plastic equilibrium for an open hole in salt should be applied only at depths less than 3,000 ft. In most oil wells the tem- perature will be less than 300F in the salt sections, therefore no appreciable temperature effects are anticipated. Serata and Gloyna2 have reported an investigation of the structural stability of salt. .They assume that the major principal stress is due to the overburden. Other stresses can be superimposed if additional lateral pressures are known to be acting in a particular region. In the present analysis an isotropic state of stress is assumed to exist in the salt before the hole is drilled, since salt regions are generally at rest. This assumption is partially verified from formation breakdown pressure data taken during squeeze-cementing operations in salt. Experimental measurements of the elastic properties of rock salt indicate a value of 150,000 psi for Young&apos;s modulus and a value of approximately 0.5 for Poisson&apos;s ratio. A value of % for Poison&apos;s ratio with finite Young&apos;s modulus would indicate that the material was incompressible. Values ranging from 2,300 to 5,000 psi have been reporteda for the unconfined compressive strength of salt. These variations may be due to differences in the properties of the salt from different locations or at least partially to differences in testing techniques. Salt is very ductile, even under relatively low confining pressures. For example, in triaxial tests reported by Handin3 strains in excess of 20 to 30 per cent were obtained without fracture. When casing is cemented in a hole through a salt section, the casing must withstand a load from the formation if plastic flow of the salt is prevented. To determine the forces which salt can impose on casing, circular steel rods were forced into Hockley rocksalt with the longitudinal axis of the rods parallel to the surface of the salt. The force required to embed rods 0.2 to I in. in diameter and 1/2 to 1 in. long to a depth equal to the radius of the rods was found to be F/DL =28,700 psi (± 3,700 psi) , .... (1) where D is the diameter, and L is the length of the rod. CASING STRESSES Since an open borehole through salt at depths greater than 3,000 ft will tend to close, cemented casing which prevents closure of the hole will be subjected to a pressure approximately equal to the horizontal formation stress after a sufficiently long time. As a first approximation the horizontal stress can be assumed to be equal to the overburden pressure. This is in agreement with the suggestion by Texter4 that an adequate cement job can prevent plastic flow of salt and result in a pressure on the casing approximately equal to the overburden pressure. He also advocated drilling with fully saturated salt mud

Jan 1, 1965

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