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By L. Russell, van Wert

During an investigation in which the solubility relations of the phases in Muntz metal (60 per cent. copper, 40 per cent. zinc) were under study, certain phenomena that had no immediate connection with the main problem were observed, which were thought sufficiently interesting to study further. Because of lack of time, only a preliminary survey was made of two of these; namely, the cleavage structure developed under certain conditions in a 60:40 brass and abnormal grain growth in this alloy. Cleavage Structure in Heat-treated Muntz Metal Carpenter noted many years ago that cold-working a brass of the Muntz metal type, which had been quenched previously from within the beta field, results in a partial breakdown of the supersaturated beta solution and the precipitation of the solute (the alpha solution) in the cleavage planes of the beta grains. This manner of rejection of a solute from a metastable solid solution is not peculiar to this particular alloy, for among others, it occurs in the cold-working of certain austenitic steels; for example, the austenitic nickel steels. In these ferrous alloys, cold deformation produces a partial decornposition of the austenite, with the formation of martensitic "needles" and zigzags in the austenitic poly-hedra. It is interesting to note that while the two solid solutions— austenite and quenched Muntz metal— are metastable and in their mode of decomposition behave quite alike when deformed in the cold, the metastability of each results from a different cause; viz., that of the austenite from the fact that it is a supercooled solution (its solvent. gamma iron, at ordinary temperatures is below its normal stable range whereas the metastability of the quenched Muntz metal is the result of supersaturation. When a 60:40 brass is quenched from above 800" C.—that is, from within the field where the beta phase alone is stable—this solution is retained practically intact and the alloy so cooled is found to consist almost entirely of polyhedra of this solution with only a little alpha present ordinarily at the boundaries of the beta grains—the result of a slight

Jan 1, 1929

By K. J. Gill, P. Chiotti, J. T. Mason

Thermal, metallographic, and vapor pressure data were obtained to establish the pkase boundaries and the standard free energy, enthalpy, and entropy of formation for the compounds in the Y-Zn system. Three coinpounds with stoichiometric formulas of YZn, YZn2, and Y2Zn17 melt congruently at 1105", 1080°, and 890°C, respectively. Four compounds with stoiclziometric formulas of YZn3, YZn4, YZn5, and YZn,, undergo perztectic reactions at 905", 895", 870º, and 685ºC, respectively. Three eutec-tics exisl in this system with the .following eutectic temperatures and zinc contents in wtpct: 875ºC, 23.2 Zn; 1015ºC, 51 Zn; 865ºC, 82 Zn. The YZn, pkase undergoes an allotropic transformation. In the two phase YZn2 -YZn alloys the trans.formation gives a weak thermal arrest at 750°C, whereas in the two phase YZn2-YZn3 alloys no thermal arrest is observed and the transformation occurs over a temperature range below 750°C. At 500°C the free mzergies of formation per lnole vavy from —18,090 for YZn to —53,430 fov YZr11 and corresponding enthalpies vary from -24,050 to -92,080. The free energies and enthalpies per g atom as a function of composition show a maximum for the YZn2 phase; the 500°C values are -9580 and -13,180, vespectively. 1 HE only information found in the literature on Y-Zn alloys was the observation reported by Carlson, Schmidt. and speddingl that Y-20 wt pct Zn forms a low melting alloy. The alloy was produced by the bomb-reduction of YF3 and ZnF2 with calcium in an investigation of methods for producing yttrium metal. The solubility of yttrium in zinc has been determined by P. F. woerner2 and reported by Chiotti, Woerner, and Parry.3 In the temperature range 495" to 685°C the solubility may be represented by the relation In these equations N represents atom fraction of yttrium and T is the temperature in degrees Kelvin. The purpose of the present investigation was to establish the phase diagram for the Y-Zn system and to determine the standard free energy, enthalpy, and entropy of formation for the compounds formed. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in the preparation of alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory yttrium sponge. Arc-melted yttrium buttons contained the following impurities in parts per million: C-129, N-12, 0-307, Fe-209, Ni-126, Mg-13, Ca < 10, F-105, and Ti < 50. Some of the alloys containing 70 wt pct or more of Zn were prepared from yttrium containing 5000 ppm Ti as a major impurity. Tantalum containers were found to be suitable for all alloys studied and were used throughout the investigation. The pure metals, total weight about 30 g, were sealed in 1 in. diam tantalum crucibles by welding on preformed tantalum covers. A 1/8 in. diam tantalum tube was welded in the base of each crucible for use as a thermocouple well. Welding was done with a heli-arc in a glove box which was initially evacuated and filled with argon. The sealed crucibles were enclosed in stainless steel jackets and heated in an oscillating furnace at temperatures up to 1150°C. Homogeneous liquid alloys were obtained within a half hr at these temperatures except for alloys containing less than 20 pct zinc. The latter alloys were held at 1000º to 1100°C for 2 to 3 days in order to obtain equilibrium. After the initial equilibrations the tantalum crucibles containing the alloys were removed from the steel containers and used directly for differential thermal analyses. Further annealing heat treatments for alloys in which peritectic reactions were involved were carried out in the thermal analyses furnace. After thermal analyses the tantalum crucibles were opened and the alloys sectioned and polished for metallographic examination. In the following discussion alloys referred to as "quenched" were obtained by quenching the sealed stainless steel jacket containing the tantalum crucible and alloy in water. The differential thermal analyses apparatus used was a modified version of the one described in an earlier paper., The graphite crucible was replaced by an inconel crucible, the nickel standard and sampie container were separated by a 1/8 in. MgO plate, no getter was used, and provisions were made to

Jan 1, 1963

By N. M. Levine, W. M. Fassell

In this laboratory study the problem of aerative conditioning to separate chalcopyrite and pyrite from cobaltite was simply effected with a sulfy-drate collector and pH by proper choice of mixing variables. It was shown that for a given impeller type and geometry, selectivity is governed by a relation between the Froude number and a modified power number multiplied by impeller tank-diameter ratio wherein the power factor is expressed as power intensity or horsepower per unit volume of contained pulp. In applying this approach to other systems, other criteria would be used in place of selectivity. The purpose of this paper is to show how solutions to problems of aerative conditioning of pulps may be enhanced by development of mixing parameters in a given system through application of a fundamental approach to agitation. The term aerative conditioning refers to a combination of processes which include mechanical gas dispersion, gas solution in the liquid phase, transport of dissolved gases and other reactants to the reaction zone, physico-chemico interaction within the liquid phase and/or at the solid surface, and, finally transport of products away from the reaction zone. Important elements of these processes are: 1) Air-Liquid Contact Area: This area limits the rate at which a given gas may dissolve in a given liquid. Thus, an aerative conditioning system should be designed for optimum gas dispersion. 2) Diffusional Factors: Such factors as concentration gradient, diffusion film thickness, and diffusivity may govern the rate at which dissolved constituents are transferred to the zone of interaction at a particle surface and the rate at which reaction products are transported therefrom. Thus, such systems would be designed for maximum turbulence to effect good mixing and to minimize diffusion film thickness. 3) Solids-Turbulent Liquid Contact Time: Sufficient time should be provided for interactions to take place at solid-liquid interfaces. The region of maximum turbulence for mechanical systems being in the impeller zone, it is important that the number of passes through this zone be optimized. This means that a proper balance should be struck be- tween flow and turbulent power to achieve optimum conditioning time. Too high a flow rate and insufficient turbulence may be improper if the reactions are diffusion limited. On the other hand, too much turbulent power and too little time in the reaction zone due to insufficient flow power may also be limiting. 4) Geometry and Impeller Design: The design of the conditioning vessel and the type of impeller employed are important factors in determining the relative distribution between flow and turbulent power and the degree of gas dispersion. Maximization of power input would be to no avail if the distribution between flow and turbulent power were improper or gas dispersion insufficient. 5. Physical Chemistry: The reactions between dissolved gases and solid surfaces may be limiting if gas solubility, activation energies and/or free energies are not favorable. J. H. Rushton, E. W. Costich, and H. J. Everett&apos; have summarized the mechanical elements of the combination of processes listed in a fundamental mixing equation. This equation was derived by dimensional analysis and relates the physical variables for a single impeller, centered in a cylindrical, vertical axis, flat-bottomed tank. It is, where T is tank diameter in feet; H is liquid depth in feet; C is height of impeller off tank bottom in feet; S is pitch of impeller; L is length of impeller blades; W is width of impeller blades; R is number of baffles; D is impeller diameter in feet; Np is the power number, pg/dN3D5; P is power in foot-pounds per second; g is the gravitational constant, feet per second; J is width of baffles; B is number of im-

Jan 1, 1961

By van Wert, L. Russell

During an investigation in which the solubility relations of the phases in Muntz metal (60 per cent. copper, 40 per cent. zinc) were under study, certain phenomena that had no immediate connection with the main problem were observed, which were thought sufficiently interesting to study further. Because of lack of time, only a preliminary survey was made of two of these; namely, the cleavage structure developed under certain conditions in a 60:40 brass and abnormal grain growth in this alloy. Cleavage Structure in Heat-treated Muntz Metal Carpenter noted many years ago that cold-working a brass of the Muntz metal type, which had been quenched previously from within the beta field, results in a partial breakdown of the supersaturated beta solution and the precipitation of the solute (the alpha solution) in the cleavage planes of the beta grains. This manner of rejection of a solute from a metastable solid solution is not peculiar to this particular alloy, for among others, it occurs in the cold-working of certain austenitic steels; for example, the austenitic nickel steels. In these ferrous alloys, cold deformation produces a partial decornposition of the austenite, with the formation of martensitic "needles" and zigzags in the austenitic poly-hedra. It is interesting to note that while the two solid solutions— austenite and quenched Muntz metal— are metastable and in their mode of decomposition behave quite alike when deformed in the cold, the metastability of each results from a different cause; viz., that of the austenite from the fact that it is a supercooled solution (its solvent. gamma iron, at ordinary temperatures is below its normal stable range whereas the metastability of the quenched Muntz metal is the result of supersaturation. When a 60:40 brass is quenched from above 800" C.—that is, from within the field where the beta phase alone is stable—this solution is retained practically intact and the alloy so cooled is found to consist almost entirely of polyhedra of this solution with only a little alpha present ordinarily at the boundaries of the beta grains—the result of a slight

Jan 1, 1929

By W. T. Cardwell

Physically absurd, triple-valued saturations appear in the straight-forward solution of the Buckley-Leverell equations for the displacement of oil by water or gas. From an engineering viewpoint, the triple value causen no difficulty. It is well known how it may be compensnted in order to obtain physically meaningful, numerical results. From a scientific viewpoint, the question still arises: What did the triple value mean? This paper explains how and why the triple value arose in non-capillary Buckley-Leverett theory. The discussion should serve as a background for the understanding and use of the modern method of characteristics in di.~pkzc(>ment theory. INTRODUCTION Displacement theory was introduced to petroleum technologists in 1 941 by Buckley and Leverett.&apos; Their first equation, which they wrote down without derivation, was equivalent to the following: ?s/?t= - qr/F ?f/?r (1) where S = saturation of displacing fluid (a fraction) r = time q,. = total volumetric velocity of both the displacing phase and the phase being displaced (usually, but not necessarily, assumed to be a constant) F = porosity (a fraction) f - fraction of the total volumetric velocity that is the volumetric velocity of the displacing phase (assumed to he a function of S only x = distance. Buckley and Leverett called Eq. I "a material balance equation". Actually it is derived from both a continuity equation, or material balance equation, and Darcy&apos;s law. Buckley and Leverett jumped from their Eq. 1 immediately to their Eq. 2, which was the equivalent of the following: (?x/?t)x = qr/F df/ds = qr/F f&apos;(s) (2) The jump from Eq. 1 to Eq. 2 involves apparently simple mathematics, but in that apparently simple mathematics lies a subtle point that is part of the key to the meaning of the triple value to be discussed here. Eq. 2 may be readily interpreted as saying that a point of constant saturation (on a saturation-vs-dis-tance curve) moves with a constant velocity that is proportional to the total volumetric rate, inversely proportional to the porosity, and is otherwise a function of the saturation itself. So that if one knows the derivativc with respect to saturation of the fractional flow function, f(S), for each saturation, one knows the velocity of each point of the moving saturation-vs-distance curve. The function f(S) can he determined experimentally and its derivative f&apos;(S) can be calculated. It turns out that the experimentally derived f&apos;(S) is not a monotonic function of S, but instead it has a definite maximum and declines away at both high and low saturations. This in turn means, in accordance with Eq. 2, that on a moving saturation-vs-distance curve, ccrtain intermediate saturations will travel faster than the saturations either higher or lower. The result is indicated in Fig. 1. In Fig. 1, the abscissas represent distances along a column of porous medium, which column is assumed to be uniform in cross-section perpendicular to the ab-scissal direction. The ordinates represent fractions of pore space occupied by the displacing phase, which may be either water or gas. It is assumed that the saturation is uniform over all planes perpendicular to the abscissal direction. The saturation is a function only of time and one space variable. Time variation of the saturation is represented by change in shape of a curve such as curve AGJ, which represents the initial saturation-vs-

By C. B. E. Douglas

The following analysis was stimulated by a previous article on evaluation of the water problem at Eureka, Nev., which describes a method using formulas especially devised to calculate flow potential of extensive aquifers characterized by relatively even porosity and permeability throughout. The present discussion submits that the method was unsuitable for solving the kind of problem occurring at Eureka, where the amount of water available, rather than the flow potential, may have been the vital factor. IN an interesting article on evaluation of the water problem at Eureka, Nev.,1 W. T. Stuart describes how a difficult water problem, or one phase of it, may be evaluated by means of a small scale test. Test data are plotted by a method rendering, under certain conditions, a straight-line graph that can be projected to show how much the water table will be lowered by pumping at any specified rate for a given time. A formula is then used to determine the size of opening, or extent of workings, necessary to provide sufficient inflow to enable pumping to be maintained at that rate. At first glance this might seem the answer to a miner&apos;s prayer, but a word of caution is in order. It may not be the whole answer. Moreover, results obtained by the method described are reliable only for conditions approximating those assumed. Even where conditions do not meet this requirement, however, it may be possible to draw helpful inferences from the results, perhaps enough to facilitate another approach to evaluation of a problem. The two formulas Mr. Stuart used, the Theis formula and the one developed from it by Cooper and Jacob, were given field checks a number of years ago in valley alluvials by the Water Supply Div. of the U. S. Geological Survey and found to be reliable when the aquifer is very large in horizontal extent and sufficiently isotropic for the test well and observation wells to be in material of the same average permeability as the saturated part of the aquifer as a whole." Extensive valley alluvials, sands, and gravels can be evaluated in this way, and there are even cases in which the method could apply to porous limestones, such as flat beds of very large areal extent that have been submerged below the water table after extensive weathering. These are sometimes prolific sources of water for towns and industries. It is necessary for them to have been above the water table for some geologically long period of time in a fairly humid climate before submergence because the necessary high porosity and permeability, and large reservoir capacity, are the result of weathering, that is, of solution by the carbonic acid (H,CO3) in rainwater formed by the absorption of CO, from the air by raindrops, and this dissolving action must cease when all the H2CO3 has been consumed by re- action with the carbonate to form the more soluble bicarbonate. Consequently this weathering process is largely restricted to a zone that does not extend much below the water level, and submergence is necessary after the weathering to provide large reservoir capacity and good hydraulic continuity. On the other hand, water courses tend to form along faults and fractures in limestone, and to become enlarged by solution, well below water level when, as often happens, fresh meteoric water is circulated rapidly through them to considerable depth by hydrostatic pressure, as through an inverted syphon. Although the reservoir capacity of such water courses is relatively small they may extend far enough to tap more prolific sources. Cavities, and sometimes caves of considerable size, are found in limestones where the acid formed by the oxidation of sulphides has attacked them. This action can take place as deep below water level as surface water is carried by syphonic or artesian circulation, because the oxygen it carries in solution will not be consumed until it reacts with some reducing agent, such as a sulphide. Moreover, the formation of acid and solution of limestone in this way is not confined to the immediate vicinity of the sulphide. Oxidation of pyrite, for example, results in formation of acid in several successive stages, each taking place as more oxygen becomes available, as by the accession of fresh water into the circulation at some place beyond the sulphides. When the acid thus formed attacks the limestone, CO, is liberated and the ultimate effect of the complete oxidation of one unit of pyrite will be the removal of six times its volume of limestone as the sulphate and bicarbonate, both of which are relatively soluble. The reaction may be continued or renewed along a water course far from the site of the sulphides, where the small electric potential produced by contact with the limestone helped to start the reaction. Mr. Stuart refers2 0 caves in the old mining area in the block of Eldorado limestone southwest of the Ruby Hill fault at Eureka, Nev., and to the cavities encountered in drillholes in the downthrown block on the other side of the fault. Although he interprets these cavities as evidence that this formation was sufficiently isotropic (evenly porous and permeable) to give reliable results by the method he describes, they may, in fact, be entirely local conditions. There is reason to think they were probably formed

Jan 1, 1956

By K. M. Rolls, J. Wulff, D. A. Colling

Solid-solution alloys of the Ta- Ti system containing up to 70 at. pct Ti were melted and fabricated into wire. Steady magnetic-field measurements of cold-worked wires at 4.2°K indicate that the resistive critical field increases smoothly with increasing titanium, reaching a maximum of 93 kG (J = 1 amp per sq cm) for a composition of about 50 at. pct Ti. The composition dependence of the resistive critical field indicates it is largely paramagnetically limited for alloys containing more than 35 at. pct Ti. For cold-worked wires the value of the critical current density, Jc , was found to be insensitive to composition changes for compositions in excess of 20 at. pct Ti. It was observed that Jc could be increased by final-size heat treatment at 400°C without altering the value of- the resistive critical field. Experimental data are used to calculate the electronic specific-heat coefficient and the "upper critical field" for the alloys studied. THE effect and importance of metallurgical structure on superconducting properties have been summarized by Livingston and Schadler.1 Specific work on solid-solution alloys such as Nb-zr2-7 and Nb-Ti5-7 have shown that critical current density (Jc) and superconducting transition temperature are structure-sensitive. Berlincourt et al.6,8,9 in their studies of transition-metal alloys find that Ta-Ti alloys remain superconducting at fields comparable to Nb-Ti alloys. 6,8 Transverse critical current tests of a Ta-10 at. pct Ti alloy10 and longitudinal critical current tests of a Ta-25 at. pct Ti alloy1&apos; indicate that such alloys are capable of carrying high currents at intermediate fields (-40 kG). The work reported in the present paper was undertaken to explore the superconducting properties of further compositions in the Ta-Ti alloy system as well as the structure sensitivity of the superconducting properties. I) EXPERIMENTAL PROCEDURE Alloys were prepared by melting tantalum (Fansteel Metallurgical Corp., 99.96 pct purity) and iodide, crystal bar titanium (Foote Mineral Co., 99.92 pct purity) mixtures in an arc furnace on a water-cooled copper hearth using a tungsten electrode. Melting was accomplished in a purified, gettered argon atmosphere at pressures from 250 to 400 Torr. Each alloy was turned and remelted fourteen times to assure complete mixing of tantalum and titanium. Ex- cessive coring in the cast samples was, nevertheless, observed. This was somewhat reduced by annealing in vacuo at 1000°C for 13 hr. The ingots were then machined to 0.250 in. diam, jacketed in Type 304 stainless-steel tubing, and swaged to 0.140 in. diam. They were then drawn to 0.010-in.-diam wire. Alloys containing up to 70 at. pct Ti were readily cold-drawn to wire in this manner. Later experiments showed that oxygen additions up to -3000 ppm could also be cold-worked into wire. Test samples for superconductivity measurements in the 2-in, air-core Bitter solenoids of the M.I.T. National Magnet Laboratory were prepared from 10-in. lengths of 0.010-in.-diam wire, cleaned of residual wire-drawing lubricant. Current contacts were made by clamping clean copper tubing over both No. 18 current lead wire and the ultrasonically indium-tinned ends of the specimen wire.12 Potential leads of No. 32 copper wire were connected to the specimen by ultrasonic soldering in an indium bath. The potential lead separation was about 4 cm, corresponding to the circumference of the Bakelite rod to which the wire was affixed with half-mil Teflon tape. The final specimen configuration is shown in Fig. 1. Specimens were lowered into a liquid helium bath (4.2oK) in a double solenoid dewar and positioned so that the maximum magnetic field was oriented transverse to the wire axis of the gage section. Measurements were made by passing a current through the specimen at a preset solenoidal magnetic field. The current was increased until a 1-pv potential difference appeared across the gage section (1/4 µv per cm). At low magnetic fields, however, it was not possible to use this criterion because power-dissipation difficul-

Jan 1, 1967

By J. C. Griffiths, D. W. Bennion

A mathematical model, which does not assume a priori that stratification exists, but was designed to test for the stratification was developed. The model segmented the reservoir horizontally into areas of common variance, then divided it vertically into strata (if strata were present). Next, trend surface techniques were used to determine the lateral extent and variation of each stratum. The model was tested on two reservoirs (sandstone and limestone) using porosity as the reservoir rock property. The sandstone reservoir contained approximately 60,000 samples from 2,000 cored wells, while the limestone reservoir had approximately 24,000 samples from 430 cored wells. Within the areas of common variance tested, the model was able to distinguish four separate lithological units or zones in the sandstone reservoir, four in the Marly section and seven in the Vuggy section of the limestone reservoir. INTRODUCTION To accurately predict the movement and production of fluids from a reservoir rock, it is necessary that the reservoir engineer have a knowledge of the rock properties and their distribution throughout the reservoir. For this study, a reservoir rock is defined as a solid containing interconnecting holes or voids which occur relatively frequently and are dispersed within the rock in a regular or random manner. The fraction of bulk volume that these interconnecting voids occupy is called porosity. The rock must also possess sufficient permeability to allow fluids to move through it and it may be composed of one or more strata or lithological units. A stratum or lithological unit as defined in this study is a body or volume of reservoir rock whose properties are so distributed that its lateral and vertical extent can be traced throughout or through a portion of the reservoir. Operationally, the existence of strata are question- able unless the variance within strata is less than among strata. Within the past few years computers have been widely used as a tool for calculating movement and production of fluids from reservoirs. Most prediction models require some type of a mathematical description of certain reservoir rock properties. In the past, most of these models have been relatively simple. Some have assumed vertical variation but no lateral variation, while others have assumed lateral variation but no vertical variation. In general, most of these models have not used functional relationships to predict reservoir rock properties as functions of position. The object of this study was to develop a model which would predict lateral and vertical variations of reservoir rock properties. Since samples are usually available from only a small portion of the total reservoir rock, it seemed logical that if measurements from these samples were to be used to infer the properties of the actual reservoir, the data should be treated statistically as a sample from the total population (reservoir). Therefore, the model developed in this study to predict reservoir rock properties was a stochastic model. The model was tested using porosity (a macroscopic reservoir rock property) measurements from two reservoirs — the first, a sandstone reservoir from which 60,000 samples were obtained; and the second, a limestone reservoir with 24,000 samples. Several investigators have proposed methods to determine the vertical and areal variation of a reservoir rock property. Stiles: Dykstra and Parsons 2 and Suder and Calhoun3 have all developed waterflooding prediction techniques which assume vertical variation but no lateral variation. Stiles developed a method to segment a reservoir arbitrarily using frequency distribution. Law4 suggested that porosity has a normal frequency distribution and that permeability has a log-normal frequency distribution. Elkins and Skov 5 proposed that when a reservoir is segmented vertically, the

Jan 1, 1967

By R. O. Williams

It is shown that Ni3Al precipitates homogeneously from nickel-rich alwminum alloys as plates on the (100) planes. Prior to actual precipitation a process occurs which is believed to be one of increasing short-range order. After precipitating the Ni3Al plates enlarge through competitive growth. Discontinuous precipitation can occur simultaneously with the above processes. Recent ideas of the origin of precipitation strengthening appear adequate to explain the hardness changes. REMARKABLY little appears to be known about the precipitation process in Ni-Al alloys in spite of their technical importance. This investigation originated to supply additional information about precipitation in general, this system in particular. Information on the structures and kinetics have been obtained through the use of hardness, X-rays, microscopy, calorimetry, and resistivity on high-purity alloys. PROCEDURES Six alloys, Table I, were prepared by melting carbonyl nickel and high-purity aluminum in alumina crucibles in vacuum and casting into 1-in. graphite molds. All rods were homogenized at least once at 1300°C for 24 hr prior to swaging and this was repeated on the first three alloys after 75 pct reduction. Alloy 4 could be reduced only 10 pct at 1000°C (probably in two-phase field) prior to fracture but 1/4-in. samples quenched from 1100°C were readily reduced cold. Alloy 5 was reduced 15 pct cold but failed on the next pass while alloy 6 of essentially the same aluminum content failed inter-granularly without apparent flow up to 1000°C. The alloys were heated in hydrogen at the elevated temperatures and formed thin, coherent aluminum oxide coatings which provided excellent oxidation resistance at lower temperatures. However, freshly prepared surfaces showed considerably less resistance at 500"to 700°C in air and apparently resulted in internal oxidation. As a consequence, low-temperature agings were carried out in evacuated tubes. RESULTS The isothermal hardening behavior of these alloys at 500"and 565C is given in Figs. 1 and 2. These results were obtained from samples cold worked 75 pct, recrystallized at 1000°C (1100°C for the 7.8 pct Al) and quenched in water. This recrystallization was used to give smaller grain sizes so as to obtain more uniform hardness values and the points represent an average of five readings. The electrical resistivity was measured on 1/16-in. wires quenched from 1000°C during aging at 495°C to give Fig. 3. The energy release and its rate are given in Fig. 4 for the 6.9 pct Al alloy during aging around 500°C. Inasmuch as this was a single run, its accuracy is not known but certainly the general shape and magnitudes are correct. The method used to obtain these results is described elsewhere.&apos; Data for the aging at 600°, 700°, and 800°C of these alloys cold worked 50 pct are given in Fig. 5. Supplementary information from microscopy and X-ray diffraction have been included to indicate recrystallization, discontinuous precipitation and the appearance of superlattice lines from the Ni3Al. The hardness of these alloys as annealed, aged, cold worked, and cold worked and aged is given vs composition in Fig. 6. Those samples which were isothermally aged, Figs. 1 and 2, were reaged at 532°C and at successively higher temperatures for the indicated times to give the data of Fig. 7. These results as well as certain others, support the idea that the level of hardness reached for temperatures above 600°C are equilibrium values more or less independent of path. This being the case, the breaks in the curves would be the complete solution of the Ni,Al. The electrical resistivity versus temperatures for some of these alloys, both aged and unaged, is given in Fig. 8 along with those data from heating slowly (10 deg per day) to high temperatures. Interesting points include the lowering of the Curie temperature (the change in slope), the lack of any indications of a solubility limit and the large temperature coefficient for the Ni3Al. A slight break for Ni3Al around 100C shows up but this is not a Curie temperature as Ni3Al is not ferromagnetic down to -190°C. Metallographically both the nickel-rich solid solution and the Ni3Al appear very much like pure nickel. Profuse twin boundaries are present both

Jan 1, 1960

By C. R. Kyle, R. L. Perrine

A transparent model of a reservoir has been used to study some characteristics of instability in miscible displacement. The linear model dimensions are 1/4 in. x 91/2 in. x 10 ft. The model is packed with spherical glass beads. Thee groups of experiments have been performed. The objectives were to measure, respectively, the rate of growth of the transition zone, flow velocity variations in the transition zone, and the effect of a graded viscosity zone on stability. All experiments were compared, where possible, with theory. The transition zone grew almost linearly with distance traveled, regardless of flow rate, where adverse viscosity ratios were used. At very adverse viscosity ratios and large distances traveled, some reduction below linear growth was noted. This could be attributed to the effects of mixing. General similarity in flow pattern was commonly shown in different tests, although exceptions occurred at the higher viscosity ratios. Injection of tracer spots permitted direct experimental measurement of velocity variations. Statistical methods were used to compare observed velocity variations with recently published theories. Surprisingly good agreement with some theoretical predictions was obtained. In the experiments using an initially graded viscosity zone, macroscopic stability was reached before predicted by theory. Under conditions theoretically considered to be slightly unstable, any fingering tendency was too slight to become observable within a 10-ft long system. The general correlation of all experiments with published theory was good, and suggests that theoretical predictions can be extended to reservoir problems. INTRODUCTION Early laboratory studies of miscible displacement demonstrated the high recovery efficiency possible with this method. Linear laboratory models showed that, under some circumstances, all in-place hydrocarbons could be recovered using as little solvent as 5 per cent of the pore volume. These results led to a series of pilot field projects. Under realistic conditions, however, other laboratory studies showed that a small solvent bank may not recover much more oil than a conventional gas drive. The cause of this lack of efficiency is unstable viscous fingering. The size of the solvent bank required to give optimum recovery is, therefore, a question of great economic significance. The object of the experiments described in this paper was the quantitative measurement of unstable flow parameters, the verification of present theories on the miscible displacement process, and correlation of these theories with ex peri mental observation. Of the theories which have been advanced, those by Dougherty, Koval and Perrine show promise of predicting reservoir performance with reasonable accuracy.l-7 The present experiments were correlated, where possible, with the theories of Koval and Perrine. Dougherty&apos;s theory was not used because of the additional computational difficulty it presented and the belief that no further information would result. EXPERIMENTAL EQUIPMENT A transparent reservoir model, consisting of a vertical reinforced plexiglass column, was used for the experiments. The column was packed with glass beads, which served as the porous medium. To induce a known velocity disturbance in the flow, a double cosine wave restriction in the transverse cross-section was placed at the top of the column. To mark the flow field and provide a means of measuring the local fluid velocity, a dye-spot injection system was provided. The column was 10 ft high by 1/2 in. wide by 1/4 in. deep. The cosine restriction was placed 16 in. from the top of the column. The glass beads were smooth and spherical and had a mean diameter of 0.0102 cm. Liquids entered the top of the column through a manifold allowing three points of entry (left, center, and right, or any combination of these). A positive-displacement pump with variable-speed drive was used to control liquid flow rates. The pump transferred viscous oil from a reservoir to an accumulator, which displaced the test liquid into

Jan 1, 1966

By L. A. Rapoport, W. J. Leas, C. W. Carpenter

A program of scaled flow model experiments has been undertaken to study the performance of five-spot water floods. The modeling procedures are discussed and the construction and operation of the flow models are described. The tests were specifically designed to investigate the effects of injection rate and of oil-to-water viscosity ratio on oil recovery. The areal sweep of five-spot water floods was also studied, and direct comparisons between five-spot and linear flooding behavior have been established to permir better utilizatfon of core analysis results for purposes of field waterflood evaluations. INTRODUCTION For a long time reservoir engineering procedures have been confined to the consideration of idealized, one-dimensional or linear systems.11* However, direct application of the linear waterflood mechanism to the evaluation of actual field performance is justifiable only for the purposes of rough approximation. To obtain a realistic analysis of field behavior, it is necessary to account for reservoir geometry and well distribution, and to take into consideration the configuration of the flow of fluids between injection and producing wells. In the past it has been attempted to account for the complex nature of the fluid movement in the reservoir by associating each well pattern with a certain "sweep-efficiency constant", e.g., a sweep efficiency of 72 per cent for the conventional five-spot pattern.&apos; More recently, methods of waterflood evaluation have been improved by the introduction of variable sweep-efficiency factors, defining the areal coverage as a function of cumulative water injection and viscosity or "mobility" &apos; ratio.""&apos; These variable sweep-efficiency factors, derived from miscible fluid displacement experiments, require the assumption of piston-like displacement of oil by water. This implies that only one fluid, either oil or water, is moving at any one point of the reservoir ht any moment. Such an assumption, however, is incompatible with the bulk of the experimental evidence and also theoretical considerations which indicate that usually in the area invaded by water, both oil and water are flowing in varying proportions, in accordance with the relative permeability characteristics of the porous medium. Another recent approach toward the evaluation of five-spot flooding behavior involves correlations of the areal sweep efficiency (observed in immiscible fluid experiments) with a "mobility ratio," based on the consideration of the "average" relative permeability to the displacing fluid. Combination of these correlations with a modification of the Buckley-Leverett frontal-drive equation leads to a computational procedure for predicting the recovery performance of areal water floods. While of considerable interest, this approach has no complete theoretical justification and, therefore, does not entirely clarify the features of five-spot water floods. Rigorous, theoretical treatment of waterflood behavior in two- or three-dimensional systems as encountered in the reservoir, including proper consideration of relative permeability and capillary-pressure functions, is as yet beyond the scope of analytical or computational methods. The, behavior of such water floods can, however, be studied by means of scaled flow model ekperiments, which is the approach followed in these investigations. The flow model experiments described in this paper simulate a uniform, horizontal formation of constant thickness with fully penetrating wells. The system under consideration is entirely liquid saturated and not influenced by compressibility effects, which is representative of the situation achieved after gas fill-up under practical conditions. Gravity segregation effects are assumed to be negligible, which implies a relatively thin reservoir formation and/or low vertical permeability. THEORETICAL CONSIDERATIONS For a flow system of uniform thickness with no appreciable effects of gravity segregation, the analysis of water-oil displacement can be confined to a two-dimensional treatment based on the consideration of a "slice" of unit thickness. Referring to previously established derivations," the displacement of oil by water in such a system can be described by the following, dimen-sionless equations:

By W. R. Kube, W. H. Oppelt

Five low-rank coals, including two lignites, a steam-dried lignite, and two subbituminous coals, were carbonized at 940°F, in a bench-scale carbon-ize~ with a nitrogen and hydrogen atmosphere, or both, using pressures from atmospheric to 1000 psig. Coking characteristics were observed, and yields, composition, and distribution of products from thermal degradation were determined. The influence of pressure on yields from coal carbonization, as well as on modification of coke structure, has long been of interest. One of the first attempts at pressure carbonization was that of Capps and Hulett1 who in 1917 investigated the effects of pressure ranging from 1 to 20 atm on yields at 600° C for bituminous and subbituminous coals. High-pressure carbonization has not been used commercially for coke production. More recently, carbonization at relatively high pressure in the presence of catalysts and hydrogen has been proposed for the production of metallurgical-grade coke from low-rank fuels.&apos; Another approach involves carbonization at high pressure in a hydrogen atmosphere to produce heating gas and a solid residue that is gasified with oxygen and steam to produce the hydrogen required for hydro-genation 3-4 or, alternatively, is burned to raise steam. Recently it has been proposed to carbonize coal under pressure, burn the gas in a gas turbine to produce power, and use the solid residue as fuel in a conventional steam-power plant.5 Our primary interest in pressure carbonization stems from an attempt to determine the influence of pressure on the coking characteristics of lignite to design a high-pressure slagging gasifier using oxygen and steam. At atmospheric pressure, North Dakota lignite is generally considered to be non-coking. However, lignite and subbituminous coals have been reported to show increased agglomeration properties in steam, hydrogen, or carbon-dioxide atmospheres at elevated pressures, although no strong coke was formed at pressures up to 3000 psig.6 If lignite would agglomerate seriously under gasification conditions, proper flow of charge through the gasifier could not be maintained without installing a mechanical stirring device or destroying the caking properties of the coal before gasification. Data on the caking properties of lignite or other gasification fuel, as well as on yields of products under conditions simulating the carbonization process in the pregasification zone, were required in the preliminary design stage of the gasifier. No information was available concerning the influence of pressure and type of atmosphere on North Dakota lignite. To provide this basic data, the U. S. Bureau of Mines investigated the effect of pressure and a hydrogen or nitrogen-rich atmosphere on the yield of products and on coke formation in a bench-scale pressure carbon-izer. SCOPE OF INVESTIGATION Five coals were tested at 940°F in nitrogen and hydrogen atmospheres, at pressures from atmospheric to 1000 psig. Yields and composition of solid, liquid, and gaseous products were determined as a function of the process pressure, and attention was given to the physical appearance of the solid residue. Percentage of carbon converted, sulfur retained in char, and thermal balances were calculated. In this paper, primary consideration is given to carbonization in a nitrogen atmosphere and to data concerning the solid phase. The effect of pressure in hydrogen is presented in detail for only one lignite. More complete information on the response of the other coals in a hydrogen atmosphere will be published in a USBM Report of Investigations. DESCRIPTION OF EQUIPMENT Details of the bench-scale pressure carbonizer are given in Fig. 1. The body of the carbonizer was

Jan 1, 1961

By Lawrence A. Shepard, Richard H. Krock

A series of ductile, two phase W-Ni-Fe composites, sintered in the presence of a liquid phase, were tested in tension. Identical room temperature stress-strain curves were obtained for specimens containing from 80 to 92 wt pct W (58 to 75 vol pct W particles). The composites exhibited a maximum elongation of 29pct at room temperature, and 10.7 pct at 77 °K. The tungsten particles in the composite elongated by the same amount at these temperatures. Single-phase alloy specimens matching the composition of the composite matrix showed about one half the flow stress of the composites. The test results demonstrated that the mechanical properties of W-Ni-Fe composites are determined by the tungsten particles alone and are independent of matrix volume fraction or mean free path over the composition range studied. A general prediction of the plastic behavior of two-phase alloys or composites from a knowledge of the properties, size, shape, and dispersion of the individual components is not, at present, possible. The excellent theoretical and experimental exposition of the dispersion-strengthening problem applies only to cases where the stronger phase is present as fine particles and in volume fractions of a few percent. Materials in which the stronger phase constitutes a significant fraction of the volume, although of broad engineering interest, have received comparatively little analytical attention. This important group of materials is the concern of the present study. The degree of deformation of each phase during the plastic working of a ductile two-phase alloy has been established by Boas and Honeycombe,1 Clare-brough,2 and Clarebrough and berger.3 These workers empirically correlated the recrystallization temperature of the individual phases with the degree of cold work sustained by each. It was shown that the deformations of both phases are equal and therefore the same as that sustained by the composite whole when the volume fraction of the stronger phase exceeds 35 pct. At yielding, however, deformation begins in the weaker phase. A direct correlation of composite strength, as a function of deformation, with the strength of the individual components cannot be made. In the presence of stronger phase particles, the flow stress of the weaker matrix phase is enhanced by an additional hydrostatic component. The development and potential magnitude of matrix strength promotion upon straining has not even been experimentally established. Quantitative work in this field has been confined to ceramic-metal composites. These materials fracture at strains considerably below 1 pct by cracking of the ceramic particles.4-6 An indication of the potential constrained matrix strength capacity is given by the observation by Nishimatsu and Gur-land4 that the maximum tensile strength of a WC-Co composite is almost double the bulk strength of the cobalt matrix. The relationship between composite strength and geometry is ordinarily expressed in terms of the mean-free matrix path (referred to subsequently as MFP) between the stronger particles.* This factor takes into account both the volume fraction of matrix phase and the average size of the particles. unke17 concluded that composite strength varied directly with the decreasing log MFP, following the Gen-samer8 relationship. However, Gurland and ~radzil~ reported a strength maximum at an MFP of the order of 1 p in WC-Co composites. A ductile two phase metallic composite was chosen for the present investigation of composite mechanical properties with the view of avoiding the difficulties and ambiguities noted above. The W-Ni-Fe heavy alloy of Green, Jones, and pitkin9 contains 80 to 94 wt pct W, and nickel and iron in a weight ratio

Jan 1, 1963

By R. D. Daniels, T. G. Oakwood

A study was made of the effects of small quantities of hydrogen on the mechanical properties of colum-bium. Tensile specimens, hydrogenated to concentrations of 20 to 200 ppm, were tested at temperatures of 300°, 191°, and 77°K. Although hydrogen was found to have little effect on the strength of columbium, the ductility of Cb-H alloys was found to be quite sensitive to both hydrogen concentration and temperature. At 300°K, an abrupt loss in ductility occurred at a critical hydrogen concentration, although some ductility was observed beyond the tolerance limit. A similar result was found at a lower hydrogen concentration at 191°K. At 77°K, however, a more gradual loss in ductility with increasing hydrogen concentration was observed. Hydrogenated columbium was thus observed to undergo a ductile-brittle-ductile transition. Metallographic examination of fractured specimens revealed extensive porosity at both 77° and300°K which was a distinct function of hydrogen content. At 191°K, although some secondary cracking was noted, the amount of observed porosity was minimal. These observations are interpreted in terms of hydrogen solubility and mobility as a function of temperature and in the role of hydrogen in promoting growth of microcracks. lHE effect of hydrogen on the mechanical properties of the refractory metals is not, at present, completely understood. A number of studies have shown these materials to be susceptible to hydrogen embrittlement. Roberts and Rogers1 have found that vanadium can be embrittled by hydrogen. It was further demonstrated that fracture undergoes a ductile-brittle-ductile transition as the temperature is lowered from 150° to -196°C; i.e., there is a ductility minimum observed at a certain temperature. The ductility is increased by either raising or lowering the temperature from this point. A more complete study by Eustice and Carlson2 on vanadium containing 10 to 800 ppm placed the ductility minimum at about -100°C with variations reportedly due to hydrogen content and strain rate. Ductility minima have also been found at certain temperatures for tantalum containing 7 ppm H3 and 140 ppm H.4 At hydrogen concentrations above 270 ppm, however, the ductility return at low temperatures was considerably reduced.4 In the case of columbium, some disagreement exists in the literature. Eustice and Carlson,5 Wilcox et al.,6 and Imgram et al.4 failed to find a ductility minimum although a composition-dependent ductile-brittle transition was observed. Hydrogen concentrations in these investigations were 20 ppm,5 1 to 30 ppm,6 and 200 to 390 ppm.4 However, Wood and Daniels7 observed a rather pronounced ductility minimum at hydrogen contents ranging from 19 to 252 ppm. Those theories of hydrogen embrittlement involving the precipitation of diatomic hydrogen which have been applies to ferrous metals8-12 do not seem to be applicable to the case of columbium and other exothermic occluders. Such theories propose that extensive crack formation and propagation occurs by the precipitation and expansion of diatomic hydrogen at internal voids and microcracks. However, photomicrographs of hydrogenated columbium do not show any evidence of damage introduced by the sorption and precipitation of diatomic hydrogen; rather, at high hydrogen concentrations, a hydrogen-rich second phase is precipitated.13&apos;14 In addition, a number of these theories require the development of high hydrogen pressures at voids in the structure.8&apos;10&apos;12 This does not appear to be feasible in the concentration ranges discussed in the aforementioned paragraphs. The possible interaction of atomic hydrogen with microcracks resulting from dislocation pile-ups15,16 remains in doubt since pile-ups have not been observed in bcc metals17 including columbium.18 Wood and Daniels7 have put forth the possibility that a hydride precipitation could be responsible for crack nucleation in columbium. Work by Longson19 has shown that hydrogen embrittlement of columbium parallels the bulk solubility limit; i.e., as the solubility increases, for instance with temperature, the amount of hydrogen necessary to cause embrittlement also increases. Although a hydride precipitation appears attractive as a means of nucleating microcracks in columbium, what require more intensive study are the low-temperature anomalies which have been observed, i.e., the ductile-brittle-d&apos;ictile transition characteristics. Also, the hydrogen concentrations where embrittlement occurs are often below the bulk solubility limits determined by Albrecht et al.13,14 and Walter and Chandler.20 This work is an attempt to determine more definitively the effects of concentration and temperature on the mechanical properties of dilute Cb-H alloys. EXPERIMENTAL PROCEDURE Ultrahigh-purity columbium rods, obtained from the Wah Chang Corp., were cold-reduced by rotary swaging. A chemical analysis is given in Table I. The material was cut into cylindrical blanks 1.50 ±0.005 in. long. Individual specimens were either given a stress relief anneal at 750°C or recrystal-lized at 1200°C. Resulting microstructures were either a "bamboo" structure characteristic of a wrought material or a recrystallized structure with a grain diameter of approximately 100 n. All heat treatments were carried out in a vacuum of 10-5 Torr or less.

Jan 1, 1969

The greatest mining center in the state of Utah is the incorporated town of Bingham about twenty-five miles southwest of Salt Lake City. The principal industry of this vicinity, prior to the early fall of 1863, was lumbering and the first saw-mill in the state was built near the mouth of Bingham Canyon. Early in the fall of that year. George B. Ogilvie discovered gold and shortly afterward the first mining district in the state was organized. Some writers place the discovery of gold in the canyon in the late fifties. If this be so, however, the matter was kept extremely quiet because no mining was engaged in until after Ogilvie&apos;s discovery. Bingham was a placer mining camp, producing about one million dollars&apos; worth of dust and nuggets from placers up and down the canyon and in Bear Gulch until early in the seventies, or about ten years after the discovery of gold, when a large body of argentiferous lead ore was discovered and soon after heavy shipments were made from a half dozen or more properties.

Jan 1, 1925

By J. C. Todd

The volume of air needed to move the combustion wave through each acre-foot of the reservoir is a very important quantity for engineering economic analyses. A new method, which involves backflowing the injection well, has been developed for determining the air requirement .for the forward combustion thermal pilot in the Delaware-Childers field. The method depends on measurement of the total volume of air injected and measurement of the pore volume in the zone swept out by the combustion front. The basic premise of the method is that the pore volume of the swept zone contains air, while the formation around this zone contains flue gas, oil and water. The pore volume of the swept zone is determined by blowing down the pilot section of the formation through the injection well after the pilot is shut down. Oxygen balance is used to differentiate between air from the swept zone and flue gas from the surrounding formation. Data indicate that air&apos;is produced from the swept zone by relatively efficient miscible displacement by the flue gas. The pore volume occupied by the air in the swept zone is determined by simple PVT relationships. The average temperature of the swept zone is calculated by heat balance from the total amount of heat generated during the pilot and losses to the surrounding formation. The new method was applied successfully at the conclusion of the pilot in the Delaware-Childers field; the air required for the reservoir conditions involved was calculated to be 19.2 MMscf/acre-ft of reservoir swept. INTRODUCTION One of the most important pieces of information to be found from a forward combustion pilot is the air requirement; that is, the volume of air needed to move the combustion wave through each acre-foot of the reservoir. Compression costs per barrel of oil recovered, which are a direct function of the air requirement, are a large portion of the expenses incurred in the thermal recovery process. Thus, the profitability of thermal recovery depends largely on the air requirement, which is a measure of the amount of fuel deposited and burned in the thermal recovery process. Several attempts have been made to correlate crude oil properties with fuel deposition and, hence, air requirement.l*2 Other attempts have been made by our laboratory to find the air requirement by material balance, gravity survey, pressure transient analysis,3 magnetic survey and the poten-tiometric model. Better methods are needed to predict more accurately the economics of fieldwide application of the process. Another method of finding the air requirement consists of operating a pilot thermal project for several years. This is followed by an extensive coring program to define the volume swept by the combustion wave. The air requirement is found from the total injected air divided by the volume of the swept region found from the coring operation. This method is costly; an adequate coring program usually costs several hundred thousand dollars. A thermal pilot was operated in a watered-out portion of the Delaware-Childers field, Bartlesville sand, from Nov., 1960, until May 3, 1965. One of the primary purposes of this pilot operation was to determine the air requirement for economic calculations which determine the advisability of expanding the project to the entire 128,000 acre-ft field. Barnes4 has described the result of this pilot operation,, including calculation of the air requirement from limited coring data. The value obtained, as calculated, was 15.8 MMscf/acre-ft. One purpose of this report is to describe a new method of finding the air requirement from a thermal pilot operation. A second purpose is to describe the application of this method to the Delaware-Childers thermal pilot. THEORY AND DESCRIPTION OF THE METHOD The combustion zone in the forward combustion process is propagated from injection w producing

Jan 1, 1970

By D. T. Peterson, T. Carnahan

The diffusion coejTicients of carbon, nitrogen, and oxyget were determined in $ thorium over the tempernilcre range 1440" io 1715°C. The diffusion coyfiicir?zls are given by: D = 0.022 exp (-27,000/RT) jor carbo)~, D = 0,0032 exp(-l7,00Q/RTj for nitrogen, and D = u.0013 expt(-11,UOU/RT) for oxygen. Cavl~orz was found to increase the hardness of thoriunz nearly linearly with concentration over the range 100 to 1000Ppm carbon. ThORIUM has a fcc structure up to 1365°C and a bcc structure from this temperature to its melting point at 1740°C. Diffusion of carbon, oxygen, and nitrogen in bcc thorium was of interest in connection with the purification of thorium by electrotransport.&apos; In addition, it was possible to measure the diffusion of all three of these interstitial solutes in the same bcc metal. Only in niobium, tantalum, vanadium, and a iron have all three interstitial diffusion coefficients been measured in a given bcc metal. Diffusion coefficients have been measured for carbon and oxygen in a thorium by Peterson2, 3 and for nitrogen by Gerds and Mallett.4 Activation energies for diffusion are reported by the above authors to be 38 kcal per mole for carbon, 22.5 kcal per mole for nitrogen, and 49 kcal per mole for oxygen. Values of the diffusion coefficients of carbon and nitrogen in 3 thorium have been reported by Peterson et al.&apos; However, these were secondary results of their investigation of electrotransport phenomena in thorium and it was hoped that the present study could provide more precise data. EXPERIMENTAL PROCEDURE The specimens used in this study were the well-known pair of semi-infinite bar type. The couple was formed by resistance butt welding two 0.54-cm-diam by 3.0-cm-long bars of thorium together under pure helium, the concentration of the solute being greater in one cylinder than that in the other. The finished couple then contained a concentration step at the weld interface and diffusion proceeded only along the axis of the rod. The thorium used in this study was prepared by the magnesium intermediate alloy method.5 The total impurity content was less than 400 ppm. The major impurities were: carbon, 100 ppm: nitrogen, 50 ppm; and oxygen. 85 ppm. The total metallic impurity content was less than 150 ppm. The high solute concentration portions of the diffusion couples were prepared by adding the solute to the high-purity thorium in a non-consumable electrode arc melting procedure. Carbon and nitrogen were added in the form of spectroscopic graphite and nitrogen gas while a Tho2 layer was dissolved by arc melting to add oxygen. High-purity thorium formed the low concentration portions in the carbon and nitrogen couples. The low oxygen portions were obtained by deoxidizing high-purity thorium with calcium for 3 weeks at 1000°C according to a method reported by Peterson.3 The high C-Th contained 400 ppm C, the high N-Th contained 400 ppm N, the high 0-Th contained 220 ppm 0, and the low 0-Th contained 25 ppm O. The high O-Th was brine-quenched from 1500°C to retain most of the oxygen in solution at room temperature. These concentration levels were all below the solubility limits in 0 thorium at 1400°C. A resistance-heated high-vacuum furnace was used to heat the couples. The samples were mounted horizontally on a tantalum support which had small grooves near each end. Spacer rods of thorium, 0.4 cm in diam, were placed in these grooves to prevent contact between the sample and the tantalum support. This arrangement should have prevented contamination of the sample by contact with the support. In further effort to reduce contamination, the oxygen diffusion couples were sealed inside evacuated outgassed tantalum cylinders lined with thorium foil. Thorium rings around each end of the samples acted as spacers in this case. Pressure during diffusion runs was about 10-6 torr after an initial outgassing stage. Temperature measurements were made by sighting on black body holes in the sample support adjacent to the samples with a Leeds and Northrup disappearing-filament optical pyrometer. Temperatures were constant during a diffusion anneal to ±5C. The observed temperatures were corrected for sight glass absorption after each diffusion run. The pyrometer was checked against a calibrated electronic optical pyrometer and a calibrated tungsten strip lamp with the electronic pyrometer being taken as the standard. All temperature readings agreed to within ±3C over the temperature range 1450" to 1690°C. Time corrections due to diffusion during heating and cooling were necessary because of the short diffusion times. The diffusion times ranged from 6 min for the oxygen sample run at 1690°C to 90 min for the carbon sample run at 1500°C. A series of temperature vs time plots were made for heating and cooling of the samples to the various diffusion temperatures. This data was then used in a method according to shewmon6 to determine the time corrections. The corrections amounted to

Jan 1, 1970

By H. G. Doll

As a continuation of the earlier paper on the general subject of the SP log, a more complete analysis of certain features of the SP log in shaly sands is given. The pseudo-static SP in front of shaly sands is compared, on a theoretical basis, to the static SP in front of clean sands, as a function of the respective amount of shale and sand in the formation, and of the relative resistivities of the shale, of the uncontaminated part of the sand. and of the invaded zone of the sand. As a conclusion, the advantage of using reasonably conduc. tive mud in this case is shown. The discussion is illustrated by field examples. INTRODUCTION The discussion reported in the present paper is based on a theoretical analysis, and not on experiment. The field examples, joined to the text. are shown only as qualitative illustrations of the essential results of this analysis. Although the hypotheses made in the theoretical developments may perhaps be somewhat improved, it seems, nevertheless, that the results obtained account reasonably well for the actual phenomena, and give a fair approximation of their order of magnitude. The paper contains a mathematical analysis of a tri-dimen-sional distribution of potentials and current lines. due to spontaneous electromotive forces arising at the contact of shales and free electrolytes. as a function of the geometry and of the respective resistivities of the different media involved. It is assumed, although this hypothesis is not proven, that the emf&apos;s remain the same even if the shale occurs in very thin layers or in dispersed particles. It has already been pointed out 1,2,3 that, all other conditions being the same, the deflection of the SP log in front of a shaly sand is smaller than opposite a clean sand. When the thickness and the conductivity of a clean sand are large enough. the deflection of the SP log reaches a limiting value which is equal to the "static SP" of the clean sand. It is generally convenient to take the static SP of shale as the reference value or "base line." As a consequence, and for the sake of abbreviation, the expression. "static SP of a clean sand," is often used to designate the difference between the static SP of that sand and that of the shales, which difference is a measure of the total electromotive forces involved in the chain mud sand-shale. A similar limiting value is; also observed for the SP deflec-lion opposite a thick shaly sand, but it is smaller. just as if the total electromotive force involved were smaller in that case. This limiting value has been called the "Pseudo-Static SP" of the shaly sand. The static SP of a clean sand depends on the salinity of its connate water with respect to that of the mud, and, to a certain extent. on the differential pressure which controls the electro-filtration potentials, but it does not depend on the resistivity of the sand. On the contrary. the pseudo-static SP of a shaly sand depends not only on the salinity of its connate water and on the differential pressure, but also on the percentage of shale and on the resistivities of the shale, of the uncontaminated part of the sand, and of the zone invaded by the mud filtrate. If the three resistivities above were equal, the pseudo-static SP would be proportional to the percentage of sand in the shaly sand, and its departure from the static SP of a clean sand having the same connate water would simply be proportional to the percentage of shale. In that case, the pseudo-static SP of a shaly sand containing 10 per cent of shale would he 10 per cent less than the static SP of a clean sand. When. however. the sand is. on the average. substantially more resistive than the shale. the percentage of departure of the pseudo-static SP from the static SP of a clean sand is much larger than the percentage of shale. For that reason, the peaks of the SP log opposite shaly sands are systematically of smaller amplitude when the sands are oil-bearing than when they are water-bearing, all other conditions being the same. This feature is observed even when the sand beds are thick. and even when they do not contain a large percentage of shale. All this has already been described in all earlier publication", but mostly in a qualitative way. The present paper will analyze in more detail the action of the local SP currents which are generated inside of the shaly sands, and which are responsible for the abnormally low value of the pseudo-static SP. The quantitative computations have been extended to the general case of thin interbedded layers of sand and shale, where the resistivities of the shale and sand streaks do not have the same value: they are summarized in charts giving values of the pseudo-static SP of a shaly sand as a function of the different parameters involved. DEFINITIONS The static SP of a clean sand has been defined as the potential that would exist in the mud opposite that sand, were the SP current prevented from flowing. Such an ideal condition is represented on Fig. I-A. By analogy, the pseudo-static SP of a shaly sand can be defined as the potential that would exist in the hole, if the circuit shaly sand — surrounding shales — mud column were interrupted by the insulating plugs placed at the boundaries

Jan 1, 1950

By Charles H. Jacoby, Stanley J. LeFond

Salt, or halite, has a long and most varied history. While we know the Chinese were producing salt as early as 3000 B.C., the first written reference to salt appears in the book of Job recorded about 2250 B.C., which reads: "Can nothing which is unsavory be eaten without salt?" We do not know when man first used or realized that he needed salt. Perhaps one of our early Eolithic ancestors noted a piece of salt shining along the shore of a salt lake or a bay. He may have been attracted by its shining luster and tasted it. He found that it had a tart, zesty, distinctive flavor and perhaps chewing a large piece, became ill. However, by experimentation he soon learned that taken in the proper proportions salt was a very pleasant additive to his food. He may have noticed, too, that it increased his feeling of well-being. Thus, when the curtain of recorded history rises, we find man using salt for his health&apos;s sake, seasoning his food with it, feeding it to his animals, and using it in many superstitious and religious ceremonies. These uses, however, are a far cry from the uses for salt today. The first attempts of white man to make salt in continental United States were reported in the year 1614, while the first commercial production was in 1753 from the Kanawha licks. Practically all this salt was for human consumption, preserving food, and curing hides. Prior to the coming of the white man, Indians are known to have made salt from salt springs such as those that existed at Avery Island, LA, Charleston, WV, Saltville, VA, and Onondaga, NY. In 1862 the first rock salt was mined in the US from the Avery Island salt dome. Almost immediately thereafter, rock salt was mined at Saltville, VA and then at Retsof, NY in 1885. Of the more than 39 million tons produced annually in the United States, about 58% or 23 million tons are consumed by the chemical industry in the production of chlorine, caustic soda, hydrochloric acid, sodium metal, and some 30 other basic chemicals. These basic chemicals, in turn, are used in the preparation of approximately 14,000 chemicals which range from soap and detergents, to such chlorinated hydrocarbons as DDT, BHC, carbon tetrachloride, etc. Utilization of cavities created in salt beds and domes has grown rapidly since 1947 until now the waste salt is creating an ecological problem. The uses for both dry- and solution-mined cavities range from the storage of liquid hydrocarbons to containerized storage of toxic wastes, from compressed air for the peak shaving of power to storage of nuclear wastes. Geology Mineralogy Properties: Because of its simple structure, halite, the mineralogical name for salt, was the first structure to be analyzed by X-rays. It has the following properties: Formula: NaCl (Na-39.34%. Cl2-60.66% ) Crystallography: isometric, hexoctahedral, 4/m 32/m Space group: Fm3m A0: 5.627 kX Cell contents: Na4CI4 Habit: usually cubic, rarely octahedral, massive, granular to compact Physical properties: Refractive index: 1.554 Twinning: observed on {111} Cleavage: {001} perfect Fracture: conchoidal, brittle

Jan 1, 1983

By T. E. Seidel, A. U. MacRae

The dependence of the electrical and crystalline properties of silicon containing ion implanted boron atoms have been studied as a function of the incident dose, substrate temperature, and annealing tempera-ture. Hall effect studies show that the compensation due to defects is negligible after annealing at and above 500°C for a dose of 1013 ions per sq cm. Steps occur in the isochronal annealing curve for the sheet resistance at 300°C and 800°C and the mechanisms responsible for these steps are discussed. The range of the ions at 150 kev is 3500 * 5001. Electron diffraction studies on samples implanted with 150 ker ions show the existence of damaged (polycrystalline) silicon closer to the surface than the range of the ions. Etching and subsequent annealing of etched and unetched specimens suggest that the poly crystalline silicon is closer to the surface than the bulk of the distribution of ions. THE purpose of this study is to investigate some electrical and crystalline properties of ion implanted boron in silicon. Sheet resistance, Hall measurement, depth distribution by chemical staining, thermal probe and electron diffraction have been used to study the properties of samples implanted in a random direction with ions having energy up to 150 kev. The boron-silicon system has been the subject of considerable study&apos;-7 due to its possible application in the fabrication of electronic devices. The implanted ions produce considerable crystalline damage to the substrate crystal before they lose most of their primary energy and come to rest. Fortunately, most, if not all, of this damage can be removed by subsequent annealing or by holding the substrate at an elevated temperature during the implantation process. Sheet resistivity measurements of the p-type layers produced by boron implantation into room-temperature silicon, reveal that the annealing occurs in a two-step process: the first occurring at -300°C and the second at -800°C.&apos; Electron-microscope and low-angle electron diffraction studies of this damaged material indicate that the bombarding ions produce an amorphous silicon region about the trajectory of each ion.&apos; At high doses, these damaged regions overlap and an amorphous surface layer results. Furthermore, the 800°C annealing step, appears to be associated with the elimination of this gross damage. The depth distribution of the as-implanted and also the annealed samples have been studied by an angle lap and staining technique as well as by Hall measurements.3-7 We find the experimentally determined ranges of the boron are less than those calculated by the Lindhard-Scharff-Schiott theorys (hereafter referred to as the LSS theory). Our results are in essential agreement with pre- vious results. In addition, we have made Hall measurements on samples bombarded with a low dose (2 x 1013 ions per sq cm) to minimize impurity banding effects, and find that deep ionized levels influence the carrier concentration and room-temperature hole mobility until the sample is annealed at temperatures above 500°C. Above this temperature, the data corresponds to that obtained when silicon is doped with boron by conventional techniques. We have also made a depth distribution determination of the crystalline damage due to the implanted boron by using glancing angle electron diffraction techniques. It was found that the gross damage depth distribution of heavily implanted samples is closer to the surface than the depth distribution of the electrically active boron. By removing this gross damage, without affecting the distribution of the implanted boron, we have determined that the 800°C annealing stage is not exclusively due to the improvement in the crystalline perfection of the amorphous material but also appears to be associated with the annealing of some point defects. These results and their relation to previous results are discussed in the following sections. IMPLANTATIONS Boron ions were implanted into silicon samples using an accelerator capable of operating from 10 to 150

Jan 1, 1970