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By M. E. Wadsworth, I. B. Cutler

Coprecipitation of anionic and cationic polyelectrolytes has been applied to floccula-tion of several mineral systems. Results obtained in a study of the flocculation of kaolinite and hematite suspensions of polycationic and polyanionic electrolytes are presented. Greatly increased settling rates were observed following precipitation of positive and negative polyelectrolytes on the surface of finely divided minerals in aqueous suspension. The ratios of polycationic to polyanionic electrolytes required to produce maximum sedimentation have been shown to correspond closely with the equivalence points obtained by light scattering studies of systems containing the positive and negative polyelectrolytes by themselves. DISPERSION of colloids has been of interest to surface chemists for many years. Flocculation studies have been employed to evaluate the limits of colloid stability. In water suspensions, colloids become unstable and flocculate when the ( potential, the potential of the kinetic solvation sheath, falls to a value at which van der Waals forces may act to draw the particles together. This may happen through an adjustment of the pH of the suspension or by addition of a salt. Optimum conditions for rapid formation of large flocs are found in the region of minimum ( potential. In addition to these well known considerations, colloids in water suspensions are known to be flocculated by certain large organic macromolecules. These polyelectrolytes in some cases minimize the i potential and in other instances increase the attractive forces by supplying sites for hydrogen bonding.' Use of organic polyelectrolytes in flocculation of mineral colloids has increased rapidly in recent years. These materials are now recognized as indispensable aids to fluid-solid separations in many extractive metallurgical operations. They have been found to increase both the settling rate in thickeners and the filtration rate of filters. In the elucidation of the characteristics of these organic reagents as floc-culants in this laboratory, it was discovered that interaction of certain polyelectrolytes had a surprisingly good effect on flocculation of mineral colloids. Experimental Procedure: The anionic flocculants used in this study were Lytron 886 and 887, produced by Monsanto Chemical Co. Both reagents are copolymers of vinyl acetate and maleic anhydride. Lime is added to Lytron 886, whereas Lytron 887 is all organic. These reagents possess two carboxyl groups for each acetate group and are therefore anionic in character. The cationic reagents used were the Peter Cooper Co. 1-X and 2-X glues. The structures are not definitely known, but the re- agents are amines and are cationic in character. The glues were prepared in the chrome-alum form. Both types of reagents may be classified as polyelectrolytes in that they are high molecular weight polymers and ionize in water. All data presented are in terms of sedimentation rate, measured in 250-ml glass-stoppered graduated cylinders. With suitable precautions such measurements are fairly reproducible and provide a sensitive means for selecting important parameters such as pH, reagent concentration, and floc size and density.2 Agitation was standardized with five complete end over end cycles of the suspensions in the stoppered graduated cylinders.

Jan 1, 1957

By H. A. Lequear, J. D. Lubahn

A sudden change from one constant strain rate to another during a tensile test causes an unusual transient in aluminum alloy 61ST. A sudden change from one constant stress to another during a creep test does not produce an unusual transient in this material. A specially devised test shows that the nature of the previous steady-state conditions, which the sudden change disturbs, is one of the factors affecting the transient behavior. Some of the observations may be explained in terms of strain aging. USUALLY a sudden change during a tensile test from one constant strain rate to another causes a small, abrupt vertical shift from one stress-strain curve to another, parallel one. This behavior is apparently characteristic of all metals at very low temperatures and of many metals for wide ranges of temperature. It is illustrated in Fig. 1 for some early data on 61ST tested at — 195oC, and in Fig. 2 for some recent data on copper at room temperature. The greater accuracy of the results of Fig. 2 over previous ones' is due to the equipment shown in Fig. 3. Three levers apply the bulk of the load, while the changes in the small remainder load are indicated sensitively by a low capacity load scale. Refs. 2 and 3 describe the recording equipment. A test like those in Figs. 1 and 2 provides the information necessary to determine the rate sensitizrity, n,4 of the metal. ( a log s ) ? log s n = ------------------------ ----------------------------= ( a logs e, ? log e logS2-logS1 log S2/S1 log i2 — log e1 log e2/e1 where S equals stress: e is logarithmic strain or natural logarithm of (final gage length/initial gage length);" i is strain rate or de/dt: and n is rate sensitivity, rate of change of log stress with log strain rate at a given strain, or (a log S/a log i),. Normally, the rate sensitivity, n, is positive, which means that an increase in stress causes an increase in rate. However, certain exceptions, attributed to strain aging,5 have been observed. Fig. 2 indicates how rate sensitivity values are derived from the measurements. Table I summarizes the rate sensitivity values derivable from Fig. 1. In contrast to the behavior of copper in Fig. 2, the aluminum alloy 61ST, which strain ages when tested near room temperature, exhibits an unusual transient when the strain rate is suddenly changed,' as shown in Fig. 4. Initially, there is a comparatively sudden vertical shift of the stress-strain curve in a direction corresponding to the rate change, but then the curve gradually shifts back again. The initial shift is not as sudden as might be expected, because the testing machine is unable to achieve the impressed rate change instantaneously, as illustrated in Fig. 2. The behavior shown in Fig. 4 will be referred to as a tensile transient, the word tensile implying that the behavior was observed in a tension type of test. The corresponding test, where the strain rate is maintained constant except for the sudden change, will be called a tensile transient test. A creep transient, by contrast, will be defined as a temporarily abnormal behavior in a creep transient test, where there is a sudden change from one constant load to another.' In Fig. 4, a naive look at the gradually decreasing and then increasing load after a sudden rate incre-

Jan 1, 1957

By C. S. Roberts

Microstructural studies of a Mg-10.3 pct Al alloy showed that discontinuous precipitation during aging multiplies the grain boundary area available for easy deformation in elevated temperature creep. An increase of strain rate for a 6.2 pct Al alloy at 400°F, where precipitation and creep are concurrent, caused an increase in the volume percentage discontinuously precipitated at the completion of the process. The relatively poor elevated temperature creep resistance of heat treated alloys of the Mg-AI-Zn type was explained in these structural terms. C resistance of the heat treatable Mg-A1 based alloys is poor compared to that of Mg-Ce based alloys. While the latter show a continuous precipitate, Mg-A1 alloys prefer a discontinuous precipitate at grain boundaries. '.:' It has been concluded that the excellent creep resistance of Mg-Ce alloys was primarily due to the continuous precipitation which especially localized at the grain boundaries.' The purpose of the present investigation was to obtain a parallel correlation, if such exists, between the poor creep resistance and the state of precipitation in Mg-A1 alloys. Discontinuous precipitation produces about three times as many true grain boundaries as originally existed. This microstructure would be expected to have a marked influence in creep, where quantity of grain boundary area is important. Experimental Procedure The two experimental alloys contained 6.2 and 10.3 pct Al. They were made from electrolytic magnesium by alloying under flux and casting in 3 in. diam permanent molds. The ingots were extruded into 1 1/4 x 1/8 in. flat stock under the following conditions: billet preheat 700°F (2 hr), container and die temperature 700°F, speed 3 fpm, and area reduction ratio 45:1. The creep specimens were machined from blanks which had been solution heat treated 24 hr at 770°F and aged 16 hr at 400°F. Attempts were made to control the grain size as closely as possible for extruded stock. The grain size after solution heat treatment was about two thousandths of an inch for the 6.2 and five thousandths for the 10.3 pct Al alloy.

Jan 1, 1957

By H. C. Theuerer

EVEN the highest purity silicon available for semiconductor use contains significant amounts of donors and acceptors, usually aluminum, phosphorus, and boron. Aluminum and phosphorus can be removed from silicon by adaptations of the zone refining techniques' widely used with germanium. Removal of boron, however, has been a difficult problem. The approximate distribution coefficient for boron in silicon is 0.8, so that while zone refining is possible, it is not very effective in any reasonable number of passes. It has been found, however, that boron can be effectively removed from silicon by treatment of a liquid zone with hydrogen and water vapor. Starting with 40 ohm-cm, n-type silicon, use of zone refining coupled with hydrogen

Jan 1, 1957

By John A. Emery, Frank G. Snyder

MINING geology has a threefold objective: to guide prospecting for new ore, to evaluate known orebodies as development risks, and to supply the detailed knowledge of ore structures necessary for more economical extraction. The role of geology in exploration is well established. This article will deal solely with orebody evaluation and the application of geology to development and mining problems as practiced by St. Joseph Lead Co. in the southeast Missouri district, which for many years has supplied approximately 30 pct of U. S. lead production. The primary concern of the present discussion is geology in the district, not geology of the district. The southeast Missouri district, locally called the Lead Belt, includes parts of St. Francois, Madison, and Washington counties. The first recorded mining was about 1720 at Mine La Motte in Madison County on surface showings of lead ore. Later discoveries near Bonne Terre, twenty-five miles to the north, led to extensive prospecting and underground mining. To date the district has yielded well over 8 million tons of pig lead, valued at more than $1 billion. By far the greater part of the lead production has come from an area of 50 sq miles, centering on the city of Flat River, as shown in Fig. 1. Role of Geology in Metal Mining The history of the use of geology in the older metal mining districts follows a simple consistent pattern that may be considered in terms of four distinct phases. Each geologic phase is a response to the economic status of the mining district; each has definite characteristics setting it apart from other phases; and each passes into the succeeding phase as the mining operation gradually exhausts the large, rich, easily discovered deposits and lives upon increasingly smaller, lower grade orebodies that are less easily found. The geologic phases and their major characteristics are as follows: Period of No Organized Geologic Program: During the early history of a great metal district ore is easily found by random prospecting and wildcat drilling. Many small operators are active, as profitable mining can be done with a relatively small capital outlay and a minimum of technical staff. Mining practice consists largely of sinking a shaft on an ore showing and following the ore in sight. When the ore is exhausted or becomes unprofitable to mine, the process is repeated on a new ore showing. The miners become familiar with certain ore habits and use this practical geologic knowledge to guide mining. The method is successful as long as large tracts of virgin mineralized area are available. This phase ends when small-scale mining methods are no longer profitable and the mines become consolidated into the hands of a few operators.

Jan 1, 1957

By S. Pearson, L. Rotherham

Measurements have been made of the variation of internal friction with temperature for OFHC copper, and for a series of binary solid solutions of high purity copper with zinc, gallium, germanium, arsenic, and silicon, to investigate the effect of alloying elements in substitutional solid solution on grain boundary viscosity. The apparatus used was of the torsional pendulum type developed by KeI1 modified so that the specimen and vibrating system could be maintained in a high vacuum. The activation energy for grain boundary relaxation in copper is 33,000 cal per mol. This is considerably less than the activation energy for self-diffusion, in disagreement with Ke's theory2 that the two activation energies should be the same. All the alloying elements increase the activation energy for grain boundary relaxation to approximately 44,000 cal per mol, increasing the grain boundary viscosity at a given temperature. The results are discussed in terms of theories of grain boundary slip put forward by MottQ and by Ke.+ Experiments have also been made to investigate the effect of small amounts of oxygen on the variation of internal friction with temperature for copper. EXPERIMENTS described in this paper were designed to investigate the effect of alloying elements in substitutional solid solution on grain boundary viscosity, using the internal friction method developed by Kel for measuring grain boundary viscosity. It was considered desirable to make the system under investigation as simple as possible by making experiments on a comprehensive series of binary alloys of copper with the elements immediately following it in the periodic table, i.e., zinc, gallium, germanium, and arsenic. These elements are within the range of favorable size factor for solution in copper, and the systems have been extensively investigated by Hume-Rothery and his co-workers." Later, in order to study the effect of the relative size of the solvent and solute atoms, experiments were made on a series of Cu-Si alloys, since the apparent atomic diameter of silicon when in solution in copper—the diameter necessary to assign to the solute atoms to account for the lattice constant of the solid solutiona—is almost the same as that of the solvent atoms. Preliminary experiments were made to measure the variation of internal friction with temperature for pure copper. Ke made some experiments on copper," but found that the curves obtained were not reproducible in consecutive experiments. The copper was maintained in an argon atmosphere during the experiments but, although he took precautions to exclude oxygen, Ke came to the conclusion that the precautions were not entirely satisfactory, and that the lack of reproducibility must be due to absorption of oxygen by the copper. Experiments have therefore been made to investigate the effect of small amounts of oxygen on the variation of internal friction with temperature for copper. Previous Work Ke made extensive experiments on high purity aluminum and was able to show that the grain boundaries behave viscously at high temperatures. He found that the relative rate of movement of the grains could be expressed as Where v is the velocity of slip, A is the constant, u is the shear stress, H is the activation energy, R is the gas constant, and T is the absolute temperature. By assuming that the boundary layer was one atom thick, he obtained a value for the viscosity which, when extrapolated to the melting point, gave good agreement with the viscosity of the liquid metal at the melting point. Ke also made experiments on other high purity and commercial purity metals:, and on some alloys." " He came to the conclusion2 that the activation energy for grain boundary slip was the same as for self or volume diffusion and for steady state creep in single crystals. Rotherham, Smith, and Greenough" have shown recently that the activation energy for grain boundary slip is not the same as for self-diffusion in tin,

Jan 1, 1957

By John P. Bingham

GRACE mine and mill, owned by Bethlehem-Cuba Iron Mines Co. and operated by Bethlehem Cornwall Corp., are being developed to produce 9600 tons of 42 ½ pct Fe magnetite ore, to yield 5760 tons per day of agglomerated iron concentrates averaging 65 pct Fe. Located about 14 miles south of Reading, the property is ideally situated in relation to good highways and railroad. Three major steel plants, at Bethlehem, Steelton, and Sparrows Point, Md., are about equidistant from the mine. Discovery of the orebody resulted from an airborne magnetometer survey, completed in 1948, con¬sisting of 7000 lineal miles of flight lines spaced one-fourth of a mile apart and extending from the Delaware River on the east to Gettysburg, Pa., on the west. After examining the magnetic maps, Bethlehem's geologists made limited surface traverses over the Grace mine and Warwick area to check the location, and realtors were engaged to purchase the desired properties over and adjacent to the area showing favorable indication of ore.

Jan 1, 1957

IN GATHERING material for this chapter on Yerington and the one to follow on Silver Bell, the A.S.& R. project near Tucson, Arizona, I was fascinated at the way the two stories paralleled each other. For example, here are a few instances: (1) The first copper mining in the Yerington district of Nevada was in the late 1860's; the first in the Silver Bell area in 1873. (2) Each district was served by a branch railroad about 25 miles long from a main line of the Southern Pacific (by quizzical coincidence); and, in each instance, the railroad was later abandoned and torn up. (3) Each district had a sizable blast-furnace smelter ten or fifteen miles from the principal mines, and in each instance the smelter was later dismantled for junk. (4) Up to 1954, the Yerington district was credited with a production of 100,000,000 lb of copper; the Silver Bell district with 80,000,000 lb. (5) In each district the entire production had come from deposits other than the low-grade ore bodies now being exploited. (6) In each instance, existence of the low-grade deposits of the Porphyry type was recognized in the period circa1910-1914 and a substantial amount of exploratory drilling had been done, on one deposit at Yerington and on two at Silver Bell. (7) In each instance, the properties containing the Porphyry ore were acquired by a strong company (Anaconda Copper Mining Company at Yerington and American Smelt-

Jan 1, 1957

By C. B. Alcock, R. G. Hudson

Sulfur pressure measurements above FeS in equilibrium with iron have been carried out by the Knudsen orifice method. A comparison is made of the weight loss of the cell per unit time obtained in the above experiments, that calculated from Richardson and Alcock's measurements of the S2 pressure above FeS in equilibrium with iron, and the dissociation constant for diatomic sulfur from spectroscopic and thermal data. EXTENSIVE equilibrium measurements have been made to determine the sulfur potentials of a great many systems of metallurgical interest.' In order to confirm their reliability, to supply data which may be of use in further thermodynamic calculations, and to establish the reliability of the Knudsen orifice in obtaining accurate thermodynamic values at high temperatures, the present investigation on the pressure of the gaseous species above FeS in equilibrium with iron has been carried out. The Knudsen orifice method has been used for these pressure measurements. Experimental The apparatus and general technique for this investigation are the same as that reported for the determination of the vapor pressure of silver.' To reduce the residual gas pressure in the evacuated chamber, a titanium getter, maintained at run temperature, was introducbed. Several types of Knudsen cells were used—platinum, zircon, and fused silica. The orifice in the zircon cell was fashioned with a small diamond wheel. The same precautions were used in this investigation as were employed in the work on Mo2S2.3 The FeS-Fe mixture was prepared by heating a sample of pure FeS,, supplied by K. K. Kelley of the Bureau of Mines, with excess iron powder, cp grade, obtained from the Fisher Scientific Co. These two substances were heated in a closed Armco iron crucible at 960°C, held in a vacuum of less than 10" mm Hg for 24 hr. The mass was then removed from the cell and ground in an agate mortar. In this form it was charged to the various Knudsen cells. Heating the Knudsen cell for an additional two days was sufficient to obtain constant rates of weight loss of the cell. The data obtained in this investigation are recorded in Table I. To establish whether or not a sulfide of iron is volatile at these temperatures, 0.7646 g of the FeS-Fe mixture, described above and containing 69.2 pet Fe, was placed in the zircon Knudsen cell. Run Nos. 103 to 109 were performed on it. After the completion of these runs, the total amount of iron left in the cell was obtained by chemical analysis. It contained 0.537 g Fe, compared to 0.529 g in the original charge. Thus, there was an apparent gain in iron of 1.5 pet. This is attributed to unknown experimental error, and the conclusion is that no sulfide of iron is volatile. The vapor pressure of pure iron4 is about one thousandth that of the sulfur pressure' at these temperatures. The vapor pressure of iron inside the Knudsen cell will be almost exactly that of pure iron, since in the iron-rich phase the percentage of sulfur is of the order of 0.025 pet.At this low percentage of sulfur Henry's law is probably obeyed by the sulfur. Thus, the iron will obey Raoult's law. In any event, the vapor pressure of iron will be lower than that of pure iron and, since the vapor pressure of pure iron is negligible compared to the pressure of sulfur, the weight loss of the cell due to the vaporization of iron should be negligible. Since neither iron nor FeS is volatile to an appreciable extent, the total weight loss of the cell must be due to the vaporization of sulfur. Discussion and Calculations On the assumption that S, is the only gaseous species present in appreciable quantity, its pressure

Jan 1, 1957

By Cyril Wells, Paul E. Busby, Donald P. Hart

EARLY workers in the field have established that the diffusion of nitrogen follows normal diffusion laws. Concentration-penetration data from layer analyses of reasonably pure iron specimens nitrided in an atmosphere of CO-NH, are given in the literature,' and were utilized to calculate diffusion constants for nitrogen. The diffusion of nitrogen in y-iron may be represented approximately by the equation D - 1.07x10-' e-:".'m'"'r The diflusion coefficients, D, given by this relation represent mean values, since carburization occurred simultaneously with nitriding. The rate of diffusion in a-iron has been determined from calculations based on data obtained by measuring the internal friction of samples at each of several frequencies and temperatures.' The expression for the diffusion of nitrogen in a-iron derived from these experiments is D= 1.4x10-1 e-it tudent Increasing carbon content decreases the diffusion of nitrogen in a-iron.3 Oxygen, either dissolved or combined, has been shown' to exert a marked influence on the diffusion of nitrogen from a nitriding atmosphere. D values increase rapidly with increasing amount of dissolved oxide in the metal, but diffusion is completely inhibited if preliminary oxidation has produced the slightest trace of iron oxide on the surface. Diffusion coefficients have also been calculated from permeability and solubility data,' but these values are of questionable accuracy since the boundary conditions assumed may not actually exist. Experimental Method The method selected for determining the diffusion coefficient of nitrogen in a-iron in the present investigation was the so-called fractional saturation method. This method consists of heating the specimen in an atmosphere of H2-NH8 mixtures of known composition for a predetermined time. Following this treatment, the specimen is analyzed for nitrogen; and the diffusion coefficient is calculated from a known relationship of the fractional saturation, time of diffusion, and dimensions of the specimen. This relation is based on a solution of Fick's second law and assumes that the surface of the specimen immediately reaches a given concentration which remains constant during the diffusion anneal. Tabular solutions are available4-5 and provide the relationship between fractional saturation and the quantity \/Dt /a, where D is the diffusion coefficient in cm2 per sec, t is the time of the diffusion anneal in seconds, and a, in the present experiments, is the half-thickness of the slab specimen in cm. The method is adequately discussed elsewhere.9-10 Material The material for this study consisted of 3/32 in. thick (0.24 cm) carbonyl iron plate. The major impurities in this iron are oxygen and carbon, which are readily removed by long time high temperature treatment in an atmosphere of purified hydrogen. In order to reduce the diffusion anneal time for saturation runs, some of this material was rolled to a thickness of 0.015 in. (0.038 cm) prior to the hydrogen treatment. Hydrogen treatments were carried out in a hydrogen-purified Armco iron tube heated in a global

Jan 1, 1957

By R. H. Atkinson

With the object of improving the melting, casting, and working of palladium and 95.5 pct Pd-4.5 pct Ru, the effects of different melting atmospheres (reducing, oxidizing, and neutral), crucible linings, and annealing atmospheres have been studied. Some interesting observations are included about the solubility and diffusion of gases in palladium. THE object of the present work was to ascertain the effect of oxidizing, inert, and reducing ambient atmospheres on the melting and casting of palladium and a Pd-Ru alloy commonly used for jewelry. The need for such a study was indicated during World War I1 when jewelers experienced difficulty in their attempts to make small castings of the torch-melted Pd-Ru alloy by the lost-wax process. When the metal was melted under oxidizing conditions similar to those used for platinum, the castings were gassy; on the other hand, if the melting atmosphere was reducing, the castings were hot-torn and brittle. General Experimental Procedure Pure palladium sponge (99.9 pct Pd) and pure ruthenium powder (99.8 pct Ru) were used for making small ingots (50 g) of palladium and 95.5 pct Pd-4.5 pct Ru by induction melting. The coil, 3 in. high by 2 in. ID with 16 turns, was energized by a 20 kva Ajax high frequency converter. The melting crucibles, so-called sand crucibles, which were made of a highly refractory fireclay, were lined with different materials, including proprietary magnesia, alundum, zircon, and zirconia

Jan 1, 1957

By C. A. Bruch, W. E. McHugh, R. W. Hockenbury

EXPERIMENTAL results of the last decade have shown that both accelerator particles and reactor radiations produce significant changes in the properties of metals. These changes, called radiation damage, are important from both academic and engineering viewpoints. An understanding of the radiation damage produced by reactor radiations is difficult, because many kinds of particles having varying energies are present. Therefore, many fundamental studies are being conducted using accelerators in order to obtain nearly mono-energetic beams of various charged particles. Furthermore, many of these experiments are conducted at low temperatures in order to freeze in the radiation-produced lattice defects, after which the specimens are annealed to study the movement of the defects. It is found that although much of the low temperature radiation damage disappears by annealing at room temperature, a significant amount remains. Because there is no assurance that irradiation followed by annealing at a higher temperature will produce the same effect as irradiation at the higher temperature, and because there is an immediate interest in reactor radiation effects during exposures at and above room temperature, a major program is in progress at this laboratory to investigate some of these effects. This paper, representing a part of the program, compares the radiation damage to a group of metals which were exposed under nearly identical irradiation conditions. The metals, representing the three major crystal systems, include copper, nickel, titanium, zirconium, iron, molybdenum, and type 347 stainless steel. The effects of reactor radiations have been treated from a theoretical viewpoint by Seitz' and Ozeroff.' The problem considered by them has been the atomic displacements produced in an infinite medium by mono-energetic beams of both neutrons and charged particles. For reactor experiments, this treatment is not wide enough in scope, because specimens and reactor components are finite, and there are continuous energy spectra of the various particles. Therefore, the theoretical considerations will be extended in this paper to cover reactor conditions and the findings will be compared with the observed radiation damage. Experimental Materials—The six basic metals for this investigation were of commercial or higher purity, and the type 347 stainless steel was of commercial quality. These materials were supplied in various forms ranging from ingots to finished rods, and were fabricated to rods approximately % in. in diam and annealed for specimen stock. A summary of data pertinent to these materials is shown in Table I. The values for chemical compositions include both actual analytical values and typical values supplied by the manufacturer. More information concerning typical

Jan 1, 1957

By P. G. Shewmon

Radioactive MgZA has been used to study the rate of self-diffusion in oriented single crystals of magnesium in the temperature range 468O to 635OC. The diffusion coefficients parallel and perpendicular to the c-axis are: Dl, = 1.0 exp (—32,200IRT) cm2 per sec and Dl = 1.5 exp (—32,500IR T) cm Qer sec. The ratio Dl/Dll was found to vary from 1.13 at 468 to 1.24 at 575 C. Assuming a vacancy mechanism, an explanation of this aniso-tropy of diffusion follows from a consideration of the difference in the saddle points for diffusion in and out of the basal plane. RECENT discovery of radioactive Mg2"'-' has made possible the study of self-diffusion in magnesium. The experimental procedure and the results of a study of diffusion in polycrystalline magnesium have been described in an earlier paper.V he present work is an application of the same techniques to the study of self-diffusion in oriented single crystals of magnesium. In the general diffusion problem the diffusion coefficient is a second order tensor relating the two vectors, the diffusion flux, and the concentration gradient. In a hexagonal lattice, such as magnesium, the complete determination of the diffusion coefficient D as a function of direction in the lattice requires a knowledge of D,, and D,, i.e., the diffusion coefficients parallel and perpendicular to the c-axis, respectively. It can be proven quite generally that in a hexagonal lattice D is independent of direction in the basal plane, and that out of the basal plane it varies with 0, the angle between the c-axis and the direction of diffusion, according to the equation D(B) = D,,cos2B + D,sin2B. [I] The proof of Eq. 1 depends only upon the symmetry elements of the hexagonal lattice and upon the transformation properties of a second order tensor." Therefore, Eq. 1 holds for any mechanism of diffusion and any c/a ratio. Experimental Procedure The experimental procedure used with polycrystalline specimens can be briefly outlined as follows. Radioactive Mg" was produced by bombarding a NaCl crystal with 350 mev protons and was chemically separated from the target as MgO. The Mg" was then vapor deposited on a specially cleaned magnesium specimen by heating the MgO on a tantalum ribbon in a vacuum. During the diffusion treatment, oxidation and vapor loss of the radioactive material were minimized by annealing the samples in pairs with the active faces in contact, each pair being inside a magnesium container, which was in turn surrounded by an argon atmosphere in a sealed Pyrex tube. The distance-activity profiles were obtained by measuring the activity of thin sections cut parallel to the original interface with a lathe. The only technique which was peculiar to this work was the preparation and orientation of the single crystal specimens. The single crystals used in this work were grown by E. C. Burke of the Dow Chemical Co., using a modified Bridgman method, in which the furnace and specimen were stationary while the temperature gradient moved.' In growing these crystals the starting material was distilled magnesium, the crucibles were machined from Acheson electrode graphite, and the furnace atmosphere was tank argon. The crystals were grown from sublimed magnesium with the following analysis: 0.0002 pct Al, 0.0017 pct Fe, 0.0009 pct Mn, 0.0001 pct Ni, 0.0006 pct Pb, and less than 0.01 pct Ca, 0.0001 pct Cu, 0.001 pct Si, 0.001 pct Sn, and 0.02 pct Zn. The two crystals used were roughly lh in. diam and eight in. long. The c-axis made angles of about 7" and 78", respectively, with the specimen axes. If the values of D obtained by the use of these two crystals are taken equal to D,, and D,, respectively, the error introduced by this assumption is less than 1 pct. This can be shown by combining Eq. 1, the identity sin% + cos'8 = 1, and the experimental fact that DJDn in magnesium was always less than 1.25.

Jan 1, 1957

By F. H. Deily, H. W. Lownie, E. A. Loria, L. W. Ledgerwood, M. W. 207-000-000-012 Mallett, J. E. Eckel

MANY investigations have been made of the residual gas content of iron and steel. Very few, if any, quantitative measurements have been made on the oxygen content of cupola-melted iron.' The fact that cast iron is a complex alloy rather than

Jan 1, 1957

By James H. Bechtold

The yield strength of annealed tungsten was found to have a strain rate exponent 12 times as great as that of low carbon steel. The effects of temperature and strain rate could be correlated through the Zener-Hollomon parameter with a heat of activation associated with yielding of 32,000 cal per g-atom. This heat of activation is independent of strain although both the temperature and strain rate dependence of the yield strength vary with strain. MOST metals have mechanical properties that are relatively insensitive to strain rate, especially at temperatures below that at which creep is important. In iron and molybdenum," however, relatively large strain rate effects are observed in the temperature range where the rapid increase in yield strength occurs which leads to the ductile to brittle transition. In this temperature range Zener and Hollomon' have suggested that the effects of strain rate and temperature T on the yield strength could be correlated through a single parameter, P, in the following manner where Q is a heat of activation characteristic of the metal and associated with some unspecified relaxation process. They also observed that if the temperature is restricted to a relatively narrow range— below room temperature for steel—that the logarithm of the yield strength could be expressed as a linear function of the logarithm of P. From this relation the logarithm of stress should be a linear function of the logarithm of the strain rate at constant temperature: where r will be referred to herein as the strain rate exponent. At a constant strain rate the logarithm of stress should be a linear function of l/T, ay(e = C) ~ eT [4] where q = Qr [5] and is referred to herein as the temperature exponent. These equations have been found to relate the effects of temperature and strain rate on the yield strength of molybdenum in the temperature range wherein the ductile to brittle transition occurs, —75° to +150°C.2 Bechtold and Shewmon3 have shown recently that the ductile to brittle transition in annealed tungsten occurs in the temperature range +150° to +350°C. In this temperature range the yield strength in-

Jan 1, 1957

By H. L. Sauder, J. L. Newman, C. Waddell

An instrument capable of measuring subsurface flow rates is described. The instrument is self-contained and may be run on piano wire line. It detects flow by means of an impeller suspended between two torsion wires. The force of the well fluid striking the impeller causes the impeller to rotate, exerting a torsional force to the wires. This force is determined by recording the angle of rotation of the impeller on film using a battery-driven, clock-controlled camera. The impeller is sensitive to flow in either direction and the same instrument can be used to measure injection as well as production rates. Changes in direction of flow, such as might be caused by thief zones, are measurable and are indicated by a reversal of the direction of rotation of the impeller. Adjustment of the sensitivity of the instrument to measure a wide range of flow rates is accomplished by the use of different size torsion wires. An umbrella-type fluid trap, which contacts the casing or wellbore, diverts the flow through the flow tube. The fluid trap remains closed while rurrning in the hole and can be opened at any point in the well. The instrument with the trap closed is 1 3/4 in. OD and may be run through 2 in. tubing. Successful flow profiles have been made on wells with flow rates ranging from 60 BID to 4,000 B/D at surface pressure up to 4,500 psi. The instrument is designed for high-pressure and high-temperature operations. INTRODUCTION The need for an instrument that will measure flow rates in a wellbore is as old as reservoir engineering itself. A number of such devices have been designed within the past few years. Some of these have been described in the literature1,2,3,4,5,6 One of these devices1. a hot-wire anemometer type, made many successful jobs in dry gas producing areas. Difficulty was encountered when this flowmeter was used in wells producing liquids and development work was initiated to overcome this difficulty. The present flowmeter is the result of this work and provides an instrument with a wider range of application in the industry. Consider- able development work has been done on the tool involving many changes in the mechanics of recording the flow readings, however, the basic principle of flow detection has remained the same since its inception. PRINCIPLE OF OPERATION The basic principle of operation of the flowmeter is the utilization of a portion of the kinetic energy of flowing well fluid to impart a rotational force to an impeller suspended between two torsion wires. This impeller, Fig. 1, is a screw-type propeller with the blades having a pitch angle of 40. As the well fluid passes through the instrument it strikes the impeller. The resulting force rotates the impeller and twist\ the torsion wires to a balance point at which the torque imparted to the wires balances the force required for the impeller to deflect the well fluid. The impeller is symmetrical and a change in direction of the flow results in a reversal of the direction in which the impeller is deflected. Thus the direction of the flow as well as its velocity is indicated. A dial is attached to the impeller by means of a hollow tube through which the upper torsion wire extends. The angular position of the impeller is recorded by photographing the dial at frequent intervals. In any given set of torsion wires the modulus of shear and polar moment of inertia remain constant and the deflection varies directly with the applied torque. The deflection imparted to the torsion wires also varies as the square of the fluid velocity. Further, the velocities represented by any two given deflections hear the following relationships: and Where V = velocity of flow stream and O ;= deflection. This is the basic relationship which is used to calculate the relative velocities represented by a given set of deflections where the velocity represented by any one of the deflection readings is a known quantity. For a given torque, the deflection of the torsion wire varies inversely as the fourth power of the wire diameter. Wire sizes ranging from ,005 in. in diameter to .022 in. in diameter can be used. The range of

Jan 1, 1957

By C. S. Matthews, M. J. Fischer

Distortions caused by dip on five-spot sweep pattern were determined by visual experiments on a model composed of parallel plates of glass with holes drilled at the well positions. This model war designed to simulate a reservoir depleted of its primary oil and containing a gas phase. Prior to interference, it was found that the injected fluid took a nearly circular shape about the injection well for the cases studied. However, these circles moved down-dip considerably under the influence of gravity. It was concluded that pattern flooding should be practical for many dipping reservoirs. A quantitative measure is given of how much the well position should be altered to allow for dip. Experimental deternzinarions of injectivity showed this to be about the same in a dipping reservoir as in a horizontal one. INTRODUCTION This investigation was undertaken at the suggestion of the Pacific Coast area, Shell Oil Co., where a pilot water flood in a dipping reservoir was being carried out at the time this paper was in preparation. Prior to the undertaking of this flood there had been considerable speculation as to how gravity would distort a flood pattern in a dipping reservoir. The thought was expressed in some quarters that a five-spot flood would not be applicable to a dipping reservoir because the flood pattern would elongate in the direction of dip and would never form a "seal" around each five-spot. If the flood pattern elongated sufficiently, both the oil and the water might flow largely downdip rather than into the pattern producers. In view of the importance of the California water floods, it was deemed important to determine the effects of gravity on a five-spot pattern in a dipping reservoir. Previous work had also been carried out in this laboratory,1 but only for the single-fluid case. The present investigation extends these results to multifluid cases. Several sets of pictures of flood fronts are presented so that the process can be visualized. From these pictures, curves are obtained which show the correct drilling position for achieving equal times of oil-bank breakthrough. Several injectivity curves are also presented which may aid in prediction of injection rate. ASSUMPTIONS The present results were obtained with a model composed of two parallel plates of glass spaced about 1 mm apart. When the inertial forces are small, as in these experiments, the flow between the plates follows Darcy's law and is analogous to flow through porous media. In using these plates, it is not possible to scale effects of capillarity correctly as regards a transition zone between injected and displaced fluid. Calculations show, however, that effects of such capillarity should not be important in determining the gross flooding pattern in the field. In fact, in this model the capillary forces tend to circularize the pattern to a greater degree than in the field. To preserve a large ratio between the viscous forces and the circularizing capillary forces in the laboratory model, viswus glycerine was used as the flooding liquid and the rate of flooding was very high. The circularizing force is believed negligible in these experiments. In addition to the effect of the surface tension y, which tends to circularize the pattern, another capillary force must be considered. This is the adhesion tension y cos, which acts at right angles to the circularizing term y. If the plates in the model are "wetted" the same all around the periphery, then the adhesion tension,

Jan 1, 1957

By G. Sachs, E. P. Klier, W. Beck

HYDROGEN embrittlement of steels has recently attracted much attention because it is asso- ciated with a variety of failures, especially those of aircraft structural components.' For instance, one of the undesirable properties of the ultra-high strength steels used for landing gears is their pronounced susceptibility to hydrogen embrittlement during plating. The presence of hydrogen in these steels becomes particularly apparent through delayed or sustained load failures of parts which have been subjected to low loads for an extended time. A number of variables are involved in causing a reduction of strength and ductility through hydrogen

Jan 1, 1957

By Daniel M. Bass, Paul B. Crawford

Laboratory investigations have been made to study the effect of variations in fluid characteristics, gas saturation, water saturation, and water injection rate on oil recovery by water flooding. Three synthetic gas-saturated crude oils having bubble points of 860, 1,540 and 1,885 psi were used as reservoir fluids. Repeated tests were made in which a and pack, saturated with water and synthetic oil, was produced by solution gas drive followed by water flooding at various pressure levels. Oil recovery by solution gas drive and subsequent water injection is shown to vary with the pressure and rate at which the water flood is conducted. The pressure at which optimum flooding conditions exist is shown to be a functiotl of the physical characteristics of the reservoir fluid. For the systems studied, increases in oil recoveries of near 10 per cent were obtained by flooding at the most desirable conditions. Va- riations in initial water saturations gave results similar to those in the literature. INTRODUCTION Most of the waterflooding studies investigating means of improving present exploitation processes have been conducted at low pressures with little effort to simulate reservoir conditions. Holmgren and Morse' performed a waterflooding study at 300 to 500 psi wherein the gas saturation was created by injecting gas, letting dissolved gas evolve from the oil, and then flushing the core with "live" oil until the desired gas saturation was obtained. Their results show increasing oil recoveries with increasing gas saturations. Data presented by Guerrero' and Kennedy, et al, indicate that in some instances water flooding at approximately 500 psi below the original bubble point results in a lower residual oil saturation than is obtained when water flooding above the bubble point. In their work gas saturations were created by primary depletion. By correcting low pressure flooding data for fluid shrinkage, Dyes found that a maximum oil recovery may be obtained by flooding with initial gas saturations of from 7 to 12 per cent. The purpose of this work was to determine the variations in oil recovery caused by initiating a waterflooding program at various stages of primary depletion of a core. This is a part of a more comprehensive study of obtaining criteria for determining when to initiate a pressure maintenance program and what fluids to in-ject. EQUIPMENT A schematic diagram of the apparatus is shown in Fig. 1. Fluid transfer was accomplished with metering pumps. Pressure control was ob-

Jan 1, 1957

By Elmars Ence, Harold Margolin

The Ti-Fe and Ti-Fe-0 systems were re-examined because of the controversy regarding the existence of Ti2Fe, and to consider all available data points to the existence of Ti,Fe. The Ti-Fe-0 system contains two ternary compounds: E, corresponding to Ti2Fe; and y. SEVERAL authors have investigated the constitution of titanium-rich alloys of the Ti-Fe system. The most extensive study of titanium-rich portions of the Ti-Fe system was by Van Thyne, Kessler, and Hansen,' who investigated this system up to 50 pet Fe and used the highest purity materials available for their alloy preparation (iodide titanium was used for alloys up to 20 pet Fe). According to Van Thyne et al., phase relationships in the region of investigation are governed by phases a,ß, and TiFe. No evidence of an intermetallic compound Ti,Fe was found. although earlier. works by Laves and Wallbaum,' and Duwez and Taylor' reported its existence. Rostoker's study on the occurrence of TilX phases" confirmed the findings of Van Thyne et al. Rostoker proposed that the compound Ti Fe found by Duwez does not exist but is actually a ternary compound, Ti1Fe3O, originated by inadvertent oxygen contamination. The partial isothermal section of the ternary Ti-Fe-0 system as reported by Rostoker' seems to confirm this explanation. In the course of phase diagram work conducted at New York University, however, certain irregularities were observed to be associated with ternary systems of the type Ti-Fe-X. The ternary phase 6, observed in the systems Ti-Fe-Mo' and Ti-Fe-V." was found to be structurally identical to the com-pound Ti2Fe as reported by Duwez and Taylor, and to Rostoker's compound Ti1,Fe2O. Since the amount of oxygen possibly present in the Ti-Fe-Mo and Ti-Fe-V systems could not account for the observed amounts of the compound, it appears that the d phase in these systems is not Ti,Fe,O. On the other hand, considering the amounts of the 6 phase, particularly in the Ti-Fe-Mo system, the location of the phase was uncertain. It was felt that the introduction of the Ti2Fe phase would alleviate some of the inconsistencies of the two systems. Because of the uncertainties relating to the phase Ti2Fe, or Ti1Fe2O, it appeared worthwhile to re-examine the Ti-Fe and Ti-Fe-O systems in the vicinity of these compounds with highly sensitive metallographic techniques and with X-ray methods. Experimental Procedure Alloy Preparation—For the study of the binary system four alloys were prepared, containing 26.9 (30 wt pct), 34.0 (37.5 wt pet), 41.2 (45 wt pet), and 56.3 (60 wt pet) atomic pet Fe, and for the ternary Ti-Fe-O system 18 alloys were prepared in the composition range of 1.6 to 16.9 atomic pet 0 and 24.3 to 55.7 atomic pet Fe. The materials used for the Ti-Fe alloys were iodide titanium (99.98 pet Ti, 0.002 pet 0) and Ferro-vac-E iron (99.95 pet Fe, 0.0052 to 0.0072 pet 0). For the Ti-Fe-O study the materials used were sponge titanium containing less than 0.06 pet 0, Ferrovnc-E iron, and Baker's analyzed TiO2. The nominal weight and atomic percentages of the ternary alloys prepared are shown in Table I. Melting—Charges of 10 to 15 g were melted in a nonconsumable arc furnace in argon atmosphere according to the technique described elsewhere.'" Since there was practically no weight loss through the various stages of melting and oxygen losses have not been observed previously, it appeared justifiable to use nominal composition for interpretation of data. Iodide titanium control buttons, of the same mass as the Ti-Fe charges, and melted under the same conditions, were used to check hardness pickup during melting. A hardness increase of 2 to 3 Vhn was found. Heat Treatment—The specimens were annealed in quartz capsules under argon. To avoid contact between the specimen and capsule material all specimens were wrapped in titanium sheet. The annealing times are given in Table 11. The attain-

Jan 1, 1957