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By Frank W. Dickson, George Tunell

Five hot spring areas of the western United States show evidences of present day deposition of HgS; two also show evidences of accompanying Sb2S3 deposition. Sulfide minerals are depositing at or near the surface from hot waters that differ for each spring ai:ea in amount and kinds of dissolved matter. All the springs contain dissolved substances that act as buffering agents and that cause increased alkalinity with increasing temperature. Transport of Sb2S3 is possible in H2O and in boron and sulfide solutions. Increasing alkalinity and temperature enhance stibnite solubility. Quantitatively important transport of HgS appears restricted to alkaline sulfide solutions that contain HgS2=. Elemental mercury probably forms in deep hot waters because HgS breaks down into mercury and sulfur above 200°C, and free S is removed by reaction with water. Elemental mercury should accompany HgS2= in solutions that were at 200°C or higher. Cinnabar deposits from saturated alkaline sulfide solutions because of combinations of temperature decrease, dilution, oxidation, and reactions with wall rock: Amedee Hot Springs, Boiling Springs, and Coso Hot Springs are areas in which HgS is the only sulfide deposited. Hot waters at Amedee and Boiling Springs are supersaturated with HgS or transport colloidal HgS. Steamboat Springs waters deposit mainly silica and stibnite, but they have deposited HgS recently. Sulphur Bank waters deposit mostly stibnite and some HgS. The hot-spring waters of all springs represent highly modified deep water. Field and laboratory studies support the concept of transport of HgS in moderately alkaline sulfide solutions as HgS2=. Fluctuating deposition of stibnite and cinnabar reflects availability of sulfide or variations in deep-source HgS and Sb,S,. Silica and HgS dissolve mutually in alkaline sulfide solutions, and cinnabar and quartz would be expected to deposit simultaneously. Free mercury given off by hot-spring waters would impregnate country rocks.

Jan 1, 1968

By J. F. Butler, H. W. Paxton

The vapor pressures of manganese in equilibrium with several alloys in the iron-manganese-carbon system between 1200° and 1275°K have been measured using the Knudsen effusion technique in conjunction with a vacuum microbalance. The effect of orifice area of the effusion cell upon the measured pressure has been determined. The binary iron-manganese system shows small negative departures from ideality, and the system of mixed carbides, (Fe, Mn)7C3, in equilibrium with graphite behaves ideally. THIS work is a continuation of the investigations in which the Knudsen effusion method has been used to determine thermodynamic activities in systems and at temperatures of interest to metallurgists. In a previous publication,' the free energy of formation of Mn7C3 was determined and some preliminary work on the solution behavior of this carbide with the hypothetical "Fe7C3" was reported. The present work deals with this latter topic and also includes data on the binary ir-on-manganese system. EXPERIMENTAL METHOD The Knudsen effusion method was used to measure the vapor pressure of manganese in both the alloy and carbide sections of this investigation. This dynamic method of vapor pressure measurement presents a problem when studying solid alloy systems in which one of the components has a much larger vapor pressure than the others. Over-all depletion of the alloy in the most volatile component will occur during evaporation so that the pressure of that component will decrease. Even more serious than the over-all concentration change is the surface depletion of volatile component in the alloy brought about by the slow rate of diffusion of this component from the interior to the surface of the solid particle. Since knowledge of this surface composition is necessary in order to relate it to the activity determined through the measurements, changes in surface composition from the analyzed bulk composition are to be avoided in dynamic vapor pressure studies of solid alloys. The system under investigation in this study presents the problem of surface depletion of manganese since its pressure at 1230°K is 105greater than iron and 1020 greater than carbon. Since the existence of a volatile manganese carbide had been ruled out previously,' the high manganese pressure relative to iron and carbon insured that the only species leaving the effusion cell was manganese. Therefore, the effusing species required no analysis so that the manganese pressure was determined directly from the weight loss of the effusion cell. In order to detect small weight losses near the beginning of effusion, a vacuum microbalance was used to weigh the cell continually. These initial weight loss data allowed the rate of manganese effusion to be determined before the surface of the alloy became depleted in manganese. The apparatus used in this investigation is shown in Fig. 1. Temperature was measured using chro-

Jan 1, 1962

For the use of those who prefer manila rope to wire rope for light hoisting and hauling, the Ingersoll-Rand Co. has brought out a new model Little Tugger Hoist which is designated No. 11. The square piston, reversible driving engine, automatic lubrication, inclosed gearing, rum release clutch and worm-operated band brake are essentially the same as in the No. 1 model which was introduced about two Years ago. The main differences are in the diameter and length of the drum, the width of the flanges and, necessarily, the main frame and overall dimensions. The new No. 11 Little Tugger has a hoisting drum 7 in. in diameter by 17 in. long with 5-in. flanges. This accommodates 300 ft. of 7/8 -in. manila, rope. The maximum capacity of this hoist is conservatively rated at 600 1b. The weight of the hoist itself is 358 lb. It is 21 ½ in. long, 31 ¼ in. wide and 23 in. high.

Jan 12, 1916

By David Cole

THE appearance of the Wilfley table in 1897 marked an epoch in the art of concentration of ores. The table has merited and received an almost unprecedented measure of public approval, lasting through its whole patent life. It has been very little improved in itself, or improved upon by competitors. The new machines bidding for popular favor have been of the Wilfley family, but without ability to do markedly better work than the parent m:-chine, or to (to more work except by the use of superimposed decks, the latter having obvious disadvantages. FIG. 1.-The- Butchart RIFFLE System. During the past three years there has been developed at Morenci a new type or arrangement of riffles applicable to the Wilfley type of concentrating table which corrects many of the objectionable features or limitations of the older system and obviates most of the difficulties encountered with it, particularly when handling ores having a low ratio of concentration. The new type is known as the Butchart1 riffle system, and its general arrangement is shown in Figs. 1 and 2.

Jan 2, 1915

By O. E. Palasvirta

Several drum-type, low-intensity dry magnetic separators have recently been described 1,2,3,4 all of which share at least two generic similarities. The magnet consists of a multiplicity of poles of alternating polarity and, the speed of the drum shell, relatiw to the magnet, is such that the magnetics are agitated through rotation of the magnetic particles around their individual axes. The speed of the drum relative to the magnet (differential speed) determines the frequency of the field reversals. For effective agitation this frequency generally has to be above a specific value, which varies according to the mean particle size of the magnetics. With separators of small diameter, say less than 11/2 ft., a sufficient differential speed for treatment of fine magnetite can be attained only by rotating both the magnet and the drum separately; separators of large diameter may attain sufficiently high differential speeds with stationary magnets. Separators of large diameter thus have the advantage of simplicity of design. The capacity of a separator of this type is directly proportional to the speed of the shell. As the centrifugal force opposing the magnetic force increases at a slower rate than the peripheral speed of the shell when drum diameter is increased, large drums can be operated with higher peripheral speeds. Thus they have a higher capacity than smaller drums. Separation is also a statistical phenomenon, i.e. the grade of concentrate improves as the number of agitations or rotations of the magnetic particles per separation increases. As separators of large diameter have space for a large number of magnets they are best suited for production of optimum grade concentrate. The statements above are general clues For separator design. In the following an expression IS derived showing a more exact relationship between the pertinent separator variables. As both magnetic attraction and centrifugal forces are directly proportional to the volume of the affected bodies, complications in mathematical analysis, arising from variable particle size, are avoided by considering the force per unit volume of affected material. For the magnetic force per unit volume Runolinna (3) gives the following equation: V " 1 + N(ur, - 1) uo dr (1) where ur and uo stand for the relative permeability and the permeability of vacuum, respectively, N is the demagnetization factor, B the intensity of the magnetic field, and r the distance from the face of the magnetic pole. The permeability of a specific magnetite ore can generally be considered as a constant. For ground, liberated material N can also be treated as a constant, and the first simplification can be made by writing ur-1 1=k1. 1 + N(ur - 1) uD k1. Fig. 1 shows the field intensity curves for two U-magnets of different size, but of roughly similar geometry of cross-section as plotted against the distance from the plane of the pole faces. The curves

Jan 1, 1961

By R. W. Nelson

The theoretical basis is presented for energy dissipation methods of measuring permeability in saturated heterogeneous media. Analysis starts with the equation for single-phase flow in heterogeneous porous media which is a first-order partial differential equation in the unknown permeability. This equation is reduced to a system of characteristic equations useful in deriving a differential expression for the permeability as a function of the known potential distribution. For steady flow systems the expression is integrable, giving the permeability integral for direct calculation of the distribution along successive streamlines. The boundary condition in permeability is presented and includes a discussion of the special requirement to assure uniqueness. Theoretical results and necessary computations are incorporated into two general computer programs capable of determining the permeability distribution in two- and three-dimensional steady flow systems. Results are then presented for an energy dissipation analysis using the methods and soltware to determine a field permeability thickness distribution. INTRODUCTION Theoretical work leading to the description of fluid flow in heterogeneous porous media has developed slowly and somewhat sporadically, although the areas of engineering applications predominantly involve flow in nonhomogeneous media. The lack of accurate and economical methods for measuring field permeability distributions has been a major limitation to realistic description of natural flow systems. The economical measurement of permeability using energy dissipation methods may overcome this limitation. Among other things, any permeability measurement method involves consideration of energy dissipation; as used here, "energy dissipation method" denotes the following general approach. The areal energy distribution is measured on an existing flow system in porous media. Then through appropriate analysis of the dissipation of energy in the flow system, the permeability distribution is determined throughout the region using the minimum boundary conditions required to assure a mathematically unique result. This paper presents the theoretical basis for such a method, as well as the techniques and computer software needed to carry out the analysis. The method and techniques are then used in a preliminary field application. EQUATIONS DESCRIBING FLOW IN HETEROGENEOUS MEDLA Heterogeneous as used here implies differing in kind, having unlike quantities or possessing different characteristics. Accordingly, a heterogeneous porous medium has unlike quantities or differing characteristics at different locations. More precisely, if a porous medium is heterogeneous with respect to some property, then that property is functionally dependent on the spatial location. (Media properties are considered here as macroscopic.) Specifically considering permeability k,** then k = G(x, y, z) ,............(1) or the permeability is a scalar function G of the location (x, y, z). Spatial variation of several other properties, of which porosity, dispersivity and medium compressibility are but a few, is implied by the broad title of heterogeneous porous media. The term will be used hereafter to imply only heterogeneity with respect to permeability. The porous medium is considered isotropic as implied by G being only a scalar function. Anisotropy

Jan 1, 1969

By M. King Hubbert

In 1856 Henry Darcy described in an appendix to his book, Les Fontaines Publiques de la Ville de Dijon, a series of experiments on the downward flow of water through filter sands, whereby it was established that the rate of flow is given by the equation: q= - K(h2- h2)/I1 in which q is the volume of water crossing unit area in unit time, I is the thickness of the sand, h1 and h2 the heights above a reference level of the water in manometers terminated above and below the sand, respectively, and K a factor of proportionality. This relationship, appropriately, soon became known as Darcy's law. Subsequently many separate attempts have been made to give Darcy's empirical expression a more general physical fornzulation, with the result that .so many mutually inconsistent expressions of what is purported to he Darcy's law have appeared in published literature that sight has often been lost of Darcy's own work and of its significance. In the present paper, therefore, it shall be our purpose to reinform ourselves upon what Darcy himself did, and then to determine the meaning of his results when expressed explicitly in terms of the pertinent physical variables involved. This will be done first by the empirical method used by Darcy himself, and then by direct derivation from the Navier-Stokes equation of motion of viscous fluids. We find in this manner that: q = (N4(p/p)[g - (l/p) gradPI = WE, is a physical expression for Darcy's law, which is valid for liquids generally, and for gases at pressures higher than about 20 atmospheres. Here N is a shape factor and d a characteristic length of the pore structure of the solid, p and IL are the density and viscosity of the fluid, a = (Nd2)(pip) is the volume conductivity of the system, and E = [g - (l/p) grad p] is the impelling force per unit mass acting upon the fluid. It is found also that Darcy's law is valid only for flow velocities such that the inertial forces are negligible as compared with those arising from viscosity. In general, three-dimensional space there exist two superposed physical fields: a field of force of charucteristic vector E, and a field of flow of vector q. The force field is more general than the flow field since it has values in all space capable of being occupied by the fluid. So long as the fluid density is constant or is a function of the pressure only, curl E = 0, E = - grad F where F = gz + dp/p The field of flow, independently of the force field, must satisfy the conservation of mom, leading to the equation of continuity div pq = — f ap/at , where f is the porosity, und t is the time. For steady rnotion ap/at = 0. and div pq = 0 .

Jan 1, 1957

By H. R. Peiffer

The increase in electrical resistivity, ?pT,at 78°K was measured as a function of elongation, E, at 78°K for a 2 pct (approximately) by weight finely divided alumina in silver material. The amount of increase in electrical resistivity (?pT) is a function of the amount of alumina present and can be represented by: ?pT = cen where c and n are constants. The constant c increases and the exponent n decreases with increasing alumina content. Approximately 33 pct of the resistivity increase is recovered upon annealing at room temperature. RECENTLY, dispersed phase alloys' have shown promise for use at elevated temperatures. These materials have a high creep resistance, a high-temperature strength considerably above that of the pure matrix, and a high electrical conductivity. These materials also show other properties such as retardation of re crystallization and resistance to flow even above the melting point of the matrix.' It is believed that high-temperature creep is retarded in these materials because the dispersed phase blocks the motion of dislocations. According to schoeck3 and also Weertman,4 the rate controlling process is the climb of dislocations around the dispersed phase particles. Any mechanical property of these materials, or any other material for that matter, can be explained on the basis of defect structures and their interrelations. It would certainly be interesting to learn something about the effect of a dispersed phase on dislocation densities and also their effect on point defect concentrations following cold work. This is the purpose of the research discussed herein. The method used was the measurement of the electrical resistivity as a function of elongation at low temperatures. This scheme has already been applied to the studies of pure metals.5 Electrical resistivity measurements conducted on pure metals such as copper, silver, gold, and so forth, have indicated that defects such as vacancies and dislocations are formed during deformation.5 It has been shown by van Bueren6 that the resistivity change, ?p, should increase with elongation, E, according to the following relation: Ap=Al/2 + B£3/2 where A and B are constants of the system; ?p is in µ? cm. The first term refers to the amount of resistivity change associated with line defects and the second term with the change associated with point defects. A later calculation yielded exponents of 3/4 and 5/4, respectively.6 Manintveld7 has shown that the resistivity of copper increases with strain according to a 3/2 power law, whereas van Bueren has shown that the resistivity of silver increases according to a 5/4 power law. Assuming then that van Bueren's calculations are correct, it appears that line defects contribute very little to the electrical resistivity. There is some doubt, however, as to the validity of van Bueren's expressions for all cubic metals.' In fact, the data on copper and silver are not conclusive. In this in-

Jan 1, 1962

By Peter R. Morris, Alan J. Heckler

THREE angles are required to specify the orientation of a crystallite with respect to a physical reference frame. The distribution of crystallite orientations in a polycrystal is thus a function of three angular variables. The most widely used experimental techniques for studying orientation in polycrystals lead directly to the pole figure representation, i.e., the distribution of the poles of certain crystallographic planes in terms of two angular variables. In recent years1-5 methods have been developed which permit determination of the (three-angle) crystallite orientation distribution from several (two-angle) pole figure distributions. In this work Roe's method has been applied to the study of orientation in hcp materials. The method is illustrated for commercial purity titanium sheet (Ti-70) which was cold rolled (65 pct reduction), annealed at 1450°F for 3 min, and air cooled. The grain shape was observed to be equiaxed after this treatment. EFFECTS OF PHYSICAL, CRYSTALLOGRAPHIC SYMMETRY In Roe's method the crystallite orientation distribution, w(?,?,F), is expanded in a series of generalized spherical harmonics 11(?,?,F) = E E E W^Zirmtye-tote-in* [l] 1=o ,,,=-I ,,=-I where { = cos 8. The set of Euler angles employed here is illustrated in Fig. 1. The axis for each rotation is denoted by a double arrowhead. The positive sense of each rotation is that of a right-handed screw advancing in the direction of the double arrowhead. The X, Y, and Z directions correspond to the rolling direction, cross direction, and normal direction, respectively. In the initial orientation (10.O), (12.O), and (00 . 1) planes are perpendicular to the X, Y, and Z directions, respectively. The IC/ rotation about the Z axis is carried out first by rotating X into X', Y into Y', and leaving 2 unchanged, i.e., Z' = Z. The 8 rotation about the Y' axis is carried out second by rotating X' into X", 2' into Z", and leaving Y' unchanged, i.e., Y" = Y'. The I$ rotation about the Z" axis is carried out last by rotating X" into X"', Y into Y"', and leaving 2" unchanged, i.e., 2"' = 2". Any specified orientation of the X'", Y'", and Z'" crystal-fixed axis system relative to the X. Y, and Z physical axes (rolling direction, transverse direction, and sheet normal direction, respectively) can be obtained by appropriate IC/, 8, and (F rotations. The Zl,, of Eq. [l] are the Jacobi polynomials, augmented by the square root of the weight function. The Zl,, are symmetric in m,n, i.e., Zl,,= Zlnm. For orthotropic physical symmetry and hexagonal crystallographic symmetry, the coefficients, W!,,, of the series are all real, W!mn = Wzfi, = Wlm~ = Wlfi~, 1 and m are even and n is restricted to 6k, where k = ...,-2,-1, 0, 1, 2, .-.. The determination of the Wlmn from pole figure data has been previously described.'~~ The Zl,, may be written in multiple angle form

Jan 1, 1970

By C. G. Dunn

Identification of the kinds of orientation relationships that may exist among crystals is an important problem in the metallurgical field. As an aid to its solution standard orientations of several orders of twins would be very useful for rapid analyses to discover high-order as well as low-order twin relationships. Although data have been published that give orientations for three generations of twins, these data are not readily useful in the form presented; i.e., in a stereo-graphic projection with one pole per orientation.' However, accurate data based on calculations of the positions of all {1001 planes for such groups would be very useful when presented in tabular form. Therefore, calculations have been made for a group of four orders of twins and the data are listed in Table 3. Illustrative applications are considered briefly, with the idea of pointing out what may be done with large groups of orientations. Method of Computing Orientation OF a Twin It is common practice to describe the orientation of a crystal in terms of the positions on a stereographic net of the poles of certain planes of the crystal. A single position on a net may be given in terms of two angle variables, two sets of which appear in the following equations: Polar Net Wulff Net x = , sin ?p cos Fbp x = r COS ?w y = r sin ?p sin Fp y = r sin ?w cos Fw % = r cos ?p z = r sin ?w, sin +, The three numbers z, y and z determine a length r as well as a direction (0, 4) in an X, Y, Z coordinate system. In the present case, r will be set equal to (h2 + k2 + L2)1/2, where h, k and I are the usual Miller indices for a crystallographic plane, a restriction that facilitates determination of the positions of poles of new planes from those of old or known ones,2 as will become evident later. Furthermore, since twinned lattices have certain planes in common, it is an easy matter to determine the orientation of a twin of a crystal if the orientation of the crystal itself is known. We start therefore with a crystal of known orientation (positions of three {Ioo} poles given) and determine where the cube poles occur in first, second, third and fourth-order twins. Methods for identifying twinned lattices and for making the calculations to find the orientation of a twin have been published.3,4' Reference 4 will be illustrated in the calculation of the orientation of a twin, even though this method differs from the one used by the writer in obtaining the following data on four orders of twins. Consider a crystal S and its twin A1, A' being one of the four {112} or {III} type* first-order twills of S. The orientation of S—i.e., the positions of poles of (I00)

Jan 1, 1945

By Edward A. Loria

Vanadium is one of the materials being considered for use in fast-breeder nuclear reactors. It is a good heat conductor and nearly transparent to radiation, properties regarded as ideal for nuclear fuel containers. The problem has been the metal lacks ductility needed for forming. In our program at Reno Laboratory the effects of the U.S. Bureau of Mines (previous affiliation) the effects of oxygen, nitrogen, and carbon have been reported21,22 nd most recently the effects of boron and boron with carbon.23 The continuing study by the Ames Laboratory of the effects of hydrogen, the most subtle and fugitive element in its relationship to structure and properties, is commendable. The solubility of oxygen, nitrogen, and hydrogen in vanadium (and other bcc metals as well) is related to material purity. With the available limit on metal purity and the interaction (clustering) of hydrogen with the other interstitial and substitutional elements present in their base metal, would the authors comment on the tolerance of hydrogen in relation to oxy- gen that will avoid intergranular fracture and above what content or how seriously harmful in oxygen at various carbon levels? Understanding the true effects of hydrogen (and other interstitial impurities) in vanadium depends on knowledge of the amount present under various conditions and its distribution between various possible positions. Significant amounts of hydrogen may be in "thermo-dynamic" solution, but not as individual atoms in interstitial positions. It may be in grain boundaries, in subgrain boundaries, in vacancies, or in dislocations. Some of the hydrogen may be paired or in complexes with impurities in substitutional solid solution in vanadium. This makes the analysis of the effect of hydrogen vastly more difficult. It should not be expected that hydrogen in grain boundaries will affect slip in the same manner as hydrogen in interstitial positions, nor will the complexes react to heat treatment the same way as hydrogen in dislocations. It is gratifying that the authors have quoted results from two of our inestiations,' but neglected one2' which applied the Petch theory to electrorefined vanadium of high purity and analyzed the effects of oxygen, nitrogen, and carbon on the ai and ky values obtained by the extrapolation and grain size methods. Details can be found in the paper. Briefly, we obtained a ui value of 10,300 psi (t = 5150 psi) at 273°K. The metal also exhibited profuse twinning with high ductility at 123" and 77°K. Nitrogen was more effective than oxygen in increasing ui, the increase being about twice as much for the same impurity level. Carbon additions resulted in only minimal changes in Ui. The corresponding ky increased as oxygen and nitrogen increased, with nitrogen being more effective. Carbon additions resulted in little change. Although the difference in yield strength of vanadium was explained on the basis of the Cottrell-Bilby model of the tearing away of dislocations from the impurity atoms,

Jan 1, 1970

By George Comstock

IT seems a common opinion among metallographists that all light-gray inclusions seen with the microscope in polished sections of steel are manganese sulphide. Examples of this belief are continually appearing, as for instance in the paper by Dr. Henry Fay on manganese sulphide as a source of danger in steel rails,1 and in Lieutenant-Commander Cook's paper on Metallography of Steel for U S. Naval Ordnance.2 Slate FIG. 1-TRANSVERSE VIEW OF THE EDGE OF A SMALL HOT-ROLLED STEEL ROD. ETCHED WITH PICRIC ACID. X 200. colored inclusions are considered to be silicates, and dove-gray inclusions, manganese sulphide. To show the danger in the latter unqualified assumption, it should be sufficient to examine the edge of any piece of steel that is covered with a fairly thick scale, and that has been polished in such a way as to prevent the scale from breaking away entirely below the polished surface. This can be done by protecting the scaled edge of

Jan 12, 1916

By Andrew Cosgarea, William R. Upthegrove, Morteza Mirshamsi

The capillary-reservoir technique was used with lead-210 and cadmium-115m to determine the self-diffiLsion coefficients of both cadmium and lead in the liquid binary Cd-Pb system. The self-diffusion coefficients of pure cadmium and pure lead were obtained and were compared with the theoretical predictions. Good to excellent agrement between the experimental and predicted values was obtained. The self-diffusion coefficients of cadmium were tneasuved in alloys containing 2.50, 9.13, 17.40, 31.00, 45.00, 69.00, and 97.00 lot pct Cd by determining- the amount of cadniiutn-115m which diffused out of a small-bore capillavy into an infinite reservoir during- a given time peviod. Sinzila7-measurements were made with lead-210 to determine the self-diffusion coefficients of lead in these identical alloys. Diffusivities were determined from measurenzents performed in the temperature interval of 290" to 480°C. The results were correlated with the Ar-vhenius equation, and the maximum variation of the equation parameters (Q and Do) was also inrestigated . THE theory of diffusion in liquids, particularly liquid metals, is relatively undeveloped in contrast to that for the gaseous and solid states. Although the practical application of liquid metals as heat-transfer media has become increasingly important, few liquid-metals systems have been investigated. Experimental data of fundamental significance in this field are not readily obtained, which may explain but not justify the present lack of knowledge. What work has been completed is primarily restricted to liquid diffusion of pure metals; little work has been done in liquid-metal diffusion of binary mixtures. A review of liquid-metal diffusion theory and research is available elsewhere.1-4 In an effort to add to the knowledge of liquid-metal systems and to increase the basic understanding of the diffusion process in liquids, a study of diffusion in the binary-liquid system, Cd-Pb, was undertaken. The capillary-reservoir technique5 was employed to measure the self-diffusion coefficients of cadmium and lead in molten binary alloys. Measurements were made with seven selected compositions and over a temperature range from 290° to 480°C. The experimental apparatus consisted essentially of the following items: constant-temperature bath, diffusion cells, capillaries, capillary-filling device, and a radioactive tracer counting system. EXPERIMENTAL APPARATUS Constant-Temperature Bath. A cylindrical steel vessel, 8 in. in diam and 15 in. deep, surrounded by an insulated heating coil was used with a sodium-potassium nitrate salt mixture heating medium. The bath was maintained slightly below the desired control temperature by the furnace-heating element; and a 250-w heater, actuated by a Bayley proportional temperature controller, was utilized for the final control of the temperature. A constant-speed mixer stirred the salt to insure a uniform temperature within the bath. Four calibrated Chromel-Alumel thermocouples were placed at various positions in the salt bath to verify the absence of temperature gradients. The observed temperature variation during any diffusion run was less than 0.l°C. The entire furnace assembly was mounted on four shock absorbers to exclude building vibrations and the stirrer propeller blades were adjusted so not to induce vibrations within the reservoir. A schematic diagram of the furnace and the constant-temperature bath is shown in Fig. 1. Diffusion Cell. The diffusion cells and associated parts were the same, except for slight modification, as the one used by walls1 in this laboratory, and are shown in detail elsewhere.' A graphite crucible, 4 in. long and 40 mm (1-1/2 in.) ID, enclosed in a 60-mm (2-1/4 in.) Pyrex tube cell about 18 in. long, was used as a container for the melt. The reservoir (molten alloy in the graphite crucible) was usually about 2 to 2-1/2 in. deep. Graphite was used because of its satisfactory nature as a refractory material and the low solubility of carbon in molten Cd-Pb alloy.677 The Pyrex cell was closed at the bottom and fitted at the top (open end) with a 2-in. Dresser coupling. A brass flange was welded to the top of the coupling. The upper part of the diffusion assembly was bolted to this flange with an O-ring seal. The lower part of the diffusion cell was supported in a 3-in. brass cylinder which was open to allow for circulation of salt around the cell. The top assembly consisted of two synchronous motors, a drive shaft, a thermocouple well, and controlled-atmosphere inlets and outlets. One motor was used for rotation of the capillaries at a rate of 1/2 rpm in the reservoir during the diffusion run. The other motor was used for the vertical positioning of the capillaries and the capillary holder by means of a simple screw drive. The capillary holder and drive assembly were lowered into the reservoir for the run and raised after the desired diffusion time at a rate of approximately 0.4 in. per min. Capillary holders were made of graphite. These

Jan 1, 1967

By J. W. Powell, F. H. Spedding

A complete review of the use of chelating agents in the sepa ration of rare earths by ion-exchange is given as well as a concise description of the recent pilot-plant operations of the Ames Laboratory. The two chelating agents which show the greatest promise are ethylenediamine-N,N,N',N'-tetraacetic acid and N'-(2-hydroxyethyl)ethylenediarnine-N,N,N '-triacetic acid. The first successful separations of rare earths by ion exchange were reported in a collection of papers which appeared in the November, 1947, issue of the Journal of the American Chemical Society.1'9 Some of this work was performed at the Ames Laboratory of the A.E.C., the remainder at the Oak Ridge National Laboratory. The processes developed at Oak Ridge, as well as some of the early Arnes methods, employed 5 pct citric acid-ammonium citrate eluant at low pH and were carried out on either H+-state or NH:-state resin beds. These techniques were successful for the separation of small quantities of either naturally occurring or radioactive rare earths and are still used for the isolation of rare-earth activities from fission products. Concentrated citrate is not economical, however, for use in moderate or large-scale rare-earth separations. For this reason, the Ames Laboratory turned its attention to lower concentrations and higher pH's in order to make more effective use of the eluting agent.10-14 Although elutions have been performed successfully over a wide range of conditions, 0.1 pct citrate at a pH of 8.0 is highly recommended for use on H+-state resin beds.15,16 Elu-tion with 0.1 pct citrate in the pH range from 5 to 9 brings about the separation of the constituent rare earths into a series of flat-topped elution bands which progress down the resin bed, head to tail, without actually pulling apart as do the rare-earth peaks which develop when trace quantities are eluted with 0.25M (5 pct) citrate at low pH's. Because of this, elution with 0.1 pct citrate at pH 8.0 do not produce pure rare earths unless sufficient quantities are present to provide developed bands which are at least several inches long on the columns. Although other eluting agents have proved more effective than citrate solutions, articles concerning the use of citric acid for separating rare earths still appear in the literature occasionally. For example, Ketelle and Boyd17 reported some further studies on the separation of rare earths with 5 pct citrate in 1951. They used 270 to 325 mesh Dowex-50 columns at 100°C and a pH of 3.28. vickery18 compared the effectiveness of a number of eluants for the separation of rare earths on NH+4 state Dowex-50 in 1952. He found that citric acid was more efficient than acetic, malic, tartaric, and aminoacetic acids. In 1953, Mayer and Freiling18 reported that citrate was inferior to malate, glycolate, lactate, and EDTA for the resolution of Sm-Eu and Y-Tb mixtures on 250 to 500 mesh, NH+4-state, Dowex-50 at 87°C. pinta20 used 5 pct citrate in the pH range 2.8 to 3.4 to obtain some rare earths for analytical work the same year. Trombe and Loriers21 reported the use of citric acid in their laboratory to separate rare earths in kilogram quantities. Lariers and Quesney22 reported some separations with citrate in 1954. They used 5 pct citrate at pH 2.8 to separate yttrium and the yttrium-group rare earths from the cerium-group rare earths. briers23 used 5 pct citrate at pH 3.2 and 90°C as late as 1956 to isolate thulium in fair purity. For the separation of tracer quantities of rare earths, Mayer and Freiling19 have recommended pH 5.00, 0.24M lactate at 87 °C on 250 to 500 mesh, NH+4-form Dowex-50. Freiling and Bunney24 have also employed lactic acid for the separation of fission-product rare earths. Cunninghame, Size-land, Willis, Eakins, and Mercer25 have reported a 4-hr separation of Y, Eu, Sm, Pm, Nd, and Pr with 1M lactic acid at pH 3.25 on Zeokarb-225 at 87°C. Stewart, et al.,26 reported separation factors for rare earths distributing between Dowex-50 and 0.25M glycolic acid. stewart27 also reported a 30-61 separation of Y, Tm, Er, Tb, and Lu tracers with buffered, 0.25M glycolic acid containing 0.05 pct Aerosol OT. The resin bed was 400-mesh Dowex-50 (X12). The pH of the ammonia-buffered eluant was 3.5. Various aminopolyacetic acids have also been used to obtain varying degrees of separation of the rare earths. In 1951, Fitch and Russell28 investigated iminodiacetic acid (IDA) and nitrilotriacetic

Jan 1, 1960

By E. R. Dean

A wire-feed mechanism has been employed to fabricute metal alloy film resistors to various sheet resistivities on oxidized silicon substrates. The effect of several thousand hours storage in air at elevated temperatures on the resistance and temperature coefficient of resistance is presented. Unprotected films of- sheet resistivity between 100 and 500 ohms per sq fabricated at 300°C substrate tenzperatures were unstable when stored at 150°Cfor extended periods. The higher sheet resistivity films exhibited the greatest instability; however, even the 100 ohms per sq films drijted excessively for device application. When stored at still higher temperatures, the normalized resistance increases to maximum, then decreases until a minimum value is obtained, then finally increases in resistance until open. The use of a protective overcoating of SiO has had considerable benejicial effects on the film stability, so that 250 ohms per sq films deposited on 300°C substrates are now stable after 1000 hr storage at 250°C and possess a temperature coefficient of resistance less than 200 ppm per C. The use of a low substrate temperature during depositon (100°C) enables the preparation oj resistors with very low tenperature coefficients of resistance (10 to 20 ppnl per 'C). However, these films are less stable than their higher substrate temperatuve counterparts. During extended storage, the resistance of the protected films always decreases with lower substrate films exhibiting larger normalized resistance decreases. This resistance decrease is accompanied by a linearly related increase in the temperature coefficient of resistance. The electrical behavior of these films may be explained by postulating That the structure of the films is in the transition region between thick continuous films and ultrathin island structure films so that the conductivity is the restlt of both electron scattering and tunneling-activated charge carrier creation between neighboring grains. The annealing behavior when thermally aged is the result of defect anneal, grain growth, and selective oxidation. TheRE is a considerable interest in thin metallic films for use as resistor elements in microelectronic circuits.1,2 These resistor films must be stable when exposed to elevated-temperature storage or operating ambient, possess low temperature coefficients of resistance (hereafter referred to as T.C.R.), and be of a high enough sheet resistivity to be useful. The resistivity and T.C.R. of a thin metallic film are determined by the structure and thickness of the film. Hence the stability of the film when exposed to stress would depend on the stability of the structure. The resistivity of a thin film is the result of the electrons' interaction with the lattice vibrations (electron-phonon scattering), scattering of electrons due to impurities, defects, and grain boundaries and specula reflection from the film surfaces.3' All of these effects serve to reduce the electron mean free path and result in a resistivity higher than the ideal bulk. In ultrathin films possessing essentially an island structure consisting of a planar array of aggregates separated by a few to a few tens of angstroms, conduction is dominated by a combination of tunneling and activated charge carrier reation. Thin films would be characterized by relatively low resistivity, positive T.C.R., and reasonable structure stability whereas ultrathin films possess unstable structures, negative T.C.R., and exhibit high resistivity. Feldman6 has investigated films intermediate between the two regions and postulates that the resistivity of a film in the transition region is composed of two linearly additive parts: that due to the resistance of the grains and that due to the gaps. The grain resistivity would represent the scattering of the conduction electrons by defects, surfaces, and phonon interaction while the gap term represents the tunneling contribution. For gold and platinum films, he found as the film structure becomes progressively less continuous, corresponding to thinner films, the absolute value of the T.C.R. becomes progressively smaller until negative values are observed with respective zero T.C.R.'s at about 35 and 150 ohm per sq, respectively. Recently the author7 investigated the behavior of a multicomponent alloy of nickel, chromium, and iron and found the T.C.R.'s of these films decrease with decreasing substrate temperature during deposition. The lower T.C.A. associated with lower substrate temperatures was attributed to an increased contribution to the total resistivity from the negatively temperature-dependent gap tunneling since it is well-known that thin films deposited on low-temperature substrates consist of a higher density of smaller grains than the same sheet resistivity films deposited on higher-temperature substrates. Under conditions of thermal anneal, the author found that, when various sheet resistivity films fabricated at 300°C substrate temperature are exposed to extended storage in air at 300°C, the thinner films increase in resistance until open, while the thicker films

Jan 1, 1967

By Arthur Baker III

The orebodies are long bedding-plane lenses of chalcopyrite and sphalerite, associated with garnetite masses. Most of the orebodies are within a 50-ft thickness of Cambrian limestone; other Paleozoic limestones and dolomites are locally metamorphosed but only slightly mineralized. Pre-mineral faults are numerous, but shallow folds were the main ore-localizing structures. JOHNSON camp is in the northwestern part of Cochise County, Ariz., about 50 miles east of Tucson. The nearest major mining districts are Tombstone and Bisbee, respectively 27 and 50 miles to the south, and the Superior-Miami-Globe-Ray porphyry copper group, about 90 miles northwest. Like many mining camps of the Southwest, Johnson camp is said to have been worked by the Spaniards. The first production on record was in the early 1880's, when an unknown amount of oxidized copper-silver ore in the Peabody mine was mined from replacement orebodies in the Pennsyl-vanian Naco formation. From 1904 to 1911 outcropping oxidized ores in the Cambrian Abrigo formation were worked, and an estimated 100,000 tons of copper ore were shipped. In 1912 the first large sulphide orebody of the district, the Republic Manto orebody, was discovered, and in the following few years some 250,000 tons of predominantly sulphide ore were shipped. The average grade of this ore was approximately 4.5 pct Cu, 6 pct Zn, 0.8 oz. Ag, and 0.001 oz Au. The Republic, Copper Chief, and Mammoth mines were the principal producers during this period. Mining ceased in the district after 1920, and until 1943 only small-scale leasing operations were carried on. In 1943 all the mines that had been productive were acquired by the Coronado Copper and Zinc Co., the present operators, and in the 10 years since that time the district production has amounted to approximately 350,000 tons of milling ore averaging 2 pct Cu and 6 pct Zn. Most of this ore was produced from the Republic and Mammoth mines, but since 1950 a large part of the production has been from the new Moore mine. The total known production from the district, then, is about 3/4 million tons of copper and copper-zinc ore of low grade. All of this ore was produced from orebodies associated with garnetite in the middle member of the Cambrian Abrigo formation. In addition to this known production, an unknown tonnage of ore was extracted from the Peabody mine orebodies that lie in the Pennsylvanian Naco formation. Published information on the geology of the district is limited. Aside from brief references in various mining journals, only three papers on the district have been published.1-3 One of these is a U. S. Bureau of Mines report on a diamond drilling program, one is a brief paper on the general geology of the district, and the third is a report on geochemical experiments, with a section on the occurrence of the orebodies. The last two are by John Cooper, of the United States Geological Survey, who has done much detailed work in the area. Stratigraphy The rocks of the mineralized area are Paleozoic sediments ranging in age from Cambrian to Penn-sylvanian. Several disconformities are present in the stratigraphic column, the most important one being between the Cambrian Abrigo formation and the Devonian Martin formation. There are no angular unconformities. Within the district, the Paleozoic sediments lie in a fairly uniform monocline, striking northwest and dipping 30" to 50" northeast. This local monocline is part of a domal struc-ture centered in the Little Dragoon mountains to the southwest. The Texas Canyon stock, a quartz monzonite body intruded probably during the Laramide revolution, lies south of the mineralized area (Ref. 2, p. 33). The Paleozoic rocks dip away from the stock, and on the surface are separated from it by at least 1500 ft of Pre-Cambrian rocks. The outcrop pattern of the northeastern edge of the stock suggests that it may dip gently northeastward, passing below the mineralized area at moderate depth. No quartz monzonite has been found in mine workings or diamond drill holes, which reach to depths of 1000 ft. The only igneous rock found in the mineralized area is a lamprophyre dike cutting the Naco limestone in and near workings of the Peabody mine. With the exception of the lowermost beds—the Bolsa quartzite and the shaly lower member of the Abrigo formation—the Paleozoic sediments are predominantly carbonate rocks, Fig. 1. The middle member of the Abrigo formation, which contains the principal ore-bearing beds, is limestone, with thin shale partings throughout most of its 250-ft thick-ness. Near the top of this member is a sandy bed some 25 ft thick. The upper member of the Abrigo formation and the lower half of the overlying Devonian Martin formation are dolomitic, with num-

Jan 1, 1954

By J. C. Bierlein, R. A. Dodd

Endurance strengths at 10' cycles, fatigue-hardening rates, and endurance strength/0.2 pct proof stress ratios have been determined jbr a range of Cu(Ni), Cu(Si), and S.R.0. Cu(Au) solid solutions. Some douht is cast on simple cross slip models of fatigue hardening in view of opposite composition dependencies of hardening displayed by Cu(Si) and Cu(Au). The temperature dependencies of hardening also are the opposite of predictions made on the basis of a cross slip model. A correlation apparently exists between the fatigue strength/0.2 Pc~ proof s1.re.s~ ratios and rates of fatigue hardening. An increase in PS/PS due to alloying or temperature change is accompanied by a decrease in hardening rate, and vice versa. In recent years there has been much interest in the determination of the dislocation structure of fatigued metals and alloys. The accumulated evidence, e.g., Refs. 1 to 5, suggests that the structure may be dependent on the stacking fault energy, 7, of the fatigued metal in the same way that fatigue hardening rates have also been shown to apparently depend on u .6' 7 The above research followed the various earlier theories relating crack nucleation to ease of cross slip, e.g., Refs. 8 to 131 so "ggesting that y may indeed be the parameter of principal significance in all facets of the fatigue process. However, comparatively little attention has been paid to correlating engineering fatigue data with observations of the above type. Certainly, it would be useful if potential engineering fatigue performance could be assessed from a knowledge of easily determined alloy properties, and the present research originated from this standpoint. TO investigate the widest Possible range of 7 would require the use of two solvent bases, e.g., aluminum and copper, but a reasonable coverage can be provided by copper-based solutions alone. Therefore, it was decided to work with Cu(Ni) and Cu(Si) solid solutions, the approximate stackillg fault energies of which are given in Table I. The y range extends from low, Cu(7.5 at- Pet Si), to moderately high in Cu(2-5 at. ~ct ~i) and two of the Cu(Ni) alloys. The values listed in Table I should be regarded as qualitative only, being derived as follows. Dillamore and smallman14 quote a value of 85 i 30 erg.cm-2 for the stacking fault energy of pure copper, based on an earlier value due to Howie and swannl5 corrected by Brown's formula.'' Since the ratios (alloy)h(pure copper) have been reported17,18 for Cu(Ni) alloys containing up to 30 pct Ni, approximate ) values for these alloys can be computed, and a rough estimate of 7 for Cu(50 at. pct Ni) obtained by extrapolation. The relatively low y value obtained in this way for Cu(50 at. pct Ni) coincides with the observation of Nakajima19 that the stacking fault probability is a maximum at this composition. Likewise, the y values for the three ~u(~i) alloys are estimates based on values given by Swann and Nuttingo corrected on the basis Of Brown's estimate that the true 7 values are probably 2.3 times greater than those originally computed. In addition to the above alloys it was decided to investigate short-range ordered (s.R.O.) CU(AU) alloys containing up to 25 at. pct Au. This last alloy has been shown to have a well-defined planar arrangement of dislocations when deformed,21,22 probably due to cross slip being restricted by the S.R.O. Engineering fatigue data was to be represented by the determination of endurance strengths, and these were to be correlated with fatigue hardening and mechanical property data. EXPERIMENTAL I, order to study the desired properties and property changes, the following alloys were prepared: Cu(2.5 at. pct Si), Cu(5.0 at. pct Si), Cu(7.5 at. pct Si), Cu(5.0 at. pct Ni), Cu(25.0 at. pct Nil, Cu(50.0 at. pct Ni), Cu(5.0 at. pct AU), Cu(15.0 at. pct AU), Cu(25.0 at. pct AU). The copper and gold were zone-refined, while the silicon was semiconductor grade. The nickel was of 99.95 p,t. purity.* All alloys were induction-melted in a *Kindly supplied by the International Nickel co. helium atmosphere, appropriate precautions being taken to avoid segregation in the Cu-Au series. Rod stock was obtained by rolling and swag,ng. A few Bridgman single crystals were grown for fatigue-hardening studies, but most material was machined into polycrystalline fatigue speciments of the design shown in Fig. 1, and into polycrystalline tensile and fatigue-hardening specimens of simple cylindrical design. All specimens except Cu(Au) were annealed; the latter were quenched from above T, to produce short-range order. A few of the quenched alloys were examined for long-range order by step-scanning over

Jan 1, 1969

By G. A. Zeito

Detailed visua1 examination of outcrops was used to ob-tain data on the lateral extent of shale breaks. Thirty vertical exposures belonging to maritie, deltaic and channel depositiorral environrrrents were exatmind, surveyed and photographed. The dimensions of the outcrops ranged from 356- to 8,240-ft long and 25- to 265-ft thick. Shale breaks were found to extend laterally for significant distances. and in some sands terminates by joining other break v much more frequently than by disappearance. Consequently with regard to flaw, a gross sand consisted of both continuous and discontinuous subunits. The degree of continuity of shale breaks as well as the occurrence and spatial distribution of discontinuities were different for the three depositional environments. Statistical eva1uations were performed to determine the confidence level with which estimates derived from outcrops can be applied to reservoir sands. Results of these evaluations revealed that: (I) the lateral continuity of shale breaks in marine. sands is si~nificatit, and the estimates of lateral extent can he applied to reservoir sands with a high degree of confidence (80 to 99 per cent of the shale breaks continued more than 500 ft, with a confidence of 86 per cent); and (2) the tendency for adjacent shale breaks to converge upon each other over small distances in deltaic and channel sands is highly significant (62 to 70 per cent of the shale breaks converged in less than 250 ft, with a confidence of 50 per cent), hut the probable magnitude of the resulting sand discontinuities cannot yet he predicted with adequate confidence. INTRODUCTION Almost all of the efforts devoted to characterization of the variable nature of reservoir sands have been focussed on permeability variations. Among the widely used concepts that have emerged from these efforts are those of stratified permeabilities, random permeabilities, and communicating and noncommunicating layers of different permeabilities. This study is concerned with the presence of interbedded shales and silt laminations. These features are impermeable or only slightly permeable to flow. Therefore, knowledge of the extent to which they continue laterally and the manner in which they terminate within the bodies of gross sands is important for proper description of reservoir flow. Initial field observations made on outcrops revealed that shale breaks and the relatively thinner silt laminae have impressive lateral continuity. They appeared to divide sand sections into separate individual sand layers. Although most of the layers were continuous across the total lengths of the outcrops, some were discontinuous because the- bounding shale breaks converged. Furthermore, the discontinuous layers appeared more prevalent in channel and deltaic sands than in marine sands. Based on these initial findings, a detailed investigation was carried out to determine, quantitatively: (1) the degree of continuity of shale breaks in marine. deltaic and channel sands; and (2) the frequency and spatial distribution of discontinuities in the three environments. PROCEDURE The procedure used to obtain field data from outcrops included visual examination, surveying and photographing each outcrop. The photographs were examined carefully and important outcrop features were traced, measured and recorded. The selection of outcrops for this study was made on the basis that each outcrop should be exposed clearly to permit detailed visual examination of vertical lithology. and it should also be sufficiently long (over 200 ft) to provide useful data on the lateral continuity of lithology. Identification of the depositional environment for each outcrop was made on the basis of bedding characteristics, vertical sequence of lithology and the presence of indicative sedimentary features. Whenever possible, hand specimens of associated shales were collected to determine depositional origin. Almost one-half of the outcrops used in this study required environmental identification; the remainder had already been identified by previous investigators. Several photographs of each outcrop were usually required to cover the entire length of the outcrop. These photographs were taken from one station or several, depending on the terrain, size of the outcrop and distance to the outcrop. A Hasselblad camera, with a standard 80-mm lens and a 250-mm telephoto lens, was used. The telephoto lens permitted photographing outcrops as far as two miles away. Slow-speed films were used. either Panatomic-X or Plus-X. The final operation conducted in the field was that of surveying the outcrops. The distance of an outcrop from a point of observation was determined by a triangulation method using the plane table. The measured distance was then combined with the angle of view of the camera lens to establish a scale to be used on the photographs. Films were processed using standard processing techniques and 4.5X enlargements made. The enlargements of each outcrop were butted together to form a single panorama. Slides were also prepared on several outcrops; these were used whenever greater magnification (wall projection) was required to bring out maximum lithologic detail. The shale breaks and bedding planes in each outcrop were traced on transparent acetate film superimposed on

Jan 1, 1966

By J. S. Ll. Leach, L. R. Rubin, M. B. Bever

The energies of formation of ordered and disordered solid solutions of composition CusAu and the energy of ordering in this alloy were determined by tin solution calorimetry. The degree of order was measured by X-ray diffraction and electrical resistance and microhardness measurements were made on ordered and disordered specimens. AMONG the phenomena associated with the order-disorder transformation of a solid solution, the change in internal energy is of special interest because of the part it plays in the various theories of ordering. Published values for the decrease in internal energy accompanying the formation of a superlattice from a disordered solid solution of composition CuAu range from —370 to —2260 cal per gram-atom. Some of these values represent calculations based on theory and others are the results of experimental measurements. The distinction between the change in internal energy, AE, and the change in enthalpy, AH, can here be neglected, because they are approximately equal for solid-state reactions at normal pressure. An analysis of ordering by Bragg and Williams' predicts an energy change of —605 cal per gram-atom for the formation of a superlattice in the alloy Cuau from a completely random solution. Peierls" application to Cuau of Bethe'sb earest-neighbor theory yields —560 cal per gram-atom for the formation of a superlattice from a matrix which initially contains short-range order. Cowley' extended the nearest-neighbor approach to include as many as five shells of neighbors; on this basis a change in energy of —500 cal per gram-atom is expected. Eguchi," using a quantum-mechanical treatment, calculated a value of —2260 cal per gram-atom for the difference in the energy of completely disordered and completely ordered Cu,Au. Sykes and Jones- eated a completely ordered alloy and measured its heat capacity as a function of temperature. This measured heat capacity agrees closely with the corresponding value found by the Kopp-Neumann (or mixture) rule up to about 250°C and above this temperature exceeds it, especially near the critical temperature for ordering. The difference between the integrals with respect to temperature of the observed and the Kopp-Neumann heat capacities was considered to be the energy of ordering. By this method Sykes and Jones found a value of —530 cal per gram-atom. This value is not adjusted for the short-range order remaining above the critical temperature. The pres- ence of such short-range order is suggested by the difference between the measured heat capacity and the extrapolated Kopp-Neumann heat capacity immediately above the critical temperature. Values reported by Weibke and von Quadt' and by Hirabayashi, Nagasaki, and Maniwaa were obtained in the course of investigations primarily aimed at other objectives. Weibke and von Quadt measured the temperature coefficient of the electromotive force of a Cu-CuAu cell. They obtained a value of —1010 cal per gram-atom for the heat of formation of the alloy at 500°C, at which temperature there is no long-range order. They also obtained —1380 cal per gram-atom as the heat of formation of the ordered alloy at 370°C. Considering the heat of formation of the disordered alloy to be independent of temperature, they estimated the energy of ordering at 370°C as —370 cal per gram-atom. At this temperature long-range order is incomplete and the degree of order changes rapidly with temperature. Hirabayashi, Nagasaki, and Maniwa," using an annealing calorimeter, investigated an alloy containing 23.4 rather than 25.0 atomic pct Au and thus could not obtain complete order. Thelr value of the energy of ordering was —490 cal per gram-atom. Orianis has recently investigated the Au-Cu system by the galvanic emf technique. He reports values for the heats of formation of Cu-Au alloys, from which the heat of formation at 427 OC of an alloy of composition CuAu may be found by interpolation. This value is —1080 cal per gram-atom. In the work here reported, disordered and ordered alloys of composition CuAu and corresponding mixtures of gold and copper were dissolved in liquid tin and the heat effects measured. These heat effects are small, since the dissolution of gold in tin is exothermic and the dissolution of copper is endothermic. The method, therefore, yields fairly precise values of the heats of formation of disordered and ordered alloys and of the energy of ordering. Experimental Procedure The calorimeter consisted of a long-necked Dewar flask immersed in a constant temperature salt bath and has been described by Ticknor and Bever." The chief changes in this equipment were an improvement in vacuum and the replacement of the mercury thermoregulator by a resistance thermometer control circuit. The solvent, which was maintained at a constant temperature near 350°C, consisted of 500 grams of 99.99 pct pure tin. The solute samples were mixtures of gold and copper in the proportion corresponding to the composition Cu,Au or solid solutions

Jan 1, 1956

By John D. Morgan, Sylvain J. Pirson

An instantaneous and continuous analysis of a mineral suspension should be of great value in controlling various mineral preparation processes. Described herein is a method of analysis based on the use of high-frequency alternating current, which, under certain restrictive conditions, could be of use. Theoretical Considerations In a suspension of conductive minerals, the electrical effect primarily responsible for the variations in electric conductivity is the capacitance. In Fig Ia, let an alternating voltage E be applied across two electrodes F and F', between which are two rows (S and T) of mineral particles, all of approximately the same size, immersed in a fluid. Let the number of rows of particles between the electrodes be R and the number of particles in each row be N. If A is the area of a particle, D is the distance separating two particles, and k is a constant depending on the fluid, the capacity, CO, of the particle system will be given by: KRA C°= ND Referring now to Fig Ib, let R, the number of rows, be held constant, but let N, the number of particles in each row (S and T), be increased X-fold. The capacity, C1, of

Jan 1, 1949