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By M. Shelef, A. W. Fletcher

The effect of alkali sulfates in promoting the sul-fation of nickel and copper in a bulk sulfide flota -tion concentrate by fluidized bed roasting has been studied in the laboratory, and it was shown that the various alkali sulfates promote sulfation to approximately the same extent. The sulfation of a mixture of synthetically prepared iron and nickel oxide and of nickel ferrite has also been studied. Nickel sulfation was promoted by high ratios of Fe:Ni and by the presence of sodium sulfate. THE work described in this paper was a continuation of earlier studies into the role of alkali sulfates in promoting the sulfation roasting of nickel sulfides1,2 in an endeavor to determine how the system was affected by the presence of compounds of iron and copper. The earlier work1 showed that, in the sulfation of NiO at 680°C, the reaction was limited by the formation of an impermeable film of nickel sulfate on the oxide surface. The relative effect of the various alkali sulfates in promoting nickel sulfation varied in the order: Li > Na >Cs > Rb > K A study of alkali sulfate/ nickel sulfate interactions at high temperatures showed that the promoting action was due to the fact that the nickel sulfate product layer sintered and agglomerated only when the more active additives were present. This resulted in the formation of discontinuities in the nickel sulfate layer so that diffusion of the sulfating gases to the NiO surface was no longer impeded and the reaction could proceed to completion. A similar explanation was used for the observation that sodium and lithium sulfates promote the oxidation of NiS to NiO at temperatures below 750°C since small amounts of nickel sulfate were formed during oxidation.2 It was of interest to study the effect of alkali sulfates on the sulfate roasting of a sulfide flotation concentrate which is typical of material treated commercially. In order to control temperature it is essential to roast sulfides in a fluidized bed and this technique was therefore used, although the batchwise operation of a small-scale laboratory reactor does not reproduce all conditions which prevail in full-scale continuous plant. The results obtained are therefore only comparative, and cannot be used for predicting the optimum conditions for metal extraction. The sulfation of synthetically prepared mixed oxides of nickel + copper and nickel + iron and of nickel ferrite was also studied to evaluate the relative effects of alkali sulfates with more complex systems. SULFATION ROASTING OF A SULFIDE FLOTATION CONCENTRATE The bulk sulfide flotation concentrate used in this work contained 7.92 pct Ni, 1.74 pct Cu, 35.66 pct Fe, and 31.28 pct S. The sulfide minerals present in order of abundance were pyrrhotite FeS, pyrite FeS2, pentlandite (FeNi)S, and chalcopyrite CuFeS2. Two samples described as coarse and fine were used. The coarse sample, which was a flotation concentrate (58 pct plus 300 mesh), was ground to 100 pct minus 350 mesh to produce the fine sample. Before roasting, the sample of sulfide concentrate was agglomerated by wetting witli a solution of the alkali sulfate (or water), thoroughly mixing, and drying at 110°C. This gave a cake which was gently crushed and screened, the -18 +100 mesh fraction being used for fluidized bed roasting. A similar-size fraction had been used by the authors in pilot plant work with a 4-in.-diam fluidized bed reactor.' In this work it was found that the molar ratio of additive to the total iron + nickel + copper content of the sulfide sample should be adjusted to a value of approximately 0.06, as this was the optimum amount necessary for nickel sulfation. Experimental. The fluidized bed reactor consisted of a quartz tube approximately 60 cm long and 30 mm in diameter resting in a vertical tube furnace. The sulfide bed (30 g) was supported on a bed of -4 +12 mesh quartz particles 3 cm high, which rested on a sintered quartz disc welded to the tube. The temperature of the furnace was controlled with a variable transformer to give a final bed temperature of 680°C. The bed was fluidized with air or mixtures of air + 10 pct v/v SO2, at a total apparent gas velocity of 60 to 65 cm per sec at 680°C. The SO2 was introduced into the fluidizing air stream only when the oxidation of the sulfides was completed. At the end of the roasting period the calcine was leached with boiling water and the

Jan 1, 1964

By P. A. Tucker, T. B. Rhinehammer, D. E. Etter, J. E. Selle

The Ce-Cu phase diagram was investigated by differential thermal analysis and rnetallography. Two congruent melting compounds, CeCu2 (817°C) and CeCua (938°C), and three incongruent cornpounds, CeCu (516°C), CeCu, (796°C), and CeCu, CERIUM and copper have been suggested as possible diluents in a liquid-plutonium fueled reactor. As part of the determination of the Ce-Cu-Pu ternary phase diagram, a review Of the Ce-Cu system (798°C), are present in this system. Eutectics exist at 28 at. pct Cu (424°C), 74 at. pct Cu (756°C), and 91 at. pct Cu (876°C). The purity of the cerium used has an important effect on the results obtained by differential thermal analysis. was considered necessary. Previous work by Hanaman was conducted with relatively impure metal: 96.7 pct Ce with 2.5 pct other rare earths and 0.5 pct Fe as major impurities. The metal had a melting point of 715°C as compared to the melting point for pure cerium of 804°C as reported by Spedding and Daane.2 Results presented in this work were obtained primarily by differential thermal analysis (DTA) and metallographic examination of slow-cooled or quenched samples.

Jan 1, 1964

By W. L. Freyberger

In a study of the kinetics of flotation of coal, employing a single-cell continuous flotation system, Jowett and Safvi1 pointed out that it was experimentally impossible to float all of the coal which could be floated in a batch tests. On the other hand, deBruyn and Modi, in a discussion of their paper, suggested that under certain conditions the recovery of floatable material from a similar one-cell continuous system would have been 100%.2 Both of these pairs of authors make the assumption that a state of perfect mixing exist in the flotation cell. This assumption, usually made by investigators studying flotation kinetics in a continuous system, has been confirmed experimentally on several occasions. The work is summarized by Arbiter and Harris.3 It is the purpose of this note to demonstrate that, for conditions of perfect mixing, one of two conditions exist: 1) the recovery of floatable material is 100%, and the flotation is infinitely fast, or 2) the recovery of floatable material must be less than 100%. This theorem can be proved simply in the following manner: 1) If recovery, R, of the floatable material is 100%, the concentration in the tailing must be zero. This follows from the definition of recovery as

Jan 1, 1964

By Y. Kondo, A. M. Gaudin

A combined method for sizing in the sub-micron range was developed using centrifugation and gamma emission. Its essential features are: 1) Centrifugation of suspended mineral in water carried out at 4°C where water has its maximal density and zero temperature gradient of density 2) Gamma activition of the sample suspension induced by irradiating it in a nuclear reactor prior to centrifugation 3) Measurement of the activity of a beam of suspension as it is sedimenting in the centrifuge, using a scintillation counter provided with a discriminator. Albite, the sodium feldspar, was used as feed to the comminution step, and the induced gamma activity of Na24 was measured. Dissolved sodium ion caused a a non-settling activity in the measurement. Other "noise" is due to scattered gamma radiation from albite particles in the centrifuge outside of the line of sight. These two activities were obtained sep arately and subtracted from the total activity counted. The relative solid concentration in the suspension under the collimating slit is proportional to this net activity. The cumulative weight per cent of undersize particles was calculated and plotted against size on logarithmic scales. The relationship was found to be linear down to about 30 mµ. The specific surfaces calculated from particle size distribution agree with those measured by krypton gas adsorption. The measurement of particle size distribution of comminution products has been of interest in clarifying the mechanism of the process. The Gaudin-Schuhmann equation1,2 relates the cumulative percentage undersize, y, to relative particle size x/k. The particle size, x, and the size modulus, k, together with the distribution modulus, m, characterize the particle size distribution, m is the slope of a plot of log (y) against log (x/k). This equation has been verified for ground particles down to 1 micron in size.3'4 For particle sizes smaller than a few microns, the precision and facility of sedimentation and microscope techniques become questionable. Use of a centrifuge which shortens settling time from weeks to hours is attractive. Many centrifugal methods have been proposed; however, determination of the solid concentration of the suspension at a reference level as a function of time is difficult, and sampling the suspension is likely to introduce errors. Measurement of particle size distribution by X-ray absorption in gravitational5 and in centrifugal6 sedimentation have also been tried. In these methods, the absorption coefficient for the solid is independent of size, since the wave lengths of the X-rays and gamma-rays are orders of magnitude smaller than the particles. Radiometric techniques7 in size distribution measurement have been developed within the last several years. They offer advantages over usual gravimetric and optical methods. PRINCIPLE OF METHOD The combined method of centrifugation and gamma emission for sizing in submicron range described in the present paper has the following essential features. 1) Centrifugation is carried out at 4 ± 0.1°C. Convection currents in the water phase due to density changes caused by temperature variation may disturb completely the settling system. To avoid this difficulty, the unique property of water having zero temperature gradient of density at 4°C is used. 2) Prior to size measurement the sample suspension is irradiated in a nuclear reactor and gamma activity induced. The gamma activity of the particles sedi-mented radially is measured by a scintillation counter provided with a discriminator. By this method, interruption of centrifugation by withdrawing samples is avoided and the counting rate at any time represents the solid concentration in the suspension at the level of the collimating slit of the centrifuge at the particular time at which the measurement is made. 3) By proper selection of the feed material and of the comminution device, gamma activities of foreign

Jan 1, 1964

By A. S. Appleton

The diffusion of carbon in Fe-Co-C austenites was studied as a function of cobalt concentration up to 12 at. pet, using an autoradiographic technique. The diffusion coefficient was found to initially decrease and then increase with increasing cobalt concentration, the trends being more marked the higher the temperature of diffusion. These effects were paralleled by variations in the activation energy and the constant for diffusion which, however, were found to be dependent also on the carbon content. The results are compared with the previously available data and their significance is discussed in terms of the kinetics of solid-state reactions in this systern. THE influence of cobalt on the diffusivity of carbon in austenite was first studied by Smoluchowski,' his data being that most commonly cited in works

Jan 1, 1964

By R. J. Arsenault

The yield drop that occurs in tantalum, Cu-AZ. and Ag-Al was investigated as a function of strain rate and at several temperatures. From the strain-rate dependence of the yield drop an activation volume was calculated and found to agree with that obtained from differential strain-mte tests. The temperature dependence of the yield drop can he explained in terms of the parameter temperature divided by activation volume. The yield drop is attributed to the rapid multiplication of dislocations during their motion. THE yield-point or yield-drop (upper yield stress minus the lower yield stress) phenomenon has been the subject of numerous investigations1-9 in both bcc and fcc metals. Also, there is no dearth of theoretical explanations10-20 to account for the yield-point phenomenon. The present explanations can be divided into two categories: the concept of dislocation locking and subsequent unlocking and the concept of multiplication of dislocations due to their motion. The Vottrell10,11mechanism of locking and unlocking, as applied to bcc metals, is the best known of the three proposed locking mechanisms. The two additional mechanisms, short-range order (SRO)7,16,17 and Suzuki-type locking,14,15 have been employed to account for the existence of yield points in fcc metals. The experimental evidence supporting the locking of dislocations, especially in bcc metals, is well-established. The dependence of the yield point on interstitial concentrations,' the kinetics of strain aging,2 and the observations by electron-transmission microscopy18 are some of these experimental results. The number of experimental observations supporting dislocation locking in fcc metals is not as extensive as in bcc metals. The unlocking of dislocations, which actually is supposed to account for the yield drop, is by no means well-established by experimental results for either bcc or fcc metals. The similar temperature dependence6 of the yielding and plastic flow is one of the experimental factors that cannot be explained in terms of the unlocking of dislocations. The mechanism based on the rapid multiplication of dislocations has been proposed by several investigators. 18-20 Johnston and Gilman19 have proposed a detailed model of yielding, which was later employed by Hahn21 to predict quantitatively the yield drop in iron. This mechanism was discussed in a previous paper22 and several limitations were pointed out. In the same paper it was shown that an activation volume could be obtained from the strain-rate dependence of the yield drop and that a correlation existed between the activation volumes obtained from the yield-drop tests and from differen-

Jan 1, 1964

By I. B. Cadoff, J. C. Bilello, R. Rosenberg

Diffiusion of magnesium into the surface of LiF crystals to controlled depths and subsequent heat treatments provided a wide range of surface zone harahesses and structure, The bend strength of the LiF crystals was increased by as much as an or-dev of magnitude. Ductility was achieved when dislocation generation occurred in the diffusion zone or when dislocations penetrated to the surface from the intevior. A critical surface hardness of 130 to 140 kg per sq mm was found helozu which generation could take place in the diffusion zone and ahoue which the zone was impenetrable, This hardness was obtainable by several methods, among them the aging of quenched MgF2 -LiF solutions to produce MgF, precipitation. Maximum hardness was ohtained in quenched specimens with no visihle evidence of MgF,. Diffusion-zone formation followed a parabolic rate law and an activation energy of 20.9 kcal per mole was obtained for the process. RECENTLY, the properties of ionic crystals as related to surface condition have been receiving much attention, specifically the transitions between ductile and brittle behavior. Originally Joffe 1 showed that NaCl crystals could be made ductile by immersion in water and related this to the elimination of surface microcracks. Aerts and DeKeyser 2 and Gorur 3' have subsequently shown that ionic crystals are inherently ductile and are embrittled through contact with air. Machlin and Murray4 hypothesized that a layer of NaCIO3 produced by contact of ozone with NaCl induced embrittlement by acting as a barrier to outward dislocation flow. westwood,' Rosenberg and Cadoff,9 and Bilello and cadoff' have reported surface strengthening of LiF crystals by coating with a magnesium compound and then heat treating for adherence. The major effect of the coat was to inhibit dislocation-slip lines from reaching the specimen surface. westwoods showed microcrack formation and fracture to be caused by slip-band interactions at the surface. The material presented in this paper is an extension of the work reported earlier by Bilello, Rosenberg, and cadoff'6,7 and illustrates the wide range of surface properties and bulk behavior obtainable by use of heat-treated magnesium-diffused surface regions in LiF crystals. EXPERIMENTAL PROCEDURE The LiF single crystals were obtained from the Harshaw Chemical Co. Some batch to batch variation was observed; therefore all specimens for a given test series were cleaved from the same crystal. The typical dimension used was 1 by 0.1 by 0.40 in. Surface damage resulting from cleavage was removed by chemically polishing in a 2 pct NH4OH solution. Each group of specimens was given a vacuum anneal at 700°C for 4 hr to provide a base standard for measuring comparative effects of various surface treatments. To produce the reacted surface zone, the annealed specimens were immersed in a boiling suspension of MgF, in doubly distilled HzO, agitated slbwly for 30 sec, removed, and dried at room temperature. Uniform coatings of MgF, were deposited with a thickness of approximately 5 mils. It should be noted that this technique can be modified for use with crystals which are soluble in water by using boiling absolute alcohol as the dissolving medium. This was found effective for the coating of NaCl with MgF2. The diffused surface zone was obtained by annealing the coated samples at elevated temperatures in a vacuum of lob4 mm Hg. Penetration depth was controlled by varying the annealing time from 1/2 to 28 hr. After heat treatment, the samples were tested for bend strength and hardness. Load was applied by four-point bending in a hard-beam testing jig. Four-point rather than three-point bending was used to provide a wide area of constant stress and to minimize the effect of localized inhomogenities in the specimen. The deflection rate was 8 x min-' and the distance between knife edges was 1/4 in. Load-time curves were obtained from a chart recorder coupled to the machine and converted to resolved shear stress on the shear plane vs deflection, as plotted in the figures. The unstressed portions of the sample outside of the two outer knife edges were used for the microhardness studies. Microhardness measurements were made with a Bergsman tester attached to a Reichert metallograph. All hardness impres-

Jan 1, 1964

By Larry Kaufman, Martin Schatz

The effect of pressure on the extension of the ? loop in the FeSi system has been determined by means of metallogvaphic studies and hardness measurements performed on a series of high-purity Fe-Si alloys containing 7.5, 11.0, and 13.9 at. pct Si, respectively. These mensurements, performed at 42 kbar and temperatures up to 1200oC, indicate that the ? loop is expanded to about 10 at. pct Si at 42 kbar as opposed to a maximum extension of 4 at. pct Si at 1 atm. Comparison of the experimental results with thermodynamic predictions of the pressure shifts yields satisfnctory results. DURING the past few years, several studies have been performed in our laboratory1-' in order to determine the effect of high pressure on phase equilibrium in pure iron and iron-base alloys. The purpose of these studies has been to elucidate the effects of high pressure experimentally and to compare the observed results with predicted pressure effects derived on the basis of known thermody-namic and volumetric data at 1 atm. These studies have included work on pure iron2,5,7 as well as Fe-Ni,1,5 Fe-cr,l,5 and Fe-c4-6 alloys. In addition, Tanner and Kulin3 have reported results of pressure studies on two Fe-Si alloys containing 2.0 and 6.25 at. pct Si. At the time of this latter study, no detailed information was available concerning the difference in volume between the a (bcc) and ? (fcc) phases in the Fe-Si system as a function of silicon content. In order to compare their observations with calculated pressure shifts, Tanner and Kulin were forced to assume that silicon had no effect on the difference in volume between a and ? iron. The resulting discrepancy between their calculation of the a/? phase boundary at 42 kbar and the observed results led them to the conclusion that silicon additions probably decrease the difference in volume between a and ? iron. Recently: Cockett and Davis8,9 have reported de- tailed studies of the lattice parameters of a series of Fe-Si alloys at temperatures ranging from 20" to 1150°C. These measurements, performed on alloys in the bcc and fcc range, show that silicon does indeed decrease the difference in volume between a and ? iron. By correcting the calculations of Tanner and Kulin in line with the observed effect of silicon they were able to show improved agreement between computed and observed pressure shifts.' The present measurements were undertaken to provide additional corroboration of this effect, by extending the range of composition, in addition to exploring a situation where large extensions of a ? loop could result in impingement of the ? field with an ordered bcc phase (based on Feo.75Sio.25). I) EXPERIMENTAL PROCEDURES AND RESULTS The alloys investigated were obtained from Dr. F. Kayser of M.I.T. They were prepared at the Ford Scientific Laboratory by vacuum melting electrolytic iron and high-purity silicon. The melts were poured under an argon atmosphere into hot-topped steel molds. Subsequently the ingots were hot-worked down to 1/2-in.-diam rods. Three alloys containing 7.5, 11.0, and 13.9 pct Si were studied. Carbon, regarded as the principal impurity, analyzed at, or below, 0.001 wt pct for all of the alloys. Prior to pressure-temperature treatment, the rod was annealed for 24 hr in vacuum at 1000°C, water-quenched, and subsequently machined into 0.100-in.-diam by 0.100-in.-long specimens. Subsequent to machining, the specimens were again annealed and then examined metallographically. They were found to exhibit a clear coarse-grained ferrite similar to Figs. 10 and 110 of Ref. 1 and Fig. 2 of Ref. 3. Subsequently, specimens of each alloy were equilibrated at 42 kbar at various temperatures in supported piston apparatus.1,3,4,6 Three specimens, one of each alloy, were wrapped in platinum and exposed simultaneously. The pressure-temperature cycle consisted of increasing the pressure from ambient to 42 kbar at 25oC, heating rapidly to the desired temperature, holding for 15 min, and quenching to 100°C, followed by slower cooling to 25°C and pressure release. The temperature was measured with a Pt/Pt-13 pct Rh thermocouple which was not corrected for pressure effects. Subsequently, specimens were examined metallographically and by

Jan 1, 1964

By F. V. Lenel, J. A. Dromsky

The influence of thermal and mechanical treatments upon the elevated-temperature stability, the microstructure, and the mechanical properties of aluminumaluminum oxide alloys is investigated. Compacts from atomized and flake aluminum powders were sintered at temperatures just below the melting point of aluminum in a vacuum of 10-4 Torr for several hours and were then hot-extruded. During this treatment the hydrated oxide present on the surface of the powder particles decomposes, the water vapor produced reacts with the aluminum forming additional oxide, and the hydrogen developed is removed by diffusion to the surface. Extrusions of compacts so treated are stable at temperatures up to the melting point of aluminum and do not form blisters and internal defects typical of extrusions from untreated powder. Electron micrographs of extrusions from unsintered compacts show long parallel oriented platelets typical of the IN previous investigations1,2 the properties and structure of aluminum alloys were described which had been produced by cold compacting aluminum powder and then hot pressing and extruding the compacts. Both the structure and the properties of these alloys differ significantly from those of commercially produced aluminum-aluminum oxide alloys. When commercial alloys are produced, they are given a sintering treatment in air at about 600°C between cold compacting and hot pressing.3 During this treatment the hydrated oxide, which forms the coating on the aluminum-powder particles from which the alloys are prepared, is decomposed.4 The chemically bound water which is released reacts with the aluminum and forms aluminum oxide and hydrogen. Most of the hydrogen is eliminated by hydrated oxide skins on the original powder particles, while the oxide particles in extrusions from sintered compacts are broken up. The strength of extrusions from treated powder is somewhat lower, but their ductility is considerably improved over that of extrusions from untreated powder. The slip-trace patterns on electron microgvaphs of extrusions which had been strained in tension before replication indicated that the grain size of the extruded alloys was approximately the same as that of the original powder particles. Coarse-grained alloys were produced by severe cold work and annealing of the extrusions. They have significantly lower room-temperature strength, but about the same ductility as the vacuum-sintered fine-grained alloys. The size and shape of oxides in the coarsegrained alloys is similar to those of the fine-grained alloys, but the particles are somewhat more uniformly distributed. diffusing to the interior or exterior surfaces of the compact, but it is difficult to eliminate all of it because the solubility of hydrogen in solid aluminum is very low even near its melting point. Extruded alloys which are not sintered before hot pressing and extrusion appear quite sound upon metallo-graphic examination, but develop severe surface blistering and internal fissuring when they are heated to elevated temperatures after extrusion. Fissures and blisters have been observed even in commercial alloys which had been sintered in air, although they are much less severe.' Because of the importance of this sintering treatment it was studied in this investigation in a modified form, using vacuum sintering rather than sintering in air, to insure more complete elimination of occluded hydrogen. The technique is described and the effect of the treatment upon the structure of the alloys is documented. It has been known for some time that extruded aluminum-aluminum oxide alloys are very finegrained, but an exact delineation of grains in electron micrographs has not been possible. In the conventional metallographic-etching techniques etchants attack the interface between the second-phase particles and the matrix in the alloys much

Jan 1, 1964

By R. A. Matuszak

This paper discusses the major portion of the hoist (drag or crowd) system and it shows how static control accomplishes its major aims. In 1959, the first truly static control for Ward-Leonard equipped electric excavators was designed, developed and placed in service. The control system, originally intended only as a more modern electronic type of alternate to the proven rotating amplifier control system has since proven to be much more. When they conceived the original system, the designers had much more in mind than simply replacing the rotating amplifier with one that had no moving parts. The long range plan, which started with the initial system consisting of an SCR (silicon controlled rectifier) preamplifier and magnetic amplifier power amplifier, called for eventually, a control system low in cost and maintenance, relatively simple in design and extremely reliable. The plan also included the elimination of as many of the shortcomings of the rotating system as possible. No small accomplishment, when it is considered that the rotating control system had been, with only minor modifications, the standard of the industry for 20 years. The final step in the original design plan called for the eventual development of an amplifier that could be used as one of the basic building blocks of the future. DEVELOPMENT RESULTS Since the successful unveiling of the first static control system, continuous development has resulted in a slow, but sure progression along the path described by the original plan. The first version of the new control corrected one of the shortcomings of the rotating system by removing the necessity of operator anticipation. This was accomplished by making the system faster in response so that the operator noticed virtually no delay between his movement of the master controller and that of the machine. Thus, after the operator became familiar with the operating characteristics of the machine, he was able to become more relaxed while digging. The natural result of this accomplishment was higher production. All of the subsequent versions of this new control were even faster than the initial design. Although it was not distinguishable by the operator, the further increase in response resulted in large gains in the limiting of transient torque peaks applied to the machine while digging. Also, a more effective control of the torque and power peaks was obtained when plugging the motion being controlled to a stop. (Plugging is the use of the Ward-Leonard ability to regenerate power and absorb energy from the load to

Jan 1, 1964

By Michael Hoch, Daniel B. Butrymowicz

The isothermal section of the Ta-Ti-Zr-0 system at 1500°C was investigated using X-ray diffraction and rrzetallographic techniques. Up to 71.4 at, pct 0 the system contains nine four -phase regions. Zsopleths at 10, 20, 30, 40, 50, and 60 at. pct 0 were constructed. The purpose of this investigation was to determine the general shape of the quaternary equilibrium phase diagram of tantalum, titanium, zirconium, and oxygen at 1500°C. The system was truncated at 66.7 at. pct 0 on the Ti-0 and Zr-0 binaries and at 71.4 at. pct 0 on the Ta-0 binary. The Ti-Zr-0 system was investigated in this laboratory.' The binary systems of interest have been compiled and discussed by Hansen and Anderk, chmidt, Hayes, Roberson, and asche, and Hoch and athur.' EQUIPMENT The Same equipment as that for the study of the Nb(Cb)-Ti-Zr-0 system was used.' The X-ray dif- fraction patterns were analyzed with the help of the ASTM card set7 and NBS circulars.' MATERIALS The tantalum powder (99 pct pure), the titanium powder (99.6 pct pure), the tantalum pentoxide, and the zirconium dioxide used in this study were purchased from the Fairmont Chemical Co., Newark, N.J. The zirconium powder (99.4 pct pure) was obtained from the Charles Hardy Co., Inc., New York. Reagent-grade titanium dioxide was purchased from the Matheson Co., Inc., Norwood, Ohio. The oxides were dried in air at 700°C for 24 hr before use. Though the materials used were not "hyper-pure", the impurities present do not affect the results (lattice parameters, phase boundaries), within the experimental accuracy. PROCEDURE The samples were heated by induction in a vacuum furnace, and examined metallographically and by X-ray diffraction at room temperature. The procedure was the same as that in the Nb(Cb)-Ti-Zr-O work,' EXPERIMENTAL RESULTS AND DISCUSSION OF DATA A four-component system can be represented by a tetrahedron at a single temperature and pressure

Jan 1, 1964

By Charles R. Cavanaugh, John F. Elliott

The activity of nickel in liquid Pb-iVi alloys which are rich in lead was measured in the temperature region of 700° to 1100°C by means of the galvanic cell: The electrolyte used was stabilized zirconia. Tlze data were correlated using the a function, and a plot of the temperature coefficient aE/aT All subsequent calculations of the thermodynamic properties are based on these two functions. The activity, activity coefficient, and molar properties of mixing of nickel are reported. Nicke1 shows extreme positive deviations frorn ideality while lead shows a very slight positive deviation in the composition range studied The study of the activity of nickel in liquid Pb-Ni alloys reported herein was undertaken to explore the use of stabilized zirconia, an oxygen-ion electrolyte, with liquid-metal electrodes, and to obtain further information on the thermodynamic properties of the liquid binary Pb-Ni system. The cell The reversible electromotive force of the cell results from the difference in the chemical potential of the oxygen at the two electrodes: po, (left) - p~ (right) = -4E5 [I] The chemical potential of oxygen on the right is fixed by the activity of nickel in the solution and pure solid nickel oxide. That on the left is set by pure solid nickel in equilibrium with pure solid NiO. By definition: Since the chemical potential of nickel is related to the chemical potential of oxygen through the equilibrium constant for the formation of NiO from nickel and oxygen gas, the electromotive force of the cell is also expressed In this case, n is 2, E is the reversible potential of the cell, and 5 is Faraday's constant. The work of Kuikkola and wagnerl and Schmalz-reid2 has shown that the stabilized zirconia electrolyte is essentially an ionic conductor at the oxygen levels encountered in the experimental arrangement of the work, i .e., PG > 10-l7 atm. THE EXPERIMENTS The advantage of this type of reversible cell over those using a liquid electrolyte is the simplicity arising because the electrolyte also functions as one of the containing crucibles. A further simplification was the choice of the Ni (sat.)-NiO electrode as the standard. This permitted a ready check on the behavior of the electrolyte, as the potential of the cell must become zero when the right electrode becomes saturated with nickel, either because of a change of temperature or because of the addition of nickel to the electrode. It also permitted the potentials being measured to lie in the most satisfactory experimental range of 0 to 100 mv. Although it was not theoretically necessary, lead was included in the standard electrode as it assured good contact between the electrode and electrolyte. Cell Design. The general arrangement of the experimental cell assembly is shown in Fig. l(a) and the details of the cell itself are contained in Fig. l(b). The anode lead wire on the interior of the cell was connected to a coil of perforated sheet nickel. Within this coil were nickel oxide pellets which were held beneath the surface of the liquid Pb-Ni alloy. A disc of nickel oxide was held at the bottom of the external crucible (alumina) by means of the thermocouple protection tube. The nickel oxide disc and pellets were compressed dry at 10,000 psi and sintered at approximately 1000°C for an hour in air. A major experimental difficulty of reversible electromotive force cells with liquid electrodes is the selection of suitable materials for connecting

Jan 1, 1964

By E. Martinez, M. L. Hollander

Sulfurization of copper oxides was investigated using differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). When mixtures of cuprous oxide and sulfur were heated, the surface of the cuprous oxide was converted to cupric sulfide at the melting point of sulfur (119°C); additional sulfuriza-tion took place when the sulfur vaporized above 200°C. Cupric oxide also reacted with sulfur to form cupric sulfide but the starting temperature was approximtely 225°C. When the cupric oxide and sulfur were physically separated, sulfurization still occurred indicating a reaction with the vapor phase of sulfur. Sulfurization was obtained in runs with cuprite, chrysocolla and basic copper carbonate. Further decomposition of cupric to cuprous sulfide was noted at somewhat higher temperatures. The DTA-TGA data made it possible to set up postulated reactions in each system. These techniques were found to be well suited for studies of this type. Because of the difficulty encountered in flotation of many metallic oxide minerals, efforts have been made to find suitable reagent combinations to sulfi-dize these minerals in the flotation circuit. Recently Bautista and Sollenberger,1 using a different approach, showed that the surfaces of many oxide minerals can be converted to sulfides by heating them with sulfur to temperatures between 150° and 225°C. This technique was effective even with chrysocolla, a mineral which is very difficult to sulfidize. The primary objective of the present study was to obtain information on the reactions between the oxide minerals and suIfur. A better understanding of the mechanisms involved might prove useful in pointing the way to improvements in the process. A secondary objective was to demonstrate the value of thermo-analysis in investigations of this type. Bollin and Kerr2 have reported the use of a modification of differential thermal analysis to study the thermal reactions which occur on heating elemental constituents in a closed system to synthesize copper sulfides and iron sulfides. Differential thermal analysis (DTA) was used to detect enthalpic changes as mixtures of minerals and sulfur were heated. The DTA indicated the temperatures at which reactions started and whether they were exothermic or endothermic. Weight change data were obtained by thermal gravimetric analysis (TGA). These data could often be used to support postulated reactions and to eliminate consideration of other possible reactions. EQUlPMENT Differential thermal analysis (DTA) involves measuring the temperature difference between the sample being tested and a thermally inert reference, generally aluminum oxide, as both are heated at a uniform rate. Series connected thermocouples in the sample and reference are used to detect the temperature differences that occur as the sample undergoes enthalpic changes.3 Crystalline transitions, fusions, vaporizations, dehydrations, decompositions and many solid state reactions can be detected. A DTA unit manufactured by the Robert L. Stone Co., Austin, Tex., was used in this investigation with a temperature rate increase of 10°C per min. The samples and reference were placed in Inconel cups with wells in the bottom into which the differential thermocouples fit, and run in a nitrogen atmosphere. Thermal gravimetric analysis (TGA) measures the changes in weight that a sample undergoes as it is heated. A Chevenard thermobalance converted electronically for graphic recording was used with a heating rate of 5°C per minute. An X-Y recorder plotted temperature on the X axis and weight changes on the Y axis. A flow of 250 ml per min of nitrogen was streamed through the furnace. Samples were placed in a porcelain crucible open at the top, unless otherwise noted. EXPERIMENTAL RESULTS Sulfur: Two sulfur samples from different sources were tested. The DTA of a high purity sulfur and a reagent grade sublimed sulfur are shown in Fig. 1. Nearly all the tests were run with the sublimed sulfur due to the difficulty in grinding and high electrostatic charge encountered with the high purity sample. Sulfur undergoes three endothermal reactions below 200°C. The first is a solid-solid crystalline transi-

Jan 1, 1964

By M. E. Volin, D. W. Fuerstenau, A. L. Mular

This paper presents the results of an investigation of the effect of feed size on the integral rate at which feed material is dry ground in a laboratory rod mill. The data are interpreted in terms of the Gaudin-Meloy distribution equation. The equation, Mo — Mt/t = Aoxo r-1, is found to hold for feed sizes smaller than some critical size or for grinding times larger than some critical time. It is shown that a feed grindability is related to this critical size, which appears to be the transition between predominately impact and predominately attrition grinding. Detailed research on feed size effects in comminution has been rather limited. Gaudin1 ground single-sieve fractions of quartz for extended time periods (four hours) in a laboratory ball mill. His work, which was designed to study the nature of size distributions, showed that there is a critical feed size above which comminution occurs primarily by attrition. For his system, the critical size was about 2-mm when using 22-mm balls. In a more recent investigation2 single-sieve fractions of quartz were ground in a laboratory rod mill for constant time periods (15 min) to determine how feed size affects the grindability of the material. This work showed that grindability is essentially independent of feed size in the rod mill after this moderately long grinding period. To further clarify this observation, a study in which feed size and grinding times are varied over a fairly wide range, and particularly, a study of the dependence of the integral rate of grinding on feed size during the initial stages of rod milling is necessary. For an analysis of such data, it is desirable to use a parameter which is very sensitive to change during the initial grinding period when reduction ratios are

Jan 1, 1964

By T. J. Whalen, S. M. Kaufman

Surface-tension measurements for liquid Fe-C-Co and Fe-C-Ni alloys were performed by the sesszle-drop technique at 1350o and 1425°C. Cobalt was shown to he more effective than nickel in lowering the surface tension of Fe-C alloys A minimum value for surface tension of 1640 dynes per cm was found in the Fe-C-Co system at a concentration of 1.5 pet C and 12pet Co. Analysis of these measurements in terms of adsorption and desorption behavior indicated that cobalt and nickel lower surface tension in Fe-C alloys by replacing carbon at the liquid-vapor interface. Comparison of results to date for Fe-C liquid alloys has shown that most substitutional-type elements having about the same atomic diameter as iron also have relatively the same influence on surface tension when present in dilute amounts. It has been shown previously that surface-adsorption behavior in liquid Fe-C ternary alloys is related to the manner in which the ternary addition affects the activity of carbon in the bulk solution.' Certain ternary additions, such as chromium, tending to decrease carbon activity cause adsorption of carbon and chromium to the liquid-vapor interface. Additions, such as silicon, increase the carbon activity, resulting in a desorption of carbon and an adsorption of silicon. Both cases were shown to cause a decrease in surface tension due to adsorption. It is the object of this paper, as part of the writers' continuing interest in the effect of alloying additions on the surface tension of Fe-C alloys, to present and discuss surface-tension data on solutions in the ternary systems Fe-C-Co and Fe-C-Ni. Available activity measurements for these systems in the solid state indicate a strong increase in carbon activity when either nickel or cobalt is added to Fe-C alloys.2, 3 EXPERIMENTAL PROCEDURE The alloy compositions used are shown in Table I. These alloys were prepared by vacuum melting in stabilized zirconia crucibles and then vacuum casting into cold-steel molds. The nominal analyses for the alloys used in this investigation are given in Table I. Surface tensions and densities were measured by the sessile-drop method4,5 in conjunction with the tables of Bashforth and bdams.' Specimens were prepared by slicing 1/4-in. cubes from the center of the vacuum-cast ingots and grinding the edges of these cubes until their shapes approximated spheres with flat bottoms. Proper handling techniques, including an acetone rinse immediately before use, assured minimum contamination from sources extraneous to the actual melting. For each experimental run a sample was placed on a BeO plaque and positioned and leveled inside a vacuum induction heating apparatus. The sample and plaque arrangement sat inside a molybdenum tube which acted as the susceptor. Diagrams of this apparatus may be found in the literature.= After heating to temperatures just above the liquidus at pressures of the order of 10-4 to 10- 5 mm Hg, photographs of the drop profile were made using its natural thermal radiation as a light source. Some measurements were made with partial pressures (-1 cm Hg) of a mixture of H2 and He gases. The H2-He atmospheres proved to be necessary at higher nickel contents to retard excessive vaporization losses. Chemical analysis for carbon and the ternary addition was performed for each alloy sample after completion of the experimental run.

Jan 1, 1964

By L. D. Clark, S. S. Saluja

A physical law, governing the rupture of rock by confined explosive charge correspondent to current expressions for determining weight of charge to rupture rock burden, W, was developed in the form Q = cVw3 by two early investigators performing unique experiments with ice. The coefficient C, is found by trial blast. Recent physical tests conducted with rock, synthetic materials and ice to establish the validity of the theory on which it and other related formulae are based indicated: (a) that failure under hydrodynamic impact pressure is by tension rather than shear as was assumed; (b) that the fundamental law of mechanics, enabling the determination of Q = cvw3, modified to the form P = R x Sa x Wb is valid when low velocity explosives are used; (c) that rock breakage under the action of low velocity explosives is entirely due to explosion gas pressure, as was believed; (d) that under the action of high velocity explosive it is due to the joint effects of scabbing and gas pressure; and that further possible modification could make the above equation also applicable to these joint mechanisms. shape could be easily frozen and because large loads would not be required. They found: (a) that the not unfamiliar shearing equation for metals was applicable to ice where P = load in lb; S = periphery of pressure surface, in.; W = burden, in.; K = modulus of rupture by shear in lb per in.2; and (b) that "the form of cavity produced by the application of gradual pressure is similar to that obtained by blasting in rock under similar conditions of free face and pressure surface!" This similarity in crater shapes leads to the conclusion that rock would rupture by shear, as did ice, and its behavior under the force of a blast could be governed by such a relationship as P = S x W x K. Three important interrelated empirical expressions were derived and rock, charging and spacing coefficients C,, C, and e were established and substantiated by trial blasts. In checking the accuracy of the main assumptions, duplication of the ice tests, substituting rock, suggested that K is not constant and that P = K x W x S, though valid for ice, does not necessarily hold for homogeneous limestone.' Conclusions from this later work raised questions making continued investigation desirable because such conclusions do not destroy the practical value of the empirical equations or theory. Further study for the establishment of the relationship between load, burden and periphery of the pressure surface and possible application of these to the mechanism of rock blasting was undertaken by the authors of this paper. MECHANICAL TESTING - EXPERIMENTAL PROCEDURE Certain inconsistencies in the results of the aforementioned tests repeated on three types of limestone suggested these inconsistencies be attributed to rock inhomogeneity. It was also suspected that the loading speed, which could not be held uniform, may have contributed. The earlier work with both rock and ice

Jan 1, 1964

By E. J. Dulis, A. Kasak, R. C. Westgren

The potential of uirought tungsten- and tantaluw-rich alloys of the W-Ta-Mo-Cb system was investigated for high-strength structural applications above 2500° F. Appreciable strengthening of tung-sten and tantalum—essentially attributable to solid-solzction effects—was obtained with binary, ternary, and quaternary alloys. Tensile strengths as high as 67,000 psi were achieved at 3000 OF. ThE quest for wrought structural materials which possess good strength properties at temperatures above 2000°F has led to a considerable research effort during the past decade. In addition to exploring the potential of various high-melting-point refractory metals (such as molybdenum, columbium, tantalum, and tungsten) for very high-temperature structural applications, alloy-development programs have been undertaken to achieve greater strengths than could be achieved with unalloyed refractory metals. The methods of strengthening refractory metal alloys have included both solid-solution and dispersion strengthening. General relationships among the relevant properties (melting point, recrystallization temperature, and high-temperature strength) of refractory metals indicate that the highest strengths at temperatures of 2500°F or higher would be obtained with tungsten-or tantalum-base alloys. Therefore, the present investigation was undertaken to determine the high-temperature strength potential of solid-solution strengthened alloys based on the binary system W-Ta; to effect further strengthening, minor additions of molybdenum and columbium (at the 6 and 12 pct levels) were made. The portion of the W-Ta-Mo-Cb quaternary alloy system of interest is shown schematically in Fig. 1. The component metals—W, Ta, Mo, and Cb—have a bcc structure at all temperatures, and their binary systems are mutually completely soluble.' Complete solid solubility in the W-Ta-Mo and W-Ta-Cb alloy systems has been demonstrated,' and, therefore, it was expected that the quarternary alloys of the system would also exhibit complete solid solubility at all temperatures. In the virtual absence of contamination by interstitial elements, all the alloys would be truly solid-solution strengthened. Twenty specific compositions of this investigation included binary, ternary, and quaternary alloys of the W-Ta-Mo-Cb system as well as unalloyed tungsten and tantalum. The compositions are shown in Table I. EXPERIMENTAL PROCEDURE Consumable-electrode vacuum-arc melting with ac power was used to produce small laboratory-sized, cylindrically shaped ingots (1-1/4 in. in diameter and 2 to 3-1/2 in. long) of the twenty compositions. A furnace was specially constructed to melt as many as four electrode rods simultaneously into molds lined with tungsten or tantalum sheet. High-purity rods of tungsten, tantalum, molybdenum, and columbium were used for consumable electrodes; the diameter of each rod was determined by the desired weight percentage of the component metal in a given alloy. The details of the construction and operation of the melting furnace will be discussed in another p~blication.

Jan 1, 1964

By Sidney Fischler

Large striation-free single crystals of bismuth have been grown from the melt by rapid freezing. Zone-refined bismuth, together with doping impurities if desired, is placed in a shallow flat-bottomed graphite boat and melted in air with a propane hand torch. The torch is then withdrawn in a manner which causes the melt to freeze direction-ally. Crystallization, which resuires only a few minutes, usually results in the formation of a single crystal even when a seed crystal is not used. Crys -tals of any desired orientation may be grown by using oriented seeds. Undoped crystals grown by this method have residual resistivity ratios greater than 200. THE growth of large single crystals of bismuth by either the Czochralski or horizontal zoning technique is not entirely satisfactory. Specifically, difficulties are encountered in producing single crystals of the required dimensions in all desired orientations, and striations caused by low-angle polysynthetic twins are frequently present in the crystals. In addition, both methods are time-consuming and require special apparatus of some complexity. A simpler method has now been developed for growing large striation-free bismuth single crystals of desired orientation in a short time. Fig. 1 shows a typical setup consisting of a rectangular graphite boat which contains zone-refined bismuth, a 1/8-in.-thick flat quartz plate which covers the entire inner bottom of the boat, and three additional quartz plates about 1/4 in. thick which are used to separate the bismuth from the graphite everywhere except at a small area at the left of the boat. The graphite boat is 1 in. high, and its sides and bottom are about 1/8 in. thick. The quartz plates should be smooth and clean. The graphite boat is heated from the right with a propane torch, as shown in Fig. 1, until the bismuth is completely melted. The melt has the shape of a triangle with a narrow neck at the apex farthest from the torch. The melt is frozen direc-tionally by gradually moving the torch toward the right, away from the boat. The bismuth in contact with the graphite, at the left end of the neck, freezes first. The freezing interface then moves down the neck into the main bulk of material, where it develops a convex shape ideal for the continuation of single-crystal growth. The interface continues to move through the melt until the entire bulk is solid. The entire procedure may be completed, in air, in a matter of minutes. The technique described almost always yields a single crystal whose basal plane is nearly perpendi,cular to the bottom of the graphite boat. In earlier experiments, in which the bottom of the melt was in direct contact with the graphite boat, single crystals were grown with basal planes parallel, perpendicular, or at some intermediate angle to the bottom of the boat. At times the orientation of the bulk of the material differed from the orientation of the material in the narrow neck. In these cases, a nucleation site initiated the growth of a differently oriented crystal, and the thermal conditions favored the new orientation over the initial one. The thermal conditions depend on a number of factors, including the heating technique, the placement, shape, and thickness of the quartz plates, the thickness of the walls and bottom of the graphite boat, and the quantity of bulk bismuth employed. All of these factors, plus the initial orientation and the presence and effectiveness of nucleation sites, will determine the orientation of the final large single-crystal slab. When a crystal of specific orientation is desired, an oriented section of a rapid-freeze crystal is shaped by spark cutting and grinding for use as a seed. To grow a doped crystal, the desired impurity is placed in the graphite boat together with the bismuth chunks and seed. Crystals doped with mercury, cadmium, lead, and selenium have been grown. The rate of freezing is so great that the distribution coefficient of any impurity approximates unity. On a gross scale, therefore, impurities should be more homogeneously distributed in rapid-freeze crystals than in Czochralski or zoned crystals. Because of the possibility of constitutional supercooling, however, it is quite possible that impurities are not homogeneously distributed on a microscopic scale in the rapid-freeze crystals. Generally the single crystal slabs which have been prepared are initially 5 to 7 mm thick. Thicker crystals may be obtained by using one of these slabs as a seed. The slab is placed in a graphite boat resting on a large aluminum block, either air- or

Jan 1, 1964

By W. N. Carr, J. R. Biard, B. S. Reed

An analysis of the semiconductor injection laser is presented which is based on a phenomenological model using device and material parameters. The intent of the laser threshold analysis is not to predict from theory the actual threshold current density but rather to provide a logical means of interpreting experimental results. The device and material parameters have been selected such that they describe both the threshold conditions and quantum efficiency of the lasev. A technique is proposed whereby the current required to obtain a population inversion is predicted from device 1-V characteristics. Experimental data are presented which support the analysis. THIS investigation is concerned with the characteristics of GaAs lasers fabricated in this laboratory. However, the assumptions used in these calculations should not limit their application to GaAs alone. It is felt that the analysis is sufficiently general to be useful in describing the operation of other semiconductor-laser materials. ANALYSIS heavily doped semiconductors to be considered. The absorption and/or generation of optical radiation may be completely specified in terms of q(E) and the probability functions f,,(E) and f,(E) which define the occupancy of the valence-band and conduction-band levels, respectively. The symbols used in this analysis are listed at the end. Following the approach of all' it can be shown that the effective gain coefficient, g, in the plane of a forward-biased P -N junction is g(E)=-ai@)[1-fv(E)-fc(E)] [1I In particular Eq. [I] holds for the photon energy at which lasing occurs, Ep. Throughout the following discussion Eq. [I] is considered only for the lasing transition E = Ep. For simplicity the functional energy dependence of the various factors is omitted in subsequent equations. Unless otherwise stated the symbols used represent the values at Ep. If the analysis is limited to the P-type side of the laser junction, the function q(l -f,,) is recognized as the band-to-band absorption in the P-type material at thermal equilibrium. Under forward-bias conditions the function f, is determined by the electron quasi Fermi level in P-type material. For sufficiently large forward bias the second term in Eq. [3] will become dominant and net gain will result; i.e., g will become positive. In order to simplify the subsequent analysis several assumptions are in order at this point. a) No conductivity modulation occurs. /„ is independent of f, and therefore go is a constant. b) The P-type material is heavily doped such that the degeneracy of the valence band permits popu-

Jan 1, 1964

By Louis E. Toth, Alan W. Searcy

A modification of Le Claire's microscopic model for self-diffusion is developed in a form suitable for prediction of activation energies for diffusion in disordered substitutional solutions as well as in pure metals Bonding is considered as a localized interaction, and the energy of bonding between atoms of different types is taken as the arithmetic mean of the energies in the pure elements. The activation energies for vacancy formation and migration in substitutional alloys are shown to depend on the empirical constants developed for self-diffusion when the equations are adjusted for the mole fractions of the two elements. The differences in activation energies between alloys and pure metals are calculated and compared with the experimental differences. MaNY different correlations have been proposed for use in predicting activation energies for self-diffusion or diffusion in dilute alloys. Usually theories for self-diffusion cannot be applied to alloys nor can theories for dilute alloys be satisfactorily adapted to self-diffusion. We present here a correlation scheme which can approximate activation energies for diffusion, vacancy formation, and atom migration in substitutional-alloy systems of any concentration. The activation energy for self-diffusion QD has been correlated to the melting temperature Tm,1, 2 the sublimation energy L,,l the heat of fusion Lf,3 crystal structure, and valence.4 Working with mechanical parameters Le claire5 proposed that the activation energy for vacancy migration Qm could be related to appropriate shear moduli. He also proposed that the activation energy for vacancy formation 62, is proportional to Ls. THEORY We consider that Le Claire's expression for 4, is satisfactory. But an alternate expression for Qm in terms of the bulk modulus is just as satisfactory from a theoretical point of view for the prediction of the energy of vacancy migration in pure metals and can more easily be used for alloys. In order for Qm to be a minimum, not only the moving atom but also adjacent and nearby atoms must undergo distortions. These distortions are neither isotropic as is implied by a correlation with the bulk modulus nor unidirectional as implied by a correlation with a shear modulus, but are complex and multidirectional. A complete analysis in terms of the bulk modulus and all the shear moduli is not yet available. In a first approximation in which only one parameter is used, there is no obvious theoretical reason to prefer the shear modulus over the bulk modulus. The bulk modulus is a much more convenient parameter for use in predicting Qm. Shear moduli are known for less than half of the metallic elements while bulk moduli are usually available. Furthermore, because of the directional dependence of shear moduli, their estimation for alloys appears inherently more difficult than is the estimation of bulk moduli. We assume that the bulk modulus Bs reflects an average value of the shear moduli such that the strain energy at the point of maximum distortion of the lattice during vacancy migration can be expressed as

Jan 1, 1964