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By Nicholas J. Grant, David S. Bloom

An investigation of the Cr-Ni system has revealed that there exists a eutectoid transformation at about 1180°C. 'The transformation in chromium implied by the eutectoid reaction was detected at about 100°C below its melting point. Associated with the eutectoid transformation, a metastable transition structure has been found. THE Cr-Ni phase diagram is shown in current literature to be a simple eutectic system in which the high chromium end of the diagram is incompletely determined, Fig. 1. The last investigation of this system was undertaken in 1936.' Because of limitations in metal purity, especially of chromium, and temperature measuring techniques, the diagram should be accepted with some reservations, as was indicated by Hansen.V or examwle.-, the wresence of the compound Cr²Ni, with a tetragonal structure," remains unverified and incompatible with the simple eutectic diagram. The work reported here began because of discrepancies that appeared in experimental studies in the binary alloys Cr-Ni and in the ternary system Cr-Mo-Ni. The existing binary Cr-Ni diagram failed to provide a complete explanation of observations made by microscope, X-ray, and thermal analyses. Experimental Methods The materials employed were of a higher degree of purity than were available to previous investigators. The Mond nickel used had a nominal purity of 99.87 pct, while the electrolytic chromium analyzed 99.03 pct with the major impurity being 0.5 to 0.7 pct oxygen with some iron. All alloys were melted in a vacuum furnace to remove dissolved gases, sufficient carbon was added to the charge to combine with all the oxygen as CO. Final analysis determined the carbon as about 0.02 pct and the oxygen around 0.06 pct or slightly more. Stabilized zirconia crucibles and thermocouple protection tips were used throughout and contributed no detectable impurity to the melts, as long as the oxygen in the chromium was kept low. Heats averaged about 250 g, which permitted about 2 in. of the thermocouple protection tips to be submerged. The temperature drop across the thermocouple protection tip was determined to be about 3°C, a minor source of error. The alloys, after removal from the vacuum furnace, were placed in a furnace operating in a purified argon atmosphere for the thermal analyses. An- nealed wolfram-molybdenum thermocouples provided the primary means of temperature determination, though a Pt-Pt-10 pct Rh couple was employed for a check when possible. A sensitive, high-speed Leeds and Northrup Speedomax recording potentiometer indicated the thermocouple output. X-ray diffraction patterns were obtained primarily on a Norelco unit, which permitted diffraction angles only up to 45" (28 = 90"). In general, either rotated or stationary solid samples were used, because it later evolved that many samples were susceptible to transformation resulting from the cold working involved in pulverizing. It was also noted that rotating a sample sometimes suppressed weak lines, so, usually, samples were not rotated. Later a high temperature camera was adapted for use at temperatures up to 1400 °C on the Norelco unit utilizing both solid and powdered samples. Unless otherwise noted, all X-ray patterns were made with a chromium tube and a vanadium filter. Further-

Jan 1, 1952

By W. S. Stahmann, F. W. Bowdish

Previously published experimental data showing that both collectable and non-collectable sulfide films may be formed on chrysocolla were analysed, and chemical mechanisms were proposed for the formation of the films. A special technique was developed by which the quantity of sulfur adsorbed was determined for samples sulfidized under different conditions of pH and soluble sulfide concentration. The data on sulfur adsorption were used together with the expression for the equilibrium constant for the proposed reaction to indicate the validity of the chemical mechanism theory. A recent paper 1 about contact angle studies on chrysocolla reported the effects of pH value and sodium sulfide concentration during sulfidization upon the character of the surfaces produced. In each experiment the surface of a specimen of chrysocolla was prepared by grinding it with fine abrasive and washing it in tap water. The specimen was then placed in the sulfidizing solution for 10 min, rinsed in tap water, treated for 15 min in a solution containing 30 mg of potassium amyl xanthate per liter, rinsed in distilled water, and tested for air adhesion in a contact angle apparatus. The results, when plotted as in Fig. 1, showed an island representing conditions giving air adherent or collectable surfaces surrounded by conditions giving non-collectable surfaces. Particular interest may be attached to the region of non-collectability to the right of and above the island in Fig. 1, and to the boundry curve separating these two regions. It is apparent that at any pH from 4.0 to 6.0, where a collectable surface may be produced, a sufficient increase in the sulfide concentration results in a non-collectable surface. Thus it appears that too much soluble sulfide has a depressing effect upon the mineral, just as it has in sulfide flotation. This paper presents some speculations regarding the chemical mechanisms by which the collectable and non-collectable sulfide films may be formed and reports on a physical-chemical study intended to support these speculations. THEORETICAL CONSIDERATIONS The experimental results presented in the previous paper were analysed in several ways in an attempt to understand better the chemical mechanisms involved. For several points on the boundary to the right of the region of contact in Fig. 1, molar concentrations of H+, OH-, HS-, and S= ions, as well as various ion concentration products, were calculated. Following the reasoning of Wark and Cox, 2,3 no single kind of ions may be credited with causing depression of the surface because none of them have a constant con-

Jan 1, 1968

By A. B. Kinzel

MUCH work has been done recently in an attempt to analyze the physicochemical mechanism involved in the production of steel by the open-hearth process. . This has resulted in reducing the process to a series of interrelated phenomena obeying the usual laws of mass action and diffusion. Of these, the reaction of the iron oxide and carbon in the molten steel is of most interest from a technical point of view as it con-stitutes the main action in the usual steelmaking processes. A. L. Feild1 has formulated a basic differential equation expressing the open-hearth reactions and Hefty has done considerable experimental work on the determination of a number of constants involved in the basic open-hearth reaction. In considering the application of the law of mass action. to the reaction FeO +C ?? CO +Fe, the iron will be taken as constant, as is the case in the open hearth and the carbon monoxide pressure will be assumed' constant at one atmosphere. From this xy = m at equilibrium, where x is the percentage weight of carbon, y percentage weight of iron oxide and m the weight-concentration equilibrium constant. While it is customary for physical chemists to express equilibrium constants in terms of molar concentrations, the constant is here expressed as the product of the percentage-weight concentrations for ease of comparison with the constants quoted by Herty and by Feild, and for more ready applicability to the open-hearth reactions. Herty and his associates have attempted to calculate the value of this constant from data on open-hearth heats. So many variables affect these results that an adequate calculation presents very great difficulties. A value of 4 X 10-2 was first arrived at, but this was later changed to 1.6 X 10-2. Feild, in order to illustrate the operation of the differential equation of the open hearth, has assumed a value considerably lower than Herty's, namely, 1.0 X 10-2, the largest value consistent with certain theoretical

Jan 1, 1929

Jan 1, 1913

The pressure of the gas in equilibrium with sphalerite has been determined in the temperature range of 680' to 825°C, using the Knudsen orifice method. A comparison of these experimental pressures with those calculated from thermal data and from other equilibrium measurements shows that the vapor above sphalerite is predominantly dissociated ZnS. Equations have been given for correctly calculating dissociation pressures using the Knudsen orifice method. It has been shown that the experimentally determined pressure is the same, whether the zinc sulphide is sphalerite or not, or a mixture of wurtzite and sphalerite. CONFLICTING points of view appear in the literature on the constitution of the vapor in equilibrium with solid zinc sulphide in the vicinity of 800°C. By comparing the dissociation pressure calculated from thermodynamic data and the vapor-pressure determination of ZnS by Veselovski,1 Lumsden2 has concluded that the vapor consists largely of dissociated ZnS. Sen Gupta,' however, concludes from his spectroscopic determinations that the vapor is largely ZnS molecules. In view of the fact that the thermodynamically calculated' dissociation pressure is higher than that experimentally measured by Veselovski, it seemed in order to repeat Veselovski's measurements. Experimental Procedure The method used for the determination of the pressures in this papel- is the Knudsen effusion cell. The apparatus and procedure were described in a previous paper- from this laboratory on the determination of the vapor pressure of silver. The only difference is that the Knudsen cell in this work is made from platinum and there is no external cover around the cell. The cell is an ordinary platinum crucible of 2.2 cm top diameter with a capsule cover. It was thought that platinum might stand up at these temperatures to the solid and gaseous ZnS, since it was found that the weight of the platinum cell itself did not change appreciably on heating ZnS in it at the working temperatures. To insure that reaction of the zinc sulphide with the cell was not giving' a false value, a stabilized zirconia cell was employed for check runs. Fig. 1 shows the comparison, which is satisfactory. Veselovski previously had measured the vapor pressure of ZnS using a silica Knudsen effusion cell. On repeating his experiment in this laboratory, it was found that ZnS at-tacked the silica cell, giving it a marked frosty appearance. This led to the belief that Veselovski's result:; may be in error. Also, he was operating at pressures above the range ordinarily considered safe for the Knudsen method. The effusion rate was measured by weighing the cell before and after each run. The weight loss during heating to temperature and cooling down was measured and subtracted from the weight loss during the actual run. The zinc sulphide used in this investigation was from two sources: Fisher cp grade, and a sample of pure sphalerite supplied by Mr. E. A. Anderson of the New Jersey Zinc Co. Before and after the series of runs with Fisher ZnS, X-ray analysis showed that both wurtzite and sphalerite were present. However, the ratio of sphalerite to wurtzite increased. All measurements were made below the transition temperature which has been reported" to be 1020°C. The data obtained in this investigation are tabulated in Table I. The pressure was calculated by the usual Knudsen formula" on the assumption that ZnS molecules were effusing. From these data, using pure sphalerite in the platinum Knudsen cell, the vapor pressure of ZnS, in mm of Hg, as a function of temperature is given by the solid line in Fig. 1. The best straight line, as determined by the method of least squares, is given by 14405 logpzns =-14405/T +11.032. A comparison of these results with Veselovski's shows that his results are about 50 pct lower. Discussion The vapor in equilibrium with solid zinc sulphide in the temperature range of this study will consist of Zn, S2, and ZnS mol, since other species of zinc and sulphur' are relatively unstable. The question to be settled is whether or not ZnS is largely dissociated. The derivation8 which follows gives the method of calculating the pressure of zinc and sulphur over solid ZnS, assuming complete dissociation, from Knudsen cell data. The free energy of the reaction 2 ZnS(solid) ? 2 Zn(gas) + S2(gas) is given by ?F?° = -RT In K = —RT In p12p2 where p1 is the zinc pressure and p is the sulphur pressure. If dissociation occurs in a closed system,

Jan 1, 1955

By M. B. Bever, A. M. Reti, A. K. Jena

The results of this investigation show that in the system SnTe-PbTe l) the solid solutions have small exothermic heats of formation relative to the binary compounds, 2) solid-solution hardening is almost absent, 3) the tin and lead atoms are .randomly distributed on the sublattice occupied by them and do not undergo an ordering transition during a thermal treatment designed to promote such a transition, and 4) the lattice parameter changes linearly with composition. These findings suggest that the solid solutions of tin telluride and lead telluride approach ideal behavior. THE binary compounds SnTe and PbTe form a continuous series of solid solutions.' Information on several physical properties of these solid-solution alloys has been published.1"3 In the work reported here, the heats of formation, microhardness, and lattice parameters of these alloys have been measured and the possibility of an order-disorder transition has been investigated. Order-disorder transitions occur in some solid solutions of binary compounds. In the system Bi2Te3-BizSes, for example, the electropositive bismuth atoms and the electronegative tellurium and selenium atoms always occupy separate layers. In the disordered alloy Bi2Te2Se, the tellurium and selenium atoms are randomly distributed on the layers occupied by them, while in the ordered alloy they occupy distinct layers.4 The NaC1-type (Bl) structure of SnTe-PbTe alloys consists of two sublattices, one of which is occupied by the electropositive tin and lead atoms and the other by the electronegative tellurium atoms; any ordering would be expected to occur in the sublattice occupied by the tin and lead atoms. PREPARATION OF SPECIMENS Polycrystalline specimens of PbTe and Sn1-xPbxTe (x = 0.25, 0.50, and 0.75) were prepared by melting stoichiometric amounts of lead (99.999 pct), tin (99.98 pct), and tellurium (99.999 pct) in evacuated and sealed Vycor tubes. Because of the deviation of tin telluride from the stoichiometric composition5 this compound was prepared by melting 49.8 at. pct Sn and 50.2 pct Te. The tubes containing the melts were quenched into water; the solidified ingots were removed from the tubes and annealed for 2 weeks in vacuum (PbTe approximately 100°C below its melting point, the three alloys 100°C below their solidus tem-

Jan 1, 1969

By G. C. Wallick

Since the appearance of the paper, "Solution of the Equations of Un-steady State Two-Phase Flow in Oil Reservoirs," by W. J. West, W. W. Garvin, and J. W. Sheldon,' a two-fold investigation of this subject has been carried out. One objective of the investigation has been to deter-mine the feasibility of solving such problems 7on a medium-size com-puter such as the Datatron*, and the other objective has been to in-vestigate the application of such cal-culations to experimental and theo-retical petroleum reservoir research. In the first Datatron calculations, the fluid and rock properties published by West, et al, were used, together with the published equations describ-ing the system. Details of the formu-lation not given in the original paper are discussed in the Appendix to this note. Reference should be made to the subject paper for the complete equations and defintion of symbols. An unexpected result of this in-vestigation was the discovery that the linear solution published by West was in error. Thus, in addition to describing the Datatron solutions and to discussing certain numerical diffi-culties which will be encountered if one uses the published method of solution, the purpose of this note is to indicate the nature of this error. LINEAR FLOW Since the linear case requires a minimum amount of scaling, a fixed-decimal point Datatron program was written for the one-dimensional flow problem and an attempt was made to duplicate the solution described by West. In the case described, fluid was produced at a constant rate, Q, until such time as well pressure reached 0.04. Production was then continued at constant pressure. From the constants and curves given by West it was determined that the ini-tial constant production rate could be approximated by Q = 0.007. An ini-tial dimensionless time step ?t = 0.434 X 10 - "as used, and each suc-cessive time step was doubled until a value of = 0.444 was reached. This constant interval was then used for the remainder of the solution. In subsequent solutions, several varia-tions in the time schedule were em-ployed, including smaller time steps and slower rates of increase in the time steps. In all cases, almost identical results were obtained regardless of the time schedule employed. However, as described below, it was noted that the time schedule had some influence on the rate of convergence of the solutions. As a check on the accuracy of the solution, the cumulative production at each time step was calculated using the two methods described in the Appendix. Satisfactory agreement was observed with the differences in these two values of the order of two parts in 50,000. It should be noted that the mass balance check as described is of questionable value, particularly with regard to the well pressure and saturation. This is especially true in the radial solution where pressure and saturation values near the wellbore would make only a negligible contribution to the numer-ical integration. It is believed, how-ever, that such a comparison is ot value in determining the over-all accuracy of a solution. In comparing the Datatron solu-tion with that published by West it was discovered that in the later stages of depletion, the pressures near the well declined more rapidly in our solution than in the West solution, and that the limiting well pressure of 0.04 was reached at an earlier time than that originally reported. It thus became evident that it would be impossible to duplicate the production schedule described by West and a constant rate of production was maintained until the well pressure was equal to 0.0. A representative comparison of the results published by West with those obtained in this investigation is shown in Fig. 1, which is a plot of GOR as a function of cumulative recovery. These two curves should be in agreement until a cumulative recovery is reached which corresponds to a well pressure of 0.04 — for the Datatron solution, a recovery of approximately 5.6 per cent. Actually, a major disagreement is evident. Subsequent correspondence

Jan 1, 1958

By John F. Abel

"The most conservative persons I ever met are college undergraduates." Woodrow Wilson said that in 1905. No one is saying anything like it today. Chaos on the campus was a cliche of the sixties. Since 1905, education has expanded in every direction. Many more people are being educated for much longer periods of time. The school-leaving age has risen from 14 years to 20 years, on an average. Many are in school until after their 25th birthday. On the surface this situation appears all to the good. Our technical society needs a massive yearly infusion of semitrained (or educated, if you prefer) new blood. The efficiency of our economy and our standard of living are tied to high individual productivity which can be achieved only with an educated work force. Our democratic institutions are said to be founded on an educated electorate.

Jan 1, 1970

By L. Guttman

THE equilibrium diagram of the indium-thallium system was of interest to us in connection with a study of the superconducting properties of metallic solid solutions in progress at this Institute. For this purpose, a series of alloys was prepared covering the range from pure indium to 75 atomic pet TI, and X-ray diffraction patterns were obtained. Roughly speaking, the results indicated a region of continuous decrease in the axial ratio of the face-centered tetragonal structure from the value ca. 1.08 in pure indium to unity at about 23 atomic pct TI. From this concentration to the solubility limit, the structure was face-centered cubic, a form not reported by Hansen.1 At this point we became aware of the work of Valentiner,2 who had found the same structures at room temperature but had not investigated further the relationship between them. To study the transformation f.c.c.??f.c.t., and to clarify the phase diagram, we undertook the work reported in this paper and that which follows." Preparation of Alloys Pure indium and thallium* (both about 99.9 pct, as estimated from spectroscopic analyses) were weighed out in quantities sufficient to prepare 10 to 25 g of alloy of the desired concentration. (Occasionally indium was mixed with a previously pre- pared solution.) The metals were melted over a flame, in an open graphite crucible, stirred with a graphite rod, and poured into a graphite trough. The rough slug was hammered and swaged into a rod of 2 to 3 mm diam, and annealed in a drying oven at about 125°C for 1 to 2 days. Samples were taken from the rod for analysis, as well as for diffraction and other measurements. The thallium was determined by electrometric titration, using a modification of the method of Beale and co-workers.' The precision of analysis was generally about 2 0.2 pct of the thallium content. The rods were sometimes found to vary in thallium content as much as 1.5 pct from end to end, but since analyses were also made close to the segments used in the various studies, the composition was usually known as accurately as the analyses could be made. Where one less significant figure is given, the error is estimated to be ±0.4 pct of the thallium content. X-Ray Diffraction Measurements Three different cameras were used: (1) A 7 cm Debye camera, with oscillating specimen (manufactured by the Picker X-ray Corp., Cleveland, Ohio); (2) a 9 cm diam Debye camera of the type designed by Bradley;" (3) a 10 cm diam symmetrical focusing back-reflection camera (manufactured by Geo. C. Wyland, Ramsay, N. J.). Samples were prepared from the homogenized rods, either by filing under liquid nitrogen, or more often, in the form of wires or foils made by working at room temperature or liquid nitrogen temperature. Sharp patterns were obtained from specimens annealed at room temperature, although higher annealing temperatures were also used (cf. below). Generally, copper radiation was used; a few patterns were obtained with

Jan 1, 1951

By A. William Johnson

It was pointed out in an earlier paper1 that our understanding of the atomic mechanism by which diffusion occurs in metallic alloys is scarcely in an advanced state. This unsatisfactory condition is the result not of any lack of interest, but of the difficulty of designing experiments that .will yield suitable data. The diffusion coefficient of an alloy, measured in the usual way, is simply a number specifying the rate of homogenization of a nonhomo-geneous metal; this number, of itself, can furnish neither the rate at which the individual atoms move nor information as to the mechanism by which they move. It does not necessarily follow, however, that such information cannot be obtained, even if the path to be followed is still not clear. Much success has been attained in the study of diffusion in ionic crystals. A number of experiments, for which there are few counterparts in connection with metals, yield information often indicating a detailed mechanism by which diffusion probably occurs. From such work, quite acceptable theories of lattice imperfections have been developed by Wagner, Schottky, Frenkel, Jost and others.2 It is postulated that real crystals of stoichiometric composition contain, in equilibrium, certain imperfections of which the most importarlt types are: (I) vacant cation sites, with an equal number of interstitial ions; (2) vacant anion sites, with an equal number of interstitial ions; (3) equal numbers of anions and cations in interstitial positions; (4) equal numbers of vacant anion and cation sites. The classification of a particular crystal according to this scheme then follows from studies of the variation of electrical conductivity with pressure of the electronegative component surrounding the crystal, with ion size, and with temperature; other physical phenomena, such as the Hall effect, have aided in establishing the classification. The relative mobility of the anion and cation may be determined by chemical analysis of the salt at the electrodes following electrolysis. With such information, and knowing that one ion never occupies the lattice site normally belonging to an ion of opposite sign, it is usually possible to ascertain the diffusion mechanism. It is clear that the same experiments are not applicable to metal crystals, and substitute experiments that yield as much information have not yet been devised. Much can be learned, however, about the mobilities of the two* kinds of atoms in alloys by the use of radioactive metals as indicators. Only one such experiment has been performed in the past. In 1933, Seith and Keil,3 in an effort to explain the great difference between the rate of diffusion of gold in lead and of lead in lead, measured the rate of diffusion of radioactive lead in 3 gold-lead

Jan 1, 1942

By A. William Johnson

It was pointed out in an earlier paper1 that our understanding of the atomic mechanism by which diffusion occurs in metallic alloys is scarcely in an advanced state. This unsatisfactory condition is the result not of any lack of interest, but of the difficulty of designing experiments that .will yield suitable data. The diffusion coefficient of an alloy, measured in the usual way, is simply a number specifying the rate of homogenization of a nonhomo-geneous metal; this number, of itself, can furnish neither the rate at which the individual atoms move nor information as to the mechanism by which they move. It does not necessarily follow, however, that such information cannot be obtained, even if the path to be followed is still not clear. Much success has been attained in the study of diffusion in ionic crystals. A number of experiments, for which there are few counterparts in connection with metals, yield information often indicating a detailed mechanism by which diffusion probably occurs. From such work, quite acceptable theories of lattice imperfections have been developed by Wagner, Schottky, Frenkel, Jost and others.2 It is postulated that real crystals of stoichiometric composition contain, in equilibrium, certain imperfections of which the most importarlt types are: (I) vacant cation sites, with an equal number of interstitial ions; (2) vacant anion sites, with an equal number of interstitial ions; (3) equal numbers of anions and cations in interstitial positions; (4) equal numbers of vacant anion and cation sites. The classification of a particular crystal according to this scheme then follows from studies of the variation of electrical conductivity with pressure of the electronegative component surrounding the crystal, with ion size, and with temperature; other physical phenomena, such as the Hall effect, have aided in establishing the classification. The relative mobility of the anion and cation may be determined by chemical analysis of the salt at the electrodes following electrolysis. With such information, and knowing that one ion never occupies the lattice site normally belonging to an ion of opposite sign, it is usually possible to ascertain the diffusion mechanism. It is clear that the same experiments are not applicable to metal crystals, and substitute experiments that yield as much information have not yet been devised. Much can be learned, however, about the mobilities of the two* kinds of atoms in alloys by the use of radioactive metals as indicators. Only one such experiment has been performed in the past. In 1933, Seith and Keil,3 in an effort to explain the great difference between the rate of diffusion of gold in lead and of lead in lead, measured the rate of diffusion of radioactive lead in 3 gold-lead

Jan 1, 1942

By H. C. Schultz

CERTAIN local conditions were known to govern in large measure the successful adaptation of liquid-oxygen explosives to the large-scale blasting at Chuquicamata. The wide variation in hardness of the rock at this mine makes necessary the use of several types of explosives. A locally manufactured, relatively cheap black powder is used in blasting the softer waste and capping material, where a thorough displacement, breaks the ground sufficiently. Before the introduction of L. 0. X., an ammonia dynamite of about 65 per cent. strength was being used exclusively in the harder underlying orebody, where a strong disruptive as well as a displacement effect is required for breaking the ore. The L. 0. X., as developed for quarry work in the United States, has a practically pure carbon cartridge material, and the explosive has an extremely high rate of detonation, which should therefore cause it to usefully develop its full disruptive effect in hard ground. The individual blasts at Chuquicamata are large, black-powder shots which dislodge masses of rock averaging 250,000 tons each, and dynamite shots which dislodge masses averaging 80,000 tons each. It was desirable, therefore, to attempt to displace with L. 0. X. the faster, higher-cost ammonia dynamite used in the smaller blasts. It was not considered practical to attempt to displace the low-cost black powder with L. 0. X., as estimated costs showed no probable saving if this were accomplished. Since it was desirable to continue shooting relatively large blasts for effective operation, it was recognized that larger storage facilities than had been in use would be needed for the liquid oxygen. Because of the difficulty of transporting and discharging large storage containers of efficient design, the better plan appeared to be storage and discharge of the liquid at the place of manufacture, and transportation of the filled soaking boxes to the blast.

Jan 1, 1928

By G. Horvay, J. G. Henzel

Nomograms and charts are provided which permit rapid determination of the mold-casting interFace temperature and the speed of solidification when a semiinfinite ingot is cast into a semiinfinite mold. The physical properties of the mold, the frozen metal, and the liquid metal are not assumed to be equal, but they are assumed to be temperature independent. The results are correlated with charts prepared by Paschkis and Hlinka—using Columbia University's Analog Computer—for the freezing of finite ingot slabs when a constant surface temperature is impressed, and with experimental cooling curves obtained by Pellini in sand and iron molds for 7 in.-sq steel castings. x = coordinate directed to right of zero (freezing direction) y = coordinate directed to left of zero (melting direction) e = position of freezing front (in x direction) ? = position of melting front (in y direction) $ = temperature (function of position and time) ? = fixed temperature 2L = width of finite slab Y = a fixed position in the semiinfinite mold, or the width of a finite mold (see Section 7) Properties y = density, lb per cu ft c = specific heat, Btu per lb deg F k = conductivity, Btu per ft hr deg F X = heat of fusion, Btu per lb k = k/Yc = temperature diffusivity, sq ft per hr* b - = = - heat diffusivity, Btu per sq ft deg F Vhr Subscripts 2 = pertaining to the still-liquid metal (case of freezing), or the medium which furnishes the heat (case of melting) 1 = pertaining to solidified metal (case of freezing), or to molten metal (case of melting)* 0 = pertaining to mold (case of freezing), or to the still-solid metal (case of melting) f = pertaining to fusion condition (eg.,?f - fusion temperature) i = pertaining to the location x = 0 (the mold-ingot "interface")

Jan 1, 1960

By Virgil Miller, F. B. Petermann, S. F. Ravitz

The Cle Elum nickeliferous iron deposit is in Kittitas County, Washington, in a rugged, mountainous region about 23 miles north of the town of Cle Elum. The Biewett Pass deposit, which is similar in character and occurrence, is in Chelan County, about 18 miles east of the Cle Elum deposit. A more or less continuous ore zone may extend between the two deposits, since iron ore is reported to have been discovered at Iron Mountain, which lies directly between them. The ore probably was formed by meta-morphism of laterite resulting from Ieach-ing of serpentine derived from peridotite. It consists largely of magnetite grains distributed through a matrix of limonitic material containing a small amount of hematite and chromite. Many of the chromite grains have shells and inclusions of magnetite. The magnetite grains range in size from 1200-mesh to 1/4-in., the average size being 48 to 65-mesh; the chromite grains range from 20 to 150-mesh. The gangue minerals are olivine and serpentine with a small, amount of chlorite, and appear both as very thin bands in the ore and 's minute fragments in the limonitic matrix. The nickel is present as minUte inclusions of a nickel silicate mineral within the magnetite and gangue par- ticles, varying in size from 1500 to about 280-mesh. Detailed analyses of 3000-lb. lots of Cle Elum and Blewett Pass ore are given in Table I. TABLE i.—Analyses of Ore Samples Per Cent Ore from Constituent cle Elum' Blewett Pass Cr....................... 2.23 2-12 Ni...................... 1.43 0.9s Fe...................... 52.9 41.4 SiOz.................... 5.6 13.4 CaO.................... 0.3 0.8 MgO................... 4-1 7-5 AI2O3................... 7.0 2.g P...................... 0.022 0.034 S....................... O.O1 o.oa Mn..................... I.I 0.4 Ba..................... nil co..................... o.oa 0.02 CU..................... 0.02 0.03 As...................... 0.03 Au..................... nil Ag°..................... O.58 Pt...................... ml Fe++.................... 8.9 5-9 Fe+++.................. 44-0 35-5 « Ounces per ton, 1 sr,cte,so,","&&$ally absent: B, W, M~, T~, V, ~i, Bi, Pb. Sb. Sn. Be, In, Hg. Zn, Zr. Cd. Preliminary Tests Attempts to beneficiate the ore by ore-dressing methods, including various 'cornbinations of sink and float, tabling, jigging, flotation, and magnetic separation, were consistently unsuccessful. A wide variety of roasting and leaching tests were made on both raw and reduced ore, but in most of the tests little or no nickel was extracted, and in none did the extraction exceed 50 Per cent. No nickel could be volatilized as the carbonyl. by treating reduced ore with carbon monoxide. Fairly good sepa-

Jan 1, 1944

By Norman Ketzlach

Manganese Products, Inc. has developed a chemical process for the recovery of high-grade manganese oxides from low-grade manganese ores. Ammonium sulphate is also produced. Manganese ore is leached with sulphurous-sulphuric acids. The impurities are removed with ammonia, heat, and air. Manganese oxides are produced by addition of more ammonia and air under pressure. Ammonium sulphate is recovered from the remaining solution.

Jan 3, 1950

By C. Zener

HE present paper has its origin in an attempt A by the author, extending over the last several years, to understand the influence of the magnetic properties of the constituent atoms upon the various properties of metals and alloys. During this study the author has been impressed by the important role which magnetism plays in the many facets of metallurgy. In writing this paper he has attempted to convey to his colleagues some concept as to the role magnetism will play in the future development of metallurgy. In some of the subjects herein discussed, such as the influence of magnetism upon phase boundaries and upon mechanical properties, only general thermodynamical properties associated with ferromagnetism are introduced. For these subjects, it is not anticipated that any serious differences of opinion will be encountered. A discussion of the other subjects requires the adoption of a quite specific model of the magnetic structure of the metal. This model is discussed under "Magnetic Shells and Their Interactions." The simple model adopted in this paper has been criticized' as being mathematically inconsistent. This criticism has been ably silenced by Dr. W. J. Carr' of this laboratory. The simple model adopted in this paper has been criticized as being inconsistent with observations on magnetic structure using neutron diffraction. This apparent discrepancy has been resolved by Bader3 who has shown that the finite velocity of neutrons prevents neutron beams from detecting the anti-ferromagnetic structure of the type predicted by the simple model adopted in this paper. Magnetic Shells and Their Interactions An electronic shell of an atom is specified by two symbols.' The first symbol is a number and denotes the total quantum number of the shell. The second symbol is a letter and denotes the orbital angular momentum of each electron within the shell. The letters s, p, d, f are used to denote an orbital angular momentum of 0, 1, 2, 3, respectively, in units of h/2a, where h is Planck's constant. As we pass from scandium to nickel in the first transition period, we eraduallv fill the 3d shell. This shell is responsible for ferromagnetism and hence may be called the magnetic shell. The component of the orbital angular momentum along some specified direction must be an integral multiple of h/2~. Thus, for a d electron this component can have any one of the values —2, —1, 0, 1, 2 times h/2a. In addition to its orbital angular momentum, each electron has an intrinsic angular momentum, hereafter called spin, due to a rotation about its own axis. This spin can have either of two components + Yz (h/2a) or — Yz (h/2~) along the specified direction. A fundamental principle of atomic structure, known as Pauli's exclusion principle, is that no two electrons in a given shell may have identical components of orbital angular momentum simultaneous with identical components of spin. The 3d shell thus may have at most ten electrons. Since an intrinsic angular momentum of a charged particle is necessarily associated with a magnetic moment, the spin of an electron may be thought of as referring to either this angular momentum or to the associated magnetic moment. The electron configuration of the ground state of the isolated atoms in the first transition row is reproduced in Table I. The superscript represents the number of electrons in each shell. For the purpose of this paper, the most important principle of atomic structure relates to the manner in which electrons are added to a shell as the atomic number is increased. This principle, commonly known as the principle of highest multiplicity or more simply as Hund's rule, states that within a given shell the maximum number of electrons have spins pointing in the same direction as is consistent with Pauli's exclusion principle. An application of this principle to the d shell is illustrated in Fig. 1, where the spin structure is given for shells containing from 1 to 10 electrons. The physical basis of Hund's rule is the exchange energy discussed first by Heisenberg in 1928. This is a coupling between electrons with parallel spins (spins pointing in the same direction), the coupling

Jan 1, 1956

By K. P. Gupta, P. C. Panigrahy

The stabilization of the R, a-Mn, and 0-Mn phases have been studied in the Mn-Ti-Fe and Mn-Ti-Co systems. Iron and cobalt both appear to stabilize the (Mn-Ti) R phase to almost the sarne extent. The R-phase region was found to extend from the lowest e/a to slightly beyond the maximunz e/a limit known for this phase. But, while iron appears to stabilize the a-Mn phase, cobalt tends to stabilize the p-Mn phase. In the two systems manganese appears to get replaced by iron and cobalt in each of the mentioned phases. The instability of the a-Mn phase in the Mn-Ti-Co system and the /3 -Mn phase in the Mn-Ti-Fe system cannot be explained on the basis of adverse size effects because atomic diameters for both iron and cobalt (C.N. 12 at. diam) are ziery similnr and not much different from manganese which they replace. Qualitatively, the reason for the stability of the a-Mn and the p-Mn phases can be traced to the more favorable e/a ratio prevailing in the respective systems and to a competing tendency between the two phases. In transition metal alloy systems the o, p,P, R, a- Mn,' and p-Mn2 phases have been claimed as electron compounds. A large volume of work has been done to establish the criterion for the formation of the o phase but until very recently practically no systematic work was done on the a-Mn and the /3-Mn phases. A recent investigation on the P-Mn phase3 indicates the e/a criterion for p-Mn phase stabilization. Since the R phase was first known to appear only in certain ternary systems1 no detailed work was then possible for this phase. The R phase has been recently discovered as a binary intermetallic compound in the Mn-Ti~ and Mn-si~-' binary systems. The existence of binary R phases opens up the possibilities of studying the effect of alloying elements on the stabilization of the R phase. Of the two binary systems possessing an R phase, the Mn-Ti system appears to be more interesting because at a suitable high temperature it is possible to find the three electron compounds, the a-Mn, p-Mn, and R phases, side by side and it is possible to study the effect of a third transition element on these three electron compounds. For the present investigation iron and cobalt, so called B elements for the formation of electron compounds, have been used as the third element to study the stabilization of the a-Mn, P-Mn, and R phases. EXPERIMENTAL PROCEDURE The alloys were prepared by using 99.9 pct pure electrolytic Fe and Mn, 99.5 pct Co, and crystal bar titanium, supplied by Semi Elements Inc., New York and Gallard Schelsinger Mfg. Co., New York. Weighed amounts of the components were melted in recrystal-lized alumina crucibles in an inert atmosphere (argon) high-frequency induction melting unit. Titanium was made into fine chips for easy dissolution and a special charging procedure was adopted to avoid contacts of titanium chips with the alumina crucibles. Up to 20 at. pct Ti, the maximum titanium content in the investigated alloys, there was no visible sign of reaction of titanium with the alumina crucibles. With a careful control of melting time and temperature the losses were minimized and were always found to be below 0.1 pct. Because of such small and almost constant weight losses, the alloys were not finally analyzed. The alloys were wrapped in molybdenum foil and annealed in evacuated and sealed silica capsules at 1000" * 2°C for 72 hr and subsequently quenched in cold tap water. Annealed samples were examined metallographically and by X-ray diffraction. For all high manganese alloys oxalic acid solutions of various concentrations and 1.0 pct HN03 solution were found suitable as etching reagents. Best contrast between the a-Mn and the R phases could be obtained by using freshly prepared 60 pct glycerine + 20 pct HN03 + 20 pct HF solution. For high iron and cobalt containing alloys, especially for alloys containing the a-Fe, y-Fe, and P-Co phases, 15 cc HNOJ + 60 cc HC1 + 15 cc acetic acid + 15 cc water solution was found to be the best etching reagent. All X-ray diffraction work was carried out (using specimens prepared from annealed powders) with a 114.6 mm diam Debye-Scherrer camera using unfiltered FeK radiation at 25 kv and 10 ma. All calculations for X-ray diffraction work were carried out using an IBM 7044 digital computer RESULTS AND DISCUSSION The two ternary systems, MnTiFe and MnTiCo, were investigated near the manganese rich end, Figs. 1 and 2, and show some common features. In both alloy systems large extensions of narrow R phase regions occur at almost constant titanium contents. At titanium contents higher than that of the single phase R-phase alloys, the same unidentified X phase was found in both ternary systems. The extensions of the X phase close to the Mn-Ti binary indicate that this phase could be the TiMns phase. Too few X phase diffraction lines were present in the diffraction patterns to make positive identification of the X phase. In contrast to this similarity the two systems show opposite behavior in the extensions of the a-Mn and 8-Mn phase regions; while iron tends to stabilize the a-Mn phase, cobalt

Jan 1, 1970

By Edward Judd

THE old Cerro de Pasco smelter at La Fundicion, near Tinahuarea, 9 miles. from the Cerro de Pasco. mines and at an elevation of 14,300 ft., has now been replaced by a thoroughly modern smelting plant at Oroya, the junction point of the company's private railroad with the Central Railway, of Peru. This site has the advantages of being closer to the Morochoca mines, as well as nearer to the port of Callao, and at the same time is 2000 ft. lower in elevation, which benefits not only the cost of transportation but also the tech-nical operation of blast furnaces , and converters. The Oroya smelter was designed with the idea of .smelting about 2500 tons of. ore per day, but having in mind the possibility of increasing its capacity, all departments of the plant can be extended within reasonable -limits; for instance, if it is found that reverber-atory smelting is cheapest, taking into consideration the cost of fine crushing and fuel, it is possible to extend the roaster and reverberatory plants accordingly. The ore handling system is modern, consisting of belt conveyors, reclaiming machines, and electrically driven calcine cars, all requiring the minimum of labor. Waste heat from the reverberatory furnaces is utilized in boilers for the production of power to operate the plant, and the power house is equipped with condensing units to obtain the highest economy. Shop installations for the making of all repairs required for the smelter are unusually complete, includ-ing iron foundry, steel foundry, forging and machine shops, carpenter and pattern shops, and an electrical shop. There is also a plant for the production of all clay and silica refractory brick used in the furnaces; this is situated on the smelter site and is conveniently arranged for receiving raw materials and delivering finished brick to the several departments of the smelter. The laboratory is in a wing. of the general office, which is a two-story brick structure, situated on the smel-ter site.

Jan 10, 1923

By WILLIAM WATERS

L HISTORY. THE Pierrefitte mines, situated in the South of France, in the district of the Hautes-Pyrenees, owe their name to the fact that the first mining operations of any extent, and of comparatively recent date, were carried out in the neighborhood of the vil¬lage of Pierrefitte, which is a branch terminus of the Midi railway. The Pierrefitte mines, however, embrace a wide extent of country and several different concessions, on most of which comparatively little exploration-work has been done. The portion of the property presently to be described is a zone running roughly E-W., over a distance of about 5 miles from the valley of Cauterets to the valley of Estaing, the ridge dividing these valleys being a spur of the main chain of the Pyrenees, and running more or less at right angles to it. According to local tradition, which various indications tend to confirm, these mines are of ancient date, the first workings being attributed to the Romans, who are supposed to have sought not only the lead but also the silver which is contained in the ore. Old slags have been found in the neighborhood which might well have been produced from the cupellation of lead-ores. These old workings, while of considerable extent at times, do not seem to have extended beyond a depth of 100 ft., even this depth being somewhat exceptional. The old notarial records of the district show that mines were known to exist, and that they were even worked, in the sixteenth century, but since the mines were abandoned (by the Romans or others) considerably prior to this period, very little

Nov 1, 1908

By W. C. Knopf, G. Samsel

For several years International Minerals & Chemical Corp. has used a radiation method to assay potassium content of products from potash and feldspar beneficiation. The procedure is rapid, accurate, and inexpensive and is easily handled, if necessary, by nontechnical personnel. Data are presented to show the accuracies that may be expected if the technique is used for control of pilot plants or large- scale plants. Natural potassium is composed of three isotopes -K39, K40 and K41. Five other isotopes, artificially produced, have been detected. In natural potassium only the K40 isotope, with a half life of 1.4 x 109 years, is radioactive. Its modes of decay are beta and gamma rays, positrons, and x-rays. Only the more abundant beta rays, however, are important in radiation measurements using geiger tubes.

Jan 10, 1958