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By B. E. Sundquist

The various methods based on solution models for obtaining free energies of mixing from miscibility-gap data have been applied to a number of binary-alloy systems. For nine of these systems there exist experimental thermodynamic data that permit a comparison of the results to experiment. It was found that the method of van der Toorn and Tiedema almost invariably leads to results that are physically unacceptable and that vary drastically with small changes in the miscibility-gap parameters. The subregular solution model is found in all cases, except the Al-Zn, Fe-Cr, and Cu-Pb systems, to exaggerate the free energy of mixing by 30 pct or more. The model developed by Lumsden is found to give results that are often in excellent agreement with experiment and which exaggerate the free energy of mixing by no more than 30 pct. These results and others give evidence that the Lumsden treatment of the effect of unequal atomic sizes and of imperfect configurational randomness due to deviations of AB bond energies from the mean of AA and BB bond energies is adequate for most systems. ANALYTIC expressions are frequently proposed for the dependence on composition of the activities of the components of a solution. Because the development of solution theory is incomplete, these expressions contain parameters which must be determined by experiment. The measurement of activities is often difficult and consequently such measurements are less readily available than are measurements of phase equilibria which, under certain conditions, can also be used to evaluate these parameters. For example, suppose it is known that two structurally dissimilar phases, each of known composition, in an n-com-ponent system are at equilibrium at a given temperature and pressure. n equations can be set up in terms of these parameters expressing the equality of the chemical potential of each component in the two phases. In addition, one can write the Gibbs-Duhem equation for each phase that also contains these parameters. Thus, if these n + 2 equations contain n + 2 parameters, these parameters can be determined (at the temperature in question) from the phase diagram alone. If the average number of parameters in each expression for the activity of a given component in a given phase is V then there will be 2nV parameters involved. Equating 2nV to n + 2 shows that, for n + 2, V = 1. If the temperature dependence of each parameter were to be expressed in some explicit form one could use equilibrium conditions at a number of temperatures to increase V. The situation is much improved when the two phases in equilibrium are structurally similar. It can then be assumed that, stably or metastably, two phases will become one at higher temperatures. Thus the number of parameters involved becomes nV instead of 2nV. Hence, V = 2 for n = 2 using only one temperature. (It is implied here that the activity expressions used are valid over the entire composition range.) In this investigation only the equilibrium of two structurally similar, two-component phases (miscibility-gap systems) will be considered. The various proposed solution models will be applied to a number of these systems and the results compared with available experimental results. All of the analytic expressions that have been proposed for the free energy of mixing of a two-component system are of the form where ?Gmix is the free energy of mixing per mole of solution, N1 and N2 are the mole fractions of components 1 and 2, respectively, and f(Ni, T) is some function of composition and temperature. In the "ideal" solution model f = 0. In the "regular" solution model f = a constant. Since these two models permit only a symmetric equilibrium diagram they will not be considered further here. The simplest model that permits a nonsymmetric miscibility envelope is the so-called "subregular" solution model proposed by Hardy.1 This model gives where the Ci(T) are functions of temperature only. The same expression for f is obtained from the "linear a function" model proposed by Darken and Gurry2 and applied to miscibility-gap systems by Wriedt.3 This model requires that the a function defined by be a linear function of composition (yi is the activity coefficient of component i). This model is not purely hypothetical for it has been found2 to hold true for a number of systems. It is readily shown3 that the f(Nl, T) obtained from this model is of the form given in Eq. [2]. It will be noted that the subregular solution model contains only two parameters and hence both of them can be determined at any desired temperature below the critical temperature, Tc, for a miscibility-gap systems in the manner described previously. At T, the two constants can be determined by equating the second and third derivatives of ?Cmix with composition to zero. Another two-parameter model was proposed by Lumsden4 who set

Jan 1, 1967

By Klaus Schwerdtfeger

The rate of formation of silicon monoxide from silica spheres has been measured at 1500°C in H2, H2-H2O, H2-He, H2-Ar, and CO-CO2 gas mixtures. Indications are that in the hydrogen-containing gases the reaction rate is mainly determined by convective diffz~sion. In the CO-CO2 mixtures the rate approches a constant value which is independent of sphere diometer (and gas velocity). This suggests that a surface reaction becomes rate controlling in CO-CO2 gas. WHENEVER silica is exposed at elevated temperature to a strongly reducing atmosphere there occurs, inevitably, a volatilization of silica by the formation of gaseous silicon monoxide. Because of the importance of this reaction in metallurgical processes and laboratory experiments, its kinetics were studied in the present work. EXPERIMENTAL The spheres made of vitreous silica were suspended by a molybdenum wire in the hot zone of a gas-tight high-purity recrystallized alumina furnace tube of 3.1 cm internal diam and 100 cm length. Molybdenum wire resistance heating was used. A purified H2, H2-H2O, H2-He, H2-Ar, or CO-CO2 gas mixture was passed through the tube, from top to bottom. The amount of silicon monoxide formed was determined by weighing the silica balls before and after the experiments. The silica balls were made from commercially available translucent fused quartz glass. In experiments with hydrogen-containing gases the silica stayed vitreous during the experiment, whereas in experiments with CO-CO2 mixtures, which were performed over longer times, the balls were always crystallized to cristobalite (as determined by X-ray examination) at the surface. Constant-pressure head capillary flowmeters were used to control the composition of H2-He, H2-Ar, and CO-CO2 gas mixtures. The oxygen and water vapor were removed from the gases containing hydrogen by passage through columns containing platinized asbestos (450°C) and an-hydrone. The CO was purified from O2 and CO2 by passing it through activated copper (200°C) and through ascarite. The H2-H2O gas mixtures were prepared by passing purified Hz through a mixture of oxalic acid dihydrate and anhydrous oxalic acid held at a constant temperature in a water bath. The equilibrium water vapor pressures of oxalic acid dihydrate-anhydrous oxalic acid mixtures were taken from the available data.1 The furnace system was checked for sufficient gas tightness at regular intervals. As an additional check, the H2O and CO2 contents were measured in the exit gas and were found to agree closely with the metered contents when H2-H2O or CO-CO2 mixtures were used. When purified H2 was used, H2O pressures found in the exit gas were always below 0.1 mm Hg. These contents originate either from an incomplete reoxidation of silicon monoxide in the cold part of the furnace or from small leaks which cannot be avoided. If the latter is the case, such small uncontrolled H2O contents decrease the partial pressure of SiO in equilibrium with SiO2 by less than about 7 pct, which is considered small in comparison to other experimental uncertainties. The temperature of the furnace was controlled automatically in the usual manner. The reported temperature was measured with a Pl-Pt/l0pct Rh thermocouple and was accurate to ± 5°C. TRANSPORT-CONTROL LED RATE OF REDUCTION The gaseous convective diffusion from the surface of a sphere can be predicted from the semiempirical relationship obtained by Ranz and Marshall2 in a study of the evaporation of water and benzene drops in air. The following equation applies:

Jan 1, 1967

[ARIZONA Established July 10, 1915 ROBERT W. HUGHES, Chairman CHARLES R. KUZELL, First Vice-Chairman GILBERT C. DAVIS, Second Vice-Chairman W. CLARK MASON, Secretary-Treasurer Inspiration Cons. Copper Co., Inspiration, Ariz. LYLE BARKER ROBERT HIGH T. G. CHAPMAN P. D. I. HONEYMAN GEORGE M. COLVOCORESSES WALTER C. LAWSON EDWIN H. CRABTREE, JR. W. H. LOERPABEL WALTER I. GARMS ALBERT MENDELSOHN WESLEY P. Goss CARL E. MILLS H. C. HENRIE JOSEPH A. WILLCOX C. F. WILLIS]

Jan 1, 1946

By I. H. Warren, E. A. Devuyst

The selective dissolution of pyrolusite (MnO2) in presence of goethite (FeO•OH) in aqueous ammoniacal ammonium carbamate solution has been investigated: various reducing agents were studied, in particular sodium sulfite (Na2SO3,) and hydrazine hydrate (N2H4•H2O). Sodium sulfite was found to be an unsatisfactory reducing agent for both goethite and pyrolusite, for the leaching rate decreased steadily with time to an impractical level because of the limited solubility of the reactions products. Hydrazine hydrate was an effective reducing agent for pyrolusite even at low temperature, whereas goethite required much higher temperatures for any appreciable dissolution. A 1-hr leach at 35°C dissolved 90% of the pyrolusite but only 0.1% of the goethite. An activation energy of 17.0 Kcal per mole was found for the dissolution of pyrolusite with hydrazine. A reaction mechanism for the leaching of pyrolusite with hydrazine is proposed in which a reduction reaction on the surface of the mineral is the rate-determining step. The application of ammonium carbamate to the beneficiation of ilmenite is briefly described.

Jan 1, 1973

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 Robert C. Linares

Cubic zinc sulfide has been grown from molten salt solutions substantially below the hexagonal-cubic phase transition of 1020°C. Crystals free of birefringence have been grown from molten lead chloride at temperatures from 500° to 800°C. Factors affecting the optical transmission and the birefringence are discussed. CUBIC zinc sulfide is of interest for electrooptic devices and as an optical coating material. However, it cannot readily be produced as large crystals which are free of birefringence. The birefringence arises from the fact that the cubic ZnS is usually grown as the high-temperature hexagonal phase and is transformed to the lower cubic phase by annealing.' This results in stacking faults, stress, and birefringence. A requirement for the growth of cubic ZnS is that it be grown below the phase transition of 1020°C.2 Crystals of cubic ZnS have been grown below 1020°C by the hydrothermal,3 flux,4 and vapor transport5 techniques. However, these all appear to have limitations in size or quality of material produced. It was felt that a new flux method might have a good chance of overcoming some of the previous problems. Mita6 reported the growth of hexagonal ZnS from molten NaCl and wilke7 reported the growth of iron sulfides from molten lead chloride solution, indicating that molten chlorides make good solvents for sulfides. An investigation of a number of possible molten chlorides as solvents showed that molten PbCl2 has an appreciable solubility for zinc sulfide and that crystals can be grown at temperatures from 500° to 800°C. EXPERIMENTAL Crystal growth was performed in open or sealed Vycor or fused silica tubes, in an argon atmosphere or vacuum. There were no deleterious effects due to using vacuum; however, a sealed essentially isothermal system must be used to prevent vapor transport mechanisms from dominating. This will be discussed later in detail. Noble metal containers were not usable as they were severely attacked by these melts. The materials used were: reagent-grade PbC12, reagent-grade ZnS, optical-coating-grade ZnS, and Irtran 2 (ZnS). Crystal growth was accomplished by both slow cooling techniques and gradient growth techniques. In the slow cooling techniques, 15 g of ZnS and 100 g of PbCl2 were used. The components were placed in the silica tube, heated at 800°C for 2 hr, and then slowly cooled (l° to 10° C per hr) to 500°C. The furnace was constructed so that the tube could be inverted, thus allowing the liquid to drain off the crystals at the end of the run. The gradient runs were made by placing the above mixtures in a silica tube at 550° to 600°c, Fig. 1. A temperature gradient was maintained such that the floating mass of undissolved sulfide was 10° to 50°C warmer than the bottom of the tube. Growth occurred on spontaneously nucleated sites at the cooler bottom. RESULTS When using high cooling rates (5° to 10°C per hr), crystals form in thin sheets perpendicular to the {111} face. Crystals 5 by 5 by 1.2 mm, Fig. 2, have been ob-

Jan 1, 1969

By C. W. Volek, J. E. Chappelear

The injection of a hot liquid into initially cool porous media, saturated with the same liquid and surrounded by two impermeable but heat conducting media (cap and base rock), has been studied both experimentally and theoretically. The temperature dependence of the viscosity was included in the theoretical model, but it was assumed that the specilic heats and densities of the various materials were independent of the temperature. Solutions to the theoretical model were approximated by numerical methods. Both theoretical and experimental results indicate that center-line temperatures are significantly higher than boundary temperatures. Comparison of experimental and theoretical results with a cold/hot viscosity ratio 01 19:1 were in reasonable agreement. Theoretical calculations show that the effect of the temperature dependence of viscosity was very significant at ratios of 100:l to 1000:1, which are typical of those that occur when injecting hot water to flood heavy oil reservoirs. INTRODUCTION We consider the problem of prediction of fluid flow and temperature distribution in an initially cold-fluid-filled reservoir on the injection of the same hot liquid by the use of mathematical and physical models. The results reported are for a two-dimensional rectangular section of the reservoir, as shown in Fig. 1. The injection and withdrawal faces are assumed to be equipotentials for fluid flow. The ultimate purpose of such models would be to predict hot-water injection performance. However, we note that in the work presented here, one of the most significant aspects of the problem — the instabilities resulting from two-phase, water and oil flow — is not included. We will not give a historical review, but refer instead to the paper of Spillette and Nielsen,1 which contains a rather complete bibliography and critical discussion. The physical problem is exactly the same as Spillette and Nielsen, except for certain simplifications in our assumptions. The mathematical details are somewhat different, and we will present the details of our method here. The mass flow equation, which is elliptic in character, is handled by successive overrelaxation. The heat flow equation, which is parabolic in character, is handled by a straightforward explicit approximation. Some difficulty arose in the over-all heat balance due to small errors in the solution of the mass flow equation, and we feel that a different formulation of the heat flow equation would be desirable for future work. In addition to the mathematical solutions for the temperature distributions in a porous medium due to the injection of hot liquids, experimental data are presented to check the validity of these solutions. A schematic diagram of the model is shown in Fig. 2. Certain qualitative physical conclusions were obtained from our numerical and experimental results. These are: 1. Assuming high (infinite) conductivity normal to the bedding plane in the reservoir is a poor approximation, and may lead to overestimates of the total heat losses (to cap and base rock) of as much as 50 percent. 2. More heat is retained in the reservoir (per unit of heat injected) for higher viscosity changes. 3. Any particular temperature isotherm moves more rapidly along the center line for higher viscosity changes. Consequently, the approximation of temperature independent viscosity is not suitable for obtaining quantitatively correct results. MATHEMATICAL MODEL Our mathematical model is that of a reservoir of thickness 2h. The problem is idealized from that of a linear hot-water drive, and we imagine that the input face is sufficiently far away from the injection wells that the stream lines enter it normally. Similarly the production wells are far enough from the outflow face that the flow lines leave it normally. The reservoir and surrounding cap and base rock

Jan 1, 1970

By CLARENCE WM. POY

THE most common difficulty faced by an engineer or mine operator when opening a new property in a new field is the lack of roads and of cheap transportation. This one item often swings the balance of success or failure in starting a project. In Alaska, as elsewhere, such problems are more or less serious. In the boom days around the Valdez district, as well as in other parts of this territory, freighting was accom¬plished by dog teams or horses, or even by men that were willing to put their shoulders into harness, because there were virtually no roads. More important, there was only one time when supplies could be transported, and that was when there was suffi¬cient snow on the ground following a heavy wind. Then, and only then, could one depend on the snow to support horses and sleighs, and be sure that the gulleys, streams, and crevices in the glaciers were filled with snow to avoid pitfalls. These methods were used when one had no roads, no streams in the summer to float a barge, or even a trail for a pack train. If the snow was deep and soft, trans

Jan 1, 1935

By Heihachi Kamura

The reduction of iron oxide, such as Fe203, to iron in the blast furnace is performed principally by carbon monoxide, but partly by solid carbon by the two following reactions: Fe2O3 + 3CO = 2Fe 4- 3CO2 2Fe2O3 + 3C = 4Fe + 3CO2 It is known that reduction by carbon monoxide takes place at a much lower temperature than reduction by carbon and that the reducing action of earbon monoxide progresses to the inside of the ore in lump form by gaseous diffusion. In the reduction by carbon, however, the reducing action takes place only at the contact surface of the ore and carbon, so that the more complete the reduction by carbon monoxide, the more efficient is the operation. However, the reduction does not progress as shown in the foregoing equation, because carbon dioxide acts oxidizingly on the metallic iron to such a degree that when the gaseous composition reaches a certain proportion of carbon dioxide to carbon monoxide, the reduction practically stops, even though the gases are moving slowly through the heated ore. The proportions of carbon monoxide and carbon dioxide in the gas depend on the kind of iron oxide and the temperature of reduction, also on the duration of time in the reaction. The longer the time of the reaction, the higher the proportion of carbon dioxide obtained in the gas, but finally it will attain to a condition of equilibrium. Chemical Equilibrium of Iron, Oxygen, and Carbon Investigations concerning the equilibrium between iron, oxygen, and carbon have been carried out by E. Baur and A. Glaessner,1 who deter-

Jan 1, 1925

R. Schuhmann, Jr. (Purdue University)— Fulton and Chipman's results on rate of silica reduction from slags are analogous in many was to the results of Parlee, Seagle, and Schuhmann10 on rate of alumina reduction from alumina crucibles. Both investigations have given comparably low rates of reduction and slow approaches to equilibrium. Accordingly, we may hypothesize that the rate-determining step is the same in both kinds of experiments; that is, oxygen diffusion across the stagnant boundary layer on the liquid-metal side of the interface between the liquid metal and the oxide phase (slag or solid oxide). I suggest that silica reduction involves the following consecutive steps: I) At the slag-metal interface: SiO2(slag) Si+ 20 II) Transport of oxygen from slag-metal to gas-metal interface: a) diffusion across liquid-metal boundary layer at slag-metal interface. b) convection within the body of liquid metal. c) diffusion across boundary layer at metal-gas interface. 111) At the metal-gas interface: C +O- CO (gas) Iv) At the graphite-metal interface: C (graphite) -C At steelmaking temperatures it is reasonable to assume that equilibrium is attained in all three chemical reactions (I, 111, and IV) right at the respective interfaces. Convection within the stirred liquid metal (step IIb) is also rapid. Transport of Si and C should be orders of magnitude easier than transport of 0, because of the relatively high concentrations of Si and C. Accordingly, we might expect the overall reaction rate to be determined by boundary-layer diffusion of oxygen, either IIa or IIc. Fulton and Chipman's demonstration that bubbling CO through the system had no major effect on reaction rate indicates that IIc is not the slowest step. Therefore, it becomes logical to estimate the maximum rate for step IIa and to compare this theoretical estimate with Fulton and Chipman's experimental data. If oxygen diffusion across the liquid metal boundary layer at the slag metal interface (step IIa) is rate-determining, In this equation, dn sio, /dt is the rate of silica reduction in moles per sec,A is the area of slag-metal interface in sq cm, Do is the diffusivity of oxygen in sq cm per sec, 6, is the boundary layer thickness in cm, c,* is the oxygen concentration right at the slag-metal interface in moles per cubic cm, and co is the oxygen concentration in the body of the liquid metal, also in moles per cubic cm. Equilibrium data" on the silicon deoxidation reaction in liquid iron and steel at 1600°C indicate that the oxygen contents of the liquid metal in Fulton and Chipman's experiments at 1600°C probably fell in the range of 0.5 x10-3 x10-3wt pct. That is, the maximum conceivable value of co*-co for the system under consideration was on the order of 10"5 mole oxygen per cubic cm. On the basis of previously published data,1O,11 it is estimated that Do/0 will fall somewhere in the range from 10-3 to 10-1 cm per sec. The surface area A in Fulton and Chipman's experiments was approximately 20 sq cm, and the weight of metal involved was about 500 grams. Combination of all these figures with the above rate equation leads to an estimate that the rate of silica reduction should fall within the range from 0.002 to 0.2 wt pct Si per hr. This estimate is consistent with the experimental data. For example, Fulton and Chipman's Fig. 2 shows a change of about 0.3 pct Si in 10 hr, corresponding to an average rate of 0.03 pct per hr. According to the proposed hypothesis, increasing the temperature will increase the reaction rate ill two ways: 1) by increasing oxygen diffusivity and 2) by increasing the oxygen concentration (oxygen solubility) in the liquid metal. The combination of these two effects accounts for the high value of the observed activation energy. Summarizing, I propose that the rate of silica reduction, like that of the carbon-oxygen reaction, is diffusion controlled and that low oxygen concentration in the liquid metal is the major factor accounting for the very low observed rates of silica reduction. John Chipman (author's reply)—The authors thank Professor Schuhmann for his interesting contribution. His proposed explanation may well prove to be the correct one. There is clearly a need for much further experimental work on this problem, and further research is in progress.

Jan 1, 1961

By Keats, J. L.

IN THE literature on the elimination of metalloids in basic open-hearth practice, there are a great many heats recorded in which excellent data on changes in slag and metal composition during refining are given, but in almost all of these heats either temperature data or weights and analysis of charge are unrecorded and observations on the physical charac- teristics of the slag are almost always lacking. With these points in mind, a test heat was made in which as complete as data possible on all the factors that affect the elimination of metalloids were obtained.

Jan 1, 1957

By G. Venturello, C. Antonione, G. Della Gatta

Results from work on the effect of inferstitials on recovery and recrystallization of' very pure iron (99.995 pet) doped with nilrogen up to 400 ppm are reported. Nitrided specimens were obtained by heating the iron in a static atmosphere of NH3 + H2. The samples were cold-rolled 80 pet, subjected to a series of isochronal and isothermal anneals, and submitted to examination by X-rays, micrographs, and hardness tests. Small additions of nitrogen show a strong effect in reducing recovery of' the mechanical properties of high-purity iron. At the temperatures of. the experiments, this effect proved greater than in the case of carbon. At 400°C pure iron recovers more than 50 pet of the total hardness increase, carburized iron vecovers 25 pet, and nitrided iron only 10 pet. On the other hand. the addition of nitrogen has, similarly to carbon, a very small effect on recrystallization; the effect is, however, slightly higher than that of carbon. When the concentration Of nitrogen is above the solubility limit in a iron at the temperattue of the experiments, an increase in the frequency of nu -cleation is also observed. THE object of the present work is to improve knowledge on the effect of interstitials both on recovery and on primary recrystallization of pure iron. In fact. at present there are no available data on the effect of nitrogen on high-purity iron. The only work which at present can be somewhat related to this problem is a work of Leak et al.1 in which grain boundary internal friction at high temperature in the presence of increasing amounts of nitrogen is studied by a torsion pendulum. The present work is a continuation of a previous one2 on the effects of carbon. EXPERIMENTAL PART Preparation of the Material. Pure iron was prepared following the same methods used in the pre- vious work2 and was nitrided using controlled quantities of ammonia in an apparatus similar to that used for carburizing. The apparatus consists essentially of a gas-tight quartz tube containing the specimens. The tube, maintained at constant pressure by means of a mercury seal, is placed in a resistance furnace. For nitriding, the NH3 + H2 atmosphere with a suitable concentration of NH3 was introduced into the tube, which had been previously carefully evacuated and degassed by heating at 600°C. The hydrogen used was carefully purified by passing it through a palladium filter. The ammonia required was prepared with the following reaction: CaO + 2NH4CI —CaCl2 + H2O + 2NH3 by heating the mixture of CaO and NH4C1 in a glass flask and then collecting the ammonia in a graduated Hempel burette. For each nitriding program a given amount of NH3 prepared by this method was introduced together with the H2 into the tube previously evacuated. Nitriding of the sample was then performed at 570°C for 48 hr. After this, to ensure a homogeneous distribution of nitrogen, the samples were further heated for 72 hr at 800°C. With this method which uses a static nitriding atmosphere, carefully controlled conditions of purity are obtained. Contrarily, with the conventional continuous-flow methods, using large quantities of circulating gas, there is a greater risk of introducing impurities into the samples. Furthermore, the required nitrogen concentration in the specimen is easily predetermined and obtained. A plot of the relation observed between the initial concentration of NH3 in the gas and the quantity of nitrogen introduced into the iron samples is given in Fig. 1. The data refer to samples of 1.2-mm thickness and to the nitriding conditions previously described. Furthermore, as a comparison, the data relative to two 0.5-mm-thick samples are reported. The presence of a reservoir in the cold zone of the reaction bulb made possible the gradual dissociation of ammonia on the sample in the hot zone. Internal-friction methods were used to determine the content of nitrogen dissolved in the iron samples. Some analyses were also carried out with chemical methods. The following table, Table I, shows a comparison of data obtained with chemical and internal-friction methods. The correspondence between chemical methods and internal-friction

Jan 1, 1964

By S. W. MEALS

TWENTY million people in this country and Canada in nearly four million homes can give thanks to our Creator for natural gas, that most wonderful natural fuel with which Dame Nature has so bountifully blessed us. It is a clean, healthy and cheerful fuel, made up almost entirely of carbon and hydrogen. There is no residue, no waste and there are no objectionable constituents; an ideal fuel for the home. It operates like magic, open the valve and it is there for your needs, winter or summer, night or day. You are not required to place your order 30 to 90 days in advance and you do not need to pay for your winter's supply in advance. No ashes to worry about, no flues or chimneys to clean, nor kindling wood to store or bother the housekeeper. We who have been so blessed do not realize what it would mean to be without it. If in place of opening a valve we had to go to the woodshed or coalhouse and then build our fire-carry out the ashes-well, some of us I am afraid would be late reaching our offices and perhaps would miss our hot cakes for breakfast. One cubic foot of gas produced from the White Sand formation contains 1130 B.t.u. and weighs 47/1000 lb.; there are about 24,000 B.t.u. in 1 lb. of gas. Temperatures of over 3400 deg. Fahr. have been obtained with natural gas. Not only is it a superior fuel for the home but it has no equal for use in many large manufacturing industries, especially with the making of glass, pottery and open-hearth steel. In an open-hearth furnace, properly constructed, 5000 cu. ft. will melt one ton of steel. It requires 1/3 ton of bituminous coal gasified in a producer to do the same work, or about 40 gal. of tar or fuel oil, or 11,000 cu. ft. of by-product gas.

Jan 1, 1926

By AIME AIME

T HE 133rd meeting of the A. I. M. E., opening in New York on Feb. 15, promises to be as successful technically and socially as any in the past. The papers submitted for the various technical sessions are unusually excellent and insure something of interest to every group. Tentative programs have already been issued, and a concise resume of the various sessions, arranged chronologically, appears on page 48. Among the many interesting technical sessions arranged, attention is directed to those of the Petroleum Division, embracing the Symposium on Production that has come to be an annual feature, and new ones on refining practice, transportation and economics. The Institute of Metals program is similarly comprehensive. It includes 15 papers, 8 on copper, 4 on aluminum and its alloys, and one each on magnesium, lead, and fatigue of metals. The Coal Committee offers as a leading contribution its report, prepared under the direction of H. N. Eavenson, giving a new analysis of the capacity of the mines and a comparison of coal with other industries. This will be supplemented by a number of other papers of especial interest to operating men, among which are "Data on Use of Loading Machines in Bituminous Mines," by Graham Bright; "Evaluation of Coal," by R. H. Sweetser; "Selection of Coals for the Manufacture of Coke," by H. J. Rose; and "Relation of Origin and State of Carbonization of Coal to Problems of Low Temperature Carbonization," by S. W. Parr. The Iron and Steel Committee has scheduled seven papers, and there will be a special session on open-hearth practice, in which will be presented the first results of the two conferences, held by the sub- committee at Pittsburgh and Cleveland. A symposium on molding sands will be a special feature of the session on non-metallics.

Jan 1, 1926

By George Bell

THE mine and milling plant of Demonstration Gold Mines, Ltd., is near the city limits of Baguio, Mt. Province, P. I. The mine road connects with the main highway to Manila. The nearest railway point is near sea level, approximately 40 miles distant. The Baguio district is very mountainous and has one of the heaviest rainfalls in the world. It is therefore difficult to maintain roads or to impound tailings and mine dumps. All supplies are trucked into the district direct from Manila or the nearest railway point, which means uncertain deliveries and high freight rates. Installation of equipment is difficult and costly. The average elevation at the mine is 4000 ft. and the climatic condi-tions.are ideal except for a three months rainy season. The company generates its own power for mining and milling opera-tions with three 400-hp. Ruston Diesel engines direct connected to 250-kw. General Electric alternating current generators. Labor conditions have been excellent, although at present social security laws are causing some unrest. Labor receives a higher average wage rate in this district than other labor in the Islands. The com-pany also furnishes free living quarters, hospitalization and work-men's compensation. Taxation has been reasonable up to the present time, but some of the new mining legislation may make it difficult to operate and pay dividends. The future depends largely upon the continuation of $35 gold and the political outcome in the Islands.

Jan 1, 1939

By C. S. Smith

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers according to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Dr. Gerhard Derge; Editorial Assistant, M. A. Redmyrski; Staff Coordinator, James J. Burke. THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Post-President; John Chipman, Vice President; T. D. Jones, Treasurer; R. W. Shearman, Secretory. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. W. Thornton, Chairman- Dennis Carney John Chipman J. C. Fulton J. H. Hollomon H. H. Kellogg, A. E. Lee, R. Moddin, J. D. sullivan, and D.' Swan. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: T. B. King, Chairman; S. J. Dickenson, R. P. Hermsdorf, R. Schuhmann, Jr., and P. T. Stroup. lnstitute of Metals DM lion: Robert Maddin, Chairman. F. Lincoln Vogel, Jr.. Vice chairman. W. A. Backofen R. W. Boliuffi J. H. Bechtold' M. B. Bever R: S. Busk C 6. Goetzel poul Gordon C. D. Grobom, Jr., Robert F. Hehe-mann R. I. Joffee F. i. Joumot Jr. lrvin R. Kromer, A. J. Leno. Horold Morgolfn, C. J. McHargue, Russell A. Meussner, J. B. Newkirk, H. W. Paxton, G. E. Pellissier, I. S. Servi, Alon U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman. T. B. King, F. C. Laogenberg, W. O. Philbrook, and T. 0. Winkler. Publishod bimonthl by the American Institute of Mining Metollurgicol and Petroleum Engineers Inc., 29 West 39th Street, New York 16, N. Y. Telephone: PEonylvanie 6-9220. Subscription $20 par yew for non-AIME members in United States and North, South and Control Americo $25 foreign; $5 for AIME members. Single copies, $4.00, single copios foreign $5,00. The AIME is 1958 by the Amarican mode or opinion axpressed in it* publications ... Copyright by the Amarican lnstitute of Mining, MataIlurgicol, and Petrolum Engineers, Inc,. . . Reg. istered cable address AIME New Yark ... Indexed in Engineering Inderx, Industrial Arts ...Index and Chemicol Number5. Absrtracis . . . Second class postage paid at New York,Indor. N. Y., Industrialond Ann Arbor, Mich.

Jan 1, 1959

By N. J. Grant, C. C. Wang

The Ti-Cr-O ternary system has been studied in detail near the titanium-rich corner within the limits of 10 wt pct 0, and 20 wt pct Cr. Studies were extended, but not in detail, to the region beyond 25 wt pct 0, (50 atomic pct) and 62 wt pct Cr (60 atomic pct). Four isothermal sections at 1400°, 1200°, 1000°, and 800°C are presented as well as two vertical sections at 1 and 2 wt pct 02. DURING the last decade much interest has been shown in the development of high strength titanium alloys for high temperature and corrosion resistant applications. Extensive research is being carried out at present, as the current literature indicates, in order to study the properties of titanium and to develop improved alloys. Two of the important alloying elements in commercial titanium alloys are chromium and oxygen and it would be desirable to know their combined influence upon titanium. For this purpose the present work was carried out to investigate the titanium-rich corner of the ternary system TiICr-0. The binary systems Ti-Cr and Ti-0 have been published recently. The Ti-Cr system was studied by several investigators " and their results are in close agreement. The eutectoid decomposition of the B phase has been shown to be extremely sluggish. TiCr, was the only intermetallic compound found in this binary system and was formed at 1350°C by a transformation from the p phase. TiCr? was established as the cubic C 15 (MgCu,) type of structure with 24 atoms per unit cell and was designated as the y phase. This terminology will be adopted in the present work. There was disagreement about the actual composition of this compound among the several investigators, although it is evident from their data that the compound probably has a solubility range of about 2 to 3 pct and is in the vicinity of 65 pct Cr. It has been indicated recently that a high temperature modification of this y phase (TiCr,) existed at a temperature above 1300°C." ' This high temperature modification was identified as a hexagonal C 14 (MgZn,) type of structure with 12 atoms per unit cell. The exact transformation temperature from the high temperature phase to the low temperature phase has not been established. A considerable hysteresis was observed and, due to the sluggishness of this transformation, the high temperature phase often co-existed with the low temperature phase at temperatures below 1300°C. A preliminary study of several Ti-0 compounds and the Ti-0 system had been carried out by Ehr-1ich."-"' The most complete binary Ti-0 system was the one reported recently by Bumps, Kessler, and Hansen." The first intermediate phase found in the system was the 8 phase which formed by a peritec-toid reaction of the phases a and Ti0 at temperatures below 925 °C. This reaction is extremely sluggish. The structure of this 8 phase was tentatively identified by these authors as being tetragonal and the lattice constants were found as c,, - 6.645A, a,, = 5.333A and c/a = 1.246A. Experimental Procedure The raw materials used for this investigation were TiO,, electrolytic chromium, iodide titanium, and sponge titanium. The TiO, was in the form of powder of chemically pure grade (99.8 pct pure). The chemical analysis of the electrolytic chromium was: 0, 0.50 pct; Fe, 0.07; Cu, N, and C, 0.01; and Pb, 0.001. The oxygen in the chromium was calculated as part of the final oxygen content of the alloys. The alloys were prepared by the cold crucible method using a tungsten arc. The entire system was evacuated and flushed with purified helium three times and then filled with helium. Each alloy was melted, turned over, and remelted at least four times to insure homogeneity. The total melting time was generally from 6 to 10 min. A master alloy of 25 pct 0,-75 pct Ti was prepared to facilitate alloying by melting compacts of TiOl powder with either iodide or sponge titanium, yielding the compound TiO. It was found necessary to bake the TiO, powder compact at about 150°C to remove adsorbed moisture. This was done to prevent the disintegration and spattering of the compact when the arc was struck. TiO, powder dissolved quite readily into the melt and no other trouble was encountered.

Jan 1, 1955

By C. A. LINDBERG

Several new methods have been developed on the Iron Range to remove the material adhering to truck bodies in freezing weather. A machine known as a Gradall, incorporating the features of digging both above and below the horizontal, digging angle of blade control, full revolving, travel almost anywhere, and operated by one man, has proven successful in trials at body cleaning. Several of these units are in use with great saving in box-cleaning costs and improvements in efficiency of the truck operation with full capacity boxes. In addition to their winter use, the same machines have been used for ditching and excavating in the summer with great saving. The latest method of combating this freezing problem is to carry the exhaust from the engine through the body, making use of the tremendous heat that is now being wasted. To do this, the present wood sandwich which is used between the bottom of the box and the wear plate is removed and replaced with angles or channels run lengthwise of the box and spaced to permit gases to flow between or through them and also provide a good sup- port for the wear plate. The channels or angles are cut a little short on each end to form a cross passage that permits the gases to flow through the area. In the front end, openings are made in the wear plate and connect to a manifold created by welding a plate across the whole front of the box, spaced from the original end by the original vertical reinforcing angles at that point. The body being described is for a Euclid truck which is the only truck that has been adapted to this body-heating idea to date. At the rear of the truck, the holes from the cross passage are made in the bottom plate of the body and lead into a triangular-shaped body cross member under the scoop end of the truck.

Jan 1, 1949

Resistant Tape A new oil-resistant tape for rapid insulation build-up on splices in large power cables has been announced by Minnesota Mining & Mfg. Co. Designated Scotch brand electrical tape No. 25 is made of synthetic rubber providing greater dielectric strength and resistance to high temperatures. The chemical-resistant qualities of the tape make it suitable for use in oil drilling, mining and underground [ ] cable operations, while the 40-mil thickness and extreme stretch (1500 pct breaking point) make possible smooth insulation wraps on irregular surfaces. Dielectric strength is 15,000 v and 10,000 v at 500 pct elongation. It has an electrolytic corrosion factor of 1.0 and an insulation resistance of 100,000 megohms. Circle No. 1 Hydra-Lift The Pitman Mfg. Co. announces that is now has in production a new model of the Pitman hydra-lift, recently-developed crane with hydraulically-powered boom that can be mounted on the frame of any truck, 1 ½ tons or larger. According to the manufacturer, the new model hydralift model B features a variety of improvements over the original production model, introduced late in 1950. Changes incorporated in the new model, according to officials, not only have resulted in improved crane, but also have given the unit a new profile which distinguishes it sharply from the original model. The two chief improvements in the new model are: a big increase in the unit's safety margin and the fact that it is now shipped almost completely preassembled, cutting the time and cost of installation. Rated capacities of the hydra-lift are based on the tipping factor of a 1 1/2 ton truck, with outriggers down, and thus have not been increased. Circle No. 2

Jan 1, 1952

By J. C. Branner

(New York Meeting, February, 1012.) DURING the past two or three years I have seen statements regarding the first discovery of fullers' earth in this country that seem to require correction or modification. One appears again in the Mineral Resources of the United States for 1909, part II., p. 738, where it is said that ? fullers' earth was first discovered in the United States at Quincy, Fla., in 1893." In this connection the following bit of unpublished history concerning fullers' earth in the State of Arkansas is worthy of attention. In April, 1891, when I was State Geologist of Arkansas, a Swede named John Olsen, formerly a copper-miner in Michigan, but then living south of Little Rock, brought me a sample of what he thought was fullers' earth. He reported that it was from near the town of Alexander, the locality being 1 S. 13 W., section 8, SW. quarter of the SE. quarter. My chemist, Dr. R. N. Brackett, analyzed the material, and reported: Per Cent. Silica, . . SiO2., . 63.19 Alumina, . AL2O3, . 18.76 Iron, . Fe203 7.05 Lime, . Ca0 0.78 Magnesia, . . MgO 1.68 Potash, . K2O 0.21 Soda, . . Na2O 1.50 Loss on ignition, . 7.57 100.74 Water at 110° to 115° C. = 7.84. Another sample from about the same locality, also brought by John Olsen, on analysis by Dr. Brackett gave

Jul 1, 1912