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By A. H. Larson, L. G. Twidwell

The influence which Au, Ag, Sb, Bi, Sn, and Cu have, both individually and collectively, on the activity coefficient of sulfur in liquid lead at 600"C zuas studied by circulating a H2S-Hz gas wlixture over a specific lead alloy until equilibrium was attained. Subsequently, the H2S concentration in the equilibrium gas mixture and sulfur concentration in the condensed phase were deterruined. The elements gold, silver, and antinzony (above 8 at. pct) increased the activity coefficient of sulfur. Bismuth had no apparent effect. Tin (above 3 at. pct) and copper decreased the coefficient. The influence of an individual element, i, on sulfur is best reported as the interaction parameter, riS, which is defined as The values o these first-order interaction zus are: ESzu = —55.0. These interaction parameters are used to predict the activity coefficient of sulfur in six fouv-component alloys and one seven-component alloy. Comparisons are made with direct experimental determinations. INTERACTIONS in dilute solution have been studied by many investigators. Most of the experimental work has been confined to solute-solvent interactions in simple binary systems and solute-solute interactions in ternary systems. Dealy and pehlke"~ have summarized the available literature on activity coefficients at infinite dilution in nonferrous binary alloys and have calculated from published data the values for interaction parameters in dilute nonferrous alloys. Interaction parameters are a convenient means of summarizing the effect of one solute species on another in a given solvent. Only a few investigators have studied interactions of the nonmetallic element sulfur in a metallic solvent. They are as follows: Rosenqvist,~ sulfur in silver; Rosenqvist and Cox,4 sulfur in steel; chipman, sulfur in alloy steels; Alcock and Richardson,% ulfur in copper alloys; Cheng and Alcock,' sulfur in iron, cobalt, and nickel; Cheng and ~lcock,' sulfur in lead and tin. The only reported work on the Pb-S system in the dilute-solution region is that of Cheng and Alcock.' Their investigation involved a study of the solubility of sulfur in liquid lead over the temperature range 500" to 680°C. The results may be summarized by the following relationship: S (dissolved in lead) + Pb(1) = PbS(s) log at. %S = -3388/T + 3.511 Experimentally, it was found that Henry's law was valid up to the solubility limit of sulfur in lead, i.e., at 600°C up to 0.43 pct. Their investigation did not include the study of sulfur in lead alloys. More accurate calculations could be made in smelting and refining systems if activity coefficients of solute species could be accurately predicted in complex solutions. One of the objectives of this study was to compare the experimental data with the values calculated from the equations derived from models for dilute solutions proposed by wagner9 and Alcock and Richardson. A temperature of 600°C was chosen as the experimental temperature to attain reasonable reaction rates and to minimize volatilization of the condensed phase. EXPERIMENTAL Materials. The Pb, Au, Ag, Sb, Bi, Sn, and Cu used for preparation of the alloys were American Smelting and Refining Co. research-grade materials. All were 99.999+ pct purity except the antimony and tin which were 99.99+ pct. The initial alloys prepared for this study consisted of twenty-one binary alloys, eleven ternary alloys, and one six-component alloy. The constituent elements were mixed for each desired alloy and were placed in a crucible machined from spectrographically pure graphite. The crucible was placed in a vycor tube which was evacuated with a vacuum pump and gettered by titanium sponge at 800°C for 8 to 12 hr. After the gettering was completed, the chamber containing the titanium was sealed and removed. The remaining sample chamber was placed in a tube furnace at 800°C for 2 hr and quenched in cold water. The final operation consisted of homogenization of the alloy for 1 to 2 weeks at a temperature just below the solidus for the individual system. The resulting master alloys were sectioned into small pieces and a random choice made for individual equilibrations. Cobalt sulfide (Cogs8) used to control the gas atmosphere in the circulation system was prepared by passing dried HzS for 24 hr over a Co-S mixture heated to 700°C in a tube furnace. This material was then mixed with cobalt metal to give a two-phase mixture which, when heated in hydrogen to a particular temperature, produced a desired H2S/H2 gas atmosphere in the circulation system. A Cu2S-Cu mixture also used in this study was prepared in a comparable manner. Apparatus for Equilibrium Measurements. The experimental technique of this study required apparatus

Jan 1, 1967

By George A. 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 conditions are ideal except for a three months rainy season. The company generates its own power for mining and milling operations 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 company also furnishes free living quarters, hospitalization and workmen'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. History The Demonstration ore body was worked by the Igorots for many years, as evidenced by old stopes and fill encountered in present operations. Attention of Americans was first attracted soon after the Spanish-American war. During the building of the Benguet road to Baguio, the engineers and foreman became interested in the geology of the district.

Jan 1, 1939

By George A. 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 conditions are ideal except for a three months rainy season. The company generates its own power for mining and milling operations 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 company also furnishes free living quarters, hospitalization and workmen'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. History The Demonstration ore body was worked by the Igorots for many years, as evidenced by old stopes and fill encountered in present operations. Attention of Americans was first attracted soon after the Spanish-American war. During the building of the Benguet road to Baguio, the engineers and foreman became interested in the geology of the district.

Jan 1, 1939

LIST OF REFERENCES COMPILED BY ENGINEERING SOCIETIES LIBRARY FUEL POSSIBILITIES IN STEEL MAKING. Iron Age, November 6, 1913, p. 1056-1059. Paper read before the American Iron and Steel Institute, by William Whigham. The author discusses the use of pulverized coal as a fuel for open-hearth furnaces. IMPROVED PULVERIZED FUEL FEED DEVICE. Iron Age, November 6, 1913, p. 1024. Brief description of the Dunn apparatus, especially intended for cement kilns, but used also in the nodulizing of iron ore. WIDER UTILIZATION OF PULVERIZED COAL, H. R. Barnhurst. Iron Age, October 23, 1913, p. 906-908. Part of discussion of paper by James Lord on The Use of Pulverized Fuel in Metallurgical Furnaces, read before the Engineers' Society of Western Pennsylvania. POWDERED COAL FOR OPEN HEARTH FURNACES. Iron Age, October 16, 1913, p. 855. Abstract from the "Coal and Coke Operator." USE OF PULVERIZED COAL AS A FUEL FOR BOILERS, R. C. Carpenter. Sibley Journal of Engineering, December 1913, p. 85. COAL-DUST FIRED BOILER. Indian Engineering, November 29, 1913, p. 301. PROGRESS IN FUEL UTILIZATION. Mining and Scientific Press, October 25, 1913, p. 638. BUFFALO GRAIN-ELEVATOR DUST EXPLOSION. Engineering News, July 31, 1913, p. 223-24. Reprinted in the National Fire Protection Association Quarterly, October, 1913, p. 149-151. Mention is made of the danger of explosions in connection with the burning of powdered coal. POWDERED FUEL AND EXPLOSIONS. Railway Age Gazette, July 18, 1913, p. 53-84. Letter by W. D. Wood. USE OF PULVERIZED COAL IN METALLURGICAL FURNACES, James Lord. Engineers' Society of Western Pennsylvania, Proc., October, 1913, p. 363-371; discussion, p. 371-417. With bibliography.

Jan 3, 1914

By P. M. Robinson, J. S. LI. Leach

The heats of solution oj' indiurrr, tin, lend, nrzd tellurium have been calculated from the measured heat effects when mechanical mixtres of indium and telLuium tin and tellurium, and lead and tellurium were added to liquid bismuth. The results are in good agreement xith publislzed values.s for the separate sollction of each eleltzent in bismuth. The heats oj solution of cadmium and tellurium calculated from the rneasuved heat effects on adding trechanical mixtures of these elements do not ugree zc,itl the published values jbv the separate solution of each element. It is shown that at 623°K Ile interaction between cadmium and tellurium dissolved in liquid bismuth is strong enough to led lo preciPitation of solid CdTc. The heats oj- jor-mation of CdTe at 273" nd 623°K (1)-c crilculated fi-or the measured heat ejlfecls. The calcnlaled az'erage deviation from the Kopp-l\'ez?,zunrz rule fov solid CdTe is less than 0.06 cat per g-atom- C over this lertzperalure range. Tlze importance 0.f these oDserl.ations to the determination of heals of formation hy metal solution calorimetry is considered. LIQUID metal solution calorimetry is a convenient method for determining the heats of formation of solid compounds. In this technique the heat of formation is the difference between the measured heat effects on dissolution of the compounds and of mechanical mixtures of the components in the liquid metal.' The heat of solution of the mechanical mixture may be calculated from the measured heat effect. At infinite dilution of the solutes, this heat of solution is equal to the sum of the heats of solution of the separate components. If the heat of solution of one of the components is known, the value for the other can be derived; if both are known, they may be used to check the accuracy of the calorimetric technique. The heats of formation of the tellurides of cadmium, indium, tin, and lead have recently been measured by metal solution alorimetr. The heats of solution of indium, tin, lead, and tellurium at infinite dilution in liquid bismuth at 623"K, calculated from the measured heat effects on solution of the mechanical mixtures, are in good agreement with the published values. The heats of solution of cadmium and of tellurium calculated from the measured heat effect on solution in bismuth at 623'K of mechanical mixtures of cadmium and tellurium, however, do not agree with values estimated from the literature. 1) EXPERIMENTAL PROCEDURE AND RESULTS The Heats of Solution of Indium, Tin, Lead, and Tellurium in Bismuth. The heat effects were measured when mechanical mixtures corresponding to the compounds In,Te, InTe, In2Te3, In2Te5, SnTe, and PbTe were dissolved in bismuth. The calorimetric procedure and the method of calculation have been described elsewhere.' The heats of solution of the mechanical mixtures were obtained by subtracting the change in heat content per gram-atom of the sample between the addition temperature (273°K) and the bath temperature (623"K), (H623°K - H273°K)S, from the measured heat effects. The calorimeter was calibrated with pure bismuth. The reported values of the measured heat effects are based on (HGoK - ^273oK)Bi = 4.96 kcal per g-atom.3 The measured heat effects are found to be linear functions of the solute concentrations of the bath in the dilute solution range. The values, extrapolated to infinite dilution, are listed in Table I, together with the heats of solution of the mechanical mixtures calculated using the published values of (H 623°K - H273°k)s for indium, tin, lead,3 and tellrium. All the error limits quoted in this work represent the spread of values obtained. The heats of solution in liquid bismuth at 623°K of mechanical mixtures of indium and tellurium in four different proportions were determined. Values of the heats of solution of the two components were then calculated from the resulting four simultaneous equations: The heats of solution at infinite dilution of tin and lead in liquid bismuth at 623°K were calculated from the heats of solution of the mechanical mixtures of tin and tellurium and of lead and tellurium using the heat of solution of tellurium calculated above. These values of the heats of solution are listed in Table I1 together with some published values for comparison.

Jan 1, 1967

By M. Metzger, T. A. Read

The strengthening effects of hydroxide and synthetic plastic films in the creep of cadmium crystals were studied. The results were broadly consistent with the naive mechanical model. The dislocation-film reactions and the significance of the macroscopic stresses associated with certain films are discussed in the paper. ALTHOUGH a number of studies have been made of the strengthening of metal single crystals produced by surface films usually less than Ir in thickness, the mechanisms underlying this phenomenon are still not well established. Roscoe' first noted the critical shear stress and the stress-strain curve of cadmium-crystal wires to be raised markedly by the presence of oxide films. Subsequent investigators2-' have confirmed the effect for several metals and films including a number of plated poly-crystalline metal films. Harper and Cottrel1" with a thin film on zinc presumed to have formed as a result of etching and washing treatments) did not detect a strengthening at a rate of extension of 10 ' sec-' although at lo-' sec-' the film raised the flow stress by 7 pct at 0.0005 extension and by 22 pct at 0.01. The marked strengthening at moderate strains thus appeared to be the result of a dynamical effect dependent on the rate and amount of plastic flow. Other observations'. " are consistent with this view. The large effects of films on the tensile creep rate of single crystals were demonstrated when the observation of Andrade and Randall," that the creep rate of cadmium crystals increased on immersion in aaueous solutions of certain cadmium salts. was shown' * to hold only when a film was present initially and was explained by the attack of the solution on the film and the removal of its strengthening effect. Changes in the creep rate interpretable in terms of the removal or formation of various films have been observed by other investigators.3,8,10,31 Certain other experiments have been reported in which surface films or liquid environments have affected the plastic behavior of metals, but these are not within the scope of the present work which deals with the effect of solid films on single-crystal slip. Possible Mechanisms—The film does not significantly reduce the load on the crystal in the elastic range (the elastic moduli of film and crystal are not too greatly different and the area of the film is so small that its share of the load is negligible) so that the initial operation of internal Frank-Read sources is not affected. However, as Fisher" has pointed out, a source terminating on the crystal surface requires only half the critical stress for activation as an internal source of the same length and a relatively strong film (even a very thin one) would pin the free ends of the surface sources so that, if surface sources are responsible for plastic flow in a clean crystal. such a film would increase by roughly a factor of 2 the stress necessary for generation of dislocation loops at a given rate. The other general possibility is that the film resists the passage to the crystal surface of internally generated dislocations. If the film is adherent and if the specimen is to exhibit slip of the same general character as a film-free specimen, the film must deform or fail in shear at the active slip planes. The naive mechanical model, where shear-stress relaxation across the active slip plane in the metal transfers load to the film until it deforms and slip can

Jan 1, 1959

By A. J. de Witte

INTRODUCTION The importance of determining dips of subsurface formations in wells, especially in wildcat wells, is self-evident and need not be enlarged upon. Various dipmeter instruments have been described in technical literature1,2,3,4 over the years. The introduction of the continuous dip-meters3,4 has made the earlier types obsolete. Continuous dipmeter logs are run by at least two different major service companies. Included as part of the service are a limited number of dip calculations—usually 10—made at different levels from the log. Very frequently this is the total result of a dip survey. It is believed that dipmeter surveys would be of considerably more advantage if geologists and engineers were able to make their own calculations from the original records. Determination of dips from the dipmeter record starts with the correlation of three log curves taken at different sides of the borehole. It cannot be over-emphasized that the quality of the results hinges primarily on this correlation. Nobody should be better qualified to correlate logs than a subsurface geologist or field engineer. The next requirement is to have an easy yet accurate way of computing the dip from the correlated points. Service companies use a mechanical device for this purpose. Directions for a graphical method were given in a recent article by B. 0. Prescotts. This paper describes a different graphical technique which, in our experience, is simpler, faster and at least as accurate. The entire manipulation is carried out on the stereonet in a number of easy moves. The paper is divided into two parts. This first part contains the introductory sections and full explanation of the geometry involved. The second part reviews the reading of data from an actual field log and summarizes the practical rules for computation of dips, the whole process being illustrated by an example. Following the outlined procedure, one could calculate a good many levels in a relatively short time, thus being able in particular to check suspected anomalies such as fault zones or unconformities in as close detail as the log will permit. GENERAL EXPOSITION OF THE METHOD Prnciple of the Dipmeter The position of a plane in space is defined by the location of three points, not on a straight line. Referring to Fig. I, if a borehole traverses a bedding plane, we can determine the strike and dip of the bed by finding three points which are not in line along this plane. Such points as A, B, and C are obtained with the dipmeter. The device consists of three electrodes (or caliper arms)1, 2, and 3 spaced at 120 angles, as schematically indicated, whose readings are separately recorded (Curves 1, 11, 111, to the right). When electrode 1 passes the boundary of the bed, Curve I will kick, etc. From these curves, we know the relative distances of points A, B, C, measured along the axis of the hole. If A is at zero, then B and C are at levels d1 and d2 up the hole,

Jan 1, 1957

Allan Gibb, Queensland, Australia (communication to the Secretary*):—It is gratifying that Mr. Edward Keller,' who has clone so much work elucidating the principles of copper-metnllurgy, should have subjected only that portion of our investigation relating to magnetic iron oxide to anything like adverse criticism. Situated as we were on a rnining-camp, it was impossible to undertake work that would cover all the intricate possibilities connected with the materials commonly classed as matte. We therefore began the investigation on matte produced from ores that contained no other components than the sulphides of copper and iron that would be likely to enter into the composition of matte. We were, accordingly, free from ally possibility of magnetic iron oxide entering the matte, unless it were formed in the operation itself. The work done on this subject was incomplete, and the results thereof recorded as giving only negative evidence as to the absence of magnetic iron oxide. It would have been better to have left the matter open, as " not proven." The trend of the investigation was to account for the insufficiency of sulphur in matte to satisfy the requirements of ferrous and cuprous sulphides. So far as our deductions are correct, it was unnecessary to consider the (in our samples) somewhat doubtful constituent, magnetic iron oxide. The mattes that mere investigated were among those mentioned by Mr. Keller, " which scarcely show ally magnetic property." The samples showed no such property. There was no unaccountable variation in the specific gravity, which only varied, as would be expected, with the proportion of ferrous sulphide. I have had experience in smelting ores of which the gangue was a siliceous magnetite, both in blast- and rever-beratory furuace. The mattes so produced contained magnetic

Jan 1, 1908

By L. S. Darken

IT has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernst1 in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and Fuoss2 with results which have recently been confirmed experimentally by Harped and Nuttall.3 This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author 4.6 who pointed out4 that "for a system of more than two components it is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepticism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley11 in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion 0f acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 1050°C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1948

By J. S. Bowles

DISCUSSION, M. Cohen presiding J. W. Christian (The Inorganic Chemistry Laboratory, oxford, Englandl)—I was very interested in Dr. Bowles' results on the suppression of the transformation by solid films of alcohol or propane. The transformation in cobalt, which is also martensitic, can be explained by a mechanism involving the reflection of "half dislocations" down a series of atomic planes.* This reflection process is similar to that considered by Frank13 for plastic deformation on a single slip plane and, as he pointed out, reflection would be impossible if the metal were immersed in a liquid of higher density. It seems possible that solid films of alcohol have a similar effect on the lithium transformation. Reflection should also be possible at a grain boundary, though a higher kinetic energy of the dislocation, and hence a lower temperature would be required. As Dr. Bowles used coarse grained polycrystalline speci- mens, transformation on cooling should still have occurred in grains which did not form part of the outside (free surface) of the metal. This may account for the X-ray lines of the low temperature phase which were found. There is thus the interesting possibility that in a polycrystalline specimen a liquid, or in some cases a solid, film of material of or or higher density will lower M,, while in a single crystal it should suppress the transformation completely. In the case of cobalt it is necessary to find a dense liquid which will not react with the metal at the transformation temperature. The most promising liquid appears to be pure lead, but it is very difficult to devise a method of investigating whether or not this does suppress the transformation.

Jan 1, 1952

By F. D. Rosenthal, F. J. Dunkerley, G. J. Mills

Activities, free energies, and heats and entropies of mixing of liquid Pb-Zn alloys have been obtained by the electrode-potential method between 400° and 650°C. The large positive deviations observed from Raoult's law are in agreement with the phase diagram, which indicates a wide immiscibility field. A vapor-pressure method was used to extend the activity measurements to 900°C, allowing the maximum of the immiscibility gap to be estimated by thermodynamic calculation. Data on the mono-tectic and eutectic points compare favorably with previously existing work. SEVERAL long-standing methods have been in use for the study of phase diagrams from measurement of the activities of the component metals.' The use of thermodynamic analysis for interpreting equilibria data is comparatively recent, however. Such analysis is usually undertaken by first evaluating the principal thermodynamic functions as, for example, the enthalpy, entropy, and free energy of the alloy constituents. These, in turn, quite often can be correlated with the interatomic potential energies and atomistics of the system, from which a clearer understanding of the causes leading to deviations from ideal behavior is gained. The present study of liquid Pb-Zn alloys is concerned with a determination of these quantities by electrode-potential and vapor-pressure measurements, using these values in calculations involving phase equilibria and to obtain a theoretical insight into an alloy system exhibiting strong positive deviations from ideal metallic solution. A considerable portion of the previously reported work is based on thermal analysis. Supplemented by optical studies of solid alloys, these techniques have revealed the essential nature of the immiscible mixtures that are formed. It is difficult, however, using the phase-

Jan 1, 1959

By John R. Green

ROTARY kilns, varying in construction, are used in a variety of processes. Products differ and operating conditions vary according to economic requirements. All of these variables influence the degree of instrumentation and type of control necessary or profitable to install. Products fired in rotary kilns are the results of combined temperature and time treatment and the interrelation of these two factors should be kept constantly in mind in the perusal of this paper. MEASUREMENTS OF KILN TEMPERATURE The securing of proper temperatures within the rotary kiln, either of the charge or of the kiln lining in the high fire zone, are basic objectives of kiln operation; therefore the measurement of these high-temperature conditions merits first consideration.. For these measurements, radiation pyrometers, properly designed and protected, have proved adequate, particularly where records or automatic control are desired, while optical pyrometers may serve as portable indicators. Light-sensitive devices or photoelectric cells in this service are capable of producing records as well as certain forms of automatic control. High-temperature measuring devices for rotary-kiln work should have the measuring unit protected from dust, as a continued accumulation of deposit would lower the readings. Fig. I shows a typical application of radiation equipment to a rotary kiln, mounted far enough away from the sighting hole through the kiln hood to be protected from puffs or stingouts and with a sighting tube having a series of settling chambers, to prevent dust from reaching the lens. Although dust conditions inside the kiln itself usually fluctuate considerably and have their effect upon the readings at that moment, such effects are not cumulative and show as a continuous fluctuation in the temperature indicated, provided the radiation unit and recorder are responsive to such slight and rapid temperature fluctuations. The ambient temperature to which a measuring unit is subjected fluctuates from possibly o° to over 200°F., therefore these changes should have no effect upon the final reading or upon the life of the measuring unit. A very narrow sighting angle is desirable, so that measurement of temperature may be made as far as possible into the high fire zone without. effect of the flame temperature. There should be some sighting means on the measuring unit, so that the proper field may be viewed. Measurement of wall temperature taken at a point where the charge has just left the wall is less affected by dusting conditions than when taken elsewhere. Factors Influencing Temperature Table I gives an outline of the factors that produce kiln temperatures and com¬ments on the possibility of measurement and control. Of greater number and of varied influ¬ence are the factors that control when, where and how the heat is delivered to the kiln, the type of flame and the rate of

Jan 1, 1941

By H. J. Rose

In a paper1 presented before this Institute in 1926,I briefly discussed the evaluation of coking coals by means of ultimate analysis. The paper contained several graphic studies in which coal analyses calculated free of moisture, ash, sulfur and nitrogen were plotted on triaxial diagrams in which carbon + hydrogen + oxygen = 100 per cent. From a study of such data for 600 coking coals of the United States, and 150 coking coals of Wales, France and Germany, it was concluded that it was usually possible to predict coking properties and by-product yields with fair success from ultimate analysis. The coals which have proved exceptions to the general rules were found to have physical peculiarities. Run-of-mine Coal It must not be forgotten that run-of-mine coal is a composite material consisting of many constituents differing in physical properties and chemical analysis. A coal sample usually contains: 1. Glossy black coal known as anthraxylon or vitrain. This constituent usually has the strongest coking properties, and the lowest ash content. 2. Dull black coal consisting of attritus containing thin layers of anthraxylon. It is also known as clarain. This constituent, in a coking coal, usually has good to excellent coking properties. 3. Mineral charcoal or fusain. This is a porous black material which is soft and crumbly (unless impregnated with mineral matter) and which has absolutely no coking properties. It is different in every respect from the other constituents in coal. The volatile matter content of mineral charcoal is less than 20 per cent. even when it is associated with high-volatile coals. As would be expected the hydrogen content is low, and the carbon content is high. 4. A coal sample may contain tough gray canneloid material which has a high-volatile matter and a high hydrogen content, but is poor in coking qualities.

Jan 1, 1930

By George A. 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 conditions are ideal except for a three months rainy season. The company generates its own power for mining and milling operations 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 company 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. HISTORY The Demonstration ore body was worked by the Igorots for many years, as evidenced by old stopes and fill encountered in present operations. Attention of Americans was first attracted soon after the Spanish- American war. During the building of the Benguet road to Baguio, the engineers and foreman became interested in the geology of the district.

Jan 1, 1939

J. L. JONES,* Pittsburgh, Pa.-If a nickel anode is cast under commer-cial conditions, will it contain nickel oxide? Will the nickel oxide affect the rate of corrosion in a double sulfate solution; or will the nickel oxide dissolve in a double sulfate solution? I would also like to ask whether a 98 per cent. pure nickel anode will corrode as fast as a 96 per cent. nickel anode; whether electrolytic nickel will corrode less rapidly than nickel containing a small amount of carbon; and whether the materials some-times used in coating molds for casting nickel anodes will affect the rate of corrosion of the anode? In other words, whether an electrically non conducting coating is likely to be present that will prevent the nickel anode from corroding rapidly. JOHN F. THOMPSON.-The nickel oxide will not dissolve in the double sulfate solution, as far as we know. We do not make the ordinary nickel anode of commerce, but we supply nickel to the nickel anode makers. Those makers almost invariably buy a high-carbon nickel shot, ranging around 0.45 per cent. carbon. In their process, they even further, car-burize it so as to get nickel that will melt easily and be fluid enough to fill the mold, so that the ordinary cast anode on the market is unquestion-ably oxide free. The only time that such an anode will have oxide will be through an error in melting. Some cupola makers of anodes have had trouble with oxidation, but as a rule the anodes are thoroughly carburized; so much so that they probably carry a couple of per cent. of carbon of which around. 1.6 per cent. is graphite.

Jan 12, 1919

THE foundation established by the partners of the late Robert W. Hunt provides for both a medal and a prize. The latter has not been given before this year, and the first award is to C. H. Herty, Jr., for his several papers on the physical chemistry of the open-hearth process.. He is the son of the well known chemist of the same name. He was born at Athens, Ga., on Oct. G 1896, graduated from the University of North Carolina in 1918, and went into war service as foreman of U. S. Chemical Plant No. 4, at Saltsville, Va. In 1919 he went to Massachusetts Institute of Technology, where he was successively instructor, research assistant, and research associate in the School of Chemical En-gineering practice receiving his master's degree in 1921 and his Ph.D. in 1924. He continued his brilliant work on the physical chemistry of the open-hearth process, much of it being done in cooperation with the Bethlehem Steel Co. at its Lackawanna plant, and dealing with the elimination of sulfur. In 1926 he joined the staff of the U. S. Bureau of Mines, in charge of its ferrous metallur-gical work at Pittsburgh, and continues to be active in research work on the physical chemistry and metallurgy of the open-hearth process. His Institute publications are: Some Factors Affecting the Elimination of Sulfur in the Basic Open-hearth Process," "Chemical Equilibrium of Manganese, Carbon and Phosphorus in the Basic Open-hearth Process" and "Desulfurizing Action of Manganese and Iron," and he will present a paper on ?Effect of Temperature on the Solubility of Iron Oxide in Iron" at the annual meeting.

Jan 2, 1928

By T. D. Tiemann

The caustic extraction of silica from Wisconsin and Minnesota taconite was investigated by bomb digestion over the temperature range from 312 to 40S°F at caustic concentrations from 25 to 500 gpl. Residual concentrates containing as much as 65 pct iron were obtained. The high rate of silica extraction is related to a microcrystalline variety of quartz, since it is shown that the rate of extraction of silica from quartz is directly proportional to its surface area. Increasing dependence on foreign ore reserves makes the need for developing the technology necessary for treatment of our low grade ores even greater than it was at the time of World War 11, when much research was conducted on the extraction of alumina from clays. Representative of these were the studies carried on at the University of Illinois.' More recently, the U. S. Bureau of Mines investigated the production of alumina from anorthosite, and currently the aluminum industry is showing renewed research interest in this field. The studies reported here are part of a continuing research program based on the above concepts and aimed at the eventual development of processes for the treatment of low grade ores, particularly those of iron. The fact that large reserves 3 of low grade nonmagnetic taconite are contained in the iron formation of the Wisconsin Gogebic range have made this ore an important and attractive target for investigation. The idea of removing silica by caustic extraction is not new.495 The digestion in caustic solution of ground flint, diatomite, and other forms of chalcedonic silica is the basis for the production of soluble sodium silicates by the wet-process. Upgrading bauxites by the caustic extraction of silica has been investigated6 and is the subject of a German patent.7 Although mention is made by Roe' of the caustic extraction of silica from low grade Michigan and Wisconsin iron ores, and he lists a number of patents and references on the subject, recent work in the field does not appear to be extensive. As far as the author knows, there has been no work in this field on these particular ores. It is hoped that this paper will stimulate further investigation which will eventually lead to an econclmic means of processing these large low grade reserbes. TACONITES The taconites investigated in this study were from Minnesota and Wisconsin. That from Minnesota, a semi-taconite, Nas obtained from the Oliver Iron Mining Division, U. S. Steel Corporation, and represents a sample of an oxidized iron formation from their King Mine on the Mesabi range. The Wisconsin taconite came originally from the trench sampling of the U. S. Bureau of Mines, and represents a composite of the Norrie, Pabst, Yale, Plymouth, and Pence members of the Gogebic iron formation. Assays on these samples are given in Table I. A typical calcu1atr:d average analysis of the Wisconsin taconite is given in Table 11. Chemically, the Minnesota semi-taconite sample contains about 39 pct iron and 39 pct silica, while the Wisconsin taconite contains 30 pct iron and 53 pct silica, both on the dry basis.

Jan 1, 1962

By S. Ramachandran, R. A. Walsh

Many investigations have shown that the manganese enhances the deoxidation power of silicon. Here it is suggested that this phenomenon could be explained in terms of the formation of impure silica. Data of Hilty and Crafts on the Fe-Mn-Si-O System has been evaluated on the basis of the reaction S_i + 20 = (SiO2) where (SiO2) denotes silica of variable activity. The activity of silica in this system is a function of aMn/aSi and the temperature, and can be described by the equation 12700 l°gaSiOz = -6.85+ - - 0.5 log aMn /asi PRACTICAL melting experience has shown that it is helpful to maintain a certain range of Mn/Si ratio in deoxidizing quality alloy steels. Herty,1 as early as 1932, reported a strong association between manganese and silicon as did schenck2 and Korber and Oelsen3 in later work. More recently, Hilty and crafts4 have studied the solubility of oxygen in the Fe-Si-O system, both with and without manganese. Their study confirmed the marked ability of manganese to increase the deoxidizing power of silicon. This phenomenon has remained unexplained in the liter,ature5 since it has been shown that manganese has virtually no influence on the activity coefficients of silicon or oxygen.= In this paper, an explanation for the role of manganese is suggested and equations are devised for quantitatively describing this influence. DISCUSSION Hilty and crafts4 equilibrated their melts under an argon atmosphere and the system established equilibrium with a self-generated slag which was not always the oxide of lowest free energy. Drawing on the early work of Korber and Oelsen,3 it was reasoned that the formation of complex Fe-Mn-silicates

Jan 1, 1963

By Robert D. Pehlke, Weldon L. Daines

The reduction of manganese oxide from a basic slag by silicon dissolved in liquid iron at steelmaking temperatures was studied to determine the rate-controlling step for the process. The experiments were carried out under an argon atmosphere in a resistance-heated vertical-tube furnace. The two liquid phases, slag and metal, were held in zirconia crucibles. Sampling and chemical analysis of the slag phase led to time-concentration curves for the system. Results obtained by varying parameters such as temperature, stirring rate, concentration, and melt geometry defined the limiting reaction mechanism. The reduction of manganese oxide by silicon is a fast reaction and reached equilibrium within 90 min. The rate of stirring has a marked effect on the reaction rate, while, on the other hand, the effect of temperature is very small. This identifies the rate-controlling step as diffusion rather than interfaciul chemical reaction. The variation of other parameters revealed that a) diffusion of manganese in the iron phase is the slow step, b) the value of D/6 for manganese in iron at 1550°C is 7x 10-4 cm per sec, c) the energy of activation for the apparent rate constant is 7 kcal per mole, and d) increasing the amount of silicon in the iron decreases the diffusion coefficient of manganese. THE equilibrium relations pertinent to the reduction of manganese oxide from a steelmaking slag by silicon dissolved in liquid iron have been studied, but little is known about the mechanisms that control the rate of the process. The purpose of the present investigation was to study the rate of reduction by silicon and to determine the rate-limiting step. The effects of stirring rate, temperature, composition, and melt geometry were investigated as a means of identifying the controlling step. On the laboratory scale, relatively little work has been done in the area of slag-metal kinetics, primarily because of the problems confronted in attempting to contain liquid slags and metals in laboratory crucibles at steelmaking temperatures. Since graphite is an ideal material for a crucible, several investigations have been carried out on the reduction of various oxides from a slag by carbon in graphite-saturated iron and on the transfer of sulfur between a slag and graphite-saturated iron. Most of this work has been performed in induction furnaces. Studies where the container was not graphite are extremely limited. A single kinetic study of manganese transfer between molten iron and basic slags was carried out by Sano, Shiomi, and Matsushita.' These investigators prepared calcium oxide and titanium oxide crucibles to contain the two-phase system. Only a few experiments were carried out and the results had to be treated qualitatively. Despite the paucity of kinetic data, a large quantity of information is available in the literature concerning the thermodynamics2-12 and physical properties'3-21 of the slags containing manganese oxide and the dilute liquid iron alloys containing manganese and silicon which were involved in this research program. EXPERIMENTAL METHOD A vertical-tube resistance-heated furnace was used in this investigation to study the slag-metal reaction Although most previous slag-metal studies were carried out in induction furnaces, a resistance furnace has several advantages including better control of temperature and stirring rate. Hence, a resistance furnace was selected for this study, and its design is shown schematically in Fig. 1. Slip-cast, fine-grained, low-porosity, lime-stabilized cubic zirconia crucibles were used for the kinetic experiments. The crucibles were 4 1/2 in. high and 2 1/8 in. OD with a 1/16-in. wall. The crucibles were only slightly

Jan 1, 1969

By Albert Sauveur

(Cleveland Meeting, October, 1912.) ALTHOUGH many metallurgists know that some pearlitic special steels can be made troostitic, martensitic, and even austenitic, without quenching, and, therefore, without exposing them to the dangers of the quenching-bath, the practical significance of such possibility does not seem to have received the attention it deserves. Let us recall briefly the mechanism of the transformation alluded to. In Fig. 1 (after Guillet) is shown the constitutional diagram of nickel-steel that; is, of alloys of iron, carbon, and nickel. Any steel the composition of which falls within the area LPO is pearlitic after slow cooling; any steel the composition of which is represented by a point within the area MLO is martensitic, and any steel within the area MNO is austenitic. Starting with pearlitic steel, then by increasing the carbon-content or the nickel-content, or both, the metal becomes martensitic and eventually austenitic; that is, its composition crosses first the boundary-line LO and then the line M0-and it remains martensitic or austenitic after slow (air) cooling.1 We have inn this way imparted to the metal without quenching it the properties of hardened carbon-steel. In other words, the steel is now self-hardening. Nickel cannot be introduced into solid steel, but by the well-known process of case-hardening it * Professor of Metallurgy and Metalllography in Harvard University. + Assistant in Metallurgy and Metallography in Harvard University. 1 The boundaries between the various zones are not, as a matter of fact, as sharp as indicated in the diagram, because pearlite is not transformed abruptly and in its entirety into martensite when a certain critical composition is attained, nor is martensite suddenly and completely converted into austenite. Greater refinement in the construction of the diagram would undoubtedly result in the introduction of troosto-pearlitic, troostitic, and troosto-martensitic zones between the pearlitic and martensitic areas and-of a martenso-austenitic zone between the martensitic and austenitic areas. Fur the purpose of this note, however, the existence of these transition-conditions may be ignored.

Nov 1, 1912