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By E. P. Bayer

MESABI RANGE ore is mined largely by the open-pit method. This involves having available at all times sufficient working places which in combination will produce ore of guaranteed analysis. Fast- loading power shovels turn out under favorable conditions 1000 tons per hour from each unit. Each unit loads ore differing materially in analysis from that loaded by the others, One may load high grade, another low grade, and another may be in a mixed bank with the lead ore so placed that the product must be mixed at the shovel before it is loaded into cars. In such cases the bank is combed with the bucket, the door being left open to permit the material to fall through.

Jan 1, 1937

By W. P. Heineken, A. T. Child

This paper presents the results of a series of experiments made in the metallurgical laboratory of Columbia University, New Pork City. The object of the investigation was to determine, as far as possible, the changes in micro-structure and physical properties caused by short periods of heat-treatment and the longer malleable cast-iron process. It was proposed to do this by means of micro-photographs, heating- and cooling-curves, and tensile tests after the various heat-treatments. I. Micro-Constituents of Iron and Steel. The list of the micro-constituents of iron and steel has grown till now it includes seven different substances, called ferrite, cementite, pearlite,* martensite, austenite, sorbite and troosite. Only the first five of these are mentioned in this paper, to facilitate the understanding of which, the following brief definitions are given: 1. Ferrite (named by Prof. Howe) is, chemically, iron free from carbon. It is the softest of the constituents, and is not colored by etching, except when long-continued. Under the microscope it is easily determined by its regular polygonal etructure; or, if structureless, as in malleable cast-iron, by the ease with which it is scratched. Ferrite appears in mild steel in small amount, in grey cast-iron, and in malleable cast-iron. 2. Cementite (also named by Prof. Howe) is now generally conceded to have the formula Fe3C. It is the hardest of the micro-constituents, having the hardness indicated by 7 of the mineralogical scale; and hence it is always left in relief after

Jan 1, 1901

By Edna A. Dancy, Gerhard J. Derge

The specific conductance of FeOx,-CaO melts in contact with iron was found to decrease from 200 ohm-1 cm-1 for FeO, to 40 ohm-1 cm-1 for a melt containing 26.3 pct CaO at 1400°C. The temperature coefficient was positive at all compositions, but became smaller at high CaO contents. Current efficiencies for electrolysis increased from 2.5 pct in FeOx to 17.3 pct at the high CaO composition, indicating a change from predominantly electronic conduction to conduction with a substantial ionic contribution. It was shown that Ca++ ions as well as Fe++ ions carry the ionic current. A subsidiary investigation on the apparent effect of atmospheres of argon, helium, and nitrogen on the electrical conductivity showed that this could be correlated with surface temperature losses, which varied with the thermal conductivities of the gases and resulted in precipitation of metal by the reaction 3 Fe++ = 2 Fe+++ + Fe. The work described in this paper is offered as a contribution to the general fund of knowledge concerning metallurgical slags. Measurement of electrical conductivity and electrolysis are comparatively trouble -free methods for investigating molten materials, but, although these methods had been used for complex slags, it was not until the work of Bockris et al.1 that the approach of examining simple binary slag systems was employed, and CaO-SiO2, MnO-SiO2, and Al2O3-Si9 were studied. Two groups have performed work of particular relevance to the present investigation. Inouye, Tomlinson, and chipman2 studied the conductivity of wustite as a function of temperature and of the addition of 5 mol pct of a number of oxides, including CaO. They concluded that molten FeOx in equilibrium with iron is a semiconductor. Simnad, Derge, and ceorge3 demonstrated the ionic nature of liquid iron silicate slags and also concluded that, although the conductivity of FeOx in equilibrium with iron is predominantly electronic in nature, there is a small ionic contribution. The work reported here on FeOx,-CaO slags consists of three main parts, namely, the determination of the specific conductance over a wide composition range, an investigation into the nature of the conductivity through current-efficiency measurements over the same composition range, and an attempt to identify the current-carrying ions, as well as a subsidiary investigation on the apparent effect of the nature of the inert atmosphere on the conductivity. EXPERIMENTAL Materials. The slags, varying in composition from FeOx to 27 pct CaO, were prepared by heating reagent- grade Fe2O3 in an ingot iron crucible with a suitable amount of CaCO3 and, in some cases, powdered iron, in air. This prefused material was then used for the runs. At the end of each run the cell was removed from the furnace and quenched by immersing the bottom half in water. After crushing, the slags were analyzed for calcium and total iron by the usual wet methods. The oxygen content was obtained by difference. Specific Conductance: Apparatus and Method. Fig. shows the experimental setup, with the conductivity cell and leads of ingot iron. The standard four-probe method for measuring high conductivities was used. In this, the potential drop across the unknown resistance is compared with the potential drop across a known resistance connected in series, i .e., same current through both resistances. Thus there are both current and potential leads to the center electrode and to the crucible, which acts as th other electrode. Both ac and dc circuits were available for the measurements; they have been described in earlier work performed in this laboratory.4,5 The geometry of the cell was such that the center electrode was equidistant from the bottom and sides of the crucible. This ensured that the current path was the same irrespective of the magnitude of the conductivity of the material in the cell. Cell constant were measured with KC1 or NaCl solutions, which have considerably lower conductivities (0.0013 to 0.25 ohm-' cm) than the slags, and this precaution in design made sure that the determined cell constants applied to the cells with contents of any conductivity. The cell-constant determinations were made with the ac measuring circuit to prevent polarization. The four-probe method eliminates lead resistance but not the resistance of those parts of the center

Jan 1, 1967

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By AIME AIME

LOCAL COMMITTEES. EXECUTIVE.-W. A. Lathrop, Chairman; R. V. Norris, Secretary; S. D. Warriner, Treasurer; Irving A.. Stearns, W. J. Richards, H. S. Drinker, C. D. Simpson. GENERAL RECEPTION.-Irving A. Stearns, Chairman. Archibald, James, Jr., Pottsville. Lawall, E. H., Wilkes-Barre. Ashley, H. H., Wilkes-Barre. Lentz, W. 0., Mauch Chunk. Ayres, WV. S., Hazleton. Lewis, Albert, Bear Creek. Beard, J. T., Scranton. Loomis, W. H., Jeddo. Bridgman, J. C., Wilkes-Barre. Markle, Alvan, Hazleton. Bunting, Douglas, Wilkes-Barre. Markle, John, Jeddo. Chase, F. M., Wilkes-Barre. Neale, J. B., Minersville. Coroner, Eli T., Scranton. Norris, R. V., Wilkes-Barre. Cote, E. B., Jr., Drifton. Oliver, Paul A., Oliver's Mills. Davies, W. H., Hazleton. Owens, W. D., Pittston. Davis, H. G., Dorranceton. Pardee, 1. P., Hazleton. Dodge, W. F., Wilkes-Barre. Quin, R. A., Wilkes-Barre.

Jul 1, 1911

By George S. Rice

The subject of violent bumps in coal mines has been again brought to attention by a recent succession of such occurrences in the coal mines of the Cumberland field of eastern Kentucky and southern Virginia, which have caused fatalities and injuries to underground employees, a report on which is being issued by the United States Bureau of Mines1. The A.I.M.E. has had two valuable papers on bumps in the No. 2 Mine, Springhill, Nova Scotia, each followed by general discussion on bumps and their causes2. This paper gives a brief review of suggested causes and remedial measures given in English, Canadian and United States reports on blimps in coal mines, and then presents suggestions arising from the writer's recent investigation of the bumps in the Cumberland mines, made at the request of the mine operators, to determine the causes and remedies. These bumps, which occur under the simplest natural conditions, provide better opportunity for analysis of causes and effects than afforded under more complex conditions. The simple conditions in this field consist of relatively thin and level coal beds and uniform roof strata free from folding and faulting. Definition of Bumps Bumps in coal mines, as defined in this paper, are sudden violent bursts of coal that usually occur without warning in the extraction of pillars and may or may not be accompanied incidentally by falls of draw slate, upheaval of bottom and smashing of timbers. They are not known to occur where the advancing longwall method of mining, accompanied by

Jan 1, 1936

By George S. Rice

The subject of violent bumps in coal mines has been again brought to attention by a recent succession of such occurrences in the coal mines of the Cumberland field of eastern Kentucky and southern Virginia, which have caused fatalities and injuries to underground employees, a report on which is being issued by the United States Bureau of Mines1. The A.I.M.E. has had two valuable papers on bumps in the No. 2 Mine, Springhill, Nova Scotia, each followed by general discussion on bumps and their causes2. This paper gives a brief review of suggested causes and remedial measures given in English, Canadian and United States reports on blimps in coal mines, and then presents suggestions arising from the writer's recent investigation of the bumps in the Cumberland mines, made at the request of the mine operators, to determine the causes and remedies. These bumps, which occur under the simplest natural conditions, provide better opportunity for analysis of causes and effects than afforded under more complex conditions. The simple conditions in this field consist of relatively thin and level coal beds and uniform roof strata free from folding and faulting. Definition of Bumps Bumps in coal mines, as defined in this paper, are sudden violent bursts of coal that usually occur without warning in the extraction of pillars and may or may not be accompanied incidentally by falls of draw slate, upheaval of bottom and smashing of timbers. They are not known to occur where the advancing longwall method of mining, accompanied by

Jan 1, 1936

By R. D. Pehlke, J. V. Gluck

A study was made of the effect of small additions of metallic solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450o to 650°C. The experimental measurements were made in a multielectrode galvanic cell using. a fused LiCl-KCl electrolyte. The activity of zinc in binary solution exhibited a strong positive deviation from Raoult's law and obeyed Henry 's law to at least 0.050 mole fraction. The ternary addition of lead, gallium, or indium increased the activity of zinc. Cadmium or tin additions slightly decreased the zinc activity. Copper, mercury, silver, or antimony caused moderate decreases, while gold strongly decreased the zinc activity. The results are expressed in terms of Wagner's interaction parameter ejZn and a second-order cross-interaction parameter. The interactions for copper, gold, silver, and antimony showed a linear dependence with reciprocal absolute temperature, while the other interactions were essentially independent of temperature over the experimental range. Since tin and antimony decreased the zinc activity, the hypothesis of a purely periodic variation with atomic number was rejected. A semiquantitative explanation was possible with a free-electron model when relative electronegativities were used to express changes in the electron/atom ratio caused by the solute addition. Random solution and quasi-chemical models correctly predicted the majority of the interactions for which binary data were available to apply them. A knowledge of the thermodynamic interactions in liquid (and solid) metallic solutions is of considerable theoretical and experimental interest in the formulation of quantitative thermodynamic relations for metallurgical processes. The approaches to defining the interactions may be either phenomenological (i.e., "What mathematical function adequately describes observed behavior and permits extrapolation to new situations?") or theoretical, such as a specific model

Jan 1, 1968

By H. Hubert

The first attempts at direct utilization of blast-furnace gas in engines were made in 1895. For a considerable time the gas had been burnt in Cowper stoves for heating the blast for the furnace, and under the boilers which supplied steam to the blowing-engines, and others serving the furnaces. It was natural, therefore, that the idea of directly employing it in gas-engines should have occurred simultaneously to several engineers, notably to Lurmann and to Lencauchez, who had pointed out the blast-furnace as a powerful gas-producer. Nevertheless, nowhere had any attempt been made to apply it to this purpose up to the end of 1894, when Thwaite proposed it to Mr. James Riley, of the Glasgom Iron & Steel Company. About the same time investigations were being made in Belgium and in Germany, independently of Thwaite's experiments, which were not generally known on the Continent. The industrial world, which up to that time had hardly favored the idea, had thus been gradually prepared to receive it. The gas-engine, long restricted to small sizes and dependent upon the use of an expensive fuel obtainable only in large centers, now began to make headway. At the Paris Exhibition of 1889 two engines of 100 h.p. were shown and excited much interest among engineers. One had four cylinders, and was made at the celebrated works of the Deutz Company, and the other was a single-cylinder engine, exhibited by two French designers, Messrs. Delamare-Deboutteville and Malandin. In the meanwhile the design of gas-producers had made important progress, completely freeing the new engine from its

Jan 1, 1907

By N. A. Gokcen, S. Fujishiro

THE pressures of Mn(g) in equilibrium with Mn7C3 and graphite have been measured by McCabe and Hudson' and Butler, McCabe, and paxton2 by means of graphite, zirconia, and Ta-Mo Knudsen cells. The details of corrections in their measurements were somewhat different from those of the authors;3'4 hence, further independent results at higher temperatures seemed to be warranted. The stoichiom-etry of Mn7C3 in equilibrium with graphite and its stability up to the vicinity of 1373 °K have been satisfactorily established by Kuo and persson5 (See also Hansen and Anderko).' The method of investigation has been described elsewhere in detail.3'4 The carbide was prepared in the manner described by McCabe and Hudson. In order to avoid possible reactions with refractory oxides, only graphite cells were used for the effusion experiments. The authors' results are the runs M-1, M-2 and M-3 listed in Table I, together with those of McCabe and co-workers. The heat capacity, c;, of Mn7C3 is not known; therefore McCable et al. plotted their data as log P vs 1/T and the results were only expressed first' as, and later2 as logP=- -14220+6.06 without further thermodynamic calculations. However, it is possible to estimate closely the necessary heat capacity as follows: When H; - &98 of CrC, or MnO, is plotted vs x, corresponding to various compounds, with temperature as the parameter, it is seen that the relationship is represented by a line of very small curvature. This relationship is also followed by other compounds which do not exhibit solid state phase transformations. In view of the fact that chromium and manganese have the atomic numbers of 24 and 25 respectively, it is reasonable to assume that H; - H;ae vs x for MnC, follows the same type of lines as those for CrC, for which adequate data are available.7 Similar correlations appear to be valid for oxides of two neighboring metals for which reliable data are available. The procedure is thus to move the lines for CrC, vertically (parallel to the axis of HT - H298) until they coincide with the points for MnC1/3, the only carbide of manganese whose H; - HO298 has been

Jan 1, 1963

By R. M. Hudson, P. E. Perry

Weight-gain data obtained by nitriding low-carbon sheet steel in an amrnonia CNH,) atmosphere indicated that the process obeyed a parabolic rate law. The calculated actization energy for nitriding in the range 964" to 1268°F agreed reasonably well with published data. At 1358"F, rate data indicated that the activation energy decreased. Weight-gain data obtained by uszng mixtures of NH3 -Nz at 1268°F containzng jrom 10 to 100 zol pct NH3 also obeyed a parabolic rate law. The rate of 'nitriding increased with an increase in the NH3 content of the gas Mixture. It is well-known that steel heated in gas mixtures containing ammonia (NH3) takes up much larger quantities of nitrogen than steel heated in nitrogen, both gases having a total pressure of 1 atm;' this phenomenon can presumably be attributed to the catalytic decomposition of NH3 on the steel surface to furnish nascent (monatomic) nitrogen. This process was studied bv Brunauer. Jefferson, Emmett, and Hend-ricks at furnace temperatures of 752" and 831°F2 using mixtures of NH3 in Hz. Englehardt and wagner3 reported that, at a furnace temperature of 914°F and under their experimental conditions, both nitriding and denitriding were controlled by the rate of gas-metal reactions at a steel surface rather than by the rate of diffusion of nitrogen in iron. The present study was undertaken to obtain information on the kinetics of nitriding low-carbon steel strip at higher temperatures so that practical rates for short-time strip-annealing treatments could be estimated. Variables studied included time: temperature, and NH, content in the annealing atmosphere. Mechanical and chemical characteristics of steel nitrided in this manner will not be considered in the present article. MATERIALS AND EXPERIMENTAL WORK The samples used were from a commercial low-carbon steel, 0.0244 cm thick, in the cold-reduced condition. The chemical composition of this steel is given in Table I. Panels were cut to 5.1 by 17.8 cm, degreased in toluene, and weighed just before treatment. Four specimens were nitrided under each of the experimental conditions. A study was made of the nitriding rate of steel in a 100 vol pct ammonia atmosphere, 740 mm pressure, at five specific temperatures within the range 964" to 1358°F. The nitriding rates of steel in ammonia-nitrogen gas mixtures containing 10, 18, 26, 50, and 100 vol pct ammonia, 740 mm total pressure, at 1268°F were also determined. All atmospheres used were dried by successively passing them through drying towers packed with soda lime and with Linde Molecular sieve Type 4A. Quoted gas compositions refer to those entering the furnace. Specimens were held in the constant-temperature zone of a vertical annealing tube furnace for times of 14, 3, 5, 10, or 15 min. Gas flow rates were maintained at 3.8 cu ft per hr, which was nineteen volume changes per hour for the system used. The rate of flow was selected to provide a high level of free NH3 for cracking on the steel surface where the ammonia gas is most effectively used as a nitriding agent. The vertical annealing tube furnace consisted of a Hevi-Duty tube furnace with a 2 1/2-in.-ID mullite ceramic high-temperature tube. The constant-temperature zone (controlled within 10°F) was about 10 in. long. After each specimen was degreased, a hole was punched in one end, for attaching the specimen by hook to a chain so that it could be lowered into or raised from the high-temperature portion of the tube by means of a power-driven winch. A stainless-steel access port with O-ring seals was connected by suitable glass-to-metal seals to the cool upper portion of the furnace tube. After the weighed specimen was placed in the access port, the furnace tube was evacuated to approximately 10"3 torr, and then the system was flushed thoroughly with the atmosphere under study. When the gas flow rate and constant-temperature zone of the furnace were established, the specimen was lowered into the constant-temperature zone. The atmosphere flowed from the top to the bottom of the vertical furnace tube and was then vented. For all these runs, during the first 3 min of the time the specimen was in the constant-temperature zone of the furnace the specimen was heating up to the tempera-

Jan 1, 1970

By B. Chalmers, L. Bäckerud

The growth temperature of dendrite tips has been measured in a binary alloy system, Al-Cu, as a function of rate of formation of solid phase. Metallographic examination has rerealed the dendritic structure dereloped during different stages of the freezing process and factors influencing the undercooling, such as solute buildup, surface tension, and kinetic effects, have been estimated. Practical implications of the results are discussed. THE development of a dendritic growth pattern during the solidification of metals and alloys has an influence at least equal to that of grain size on the properties of the casting or ingot being produced. and consequently much interest has been devoted to the study of this phenomenon. A review of the knowledge gathered up to 1964 has been given by Chalmers.' Among recent publications in the area the works of Jackson et al 2 and Flemings and his coworkers3,4 are of special interest. This work is an experimental study of the factors which influence the development of a dendritic pattern during the solidification of a typical binary alloy system, A1-Cu, when there is no heat source in the liquid. This means that the temperature and the temperature gradient are controlled by the heat extraction from and latent heat evolved by the growing crystals. EXPERIMENTAL PROCEDURE Samples were prepared from a master alloy made up of aluminum, 99.995 pct, and copper. 99.99 pct, of the concentrations given below and of sufficient size to fill cylindrical graphite molds of 35 mm ID and 35 mm height. Bottom. wall. and lid of the graphite molds were all of 6 mm thickness, Fig. 1. Thin ceramic thermocouple shields could be introduced at different positions in the sample through holes in the lid. The assembly was heated in a small vertical resistance furnace to a suitable temperature. 700° to 720°C. which is well above the melting point of the sample. It was thereafter taken out of the furnace and chilled at selected rates, and the temperature changes in the sample were recorded. For high sensitivity in the temperature recordings, a reference thermocouple was held in a solidifying pure aluminum melt. which was very well insulated and therefore was at a constant temperature. 660°C, for nearly half an hour. The thermocouples were connected so that the difference voltage was fed into the recorder of which the most sensitive range was 1 mV. Temperature variations could be read to within 0.l°C. The thermocouples used were of the Chromel-Alumel type (28- or 38-gage wires) and the recorder a two-pen Moseley strip chart recorder. The different rates of chilling were obtained in the following way. a) The graphite crucible was wrapped in one or two layers of an insulating. feltlike material (Fiberfrax paper from the Carborundum Co.). The drop in temperature per unit time after complete solidification could thereby be varied from 8" to 18°C per min. This corresponds to a rate of heat extraction in the given samples from 0.08 to 0.17 cal cm-' sec-I. 6) The bare graphite mold was placed free on a piece of firebrick. The measured temperature drop was around 50°C per min (-0.5 cal cm-" ' sec- I). c) By blowing compressed air through a tube with many holes surrounding the mold in a ring shape. the rate of heat transfer could be raised to 150' to 200°C per min (-1.7 cal cm-3 sec- I). d) Cooling rates around 1000 C per mill (-9.4 cal cm-3 sec-l) were obtained by substituting the air in the device used in c by water. The range of cooling rates used in these experiments correspond to technical casting processes from slow solidification as obtained in sand molds to very rapid freezing which occurs in some continuous casting and welding processes. EXPERIMENTAL RESULTS The A1-Cu system was chosen for the experiments: the relevant part of the phase diagram is reproduced in Fig. 2. Observation of the Center Temperature. When a thermocouple is inserted in the center of the melt. the type of cooling curves obtained at slow solidification rates differs little from numerous published curves from similar systems. and the solidification pattern

Jan 1, 1970

WILLIAM L SAUNDERS, President GEORGE H PEGRAM, 1st Vice-president ALFRED D FLINN, Secretary J V W REYNDERS, 2d Vice-president JACOBS LANGTHORN, Treasurer HENRY A LARDNER Assistant treasurer Finance Committee House Committee GEORGE H PEGRAM, Chairman ; ALFRED D FLINN. Chairman J VIPOND DAVIES FREDERICK F SHARPLESS BANCROFT GHERARDI JOHN H DUNLAP WILLIAM L SAUNDERS CALVIN W RICE W F M GOSS, ex-officio F L HUTCHINSON

Jan 1, 1923

By W. E. Wrather

CURTAILMENT of production was a matter of far more serious concern to the oil industry through 1933 than the search for new supplies of oil. The huge reserves of crude, built up during past years, instead of inspiring a feeling of security, were viewed apprehensively. The status of past laws and court decisions seemed to guarantee to operators the right to produce oil at will, and this entrenched privilege was so widely adhered to that the market was-in a constant state of chaos. The more modern idea of the ownership of oil in place and correlative rights gained headway slowly, since usually there were enough belligerent producers, staunch believers in the old established order, to defeat the efforts of the majority who sought to' introduce order and restraint. State regulatory commissions were unable to cope, with the rebellion among producers with the result that those who abided by proration rulings were penalized, while those who flouted the rulings and produced unrestrainedly were able to make profits on large volumes of flush oil even at low prices. This situation, known in the vernacular as the "hot 'oil" problem, became so acute that the industry was threatened with ruin. The low price for 36c A.P.I. in the Mid-Continent came in April. at 25c per barrel 'but gradually moved upward to the long-hoped for price of $1.00 per barrel in October, after the Federal Government had taken a hand in the matter and effectively allocated production among the oil producing states and materially curbed the "hot oil" runs.

Jan 1, 1934

By A. W. Schlechten, A. H. Larson

Equilibrium H2S/H2 ratios were determined as functions of temperature (500o to 900°C) and composition in a hydrogen-circulation apparatus. Within the composition range studied there exists a two-phase region of "Zr3S4" and "ZrS2". The upper composition limit of this two-phase region is hounded by a disulfide phase and is practically constant over the temperature range investigated. The lower composition limit of this two-phase region is bounded a "Zr3S4 " phase and varies appreciably with tem- perature. The upper composition limit of the homogeneous region of the disulfide phase is not definitely determined, but it appears to he bounded by the stoichiometric composition of ZrS2. The lower composition limit of the homogeneous region of the Zr3S4 phase could not he determined due to the extremely low values of the equilibrium H2S/H2 ratios. Various thermodynamic quantities are evaluated from the data. PUBLISHED free-energy data for the Zr-S system are practically nonexistent. Strotzer, Biltz, and Meisel1 measured the sulfur pressures for the reaction 2ZrS2(s) + S2(g) = ZrS3(s) in the temperature range 783" to 874°C. The average heat of reaction calculated from the temperature dependence of the sulfur pressure is -47 keal. It should be noted, however, that according to these investigators, the two-phase region as determined by sulfur pressure constancy under isothermal conditions extended from approximately ZrS2, 3 to ZrS2.7. From consideration of X-ray data they concluded that the homogeneous regions of the disulfide and trisulfide phases are ZrS1.8-2.0 and ZrS2.8-3.2, respectively. Hahn and coworkers2 have made a structure study of the zirconium sulfide phases. They summarized the zirconium sulfide phases as follows: the compounds ZrS3 and ZrS2 with narrow homogeneous regions, a "Zr3S4" phase with a homogeneous region roughly within the limits of ZrSl.5 and ZrSo.9, the compounds ZrS and Zr4S3, and a "Zr3S2" phase with a homogeneous region within the limits ZrSo.8 and ZrSo.5. It is noted that the compounds ZrS and Zr4S3 are only formed in the gaseous state through sublimation of a phase which has the approximate composition of the compound. This paper describes the determination of the stability of the zirconium sulfide phases by a hydrogen-reduction method in which hydrogen is circulated over the heated sulfide until equilibrium is attained. The resulting H2S-H2 mixture is then analyzed. Partial molar free energies, enthalpies,

Jan 1, 1964

By E. C. Wright

FOR many years the cost of making pig iron and steel in the Birmingham district has been about the lowest in the United States. The close proximity of the important raw materials such as coal, iron ore, limestone, and the large available scrap supply made it possible to assemble all of the important ingredients necessary for steel- making with only nominal costs for transportation. Both iron ore and coal were being mined in this district at one time for about $1 per ton from underground operations. At that time mining wages were low everywhere and the labor rate in the South was considerably below that of other mining districts. This situation persisted until the emergence of labor unions as an economic and political force, emigation of southern labor to northern plants, and continued growth of industry in the South in the years following the depression of 1932. Since that time union organizing of miners and steel workers throughout the nation has increased labor costs in mining and steelmaking. This influence has been felt particularly in underground mining operations since the proportion of labor cost to total cost is still high. The previous advantage in basic labor rate in the South has been almost entirely eliminated by the equalization of labor rates in basic industries by national unions. Since 1945 these influences have been especially noticeable in increasing the cost of mining coal and iron ore in the South. The northern steel districts are still being largely supplied with iron ore from the Minnesota open-pit mines and the cost of this ore has not increased nearly as much as the cost of ore obtained from underground mines in Birmingham. A similar situation exists in coal mining; the thinner seams in Alabama are not so amenable to mechanization as the northern mines and, as a result, the output per man-day in southern mines is only about three tons of coal as compared to five or six tons per man-day in the large captive mines of West Vir-

Jan 1, 1950

By D. Bergekoff

IN the routine examination of a wide variety of metal specimens it is sometimes necessary to have special methods of polishing in order to retain and reveal certain details in each specimen. Among such special cases is the retention of graphite in malleable and gray cast irons, the preservation of all types of nonmetallic inclusions in both hard and soft steels, obtaining a scratch-free surface with soft metals, and avoiding the usual relief effects with very hard specimens such as tool metals con-taining various carbide and nitride phases. It is the purpose of this paper to give an account of some of these special polishing methods in use at the Union Carbide and Carbon Research Laboratories. The polishing procedures outlined have been found to give uniform results. It is obvious that only general rules and the most important working details can be given here. Following these rules, the polisher can obtain satisfactory results if he possesses the necessary patience and has a sincere desire to give as nearly perfect a finish as possible to his work.

Jan 1, 1939

By R. R. Harvey

Recent evidence has indicated that the films forming at crude oil-water interfaces are the result of naturally occurring su,rface-active components in the crude oil rather than oxidation products resulting from exposure of the oil to air. Since the presence of such films may strongly affect the displacement of oil from porous media, a knowledge of their composition and formatiorz is of fundamental importance. In this study, without the assumption of a specific mechanism, film formation is considered to involve the transfer of a weakly surface-active species in solution in the oil to the oil-water interface. The film gas law and the Gibbs adsorption equation may thus he applied to the system. The rigid films which form upon decrease of the oil-water interfacial area are considered a result of the very slow rate of re-solution of the film material into the oil. When the shrinkage of the interface is very rapid, the amount of film material leaving the interface is negligible, and the system may then be treated in the same manner as an insoluble film. The combination of these treatments leads to a new concept of the film factor in which it may he quantitatively related to the concentration of film-forming material at the interface. Suitable experiments can then yield the following information. 1. Original concentration of surface-active species in the oil. 2. The change of concentration with time. 3. Concentration of surface active species at the interface. 4. The change of this concentration with time. 5. Interfacial tension of the system at any time and its variation with time. 6. Equilibriunz concentrations for a given set of conditions. 7. Concentration requirements for solid film formation. 8. Molecular diameter of the adrorbed species. These calculations may be made solely from data taken from measurements on the original oil. While using the pendant drop method of interfacial tension measurement of crude oil-water systems, Bartell and Niederhauser' remarked on the thin, transparent, pliable, solid films or membranes which were often formed at the interface between crude oil and water. As a result of their observations of these films, Bar-tell and Niederhauser concluded: 1. The films are formed by material from the oil adsorbed at the interface rather than by a reaction at the interface. 2. The adsorption of the film-forming material is a rather slow process. 3. There are good indications that the process is reversible; i.e., the film constituents may re-dissolve into the oil. 4. The film will spontaneously spread over any new surface formed. 5. The process of adsorption at the interface is accompanied by a decrease in the interfacial tension of the system. Although they had proved that film formation was not due to a reaction at the interface, Bartell and Niederhauser were unable to demonstrate conclusively whether these film-forming constituents were present in the original reservoir oil or whether they were formed as oxidation products after exposure of the oil to air. Recent evidence seems to point to their presence in the original oil. Although the true nature of the film-forming constituents is still uncertain, these conditions would be fulfilled by the assumption of the presence of a slightly soluble surface-active component in the original oil. This component would migrate to a freshly formed interface because it would thereby lower the free energy of the system. The component at the surface constitutes an expanded monolayer which would become compressed, upon retraction of drop, due to the slow rate of re-solution of the film components into the bulk of the oil. It is possible, by involved extraction processes, to separate or at least concentrate this film-forming fraction. However, using the assumptions made above, the technique of monolayer film study may be applied to reveal much of the nature of the adsorbing material without resorting to an actual separation of the film-forming constituents.

By M. J. Pool, P. J. Spencer, R. V. Miner

The partial molar heat of solution of rhodiunz in liquid lin and Rh-Sn alloys has been measured as a function of rhodium concentration at 700" , 725" , 750" , and 775°K. The values at infinite dilution are very exo thermic, ranging from -29,950 to -28,260 cal per g-atom Rh at 700" and 775"K, respectively. At the solubility limit the heat of solution becomes sharply nzore exothermic and has permitted the liquidus boundary to be accurately established at each temperature. From the measurements in the two-phase region of liquid Plus RhSn, the heat of formation of RhSn,has been determined. A large increase in the heat of formation between 725" and 750°K suggests the possibility of a phase transformation in this compound. V ERY few measurements have been made of the heats of solution of transition metals in liquid tin; yet those values that are available are of great interest because of their very large exothermic nature. For example, the heat of solution at infinite dilution of palladium in tin has been measured as about -26,000 cal per g-atom (625" to 800°~),' while the heat of solution at infinite dilution of platinum is even more exothermic at -28,591 cal per g-atom (914°K).' These values are of the same order of magnitude as the heat of formation of many intermetallic compounds and as such clearly indicate that very strong bonding must exist between the solute and tin atoms in the liquid solutions. Rhodium might be expected to display similar solution characteristics in tin in view of its close electronic resemblance to palladium and platinum. Since no thermodynamic data are available for Rh-Sn alloys, rhodium was chosen as an appropriate solute for further investigation of transition-metal systems with highly exothermic heats of solution at infinite dilution. EXPERIMENTAL The heat of solution of rhodium in dilute Rh-Sn liquid solutions was measured as a functlon of rhodium concentration at 700°, 725", 750°, and 775°K. The liquid-metal solution calorimeter used in this work has been fully described elsewhere. At the start of each series of measurements, the solvent bath consisted of about 0.5 g-atoms of 99.9+ pct pure tin. To this was made a number of small rhodium additions, about 0.0005 g-atoms each, and the heat of solution was measured for each. Rhodium of 99.9+ pct purity in powder form was used in order to promote rapid dissolution in the liquid tin. The powder specimens were contained in tin foil stated to be purified (lead-free). This foil was found to have no measurable heat of solution in pure tin so the effect of any impurities could be neglected. The energy equivalent of the calorimeter was experi- mentally determined by dropping tungsten and/or tin specimens at intervals during each series of rhodium drops. The tungsten and tin used were 99.95 and 99.999+ pct pure, respectively. The only heat effect due to a tungsten drop, or a tin drop at low rhodium concentrations in the bath, is the sensible heat of the specimen. The heat content of these materials is well-established and is presented in the compilation of Hultgren et al. 4 As the rhodium concentration in the tin bath increases a small heat effect arises from the reaction: Sn (liquid, T) — & (soln, T) where T is the temperature of the tin bath. Where necessary, this heat of solution of tin was determined by Gibbs-Duhem integration, and corrections were made to the heat effect of the tin calibration specimens and the tin foil containing the rhodium specimens. RESULTS AND DISCUSSION The calculated values of the heat of solution of rhodium in dilute Rh-Sn alloys as a function of composition are shown graphically in Fig. 1. The values have been corrected for the sensible heat of the specimens, initially at 273"K, and apply to the reaction:

Jan 1, 1969

By B. C. Allen

Liquid surface tensions of copper and 18 Group IV-A to VIII transition metals (Ti, Zr, Hf, V, Cb, Ta, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt, Fe, Ni. Co) have been measured by the static pendant-drop and dynamic drop-weight methods on the same rod sample. The drops were formed by electron-bombardment heating in high vacuum. Application of necessary corrections enabled determination of surface tensions to k2 pct and agreement between methods to * 1 to 4 pct for all the metals studied. Evidence is presented that the liquid surface was well screened by metal vapor, suggesting negligible adsorption of gaseous impurities and that the surface tensions measured are characteristic of the metals involved. Correlations between liquid surface tension and melting point, molar volume, heat of vaporization, and atomic number are presented and discussed. Temperature coefficients of surface tension were calculated using Eötvös' law. SURFACE tension and interface energies of metals are the result of incomplete atomic coordination resulting in a force perpendicular to the boundary, tending to minimize its area. These energies are important in many phases of metallurgy, including microstructure, sintering, joining, electronic emission, and lubrication, which in turn affect many physical and mechanical properties of metals. Liquid surface tension refers to the interface between the liquid and its own vapor or nonreactive atmosphere, and is considered a physical property of the liquid. Since equilibrium shapes can be readily obtained with liquids, the units of surface tension (force per length) and interface energy (energy per area) are interchangeable. Thermo-dynamically, the surface tension ?LV is given by the change in free energy F with surface area A at constant pressure P, temperature T, and composition N: for commercially important refractory metals, vanadium, columbium, tantalum,13,14 molybdenum,14 and tungsten,l5 and none for the rare platinum-group metals and rhenium. Measuring the surface tensions of transition metals is difficult because of their high reactivity and melting points. Of the many techniques available,16-18 the pendant-drop 19-21 and drop-weight methods17,22 are considered superior because they can be modified to eliminate persistent sources of contamination such as supports and capillaries necessary in the popular sessile drop, capillary rise, and maximum-bubble-pressure techniques. The necessary modification is to melt a drop on the tip of a vertical rod, which provides support through a solid of the same composition.13,15 The object of the work was to study the surface-tension behavior of copper and transition metals, having reasonably low vapor pressures. Liquid surface tension of each pure metal was systematically determined by using a combination of the static pendant-drop and dynamic drop-weight methods on the same rod. Liquid drops were formed by electron-bombardment heating in high vacuum. EXPERIMENTAL WORK As indicated in Table I, the metals studied were high purity and generally were obtained in rod form. The exceptions were titanium and zirconium, which were machined from crystal bars, and molybdenum (tot 11, osmium, and ruthenium, which were sintered and arc cast into rods. All the metals were ground or swaged to desired sizes between 1- and 7-mm diam, and centerless ground round and smooth to a finish better than 50 µ in., rms. Each rod was thoroughly cleaned with steel wool, degreased, acid etched, and dried. In a typical run, the rod was vertically clamped in a modified floating-zone electron-bombardment furnace designed after Calverley23 and Carlson.24 The specimen was outgassed and maintained positive at several kilovolts in a dynamic vacuum of 10-5 to 10-7 mm. The bottom end was enclosed by a tantalum pillbox and heated by electrons emitted from a hot concentric tungsten filament mounted on a movable bracket. The bombardment power was slowly raised until melting was observed. Power requirements ranged from 30 w for copper to 1300 w for 4-mm tungsten. The stabilized and out-gassed drop of near-maximum size was photographed at 4. 1X on panchromatic film at desired time inter-

Jan 1, 1963