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By J. D. Verhoeven

In the past 15 years a considerable amount of experimental and theoretical work has been done concerning the onset of convection in liquids as a result of interm1 density gradients. This work, which has been doue in many different fields, is reviewed here and extended slightly to give a rrlore quantitative understanding to the probletrz of conzection in liquid metal dlffusion experinletzts. In liquid metal systems the capillary reservoir technique is currently used, almost exclusively, to measure diffusion coefficients. In this technique it is necessary that the liquid be stagnant in order to avoid mixing by means of convection currents. Convective mixing may result from: 1) convection produced as a result of the initial immersion of the capillary; 2) convection produced in the region of the capillary mouth as the result of the stirring frequency used to avoid solute buildup in the reservoir near the capillary mouth; 3) convection produced during solidification as a result of the volume change; and 4) convection produced as a result of local density differences within the liquid in the capillary. The first three types of convection have been discussed elsewhere1-a and are only mentioned for completeness here. This work is concerned only with the fourth type of convection. Local density differences will arise within the liquid as a result of either a temperature gradient or a concentration gradient. It is usually, but not always, recognized by those employing the capillary reservoir technique that the top of the capillary should be kept slightly hotter than the bottom and that the light element should be made to migrate downward in order to avoid convection. In the past 15 years a considerable amount of work, both theoretical and experimental, has been done in a number of different fields which bear on this problem. This work is reviewed here and extended slightly in an effort to give a more quantitative understanding of the convective motion produced in vertical capillaries by local density differences. The Stokes-Navier equations for an incompressible fluid of constant viscosity in a gravitational field may be written as: %L + (v?)v = - ?£ + Wv - g£ [1] where F is the velocity, t the time, P the pressure, p the density, v the kinematic viscosity, g the gravitational acceleration, and k a unit vector in the vertical direction. A successful diffusion experiment requires the liquid to be motionless, and under this condition Eq. [I] becomes: where a is the thermal expansion coefficient [a =-(l/po)(dp/d)], a' is a solute expansion coefficient [a' = -(l/po)(dp/d)], and the solute is taken as that component which makes a' a positive number. Combining with Eq. [3] the following restriction is obtained: Since there is no fixed relation between VT and VC in a binary diffusion experiment, Eq. [5] shows that the condition of fluid motionlessness requires both the temperature gradient and the concentration gradient to be vertically directed. Given this condition of a density gradient in the vertical direction only, it is obvious that, as this vertical density gradient increases from negative to positive values, the motionless liquid will eventually become unstable and convective movement will begin. The classical treatment of this type of instability problem was given by aleih' in 1916 for the case of a thin fluid film of infinite horizontal extent; and a very comprehensive text has recently been written on the subject by handrasekhar.' It is found that convective motion does not begin until a dimensionless number involving the density gradient exceeds a certain critical value. This dimensionless number is generally referred to as the Rayleigh number, R, and it is equal to the product of the Prandtl and Grashof numbers. For the sake of clarity a distinction will be made between two types of free convection produced by internal density gradients. In the first case a density gradient is present in the vertical direction only, and, since the convection begins only after a critical gradient is attained, this case will be called threshold convection. In the second case a horizontal density gradient is present and in this case a finite convection velocity is produced by a finite density gradient so that it will be termed thresholdless convection. Some experimentalists have performed diffusion experiments using capillaries which were placed in a horizontal or inclined position in order to avoid convection. These positions do put the small capillary dimension in the vertical direction and, consequently, they would be less prone to threshold convection than the vertical position. However, if the diffusion process produced a density variation, as it usually does, it would not be theoretically possible to avoid thresh-

Jan 1, 1969

By J. R. Thoenen

The Bureau of Mines has used various sizes of core barrels above 2 in. and below 10 in. in diameter to core manganese, potash, coal, brown iron ore and bauxite. The paper describes in some detail the methods and types of equipment used to obtain maximum sampling accuracy. Introduction On December 11, 1946, R. D. Longyear, in his capacity as Chairman of the Subcommittee on Exploration Drilling, wrote the author requesting him to prepare a paper presenting the collective ideas of engineers in the Bureau of Mines on the design, standardization and application of core barrels using diamonds or other hard cutting media for drilling holes larger than two inches and less than ten inches in diameter. In subsequent correspondence it was indicated that similar papers covering the experience of other government agencies would be solicited and all such papers received would be combined in a symposium on the subject for discussion at the March 1947 meeting of the Mining Methods Committee AIME. In soliciting such information from other Bureau engineers, it developed that most Bureau experience had been confined to standard core size, two inches or less in diameter, and that larger sizes had been used only for special purposes. It is hoped the data contained herein will be of help to other operators in solving problems encountered in the field. Acknowledgments This paper was made possible by the request of Lowell B. Moon, Chief, Mining Division, Bureau of Mines, to all Division engineers to send to the author any data they had on the subject. Engineers of the Mining Division contributing were: M. H. Kline, Chief, Raleigh Branch. Paul T. Allsman, Chief, Salt Lake City Branch. J. H. Hedges, Chief, Tucson Branch. C. H. Johnson, Chief, Rolla Branch. A. M. Evans, Mining Engineer, College Park Branch. Wing Agnew, Engineer in charge, Mount Weather, Virginia. Andrew Brown, Mining Engineer, Tus-caloosa Branch. In addition Albert L. Toenges, Supervising Engineer, Bituminous Coal Mining Section, Pittsburgh, contributed his experience in coring coal beds. The author's experience in the use of cores within the limits stated has been confined to the brown iron-ore work described by Brown and coring bauxite and clay in Arkansas. Design and Standardization of Core Barrels Bureau engineers are primarily interested in obtaining core that will best represent

Jan 1, 1949

By J. R. Thoenen

The Bureau of Mines has used various sizes of core barrels above 2 in. and below 10 in. in diameter to core manganese, potash, coal, brown iron ore and bauxite. The paper describes in some detail the methods and types of equipment used to obtain maximum sampling accuracy. Introduction On December 11, 1946, R. D. Longyear, in his capacity as Chairman of the Subcommittee on Exploration Drilling, wrote the author requesting him to prepare a paper presenting the collective ideas of engineers in the Bureau of Mines on the design, standardization and application of core barrels using diamonds or other hard cutting media for drilling holes larger than two inches and less than ten inches in diameter. In subsequent correspondence it was indicated that similar papers covering the experience of other government agencies would be solicited and all such papers received would be combined in a symposium on the subject for discussion at the March 1947 meeting of the Mining Methods Committee AIME. In soliciting such information from other Bureau engineers, it developed that most Bureau experience had been confined to standard core size, two inches or less in diameter, and that larger sizes had been used only for special purposes. It is hoped the data contained herein will be of help to other operators in solving problems encountered in the field. Acknowledgments This paper was made possible by the request of Lowell B. Moon, Chief, Mining Division, Bureau of Mines, to all Division engineers to send to the author any data they had on the subject. Engineers of the Mining Division contributing were: M. H. Kline, Chief, Raleigh Branch. Paul T. Allsman, Chief, Salt Lake City Branch. J. H. Hedges, Chief, Tucson Branch. C. H. Johnson, Chief, Rolla Branch. A. M. Evans, Mining Engineer, College Park Branch. Wing Agnew, Engineer in charge, Mount Weather, Virginia. Andrew Brown, Mining Engineer, Tus-caloosa Branch. In addition Albert L. Toenges, Supervising Engineer, Bituminous Coal Mining Section, Pittsburgh, contributed his experience in coring coal beds. The author's experience in the use of cores within the limits stated has been confined to the brown iron-ore work described by Brown and coring bauxite and clay in Arkansas. Design and Standardization of Core Barrels Bureau engineers are primarily interested in obtaining core that will best represent

Jan 1, 1949

Abbott, Robert H., (S'42) Agricultural & Mech. College of Texas, College Sta.. Texas. Abrahamson, Guy C., (S'43) Univ. of California, Berkeley. Calif. Abrego, Alfredo, (S'43) Texas College of Mines & Metallurgy, El Paso, Texas. Ackermann, K. G., (S'43) Univ. of Alabama, University, Ala. Adamec, Lew, (S'42) Colorado School of Mines, Golden, . Colo. Adams. Charles E., (S'42) Univ. of California, Los Angeles, Calif. Adams, Charles W., (S'30) Asst. Met., Canada Foundries & Forgings Ltd., Welland, Ont., Canada. Adams, John W., (S'42) Univ. of Texas, Austin, Texas. Adams, Karl S., (S'43) Univ. of New Hampshire, Durham, N. H. Adamson, Charles R., (S'41) Univ. of Utah, Salt Lake City. Utah. Adler, A. G., (S'41) Met. Engr., Flotation Operator Helper. Utah Copper Co.. Garfield, Utah. Adler, Frank J., (S'42) Colorado School of Mines, Golden, Colo.

Jan 1, 1943

By Gary B. Williamson, Barton K. Cross

Digital simulation is a modern analysis tool which allows the mine operator to evaluate the result of making a decision without actually changing the organization or buying the equipment. The purpose of this paper is to demonstrate the use of digital simulation in evaluating a decision of whether or not to introduce dispatching in an open pit mine. The analysis shows that appreciable savings can be realized by dispatching. In certain cases, an operator can reduce the number of trucks required to move a specified tonnage. A second analysis evaluates the alternatives of using one large shovel or two smaller units. In this case, the operating cost of the haulage equipment necessary to support the shovels turns out to be the critical factor in this decision.

Jan 1, 1969

By B. N. Das, H. E. LaBelle, G. A. Wolf

ZnxHg1-xTe and GUPxAS1-x crystals have been grown from solution by a traveling heater method (THM). In a floating zone type fashion a solution zone sandwich of liquidus composition is made to migrate through feed material of solidus composition by a slow-speed movement of <0.25 mm per hr of the total charge through a stationary radiation or rf heater. ZnxHg1-xTe of composition 0 < x < 0.3 and GUPxAS1-x of composition 0.5 < x < 0.7 have thus been grown from their solution in liquid tellurium and gallium, respectively. A simplified analysis of heat and material transport is given. In this method, Proper adjustment of the temperature distribution along the liquid solution zone axis eliminates instability of the crystal growth front and constitutional supercooling. 1) ZnxHg1—xTe: The solid-solution telluride was grown in sealed quartz tubes at a temperature of 500 to 650°C. For first Preparations mechanical mixtures SINGLE crystals of solid solutions of III-V and II-VI compounds have been grown by various techniques from the melt, from the gaseous phase, or from solutions in of ZnTe and HgTe were used. X-ray determinations showed the resulting crystals to be homogeneous throughout their entire length, except for the end sections. The homogeneity is greatly improved by reusing the ingots obtained from first Preparations as feed material in subsequent crystal growth runs. Ingots of up to 4.5 cm have thus been obtained. 2) GaPxAs1-x: Crystals were grown in a EN crucible at a temperature of 1050°C. For first Preparation a mechanical mixture of Gap and GaAs was cemented together by a minimum amount of liquid gallium through "wet" grinding of Gap and GaAs crystals in the liquid metal and subsequent exuding of excess gallium by compacting of the charge in the EN crucible. Electron microprobe measurements using P-Ka and As-Ka radiation showed uniformity over a length of 0.4 cm. Properties of the various Preparations are described. liquid metals.&apos;-&apos; Their growth from the melt by passing a liquid zone of pseudobinary liquidus composition through a solid rod of solidus composition is generally a convenient method of growth of single crystals of solid solutions of homogeneous composition. This method loses much of its usefulness, however, if the melting point or the vapor pressure of the solid solution is high. In the case of a compound having a high melting

Jan 1, 1969

MINING METHODS W. J. COULTER, Chairman P. B. BUCKY, Vice-Chairman CLYDE E. WEED, Vice-Chairman ROBERT S. PALMER, Secretary Alluvial Mining CLINTON BERNARD O. B. PERRY NORMAN CLEAVELAND C. M. ROMANOWITZ R. B. EARLING J. B. STAPLER BENERE H. GRANTCHARLES THURMAN Open-Cut Mining Iron. A. D. CHISHOLM EARL E. RUNNER G. E. DIEHL G. E. LEVEQUE P. G. HARRISON SIMPSON RICHEY W. A. STERLING

Jan 1, 1943

By Ken-ichi Hirano, B. L. Averbach, Morris Cohen, N. Ujiiye

The influence of plastic deformation in compression on the self-diffisivity of a iron has been measured in the temperature range of 742º to 885°C. The diffusivity is enhanced in proportion to the strain rate, but this dependence decreases with increasing temperature. The magnitude of the strain is relatively unimportant in this connection. Strain rates from 0 to -2 x 10-3 sec-1 were investigated, with a corresponding increase in diffusivity up to 3 x 103 times. The results are analyzed in terms of vacancy diffusion and the excess vacancies introduced during dejornzntion. It is concluded that grain boundaries are the main vacancy sinks in polycrystalline iron and that the vacancy lifetime is therefore dependent on the grain size. A typical vacancy lifetime at 800°C with a nzean grain-boundary intercept of 0.3 cm is of the order of 1 sec. LATTICE imperfections are considered to be the dominant mechanism of diffusion in close-packed crystals. Vacant lattice sites are usually the most important defect, but the enhancement of diffusion along grain boundaries and other short-circuiting paths has been well documented. Inasmuch as plastic straining produces a variety of defects, it would be expected that the application of stresses sufficient to cause plastic flow during a diffusion run might result in an increase in the self-diffusivity. Enhanced self-diffusion in a iron under compressive creep has been observed by Buffington and Cohen&apos; and subsequent coworkers.2 Lee and Maddin3,4 have also found an enhancement in the self-diffusivity of silver single crystals undergoing torsional deformation. On the other hand, Darby, Tomizuka, and Balluffi5 have not observed any significant diffusion increase in single crystals of silver deformed either in tension or in compression, although the results in this case may have been affected by the occurrence of recrystallization. With poly crystalline silver, however, Forestieri and Girifalco6 have found en- hanced diffusion during compressive creep. A small decrease in the self-diffusivity of zinc single crystals under compressive loading has been reported,7 but the applied stresses in these experiments were too low to cause appreciable plastic deformation. For the cases in which enhanced diffusion has been found, a number of common effects have been noted. Usually, the ratio of the diffusivity during straining, Ds, to the diffusivity in the unstrained condition, D,, varies linearly with the strain rate, and does not seem to be a function of the plastic strain, at least up to ? = 0.2. Values of Ds/Du of the order of 100 have been reported&apos;-4 but the enhancement decreases with increasing diffusion temperature. The activation energy for diffusion decreases markedly with increasing strain rate and approaches a level of roughly one-half the unstrained value. Most of the current explanations of these observations assume that excess vacancies are generated by the deformation, but rather large concentrations of excess vacancies and/or long lifetimes are required by these theories.&apos;,&apos;,&apos;,&apos; Since the original work on iron, there has been an important improvement in the compressive-loading technique.2 The early data were also analyzed without taking into account the motion of the coordinate system in the specimens undergoing plastic deformation. This problem has now been solved by a number of investigators (see Refs. 11, 12, and the appendix of the present paper). Consequently, the strain-diffusion runs on iron for the Ds measurements were repeated and extended over wider ranges of temperature and strain rate. In addition, the original diffusivity data9 on the unstrained iron have been corrected for the divergence of the beam in the counting system and new data points have been added, resulting in somewhat different values for the self-diffusi-vities in a iron.10 The new values for Du are used in this paper. A comparison of Ds and Du confirms the large enhancement in the self-diffusivity of iron during compressive creep, as previously reported.&apos;,2

Jan 1, 1963

By J. F. Breedis

The morphology and crystallography of marten -site formed during quenclzing were examined by transmission electron microscopy in alloys whose compositions lie between Fe-19 wt pct Cr-11 wt pet Ni and Fe-33 wt pet Ni. Depending upon composition, four types of transformation products were observed in this portion of the Fe-Cr-Ni system. Three of these products are denoted as lath, plate, and surface martensite. The hcp structure found in association with martensite it? certain higlz-clzromium stairzless steels does not influence the transformation crystallogyaphy and cannot he Considered to act as a transitional structure in the transformation from austenite to martensite. DISTINCT changes in the characteristics of mar-tensitic transformations are produced by the partial replacement of nickel by chromium in austenitic iron alloys. Large, discrete martensite plates form in Fe-30 pct Ni, while aggregates of small crystals form in sheets parallel with (111)A austenite planes in stainless steels containing in the vicinity of 18 pct Cr and 8 pct Ni. These transformation structures are termed plate and lath martensite, respectively. In addition, an hcp structure (E) has been observed in certain high-chromium stainless steels in association with martensite. It has been suggested that the E structure acts as an intermediate step in the nucleation of martensitel-&apos; and influences the morphology and crystallography of the final transformation product. However, this structure may be the consequence of the deformation of austenite arising from the shape distortion accompanying the transformation to bcc martensite.&apos; An hcp stacking of atoms is produced in an fcc lattice by the introduction of an intrinsic stacking fault on alternate (111)A planes. At present, the arguments behind each explanation for the E structure are based on circumstantial evidence. This investigation seeks to determine the importance of the hcp structure to the martensitic transformation, and to examine the crystallography and morphology of the structures produced in bulk samples by quenching in alloys whose compositions lie between Fe-19 wt pct Cr-11 wt pct Ni and Fe-33 wt pct Ni. These aspects of the martensitic transformations occurring in these alloys have been studied by electron metallography and selected-area diffraction of foils examined in transmission in the electron microscope. EXPERIMENTAL METHODS The alloys have been prepared from thoroughly mixed powders of pure iron (99.6+ pct, 0.06 max pct C, 0.15 max pct N), chromium (99.9+ pct), and nickel (99.9+ pct). After sintering in an Ar-H2 atmosphere, the mixtures were melted by induction heating in recrystallized alumina boats under purified argon. The ingots were cold-rolled to 0.4-mm sheets (100 pct reduction in thickness) after the removal of at least 1.5 mm from their surfaces by grinding. Three-millimeter discs were punched from the cold-rolled sheet and annealed at 1150°C for approximately 24 hr in evacuated quartz capsules. The average grain size was 40 µ Thin foils for examination in transmission in the electron microscope were prepared from discs quenched to liquid-nitrogen temperature. A depression was first jet-machined into the center of a disc and a thin area (less than approximately 3000A in thickness) was produced at the base of the depression by electropolishing. Electron-microscope studies utilized the RCA EMU-3 and the Philips EM-100B microscopes operating at 100 kv. X-ray examination of the polycrystalline alloys was performed either in a diffractometer or in a

Jan 1, 1964

LEHIGH UNIVERSITY On April 25, the Mining and Geological Society of Lehigh University held a meeting and elected. the following officers for the college year 1918-1919: C. S. SCHUBERT, President, C. G. GILMAN, Vice-president, H. TSAI, Secretary, E. D. HOLLINSHEAD, Treasurer, C. N. TOMLINSON, A. A. KORVES, Curators. After a short business meeting the Society was favored by three interesting and instructive talks. Mr. C. A. Bonine spoke on the "U. S. Geological Survey" and showed a number of beautiful lantern slides; Mr. R. Rosenbaum read a paper on "Geodes;" and Prof. B. L. Miller presented a brief discussion on "War Minerals." H. TSAI, Secretary.

Jan 7, 1918

By N. J. Grant, D. Carne, J. B. Seabrook

IT is unnecessary to review much of the literature on hydrogen embrittlement of steel since several excellent reviews and bibliographies exist.1-3 Hot acid pickling and cathodic charging have been known to cause hydrogen embrittlement of steel and have been used as laboratory methods to charge steels with hydrogen.4-8 Experimental Procedure The problem of prime concern in all instances, except in the work of Sims and coworkers,10 is that at no time was there a definite known hydrogen value reported which could be related to a particular value of the degree of embrittlement. It was the purpose of this research to determine the relationship between hydrogen content and degree of em-brittlement quantitatively. The 1020 stock used for the specimens was hot-rolled 7/16 in. diam rod of the following analysis: 0.19 pct C, 0.40 pct Mn, 0.012 pct P, 0.036 pct S&apos; Vacuum-fusion analyses for nitrogen and oxygen gave 0.014 pct O2 and 0.0011 pct N2. Cathodic charging was used to cause embrittle-ment. The advantages of this method were that no quenching was necessary, the impregnation was reasonably controllable, and representative samples for analysis could be prepared simultaneously with the charging of the tensile bars. Analyses for hydrogen were made in a vacuum-fusion type of apparatus which extracted gas from the samples by fusion in a molten tin-iron bath&apos; This apparatus, which has recently been described in detail elsewhere, will not be discussed here.". " Consecutive samples can be analyzed every 15 min with an accuracy of 0&apos;03 ppm. A A from an electrolytic or pickling bath can be charged for analysis in about 3 min, and analysis completed in 15 min. Samples of as-received 1020 stock were analyzed and found to contain a negligible amount of hydrogen (0.06 ppm). Preliminary pickling and electrolytic charging gave highly variable results. Cold-worked samples showed higher values but ranged from 0.6 to 6.0 ppm of hydrogen. Charging at 90°C gave higher values of charged hydrogen, but troublesome films on many of the specimens resulted. It was not until a few drops of a catalytic poison, prepared from 2 g of yellow phosphorus dissolved in 40 ml of carbon disulphide,8 was added to the electrolytic cell that fairly consistent high values of hydrogen could be charged into the as-received 1020 steel at room temperature. The cell used is sketched in fig. 1. The anode and fixture for the tensile specimens were fastened to the cell cover as shown, and the specimen was screwed in place, centrally located with respect to the anode. At first, anodes of lead and graphite were tried, but they contaminated the electrolyte and gave a slight deposit on the specimen. Later, a platinum wire was used in the form of a uniform helix. A current of 2 amp, corresponding to about 0.5 amp per sq in. of cathode, was used for most specimens. The electrolyte was 4 pct H2SO4 solution. Fig. 1 shows the form of the special tensile bar, the main portion of which was an ordinary 1/4 in. diam, 1 in. gauge length test bar, except that two to four small cylinders of stock were left attached by small links to the bottom end of the tensile bar for the purpose of providing samples for hydrogen analysis. Thus the bars and samples were charged with hydrogen simultaneously and an analysis could be made while the bar was being tested mechanically. Experiments were performed to determine how representative the test cylinders were of the middle of the test bar proper. While the bar center was being analyzed, the small cylinder was stored in dry ice, since it had been shown that such storage prevents loss of hydrogen for many hours.12 The results of these checks are shown in table 1. The checks are very good (0.3 ppm) and indicate that it is permissible to use the small end cylinders to establish the hydrogen content of the tensile test bar proper-

Jan 1, 1951

By Edward Saibel

The object of this study is to investigate the effect of prior tensile strain on the fracture stress of a metal. This is done in a theoretical manner starting from the point of view developed by the author in his thermodynamic theory of the fracture of metals. The results are compared with experimental findings and a rational interpretation is given to work that shows the variation of fracture stress with prior tensile strain. Theory op Fracture In the thermodynamic theory of the fracture of metals developed earlier,&apos; it was shown that a critical strain energy per unit volume exists. This is characteristic of the material and may be calculated from basic thermodynamic data. When the area under the flow curve reaches this characteristic value, fracture occurs. The general criterion for fracture is expressed in the form « ± u. = JLJW/V [r] where L, is the latent heat of melting of the unit volume, AV/V is the ratio of the change in volume of the unit volume to the original unit volume on passing from the solid to the liquid state, uo is an initial energy density, and J is a conversion factor, which changes energy from heat to mechanical units. As a first approximation, it will he assumed that the stress-strain curve is the straight line that extends from the point of maximum load onward, extrapolated back to the axis of zero strain, for example, line AC of Fig. I. If the point of intersection of the straight line with the axis of zero strain is represented by v., and the slope of the straight line is p, the analytic form of the flow curve is a = (To + pd [2] and the strain energy per unit volume evaluated from Jud6 becomes (u,6 + pa2/2). When this latter term reaches the critical value JLbVIV (designated hereafter by M), it is assumed that fracture occurs. This leads to the following expression for the fracture stress: a; = V«r.2 + iMp [3] The strain at fracture may be calculated from Eqs 2 and 3. It is assumed in this paper that the initial energy density is either zero or that it may be neglected. Furthermore, the complicated states of stress and of strain existing in the necked region of the tensile specimen after "necking" has occurred will also be neglected for the present, so that average conditions will be assumed to prevail. Flow and Fracture Curves LudwigZ attributed to materials two fundamental properties: (I) a resistance to flow and (2) a resistance to fracture. He reasoned that at each instant the

Jan 1, 1948

By Edward Saibel

The object of this study is to investigate the effect of prior tensile strain on the fracture stress of a metal. This is done in a theoretical manner starting from the point of view developed by the author in his thermodynamic theory of the fracture of metals. The results are compared with experimental findings and a rational interpretation is given to work that shows the variation of fracture stress with prior tensile strain. Theory op Fracture In the thermodynamic theory of the fracture of metals developed earlier,&apos; it was shown that a critical strain energy per unit volume exists. This is characteristic of the material and may be calculated from basic thermodynamic data. When the area under the flow curve reaches this characteristic value, fracture occurs. The general criterion for fracture is expressed in the form « ± u. = JLJW/V [r] where L, is the latent heat of melting of the unit volume, AV/V is the ratio of the change in volume of the unit volume to the original unit volume on passing from the solid to the liquid state, uo is an initial energy density, and J is a conversion factor, which changes energy from heat to mechanical units. As a first approximation, it will he assumed that the stress-strain curve is the straight line that extends from the point of maximum load onward, extrapolated back to the axis of zero strain, for example, line AC of Fig. I. If the point of intersection of the straight line with the axis of zero strain is represented by v., and the slope of the straight line is p, the analytic form of the flow curve is a = (To + pd [2] and the strain energy per unit volume evaluated from Jud6 becomes (u,6 + pa2/2). When this latter term reaches the critical value JLbVIV (designated hereafter by M), it is assumed that fracture occurs. This leads to the following expression for the fracture stress: a; = V«r.2 + iMp [3] The strain at fracture may be calculated from Eqs 2 and 3. It is assumed in this paper that the initial energy density is either zero or that it may be neglected. Furthermore, the complicated states of stress and of strain existing in the necked region of the tensile specimen after "necking" has occurred will also be neglected for the present, so that average conditions will be assumed to prevail. Flow and Fracture Curves LudwigZ attributed to materials two fundamental properties: (I) a resistance to flow and (2) a resistance to fracture. He reasoned that at each instant the

Jan 1, 1948

By Shiro Ban-ya, John Chipman

The effects of many alloying eletnents on the acticity coefficient of sulfur in liquid iron have-been studied by the equilibriutn in the reaction Sfin Fe) + Hz = HzS at 1550°C&apos;. Results are expressed in terms of a concentration variable for a nonmetallic or for a substitutional metallic solute. Activity coefficient of sulfur, defined as increased by B, Al, C, Si, Ge, Sn, P, As, Sb, Mo, W, Co, and PI. It is decreased by Cu,Au, Ti. Zr, V, h&apos;b, Ta, Cr, ,23n, and Ni. Irulues oj. the interaction coejficient 0i = 6 In are labulated. The same interactions are expressed also in terms of atom fraction and of weight percent. The thermodynamic properties of sulfur in liquid iron have been fairly well established. Our recent paper1 reported new determinations of activity coefficient up an atom fraction of 0.12 and equations based on a careful review of all published data. The effects of alloying elements on the activity of sulfur have been studied by several investigators,2"11 especially by Morris and Williams for silicon,&apos; by Morris and Buehl for carbon,~ and by Sherman and Chipman for manganese. phosphorus, and al~minum.~ However, the effects of some important alloying elements remain to be determined. The purpose of this investigation was to determine the effects of many alloying elements on the activity of sulfur in Fe-S-j ternary systems. EXPERIMENTAL METHOD This study was based on experimental determination of equilibrium in the reaction at 1550°C: The same apparatus and procedure as described in our previous paper have been retained, and the same corrections were applied for dissociation of H2S. The alumina crucibles used in the experiments consisted of four separate compartments. In a given experimental run. kach of three alumina crucibles held four different samples of about 3 g each which reached equilibrium in the same gas atmosphere and temperature. The charges were made up of electrolytic iron, pure iron sulfide, and desired alloying elements, which were pure metal or master alloys made in the laboratory. The weighed samples were held for 4 to 12 hr in the prepared atmosphere at 1550°C. They were then low- ered to be cooled as quickly as possible. The quenched metal beads were crushed to avoid the errors of segregation in the ingot. The sulfur content was determined gravimetrically and alloy content by appropriate chemical analysis. CALCULATIONS The apparent equilibrium constants of Eq. [I] are expressed as follows from the corrected gas ratios and sulfur concentrations: The term K" is the observed equilibrium constant in any given ternary solution, K&apos; is the value for the Fe-S binary solution. and the limiting value of K&apos; in the infinitely dilute solution is designated by K, which is the true equilibrium constant in Eq. [I]. In the thermodynamic treatment of nonmetallic elements in a metallic solution, it has been suggested1&apos; that the lattice ratio has certain advantages over other variables to express the concentration of solute. In interstitial solid solutions the lattice ratio zj is proportional to the ratio of filled interstitial sites to those which remain unfilled. The equations derived for the activity of the solute using zj as the concentration variable are found also to be applicable to liquid solutions containing nonmetallic solutes when the nonmetal is treated as if it were interstitial. For this purpose we adopt the following definitions: The quantity vj which is negative for interstitial solutes is taken as -1 for nonmetallic and +1 for metallic solutes. For purposes of calculation however ; j may be assigned a value which results in a linear relation such as shown in Figs. 1 to 15. The activity coefficient of sulfur, Qs, and equilibrium constant. K(z). are defined as follows: According to a Taylor series expansion. the logarithm of the activity coefficient of sulfur in Fe-S-j ternary system is: However, the value of 6 In */6zi remains constant through a broad range of dilute solutions and the terms of higher order are negligibly small. As a consequence, Eq. [6] is simplified as follows:

Jan 1, 1970

*J. H. Brennan, Union Carbide Metals Company, Niagara Falls, N. Y. S. B. Casey, Jr., Swindell-Dressier Corporation, Pittsburgh, Pa. C. M. Cosman, Vanadium Corporation of America, New York, N. Y. H. E. Dunn, Vanadium Corporation of America, New York, N. Y. C. S. Finney, Eastern Gas and Fuel Associates, Boston, Mass. M. O. Holowaty, Inland Steel Company, East Chicago, Ind. John Mitchell, Eastern Gas and Fuel Associates, Boston, Mass. Leo F. Reinarts, Armco Steel Corporation, Middletown, Ohio H. E. Rowan, Dwight-Lloyd Division, McDowell Company, Inc., Cleveland, Ohio R. W. Shearman, The Metallurgical Society of AIME, New York, N. Y. C. M. Squarcy, Inland Steel Company, East Chicago, Ind. F. Weston Starratt, The Metallurgical Society of AIME, New York, N. Y. A. B. Wilder, National Tube Division, United States Steel Corporation, Pittsburgh, Pa. *Deceased

Jan 1, 1961

By Vard H. Johnson

IN 1943 the U. S. Bureau of Mines undertook drilling in an effort to develop new reserves of coking coal in an area near Paonia, Colo., as a part of an attempt to alleviate the shortage of known coking coal of good quality in the western United States. Geologic mapping of the area was undertaken by the U. S. Geological Survey with the purpose of first furnishing guidance in location of drillholes and later aiding in interpreting the results of the drilling. The drilling program was under the general supervision of A. L. Toenges of the U. S. Bureau of Mines. J. J. Dowd and R. G. Travis were in charge of-the work in the field. Geologic mapping was started by D. A. Andrews of the Geological Survey in the summer of 1943 and was continued from the spring of 1944 to 1949 by the writer. The first few holes drilled failed to locate coking coal, but in the summer of 1944 coking coal was discovered by drilling 6 miles east of Somerset, Colo., the site of present mining. In the succeeding years, 1945 to 1948, 100 to 150 million tons of coal suitable for coking were blocked out by drilling. The ensuing discussion of the geologic controls on the distribution of coking coal in the area is based on the geologic mapping as well as the drilling done in the Paonia area, more complete descriptions of which have appeared or are in process of publication.1-5 In order that the possible geologic controls affecting the present distribution of coking coal may be considered, it is necessary to discuss briefly the indicators. of coking quality coals. Coking Coal Coal that cokes has the property of softening to form a pastelike mass at high temperatures under reducing conditions in the coke oven. This softening is accompanied by the release of the volatile constituents as bubbles of gas. After release of the contained gases and upon cooling, a hard gray coherent but spongelike mass remains that is referred to as coke. This substance varies greatly in physical properties and, to be suitable for industrial use, must be sufficiently dense and strong to withstand the crushing pressure of heavy furnace loads. Western coals have a generally high volatile content and therefore form a satisfactory coke only when they attain a rather high fluidity during the process of heating and distillation in-the coke oven. When this high degree of fluidity is developed, the volatile constituents escape and leave a finely porous coke. On the other hand, when the degree of fluidity is low the product is an excessively porous and therefore physically weak mass that is called char.6 Small quantities of oxygen present in coal are believed to decrease the fluidity of the material during the coking process and to favor the development of char rather than coke. In consequence, coal chemists have for some time considered the possibility of developing an index to coking. qualities by inspection of chemical analyses of coals.7 A formula has now been developed that does permit a rough preliminary estimate of the cokability of coal on the basis of the analysis on an ash and moisture-free basis. Coals may be eliminated as possible coking fuels if the oxygen content is greater than 11 pct. Similarly the ratio of hydrogen to oxygen must be greater than 0.5 and the ratio of fixed carbon to volatile constituents must be greater than 1.3. If the coal, on the basis of these limiting factors, appears to have possible coking qualities, the following formula permits determination of the coking index: Coking index =[ a+b+c+d 5] a equals 22/oxygen content on ash and moisture- free basis, . b equals two times the hydrogen content divided by oxygen content on moisture and ash-free basis, c equals fixed carbon/1.3 x volatile matter, and d equals the heating value on moist, ash-free basis/13,600. Coking indices higher than 1.0 suggest that the coal will coke, and indices above 1.1 indicate good coking tendencies. Although generally usable, this formula is not completely satisfactory because the percentage of oxygen shown in ultimate analyses is derived only by difference; i.e., by subtracting the sum of the percentages of the constituents determined analytically from 100 pct.8,9 Although the coking index indicates the coking tendencies of coal, it is necessary to make physical tests of coke before its industrial value can be determined. The U. S. Bureau of Mines has developed a standard procedure for determining the approximate strength of coke that would be formed from a given coal. In this test one part of ground coal, mixed with 15 parts of carborundum, is baked to form a standard briquette. The weight, in kilograms, necessary to crush the briquette is termed the agglutinating index. This test determines the relative fluidity attained in the coking process by measuring the cementing strength of the coal in the briquette. A

Jan 1, 1952

By N. F. Schulz, H. A. Lex

Representative samples of typical manganiferous iron ores from the Cuyuna Range, Minn., were reduced to the metallic iron state at temperatures just short of fusion with an excess of coke in the manner prescribed by the R-N Direct Reduction Process. The magnetic separation characteristics of the reduced ores were determined at several grinds by means of the Davis magnetic tube concentrator. The efficiency of metallic iron concentration by magnetic separation was a direct function of the degree of metallization of the ore sample and of the degree of liberation at-tained in grinding. Some improvement of liberation characteristics was observed if a small amount of sodium chloride was present in the ore during reduction. Despite the extremely fine-grained structure of the crude ores, iron concentrates containing more than 90% Fe at iron unit recoveries of 90% or more were obtained from well-metallized samples of three of the four ores tested. The rejection of manganese to the tailings corresponding to such separations varied from 80% to 95%. The manganiferous iron ores of the Cuyuna Range in Minnesota constitute a major potential source of manganese in the United States provided that a technically and economically feasible process can be devised for its recovery. The iron and manganese of these ores occur chiefly as oxides or carbonates in the form of very small, irregular, discrete grains embedded in a matrix of quartz or other siliceous gangue. The present investigation was undertaken as a sequel to an earlier one conducted jointly by the U.S. Bureau of Mines and the R-N Corp. Those results indicated that the R-N Direct Reduction Process might be a means for recovering both a metallic iron concentrate and a marketable manganese by-product from Cuyuna manganiferous iron ores.&apos; The R-N Process is one of many proposed schemes for the treatment of crude iron ores involving the di- rect reduction of the iron content to metallic iron followed by physical extraction of the iron. In general, it consists of the following stepsz2 1) Iron oxide in crushed natural ores or iron concentrates is about 95% reduced to metallic iron at elevated temperatures but without fusion in a rotary kiln in the presence of a solid carbonaceous fuel (usually coke), limestone, and combustible gases. 2) The kiln product, consisting of metallized ore, excess coke, lime, and coke ash is cooled. The excess coke is recovered and recycled to the kiln feed. 3) The metallized ore is ground for liberation and magnetically separated to yield a metallic iron concentrate. 4) The metallic iron concentrate is agglomerated by a briquetting process. The reduction kiln temperatures must be high enough for the desirable chemical reactions to proceed at practical rates without causing fusion of any of the ore constituents. The time of exposure of the ore to the reducing conditions must be ample for 90% to 95% metallization of the iron oxides present. If more than 95% of the iron is metallized, however, difficulties may arise in the briquetting step, presumably because of accompanying higher carbon content of the metallic iron. Although not always necessary, powdered limestone or dolomite may be added at some time during reduction to aid in eliminating sulfur and phosphorus from the final product.3,4 Other additives, notably sodium chloride, when present during reduction, result in improved liberation characteristics of the metallic iron from certain reduced ores.&apos;v6 Under the reducing conditions normally employed, P(co + H2)= 1 atmosphere, and 1830&apos; to 2150°F (1000° to 1170°C), the R-N Process is claimed to be adaptable to a wide variety of low, medium, and high grade iron and manganiferous iron ores. The manganese oxides and carbonates are reduced mostly to nonmagnetic MnO which is rejected to the nonmagnetic tailings. Manganese-bearing pyroxenes of the original ore, however, may be rejected poorly, if at all, apparently because these minerals occur within the iron lattice or are entrapped in the metal particles.7 The investigation was limited to studies of the Cuyuna ores listed in Table I, which were reduced to the metallic iron state under various conditions

Jan 1, 1969

By Albert D. Brokaw

THE accompanying chart was devised to provide a rapid and simple method of correcting for temperature and compressibility (deviation from Boyle&apos;s law) of gas under relatively high pressures and temperatures, such as are encountered in many deep reservoirs. The chart was prepared by interpolating for the desired values in the experimental data of Burke and Keyes1 and Kvalnes and Gaddy2 on the compressibility of methane, after adjusting their results from 0°C. to 60°F. and combining the correction factors for compressibility and temperature into a single multiplier, which, applied to the product of pressure and reservoir volume, gives at once the volume at one atmosphere (14.7 lb. per sq. in. abs.) and 60°F. The relationship 0f this multiplier to the compressibility factor Z, as used in most discussions, is simply: [Multiplier = 460° + 60°ZT –] where Z is the compressibility factor and T the absolute temperature (Rankine). Fahrenheit temperatures are shown on the vertical axis and pressures in pounds per square inch absolute on the horizontal axis. Correction factors or multipliers at intervals of 0.05 from 0.55 to 1.40 have been plotted on the chart and are calculated t0 give volume of gas at one atmosphere pressure (14.7 lb.) and 60°F. The operation is as follows: The reservoir volume, times the number of atmospheres pressure, times the multiplier, gives the volume of gas measured at one atmosphere (14.7 lb. per sq. in.) and 60°F. For example, a reservoir is estimated to have a volume of 10,000,000 cu. ft., bottom-hole pressure is 2940 lb. per sq. in. and temperature is 184°F To make the correction for methane, follow the 184° line horizontally to the 2940-lb. pressure line. The intersection lies between the 0.85 and 0.90 correction lines, and by interpolation we may estimate the multiplier at 0.863. The computation is simply: [ ] Using the chart for methane prepared by Prof. G. G. Brown3 and his associates, the multiplier is found to be 0.867. Details 0f computation are as follows: Correction factor to apply to PV to correct for deviation from Boyle&apos;s law and adjust to measurement basis of 60°F.: [ ]

Jan 1, 1941

By W Lindlief, Cyril Stanley Smith

Several investigators, mainly concerned with the mechanical properties of the alloys, have studied the so-called aluminum bronzes after various quenching and reheating treatments. Of these works, perhaps the most complete is that of Bouldoires, who studied changes of length, electrical conductivity, thermoelectric force, hardness and micro-structure on tempering quenched alloys containing 5 to 20 per cent of aluminum, although the work of Carpenter and Edwards,² Curry13 Greenwood,4 Braesco,5 Matsuda,67 Grard8 and others has added much to our knowledge of the changes occurring during tempering. The so-called acicular ß decomposes on tempering at temperatures between 350" C. and the eutectoid, giving rise to a Widmanstätten structure of a needles in a matrix of 6 or fine a + 6, associated with an increase in hardness and almost complete loss of ductility. Matsuda studied the eutectoid transformation by means of dilatation and electrical conductivity measurements during cooling at different rates. He found that on cooling at the rate of 10" C. per minute there was a decrease in electrical resistance and in length instead of the usual increase which occurred with slow rates of cooling. On tempering the rapidly cooled samples, the increase commenced at about 400" C. and at 520" C. the resistance and length had reached the equilibrium values. These peculiarities he accounted for as being due to a transitional phase ß&apos; being formed, ß&apos; having an electrical resistance and volume less than either ß or a + 6. Obinata9 published some electrical conductivity curves for copper-aluminum alloys showing a double break at the eutectoid temperature,

Jan 1, 1933

By L. F. Mondolfo, W. T. Collins

A study of the relationship between undercooling for nucleation and structure in Sn-Cu alloys with 0.1 to 5 pct Cu has shown that in hypereutectic allojls the halo of tin that surrounds the primary crystals of Cu3Sn5 is larger, the larger the undercooling for nucleation o,f the tin. This increase of halo size results in a decrease of coupled eutectic, and, in alloys far from the eulectic composition, may produce its complete disappeavance, with the formation of a divorced eutectic structure. This was confirnred by the excrrnination of other alloys in which divorced eutectic slructuves are formed, and leads to the conclusion that they ave only an extrenle case of halo forrtzalion , which results when the two phases freeze one at a time and solidification of the first is completed Defove the second starts. It was also found that under proper conditions of nucleation all types of eutectic structures can be formed in the sartte system , and therefore divorced eutectics, like normal and anomalous, are not characteristic of the syslett~, but are mainly controlled by nucleatiorz. Dizlovced eutectics are formed when the phase that tutcleates the eulectic vequires a large undevcooling for ils nucleation and when the cotnpositiorz of the alloy is far from the eutectic., on the side of the primary phase that does not nucleate the other phase. It is recommended that the tevm "divorced" be used in preference to degenerate because it is more desct-iptice of the morphology and mode of forinalion of the structures. ThE variety of structures found in eutectic alloys has been extensively investigated and classified. The most accepted classification is the one by ~cheil,&apos; in which three different types of eutectic were distinguished: 1) normal, 2) anomalous, 3) degenerate (divorced). ATornlal eutectics are typified by the simultaneous growth of the two phases ("coupling") by which the two phases appear as interpenetrating crystals. The presence of a crystallization front, in which the two phases grow side by side, creates the eutectic grains, with the boundaries where the fronts meet. The presence of eutectic grains is the .distinguishing feature of a normal eutectic, according to Scheil. Straumanis and Brakss2 examined the Cd-Zn system and showed that there was a crystallographic relationship between the phases. Later, others4 also investigated additional systems and found definite crystallographic relationships in the coupled eutectics. The anornalous eutectic shows much less coupling than the normal; the two phases are intimately mixed but &apos;grow without a uniform crystallization front—a consistent crystallographic relationship— and the eutectic grain is conspicuously absent. As in the normal eutectics faster rates of growth result in a finer structure, but there is not the typical uniform spacing of normal eutectics. The degenerate eutectic shows no coupling; in fact the two phases attempt to minimize their area of contact and to form separate crystals. It has been suggested5" that slow cooling may favor this type of structure. Scheil believes that normal eutectics are formed when the two solid phases are present in more or less equal proportions, whereas both anomalous and degenerate eutectics form when one of the phases is present only in small amounts. spengler7 extended much farther this qualitative relationship between the eutectic type and the ratio of the two phases, and added a relationship to the melting point of the constituents. On this basis he proposed two equations for determining into which of Scheil&apos;s classifications an alloy belongs. The first equation is: where TI is the melting temperature of the lower-melting component, Tp of the higher-melting component, and Te the eutectic temperature. The second equations is: where is the volume percent of the lower-melting phase and $2 of the higher-melting phase at the eutectic composition. If 0 and/or 4 are in the range 0.1 to 1, a normal eutectic is formed; if in the range 0.01 to 0.1, anomalous; if less than 0.01, degenerate. Although the examples given by Spengler show a good agreement with the formulas, chadwick found that the Zn-Sn eutectic is normal to all growth rates, even though the volume ratio is 12/1, and Davies9 reports that the A1-AlgCo2 eutectic is normal, with a volume ratio of more than 30/1. Many more discrepancies of this type can also be found. Neither Scheil nor most of the other investigators have considered nucleation as a factor in the formation of divorced eutectics. Daviesg states that divorced eutectics form when neither phase acts as

Jan 1, 1965