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By Robert H. Richards

Jan 1, 1883

By G. R. Smithson, John E. Hanway

This paper, the first of two papers covering the development of a metallurgical process for the treatment of a complex ore, describes the bench-scale experimental Program undertaken as a basis for initial process design. The results of using various potentially applicable process steps are detailed and the basis for selecting certain of these steps for Pilot-plant development is outlined. A process consisting of the steps of sulfate roasting, leaching, copper recovery, solution purification, zinc electrolysis, and brine leaching for lead recovery was recommended for further study. THIS paper describes the bench-scale development of a sulfate roasting process designed to recover copper, lead, and zinc from a complex ore. The extrapolation of the bench-scale results to pilot-plant design and the results of pilot-plant operation will be described by Lund, et al.' in a subsequent paper. Several years ago, the research divisions of the St. Joseph Lead Co. became responsible for the development of a metallurgical procedure to treat a complex sulfide ore containing copper, zinc, and lead sulfides. The primary objective was to devise a procedure which would permit economic recovery of the nonferrous values. As could logically be expected, the study of conventional flotation procedures was undertaken; in addition, however, because the physical nature of the mineral association in the complex ore indicated that physical methods of ore beneficiation might not prove to be entirely satisfactory, a program also was established to investigate alternative methods of direct metallurgical treatment for recovery of the metal values. Exploratory test work by the St. Joseph Lead staff led to the conclusion that a sulfate roasting technique represented the most attractive approach for a direct metallurgical process. Sulfate roasting would provide for the selective conversion of the nonferrous values to forms soluble in conventiona1.1 leaching agents and would permit their efficient separation from the insoluble iron and other gangue materials. It should allow efficient utilization of the thermal energy available from oxidation of the sulfide raw material, and might provide an opportunity for recovering byproducts such as iron and sulfur. The decision to evaluate a selective sulfation procedure as a basic processing step also was influenced by the excellent results obtained by the St. Joseph Lead Co. in using this procedure for the recovery of cadmium from zinc sulfide concentrates. The choice of selective sulfation as a major processing step served as a basis for an extended experimental investigation of the process with bench- and pilot-scale equipment to prove its feasibility. St Joseph Lead Co., aware that Battelle Memorial 1nstitute had participated in the development of several fluidized-bed sulfate roasting procedures, asked Battelle to undertake the bench-scale development of a suitable sulfation process. This paper describes the procedure used and the results obtained at Battelle in the treatment of the complex sulfide ore. EXPERIMENTAL WORK Nature of the Raw Material. The sulfide ore deposits of interest are essentially a massive sulfide, with the indivudual ore minerals being extremely fine grained and intimately intergrown with each other and with the associated gangue. The zinc in the ore is present mainly as sphalerite (ZnS), the lead as galena (PbS), and the iron either as pyrite (Fes2) or as pyrrhotite (FeS). Table I shows the chemical analysis of various individual samples of the ore. These analyses illustrate the variability of the ore body and impose a rather severe requirement on any type of metallurgical process—that of being able to tolerate probable wide variations in the assay of the head ore. The tentative flowsheet designed to serve as a guide for the initial experimental investigation of

Jan 1, 1962

By Sir Robert A. Hadfield

The Hadfield method of producing sound steel ingots has been the subject of a paper read before the Iron and Steel Institute, so that it will be unnecessary to describe it fully here. The object of the method is to make poseible the production of steel ingots in which the pipe is almost entirely obliterated, and it is applicable particularly to the production of sound ingots, from which good rails could be rolled. The method in brief consists in casting the ingots on cars, usually with the small end down. Each ingot mold is provided with a sand top, rammed up in the well-known manner. After the mold is filled to the desired height with steel, a layer of slag about 0.5 in. thick is placed upon it and the balance of the mold is then filled with charcoal. Then, through suitable piping, an air blast is directed in numerous jets upon the charcoal, which is burned thereby, the combustion supplying addi, tional heat to the top of the ingot, which helps to keep the top fluid and to retard its solidification, while the lower parts are rapidly losing heat by its transfer to the mold. By one plan the ingots are cast in molds placed upon bogies, movable trucks, or platforms, in the position A, Fig. 1. The ingots are cast vertically on bogies, say four or more ingots on each bogie, as may be found most convenient, and the upper surface of the steel is maintained in a molten condition during the transit of the ingots from the casting pit to the stripper. This is effected by a series of air pipes, for example, three in number, with jets or holes on the under surface of such pipes, placed preferably horizontally, arranged in such a manner as to cause jets of air to impinge on the upper surface of the ingots. These holes or jets are made throughout the entire length of the overhead pipes, the length of such pipes being

Jan 1, 1914

By R. R. Jones, R. W. Kraft

Zn-Mg2Znn eutectic alloys nzay freeze willr either rodlike or lanzellar rnorphology. Alloys with slighlly more than /he eutectic arrzount of rnagnesillrn usually contain three-cnned dendrjles of MgzZnll in a eutec-lic ttlulris. All three morphologies haue the same cryslallographic orientution relationship: (0UOl) zn - 11 (111) Mg2Znll and (2310)Zn 11(101) Mg2Znll, but u3ith different prej-erred groulth direclions. The lurnellae lo rods transifion in con/rolled ingols qf euleclic cotnposition occurs because lhe large kinelic undercooling due to MgzZnll minirrzizes /he ejj-ecl of the solid-solid inlerface energy. The eutectic morphology is influenced by the presence of lhree-nned dendrites 0-f MgzZn11 which may conlrol /he rricroslrccture by acting as nuclealion sites. In recent years there has been much interest in eutectic solidification and several theories have been proposed. One of the confusing factors is the existence of various morphologies in which the solidified phases may form. The lamellar microstructure seems to be most common in metal eutectics, and it has been claimed' that all regular eutectics should be lamellar if sufficiently pure. However, there still remain eutectic alloys which are not lamellar or which change their morphology as a function of growth conditions. The eutectic between zinc and the intermetallic phase Mg2Znll was chosen for this investigation because it has been found to solidify in more than one morphology. The diagram in anssen' locates the eutectic point at 3.0 wt pct Mg and 367°C. lliott gives 364°C as the eutectic temperature, leaving the phase compositions unaltered. Since the growth conditions determine the micro-structure of the solidified alloy, the factors controlling the transition from one morphology to another could be studied. The lamellae to rods transition is of particular interest. PROCEDURE Alloys were prepared from carefully weighed portions of 99.999 pct Zn and 99.97 pct Mg by melting in Pyrex containers under argon and casting into graphite boats. The resulting ingots were remelted under argon and solidified unidirectionally in a horizontal tube furnace at growth rates ranging from 2.0 to more than 50 cm per hr under a temperature gradient, measured over a 5-cm length, of 9" to 14°C per cm. The solid-liquid interface appeared to be planar at all growth rates although no attempt was made to confirm this by decantation or quenching. A few ingots were allowed to freeze uncontrolled. Most alloys were of the nominal eutectic composition, 3.0 wt pct Mg according to Hansen2 and lliott, but some contained as much as 3.35 wt pct Mg. Chemical analyses were not run since metallographic examination confirmed that the desired composition was achieved. Specimens were cut from the middle portion of the ingot normal to the growth axis, polished mechanically, and etched with 2 pct Nital. Suitable areas were selected for the determination of crystallographic orientation relationships by a tiontechniqueof described previously by one of the authors.4 The (2310) planes of zinc and the (8701, {944}? (1032) planes of Mg2Znll were found suitable for orientation determination; experimental error was on the order of 2 or 3 deg. RESULTS Three different morphologies were found in the unidirectionally solidified alloys: lamellar eutectic, rod-like eutectic, and a structure whose most predominant characteristic was the presence of three-vaned (cellular) dendrites of Mg2Znll. These dendrites were only found in alloys with more than the eutectic amount of magnesium. In some ingots fine hexagonal needles of Mg2Znll surrounding a core of MgZn2 were observed. They were probably due to incomplete alloying and seemed to have no effect on the eutectic morphology. In addition hexagonal spirals like those discussed by Fullman and wood5 and Hunt and acksonh ere observed in some ingots frozen without directional control. Both MgZZn,, and MgZnz were detected by X-ray diffraction in these alloys. Since the morphology could not be grown unidirectionally and no characteristic orientation relationship between the phases was found, further study was limited to the lamellar: rodlike, and three-vaned dendrite morphologies. Alloys of Eutectic Composition, No Dendrites. The mcrostructures of allovs with no three-vaned dendrites were either lamellar or rodlike depending on the growth rate. At rates below 10 cm per hr the morphology was lamellar, consisting of two sets of parallel plates intersecting at about 54 deg like the Mg-MgzSn eutectic described by raft.7 At growth rates faster than 14 cm per hr the microstructure showed rods of zinc in a matrix of MgnZnll, while intermediate rates yielded mixtures of rods and lamellae in small groups. The lamellar "grains" were often several millimeters in cross section, but contained small irregular areas which divided each grain into perfect islands 100 or 200 p in diam. Lamellae were parallel to each other throughout the grain in spite of these defects in the structure, Fig. 1. Rods, on the other hand, could only be produced in small groups arranged like fish scales and separated by irregular areas of appreciable thickness, Fig. 2. Alloys Not of Eutectic Composition, With Dendrites. In alloys with 3.1 to 3.35 wt pct ME,-. three-vaned dendrites bf MgzZnll were usually found surrounded by eutectic. At growth rates slower than about 10 cm per hr the dendrites were separated from each other by small areas of both lamellar and rod eutectic, Fig. 3.

Jan 1, 1969

By C. Zener

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

Jan 1, 1956

By R. R. Angel

Drilling rate is a parameter that should be considered in determining the volume requirements for air and gas drilling. The use of past methods which ignore the effects of the solids content upon the pressure and velocity of the annulus flow stream can result in undercalculation of the required volurne by as much as 50 per cent. A vertical-flow equation is presented for determining volume requirements. This equation includes the effect of the solids that are transported up the annulus in the flow stream by incorporating the drilling rate as one of the parameters. The effect of down-hole temperature on required circulation rates is also ana-lvzed. A simple approximate method of determining volume requirements is presented. This method is more accurate than the methods used in the past. Hole cleaning difficulties are analyzed for a recent air drilling job where past methods indicated that - excess air was being used. Sample curves of calculated boitom-hole pressures are presented for air and gas drilling in several hole sizes. INTRODUCTION In certain areas the use of air or natural gas as a circulating medium for drilling oil and gas wells is becoming a common practice. Large increases in penetration rate and bit life are achieved through the use of these media in preference to mud or water. Drilling rates as high as 90 ft/hr have been obtained in shales. The importance of maintaining adequate circulation rate is generally recognized; however, much disagreement exists among drilling operators as to what constitutes "adequate" circulation rate. In quarry drilling, where annular velocities can be accurately determined, an annular velocity of 3,000 ft/min of standard air is required for best results in rocks having approximately the same density as those commonly penetrated in drilling oil or gas wells'. Although this standard air velocity has proven satisfactory for quarry drilling, some oil and gas well drilling operators believe that an equivalent annular velocity of more than 4,000 ft/min is required; others believe that as little as 2,000 ft/min . is sufficient. Much of this disagreement results from determining the required circulation rates with methods which fail to incorporate the drilled solids in an equation which is applicable to vertical flow. Hughes Tool Co. Bulletins No. 23' and 23-A3 present data for determining circulation rates based on the Weymouth formula. These data do not include the drilling rate as a parameter and, therefore, neglect the effect of the solids being transported up the annulus. In spite of this apparent defect and the fact that the Weymouth formula is not applicable to vertical flow, the Hughes data have well served the drilling industry in many areas and are important and timely contributions to the science of air and gas drilling. The Hughes data purposely omit a correction for increasing down-hole temperature. At slow drilling rates this effectively compensates for the use of a formula which is not valid for vertical flow; however, volumes determined by the Hughes method are not sufficient to support rapid drilling rates at moderate and great depths. For example, Phillips Petroleum Co.'s Cauthorn "D" No. l in the Vinegarone field for Val Verde County, Tex., was air drilled from 1,500 to 9,300 ft using a compressor delivering 1,400 cu ft/min. The 8 3/4-in hole was drilled with 5-in. drill pipe, and drilling rates as high as 90 ft/hr were obtained between 7,000 and 9,300 ft. No water or caving hole was encountered. At 7,728 ft it was necessary to wash-out 60 ft of cuttings to reach bottom after a trip to change bits. At 8,130 ft a twist-off occurred and the drill col-lars were stuck in drill cuttings. These difficulties indicate that the 1,400 cu ft/min of air was not sufficient to keep the hole clean. Hughes data indicates that 1,180 cu ft/min is sufficient to produce an annular ve-

Jan 1, 1958

By S. G. Epstein

Electromigration has been measured in dilute liquid alloys of lead in antimony and antimony in lead. In these alloys antimony migrates with the electron current; lead migrates in the opposite direction. These results, which contradict the mass criterion, were predicted by the electron drag model for electromigration in liquid alloys. The existing experimental data are shown to correlate with the difference in electrical resistivities of the alloy components. FOR many years investigators have attempted to relate observed electromigration phenomena in liquid alloys to the physical properties of the alloy components. The most successful correlation was found by Angus et' al.,1 who in 1959 proposed an empirical criterion for predicting the relative direction of motion of the components of a liquid alloy in an electric field: the component with the smallest atomic mass concentrates at the cathode. While this criterion is obeyed in nearly all the alloy systems which had been investigated, the physical basis for such an effect was not understood. It was also disturbing that the mass criterion predicted the wrong sign for the Haeffner effect; observations with pure liquid metals revealed that in every instance the lighter isotope was transported to the anode.2 Klemm3 explained these isotopic separations by suggesting that the lighter isotopes were more mobile and more easily carried to the anode with the electron stream. Additionally, several deviations from the mass criterion have been found in liquid alloys, notably involving transition metals such as chromium, nickel, palladium, and zirconium, which migrate to the anode in liquid bismuth.4'5 Recently, a model has been proposed6 in which electromigration in liquid alloys is attributed primarily to the interaction between the electron stream and the metal ions. In essence, this model predicts that the component with the greater electron-ion scattering cross section will be preferentially transported to the anode, displacing the other component to the cathode. The electrical resistivity of each pure component at its melting point is taken as the measure of its scattering cross section. This model was developed from the results of systematic studies with various solutes in liquid mercury,7'8 bismuth,9 and sodium.10 In every alloy, the component with the greater resistivity has centrates at the anode. Coincidentally, in every instance the component with the greater resistivity has also the greater mass, apparently satisfying the mass criterion. In order to differentiate between electron-ion coupling and atomic mass as the relevant physical prop- erty influencing electromigration, measurements were made with Pb-Sb alloys. Lead has an atomic mass nearly twice that of antimony, but lead has an electrical resistivity of 91 microhm-cm while antimony has a value of 113.5 microhm-cm at their respective melting points. The mass criterion predicts that in an alloy of the two antimony will concentrate at the cathode; the electron drag model predicts that antimony will concentrate at the anode. EXPERIMENTAL To conclusively determine the relative motion of lead and antimony in each other, solute electromigration was measured in dilute liquid alloys of antimony in lead and lead in antimony. Both starting materials were 99.999+ pct pure. The measurements were made with the same capillary-reservoir technique previously used for measuring electromigration in liquid bismuth alloys.11 Several changes in the experimental apparatus were necessary, however, to accommodate liquid antimony, which has a higher melting point than bismuth. The modified apparatus is depicted in Fig. 1. In each experiment four quartz capillaries were filled with the molten alloy. A direct current was passed through two of the capillaries; the electrode in one of these capillaries was made the cathode, and the electrode in the other was made the anode. The remaining two capillaries sampled the alloy in the reser-

Jan 1, 1969

By P. M. Kelly, E. P. Butler

The stability of a 70/30 Mn-Cu alloy aged to peak damping has been investigated using electron microscopy, X-ray diffraction, and torsional pendulum measurements. Storage at room temperature or at 100" C causes a reduction in damping capacity. This is shown to be due to the formation of subdomains which "lock" the main domain structure and so hinder their movement. After storage the damping capacity can be restored by a retransformation treatment, which generates structures identical to those found in newly aged specimens. Plastic deformation by rolling also causes a decrease in damping capacity. In this case the damping capacity can only be restored by retransformation if the amount of deformation is less than about 5 pct. THE general metallography and structure of these high damping capacity alloys has been discussed in Part I of this work.1 Part II deals with some of the variables that affect the damping capacity. In particular, the stability of the damping capacity of a 70/30 alloy aged for 2 hr at 425° C and quenched has been investigated. The temperature sensitivity of the damping capacity of a 70/30 alloy aged for 2 hr at 450° C has been reported by Birchon.2 The damping capacity begins to decrease with increasing temperature, and is very low above the M, temperature of 125°C. The cubic — tetragonal transformation is completely reversible and there is no apparent thermal hysteresis associated with the change in damping capacity. Another important effect was first reported by Dean and his coworkers.3 They noticed a decrease in the damping capacity with time for specimens of a quenched tetragonal alloy. More recently workers at the Admiralty Materials Laboratory 4 have studied the stability of an aged 70/30 alloy. They found that the damping capacity decreased to half its original value after about 1000 hr at room temperature. EXPERIMENTAL The techniques used for electron microscopy and X-ray diffraction have been described in Part I. The damping capacity was measured by means of a torsional pendulum, using rectangular specimens, 3 by 0.3 mm with a 6 cm gage length. The specific damping capacity, S.D.C., was calculated as a percent amplitude decay in free vibrations over 10 cycles, starting at an amplitude which corresponded to a 700 psi surface shear stress. Because of the stress dependence of the damping,' the values obtained were about a third those reported for a 5000 psi surface shear stress.' RESULTS a) Effect of Aging Temperature. The effect of aging temperature on the damping capacity is shown in Fig. 1. The damping capacity reaches a peak of 12 pct after aging at 400° to 425°C) then begins to decrease as the volume fraction of a Mn increases. At higher aging temperatures the structure becomes cubic again with a low damping capacity. b) Stability of the Aged Structure. The damping capacity of the aged alloy decreases with time at room temperature. This process could be accelerated by storing at 100°C, when about 100 hr were required for the damping to fall to half its original value. The results of room temperature and 100°C storage, for times up to 1000 hr, are shown in Fig. 2. The damping capacity starts to decrease after about 24 hr at 18° C and 1 to 2 hr at 100°C. It was found, however, that the damping could be almost completely restored by retransformation. The specimens were held at a temperature above the M, for a short time, 250° C for 5 min, and then quenched. The values of damping capacity for specimens that were aged, stored, and then retransformed are shown by the full points in Fig. 2. X-ray measurements of the c/a ratio and hardness readings on the specimens did

Jan 1, 1969

By C.H. Lorig, M.C. Udy

Through the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the genera1 effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. Literature Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H2O, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnasl published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at One temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1943

By M. C. Udy, C. H. Lorig

Through the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the genera1 effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. Literature Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H2O, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnasl published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at One temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1943

By O. A. Cheadle, F. E. Lane

ThE computer program for arbitrary crystal systems reported by Camp and Clum' has been modified to make it more convenient for hexagonal crystals. The program' uses the Miller indexes (hkl) which can be confusing for hexagonal crystals while the modified program uses the Miller-Bravais indexes with four axes; e.g., the angles between the (110) planes, Fig. 1, are 0 and 90 deg but in the (hkil) system the angles between the (1150) planes are 0 and 60 deg. If a Laue photograph is taken of a crystal oriented with the prismatic planes nearly parallel to the film then the spots on the stereo graphic projection will be from high-index planes. The probable positions of the low-index planes, e.g., (0001) plane, can only be obtained from the intersection of zones and this is not accurate to 1 or 2 deg. The number of planes considered by the program (card 1)' has to be limited to the ones of low index or the program time is excessive but a solution will not be obtained if one of the spots has an index that is not being considered. To overcome this problem the program1 was modified so that if no fit was obtained at *1 deg (card 3) of the tabulated angles then ±2 or ±3 deg was tried. If still no solution was obtained either due to one of the angles not being measured correctly to ±3 deg or because one of the spots was from a high-index plane, then the last spot was discounted and a fit tried for the remaining spots at i1 deg, and so forth. The minimum number of spots that the program will try to fit is five. If the limit on any individual index is 4 (card 1) and (h + k + l + 1) is six then twenty-three planes are considered and there are over 1000 interplanar angles. Many pairs of planes have very similar interplanar angles and with the errors previously mentioned the program will often produce several alternative solutions to a group of spots particularly at ±2 or ±3 deg. However without the program the alternative solutions would probably not have been found. If a large number of spots are used the number of possible fits is reduced. In the example shown in Fig. 2, if only spots which are on the film are used (case 1) the program gives six possible solutions, Table I. However if points 7 and 8 are also used (case 2) the program gives only one fit which also agrees with a standard projection of the crystal. In addition to time-saving the program ensures that a correct solution is obtained since it is unlikely that all the alternatives would have been gound manually; the first would probably be assumed to be the correct solution. The program has been used for zirconium crystals but is equally suitable for other hexagonal materials.

Jan 1, 1969

By M. C. Udy, C. H. Lorig

THROUGH the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the general effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. LITERATURE Two general factors should he considered in a study of reduction of iron oxide: (1) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe3O4-FeO-H2-H2O, Fe304-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnas1 published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at one temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1942

By J. B. Conway

Stress-vuptuve data for several of- the refractory metals are frequently found to yield a linear relationship between the Larson-Miller parameter and the logarithm of the applied stress. In such cases linear stress-rupture isotherms result with slopes bearing a definite relationship to the temperature. It also follows that the stress to produce rupture in a certain period of time will be linear in temperature. Data for several refractory metals have been reviewed and excellent linearity is shown in this type of isochronal plot. In addition, the af ore - mentioned lineavity leads to a linear relation between the log of the stress to produce rupture in a certain time and the homologous temperature. This has been illustrated for the Group VI-A metals, tungsten and molybdenum. EXTENSIVE use has been made of the Larson-Miller' parameter in the interpolation and extrapolation of stress-rupture and creep data. In those cases where this particular parametric approach is applicable a convenient and fairly straightforward procedure is made available for the correlation of experimental stress-rupture data. It is quite common to employ this parameter in the form of a master rupture plot in which the parameter, T(C + log tr), is expressed as a function of log stress. In many cases this functional relationship in log stress is linear within acceptable accuracy and hence the following relation results: where P is the parameter, C is the Larson-Miller constant, T is the absolute temperature, t~ is the rupture time, a is the stress, and a and b are constants. Examples of such a relationship are contained in the work of Green, Smith, and 01son2 dealing with high-temperature rupture behavior of molybdenum and in the work of Green' dealing with the high-temperature behavior of tungsten. In addition, pugh4 has shown a similar linearity for some fairly low-temperature data for molybdenum. It can be shown that when the relationship in Eq. [I] is exhibited certain generalizations can be made concerning the form of the stress-rupture isotherms. For example, rearranging yields: For a given material (constant C) at a given temperature the first term on the right-hand side of Eq. [2] is a constant and hence this equation defines a straight line when log stress is plotted as a function of log-rupture time. This is recognized as the standard form usually employed in this type of data presentation. Such linearity then suggests the linear form of the Larson-Miller parameter. Or, in other words, the linear parametric relationship in Eq. [2] results only when the stress-rupture data are linear on a log-log plot of stress vs rupture time. Another interesting observation can be made in regard to Eq. [2]. It can be noted that the slope of the stress-rupture isotherms is given by - T/b and hence a direct calculation of the constant b is available. It also follows that since the value of b is the same for all temperatures the slopes of the various isotherms on the log-log stress-rupture plot cannot be the same. Indeed, the existence of the relationship in Eq. [2] precludes a system of parallel lines on this common stress-rupture plot. As a matter of fact it further specifies that in addition to being nonparallel the slope of these isotherms must decrease (i.e., become more negative) with increasing temperature. Such a condition is indeed found to exist in the case of the stress-rupture data reported for molybdenum.' As a corollary to the above, it may be stated that stress-rupture data which do not lead to a linear log-log stress-rupture plot or whose isotherms do not exhibit a decrease in slope as the temperature increases will not yield the linear relationship of Eq. [I]. Applying Eq. [2] to two different temperatures and solving for C yields: Eq. [3] affords a simple and rapid method for calculating the Larson-Miller constant from the log-log stress-rupture plot. The slope of a given linear isotherm is measured and the value of "b" calculated based on Eq. [2] as: slope = - -Tb Then at an abscissa value of 1.0 hr (making log tr in Eq. [3] equal to zero) read the stress corresponding to rupture for two different temperatures. Substitution in [3] yields: A value of the Larson-Miller constant can thus be calculated from a few simple mathematical procedures employing data read directly from the log-log plot of the stress-rupture data. Of course, it is not to be overlooked that the above reasoning has been based on the linear relationship of Eq. [I] being applicable. However, if as mentioned above the log-log plot is

Jan 1, 1967

By B. Ladanyi, B. Hoyaux

A first requirement for assessing the safety of a rock slope, either artificial or natural, particularly if the rock behaves in an elastic-brittle manner, is a propw knowledge of the distribution of stresses within the slope and their development with time and advancement of workings. There are a uumber of different methods that can be used, in principle, for obtaining this information, such as (1) stress measurement in situ, (2) photoelasticity,1 (3) analytical methods, and (4) numerical methods. In cases where the stress distribution cannot be obtained by classical analytical methods, as in the one considered herein, either photoelasticity or numerical methods are norrnally used. However, actually, due to the rapid development of high-speed computers, increasing preference is given to the numerical methods. Among the latter, the most successful ones, to date, for determining the stress distribution in slopes have been (1) the finite difference method,2-4 (2) the lumped parameter method,5 and (3) the finite element rnethod.6 However, for determining gravity stresses in a natural rock slope, only the finite difference method has been used until now.7,8 A solution of the same problem by the finite element method will be shown here in which a particular reference is given to the development of tensile fracture zones within the slope. FINITE ELEMENT METHOD The stress analysis using the finite element method originates from an extension of the matrix analysis of structures.9 It consists in decomposing a continuous medium, assumed herein to be homogeneous and isotropic,

Jan 1, 1972

By Ernest F. Burchard

MOST of the iron ore smelted in Alabama blast furnaces is mined within Alabama, although deposits in the neighboring States of Georgia and Tennessee may be drawn upon when occasion requires. Of the four commercial kinds of iron ore, the anhydrous ferric oxide, hematite (Fe2O3) ; the hydrous ferric oxide, mostly the type commonly known as limonite (2 Fe2O33H2O) ; the carbonate, siderite (FeCO3) ; and the magnetic oxide, magnetite (Fe:3O4) ; the first two are found in abundance in Alabama, the third in less than commercial quantities, and the fourth only rarely. Both the hematite and the hydroxide are found in somewhat different forms according to their geologic environment. The Red Mountain hematite, of Silurian age, that crops out in well¬defined beds for 1.50 miles northeast-southwest and 40 miles northwest-southeast is the predominant source of ore. Only a small part of this area carries ore of commercial value; Birmingham and Gadsden are now the only centers of production. The ore is of sedimentary origin, probably altered from vast deposits of greensand mixed with calcareous, fossiliferous. marine debris. Other types of hematite not vet mined commercially are in metamorphosed rocks-red ore in slates in Columbiana Mountain and specular hematite (gray ore) in quartzite in the Talladega Hills.

Jan 1, 1938

By J. B. Hiskey

The hydrometallurgical application of thiourea in processing precious metal ores and concentrates has reached the development stage. This paper reviews recent technical literature covering the process development of thiourea leaching. In addition, recent fundamental contributions are discussed. Most of the interest in thiourea leaching has involved treating high grade concentrates that have sufficient value to just the use of thiourea as a reagent. An important development in thiourea technology is the addition of SO2 to the leaching solution. This procedure effectively reduces the decomposition of thiourea and eliminates the problems of passive surface layers that limit the leaching efficiency. Results for the thiourea leaching of a bulk sulfide concentrate and a residue from the autoclave leaching of a smelter flue dust are also reported. As determined by a standard bottle roll cyanidation test, the bulk concentrate was extremely resistive to cyanide leaching yielding only 16% gold and 2% silver extraction in 24 hours. Leaching with a relatively concentrated thiourea solution (1MCS (NH2)2) resulted in 83% gold and 75% silver extraction in four hours. With the treated flue dust residue, gold extraction was about 60%. Gold and silver extraction with cyanide was sensitive to both cyanide concentration and oxidizing conditions. Cyanidation resulted in 59% gold extraction and 77% silver extraction in 24 hours.

Jan 1, 1985

By William C. Aitkenhead, John A. Jaekel

Uranium deposits in the Spokane Indian Reservation, as well as those around Mt. Spokane, are essentially low grade, much of the ore containing less than 0.2 pct U808. The Mining Experiment Station of the Division of Industrial Research, State College of Washington, has been engaged in intensive research on the amenability of these low grade ores to froth flotation. The results: successful flotation of autinite, chief mineral constituent. At the outset of this work the goal was a concentrate of 1 pct U308 with a 90 pct recovery from ores containing less than 0.2 pct U3O8. Most of the work has been done on argillite ore from the Midnight mine on the Spokane Indian Reservation. The goal has not been attained using this ore, but samples of the granite ore from Mt. Spokane yielded successful results. For example, a concentrate containing 11.2 pct U308 was produced from a Mt. Spokane high grade ore containing 1.27 pct U3O8 with a recovery of 97.8 pct. Another Mt. Spokane ore yielded a concentrate of 5.0 pct U3O8 from an ore containing 0.13 pct U3O8, with a recovery of 85 pct. This same ore gave a recovery of 93.5 pct when the grade of concentrate was reduced to 2.0 pct.

Jan 1, 1959

Jan 1, 1920

By K. A. Slagle, D. K. Smith

weight obtained. Additives used in conjunction with salt in these slurries have included silica flour, calcium ligno-sulfonate and cellulose retarders, granular lost-circulation materials, bentonite and selected low-water-loss additives that are not significantly deteriorated by the presence of the chloride ion. In some other areas of South Texas, the salt-saturated slurries have been used quite extensively for improvement of the flow properties of slurries and attainment of better circulation characteristics at lower displacement rates. Concurrently with this property, the protection of shales and shaly sands is also realized, as well as useful retardation of the slurry. Resultant superior cementing jobs have been indicated by both communication tests and acoustic logs for bonding to pipe and formation.' In one section of Louisiana, a major oil company has been using salt-saturated API Class A cement with calcium lignosulfonate retarder for cementing through the Miocene at 9,000 to 10,000 ft. This is another of the situations where interbedding of sands and shales exists, creating difficulty in maintaining formation competency when a fresh-water slurry contacts the clay minerals of the formation. Further work has also been done in the shaly Miocene formation at 13,000 to 15,000 ft where fairly close water or gas contacts are encountered. Indications thus far are that better segregation of these various fluids is obtained by use of the saturated salt slurries because of their improved formation bonding characteristics. In addition to the properties of salt in this situation, attainment of turbulent flow at minimum displacement rates has also been accomplished by use of an additive to help provide exceptional dispersion and viscosity reduction of the slurry. Another oil company was encountering considerable expense in completing wells in Southwestern Louisiana due to extensive block squeeze requirements for effective separation of zones. A very effective mud program was being used to minimize washout in the shale sections and, apparently, a nearly gauge-size hole was being obtained. However, primary cementing results with fresh-water slurries were generally poor. On a few occasions when slurry was actually circulated to the surface, large pieces of shale formation were brought out of the hole with the slurry, indicating a severely water-sensitive, sloughing formation. Inhibition of shale heaving was being accomvlished in the drilling program, and immediately indone ipon circulation of the fresh-water slurry even though it contained a low-fluid-loss additive to reduce filtrate damage in the sands. The subsequent change to salt-saturated slurry yielded 11 successful primary cement jobs out of 12, compared to the previous success ratio of practically zero. Since these were deep, high-temperature wells in the range of 13,000 ft with high-pressure zones necessitating 17.5-lb/gal fluid densities, the slurry used was API Class E cement, silica flour, weight material, retarder, salt saturation (which also reduced the amount of weight material) and maintenance of low fluid loss by use of a salt-compatible additive. Other salt slurries have been used to a limited extent in this same general area for similar problems at depths ranging from 5,000 to 17,000 ft. In the shallower wells, the cement has usually been API Class A where the salt functions as a retarder, and in the deeper wells API Class E cement is used with the additional salt advantage being its increased slurry weight and inability to dissolve salt stringers. A considerable number of squeeze jobs have also been done on older wells using the salt-saturated slurries with very good results. MID-CONTINENT In North Texas, salt-water slurries have been used for cementing the Woodbine sand, Strawn sand, KMA sand and Pettit lime. Shales surrounding these formations have created the same difficulty in obtaining separation of producing zones that has been the problem in other areas. Depths in this area range from 3,400 ft for the Strawn to 7,400 ft for the Woodbine, and concentration of salt has varied accordingly. In the deeper wells, where retardation is desired, saturated salt-water cement is used; for the shallower wells, in order to provide shorter waiting-on-cement times, the amount of salt has been 18 per cent by weight of the mixing water. Results have been excellent with no reported failures on any of the salt cement jobs; where acoustic bond logs have indicated indifferent bonds previously, they are indicating very good bonding for the salt slurries. In Oklahoma various shales of Pennsylvanian age exhibit a high degree of sloughing in the presence of fresh water, causing severe washouts above and below sand formations which it is desired to isolate. This situation exists to some degree in practically all parts of Oklahoma and includes formations of other ages such as the Wood-ford shale. For the past few years, salt-saturated cements and displacement rates as high as practical have been used as a remedy for this problem, with very good results. The Layton and Bartlesville formations are two examples of shaly sands where saturated slurries have been helpful. In one area where five wells were drilled through this type of problem shale without obtaining a satisfactory primary cement job, a change was made to salt-saturated cement preceded by a suitable chemical wash for the drilling mud involved. Acoustic bond logging indicated excellent bonding, and final completion bore out this result by being trouble-free. This type of slurry has also been used extensively on squeeze jobs where shales have been heaving around the producing formations. Predominantly, the basic slurry has been either API Class A cement or a pozzolan cement—although, as deeper wells are being drilled, the use of salt in Class E cement is also increasing. Salt cement in West Texas has been used primarily to help prevent channeling through the shales around the Delaware sand, Queens dolomite and Hope lime. Many of the shaly and dirty sands of this area are sensitive to the filtrate from a fresh-water cement. Salt at 16 to 18 per cent by weight of mixing water has been added to centent, and has been effective in controlling formation damage and communication between zones in these formations. Use of these lower salt concentrations is dictated in this area by the relatively low formation temperatures where retardation of the slurry would create unduly long waiting-on-cement times. Also, quite a bit of cementing has been done in this area using salt concentrations in the accelerating range— that is, 2 to 5 per cent by weight of water. Specifically, these concentrations have been used in coiljunction with high percentages of gel to overcome the retarding effect of the calcium lignosulfonate dispersant, although there are probably several shales where these concentrations could provide some degree of formation stability. On several occasions, the salt has also been used to lower the critical velocity or rate for turbulence with the slurry, particularly in the pozzolan cements. On wells in the Hope lime, it has usually been necessary to squeeze the shale above and below the lime to get a water-free completion. Use of salt-saturated slurries has largely eliminated this

By Robert Pike

THE first authentic description of an iron bath for the deposition of iron is probably that of Bottger in 1846, who used a bath containing ferrous sulfate and ammonium chloride. In 1861, Kramer deposited iron from ferrous chloride solution. Electrolytic iron was produced in 1.869 by Bietz, who used it for making some magnetic tests. In the same year, Klein is said to have worked out his process. Jacobi1 in 1869 described the results obtained in electroplating with iron on copper for making dies and plates for bank notes, by Klein's process. A letter from Klein to Jacobi describes the bath more fully. It consisted of FeSO4 + (NH4)2S04. Lenz2 described ?some properties of electrolytically precipitated iron. He used Klein's bath, FeSO4 + MgSO4 + MgCO3, to neutralize and obtained fine-grained and hard iron. His conclusions were as follows: 1. Electrolytic iron and copper contain gases, notably hydrogen. 2. The volume of gas absorbed by iron varies within wide limits, but it is easy for iron to take up very considerable quantities of gas. 3. The absorption of gas is principally in the first formed layers of iron. 4. When iron is heated, gas begins to come off below 100°, principally hydrogen. 5. Heated to redness, reduced iron oxidizes in water, in part at least at the expense of the oxygen of the water, decomposing it and setting free hydrogen, which is partly or wholly absorbed. Siemens,3 in 1889, was the first to propose a general process embodying a step for leaching a sulfide mineral with ferric chloride or sulfate and a step for regenerating the leach and depositing iron on a cathode in a diaphragm cell. So far as is known, Siemens did not carry out his patent

Jan 1, 1930