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By Richard Pearce

IN looking around me for some subject on which to frame an address for this meeting, it has occurred to me that some results of observation and investigation, in regard to the varied conditions under which gold is found, may possibly prove of interest. The subject is one which frequently crops up in discussions at our meetings, but there is always an immense amount of uncertainty expressed as to the actual condition in which the gold exists in any particular ore. It follows, therefore, that any light which might be shed on this rather complex subject, would be of value to science and of service to mining and metallurgical practice. In some investigations which I have, from time to time, been led to make, for the purpose of determining to what extent an ore might be concentrated, I have been astonished at the very varied and apparently inexplicable results encountered, and have been naturally led to inquire into the causes for such seeming inconsistency. The mines of Gilpin county, Colorado, where gold was first discovered in that State, furnish an infinite variety of examples of its occurrence, and it was here that difficulties first presented themselves to the Colorado miners, in the sudden transition from what is called " free-milling gold-ore " to an ore characterized by properties which make the ordinary treatment by amalgamation stamp-mills utterly impracticable. So long as mining was limited to what might be called the zone of oxidation in the veins, just so long might amalgamation be conducted without difficulty; but directly the miner reached a point beyond the influence of the oxidizing power of the surface waters, the gold resisted all attempts at amalgamation, and recourse • was had to smelting.

Jan 1, 1890

By Murray F. Hawkins

One problem of reservoir engineering is the early estimation of the size of newly discovered reservoirs. Often these reservoirs are the expansion type in which sizeable pressure drops occur incident to the production of small fractions of the oil reserve, above the bubble point, and a material balance equation may be solved to find the reserve. The early form of this equation' considered only the compressibility of the oil. Later Hall2 showed that the compressible nature of the formation rock is a significant factor in production above the bubble point, and he presented a new equation which includes a formation (rock) compressibility term. This note presents a further extension of the material balance equation as applied to volumetric, unsat-urated reservoirs above the bubble point by including a term for the presence and compressible nature of the interstitial water. DERIVATION OF EQUATION During a decline in average reservoir pressure, ?p ?p, — p1 the initial reservoir volume V,, will decrease to some value V, due to the reduction in pore volume as a result of a decline in the hydrostatic pressure within the formation, and v, = V,, [l — cr ?p]......(1) The formation compressibility c, is expressed in terms of change in pore volume per unit pore volume per psi. Simultaneously the connate water within the formation expands from an original volume V,, = S,V,, to a new volume V,, V, = s,v,, [I + c,npl.....(2) The difference [Vp — V,] is the hydrocarbon pore volume at pressure p and may be equated to the volume of the remaining oil, or [N — N,] B, = V,,, [I - C~A;] - S,.Vpi [l + cwnjl.........(3) But the initial oil in place in terms of the initial reservoir volume, connate water, and formation volume factor is Ilividing Equation 3 by Equation 4 eliminates V,, to give,

Jan 1, 1956

By G. C. Gould

The nature of freckle segregation is determined by chemical analyses, microradiograplzy, and electron microprobe. In addition, the influence of chemistry variation on freckle formation is studied in laboratory experiments. It is demonstrated that controlled laboratory solidification can produce freckle segregation. "FRECKLE" segregation is a discontinuous, rod-like segregation observed in vacuum consumable -electrode ingots. Figs. 1 and 2 show this segregation as pencil-like, dark etching areas of segregation found in longitudinally and transversely sectioned consumable-electrode ingots. In most cases the segregation is perpendicular with respect to gravity and parallel to the longitudinal axis of the ingot. The segregation is most often encountered at or around midradius in large vacuum consumable-electrode ingots. The austenitic alloys, A-286* and 718, † have shown particular susceptibility to this mode of segregation. The origin of these rodlike pockets of segregation is not well-understood. It has been suggested that the segregation is a result of a portion of the electrode dropping off and passing through the arc un-melted. On the other hand, smeltzer1 has demonstrated the freckle segregation in A-286 to be comprised of low-melting constituents relative to the matrix melting point. The discontinuous nature of the segregation is the most perplexing facet of the freckle-segregation problem. It was to gain some insight into this part of the problem that this work was undertaken. I) PROCEDURE At the outset of the work identification of the phases present and the elements concentrated in the freckle areas was undertaken. The electron micro-probe was used to determine general enrichment as well as -specific phase chemistry. Microradiography using cobalt and chromium radiation was also used on the freckle areas again to determine the elements involved in the segregation. X-ray diffraction patterns were made from portions of these same foil specimens. Optical microscopy and Knoop hardness measurements were also used

Jan 1, 1965

By John T. Norton, V.G. Mooradian

The diffusion of metal atoms into the crystal lattice of another metal and the assumption of regular positions to form a homogeneous alloy are some of the most fundamental phenomena of structural metallurgy. The mechanism of this process has been the subject of a great deal of study from many viewpoints, but the picture is still far from complete. It is generally believed that if one metal is to diffuse into another, the first must have some solubility in the second1. This means that the solvent must be able to accommodate the stranger atoms, either on points of its own lattice or in the interstices between, without losing its own crystal-lographic identity. It is also a general observation that cold-working is a distinct aid in the diffusion process, causing it to take place with greater rapidity at the same temperature or with the same speed at a lower temperature. There is considerable doubt, however, as to the real significance of the deformation in its effect on the diffusion mechanism. Several factors associated with the cold-working may be responsible for the increased diffusion rate. The plastic deformation causes a distortion of the solvent lattice, which may be an aid in the assimulation of atoms of another kind. There are many references2 in the literature that suggest that some distortion or "loosening" of the lattice is necessary for atomic migration and that diffusion cannot take place in the undis-torted lattice. On the other hand, it may be that the cold-working causes an increase in surface of contact between the two metals through fragmentation or provides a more intimate contact that is necessary for diffusion. If it is true that lattice distortion is an important factor in diffusion, it seems as if there should be some particular relation between

Jan 1, 1935

By V. G. Mooradian, John T. Norton

The diffusion of metal atoms into the crystal lattice of another metal and the assumption of regular positions to form a homogeneous alloy are some of the most fundamental phenomena of structural metallurgy. The mechanism of this process has been the subject of a great deal of study from many viewpoints, but the picture is still far from complete. It is generally believed that if one metal is to diffuse into another, the first must have some solubility in the second1. This means that the solvent must be able to accommodate the stranger atoms, either on points of its own lattice or in the interstices between, without losing its own crystal-lographic identity. It is also a general observation that cold-working is a distinct aid in the diffusion process, causing it to take place with greater rapidity at the same temperature or with the same speed at a lower temperature. There is considerable doubt, however, as to the real significance of the deformation in its effect on the diffusion mechanism. Several factors associated with the cold-working may be responsible for the increased diffusion rate. The plastic deformation causes a distortion of the solvent lattice, which may be an aid in the assimulation of atoms of another kind. There are many references2 in the literature that suggest that some distortion or "loosening" of the lattice is necessary for atomic migration and that diffusion cannot take place in the undis-torted lattice. On the other hand, it may be that the cold-working causes an increase in surface of contact between the two metals through fragmentation or provides a more intimate contact that is necessary for diffusion. If it is true that lattice distortion is an important factor in diffusion, it seems as if there should be some particular relation between

Jan 1, 1935

By H. I. Aaronson, H. A. Domian

The self-diffusivity of Ag10 has been measured as a function of temperature and composition in AgMg. a CsCl-type intermetallic compound with a substitutional defect structure on both sides of the stoichiometric (50 at. pct Mg) composition. These measurements show that In D increases linearly, and both In Do and Q decrease linearly with deviation from stoichiometry. The slopes of these lines are significantly steeper in magnesium-rich alloys. Equations for the variation of Q with composition have been derived by application of the theory of random walk processes on the assumption that diffusion in compounds of this type takes place by the six-jump cycle mechanism of Huntington, Elcock, and McCombie. The favorable agreement obtained with experiment furnishes fresh support for the correctness of this assumption. A principal result of this treatment is that. although the concentration of vacancies is considerably higher in the silver sublattice than in the magnesium sublattice, the acfivation energies for movement of the magnesium sublattice vacancies are so much lower that these vacancies are responsible for effectively all diffusion of silver in this compound. A tendency for vacancies of both types to be kinetically bound to wrong atoms is also noted. THIS study was undertaken to examine the influence of substitutional defects upon self-diffusion in an intermetallic compound, AgMg, with a CsCl-type crystal structure. The CsCl structure is exception- ally simple. At the equiatomic or stoichiometric composition in a binary alloy, it consists of two interpenetrating simple cubic sublattices, each of which is exclusively populated by the atoms of one species. When atomic size and other factors are favorable, deviations from stoichiometry can be entirely accommodated by the substitution of atoms of the species present in excess of 50 at. pct on the sublattice of the other species on a one-for-one basis. Under this condition, the only vacancies present are those formed by thermal activation. The excess atoms thus incorporated into the sublattice of the minority species may be considered as substitutional defects in this sublattice. Several X-ray studies have shown that the defect structure of AgMg is entirely of the substitutional type on both sides of the stoichiometric composition.1"3 The thermodynamic investigation of Kachi indicates that, aside from a low level of thermal disorder and these constitutional defects, order is maintained to the solidus temperature. This compound is therefore a particularly useful vehicle for a study of the influence of substitutional defects upon diffusion kinetics. Other advantages of AgMg for this purpose include: the broad composition region, as much as approximately 10 at. pct on either side of the stoichiometric (50 at. pct Mg), in which the compound is stable; the comparatively low temperature range of the solidus (820°C and below),5 making diffusion anneals near this range experimentally convenient; the reasonably good machinability of the compound, permitting utilization of the standard sectioning method of radiotracer analysis; and the availability of a good tracer, A for one of the constituent species. While this investigation was in progress, Hagel and westbrooks reported data on the self-diffusion

Jan 1, 1964

By G. V. Jere, C. C. Patel

Chlorination of the various constituents of ilmenite by different chlorinating agents in presence of various reducing agents, have been considered on the basis of the standard free energy and standard enthalpy changes as a function of temperature. The standard free energy change considerations show that it is beneficial to chlorinate ilmenite by chlorine in the presence of carbon and also that iron constituent of ilmenite can be preferentially chlorinated by clzlorine, titanium tetrachloride or their mixture. These findilzgs have been corroborated from the published work. METALLURGICAL processes involving the use of titanium tetrachloride have gained in importance because of the use of the latter in the manufacture of titanium metal. Since ilmenite is more abundant in nature than any other titanium mineral, the future of the metallurgical processes depends on the utilization of ilmenite for the production of titanium tetrachloride. In these laboratories, investigations have been carried out on the chlorination of ilmenite under a variety of conditions.1'2 During these studies, it was noticed that 1) preferential chlorination of iron was effected at low temperatures (400° to 600°C) and at low carbon content (6 to 7 pct), 2) carbonyl chloride retarded the chlorination of iron oxides and titania perceptibly, while 3) carbon-tetrachloride, compounds of sulphur and some other catalysts favored the chlorination. Moles3 has found that oxides of iron are chlorinated in preference to titania at high temperatures, while wilcox4 has claimed the preferential chlorination of titania between 1200" and 1500°C. It has been shown in this paper that preferential chlorination of titania claimed by Wilcox is not likely to occur. Daubenspeck and coworkers5,6 have claimed the preferential chlorination of iron by chlorine or by a mixture of titanium tetrachloride and chlorine between 700° and 1050°C in the absence of carbon. Even when plain titanium tetrachloride is employed as the chlorinating agent, pascaud7 noticed the preferential chlorination of iron and other oxides. The purpose of this paper is to explain from thermodynamical considerations, the various chlorination reactions studied so far. ILMENITE CONSTITUENTS AND THEIR CHLORINATION PRODUCTS Although the general composition of the ilmenite mineral is represented as FeTiO,, most of the ilmenites found in nature have variable quantities of TiO2 (44.6 to 64 pct), FeO (4.7 to 36 pct) and Fe2O3 (6.9 to 28 pct).8 The higher content of ferric iron in ilmenites was attributed by Millerg to the presence of arizonite (Fe2O3.3TiO2). But the X-ray studies by Overholt, Vaw, and odd" have shown that arizonite is a mixture of haematite, ilmenite, anatase, and rutile. Except for the anatase, similar views have been advanced by Lynd, Sigurdson, North, and Anderson8 from magnetic, X-ray, and optical and electron microscope studies. The ilmenite ores can, therefore, be assumed to consist of mineral aggregates of ilmenite, rutile and haematite. From the free energy of formation of ilmenite (FeTiO3), it has been shown by Kelley, Todd, and King11 that ilmenite is stable even up to its melting point (1367°C) and would not undergo decomposition into its constituent oxides. Schomate, Naylor, and Boericke12 have found that in the presence of a reducing agent the iron constituent of ilmenite is selectively reduced. The reaction of chlorine with ilmenite in presence of a reducing agent can, therefore, be synonymous with that of the reaction of chlorine with the constituents of ilmenite, viz., TiO2, FeO, and Fe2O3. Most of the reaction products of chlorination of ilmenite in the presence of reducing agents will be in equilibrium with their dissociation products, depending on the temperature. The titanium tetrachloride is, however, quite stable up to 1500°C due to its covalent nature. The equilibrium for the ferric chloride system has been investigated by Kangro and Bernstorff, 13, schafer14 and Kangro and petersen,15 and the results are summarized in Fig. 1, curves a, b, and c respectively. From these results, it is clear that the ferric chloride disociates as follows: 324° to 700°C FeaCl6(g) ?2FeCl2(c) + Cl2(g) [1] 324°to 900°C Fe2Cl6(g) =2 Fe Cl2 Reaction [I] (curve a) occurs in the forward direction to about 6 pct at 400°C but falls off very rapidly with increase in temperature and beyond 600°C, it is practically negligible, perhaps due to the formation of the stable monomer, FeC13(g). As the temperature is further increased, the amount of FeCl,(g) in-

Jan 1, 1961

By R. E. Hudrlik, G. W. Preckshot

The diffusion coefficients of silver from solid silver in molten lead were measured to within ± 0.8 pet in a columnar type diffusion cell ower, the temperature range of 326° to 530°C. Fick's law describes the process up to 530°C where the laminar mechanism appareltly breaks down. These is negligible resistance at the interface as shown by mathematical analyses. The diffusion coefficients are found concentration independent. IT would seem that diffusion in liquid metals would be free of such effects as molecular structure, dissociation. polarization. and compound formation. This view was taken by Gorman and preckshot in their study of diffusion of copper from solid copper into molten lead. They reported diffusion coefficients which were independent of the concentration over the range of 478° to 750°C. They found that the Stokes-Einstein equation with constant radius of the diffusing specie represented the diffusion data better than Eyring's rate theory equation and Sheibel's correlation. The radius of diffusion was found to be that of the doubly charged copper. There appeared to be no resistance across the solid-liquid boundary. In the present work the diffusion coefficients for silver in liquid lead were measured over a range of temperatures of 350° to 505°C. The solubility of silver in lead over the range of 303° to 630°C was also obtained. These results are compared with calculated or correlated values or with data in the literature. EXPERIMENTAL Procedure—The experimental equipment techniques and procedures were those reported in detail by Gorman and preckshot9 and will not be repeated here. Measured values of WT, Co, A. L were obtained for various diffusion times and the diffusion coefficient was computed for the case of no resistance at the interface9, 11 by: WT/CoAL = 1- 8/p2 n=1 1/(2n - 1)2 exp[-(2n - 1)2p2 Dt/4L2] [1] or where there was resistance at the interface by: WT = 1- ?n=1 2h2/ap2L [sxp [-Dan2t]/[(h2 + an2) L + h] The roots an are those of the transcendental equation3 tan (an L) = Iz/cun. The diffusion coefficient is that defined by Hartley and Crank.7 The total silver in the lead cylinder and equilibrium slug was determined by a cupellation technique' with proper correction for losses. Analysis of known samples showed that this method is surprisingly accurate. The amount of silver in the lead adhering to the silver cylinder was obtained in the same fashion as shown by Gorman and preckshot.9 The small errors involved in this determination are not critical since the silver in this adhering lead layer is only 3 to 15 pet of the total diffused. Materials—Electrolytic silver containing 99.9+ pet Ag obtained from General Refineries of Minneapolis, Minn. was used for all but runs 7 and 8. For the balance of the runs this silver was reduced with hydrogen at 1100°C and its oxygen content was found to be about 0.017 pet. For the runs. 7 and 8, phosphorous-reduced silver of the same purity was obtained from Handy and Harman Co. of Chicago, Ill. The densities of the phosphorus-reduced silver and the hydrogen-reduced electrolytic silver were 10.484 and 10.487 g per cm3, respectively. These values agree with those reported for pure silver. Silver which was reduced at 900 C had an average density of 9.998 g per cm3, indicating porosity. This silver was used for a number of runs which were not tabulated in Table I. These are indicated by crosses on Fig. 2. The 99.999 pet Pb was obtained from the National Lead Co. Research Laboratory of Brooklyn, New York. DISCUSSION OF RESULTS The diffusion and solubility results are reported in Table I for eleven runs using either phosphorus-reduced electrolytic silver or hydrogen-reduced silver at 1100° C. The solubility data shown in Fig. 1 show the excellent agreement with that reported by Heycock and Neville.8 The data of Friedrichs5 apparently are in error. The experimental solubility data of this work are reported to 0.3 pet. The experimental diffusion coefficients computed from Eq. [1] are reported within 1.2 pet of the mean and are plotted in Fig. 2. These are expressed within +0.8 pet of the experimental values over the entire temperature range by: D= 8.26 x 10 -5 e-1925/RT . [3] There appears to be little difference due to the

Jan 1, 1961

By D. G. Westlake, D. T. Peterson

The saturation solubility of thorium dihydride in thorium was studied by saturation of samples and subsequent analysis. The solubility increased from about 1 at. pct at 300°C to above 20 at. pct at 800 °C. Over this temperature range the log of the solubility was a linear function of the reciprocal absolute temperature for thorium of good purity. The heat of solution of thorium dihydride was found to be 7.9 kcal per atom of hydrogen in crystal bar thorium and 6.6 kcal per atom of hydrogen in Ames thorium, The important effect of hydrogen on the physical and mechanical properties of many metals is receiving increasing recognition. The basic physical and chemical data necessary to help explain the observed effects of hydrogen on the mechanical proper ties of metals are all too often not available. The solubility of hydrogen in thorium metal was determined to provide a portion of this basic data for the thorium-hydrogen system. The absorption of hydrogen by thorium metal and the formation of thorium hydrides was studied by several investigators, beginning in 1891, and their work is summarized in Gmelin's Handbuch.1 No effort was made to determine the extent of solid solubility in the metal in these early investigations and the impure metal available made interpretation of the results uncertain. Nottorf2 reported the results of a careful study of pressure-composition isotherms for the thorium-hydrogen system. The principal interest in this work was in the composition and dissociation pressures of the thorium hydrides. Mallett and campbel13 reported the pressure-composition isotherms for the thorium-hydrogen system up to the composition of thorium dihydride. The saturation solubility of thorium dihydride in thorium was reported to be 13 at. pct at 650°C and 23 at. pct at about 900° C. Mallett and Campbell used thorium metal which had been prepared by the calcium reduction of thorium tetra-fluoride or thorium oxide. The results obtained with thorium of these two types agreed within the experimental error. PROCEDURE AND MATERIALS Procedure—The method used to determine the solubility was to saturate a sample of thorium with hydrogen and analyze a portion of the saturated sample. This method was chosen rather than a determination of pressure-composition isotherms since it was much less time consuming and could be applied at temperatures at which the equilibrium hydrogen pressure was too low to measure. The

Jan 1, 1960

By Fred D. DeVaney

MINNESOTA taconites are extremely hard, and fine grinding is required to produce an acceptable concentrate. To reduce grinding costs, waste material is rejected by magnetic separators as soon as it is liberated. Cyclones are now used in all Minnesota taconite plants to close the grinding circuits. Erie Mining Co. installed its first grinding section at Aurora, Minn., in 1948-a 9 ½ x12-ft. mill and a fine grinding section consisting of a 10 ½ x12-ft ball mill in closed circuit with a duplex 60-in. spiral classifier. Concentrates from the magnetic cobbers treating the rod mill discharge passed directly into the classifier; the ball mill discharge was also treated in magnetic separators and the concentrate from these machines also went to the spiral classifier. Both concentrates passed through ac demagnetizing coils. It is axiomatic that for proper classification the material in suspension must be well dispersed, and it follows that magnetic concentrate must be almost completely depolarized if classification is to be successful.

Jan 8, 1957

By Alfred Weiss

Daniel C. Jackling's innovative concept for handling low grade ores ushered in a new philosophy of open pit mining. As one of the greatest minemakers of all times he revolutionized major segments of the industry and helped strengthen US defense efforts during World Wars I and II by making possible the tremendous copper supplies from US mines. Many great mining men have since followed in his footsteps with their discoveries of new orebodies or development of new mines. Their brilliance in leadership can also be traced to the coupling of a new idea to the physical nature of the materials in the earth's crust or to the extractive stages of minerals recovery. The minerals industry is now in another era of change and must again devise techniques to meet the challenge. The task is not only to create new exploration techniques and develop new mining methods, but, I believe, to optimally apply new concepts and tools in daily decision-making.

Jan 11, 1978

By D. A. Elgillani, M. C. Fuerstenau, M. C. Kuhn

The species responsible for flotation when xanthate is added as collector for pyrite is dixanthogen. Measured oxidation potentials of these systems show that xanthate should be oxidized to dixanthogen, and the presence of dixanthogen on the pyrite surface is confirmed by infrared absorption. Zeta potential measurements are presented and related to collector adsorption. In spite of the normal presence of pyrite in most sulfide ore deposits, only a modest amount of study has been devoted to the xanthate-pyrite flotation system in the absence of activators and depressant~.'-~ As a result, little is known about the mechanism of xanthate adsorption on pyrite. From the few studies that have been made, however, a number of significant observations have been forthcoming. For example, the dependence of flotation response on the state of oxidation of the surface was noted in two studies — one conducted by Plante and Sutherland4 and a later one by plaksin.~ In another study, Gaudin and wilkinson3 found that ferric xanthate was not present on a pyrite surface. In a later investigation, however, Gaudin' and his colleagues did extract a small amount of ferric xanthate into benzene when pyrite was ground in an evacuated mill with water, benzene, and xanthate. This quantity was apparently

Jan 1, 1969

By J. H. Anderson, G. A. Parks, B. K. Jindal

Both temperature and humidity are important variables in electrical separations. By independent control of temperature and water vapor pressure, it is shown that charge depends primarily upon relative humidity, not on temperature or water pressure alone. All the effects of temperature changes other than modification of humidity are apparently small. However, humidity control can be achieved through manipulation of the more tractable variable, temperature. Both temperature and humidity are important variables in electrical separations. Some of their effects have been described in general by Fraas1,2 and by Ralston.3 The influence of temperature and humidity may be considered a problem in industrial separations because humidity, especially, is not normally controlled, hence leads to unpredicted quality control problems. The problem is significant whether the separation is based on conductivity differences or on contact electrification. There is no doubt that water adsorbs from humid atmospheres onto mineral surfaces resulting in conductivity changes.'-8 An empirical relationship between conductivity and humidity is1.4-6,8 where a and b are constants peculiar to the substrate, and s and h are the conductivity and relative humidity respectively. Some authors have taken advantage of differences in a and b among minerals to make or propose electrodynamic separations in which h is the key control variable. Fraasl,2 reported that the charge developed on quartz and feldspar through contact with aluminum is sensitive to humidity, as illustrated schematically in Fig. 1. Lawver9 found that the charge developed by quartz on contact with several materials was tem-

Jan 1, 1967

By H. J. McQueen, G. C. Kuczynski

ThE useful properties of k6-Alfenol and the thermenol alloys (summarized by J. E. Nachman and W. J. Buehler') have encouraged research into those alloys which, having compositions near 25 at. pct Al, 75 at. pct Fe, undergo an ordering transformation between 500° and 550°C. The equilibrium diagram of the iron-rich iron-aluminum alloys was first determined by Bradley and Jay.2,3 They distinguished three structures: the disordered, which is bcc; FeAl, which is simple cubic with one Fe atom and one Al atom per lattice site; and Fe3Al, which is fcc with three Fe atoms and one Al atom per lattice site. This last structure may be conceived as eight body-centered cubes with Al atoms at the centers of alternate ones, so that Al atoms have only Fe as first and second nearest neighbors. Later, Osawa and Murata4 determined the boundaries of the different superlattice regions in the iron-rich Fe-Al solid solution by dilatometric and X-ray methods. Two of the six phases, which they found between 0 and 50 at. pct Al, were never identified by other workers. A. Taylor and R. M. ones,' concurrently with and independently of this research, redetermined this diagram by measuring lattice parameters at temperature. Further reference will be made to their results. EQUILIBRIUM DIAGRAM A) Experimental Procedure—The alloys were prepared from NRC gas-free iron (99.9 pct Fe) and 99.99 pct Al. They were melted in alumina' crucubles under vacuum in an induction furnace. If the ingots were unsound or showed more than a 3 pct weight loss, they were rejected. The ingots were homogenized at 1100°C for 24 hr before hot-rolling at 700" to 900°C from 1 in. to 0.25 in. thick. It is interesting to note that alloys containing more than 28 at. pct Al were able to take an 80 pct reduction of area in the ordered FeAl region. The dilatometer specimens and specimens for chemical analysis were cut from these plates. A Leitz dilatometer was used to measure the coefficient of linear expansion as a function of temperature. The specimens were slowly cooled from 900" to 300°C where they were annealed for 10 hr before slowly cooling to room temperature. The expansion was recorded photographically as the alloys were heated and cooled at 1.5oC per min between 100" and 1000°C. The magnetic measurements determining the Curie points were performed on the dilatometer specimens in the dilatometer, by using direct current in the furnace windings both to heat the specimen at 1.5°C per min and to serve as the primary coil. The regular specimen holder was replaced by a thin alundum tube on which was wound, as a secondary, a closely spaced coil of fine copper wire. A reversal of current in the furnace windings produced, in the secondary, an emf which was proportional to the induction in the specimen, and which could be detected on a galvanometer. In this way, it was possible to determine the Curie points of alloys to within * 5°C. B) Results and Discussion—The coefficients of linear expansion, as obtained from the dilatometer curves, are plotted as a function of temperature and composition in Fig. 1. Since in many cases the heating and cooling curves were superimposed, it was decided to measure slopes of heating curves only. Definite high peaks, due to the transformations, were observed on each curve between 400" and 520°C, and, for alloys containing more than 23 at. pct Al, a second set of smaller peaks at temperatures above 660°C. The sharpness of the peaks indicates that ordering to Fe3Al is a first-order reaction. The compositions and the temperatures of these peaks are listed in Table I. When these temperatures are plotted as a function of the composition, the result is the constitution diagram presented in

Jan 1, 1960

By R. E. Goodman, M. A. Mahtab

The, state of stress around a vertical wellbore in rock following nonlinear stress-strain laws is examined by means of finite element analysis. The wellbore, is considered an axisymmetrier body with axisymmetric loading. The initial vertcal and borizontal stresses are "locked" in the rock elements around the wellbore and a new state of stress is generated by the displacements which occur around the borehole. A point-uise variation of the elastic moduli is made on the basis of the new stress state and the triaxial data. The initial stresses tire now reintroduced along with tile changed moduli and original boundary constraints. This procedure is repeatrd until convergent stresses are reached. The effect of nonlinearity on streases is examined for a 6,000-ft wellbore in a scbistose gnezss and Berea sandstone using results of laborratory triaxial compression tests. The results sbou that the effect is restrited to one well radius from the bottom periphery of the bole. Beyond a distance of one-quarter radius, the elfect of nonlinearity on stresscs IS almost always less than percent for the cases conszdered, The consideration of a static pressure inside the well does not magnify the effect of monlinearity on borehole stresscs. INTRODUCTION The terms " wellbore" and "borehole" here designate cylindrical openings in the ground with vertical axis and a circular cross-section. A knowledge of the stress redistribution that occurs on excavating a wellbore is important in understanding (1) the behavior of the lined or unlined hole, (2) hydraulic fracture response, and (3) the effect of stress redistribution on drillability; also it is important in predicting initial stresses in the virgin ground, and in analyzing the response of measuring instruments placed in the borehole. Our knowledge of the state of stress around a wellbore has been restricted to homogeneous, isotropic, elastic material and derives chiefly from the analysis by Miles and Toppingl and the photoelastic work of Galle and Wilhoit2 and Word and Wilhoit.3 In this investigation the state of stress is examined for a nonlinear elastic material by means of finite element analysis. Many rocks possess stress-strain curves that depart notably from straight lines in their initial or final portions. While the literature contains abundant stress-strain data from triaxial tests (axisymmetric loading) on cylindrical rock specimens, there is little information on rock deformability under nonaxisymmetric loading conditions such as occur at each point around the bottom of a wellbore. Although there is some knowledge of the effect of intermediate principal stress on rock strength, there is virtually nothing known about its effect on rock deformability; therefore, we have assumed here that the effect of intermediate principal stress can be ignored. A schistose gneiss4 and Berea sandstone5 were selected as representative rocks for this analysis. The traditional graphs of deviator stress (ol -o3) vs axial strain were reworked to give the tangent modulus as a function of the deviator stress for varying values of the minor principal stress. The result is a nesting family of skewed, bell-shaped curves for tile gneiss (Fig. 1A) and the sandstone (Fig. 2A). A similar replotting of the lateral strain data defines the variation of Poisson's ratio (v) with the deviator stress and confining pressure. These curves, shown in Fig. 1B for the gneiss and in Fig. 2B for the sandstone, are not so well ordered as the tangent modulus curves. However, all of these display an increase of v with deviator stress application, but the rate of increase diminishes with confinement. The ET and v curves for the two rock types are tabulated in Tables 1A and 1A for use in a digital computer so that material properties corresponding to a given state of stress can be assigned by interpolation. STATEMENT OF THE PROBLEM Given a state of stress in the ground prior to drilling a hole (initial stresses), we assume that

Jan 1, 1969

By Ulf S. Landergren

Diffusion coefficients and marker movements have been determined in brass using welded couples. Three different concentration ranges were employed at 750°C, while a fourth concentration range was measured at 500°, 600°, 700°, and 800°C. Marker displacements toward and porosity development in the high zinc side of the couple were observed in all cases. The results were interpreted as favoring a vacancy diffusion mechanism. IN the large amount of diffusion literature which has accumulated during the past half century, very few experimental data have been presented on body-centered-cubic metallic phases. The impressive combination of experimental and theoretical studies which has given the vacancy mechanism a fairly secure position as the preferred mechanism for most face-centered-cubic metals has no counterpart for body-centered-cubic phases, although the theoretical picture seems to be in a better state than the experimental work. The attempts to select diffusion mechanisms by the theoretical calculation of the activation energy for the various conceivable unit diffusion processes and the energy of formation of the type of lattice defect required have been based on models of two kinds. The first kind utilizes potential functions fitted for certain properties of pure crystalline copper; the second kind is fitted for sodium. The latter is an example of an open metal in which the metallic ion is small compared with interatomic distance,&apos; while the former is characteristic of the larger class of metals in which the ions have diameters about as large as the interatomic distance. brass should resemble copper in this fundamental property. It should be evident that results on the mechanism of diffusion obtained for one of these classes need not necessarily apply to the other. Huntington and Seitz, using a model of the copper type, showed that the activation energies to be expected for interstitial migration or a two-atom direct interchange were much higher than that for vacancy diffusion. Zener pointed out that a four-atom ring rotation would involve an activation energy considerably lower than the two unlikely mechanisms although still higher than the vacancy mechanism in the face-centered-cubic structure. Furthermore, he argued, the four-atom rotation would be relatively easier in a body-centered-cubic lattice and might be competitive with the vacancy mechanism. Paneth showed that a body-centered-cubic crystal-like sodium could form interstitial defects of special type, called a crowdion, by crowding an extra atom into < 111 > directions where the defects would affect a line of about eight atoms. The defect was constrained to move along the defining line. Unlike the face-centered-cubic case, therefore, the theoretical calculations for the body-centered-cubic mechanism do not provide a very clear-cut answer, and the absence of adequate experimental studies is the more serious. This investigation was undertaken for the purpose of obtaining useful information on diffusion in body-centered-cubic phases. brass was chosen for several reasons: 1—the phase field is sufficiently wide at high temperatures to permit the use of diffusion couples with adequate concentration ranges for satisfactory chemical analysis, 2-—thermodynamic activity data are available for the calculation of mobilities from diffusion coefficients, 3—the phase is as close to the theoretical model of the copper -type on which the calculations have been done as any body-centered-cubic metallic phase is likely to be. Measurements of the movements (if found) of inert markers during the diffusion process would indicate that a vacancy or Or mechanism played a major role in diffusion in brass. If no marker movement should be found, a ring mechanism would be indicated but not assured. Experimental Procedure The alloys used in these experiments, listed in Table I with analyses, were supplied by the Naval Research Laboratory. They were from ingots of 3x3 in. cross-section, heated to 760°C, reduced under a

Jan 1, 1957

By P. Greenfield, P. A. Beck

RECENT work by J. Darby, Jr. in this laboratory has shown that the reported vanadium-rich limit of the s phase in the Co-V system at 1200°C is in error. The appearance of a second phase in s actually is restricted to alloys containing over 68 atomic pct V. The error in the original value is due apparently to a reaction that takes place along the numerous cracks in the s specimens between the alloy and the impurities present in the He + 8 pct H atmosphere in the annealing furnace. Such a reaction and the consequent appearance of a second phase can be suppressed if the alloys are sealed under vacuum in Vycor tubing. The new value of 68 atomic pct V for the vana-dium-rich limit of the s phase in the Co-V system effects slightly the s compositions calculated from average values of N, and N,. for various s phases. The standard deviation between experimental mean compositions and those calculated from the assumption that s is characterized by a constant number of 3d + 4s electrons per atom (N,), is slightly reduced from 9.1 to 8.8 pct. The maximum divergence for the V-Mn s phase is reduced from 15.5 to 14 atomic pct. The standard deviation calculated from constant electron vacancy numbers given by N.. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2(Fe) + 1.71(Co) + 1.6(Ni) is now greatly reduced, as the maximum divergence for this correlation previously occurred in the V-Co system. This maximum divergence is reduced from 7.6 to 2.3 pct, and the standard deviation for all s- phases is reduced from 4.1 to only 2.9 pct. The correlation for electron vacancy numbers given by N. 5.66 (V when with Ni or Co) + 4.88 (V when with Mn or Fe) + 4.66 (Cr + Mn) + 3.3 (Mn) + 2.66 (Fe) + 1.71 (Co) + 0.61 (Ni) is made slightly worse, and the standard deviation increases from 2.8 to 3.9 pct. These changes, however, do not affect the conclusions of the paper.&apos; The deviation between calculated and experimental s compositions is much less for either one of the electron vacancy correlations than for the correlation with the number of 3d + 4s electrons.

Jan 1, 1955

By Noel Cunningham

Many excellent descriptions of the mills of the Porcupine district have been written, but no discussion exclusively devoted to the metallurgical technology has been given. These notes are intended to cover this feature briefly. They are based upon 21/2 years&apos; mill operation in the district—i.e., practically since the beginning of metallurgical operations. Character of the Porcupine Ore.—There is no oxidized ore in the district, the surface having been deeply planed by glacial action in recent geologic time. The precious-metal content is about in the proportion of 85 of gold to 15 of silver by weight; hence, the silver is practically negligible. There are two classes of Porcupine ore, having very different characteristics; these will be referred to throughout this paper as Class A and Class B. Class A ore is a pure quartz with inclusions of schist. Generally it is heavily fractured and breaks down readily to sharp, hard grains, about minus 10 plus 20 mesh, requiring further comminution to release the gold. It carries very little pyrite; the gold is entirely free and apt to be coarse, but often spongy, going into solution readily on that account. This gold is 60 per cent. to 85 per cent. free milling, depending on the grade of ore. Class B ore is an iron silicate schist, strongly laminated, carrying 4 to 5 per cent. pyrite; its specific gravity is 2.8 to 3.0, depending upon the amount of mineralization. In breaking the ore in the mine, generally over 25 per cent. of material through a 1/2-in. ring is made; the ore readily breaks down in milling and makes a comparatively large amount of non-crystalline slime; owing to its high specific gravity, however, it is quick settling. In my opinion, the gold in this ore is free, but so finely divided that it will neither pan nor amalgamate; it appears to be disseminated through the rock and not chiefly associated with the pyrite. Veins of Class A ore occur with or without side walls of Class B, and veins of Class B occur unassociated with Class A; more often the veins are closely banded, Class A and Class B alternating, generally with Class B in excess. Both classes of ore are more or less blocky at times, and with reference to Class B this is indicative of low gold content.

Jan 1, 1915

By F. S. Buffington, Morris Cohen

THERE is little quantitative information available concerning the effect of applied stress, in both the elastic and plastic ranges, on diffusion kinetics. Accordingly, a program has been undertaken to determine the rate of self-diffusion in high purity iron, with the specimens subjected to stress during the course of diffusion. Results are reported here for body-centered cubic iron at a diffusion temperature of 890°C. The iron used was 99.97 pct Fe, the principal impurities being 0.002 pct C, 0.008 pct 0, and 0.02 pct Si. The surface-decrease method of self-diffusion analysis was employed, and Fe55 Mn x-radiation, 2.9 years half-life) was the tracer element. Details of specimen preparation and equipment are given elsewhere.&apos; Disks of the high purity iron, % in. diam x 1/4 in. thick, were annealed at 890°C for 18 hr in dry hydrogen to produce large grains of a ferrite. The faces of the disks were then surface ground, and possible grinding stresses were relieved by annealing at 890 °C for 45 min in vacuum. A layer of radioactive iron 0.00186 cm thick was electroplated on one face of each disk. The self-diffusion coefficient was calculated from the ratio of the radiation intensities emanating from each of these faces, as measured before and after diffusion.&apos; The heating was carried out in a vacuum furnace (10-5 mm Hg) controlled to ±1.5°C. The specimens were loaded in compression between two quartz disks during the diffusion runs by means of a lever system operating through a vacuum seal. Thus one quartz disk was pressed directly against the radioactive face of the specimen, minimizing the vapor loss of radioactive iron. Steady-state creep occurred in all instances where permanent deformation could be detected, but the specimens did not exhibit appreciable transverse barreling until natural strains of 0.2 to 0.3 were attained. Essentially, the diffusion took place under uniaxial stress. The plastic strain in each case was obtained at the diffusion zone by measuring the diameter d there before and after the run: e = 2 In — do Let Du equal the self-diffusion coefficient which would have prevailed at the given temperature if no stress had been applied. This was calculated from the temperature-dependence equation which had been previously determined: —59,800 D, = 6.2 exp ( I sq cm per sec* [I]

Jan 1, 1953

By Paul Billingsley, Augustus Locke

Certain adequately developed mining districts give complete three-dimensional patterns of ore bodies as clusters rising from roots in basement rocks with details controlled by structure of cover rocks. Examples are Goodsprings, Tintic, Bisbee, Leadville, Hedley, Eureka, Ely and Goldfield. In these and others the controlling structures in both basement and cover rock are elements of the neighboring regional structure and have been produced by rock movements in harmony with continental adjustments, which are usually steep tear faults in basement and thrust crumples in cover. Invariably the structures and movements in the districts have long geologic history and result from intersecting or superimposed deformations of different ages. Salt Lake districts show intersecting Uinta and Cordilleran elements; Colorado districts show intersecting pre-Cambrian and Tertiary elements, and Bisbee shows Tertiary superimposed on fina1 Paleozoic folding. Thus the position of districts has been determined by the patterns of North American orogenic belts, which make crossroads in Rocky Mountains and blocks of superimposed deformation in Sierra Nevada, northwest Coastand Canadian Coast Ranges. Essential function of repeated deformation is to strengthen rock, as from shale to slate to schist to gneiss, and thus make it competent to carry channels to depth with or without addition of intrusives. The essence of a mining district is the presence of such competent rocks with long-lived, deep, penetrating breaks reopened to permit passage of heat and associated products from depths to surface. It is suggested that melts such as magmas; metamorphism up to and including granitization; alteration, such as orthoclase-quartz or quartz-sericite or garnet, and also mineralization, may all be by-products of such heat escape along channels made by tectonic forces at specific foci. Magnitudes of Districts (Fig. 1) Any synthesis of ore deposits must deal with comparable units. Ore deposits are innumerable, but great ore deposits, commercially important for a generation or more, are few. The bulk of metals has come from districts of the first and second magnitudes (over $1,000,000,000 and over $250,000,000, respectively), and of these the United States and adjacent provinces of Canada and Mexico contain only 28, of which 9 are first magnitude: Butte, Coeur d&apos;Alene, Bingham, Bisbee, Sierra Gold, in the West; Tri-State, Southeast Missouri, Michigan copper, Sud-bury, in the East. Another 28 or 30 districts are of third magnitude (over $50,000,000).

Jan 1, 1941