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By B. S. Gottfried

This paper is concerned with possible transport mechanisms which occur during segregated burning (i.e., burning in an oil reservoir in which the oil-bearing formation is overlain by a "clean" porous zone containing only gas). ,Two analytical models are presented. In the first, burning is assumed to occur at the gas-oil interface, and the dominant mechanism is taken to be the rate at which oxygen diffuses to the interface. The second model assumes that combustion occurs within the clean zone, with the dominant mechanism being the mechanism of fuel deposition from the oil-bearing formation to the clean zone. ,Comparison of the results of the analyses with limited experimental data indicates that the latter mechanism is much more plausible. Both models are idealized representations of the actual process and are somewhat conjectural, however, owing to the lack of more definitive laboratory or field data. INTRODUCTION In recent years there has been considerable theoretical and experimental research directed toward understanding the recovery of crude oil by underground combustion. Although two different recovery schemes have been proposed, known as forward and reverse combustion, it is only forward combustion that shows promise of becoming a practical recovery technique.17 Most of the analyses of the forward combustion process have considered it to be pistonlike; i.e., oil is displaced by a vertical combustion zone which, with its ensuing gases, pushes die oil forward as the flame front is propagated through the reservoir.l-8,ll,l2,14-16 However, information gained in field pilot studies indicates that, at least to a certain extent, forward combustion proceeds in a segregated manner in oil reservoirs.10 An ideal segregated system is one in which the oil-bearing formation is overlain by a "clean" porous zone containing only gas. The location of the combustion zone in such a system is not immediately evident, although combustion is believed to occur either at the gas-oil interface or within the clean zone. In either case, the combustion zone may be horizontal and it moves in parallel rather than in series with the produced oil. The purpose of this paper is to explore the likely mechanisms by which segregated burning can occur, and to determine the sensitivity of the resulting models to changes in various physical parameters. Two governing mechanisms are considered: the case of a horizontal combustion zone at the gas-oil interface with the rate of combustion governed by the rate at which oxygen diffuses to the interface, and the case of combustion within the clean zone with the combustion process controlled by the transport of fuel from the oil-bearing formation to the clean zone. Both models are somewhat hypothetical and involve considerable simplification of the actual process. However, the results allow some preliminary understanding of segregated burning which is useful in the absence of more definitive laboratory or field pilot data.

Jan 1, 1967

By H. A. Bright, H. C. Vacher, J. G. Thompson

The methods employed for the determination of oxides and oxygen in ferrous materials may be roughly classed in two groups, "wet" methods and "hot" methods, the first group including the iodine, electrolytic, mercuric chloride, hydrochloric acid, nitric acid, and chlorine methods; the second group including the vacuum-fusion and hydrogen-reduction methods. The wet methods depend upon preferential solubility in a selected medium to separate the metallic portion of the sample from the oxygen-containing constituents. Subsequent analysis of the insoluble residue permits the isolation and separate determination of individual oxides and compounds. The hot methods depend upon the reduction of the oxide constituents of the sample by means of carbon or hydrogen at elevated temperatures. With the exception of the recently developed fractional vacuum-fusion method, the hot methods do not identify individual oxides and compounds but yield only a single value representing the sum of the oxygen contents of several or all of the oxide constituents present. With such diversity in the principles and aims of the different groups, it is not surprising that concordance of results by different methods has usually been difficult to obtain. The present cooperative attempt to define more rigorously than has been possible heretofore the accuracy and limits of usefulness of the various methods, originated in correspondence between Dr. John Johnston, Director of Research of the United States Steel Corporation, and other interested metallurgists. The plan was, briefly, to submit identical samples to a number of laboratories for analysis by different methods and to collate the results of these analyses. The project was endorsed by the Iron and Steel Division of the American Institute of Mining and Metallurgical Engineers at the annual meeting in February, 1933, and has been conducted under the joint sponsorship of the Iron and Steel Division and the National Bureau of Standards. The latter organization undertook

Jan 1, 1937

By J. L. Brimhall

Slip-line formation during bending has been studied on neutron-irradiated molybdenum single crystals. For equivalent strains, the slip lines are coarse and distinct in the irradiated molybdenum and not resolvable in the unirradiated molybdenum. The slip lines have been directly correlated with dislocation channels present in the irradiated and deformed thin foils. The heterogeneous distribution of the dislocations during deformation in the irradiated material results from dislocation interaction with the dejects produced during irradiation. Impurities , in the form of' carbides, affected the dislocation channeling Principally by acting as dislocation sources. ALTHOUGH the mechanical behavior of irradiated materials has been studied extensively, the precise mechanism of irradiation hardening has not been established. Some information on the microstructural species responsible for hardening of irradiated materials has been derived from direct and indirect observations. The direct observation of the structure of deformed irradiated metals, particularly by transmission electron microscopy, is a relatively new and unexplored area. Slip-line studies in fcc metals have been restricted primarily to copper.1-3 Very coarse slip lines, representing slip on many closely spaced planes, have been observed in deformed, irradiated copper. Coarse slip lines have also been observed in irradiated aluminum.4 Clear channels in irradiated copper caused by dislocation motion through the defect structure have been seen by transmission electron microscopy and correlated with slip lines.5-6 To date, little work has been reported on the irradiated bcc metals. Eyre described the slip lines around hardness indentations on irradiated iron and found them to be more distinct than lines in unirradiated material.' Mastel et al.' have observed channels in deformed irradiated molybdenum similar to those reported in copper. As part of a program concerned with the effect of neutron irradiation on metals, the slip-line

Jan 1, 1965

By Rex O. McLellan

The formation of a monovacancy in a metal is simulated in an elastic model by the displacement of the surface of a small spherical cavity in a large elastic continuum. The application of linear elasticity to this distortion results in a well- known formula for the energy and an expression for the concomitant entropy change due both to the shear strain in the continuum and also to the dilation of the solid resulting from the boundary conditions at the surface of the solid. Elastic data (the sliear modulus and its temperature coelficient) are used to calculate the entropy and energy of formation for many metals. Despite the simplicity of the assumptions involved, the agreement between the calculated entropies and energies and experimental values is remarkably good. In recent years there has been a large increase in measurements of the absolute concentration of mono-vacancies in metals as a function of temperature. Hence new data for both the energy and the noncon-figurational entropy of formation of monovacancies has become available. Recent measurements&apos; of the anomalous (non-Arrhenius) self-diffusion in many bcc metals has also focused interest on the prediction of the thermodynamic parameters of mono- and multi-vacancies in those metals for which no data are available. Damask and Dienes&apos; have discussed the various theoretical calculations of the energy of formation EL, of a monovacancy. These include simple models involving the breaking of atomic bonds on moving atoms from the interior of a crystal to the surface, models combining elastic calculations with surface-energy terms and detailed quantum mechanical calculations. The simler models give the correct order of magnitude of &, but tend to overestimate it by a factor of about two. The quantum mechanical calculations4"7 have been carried out for the noble and alkali metals with generally reasonably good agreement with the available Ef data. The calculation of entropy of formation Sfv14 lnvolves a fundamental calculation of the perturbation of the phonon spectrum caused by the creation of a vacancy. Huntington, Shirn. and wajda8 have given an approximate evaluation of sJV by considering an Einstein model for the localized vibrations in the immediate neighborhood of the defect and then using elastic theory to calculate the entropy associated with the shear stress field in the distorted crystal (as originally proposed by Zenerg). They also included a term due to the dilation of the crystal. They obtained a value of 1.47k for copper, in good agreement with the experimental value (1.50k). However, Nardelli and Tetta- manzi1° have recently shown that neglecting the coupling between atoms (Einstein Model) may lead to a serious error so the agreement may be somewhat fortuitous. In this work simple linear elastic theory is used to calculate the entropy and energy of formation of mono-vacancies. Despite the simplicity of some of the assumptions involved, the agreement with the available experimental data is remarkable. However. the reasonable degree of success in the application of linear elastic calculations to the excess entropy of a solute atom in a dilute solid solution1&apos; indicates that the application of elastic theory to vacancies. where the interaction of different atomic species is not involved, may not be inappropriate. THE ELASTIC MODEL The metal is assumed to be a spherical elastic continuum. A small spherical cavity of volume V = 4i;v:&apos;/3 is cut from the center. removed. and dissolved rever-sibly in the bulk of the material. TO a good approximation no net atomic bonds are broken and the material does not undergo a volume change although the externally measured volume of the body would increase by V. The radius of the sphere of metal is much larger than r Next a negative pressure is applied to the cavity causing its surface to be displaced inward by an amount simulating the relaxation of the lattice around a monovacancy. In this model the energy and entropy accompanying the distortion are taken as 4, and <. As a first approximation the equation of state for the solid is taken as: r = ro(i + *~D LiJ where K is the bulk modulus. P the hydrostatic pressure. Vo the volume of the material at 0°K and zero pressure. and d+/dT = 30. where 0 is the linear thermal expansion coefficient. The variation of entropy with hydrostatic pressure is given by the Maxwell equation: These equations give the entropy change resulting from increasing the hydrostatic pressure from 0 to P as: and since • we have: This is the entropy arising from the dilation resulting

Jan 1, 1970

By J. L. Taylor, P. Duwez

PARTIAL phase diagrams of titanium with iron, cobalt, and nickel have been established by previous investigators.1-3 These diagrams seem to be reliable, at least for concentrations of titanium ranging from 0 to about 50 at. pct. More recently, Long and his collaborators have presented a tentative titanium-nickel diagram covering the titanium-rich side.&apos; These various studies indicate that in each system three intermediate phases exist and correspond to the compositions Tia, TiX, and TiX2 (or TiX3). The purpose of this paper is to review the available information on the crystal structure of these phases and to give the results of additional X-ray diffraction studies. Previous Work A summary of the work of Wallbaum and his collaborators"-&apos; is presented in table I. The first intermediate phase on the titanium-rich side of the three systems, with iron, cobalt, and nickel, is of the Ti2X type and has a face-centered cubic structure. Although it is stated that the unit cell contains 96 atoms: no lattice parameters are given. The second phase is centered around the compositions TiX for the three systems. The crystal structure of this phase is mentioned in a short note" as being body-centered cubic (CsCl type), but no parameters are given. The analogy between the three systems, which is perfect as far as the two phases of the type Ti2X and TiX are concerned, disappears at the titanium-poor end of the diagrams. In the system titanium- iron, TiFe2 has an hexagonal (MgZn2 type) struc-ture with the parameters given in table I. The existence of TiFe3 has also been reported8 (table I) but was questioned by other investigators2 and is also refuted by the present study. In the system titanium-cobalt, a phase corre-sponding to the composition TiCo2 has been investi-gated by Wallbaum and Witte6 who claim that the structure is cubic (MgCu2 type) for alloys slightly deficient in cobalt and hexagonal (MgNi2 type) for alloys slightly deficient in titanium. The parameters of the two phases are given in table I. In the system titanium-nickel, the nickel-rich phase corresponds to the composition TiNi3 and has been described as hexagonal7 with the parameters given in table I. The present investigation was initiated for the purpose of filling in the gaps in the knowledge con-cerning the structure of the various phases sum-marized in table I. Since the titanium used by Wallbaum and his collaborators was only 95 pct pure,&apos; it was found desirable to redetermine the lattice parameters of the alloys prepared with a

Jan 1, 1951

By G. H. F. Gardner

The velocity and attenuation of elastic waves in sandstones were measured as a function of both pressure and fluid saturation. A large change occurs in these quantities if water is added and the rock is not compressed, but the change is small if the rock is subjected to a large overburden pressure. Measurements were made by vibrating cylindrical samples in both the extensional and torsional modes at frequencies up to 30,000 cycles/sec. Formulas were derived which enable the attenuation of dilatational waves in dry rocks to be deduced from the data. Similar experimental methods were used to investigate the properties of unconsolidated sands. Velocities were found to vary with the 1/4 power of the overburden pressure and attenuations to decrease with the 1/6 power. The effects of grain size, amplitude and fluid saturation were studied. Formulas by which the effects produced by a jacket around the sample may be calculated were derived. The practical application of these results to formation valuation is discussed. INTRODUCTION The attenuation of elastic waves in the earth has been of interest to the seismologist and geophysicist for many years, but only recently to the petroleum engineer. Engineering interest has been brought about by the success of velocity logging devices, for it is possible by modification of these instruments to measure the attenuation of sound waves in addition to their velocity and, hence, deduce the mobility of formation fluids as well as the porosities of the rocks which contain them. The main problem is to decide whether field measurements can be made with sufficient accuracy to be of practical use. This problem can only be solved after we know the magnitude of the attenuations which are typical of the earth at various depths. The logarithmic decrement of a fluid-saturated rock is the sum of a "sloshing" decrement and a "jostling" decrement, the former caused by the mobility of the fluid contained within the rock and the latter by the granular framework of the rock. Sloshing decrements can be calculated&apos; using Biot&apos;s theory, but the jostling losses are less well understood. The present paper reports an experimental investigation of jostling losses in consolidated and uncon- solidated sands, particularly with respect to the effect of overburden pressure and fluid saturation. Born&apos; showed that the decrement of a sandstone may increase dramatically when only a few per cent by weight of distilled water is added, and that the additional loss is proportional to the frequency of vibration. His measurements were made with no compressive stress on the framework of the rock. M. Gondouin3 investigated similar phenomena for fluid-saturated plasters but also did not compress the samples. In the present paper it is shown that compression of the framework reduces this effect, so that at depth the jostling decrement of a sandstone may be expected to be almost independent of fluid saturation and frequency. Decrements for many sedimentary rocks have been given by Volarovich,4 but all for the state of zero overburden pressure. Anomalously low velocities have been logged in shallow unconsolidated gas sands. Results of the present investigation confirm that these velocities are not caused by correspondingly high attenuations, because the jostling decrement in a packing of sand grains is small and much less than in a consolidated sandstone at the same depth. Velocities in sands have been measured by Tsareva5 and by Hardin6 as a function of pressure, but the corresponding decrements do not appear to have been measured previously. The widely used "resonant bar method" of measuring velocities and decrements was employed. Comments on variations of this technique have recently been published by McSkimmin.7 The main novelty of the present technique was the application of pressure to the samples. It was found possible to do this by placing the apparatus inside a pressure vessel, provided the conditions leading to large additional losses were avoided. These conditions are discussed below. EXPERIMENTAL TECHNIQUE Cylindrical samples were caused to vibrate in both the extensional and torsional mode of vibration and the amplitude of vibration was measured as a function of frequency in the neighborhood of a resonant frequency. The resonant frequency, fr, is related to the corresponding elastic modulus by the formulas where E and N are Young&apos;s modulus and the modulus of rigidity, p is the density of the sample, and A the wavelength of the vibration.

Jan 1, 1965

By Carl Davis

A description is given of grinding practice on the Rand and of experiments made to improve that practice. The paper includes a description of the experimental plants and methods and the results obtained. THE first tube-mill on the Rand was put into operation in May, 1904, at the Glen Deep Mine. From that time onwards, tube-mills were added to various plants, although little was known regarding the capacity of a given tube-mill when working on banket ore. Within a few years, however, the so-called standard size (length of shell 22 ft. 0 in. diameter 5 ft. 6 in.) was generally used until the last year or two. Practically the only exceptions were about 30 tube-mills having a length of 16 ft. and a diameter of 6 ft., and a few open-end mills of the roller-supported type. Most of the information obtained during the last 15 years has been obtained with mills of the standard dimensions. The adoption of the tube-mill as an accessory to the stamp mill was rapid; and where 3 tube-mills were working on the Rand at the end of 1904, 244 were in use seven years later.1 By 1910, good practice provided 1 tube-mill for 20 stamps of 2000-lb. falling weight. The horsepower of the motors driving the tube-mills had increased from. 80 to 100 and then to 125 at this date. Broadly speaking, current practice at that date aimed at a final product of which 60 per cent. was suitable for sand treatment and 40 per cent. for slime. The sand grading was +60 mesh, 6 per cent.; +90 mesh, 25 per cent.; -90 mesh, 69 per cent.; and the slime grading -200 mesh, 2 per cent.; -200 mesh, 98 per cent.

Jan 12, 1924

By R. W. Baldwin

On page 309, column 1, the second equation should read: Ma-M1 = dlog_Pa M2-M1 d log P2

Jan 1, 1961

By AIME AIME

ANDREW FLETCHER, newly elected Treasurer and Director, has spent his entire mining career in the employ of the St. Joseph Lead Co. and brings to the Institute Board a career rich in financial experience and varied in interest and accomplishment. "Drew" Fletcher was born in New York City on Feb. 6, 1895. After graduating from the Sheffield Scientific School of Yale in 1916 as a mechanical engineer, he became a shipyard mechanic in Wilmington, Del. The next thirteen years saw. him gradually enlarging his responsibilities until he ultimately became the head of the W. & A. Fletcher Co., in Hoboken, N. J., ship repairers. In 1929 his program for merging the Fletcher plant with five other New York shipyards was finally consummated in the formation of the United Dry Docks, Inc., which subsequently was purchased by Bethlehem Steel, with the result that today the old Fletcher yard and organization has been expanded into one of the finest ship repair units in the United States.

Jan 1, 1944

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

A. U. Seybolt (General Electric Research Laboratory)—The authors should be commended for adding some important information to our knowledge of the solubility of interstitial elements in metals. It is becoming increasingly evident that the effect of even traces of such elements have very far-reaching effects upon the mechanical properties of the body centered cubic metals. Those who have worked in this area know that the accurate determination of the small solid solubility limits in systems of the type reported by the authors is a quite difficult task, and it is therefore not surprising that frequently the results of different workers are not in agreement. It is instructive, and usually helpful, to plot the solubility results on log weight or atomic percent -1/T coordinates to find out if a straight line is obtained. A straight line is expected because in systems displaying solubilities of the order of 1 to 3 at. pet or less, Henry&apos;s law is usually obeyed—or at least well enough obeyed so that the deviation from linearity is not very appreciable. If Henry&apos;s law is obeyed, one canthen use the Van&apos;t Hoff Equation in the form In N = ?H/RT + C, where N is mole fraction, at. pet, or wt pet for small values, and AH is the partial molal heat of solution of the solute. R and T have the usual significance, and C is an integration constant. If one plots the reported nitrogen solubility values as indicated above, the three points fall reasonably well on a straight line. The oxygen values for the two upper temperatures fall very closely to the nitrogen values as shown in the authors&apos; Fig. 15. However, the value at 500°C departs widely from the straight line established by the data at 1500" and 1000°C. It is, of course, true that one cannot place too much emphasis on the significance of a line established by only three points, but in the absence of reasons for anticipating deviations, data exhibiting wide departures from linearity should at least be examined closely. Fig. 16 shows the log at. pct -1/T plots for the authors Ta-O and Ta-Ndata including a solid circle point at 500°C and 1.8 at. pet for Ta-O, which is simply extrapolated from the two higher temperature points. In addition, the data of R. P. Elliott9 for Nb-O are shown. These points were picked off his curve and are not very exact, but as can be seen they line up well on a straight line. It is interesting, and probably significant, that the slope of Elliott&apos;s results is not far from those of Vaughn, et al. This is probably to be expected because one would anticipate that the partial molal heats of solution of oxyten in these two very similar metals should be not too far apart. AH for Ta-O is about -1900 cal per mol, while for Nb-O it is near -2300 cal per mol. Hence, this lends some support to the thesis that the point at 500°C for Ta-O is much too high. The data of Gebhardt and Preisedanz10 are also plotted, and it is seen that their data while lying on a linear plot, have an appreciably steeper slope. The possible reasons for this will not be discussed here except to point out that their pressure-composition data show anomalies which suggest that they may have been dealing with a different equilibrium from that being discussed. There is another consideration which would also suggest that the solubility at 500°C is lower than shown. The solubility values were obtained by the classic method of first establishing a lattice parameter-composition curve. This the authors did, and there is probably little doubt that it is quite accurate. Such a plot is generally almost error-free because it has a self-correcting feature in that any deviation from linearity makes a data point immediately suspect, and subject to confirmation. Unfortunately, this is not true with respect to the actual solubility values. These are obtained ordinarily by taking an alloy containing more solute than is soluble at some temperature and then thermally

Jan 1, 1962

By T. D. Thomas

CONTENTS PAGE T. D. Thomas-Misfires in Anthracite Coal Mines 3 W. H. Forbes-Misfires in Bituminous Coal Mines 12 A. W. Worthington-Misfires in Non-metallic Mining (Limestone) 18 Misfires in Anthracite Coal Mines BY T. D. THOMAS,* LANSFORD, PA. (New York Meeting, February, 1929) IN THIS paper, major attention is given to misfires in mines where electric multiple shot-firing is the system used. Misfires are sometimes caused by one action or condition and at other times by a combination of two or more. They may be divided into two classes: (1) those caused by workers in the mines, (2) mechanical or manufacturer&apos;s causes. The second cause will be discussed first. MISFIRES CAUSED BY FAULTY DETONATORS The important part of an electric blasting cap, to the user where multiple shot-firing is done, ass in the steep-pitch, thick-vein, anthracite mines, is the bridge wire. In single shot-firing this factor is not apparent, but in mines where multiple firing is done any variation in the resistance of the bridge wire, where full or even rated battery capacity is required, will most likely cause a misfire The reason for this is obvious. If the resistance in the bridge wires is not the same, some of the detonators will fire because of their greater comparative resistance. Variance in resistance of bridge wires is caused by a slight difference in the diameter of the bridge wire, also to a difference in the composition of the bridge wires. Again, where the bridge wires have become rusted, there will be a variance in resistance. About the year 1922, one of the large coal companies was greatly alarmed by the number of serious and fatal accidents caused by misfires. The general manager issued an order that these accidents must be greatly reduced, and if possible, entirely prevented.

Jan 1, 1929

THE translators wish to record their appreciation of the help given by many individuals with whom they have discussed various details of the work. They are particularly indebted to Mrs. Anne Noble McKeachie, who initiated their collaboration; to Miss Cora Adamson, who spent many hours in making an accurate copy of a much-mutilated &st draft of the translation; and to the Yale University Library which gave access to its excellent collection of books on all aspects of the history of the sciences. The reader will share with the translators their obvious indebtedness to Mr. Carl P. Rollins, Mr. James W. Boyden, and the staff of the Printing-Office of the Yale University Press. The publication of this translation by the American Institute of Mining and Metallurgical Engineers has been made possible by a grant from the Seeley W. Mudd Memorial Fund, administered by a committee composed of Harvey S. Mudd, H. DeWitt Smith, and George Otis Smith. The translators are gratified that their work has been judged to fall within the scope of this Fund, which was established for the advancement of the sciences of mining and metallurgy by the encouragement of research and the dissemination of knowledge, and especially for the furtherance of such activities as might benefit the younger members of the profession. While Biringuccio&apos;s book would scarcely serve as a dependable text for the young mining student or metallurgist, it can give him a sense of his membership in a long-standing and honorable profession and enable him better to see his own work in true perspective. It is hoped that this English edition of a sixteenth-century Italian work will be read by the practicing metallurgist as well as by those who have already found pleasure in exploring the past of their profession. A man always feels more at home in a foreign country with men of his own craft than in his birthplace with those of different interests: As in space, so in time, and the modem metallurgist who may be unmoved by the literary and artistic Renaissance will quickly appreciate the spirit of that exciting period as he talks shop with Biringuccio on a visit to mine, smelter, forge, and foundry; as he sees in different forms the very furnaces and machines whose operation and response he knows so well; and as he discusses with this engineer of four centuries ago such topics as the best kinds of fuel or refractory for a given operation, and the importance of adequate supplies of power and material.

Jan 1, 1942

By K. W. John, L. Mueller

The rock mechanics approach to stability problems of steep rock slopes dealt with in this article has particular reference to the concept and methods of analysis developed by the Salzburg, Austria, school of rock mechanics. These theories are based on the principal postulate of the anistropy of the technological properties of in-situ rock masses. The present approach, which is more in line with geological engineering concepts, differs distinctively from the soil mechanics and engineering geological concepts commonly practiced in the United States. PRINCIPAL ENGINEERING APPROACH TO GEOTECHNICAL PROBLEMS AVAILABLE ENGINEERING CONCEPTS At the present time two different concepts are available for engineering analysis of underground structures and foundations in different earth material: soil mechanics and rock mechanics. Of these two branches, soil mechanics is, after 40 years of initially revolutionary and more recently evolutionary development, well established. Its principal concept of replacing in-situ soils or rock masses by perfectly homogeneous substitues has resulted in many practicable methods of analysis which, if applied with judgement, have resulted in successful applications throughout the world. Conversely, rock mechanics is still in the early stages of revolutionary development. Few, if any, standard concepts or methods of analysis have been established. Opinions vary widely. At present the professional background of an investigator very often determines the engineering concept to be applied to a particular problem, rather than its actual requirements if considered objectively. This paper stresses the rock mechanics or geological engineering point of view advocated by the Salzburg group. A review of the soil mechanics concepts is considered beyond the scope of this paper. THE "SALZBURG APPROACH" TO ROCK MECHANICS The rock mechanics concept as outlined here was initiated by Stini, based upon work by sander.1 Since

Jan 1, 1963

H. 0. HOFMAN, Boston, Mass (written discussion*).-The paper by Mr.. Pyne gives clear evidence of the difficulties the metallurgist is likely to encounter when he tries to recover in the blast furnace the metal from old chromite lining used as a refractory material in the copper reverberatory furnace. It appears that chromite cannot be fluxed at temperatures which usually prevail in copper blast furnaces. This calls to mind the freezing-point curve drawn by M. Simonis1 of mixtures of chromite and kaolinite. The chromite used in the experiments contained 52.9 per cent. Cr203, 22.6 FeO, 4.8 AI203, 9.6 Si02, .10.1-MgO; FIG. 1. the kaolinite was clay from Zettlitz with 98.5 per cent. clay-substance: The accompanying curve shows that the eutectic mixture with 35 per cent. kaolinite and 65 per cent. chromite freezes at Seger cone No. 15 (1435° C.), while kaolinite fuses at cone No. 35 (1770° C.) and chromite at cone No. 42 (2000° C.). The curve indicates that the difficulty in the blast furnace can be overcome by having at the smelting zone a temperature much higher than is usual in copper smelting; a charge composition similar to that prevailing at the Mansfeld copper smeltery -which gives with 23 per cent. coke a, slag of the composition Si02, .49.09; .(FeMg)0, 5.58; (CaMg)0, 16.02; A1203,-16.02-might flux and fuse chromite.

Jan 3, 1918

By G. N. Goldberg, Robert A. Rapp

The steady-state kinetics and microstructures of simultaneous internal oxidation and external scale formation were investigated for the oxidation of Cb-Zr and Ch-Zr-Re alloys in pure oxygen at 1000°C. For each binary alloy, a constant rate of scale formation was observed at steady state; the internal oxidatton zone reached a steady-state, time-independent thickness. The dependence of the scaling rate on zirconium content exhibited a maximum at a low zirconium colttent; more concentrated alloys oxidized at a slower rate than pure columbium. This composition dependence of the scaling rate may be partially attributed to the effect of the internal oxidation process as an intenla1 sink for oxygen, with the formation of voluminous, and relatively impermeable ZrO2 precipitates. However, the morphologies of the ZrO2 internal oxide precipitates also affected the scaling rate. The internal oxide precipitates were distributed uniformly in the external scale. The steady-state thicknesses of the internal oxidation zones were not in agreement with those predicted theoretically from an idealized simple model. However, in this particular alloy systen1 the ideal model is not satisfied experitmentally. For ternary Cb- Zr - Re alloys with Nr10e = 0.02 or 0.05, the steady-state thicknesses of the internal oxidation zones were less than those for the corresponding binary Cb-Zr alloys. For ternary alloys with NRe(0) - 0.05, a more adherent and much less porous external scale was formed, and a reduction in the kinetics of scale formation was observed. A number of authors&apos;-7 have reported linear oxidation kinetics for the reaction of pure columbium at 1000°C in air or in oxygen of about 1 atm pressure. A thin and tightly adherent oxide layer is found at the metal/oxide interface beneath a porous external layer of scale. Although the suboxides CbO and CbO2 represent thermodynamically stable phases at 100O°C, generally only Cb2O5* is identified as a reaction product in quenched specimens. Studies at 1000°C at lower oxygen pressures8,10 (Po2 - 10-4 Torr) show that both CbO and CbO2 do form and that CbO2 is a protective oxide. The growth of CbO2 results in parabolic kinetics until Cb2O5 is nucleated and grows. Apparently because of the large volume change associated with its formation, Cb2O5 is porous and does not serve as a diffusion barrier; linear kinetics prevail after the surface is covered with Cb2o5. On the basis of these observations, several authors5,9,10 have suggested that the linear oxidation of pure columbium at 1000°C in air or oxygen of 1 atm is limited by a Loriers-type mechanism,11 whereby the total rate or reaction is controlled by ionic diffusion through a thin layer of CbO2 which is maintained at a constant thickness throughout the linear oxidation. However, the concept of a Loriers model for a three-phase CbOlCbO2 Cb2O5 scale, with the only oxygen activity gradient across the NbO2 phase, is not self-consistent. Further, the suboxides CbO and CbO2 were not observed in the high-temperature X-ray diffraction study of columbium oxidation by Goldschmidt.8 From investigations in which the large PO2, dependence of the linear scaling rate was demonstrated, the importance of an oxygen adsorption or dissolution step has been suggested.4,5,7,10,12 Thus the mechanism for the linear oxidation of pure columbium remains quite controversial. Since further insight into the oxidation mechanism of pure columbium is not provided by this investigation, the authors wish to emphasize at the outset that their experimental results are not interpreted in terms of a particular rate controlling step for the oxidation of pure columbium. Previous investigations13-18 of the oxidation of Cb-Zr solid-solution alloys in air or oxygen at 1000°C suggest a remarkable dependence upon zirconium content. For an alloy of bulk zirconium mole fraction, N2r(0) equal to 0.05 or 0.10, the oxygen uptake is reported to be as high as four times greater than that for pure columbium;13,14 for alloys with NZr(0) 0.05 or 0.10 the oxygen uptake is reported to decrease with increasing NZr(0); to a minimum uptake of about one quarter that for pure columbium at NZr(0): = 0.50.13-15Since zirconium forms a more stable oxide (ZrO2) than the lowest columbium oxide (CbO), and since columbium exhibits a high solubility19,20 and diffusivity21,23 for oxygen, the internal oxidation of the zirconium component to ZrO2 is expected at a reaction front ahead of the advancing metal/scale interface. The external scale is then formed at the metal/scale interface by the inward migration of oxygen through the scale, probably through a series combination of molecular and ionic diffusion. Internal oxidation in conjunction with external scale formation has been investigated by Maak24 for the oxidation of dilute Cu-Be alloys in pure oxygen at 850°C. For cu-Be and many other binary alloys,24-27 very small, essentially uniaxial internal oxide particles are formed in the most dilute compositions; for somewhat more concentrated alloys. the internal oxide particles precipitate as platelets or needles. From pertinent solutions to the diffusion equation, Maak28

Jan 1, 1967

By L. C. Chang, T. A. Read

Diffusionless transformation in Au-Cd single crystals containing about 50 atomic pet Cd was investigated by means of X-ray analysis of the orientation relationships, electrical resistivity measurements, and motion picture studies of the movement of boundaries between the new and old phases during transformation. The nucleation of diffusionless transformation by imperfections and the generation of imperfections by diffusionless transformation were discussed. THAT connections exist between plastic deformation and diffusionless phase changes has long been recognized. Thus it is often possible to produce a diffusionless phase change in a temperature range, above that in which the change occurs spontaneously, by cold-working the initial phase. Certain aspects of the dislocation theory of the plastic deformation of crystalline solids also provide for a rather direct connection between the processes involved in plastic deformation and in diffusionless phase changes. Heidenreich and Shockleyl have pointed out that simple edge dislocations in f.c.c. metals are probably unstable, and that the more probable lattice imperfections, called extended edge dislocations, consist of two half dislocations separated by a distance of the order of magnitude of 100A. The region about two atomic planes thick between the half dislocations because of this stacking fault may be described as having the hexagonal close-packed structure. Presumably the stacking faults observed by Barrett" fter cold-working f.c.c. Cu-Si alloys resulted from the passage of such half dislocations through the lattice of the initial phase. It is now becoming clear that the development of a detailed theory of the atomic movements involved in diffusionless phase changes will require a consideration of the role played by lattice imperfections, just as such considerations are necessary to the understanding of plastic deformation mechanisms. This point of view has been recently set forth, for example, by Cohen, Machlin, and Paranjpe3 who pointed out the role which might be played by screw dislocations in nucleating diffusionless phase changes. The present paper reports on some aspects of the diffusionless phase change in single crystals of the beta phase alloy Au-Cd which serve to emphasize further the importance of lattice imperfections in diffusionless phase changes. The diffusionless phase change of Au-Cd possesses several remarkable features. One of these is that the interface between the high-temperature beta phase and the low-temperature orthorhombic phase typically moves with a low velocity, in contrast to the behavior observed in the transformation of austenite to martensite. Motion pictures of this slow interface motion have been prepared in the course of the work reported here. Another important feature of the Au-Cd transformation is the small amount of undercooling observed. The reverse transformation occurs on reheating to a temperature only 20" higher than the transformation temperature observed on cooling, and under some circumstances the hysteresis observed is substantially less than this. This narrow temperature range between transformation on heating and cooling is presumably in part a consequence of the fact that the transformation requires a lattice shear of only about 3". Finally, the orthorhombic product phase possesses unusual mechanical properties, as was first pointed out by olander&apos; and Benedicks." After completion of the transformation on cooling the specimen can be severely deformed, yet on the release of load it springs back to its original shape in a rubber-like manner. Explanation of this phenomenon will require an understanding of the lattice imperfections in the orthorhombic structure and, correspondingly, of those in the initial body-centered cubic structure. Single crystals of Au-Cd alloy containing 47.5 and 49.0 atomic pct Cd were prepared from fine gold (99.95 pct purity) and chemically pure cadmium (99.99 pct purity) by melting the alloy in an evacuated and sealed fused quartz tubing and growing into single-crystal form by the Bridgman method. The Au-Cd alloy containing 47.5 atomic pct Cd undergoes a diffusionless transformation from an ordered body-centered cubic structure to an orthorhombic structure when it is cooled to about 60°C, while the reverse transformation takes place when the alloy is heated to about 80°C, according to electrical resistivity studies. The structures of these two phases have been studied by Blander,4 reinvestigated by Bystrom and Almin.e he lines of Debye photo-gram of powdered samples of Au-Cd alloy containing 47.5 atomic pct Cd prepared in this laboratory were identified and agreed fairly well with those of

Jan 1, 1952

By Frederik W. de Klerk

INTRODUCTION During the past 40 years, there has been in the United States of America and other industrialised Western countries a distinct displacement in the procurement of minerals from domestic sources towards an increased dependence on imported minerals. This was caused in part by one or each of the following: a lack of local supply of particular minerals, domestic source depletion or exhaustion and the relative ease and inexpensiveness of obtaining minerals from comparatively unexploited sources in underdeveloped and some developing countries, notably in the Middle East, South America, Southern Africa, and Australasia. Governments of the industrialised nations, concerned about the reliance of their economies on imported raw minerals examined both the degree of reliability and the extent of mineral resources in the countries and regions supplying the essential minerals. This brought a painful awareness of the vulnerability of industrialised countries as a result of the possible interruption of their mineral imports. In this regard, the United States of America may be quoted as a case in point: a report by a House of Representatives Subcommittee on Mines and Mining (Santini Subcommittee)1 revealed that the United States in 1980 was dependent on foreign sources for more than 50 per cent for 24 of the 32 minerals essential for national survival. The Subcommittee also acknowledged that although the United States may develop its own alternative energy sources, there are in many cases no substitutes for the strategic + minerals imported from foreign sources, from countries which are often unstable at best, hostile at worst. This resulted in various policy responses as well as contingency measures, amongst other, renewed emphasis on the utilisation of domestic mineral resources, an intensified search for substitutes of critical minerals and increased stockpiling programmes. Increased attention was devoted to analyses of the political and economic conditions prevailing in the regions from which strategic and other minerals are exported to the industrialised countries, and the formulation of policy measures vis-a-vis those regions. One region which attracted a considerable degree of attention has been Southern Africa, and in particular South Africa.2 The Santini Subcommittee affirmed that while the bulk of the minerals imported by the United States is supplied by a number of source countries, a host of critical[t] minerals vital to the well-being of that country (and this includes all the Western industrialised countries) originates from Southern Africa, a region, deservedly referred to as the "Persian Gulf of Minerals". Apart from the Republic of South Africa the mineral-rich countries concerned are Angola (diamonds, iron ore, oil), Botswana (diamonds, coal), South West Africa/Namibia (diamonds, uranium), Zambia (copper, cobalt), Zaire (industrial diamonds, copper, cobalt) and Zimbabwe (gold, nickel, chromium, asbestos). The Subcommittee however noted that, with the exception of cobalt, the greatest portion of the reserves of the critical minerals listed, lies within the borders of South Africa. SOUTH AFRICA A RELIABLE PURVEYOR OF MINERALS In view of the continual instability and political risk, along with the nationalisation of mineral industries in third world countries, importing industrialised nations have in recent years become more and more concerned about security of long-term supply, and have in consequence begun to diversify their mineral enquiries to areas where the following conditions prevail: • Long-standing record of consistency of supply; • An economic system of private enterprise; • Political stability; • A well integrated infrastructure, with a maintenance of transportation and development costs at realistic levels, and • Attractive investment opportunities, with security of the return of profits.

Jan 1, 1982

By T. Busch, R. A. Dodd

The solubility of hydrogen in pure iron and pure nickel, and of nitrogen in pure iron, has been determined and agrees well with earlier data. Nitrogen is insoluble in pure nickel and cobalt. The solubility of nitrogen in Fe-Ni alloys also confirms earlier- work. The solubility of hydrogen in Fe-Ni alloys increases non-linearly with increase in nickel content, but the solubility of hydrogen in Ni-Co and Fe-Co alloys reaches a minimum at 75 and 50 at. pet, respectively. The solubility of nitrogen in Fe-Co alloys decreases approximately linearly with increase in. cobalt content. Nitrogen is insoluble in Ni-Co alloys. Determined interaction parameters are in good agreement with predictions of Gokcen and Ohlani. THE solubility of hydrogen and nitrogen in liquid iron and iron alloys has been studied by various investigators.&apos;-l&apos; The method of solubility measuremerit due to Sievertsl is usually preferred when the vapor pressures of the liquid components are sufficiently small, but other techniques such as sampling the equilibrated melt and then analyzing by vacuum fusion have been used quite often. Previously reported data on the solubility of hydrogen and nitrogen in ostensibly pure liquid iron are summarized in Table I; certain of the quoted results were obtained by interpolation of the published data. Agreement between the various investigators is only fair, indicative of the experimental difficulties involved in obtaining gas solubility data. The only report found on the solubility of hydrogen in pure nickel is that of Sieverts.2 The solubility of nitrogen in iron-nickel alloys has received some attention, 10, 11 the results indicating that the solubility decreases with increase in nickel content, becoming zero for pure nickel. There is no published information on the solubility of these gases in either pure cobalt or alloys containing cobalt EXPERIMENTAL PROCEDURE Sieverts&apos; method of solubility measurement was used throughout the investigation. The construction of the melting chamber is somewhat different from A. Optical pyrometer F. Alundum cover B. Vycor chamber G. Alumina crucible C. Furnace coils H. Alundum sand D. Glass water jacket I . Alundum thimble E. Chamber support J . Detachable vycor base sealed with de Khotinsky cement

Jan 1, 1961

By M. R. Todd, J. Szekely

THE mechanism of carbon oxidation in steelmaking processes has attracted considerable attention in recent years. The generally accepted model postulates that the reaction between carbon and oxygen occurs at the surface of CO bubbles that originate at the suitable nucleation points and subsequently rise through the metal bath.1-4 Although this model describes adequately the behavior of open-hearth type operations, it is not a satisfactory representation of carbon oxidation in oxygen steelmaking processes since it cannot account for either: i) the very high rate of oxidation per unit bath area,or ii) the commonly reported shapes of the curves showing the dependenie of the oxidation rate on the carbon concentration. The very high decarburization rates commonly encountered in oxygen steelmaking processes need no further elaboration; some typical plots of the rate of carbon removal against carbon concentration, taken from a publication by Li, Dukelow, and smith,&apos; are reproduced in Fig. 1. It is seen from the curves that the decarburization tends to decrease from a peak or a plateau once the carbon concentration falls below a certain value; in the experiments reported, this critical value ranged from 1.2 to 0.2 wt pct C. The apparent dependence of the decarburization rate on the carbon concentration indicates that within this region phenomena associated with the transfer of car- bon must play an important if not predominant role. Since the concentration of oxygen in molten iron at steelmaking temperatures (removed from the immediate impact zone) is only about 0.1 wt pct,6 it is clear that simple simultaneous diffusion of carbon and oxygen to the surface of CO bubbles could not account for the rate of carbon transfer being the controlling step at carbon concentrations as high as 1.0 wt pct. The purpose of this communication is to present an alternative model which may explain at least qualitatively the apparent anomalies mentioned and may stimulate further experimental work. The Physical Model. It is suggested that the principal mechanism of decarburization is the reaction between CO bubbles and an emulsion consisting of molten iron and molten iron oxide particles in the vicinity of the "slag-metal interface9&apos;.* This mech-

Jan 1, 1968

By H.A. Bedworth

AlloTs of copper and silicon have been known for one hundred years or more but the commercial development of this type of alloy has taken place during the past few years. In 1905, Sperry l proposed the use of copper-silicon alloys for springs and other purposes for which copper-tin bronzes were used. Some attention was given to this proposal at the time but no one succeeded in producing a practical alloy containing more than a fraction of a per cent. of silicon. The equilibrium relations of the copper-silicon system were studied first by Rudolfi2 and later by Sanfourche 3 and Corson. 4 The constitution of the system has also been recently investigated by Matuyama, 5 and in the laboratories of the American Brass Co. by Smith. 6 Some of the physical properties of the copper-silicon alloys have been investigated by Norbury7 and by Geiss and Van Liempt.8 Summarizing the results of various investigators of the constitution of copper-silicon alloys, the solubility reaches its maximium value, 6.7 per cent. silicon, between 721" and &apos;782" C. At 852" (1. the solubility is 5.25 per cent., while at 400" C. it is only 4.1 per cent. silicon. The copper-silicon alloy begins to get so hard at about 3 per cent, silicon that it is difficult to manage. It was found by Jacobs that the addition of manganese to this alloy considerably improved the working

Jan 1, 1929