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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 C. B. Post, G. V. Luerssen

It is generally recognized that non-metallic inclusions in steel come from two principal sources. First are the chemical reactions in the furnace, or in subsequent deoxidation, resulting in slag which does not free itself from the metal. Much information has been published concerning these chemical reactions and their control through proper attention to slag viscosity, composition of deoxidizers, and other qualities. The studies of this subject by C. H. Herty, Jr. and others through the medium of physical chemistry have yielded much information for the steelmaker. The second source is erosion of ladle refractories, such as lining brick, stoppers, nozzles and runners, causing entrapped particles of globules of fluxed silicate material. In contrast with the large amount of information available on the first source, relatively little has been published on the subject of erosion which, in the case of basic electric melted steel, is the principal source of nonmetallics. This is probably due to the fact that the problem was assumed to be one of simple mechanical erosion, which could be solved primarily by modification of ladle practices. Good improvements have been made by elimination of slurries in the ladle, better ladle and runner refractories, and more attention to pouring temperatures. It is doubtful, however, that this problem has been recognized in its true light since it is not one of simple mechanical erosion but rather one of chemical reaction between the metal and the refractories; and in this sense is as much a problem of physical chemistry as the reactions involved in the actual steelmaking process. The influence of ladle refractories on the resulting cleanness of steels was early recognized by A. McCancel who examined large inclusions in steels made by both acid and basic practices. His chemical analyses showed the large influence exerted by the manganese content of the steel on erosion of the ladle and nozzles used in those days. The presence of MnO in such inclusions led McCance to the hypothesis that both basic and acid steels react chemically with the ladle refractories so that small globules of fluxed refractories are carried in the stream into the molds. This early work of McCance was checked by one of the present authors on basic electric bearing-steel, and it was found that on steels containing as low as 0.40 pct manganese the fluxed surface of the ladle lining after delivering such a heat showed as high as 25 pct MnO by actual analysis. Furthermore, by lowering the manganese content of the steel to 0.20 pct, ladle erosion was decreased with a corresponding decrease in silicate inclusions in the steel. Limitations placed on the manganese content for the required inherent properties made it impossible to pursue this line further, and subsequent attention was concentrated on improved ladle refractories, care in keeping the ladle clean and free from loose refractories up to the time of tapping, and pouring the steel at optimum temperature. Our study of the chemical reactions at the metal-brick interface between steel and ladle refractories was revived in 1939 as a result of an experimental observation made on the cleanness of alloy steels of the SAE types. This observation showed that the relative cleanness of such steels made in basic electric arc furnaces of 12 ton capacity and poured in ingots ranging from 1100 to 2200 lb weight was determined to a large extent by the ratio of the manganese and silicon contents, provided other steelmaking variables such as tapping temperature, pouring temperature, pouring time, amount of aluminum added for grain size control, and degree of deoxidation in the furnace were kept reasonably constant. Detailed studies made on the deoxidation and slag practice during the refining period of basic electric furnace practice showed that these two variables exerted some influence on the resulting cleanness of steel in the form of bars and forgings. The important variable, the manganese-silicon balance, was not apparent until heats were made in succession by the best furnace practice kept under fairly rigid metallurgical control. Another observation pertinent to this work concerned the similarity in the microscope of slag particles causing magnaflux or step-down indications in subsequent rolled bars, and the patches of slag frequently seen on the surface of ingots. These patches are generally believed to come from the glassy metal-brick interface in the ladle and represent an entrapment of such glass (both from the ladle brick and nozzle) in the metal as it flows over the refractories in the neighborhood of the nozzle. These glassy particles are carried down into the mold with the liquid steel, and gradually coalesce into a slag "button" which floats on the surface of the steel as it rises in the molds. Periodically the button is washed to the side of the ingot where it is trapped between the surface of the ingot and the mold, later appearing as a slag patch on the surface of the ingot after stripping. Even though most of the small glassy particles coalesce into a slag button while the ingot is being poured, it is logical to suspect this step in the steelmaking process as being a source of slag lines large enough to cause trouble

Jan 1, 1950

By Francis T. Christy

One aspect of ocean mining that is frequently overlooked in discussions is the problem of establishing some form of legal control over the seas. Much of the discussion centers on mining in territorial waters, which are controlled by the various countries according to the Geneva Convention on the Continental Shelf, and perhaps by political subdivisions of countries such as the individual states of the U.S. But as technology improves and the mining of deeper waters becomes feasible, the problem of rights outside the continental shelf and territorial waters becomes a significant factor for anyone expending the time and capital for development. Several schemes are possible for regulating ocean mining but as yet none have been instituted, except what might be termed the "wait and see" approach. Even some of the coastal states in the U.S. have no regulations governing mining in the territorial waters under their jurisdiction. Until some regulation is formulated, there may well be little development in ocean mining due to the high risk of capital involved, both with respect to companies wishing to invest their own funds and financial institutions funding a venture to develop offshore mineral deposits.

Jan 7, 1968

By B. B. Rath, Hsun Hu

In wedge-shaped bicrystals of zone-refined aluminum it is observed that (111) pure tilt boundaries migrate under the driving force of their own inter-facial free energy. The boundary velocity is a power function of the driving force. The driving force exponent decreases with decreasing angle of misorien-tation. For example, at 64O°C, the exponent decreased from 4.0 for a 40 deg to 3.2 for a 16 deg tilt boundary. An evaluation of the driving force acting on the boundaries during their motion indicates that for low driv-forces, up to about 2 x l03 ergs per cu cm, the velocity is relatively independent of misorientation, whereas at higher driving forces a 40 deg tilt boundary exhibits the highest velocity. The measured activation energy for boundary migration approaches that for bulk self-diffusion at low driving forces, decreasing from 33 to 27 kcal per mole as the driving force is increased from 1 x l0 to 5 x l03 ergs per cu cm. These results are compared with current theories of grain-boundary migration. In previous experimental studies of grain boundary migration the driving force has been limited to a difference in stored energy across the boundary. This stored energy has been introduced into the crystal either by prior deformation1-3 or by grown-in lineage structure. A part of the energy stored in the deformed crystal is released by recovery either prior to or concurrently with grain boundary migration, thus introducing an uncertainty as to the magnitude of the driving force responsible for grain boundary migration. The grown-in lineage structure, though thermally stable during annealing, neither provides conditions under which different levels of energy may be stored in the imperfect crystal nor provides a control of orientation difference across the migrating boundary of a growing grain. Furthermore, because of variation in the lineage structure, it is difficult to determine accurately the energy stored in the imperfect crystal. Several investigations of grain boundary migration during normal grain growth have also suffered from difficulties in estimating the driving force because of uncertainties in the principal radii of curvature.~ In the present investigation the velocity of pure tilt boundaries in zone-refined aluminum bicrystals of selected orientation (40, 30, and 16 deg around the [Ill] tilt axis) has been measured in the absence of a dislocation density difference across the moving boundary, thus eliminating the previous experimental difficulties. The driving force for boundary migration is derived from a gradient of the total interfacial free energy of the migrating boundary in wedge-shaped bicrystals. A similar method was attempted by Bron and Machlin in a study of grain boundary migration in silver. However, they found that one of the crystals was deformed and consequently the motion of the boundary was partly due to a difference of stored energy across the boundary. The observed behavior of boundary velocities as affected by the driving force is examined in the light of the predictions of the current theories of grain boundary migration.7"10 The effect of boundary misorientation on velocity is compared with the theory of " which is based on a dislocation core model for high-angle boundaries. EXPERIMENTAL METHOD Seed-oriented bicrystals of zone-refined aluminum, 2.5 cm wide, 0.5 cm thick, and 12 cm long, containing tilt boundaries with a common (111) axis, were grown from the melt in the direction of this axis. Spectro-graphic analysis, reported earlier,'' indicated the purity of the crystals to be 99.999+pct. Three such bicrystals containing 16, 30, and 40 deg tilt boundaries were used. Wedge-shaped specimens were prepared from these bicrystals by spark cutting followed by electrolytic polishing. The angle of the wedge was usually 40 deg and the specimens were usually 0.25 cm thick. The intercrystalline boundary was located within 0.2 to 0.5 cm from the tip of the wedge. Fig. 1 shows a section of an oriented bicrystal containing an outline of a wedge-shaped specimen. The crystallographic directions shown in Fig. 1 represent the orientation of one of the crystals (the larger section of the bicrys-tal); the orientation of the other crystal differs only by rotation around the common [lil] axis. The parallel faces of the wedge always corresponded to the common (171) planes in both crystals, whereas the orientation of the side faces varied, depending on the misorientation angle. The bicrystal orientations were determined

Jan 1, 1970

By Sidney Wise

WHILE the installation of mine bulkheads to retain water under high pressure is y no means a rarity, the following points Which arose in the designing and placing of two of these bulkheads may be of interest: The Hibernia magnetite mine, located about 40 miles west of New York, in the State-of New Jersey, is partly filled with water. This mine is located on an ore lens, the outcrop of which is over a mile long. The ore has been mined from this lens from the surface to a depth of more than 1,500 ft. It was held desirable to- separate the old workings from the new, and to allow the former to fill to the 850-ft. level. Two weak places existed between the new and old workings below this level: namely, a temporary bulkhead on the 10th level and a rock bulkhead of indeterminate thickness on the 16th level. When the matter of allowing the old workings to fill was investigated, the fact was developed that if these old workings were filled, the bulkhead on the 10th level would be subjected to a water pressure of about 50 lb. per square inch, and that 200 lb. per square inch would act on the 16th-level bulkhead. As the above-mentioned barriers were not deemed of sufficient strength to permit of these pressures, it became necessary to design and install new bulkheads. Design As the 16th-level bulkhead was required to withstand a pressure of 200 lb. per square inch, it presented some difficulties. A careful consideration of the various types of mine dams now in use led to the adoption of a design of the form of a truncated wedge. In this, the pressure side of the dam is of greater area than the back, so that the resultant action is similar to driving the wedge. By cutting generous skewbacks in the walls, roof, and floor, this type in reality becomes an invisible arch. The wedge feature tends to compress the materials in the bulkhead, thereby adding to its imperviousness.

Jan 8, 1914

The Western World's gold reserves now exceed 23,000 mt (750 million oz), 65% of which exist in South Africa. Although several major mines are reducing production or closing because of depletion of reserves, new mines or expansions of existing mines are coming on-stream which will maintain an annual production of 684 mt (22 million oz) of gold well into the 1990s. These new operations by the South African mining industry represent the largest expansion since the opening of the Witwatersrand gold fields in 1886. Included in three new mines being opened is that of Anglo American Corporation's Elandsrand plant, their fir& new gold venture in South Africa in seventeen years. Current average grade of South African mines is 8.2 g Au per mt (0.24 oz per st); and while the cost of the Elandsrand 135,000 mt (149,000 st) operation, including mine development, was about $314 million, it is estimated that the cost of a comparable operation started today and completed in the mid-1980s would be of the order of $480 million. New mines to exploit low-grade ore bodies are, therefore, likely to be few in number, and further expansion will undoubtedly be in the form of extensions to existkg operations where cash flow can be used to finance development. The authors' first monograph, "Gold and Silver Cyanidation Plant Practice," devoted a section to South African cyanide plant operation; and it is believed that this new volume would not be complete without a description of Elandsrand, South Africa's newest gold plant. The Elandsrand mine is adjacent to Anglo American's Western Deep Levels on the Far West Rand. The decision to go ahead with the development was taken in mid-1974 from the results of exploration drilling carried out over a period of .lo years. Results of 17 bore holes and 68 intersections of the Ventersdorp Contact Reef had indicated a gold-.bearing reef less than one meter thick at a depth of 1,800 to 3,000 meters (5,900 to 9,840 ft). Preliminary studies indicated a mine of 900 km (560 miles) of underground workings would yield 725,000 kg (23. 3 million oz) of gold from 60 million mt (66 million st) of ore to be milled over a period of 34 years. Eventually, when the mine is in full production, the total hoisting capacity will be 300,000 mt per month (331,000 st) for a milling capacity of 225,000 mt per month (248,000 st). The Elandsrand surface facilities have been built on a low range of 0 hills to take maximum advantage of the 10 slope in transporting ore

Jan 1, 1981

The Institute maintains for the use of members (and especially for the use of out-of-town members) a reading and writing room, where all usual office facilities are available, including telephone, telegraph, receipt, forwarding and care of mail and express packages, etc. A file of current magazines is also maintained in this room, and the Institute's staff will lend its best efforts to serving the members in connection therewith. The Institute also maintains for the use of its members free dressing rooms, library research department, etc. Attention is called to these facilities at the present time in the belief. that they may be especially useful to out-of-town members in connection with the Meeting.

Jan 5, 1918

By E. A. Gulbransen, K. F. Andrew

The gas-metal reactions of zirconium are very interesting. The metal is extremely stable at room temperature to reactions with the several gases present in air and the metal will stay bright indefinitely. However, at temperatures of several hundred degrees higher the metal reacts readily with oxygen, nitrogen and hydrogen. This behavior, in addition to the fact that zirconium is one of the higher melting point metals which might have high temperature applications under the proper conditions, resulted in the work reported in this communication. There are several factors which indicate that zirconium might have good oxidation resistance at elevated temperatures. These are: (1) the high melting point of approximately 1860°C, (2) the high melting point of the oxide of approximately 2675°C, (3) the high degree of thermodynamic stability of the oxide to chemical reaction and the low decomposition pressure of the oxide and (4) the possible formation of a continuous oxide film since the volume ratio of oxide to metal is greater than unity. The unfavorable factors are: (1) the metal reacts to form nitrides, hydrides and carbides, (2) the oxide is soluble at elevated temperatures in the metal and (3) the oxide ZrO2 undergoes crystal structure transformations at high temperature. The oxidation resistance of this metal is not only a question of the rate of film formation but is complicated by the fact that the oxide and other reaction products dissolve in the metal which in turn will affect the physical and mechanical properties of the metal. The protection of the metal to nitride formation must be considered separately from the oxide problem. One unfavorable factor is that the volume ratio of the nitride to the metal is about unity. This indicates that a discontinuous film might be formed. This paper will present measurements on the rates of reaction of the metal with O2, H2 and N2 over a wide temperature and pressure range. The reaction in high vacuum and the stability of the several compounds formed will be presented. The results are correlated with fundamental rate theory and with the physical and chemical structure of the metal and film. Literature Although many papers have been published on the chemical reactions of zirconium with various gases, comparatively few are concerned with the protective nature of the metal and its reactions at normal pressures. The studies in the pressure range below 0.01 mm of Hg gas pressure are largely of interest in the nature of the adsorption of gases by hot filaments in high vacuum apparatus. The reactions of zirconium in this pressure range have been reviewed by Fast8 and by RaynOr.27 In spite of certain differences of opinion as to the maximum adsorption temperatures for various gases, the low pressure range is qualitatively understood. Some of these papers will be mentioned briefly here. 1. LOW PRESSURE Ehrke and Slack' find that oxygen reacts above 885°C and hydrogen above 760°C. Nitrogen does not react up to a temperature of 1527°C. Fast9 on the other hand observes that oxygen is absorbed above 700°C and nitrogen at temperatures exceeding 1000°C. Hydrogen is absorbed from 300" to 400°C and liberated between 500" and 800°C. It is readsorbed at 862°C and released above 862°C. Hukagawa and Nambo22 find a rather complicated picture for the absorption of oxygen. A rapid initial absorption is found between 180" to 230°C. Further oxygen is not taken up until a temperature of 450°C is reached. The optimum temperature for complete absorption is 650" to 700°C. Nitrogen is found to be completely adsorbed at 600°C. However some of the gas is evolved at higher temperatures. Their data on the absorption of hydrogen indicate some of the gas is removed at 550°C. Guldner and Wooten17 in a study of the low pressure reactions of zirconium with various gases observed that the reaction with oxygen occurs at temperatures above 400°C and that the oxide is formed. The reactions with carbon monoxide and carbon dioxide occur rapidly at temperatures of about 800°C with the oxide and carbide being formed. Zirconium reacts at temperatures of 400°C slowly and at 800°C rapidly to form the nitride and with hydrogen and water at 300°C to form the hydride and a mixture of the oxide and hydride respectively. 2. NORMAL PRESSURE DeBoer and Fast3 in a study of the electrolysis of oxygen in zirconium find that the metal absorbs up to 40 at. pct of oxygen without forming a new phase. The solubility of nitrogen in the lattice has been studied by de Boer and Fast4 and Fast10 and is found to be considerable. At higher temperatures the oxide dissolves in the lattice at an appreciable rate according to Fast10 and the zirconium surface becomes active. De Boer and Fast4 and Hägg18 have studied the solubility of hydrogen and find that at room temperature the solubility corresponds to ZrH1.95 Desorption occurs on lowering the pressure. Hydrogen is stated to be more soluble in the ß-form and the

Jan 1, 1950

Ocean environmental factors are an intriguing new set of parameters to be dealt with in the prospecting and exploration phases of resource development for both the continental margins and the deep ocean. While information and data gathering programs for ocean minerals would parallel onshore procedures, their costs generally run higher. Commercial Prospecting-Identification of Mining Sites Two modes of prospecting can be identified-commercia1 prospecting (in which the ultimate objective is to define potential mining sites), and scientific prospecting, which is conducted with different objectives in mind. For ocean exploration, both types of prospecting are carried out prior to the obtaining of any exclusive rights to explore and exploit a specific deposit. Deepsea's John Flipse adds: "Any commercial prospecting program should by its very nature require the freedom to search wherever minerals might occur with maximum flexibility."

Jan 4, 1975

By J. B. Newkirk, A. H. Geisler

The alloy Cu4Pd has a disordered face-centered-cubic structure when quenched from temperatures between 478ºC and the melting point (about 1100°C). Below 478ºC an ordered phase is stable. The results of a Debye-Scherrer X-ray analysis indicate that the ordered phase has a tetragonal unit cell described by the space group C24h — P42/mt with 2 Cu in 2a, 2 Cu in 2f, 4 Cu in 4j (x = 0.2, y = 0.6), 4Pd in 4j (x = 0.4, y = 0.2), and 8 Cu in 8k (x = 0.1, y = 0.3). The orientation relationship between the face-centered-cubic phase and the ordered tetragonal phase is given by: [100],,. // [130]al,. COO1Ia.d.//COO1I,,.. • The behavior of Cu,Pd is typical of ordering alloys except that the transformation is very sluggish. The increase in hardness and the microstructural and X-ray diffraction effects are interpreted in terms of coherency strains caused by the ordering. AN anomalous construction in the Cu-Pd phase diagram (Fig. 1) was reported in 1939 and has been allowed to stand without further published attention since that time. The odd figuration about the composition 10 to 27 atomic pct Pd is derived mostly from the work of Jones and Sykes.1 Evidently several features of this binary system require further study if the constitutional forms are to be well understood. The present paper includes a study of one of these features, that is, the crystal structure of a single ordered alloy containing nominally 20 atomic pct Pd. This choice of composition was suggested by the work of Harker and associates who determined the structure of Ni4Mo2 and Ni4W.3 The nature of the ordering process in Cu4Pd was studied also by observing the hardness, microstructure, and Debye-Scherrer patterns of specimens which had been aged at various temperatures after quenching from an initial disordering treatment. Experimental Methods A 20 gram ingot of Cu4Pd was made by melting spectrographically standardized copper from Johnson, Matthey, and Co., and commercially pure (99.5 + ) palladium in an argon-filled quartz tube. Chemical analysis showed that the ingot contained 80.0 atomic pct Cu. The ingot was rolled about 60 pct to a strip 0.060 in. thick and was homogenized for 16 hr at 950°C in low pressure argon. Rods cut from the rolled strip were worked into wire 0.015 in. in diameter, and specimens for hardness and microscopic examination were cut from the remaining strip. All specimens, with the exception of some of the wire, were given an initial disordering treatment by heating for 16 hr at 950°C, followed by water quenching. A 10 cm length of as-drawn wire was water quenched after being held in a temperature-gradient furnace4 for 89 days. Room-temperature Debye-Scherrer photograms were then made at points along the wire to determine the temperature below which the ordered phase was stable. Although the accuracy of temperature determination in the gradient was only about ±10 °C, the temperature gradient was sufficiently gradual that the sensitivity was much better and locations which had differed by as little as 1°C could be distinguished. An analysis of the crystal structure of the well ordered alloy was made by X-ray diffraction using a specimen cut from this wire. The change of Debye-Scherrer pattern as ordering progressed was studied by using isothermally aged samples of initially disordered wires. The wires were sealed under low-pressure argon in small quartz tubes for heat treatment. After the aging treatment, the tubes were quenched in water and photograms were made at room temperature in a 10 cm diam camera using filtered Cu kX. (A = 1.540511) Hardness was measured on a Vickers hardness tester using a 10 kg load and 2/3 in. objective lens. Reported values are the average of at least three impressions made on flat specimens 0.060 in. thick. After the hardness of a heat-treated sample had been measured, it was resealed in low-pressure argon and returned to the furnace for continued aging at the same temperature. In this way, two samples served for all aging times at each temperature. Hardness specimens which had been aged 500 hr or more were used for metallographic examination after the final aging treatment. A dilute potassium-dichromate etching solution was used.

Jan 1, 1955

By J. L. Meijering

Oxidation hardening of cylindrical and spherical specimens first decreases with depth below the surface, but then increases again as the center is approached. This is in agreement with the view that this change in hardness is mainly determined by the change in velocity of the oxidation boundary, which affects the dispersion of the oxide. WHEN a thick slab of silver containing 0.3 pct Mg by weight is internally oxidized, the hardness measured on a cross section is found to decrease considerably with distance from the surface.&apos; This phenomenon has been attributed to the diminution of the velocity of the oxidation boundary. The smaller this velocity is, the more slowly the free-oxygen concentration rises towards the concentration in equilibrium with the oxygen gas. And a small 0 concentration favors dissociation and thus conglomeration of the oxide. For instance, the hardness decreases more rapidly during long annealings in nitrogen than in air.&apos; Measurements by Gregory and Smith3 on sections through internally oxidized Al-silver wire showed a smaller variation in hardness, probably because the wire diameter was only 0.9 mm. Wood4 found a drop in hardness with depth in internally oxidized Al-copper strip, and also—by electron microscopy—the concomitant increase in Al2O3 particle size. Under certain circumstances internal oxidation leads to formation of rather irregular inner oxide films in the midst of dispersed oxide. This special sort of conglomeration—discussed in Ref. 5—is also favored by greater depth below the surface.3,5 In this paper hardness measurements in large diameter cylindrical and spherical specimens are described. Here the oxidation velocity* goes through ness initially decreases with depth but increases again towards the center. Normally, the diffusion coefficient D1 of oxygen is very large compared to D2, that of the dissolved metal. If, furthermore, the atomic fraction c2 of the latter is much larger than the O-solubility cl- but c2D2 << c1D1- the velocities in question are easily calculated2 to be: for the cylinder and for the sphere. Here p is the radial coordinate of the oxidation boundary and R the specimen radius, which in dilute silver alloys is constant, as no external oxidation occurs. These equations have been derived for a divalent solute; for nondivalent solutes c2 has to be multiplied by half the valency. The equations are not valid near the center. For which can be considered as a standard case,2 the Eqs [I] and [2] begin to yield U-values which are appreciably too high for p/R = 0.05 and 0.15, respectively. But at the v-minima they are still very good approximations. These minima lie at p = emlR= 0.37R in the cylinder and p = 1/2 R in the sphere. Other factors besides the velocity v will also influence the hardness. The oxide concentration cox is constant in a flat strip, apart from a narrow region in the middle,2 but in cylindrical and spherical specimens cox decreases steadily with depth. When C1 << c2 and c1D1 >> c2D2 one can calculate

Jan 1, 1961

By C. H. Herty

Almost every metallurgist who has given the Howe Memorial Lecture has had a personal contact with the distinguished gentleman to whose honor this hour is devoted. Unfortunately for me, such personal contacts were not possible. However, in the preparation of a thesis on the open-hearth process, one of my earliest tasks was to make a survey of the literature, and it was from Professor Howe&apos;s Metallurgy of Iron and Steel that I drew a number of references to previous work which formed the foundation for my reading. In his volume there is such a complete exposition of the then current thought on the subject of slags and on their role in the elimination of phosphorus from steel that I feel no hesitation in discussing in this Howe Lecture the subject of "Slag Control." In the present era of close specification, the drive for uniformity of product, and the close inspection of the product and of the cost sheet, the utmost efforts must be made to control the steelmaking variables to the best advantage of the steel producer. One of the major variables is the slag in the furnace and its effect upon the composition and quality of the metal. What advantages are to be gained from slag control? In the broad sense the advantages must be tremendous, because the very foundations of good steel melting are based on "shaping up" the slag to a point where, with proper temperature, the heat is ready for the final additions. Every melter works toward these ends through his experience with innumerable heats of steel. The elimination of undesirable constituents such as phosphorus and sulphur is entirely a matter of slag composition and physical nature, a point well known for over half a century. The role played by the slag in assisting in proper heat transfer from roof and flame to the steel has been equally well known. In more recent years there has come the problem of oxygen control in the more accurate gauging of additions for making high-grade rimmed steel for the new strip mills, and in the deoxidizing additions for grain-size control and cleanliness of forging steels, both carbon and alloy. In this problem the oxidizing characteristics of the slag are of prime importance.

Jan 1, 1940

By C. H. Herty

Almost every metallurgist who has given the Howe Memorial Lecture has had a personal contact with the distinguished gentleman to whose honor this hour is devoted. Unfortunately for me, such personal contacts were not possible. However, in the preparation of a thesis on the open-hearth process, one of my earliest tasks was to make a survey of the literature, and it was from Professor Howe&apos;s Metallurgy of Iron and Steel that I drew a number of references to previous work which formed the foundation for my reading. In his volume there is such a complete exposition of the then current thought on the subject of slags and on their role in the elimination of phosphorus from steel that I feel no hesitation in discussing in this Howe Lecture the subject of "Slag Control." In the present era of close specification, the drive for uniformity of product, and the close inspection of the product and of the cost sheet, the utmost efforts must be made to control the steelmaking variables to the best advantage of the steel producer. One of the major variables is the slag in the furnace and its effect upon the composition and quality of the metal. What advantages are to be gained from slag control? In the broad sense the advantages must be tremendous, because the very foundations of good steel melting are based on "shaping up" the slag to a point where, with proper temperature, the heat is ready for the final additions. Every melter works toward these ends through his experience with innumerable heats of steel. The elimination of undesirable constituents such as phosphorus and sulphur is entirely a matter of slag composition and physical nature, a point well known for over half a century. The role played by the slag in assisting in proper heat transfer from roof and flame to the steel has been equally well known. In more recent years there has come the problem of oxygen control in the more accurate gauging of additions for making high-grade rimmed steel for the new strip mills, and in the deoxidizing additions for grain-size control and cleanliness of forging steels, both carbon and alloy. In this problem the oxidizing characteristics of the slag are of prime importance.

Jan 1, 1940

DEVELOPMENT of a chemical process for the extraction of pure metals from mill concentrates or metal scrap has progressed beyond the pilot plant stage and may prove an important adjunct to present smelting and refining methods if initial commercial operations prove economically successful. Developed by the Chemical Construction Corp., the new process involves the treatment of oxide and sulphide ore concentrates by chemical methods, instead of the usual smelting and refining techniques. Several of the many applications are now scheduled for commercial use. Refiners using the new process will prepare ore concentrates by standard flotation methods, introduce the concentrate as a slurry into an autoclave along with water and an acid or ammonia. From the resulting leach solution, recovery of individual metals is made by use of suitable reducing agents. By varying conditions during treatment, different metals in the ore are produced separately as pure powders, which may be pressed into forms ready to market, or in the case of copper, extruded as rods or pipe. The reagents are generally recovered. By manipulating the variables during reduction, selective separation of nickel, and/or cobalt, and/or copper can be made simultaneously. The separation is a continuous operation. Low metal prices are not immediately in view because of the tremendous demand at this time. However, reduced metallurgical treatment costs will allow economical mining of orebodies with lower metal content, permitting increased production to meet demand. Although the practical horizon for use of the new process appears to be limitless, one factor may enter into its employment. Just how low grade a concentrate can be economically used is unknown. In addition, for present practical considerations, only metal below zinc in the electromotive series may be processed. Each commercial application requires specific technique adaptation and pilot-plant data for engineering design. A nickel-cobalt-copper process has been researched and piloted in collaboration with Sherritt Gordon Mines, Ltd., for the firm&apos;s Lynn Lake properties. In addition, processes were tailored for cobalt concentrates of Howe Sound Mining Co., and National Lead Co., in view of the urgent need for this specific metal. Major General William N. Porter, president of Chemical Construction, says of the new process, "piloting experience has shown that production cost, from ore concentrates to pure metals should be considerably below current costs." Other savings may be realized by cutting transportation and personnel costs, and by reducing the time lag between mining and pure metal from months to a matter of hours. First commercial use of the process will start sometime this summer. Chemico is slated to finish building a $2.5 million cobalt refinery for Howe Sound Mining near Salt Lake City. The plant is expected to raise world cobalt production by 40 pct. The plant will process 35 tons of 20 pct cobalt concentrates from Howe Sound&apos;s Blackbird mine near Cobalt, Idaho, daily. Yearly production is expected to reach 2000 tons of pure metal, about one half of U. S. consumption in 1950. Steps in the Howe Sound application of the process are: 1. Acid oxidation leach. 2. Filtration (residues thrown away are insoluble compounds-gangue, iron, arsenic). 3. Cementation (for Cu removal because Cu content is too low for recovery). 4. Reduction from ammoniacal solution. 5. Separation of Co and Ni as mixed metals (95 pct Co and 5 pct Ni). 6. Recovery of ammonium sulphate. Under construction at the Fredericktown, Mo., mine of National Lead is a $5 million refinery sched- [ ]

Jan 1, 1952

By R. S. Dean

PROCESSES for the direct production of iron and steel from ores are hardy perennials, and new processes and revivals of old ones are continually being brought to the attention of the investing public if not to the attention of metallurgists. Direct production of iron and steel is so simple that it offers a fertile field for the promoter. Unfortunately in this way direct processes have acquired a bad name, not always deserved, with conservative capitalists and metallurgists. Direct processes cannot, except in special instances, be looked upon as a substitute for any single operation in present iron and steel practice but must be considered, as one link in an entirely new chain of metallurgical process from ore to finished steel. Thus it is, in my opinion, inadvisable to consider the use of sponge-iron processes as a means of treating ore of ordinary blast-furnace grade to produce open-hearth feed. In time I think it will be found equally inadvisable to smelt iron-ore concentrates in the blast furnace.

Jan 1, 1935

By S. C. Sun, T. Chao

The reaction of gaseous sulfur trioxide with different aluminum-bearing minerals for the conversion of their alumina content into water soluble sulfates has been investigated. Theoretical considerations indicate that this reaction is thermodynamically feasible and that preferential sulfatization can be accomplished. The five minerals tested were gibbsite, boehmite, diaspore, kaolinite, and halloysite. In general, over 90% sulfatization could be achieved in 1 hr when using sodium sulfate as an additive at a temperature between 500° and 600°C. It was found that sulfates of the light alkali and alkaline earth metals exhibited some effectiveness in promoting the sulfa-tizing reaction. Selective sulfatization of alumina in a mixture of calcined halloysite and ferric oxide was accomplished. The gas-solid type of sulfatizing reactions have become increasingly important in recent years for the treatment of the oxides of such nonferrous metals as cobalt,&apos; nickel,&apos; manganese,3 zinc, and copper.4-6 Similar reactions were attempted in the present investigation for the recovery of aluminum from the low grade aluminous ores. Unlike the Bayer process in which silica is a serious contaminant, or the acid processes whereby iron usually causes difficulties, the reactions between gaseous sulfur trioxide and various aluminous minerals could hopefully be selective for aluminum. THEORETICAL CONSIDERATIONS Reactions between aluminum-bearing minerals and gaseous sulfur trioxide have been shown respectively in Table I and Fig. 1 to be thermodynamically favorable for temperatures below 1000°K approximately. Calculations of the thermodynamic functions were where ?G, ?H, ?Cp and ?S are changes in free energy, enthalpy, constant-pressure specific heat, and entropy of the system under consideration, respectively; T is the absolute temperature, R the universal gas constant, and K the equilibrium constant. Thermochemical data so far available for these calculations were based on sources given by T. Chao.7 In Table I, the free energy values indicate that reactions between the gaseous sulfur trioxide and

Jan 1, 1968

By F. R. Brotzen, D. L. Davidson

ALTHOUGH much effort has been devoted to the problem, the nature of plastic flow in bcc metals is still not fully understood. Some of the difficulties encountered stem from the scarcity of information on orientation effects and the uncertainty as to the glide system in these metals. In an attempt to provide some of this information, the present investigation was carried out, using zone-refined molybdenum single crystals deformed in tension and in direct shear. Considerable evidence exists to indicate that the primary slip system for molybdenum is (110) <111>.1,2 Figs. 1 and 2 indicate that this is, indeed, the case for direct shear at room temperature (see Ref. 3 for a description of the shear-testing equipment and procedure). Moreover, from Fig. 2, the shear stress on the (123) is lower than that on the (112). This would be the case if, as has been suggested,4,5 slip on these two planes is in reality com-

Jan 1, 1965

By Arthur S. Dwight

THE professional career of Thomas Septimus Austin, who died at El Paso, Tex., August 23, 1906, was contemporaneous with the growth of the silver-lead smelting-industry of the Far West, to which his talents and zeal contributed in no small degree. Born at Stratford, Conn., December 7, 1853, he was the seventh son in a family of thirteen. His parents were well-to-do; and he received a thorough preliminary training at the Hopkins Grammar School, New Haven, Conn., passing thence to the Columbia School of Mines, in New York, where he was graduated in 1876. His first professional work was that of analytical chemist with a Cuban sugar company. In this position he spent a year, and, whatever else of benefit he may have acquired during that year in Cuba, he gained a facility of speech in the Spanish language which was of inestimable value in his subsequent work in Mexico and the southwestern United States. In 1877, he went to the Rocky Mountains, and, under the firm name of Murphy & Austin, opened an assay-office in Leadville, Colo., which was just then coming into public notice as a rich silver-lead camp. The next year, however, he entered the service of the Germania Smelting & Refining Co. at Salt Lake City, Utah, where he remained until 1882, first as assayer and chemist, and later as Assistant Superintendent. The Germanic bears the honorable distinction of being one of the first of the large " custom " lead-smelters erected in the West. Its founders may be called the pioneers of the modern lead-smelting practice, and the Germania served, to a large extent, as a model for the many plants that sprang into existence during the next few years in Utah, southern Idaho, Colorado and other lead-producing districts. The formulation, for the first

Jan 1, 1908

By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of liquid Mg-Ge alloys have been determined between 1000°and 1500°K by an isopiestic method. Germanium specimens, heated in a temperature gradient and contained in covered graphite crucibles of special geometry, were equilibrated with magrtesium vapor in closed titanium tubes. The crucible design allowed free access of magnesium vapor to the samples during the equilibration to form alloys of magnesium and germanium, but prevented magnesium losses from the crucibles on quenching the titaniuin tubes to terminate the experimental runs, thus preserving the equilibrium alloy compositions. The activities and partial molar enthalpies of magnesium and the integral thermodynamic properties of the system were calculated from the experimental data. THE Mg-Ge phase diagram&apos; shows one congruent melting compound, Mg2Ge, of essentially stoichio-metric composition, two eutectics, and very limited terminal solid solubilities. Very little information is available on the thermodynamic properties of the Mg-Ge system. The free energy of formation of Mg,Ge was recently deter-mined2 by a Knudsen cell technique in the temperature range 610° to 760°C. The standard enthalpy of formation of Mg,Ge was measured calorimetrically by Bever and coworkers.3 The present study was undertaken as part of a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,4 Mg-Sn,5 Mg-Ge, and Mg-Si. An isopiestic technique was used which was developed by the authors5 for investigating the thermodynamic properties of liquid Mg-Sn alloys. Specimens of the nonvolatile component, contained in covered graphite crucibles, are heated in a temperature gradient in an evacuated and sealed titanium reaction tube, and equilibrated with magnesium vapor of known pressure. The method employs crucibles of special geometry which preserve the high-temperature equilibrium composition of liquid alloys having a highly volatile component such as magnesium on termination of the experimental runs by quenching the crucibles to room temperature. EXPERIMENTAL PROCEDURE First reduction germanium of 99.999+ pct purity (Eagle-Pitcher Co., Cincinnati, Ohio) and 99.99+ pct magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) were used. The graphite crucibles were machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non-reactivity of graphite with germanium at the temperatures used in this study had been previously established by Scace and Sleck.6 The experimental procedure has been previously described in detail.5 The selection of a particular crucible geometry for a run was determined by a combination of imposed experimental conditions, the principle being that more tightly covered crucibles were required to preserve alloy compositions during quenching when higher magnesium pressures and higher specimen temperatures were used. Depending upon the composition range of the equilibrated alloys the source of the magnesium vapor was either pure magnesium or a two-phase mixture of Mg2Ge + Ge-rich liquid of known magnesium pressure. The experimental runs can be divided into the following three groups on the basis of crucible geometry and magnesium source material. Crucibles with Small Holes and Pure Magnesium Reservoirs. The crucible dimensions were identical to those of the Mg-Sn investigation5 except that the hole diameters were reduced to 0.010 in. because of the higher temperatures and higher magnesium pressures involved in the Mg-Ge system. During an equilibration run, magnesium vapor diffused from the reservoir to each specimen through the small holes, one drilled through the crucible lid and two others drilled through graphite baffles positioned vertically inside the crucible between the lid hole and the specimen. Since the magnesium pressure was high, i.e., in the range 117 to 277 Torr, during the equilibration time of approximately 24 hr, equilibration was not impeded by these holes. A specimen composition at equilibrium was fixed by the relative temperatures of the specimen and the reservoir, and by the thermodynamic properties of the system. Upon brine quenching the titanium reaction tube to end a run the vapor pressure of magnesium above the liquid alloys decreased exponentially with decreasing temperature, and the small cross-sectional areas of the holes (4.9 x 10"* sq cm) drastically reduced magnesium losses from the crucibles. Because of its low vapor pressure, germanium losses from crucibles during a run were at most 0.2 mg for pure germanium and correspondingly less for the alloys. This crucible geometry satisfactorily retained the equilibrium alloy compositions on quenching for magnesium-rich (from 3 to 33 at. pct Ge) alloys provided their temperatures were below the melting

Jan 1, 1967

By Carl A. Zapffe, George A. Moore

IN a previous publication from this laboratory1 the conclusion was drawn that the embrittling effect of occluded hydrogen on iron and steel must result from the precipitation of the gas within small openings through the crystal structure. A review of the literature then published indicated the real existence of crystal sub- structures of the mosaic type and gave presumptive evidence that the "rift openings" associated with hydrogen occlusion are the same as the "disjunctions" of the mosaic theory. Inasmuch as no clear conception of the actual nature of the crystal fragments and openings inherent in these theories has been established, it was considered desirable to obtain direct micrographic evidence of their true configuration. In this direction the standard methods of metallographic attack have proved useless. Recourse was had, therefore, to the direct examination of the surfaces upon which failure by cleavage had resulted from the presence of hydrogen. It was expected that such a surface, un- affected by chemical attack and undistorted by polishing, would reveal the fine openings penetrated by the gas and thus indicate the real nature of the substructures. MATERIALS STUDIED In commercial steels, defects caused by hydrogen take various external forms ac- cording to such factors as structure and purity, and to the extent to which hydrogen either occludes or produces chemical changes. The present work relates only to the well-known transcrystalline hydrogen embrittlement-"pickling brittleness"-in which elemental hydrogen occluded within the grain develops cleavage characteristics. For example, hydrogen embrittlement resulting from hydrogen reaction products is excluded from detailed study. It was also desirable, as far as possible, to have the study uncomplicated by other elements which themselves cause brittleness. Three types of iron were used. These included ingot iron, decarburized free- machining steel, and a specially prepared, aluminum-killed, electrolytic iron. This , choice allowed a comprehensive selection of unavoidable minor impurities and inclusions, which could subsequently be shown to have no specific effects on the structures within the grains. Carbon, and any other impurities free to react with hydrogen, were first removed by a preliminary annealing treatment in hydrogen. Subsequent treatment in vacuo extracted much of this hydrogen and its gaseous reaction products. The resultant ductile iron was then embrittled either by a second anneal in hydrogen, followed by rapid cooling, or by cathodic electrolysis. Group I: Prepared from Armco Ingot Iron As shown in Table I, the principal impurity in this iron was oxygen, which survived the purifying treatment to a large extent. Two series were prepared. The first (Nos. SIO-24) was purified only one day in hydrogen and dehydrogenized one day in nitrogen. Containing both hydrogen and its

Jan 1, 1943