Search Documents

By H. L. Teichman, E. M. Sipprelle

ENACTMENT' of Public Law 290 by the 78th Congress authorized the U. S. Department of the Interior, Bureau of Mines, to conduct an experimental program to develop the technology for obtaining oil from oil shale. In adopting and later extending this legislation, the Congress recognized the impending necessity of supplementing ground petroleum reserves with synthetic fuels. Under the provisions of this legislation, the Bureau of Mines, among other things, was charged with the responsibility of developing mining techniques, methods, and equipment for mining the oil shales of the Green River formation of Colorado, Utah, and Wyoming. The oil shales of western Colorado are apparently richer, more accessible, and more amenable to exploitation than elsewhere in the Rocky Mountain region. The site chosen for the Bureau's Experimental mine is about 10 miles west of Rifle in northwestern Colorado. It is within a 1000-sq-mile area from which, it has been estimated, 300 billion barrels of shale oil could be produced from a 500-ft measure near the top of the formation. One hundred billion barrels of this amount could be produced from the Mahogany ledge, a 60 to 100-ft section near the bottom of the 500-ft measure. This ledge is considered to have economic importance at present. The Green River formation was laid down as sediment in the bottom of vast, shallow inland lakes during Eocene time. The deposit is flat-lying, and there are no faults, fissures, or local rolls. Oil shale is actually a strong, tough magnesium marlstone, which will stand unsupported over relatively wide spans. These and other natural physical characteristics favor mechanized, low-cost mining, which is essential for establishment of an oil-shale industry. It was realized from the outset that an extensive research program would be necessary to develop mining methods, equipment, and techniques for a mechanized, low-cost operation. The program was designed to include research. into all the productive phases of mining, such as drilling, blasting, loading, transportation, and maintenance of the mine structure. The methods, equipment, and techniques developed as a result of this research have established a production of 116 tons per man-shift total labor at a direct cost of $0,292 per ton. Another important phase of the research program that has received little publicity because of its theoretical nature is study of the roofstone behavior and determination of mine structure stresses. This paper purposes to discuss this phase of the research program. Preliminary studies of the physical properties of the Green River oil-shale formation were made in the Barodyramics Laboratory at Columbia University during the latter part of 1945 and the early part of 1946.* The purpose of these studies was to determine the maximum size of unsupported underground openings that would be commensurate with safety and still permit the use of large, efficient mining equipment. Also to be determined were the pillar support to extraction ratio and the shape, size, and spacing of supporting pillars. Selected samples of possible roofstones near the top of the Mahogany ledge, as well as representative samples of different rock types found within the ledge, were obtained from the Bureau's oil-shale mine for these studies. The maximum safe unsupported roof span calculated from this work was 200 ft. Using a safety factor of four, it was theoretically determined that openings 60 ft wide could be advanced under a roofstone at the top of the Mahogany ledge. To support the overburden, 60-ft-sq pillars would be left in a checkerboard pattern. From visual observations made of core samples through the selected roofstone at the oil-shale mine, it was determined that the roofstone was actually a plate 6 to 8 ft thick. Because the calculations were theoretical and allowance had to be made for unknown cracks and fractures in the formation, openings 50 ft wide and pillars 60 ft sq were originally contemplated in the Bureau's Experimental mine. This would be the minimum allowable width that would permit use of large underground mining equipment. For lower mining costs and greater efficiency larger openings were desirable. Different but analogous approaches were made to the problem at the Bureau of Mines Applied Physics

Jan 1, 1951

By Otto H. Henry, Edward L. Badwick

Up to the present time, according to Hansen1 and Haughton,2 the constitution of the bismuth-indium system has not yet been published. The generally accepted value for the melting point of indium, as listed in most scientific journals and textbooks, is 155°C. Recently, however, H. M. Davis3 has determined a new melting point for indium of 257.3°C ± 0.1°C. Since bismuth has been used in preponderance as an alloying element in the majority of low-melting alloys, and indium has been used with considerable success in lowering the melting points of low-melting alloys,4,5 an interest has been developed in the application of these two metals, making a complete knowledge of the constitution of its alloys desirable. In this investigation, the melting point of indium reported by H. M. Davis has been found to be substantially correct. A value of 157.2°C ± 0.5°C was determined. The two eutectic compositions have been placed at 34 and 50 pct bismuth with their respective eutectic temperatures as 72.4'C ± 0.5°C and 90°C ± 0.5°C. The bismuth-indium phase diagram has been determined by thermal and microscopic analysis and is shown in Fig I. THERMAL ANALYSIS Granulated bismuth and indium shot, having a guaranteed purity of 99.99 and 99.95 pct, respectively, were melted in a carbon crucible by means of a laboratory heater. To minimize oxidation of the alloys, a heavy mineral oil (Nujol) having a high flash point was used. A platinum-platinum rhodium thermocouple 0f fine wire encased in a thin-walled Pyrex glass tube, about 1/8 in. in diameter, was connected to a type K potentiometer for temperature measurements. The thermo-couple was calibrated against the melting points of tin, bismuth, and the silver-copper eutectic and the boiling point of water. Since the temperature readings could be reproduced to 0.2°C, and the accuracy of the temperature standards in this range is slightly better than 0.5°C, it seems reasonable to assume that the temperature readings are reliable to approximately 0.5°C. The cooling rate could be controlled by varying the amount of insulation surrounding the crucible. Three or four layers of asbestos paper, 1/16r, in. thick, sufficed to give a cooling rate of from 1° to 2°C per minute. Undercooling was slightly noticeable. This condition was minimized by vigorous stirring, since the advantage of using slower rates was too small to justify the greater expenditure

Jan 1, 1947

By Joe B. Alford

Founding of the Institute The advance of population and civilization in the U. S. moved through the woodlands of the East, and reached the edge of the great central plains about the middle of the nineteenth century. There the advance paused for almost a generation - ahead were vast reaches of prairie country, uncharted, forbidding, and populated by hostile tribes of the native Indians. The turmoil of the Civil War, and the readjustments following it, further delayed the advance. By about 1870, the Nation was becoming stabilized again, the conflict with the Indians was closing, and the pressure of growth was forcing population to resume its westward movement. In addition to geography, the Nation had another frontier: the development of its immense natural resources. Conditions of the time brought into sharp focus the need for coal, iron, steel, gold, silver, and other minerals. The application of engineering and science was necessary for the production of these minerals and their manufacture into products to meet the needs of a growing nation. The requirements of the time were eloquently expressed in a paper by AIME member Edmund C. Pechin in 1872 : We find, the world over, the most intense activity everywhere displayed in enterprises requiring prodigious quantities of iron. Railways of colossal magnitude are projected. . . . The growing scarcity of timber is compelling the use of iron in buildings; bridges of wonderful size and strength; huge ocean steamships; barges and boats for lake and river traffic; churches; cars, and thousands of minor articles of every shape and size. . . . The time has come when scientific research is to assume its true position - the day of "sheer force and blind stupidity," whose only protection is a high tariff, has gone forever . . . the physicist, the geologist and mineralogist; the chemist, the engineer, are as essential to success as the [blast] furnace itself. . . . There is no merely practical man, no matter how varied may have been his experience, or how long his practice, that will not benefit from the results of scientific investigation. That there is a growing sense of the importance of having thoroughly prepared scientific men in every department of business is evidenced by the institutions [of learning] that are springing up in different quarters, provided with

Jan 1, 1971

By C. S. Matthews, M. J. F. Rosenbaum

The purpose of thir work wax to lcarn it~lzut infori~lation could he obtained from various typs of pilot water floods and to attempt to find the optunum pilot patter11, for a revervoir which had previously been depleted by a solution gas drive. The study was made in the laboratory with mathemetical methods a dynamic analog and a potentiotnetric analog. Results werp tested against the field llistorics of a nrrnlber of pilot water floods. At a reasonable valrre of currzulative injection, the total production rate for the one-injector five-spot should reach about 6.5 per cent of injection rate, and for a four-injector five-spot, about 9 per cent. Accurate estimates of ultimate recovery cannot be made on the basis of such snzall prorluction rates. However, with a pilot composed of nine ir1jector.s and 16 producers the production rate is approximately 50 pcr cent of injection rate at a reasonable value of camulative injection. Sonle inforn~ation for extended performance predictions might he obtained from such a large pilot. These conclusions were drawn on the basis of results obtained for unit mobility ratio, and a sturly using tlre potentiometric analog was made of the effect of other mobility ratios to determine the range of applicability of these predictions. For the four-injector, five-spot pilot with the ratio of production to injection rate (before water breakthrough) is about twice that for with it is about two-thirds; and with M0= 10, it is about one-third For high mobility ratios, it was found that the production rate increased considerably as water-cut increased. These result can be used to modify, qualitatively, the inter.pretntions based on curves for the unit rnobilit\. ratio CaSeS. It was found that the maximum ratio of production rate to injection rate obseriled in field pilot floods was of rhe scime order as that prerdicted by these methods. The time required to reach thisr maximum did not generally agree with the time predicted for a homogeti~orir reservoir. The differcrlce between predicted and observed time of response gives an indication of the permeability profile and of the condition of the producin,g wells. Pilot water floods of the pattern type are generally carried out in reservoirs which have been depleted by solution gas drive and are at low pressure. Under these conditions, oil and water can be considered incompressible. It is assumed that, as the water is injected, an oil bank forms ahead of it and that there is a distinct interface between the water zone (or bank) and the oil zone (or bank) and between the oil zone and the region ahead of the oil zone. It is further assumed that only gas is mobile in the unflooded (gas) region, only oil is mobile in the oil bank and only water is mobile in the water bank. The saturations and the mobilities associated with each zone are assumed uniform. We idealize our reservoir to be homogeneous, horizontal and of constant thickness. Effects of gravity within the producing layer are assumed negligible. If the actual time-dcpendent flow problem is approximated by a acries of steady-state problems. the potential and stream function in the oil bank and water hank satisfy Laplace&apos;s equation in two dimensions. We can therefore use a poteiitiometric analog of this system. Potentiometric models have yielded uscful results in this laboratory&apos; and clsewhere in the study of a variety of secondary recovery problems. For the case where M = I, we generally prefer to use theoretical mcthods as well as a simpler dynamic analog. Except where otherwise noted, the ratio, side of five-spot/wellbore radius. is taken to be 3,600. a figure which corrcsponds to a normal-size wellbore in a 10-acre well spacing. THEORETICAL EVALUATION OF VARIOUS PILOT PATTERNS, Mw0 = 1 <&apos;he theoretical models which we used to examine the performance of various pilots are shown in Fig. 1. Image theory was used to determine the ratio of production rate to injection rate as a function of the volumc of the flood. The ratio of production rate to injection rate was chosen because this is an easily measurable quantity which is characteristic of a pilot

By Floyd C. Kelley

THE literature of the last decade is rich with information relating to the cause and means of control of grain growth in pure metals, but is deficient concerning the role diffusion plays in grain growth, although during this period many new products that depend on diffusion for their properties and success have been developed. Among these are cementation products, produced by calorizing, chromizing, and carbonizing, or by mixing, pressing, and sintering powdered metals such as Syke&apos;s iron-molybdenum die material, Genelite, and Elcon Metal (copper, tungsten) etc. This is a fertile field for new developments, but before it can be utilized to the fullest extent there must be a thorough investigation of the processes by which diffusion and grain growth take place. Grain growth plays no small part in the process and certainly the physical properties of these products depend largely on the grain size and state of equilibrium produced. The field of investigation does not end here, but may be extended to the effect of diffusion on impurities, segregations and dendrites in the broad field of ferrous and non-ferrous metallurgy. A number of years ago the author investigated several of these cases and noted, with striking regularity, the pronounced effect of diffusion in promoting recrystallization and grain growth. An example of this phenomenon is given in his paper on chromizing1 which contained photomicrographs of large radial or columnar crystals produced by diffusion of chromium in the solid state. Another manifestation of this effect was discussed by Austen,2 who showed the part hydrogen plays in the decarburization of steel and the effect of diffusion upon the grain structure. DIFFUSION OF METALS IN IRON It seems to be a general law, whenever two metals are brought into intimate contact at a temperature at which diffusion takes place, that a comparatively rapid, or abnormal, grain growth results. The grains

Jan 1, 1928

By Sherwin Kelly

The prime objective of geophysical exploration is to promote the economical and rapid dis-covery of mineral or oil deposits of commercial value. To a few this concept as applied in min-ing may signify the direct discovery of ore-bodies, but to the geophysical engineer this latter Idea is one of the most insidious and detrimental misapprehensions which he has to combat. The destruction of this annoying obstacle to the progress of geophysical exploration reveals the kernel of truth behind it, that the exploration geophysicist has for the better part of two decades been concerned primarily with the discovery of mineral formations favorable to the occur-rence of commercial ore. There is a very real distinction here, since geophysical methods are capable of discovering certain mineral formations such as sulphide bodies or quartz veins, but are totally incompetent to predict whether or not they constitute ore; that is. whether or not they contain minerals of economic value in the amounts requisite to repay extraction. The art of geophysical exploration is now, however, rapidly outgrowing these early limita-tions. The rate of this growth will in large measure depend on the recognition by the mining industry of the fact that geophysics can play a role far wider and more important than it usual-ly does now, in guiding the future exploration and development of mineral deposits. It is my own firm conviction that as time marches on we will see the methods of applied geophysics turned more and more to the delineation of both minor and major structural features. The outlining of such features having a bearing on the probable loci of mineral deposition will be of inestimable value in guiding the development of a mining district. It is in this field that there will In-evitably occur a meeting and overlapping of the activities of the exploration geophysicists and

Jan 1, 1940

By R. C. Ku, A. J. McEvily, T. L. Johnston

The microplastic response of a series ofas-quenched Fe-Ni-C martensites has been measured at 77°K. At strains less than JO&apos;3 the flow stress is governed primarily by the transformation-induced dislocation structure of the martensite. Only at strains in excess of 10-3 is the influence of carbon manifested in the flow stress. At these macroscopic strains, typically 10-2, the solid-solution hardening is proportional to (wt pct C)1/3, and, in an alloy containing 0.39 wt pct C, amounts to 50 pct of the flow stress. THE technological significance of high-strength ferrous martensite has stimulated many investigations of its structure and properties. Although our knowledge of the characteristics of martensite has increased immensely, especially with the advent of high-resolution techniques, an understanding of the basic strengthening mechanism still remains elusive. The purpose of the present paper is to consider certain aspects of micro-plastic behavior of Fe-Ni-C martensite which we feel can help to resolve this important problem. Such alloys are particularly suitable for experimental investigation because their compositions can be adjusted to reduce the M, to a temperature low enough essentially to eliminate the diffusion of carbon in the freshly formed martensite.1 The mechanical properties in this condition are of interest inasmuch as they reflect a state that is free of the important but complicating influence of precipitation processes. In this virgin martensite the carbon is distributed as it was inherited from the parent austenite; i.e., it is present interstitially, and gives rise to tetragonality through strain-induced ordering.&apos; In order to determine the source of strength of such alloys, Winchell and Cohen1 investigated the low-temperature macroscopic stress-strain behavior of a series of virgin martensites of increasing carbon content but of common M, temperature (-35°C). They found that the flow stress increased rapidly with carbon content up to 0.4 wt pct; beyond this point the flow stress increased at a much slower rate. It was concluded that martensite is inherently strong. To account quantitatively for the strength of virgin or as- quenched martensite in terms of the role of carbon, Winchell and cohen3 suggested that the carbon atoms, trapped in their original positions by the diffusionless martensite transformation, interfere with dislocation motion according to a model akin to that of Mott and Nabarro. 4 In this treatment, individual carbon atoms are considered to constitute centers of elastic strain and thereby generate an average stress resisting the motion of dislocations throughout the lattice. The additional stress necessary to move dislocations, over and above that necessary for motion in a carbon-free martensite, is given by where L is an effective length of dislocation capable of motion. L was assumed to be limited to the spacing between the twins that are an essential structural element of Fe-Ni-C martensites. They assumtd the spacing to be invariant and of the order of 100A. However, recent work5 has shown that L is variable and can be in excess of 1000Å, so that the assignment of an appropriate value of L is not straightforward. In contrast to the above conclusion that there is an intrinsically high resistance to plastic flow, it has been suggested by Polakowski6 that freshly quenched martensite is in fact "soft" in the sense that dislocations are initially free to move upon application of stress. The high indentation hardness and macroscopic yield stress of ferrous martensites are then a consequence of rapid strain hardening that depends upon carbon in solution. Consistent with this point of view are the results of Beau lieu and Dubé who measured the rate of recovery of internal friction as a function of aging (tempering) temperature in a freshly quenched steel containing 0.90 wt pct C, 0.37 wt pct Mn, 0.1 wt pct Cr, and 0.07 wt pct Ni. The kinetics were clearly consistent with the idea that many dislocations are unpinned in the as-quenched state and that during aging they become progressively pinned by carbon at a rate controlled by carbon diffusion in the body-centered martensite lattice. In order to provide a basis upon which to distinguish between the "hard" and "soft" interpretations indicated above, we have made studies of the initial stages of plastic deformation in Fe-Ni-C martensites similar to those&apos;used by Winchell and Cohen. It will be shown that the results support the contention that dislocation segments in as-quenched material are indeed

Jan 1, 1967

By Michael J. Callow

THE PROPERTY of Mount Isa Mines, Ltd., is located at Mount Isa, Northern Queensland, Australia, at roughly 20" south latitude. It is 600 miles from Townsville on the east coast, the port for Mount Isa, 1200 miles from Brisbane and approximately 1600 miles from Sydney in New South Wales. Living conditions in the camp, though wild and crude at the commencement of building, are now excellent and little has been left undone to provide comfort and attractiveness. The climate being warm and dry, many of the buildings are built on posts, 8 to 10 ft. off the ground, with spacious screened-in verandas. Club houses, stores, school, hospital and ice plant have all been provided by the company as well as modern conveniences, such as running water, shower baths, electric lights, septic tank arrangements, tennis courts and amusement grounds.

Jan 1, 1932

By William Fink

THE investigation of the phase relations of high-purity aluminum-base alloys is a part of the fundamental research program of the laboratories of the Aluminum Company of America. The results of a number of binary and ternary systems have previously been published in the transactions of this society. The aluminum end of the binary aluminum-titanium system has been studied. This system has received relatively little attention. To the authors&apos; knowledge, there are two previous papers on this subject. E. van Erckelens1 determined the constitutional diagram reproduced in Fig. 1. .According, to this diagram, the liquids represents the separation of TiAl4 (Ti = 30.7 per cent.). He concluded that this is the composition of the compound, because in his work the eutectic horizontal terminated at 30.7 per cent. titanium and the metallographic examination of a sample of this composition revealed only one phase. According to the constitutional diagram developed by W. Manchot and A. Leber,2 reproduced in Fig. 2 from data given in their article, the liquidus represents the separation of the compound TiAl3 (Ti = 37.2 per cent. ). The composition of the compound was derived in a manner similar to that utilized by van Erckelens. Moreover, Manchot and Leber confirmed the composition of the compound by analysis of the constituent left as a residue after dissolving the alloys in weak sodium hydroxide solution. Although these are the only publications describing the constitution of the system, other investigators have studied the composition of the titanium compound. L. Wöhler3 says that there is a compound TiAl3 which was later confirmed by W. Manchot and P. Richter4 and by

Jan 1, 1931

By Mark J. Klein

The creep of 043 was studied over the temperature range 1650" to 3200°F and over the stress range 3000 to 44,000 psi. The steady-state creep rate over this range of stress and temperature can be expressed by the equation where A is a constant, is the stress, and is -0.8 x 103 psi-&apos;. Over a narrow range of stress variations c0 a and for this proportionality n varies from 3 to 30 in accordance with the relation n = aB. Above about 2400° F, H, the apparent activation energy for creep, is 110,000 cal per mole, a value about equal to that estimated for self-diffusion in this alloy. Below 2400°F, H increases with decreasing temperature reaching a value of -125,000 cal per mole at 1700° F. In this temperature region, H appears to be a function of the interstitial concentration of the alloy. MOST of the detailed creep studies of dispersion strengthened metals have been concerned with metals having fcc structures. However, there are a number of important refractory alloys with bcc structures that derive part of their high temperature strength from an interstitial phase and whose creep behavior has not been well defined. This paper describes the creep behavior of the bcc alloy, D43, over the temperature range 1650" to 3200°F (0.4 to 0.7 Thm) and over the stress range 3000 to 44,000 psi. In addition to colum-bium, this alloy contains 10 pct W. 1 pct Zr, and sufficient carbon (-0.1 pct) to form a carbide dispersion throughout the matrix of the alloy. The effects of variations in temperature and stress on the steady-state creep rate of this alloy are presented in this paper. EXPERIMENTAL PROCEDURES Creep tests were made in a vacuum of 106 torr under constant tensile stress conditions using a Full-man-type lever arm.&apos; Creep specimens were machined from 0.020-in. D43 sheet (grain size -5 x l0-4 in.) processed in a duplex condition (solution annealed -2900°F, 40 pct reduction in area, aged 2600°F). The specimens were tested in this condition without further heat treatment. Specimen extensions over 1-in. gage lengths were continuously recorded using a high temperature strain gage extensometer. Differential temperature and stress measurements were used to determine temperature and stress dependencies of the creep rate. Activation energies were calculated from the changes in strain rate induced by abrupt shifts in the temperature during constant stress creep tests. The 100°F temperature shifts used in most of the activation energy determinations required 15 to 90 sec depending upon the temperature at which the shift was made. The dependence of strain rate on stress was determined by measuring the change in strain rate for incremental stress reductions during constant temperature tests. It has been shown that columbium-base alloys such as D43 are susceptible to contamination by gaseous interstitial elements during vacuum heat treatments.&apos; In this regard, it is unlikely that these alloys can be heat treated without some loss or gain of interstitial elements despite the precautions taken to control the heat treating environment. However, several factors suggest that changes in interstitial concentrations of the specimens during testing did not affect the results presented in this paper. First, the dependence of the creep rate on the stress or temperature determined during the course of a single creep test showed no variations with the duration of the test. A variation would be expected if a loss or gain in interstitial concentration during the course of the test affected results. In addition, precautions taken during this investigation to minimize interstitial contamination by wrapping the gage lengths of the specimens with various foils2 (Mo, Ta, W) did not produce a detectable change in the stress and temperature dependencies relative to the unwrapped specimens. The averages of duplicate analyses for carbon and oxygen in several specimens determined before and after creep testing are listed in Table I. The combined nitrogen and hydrogen concentrations which were ordinarily less than 50 ppm did not change in a detectable way with creep testing. The analyses show that only minor changes in carbon concentration occurred during creep testing except for specimen 4. This specimen which was tested at 3100°F lost a significant amount of its carbon concentration to the vacuum environment. Specimen 1 gained 100 ppm of O, while specimens 2, 3, and 4, which were tested at progressively higher temperatures, lost increasing portions of their initial oxygen concentrations during testing. RESULTS AND DISCUSSION The Temperature Dependence of the Creep Rate. The apparent activation energy for creep, H, was de-rived from creep curves similar to that shown in Fig. 1. Steady-state creep was rapidly attained at the beginning of the test and with each change in temperature. This behavior suggests that the alloy rapidly attains a stable structure with each shift in temperature or that the structure is constant throughout the test. Since the dispersion will tend to stabilize the structure, the latter is probably the case. The activation energy was found to be independent of the direction of the temperature shift and the magnitude of the shift (50" or 100°F). Although H was approximately independent of the strain, there was a tendency for it

Jan 1, 1970

By R. F. Domagala, M. Hansen, D. J. McPherson

Iodide zirconium was combined with calculated amounts of nitrided zirconium sponge and arc melted to prepare alloys in the 0 to 6 wt pct N region. Annealing treatments were carried out at 21 temperature levels. Metallographic examination of the heat-treated specimens permitted construction of the binary phase diagram from 0 to 6 pct N. Features of the diagram include the peritectic formation of both a and ß solid solutions. The maximum solubility of nitrogen is 0.8 pct in 8 zirconium and 4.8 pct in a zirconium. An X-ray study of nitrided materials was made in the range 6 to 13 wt pct N region because serious nitrogen losses were experienced when attempts were made to arc melt these high nitrogen alloys. PHASE relationships in the Zr-N system have been determined. Due to the inability to retain nitrogen in nitrogen-rich alloys subjected to arc melting, definitive work was possible only in the range 0 to 6 wt pct (0 to 30 atomic pct) N. Sufficient complementary X-ray work was done to permit construction of the binary phase diagram up to 13.3 wt pct (50 atomic pct) N (ZrN). Small ingots were prepared by arc melting master alloys with enough zirconium to produce an alloy of the desired composition. Following pretreatment, alloys were annealed at temperature levels between 600" and 2020°C. Determination of the phase boundaries was then accomplished by metallographic evaluation of specimens quenched from the various temperatures. Incipient melting techniques were used to corroborate solidus curves, and X-ray diffraction was employed to study the nitrogen-rich region of the a + ZrN phase field. Materials Westinghouse Grade 1 iodide zirconium crystal bar served as the base material for this investigation. The as-received bars were lightly sandblasted, pickled in a 20 pct HN0-5 pct HF aqueous solution, rinsed in water and acetone, and dried. They were rolled to about 1/32 in. strip and acid-pickled, followed by water and then acetone rinses. The material was sheared to approximately 1/4 in. squares, cleaned with acetone, and stored for use. Pure zirconium nitride is not commercially available, according to correspondence with possible suppliers. A literature survey indicated that nitrogen may be introduced into zirconium metal by passing nitrogen or ammonia gas over zirconium at an elevated temperature. After considerable experimentation, a train was devised whereby high quality nitrogen was passed through a series of bubblers to remove the last traces of oxygen, through an H,SO, bubbler and a cold trap to remove moisture, and finally over zirconium within a resistance furnace. Hand-picked Bureau of Mines magnesium-reduced zirconium sponge proved more amenable to nitriding than the crystal bar. The nitrogen used was extra pure gas purchased from Linde Air Products Co. The first two bubblers through which the gas was passed contained a solution suggested by L. F. Fieser" as being ideal for removing the last traces of oxygen from nitrogen. The solution contains 20 g KOH, 2 g sodium-anthraquinone ,9-sulphonate, and 15 g NaHSO, dissolved in 100 ml water. It is blood-red and turns brown when contaminated with oxygen. A saturated lead acetate solution, next in the series of bubblers, removed any H2S which might have formed in the 0, removal stage. An H,SO, bubbler and cold trap removed moisture before the nitrogen was passed over the zirconium. The zirconium was contained in a stainless steel screen within a Vycor or quartz tube in a resistance furnace. Unreacted nitrogen passed out of the system through a mercury bubbler. A nitriding run was performed in the following manner: Zirconium was placed in the screen within the furnace tube. The unit was assembled, suitably clamped off, and evacuated to remove the air and moisture within the tube and that trapped by the zirconium sponge. The unit was flushed with nitrogen and evacuated twice. After nitrogen was allowed to pass over the zirconium for about 30 min, the furnace was turned on; several hours were required to reach temperature. The reaction was allowed to continue at temperature for about 4 hr and the screen was then withdrawn from the hot zone of the furnace by means of a Nichrome or Kanthal rod. The screen and its contents were allowed to cool at the end of the tube and were then removed. At 800°C no more than about 5 pct N could be introduced into the sponge zirconium. This material was designated M-1 (master alloy No. 1) and reserved for the preparation of alloys in the dilute nitrogen region. A second set of experiments was conducted at 1000°C; no more than 7.2 pct N could be introduced into the zirconium at this temperature. Enough material (M-2) of this nitrogen content was prepared to produce a second set of alloys to complement the first and to provide alloys in the 0 to 6 wt pct N range. It was hoped that a diffusion anneal plus a re-nitriding might yield a material of higher nitrogen content. The material containing about 7 pct N was therefore given a homogenization treatment at 1000°C for 6 hr under an argon atmosphere. It was

Jan 1, 1957

By W. M. Tuddenham, R. J. P. Lyon

In many areas surrounding the orebodies in mining districts rocks have been bleached and altered by the ore-forming solutions and have been oxidized during later weathering processes. A number of the rock-forming silic-ates have been broken down to clay, sericitic micas and chlorites have been developed, and pyrite may be found hundreds of feet outside the economic limits of the orebody. These halos of altered ground are prime targets used by geologists in many districts to delineate promising sites for drilling. Both in the field and in the laboratory it is often difficult to map these mineralogical changes in the halos in detail without numerous petrologic examinations. The secondary minerals are generally fine-grained, and since conversion of one mineral to another is often progressive, many alteration processes have not proceeded to completion (feldspars to clay to sericite mica). Qualitative detection of these minerals is difficult; quantitative determination is frequently impossible.

Jan 1, 1960

By Richard L. Gordon

Minerals long have been important commodities in international trade. As an inevitable result, the governments of the world have employed a wide variety of programs that affect the flow of trade. Roughly speaking, we may distinguish between the desire of more developed countries (MDCs) like the United States, western Europe, and Japan to control imports of minerals and the concern of less developed countries (LDCs), like India, about exploiting and exporting their minerals. The terminology used to describe different countries and the classification of specific countries into groups is unsettled and often changing. The poorest countries have been characterized as backward, undeveloped, underdeveloped, and developing. The problem seems to be in selecting a term that is both accurate and polite. Less developed seems, for reasons outlined by Hagen [pp. 51-57], the most convenient term. The borderline between an LDC and an MDC is always open to dispute. Objective measures are difficult to develop because of deficiencies in basic data, and enormous conceptual problems arise in making valid comparisons from even good data [see Hagen, pp. 7-28]. Thus, policies of the MDCs can be evaluated chiefly by using a few basic arguments for protectionist attitudes towards international trade. In dealing with the LDCs, a more far-ranging evaluation that covers general economic policy goals, the role of foreign investment, and the indirect effects of trade is required. This duality breaks down when trying to deal with the depressed areas in an MDC; here the issues are more akin to those associated with problems in an LDC. Similarly, variants of arguments used in LDCs appear in debates about foreign investments in MDCs. The whole discussion of minerals in LDCs, moreover, has obvious implications for MDCs like Canada and Australia. They, too, must face problems about the best utilization of their resources. THE RESTRICTION OF MINERAL TRADE BY DEVELOPED COUNTRIES[a] At least to some extent, the world&apos;s leading industrial nations have intervened to control the inflow of minerals. Such regulation is particularly pronounced for energy. Both the United States and western Europe employ

Jan 1, 1976

By J. L. Lehman, J. D. Sudbury, J. E. Landers, W. D. Greathouse

A full scale field experiment on cathodic protection of casing answers questions concerning (1) the proper criteria for determining current requirments, (2) the amount of protection provided by different currents, and (3) the transfer of current at the base of the surface pipe. Three dry holes in the Trico pool in Rooks County, Kans., were selected for cathodic protection tests. The three holes were in an area where casing failures opposite the Dakota water sand often accur in less than a year. Examination of the electric togs showed the wells to be similar to other wells in the field where casing in four of seven producing wells has failed. The three holes were cleaned out and cased with 75 joints of new 51/2-in. 14-tb J-55. Each joint was visually inspected and marked before it as run. The casing was bull plugged and floated in the hole 50 that the inside might remain dry and free of excessive attack. Also, if a leak occurred, a pressure increase could be observed on gawge at the surface. Extensive testing was done, including potential profiles, log current-potentid curves and electrode measurements from both surface and downhole connections. Based on these data, a current of 12 amps was applied to one well and 4 amps to mother. The third well was left to corrode. During the two-year period when the casing was in the ground, [he applied current was checked weekly, and reference electrode measurements were made about every two months. Three sets of casing potential profi1e.c were run. When the three strings were pulled, each joint was examined for type of scale formed, presence of sulfate-reducing bacteria, extent of corrosion nttnck and pit depth. Since the pipe was new when run, quantitative determination of the protection provided by current was possible. This is the first concrete field evidence to help resolve the many arguments about the proper method for selecting adequate current for cathodic protection of oilwell (-using. INTRODUCTION A casing string is run when a well is drilled. This pipe is supposed to protect this valuable "hole in the ground" for the life of the well. Often the casing does not last the life of the well; it is with these casing failures that this work is concerned. The cost of repairing a casing failure varies from field to field—from as much as a $30,000 per leak average in California to $5,000 per leak in Kansas. Additional costs other than actual repairs are also important. These include formation damage, lost production, etc. Casing damage caused by internal corrosion is important in some areas. Treatment normally consists of flushing inhibitor down the annulus, but further research is being done on control measures. The test described in this paper is concerned only with external corrosion. The problem of casing failure from external attack has appeared in several areas including western Kansas, California, Montana, Wyoming, Texas, Arkansas and Mississippi. Cathodic protection is currently being used in an attempt to control external corrosion. From reports in the NACE there are thousands of wells currently under cathodic protection. The quantity of current being applied ranges from 27 amps on some deep California wells to a few tenths of an amp being supplied from magnesium anodes on wells in Texas and Kansas. Considerable field and laboratory effort1,9,5,6 was exented on the problem of cathodic prctection of casing, and it became fairly obvious that this method could be used to protect wells. Early workers showed that current applied to a well distributed itself over the length of the casing and was not concentrated on the upper few hundred feet. Basic cathodic protection theory had shown that corrosion attack could be stopped by applying sufficient current. The problem resolved itself, then, into one of trying to decide just how much current was necessary. Various criteria were utilized in installing the many existing cathodic protection installations. These methods included the following. 1. Applying sufficient current to remove the anodic slope as shown by the potential profile." 7. Applying enough current to maintain all areas of the casing at a pipe-to-soil potential of .85 v.&apos; 3. Applying the current indicated by a log current-potential (or E log I) curve." 4. Supplying the current necessary to shift the pipe to-soil potential .3 v." 5. Applying 2 or 3 milliamps of current per sq ft of casing."

By H. Shaw

GRAVITATIONAL measurements made by means of the Eötvös torsion balance over any area enable a representation to be obtained of the total gravitational effects over the surface of that area arising from the combination of all sources of gravitational disturbance. The investigation of gravitational anomalies occurring in the upper layers of the earth&apos;s crust, in this way, has been attended with considerable success, and, especially in areas in which no undesirable disturbing factors were present, it has been possible to locate geological structures and mineral deposits with remarkable accuracy and also to delineate their confines and to indicate their depth below the surface with a certain amount of precision. Before this can be done successfully, however, it is necessary to determine the gravitational effect arising from all other extraneous .anomalies in order that these may be satisfactorily eliminated. Disturbing features giving rise to these gravitational anomalies may be divided into two classes, according to whether they are situated at or below the surface. The former are determined readily by a detailed leveling of the ground surface, and may be satisfactorily eliminated provided the specific gravity of the terrain material is known, but the latter are generally unknown, and can only be ascertained with difficulty. When, therefore, the observations obtained by means of the Eötvös torsion balance have been corrected for all surface irregularities, known as terrain and topographical effects, there remain residual gravitational values which are due entirely to subterranean conditions. The task of interpreting these results consists in disentangling the various subsurface anomalies, and subsequently in computing and recombining the effects of these various masses in order to verify the interpretation. When the gravitational anomalies are due to large and comparatively simple structures it is a matter of little difficulty to arrive at a satisfactory interpretation of the subterranean conditions, but in more complex areas, where the geological conditions are more complicated and several irregular features exist, the process of disentangling the various constituents of the complex mass arrangement is more difficult and requires the expenditure of considerable time and labor.

Jan 1, 1929

Discussion of the paper of Archer E. Wheeler and Milo W. Krejci, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 80, August, 1913, pp. 1831 to 1880. BRADLEY STOUGHTON, New York, N. Y.:-I would like to ask Mr. Krejci whether they have tried mixing coke dust with the lime in those converters and, if so, if any advantage has been found. It has been a very great advantage in the steel converters where coke dust has been mixed with the lime near the tuyeres. Of course the agent that causes the corrosion at that point is oxide of iron, and coke seems to prevent the formation of the oxide of iron and so protect the tuyeres. It would be interesting to know if it had the same effect in the copper converters. MILO W. KREJCI:-We have never tried it here. At Anaconda the tuyere section was formerly put in by mixing magnesite with tar and ramming that into the tuyere section, but they have abandoned that. Might I ask how you would apply the coke dust? How get it into the tuyere section ? How hold it there ? BRADLEY STOUGHTON :-The coke dust is mixed with silica and clay and then rammed in and burned. I suppose in your converters it would be mixed with the magnetite or magnesite and then agglomerated with the material in place. MILO W. KREJCI:-We never tried it here. PROF. JOSEPH W. RICHARDS, South Bethlehem, Pa.:-I would like to ask how thick this deposit of magnetite is on the lining. How thick a layer would be practical ? MILO W. KREJCI:-About 21 in. would be sufficient. SOLOMON LE FEVRE, Mineville, N. Y.:-I was interested to hear of the use of magnetite in connection with the copper smelter. I am interested in the mining of magnetite, but was not aware that it had been used at all&apos; by the copper metallurgists.

Jan 11, 1913

By C. O. Lee, Z. W. Bartlett, R. H. Feierabend

The Grand Isle sulfur mine is located in the Gulf of Mexico, approximately seven miles off the coast of Grand Isle, Jefferson Parish, La. The deposit is on acreage covered by oil, gas, and mineral leases originally issued in favor of Humble Oil & Refining Co. by the State of Louisiana which were continued, maintained, and redesignated by the U.S. Department of the Interior after passage of the Outer continental Shelf Lands Act. The sulfur deposit was discovered in 1949 when Humble Oil & Refining Co. penetrated more than 200 ft of sulfur-bearing limestone in a zone between 1813 and 2075 ft below sea level. In 1954, Humble drilled ten more sulfur prospect holes, eight of which encountered sulfur ore.

Jan 6, 1960

By A. H. Grobe, F. N. Rhines

THE constitution of the indium-zinc alloy series has been investigated by Wilson and Peretti,1 who determined the liquidus and eutectic temperatures by the conventional method of cooling curves and the eutectic composition by analyzing eutectic exudations. Recent developments affecting the availability of indium and consequent increased interest in its applications make a more complete knowledge of the constitution of its alloys desirable. As a part of a program for the reexamination of the constitution of indium alloys by precision methods, the indium-zinc phase diagram [ ] (Figs. I and 2) has been redetermined in its entirety. The eutectic temperature (143.5°C.) reported by Wilson and Peretti has been confirmed exactly, but their value of the zinc concentration at the eutectic, 4 per cent, was found to be high; the new value is 2.8 per cent of zinc. There is also a rather large difference between the forms of the liquidus curves of Wilson and Peretti and those found in the present studies. The solidus curves herein have been located for the first time and the limits of solid solubility have been tenta-

Jan 1, 1944

By R. L. Ash, R. R. Rollins, C. J. Konya

An investigation was performed to determine conditions for optimizing the spacing of simultaneously initiated multiple explosive columns. This was done by using models of mortar, dolomite, and Plexiglas with 10-grain mild detonating fuse as the explosive charge. It was desired to simulate blastholes with multiple primers initiated by detonating fuse or when high-velocity explosives are used in low-velocity materials. It was found that optimum spacing between multiple charges was strongly influenced by charge length. At less than optimum charge length, the spacing at which complete shearing was possible between adjacent charges decreased exponentially with a subsequent loss of broken material volume. For charges fired simultaneously, larger burdens and spacings were possible as compared to those necessary for single-crater charges. For each material studied, there was a characteristic optimum charge length and a maximum attainable spacing at any given burden. Proper selection of the spacing distance between charges is fundamental to successful blasting. Its value directly affects the cost of drilling and explosives used per unit of broken material. In addition, the choice of a spacing that is Compatible with a given set of blasting conditions aids in the control of fragmentation sizing, ground vibrations, overbreak, and throw which in turn, influence other production costs. For example, normally loaded blastholes that are spaced too closely invariably promote overbreak and usually give coarse fragmentation. Unless care is taken, airblast and violent flyrock will occur and under certain conditions cutoffs and misfires may result. Too large a spacing, on the other hand, frequently leads to conditions that form bootlegs or toes. The choice of a particular spacicg to use, however, is largely a matter of individual experience and judgment, usually based on trial and error. Very little is known or can be found in the literature with regard to how the spacing between charges is related to field conditions and charge geometry. As a general rule, the firing time sequence of adjacent charges and properties of a material are thought to have the most significant influence on the spacing distance best suited for any given field condition. For example, delayed initiation of adjacent charges usually always requires a closer spacing than when charges are fired at the same time. This should be expected if one considers that the energy normally dissipated and lost in the surrounding ground from charges fired independently would be captured and utilized for breaking material between charges when they are initiated together. Spacing can be extended also when charges are aligned with structural planes of a material, such as jointing, along which shearing is relatively easy. It is customary to relate the spacing (S) between charges to their common burden (B) in the form of a spacing ratio, or SIB. The burden normally is considered as the optimum depth or distance from any single charge perpendicular to the nearest free or open face at which the desired fragmentation and maximum crater yield are obtained. For production blasting, value of the ratio is generally considered to vary from 1 to 2, depending on conditions.1-6 When adjacent charges are fired independent of one another, the value varies from 1 to about 1.4, the closer amount being employed to square corners or produce craters having the ideal 90" apex angle. The larger ratio is the geometric balance value for craters having an apex angle of 135". The basic ideal crater forms in the plane of the charge diameter for charges fired independently are shown in Fig. 1. In the event charges are fired simultaneously, geometric balance in the plane of their charge diameters suggests that a spacing ratio near 2 would be appropriate, as illustrated by Fig. 2. In practice, however, some compromise ratio value must be selected to conform with the specific ground conditions. An example would be where the jointing planes tend to produce 60° or 120° crater angles, the appropriate geometrically balanced charge arrangement being given by Fig. 3. In this condition, the spacing ratio is 1.15, not 1 or 1.4 as suggested for the 90° cratering of independently fired adjacent charges. In view of the foregoing, it would seem logical to assume that whenever charges all having the same burden are fired at the same time, spacing distances always can be greater than those permitted by charges fired independently. In practice this is not the case, however.

Jan 1, 1970

By P. G. Shewmon, H. E. Collins

We have studied the effect of adsorbed sulfur on the surface self-diffusion of copper using eight diflerent surface orientations and the grain boundary grooving method. The eight orientations studied were the four lying near the low-index surfaces—(loo), (Ill), and two directions in the (110)-plus four higher-index surfaces. Surface-diffusion measurements were made over a range of HZS concentrations (in Hz) from 3 to 1500 ppm between 830°and 1050°C. The results can be divided into two groups—Group 1 contains the two (110) surfaces while Group 2 contains the remaining six surfaces. In Group 1, increasing the temperature increases the effect of Hz S on DS for the Hz S range 5700 ppvn. Qs and Do increase with increasing H2S concentration in this Hz S range. Beyond this range, increasing the temperature decreases this effect on D,; also Q, and Do decrease. In Group 2, increasing the telnperature decreases the effect of H2 S on D, for the H2S range studied, and Qs and Do decrease with increasing Hz S concentration. In any study of surface phenomena, there invariably arises the question of the possible presence of and effect of adsorbed impurities. Such questions are well-founded since the presence of adsorbed atoms can sometimes produce marked changes in the kinetics of surface-energy-driven processes. In the last few years, values of the surface self-diffusion coefficient, D,, have been determined on a variety of metals by studying the decay of scratches or the growth of grain boundary grooves.L~3-L0~L3 Yet there has been relatively little work done in which the concentration of an adsorbed impurity was systematically varied and the effects observed. Work of this sort would provide some basis in fact for the assertions often made about the ro1.e of adsorbed impurities in the differences between the results of different workers in different atmospheres and on different metals. It also is relevant to those cases in which surface monolayers produce profound effects in commercially important processes. The most marked example of such effects is the ability of nickel or palladium to increase the sintering rate of tungsten by many orders of magnitude.&apos; The aim of this work was to study the effect of sulfur partial pressures on the surface self-diffusion of copper. It was felt that this in conjunction with a study of the degree of adsorption and type of active sites involvedL8 would provide a wide range of data for one system and hopefully lead to some insight into the mechanism by which sulfur adsorption influences copper diffusion. The main reasons for choosing the Cu-S system were, first, faceting was reported not to accompany the adsorption of sulfur. This is required if our experimental technique is to work. Second, Oudar has determined a high temperature adsorption isotherm for this system, an event which puts the Cu-S system almost in a class by itself.I4 EXPERIMENTAL PROCEDURE Initially, we considered studying the effect of an adsorbed impurity on surface self-diffusion of copper using isolated (or single) scratch smoothing as the technique and oxygen as the impurity. Copper was chosen as the material because the effects of orientation and anisotropy of the surface self-diffusion coefficient, D,, of copper in a dry hydrogen atmosphere had been studied extensively by Gjostein&apos; and by Shewmon and ~hoi.~,~ The isolated scratch technique was chosen because both the effects of surface orientation and anisotropy of D, in a given surface could be easily studied with this method.~ Oxygen was tried as the impurity because Robertson and Shewmon""~ had studied its adsorption on copper at 1000°C over the range of oxygen partial pressures of 10"22 to 10-l3 atm. After several preliminary runs, it became evident that neither the scratch technique nor the impurity oxygen would be satisfactory for this work. Scratching deforms an annealed surface so that the region near the scratches recrystallizes, thereby disrupting the scratch profiles. One can avoid this by deforming the specimen sufficiently before scratching to give complete recrystallization on subsequent heating.4 However, as a result of Gjostein&apos;s success in scratching and annealing undeformed gold single crystals without local recrystallization,13 we attempted something similar with copper single crystals using a 0.7-mil diamond phonograph needle mounted in a Tukon hardness tester. All specimens recrystallized upon being annealed. Also, some copper specimens were sent to Gjostein to be scratched using his technique. The results were the same. As a result, the scratch technique was dropped in favor of the grooving of symmetric grain boundaries. Preliminary work using oxygen showed that faceting began to occur before oxygen adsorption had any measurable effect on D, at 938°C (at Pbo/P, = 0.12). Since heavy faceting would interfere with the measurement, we decided to use a sulfur-containing atmosphere (H2S/H2). Work by Oudar and Benard&apos; and Robertson" showed that sulfur absorbed on copper and that faceting was not observed.

Jan 1, 1967