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By Alexander R. Troiano, Eugene P. Klier

SINCE the very early work on quenched structures, where the products of the martensite transformation had been recognized, this transformation has provoked much interest and study. Theoretically it was desirable to account for the extreme changes in physical properties resulting from the formation of martensite, as that information might lead to results of practical importance. Desirable information, therefore, was on the kinetics of transformation from austenite to martensite as well as on the physical constitution of the martensite. It has been known for years that certain steels quenched to room temperature will contain persistent austenite as well as martensite. Other important and now well- established features of the martensite reaction are the progress of the reaction on cooling only and the independence of Ar" with cooling velocities exceeding the critical velocity. These facts have been experimentally determined by various methods and investigators. Notable among the early investigators were Tammann and Scheill and Wever and Engel.2 Unfortunately, all investigators did not fully interpret their results, which, coupled with several investigations that yielded conficting results, caused a state of confusion that was not clarified until quite recently. X-ray investigations of martensite in steels3-6 indicate it to be a supersaturated solid solution of carbon in alpha iron. This supersaturation is evident from the appearance of a body-centered tetragonal structure with the addition of sufficient carbon. The dimensions of this tetragonal structure are alinear function of the carbon content within the limits of accuracy of the determinations. Slight tempering of tetragonal martensite leads to the destruction of the tetragonal structure, which is converted to a body-centered cubic structure. This phenomenon has precipitated a controversy concerning the nature and mechanism of the tempering of martensite. The facts in the case have been outlined by Epstein7 and more recently by Antia, Fletcher, and Cohen.8 The significance of Ar" on theoretical grounds is not clear, however, although considerable study has been devoted to its determination. The precise position of Ar" as a function of carbon content was first stated by Greninger and Troianos for steels covering a range of approximately 0.7 to 1.8 per cent carbon. The effect of alloying elements on Ar" has recently been the subject matter of investigation by various methods.

Jan 1, 1945

By A. W. Jenike

A theory of gravity flow of bulk solids like ores, concentrates, coal is outlined and an example of design for unobstructed flow is given. Mass-flow and plug-flow patterns are defined and related to the geometry of the bin. The effect of these patterns on segregation, first in-first out flow, and caking is described. This paper is a report on the results from the AIME sponsored project "Flow of Bulk Solids" which was carried out under the author's direction at the Utah Engineering Experiment Station, University of Utah, during the period 1956-1962. The theory has been applied to the design of numerous industrial storage plants. A QUANTITATIVE METHOD OF DESIGN FOR FLOW There is hardly an industry which does not store and handle solid materials in bulk form. When the volume of the solids is large, gravity is invariably relied upon to cause the solids to flow out of storage, through channels and chemical reactors. Such materials as ore, coal, cement, flour, plastics, clay, soil, to which a general term of bulk solids is applied, flow by gravity or are expected to flow by gravity in thousands of installations and by billions of tons annually. The chemical and process industry depends on gravity flow of solids in process and out of storage. Mining relies on gravity flow in block-caving, in ore passes, as well as in storage and loading bins. Agriculture uses gravity flow in elevators, in feed plants, and in farm silos. In practice, satisfactory gravity flow is seldom attained. Such problems as doming, piping (rat-holing), lack of live capacity, segregation, deterioration in storage, harass industry. In spite of the universality of these problems, until recently, there has been no theory of solids flow, no method of predicting how a solid would behave, and how the channel, bin, or hopper should be designed. In the late nineteen forties and early fifties, the theory of plasticity came of age and simultaneously the computer became widely available. These two factors permitted the development of a theory of flow of bulk solids. The work was conducted during the years 1953-1961. In conjunction with the development of the theory a method to measure the flowability of solids was also developed1-7 and the theory was ap-plied to the design of ore pockets, storage plants,16 chemical reactors and adsorption columns. A comprehensive report of this work is given in a previous work." THEORY OF FLOW The most important question which a theory of flow has to answer is: what conditions need to be satisfied for a given solid to flow uniformly and without obstructions through a channel? First of all, the following observations are made:

Jan 1, 1967

By L. G. Huntley

I. HISTORY OF OIL DEVELOPMENT IN MEXICO THE occurrence of oil or "tar" in Mexico was mentioned as early as the seventeenth century by Friar Sagahun, who gives the Indian name "chapopote," by which these asphalt seepages are still called. This asphalt was apparently used, as it has been used by primitive people in many parts of the world, in religious ceremonies and for medicinal purposes. Travellers also report that the ruins in Yucatan and the pyramids in southern Mexico show traces of the use of "chapopote" as a building cement.1 DeGolyer says that the first attempt to exploit oil or gas in Mexico in a commercial way is shown by the records of the Memoria de Fomento of 1865, when permission was granted to a Senor Ildefonso Lopez to exploit the deposits of petroliferous substances in the San Jose de Ias Rusias area in the State of Tamaulipas. Other concessions follow, and probably refer to surface seepages which occur in that district. This was several years after the discovery of oil in Pennsylvania. In 1868, a well 125 ft. deep was drilled by a company organized in Mexico City, in what is now known as the Furbero district, and a little oil was refined there. In 1873, residents of Tampico denounced seepages along the Tamesi River, and asphalt was mined near Tempoal in the Canton of Tantoyuca. No drilling was attempted. But between 1880 and 1883 several shallow wells were drilled for oil in Mexico, two of them being near the present Potrero de Llano field west of Tuxpam. The wells were drilled by a Boston company with Canadian rigs, and are said too have reached a depth of about 400 ft., while one is reported to have flowed. Several other abortive attempts were made to drill for oil between 1885 and the beginning of the present century, about which time the Mexican, Petroleum & Liquid Fuel Co., Ltd., in which Cecil Rhodes was interested drilled 24 wells unsuccessfully, several of them as deep as 1,500 ft., in the State -

Jan 9, 1915

By C. H. Wilson, J. W. Daly, J. J. Jakosky

Meteor Crater, Arizona, is a natural wonder which for years has been the subject of considerable discussion and study as to its origin and age (Fig. 1). Of the various theories advanced regarding the origin, two have been considered as most probable by a majority of investigators. The first theory is that the crater was formed by a meteorite or a swarm of meteoric material striking the earth at a high velocity and burying itself. The second theory is that the crater was formed by a "steam explosion" from hot solutions or gases coming from underneath the present sedimentary beds which overlie the area. In order to obtain more detailed information regarding the conditions existing at the crater, the present management decided to have a detailed geophysical examination made. The origin of the crater is of considerable scientific importance and interest. More or less active mining operations have been carried out during the past 20 years by various groups who believed that the crater was of meteoric origin, and who hoped that sufficient quantities of such material had been buried to be commercially valuable. Fragments of meteoric material found on the surface of the ground in the debris around the rim gave analysis of approximately 92 per cent iron and 8 per cent nickel, with some platinum and iridium. The material having a gross value of approximately $50 per ton, mining would be commercially profitable if sufficient quantities of the material existed in condition for mining. In the early work numerous drill holes and shallow shafts were put down, mainly in the northern portion of the crater. Pulverized material and debris caused considerable difficulty, and in an effort to overcome this the present management started a 1500-ft., two-compartment shaft on the south rim of the crater and outside of the fill zone. The intention was to sink the shaft in the solid rock outside of the crater, and then to crosscut toward the crater at a depth of 1500 ft. The work was finally stopped when a depth of 650 ft. was reached, because water poured into the shaft through large cracks and fissures in the rock. The enormous force responsible for the crater had also broken

Jan 1, 1932

By D. Walton, B. Chalmers

A preferred orientation is known to occur frequently in the columnar zone of castings. This has been attributed to a preferred direction of growth. However, no satisfactory mechanism was proposed by which the preferred direction of growth led to the preferred orientation. The purpose of this work has been to establish this mechanism. It has been found that in general the observed preferred orientations only develop when the preferred directions of growth reveal themselves by dendritic growth. A mechanism based on this premise is found to be in agreement with the experimental data obtained in the course of this work. WHEN a liquid metal is allowed to solidify in a mold, it usually freezes in three stages, distinguished from each other by the size and shape of the grains. The first zone to freeze (the chill zone near the mold wall) consists of relatively fine grains that are equiaxed in shape and random in orientation. The next zone consists of crystals that are elongated in the direction of heat flow, i.e., normal to mold wall. These crystals are much larger in cross section than the crystals of the chill zone and have a very strongly preferred orientation. This is the columnar zone. The final zone, which is absent in very pure metals, is again equiaxed and randomly oriented, but usually has a much coarser grain size than the chill zone. The purpose of this study is to describe and account for the crystal size and orientation in the columnar zone. The occurrence of a preferred orientation in the columnar zone is well known, and in 1940, Greninger' suggested that it is apparently related to dendritic growth although at that time the only data were for metals with the face-centered-cubic structure. Table I shows that the direction of dendritic growth and the crystal axis that follows the heat flow direction coincide in all cases so far studied. The term "dendritic growth" is used here to represent the branched type of morphology that is characteristic of growth into supercooled melts.' In addition to the supercooling which is necessary before nucleation will occur at the mold wall, the necessary supercooling for continued dendritic growth can be provided in a mold by heat flow into the already formed solid at an interface whose Liquidus temperature is depressed by an accumula-

Jan 1, 1960

By Bryan J. Travis, Thomas L. Cook

INTRODUCTION Our growing concern for adequate and secure sources of energy and minerals has stimulated vigorous exploration for new sources, research toward a better understanding of geological processes, and development of new extraction technologies. The need for control, or at least prediction, of subsurface fluid flow is important for many of these technologies for example: primary, secondary and tertiary recovery of oil; ground water and waste management; in-situ fossil energy extraction (oil shale, coal, tar sands); and solution mining of uranium, copper and other minerals. These technologies, especially the last two, are characterized by highly complex systems. A partial list of the physical processes occurring would include flow in porous/fractured media, multi-phase and multi-component flow with heat transport, chemically active fluids and soils, tracers, diffusion and dispersion, fracturing and dissolution. A great deal of understanding of how these processes behave and interact can be obtained from models. MODELS Theoretical models are valuable because they: 1) provide a frame of reference for interpreting results of laboratory and field experiments; 2) once validated by experiments, allow a variety of geometries, injection/production strategies, etc., to be examined (at relatively low cost) for efficiency and stability; 3) can provide guidance to the design of experiments and field operations. Most models are based on the fundamental principles of mass, momentum and energy balance. But from this starting point, many paths can be taken. For example, there is the theory of Payatakes (1973) which concentrates on the microscale dynamics. In this approach, the rock or soil matrix is represented by a complex of characteristic channels (such as periodically constricted smooth tubes). Detail of flow within the characteristic channel is calculated very accurately. A difficulty with this model is that description of a representative channel can require several parameters which may not be easily measured. Also, it is not clear how the channels can be combined practically to model a large scale flow. Another type of model is the "global" one described by Bear (1972). Here, the continuum equations for conservation of mass, momentum and energy are averaged over a distribution of pore channels, resulting in a set of conservation equations in which the small scale structure of the medium is replaced by quantities such as porosity, permeability, dispersion coefficients and tortuosity. This approach allows computation of large scale flows. However, additional constitutive equations are needed which relate averaged quantities such as permeability to observables such as local saturation, particle size distributions, and others. An important difference between models is the way they handle the momentum equation. Payatakes' model solves the full equation. In others, it is replaced by a simpler relation such as Darcy's law (valid for slow flow rates) or by Forchheimer's equation which extends Darcy's law to higher flow rates. These simple relations can nevertheless match a great deal of experimental data (Dullien 1975). The permeability term which appears in Darcy's law and in Forchheimer's expression has been related to other quantities such as porosity and particle surface area. The Kozeny-Carmen equation is a well-known example, valid for some ranges of porosity and particle sizes and for some materials. Several other semi-theoretical, semi-empirical formulations have been devised, none of which are entirely satisfactory. One goal of researchers has been the ability to predict permeability of a porous material from basic measurable quantities such as grain size distributions without recourse to adjustable parameters. This effort has proceeded from consideration of distributions of idealized, non-intersecting channels, to intersecting channels, to consideration of both distributed pore radii and pore neck radii. This last approach has been used successfully to predict permeabilities (ranging over several orders of magnitude) in sandstones (Dullien 1975). Additionally, studies on explicit networks of channels (e.g., Fatt 1956) and percolation theory (e.g., Larson et. al. 1981) have been used to examine interconnectivity effects in porous media with the hope of eventually being able to predict permeability accurately. To be of more than theoretical interest, a model must be compared s controlled laboratory conditions where boundary and initial conditions and relevant material properties can be accurately determined. Also, extraneous forces can be eliminated so that the interactions between processes of interest can be clearly seen and flow models can be vigorously tested. In contrast to the well-defined environment and

Jan 1, 1982

By H. A. Bedworth

ALLOYS of copper and silicon have been known for one hundred years or more but the commercial development of this type of alloy has taken place during the past few years. In 1905, Sperry1 proposed the use of copper-silicon alloys for springs and other purposes for which copper-tin bronzes were used. Some attention was given to this proposal at the time but no one succeeded in producing a practical alloy containing more than a fraction of a per cent. of silicon. The equilibrium relations of the copper-silicon system were studied first by Rudolfi2 and later by Sanfourche3 and Corson.4 The constitution of the system has also been recently investigated by Matuyama,5 and in the laboratories of the American Brass Co. by Smith.6 Some of the physical properties of the copper-silicon alloys have been investigated by Norbury7 and by Geiss and Van Liempt.8 Summarizing the results of various investigators of, the constitution of copper-silicon alloys, the solubility reaches its maximum value, 6.7 per cent. silicon, between 721° and 782° C. At 852° C. the solubility is 5.25 per cent., while at 400° C. it is only 4.1 percent. silicon. The copper-silicon alloy begins to get so hard at about 3 per cent. silicon that it is difficult to manage. It was found by Jacobs that the addition of manganese to this alloy considerably improved the working

Jan 1, 1929

By C. N. J. Wagner, E. N. Aqua

Dilute Fe-Si alloys (0 to 5 wt pet Si) were cold-worked by making filings at room temperatuve. The analysis of the broadening of the X-vay powdev pattern peaks yields anisotropic particle sizes normal to the (110), (100), and (112) planes which are a consequence of deformation faults (probability a) and twin faults (probability p). The combined fault probability (1.5a +ß) increases from 0.01 in pure iron to 0.02 in Fe-5 pct Si. The root mean square stvains vary with crystallographic ovientation due to elastic anisotropy of the alloys, and increase from about 0.0035 in pure iron to 0.005 in Fe-5 pct Si measured in the [100] direction. Assuming that deformation and twin faults occur with equal probability, the X-ray data would imply that the stacking-fault energy does not change upon alloying. THE crystallographic aspects of the plastic deformation of dilute Fe-Si alloys has been studied many times since the observation of glide band structures by Barrett et a1.l These glide bands were much straighter than the wavy bands observed by Gough2 in unalloyed iron nearly 40 years ago. This difference in the morphology of the slip band structure has been verified many times, most recently by replication electron microscopy3 and dislocation etch-pitting methods.4,5 These observed differences in deformation behavior have been considered to result from the degree of cross slip that occurs in pure iron and in the Si-Fe alloys. The lowered tendency for cross slip would result from a lowering of the stacking-fault energy of iron by the silicon alloying addition. Experimental evidence for this lowered stacking-fault energy in the Si-Fe alloys, obtained with transmission electron microscopy, is the observation of dissociated dislocations in Fe-6 pct si6 and Fe-3 pct Si alloys,7 and the observation of sharply defined cellular substructures in Fe-3 pct si6,7 compared to the more diffuse substructure in zone-refined iron.' The activation energy for recovery of cold work is greater in the Si-Fe alloys than it is in pure iron, indicating that cross slip has become a more difficult process.9 The purpose of this investigation is to determine the change in stacking-fault probability from the broadening of powder pattern peaks in dilute silicon-in-iron solid solutions, when cold-worked at room temperature. The knowledge of the stacking-fault probability and the dislocation density, both of which can be deduced from line-broadening analysis of two orders of reflections from (110), (200), and (112) planes, will permit us to calculate the change in stacking-fault energy upon alloying silicon into iron. Previous X-ray investigation of cold-rolled Fe-5 wt pct Si (100)[001 ] single crystals did not reveal any line broadening, whereas cold-rolled Fe-3.1 wt pct Si (001) [110] and (001)[100] single crystals10 showed line bro2dening as a consequence of small particle sizes (-200A) and root mean square strains (-0.25 pct), which are comparable to those found in cold-worked iron filings.11 EXPERIMENTAL PROCEDURE A series of five Fe-Si alloys containing nominally 1 to 5 wt pct Si and pure iron were cold-worked by making filings at room temperature. The actual silicon content deviated at the most by +0.1 pct which is of no significance in the present study. The carbon contents of these materials were less than 0.02 pct. The X-ray diffraction patterns were measured with molybdenum, cobalt, and iron radiation using a GE and a Philips diffractometer. The (110)-(220), (200)-(400), and (112)-(224) pairs of reflections were

Jan 1, 1968

By A. H. Bromly

THE small agricultural village of Santa Barbara, in the State of Guanajuato, has been the center of spasmodic tin-mining operations during recent years. The deposits, so far as I know, are unique, and a few brief notes may be of interest. Santa Barbara, about 12 miles west of San Felipe station on the Mexican National Railway, and at an elevation of 2,400 m. above sea-level, is situated in a flat valley extending east and west, and bounded north and south by broken rugged bills rising about 330 m. above the general level of the valley. Tin-mining operations have been conducted-at the Queensland mine, near this village. A small concentrating-mill was erected and attempts were made to smelt the ore in reverberatory furnaces. The country-rock of the district for many miles is rhyolite of great thickness. There are some local variations due to differences in cooling, or subsequent alteration or impregnation; but throughout the whole district the principal constituents of the rocks remain the same, viz., free silica, orthoclase-feldspar and sanidine. The latter is especially marled. The crevice and joints of the rock are frequently filled with calcedonic and opalescent quartz. The ore-formation at the Queensland mine is of an unusual nature, consisting of cracks in the rhyolite which have been filled with clay. This phenomenon is largely developed over a width of from 80 to 100 m., in which the principal fissuring follows an approximate direction of north and south. The av¬erage clip ranges between 70 to 80 degrees. Some of the fissures bold sufficiently true for a time to afford the impression that they are clue to dynamic causes, or earth-movement. This may be true of some of the north by south fissures; but considering

Jul 1, 1905

By C. G. Bieber, R. F. Decker

The effects of minor constituents on the malleability of nickel alloys are described. These effects are related to the atomic diameter, valence, and position on the Periodic Table. The basic methods for removal or neutralization of deleterious elements are then reviewed. Finally, practical methods for melting nickel alloys are described in detail and related to minor constituent control. L HE first malleable nickel was produced by Fleit-man in about 1870 by the addition of manganese and magnesium to the molten metal to counteract the harmful effects of sulfur. Merica and Waltenbergl explained the mechanism by which these elements accomplished the desired result. They showed that sulfur in concentrations in excess of about 0.005 pct produced films of a brittle low melting eutectic of nickel-nickel sulfide which completely surrounded the grains. When manganese was added to molten nickel it reacted with the sulfur to form manganese sulfide which precipitated as widely scattered globules in the grain boundaries. The further addition of small amounts of magnesium converted the sulfur to a very stable sulfide of magnesium which was relatively insoluble in both the liauid and solid states and therefore occurred as finely divided particles within the grains where it had relatively little detrimental effect upon the malleability of nickel or its alloys. The practice of treating nickel with manganese and magnesium came to be called "deoxidation" and was employed without appreciable modification for the commercial production of wrought nickel and high nickel alloys (in this paper—50 pct or more nickel) until about 1930 even though the results were never entirely satisfactory. At that time a more extensive study was made of the effects of minor constituents on malleability and metallurgical quality. The results, small portions of which have been published,2-4 are presented here with other pertinent data. EFFECTS OF MINOR CONSTITUENTS UPON NICKEL Systematic additions were made of 0.5 pct or less of each of most of the elements of the periodic ta- ble. It was established in this study that some minor constituents other than manganese and magnesium were extremely influential. The malleability, as evaluated by the reduction of area in tension tests, depended roughly on temperature as shown in Fig. 1. Four temperature zones are of interest; the cold malleable zone (up to about 1000° F), the red short zone from roughly 1000° to 1500' F, the hot malleable zone around 2000° F and the incipient melting zone. Most of the malleability problems are associated with the red short zone and the discussion will concern this mainly. The reduction of area in normal tensile tests on high-purity nickel (see curve A of Fig. 1) appeared to have no

Jan 1, 1962

By Richard Hunt

BINGHAM has produced 6 per cent. of this country's copper. In total production, it ranks fourth among the copper camps of North America, the order being Butte, Michigan, Bisbee, and Bingham. In its annual production, it held that same rank until 1919, when its production was exceeded by the combined production of the Globe-Miami district of Arizona. Bingham has also been a lead camp of the first order. Utah ranks third among the lead-producing states, and its production comes largely from three camps which, in the order of their productivity, are: Bingham, Tintic, Park City. Bingham's silver production is important, but it does not rank high as a silver producer. Utah owes its rank as first among the silver-producing states to Tintic, a camp 40 miles due south of Bingham. The United States Mineral Resources reports a total production from Bingham for the period 1865-1920 having a gross value of $528,043,432. Bingham is on the eastern flank of the Oquirrh range 30 miles south-west of Salt Lake City, from which it can be reached in an hour by auto, or by the Denver & Rio Grande or the Bingham & Garfield railroads.. The automobile route is a paved road across the floor of Great Salt Lake Valley, through farming country. The Bingham & Garfield railway leaves the level of Great Salt Lake at the northern end of the Oquirrh range, and in 20 miles it climbs 2100 ft., and deposits the traveler upon a shelf cut in the side of Bingham Canyon below most of the mines, which are farther up Bingham Canyon and its tributary Carr Fork. Below lies the town, a narrow ribbon running for a couple of miles along the bottom of a canyon 2000 ft. deep-an almost impossible site for a community numbering, in prosperous times, 5000 to 7000 inhabitants drawn from all quarters of the globe. Up the canyon and down, and beneath the steep slopes nearby, and beneath the town itself, are the mining operations of over half a century.

Jan 3, 1924

By N. J. Grant, C. C. Wang

The Ti-Cr-O ternary system has been studied in detail near the titanium-rich corner within the limits of 10 wt pct 0, and 20 wt pct Cr. Studies were extended, but not in detail, to the region beyond 25 wt pct 0, (50 atomic pct) and 62 wt pct Cr (60 atomic pct). Four isothermal sections at 1400°, 1200°, 1000°, and 800°C are presented as well as two vertical sections at 1 and 2 wt pct 02. DURING the last decade much interest has been shown in the development of high strength titanium alloys for high temperature and corrosion resistant applications. Extensive research is being carried out at present, as the current literature indicates, in order to study the properties of titanium and to develop improved alloys. Two of the important alloying elements in commercial titanium alloys are chromium and oxygen and it would be desirable to know their combined influence upon titanium. For this purpose the present work was carried out to investigate the titanium-rich corner of the ternary system TiICr-0. The binary systems Ti-Cr and Ti-0 have been published recently. The Ti-Cr system was studied by several investigators " and their results are in close agreement. The eutectoid decomposition of the B phase has been shown to be extremely sluggish. TiCr, was the only intermetallic compound found in this binary system and was formed at 1350°C by a transformation from the p phase. TiCr? was established as the cubic C 15 (MgCu,) type of structure with 24 atoms per unit cell and was designated as the y phase. This terminology will be adopted in the present work. There was disagreement about the actual composition of this compound among the several investigators, although it is evident from their data that the compound probably has a solubility range of about 2 to 3 pct and is in the vicinity of 65 pct Cr. It has been indicated recently that a high temperature modification of this y phase (TiCr,) existed at a temperature above 1300°C." ' This high temperature modification was identified as a hexagonal C 14 (MgZn,) type of structure with 12 atoms per unit cell. The exact transformation temperature from the high temperature phase to the low temperature phase has not been established. A considerable hysteresis was observed and, due to the sluggishness of this transformation, the high temperature phase often co-existed with the low temperature phase at temperatures below 1300°C. A preliminary study of several Ti-0 compounds and the Ti-0 system had been carried out by Ehr-1ich."-"' The most complete binary Ti-0 system was the one reported recently by Bumps, Kessler, and Hansen." The first intermediate phase found in the system was the 8 phase which formed by a peritec-toid reaction of the phases a and Ti0 at temperatures below 925 °C. This reaction is extremely sluggish. The structure of this 8 phase was tentatively identified by these authors as being tetragonal and the lattice constants were found as c,, - 6.645A, a,, = 5.333A and c/a = 1.246A. Experimental Procedure The raw materials used for this investigation were TiO,, electrolytic chromium, iodide titanium, and sponge titanium. The TiO, was in the form of powder of chemically pure grade (99.8 pct pure). The chemical analysis of the electrolytic chromium was: 0, 0.50 pct; Fe, 0.07; Cu, N, and C, 0.01; and Pb, 0.001. The oxygen in the chromium was calculated as part of the final oxygen content of the alloys. The alloys were prepared by the cold crucible method using a tungsten arc. The entire system was evacuated and flushed with purified helium three times and then filled with helium. Each alloy was melted, turned over, and remelted at least four times to insure homogeneity. The total melting time was generally from 6 to 10 min. A master alloy of 25 pct 0,-75 pct Ti was prepared to facilitate alloying by melting compacts of TiOl powder with either iodide or sponge titanium, yielding the compound TiO. It was found necessary to bake the TiO, powder compact at about 150°C to remove adsorbed moisture. This was done to prevent the disintegration and spattering of the compact when the arc was struck. TiO, powder dissolved quite readily into the melt and no other trouble was encountered.

Jan 1, 1955

By R. L. Dalton, L. A. Rapoport, C. W. Carpenter

Procedures have been developed to study the performance characteristics of unconfined pilot water floods using scaled laboratory models. The effects of operating conditions on pilot performance for variozrs well patterns have been investigated. The limitations of the laboratory model studies are outlined. Relationships between the oil recoveries of pilots and large-scale floods have been established. The applications of model studies to the prediction of large-scale waterflood performance and pilot flood design are discussed. INTRODUCTION Pilot water floods are undertaken to evaluate operational procedures and to gain advance information about the performance of an extensive water flood. In general, however, the performance of a pilot flood is not directly indicative of what can be expected from a large-scale pattern water flood. This difference stems from the fact that the over-all flow configurations are not the same for the two systems. A water flood normally consists of an array of identical well patterns. In such an array, the perimeters of the well patterns are axes of symmetry and act as impermeable boundaries. Thus, an extensive, pattern water flood can be visualized as a repetition of "confined" floods. In contrast, a pilot water flood involving only one or a few well patterns is "unconfined". Here the well patterns are not balanced by other flood units; hence, the perimeter of the pilot area does not act as an effective boundary. Accordingly, only a portion of the fluids injected (and also of those originally contained within the pilot area) is captured by the producers of the pilot. The rest escapes into the surrounding reservoir. This usually causes the amounts of oil and water produced in the pilot to be different from those recovered by a producer in an extensive water flood. Moreover, the recovery observed in the pilot can be expected to be greatly influenced by operating conditions, i.e., by the bottom-hole pressures at the injection and producing wells. The above considerations show that full utilization of pilot test results and reliable prediction of large- scale water floods require a knowledge of the relationship between the recovery performance of confined and unconfined well patterns. To date, only limited basic information is available on the behavior of pilot water floods. Craig, et al,' have investigated the effects of initial gas saturation, oil-to-water mobility ratio, and well damage on the oil recovered from a single, "normal" five-spot pilot pattern (Fig. 1). Rosenbaum and Matthews2 studied the effect of initial gas saturation and mobility ratio on the ratio of production rate to injection rate for various groupings of five-spot patterns. Paulse113 investigated the effect of mobility ratio and distance from the pilot to the edge of the reservoir on the areal sweep in a single "inverted" five-spot (Fig. 1). However, none of these studies considered the effect of operating conditions on pilot flood behavior. Moreover, hardly any of the work to date dealt explicitly with the oil-recovery performance of the pilot floods. The purpose of this paper is to introduce the concept of interrelation between pilot flood behavior and operating conditions, to illustrate this interrelation by means of experimental data and to compare the recovery performances of dif-

By E. Martinez

Samples of chrysocolla, a hydrated copper silicate, from several sources were submitted to differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). Pure samples of chrysocolla are difficult to obtain, but comparison of the thermograms revealed that certain reactions occurred in all the samples and it is believed that these are due to chrysocolla. Endothermic reactions occurred at 50' to 175°C, 350° to 650°C, and 980° to 1100°C each of which caused a weight loss. The first was due to loss of absorbed water, the second to a dehydroxyla-tion, and the last to conversion of cupric oxide to cuprous oxide. In addition, two exotherms were detected at 685° to 695°C and 935° to 950°C. Infrared spectra of heated samples indicated the exotherms were due to changes in the Si-O bonds leading to the formation of cristobalite. The results suggest that thermoanalysis may be a more sensitive and reliable method for detection and identification of chrysocolla than X-ray diffraction, infrared spectroscopy, or optical techniques. The recovery of copper from oxide ores has been the subject of much research in recent years. One of the principal oxide copper minerals is chrysocolla, a hydrated copper silicate. The information available indicates that it has widely varying properties depending on the origin of the sample. Chrysocolla usually is found associated with cuprite, malachite, azurite, and native copper. Most of these other minerals are recoverable by present day flotation practice, but chrysocolla is lost in the tailings.1,2 Reagent combinations that are successful in laboratory chrysocolla flotation with ore from one source have been found to be ineffective with another. 3 The copper segregation process offers an altemative to beneficiation of oxide copper ores.4'5 The process is of particular interest in processing ores that cannot be treated by conventional hydrometal-lurgical methods because of high acid consumption.6 Fuller understanding of the properties of chryso- colla may prove of value in the search for improvements in both the flotation and segregation processes. Chrysocolla samples from Arizona, Nevada, Chile, Australia, and South Africa were studied by differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). In addition, a sample from Miami, Ariz., was submitted to X-ray diffraction, infrared spectrophotometry, and surface area determination. EQUlPMENT Differential thermal analysis (DTA) detects, amplifies, and records exothermic-endothermic reactions occurring in a sample as its temperature is raised at a constant rate, usually 10°C per minute. A unit made by the Robert L. Stone Co. was used in this study. The tests can be run if desired with a gas streaming through the sample. A thermobalance records weight losses or gains in a sample as its temperature is raised at a uniform rate. The gravimetric analyses (TGA) were run on a Chevenard thermobalance converted electronically for graphic recording. A heating rate of 5°C per minute up to 1100°C was used in these tests. A Perkin Elmer Infrared Spectrophotometer, Model 221, was used with sodium chloride optics obtaining IR spectra in the 2 to 15 region. A pressed pellet technique with potassium bromide was used in preparing the samples. DESCRIPTION OF SAMPLES Chrysocolla is found in the oxidation zones of copper deposits commonly associated with malachite, azurite, and limonite. It is described as varying in composition and in color from bluish green to brown or black. Inclusions of other minerals are usual so chemical analysis of chrysocolla samples may be suspect. However, it is considered by many to be a solid solution of CuO, SiO2 and H2O with a general formula of CuO.SiO2.2H2O or 2CuO.2SiO2. 3H20. Chukhrov7 has described a sample from the Urals as CU3,5(OH)2 (A1Si3) O10.nH2O and stated that chrysocolla is a montmorillonite-type mineral. On the basis of X-ray analyses, DTA, and infrared spectra of chrysocolla from the Inspiration Mine, Ariz., Sun8 concluded that there was no substantial evidence to classify it as a montmorillonite mineral. Chrysocolla samples from many sources throughout the world were used in this investigation. The following is a brief description of each:

Jan 1, 1963

By Arthur T. Ward

DESPITE the intense preoccupation of most of those members connected with the mining, concentration, and reduction of iron ores, the luncheon and subsequent technical session of the Eastern Magnetite Committee were exceedingly well attended. Many of the older faces were absent, but new ones took their places. More than sixty, all told, took in the technical session. Chairman Crockett opened the session by calling upon Meredith E. Johnson, whose paper, with its accompanying graph, was in reality a comprehensive historical review of iron mining from colonial days to the end of 1941. with some notes on current expansion which indicates that New Jersey is destined to become a still more important. factor in the production of magnetite ores.

Jan 1, 1942

By R. W. Raymond

ALL history testifies that the mineral resources of a region have furnished both the impulse for its first development by man, and the foundation for its subsequent occupation by civilized and prosperous communities. In the pre-historic ages, the hunters, fishers, shepherds and gardeners of the world may have wandered or tarried without regard to the attractions of the mineral deposits which they could not utilize, and therefore did not value. But with the rise of civilization, as expressed in manufactures and commerce, the national value of such deposits began to be realized. Barbarous and remote tribes, possessing the sources of such supplies, won recognition in trade long before they could attain it through any other means. Thus, the North American Indians of Lake Superior exchanged their native copper for the mica of North Carolina; the ships of Tyre sailed all the way to Spain for lead and to Britain for tin; and the fleets of Solomon brought gold from Tarshish. In more modern times it has been chiefly the precious metals that have stimulated exploration and conquest. The inherent qualities and the traditional value of gold and silver sufficiently explain this historic fact, the continued existence and potency of which is evidenced, even in our own times, by the occasional rush of eager adventurers to new districts where gold and silver have been discovered. The history of North and South America has been peculiarly influenced by this factor. It was the prospect of obtaining gold and silver that led the Spanish adventurers to the shores of America, and the conquests of Mexico by Cortez and of Peru by Pizarro were inspired by the stories of the wealth of the Aztecs and the

Mar 1, 1909

By K. E. Gray, G. M. Myers

In previous publications,5 results of single-blow bit tooth impacts on saturated rocks at various stress states were reported. This paper extends these earlier works to include study of bit impact tests on salt water-saturated Berea and Bandera sandstone samples under conditions of elevated confining and pore pressure. During the tests dynamic filtration and deposition of a mud cake were occurring due to the presence of drilling mud in the borehole and a borebole-to-formation pressure differential. Results indicate that saturation of these sandstones with salt water tends to make them weaker than when saturated with nonreactive fluids. Plastic failure often occurs even when extremely high fluid-loss muds are present in the borehole. The failure mode tends toward plasticity with decreasing fluid loss. Brittle failure of sandstones in mud-filled holes is apparently relatively rare. Depending on the stress level, and the associated failure mode, withdrawal of the bit tooth induces a tensile force that seems rather important relative to the quantity of rock removed by vertical tooth impact. INTRODUCTION A vast majority of the oil wells drilled today involve the use of colloidal muds having a measurable mud filtrate loss. It is known from field experience that reduction of the water loss of a mud generally results in a reduction of the penetration rate. This paper describes an investigation of crater formation at simulated bottom-hole pressure conditions for drilling fluids having different water losses. The literature on single bit tooth impact (cratering) at atmospheric conditions is extensive, but only a limited amount of work has been performed at the stress conditions similar to that found in oil wells. Spherical penetrator cratering tests on rocks at hydrostatic pressure were performed by Payne and Chippenda1e.1 Chisel impact studies on limestone with independently varying overburden and borehole pressure and atmospheric pore pressure were reported by Garner, et al.2 Gnirk and Cheatham3 performed "static" penetrator tests on dry rocks at equal overburden and borehole pressures. Podio and Gray4 studied the effect of pore fluid viscosity at atmospheric pore and borehole pressures and varying overburden pressures. Their results illustrated the importance of fluid saturation of the rock. Yang and Gray5 reported single tooth impact tests on saturated rocks at elevated borehole, pore and confining pressures, but with equal pore and borehole pressures. For the work reported in Refs. 4 and 5, filtration across the hole bottom purposely was avoided. Maurer6 has investigated the effect of independently varying pore and borehole pressures at elevated overburden pressures by using a zero water-loss mud in the borehole. His tests were carried out under conditions that allowed independent control of overburden, pore and borehole pressures, but without control of filtration at the hole bottom. EXPERIMENTAL APPARATUS AND PROCEDURE APPARATUS The single blow chisel impact apparatus used by Garner,2 as modified for this study, is shown in Fig. 1. A cross section of the pressure vessel is shown in Fig. 2. Several pieces of auxiliary equipment were added to the original apparatus in order that the borehole and pore pressure could be applied in a manner analogous to the actual bottom-hole situation. The pore-pressure system included a filtrate volume-measuring transducer and had sufficient surge capacity to allow filtrate to be injected into the sample without significant changes in pore pressure at points remote to the borehole. The borehole-pressure system contained a cross connection to the pore-pressure system so that both systems could be pressured simultaneously. The borehole-pore pressure differential was applied rapidly by the use of a quick and full-opening valve. The operation of this valve triggered two industrial

Jan 1, 1969

By Charles Smeal, Robert J. Schafer, Max Quantinetz

Normally metal powders cannot be ground to sub-micron sizes because of welding and agglomeration phenomena. Through the use of selected grinding aids and grinding fluids, nickel and other metal powders have been ball-milled as fine as 0.1 It was found that certain inorganic salts are more effective grinding aids for metal powders than conventionally used surfactants. METAL and alloy powders are used to produce reagents, pigments, coatings, solders, brazes, and parts for industry by powder metallurgy techniques. They are also combined with refractory compounds to produce cermets and dispersion-hardened products. One of the interests at the Lewis Research Center has been to explore the potentialities of the dispersion strengthening process. Since the work of Ir-mann, many investigators have shown that the strength of dispersion-hardened products may increase with decreasing interparticle spacing.24 One approach to achieving small interparticle spacing is to combine fine refractory compounds and metal powders, preferably below 1 in size. In attempting to obtain fine metal powders, it was found that until very recently the best that could be obtained from commercial suppliers, particularly of ductile metals, was about 1.0 . Interest was therefore developed in providing finer metal powders for dispersion-hardening studies. Information obtained from the literature, from others working in the field, and from prior experimental work performed at NASA, led to a consideration of ball-milling as a technique to produce the desired materials. Some of the variables associated with ball-milling are the size, material, and nature of construction of the grinding container; the nature and amount of the grinding material and material to be ground; and the nature and amount of the grinding liquid and grinding aid, if employed, and the grinding time. In all ball-milling, welding and agglomeration can oc- cur as well as grinding. Because of the tendency of ductile metals to weld together, they are difficult to grind.5 The ultimate particle size obtained on grinding is generally the one at which the rate of grinding becomes equal to the rate of welding. To help delay welding and thus obtain smaller particle sizes, grinding aids are often employed. The principal objective of this investigation was to produce submicron metal powders by ball-milling the powders with selected grinding aids and grinding fluids. A secondary objective has been to attempt to explain the variations observed in grinding behavior by considering possible grinding mechanisms and correlating various parameters with grinding effectiveness. Three groups of ball-milling experiments were run; one in which the grinding aid was varied, a second in which the grinding fluid was varied, and a third in which the material being ground was varied MATERIALS, APPARATUS, AND PROCEDURE In the first group of experiments in which the grinding aid was varied Inco Carbonyl Grade B nickel powder initially 2.5 (all sizes refer to average particle size as measured by Fisher Sub -sieve Sizer) was used as the material being ground and 200-proof ethyl-alcohol as the grinding fluid. Surfactants, representative of typical organic structures, were selected as grinding aids. Inorganic salts used as grinding aids were chosen on the basis of the size and valence of their ions. Water soluble salts were used in order to facilitate their removal from the slurry after grinding. In the second set of experiments, grinding of the 2.5- Ni powder was tried in four different grinding liquids; water, cyclohexane, n -heptane, and methy-lene chloride. In this study seven grinding aids selected from those tried in the first group of experiments were employed. In the third group of experiments 200-proof ethyl alcohol was again used as the grinding fluid to mill Cu, Cr, Fe, Ag, and Ni powders of various initial particle sizes' All mill charges contained 300 ml of grinding liquid and 3000 g of 1/2 in. stainless steel balls. When inorganic salts were used as the grinding aid, 70 g of salt and 210 g of metal powder were employed, and with surfactants 6 g of grinding aid and 300 g of

Jan 1, 1962

By L. F. Porter, G. J. Dienes

The effect of netltron irracliation on mart ensite transformation in the iron-nickel system was studied by means of electrical resistance and magnetic induction measuremertts. Irradiation lowers the M8 temperature of the allay, causes changes in the electrical and magnetic properties of the high-temperature phase which indicate either an accelemtion of phase separation or a clustering of nickel, and enhances strain recovery on specimens partially transformed to martensite prior to irradiation. Possible mechanisms to account for the effects; are discussed. 1 HERE is a good deal of evidence to indicate that neutron irradiation is capable of affecting phase changes in metals and alloys. While the mechanism of the effect often is not well understood, such studies hold promise of improving our understanding not only of irradiation damage but also of the phase changes involved. To date systematic and detailed investigations have been made of the influence of nuclear radiation on order-disorder transformations in the copper-gold, nickel-manganese, and copper-zinc system, and on precipitation reactions in the copper-iron, nickel-beryllium, and copper-beryllium system.' These solid-state reactions are diffusion controlled and the results can be explained largely on the basis of enhanced diffusion due to the presence of irradiation produced vacancies. Reversion of low-temperature eutectoid phases to the high-temperature phase has been observed in the fissionable uranium-molybdenum and uranium-niobium systems.2 Here it is necessary and logical to postulate a displacement spike mechanism to account for the effect. The only case of irradiation induced diffusionless transformation in metals is the allo-tropic transformation of p to a tin reported by Flee-man and Dienes. 3 They found that neutron irradiation markedly decreases the incubation time for transformation, but the mechanisnl is not well understood. Another diffusionless transformation which one might expect to be influenced by neutron irradiation is the martensite transformation. This transformation is known to be sensitive to strain, structural hardening, and the presence of imperfections.6,7 Since the transformation is diffusionless, one also

Jan 1, 1960

By M. A. Goudie

The deposits occur in a large salt basin of Middle Devonian age. The potash, the final deposit in the salt basin, results from several interrupted cycles of evaporation and dessication. The deposits are extensive, and, at first glance, relatively undisturbed. With more and more wells being drilled, it has now become evident that salt solution has played a large part in changing the original deposits, resulting in some cases in partial to complete removal of the potash and the underlying halite. The most dominant factor in the removal of salt by solution appears to have been tectonic movement and consequent faulting, probably of relatively minor dimensions but of major importance. Evidence which indicates the tilting of the evaporite basin to the north and northwest is shown by the changing pattern of the basin during succeeding eras of potash deposition. The potash minerals of most importance economically are sylvite and carnallite. Reserve calculations indicate that 6.4 billion tons of recoverable high grade potash in K2O equivalent exist in the basin. The Devonian salt basin, which contains the Saskatchewan potash deposits, extends from just east of the foothills in Alberta, north as far as the Peace River area, across Saskatchewan and into Manitoba as far east as Range 10 west of the First Meridian and south into Montana and North Dakota (Fig. 1). The basin is closed everywhere except to the northwest. The known potash deposits are confined almost entirely to the Province of Saskatchewan, with the exception of a small area in western Manitoba bordering the Saskatchewan boundary. The following discussion will concern only the Saskatchewan part of the basin. The evaporite series in the basin is defined as the Prairie Evaporite Formation of the Elk Point Group, of Middle Devonian age. Recent work done by potassium-argon dating methods has indicated an Upper Middle Devonian (Givetian) age of from 285 to 347 million years for the potash. The Elk Point Group consists in ascending order of the Ashern, Winnipegosis, and Prairie Evaporite Formations. The Ashern formation, with an average thickness of 30 ft, sometimes called the Third Red Bed, consists of dolomitic shales and shaly dolomites. The Winnipegosis, is a reef-type dolomite, usually with good porosity, and in many cases oil-staining, although to date no production has been obtained. The thickness varies from 50 to 250 ft. The Prairie Evaporite formation, varying from 0 to 600 ft in thickness, consists of halite with interbedded anhydrite and shale, with considerable amounts of potassium salts in the upper part of the formation. The potassium salts are chiefly chlorides, although very minor occurrences of sulfates have been re- ported. The anhydrite beds do not appear to be continuous, although generally one or two bands of anhydrite underlie the lowest potash zone and are used as marker horizons. The shale occurs as seams interbedded with the salts, as large irregular inclusions in the salts and as very fine particles in intimate mixture with the salts. The Prairie Evaporite Formation is overlain by the Second Red Bed member, the Dawson Bay Formation and the First Red Bed Member of the Manitoba Group, listed in ascending order. The Red Beds are shales which vary in color from red to green, maroon, grey, grey-black, and reddish purples. They serve as marker horizons for coring the potash. The Second Red Bed averages 14 ft in thickness, the First Red Bed 35 ft. The Dawson Bay Formation, which everywhere overlies the First Red Bed and the Prairie Evaporite Formation in the area under discussion, is a reef type of carbonate, in some places limestone, in others limestone and dolomite, with vugular to pinpoint porosity averaging 130 ft in thickness. In some parts of the area, it has a salt section near the top of the formation, usually with interbedded shales and limestones. In other parts of the area, it is waterbearing and the salt is absent. Detailed mapping has indicated that the areas in which the Dawson Bay is water-bearing are areas which have been disturbed by faulting. Where the Dawson Bay is salt-bearing, the porosity has been plugged by salt. The total thickness of the salt varies from between 600 to 700 ft in the center of the basin to zero at the northern edge of the basin (Fig. 2).* The salt-free area in the center of the Province is believed to have resulted from removal of salt by solution. Evidence from several wells suggests that salt removal has been a continuing process from the time of deposition to the present day. One well drilled between the Quill Lakes for potash information encountered

Jan 1, 1961