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By H. O. Hofman, H. L. Norton

Zinc smelters in the central western States have established a very high standard of purity for blende-concentrates, viz., zinc 60, iron less than 3, and lead less than 1 per cent. The very low percentage of iron is made possible by the blende containing less than 0.5 per cent. of isomorphous iron sulphide and by the sparing occurrence of pyritic material in the large blende-deposits of southwestern Missouri and southeastern Kansas. The blende in these districts occurs in sub-carboniferous limestone, and is associated with chert, residual clay, cal-cite, pyrite or marcasite and bitumen. The different minerals are coarse and therefore readily separated by mechanical washing from the blende, with the exception of pyrite and marcasite, as blende has a specific gravity of from 3.9 to 4.1; marcasite, from 4.85 to 4.90; and pyrite, from 4.95 to 5.10. The common procedure of dressing the ores' is to crush in a breaker, size in a trommel with 0.5-in. holes, pass the over-size through roughing-rolls and then jig the ore, now reduced to 0.5 in. maximum size, in roughing multiple-sieve jigs. The products of these are waste-tailings, side-discharge coarse concentrates, side-discharge coarse middlings and bottom-discharge fine middlings. The coarse concentrates are sent to the market. The coarse middlings are crushed in middlings-rolls and brought back into the system by feeding into the main trommel. The fine middlings are cleaned upon finishing-jigs. Any pyrite or marcasite present follows the blende and increases the percent- +1MASSACHUSETTS INSTITUTE OF TECHNOLOGY, BOSTON, MASS.

Jan 1, 1905

By E. C. Potter

It is not the purpose of this paper to enter into the minutiae of a subject so vast, upon which volumes have already been written and volumes more might still be written, but simply to pass in review the characteristic features of that practice, which, dating from the blowing-in of the Edgar Thomson "A" furnace in 1879 and continuing down to the present day, has given to American blast-furnace operations a new significance. The blowing-in of " A" furnace marked the beginning of a new era in the science of iron-smelting if, indeed, it was not the very birth of science as applied to this industry in the United States. American blast-furnace practice in its generic sense and world-wide significance dates from that day, and really all that is valuable, all that is remarkable or worthy of discussion, is embraced in the experiences and achievements of the past fifteen years. Back of that we find only the dead level of mediocrity, or worse, a dispoition to " let well enough alone;" a general, almost universal, employment of " rule of thumb " methods. The application of scientific principles and methods was rare and, indeed, previous to the introduction of the Bessemer process in the early seventies, science had no place in controlling the operations of the American blast-furnace. The old practice consisted mainly in dumping raw materials in at the top of the furnace and tapping out iron and slag at the bottom, for the successful consummation of which the furnace-manager directed his best energies toward keeping the furnace as free as possible from "gobbing" with, alas ! but indifferent success. The burdening of the furnace was based largely on Mark Twain's receipt for " Johnny-cake," altered to suit the circumstances, viz.: a lot of ore, a lot of fuel and about a quarter of a lot of flux. The possible capacities of furnace-plants were not nearly realized. Enormous wastes were permitted, unheeded because not understood. In the use of fuel quantum suff. was always the rule. Increase of product was not thought of because it was not deemed wise or safe to attempt

Jan 1, 1894

By J. E. Sandor, P. F. Schmidt

A general review of the present knowledge of the semiconductor/oxide interface is given, with emphasis on silicon and germanium. The electrical properties of clean surfaces and the changes that occur upon oxidation are described. A brief disczcssion of the methods and mechanisms of oxidation of silicon is given, and the interaction between the semiconductor substrate and the oxide phase is considered. Physical properties of the oxide film, charge storage effects due to the dielectric, and some device applications of oxide films on semiconductors are discussed. THIS paper will be heavily preoccupied with the elemental semiconductors germanium and silicon. Undoubtedly some injustice is done thereby to other semiconductor-oxide systems, but it is not readily possible to cover all aspects of so vast a field in the present review. In considering the semiconductor/oxide interface, we may start out by discussing briefly an idealized clean semiconductor surface, and may then follow the changes brought about by oxidation, as the oxide is allowed to grow progressively thicker. The references given are not a complete list, but are to be taken as guides to the literature. Tamml suggested in 1933, based upon the study of a one-dimensional asymmetrical potential model, that localized surface states may appear at the surface of a crystalline lattice; it was pointed out by Fowler that these states should occur in pairs. shockley3 examined the origin of such surface states on the basis of a more general one-dimensional model and found that surface states may appear in the forbidden region between the highest filled and the lowest vacant band. This happens when the two bands overlap, as, for instance, the "s" and ('p" bands of the diamond structure. In a three-dimensional model these levels would produce a surface band which is half-filled for diamond, and the number of surface states should be approximately equal to the number of surface atoms. This picture of the surface has been refined by more recent theoretical work, like Handler's4 and Koutecky and Tomasek's~ without introducing essential modifications. When these concepts were applied to semiconduc-

Jan 1, 1965

By Stephen Burke

THE oxidation of pyritic sulphur associated with coal is important for the following reasons: 1. It is the predominant cause for the formation of acid mine drainage issuing from bituminous coal seams. This drainage pollutes the streams in coal regions, making the water unfit for industrial purposes and causing the disappearance of fish and wild life. As a consequence the movement of industry and especially recreational industry, so important to the population of these areas as an alternative means of livelihood, is impeded. 2. It is instrumental in effecting a series of reactions, which bring about the degradation and ultimately result in the spontaneous combus-tion of bituminous coal in storage. 3. It contributes to the breaking and shattering of the coal structure and is one of the causes of roof falls and floor lifts in mines. 4. It is the primary cause of the many nuisances associated with gob piles and the refuse of cleaning plants. 5. Its proper control and application might possibly be employed in the preparation of coal to reduce the inorganic sulphur content. The research that has been conducted on the oxidation of the various forms of iron sulphides is extensive and the literature voluminous. Nevertheless, few efforts have been made to determine experimentally and with some precision the mechanism of the reaction under the condi-tions of its occurrence in bituminous coal mines. It has generally been accepted that the oxidation of pyritic sulphur proceeds according to the reaction 2FeS2 + 21120 + 702 --> 2FeSO4 + 2H2S04 [1] The ferrous sulphate in the drainage streams is further oxidized by air to produce ferric hydroxide and more acid. Yet the literature fails to dis-close any pertinent investigation on the mechanism of this reaction. The present contribution is concerned primarily with this aspect of the problem and while the work to be reported is not yet complete, it has yielded results from which interesting and significant conclusions may be drawn.

Jan 1, 1937

By W. W. Stephens, W. J. Kroll, H. P. Holmes

THE only two methods for producing commercial quantities of malleable zirconium, up to now, have been using magnesium reduction of the anhydrous chloride under a neutral gas, and using purification of raw zirconium by the iodide dissociation method on a hot filament. The purity of the metal obtained by the latter process is about the same as that resulting from the chloride reduction, with the exception of the oxygen content, which may be about 0.05 pct lower in the iodide metal. Even traces of oxygen have a strong hardening effect on zirconium. Since, in the iodide process, the impurities, Si, Al, Fe, Ni, and Mg in the raw zirconium used, are carried over, it would appear uneconomical to use this method of refining solely to eliminate the traces of oxygen, unless very soft metal is desired. One important step to improve the iodide method, namely, dissociating pure iodide made from carbide and recycling the iodine, which would change this refining process into a method for extracting zirconium from the ore, has not yet been made. The Bureau of Mines, by using the chloride reduction, wanted to produce quantities of a reasonably pure and malleable metal at low cost for large-scale industrial use. This aim has been achieved, and a pilot plant permitting production of 600 lb of malleable zirconium per week will be described (fig. 1). Briefly, the Bureau of Mines process consists of reducing purified gaseous anhydrous zirconium chloride with fused magnesium under a noble-gas atmosphere. The reaction product, magnesium chloride, and any excess magnesium metal present are removed from the sponge zirconium in the next step by fusion and evaporation in a good vacuum at about 925°C. In this process, care is taken to keep air out of contact with the hot metal, which otherwise would contaminate the product with oxygen and nitrogen. Both these impurities embrittle zirconium even when present in an amount as low as 0.1 pct. A number of previous reports1-3 describe the method and the various improvements that finally led to a workable process. The major steps made were the production of large quantities of carbide, which is the raw material for producing the chloride, its chlorination with reasonable efficiencies, and the elimination of iron trichloride contained in the raw chloride, as well as that of the zirconium oxide which is always present in this product. The physical nature of the anhydrous chloride, which sublimes at 331°C at atmospheric pressure and melts at 420°C under a pressure of 25 atm, made it necessary to provide a special safety device on the purification and reduction vessels in the form of a lead-alloy seal, permitting escape of excess gases if pressure tended to build up. The main difficulties encountered in the reduction and in the following step, salt separation in a vacuum at elevated temperature, were caused by the material from which the reaction pot was constructed—iron. This metal reacts with zirconium at about 940°C with formation of a eutectic. The last step, salt separation by evaporation of the magnesium and magnesium chloride in a vacuum, is quite unconventional and has not been used before on such a scale. It is only due to the improved construction of high-vacuum pumps, especially oil-diffusion pumps, that such a method could be used. The various steps of the Bureau of Mines process, as described in the general outline above, may be summarized as follows: (1) production of the carbide, (2) chlorination of the carbide, (3) purification of the raw chloride, (4) reduction of the pure chloride with fused magnesium, (5) separation of excess magnesium and magnesium chloride in vacuum at elevated temperature, and (6) melting of the sponge obtained. Production of Carbide The arc furnace, described in a previous report,' was improved both to reduce the graphite consumption caused by the burning of the bottom plates and to concentrate the heat in order to obtain better power efficiency. This was achieved by providing the bottom with graphite plates entirely embedded in refractory bricks, the contact with the current being made with three water-cooled copper plugs. Figs. 2 and 3 show the arrangement. The crucible, made

Jan 1, 1951

By W. A. Schaeffer, M. Albertson

The Yates field is situated in northeastern Pecos County, Texas. Its productive area is about 15,000 acres. Production is chiefly from limestone of Permian age. Depths of wells vary from 1100 to 1800 ft. Initial productions range from a few barrels to 8000 bbl. per hour. The field outlet has always been prorated. Gas-oil ratios originally varied from less than 100 cu. ft. up to 8000 cu. ft. per barrel at allowable production rates. The average ratio was about 500 cu. ft. Fig. 1 shows the structure of the field and the location of the Tippett lease, on which the original experimental tubing work was done. Before the latter part of the year 1929, little actual effort in practice had been given to determination of the conditions under which the highest efficiencies may be realized in naturally flowing wells. For the preceding few years attention had been given to gas-oil ratios and their possible reduction by maintenance of back-pressure by choking at the well head. Some attempts had been made toward reduction of ratio by bottom-hole choking. In late 1929, the Shell Petroleum Corp. started the experimental installation of specially designed flow columns adapted to high-pressure flowing conditions in the Yates field. The objectives in view were the attainment of low gas-oil ratios at low rates of flow and the maintenance of high bottom-hole pressures. All naturally flowing wells should be provided with a suitable eductor string immediately upon completion of the well, so that the benefits of efficient flow will be derived from the beginning. This paper presents a method of tubing for efficient flow and a discussion of some complex factors which influence well behavior. Factors Influencing Gas-oil Ratios Many factors influence the production of gas from naturally flowing wells. The writers believe that in some instances gas control is effected mainly in the reservoir itself, in others in the well bore, and in still others both sets of factors may be significant. Some wells apparently have penetrated productive zones in which practically all of the gas is closely associated with, and mostly dissolved

Jan 1, 1932

By E. F. Raffo

THE design of the Chuquicamata concentrator offered an unusual combination of problems, all of which had, in one way or another, a definite effect upon the final arrangement of all the equipment and necessary facilities. First of all, a remotely located project of this magnitude required careful selection of equipment with an adequate supply of replacement parts and in some cases necessitated stand-by spare equipment ready for immediate use. Fortunately, in the course of determining the proper flowsheet, in itself a prime factor in the concentrator design, it was possible to conduct numerous grinding and flotation tests at the Anaconda and Andes concentrators. As a result of these tests made under actual operating conditions, most of the major equipment best suited for treating the Chuquicamata ore efficiently was decided upon while preliminary design layouts were still being made. The design has been based primarily on the treatment of sulphide ore crushed to about 3/4 or 1 in. However, until the new sulphide crushing plant is completed it will be necessary to handle ore crushed to 3/8 in. in the existing oxide crushing plants and to some extent a mixed ore which has had its oxide copper content removed by leaching. This mixed ore, known as leached residue, will contain a certain amount of sulphuric acid from the leaching process which necessarily requires special protective measures. Several factors influenced the final location of the Concentrator. The only established fact known during preliminary design layout was the elevation of the dumping floor over the fine ore bin. This was predetermined by the desired level railroad grade across part of the existing tailing and leached residue dumps from the oxide plant to the bin. Next it was necessary that a site be chosen that would not require an excessively long haul from either the present oxide plant or the mine and in addition provide a fairly constant natural ground slope sufficiently wide to accommodate the length of the ultimate concentrator. The site as finally chosen to meet the foregoing restrictions provided a natural ground slope of 6 to 7 pct. This was excellent, especially in a region subject to earthquakes, as it assured that foundations of heavy equipment and footings for building and crane columns would rest on cut or undisturbed ground. However, this shallow slope, although having some definite advantages in the overall consideration of plant layout, resulted in the need for extensive studies in the general arrangement of equipment. Wasteful and excessive vertical drops had to be eliminated in the

Jan 1, 1952

By David L. Holt, Walter A. Backofen, Anwar-uI Karim

Specimens of a hydrided Mg-0.5 Zr alloy were strained in tension at 500°C and constant rates of 2 x10-3 5 x 10-3, and 2 X 10" min-1. Hydride-denuded zones formed at grain boundaries normal to the tensile-stress direction as a result of magnesium transport during difusional flow. The width of the zones could be measured and the measurement used for calculating the diffusional component of the imposed tensile strain. The strain from diffusional flow was found to increase with imposed strain at a diminishing rate, tending to saturate at approximately 12 pct. Strain rate sensitivity of flow stress was low. The apparent non Newtonian character of the diffusional flow is attributed to a non Newtonian process acting in parallel with it which could be boundary shear. Fracture grows out of voids that form in the denuded zones. DEFORMATION of a grain by diffusion of atoms from boundaries stressed in compression to boundaries stressed in tension is Newtonian viscous,1-3 and evidence has accumulated in recent years that such a process may be responsible for the high strain-rate sensitivity of the flow stress of super-plastic alloys.4"7 One piece of evidence is that experimental stress: strain-rate relationships can be quantitatively explained.5-7 There is also metallo-graphic evidence of diffusional flow in superplas-ticity, but in a limited amount. The formation of striated bands on the surface of superplastically deformed specimens has been attributed to diffusional flow.5"7 The basis of that attribution came from experiments on a coarse-grained, nonsuperplastic and hydrided Mg-½ wt pct Zr alloy which formed hydride-denuded, light etching zones at tension-stressed boundaries when strained in tension at 270?C.6 The origin of these zones had already been traced to the diffusional flow of magnesium atoms to the boundaries.' The particular observations in the more recent work were of striated-band formation on the surface and denuded-zone formation internally, with both the bands and zones having the same width and appearing at tension-stressed boundaries. It was argued that the bands were a surface manifestation of the zones and hence of diffusional flow. Of course in superplastic alloys which do not contain internal metallographic "markers", the surface bands can be the only metallographic indication. In the present work, denuded-zone formation was utilized, as it has been by others,9-11 to extend the observations of diffusional flow and to measure the strain, ed, resulting from it. Grain size had to be large to measure ed with accuracy. The grain size chosen for this study was -30 , and with that a strain of 10 pct from diffusional flow produces a denuded zone only 3 µ in width. The large grain size naturally precludes superplasticity. The observations of diffusional flow were complemented by determining the strain from the other operative deformation modes: slip, e,, and grain boundary shear, egb. An incremental specimen extension is the sum of increments from slip, and grain boundary shear as well as diffusional flow. Division by a common length is required to convert to strain. If this length is taken as the initial specimen length, then imposed engineering strain, e, is given in terms of the component engineering strains by e = ed + es + egb [1] Stress:strain-rate relationships are determined by the way in which this "strain balance" is made up. EXPERIMENTAL Material. Zirconium hydride markers were introduced into the Mg-0.5Zr alloy by annealing in hydrogen at 450°C for 30 min. The hydride concentration was particularly high at zirconium rich stringers, which was fortunate in that the transverse boundaries at which denuded zones form lie perpendicular to the stringers. Grain size after annealing was 30 µ. Photomicrographs of unstrained and strained material are shown in Fig. 1. Procedure. Specimens were strained in tension with an Instron machine at crosshead velocities of either 2 x 10"3, 5 x X or 1 x 10-2 in. min-'. Specimen length and diameter were 1.0 and 0.2 in., respectively, so that initial strain rates in tests at constant crosshead speed were 2 x 10"3, 5 x X and 1 X l0-2 min-1. Tests were made at 500°C which is a compromise temperature at which diffusional flow is still measurable but grain growth is not active enough to interfere with metallographic measurements. The tests were made in a hydrogen atmosphere. Strain Balance. An equation additional to [I] is eg = ed + es [2] where eg is strain measured from grain elongation. Measurement was made of ed, eg, and, of course, e, which enabled all the strains in Eq. [I] to be determined. For this purpose, strained specimens were sectioned longitudinally, polished, and etched. The strain from diffusional flow, ed, was computed by measuring on photomicrographs the width in the tensile direction of denuded zones at either end of a grain XI, X2, adding them, and dividing by twice the initial longitudinal grain dimension L0, Fig. 2. Reported values are the results of measurements on seventy randomly selected grains; 95 pct confidence limits on ed were +1.5 pct strain. To measure eg, the maximum length, L, and the maximum width, W,

Jan 1, 1970

By R. E. Reed-Hill, W. H. Hartt

High-purity magnesium single crystals, oriented with basal plane parallel to stress axis, were deformed in tension at room temperature so as to form second-order (1011)- (1012) twins. Investigation by optical and replica electron microscopy revealed that these twins can support very large internal strains approaching 1000 pct and that fracture follows as a direct consequence of these strains. At low strains the basal plane within (10i1)- (10i2) twins rotates with increasing deformation until it becomes approximately parallel to the twin boundaries. This rotation is not consistent with deformation by basal slip in the double twin, but may be rationalized in terms of nonbasal slip. Observations also indicate that basal slip in the primary (1011) twin, prior to second-order twinning, may contribute to this rotation. Deformation markings that are difficult to interpret in terms of slip on previously observed systems were noted in the twin bands. A possible means of rationalizing these markings is to relate them to grain boundary shear. The fracture associated with these twins is thought to initiate by formation of voids at the twin boundaries. These grow into microcracks, with ultimate fracture occurring by tearing of the interconnecting regions. THE significance of deformation and fracture along second-order (10i1)-(10i2) twins in polycrystalline magnesium1-' and many magnesium alloys4 was discussed in a previous paper.5 It was noted that this double twinning mode effectively controls the room-temperature deformation and fracture of magnesium single crystals, oriented with the basal plane parallel to the tensile axis. Reed-Hill and Robertson6 observed that, although these crystals may fracture at a macroscopic strain of less than 1 pct, shear strains up to 1000 pct could occur within (1011)- (10i2) twin bands. They concluded that the fracture was "ductile" and resulted from concentrating the deformation into a very small volume. The present research was undertaken to obtain a better understanding of the deformation and fracture associated with these twins. EXPERIMENTAL TECHNIQUES The experimental procedure involved straining high-purity magnesium single crystals in tension at room temperature. Specimens were oriented so that the applied stress direction was within 2 deg of the [1010] crystal axis. The specimen cross section was rectangular with faces closely parallel to (1210) and (0002). The specimen preparation and testing procedures have been described in detail elsewhere.5 Second-order (1011)- (1072) twins nucleated during straining were studied using optical and replica electron microscopy techniques. For the latter, cellulose acetate-carbon double replicas were employed. Observations were made on the (1210) crystal surface, which is the plane of shear for twins of this type. In addition to the single crystals, some investigations were carried out on longitudinal polycrystalline specimens. These were obtained from high-purity magnesium plate with a texture in which the basal planes of the grains tended to be nearly parallel to the specimen axis. All. polycrystalline specimens were annealed prior to testing in order to produce a coarse grain structure, permitting Laue back-reflection X-ray photographs to be obtained from grains of interest. EXPERIMENTAL RESULTS a) Deformation Within ( 101 l )-( 1072) Twins. Fig. 1 is an optical micrograph demonstrating the extent of the plastic deformation that can occur in (1011)-(10i2) twin bands. Notice at the lower left corner of the photograph the large displacement of the dark band (a polishing step) where it crosses the twins. The shear strain in the twin band at this position was computed to be 700 pct, using the ratio of step width to twin thickness. It was previously shown5 that (1011)- (1012) twin bands are often composed of small, separate twins aligned close to the macroscopic habit plane. Fig. 2 is an electron micrograph from near the upper end of the twin band in Fig. 1. This illustrates that the twin habit often does not coincide exactly with the macroscopic band habit, but may be inclined at a slightly smaller angle to the matrix basal plane. Figs. 3 through 6 are electron micrographs of the twin band in Fig. 2 illustrating successive steps in the development of deformation inside the band. A twin band such

Jan 1, 1969

By T. S. Fuller

THE work of D. J. McAdam1,2 at the U. S. Naval Engineering Experiment Station, Annapolis, Md., on what has been called by him "corrosion fatigue" has focussed the attention of the engineering profession in general, and of those interested especially in the study of corrosion in particular, on the importance of making tests which will indicate as nearly as possible what can be expected from a given material in service. Pitting is unquestionably the chief agent operating so tremendously to reduce fatigue limits, but in the light of previous work3, 4, 5, 6, 7, 8 it is fair to assume that absorbed hydrogen resulting from the action of the corroding medium upon steel may, under certain conditions, have a perceptible influence. The experiments described in this paper deal more precisely with stressless corrosion, or "prior-corrosion fatigue, "9 and have been carried out to test such an assumption, to segregate, if possible, the effect of pitting from that of absorbed hydrogen, and although very preliminary in nature they indicate results which are striking.

Jan 1, 1929

By Reino Kurppa

The Pyhäsalmi mine of the Outokumpu Co. is located in central Finland (Fig. 1). The deposit was discovered in the autumn of 1958. Construction of the mine was started a year later, and production began on Mar. 1, 1962 (Fig. 2). At present, 750,000 metric tons (mt) of ore and a nearly equal amount of country rock are mined annually. Slightly over one-half million tons of various concentrates are produced per year, of which 85% is pyrite concentrate, 10% zinc concentrate, and 5% copper concentrate. The pyrite concentrate is treated in the company's pyrite smelter,1 yielding elementary sulfur, sulfur dioxide, and iron-oxide cinders, as well as electric power. Thus all the sulfides, totaling 75% of the ore, are of economic value. This is a fact which had a bearing on the development of the stoping method. GEOLOGY The ore is of breccia type containing fragments of country rock of varying sizes. It is coarse-grained pyrite ore containing sphalerite and chalcopyrite as a matrix between the pyrite grains. Only small amounts of pyrrhotite have been observed in certain marginal parts of the orebody. The ore averages 0.85% Cu, 3.0% Zn, 38% S, and 33% Fe. The orebody extends from the surface down to at least 500 m, which is the lowest level from which present information has been obtained. Horizontally, the orebody is 650 m long. It is 75 m wide at its central part, narrowing towards the ends (Fig. 3). At a depth of 115 m, the orebody suddenly narrows down to a thickness of 25 to 30 m. In the northern part of the orebody, the dip is 50° to 70°, but elsewhere it is almost vertical (Fig. 3).

Jan 1, 1969

By R. W. Balluffi, R. Resnick

NUMEROUS investigations of chemical diffusion in a brass have been made and the results are collected in several places.1-3 This work has been mainly concerned with the determination of the chemical diffusivity as a function of composition and temperature. In 1947 Smigelskas and Kirken-dall&apos; showed that zinc and copper diffuse at different rates in face-centered-cubic brass, and since then, a number of efforts have been made to determine the intrinsic diffusivities of zinc and copper in this alloy.1, 5-9 Horne and Mehl8 in particular have recently determined the intrinsic diffusivities as functions of temperature and composition using sandwich-type couples and inert markers. Inman et al." also have determined the intrinsic diffusivities in homogeneous alloys using tracer techniques. When the present work was started, no information of this type was available. Consequently, measurements of the intrinsic diffusivities were made as a function of temperature at a constant composition of 28 atomic pct Zn with vapor-solid diffusion couples where the zinc was diffused into the diffusion couple from the vapor phase. The application of these couples to the study of diffusion in a: brass has been described previously.0,7 The temperature dependence of the intrinsic diffusivities was found to follow the relation D, = A, exp(-Hi/RT) and the values of Hzn, and Hcu, were found to be closely the same. It is emphasized, however, that the chemical dif-fusivity (D = N1D2 + N2D1) is a composite diffusivity and does not necessarily follow this exponential form. It is usually found to do so within experimental error for substitutional alloys because the heats of activation of the intrinsic diffusivities generally are not greatly different.&apos;" Also, at the onset of this work, there was no information available concerning possible unequal diffusion rates of individual components and the existence of a Kirkendall effect in alloys with other than face-centered-cubic structures. Since then, two reports indicating a Kirkendall effect in body-centered-cubic ß brass have appeared. Landergren and Mehl" have published a note describing Kirkendall diffusion experiments with sandwich-type couples. Inman et a1.9 also find a Kirkendall effect in this alloy using the tracer technique. In the present work, several aspects of the Kirkendall effect in ß brass were further investigated using vapor-solid couples. Two different couples were used, one in which the zinc was diffused into the specimen from the vapor phase and the other in which the zinc was diffused out of the specimen into the vapor phase. Briefly, the existence of a Kirkendall effect is confirmed and it is found that Dzn/Dcu = 3 at about the 46 atomic pct composition in this alloy at 600°, 700°, and 800°C. As a result of the unequal diffusion rates of zinc and copper, volume changes occur and subgrain formation is observed in the diffusion zone. In addition, significant porosity is produced by the precipitation of supersaturated vacancies. Diffusion in this alloy is therefore outwardly similar to diffusion in a brass where these effects are also observed, a Brass Experimental Methods—The use of vapor-solid couples in studying diffusion in a brass has been described in previous articles.6,7 The method briefly consists of sealing a copper specimen with Kirkendall markers initially placed on its surface in an evacuated quartz capsule along with a large zinc source of fine a brass chips and then diffusing the zinc into the specimen through the vapor phase. The zinc concentration at the specimen surface rises rapidly enough to a value near that of the a brass source so that the surface concentration may be regarded as constant during diffusion. Under these boundary conditions, values of the chemical diffu-sivity may be obtained by applying the Boltzmann-Matano analysis to the concentration penetration curve, and the intrinsic diffusivities may be obtained from Darken&apos;s5 equations when the velocity of marker movement is known. The diffusion specimens were made from OFHC copper in the form of disks 3.2 cm diam and 0.5 cm thick with faces surface-ground parallel to within +0.001 cm. Markers in the form of fine alumina particles <0.0002 cm diam were placed on the specimen surface. These specimens were then sealed in quartz capsules along with enough a brass chips of a 30.0 atomic pct Zn composition to keep the source concentration from decreasing by more than 0.3 atomic pct Zn as a result of the loss of zinc to the specimen during diffusion. The quartz capsules which were initially evacuated to a pressure of

Jan 1, 1956

By K. Thirumalai

Rock response to heating depends on properties of rock material and varies widely between different rock types. By dissipating energy, surface melting limits rapid heating and fragmentation of rocks achieved by surface heating methods. This study advances a concept of rock fragmentation by rapid internal heating of a localized inner volume of rock. The working of the method to achieve fragmentation of rocks (Charcoal granite and Dresser basalt) having poor response to surface heating is analyzed. Experimental data on elevated temperature rock properties required for the study are presented. Based on the properties of test rocks, a high frequency (50 MHz) dielectric heating method of generating localized internal heating was selected for experimental study. The test rocks were fragmented without melting under localized heating below 600ºC. The heated volume required for fragmentation was observed to be less than 2 percent of the test block volume. A practical application of the method for in situ fragmentation of rocks is suggested.

Jan 1, 1971

By B. H. Caudle, W. J. Bernard

Factors which influence the success or failure of a waterflood can seldom be determined in the laboratory. For this reason pilot waterfloods are initiated in a repreventative portion of the oil reservoir in question. For a pilot flood to predict quantitatively the recovery to be expected in a field-wide waterflood operation, the pilot area must behave as though it were confined (surrounded by similar areas). In this study, laboratory fluid-flow models were used to determine the simplest pilot pattern, for particular conditions of mobility ratio and initial gas saturation, that would behave as though it were confined. Pilot patterns studied ranged in complexity from a single inverted five-spot to a grouping of nine regular five-spots. Only the innermost producing well in each pattern was studied. Model results showed that the optimum number of wells in the pattern depends upon the oil-water mobility ratio and the expected oil-bank size. Unfavorable mobility ratios will, in general, require more wells in the pilot pattern than will favorable mobility ratios. Pilot patterns in reservoirs which contain a dispersed, flowable, free gas saturation will require fewer wells than for the under-saturated case. The single inverted five-spot pattern was found to be unsatisfactory for predicting behavior of fully developed waterfloods. In particular, it is possible that, in reservoirs which contain a flowable, dispersed gas phase, the oil bank will never be observed at the producers due to the large amounts of free gas which continue to be produced with the oil. INTRODUCTION One method which has been used to predict the performance of a waterflood is the pilot flood. The pilot waterflood is a flood which involves only a small cluster of the reservoir wells and is located in a small, representative portion of the reservoir. The object is that oil produced from the pilot can, in some way, be related to the oil recovery to be expected from a field-wide expansion of the waterflood. However, these field pilot waterfloods have often been unreliable in the prediction of oil recovery in a fully developed waterflood. This unreliability has also been demonstrated in several laboratory studies of pilot floods. Some of the investigators have shown that there are situations in which the pilot flood oil production is far too optimistic with respect to the oil recovery in the fully de- veloped flood. Others4-G have shown that the pilot results can also be pessimistic, especially if the pilot waterflood is initiated in an oil reservoir which has been depleted by primary recovery and is at very low pressure. The major reason for this unreliability of pilot water-floods is the migration of fluids into or out of the pilot area. By the well-known method of images, if straight lines can be drawn to represent vertical planes of symmetry in a porous medium which contains pressure sources and sinks (injectors and producers), then these lines are invariant streamlines, or lines across which there is no potential gradient, and therefore no flow. In an actual reservoir, these lines of symmetry can never be established exactly because of reservoir inhomogeneities and irregular reservoir boundaries. However, if the reservoir is relatively large and contains wells in repetitive patterns, these lines of symmetry are commonly assumed to exist for the pattern units sufficiently far removed from the reservoir boundary. Lines of symmetry for the five-spot injection pattern are shown in Fig. 1. Each five-spot unit in this figure can be considered confined with respect to flow across its boundary. In pilot floods this is not the case. The lines of symmetry for the pilot patterns investigated in this study are shown in Fig. 2. It is obvious that the fluid within these pilots is not confined and is therefore able to migrate into or out of the pilot area. Intuitively, one can see that, if more wells are added to the pilot, the innermost unit tends to behave more and more like the confined pattern. However, there is a practical limit to the number of wells which should be placed in the pilot. This limit is usually determined by economic factors. It was the purpose of this study to use laboratory fluid-flow models to determine which of the previously mentioned pilot patterns will force the innermost producing well to behave as it would in a fully developed waterflood. Since fluid migration is influenced by initial saturation conditions and the mobility ratio, these factors were included in the study. The ultimate objective of this study was to develop data which would allow the operator to choose a pilot pattern and operating conditions that will yield a production history which can be applied directly as an estimate of the performance of each production well of the fully developed waterflood. BASIS FOR THE STUDY The basic problem of field pilot floods is the migration of the reservoir fluids into or out of the pilot area. This problem has been the subject of previously reported model studies on pilot floods. These studies have been concerned mainly with the development of arbitrary "correction factors" to be applied to the simple, unconfined pilot systems such as the single five-spot. The correction factors were intended to adjust the production history of the un-

By I. J. Lin, A. Mitzmager

This paper describes a series of experiments conducted to determine how the physicochemical properties of the suspending fluid affect the size reduction of quartz in a ball mill. Particular attention was directed toward the differences in rate of grinding and particle size distributions when either polar or non-polar fluids were the suspending liquids. Grinding was performed with water, carbon tetrachloride and methylcyclohexane as the liquids, and also in nitrogen for comparative purposes. From the results ob- tained, the authors have concluded that the presence of water greatly enhances efficiency in the grinding of quartz. Comminution is generally regarded as a purely physical process in which fragmentation of a solid is obtained by the application of suitable forces. In 1944, however, Rehbinder et al.1 pioneered the idea that the interfacial forces between the solid and the media plays an important role in comminution. Since then, a number of researches have shown conclusively that comminution is affected by surface chemical phenomena,2-5 and Gaudin went as far as to compare comminution to a chemical reaction.6 The effect of the viscosity and the density of the fluid media in grinding was also investigated, but

Jan 1, 1969

By C. W. Burrows

The burden a man can endure depends on its magnitude and the number of times it is applied, as well as on many other factors. The resisting power of steel likewise is dependent on many factors. The maximum load it can support indefinitely is much less than its possible momentary burden. A light load straining the metal far within its elastic limit, if repeated indefinitely, ruptures the metal. The magnitude of the stresses that may be alternately applied and removed without rupturing the material depends on the number of repetitions of the cycle; the intervening periods of rest; the thermal, electric, and magnetic conditions, as well as the presence of secondary streessses. While we are unable to formulate the law between the magnitude of repeated stresses necessary to produce rupture and the length of time during which these alternating stresses may be applied before rupture, my experience is that the time increases as the magnitude of the force decreases, according to a law which! to a first approximation, is exponential. In other words, F = Ce-t where F= magnitude of alternating stresses; t= time for which stresses are continued; C = constant, which depends on the conditions under which the operations are carried out. It is quite probable that the same type of law holds for the magnitude of a continuous force and its duration. When a rod of steel is subjected to the blows of a drilling hammer several things happen. First, one end is struck by the hammer and the other end is driven into the rock, thus causing a bodily displacement of the entire material of the steel drill. The greatest stresses involved in this bodily displacement are located at the two ends of the steel and manifest themselves by the distortion of these parts. Second, after the blow has been delivered, the steel drill, due partly to its own resiliency and partly to the resiliency of the rock, experiences a vibratory motion as a whole, this motion is quite similar to the bouncing of a rubber ball thrown violently upon a smooth pavement. Third, the free vibration of the drill is determined only by its own natural period of vibration. This motion involves all the characteristics of any vibrating body emitting sound. Certain elements of the rod will experience alternations of condensation and rarefaction and, in these regions, the individual steel

Jan 1, 1922

By R. L. Manegold

IN RECENT years there has been a decided trend toward bringing ores and coal out of open-pit and underground mines by long, sloping single-stage belt conveyors. Because the high investment cost of haulage conveyors dictates maximum speed and full loading for economy, conveyor belts are running faster than ever before, with a greater burden on the belts. In addition, larger blocks of ore are being mined and conveyed. Rougher use of large mining equipment generates more tramp iron; mechanical loading rejects nothing. Therefore the extraction of tramp iron and other deleterious materials for the protection of haulage conveyors at transfer points, chutes, and idlers is becoming an increasingly difficult job. In our experience, the best method of protecting long haulage conveyor belts is to extract the tramp iron, at least the large tramp iron, ahead of the main haulage conveyor or series of conveyors. It is most practical to collect the tramp iron at the earliest source -possible, usually directly after the primary car unloading dump or after the primary crushers, which are ordinarily not affected by tramp iron, see Fig. 1. The coal or ore from its primary source is fed by chutes or feeders onto a buffer or shock belt conveyor, a short, ruggedly built conveyor system that can be considered somewhat expendable. Its primary function is to bring the ore up to speed for transmission to the haulage conveyor. There is no assured method of protecting this conveyor from tramp iron damage at its feed end. Likewise, there is a possibility, although remote if the magnet applied to this belt is installed correctly, that the tramp iron extraction process will damage the shock belt, which is, however, short and comparatively inexpensive. Magnetic head pulleys with their maximum effective range of about 8 or 10. in. cannot be considered for large installations, even though they are desirable because of the continuous and, automatic tramp, iron removal feature. Further, the most dangerous form of tramp iron with respect to potential damage to a haulage conveyor is the long rod, roof bolt, or rail segment, which is not extracted satisfactorily because of the limited tangential contact of such an iron shape with the magnet. Magnetic head pulleys are also undesirable because the dribble or fines from the head pulley discharge at the same point as the tramp iron. Screens must be used to separate the fines from the magnetics, resulting in additional expense and loss of head room. Magnetic detectors have been used with success, but they only indicate the, presence of iron, and the conveyor belt must be stopped for its manual removal. The, stoppage of any conveyor means that all preceding equipment must be stopped or a cascade of material on the idle conveyor will result. Occasionally combinations of detectors and magnetic, head pulleys are used. The detector precedes the magnetic head pulley and detects only large pieces of tramp iron, while the magnetic pulley subsequently takes out the smaller ferrous metals. Suspended magnets overcome the disadvantages of magnetic head pulleys, detectors or a combination of both. There are several magnetic extraction problems involved in applying a suspended magnet at this

Jan 1, 1952

By Gilbert Thiessen

THE purposes of this paper are (1) to show that the mineral matter content of coal is satisfactorily represented by the Parr formula; that is, Mineral matter = 1.08 Ash + 0.55 Total sulfur (2) to compare ash-to-mineral-matter ratios with factors by which ash values must be multiplied in order that dry, factor-times-ash-free values shall equal Parr unit coal values; (3) to examine such ash-correction factors and to compare them with similar factors corresponding to certain simplifications or modifications of the Parr formulas and (4) to show that ash-correction factors used for simplification in calculating approximate unit coal calorific values cannot be. correctly used for the conversion of other determined values in an analysis to the unit coal basis, but that each type of calculation requires separate treatment in simplification.

Jan 1, 1934

By H. L. Talbot, A. J. Hall, R. S. Young

A method for the chemical differentiation of oxidized cobalt from sulphide cobalt in complex mine and concentrator products is of considerable interest to a number of mining companies throughout the world. At Rhokana Corporation, in Northern Rhodesia, for instance, cobalt is found chiefly in the sulphide form, as carrollite, but a cobalt oxide mineral also occurs irregularly underground, and relatively small quantities in the mill feed from time to time are difficult to detect visually at the concentrator. The oxide cobalt is not amenable to the sulphide flotation process used at Rhokana and nearly all of it passes into the tailing. The occasional period when high tailing losses occur with no appreciable change in the cobalt content of the mill feed has naturally been disturbing to the concentrator staff, who had no means of determining whether an influx of cobalt oxide ore or laxity on the part of the mill flotation operators as responsible for these results. A procedure for determining oxidized copper minerals, based on their solubility in dilute sulphuric acid saturated with SO2, has been used for many years in the copper industry. In the presence of cuprite the procedure fails, but otherwise it gives results quite satisfactory for control pur- poses. Empirical methods for determining oxidized forms of zinc and lead have been proposed, but they are generally unsatisfactory except in isolated cases of a very simple ore. No published procedure for determining oxidized forms of cobalt or siinilar elements has come to the authors&apos;notice. Experimental Procedure There are obviously two alternatives in attacking a problem of this nature. One is to employ a solvent for oxide cobalt that will not dissolve cobalt sulphide. The other is to find a substance capable of oxidizing the cobalt sulphide to sulphate, which of course is water-soluble and can then be leached from the water-insoluble oxide cobalt. A representative sample of Rhokana cobalt oxide ore was secured, ground to minus 200-mesh, and carefully rolled to furnish a standard sample for this work. The analysis of this material gave the following percentages: Co, 0.55; Cu, 1.64; Fe, 2.98; S, 0.08; SiO2, 41.42; Al2o3, 11.20; CaO, 13.82; MgO, 3.80. As a source of cobalt sulphide a similar large sample of carrollite was prepared, analyzing Co, 23.36 per cent; Cu, 27.32; and S, 31.13. This sample of course was not pure carrollite, but was the best obtainable in quantities sufficient for a standard intended for considerable work. It was a pure sulphide sample, microscopic examination showing only carrollite, a little bornite, and gangue, with no visible sign of oxidized ore present. A wide variety of reagents as used in an effort to selectively dissolve oxide cobalt or to oxidize sulphide cobalt to

Jan 1, 1949

By T. Clinton Taylor

QUALITATIVELY, galena (native lead sulfide) reacts with aqueous solutions of the xanthates,1 and has its surface sufficiently altered so that there is a tendency for air bubbles to attach themselves to the mineral crystals where there was no such effect before the treatment. This property is utilized in froth flotation operations where the mineral sulfide particles are raised into the froth and the gangue whose surface is not altered remains behind. The results of a study of this reaction were reported" recently and certain tentative suggestions about the interaction of galena and the alkali xanthates were offered. In this paper, there is set down the results of a detailed quantitative investigation of the ions involved in this inter-action with a view to finding out more about the condition existing imme-diately at the surface of a crystal like a heavy metal sulfide after treatment with an organic reagent. Past experimental experience showed that finely ground galena shaken with aqueous potassium xanthate abstracts xanthate ion and at the same time sulfate ion, reducing ions of the type (SmOn)= where the ratio of m to n is less than 4:1 (as in sulfate), sometimes hydroxyl ion are thrown into solution.,

Jan 1, 1933