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By F. R. Morral, E. P. Miller

Hot-dipped heat-treated zinc coatings on sheet steel were examined with X-rays. The phases identified were compared with those listed in the modern literature 01 the zinc-iron system. The zeta (FeZn13) phase is shown to correspond to the phase found by Schueler (1925) in heat-treated zinc coatings. An investigation was undertaken to determine the phases present in hot-dipped heat-treated zinc coatings on steel sheets and wire. This kind of coating on wire was studied some years ago by Schuelerl by microscopic and chemical methods. He reported a new phase, FeZn10. Later, Clark and Stillwell,2 using X-ray crystal analysis, identified a new phase in ordinary galva. nized wire, which was assumed to be the FeZn10 phase. Since the extensive review of the iron-zinc alloys presented a few years ago,3 much new work has been published, some of which5-l6 was too late to be included in the recent edition (1939) of the American Society for Metals' Handbook.4 Figs. 1 and 2 are reproductions of the latest iron-zinc diagram proposed by Schramml1 as a result of his investigations by microscopic, thermal, magnetic susceptibility and X-ray methods. Table 1 summarizes all the known published X-ray data of the phases Present. The solubility of iron in zinc has been determined by x-ray methods.10 In the same manner the homogeneity range of the P phase was studiedlo using the principle that the parameter of an intermetallic compound changes while the concentration of One of the constituents changes. Schramm10 has found some 80 alpha lines in X-ray powder photograms of phase d1, and from these he believes that this phase is related to the P phase. Previous investi-

Jan 1, 1941

By A. B. Kinzel

Precise knowledge regarding the effect of heat treatment on the properties of steel has made possible the detailed specifications and instructions covering optimum heat-treating temperatures and practices that are in current use. A distinct contrast is presented by the metallurgical treatment of steel adjacent to a fusion weld, as such steel is subjected to each temperature from room temperature to fusion temperature, and cooled at a rate that is not generally controllable but is predetermined by the nature of the assembly to be welded, the kind of welding used, and the surrounding conditions. This is true regardless of the type of fusion welding: oxyacetylene, electric arc, thermit or flash resistance. Therefore it seemed desirable to investigate the effect of this metallurgical treatment on the characteristics of carbon steels commonly used for welding, by a detailed study of metal subjected to each temperature range; i.e., each heat-affected zone. Oxyacetylene welding was chosen for the investigation because of the experimental facility of accurately segregating and studying each temperature zone. The nature of the zones produced by other types of welding is the same. The difference is primarily a matter of dimensions of each of the temperature zones involved. The advantages and disadvantages of the extent of the zone are of prime moment, and are discussed after the presentation of the detailed zone study. No mention is made of the fused metal proper, as this has been the subject of much published research and the nature of the solidified metal is fairly .ell known. General Method The scheme of procedure in the work herein reported involved the testing of the metal of each temperature zone adjacent to the weld in so

Jan 1, 1935

By J. Campbell

The negative pressure developed within a solidifying sphere of pure iron is investigated theoretically assuming an elastic-plastic model. The maximum hydrostatic tension attainable is shown to be an order of magnitude smaller than that required for the homogeneous muclealion of pores in the liquid cove, and four orders of magnilude smaller than that predicted from) a rigid shell model. It is well-known that liquids can withstand large hydrostatic tensile stresses, or negative pressures. The various experimental investigations of the tensile strengths (often called the fracture pressures) of liquids are reviewed by Dean,1 and the theoretical attempts at estimating fracture pressures are critically assessed by wakeshima.2 Using Fisher's3 quation, the fracture pressure of pure liquid iron is about -70,000 atm, which may be too large by as much as a factor of 4, but is certainly correct to within an order of magnitude.' In view of the great importance of the problem of the nucleation of shrinkage cavities in castings it is of interest to determine exactly what tensile stresses can exist in the residual liquid in a solidifying casting; it has often been assumed that, because of the very low strengths of solid metals near their melting points, no interior stresses are developed at all. Nussey4 has determined theoretically the pressure in the liquid core of a solidifying metal sphere assuming that the solidified shell does not deform (i .e., is perfectly rigid), so that because of the contraction accompanying solidification (a) (about 3 pct for most metals) the progressive deposition of solid onto the inner surface of the shell causes the remaining liquid to be expanded to make up this difference in volume. This leads to a relation between the pressure P in the liquid, the initial pressure, PO, the bulk modulus of the liquid, K, and the inner and outer radii of the solid shell, o and b, respectively:

Jan 1, 1968

By E. P. Miller, F. R. Morral

Hot-dipped heat-treated zinc coatings on sheet steel were examined with X-rays. The phases identified were compared with those listed in the modern literature 01 the zinc-iron system. The zeta (FeZn13) phase is shown to correspond to the phase found by Schueler (1925) in heat-treated zinc coatings. An investigation was undertaken to determine the phases present in hot-dipped heat-treated zinc coatings on steel sheets and wire. This kind of coating on wire was studied some years ago by Schuelerl by microscopic and chemical methods. He reported a new phase, FeZn10. Later, Clark and Stillwell,2 using X-ray crystal analysis, identified a new phase in ordinary galva. nized wire, which was assumed to be the FeZn10 phase. Since the extensive review of the iron-zinc alloys presented a few years ago,3 much new work has been published, some of which5-l6 was too late to be included in the recent edition (1939) of the American Society for Metals' Handbook.4 Figs. 1 and 2 are reproductions of the latest iron-zinc diagram proposed by Schramml1 as a result of his investigations by microscopic, thermal, magnetic susceptibility and X-ray methods. Table 1 summarizes all the known published X-ray data of the phases Present. The solubility of iron in zinc has been determined by x-ray methods.10 In the same manner the homogeneity range of the P phase was studiedlo using the principle that the parameter of an intermetallic compound changes while the concentration of One of the constituents changes. Schramm10 has found some 80 alpha lines in X-ray powder photograms of phase d1, and from these he believes that this phase is related to the P phase. Previous investi-

Jan 1, 1941

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

By F. W. Jessen, James N. Howell

The accumulation of paraffin deposits in tubular goods has been recognized as a major production problem since the inception of the petroleum industry. This problem is not limited to any particular geographical area nor is it limited to a specific type of crude oil.' Generally speaking, "paraffin" deposition pertains to the deposition of any predominately organic material in flow lines, and possibly even at the sand face, which would hamper the production of oil. In some fields, a continuous effort is required to remove deposits of paraffin and in order to accomplish this, many unique methods have been devised. The best solution to this problem, however, is to prevent the formation of such deposits. One method which has been tried in a number of fields is the use of plastic pipe. The purpose of this investigation is to compare the relative effectiveness of several plastic materials to aid in the reduction or prevention of paraffin accumulations in surface flow lines. COMPOSITlON OF PARAFFIN DEPOSITS By definition, paraffin deposits are those materials which are insoluble in crude oil at the prevailing producing conditions of temperature and pressure. Such deposits1 s usually consist of small particles of petroleum wax intermixed with resins, asphaltic material, and crude oil. They may also contain a variety of foreign materials such as sand, silt, water, various metal oxides, sulfates and carbonates of iron. barium, and calcium. The petroleum waxes deposited in flow strings usually consist of both a "hard" and a "soft" wax fraction. These waxes are largely aliphatic hydrocarbons with smaller amounts of aromatic and naphthenic compounds. Nathan' has classified the hard and soft wax fractions. The aliphatic hydrocarbons present are those of high molecular weight with high melting points. Reistle3 pointed out that these high molecular weight compounds first separate from the oil due to a sharp decrease in solubility as the melting point increases. The identification of the resins and asphaltic materials rests, at present, on an arbitrary solubility procedure. Under certain conditions, materials which are insoluble in pentane (ASTM D-893) are defined as resins and asphalts. Subgrouping of these materials is made on decreasing solubility in benzene and carbon disul-fide. Shock' found some correlation be-tween the solvent response and the pentane insoluble content of paraftins: higher pentane insoluble fractions are less soluble in any of the commonly used commercial solvents. PARAFFIN CONTROL METHODS The methods used in oil fields to prevent and remove paraffin accumulations can be grouped into four general classes: (1) operative methods, (2) physical methods, (3) chemical methods, and (4) combination of any of these. Operative methods attempt to prevent the formation of paraffin deposits while the other methods are concerned primarily with the removal of these deposits. Plastic coated pipe has been used for a number of years to prevent cor- rosion in wells, and in manv instances paraffin deposits have -been greatly reduced. Field observations have indicated that plastic coated pipe not only reduced paraffin accumulation but in some cases eliminated deposition completely; however, data are needed to demonstrate the relative effectiveness of plastic materials. Deposition Apparatus The pipe used to determine the effect of velocity on rates of deposition was %- and 2-in. nominal diameter, and 5 ft in length. Steel, butyrate, rigid PVC, kralastic resin-type plastic pipes, epoxy coated pipe, PVC lined glass fiber pipe, and aluminum pipe were tested. Steel pipe was used as a control. Fig. 1 is a schematic diagram of the apparatus showing the relative position of the separate units making up the equipment. In order to facilitate the installation and removal of the test pipes in the apparatus, O-ring seals capable of sustaining pressures of 50 psi were provided at each end. Test pipes were submerged in a cold water bath maintained at or below room temperature by circulating water through copper cooling coils packed in ice. A hot water bath equipped with immersion-type heaters, stirrers, and a thermoregulator was used to maintain the temperature of the oil prior to introduction into the piping manifold. The capacity of the oil reservoir was 30 gal. A 33-gal/min centrifugal pump, capable of producing turbulent flow velocities in the test pipes, was used to circulate the oil through the system when using %-in. pipe; and a 70-galjmin centrifugal pump was used in later tests using 2-in. pipe. A by-pass arrangement made it pos-

By S. S. Shen, M. J. Pool, P. J. Spencer

Heats of solution of gold and copper in dilute Au-Cu-Sn alloys have been determined using a liquid metal solution calorimeter. The self-interaction coefficient, Au - has been calculated at constant copper concentrations and n cu has likewise been determined at constant gold contents. Good experimental agreement is obtained between the interaction coefficients and nAu Cc thus demonsbating the reliability of the measured heat values. The measured data are compared with the Predictions of certain solution models. In previous publications,1,2 the results of calori-metric investigations of dilute Ag-Au-Sn and Ag-Cu-Sn alloys have been presented. The present work on the Au-Cu-Sn system concludes a program of studies of enthalpy interaction coefficients in dilute alloys of the Group IB metals with tin. Since the definition and derivation of an enthalpy interaction coefficient has been discussed previously,1,2 no restatement of this theory will be presented here. From the determination of the partial heat of solution of gold and copper in ternary alloys of various copper and gold contents, values of the interaction coefficients can be calculated. These coefficients give an insight into the various solute interactions that occur in the liquid solutions since changes in their magnitude and sign reflect bonding changes that are taking place in alloys of varying solute contents. EXPERIMENTAL Details of the design and operation of the liquid metal solution calorimeter used in this work may be found in a paper by Poo1.3 For the present studies copper of 99.999 pct purity was supplied by American Smelting and Refining Co., gold of 99.999 pct purity by A. D. Mackay, Inc., and tin of 99.99 pct purity by Baker Chemical Co. At the commencement of each series of experimental drops, a tin solvent bath consisting of between 70 and 90 g of the pure metal was inserted in the calorimeter. The weight of the bath was accurately determined and to it were added appropriate amounts of gold or copper to give alloys of the desired composition. For determinations of approximately 0.0015 g-atom samples of Cu were used and for measurements of ?HAu approximately 0.0025 g-atom additions of Au. The heat capacity of the bath was determined at regular intervals during a series of drops using tin calibration samples. Measurements were made of the heat of solution of copper in alloys containing a constant 0.01, 0.02, 0.03, and 0.04 mole fraction of Au, respectively, in order to determine ?HCu in each alloy, and the same mole fractions of copper were used to determine equivalent values for nAu at constant copper concentrations. The composition of the bath was maintained at the desired constant gold or copper content by making calculated additions of the appropriate solute throughout the experiments. The limiting values ?HAu in alloys of constant copper content and of %c, in alloys of constant gold content were studied as a function of the mole fraction of copper or gold respectively in order to determine and nCu. Heat content and heat capacity data used in calculating values of ?ºHAu and ?HCu at the experimental temperature of 720°K were obtained from Hultgren et a1.4 ' RESULTS AND DISCUSSION Determinations of ?HAu. The partial heat of solution of gold in pure tin as a function of gold concentration was determined in the previous study of dilute Ag-Au-Sn alloys1 and can be represented by the least-squares expression: ?HAu(l) =-8075 + 2413xAu [l] which is valid between XAu= 0.00 and xAu = 0.05. The standard error in the constant term, which represents the partial heat of solution of gold at infinite dilution in tin,?HºAu(l)is 35 cal per g-atom, while the standard deviation of the slope, which represents n Au is ± 619 cal per- agtom. Corresponding expressions for ?HAu(l) in alloys containing constant mole fractions of 0.01, 0.02, 0.03, and 0.04 copper were obtained from the data listed in Table I and are themselves given in Table II. Fig. 1 illustrates the partial heat of solution of gold as a function of its concentration in each of the alloys. For the four alloys of constant copper concentration, the values obtained for ?HºAU(l) (in order of increasing copper content) are -8141 i 36 cal per g-atom, -8210 ± 42 cal per g-atom, -8202 ± 46 cal per g-atom and -8268 ± 51 cal per g-atom. The corresponding values of the self-interaction coefficient, n Au, for these alloys are 3103 * 644 cal per g-atom, 2425 ± 676 cal per g-atom, 2574 * 717 cal per g-atom and 2523 ± 899 cal per g-atom. In Fig. 2 these values of n Au are plotted as a function of the copper content of the alloys and are seen to remain approximately constant within the experimental limits. The addition of increasing, small amounts of copper to dilute binary Au-Sn alloys thus has no apparent effect on Au-Au interactions in these dilute liquid solutions, although more exothermic values of ?HºAu(l) do result from an increase in the copper content of the alloys. Analogous behavior was observed with additions of silver to dilute Au-Sn alloys.' By

Jan 1, 1970

By C. C. Mattax, J. E. Bobek, M. O. Denekas

ABSTRACT investigations in recent years have shown that rock wettability can exert a profound influence on the displacement of oil by water from oil producing reservoirs. Core analyses frequently show oil recoveries from preferentially water-wet rock to be significantly greater than those from preferentially oil-wet rock. Thus, an accurate prediction of water-drive or waterflood oil recovery is dependent on the evaluation of reservoir rock wettability. Laboratory and field studies have been undertaken to examine and develop methods which may be used to measure rock wettahililiy, to investigate factors which may alter the wettability of reservoir rock, and to determine the wettability of specific reservoirs. It has been found that measurement of the rate and volume of spontaneous imbibition of the wet-ting phase by a rock is a reliable and reproducible test for semi-quantitarive determination of preferential rock wettability. Laboratory tests have shown that the wettability of reservoir rock may depend on both the crude oil composition and the rock type. Field and laboratory tests have indicated that coring flulids and core handling techniques can cause significant changes in the wettability of rock surfaces. However, a few fluids, brine in particular, appear not to affect core wettability and may be used when coring to determine reservoir wettability. Core handling and packing procedures have been developed which preserve core wettability during storage and laboratory testing. The wetfability characteristics of six reservoirs have been evaluated by wettabilify tests performed in the field on fresh cores cut with brine or special water-base muds. The tests indicated that all six reservoirs are water wet; however, the de-gree differed from one reservoir to another. INTRODUCTION Although surface properties of reservoir rock and interfacial characteristics of rock, crude oil, and water systems have been discussed for many years, the full significance of these properties to the production of oil is still in the process of evaluation. It is known, however, that one surface characteristic—preferential wettability of the reservoir rock—-is of paramount importance when the reservoir is being produced by water-flood or water-drive mechanisms. The importance of rock wettability has been pointed out by several authors'.',%* who have found that pref- erentially water-wet cores flood more efficiently than oil-wet cores; that is, more oil is recovered from water-wet cores in the early flooding stages than from oil-wet cores. Other authors'," indicate that waterflood oil recovery from cores of intermediate wettability may be greater than that from either strongly water-wet or strongly oil-wet cores. These recent investigations emphasize that the true wettability of a reservoir must be known before the performance of waterflood or water-drive reservoirs can be accurately evaluated. When reservoir wettability is to be determined by core analysis, precautions must be taken to maintain the original wettability which can be altered readily during coring5 nd testing.' In the coring operation the core may be partially or completely penetrated by the drilling fluid which, if it contains surface active materials, may drastically change the wettability of the core. Also, improper core handling during stcrage and testing may change its wettability because of evaporation of fluids or exposure to oxygen or surface active contaminants. One purpose of this paper is to discuss methods for obtaining, preserving, and testing cores without altering their original wettability. In addition, the results of wettability tests on fresh and preserved cores from six reservoirs are presented where special precautions were taken to obtain samples without altering their wettability during the coring operation.

By P. B. Baxendell

The performance of a water-drive reservoir having a gas cap depends primarily on the movement of the gar-oil and oil-water contacts. The movement of the contacts during production depends in turn on fluid withdrawals and how the reservoir pressure changes as fluids are produced from the reservoir; that is, on how effectively the aquifer maintains pressure by replacing withdrawals. inasmuch as pressure changes, fluid withdrawals, contact positions, and produced gas-oil and oil-water ratios are interdependent, the analysis and prediction of the performance of a reservoir produced in a given way must take into account this interdependence throughout depletion. This paper presents an analysis which, within the limitations of the assumptions made, yields an engineering approach to predicting future performance based on reservoir pressure and production history. The most significant assumption is the method of extrapolation of future gas-oil and water-oil ratios. The extrapolation procedure smoothly increases both ratios to preselected values as the remaining oil column undergoes a specified decrease in thickness. This preselection is made on the busis of previous field experience in depletion of similar reservoirs under similar conditions. For computing future performance a vdumebic balance L combined with the differential equation defining pressure distribution in the aquifer to obtain positions of water-oil and gas-oil contacts. From these positions are extrapolated produced water-oil and gas-oil ratios. Reservoir performance can be investigated when oil production rates are dependent upon various factors including the performance of the reservoir itself. Examples of practical application of the procedure are included. INTRODUCTION To predict performance of water-drive reservoirs with gas caps and thin oil columns, it is necessary to describe the motions of the fluids within the reservoir during the entire production period to depletion. These motions depend on the pressure changes and on the withdrawal of oil, gas and water. Production of oil from the oil zone primarily causes water to move in to take its place; production of gas from the cap tends to cause oil to migrate into its place. In addition, the volumes of oil and gas remaining in the reservoir depend on changes in the pressure, since a decrease in pressure causes fluid expansion, gas liberation and oil shrinkage. A method of relating the future pressure to total withdrawals is used to describe the motions of fluids within the reservoir under conditions arising in possible modes of production. The analysis is based on two relationships and will reduce the problem to one amenable to digital computation. The first of these concerns the dependence of the pressure distribution in the entire aquifer furnishing the water drive upon the total reservoir withdrawals. This dependence is dictated by the permeability distribution and the extent of the aquifer; at present, such information is most readily obtained from the performance history by means of the resistancecapacitance reservoir analyzer. The second relation involves withdrawals, pressure in the reservoir, and movement of oil, gas, and water within the reservoir. The analysis is subject to certain simplifying assumptions that are necessary to permit solution of the problem. A comparison of the methods of this paper with those presently practiced is pertinent. One method of analysis is to use the reservoir analyzer to predict reservoir behavior based on aquifer characteristics determined from production history. Inasmuch as the total withdrawal rate depends upon the gas-oil and water-oil ratios, which depend in turn upon, among other things, the positions of the gas-oil and water-oil contacts, these ratios must be assumed in advance. In this paper these ratios are, instead, related to the computed positions of gas-oil and water-oil contacts. Thus, our method can be applied to problems in which the oil production rate is limited by produced gas-oil ratio, or to problems in which it is desired to determine the variable gas injection rate that will maintain the gas-oil or water-oil contact stationary. These problems cannot be worked satisfactorily on the analyzer. Another method presently used is based on a paper by Hurst.' Since his procedure is dependent upon using the solution of the heat flow equation, which requires constant permeability within the aquifer, and our procedure recognizes variations of permeability in

By Milton E. Wadsworth, John N. Ong, W. Martin Fassell

The temperature and oxygen concentration dependence on the reaction of sphalerite in oxygen at pressures from 6 to 640 mm Hg have been investigated in the temperature range 700° to 870°C. Sphalerite has been found to oxidize linearly over this entire temperature and pressure range. At higher rates, considerable self-heating was observed. The dependence of the oxidation rate on the oxygen concentration may be expressed by: Rate = k' where k' is the specific rate constant and 0 = K1[O2]/(1 + KI[O2]), where K1 is the equilibrium rate constant for the adsorption of oxygen on sphalerite. Values of the activation energy and the enthalpy of adsorption were found to be 60.3 and —59.6 kcal per mol, respectively. Data have been presented that indicate conditions under which either a sulphatizing or an oxidizing roast may be obtained. ROASTING processes have been employed in the metallurgy of a great number of basic metals in use today. Until recently, however, little attempt has been made to deduce the fundamental mechanism by which oxidation takes place. Structural changes upon oxidation have been investigated1 = and thorough work has been performed with regard to the reaction products and the thermodynamics of the oxidation reactions. The objective of this investigation was to determine the rate of oxidation of sphalerite and to apply the absolute reaction rate theory in the theoretilcal interpretation of the experimental results." "O Description of Apparatus The apparatus contains the following features: 1—a furnace with gas system, 2—an autographic weighing system, and 3—a temperature control system. Furnace With Gas System—The furnace was mounted by a yoke on each end and was free to travel up and down on steel guide rods, permitting the introduction and removal of samples from the apparatus with minimum difficulty. The furnace was heated by three sections of Kanthal wire wound externally on a zirconia tube and insulated with Fiber-frax. Pure gases or mixtures of gases were introduced into the lower end of the furnace through two flowmeters, a mixing chamber, and a gas-tight sparger, Fig. 1. The gaseous products of the reaction and the unused gases were prevented from escaping to the atmosphere by maintaining a small negative pressure on the system. This procedure permitted air from the outside to enter through the small an-nulus around the quartz suspension fiber and prevented the escape of the internal gases. Autographic Weighing System—The autographic weighing system consisted of an adapted gold balance, a photoelectric circuit, and a weight recorder, Fig. 2. The sample was suspended from one end of the balance beam by means of a platinum chain outside the furnace and a long thin quartz fiber on the inside of the furnace. On the other end of the balance beam, the necessary weights were added to counterbalance the sample. In addition, a calibrated chain was added to the balance which was linked directly to the weight recording unit. Control was effected by means of a photoelectric circuit." A parallel beam of light from a strong source was directed onto a small front-surfaced aluminum mirror mounted in the middle of the balance beam and then to a front-surfaced mirror mounted on the ceiling of the room. The beam was then reflected onto a front-surfaced right prism at a distance of 9 ft from the balance

Jan 1, 1957

IN the preceding chapter on thermochemistry and the reactions in and between metal and slag phases and in the following chapter on fuel combustion the main emphasis is placed on the equilibrium or "static" conditions. This equilibrium viewpoint is not concerned with the rate of change in the process or with the mechanisms or paths followed between initial and final states. The questions of just "how it works" and "how fast" belong to the kinetic aspect of any process; their answers are helpful in speeding up or slowing down and thus controlling its operation, and also in understanding its limitations. Any treatment of kinetic factors in the open hearth such as is attempted here and in Chapter 22 must at present be largely qualitative and incomplete. We are only beginning to get quantitative data on rates of reaction and diffusion at high temperatures, as indicated in Chapter 15. Empirical data in the literature on furnace operating rates do not help much to illuminate the details of gas-flow patterns and the complexities of heat flow in the many parts of the furnace system. This chapter is intended to give the reader an introduction to the problems of the flow of gases through the furnace system and the flow of heat in this system. An adequate discussion would require several times the space available here; it is possible here only to outline a few fundamentals and to indicate some of the conditions of heat and gas flow peculiar to the open hearth. Several good general treatments of these subjects may be found in the literature (see references at the end of the chapter). For the designer of open-hearth furnaces, the principles of gas flow are of paramount importance. They are also important to the operation of the process, at least to the extent of a general qualitative picture of the movement of gases in the system. MOTION OF GASES IN FURNACE DUCTS Fluid flow in general can vary between the extremes of laminar or streamline flow with a minimum energy loss, to irregular

Jan 1, 1951

By P. Hudock

Thin films of PbS and CdS have been deposited on insulutiug- sapphire substrates by euzploying a subliwzation technique rising near-equilibriurum conditions in ultrahigh vacuum. Oriented polycrystalline PbS and CdS films on sapphire have mobilities approachitzg values characteristic of bulk crystals. In the case of CdS, special purification procedures were crucial in obtaining high-mobility films. By performing the depositiotz of a compound within a small chamber heated to a UNiform temperature within a Vacuum systerrz, it is possible to approach equiilibrium cod-tions r.~litl~irs the chamber. In this way; the sublimation and condensation proceed under near equilibrium co?zditions, and it was found that the properties of dePosited corrzpounds were similar to those of the source material. Oriented PbS films on sapphire have a roor?l- temperature unobility of 700 sq cm per v sec and a T-5/2 temperature dependence characteristic of bulk crrystnls. CdS layers on sapphive Izazse a resistivity ~uhich is corrlpamble to the resistivity of the souvce crystals over a range of four ordem of rrlagnitude. Irz contrast, Ihe resistivity of CdS films prepared by conventional evaporation depends largely upon the substrate terrzperat~ire and postheating treatrrletlt, vather than upon the properties of' the solirce rrraterial. In the case oj the CdS films the achievment of high carrier mobility required the cargful exclusion of cont~~~~ii~unts from the films. The steps taken to accomplish this included presublimation of the source material, performance of the deposition at a backg-m~ozd pressure less than 10-8 Torr, and a solvent extraction with liquid cadminum, similar to that described by Aven and woodbury. The deposition of ,films under near-equilibrium conditions is being op-plied to other classes oj COmpounds. II should he of 1:allce ,tor llle deposition of nny matevial that decomposes in the vapor state. THIN films of PbS and CdS have been deposited on insulating sapphire substrates by employing a sublimation technique using near-equilibrium conditions in ultrahigh vacuum. Oriented polycrystalline PbS and CdS films on sapphire have Hall mobilities approaching values characteristic of bulk crystals. In the case of CdS, special purification procedures were crucial in obtaining high-mobility films. Depositions were performed in a small quartz sublimation cell shown in Fig. 1 that contained the compound and the single-crystal sapphire substrate. The substrates were etched in tapered solutions of hot phosphoric acid, rinsed in deionized water, dried, and transferred to the cell under dry nitrogen. Graphite crucibles and substrates were used in experiments where it was necessary to provide an inert test vehicle for the analytical determination of impurities in the source crystals and deposited films. The crucibles and substrates were machined out of spectrographic-grade graphite having less than 1 ppm of impurities. A quartz mask was sometimes used to define a pattern which could be used for Hall and resistivity measurements. Close spacing between the compound and substrate was maintained to insure better transport of each component from the source material.

Jan 1, 1968

By H. E. Wilborg, G. V. Henderson

This chapter deals with those sands employed by foundries for the manufacture of cores and molds used in the casting of such common metals as steel, gray iron, ductile iron, aluminum-based alloys, and copper-based alloys. Most metal is cast in "green sand" molds in which the sand mixture, consisting primarily of silica, clay, and water, forms a plastic material. This plastic material is rammed around a pattern in a split box called a flask, then the box is separated, the pattern is withdrawn, and the metal is poured. These green sand molds are broken apart when the metal has solidified. The sand is then remixed and a new mold made for the next casting. To a lesser extent silica sand is mixed with resins or oils and, after forming, the mixture is hardened by either heat or chemical reaction. In any case, the foundry mold or core is used just once before being broken up and remixed for manufacturing another core or mold. By far the greatest consumption in the foundry is of those types of sand high in silica, low in clay (under 0.5%), and occurring in numerous locations thoughout the United States. Consumption End Uses Foundry sands fall into four distinct categories: silica sand, lake sand, bank sand, and natural molding sand. Silica sand is a general term used to describe washed, graded, dried, and cooled clay-free sands which are found in many parts of the United States. They generally contain 90 to 100% silica but vary greatly in chemical analysis and grain structure. Lake sand is the sand dredged from Lake Michigan or dug from the dunes bordering that lake. Bank sand is composed primarily of silica grain but containing up to 5% clay. It is shipped in both the damp and dry state but the normal processing of bank sand consists only of drying and scalping. Occasionally two different grades of bank sand are blended prior to or during loading. Natural molding sand is a term used to describe a sand containing sufficient clay as mined to be suitable for molding purposes. Clay content may vary from 10 to 24% with the balance of the material consisting primarily of silica sand. These sands range in fineness from one peaked on the 20 mesh to one which contains more than 50% of the particles passing the 270 mesh. Lake sands are relatively coarse and are used in great quantities for the production of automotive castings. Bank sands and natural molding sands are gradually phasing out as the production of castings becomes more a science and less an art. The vast majority of foundry sands used today are those known as the silica sands and lake sands. Foundry sands are used in two basic ways. The majority are used in the green or uncured state with the balance used in the cured or set state. Green sand is grain bonded with clay and contains varying amounts of water to plasticize the clay in order to bond the grains together. Green sand is either naturally bonded or "synthetic" sand. The naturally bonded molding sands are generally found in the Hudson River Valley of New York State, Cumberland County in New Jersey, and in Tennessee and Mississippi. Synthetic sand is molding sand compounded in the individual foundry. It is made up primarily of graded silica sand, western or southern bentonite, water, and carbonaceous and/or cellulosic materials. Green sand is used primarily in making molds. The use of naturally bonded green sand has been declining for many years, primarily because naturally bonded sands are more difficult for the foundryman to find and control. Synthetic green sand, on the other hand, can be

Jan 1, 1983

By Charles E. Nelson

THIS paper will outline briefly the practices commonly followed in this country for the melting and refining of magnesium and its alloys. The processes used for the various forms of primary magnesium, as jar as there are differences in the physical shape or behavior, will be discussed. The refining of general fine scrap or secondary magnesium was presented in an earlier paper and will be discussed briefly.1 Inasmuch as the use of fluxes is an essential part of all the melting and refining processes, this paper will deal with these in sufficient detail to point out their unique characteristics, in order to make their use more effective. The outline of this discussion will closely follow that of an earlier paper,2 with such changes and additions as seem necessary to bring it up to date. TYPES OF MELTING PRACTICE All melting and refining processes for magnesium and its alloys require the use of fluxes. These fluxes have a magnesium chloride base and other halide salts or oxides are added to give a density or behavior exactly suited to the particular melting practice. The successful handling of magnesium depends upon the proper use of the correct fluxes. There are four general methods of melting, summarized in the following paragraphs and treated in more detail in the section on Melting and Refining. Open-pot Method The open-pot method makes use of No. 230 flux, which provides protection during melting and a molten pool of flux into which the solid magnesium melts. The flux is stirred through the molten metal bath and agglomerates oxide or similar foreign bodies;, on quiet standing, it separates away, leaving the refined metal ball floating in an encircling layer of molten flux. It forms only a thin fluid film over the surface of the molten metal, which may be parted for hand-ladling processes and tends to cover the metal again after the ladle is removed. A very light dusting of the pot surface with fresh flux immediately after the ladle is removed is desirable. The open-pot method is used generally in the following processes: (I) alloying and remelting in the production of ingot, (2) in sand foundries for premelting and to a smaller extent for the production of small castings, (3) in permanent-mold founding for premelting and also direct ladling to castings, (4) for continuous methods of preparing metal in the production of billets or ingots from which wrought products are fabricated, (5) in general scrap recovery. Crucible Process The crucible process makes use of No. 310 flux, which has the property of being thinly fluid at the start, to provide protection and refining qualities, and then drys out or thickens after a time, leaving a protecting crust on the pot surface until the time of casting. At that time it can be readily skimmed off or held back, thus allowing the contents of the crucible to

Jan 1, 1946

By H. J. R. Way

THE work to be described was undertaken at various periods from 1937 to 1939 on the Busia gold field, in the eastern province of Uganda. It was decided to examine the possibility of reef prospection by the resistivity method, for it was not known how far the usually disintegrated nature of most reefs in the ubiquitous laterite near the surface would obscure indications obtained by resistivity traverses. The work at the commencement was therefore largely experimental, but the results obtained thereby were satisfactory, and a survey was started at the Government closed area at Amonikakine. With the limited time and resources at the writer's disposal, it was not possible to complete the survey to his satisfaction or to follow up exhaustively all the geophysical indications, but some of the results of the experimental work and the survey were of sufficient interest to be worth recording; in particular the relation between the width of reef, electrode separation and shape of the curve, and the interference effect of constant separation curves over zones of float are significant and useful. Three new veins were located, but only one contained sufficient gold to warrant detailed prospection. This was called the Geophysical reef, and was uncovered over a strike distance of 1140 ft., and there are indications that it extends over a distance of 1990 ft. These results and the recommendations consequent therefrom were embodied in a special report to the Uganda Geological Survey. HISTORY OF THE FIELD The Busia field is in the southeastern corner of Uganda near the Kenya-Uganda border, and is about 17 miles north of the northeastern corner of Lake Victoria. Gold was first discovered in the area in the stream beds by Davies1,2 in 1932. Subsequently numerous small alluvial claims were worked by prospectors and the area was prospected for reef by a company for periods varying from three to nine months, but was finally abandoned, as the results were considered unfavorable. Further prospecting by the Geological Survey in 1935-1936 under Davies3 and later under the writer4 uncovered three reefs with sufficient gold values to be of economic interest. These were finally taken over by a company known as Borderland Syndicate, which still owns the area, and from September 1937 to the end of 1941 about 13,000 oz. of gold was extracted from reefs of the area proved by the Geological Survey. Opencast mining operations are still proceeding (February 1943). The Amonikakine area lies to the immediate north of that of Borderland Syndicate. A certain amount of prospecting had been done when the writer started work there. As a result of his report, this area was taken over by another syndicate, but little further work was accomplished before it ceased operating because of difficulties of wartime working.

Jan 1, 1944

By T. A. Rickard

The province of Otago consists, roughly speaking, of the southern half of the South Island* of New Zealand. On three sides it is washed by the Pacific Ocean and on the north it abuts against Westland and Canterbury. It covers an area of over 20,000 square miles, and for the most part has an extremely broken surface; the narrow plains of the sea-board are bounded by the rounded foothills which in turn are overlooked by range after range of the snowy summits whose varied beauty has made the island known as the Switzerland of the southern hemisphere. The gold-fields are confined to the quartzose schists which, in a broad band, 70 to 75 miles wide, cross the district, extending in a northwesterly direction from the shore of the western ocean into the northern provinces. These quartzose schists are the characteristic rocks of Otago, and to their curious structure are due the interesting differences exhibited by the mining districts in the modes of occurrence of the gold. These rocks, which are almost unbroken over their full extent, have been divided by the Provincial Geologist, F. W. Hutton, into two series of beds, named respectively the Wanaka and Kakanui formations. The only reason given for this division is the desire " to divide such an enormous thickness of rocks in order that the map might display somewhat of the geological structure of the district." As Hutton and others have pointed out, there is in fact no dividing line. The changes noticeable in the ascending series of schists are very gradual, and are due to the slowly decreasing effects of metamorphism. Hutton estimates the thickness of the Wanaka series at as much as 50,000 feet, and the

Jan 1, 1893

By C. E. Lawall, C. T. Holland

When this study was started very little information was available regarding the physical characteristics of West Virginia coals. This was particularly true of friability and of crushing strengths of the coals. Some work had been done on specific gravity studies but the available information applied to only a few coals. In practically all coal-classification systems thus far proposed, the predominating factors of classifications are largely based on the chemical characteristics of the coal. Recently some investigators have pointed out that a classification based on chemical and physical properties of coal might serve to place coals in their proper group better than classification systems based on chemical properties alone. One of the aims of this study was to obtain some data on the physical properties of coal which might help to classify West Virginia coals. The Samples Fig. I shows where the coal samples were obtained and the approximate division line of the high and low-volatile coal fields of the state. The relative geological horizons of the coal beds tested are shown in Fig. 2. In securing samples of coal for friability and specific gravity tests, it was the aim always to obtain a representative sample of lump coal produced at a particular mine. The samples were obtained from the loading boom, the railroad car, or the mine cars. Wherever it was possible to secure samples from a loading boom they were taken from it by taking shovelfuls of coal from the loading boom every minute until about 200 lb. of coal was obtained. If there were no loading booms used at the mines sampled, the coal sample was taken from a loaded railroad car by systematically taking shovelfuls of coal at definite intervals over the whole top of the car until about 200 Ib. of coal was obtained.

Jan 1, 1932

By G. L. Boxer, C. B. Smith, W. J. Atkinson

Since the inception of the Ashton (formerly Kalumburu) Joint Venture in 1972 the parties have expended $24 million in exploration for diamonds in the Kimberley region. This has resulted in the discovery of the currently subeconomic Ellendale deposits in 1976/77 and the economic Argyle - Smoke Creek Deposits in 1979/80. In addition to Argyle and Ellendale, some 90 kimberlitic and lamproitic bodies have been discovered grouped broadly into three provinces, on the west, east and north margins of the Kimberley block. These bodies range in size from dyke-like features less than 1 m (3 ft) in width to pipes with a surface area of 128 ha (316 acres). The bodies with larger surface area are volcanic crater deposits, infilled with air-fall and water deposited tuffs and epiclastic sediments. Diamond content ranges from trace to economic concentrations. The exploration discoveries were facilitated by early recognition that the petrography, mineralogy and chemistry of the diatremes varied from the classical kimberlites of Kimberley, South Africa, to unusual more highly fractionated, alkaline, silicic varieties having affinities with leucite-lamproite. Indirect methods of exploration were used, primary reconnaissance work being stream gravel sampling for kimberlitic indicator minerals. Evaluation showed Ellendale diamonds are 90% gem and near gem, but the low grades and tonnage render the deposits unpayable at today's diamond prices. After discovery in late 1979 and completion of a feasibility study by the end of 1982, evaluation studies proved Argyle to be economic. Alluvial diamond mining commenced in 1983 producing 6.2 million carats (Mct) that year, 60% being of industrial quality. Open-pit mining of the AK1 lamproite should start in 198511986 at a rate of 3 million t/a (33 million stpy) and produce 25 Mct/a, making this mine, and Australia, the world's largest producer of diamonds by weight. The revenue from diamond deposits is a function of the grade and the value of the diamonds. The grade is the product of the frequency of occurrence of the diamonds (stone density) and the mean stone size; the value of the stones is strongly related to their size distribution. During evaluation of the West Australian deposits, the diamond distribution was found to vary markedly in stone density and stone size. These variations corresponded with changes in the rock type hosting the mineralization. As a consequence, geological mapping of individual lamproites within the multiple vents and careful monitoring of the diamond distribution became an important part of the evaluation work. Similar variations in stone size and frequency were found to accord with separate alluvial terraces and fan gravels derived by erosion from the Argyle AK1 lamproite.

Jan 1, 1985

By Christie A. Callender, Harry M. Dahl

The Hobson uranium deposit is located in Karnes County, Texas, along the prominent south Texas uranium trend. The uranium mineralization occurs in the Deweesville Sandstone of the Whitsett Formation of the Eocene Jackson Group. The host rock is a friable, fine-grained, well-sorted, highly porous and permeable sandstone interpreted to be an ancient beach deposit. The sandstone contains significant volcanic constituents and ranges in composition from arkosic to tuffaceous. Locally, the host sandstone contains hard, dense opal cement. Bentonitic shales underlie and overlie the mineralized sandstone unit. Geometrically, the Hobson uranium-bearing zone resembles an elongated roll front type deposit. Chemical uranium values compared with gamma ray equivalent uranium values indicate that the uranium has been dissolved from the updip side and precipitated on the down- dip side of the roll front. Details of the uranium mineralization were studied using thin section microscopy, autoradiography, x-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) techniques. The uranium mineralization occurs in the pores of the sandstone, as grain coatings and as replacement of sand-size and smaller grains. It is commonly associated with pyrite and other opaque minerals. Other favored hosts for uranium (other than pore openings) appear to be clay aggregates, altered rock and glass fragments, and carbonaceous plant debris. Aggregates of coffinite were identified by XRD and SEM/EDS analyses. Some uranium mineralization also appears to be dispersed and is postulated to be adsorbed on the clay and carbonaceous matter.

Jan 1, 1985

By W. B. Devereux

The special mriditions under which gold occurs in the Potsdam formation of the Black Hills prew~lt features worthy of a more systematic pesentation than they have heretofore received. The notes

Jan 1, 1882