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By Kefton H. Teague

Olivine is a mineral containing a mixture of forsterite (Mg2SiO4) and fayalite (Fe2SiO4) in solid solution. The name olivine was first applied by Werner in 1790 (Hunter, 1941) because of the olive-green color of the mineral. Olivine is the principal component of the rock dunite, which itself is a member of the peridotite group of ultrabasic igneous rocks. European uses of the terms olivine and dunite are somewhat different than US usage. In commerce European usage defines dunite as containing 36 to 42% MgO, 36 to 39% SiO2, and loss on ignition of approximately 10%. The term olivine is used to designate a material containing approximately 85% forsterite, with a chemical composition of approximately 45 to 50% MgO, 40 to 43% Si02, 5 to 8% Fe2O3, and ignition loss of 1 to 2%. Uses The principal use of olivine is in various applications involving hot metal. Table I shows the best estimate available as to the amount of olivine consumed by various industries worldwide. In excess of 90% of world uses involve hot metal, with approximately 75% as a slag conditioner in the blast furnace production of pig iron. Approximately 15% of total olivine usage is as a special foundry sand in mold making for the brass, aluminum, magnesium, and manganese steel foundries (Schaller, 1957, 1958; Snyder, 1957; Anon., 1977). Olivine was first used as an industrial mineral in the early 1930s for a refractory material (Anon., 1970; Hunter, 1941). As a refractory raw material, olivine was first introduced in the United States as hand-cobbed, selected, shaped blocks of crude olivine. This use met with limited success. More recently, finely ground olivine blended with MgO and pressed into bricks, which are then fired, has found use in glass tank furnaces and open-hearth furnaces. Ramming or gunning mixes for basic furnace linings also utilize olivine. Olivine has been used in ladle linings with varied success. In Europe, substantial tonnages of olivine are utilized in refractory brick for night storage heaters (Anon., 1970). A limited amount of olivine has been used in the past as a fertilizer (magnesium source) and has been fused with rock phosphate to produce a magnesium phosphate as a plant food. The relatively high magnesia (MgO) content of olivine also attracted attention to it as a potential source of both magnesium compounds and as a source of metallic magnesium (Bengston, 1956; Hunter, 1941). The use of olivine as an additive in the blast furnace is relatively new, having been developed during the last decade. J.W. Currier (Private communication, 1978) describes the behavior of olivine in the blast furnace as follows: Olivine (Mg, Fe2, Si04) represents a unique lime-free source of magnesia and silica as a blast furnace charge component. Only recently has the magnesia-rich mineral been recognized as beneficial cleaner for blast furnace experiencing the problems associated with excessive alkali inputs and/or low coke stabilities. For some time it has been known that alkalis tend to recycle and accumulate in blast furnaces. In the high temperature region of volatilization the elemental alkalis formed attack the integrity of the graphite structure. This alkali attachment is enhanced when poor coke is used. Higher in the furnace stack volatile alkali cyanides condense and oxidize. This accumulation of alkalis tends to agglomerate the burden materials, producing scabs and scaffolds. These structures not only inhibit the downward movement of burden materials and the upward passage of wind, but also lead to erratic furnace performance

Jan 1, 1983

By C. E. Lawall

ONE of the most important developments in the coal industry during 1940 was the continued uptrend in the production of bituminous coal. Estimated production for the year is 450,000,000 tons, with an additional production of anthracite of 50,000,000 tons making a total of approximately 500,000,000 tons. This is an increase of 12.5 per cent over 1939. Despite an estimated decrease of about 3.5 per cent in anthracite production, all of the major coal-producing states had increases in production for 9140. The national defense program, with the consequent increase in industrial activity, undoubtedly had an important effect on the increased demand for coal.

Jan 1, 1941

By P. E. Demmler

Phosphorus combines with copper in various proportions, forming true alloys, some of which are of commercial importance. These materials find wide application as deoxidizers and as a means of introducing phosphorus into other alloys, as in phosphor-bronze. Phosphor-coppers containing 10 and 15 per cent. of phosphorus are the commercial grades that are most generally offered. Each has certain advantages when used in making other alloys. The 10 per cent, grade of phosphor-copper has an advantage over the 15 per cent. in that it has a much lower melting point and can be prepared by certain methods with a much lower loss in phosphorus. The 15 per cent. grade has the advantage of lower freight rates per unit of phosphorus and, by the method to be described, a uniform product can be prepared with practically no loss of phosphorus. Alloys of copper and phosphorus containing any desired percentage of phosphorus lower than 15 per cent. can be prepared by melting together the requisite amounts of copper and 15 per cent. phosphor-copper. Processes for making phosphor-copper may be divided into two classes as follows: (1) Those depending on the smelting of phosphate rock or superphosphate of calcium with copper or copper-bearing materials, and coal or other carbonaceous material; (2) those depending on the direct combination of metallic copper and elemental phosphorus. A number of formulas for preparing phosphor-copper according to the first method have been published. The Metal Industry' gives the following: Superphosphate of calcium, 60 lb.; granulated copper, 30 1b.; finely powdered coal, 10 1b. Similar formulas are given by Brannt2 and others, and detail variations are covered by patents, such as those of L. A. Jeffs3 and H. A. Webster.4 Among the objections to this method of producing phosphor-copper are the large amounts of raw material and resulting slag to be handled, and the difficulty of getting a satisfactory fusion. S. Skowronski5 found that at 1300' C. (2372' F.) it was impossible to get a good fusion

Jan 1, 1921

By M. T. Simnad, C. E. Birchenall, M. H. Davis

The transport mechanisms previously proposed in wustite and hematite have been confirmed by movement of inert markers during the growth of these phases. By similar measurements the mechanism for magnetite has been determined. The rates of growth of multilayer scales on iron, magnetite and hematite on wustite, and hematite on magnetite have been measured. All rates are found to be diffusion controlled under the conditions of the experiments. MANY studies have been made of the rate of oxidation of iron in both the low temperature, film-forming region and the high temperature scaling range. The interpretation of the results has been greatly complicated by the formation of multi-layered scales containing the various phases of iron oxides. In most cases no attempt has been made to determine the composition of the scale and its dependence on time of oxidation in a quantitative manner. However, several recent studies'" have taken this variable into account. It is generally agreed that the growth of thick scales on iron follows a parabolic rate law for the increase of total thickness. In the thin film region agreement has been claimed with parabolic equations of various forms and with logarithmic equations. The discussion here will be concerned only with the formation of scales of considerable thickness, greater than several microns, although some of the conclusions may be applicable to thin films. A brief survey will be given of the solid phases of the iron-oxygen system, the stability of wiistite in bulk and in thin films, the relative densities of iron in the metal and oxides, and the kinetics of forma- tion of oxide scales on iron. New experimental results will be introduced at several points during the discussion, and an attempt will be made to formulate a mechanistic picture consistent with these observations. The experimental techniques are described in an appendix. Iron-Oxygen System Fig. la shows the iron-oxygen phase diagram. Wüstite ("FeO"): The lowest of the oxides has a NaCl type cubic lattice formed by close-packing of the relatively large oxide ions with the smaller iron ions arranged in the interstices. The ionic radius for 0' is about 1.3 A, while Fe++ has a radius of about 0.8A and Fe"' about 0.7A. Its range of existence on the phase diagram is very wide for an ionic material of this type and does not seem to include the stoi-chiometric composition FeO. These deviations appear to be well established as vacancies on iron lattice sites by the comparison of lattice parameters and densities for a series of compositions by Jette and Foote.4 The limits of the field are disputed, but the work which seems most reliable" indicates vacancies in from 5 pct to more than 12 pct of the iron sites. In order for the crystal to be electrically neutral, there must be electron holes which correspond to the formation of trivalent iron ions equal to twice the number of vacancies. Magnetite ("Fe³O4"): Considerable disagreement also exists in the literature about the stable range of the Fe³O4 field. Some diagrams show the Fe³O4 composition to be lower in oxygen than the formula indicates, but Schenck6 gives a diagram from the

Jan 1, 1952

By B. A. Eaton, R. H. Jacoby

This paper presents the depletion-performance correlations developed using data from PVT studies and well-completion tests of 27 rich gas-condensate and volatile-oil reservoir fluids. The PVT behavior for each fluid war determined experimentally in the laboratory, and the depletion performance of each fluid was then calculated. Well-completion test data consisting of reservoir pressure and temperature, initial total gas-oil ratio, and stock-tank oil gravity were used with the depletion-performance data to develop general performance correlations. Three correlations are presented. The first equation shows the empirical relation of gas in place per barrel of hydrocarbon pore space with reservoir pressure and temperature, and initial total gas-oil ratio. The second equation is the correlation of stock-tank oil in place per barrel of hydrocarbon pore space. The third equation relates stock-tank oil production (to 500-psia depletion pressure) with pressure, temperature and oil gravity. All three correlations are also presented in convenient graphical form. Gas production to 500-psia depletion pressure is approximately 92.6 per cent of the gas in place for each fluid, so no correlation was developed for gas production. INTRODUCTION The rate of discovery of shallow, low-pressure and low-temperature oil reservoirs in the United States has been declining in recent years. For this reason, the search for oil has gone to greater depths where high pressures and temperatures are encountered. A high-pressure and high-temperature reservoir is the environment in which many rich gas condensates and highly volatile oils are found. Because of this trend, the performance prediction of such reservoirs has become an important task of the reservoir engineer. The need and usefulness of a performance correlation based on field data that are available from the usual well-completion tests have previously been established. These earlier attempts have shown that the phase behavior of rich gas-condensate systems and volatile-oil systems can be correlated with fluid properties, pressure and temperature. However, very little information on gas-condensate depletion performance5 was available at the time of these earlier attempts. The availability of more recent data has made possible the development of an improved correlation. The data, as listed in Tables I and 2, are for 25 gas-condensate and two volatile-oil systems that were studied. The problem was to correlate the data for in-place fluids and the production data with the initial total gas-oil ratio, initial reservoir pressure and temperature, and stock-tank oil gravity. These correlations were obtained by multiple regression analysis, whereby the data were fitted to an equation by the method of least squared error. BASIS OF THE CORRELATIONS 1. The data used in the development of these correlations were obtained from depletion-performance calculations6 and well-test or production measurements. 2. All of the independent variables used in the correlations are available from the usual well-test completion data. 3. The reservoir volume considered is 1 bbl of hydrocarbon pore space (HCPS). 4. The gas-oil ratio used is the total standard cubic feet of gas (at 14.7 psia, 60F) coming off the entire separator train per barrel of stock-tank oil. This minimizes the effect of separator conditions which might vary from system to system. 5. The correlated pressures are the actual reservoir pressures which might or might not be the saturation pressure of the reservoir fluid.

Jan 1, 1966

By Harry M. Bendler, W. A. Wood

Electron metallography has been applied to the study of the torsional fatigue of polycrystalline OFHC* copper. The development of slip bands, fis- sures, and microcracks has been followed as a function of strain amplitude and number of cycles. Those factors that have been found to be relevant to a geometrical theory of the fatigue process are described. From the point of view of this theory it is important to distinguish between the effects of cycling at large amplitudes and at small amplitudes (true fatigue deformation). EARLY investigations showed metal fatigue cracking is caused by continued reversal of a small plastic strain. Fundamental study of fatigue, therefore, has been largely concerned with the cumulative effects of these plastic reversals on the metal structure. In particular, recent work has shown that the plastic reversals produce slip movements that are finer than the slip movements produced by unidirectional increments of plastic strain; individual slip movements in fatigue, for instance, are too fine to see by optical microscopy.2 It has also been shown that the fine slip movements of fatigue tend to concentrate in bands and that in this way they can build up, after enough cycles, a progressive surface disturbance. It is this disturbance which, in effect, makes the slip movement visible. It is also in this disturbance that the first cracks appear to form. From this point of view, therefore, the problem of fatigue becomes one of finding why the fine slip movements should concentrate in bands and why the. bands should finally open into cracks. Thus far, study of the slip bands has been limited to the changes they produce at the surface only. These studies have given interesting results. Ewing and Humfrey3 many years ago showed that the bands in iron could extrude debris. Forsyth found that bands in aluminum alloys could extrude thin tongues of material. Thompson showed that, after lightly dissolving away the surface of copper specimens, some bands persisted as superficial cracks might, and that the life of a specimen under fatigue deformation might be prolonged by dissolving away the surface at intervals. Thus these and related results have suggested that the metal structure in fatigue bands may disintegrate and that this may happen long before obvious cracking. These surface studies, however, have not shown definitely how cracking may begin, for they do not show sufficiently what is happening in depth. However, some advance in this direction has been made recently by a new approach, summarized later, which reveals slip bands and their surface disturbances in section. In the work done thus far, the sections have been studied by optical microscopy only. In the present work they have also been studied by electron microscopy with extended results. This paper also describes some observations on the surface disturbances prior to sectioning. These observations are relevant to a suggested theory of fatigue cracking. REVERSED SLIP MOVEMENTS Slip movements in fatigue deformation must reverse direction in each cycle. The question arises: DO the "backward" and "forward" movements take

Jan 1, 1962

By O. E. Palasvirta

Close examination of most so-called n.eu processes in mineral dressing reveals that they were conceived and developed a long time ago. High-intensity magnetic separation is no exception. Although its application in iron ore beneficiation seems new, in Germany the process has been commercially successful for almost two decades. High-intensity separators have long been standard equipment in the glass sand industry; they have also been used in concentrating some of the more unusual para-magnetic minerals. The basic features of an induced-rotor, high-intensity magnetic separator were described by Desire Korda in Paris in 1905,' and many patents have since been issued for improvements on the original design. Fig. 1 shows the basic design of an induced-rotor separator. Several U. S. manufacturers have been supplying induced-rotor separators for many years, but these are all devices of relatively low capacity, not suitable for treating such low-cost commodities as iron ore. On the other hand, two German manufacturers are offering induced-rotor separators of high capacity, both proven in the field. The present investigation was prompted by the apparent success of the German installations and by the discovery of iron ores on this continent which may be amenable to high-intensity separation. The objective was to gain better insight into the underlying principles of separation in a high-intensity field and to use this knowledge in selecting or designing an optimum separator. THEORETICAL CONSIDERATIONS he well known low-intensity magnetic separators are. without exception, of the the magnet type with more or less similar field shapes. It is therefore permissible to speak of their comparative strengths in terms of field intensity alone. However, proper understanding of the high-intensity magnetic separation process requires somewhat deeper analysis of the relationship between the magnetic field and the attractive force. Contrary to a widely held belief, a magnetic field of parallel lines of flux exerts no attractive force on a magnetically susceptible particle, but merely aligns its poles parallel to the lines of flux. On the other hand, a non-uniform field attracts a magnetically susceptible particle in the direction of the converging lines of flux. Thus the force of magnetic attraction varies as the product of the field intensity and the field gradient: dH ds As the induced-rotor magnetic separator is primarily intended for separating feebly magnetic materials, it is important that maximum attraction be attained. For the designer, then, the relationship between the magnetic field and the attractive force has the following implications: 1) Insofar as possible, the separation gap must be saturated with flux. 2) The rotor surface must be shaped to insure maximum convergence of lines of flux toward the rotor. 3) The primary pole face (opposite the rotor, on the other side of the separation gap) must be shaped so that the lines of flux do not diverge from it at any location in the effective separation zone. The actual attractive force of the rotor, and its critical speed, can be calculated as shown by Runo-linna, provided that the true flux density, the field gradient, and the magnetic susceptibility of the mineral can be measured with sufficient accuracy. The irregular shape of the rotor surface makes flux measurements difficult, but it can be done if a suitable gaussmeter is available (see Fig. 2). Calculations by the author, and comparisons with the centrifugal force exerted by the rotor, indicate that the force pinning a hematite particle to the rotor is of the same order of magnitude as the force holding a

Jan 1, 1960

By Haydn H. Murray

The term clay is somewhat ambiguous unless specifically defined because it is used both as a rock term and as a particle size term. Actually most persons using the term clay realize that it has a double meaning and in most instances define it. As a rock term, clay is difficult to define because of the wide variety of materials that compose it so that the definition has to be general. Clay is a natural, earthy, fine-grained material composed largely of a limited group of crystalline minerals known as the clay minerals. Many definitions state that a clay has the property of plasticity when wet, but some clays are not plastic, i.e., halloysite and flint clay; however, most clay materials are plastic when wet. As a particle size term, clay is used for the category that includes the smallest particles. The maximum size particles in the clay size grade are defined differently on some grade scales. Soil investigators and mineralogists generally use 2 microns as the maximum size. The Wentworth scale' defines clay as material finer than approximately 4 microns. Grim' has found it convenient to use the term clay material for any fine-grained, natural, earthy, argillaceous material and in this way can include clays, shales, or argillites, and some soils if they are argillaceous. Even though no standard definition of the term clay is accepted by geologists, agronomists, engineers, and others, still the term is generally understood by all who use it. Clay is an abundant natural raw material and has an amazing variety of uses and properties which will be discussed in this chapter. In order to understand better the relationships between the clays and their uses, a brief discussion of the structure, chemical composition, and identification of the clay minerals is given. Mineralogical Composition of Clays Clays are composed of certain groups of hydrous aluminum, magnesium, and iron silicates that may contain calcium, potassium, and other ions, which are called the clay minerals, and other minerals of variable composition, which are nonclay minerals. Both clay minerals and nonclay minerals influence the properties of a clay material. In order to understand the relationship between clay minerals and the properties of a clay material, a short summary of the structure and composition of clay minerals is necessary. Any scheme of classification tends to impose a certain rigidity and as new and additional data become available it is necessary to revise classifications. Brindley3 has discussed the classification and structural mineralogy of clays in very lucid fashion and chose a classification based on structural features and chemical composition. Grim2 proposed a tentative classification which is based on the structural attributes of the various clay minerals. This classification is relatively simple and workable, and is shown as follows: I. Amorphous Allophane group II. Crystalline A. Two-layer types (sheet structures composed of units of one layer of silica tetrahedrons and one layer of alumina octahedrons). 1. Equidimensional Kaolin group kaolinite, dickite, nacrite 2. Elongate Halloysite group

Jan 1, 1960

By W. F. Kieschnick, and W. J. McGuire&apos, Eugene Harrison

This paper concerns the induction and extension of fractures into rock formations as involved in drilling, completing, and production stimulating operations on wells. Conclusions concerning formation breakdown are derived from (I) a review and extension of published analyses relating to mechanical theories of rock stress and the state of stress in the earth's crust and (2) a correlation of field data from fracturing operations. Conclusions concerning the mechanics of fracture extension, which indicate the relationship between fracture dimensions and rock properties, depth, and volume of injected fluid, are tentative and largely establish limits of relationships. These conclusions are derived from stress calculations, limited field data, and laboratory experimental studies. The experimental work involves the study of the stresses at the fracture boundaries and the geometry of pressurized fractures by means of photo-elastic modeling methods. Results of this investigation indicate that a large majority of pressure induced wellbore fractures are vertical, particularly in deeper wells; and variations in the pressures necessary to create and extend fractures can be explained largely on a basis of established rock properties. It is also shown that variations due to tectonic forces should usually be expected to be slight. Other results indicate that during that extension of fractures rather large fracture volumes are temporarily created by the parting of the formation. The purpose of this paper is to present the results of calculations and laboratory experiments concerning the mechanics of fracture induction and extension with a view to broadening existing knowledge relating to these phenomena. It is believed that continued progress in developing knowledge of this type is important to the further development of techniques for drilling and completing wells. When a wellbore is subjected to sufficiently high pressure, fracturing of the formation surrounding the well occurs. This phenomenon is a common cause of lost circulation during drilling operations, is a deliberately planned factor in most squeeze cementing operations, and is the controlling factor in many productivity stimulation operations. The exploitation of formation fracturing in recent years has been particularly impressive in sand-viscous fluid well stimulation treatments which were first introduced to the industry by the Stanolind research group1,2,3 several years ago. The borehole fracturing phenomenon has been analyzed mathematically by application of the principles defining the elastic and inelastic behavior of thick-walled cylinders of homogeneous, isotropic, and impermeable material.1,5,6 This basic argument is re-presented in this paper along with new considerations which strengthen it. In addition to these arguments relating to fracture induction some calculations and experimental results relating to the mechanics of fracture extension are presented. Since the nature of the pressure induced fracture at distances from the well is of great importance in considerations of well stimulation procedures there appears to be a need for an integrated approach which deals with the mechanics of fracture extension as well as with wellbore rupture.

Jan 1, 1955

By T. M. Gurr

The United States is the world's leading producer of phosphate rock. In 1975 according to the US Bureau of Mines' statistics, 44.3 million tonnes (48.8 million st) of phosphate rock were produced in the United States, 1 which is 40.6% of the world's production.2 The major phosphate producing areas of the United States are located in Fig. 1 and the production for 1975 is listed as follows:

Jan 6, 1979

By J. H Lightfoot, Stuart E. Buckley

Deep drilling has led to the development of numerous pools which yield products consisting predominantly of natural gas accompanied by high-gravity water-white or slightly straw-colored liquid. Yields of this "condensate" or "distillate," as it is commonly called, vary from traces to over a hundred barrels per million cubic feet of gas. The fact that this liquid exists in the reservoir as an integral part of the gas phase and is formed by condensation attending simultaneous reduction of pressure and temperature after its entry into the well was apparently first recognized about 1932.l The nature of the physical phenomena involved in this condensation was clarified for the petroleum industry in 1933 by a report by Sage, Schaafsma, and Lacey2 of the results of an experimental investigation of the behavior of mixtures of methane and propane. Search of the literature has revealed that the condensation of liquid from gaseous mixtures by isothermal pressure reduction is not a new discovery. Kuenen was led by theoretical considerations to expect such a phenomenon, and in 1892 reported3 the results of experimental verification of his deductions. This was followed by a considerable amount of work on the phase relations of mixtures by Kuenen 4,5,6 and by 0thers,7,8 mostly in European universities. Since 1930 investigators in this country have reported experimental data on the properties and behavior of a number of hydrocarbon systems."' It is now generally known that in the presence of natural gas the solubility in the gas phase of the heavier and normally liquid hydrocarbons increases rapidly with increasing pressure above 500 to 1000 Ib. per sq. in. Thus, at pressures of 2500 Ib. per sq. in. or higher a gas may contain appreciable quantities of hydrocarbons with normal boiling points as high as 6o0°F., which in turn may be condensed from the gas phase by the reduction of their solubility therein attending pressure reduc-tion. The combined effects of pressure and temperature on condensation and vaporiza-tioi of mixtures are most readily visualized by the study of phase diagrams. Since the construction, application, and interpreta-tion of such diagrams have been described fully in readily available literature, 18-20 this paper will not review the theoretical aspects of this subject. While the behavior of gas-distillate sys tems is now clearly understood, at least in a qualitative way, most of the published work deals with the results of laboratory studies of binary systems or of synthetic mixtures of hydrocarbons, and although several systematic investigations of the effects of separator pressure and temperature on the yields of liquid product from gas-distillate wells have been made21,12z it appears that in all cases the limitations have precluded the construction of even approximately complete phase diagrams for naturally occurring systems. There has 2

Jan 1, 1941

By J. H. Lightfoot, Stuart E. Buckley

Deep drilling has led to the development of numerous pools which yield products consisting predominantly of natural gas accompanied by high-gravity water-white or slightly straw-colored liquid. Yields of this "condensate" or "distillate," as it is commonly called, vary from traces to over a hundred barrels per million cubic feet of gas. The fact that this liquid exists in the reservoir as an integral part of the gas phase and is formed by condensation attending simultaneous reduction of pressure and temperature after its entry into the well was apparently first recognized about 1932.l The nature of the physical phenomena involved in this condensation was clarified for the petroleum industry in 1933 by a report by Sage, Schaafsma, and Lacey2 of the results of an experimental investigation of the behavior of mixtures of methane and propane. Search of the literature has revealed that the condensation of liquid from gaseous mixtures by isothermal pressure reduction is not a new discovery. Kuenen was led by theoretical considerations to expect such a phenomenon, and in 1892 reported3 the results of experimental verification of his deductions. This was followed by a considerable amount of work on the phase relations of mixtures by Kuenen 4,5,6 and by 0thers,7,8 mostly in European universities. Since 1930 investigators in this country have reported experimental data on the properties and behavior of a number of hydrocarbon systems."' It is now generally known that in the presence of natural gas the solubility in the gas phase of the heavier and normally liquid hydrocarbons increases rapidly with increasing pressure above 500 to 1000 Ib. per sq. in. Thus, at pressures of 2500 Ib. per sq. in. or higher a gas may contain appreciable quantities of hydrocarbons with normal boiling points as high as 6o0°F., which in turn may be condensed from the gas phase by the reduction of their solubility therein attending pressure reduc-tion. The combined effects of pressure and temperature on condensation and vaporiza-tioi of mixtures are most readily visualized by the study of phase diagrams. Since the construction, application, and interpreta-tion of such diagrams have been described fully in readily available literature, 18-20 this paper will not review the theoretical aspects of this subject. While the behavior of gas-distillate sys tems is now clearly understood, at least in a qualitative way, most of the published work deals with the results of laboratory studies of binary systems or of synthetic mixtures of hydrocarbons, and although several systematic investigations of the effects of separator pressure and temperature on the yields of liquid product from gas-distillate wells have been made21,12z it appears that in all cases the limitations have precluded the construction of even approximately complete phase diagrams for naturally occurring systems. There has 2

Jan 1, 1941

By Ralph Monaghan, Arthur Youmans

General principles of scintillation counter-type instruments for radioactivity logging are discussed and the various possible causes for instability are examined. It is shown how instrumentation problems are solved. Means are discussed for minimizing drift and instability due to "fatigue" of the photomultiplier tube and neutron activation of the crystals. INTRODUCTION Neutron and gamma-ray logs made with logging instruments employing scintillation counters are now routinely available from most of the logging service companies. The superior characteristics of scintillation counters by comparison with older types of detectors promises to bring about important improvements in quantitative interpretation of radioactivity logs. Moreover, new types of logs can be made with scintillation counters which are not possible with other detectors. But in spite of the obvious superiority of these counters with respect to efficiency, speed, and versatility, they suffer from a number of inherent difficulties and weak- nesses. Unless these inherent diffi-culties are fully recognized and satisfactorily overcome by sound engineering of the associated instrumentation, scintillation counter logs are particularly likely to exhibit drift and instability of sensitivity. This defect in logs when they are intended for quantitative interpretation is intolerable and more than outweighs any advantages over the older type of instrumentation when the latter is operating correctly. SCINTILLATION COUNTER OPERATION In general all radioactivity logging instruments consist of a detector sensitive to gamma radiation or to neutron radiation coming from the strata. This radioactivity is either due to naturally decaying radioactive elements in the rock, radioactivity induced in the rock by a neutron source in the instrument, or scattering by the rock of neutrons or gamma rays coming from a source in the instrument. In the scintillation counter the gamma radiation or neutron radiation reacts with the scintillation phosphor to produce light pulses. These light pulses are then converted to amplified electrical pulses by the multiplier phototube. Basically the problem of making a good scintillation counter logging instrument is to make the radiation sensitivity of the system as nearly constant as possible. The size of each scintillation counter pulse is dependent on the energy of the individual quantum of radiation being detected. In normal radiation logging, gamma rays of all energies, up to some maximum value, reach the detector. If a suitable scintillator is used, such as a sodium iodide crystal, each gamma ray produces a number of photons proportional to the energy absorbed by the crystal from the impinging radiation. The light flashes are detected by means of a photo-multiplier tube which contains not only a photo-sensitive cathode from which photoelectrons are collected, but also an amplifier, called an electron multiplier, built inside the photomultiplier tube; the electron multiplier usually has about 10 stages, having an over-all gain of perhaps 500,000. In an ordinary gamma-ray log one wishes to detect all gamma rays down to the lowest possible energy; therefore, one wishes only to reject the "noise" pulses which are invariably present due to thermal emission of electrons from the photo-cathode of the photomultiplier. In other radioactivity logs it may be desired to measure the radiation within a particular energy band, or above

Jan 1, 1958

By Charles Hart

The art of electric smelting came with the turn of the present century and owes its existence to the introduction of alternating current, which found its first wide use in the establishment of the great power plants at Niagara Falls, N. Y. Prior to that time current was largely direct. The furnaces were electrolytic in nature and found their first metallurgical use in the production of aluminum, and this process still prevails. The normal production of pig iron up to that time was carried on in blast furnaces in which charcoal, coke and anthracite were used as the fuel. This new electric process called for sufficient carbonaceous material to reduce the oxides and impregnate the pig iron with sufficient carbon, but the remainder of the energy was to be supplied by electric power. The chemical reactions are essentially the same in electric smelting as obtains in the older blast furnace. All of these data are so well known in both methods as to need no discussion at this time, for they can be found in scientific : publications and books written during the first two decades of this century. Types of Furnaces The 40 years devoted to the practice of electric smelting may be divided into two . periods of 20 years each. The first was devoted to experimentation with furnace types and with many publications on theories and processes. The second half of this term was devoted to perfecting the types of furnaces and their active commercial operation. The arc furnace may be found in three types: (1) the direct-heating arc furnace with the positive electrode included in the bottom and the other electrode suspended above; (2) the independent arc furnace with its electrodes entirely above the charge, which of necessity depends upon heat reflected from the roof; (3) the direct-heating series arc furnace equipped with two or more electrodes suspended from the roof. Of these three types, only the last is used in electric smelting of iron ore at the present time. The elimination of the other types automatically removed many of the early designs, to the end that there are now only two general types in operation: (I) the " Electrometalls" or high-shaft furnace of Sweden, and (2) the low-shaft or pit-type furnace as offered by Tysland-Hole and Siemens-Halske. The "Electrometalls" furnace takes its name from the corporation formed by the engineers that had undertaken its perfection. After trying several designs they brought forward the furnace shown in Fig. I, which by the way is the highest development of this type of furnace as of today.l Note the trend in the lines, which have kept pace with modern blast-furnace design. The high-shaft furnace lends itself to skip filling and is fitted with tuyeres immediately under the crucible roof, whereby the gases are recycled and the roof preserved. The failure of the Electrometalls furnace in Norway, because of its inability to meet

Jan 1, 1941

By Charles Hart

The art of electric smelting came with the turn of the present century and owes its existence to the introduction of alternating current, which found its first wide use in the establishment of the great power plants at Niagara Falls, N. Y. Prior to that time current was largely direct. The furnaces were electrolytic in nature and found their first metallurgical use in the production of aluminum, and this process still prevails. The normal production of pig iron up to that time was carried on in blast furnaces in which charcoal, coke and anthracite were used as the fuel. This new electric process called for sufficient carbonaceous material to reduce the oxides and impregnate the pig iron with sufficient carbon, but the remainder of the energy was to be supplied by electric power. The chemical reactions are essentially the same in electric smelting as obtains in the older blast furnace. All of these data are so well known in both methods as to need no discussion at this time, for they can be found in scientific : publications and books written during the first two decades of this century. Types of Furnaces The 40 years devoted to the practice of electric smelting may be divided into two . periods of 20 years each. The first was devoted to experimentation with furnace types and with many publications on theories and processes. The second half of this term was devoted to perfecting the types of furnaces and their active commercial operation. The arc furnace may be found in three types: (1) the direct-heating arc furnace with the positive electrode included in the bottom and the other electrode suspended above; (2) the independent arc furnace with its electrodes entirely above the charge, which of necessity depends upon heat reflected from the roof; (3) the direct-heating series arc furnace equipped with two or more electrodes suspended from the roof. Of these three types, only the last is used in electric smelting of iron ore at the present time. The elimination of the other types automatically removed many of the early designs, to the end that there are now only two general types in operation: (I) the " Electrometalls" or high-shaft furnace of Sweden, and (2) the low-shaft or pit-type furnace as offered by Tysland-Hole and Siemens-Halske. The "Electrometalls" furnace takes its name from the corporation formed by the engineers that had undertaken its perfection. After trying several designs they brought forward the furnace shown in Fig. I, which by the way is the highest development of this type of furnace as of today.l Note the trend in the lines, which have kept pace with modern blast-furnace design. The high-shaft furnace lends itself to skip filling and is fitted with tuyeres immediately under the crucible roof, whereby the gases are recycled and the roof preserved. The failure of the Electrometalls furnace in Norway, because of its inability to meet

Jan 1, 1941

By J. S. Hegwer, P. M. Dunlap

An improved acid for the treatrrzent of sulfate-con-raining limestones and dolomites is described. The acid is designed to reduce he reprecipitation of dissolved calcium sulfate and the possibility of plugging permeable flow channels. In addition, this improved acid has a much lower reaction rate than that of regular acid; the advantages of a "retarded" acid are obtainable. Field testing of the acid has shown it suitable for use in sulfate-containing formations. Substantial improvements in productivity generally resulted. INTRODUCTION Acid treatments of limestones, dolomites and other formations bearing carbonate deposits are frequently unsuccessful when the calcareous formation contains sulfate, either as anhydrite (CaSO,) or gypsum (CaSO4. 2H2O). Preliminary dissolution in acid followed by redeposition of calcium sulfate appears to be a major factor contributing to poor well performance after acidizing. The precipitate is usually the gypsum form of calcium sulfate, but in higher temperature formations it may be anhydrite. The freshly precipitated crystals are nearly always very small and needle-like. They may occupy a gross volume many times that of the original anhydrite crystals and will obviously constitute an impediment to flow through newly enlarged flow channels. It is believed that the redeposition problem is most severe when anhydrite lines the fracture systems and large pores which supply the effective permeability of a formation. Microscopic inclusions of calcium sulfate also present large sulfate surface areas for dissolution in acid. In either case, great amounts of calcium sulfate may dissolve before the acid can be spent on formation carbonates. For regular spent acid (originally 15 per cent hydrochloric acid) the precipitate could be as much as 270 Ib gypsum/1000 gal acid. Two techniques have been applied by the industry for reducing sulfate plugging during acidizing. The method'.' commonly employed in the field is the attempted removal of a quantity of regular treating acid before it has reacted completely with the formation. This is practiced because the solubility of calcium sulfate is greater in a solution that is still acidic than in one which has been largely spent on the formation rock. The chance of precipitative plugging is therefore reduced if the withdrawal is successful. However, it is often impossible to get the acid out of the formation before precipitation occurs. A second possible method, which at first glance appears practical, involves addition to the acid of sequestering agents which form strong soluble complexes with calcium ions. These chemicals do increase the "solubility" of calcium sulfate in fresh acid, but to a lesser extent in spent acid. The sequestering agents have, therefore, proved unsatisfactory because the amount of sulfate eventually deposited from the spent acid may be greater than that from regular acid. Another logical approach to the problem of calcium sulfate reprecipitation is the prevention of the initial dissolution of calcium sulfate by the common ion effect. This may be accomplished by adding a soluble calcium salt to the fresh acid. The use of calcium salts in treating acids is not entirely new. An earlier suggested use of a soluble calcium salt in hydrochloric acid apparently failed to recognize the full extent to which the solubility of calcium sulfate could be suppressed. The present study extends this earlier work and adds certain improvements toward the development of a practical anti-anhydrite acid. LABORATORY DEVELOPMENT Calcium Sulfate Solubility Table 1 shows the results of a laboratory study performed to establish the effect of calcium chloride concentration on gypsum solubility. Because of the strong tendency of calcium sulfate to form supersaturated solutions, accurate solubilities are difficult to determine. These solubility data probably are reliable to within ± 15 per cent. The solubility of calcium sulfate in 15 weight per cent hydrochloric acid increases with increasing temperature. This trend is also followed in hydrochloric acid which cantains calcium chloride. This is contrary to the solubility behavior of calcium sulfate in water, wherein the solubility decreases with increasing temperature.

Optimism over the continued growth of coal ex- ports received a significant shot in the arm September 18 at Norfolk, Va., when huge, new ship coal-loading facilities of the Norfolk & Western Railway were formally dedicated before a large audience of American and foreign dignitaries. Guest of Honor at the occasion was Christian A. Herter, Special Representative for Trade Negotiations, who, in a speech, stated, "The prospects for the expansion of our coal exports are excellent. The competitive pricing and high quality of our coals, whether for the production of coke for steel mills or for the generation of electric power, have won the respect of consumers everywhere in the world. Last year, the United States coal industry exported over 40 million net tons. . . . There are excellent reasons to believe that by 1970 we shall be exporting at double this rate."

Jan 10, 1963

Mounting pressures to increase efficiency and yield, conserve energy, or minimize pollution have all taken their toll on the minerals industry. As management and technical personnel take a harder look at their operations for ways to shave cents off operating costs or to squeeze a bit more productivity out of existing equipment, instrumentation often comes up as the most effective answer. When Amax Lead installed an automatic grind control system in its Buick mill, ore throughput increased by 3 to 5%. Mill operators calculate that the initial investment is returned to them several times annually.

Jan 2, 1978

By William Fink

THE constitution of the aluminum-cobalt alloys has been the subject of relatively few investigations. Brunck1 analyzed the residue which remained after treating the 17 per cent cobalt alloy with dilute hydrochloric acid. The results of the analyses indicated the existence of a compound Co3Al13. Guillet2 published a liquidus for the aluminum-cobalt system which contained two maxima corresponding to CoAl6 and CoAl2 and two eutectic points at 30 and 74 per cent Co. The most extensive investigation of the system was carried out by Gwyer,3 whose results are summarized in Fig. 1. It will be noted that at the aluminum end there is a suppressed eutectic at 644° C. By extrapolation of the duration of the eutectic arrest to zero, the composition of the compound was placed at Co3Al13. Another thermal arrest was noted at 550° C., which Gwyer attributed to a peritectic reaction. The present investigation of the aluminum end of the aluminum-cobalt system is the eleventh of a series dealing with the constitution of aluminum; rich alloys prepared from electrolytically refined aluminum.4 Preparation of Alloys.-The alloys used in this work were all prepared from electrolytically refined aluminum, the analysis of which is shown in Table 1. In preparing some of the alloys, metallic cobalt (98 to 99 per cent) was used either directly or in the form of an intermediate alloy, the composition of which is given in Table 1. In order to obtain alloys of higher purity, cobalt was introduced into some of the alloys by means of chemically pure cobaltous chloride which was readily reduced by the aluminum. A small electric furnace with nickel-chromium heating elements was used in the preparation of the alloys.

Jan 1, 1932

By C. M. Tucker, K. R. Van Horn, W. P. Sykes

Recent investigations of the molybdenum-carbon alloys have been reported by Becker and Ebertl,‡ Westgren and Phragmén2, T. Takei3, and H. Tutiya4. Takei3 studied the Mo-C system by employing metal-lographic and X-ray methods, and the other publications described the determination of the crystal structure of the molybdenum carbides. In exploring this system by a technique previously applied to the tungsten-carbon series5, the results of Takei were confirmed with two definite exceptions; i.e., first the composition of the eutectic, and second the nature of the carbon-rich intermediate phase. Consequently, a more thorough examination of the molybdenum-carbon constitution was initiated in an effort to correlate the data supplied by the microstructures, diffraction patterns and chemical analyses. Metallographic Investigation A briquette of molybdenum powder when heated in a carburizing atmosphere at 1500" to 1600" C. for several hours develops the carbon-rich layer shown in Fig. 1. The carburization was accomplished by placing the briquette in a carbon tube, which was heated in the hydrogen atmosphere of an alundum muffle wound with tungsten resistor. While the macrostructure indicates two distinct shells, and suggests the possibility of two carbon-rich phases, no evidence of this condition could be detected by the microscope, which revealed but one high-carbon constituent. This carbide forms next to the molybdenum as a relatively dense, light-colored zone (Fig. 2) which passes abruptly into an outer layer of spongy texture. As will be noted later, only one intermediate phase was observed in the X-ray photograms prepared of different locations in the carburized zone. The metallographic structure at the inner border of the shell, reproduced in Fig. 3, shows a marked porosity accom-

Jan 1, 1935