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By N. O. Gray, John Henderson

Hydrogen-reduction data for naturally occurring single crystals and Prepared polycrystals of dense hematite have been presented. Results cover the temperature range 400o to 1000oC, for particles from ten sources, ranging in size from 0.07 to 10 mm and in shape from spheres to cylinders, cubes, and thin slabs. A consistent pattern of behavior has been demonstrated for single crystals and the reduction mechanism shown to be temperature-dependent. Below 579oC reduction is a simple topochemical process but at higher temperatuves it is complex and occurs in two distinct stages. Prepared particles from these laboratories behave in a similar manner to the single crystals. Data from two investigators showing topochernical reduction of Prepared particles above 575°C are inconsistent with that for other dense hematites. It is concluded that topochenzical reaction should not be used as a model for generalized rate expressions for dense hematites. SINCE 1958, McKewan1-6 has brought to prominence a simple concept of dense hematite reduction. This model is that oxygen is lost from a hematite particle undergoing reduction only from an oxide-iron interface that recedes in such a way that the oxide remaining retains the original shape of the particle, i.e., reduction occurs topochemically. An adjunct to this concept is that any intermediate oxides in the transition from hematite to iron only form thin layers so that oxygen cannot be lost from the particle without movement of the oxide-iron interface. Further, the rate of oxygen loss from the particle is said to be proportional to the area of the receding interface so that the iron layer grows linearly with time and the over-all reduction process can be described by the equation where ro and do are the initial particle radius and density, respectively, R is the fraction of the original oxygen lost, i.e., the fractional reduction, at time t, and K is the rate constant. The idea of an underlying simplicity in hematite reduction is attractive because it gives a tractable basis from which general theories of hematite reduction can be developed and it has received wide support,7-14 based mainly on the large amount of data13 that can be fitted to Eq. [I]. However, despite the fact that this equation has been derived for dense materials, the bulk of the data that have been used to test it13 have been for materials of only about 90 pct of theoretical density (5.26 g cm-3) or less, so that its generality for dense hematites has not been demonstrated. In any case, as will be seen, adherence of reduction data to Eq. [1] does not necessarily imply that reaction occurs topochemically. In this work only data for hematites approaching theoretical density are considered and it will be shown that in only one study besides McKewan's is topochemical behavior observed over the whole range of temperature investigated. For the majority of materials a linear rate of interface advance is observed to complete reduction only when wustite is not a stable intermediate phase in the transition of hematite to iron, i.e., at temperatures below about 575°C. Above this temperature, reduction is an exceedingly complex series of reactions that takes place in two distinct stages and it is only in the first stage that reaction in any way resembles a topochemical process. This means then that, far from representing general behavior as has commonly been supposed, topochemical reaction for dense hematites is only a particular behavior that may be observed under some circumstances. EXPERIMENTAL Hydrogen-reduction data have been collected and cross-checked in these laboratories by three techniques, weight loss, collection of water evolved in the reduction reactions, and direct metallographic examination. Details of these techniques are discussed elsewhere," where it is shown that results obtained by the three methods are in close agreement. The weight-loss method, by which most of the results were obtained, consisted of hanging the sample in a platinum mesh basket from an Ainsworth Model AV-AU-1 vacuum recording balance inside a vertical l 1/4-in.-ID alumina tube furnace. Dry deoxidized hydrogen was flowed downwards through the tube at 2 to 4 liters min-1 (stp). Single crystals from two sources and artificial oxides from three sources have been examined. The single crystals were from hematite deposits at Yampi Sound, Western Australia, and Brazil, the latter being obtained from Gregory, Bottley and Co., London, U.K. The "Yampi Blue" crystals were hand-picked from washed, magnetically concentrated, sized fractions, -200 mesh BSS (mean diameter ca 0.07 mm) and —36 + 44 mesh BSS (mean diameter ca 0.4 mm) while 10-mm cubes were cut from the Brazilian crystals with a diamond saw. The starting materials for the prepared particles were hematites designated, respectively, "Specpure Iron Oxide", Laboratory No. S639 from Johnson Matthey & Co. Ltd., London, U.K., "Calcined Ferric Oxide" from B.D.H. Laboratory Chemicals Division, Poole, U.K., and "Pigment Grade Oxide", EPR-50, from C. K. Williams & Co., Easton, Pa., U.S.A. Approximately spherical particles were prepared from the artificial oxides by rolling the material, moistened if necessary, in a glass jar, and cylindrical compacts approximately 10 mm in diam and of approximately equal height were pressed in a steel die at 200 psi. These spheres and cylinders were subsequently fired in oxygen for 20 to 100 hr at 1370°C. The

Jan 1, 1967

By John Johnston

WHEN I was honored by being invited to give the Howe Memorial Lecture, I decided to read Howe's book, "The Metallography of Steel and Cast Iron," published in 1916-that is, about 25 years ago-in search of a text. I found the book written in fine, clear, attractive, yet precise style, as I expected, knowing that his father ¬Dr. Samuel Gridley Howe, his mother-Julia Ward Howe, and all of his four brothers and sisters had lived in a New England literary atmosphere and had written books. This leads me to suggest that many authors of metallurgical papers and books could well study Howe's writings with a view to the improvement of their own. I failed to find a specific text, but did find a subject, for in reading his book I was struck by the few instances in which time is considered explicitly as a factor in the phenomena examined, and by the fact that many of the hottest arguments would have been settled had time been taken properly into account. Indeed, Howe hardly mentions time except in a rather incidental way, as in a few references to lag; for instance: The lowering of temperature at which the transformation occurs by rapid cooling . . . is a phenomenon of undercooling or lag. It is in part explained by the fact that the transformation itself is a time-consuming reaction which, setting in during a rapid fall of temperature. is naturally protracted till the temperature has sunk far below that at which it is due. He does discuss, quite fully, the iron-carbon equilibrium diagram, as known at that time, introducing it by stating: As he is a reasonable man who is not deterred from using a hand truck for moving his trunk by the consideration that he has thus to move a trunk plus a truck, so am I reasonable in putting into your hands this useful, indeed indispensable, tool for mastering the ABC of iron metallurgy. Somewhat later, in introducing a discussion of the phase rule, which "it would be hardly proper to pass . . . by without an attempt to outline its meaning," for "a clear exposition of its applicability or jurisdiction is needed to restrain the half-initiated from misusing it and the uninitiated from being misled by these misuses," he writes-and I quote his statement because we cannot properly discuss the influence of time on a process until we know the state of equilibrium which would ultimately be reached by the system under consideration It is a most remarkable and valuable generalization, its conceptions help greatly toward getting a broad outlook on metallography, but its misconception has brought out a flood of obscuring writings. It tells us about the constitution towards which alloys tend, that which they reach when equilibrium is complete, when all tendencies have corrected themselves and have been complied with completely. Its application, in absence of true equilibrium, is like determining density with a telescope or even with a tuning fork; it is like the mad tea party at which the butter put into the works "f the watch was the best butter. If the reader learns no more than to beware of attempts to decipher the conditions of inequilibrium by a law which touches only the conditions of exact

Jan 1, 1942

By L. E. Young

MUCH has been said and written on this subject and probably little new can be said. However, the point of view of the operating company changes from time to time, and more stress may be laid upon a subject today than was done some years ago, and it is with this changing point of view that the following observations are presented: The writer wishes to limit the discussion to views of a company mining bituminous coal, particularly to what the production department expects of the college grad¬uate. In an editorial in MINING AND METALLURGY for February, 1929, entitled "Is. Mining Engineering Passing?" it is stated that: It is not by accident that mining engineering courses have been general rather than special and form even today the only general engineering courses widely offered and followed by engineering students.'* * * even in this age of specialization, the mining engineers remain a body characterized particularly by broad knowledge.

Jan 1, 1929

By Etienne A. Ritter

INTRODUCTION. THE Evergreen mine, located at Apex, in the northern part of Gilpin county, Colorado, has opened a very peculiar and interesting copper-deposit, in which both bornite and chalcopyrite occur as rock-minerals. The country-rocks are crystalline schists cut by dikes of granulite and of pegmatite. At the Evergreen property they have been cut by a dike of a new kind of eruptive rock, to which I have given the name " Evergreenite" The rock is composed of quartz, alkali feldspars, orthoclase and albite (often interlocked as microperthite), with augite of the aegirine variety and long needles of enstatite and diallage. For reasons stated below, I believe the dike to be of Tertiary age. It is- easily traced on the surface of the ground, from a point in the bottom of Pine creek, about a mile below Apex,. to the top of Nevada hill, 1,500 ft. beyond and 600 ft. above it. (See Fig. 1.) It varies from 3 to 12 ft in width, and is bounded on both sides by contact-zones about 60 ft. wide, in which the crystalline schists have been changed into pseudo-quartzites or pseudo-gneisses, according to the injection of an excess of quartz or of feldspars through the special layer of the schists.. The most interesting feature is the presence of the pyroxenes, which are always found, though in very variable proportions from place to place, in the layers of these' metamorphosed crystalline schists. The dike has torn from its walls a large number of fragments of the wall-rock. It must have been in a viscous state when that happened, because these fragments of the wall-rock do not show any sign of resorption or of assimilation by the magma. In places they are so distinct and so numerous that the rock looks to the naked eye like a pseudo-breccia, of which, never-

Jan 1, 1908

THE subcommittee on Coal Mining, since its appointment, has been engaged in collecting data about subsidences in coal mines in this country, and it now feels that almost all of the available data about occurrences of this sort in bituminous mines has been collected. As most of the bituminous seams are nearly level, the records obtained give the problem in its simplest form, without complications due to the pitch of the seam. Similar data is being compiled for the anthracite regions and it is hoped that this will be ready for the 1927 meeting. Copies of the questionnaire, Appendix A, were mailed to all of the coal operators' associations, to most of the large operating companies and to many engineers, with the request that any data on the subject be returned to the committee, or that advice of any subsidences known be given. The replies to most of the questionnaires were general only, although some specific cases were given. Many of the companies were unable to reply to all questions, as they lacked the necessary data, but in nearly every case where accurate data was available, it was cheerfully furnished, and any additional information requested was secured. All specific cases of subsidence were followed up by correspondence, and in several cases by personal inspection. Figs. 1 to 31 were made from the information furnished. Table 1 gives measurements of elevations taken in one case at intervals from October, 1913, to May, 1918. With one exception, where the evidence cannot yet be released on account of a lawsuit, it is believed that the cases submitted with this report include practically all that have happened in bituminous coal mining in this country of which actual measurements were secured. Some of these have already been published in the excellent report by Young and Stoek,1 and some instances have been secured from other publications. In collecting these data, the subcommittee had the Engineering Societies Library extend the bibliography given in the bulletin mentioned above to date. This list is given in Appendix B.

Jan 2, 1926

By J. G. Balkestein, J. W. R. Baerts

During an attempt to develop a method for accurate, rapid, continuous analysis of ash content of wal, the Dutch State Mines Laboratory found that the absorption coefficient for X-rays was related to ash content. This relationship was utilized in the development of an apparatus called CendreX, used to measure the absorption and in turn the ash content. The principle, procedure, accuracy, and applications of the CendreX automatic determination of ash in coal are discussed in detail. Until recent years coal preparation research was concentrated on the possibilities and efficiency of preparation equipment. Ever increasing demands for quality in coal, however, have caused researchers to become concerned with quality control. One of the characteristics strongly influencing quality (calorific value) and, consequently, the price of coal is ash content. Both customer and producer require that the ash content be controlled. To make this possible it is necessary for the producer to collect samples from the coal stream in the washery and to determine their ash content. On the strength of the results obtained the production process can then be adjusted, if required. Until recently incineration was the only method for determining ash content. When coal is incinerated with oxygen, it takes at least 15 min to determine the ash content. Even then some time may be lost in passing on the data. Therefore, this discontinuous and time-consuming method does not make a suitable starting point for checking, re-adjusting, or modifying the production process. Since it was not possible to accelerate incineration by mechanization and automation, another type of rapid continuous analysis had to be found. This would have to depend on some coal characteristic closely linked with ash content. At the Central Laboratory of Dutch State Mines, Dijkstra and Sieswerda found that the absorption coefficient for X-rays was suitable for this purpose. An apparatus based on the measurement of this characteristic was developed. Named CendreX,* this patented equip- *A Stamicarbon N. V. registered trademark. ment, used in combination with a sampler and conditioning apparatus, permits continuous determination of ash content with satisfactory exactness to within 3 min.t At the American Mining Congress meeting of May 1961, Log A. Updegraff, surveying aspects of continuous analyaia, reported on the CendreX appartus (Mining Congress Journal, August 1961). Since the first Condition for correct ash determination, whatever the method used, is always a sample taken in the right way, some practical aspects of sampling will be discussed first. SAMPLING In coal handling operations, each grain has its characteristic properties. In both the cross-sectional and longitudinal direction of the product stream the mixture of these grains is imperfectly blended. The elimination of the factor of segregation between the cross-sections from the direction of the stream is the principal aim of continuous analysis. Therefore, the samples to be analyzed are withdrawn in various places from the segregated product stream in such a way that they form a semi-continuous flow. In order to be truly representative of the product stream, the sample flow must fulfil two conditions: 1) The sample flow must be sufficiently large to insure that adventitious differences between the composition of the product stream and sample flow will be as small as possible. 2) All grains through the entire cross section of the product stream must have an equal chance to get into the sample flow. Since there is always a segregation through the cross section the sample flow will have a bias if the sampler collects only part of this section. In order to prevent the volume of the sample flow from becoming too large, the cross sections are taken discontinuously. However, this discontinuity gives rise to the adventitious differences that arise between the composition of product stream and the sample flow, and these differences become greater and are more deranging as the fluctuations follow each other more quickly. Moreover, the intervals between the morrnents of sampling mean a delay in the analysis. The aim will, therefore, be to collect small samples, or in other words thin cross-sectional increments, taken at sufficiently high frequencies. The following points should also be taken into account: 1) The smallest dimension of the openings in the sample collector must be equivalent to at least 3 d in

Jan 1, 1962

By James Terry Duce

Production of oil in Bahrein for the war years was as follows: YEAR BBL PER YEAR Prior to 1939 . . . . . . . . . . . . . . 22,287,055 1939 . . . . . . . . . . . . . . . . . . . . . . 7,588,554 1940 . . . . . . . . . . . . . . . . . . . . . . 7,073,919 1941 . . . . . . . . . . . . . . . . . . . . . . 6,794,157 1942 . . . . . . . . . . . . . . . . . . . . . . 6,240,627 1943 . . . . . . . . . . . . . . . . . . . . . . 6,571,609 1944 . . . . . . . . . . . . . . . . . . . . . . 6,713,795 1945 . . . . . . . . . . . . . . . . . . . . . . 7,308,938 Total to Jan. 1, 1946 . . . . . . . . 70,578,654

Jan 1, 1946

By F. D. Rosi, C. A. Dube, B. H. Alexander

WHEN a deformed polpcrystalline metal is heated to a sufficiently high temperature, a recrystallized structure develops which consists of small, essentially stress-free grains. This transformation is referred to as primary recrystallization. Under certain conditions, on prolonged annealing of the specimens, a type of grain coarsening occurs in which a small number of grains commence to grow at various points by devouring the neighboring finegrained primary structure, which, in itself, exhibits a marked stability toward normal grain growth. This grain coarsening process has been referred to by Burgers' as "secondary recrystallization" or "exaggerated grain growth." Although much work has been done on recrystallization and growth processes, present knowledge of the factors which determine the occurrence and growth of secondary grains is inadequate for the advancement of a theory which accounts for the observed characteristics of this recrystallization phenomenon. In this respect, it would be important to make measurements of the velocity of growth of these large secondary grains. The early work of Feitnecht2 on aluminum showed that the size of secondary grains increased with temperature and time, suggesting that such measurements would be possible. More recently, Burgers1 found that the growth velocity of these grains in aluminum was constant over a large time interval, as is generally found for the growth velocity of primary grains in a uniformly deformed test piece.3-5 It is reasonable to expect that the determination of the activation energy of the secondary growth process might lead to a better understanding of the underlying atomic mechanism. This investigation, therefore, is one of a series primarily designed to measure the growth velocity of secondary grains at various temperatures for silver, copper, and aluminum. It is hoped that these studies along with those of orientation relationships, will establish a sound basis for theorizing as to the origin and nature of the secondary transformation. Experimental Procedure The metal used in the present investigation was high-purity silver (999.9 fine), which was supplied in the form of cold-rolled plates 0.250 in. thick. These plates were annealed at 500°C for 1 hr and then straight-rolled to a thickness of 0.04 in. in three reductions of approximately 45 pct, followed in each case by an anneal at 450°C for 1/2 hr. The 0.04 in. sheets were given a final reduction of approximately 50 pct, which resulted in a thickness of 0.02 in., thereby insuring two-dimensional crystal growth. Individual specimens of this material about 1x3 cm were used for all heat treatments, unless otherwise noted. The annealing was carried out under an atmosphere of argon in an Inconel tube furnace whose temperature was controlled to within -+2°C. Metallographic examination of the secondary transformation was accomplished by mechanically polishing the specimens on one side to approximately one half their thickness through 2/0 metallographic emery paper, and then electrolytically polishing in a solution of potassium ferrocyanide and sodium cyanide. With a current density of approximately 20 amp per sq dm, the time required to obtain a satisfactory surface varied from 3 to 5 min. Standard potassium bichromate was used to etch the electrolytically polished surfaces. A heavy etch with this solution produced a sharp contrast between the secondary grains and the fine-grained primary structure, darkening the latter while leaving the large secondary grains bright. All area measurements of the secondary crystals were made with a planimeter on enlarged tracings of the grains.

Jan 1, 1953

By A. Heim, M. Gondouin

Invasion experiments were run on Berea sandstone cores to get laboratory measurements of resistivity and saturation profiles characteristic of water and oil sands invaded by mud filtrate. Injection rates were as low as 1.13 cm/D, and the cores were 30 to 36 in. long, cut parallel to the bedding planes. In the water-sand case, the resistivity profiles revealed the existence of an extensive transition zone between flushed and uncontaminated zones. In the linear geometry of the experiment, the width of the transition zone increased as the square root of the injected fluid volume. For the oil-sand case the core was prepared by displacing the formation water with kerosene to minimum water saturation. During the subsequent invasion experiment. oil saturation was measured directly by means of an oil-soluble radioactive tracer, and resistivity profiles along the core were taken at the same time. These data were interpreted in terms of an oil-water front, followed by a formation water bank, a zone of mixed waters, and finally, invaded mud filtrate near the borehole. Micro-fingering and capillarity seemed to affect considerably the resistivity profiles observed in the invaded oil-sand experiment. Beyond the regular conductive annulus or "low zone", it was found that a resistive "anti-annulus" could also be formed. As a result of these experiments, some simplified invasion profiles have been accepted and are being used in Grand Slam* interpretations. INTRODUCTION The importance of the mud filtrate-invaded zone in interpreting electrical logs has long been recognized.',* In trying to account for its effect, only very simple models of the resistivity profiles in the radial direction from the borehole have been used. In fact, most log interpretation charts have been based on resistivity models consisiting of two media of uniform resistivity (R, and R,) abruptly separated at the diameter of invasion. Such a clean separation of the media of different resistivities seems unrealistic, since flushing may not be perfect and may vary with radial distance into the formation.3** The nature of the transition zone, when it is within the radius of investigation of the surveying devices, may affect the log readings. Campbell and Martin' verified that a conductive annulus containing a high percentage of formation water may be formed when mud filtrate invades an oil-bearing sand. Interpretations which are to include the effect of such an annulus require the addition to the model of a conductive zone located at the outer rim of the invaded zone.' Using the Buckley-Leverett relations,6 aturation profiles may be derived, from which resistivity profiles can be calculated. Results of such computations by K. S. Kunz and J. H. Moran were given in a paper by Dumanoir. Tixier and Martin,7 and led to the construction of log interpretation charts which were based on a representation with three media of resistivities R, R0 and R1. Fig. 1 shows a schematic representation of a resistivity profile which includes an annulus. Campbell and Martin realized that, during the invasion of an oil sand, both capillarity and mixing would contribute to rounding of the profile shown in Fig. 1. Capillarity tends to draw some of the formation water from the annulus into the uncontaminated (Rt) zone, whereas mixing of the mud filtrate with formation water of the

Jan 1, 1965

By H. S. Price, D. A. T. Donohue

The system of equations describing displacement of a hydrocarbon liquid by a hydrocarbon vapor in a porous medium where mass transfer takes place between the phases is solved numerically for a variety of gas injection processes. Even though the method of solution is quite general, only systems with three hydrocarbon components are considered. Computer simulations of displacement processes wherein mass transfer between phases is both considered and neglected are compared, and it is shown that neglecting mass transfer can give pessimistic displacement efficiencies. INTRODUCTION The role of the gas displacement process in the recovery of petroleum has been subjected to a series of detailed analyses; as a result, a number of predictive models have been published in the literature. However, because of major simplifying assumptions, most of these models do not completely represent the physical system. As a result, the effect of making the simplifying assumptions is unknown. Therefore, a complete representation of this process — one without major simplifying assumptions —should lead to a fuller understanding of the process, and perhaps to methods of improving it. The general method of developing a model for two-phase fluid flow in a porous medium is to solve simultaneously the continuity equation, the energy equations and the equation-of-state for each phase under the prescribed initial and boundary conditions. For an isothermal system, the energy equations reduce to the momentum equation. Darcy's law. However, since natural gas is the vapor state of the reservoir liquid, interphase mass transfer may take place with concomitant changes in both the intensive and extensive thermodynamic properties of each phase. It is this phenomenon that has often been omitted in previous mathematical models. An additional relation, then, which accounts for mass transfer between the phases, must be included with the other equations to specify a complete model. Completely formulating the equations to be solved is not a difficult task1 but obtaining their solution has been intractable up to now. Availability of large-memory, high-speed digital computers now makes an attack on this formidable problem possible. This paper presents a preliminary study of the problem. Since this investigation is intended to be exploratory, it is restricted to the linear, horizontal, isothermal, two-phase viscous flow of oil and gas in an oil reservoir. In the early development of predictive models of this process, the reservoir system was considered as a unit and various forms of the material balance equation were proposed.2-4 Pressure and saturation gradients were then added in the Buckley-Leverett model.5 The Buckley-Leverett formulation considered the fluids to be incompressible; thus, the mathematical model reduces to a steady-state system. In the 1950's, studies incorporating numerical techniques were being published.6-9 These mathematical models differed in the efficiency of finite difference techniques, the inclusion or exclusion of capillarity or the number of space dimensions considered. To solve these nonlinear, partial differential equations, each phase was considered to be homogeneous with time; therefore, mass transfer between phases was neglected. The effect of mass transfer on the gas displacement process was first reported by Attra. 10 He simulated the one-dimension flow system by a series of cells in each of which the fluids were equilibrated during a time step. In addition, the pressure throughout the system during each time step was predetermined and constant-phase velocities were calculated according to the Buckley-Leverett incompressible fluid flow model. Welge et al.11 developed a model for the displacement of oil by an enriched gas where composition is considered to be a dependent variable. Fluid

By George H. K. Schenck, Peter G. Donald

There is an accelerating acceptance of change by management of cement companies. Diversity of response is noticeable in efforts across the country to reverse the downward trend in profits that brought margins in 1966 to the lowest point in 20 years. New concepts are emerging among managers as they seek to increase the efficiency in use of the basic corporate resources of men, capital and technology. The shift towards computerized control of cement manufacturing is making new gains as is diversification of cement companies into allied fields such as production and sale of natural and light- weight aggregates, crushed stone and concrete products. Increased interest in special products such as white cement and further moves overseas are also significant. Perhaps the most dramatic event of recent years occurred in Washington at hearings before the Federal Trade Commission where cement producers split on whether there should be FTC guidelines that would prevent ownership of ready-mixed concrete producers by cement companies.

Jan 4, 1967

By Frederic L. Kadey

Diatomite is a siliceous, sedimentary rock consisting principally of the fossilized skeletal remains of the diatom, a unicellular aquatic plant related to the algae. Thus, it has-been formed by the induration of diatomaceous ooze, and consists mainly of diatomaceous silica, a form or variety of opal which is first formed in the cell walls of the living diatom. Diatomaceous silica is not generally regarded as a synonym or the equivalent for diatomite, although it has been so used at various times. Accurately, diatomaceous silica is the preferred name for the principal mineral component of which the rock, diatomite, is composed. The terms diatomaceous earth and kieselguhr are used as synonymous with diatomite. The designations tripoli, tripolite, infusorial earth, etc., were used at one time but are now obsolete. With the changing nomenclature, these terms that were at one time correct when proposed and used for generations would be considered incorrect if used today in the light of current knowledge. The designation diatomite is reserved for those accumulations of diatomaceous silica that are of sufficient quality, size, and minability to be considered of potential commercial value. Processed diatomite possesses an unusual particulate structure and chemical stability that lends itself to applications not filled by any other form of silica. Foremost among these applications is its use as a filter aid, which accounts for over half of its current consumption. Its unique diatom structure, low bulk density, high absorptive capacity, high surface area, and relatively low abrasion are attributes responsible for its utility as a functional filler and as an extender in paint, paper, rubber, and in plastics; and as an anti-caking agent; thermal insulating material; catalyst carrier; and chromatographic support; polish, abrasive, and pesticide extender to name a few representative applications. The United States is the principal producing country, although diatomite is found in numerous other locations.

Jan 1, 1975

By W. C. Hauber

Techniques previously published to predict the production performance of a water flood when the mobility ratio is not unity have been primarily restricted to a five-spot well pattern. When other types of well patterns are considered, the prediction of performance has required either a model study or a complex numerical solution of a multiple-fluid system with a high-speed digital computer. Simple methods are developed in this report for predicting the areal sweep efficiency and injectivity history of a water flood for arbitrary well patterns and mobility ratios. The effect of an initial gas saturation can be incorporated into this method of prediction. With the layer superposition concepts published by Prats, et al.,1 these methods can be used to predict the production performance of a water flood in a reservoir having a wide range in permeability. A reasonably good agreement is shown by comparisons of the results calculated by this method with those obtained either by model studies or by complex numerical solution of multiple-fluid systems. Therefore, it has been concluded that a reasonably accurate method has been developed for predicting the production performance of a water flood employing an arbitrary type of well pattern for any given mobility ratio. A medium-speed digital computer can be used in applying this method. INTRODUCTION Production performance of multi-fluid five-spot water floods can be predicted by the techniques published by Prats, et al.1 This technique takes into account the effects of initial gas saturation, mobility ratio and vertical variations in horizontal permeability. A basic assumption in applying this technique is that unit displacement efficiency does not vary with time after the passage of the flood front. Prats, et al. demonstrated that this assumption is valid for normal waterflood applications with small mobility ratios. To extend Prats' technique to other types of well patterns has required either an experimental model study or a numerical solution of a multiple-fluid system to describe the performance of an individual homogeneous layer. Sheldon and Dougherty2 presented an exact numerical solution employing any arbitrary well pattern. This technique is complex to apply, requiring (1) numerical solution of the single-fluid system, (2) conformal mapping of the streamlines and iso-potential lines to form a new grid network, and (3) a numerical solution of the multi-fluid system on the new grid network. A method was developed in this paper to approximate areal sweep efficiency and injectivity as functions of time for an individual homogeneous layer for arbitrary well patterns and mobility ratios. Analytic expressions were derived to directly apply this method to five-spot and direct line drive well patterns. For other types of well patterns, this method is similar to the approach of Higgids and Leighton,6 in that it utilizes the stream tubes and iso-potential lines obtained by the solution of differential equations when the mobility ratio is unity. However, this method is easier to apply than the Higgins-Leighton method since it does not require knowledge of the variation between oil and water relative permeabilities and saturation. Using the relationship between areal sweep efficiency, injectivity and the volume of water injected into an individual homogeneous layer as obtained by the method presented in this paper, and Prats' technique for the superposition of individual layers, one can predict the production performance of any water flood. ASSUMPTIONS GENERAL Basic assumptions made in this report are that fluids are incompressible and the layers are horizontal, homogeneous and uniformly thick. It is assumed that as water is injected into the layer, three distinct regions are formed —a water bank, an oil bank, and an unflooded region. Each region is assumed to displace other regions in a pis-tonlike manner, with only one fluid flowing in each region, so that there is no change in unit displacement efficiency with time after the flood front has passed in the reservoir. Therefore, the residual oil saturation in the water bank and the oil saturations in the unflooded region are constant throughout the layer. The ratio (F) of the bulk volume of a layer occupied by the oil and water banks at any time before oil breakthrough, to the corresponding bulk volume of a layer occupied by the water bank, is given' by the equation BREAKTHROUGH AREAL SWEEP EFFICIENCY To predict the behavior of any type of waterflood pattern, one must know the breakthrough areal sweep efficiency Eb(Mc,o, F) for the pattern for any water:oil mo-

Jan 1, 1965

By Worthen Bradley, R. G. Hall

THIS paper will attempt to show how a metallurgical problem at one California quicksilver mine was solved, and how the solution was applied successfully at another mine. The pronouns "we" and "our," as used below, refer to the Bradley Mining Co. of San Francisco. The term "concurrent firing" for the purpose of this paper can be defined as feeding and firing a rotary kiln at the same end-that is, of course, the upper end. This is as opposed to "counter-current firing," the orthodox method, in which a kiln is fed at the upper and fired at the lower end. The terms "quicksilver" and "mercury" are used interchangeably. EARLY REFERENCES The earliest work on nonferrous metallurgy, we believe, was The Pirotechnia of Vannocio Biringuccio,1 its first edition having been printed in Italy in 1540. Quoting from its chapter entitled "Concerning Quicksilver and Its Ore": Quicksilver . . . is one of the gods and has divine strength in itself, and also, to the annoyance of the alchemists, it is winged. Hence, when it sees that it is in gravest danger, it loosens itself from . . . every bond . . . and flies away into the heavens, escaping from the hands of those who crucify it. Almost laughing, it leaves all its adversaries mocked and scorned, with their phials and filters empty . . . How thorough a job, under certain conditions, it can do of mocking its adversaries and leaving their phials and filters empty, was found out four centuries later at the Sulphur Bank mine, on the east shore of Clear Lake, in Lake County, California. The other mine mentioned in the title is the Reed, in Yolo County, California, 35 miles by road southeast of Sulphur Bank. Reed and Sulphur Bank ranked respectively fifth and seventh in U. S. production in 1943. The earliest direct reference we can find to furnacing troubles at these mines was by Thomas Egleston in 1890.2 Speaking of Sulphur Bank, Egleston says: Sometimes there is more sulphur than cinnabar in the ore, which is a detriment to both . . . making the sulphur impure, and rendering the cinnabar difficult to work on account of the soot. In some of the early . . . furnaces the accumulation of soot from the excess of sulphur has been known to penetrate as far as the fan blower at the end of the . . . condensers, and completely prevent its revolution. In order to get rid of the inconvenience of this accumulation . . . , as well as to get a commercial value from the sulphur, it (the sulphur) is now separated by steam and sold. It is claimed that the sulphur alone pays all the expenses of . . . the mine. The mine was first worked for sulphur, and the cinnabar it contained was considered to be an inconvenience, and was carefully picked out and thrown away. as its richness and value were not

Jan 1, 1945

By J. G. McCullough

The paper is a general description of the U.S. lead and zinc industries as they are now compared to ten years ago and the effect of recent world-wide developments. Topics of interest concerning lead are the present and potential growth of the lead-acid battery business, the potential hazards of having one outlet for a major proportion of production, the expanding U.S. secondary lead production, the hardships of stringent hygiene and environmental regulations and the future supply and demand outlook. The present poor condition of the U.S. zinc industry caused by an oversupply of zinc metal - mostly in Europe - is discussed and also the shifting markets influenced by the automotive programs to reduce the weight of cars and the continuing high mine production due to the mixture of metals contained in the massive sulphide deposits which contain a major portion of the zinc metal reserves. This is all tempered by technical advances in die casting and the emphasis on the protecting of steel with zinc to prolong its useful life. New U.S. mine and smelter production facilities will be restrained due to lower cost foreign zinc from better grade ore deposits and the insistence by Governments for refining capacity to be constructed in the country that the ore is mined.

Jan 1, 1977

Jan 1, 1968

By G. K. Burgess

THE question of the allotropy of iron, in spite of a vast amount of experimental work and perhaps an even greater amount of theorizing, is not yet settled. That there is a definite transformation in iron near 900,° the A3 point, is generally recognized, as well as the fact that the temperature of this transformation is lowered by the addition of carbon and metallic elements. On heating, the transformation Ac3 is always found at a higher temperature than the transformation on cooling, Ar3. Whether the A3 transformation is sharp like the melting point of a pure substance, or extends over a considerable range of temperatures, embracing perhaps as a lower limit the A2 change, appears to be still an open question for pure iron. The nature and identity of the A2 transformation, it would appear from recent publications, has not yet been satisfactorily settled. In the present paper a critical, historical summary is given of the experimental investigations of the location of A2 and A.3 in pure iron, together with brief mention of some of the theoretical aspects of the subject, and an account is given of a series ?of experiments carried out with several samples of very pure iron which were studied by two methods of thermal analysis in the range from 5000 C. to 1,000° C., and which it is believed furnish a contribution of considerable interest as to the location and nature of the A3 and A2 transformations. Great attention has been given to the details of experimental manipulation and to the preparation of the samples, as it was soon found that some of the discrepancies noted in the work of many experimenters may be traced largely to lack of precautions which we have found essential. For example, to anticipate somewhat, it is necessary to provide a suitable practically gas-free furnace, the heating and cooling of which may be regulated to a nicety. To render a minimum the deforming effects on the cooling and heating curves of the poor conduction of the sample, it must be of a form and mass to pass on its heat rapidly and completely to the thermocouple; and finally the sample itself must be freed from gases which, if present, further mask the definiteness of the heating and cooling curves. We, have also varied within wide limits the several factors which may influence the determination of the exact location and shape of the transformation ranges, especially the mass and preparation of sample, rate of heating and cooling, design of furnace; and finally, as nearly as it is experimentally possible, we have worked with a substance approaching pure iron, free from occluded gases and other impurities, and contained within a vacuum.

Jan 10, 1913

By M. A. Dayananda, R. E. Grace

Vapor-solid diffusion couples were employed in a study of ternary diffusion in the single-phase copper-rich corner of the Cu-Zn-Mn system Interdiffusion coefficients were measured at three different compositions corresponding to the intersections of diffusion paths determined at 850°C. Intrinsic diffusion coefficients were determined at two compositions by the Philibert-Guy method. New relations between the various intrinsic diffusion coefficients are also presented. MOST of the investigations of ternary diffusion have been made with "sandwich" couples formed by welding together two homogeneous solid solutions with or without markers placed at the interface. With such couples Kirkaldy and his coworkers1,2 have determined interdiffusion coefficients which describe ternary diffusion in the substitutional alloy systems, Cu-Mn-A1 and Zn-Cu-Al. Guy and Leroy3 have reported intrinsic diffusion coefficients for Co-Ni-Cr alloys as a function of composition using the analysis of Philibert and Guy.4 The use of semi-infinite diffusion couples, for example, vapor-solid couples, where the diffusing species are supplied from a vapor source in contact with a diffusion disk, has so far been confined to studies of binary diffusion. Balluffi et a1.5,6 have successfully determined the interdiffusion as well as the intrinsic diffusion coefficients in several binary metallic systems employing vapor-solid couples with markers initially placed at the vapor-solid interface. They have also discussed the general advantages and limitations of such couples. Vapor-solid diffusion couples can successfully be employed in ternary diffusion studies. The importance of such couples in ternary diffusion lies in the fact that inert markers lie close to the vapor-solid interface, and the composition of the marker plane is virtually known before experimentation begins. Another minor advantage is that the method of Philibert and Guy4 may be used with three alloys instead of four. Lastly, the diffusion paths need not be S-shaped, as pointed out by Meijering7 for "sandwich" couples. The Cu-Zn-Mn system is convenient for ternary diffusion studies because of the large single-phase field in the copper-rich corner. The vapor pressure of zinc above such alloys is known, and X-ray measurements indicate that the molar volume is nearly constant over a wide range of compositions.8,9 It is the purpose of this paper a) to extend the analysis of Balluffi and seigle5 to permit an evaluation of interdiffusion coefficients in ternary vapor-solid couples, b) to use the method of Philibert and Guy to determine intrinsic diffusion coefficients with such couples, and c) to present experimental data on both interdiffusion and intrinsic diffusion coefficients for the Cu-Zn-Mn system at 850°C. INTERDIFFUSION IN TERNARY VAPOR-SOLID COUPLES The analysis of Balluffi and seigle5 is extended in this section to a vapor-solid couple where two solutes diffuse from a vapor source into a ternary solid solution. To take into account the expansion of the diffusion disk caused by the absorption of mass from the vapor phase, the total fluxes are expressed on the basis of a coordinate system that moves with the velocity of the vapor-solid interface; thus. where D3ij are the intrinsic diffusion coefficients,4 v(x, t) is the local Kirkendall velocity of mass flow, and F(t) is the negative velocity of the vapor-solid interface (x = 0). Both these velocities are based on a fixed coordinate system far removed from the diffusion zone. Using the continuity relations and Darken's method1' for a ternary system in which components 1 and 2 diffuse from the vapor phase into a solid of negligible vapor pressure, one obtains

Jan 1, 1965

By Frank L. Gaddy

Falls of roof account for over 50% of the fatalities that occur in coal mines in the U.S. Thus, roof control is one of the more important phases of underground mining. In reality, the control of roof influences the system of mining and is a major determinant of the width and spacing of working places, operations at the mining face, ventilation control, and surface subsidence. Frequently, the control of roof is the largest single cost item. Roof control is a never-ending task, not only at the working face and throughout sections where men are working, but along haulways and airways that must be maintained for the life of the mine. This is because roof, even the best of roof, slowly deteriorates, so it must be frequently examined, with corrective support applied when needed. As coal is excavated, stresses are set up in the roof became the previous equilibrium is upset, resulting in pressures that cause fractures and slight, movements that are, frequently, hard to detect. Unless the immediate roof, in the excavated area, is given support by artificial means, it might fall or there might be a succession of falls, varying from a thin scale to several feet, depending on the nature of the top. Exceptions to this are those rare mines, or sections of mines, with hard, strong, nonweathering roof that requires no support. GENERAL CLASSIFICATION OF ROOF There are two broad types of roof as far as support is concerned, the immediate roof above the coal and the main roof. Artificial support for mining purposes is only concerned with the immediate roof as nothing except large blocks of solid coal, or massive concrete, will support the main roof. The immediate roof is generally a few feet thick but can vary from inches to 20 ft or more. There are examples of where there is no immediate roof as the massive main roof lies directly on the coal bed, but this is rare. Impossibility of supporting the main roof and all of the cover

Jan 1, 1973

By D. I. Bardos, Paul A. Beck

The 1100°c isothermal, sections of the V-Fe-Si, V-Co-Si, and V-Ni-Si systems were studied at silicon contents between 0 and 40 at. pct. The single-phase fields in the 30 and 50 at. pct Mn sections of the 1100°C tetrahedron of the V-'Wn-Fe-Si system were also determined. The direction of extension of the elongated O, R, D, and a-Mn Phase fields suggests that the stability of these phases is determined largely by the electron concentration. The peculiar shape of the above ternary a phase fields, as well as of the a phase fields in the V-;Mn-Si and Cr-MTZ-Si systems is accounted for on the assumption that in manganese-(iron-, coball-, nickel-) rich alloys silicon atoms do not exclude d electrons , while in alloys low in the above components they do. This assumption also leads to the expected electronconcentrations for q and ß-Mn phases formed by transition metals with aluminurn. In earlier work it was shown that in ternary alloy systems of transition elements the a a and certain other phases with complex structure, such as the p and R phases,3 form elongated phase fields extending in a direction corresponding to a constant electron concentration. Recently similar behavior was observed in manganese-rich ternary ß-Mn solid solutions with another transition element and with silicon, germanium, or tin,4 confirming earlier indications3 that ß-Mn is also an electron phase. The alloying behavior of silicon in these manganese-rich alloys sug- gested that the four outside electrons of silicon participate in the bonding and that the predominantly d-like bonding electrons are not excluded from the silicon sites. Presumably, some of the normally unoccupied 3d states associated with the silicon atoms are in these alloys lowered to the Fermi level;4 thus silicon behaves as if it, too, were a transition element. The manganese-rich boundary of the a phase in the V-Mn-Si system,4 as well as in the Cr-Mn-Si sys-tem,4,5 extends approximately parallel to the ß-Mn phase boundary, corresponding to the transition ele-mentlike behavior of silicon described above. However, at lower manganese contents (i.e., in the high-vanadium or -chromium region) the a phase field in both ternary systems mentioned extends in a direction roughly perpendicular to that of its manganese-rich boundary, a phenomenon that is apparently inconsistent with the behavior of silicon in the manganese-rich alloys. A similar, although somewhat less pronounced, extension of the a phase occurs also in the high-vanadium (low-iron) region of the V-Fe-Si system at 1175C, but reportedly not in the V-Co-Si or V-Ni-Si systems at the same temperature.5 The present work was undertaken to investigate in more detail the extension of the a phase (as well as of other electron phases that may be present) in the last three systems and to elucidate this phenomenon, which has not been satisfactorily explained previously. EXPERIMENTAL PROCEDURES Most of the alloys were melted in an arc furnace, using a water-cooled copper crucible under helium atmosphere. The transition metals were of better than 99.9 pct purity and the silicon used was 99.98 pct pure. Alloys containing less than 20 pct V were induction-melted in recrystallized alumina crucibles under argon atmosphere.

Jan 1, 1967