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By Douglas W. Fuerstenau, Kalanadh V. S. Sastry

A mathematical model is developed for flotation in a countercur-rent column where continuously generated air bubbles rise through a downward flowing pulp. The model is based on the assumption of axially dispressed plug flow of both the liquid and air-bubble phases. An appropriate flotation-rate expression, which takes into account the changing concentration of solid particles on the bubble surface, is formulated and applied to the column flotation process. Although a complete solution of the resulting equations is not possible for the general case, solutions for specific limiting cases have been obtained. From these, it is possible to predict theoretically the dependence of the column performance on certain variables. Specifically, concentration profiles as a function of height in the column have been calculated for various values of the characteristic dimensionless parameters. The effect of axial dispersion on the perforance of the equipment is pointed out. In recent years, there has been considerable progress in delineating the fundamental physicochemical principles underlying the unit operation of flotation and in advancing methods for kinetic analysis and process modeling of flotation.' In general, nearly all such process research has been concerned with the analysis of conventional flotation equipment and circuits. From these investigations, the possibility of developing and designing flotation apparatus for more efficient separation appears limited with conventional equipment. How- ever, recently there has been an attempt to apply coun-tercurrent flow techniques to flotation in the context of a flotation column.- some of the results from pilot-plant studies2 indicate possibilities for success of this process at least in obtaining higher-grade concentrates though not higher recoveries. A flotation column operates on countercurrent principle in which bubbles continuously generated at the bottom of the column rise through the downward flowing slurry. A schematic diagram of the flotation column is shown in Fig. 1. The physicochemical principles of bubble-mineral attachment, using this flotation column, are essentially the same as those which prevail in conventional equipment, the only differences being in the flow patterns of the various phases. The salient operating feature of the column as compared to those of a conventional cell is that neither mechanical nor turbulent pneumatic agitation is employed. The column is

Jan 1, 1971

By A. A. Rauth

In this paper, the author derives a series of formulas from basic principles and illustrates the application of these formulas to practical grinding charge problems. The paper establishes the nearly proportional relationship of mill power to charge level and shows how this relationship can be used to advantage in the design, manufacture and operation of grinding mills. The procedures outlined offer a rapid means of anticipating the power requirements for a given charge or determining makeup charges for a given power reading. The theories which have been developed concerning the dynamics of grinding have been motivated largely by the desire to derive workable formulas for the accurate determination of grinding mill power. This accurate determination has always been handicapped by the large number of variables to be considered, some of which are mill diameter, length, speed, liner design, grinding charge and material density, volumetric mill loading, internal friction, and charge size and gradation. In efforts to determine mill power, attempts have been made to utilize torque concepts. The formulas derived consider the grinding mass as a rigid body and utilize factors that are based on empirical data so that the movement of the charge within the mill is compensated for. These formulas are of principal interest to the mill designer since he is charged with the responsibility of analyzing all of the variables and from them predicting a mill size and a motor size which are compatible both with each other and with the grinding job for which they were intended. The mill operator, on the other hand, has an entirely different problem. The mill dimensions are already established and so is the driving motor. The operator's main concern is to obtain maximum performance from the mill he already has. For him, the many variables which perplex the mill designer are fixed values. Mill diameter, length and speed are set and, to a large extent, so are the conditions inside the mill from which the torque formula advocates derive their empirical data. It is conceivable that if the major mill dimensions which affect power demand are held constant, and if the variables influencing empirical factors are held fairly constant, as they are in an operating mill, then the only major variable remaining which affects power is the level of the charge itself. Under this condition.

Jan 1, 1970

By S. Usui, I. Iwasaki

The adsorption mechanism of dodecylammonium acetate (DAA) on mercury in potassium fluoride solutions at natural, near neutral pH was investigated. Difler-ential capacity combined with electrocapillary measurements on a dropping mercury electrode were found to provide a sensitive and reliable approach. A shift in the electro capillary maximum (or the point-of-zero-charge) towards positive polarization of the surface due to the adsorption of amine indicated a specific affinity of dodecylammonium ion for mercury surfaces. The amine was shown to adsorb competitively with potassium ion on mercury. Through correlation of the adsorption density of the amine, calculated from the thermodynamic analyses of the electrocapillary curves, and of the diflerential capacity curves, the adsorbed state and the orientation of the amine at the interface were considered. The similarities and the differences in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide were evaluated. With the promise of flotation providing a cheap and large-scale process for the upgrading of low-grade ores and magnetic concentrates, the iron ore industry has made a sustained search over the years for a flotation reagent of general applicability and high selectivity. Having shelves full of commercial reagents already on hand and anticipating more, both the users and the suppliers are in need of an experimental approach sensitive enough to differentiate the individual characteristics in each group of reagents. Therefore, the adsorption behavior of various flotation reagents on mineral surfaces from aqueous solutions has been a subject of much investigation. The current view of adsorption based on the electrical double-layer theory is formulated on the assumption that certain ions in solution act as potential-determining ions. Their concentrations fix the potential drop across the double layer and their adsorptions govern the surface charge.' Two methods used to study the adsorption

Jan 1, 1971

By G. B. Craig, B. Ramaswami

The temperature and strain rate dependence of the flow stress ratio and the stvain rate dependence qi the flow stress of annealed polycrystalline a zirconiur were determined over the temperature range 30 0" to 1000°K. Some evidence was found for strain aging and discontinuous flow in the temperature ranges 520" to 650°Kand650" to 760°K, respectively. The Cottvell-Stokes relationship was obtained when deformation occurred by twinning as well as slip. The flow stress ratio showed a strong dependence on temperature and strain rate above 800°K. The expevirnental evidence indicated that the rate-controllitzg mechanism for the deformation of a zirconium above 800°K was dislocation climb, and that the deformation was not thermally activated in the range 520" to 800°K. The stacking-fault energy of a zirconium was estimated to be about 250 ergs per sq cm. A knowledge of the temperature and strain rate dependence of the applied stress necessary to deform a crystalline solid is essential for understanding the thermally activated processes occurring during deformation.' Several experimental techniques have been developed for studying these processes.273 One of the techniques is the deter mi nation of the strain rate dependence of the flow stress at constant temperature. In close-packed crystals, it has often been observed that the change in stress due to a change in the strain rate varies linearly with the flow stress, (~1,' This relationship, known as the Cottre ll-Stokes law, is obeyed when deformation occurs by glide alone. However, when deformation occurs by twinning as well as glide, there is disagreement among different investigators on whether the Cottrell-Stokes law is observed. Whereas Thornton et ~1.~find departures from Cottrell-Stokes law when twinning occurs in copper, ~avis~ and sasinski? find that Cottrell-Stokes law is obeyed when deformation occurs by twinning as well as slip in cadmium and magnesium, respectively. One of the main objectives of this study is to determine whether the Cottrell-Stokes law is obeyed when deformation occurs by twinning as well as slip. The second technique that has been used extensively to study the thermally activated deformation of crystals is the determination of the ratio of the flow stresses, at identical dislocation structures and con-

Jan 1, 1968

By E. C. Tveter, R. B. Tippin

The separation of minerals by heavy liquids is a standard laboratory technique which goes back at least 50 years, but commercially economic application of this principal to ore concenfration has been prevented by problems of liquid recovery. Recent investigations which demonstrate the different types of liquid-solid systems on various ores using the two major heavy liquids - methylene bromide and tetra-bromoelhane — are discussed in this article. As a result of these studies, over-all liquid recovery, and especially desorption of heavy liquid from the mineral surface, was improved by the use of surfactants as well as both thermal and mechanical energy. The examples given in the article indicate that heavy liquids which should find major commercial use in ore concentration are now available. The sink-float process using a heavy liquid medium has long been recognized as a nearly perfect method of mineral separation based on the differences in density of the minerals. The use of heavy liquid separation (HLS) offers the potential of an ore dressing method that provides the maximum possible natural concentrate grade and high recovery. In addi- tion the process requires no water, causes no waste disposal problems, and is extremely simple — the crushed ore is merely introduced into a liquid whose density is between that of the minerals to be separated. The minerals lighter than the liquid float while those heavier than the liquid sink. As such, HLS has become a standard laboratory tool but major commercial application has been prevented by the requirement for complete recovery of the heavy liquid, imposed by economics and materials handling hazards. Investigations, both in the United States and abroad, have shown that improved liquid stability as well as improved chemical engineering techniques brighten the future for HLS in ore dressing. The available commercial heavy liquids suitable for mineral separation cost from $2.00 to $20.00 per gallon1 and on this basis alone their complete recovery is economically desirable. Possibly of even greater importance is the fact that any residual heavy liquid remaining on the products could create a serious toxicity hazard. Consequently, to make the process commercially attractive requires (1) essentially complete removal of the liquid from the ore products and (2) optimum recovery of the liquid for reuse. Until recently these two stipulations have remained as obstacles but laboratory and pilot plant research now in progress suggests that these may soon be overcome. Various heavy liquid recovery systems have been proposed to meet these requirements and might be classified into one or more of the following three general classes: Solvent Wash (Fig. 1): The dissolution of the heavy liquid from the ore with a less expensive solvent,

Jan 1, 1969

By M. C. Flemings, F. R. Mollard

Conditions necessary for plane front growth of two-piwse solids from a single-phase melt are discussed. Alloys consideved are those from a simple binary system containing a eutectic, but are not, in general, of eutectic cornposition. It is concluded that: 1) plane front solzdification is favored by low growth rate, steep thermal gradient, and essential absence of convection; and 2) for steady-state solidification, the structure should resemble that of directionally solidified eutectics (lamellar, rodlike). Factors affecting THERE are many materials, including metals, available today with strengths in excess of 10' psi when in whisker or fiber form. The challenge facing those interested in practical application of such materials has been, and remains, the economic production and incorporation of the whiskers or fibers into useful engineering composites. solute redistribution along the growth direction are described quantitatively, by numerical solution of the diffusion equation. Effects of variations in growtlz rate on average composition of the solidifying composite are significant. For alloys not too close to a single-phase region, the initial transient at constant gvowth velocity is the order of D/R where D is diffusion coefficient in the liquid and R is interface velocity. Composites consisting of the reinforcing phase within a metallic matrix have excited particular interest in recent years because of their potential for high strength at elevated temperature and for resistance to brittle fracture. Techniques employed to incorporate the whiskers or fibers in the metallic phase have included 1) liquid metal infiltration, 2) solid or liquid phase sintering, and 3) direct growth of composites from the melt, of rodlike or lamellar morphology, by directional solidification of eutectic alloys. Two recent books"2 have reviewed the status of this growing field. Concerning the last method, growth of eutectics, it has been shown that the reinforcing phase (e.g., rods)

Jan 1, 1968

By Alden Greninger

METALLURGISTS have long believed that martensite in steel forms as plates along the octahedral {111} planes of austenite. Much has been written about mechanisms whereby units of the austenite lattice are pictured as transforming to martensite by shearing movements initiated along the octahedral planes of austenite, supposedly resulting in plates of martensite lying parallel to these planes of shear. A critical inspection of two or three photomicrographs of quenched hypereutectoid steel led us to the conclusion that the orientation habit of martensite, at least in hypereutectoid austenite, could not possibly be octahedral. Inasmuch as recent studies30,31 of the martensite-type reaction in nonferrous alloy systems have established the irrational orientation habit as characteristic of this type of lattice transformation, the need for a thorough restudy of the crystallography of martensite formation in steel was evident. The present paper reports the results of such a study, extended to include both cementite and some of the products of constant-temperature decomposition of austenite. Also reported are a few of the results obtained from a microscopic and X-ray study of the austempering process in very high-carbon steel.

Jan 1, 1940

By A. W. Furbank

IN reviewing the aerial cameras produced in different countries, it becomes apparent that in nearly all of them an attempt has been made to secure the greatest possible angle of view. This angle, of course, is determined by the objective. The objectives most commonly in use in aerial cameras have a maximum angle of 65°. The objective developed for this new Zeiss camera combines freedom from distortion and brilliant definition, with an angle of 95°. Aerial mapping, it is claimed, has been placed on a different economic basis, and new possibilities presented, par-ticularly in connection with automatic stereoscopic plotting instruments, to which some short references are made. One way of enlarging the angle of view is to couple several instruments with their axes convergent, thereby producing a multilens camera. Typi-cal of cameras of this sort in the United States is the Bagley four-lens camera, which later was developed into the five-lens camera (T3-A) of the U. S. Air Corps. More recently, in order to get away from the unfavorable Maltese cross image field of the five-lens camera, and to obtain a more practical form, two five-lens cameras were combined. By using them in tandem and rotating them by 45° relatively to each other, a ten-lens camera was produced, covering an octagonal ground area, with a total angle of view of 140°. Similar designs have been evolved in other countries. In all of them, however, a number of difficulties have arisen, quite apart from their large weight and high cost. Because of their complex mechanism, numerous shutters and magazines, and the high precision with which these parts must be interadjusted and synchronized, these cameras are far from dependable. Moreover, a multilens camera by itself does not yet constitute a complete outfit for producing pictures suitable for photogrammetric survey. Because all the component pictures, except the central one, are obliques, it is always necessary to employ rectifying apparatus which transforms the marginal views to the perspective of the central one. In multilens cameras with many individual magazines, it is not convenient to

Jan 1, 1938

By V. E. Elliott, C. L. Meyette

THE conditioning of semifinished steel products such as billets, blooms, and slabs to remove surface defects before further processing to finished products is a necessary accompaniment to steel mill rolling operations. A knowledge of the kinds of defects which occur and of the conditions in melting, teeming, and rolling that may lead to their occurrence is favorable to the production of quality products. Surface defects may be classed as either of mechanical origin such as those that occur in the heating and rolling operations and include breaks, tears, guide marks, mechanical laps and the like, or they may have been in the ingot before heating and rolling. Examples of the latter are ingot cracks, blow-holes, scabs, and inclusions which lead to the numerous known types of seams -and surface flaws. Most of the common types of surface defects and methods for their identification by visual examination or by the aid of macro-etch tests are well known. The conditions which caused their formation are also appreciably understood and this knowledge has been instrumental in the establishment of methods for metallurgical control. There are, however, defects of doubtful origin. In any endeavor to trace the causes for their occurrence, the question of first concern is: I. Whether they were formed in the rolling procedure. 2. Whether they existed in the ingot prior to rolling. In the case of semifinished products which are rerolled to finished products there is also the question of whether they were formed in the primary or in the secondary rolling. In metallurgical laboratories where numerous or routine examinations of the quality of rolled products are made over the course of time, there will doubtless be many puzzling cases of defect origin. Microscopic examination of the defects may, however, reveal a characterizing condition that can be used to classify them broadly with respect to their origin. Such a condition has been observed and, after detailed investigation, is described here with the thought that it may offer a useable and relatively simple solution to a bothersome problem. BASIS FOR CLASSIFYING In this discussion the term "mechanical type defects" will be used to designate those that have occurred as a result of the rolling operations such as in rolling from the ingot to billets, blooms, or slabs or in rerolling to finished products. The term "steel type defects" will he used to designate those that were present in the ingot prior to primary rolling or that were in the semifinished product prior to secondary rolling to finished product. The basis for distinguishing between the two types of defects lies in the relative degree of subscale formation surrounding them. Subscale is defined' as a zone of

Jan 1, 1948

By C. Pin, J. Bruce Wagner

In order to demonstrate the role of defect chemistry in the solid state to a process-metallurgy reaction, laboratory experiments were carried aut to remove copper from liquid lead using lead sulfide which had been doped to provide definite concentrations of cation vacancies. The removal of copper decreases in the order: bismuth- or antimony-doped PbS, undoped PbS or tin-doped PbS, and silver-doped PbS. The data are explained using the simple mass -action law and in terms of the exceedingly rapid interstitial diffusion of coppw in PbS to vacant cation sites. Results are in agree-ment with thermodynamic predictions and certain industrial practices that copper may be removed from lead below the limit of its coexistence with pure Cu,S and pure PbS. The role of defects in solids has been exploited in semiconductors and many device applications, in explaining tarnish formation, dissolution rates, and mechanical properties. The application of these principles to many process-metallurgical problems has not received as much attention. It was the purpose of this study to illustrate the role of defect structures of solids in a process-metallurgical application. When lead is refined, the ore, galena (PbS), is reduced by a series of operations to liquid lead (lead bullion) containing impurities such as copper, bismuth, antimony, arsenic, and silver depending on the original composition, the fluxes added, and the particular type of operation, see Fig. 1. In order to produce a pure lead, a series of refining operations are carried out. A typical lead-bullion analysis before drossing is shown in Table I. Copper is removed first as its presence increases the zinc consumption during the desilverizing process. For preliminary copper removal the lead bullion is brought to a temperature of 440°C in a kettle of 60 metric tons capacity. Some tar (or sawdust or resins) is usually added and the kettle is cooled slowly to 400°C while the liquid is stirred. A solid phase, called a dross, floats on top of the liquid and the particles of the solid phase adhere to the tar. This "hot dross" is collected. It contains mostly lead and copper which are partly oxidized and/or sulfurized if the lead bullion contains some sulfur.*

Jan 1, 1963

By George A. Grandy, D. W. Fuerstenau

Simulation of nonlinear grinding systems is discussed in the context of the size-discretized batch-grinding model. A linear approximation of environment-dependent (or nonlinear) selection functions is postulated for systems which exhibit feed grinding orders less than unity. For this, a convex linear combination of zero and first-order selection function forms is used to obtain an analytical solution that can be used for simulation. An example in which marked nonlinear behavior occurs is rod-mill grinding. Accordingly, a series of grinding experiments was carried out in a batch laboratory rod mill to test these techniques; agreement between experiment and the model was found to be very good. Recently, significant progress has been made in the simulation of linear grinding systems by using a population balance mathematical model. Herbst and Fuer-stenaul presented a parameter estimation scheme that can be used with the size-discretized batch-grinding model, and Gumtz and Fuerstenau3 have extended these techniques to the simulation of locked-cycle grinding. Grandy et aL." summarized the simulation of linear systems and noted important alternate solutions to the batch-grinding equation. Kelsall et a1.'-" discussed the dynamic simulation of linear batch grinding, as well as linear open and closed-circuit grinding. In all of these, the key word is linear, which certainly restricts the engineer trying to simulate a variety of grinding systems. This paper discusses an approach for the simulation of non-linear grinding systems, particularly those which exhibit grinding orders less than unity. Experimentally, dry rod-mill grinding is used to evaluate the technique presented. Batch Grinding Model The size-discretized batch-grinding model has been discussed in detail by Mika et al.'.' and by Herbst and Fuerstenau,' and therefore, will only be briefly developed here. The model is formulated by making a differential mass balance of each size fraction in such a manner that the equation parameters are precisely defined in terms of selection and breakage functions,' which can be either calculated'.' or estimated1 from experimental data. The model is phenomenological because it averages all stress-application events in the system and, therefore, does not distinguish the manner in which individual particles are stressed.' For this average environment, the resistance of all particles in a size fraction to breakage is defined by that size-frac-tion's selection function; and when fracture occurs from an average event, the breakage product size distribution is defined again by that size-fraction's breakage function. The model is deterministic and is derived in terms of a continuous time variable and a discretized size variable,' i.e., the n mass fractions associated with the n defined size intervals (see Table 1 for nomenclature).

Jan 1, 1971

By D. M. Blacknall, N. N. Winogradoff, E. W. Williams

Low-temperature measurements of photolumines-cence were used to evaluate the progvess in materials development. Variation of the impurity type, impurity concentration, and method of growth were used to clarify the chemical origin of defects in GaAs. Melt-g~ozun, epitaxial vapor-, and solution-grown samples were studied. A comparison of measurements at 77" and 20°K shows that more defects can be observed at the lower temperature. Th'vee residual defects were identified in relatively pure GaAs. These were: silicon, copper, and a gallium vacancy-donor complex. Solution growth from a gallium solution inhibits the formation of the latter two. Eleven defects were studied and the "optical" activation energy of some of these, namely, silicon, cobalt, and chromium, has not been reported in the literature before. THE discovery of the injection laser in 1962 prompted extensive measurements of the photoluminescence of GaAs. The measurements were made at 77°K on GaAs doped with shallow impurities at various doping levels and compared with electroluminescence1'2 and absorp- tion data.374 In addition, lower-temperature studies were made on relatively pure GaAS' and on GaAs doped with oxygen,5'" manganese,' and copper.' The observation of defects* in GaAs with photolu- *The word "defects" ~efers to both chemical impurities and native defects. minescence at low temperatures makes photolu mines-cence an invaluable tool in evaluating the progress in materials development. The only previous evaluation was done at 77°K when solution-grown and melt-grown GaAs were compared.O No identification of defects was made but it was shown that some of the deep-level luminescence seen in melt-grown GaAs was absent in solution-grown GaAs. The present work extends the comparison of preparation techniques to lower temperatures and to a study of epitaxial vapor-grown GaAs. It is particularly valuable for thin epitaxial layers since they cannot be analyzed by conventional analytical techniques. In addition, by varying the impurity type and impurity concentration the chemical origin and nature of defects in GaAs was demonstrated. Eleven defects were studied in all. Three of the defects were identified as residual defects which often contaminate GaAs prepared from the melt and the vapor. Only one such defect was observed in GaAs grown from a gallium solution and this was identified as silicon.

Jan 1, 1968

By G. A. Mancini, V. Bharucha, J. W. Spretnak, G. W. Powell

The characteristics of the motion of the a interface during the "down" transformation was studied in zone-refined iron and dilute binary alloys containing nickel and molybdenum by means of the thermionic emission microscope and high speed photography. The frontal movements were found in all cases to be definitely discontinuous with time and an appreciable number of incremental jumps were found to proceed in the reverse direction (a to b). Molybdenum was found to be particularly effective in increasing the frequency of the increments of transformation from the stable to the metastable phase. A knowledge of the mechanism by which alloying elements affect the hardenability of a steel is desirable from both the practical and scientific viewpoints. It is well established that microstructures consisting of tempered martensite and lower bainite exhibit the best performance in terms of toughness and resistance to crack propagation. The presence of some upper transformation products, namely ferrite and pearlite, is in general undesirable. Various researches have indicated that the ferrite matrix grain structure is a very important difference between the upper and lower transformation products, namely equi-axed vs acicular. Any comprehensive theory of the decomposition of austenite should explain the dependency of the morphology of the matrix on undercooling. The contribution of various alloying elements to hardenability has been determined experimentally and catalogued in considerable detail. A rationalization of the basic mechanism or mechanisms by which individual elements affect the kinetics of the decomposition of austenite to products other than the phase "martensite" has not been evolved as yet. Interest in this problem was stimulated by the effects of minute quantities of boron in hardenable steels. This paper deals with one aspect of this problem, namely the characteristics of the ?-a transformation in high-purity iron and in two carbon-free iron binary alloys. A detailed historical account of the scientific developments in the study of the decomposition of austenite would be a prodigious undertaking and will not be attempted here. There are several excellent reviews in the literature on the formation of pearlite, martensitic reactions, and kinetics of solid-state reactions. The thinking on reaction mechanisms has been influenced to a large degree by the "classical" Tammann nucleation and growth model, in which an embryo springs into being by a fluctuation, and grows to a critical size through atom by atom deposition. Such a process is expected, accordingly, to be diffusion controlled. Considerable research attempting to relate the contribution of alloying elements to hardenability on the basis of their effect on the diffusivity of carbon in iron has not been productive from a mechanistic viewpoint. The formation of pearlite and ferrite has been treated in terms of nucleation and growth processes in which presumably the lattice transformation also occurs by a diffusion process. The other prominently considered mechanism is the "martensitic" or cooperative shearing mechanism. It seems generally, but not entirely, agreed that the phase "martensite" forms by this mechanism, and that it is involved to some extent in

Jan 1, 1962

By B. Habermann

Artificially consolidated sand models, representing one-quarter of a five-spot, have been developed and used to study factors aflecting misciblt. displacrmenr. Sweep efficiency at breakthrough, size of the mixing zone between two miscible liquids and per cent area contacted by drive after breakthrough were determined tor the high mobility ratios encountered in actual resvrvoirs. Quantitative relationships between the degree of viscous fingering and mobility ratio were obtained by measuring the length of the fluid interface. Scaled miscible-slug experiments, supported by field evidence reported in the literature, have shown that when the slug is followed by dry gas the process is less efficient than expected. In addition to low areal sweep efficiencies encountered for high mobility ratio displacements, the effectiveness of a miscible slug is greatly reduced. This is caused by an accelerated growth of the mixing zone between the driving and the displacing fluids. INTRODUCTION Considerable interest in miscible displacement as a secondary recovery process has been shown by the oil industry in recent years. In addition to extensive laboratory investigations, numerous field operations have been initiated so that 39 miscible displacement projects had been reported' in the United States by early 1959. By far the most popular approach in these projects is the use of an LPG slug followed by dry gas. Laboratory tests have indicated that with a small miscible slug, amounting to several per cent of the hydrocarbon pore volume, practically 100 per cent recovery of the oil in place can be achieved and that all of the slug material can be recovered by a subsequellt gas drive. However, these experiments were conducted on small-diameter long cores that can be considered as essentially uni-dimensional reservoirs that do not represent actual field conditions. It soon became apparent that the inherently adverse mobility ratios existing in the reservoir cannot be ignored in any miscible displacement field project. When a less viscous fiuid such as an LPG slug drives a more viscous reservoir oil, fingers develop that reduce the areal sweep efficiency. The slze of the miscible slug to be used is a subject of some controversy. It has been proposed that the size of siug needed be calculated by setting lengths of the mixing zone proportional to the square root of the distance traveled. This proposal is based on experimental evidence' and theoretical considerations"' in which fingering was not a factor. A prerequisite for successful application of the miscible displacement process to field operations is a better understanding of the following factors. L What is the effect of mobility ratio on the rate of deterioration of a miscible slug? 2. How large a slug should be used for given reservoir conditions? 3. What is the sweep efficiency? The purpose of this investigation was to provide some additional laboratory data that should help to answer these questions. More specifically, it was intended to study more quantitatively the effect of viscous fiinger-ing, mobility ratio and slug size on the efficiency of this relatively new secondary recovery process by means of experiments on thin, horizontal, porous medium models.

By R. A. Burton, J. T. Hansford, D. A. T. Donohue

Substantial evidence indicates that many petroleum producing horizons contain naturally occurring, ordered fracture systems and that within a particular geologic zone, vertical fractures induced in wellbores often will be directed along a particular compass direction. Both conditions will seriously alter the fluid displacement behavior within reservoirs. In this study the effect of induced fracture orientation and length on sweep efficiency is determined for a five-spot pattern. In general, it is assumed that all wells are fractured and directed along the same compass direction. Using the electrical analog to steady state, two-dimensional fluid flow in porous media, boundary conditions are obtained from which flood fronts are tracked numerically. The numerical computations require a particle tracking routine for approximating flood front histories. It is shown that recovery is sensitive to the length and orientation of fractures for the pattern studied. with the proper design of fracture-pattern systems, recovery can be enhanced considerably. INTRODUCTION Hydraulic fracturing introduced in 1949l gave the industry a rather inexpensive means of increasing the fluid injection or production capacity of wells. It has been used with particular success to increase the production rate of wells completed in tight formations, such as in western pennsylvania2 where producers have fractured in depleted or near-depleted fields and observed economic responses. Once the natural energy declines in such a reservoir where all wells have been fractured, waterflooding is generally suggested as means of further increasing recovery. Of the dual objective sought in waterflooding — high injectivity and high breakthrough sweep efficiency — the former condition can be obtained if all wells in the flood pattern are fractured; the latter condition should depend on the nature of the fracture system. Considerable theoretical work has been published on the nature of fractures induced in boreholes.3-5 Although discussion persists concerning the possibility of forming a horizontal fracture at a given point within the wellbore, it is generally conceded that only vertical fractures will develop below a given depth, i.e., where the fracturing Pressure is less than the overburden load. Given the fact that fractures will be vertical in most cases of interest, it is also important to know whether there is order to fracture orientations within a given geological region. Kehle has suggested that in tectonically relaxed areas of uncomplicated geology, the stresses are fairly uniform and all fractures in the region should be parallel.5 Dunlap arrived at a similar conclusion in a theoretical investigation of localized stress conditions surrounding the borehole.6 He concluded that most vertical fractures are propagated in a preferred azimuthal direction. Fraser and Pettitt, in extending these theoretical suggestions to a specific field case, used an impression packer to record both a vertical fracture and the orientation of this fracture in the wellbore of a well in the Howard Glasscock field, Tex.7 Use of this information enhanced the waterflood recovery of the field. Anderson and Stahl also used impression packers on three fractured wells in the Allegheny field. N. Y.. and found that the fractures were oriented more or less along the same compass direction.8 Orientation of the fractures in this manner depends on the stress condition within the formation during fracturing. Elkins and Skov have demonstrated that a natural, oriented, vertical fracture system exists within the Spraberry field? Heck suggests

Jan 1, 1969

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

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

Jan 1, 1957

By Waynw P. Myers

Electricity, as normally thought of by a layman's definition, is a man- made force that has no color, no odor, is not visible, cannot be heard, yet man can control it and make it perform his work for him. A person dare not cheat on it, for it then will master him. It has laws, rules, and regulations that must be strictly adhered to if it is to perform in the safest, most reliable, and economical manner. In the early days of coal mining the power source was man himself. Later man employed steam and compressed air to reduce his muscle power requirements needed in the extraction of coal. By the turn of the 20th century, electricity had become the most common source of power for the coal industry. Steam and compressed air are still found in use in isolated cases today for specific applications; however, they are rapidly being replaced by electricity. Electrical laws and regulations are quite extensive and somewhat complex for the proper generation and use of electricity. Man-made laws, rules, and regulations for the care and handling of electricity, designed for man's safety, are rigidly enforced by Mine Safety and Health Ad- ministration (MSHA), as well as the various state departments of mines. BACKGROUND Until recent years most underground coal mines used direct current exclusively for all movable and for some stationary equipment. Exceptions were for permanent pumps, tipple, fan, and outside buildings where alternating current was normally employed. However, over 60 years ago there were mines with dual systems. Alternating current was used for cutting machines, drills, and pumps ; direct current for locomotives. There were no other machines as these were hand-loading mines. Later, during early mechanization in the 1920s, alternating current was also applied to loading machines at some mines. Use of dual electric systems then declined until fairly recently when

Jan 1, 1981

By Michael H. Kuryla, Galen H. Clevenger

Some years after Nobel made his epoch-making contribution to the knowledge of high explosives, Sprengell described a new class of detonating explosives consisting of mixtures, made immediately before use, of an oxidizing agent and a combustible substance.2 The novel feature of the Sprengel explosives is that the constituents alone are non-explosive during manufacture, storage and transport. Despite this advantage, and although some of these have been used in important work, they are now little used, possibly on account of the greater inconvenience to the user, compared with explosives supplied by the manufacturer in final form. Liquid-oxygen explosives are a type of Sprengel explosive in that the oxidizing agent (liquid oxygen) and the combustible substance or substances (solid carbonaceous matter alone or in combination with liquid hydrocarbons or even metallic powders and, at times inert absorbents) are brought together immediately before use. The components separately are non-explosive. The possibility of using liquid oxygen as one of the components of an explosive was perhaps first suggested by Sprengel, who stated that the beau ideal of a detonating explosive was a mixture of eight parts of liquid oxygen with one part of liquid hydrogen. Although the liquefaction of air3 had been accomplished in the laboratory as early

Jan 1, 1923

By C. E. Hottman, R. K. Johnson

Fluid pressure within the pore space of shales can be determined by using data obtained from both acoustic and resistivity logs. The method involves establishing relationships between the common logarithm of shale transit time or shale resistivity and depth for hydrostatic-pres-sure formations. On a plot of transit time vs depth, a linear relationship is generally observed, whereas on a plot of resistivity vs depth, a nonlinear trend exists. Divergence of observed transit time or resistivity values from those obtained from established normal compaction trends rinder hydrostatic pressure conditions is a measure of the pore fluid pressure in the shale and, thus, in adjacent isolated permeable formations. This relationship has been empirically established with actual pressure measurements in adjacent permeable formations. The use of these data and this method permits the interpretation of fluid pres.rure from acoustic and resistivity measurements with an accuracy of approximately 0.04 psilft, or about 400 psi at 10,000 ft. The standard deviation for the resistivity method is 0.022 psi/ft, and for the acoustic method 0.020 psi/ft. Knowledge of the first occurrence of overpressures, and of the precise pressure-depth relationship in a geologic province, enab1es improvements in drilling techniques, casing progroms, completion methods and reservoir evalzmtions. INTRODUCTION CENKRAL STATEMENT Operators engaged in the search for and production of hydrocarbon reserves in Tertiary basins are more and more frequently confronted with complications associated with over pressured (abnormally high fluid pressure) formations. This is particularly true in the Texas-Louisiana Gulf Coast area. The problems associated with these formations are of direct concern to the combined activities of all phases of operations, i.e., geophysical, drilling, geological and petroleum engineering.' - Knowledge of the pressure distribution of a given area of operations would greatly reduce the magnitude of many of these complexities and in some cases would completely eliminate specific problems. his pape; presents techniques developed for estimating formation pressures from interpretations of acoustic and electric log data. Specifically: the acoustical and electrical properties of shales, reflected by conventional acoustic and electrical surveys, can be used to infer certain reservoir properties, such as formation pressure, at any level in a well. It has been possible to develop these techniques because of a firm understanding of the basic principles that govern and apply to such overpressured provinces. NORMAL PRESSUKES Normal pressures refer to formation pressures which are approximately equal to the hydrostatic head of a column of water of equal depth. If the formations were opened to the atmosphere, a column of water from the ground surface to the subsurface formation depth would balance the formation pressure. On the Gulf Coast, the shallow, predominantly sand formations contain fluids which are under hydrostatic pressure. These formations are said to be normally pressured or to have a normal pressure gradient.* Experience has shown that the normal pressure gradient on the Gulf Coast is approximately 0.465 psi/ft of depth. OVERPRESSURES Formations with pressures higher than hydrostatic are encountered at varying depths in many areas. These formations are referred to as being abnormally pressured, abnormally high pressured, or overpressured. Formation pressures up to twice the hydrostatic pressure have been observed. These formations require extreme care and much expense to drill and to exploit. COMPACTION-FLUID PRESSURE RELATIONS THEORY The generation of overpressured formations in Tertiary sections of the Gulf Coast and several other Tertiary sedimentary basins is, in general terms, considered to be primarily the result of compaction phenomena.' This portion of the paper presents a brief review of the theory which associates compaction and fluid pressure relations, and should thus provide the necessary background for an understanding of the techniques presented. See Hubbert and Rubey' for a more comprehensive treatment of this subject. The theory of the consolidation of a water-saturated clay' has been well established by workers in soil mechanics. The concept is explained by a model with perforated metal plates separated by metal springs and water and enclosed in a cylindrical tube. Fig. 1 is a schematic representation of such a model (see Ref. 5, Fig. 27, page 74). The springs simulate communication between clay particles, and the plates simulate the clay particles. Mano-

Jan 1, 1966

By M. P. Tixier, F. Segesman

Explanations bused on theory and laboratory tests tire offered for certain unusual features of SP logs which may befog their interpretation, namely the "sawtooth" SP and the reduction or increase of SP with time. The sawtooth SP is frequently seen in SP recordings of thick, very permeable watcr. sands of the Louisiana Gulf Coast. Using SP data from a resistor network analog, this anomaly is explained on the basis of a thin shale streak within the sand. under which the invading filtrate accumulates by gravity segregcitiorr. The electromotive force then appearing across the shale streak gives rise to the anomalous SP. Reduction of the SP on successive logging runs Ira often been observed in very permeable sands when as indicated by the resistivity curves, the invasion depth has been reduced to practically zero. Laboratory results verify that this phenomenon may be due, to the presence of air electromotive force, across the mod rake when the fluids on either side differ in activity. Also, there is, in some cases; an increase of SP deflection on successive logging runs, because the emf initially present across the mud cake disappears as the somewhat saline water just behind the mud cake is progressively flushed out by the invading filtrate.. Field example and laboratory data are presented. I N T R ODUCT1ON Some unusual features are frequently observed on certain SP logs which make interpretation difficult. The purpose of this paper is to offer explanations of several cases of interest. All of these arc related to the conditions of invasion. The cases to be discussed are as follows. 1. The sawtooth SP anomaly which is frequently seen within the thick, highly permeable saltwater sands of the Louisiuana Gulf Coast 1. Reduction of the SP deflection from the usual sand line in very permeable sections when the depth of invasion is practically nil. As will be explained, such a reduction is attributable to a membrane electromotive force across the mud cake. 3. An increase of the SP with time just after the iormation is drilled as a result of progressive flushing of the invaded zone. FUNDAMENTALS OF SP PHENOMENA An explanation of SP phenomena must begin with the following basic ideas. 1. The SP log derives its character from ohmic potential differences in the hole produced by currents flowing through the mud.' These currents are driven by electromotive forces which are primarily electrochemical in origin. Other possible types of SP-producing electromotive forces may be disregarded for the purposes of this paper. 2. The electrochemical emf's associated with permeable formations are now understood to consist of liquid-junction emf's and membrane emf's.',' As schematically shown by thc battery symbols in Fig. 1, the liquid-junction emf, E,,,, exists at the contact between waters of different chemical activities, a,,,, (mud filtrate) and tr,,. (formation water); the shale membrane emf, lS.sn. exists across the adjacent shales whcn they separate waters of different activities. The emf's just cited are additivc in producing SP currents (arrowed circles of Fig. I). Thus, neglecting for the moment any possible membrane emf across thc mud cake, the total electrochemical emf, E,, will be given by their sum, where K,., -! K,q,, = 12 + 59, or 71 at 75 °F. In the log interpretations the SP of a thick sand (i.e.. the static SP) is generally related to the activities of the filtrate and formation water through Eq. 1. by setting the static SP equal to - E,.