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By G. A. Vissac

In the presentation which follows, wash-ability curves, such as are commonly used in making studies preliminary to the cleaning of any coal or to the concentration of any mineral, have been reduced in each instance to a single straight line; thus all the most important characteristics of the coal or mineral are represented in a form more advantageous than that in which such data usually are shown. To obtain consistent results, float-and-sink data must be based on a single definite narrow size range, which may be designated "a coal unit." It will be shown that such units, each embodying a different size range, can be grouped to form what may be termed "a composite coal." A three-dimensional presentation will emerge, which will closely identify the coal, illustrate its characteristics in a new manner and explain many obscure facts. Float-and-sink Tests For the preliminary study of any cleaning or concentration problem, or in the control of any operation, float-and-sink tests must be made. The results of these tests are grouped in tabular form and then illustrated in various systems of curves; but if such a graphic representation is to have the utmost practical value, it must offer at least the following advantages: (I) It must be easier to read than the tabular results, and (2) it must be easy to plot, check and interpolate. The first requirement will be attained by reducing the number of curves to a minimum, and the second by some system of representation that will use only straight lines. Of the many washing curves now in use, only the "recovery curve," often known as the "composite curve"—a somewhat misleading term—will be considered; Any point on the recovery curve will show what percentage of weight of clean coal can be recovered when the mineral is washed at a certain specific gravity. As an example, the tests listed below Fig. I are illustrated in the drawing by a curve obtained by plotting (I) as abscissas the ash content of the coal recovered and (2) as ordinates the corresponding percentage of refuse discarded; but, in general practice, instead of writing down that weight, it is customary to set down its complement, which is the corresponding weight of coal recovered. From this curve can be deduced the information necessary for the solution of most practical problems. New Form of Graphic Presentation The resemblance of the recovery curve ill Fig. 1, or, for that matter, the recovery curve obtained in common practice! to a Power curve is apparent. The general equation of such a curve is Y = axn, where n is negative. Taking logarithms: log y = a + n log x. Using a logarithmic scale, the equation of the recovery curve will be Y = A + bX. On this logarithmic basis! the recovery graph will be a straight line, using the same variables as in Fig. I; namely, the ash con-

Jan 1, 1942

By G. A. Vissac

In the presentation which follows, wash-ability curves, such as are commonly used in making studies preliminary to the cleaning of any coal or to the concentration of any mineral, have been reduced in each instance to a single straight line; thus all the most important characteristics of the coal or mineral are represented in a form more advantageous than that in which such data usually are shown. To obtain consistent results, float-and-sink data must be based on a single definite narrow size range, which may be designated "a coal unit." It will be shown that such units, each embodying a different size range, can be grouped to form what may be termed "a composite coal." A three-dimensional presentation will emerge, which will closely identify the coal, illustrate its characteristics in a new manner and explain many obscure facts. Float-and-sink Tests For the preliminary study of any cleaning or concentration problem, or in the control of any operation, float-and-sink tests must be made. The results of these tests are grouped in tabular form and then illustrated in various systems of curves; but if such a graphic representation is to have the utmost practical value, it must offer at least the following advantages: (I) It must be easier to read than the tabular results, and (2) it must be easy to plot, check and interpolate. The first requirement will be attained by reducing the number of curves to a minimum, and the second by some system of representation that will use only straight lines. Of the many washing curves now in use, only the "recovery curve," often known as the "composite curve"—a somewhat misleading term—will be considered; Any point on the recovery curve will show what percentage of weight of clean coal can be recovered when the mineral is washed at a certain specific gravity. As an example, the tests listed below Fig. I are illustrated in the drawing by a curve obtained by plotting (I) as abscissas the ash content of the coal recovered and (2) as ordinates the corresponding percentage of refuse discarded; but, in general practice, instead of writing down that weight, it is customary to set down its complement, which is the corresponding weight of coal recovered. From this curve can be deduced the information necessary for the solution of most practical problems. New Form of Graphic Presentation The resemblance of the recovery curve ill Fig. 1, or, for that matter, the recovery curve obtained in common practice! to a Power curve is apparent. The general equation of such a curve is Y = axn, where n is negative. Taking logarithms: log y = a + n log x. Using a logarithmic scale, the equation of the recovery curve will be Y = A + bX. On this logarithmic basis! the recovery graph will be a straight line, using the same variables as in Fig. I; namely, the ash con-

Jan 1, 1942

By L. M. Barker, E. G. Lewis

THE literature of milling is replete with papers devoted to the subject of ball milling, all of which no doubt have contributed in one way or another to progress in that art. In this paper reference will be made to only a few of the many authors, but the value of the contributions of all who have written on that subject is hereby acknowledged. With a few exceptions the efforts of most students of the subject have been devoted to laboratory investigations of principles. Davis1 was one of the first to report on plant-scale investigations and to present to mill men certain criteria for the guidance of ball-milling practices. His conclusions with respect to the significance of sizing analyses of classifier sands in their relation to the factors of mill speed and ball sizing are particularly referred to. Those conclusions were: I. If the balls are large or the speed of the mill is high, crowding will appear at the finer sizes in the classifier sands. 2. If the balls are small or the speed is low, crowding will appear at the coarser sizes in the classifier sands. 3. The indications are that best efficiency is obtained when the screen analysis of the sands show a minimum crowding at any size. The last conclusion was qualified by the statement that it had not been proved conclusively. It is surprising, however, that the literature of later years reveals little evidence that millmen have made any serious attempt to apply those criteria. This may, perhaps, be explained by the fact that the average plant-scale ball-milling problem presents so many variables that an investigation of any one of them encounters the problem of control of the others-a problem that often is unsurmountable in a small plant. In a large plant, in which there is a duplication of grinding units in parallel operation, opportunity may be afforded for determining the value of such criteria. Nevertheless, a study of published data from grinding circuits of both large and small plants suggests that either Davis' criteria have been tried and found inapplicable or have never been given consideration. For the purpose of testing Davis' conclusions and with improvement of ballmilling efficiency as the final objective, a test program was initiated in the concentrator of the New Cornelia branch of the Phelps Dodge Corporation early in 1938. The practices of that plant have already been described.2 The fine-grinding units are arranged so that any one of eight units may be operated as a test unit and its results compared with those of the remaining units. All units receive similar feed from a common storage bin, in which the product of the fine-crushing plant is bedded by traveling tripper. The ball mills are all similar in size and operated at the same speeds, and are individually metered. The feeder conveyors of each unit are equipped with Merrick weightometers. The test program as initially outlined proposed investigation of the following:

Jan 1, 1941

By F. M. Stewart, F. H. Callaway, R. E. Gladfelter

In this paper oil initially in place is calculated by the various methods commonly used for analysis of water drive fields using data available as time progresses. Rate and pressure are predicted by means of the same methods using data available at the end of two years' history. These predictions are then compared with subsequent performance permitting an evaluation of the methods, which are Modified Schilthuis, Simplified Hurst, van Everdingen et al (1952), and the Electric Analyzer. INTRODUCTION Several variations of the material balance equation, differing in the term used to evaluate water influx, are in common use for estimating oil in place, predicting rate and volume of water influx, and forecasting producing rates and reservoir pressure in water drive reservoirs. The electric analyzer with an electrical network set up to simulate the oil reservoir and aquifer and their contained fluids may be used for the same purpose. Examples of the application of one or another of these methods have appeared in the literature. The accuracy and reliability of the material balance for calculating oil in place have been covered.' However, there have been few articles in which more than one method has been applied to an actual field allowing a comparison. It is felt that a field example, simple in nature, where the Modified Schilthuis, Simplified Hurst, van Everdingen et al (1952), and the Electric Analyzer have been applied would be of benefit in providing an evaluation of these methods as to their comparative usefulness and reliability in calculating initial oil in place and predicting performance. The Torchlight Tensleep reservoir is a small field in a large aquifer. The reservoir oil is greatly under-saturated, having a bubble point of only 55 psi and 2 cu ft/bbl of gas in solution. Changes in the reservoir volume factor in the range of pressures encountered are small, meaning little error in converting production to reservoir conditions. The pressure has declined from 1,618 psi initially to 137 psi during the first four and one-half years. Water production has been negligible. For Torchlight, the material balance equation as discussed later is considerably simplified by the omission of terms having to do with free gas. Thus with simpler equations, less variables to consider, the large pressure drop, the absence of a gas phase, and rapid pressure-rate adjustments, which mean an unusual amount of history in a short time, the reservoir appears suitable for comparing the methods listed above. GENERAL INFORMATION ON THE FIELD The Torchlight field is located on the eastern side of the Big Horn Basin, Big Horn County, Wyo., approximately 3 miles east of the town of Basin. The Tensleep reservoir was discovered in September, 1947. It lies at a depth of about 3,000 ft and produces oil of 35" API gravity. A total of five wells have been completed in the Tensleep, but only four are now producing. The reservoir is well defined in areal extent in that a total of 13 wells have penetrated the Ten-

Jan 1, 1955

By K. L. Moazed, G. M. Pound

An investigation was made of the deposition of silver from a thermal beam onto tungsten field-emitter tips at 300°K. "Island"-type nuclei were observed to form and grow. The nucleation of silver crystals occurs preferentially on non-close -packed planes of a tungsten tip at a critical volume free-energy change of about —2900 cal per cc. The adatom population which is critical for appreciable nucleation rate of silver crystals is about 0.2 of a monolayer and is essentially independent of beam flux, time, and source temperature. This result is strong evidence that a metastable equilibrium exists between adatoms and critical nuclei, as assumed in the present theory. SOME of the more significant studies of nucleation in deposition of metals from vapor beams have been conducted by measuring the thermal beam flux which is critical for appreciable rate of nucleation on a substrate surface held at a given temperature.'2 The observed critical supersaturations may be described in terms of Eq. [7] which was derived3'3a on the model of an adsorption, surface migration, and statistical fluctuation mechanism. However there usually made with a low-power optical microscope, a fairly insensitive method of detection. The object of the present study was to overcome some of these difficulties by measuring the critical supersaturation for condensation of a thermal beam of silver onto a tungsten field-emitter tip. Such a tip may be cleaned by electrically heating it to a high temperature in situ, and the high vacuum obtainable in a field-emission tube (10-10 torr) precludes adsorption of residual gases for convenient periods of time. Furthermore, the degree of cleanliness, the orientation, and the state of imperfection of the tip may be ascertained from the field-emission pattern. Detailed explanations of theoretical considerations and experimental procedures relating to the field-emission microscope may be found in a number of excellent review articles12'13 and thus only a brief description will be given here. The electronic work function of a metal is defined as the energy that an electron needs to escape from the potential field of the solid. By applying a large field between the surface of the solid and a suitable collector, it is possible to free the electrons by the tunnel effect. Fields of approximately 30 million v per cm are needed to produce this effect, and such fields are obtained in practice by using microscopic surfaces of high curvature (tips). Because the work function of a metal is a function of surface orientation, the emission from the various planes is different, and thus it is possible to obtain a representation of the surface in the emission microscope. In general, the work function is higher for the more densely packed planes. Fig. 1 shows a pattern for "clean" tungsten in which the central dark region represents the (110)

Jan 1, 1964

By J. G. Tilton

While most of the Pittsburgh coal horizon is dependably regular, there are areas where it is dis-turbed by sandstone cutouts which can seriously hamper mining operations. Because these channel sandstones often cut out the coal abruptly, they are difficult to detect by core drilling; and mine operators, for want of a better way to discover them, have largely trusted to luck to avoid them. This paper, based on a study the author is presently conducting, is an attempt to point out some sources of information and signposts which might aid the operator in determining the presence of a cutout before he begins to mine. The presence of sandstone cutouts in the Pittsburgh coal has been known for many years. Some of these irregularities were observed at outcrops and others were discovered by drilling, but the majority were and are found during mining operations. These sandstone cutouts are commonly called "faults" and have been a bane to mining companies wherever they have been encountered. Profiles of some typical deposits appear in Fig. 1. The cutouts disrupt the normal system of mining, replace valuable coal reserves, create ventilation problems by emitting large quantities of gas and sometimes oil, limit the number of entries that can be economically driven, affect the quality of the coal, disrupt the normal structure of the coal, and create roof control problems. It might be expected that such severe disturbances in the structural regularity of the coal would instigate determined and extensive searches for possible cutouts prior to mining operations, but this apparently has not been so except in isolated cases. Two reasons may be cited to explain this lack of exploratory work. The first and probably the strongest reason is the over-all regularity of the Pittsburgh coal. No coal seam in the country exhibits the horizontal continuity and relative regularity of the Pittsburgh coal. It lies in an almost unbroken sheet across southwestern Pennsylvania, eastern Ohio and northern West Virginia, and has been recognized as far east as the Potomac Basin of western Maryland. Over 5729 square miles are underlain by this coal, of which 2077 square miles are in Pennsylvania, 2214 square miles in West Virginia, 1410 square miles in Ohio, and 28 square miles in Maryland. The area covered by this study is outlined by the map in Fig. 2. Over most of this territory the coal has the following characteristic structure as illustrated in Fig. 3: roof coal, draw slate, breast coal, parting, bearing in coal, parting, brick coal, parting, and bottom coal. With such regularity of thickness and structure, mines were opened and laid out with confidence that the coal would be present. Extensive drill testing was considered unwarranted and it was also quite expensive because the coal dipped to the west away from the Monongahela River. Consequently, drill holes were widely spaced and rarely encountered ad-

Jan 1, 1968

By Norman Weiss

Most papers on xanthate have dealt with principles rather than practice. On the assumption that many millmen are interested in knowing where and in what manner the xanthates are being used in mills other than their own, this paper will summarize the results of a recent survey of North American plants. A brief background story and a description of the xanthates will be followed with the results of that survey; then a few observations will be made on storage, feeding, and ore testing. The first xanthate was made in 1822 by Zeise of the University of Copenhagen. With commendable scientific detachment (or perhaps a bad cold) Zeise ignored a more pervading quality of the substance and named it for its color, after the Greek word "xanthos," meaning yellow. During the first 80 years of its recorded existence xanthate found use only in small quantity as an insecticide; after the turn of the century there was some further demand for it in the vulcanization of rubber. It was not until 1922, by coincidence the centennial of Zeise's discovery, that C. H. Keller of San Francisco, seeking sul-phidizing agents, recalled xanthate in connection with his experience years earlier when he had seen this material used in Europe to combat grape phylloxera. His successful tests with the new flotation reagent culminated in the basic xanthate patent (U. S. 1,554,216) in 1925. In the minds of many metallurgists the introduction of xanthate as a flotation reagent is identified with the beginnings of alkaline circuits, the first use of chemical collectors, and the beginning of selective flotation. Actually, these preceded xanthate by a number of years. The alkaline circuit in lead-zinc flotation was introduced by Lyster as early as 1912. In 1922 Sheridan and Griswold made their momentous discovery (Timber Butte) that alkali cyanides and zinc sulphate effectively inhibited the flotation of pyrite and sphalerite in pulps made alkaline with sodium carbonate or bicarbonate. The use of lime to retard pyrite in copper flotation began within two years after Ralston directed attention to its possibilities in 1917. These were the beginnings of modern selective flotation, which was practiced successfully on copper-iron ores at Nacozari in 1922, and at Inspiration, Cananea, and others only shortly afterward. In the lead-zinc mills, selective flotation was of even greater economic importance at that time. The Sunnyside plant of U. S. Smelting, Refining, and Mining Co. used the process earlier than 1920, and Consolidated, Timber Butte, and others soon followed. As a chemical collector xanthate was relatively a latecomer, for the Corliss patent of 1917 covered the first of these, alpha-naphthylamine, and the Perkins patent of 1919 the second, thiocarbanilid. Both of these were in extensive use before Keller's xanthate made its commercial debut in 1923. There is general agreement, nonetheless, that the introduction of xanthate was

Jan 1, 1949

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

IT is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investigators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from 1100° to I700°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxidation of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,5 the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery6 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid,i.e., the sulphur was in combination with the silica. Orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By H. Hooykaas

A few years ago Marsal published a method of predicting oil recovery as a function of time for an edge-water-drive reservoir with several rows of wells.' The method is based solely on oil- and water-production data obtained during a short period for the first row of wells and the gross productions (past and future) of all wells. This paper presents a streamlined version of the original publication and experimental evidence showing the reliability of this version. For this purpose scaled experirnents were performed in a large model (750 X 500 X 23 cm, 24.4 ft X 16.2 ft X 8.9 in.) in which edge-water-drive reservoirs with three rows of production wells were simulated. From the results of the experiments it is concluded that the method gives a fairly accurate prediction of the future production behavior of the reservoir and enables us to select the most profitable production plan. Results obtained with the method were always slightly conservative. INTRODUCTION The calculation method developed by Marsal aims at forecasting future reservoir behavior.' It can be applied to floods in which a number of down-dip wells are rapidly going to water. Essentially it is a method for predicting the future behavior of the up-structure wells on the basis of the observed behavior of the down-structure wells. As such, the method is especially useful for predicting behavior of edge-water drives toward several rows of wells. The requirement to be met for justifying the approach is identity of production mechanism in all regions of the reservoir. The attraction of the method then lies in the fact that it applies even when we have no complete description of the prevailing production mechanism. The original publication was in the German language and for this reason, perhaps, did not attract widespread attention. In our opinion it deserves to do so because it does offer in a simple way results which are in fair agreement with observed data. The aim of the present paper is to bring the method to the attention of a wider audience. The method in its most simplified form is reviewed and experimental data in support of it are presented. PRINCIPLES To show Marsal's principle. we will first write the continuity equation for very simple conditions, linear flow (in the positive x-direction) in an incompressible porous body [cross-section A(x), porosity +(x)], saturated with incompressible fluids (oil saturation S). When the oil in this formation is displaced by water, injected at x = 0 (inlet face), we get where q(t) is the total gross displacement rate and f the fractional oil flow. The equation can be solved if we make the assumptions: (1 ) that the fractional oil flow (f) is a univalent function of saturation (S); and (2) that the function is the same throughout the porous medium. Then: f = f(S) Solving this equation with the method of characteristics, we obtain

Jan 1, 1966

R. H. Sweetser.—Mr. Reinartz spoke of slag containing 18 per cent FeO. I think he expressed the iron as oxide. I should like to ask at what point, in iron contents, it is usual practice to quit sending that open-hearth slag to the blast furnace? L. F. Reinartz.—NO problem is involved in disposing of open-hearth slag to our blast furnaces because, on account of the grades of iron and steel made by our company, the iron oxide in the slag is sufficiently high to make it very acceptable to the blast-furnace operator. I have been told that if the total iron oxide in the slag is under 18 to 20 per cent, it is not economical to use such slag in a blast furnace. J. T. Mackenzie,* Birmingham, A1a.—Mr. Reinartz mentioned sulfate in the limestone. I wonder if he did not use the wrong word. We always have assumed that the sulfate sulfur is practically harmless. Most limestone carries some pyrite (sulfide sulfur) which we thought was what gave the sulfur pick-up. L. F. Reinartz.—I have had no experience, personally, in the use of limestone high in sulfates. I have been told, on several occasions, by other open-hearth men, that the sulfates will be reduced and increase the sulfur content of the metal. We have never found any pyrite in our limestone. A. Hayes,† Middletown, Ohio.—I should think that sulfates would be readily reducible to sulfites, and possibly to sulfides at various distances through the slag layer, from the top down to the interface between the bath and the slag, because reducing conditions are certainly sufficiently strong next to the bath in the slag to reduce sulfates to sulfides. A. L. Feild,‡ Baltimore, Md.—What is Mr. Reinartz's theory as to the effect of silica in the slag on the iron oxide content of the metal? L. F. Reinartz.—I have no particular theory as to the effect of silica in the slag on the iron oxide content of the metal. I know from practical experience that it does have an influence on reduction of iron oxide in the metal. We know that if the silicon content of the charge, and, therefore, the silica of the slag is increased, the iron oxide in the slag will be decreased. Based on Dr. Herty's work, we assume that the iron oxide is correspondingly decreased in the metal. C. H. Herty, JR.,§ Bethlehem, Pa.—In the theory of iron oxide control, we have tackled the matter from the physical standpoint, rather than the chemical standpoint or from the slag itself, and we worked on the basis that the change in iron oxide content in a slag—that is, whether the slag increases or decreases in iron oxide—is due to the simple fact that if you put more iron oxide into the slag from the gas than you put oxygen from the slag into the metal, the slag must increase in iron oxide;

Jan 1, 1935

By Basil B. Zavoico

The World War I1 spread to Russia on June 22, 1941, when the German Armies began their invasion. The Soviet industries, which were already engaged in a tremendous armament program, further accelerated the flow of munitions, and equipment and supplies for all purposes not directly military were either entirely eliminated or reduced to an absolute minimum. With the occupation by German armies of the Dniepr and Kharkov industrial regions, this trend was necessarily further accentuated. The oil industry of Russia, in consequence, was left to rely more and more upon itself, its own very limited manufacturing facilities, extensive repair shops and probably much used equipment out of order stacked in the warehouses. All evidence available to date points to the fact that the new situation not only did not affect the production either quantitatively or qualitatively, but, on the contrary, caused a larger flow of much needed fuels to the country's war machine, primarily by renaissance of both management and labor. The oil industry of the Soviet Union, left to depend entirely upon itself for equip ment and supplies, and even for new workers and technicians to replace those called into the services, did and is still doing a good and effective job. Since it could not hope for new equipment and parts and could not blame any other industry for the delays in delivery, it dragged out old machines from storage and repaired them in its own machine shops. Often such stored and used equipment was but slightly defective, waiting for some small part from factories in Central Russia, plants that now were either in German hands or entirely converted to the manufacture of munitions. More particularly, instead of the pipe that could not be taken to the Caucasus from Central Russia, casing reclaimed from abandoned or submarginal wells was used, or pipe from the abandoned or but slightly used pipe lines; and this practice is being continued even now on a large scale, to create an ample reserve for the duration of the conflict. Indirectly such a development was even an improvement on pre-war days, when many wells about to be completed had to wait for weeks, even months, for the arrival of new pipe, all blame then being placed outside of the industry on the factories in Central Russia. For the purpose of reclaiming equipment and pipe still usable, special crews were organized. The war also caused much quicker adaptation of certain American practices and introduction of many emergency measures, such as: removal of derricks upon completion of wells and the use of drilling equipment mounted on skids for rapid transfer from location to location—both of these practices, while standard in the U.S.A., being new in Russia; installation of simplified surface pumping units; substitution of wooden bearings in the surface pump equipment; completion of wells in the Ural-Volga district, where formations are hard and tight throughout the sedimentary column, without either casing or

Jan 1, 1942

By O. J. C. Runnalls, L. M. Pidgeon

J. M. Blocher, Jr. and I. E. Campbell (Battelle Memorial Institute, Columbus, Ohio)—Since the de Boer-Van Arkel process for making titanium metal involves a number of steps in a fairly compact unit, it is difficult to determine simply which of the steps is rate controlling. In any statement as to which step constitutes the rate-controlling process, qualifications appear to be in order. It is possible to design a reaction bulb in which any one of a number of steps is made to be controlling. I—With the filament removed some distance from the crude, as in the case of the authors' experiments, the interdiffusion of iodine and iodide may be controlling. 2—If, as is usually done, the crude metal is placed in a perforated cylindrical basket, or as a briquetted mass, in close proximity to the filament, the rate of deposition is increased (we obtained rates of deposition 5 to 10 times those cited in the authors' paper), and another rate-limiting factor, such as the reactivity of the crude, may take over. In this regard, we have noticed radically different rates of deposition with different crudes, and with crudes in various stages of exhaustion. 3—With a very reactive crude metal and with optimum practical geometry, still another process may be controlling. It is felt that this is a diffusion process in the immediate vicinity of the filament involving the fundamentally adverse situation of a net flow of particles away from the filament. The separate experiments on the reactivity of iodine with titanium are interesting but somewhat inconclusive. Data is still needed on the partial pressure of iodine in an operating decomposition bulb. A knowledge of the gradient of iodine partial pressure from the crude to the filament would be particularly enlightening. Optical absorption may be a useful technique here. Accurate measurements of the total pressure within a decomposition bulb under various conditions would be quite revealing. Preliminary measurements have been made at Battelle in following this line of attack. It is interesting to note that the authors' data on the temperature dependence of deposition rate indicate that the overall rate is not controlled by the kinetics of the decomposition reaction at the filament: TiI1 ? Ti + 4I Any reasonable estimate of the activation energy of this reaction would, if its kinetics were controlling, dictate a much greater temperature dependence than is observed here. The authors apparently attribute the drop in deposition rate (eventually to zero) with increased TiI4 pressure solely to a decrease in diffusion rate. However, there is an equilibrium factor involved here that must not be overlooked. As the partial pressure of TiI4 is increased, a point is reached where, due to the competing reaction of the tetraiodide with titanium to form lower iodides, the equilibrium partial pressure of titanium is reduced to the point that it equals the vapor pressure of titanium at the filament temperature and the deposition rate falls to zero. This effect would

Jan 1, 1953

By F. J. Fayers, S. A. Hovanessian

The one-dimensional displacement equation for a homogeneous porous medium, including the effects of gravity and capillaty forces, has been solved by a numerical method. A finite-difference scheme is developed for obtaining saturation, pressure and fractional flow profiles in waterflood recovety problems. From the numerical examples given, it is concluded that the gravitational forces have a pronounced effect on the saturation profiles and the pressure distribution curves of the system. INTRODUCTION Within the past 20 years, a number of papers have appeared in the literature dealing with the quantitative treatment of waterflood recovery problems. In their celebrated paper, Buckley and Leverett1 described a method for calculating saturation profiles when the effects of capillary pressure and gravity are excluded. Terwilliger, et al,2 included the effect of gravity in their theoretical and experimental investigation of oil recovery problems and obtained close correlation between experiment and theory. welge3 described a simplified method for obtaining the average saturation and the oil recovery from an oil reservoir. The effect of gravity can be included in this calculation. More recently (1958) Douglas, et al,4 presented a method for calculating saturation profiles which includes the effect of capillary pressure. The authors start with the one-dimensional displacement equation (which is nonlinear in the derivative) and, by a change of variable, transform this equation to a semi-linear partial differential equation. This equation is then solved by a finite-difference method on a high-speed digital computer. Fayers and Sheldon5 obtained the solution of the one-dimensional displacement equation by directly replacing the differential equation by a finite-difference equation. The effects of capillary pressure and gravity were in- cluded in their solution. Here, since the movement of the foot of the saturation front is governed by a separate equation, the elapsed time in attaining a particular saturation profile cannot be obtained. The results of these two papers indicate that the inclusion of capillary forces eliminates the triple-valued Buckley-Leverett saturation profiles. In the present paper, the one-dimensional displacement equation for a homogeneous permeable medium, including the effects of capillary and gravity forces, is solved. The method of solution resembles that described in the paper by Douglas, et al, since it involves a similar transformation of variable. However, it extends their work in that the effect of gravity is included and, in addition, pressure profiles may be calculated. Also, the functions of saturation [kro(S), krw(S) and Pc (S) ] required are entered in tabular form rather than as low-order polynomials. This simplifies data preparation and permits the use of a greater range of function types. Unlike the method of Fayers and Sheldon, the corresponding elapsed time required for the development of each saturation profile is calculated and, also, saturation profiles may be calculated after breakthrough. THEORETICAL CONSIDERATIONS The dimensionless form of the one-dimensional displacement equation for a homogeneous porous medium as obtained from Darcy's law and material balance relations can be written as follows.

By H. R. Ogden, A. G. Imgram, D. N. Williams

The effects of composition on the mechanical properties and aging characteristics of several alloys in the Ti-V-Cr system, with and without aluminum modifications, were evaluated. Increasing the chromium, vandium, or aluminum content increased the strength of quenched structures with chromium being the most effective strengthener. Appreciable aging response was obtained with low chromium alloys, but high chromium alloys age softened rather than. hardened. High vanadium contents had a similar effect. Aluminum additions shifted the aging behavior toward that observed in lower chromium alloys, enabling high chromium alloys to be age hardened. DURING the course of titanium alloy development many a and a-ß alloys have been evolved to commercial status. However, only one all-ß alloy has achieved this same stature. This is the Ti-13V-11Cr-3Al alloy. It is characterized by a very sluggish ß-phase decomposition reaction such that very slow cooling rates can retain the 0 phase at room temperature. In addition, very high strength levels can be obtained by long-time aging treatments. Combinations of cold or warm working followed by aging produce even further improvements in strength. This paper describes the results of a research program in which the effects of composition on the mechanical properties and aging characteristics of several alloys in the Ti-V-Cr system, with and without aluminum modifications, were evaluated. EXPERIMENTAL PROCEDURES Electrolytically refined, high-purity titanium was used as the alloy base for these studies. Iodide chromium, electrolytically refined vanadium granules, and high-purity aluminum sheet were used as alloying additions. The compositions of interest were melted as 250-g ingots in a direct current arc melting furnace under a flowing atmosphere of argon. The ingots were hot forged to 3/4-in.-diam bars, vacuum annealed for 6 hr at 1800°F to reduce residual hydrogen content, and then hot swaged to 1/4-in.-diam rods. Fabrication history, and interstitial analyses after fabrication are given in Table I. All specimens to be heat treated were sealed in Vycor capsules under a partial pressure of argon. Samples used to define the ß transus were quenched from temperatures ranging from 1350° to 1100°F after holding at temperature for 15 min. Samples for aging studies were quenched from above the ß transus temperature and then aged for up to 64 hr at 750°F and for 100 hr at 850°, 900°, and 950°F. The effects of straining prior to aging were also investigated. The results of these studies were used to select the heat treatments for the tensile specimen blanks. Heat treatments of the tensile specimens are described in Table 11. Alloys were aged after solution heat treatment or after solution heat treatment and cold swaging to 50 pct reduction in area. Standard 0.125-in.-diam tensile specimens were machined from the heat-treated blanks. All tensile tests were performed in a Baldwin-Southwark uni-

Jan 1, 1963

By Basil B. Zavoico

The World War I1 spread to Russia on June 22, 1941, when the German Armies began their invasion. The Soviet industries, which were already engaged in a tremendous armament program, further accelerated the flow of munitions, and equipment and supplies for all purposes not directly military were either entirely eliminated or reduced to an absolute minimum. With the occupation by German armies of the Dniepr and Kharkov industrial regions, this trend was necessarily further accentuated. The oil industry of Russia, in consequence, was left to rely more and more upon itself, its own very limited manufacturing facilities, extensive repair shops and probably much used equipment out of order stacked in the warehouses. All evidence available to date points to the fact that the new situation not only did not affect the production either quantitatively or qualitatively, but, on the contrary, caused a larger flow of much needed fuels to the country's war machine, primarily by renaissance of both management and labor. The oil industry of the Soviet Union, left to depend entirely upon itself for equip ment and supplies, and even for new workers and technicians to replace those called into the services, did and is still doing a good and effective job. Since it could not hope for new equipment and parts and could not blame any other industry for the delays in delivery, it dragged out old machines from storage and repaired them in its own machine shops. Often such stored and used equipment was but slightly defective, waiting for some small part from factories in Central Russia, plants that now were either in German hands or entirely converted to the manufacture of munitions. More particularly, instead of the pipe that could not be taken to the Caucasus from Central Russia, casing reclaimed from abandoned or submarginal wells was used, or pipe from the abandoned or but slightly used pipe lines; and this practice is being continued even now on a large scale, to create an ample reserve for the duration of the conflict. Indirectly such a development was even an improvement on pre-war days, when many wells about to be completed had to wait for weeks, even months, for the arrival of new pipe, all blame then being placed outside of the industry on the factories in Central Russia. For the purpose of reclaiming equipment and pipe still usable, special crews were organized. The war also caused much quicker adaptation of certain American practices and introduction of many emergency measures, such as: removal of derricks upon completion of wells and the use of drilling equipment mounted on skids for rapid transfer from location to location—both of these practices, while standard in the U.S.A., being new in Russia; installation of simplified surface pumping units; substitution of wooden bearings in the surface pump equipment; completion of wells in the Ural-Volga district, where formations are hard and tight throughout the sedimentary column, without either casing or

Jan 1, 1942

The Du Pont Magazine for August and September gives the following interesting information regarding recent progress in the use' of explosives. Blasting -Clay.-"The place where I tried blasting down clay for a brick yard had been worked for some years by old-time pick and shovel method. There was a large shallow pit, irregular in shape, with a perpendicular face at one end. I put down a line of holes 3 ft. deep and 6 ft. back from this face, loading each hole with one and one-half car-tridges of Red Cross Extra 40 per cent. dynamite. The charges were connected up to a blasting machine circuit and fired electrically. "Two of these shots kept the brick yard men very busy for two days taking out the loose clay. "I am convinced that if any brick yard man will try this method he will always have a blasting machine and dynamite on hand thereafter, because it cuts labor cost almost in two to get down the clay in. this way." In some clay pits the practice is to blast a large amount of clay in the fall, allowing it to freeze and thaw through the winter. Such clay is much easier to puddle in the spring than freshly dug or blasted clay. When the clay contains stones, the blasting loosens them and makes their separation-easy. Well-Drill Holes in Quarrying.-The well drill or cable drill method of working a quarry face is now in quite common use. The use of large drills is constantly increasing among quarrymen. In fact the growing tendency is for large machinery of all kinds such as mammoth crushers, steam shovels, etc. Volume is what is wanted nowadays. The advantages of the big drill over the piston driven drill are numerous. By carrying the holes the full depth of the face the stone is loaded and treated on one working floor. It eliminates the cost of bench cleaning. Loading operations are less frequent, thus lessening the danger. Stone can be shot down in greater volume and in better shape, making it economical to use a steam shovel. No bench cleaning makes it safer for the men. It is cheaper and can be used in outlying and temporary operations where the cost of installing a power plant would be out of the question. It permits a greater spacing of bore holes and eliminates the necessity of "squibbing" or springing. In this method usually holes from 4 in. to 6 in. in diameter are drilled the full depth of the face from 15 ft. to 2,0 ft. apart, and as far back and the whole face shot down at one time. The cost of well drilling may vary all the way from 20 cents to 75 cents: per foot, and in extremely hard rocks up to $1.50 per foot.

Jan 10, 1916

R. H. Sweetser.—Mr. Reinartz spoke of slag containing 18 per cent FeO. I think he expressed the iron as oxide. I should like to ask at what point, in iron contents, it is usual practice to quit sending that open-hearth slag to the blast furnace? L. F. Reinartz.—NO problem is involved in disposing of open-hearth slag to our blast furnaces because, on account of the grades of iron and steel made by our company, the iron oxide in the slag is sufficiently high to make it very acceptable to the blast-furnace operator. I have been told that if the total iron oxide in the slag is under 18 to 20 per cent, it is not economical to use such slag in a blast furnace. J. T. Mackenzie,* Birmingham, A1a.—Mr. Reinartz mentioned sulfate in the limestone. I wonder if he did not use the wrong word. We always have assumed that the sulfate sulfur is practically harmless. Most limestone carries some pyrite (sulfide sulfur) which we thought was what gave the sulfur pick-up. L. F. Reinartz.—I have had no experience, personally, in the use of limestone high in sulfates. I have been told, on several occasions, by other open-hearth men, that the sulfates will be reduced and increase the sulfur content of the metal. We have never found any pyrite in our limestone. A. Hayes,† Middletown, Ohio.—I should think that sulfates would be readily reducible to sulfites, and possibly to sulfides at various distances through the slag layer, from the top down to the interface between the bath and the slag, because reducing conditions are certainly sufficiently strong next to the bath in the slag to reduce sulfates to sulfides. A. L. Feild,‡ Baltimore, Md.—What is Mr. Reinartz's theory as to the effect of silica in the slag on the iron oxide content of the metal? L. F. Reinartz.—I have no particular theory as to the effect of silica in the slag on the iron oxide content of the metal. I know from practical experience that it does have an influence on reduction of iron oxide in the metal. We know that if the silicon content of the charge, and, therefore, the silica of the slag is increased, the iron oxide in the slag will be decreased. Based on Dr. Herty's work, we assume that the iron oxide is correspondingly decreased in the metal. C. H. Herty, JR.,§ Bethlehem, Pa.—In the theory of iron oxide control, we have tackled the matter from the physical standpoint, rather than the chemical standpoint or from the slag itself, and we worked on the basis that the change in iron oxide content in a slag—that is, whether the slag increases or decreases in iron oxide—is due to the simple fact that if you put more iron oxide into the slag from the gas than you put oxygen from the slag into the metal, the slag must increase in iron oxide;

Jan 1, 1935

By C. O. Bundranl, Peter Dehlinger, W. H. Browne

Brief laboratory investigations are described which attempt to determine optimum .sand concentrations in gel-sand and oil-sand1 well-treatments. The investigations apply to the case where sand acts as a propping agent in formation fractures. Both analytically and experimentally it is demonstrated that optimum sand concentrations can be defined. It is difficult to translate laboratory results to field treatments, however, since the relative distribution of sand and fluid in fractures may not be the same as injected. This is because fluid may penetrate the furtherest narrow portions of fractures, which would not pass sand. Optimum concentration of a monolayer of Ottawa sand in fractures of 0.025-in. width at the usual range of pressures encountered in treatments appears to be about 95 to 2 lb/gal. of gel. An investigation of abrasion of rock-walls by sand in treatments, described in the Appendix, shows that such abrasion is not probable in significant amounts. INTRODUCTION Experience in the Spraberry formation of West Texas, as well as in other formations, has shown that. sand is a necessary and vital part of gel-sand and oil-sand treatments. Many observers of treatments have also concluded that there seems to be an optimum range of sand concentration for these injections. Brief laboratory investigations were made at Battelle Memorial Institute to study flow in fractures with different sand concen- trations. To investigate the existence and range of optimum concentrations in the laboratory, however, necessitates knowledge of the mechanism by which the sand aids in increasing subsequent production. The action of sand in fractures is usually thought to be either that of a propping agent, thus providing a greater effective formation permeability; that of an abrasive in eroding fill material in fractures; or that of an abrasive eroding rock-wall irregularities along fracture surfaces. Investigations described in the Appendix show that sand does not appear to erode rock-wall materials appreciably. In a subsequent paper it is reasoned, at least for the Spraberry formation of West Texas, that the primary action of sand is not in removing fill materials in fractures. In this formation, and probably others, too, the main effect of sand appears to be that of a propping agent. Both analytical and experimental investigations were made for the case of a monolayer of sand acting as a propper, in which sand concentrations were determined that would, after treatment, permit flow of the maximum quantities of oil from the formation into a well. If too few sand grains are injected into fractures in which the bottom hole pressure has decreased appreciably below the original formation pressure, the confining pressure in the formation may become relatively large, thus compress the rock-walls around the sand grains, essentially close fractures, and so decrease the subsequent flow of oil. Similarly, if too much sand is used, the flow of oil will he impeded by the volume of sand present. THEORY Although an analytical approach to determining optimum sand concentrations involves gross assumptions.

Jan 1, 1955

By Cyril Stanley Smith

ON the 6th of February 1684, Dr. Martin Lister mentioned at a meeting of the Royal Society1 that "brass is magnetical," and promised to give an account of that assertion at some other time. He repeated his promise but never fulfilled it, and it was left for William Arderon2 to show, in 1958, that brass could be made magnetic by hammering and that it would retain polarity after magnetizing. Twenty-seven years later Cavallo3,4 examined the matter in great detail. Working with cast calamine brass, he showed that it could be made magnetic by hammering and nonmagnetic by subsequent annealing at a red heat. He found that annealing at a very high temperature caused the samples to lose their magnetic quality permanently, even after subsequent cold-working, but that remelting and cold-working restored it. He encountered some samples of brass that could not be rendered magnetic by any treatment. Experiments in which these were remelted with iron additions gave negative results, and Cavallo concluded that iron impurity was not the cause of the magnetism. He worked with 50-grain (3-gram) samples melted under the blowpipe, hence cooled very quickly. Bennet5 made whole crucible charges from copper and zinc, and found the resulting brass ingots to be magnetic only when iron had been added and then only after cold-working. All these observations applied to material in the cast condition, in which coring would produce a continuous spectrum of composition and cooling would result in varying degrees of precipitation. This knowledge of the subject seems to have been forgotten in the nineteenth century. The older brass was made by the calamine process and frequently contained iron in amounts of 0.5 per cent or more, absorbed from the impure ore with which the copper and charcoal were heated in making the brass. When metallic zinc became available in commercial quantities, calamine brass gradually disappeared, and with it the knowledge of its curious magnetic properties. Only when sensitive apparatus replaced the compass needle of the earlier investigators could the effects be detected in relatively pure metal. The effect of cold-working in inducing ferromagnetism was rediscovered by Bitters in 1930 in a sample of impure copper, and this was confirmed by Lowance and Constant,9 Honda and Shimizu, 10,11 and others. In the same year, Tammann and Oelsen12 showed that copper-rich copper-iron alloys after certain heat-treatments could be rendered ferromagnetic or made more strongly ferromagnetic by cold-rolling. Kussman and Seeman13 showed that the change of susceptibility of relatively pure copper on cold-working was associated with the iron content, and concluded that actual precipitation of iron was caused by cold-working, which is a satisfactory theory until one considers the improbably high rate of diffusion that this would involve. When studying precipitation phenomena in

Jan 1, 1941

By J. B. Macelwane

Geophysics differs from geology and physics in in many respects. In the first place, geophysics is a complex science embracing the fields of seismology, geomagnetism, geoelectricity, geodesy, meteorology, vol-canology, physical oceanography, physical hydrology, tectonophysics and exploration geophysics. Geology is also a complex science and so extensive in its various fields that no one can master them all, and no part of geology deals in any sense with several of these fields of geophysics. In the second place, geophysics makes use of methods and instruments that are derived primarily from the science of physics. Geology, on the other hand, has methods of its own and it draws its borrowed techniques and its instrumental equipment not only from physics but also and perhaps primarily from chemistry and biology. The difference, therefore, between the geophysicist and the geologist lies partly in the phenomena that are observed, partly in the methods and instruments with which each carries on his exploration; but partly also, and perhaps principally, in the habitual attitude of mind and in the background of specialized training with which each approaches the problems presented by this planet of ours. The geologist as such, therefore, is no geophysicist. On the other hand, the physicist is not a geophysicist either. Isolation of each problem in a closed laboratow system under complete control is fundamental to the methods of the physicist. The geophysicist must apply physical instruments and physicomathematical reasoning to the study of physical quantities in their undisturbed natural environment. What, then, is a geophysicist? In the sense that he is a trained expert in all of the geophysical sciences, I do not believe that such a person ever existed. It would be beyond the possibilities of a single lifetime. I think there is confusion in our ideas and in our use of terms. We are not all thinking of the same thing when we say geophysics or geophysicist; yet we seem to talk as though we were. It is as absurd to say that the whole of geophysics belongs to geology because the field of a particular type of geophysicist—the exploration geophysicist —calls for some knowledge of geology as it would be to say that the whole of biology belongs to geology because a particular type of biologist—the paleontologist— needs some knowledge of geology. Development of a Geophysicist Since it is impossible to become an expert in all the fields of geophysics, and since students entering college seldom know the field they will choose as a career, what would we suggest as the best general preparation for work in geophysics, whether as a meteorologist, an oceanographer, a seismologist, a geodesist, a geomagneticist, a volcanologist, a tectonophysicist, a hydro1 ogist, or an exploration geophysicistp we may distinguish five phases in the development of a geophysicist: (I) his mathematical and scientific studies in high school; (2) the general mathematical and scientific

Jan 1, 1946