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By D. B Kibler

The Florida hard-rock field extends from Suwanee and Columbia Counties in northwest Florida to south of Croom, Florida, in Hernando County. This area is approximately 100 miles long and varies from 2 to 30 miles in width. Florida hard-rock phosphate was discovered at Hale Springs, about one mile northwest of the town of Dunnellon, Marion County, in the year 1888, by Alber-tus Voight, who lived within a few hundred yards of the spring. Soon after this discovery there was a great influx of land speculators and wildcat operators into the vicinity of Dunnellon. A few years later phosphate was found in Alachua, Levy, Citrus and Hernando Counties, and a great number of small crude plants were built from Newberry, Alachua County, all the way to Croom, Hernando County. Phosphate was found in many places as "outcrops." Looking for outcrops was the first method used by the early prospectors in searching for deposits. Several years passed before any systematic method of prospecting was used. Early Mining The early method of mining hard-rock phosphate was with picks and shovels, wheelbarrows, mules and wagons. The pick-and-shovel method was used altogether until about 1900, when some of the larger operators began to use railroad-type steam shovels of from ½ to I-yd. capacity Picks and shovels, with negro labor loading the phosphate ore (called "matrix") into wooden side-dump skip-cars, was continued until about 1907. From the discovery of hard-rock phosphate until approximately 1905, overburden was removed with mules and scrapers. At some places, the overburden was loaded into side-dump skip-cars by negro laborers and the cars were then pulled up an incline with a steam hoisting engine. The maximum depth of overburden that could be economically removed by hand labor, mules and scrapers was approximately 15 feet. About 1905 one of the companies erected a producer-gas power- I house near Dunnellon and generated its own electricity and about the same time the larger companies began using hydraulic methods for the removal of overburden. From the year 1888 through the year 1939 approximately 75 companies were operating at one time or another in the hard-rock territory, on approximately 500 locations. The hard-rock deposits are more irregular and have higher mining costs than the pebble-rock deposits, therefore 1 they have not been competitive in the domestic market, but because of the higher grade of the hard rock it is in demand for I the export trade. Discovery of phosphate outside of the United States has made it increasingly difficult in recent years for the hard-rock companies to survive, so today i only three companies are operating. These

Jan 1, 1942

By D. B. Kibler

The Florida hard-rock field extends from Suwanee and Columbia Counties in northwest Florida to south of Croom, Florida, in Hernando County. This area is approximately 100 miles long and varies from 2 to 30 miles in width. Florida hard-rock phosphate was discovered at Hale Springs, about one mile northwest of the town of Dunnellon, Marion County, in the year 1888, by Alber-tus Voight, who lived within a few hundred yards of the spring. Soon after this discovery there was a great influx of land speculators and wildcat operators into the vicinity of Dunnellon. A few years later phosphate was found in Alachua, Levy, Citrus and Hernando Counties, and a great number of small crude plants were built from Newberry, Alachua County, all the way to Croom, Hernando County. Phosphate was found in many places as "outcrops." Looking for outcrops was the first method used by the early prospectors in searching for deposits. Several years passed before any systematic method of prospecting was used. Early Mining The early method of mining hard-rock phosphate was with picks and shovels, wheelbarrows, mules and wagons. The pick-and-shovel method was used altogether until about 1900, when some of the larger operators began to use railroad-type steam shovels of from ½ to I-yd. capacity Picks and shovels, with negro labor loading the phosphate ore (called "matrix") into wooden side-dump skip-cars, was continued until about 1907. From the discovery of hard-rock phosphate until approximately 1905, overburden was removed with mules and scrapers. At some places, the overburden was loaded into side-dump skip-cars by negro laborers and the cars were then pulled up an incline with a steam hoisting engine. The maximum depth of overburden that could be economically removed by hand labor, mules and scrapers was approximately 15 feet. About 1905 one of the companies erected a producer-gas power- I house near Dunnellon and generated its own electricity and about the same time the larger companies began using hydraulic methods for the removal of overburden. From the year 1888 through the year 1939 approximately 75 companies were operating at one time or another in the hard-rock territory, on approximately 500 locations. The hard-rock deposits are more irregular and have higher mining costs than the pebble-rock deposits, therefore 1 they have not been competitive in the domestic market, but because of the higher grade of the hard rock it is in demand for I the export trade. Discovery of phosphate outside of the United States has made it increasingly difficult in recent years for the hard-rock companies to survive, so today i only three companies are operating. These

Jan 1, 1942

By J. E. Chappelear

We are concerned with the problem of calculating the forces produced by passing waves on a submerged object (in particular a drilling barge) located on the ocean floor. We employ the linearized theory of waves (the Airy1 theory), since solutions are generally more easily obtained in such a theory. It will be indicated how an approximate solution to the problem can be obtained for waves of finite height by use of a linear combination of Airy waves. We shall assume the submerged object has an infinite length, thus neglecting diffraction and making the problem two-dimensional. We find that there is not a considerable difference between our solution and the usual engineering solution. The force, as a function of time, is plotted in Figs. 4 and 5, together with the usual solution for easy comparison. So far, no experiments have been found to compare with the results. As will be shown, the calculations can be extended to waves of finite height (Stokes2-Struik3 waves) in an approximate fashion. This can be done by calculating the force produced by each Fourier component of the wave, separately, and omitting the coupling between the various harmonics produced by Bernoulli's theorem. The problem and its boundary conditions will be briefly stated. We seek a function, +, the velocity potential, which is harmonic, ?2?=0...........(1) and which satisfies the boundary conditions ??/?n =0 .......(2) (the normal derivative of + is zero) on the ocean floor and the sides of the barge, and s??/?y = ?..........(3) on the ocean surface, where s = g/w2........(4) The physical reasons for these choices and an interpretation of ? are given by Lamb.' As previously stated, we assume also that the problem is two-dimensional. We set up our coordinates such that x = 0 is the center of the barge and y = 0 is the ocean floor. The coordinates are shown in Fig. 1, together with the location of the barge on the bottom. Our solution may be decomposed into a function which is symmetric about x = 0,?e, and one which is antisymmetric, +,, ? = ? + ?o...........(5) Thus directly above the barge we have as boundary conditions that for x = 0, ?o = 0, ...........(6) and ??e/?x = 0........(7) Now, far from the barge, we have that (for x positive and assuming the waves are incident from the left) ?e ? Ae cosh ky cos k (x + a) , . . . (8) and ?e ? Ao cosh ky cos k (x + ß) . . . . (9) where + means ". .. approaches ... for x large." Let us put Ae, Ao, and k equal to one, and remember that, in accordance with the derivation of Eq. 3, a sinusoidal time factor is to be supplied. Then we may rewrite Eq. 8 for ?e, and we find that

Jan 1, 1958

By G. W. Gross

A commercial deposit of white kaolinite clay contained in the sandy overburden of the Cambrian Gatesburg formation in Central Pennsylvania was successfully mapped by combined SP and resistivity methods and results were checked by drilling. Resistivity minima in the range between roughly 2000 and 3500 ohm-meters coupled with second-order SP maxima of 50-60 mV contrast were found to characterize commercial white kaolinite clay beneath not more than 30-40 ft. of sandy overburden in the area stdied. This investigation supports the hypothesis, established previously, that certain SP phenomena may reasonably be ascribed to diffusion and membrane potentials produced by interaction of clay lenses, sandy matrix, and ground waters. The success of this test proves that this prospecting technique can assist in locating clay deposits in sandy overburden derived from the weathering of sandstones and carbonate rocks such as the Cambrian formations of Central Pennsylvania. In a recent paper, Gross and Moore (1959) described broad self-potential minima above the outcrops of the Cambrian Gatesburg formation. These "first-order" SP anomalies, of 220-350 mV contrast (Figure 7), are related to the peculiar sandy residual soil covering the Gatesburg formation. Small positive ("second-order") peaks of 50-60 mV contrast are superposed on the bottom or flanks of the first-order troughs. They appear to be related to lenses and layers of kaolinite clays within the sandy Gatesburg overburden. Both first-order and second-order anomalies show a characteristic inverse relationship with apparent resistivity profiles in most cases. An explanation in terns of liquid-junction and shale potentials was advanced. According to this working hypothesis, shale potentials are generated: 1) at the contact of the sandy Gatesburg overburden with the more argillaceous soils of surrounding formations; 2) at the boundary of clay lenses contained in the sandy matrix of that overburden. Concentration gradients between interstitial infiltration waters and perched water tables within the Gatesburg overburden are believed to give rise to the liquid-junction potentials. In order to test this hypothesis further, a detailed study was carried out of a second-order positive anomaly on the property of the Woodbury Clay Co. at Mines (Blair County, Pa., Hollidaysburg folio of the U.S. Geological Survey). A second aim was to establish if combined SP and resistivity surveys are suitable as a practical method for delimiting favorable areas in which commercial kaolinite clay de~osits may be found by drilling. Drilling control was provided by the Woodbury Clay Co. PROCEDURES Instrumentation used for SP measurements was the same as described in the paper mentioned. For resistivity surveys, a direct-current voltmeter-ammeter device built by Georator Gorp. of Manassas (Va.) was used in combination with non-polarizing electrodes from the same manufacturer. Power was supplied by one to six 45-volt, heavy-duty B-batteries

Jan 1, 1961

By J. G. Patchett, R. W. Rausch

Fresh waters and the presence of clay in many Rocky Mountain and West Coast sands require special methods of log analysis. Archie's saturation equation requires addition of a shale correction term, and the SP equation must also be modified to account for clays. Suitable equations were developed several years ago, but have not been widely used due to the algebraic complexity. A computer-oriented method has now been developed to overcome this problem. The basic shaly sand equations are rearranged in four different ways to permit solution for various sets of available input data. Essential to application of the method is the correction of observed SP values to those that would be observed if the resistivity of the formation waters were exactly interchangeable with the activity. A graphic method for doing this is given. Where conditions require consideration of the effect of clay in the sands, the method presented has been found to improve the accuracy of water-saturation determinations. INTRODUCTION Log interpretation in many Rocky Mountain and West Coast basins is complicated by rapid vertical and lateral changes in water resistivity. Calculation of formation water resistivity from the SP curve becomes difficult in zones that contain clay, since changes in SP deflection may be due to changes in either clay content or water salinity. In hydrocarbon-producing reservoirs, the problem is further complicated because hydrocarbon saturation also reduces the SP.1 A log interpretation system using computers has been developed to provide a solution to this problem, based on equations proposed by de Witte.2 Four different simultaneous solutions of de Witte's equations have been made. Each solution method uses a different set of input data as independent variables. Thus, a choice of solution method is possible, depending upon the logs run and the availability of other data. Two of the solutions do not require a knowledge of water resistivity. This system is intended to be used primarily in multiple sandstone-shale sequences of low and moderate resistivities where the principal contaminant in the sandstones is clay. However, where sufficient regional data are available, interpretation in single-zone sandstone reservoirs can also be improved by using the method. THEORY AND HISTORY OF SHALY SAND ANALYSIS The log interpretation formula originally proposed by Archie3 in 1941 is applicable only to rock-fluid systems wherein the rock has negligible electrical conductivity. In 1949, Patnode and Wyllie4 showed that if the rock itself can be considered conductive due to the presence of clay, a different calculation approach is necessary. During the following years, this problem was investigated at great length, as was the related problem of the effect of rock conductivity on the SP.5-11 These investigations established functional relationships between SP, resistivity, water saturation and water resistivity for such a formation. Refs. 2 and 12 provide summaries of these studies. Unfortunately, practical use of these relationships required that water resistivity be known independently from the SP. Although log interpretation methods for rock systems containing clay were proposed at that time,' they were not generally accepted for routine use. There are three principal reasons for this. First, in many field situations involving high-salinity water, rock conductivity may be neglected (even if present) without introducing appreciable error. This may be seen by considering the following expression for waier-saturated rock.' 1/R2=1/R1+1/FRn....(1) where 1/R, is conductivity due to clay. As Rw becomes small, I/FRw becomes much greater than 1/R, which may be neglected. Where 1/R, may be neglected, the sandstone is called clean. If the term may not be neglected, the sandstone is termed dirty or shaly. For resistivity purposes, the classification between clean and shaly sands then depends not only upon the conductivity due to shale in the sand, but also upon the resistivity of the associated water (shale is used here to mean surface condition due to disseminated clay). A sand of given conductivity might safely be treated as clean in association with high-salinity water, but would require shaly sand methods if associated with fresher waters. Shaly sand methods are not required in many areas having saline waters; but in Rocky Mountain and West Coast sands having relatively fresh waters (often more than 0.3 ohm-m resistivity at formation conditions), the shaly sand methods are needed. Errors Rw calculations from the SP due to the presence of shale are likewise related to water salinity. In saline water formations drilled with fresh mud, the ratio of mud filtrate resistivity to water resistivity is high, the SP is large and the presence of shale can introduce large errors in water resistivity calculated by the conventional method. When the resistivity ratio is low, the errors are smaller. At zero SP, no error would result from shale. Thus, from the SP viewpoint, a given rock could be shaly if associated with a saline water, and clean in association with a fresh water, which is the opposite of the resistivity-oriented definition above.

By H. E. Cline, J. L. Walter

Grain boundary sliding and migration were studied in pure aluminum bicrystal and polycrystal samples with two-dimensional grain structure. Scratches, 50 P apart, were used for measurement of sliding and migration distanceso. Samples were deformed at constant rate at 315C and events recorded continuously on wrotion picture film. Electron micrograPhs of boundary-scratch intersections were obtained. Yield and flow stress values were measured. The sequence of sliding and migration events for a three-grain junction is described in detail. Sliding depended only on the resolved shear stress imparted to the boundary. Sliding was accowmodated by formation of shear zones in grains opposite triple points and adjacent to curved boundaries. These shear zones provided the driving force for grain boundary migration. Migration caused rumpling of the boundaries, decreasing the sliding rate. Sliding and migration generally began at the same time, occurred simultaneously and ended at the same time. In the bicrystal, sliding and migration rates were proportional. Initial sliding rules of 5 X joe cm per sec. were measured for the polycrystal and bicrystal samples. These sliding rates agree wilh the internal friction experirnents of K;. The observations seem consistent with a viscous boundary sliding nzechanism. GRAIN boundary sliding is the translation of one grain relative to its neighbor by a shear motion along their common boundary. Sliding is thought to be an important mode of deformation at elevated temperatures and at low strain rates such as prevail in creep,' and perhaps in the area of superplastic behavior.2"4 Although much work has been done to investigate grain boundary sliding, the effort has not led to the identification of a mehanism. KG showed that grain boundaries in aluminum exhibit a viscous nature under very small displacements of internal friction measrements. Various dislocation mechanisms have been proposed but are without conclusive experimental support. Attempts to relate sliding to 6's viscous boundaries have been unsuccessful in that measured rates of sliding are always several orders of magnitude lower than KG'S results would predict.= In bi crystals7and polycrystalsR of aluminum tested under constant load, the grain boundary sliding was found to be proportional to the total creep elongation which indicated that sliding might be controlled by deformation of the grains. Shear zones were observed to extend beyond grain boundaries at triple points to accommodate the sliding.8 Surface observations brought forth the opinion that sliding and migration occurred alternately, in sequence.' Measurements of sliding at the surface have been criticized because they might not be representative of the interior of the sample. Generally speaking, it seemed that much of the previous work and knowledge was based on observations made at relatively low magnification and examination of samples after deformation had been accomplished. Thus, it was the purpose of the present study to continuously record, at high magnification, the events occurring during the deformation of pure aluminum. Samples with two-dimensional grain structures were used to simplify interpretation of the results. The sliding and migration of small areas of many samples were continuously recorded by time-lapse motion pictures. Replicas of the surface were used to provide high-resolution electron micrographs. These observations, coupled with tmsile strength data, provide sufficient information to arrive at an understanding of the phenomenon. EXPERIMENTAL PROCEDURE An ingot of 99.999 pct A1 was rolled to sheet, 0.127-cm thick. Tensile specimens, with a gage length of 0.85 cm, were machined from the sheet. Bicrystal tensile specimens, of the same dimensions, were spark cut from a large bicrystal ingot. The grain boundary was oriented at 45 deg to the tensile axis. The surfaces of the tensile samples were ground flat on fine metallographic paper and were then electropolished in a solution of 75 parts absolute alcohol and 25 parts of perchloric acid. The solution was cooled in an ice-water bath. Using a weighted sewing needle suspended from a small pivot on a precision milling machine, a grid of fine scratches, 50 p apart, was scribed on one surface of the sample. The polycrystalline samples were then annealed in hydrogen for 15 min at 350" to 400°C to produce a two-dimensional grain structure of about 0.2-cm average grain diameter which would not undergo further growth at the test temperature, 315OC. Examination of both surfaces of the samples showed that the grain boundaries were perpendicular to the surface of the polycrystal and bicrystal samples. A hot-stage tensile machine was constructed for use with an optical microscope as shown in Fig. 1. The specimen is shown mounted in the grips. The grips ride in V-ways so that the sample can be mounted without damage. The rear grip is free to slide so that when the sample expands during heating it is not put under a compressive stress. When the grips and samples are at temperature, the rear grip is locked in place by two set-screws. The other grip is connected to a synchronous drive motor which, through a worm gear and a fine-threaded rod, deforms the

Jan 1, 1969

By H. H. Alexander

PRIOR to 1915, numerous attempts were made to treat tin concentrates in the United States, but for various reasons they were unsuccessful. Tin ore is said to have been found in nearly every state, but none of the deposits have proved to be of commercial importance. The only domestic production is in Alaska, but only a few hundred tons annually have been produced; hence any considerable production of tin in the United States must be from foreign ores. The most promising occurrence of tin was found in the Black Hills, S. Dak.; in the early development stage, it was called the Cornwall of America. Associated with the tin is tungsten. The story is told that an exceedingly fine specimen of the Black Hills ore was sent to England to encourage stock promotion; the desired effect was produced until a skeptic chipped off a small piece, which the analysis showed to be wolframite. FIRST ATTEMPTS AT SMELTING One of the first promising attempts at tin smelting in the United States was made by R. T. White at Bayonne, N. J., in 1903. Mr. White, after spending some time in England studying the methods of tin smelting, organized a company called the International Tin Co., and erected a plant to treat tin concentrates from the Straits of Malacca. About the time the plant was completed, the English Government placed an export duty of 40, per cent. ad valorem on tin .concentrates exported to other than British smelters, which duty made it impossible to operate this plant so the enterprise was abandoned. As this export duty is still effective, the only source of tin-ore supply for 'the United States is the Bolivian concentrates.

Jan 3, 1924

By Arthur Tauber, Horst Kedesdy

FERRITES are sintered metallic oxides of the spinel structure type1 and belong to the class of soft ferromagnetic materials. Similar to a ceramic, they can be formed and fired to a dense body, exhibiting a high electrical volume resistivity ranging from 102to 107 ohm-cm as compared with 10-6 ohm-cm for some of the metallic magnetic materials. This high resistivity, with resulting low eddy current losses, finds special application at high frequencies. The dispersive susceptibility of ferrites at microwave frequencies has also led to many applications in this field. Ferrites are used in low frequency applications where high resistivity with high permeability is desirable. During the last few years ferrites exhibiting rectangular hysteresis loops have been developed for computer and magnetic memory systems. The general formula for ferrites is MeFe2O4 where Me is a divalent metal ion such as Ni, Zn, Mg, Mn, Cu, Cd, and Fe. Only two of these ferrites are nonferromagnetic, namely, those with Zn and Cd. Solid solutions can be formed between different ferrites, and it is of interest to note that solid solutions of a ferromagnetic ferrite with a nonferromagnetic ferrite yield much better magnetic materials than the basic ferrite body. In general, it can be said that the solid solution formation between ferrites has widened the field of ferrite synthesis and has led to methods of preparing materials with a large variety of magnetic properties. During the last two decades the synthesis of ferromagnetic oxides has been the object of extensive research, but commercial production has been started only within the last ten years. Along with more fundamental studies, there remains the never- ending task of developing ways to realize the optimum characteristics of materials in large-scale production. Ordinarily, to produce a ferrite material it is necessary for the constituent oxides to be mixed intimately, pressed, and then fired at temperatures above 1000°C. Ferrite Synthesis: Formation of a basic ferrite by solid state reaction from Fe2O3 and a monoxide such as NiO, under normal atmospheric conditions, is governed by a progressive diffusion of cations between adjacent particles of the constituents. Firing temperature, furnace atmosphere, and cooling can vary the magnetic properties, however. If, for example, a dioxide, a sesquioxide, or an oxide of the Me3O4 type is substituted for the monoxide, the reaction mechanism becomes more complex and extremely dependent on atmospheric conditions and firing cycles. For this reason reproduction often

Jan 1, 1958

By James O. Lewis

Gravity drainage is the self-propulsion of oil downward in the reservoir rock. Under favorable natural and operational conditions, it has been found to effect recoveries comparable to water displacement. With modern technical knowledge, the operator can often make a choice between dissolved gas drive, water drive and gravity drainage as the principal recovery agent in a reservoir. It is desirable that the opeator be able to determine which of the three agents will be most effective under each set of conditions. So far, gravity drainage has received less consideration than the other two. In this paper. an endeavor is made to set forth some of the principles of gravity drainage, to point out the types of reservoirs favorable for it, and to show how it may be applied in them. Field examples are described and discussed. Introduction Since early in the history of the oil industry, it has been recognized that gravity is one of the three important natural forces for expelling oil from the reservoir rock. As knowledge of the technology of oil recovery progressed, ideas changed with respect to the relative importance of the three forces and with respect to the manners in which they functioned. For a time, disproportionate emphasis was placed on the importance and function of gas and the need for conserving gas pressures. More recently, disproportionate emphasis has been placed on encroaching edge water. Only lately has there been evidence that the function and importance of gravity was to receive due consideration. Study of this neglected phase of oil recovery is needed to round out our knowledge of reservoir behaviors and to gain a balanced viewpoint of the interplay of forces that may operate in varying importance in reservoirs. The purpose of this paper is to discuss mainly in a qualitative way, the functions of gravity, to present some concrete instances where it has been important and to raise some questions that should be investigated further. Oil-recovery Agents The important natural agents for effecting oil recovery that may be originally available in a reservoir are gas, both dissolved in the oil and free in gas caps, encroaching edge water and gravity. Each of these agents can act in a dual capacity—physically to overcome the surface energies that hold the oil within the pores and mechanically to overcome viscous . resistance and to propel the oil through the porous reservoir rock to the wells. Advancing edge water displaces the oil from the pores and lifts it updip to structurally lower wells. Gravity drains the oil from the pores and flows it downdip to the wells. Gas displaces oil from the pores, entrains it in the gas stream and flows it to the wells, but gas in solution also affects the physical properties of the oil and thus can influence oil recovery by the other agents, whether or not the mechanical energy in the gas is utilized. Of the two functions of these agents, the more important is the ability to dis-

Jan 1, 1944

By James O. Lewis

Gravity drainage is the self-propulsion of oil downward in the reservoir rock. Under favorable natural and operational conditions, it has been found to effect recoveries comparable to water displacement. With modern technical knowledge, the operator can often make a choice between dissolved gas drive, water drive and gravity drainage as the principal recovery agent in a reservoir. It is desirable that the opeator be able to determine which of the three agents will be most effective under each set of conditions. So far, gravity drainage has received less consideration than the other two. In this paper. an endeavor is made to set forth some of the principles of gravity drainage, to point out the types of reservoirs favorable for it, and to show how it may be applied in them. Field examples are described and discussed. Introduction Since early in the history of the oil industry, it has been recognized that gravity is one of the three important natural forces for expelling oil from the reservoir rock. As knowledge of the technology of oil recovery progressed, ideas changed with respect to the relative importance of the three forces and with respect to the manners in which they functioned. For a time, disproportionate emphasis was placed on the importance and function of gas and the need for conserving gas pressures. More recently, disproportionate emphasis has been placed on encroaching edge water. Only lately has there been evidence that the function and importance of gravity was to receive due consideration. Study of this neglected phase of oil recovery is needed to round out our knowledge of reservoir behaviors and to gain a balanced viewpoint of the interplay of forces that may operate in varying importance in reservoirs. The purpose of this paper is to discuss mainly in a qualitative way, the functions of gravity, to present some concrete instances where it has been important and to raise some questions that should be investigated further. Oil-recovery Agents The important natural agents for effecting oil recovery that may be originally available in a reservoir are gas, both dissolved in the oil and free in gas caps, encroaching edge water and gravity. Each of these agents can act in a dual capacity—physically to overcome the surface energies that hold the oil within the pores and mechanically to overcome viscous . resistance and to propel the oil through the porous reservoir rock to the wells. Advancing edge water displaces the oil from the pores and lifts it updip to structurally lower wells. Gravity drains the oil from the pores and flows it downdip to the wells. Gas displaces oil from the pores, entrains it in the gas stream and flows it to the wells, but gas in solution also affects the physical properties of the oil and thus can influence oil recovery by the other agents, whether or not the mechanical energy in the gas is utilized. Of the two functions of these agents, the more important is the ability to dis-

Jan 1, 1944

By T. Egleston

The origin of gold both in placer deposits ancl in veins, and especially the origin of nuggets, has been the subject of repctated discussions and investigations, which have been recently brought to my attention by several extremely interesting specinlens sent to me for examination, and mare especially by the one exhibited at the meeting of the Institute in February, 1880.* In the year 1874 I made some exan~inations of the hydraulic mines of California, and was very nluoh struck with the distribution of the gold throughout these deep placers, which were almost invariably poor on'the surface, while gradually growing richer towards the bedrock. The constant presence of fossil wood, and the large quantity of organic matter contained even low down in these beds, was also remarkable. Not being satisfied with the various theories advanced to account for the formation of these deposits, I began an investigation early in the pear 1879 on the conditions of solubility of gold and the causes of the loss in working gold ore in a large way. The researclles which I have undertaken show that gold must be considered a soluble rather than an insoluble metal, and that the conditions of solution are such as will be found anywhere where gold is likely to occur, and the solution may take place even under the ordinary circumstuncee of surfiace drainage, and may be going on freely even where the presence of gold has never been suspected, and that there are causee enough in nature to produce the solution of the gold in sufficient quantities to account for all the phenomena of both the vein and placer formations. The general theory with regard' to the formation of these placer deposits and nuggets has been that they were the result of the deatruction of pre-existing. vein-matter, which does not accord with the fitcts as sholvn in the deep placer deposits. The gold in such case would be distributed in layers of unequal richness throughout

Jan 1, 1881

By Wm. R. Webster

THIS is a contribution for the proposed new discussion on the physics of steel. The former discussion on the subject started with the consideration of five papers presented at the Chicago meeting in 1893, and continued for several years. The Suggested Lines of Discussion, prepared by Doctor Howe, covered a wide field and added greatly to the success of the work. Naturally, the first step in a new discussion will be to remodel and bring up to date the old Suggested Lines of Discussion so as to embody all the important advances in the metallurgy of steel that have a bearing on the physics of steel and keep the papers and discussions within the field of work undertaken. This paper will be devoted to the practical application, in rolling steel, of the effects of carbon, phosphorus, and manganese on its tensile strength, with some suggestions on further research work. Dr. J. E. Stead, in his paper Influence of Some Elements on the Mechanical Properties of Steel,1 gave a complete review of all that had been done during the past thirty years. He gave full credit to all investigators who worked on these lines, also their results, with his views on same, and in many cases his own results. All of this data and much new valuable information were put in convenient shape for reference and study. To do this required a great deal of work, which is fully appreciated by the steel manufacturers and investigators. The variations in the values given by the different investigators for the increase of the tensile strength of steel for each 0.01 per cent. of carbon, phosphorus, and manganese were largely due to the steels they worked on, the large or small variations in the amount of the elements present, and the omission to take into consideration all the factors, from the blast furnace through to finished rolled material, that affect the character of the steel. For instance, a poorly made dirty steel requires considerably more carbon to give the same ultimate strength than a well-made clean steel with the same phosphorus and manganese content.

Jan 3, 1921

By Ligon Johnson

ONLY the acute phase of the smelter fume problem is new. The problem itself is older than the Christian era. While both lead and copper were mined and crudely smelted ; on: 3,000 years ago, it was not until the Roman occupation of the Iberian Peninsula and the British Isles, which occurred but shortly before the beginning of the Christian era, that there was any evidence of smelting operations on a scale sufficiently large to permit a fume problem. Around Huelva, Spain, are found more than 30 million tons of slag from lead smelting conducted there by the Romans. Pliny tells us that more than 20,000 slaves were employed in the Iberian mines. Extensive mining and smelting by the Romans in England and Wales were coincident with the Iberian proceedings. These metallurgical operations were upon a sufficiently large scale to produce marked results both upon the surrounding country and the smelter workers, but, as they were those of a conqueror upon conquered soil, conducted by slaves, imperial Rome failed to recognize that such a thing as a smoke problem did or could arise, and whatever fume question there may have been at that .time remained a question only to those who had no chance to answer any phase of it. The smelting operations of the Romans extended over about 400 years, and little is "recorded of lead and copper smelting from that time until the 16th century. From the revival beginning at this period up to the present century, the growth of smelting has been comparatively gradual. In Great Britain, smelting was conducted almost wholly in localities where metallurgical operations were of paramount importance, and the communities that grew up in smelter localities were due to and dependent upon the mines and smelters. This fact had much to do with the comparative freedom of British smelting from burdensome fume litigation and legislation. To a lesser degree these conditions applied to the German operations which, when coupled with the further fact that most of the early German operations were to a greater or less degree fiscal workings of Prussia, Saxony and Brunswick-Hanover; accounts for

Jan 5, 1917

By T. J. Woods

Tars paper deals with the origin, definition and prevention of scabs an semifinished rolled-steel product. Mold coatings, which are considered essential in scab prevention, were found to be effective only in relation to the ingot surface of semikilled and killed steels and not necessary for the rolled product. That is to say, the scabs on ingots caused by having been cast in uncoated molds are eliminated in the soaking and rolling operations, therefore are not present on the rolled product. This fact, which is contrary to the average opinion, was established after extensive and thorough experiments had proved the ordinary conception of the origin of scabs to be incorrect. This subject may be of little or no concern to steel plants producing small ingots for the manufacture of small billets and bars, except as it may be of interest in showing why their surface troubles with scabs do not exist on the product of heats with normal pouring practice. But to the producer of large ingots to be rolled into slabs for large plates used in shipbuilding, it is a very important subject. DEFINITION OF A SCAB The generally accepted opinion is that the individual scabs present on rolled products (as shown by Fig. I) are considered to have been individual splashes on the ingot surface. This opinion was found to be incorrect. Experiments showed that there were no individual scabs on the product that had appeared as individuals on the ingot surface. The single scabs seen are either pieces of a shell that is present near the bottom of all top-cast ingots, or a veneer that may be present on any part of an ingot improperly poured, as when the stream strikes the mold wall. This definition is based on a detailed study of scabs and their characteristics in which the following have been found true: Location.- On the product of heats poured without trouble, scabs, if present, are always on the product that corresponds to the bottom end of the ingot, and usually occur in clusters, This is true whether molds are coated or not. Shape.-There is no regularity as to shape, size or thickness. It is sometimes possible to separate a few pieces and place them together, like pieces of a jigsaw puzzle, indicating that at one time they had been united as one piece. If individual splashes were the origin of scabs, the foregoing would not be true. Instead, the splashes, which occur throughout the pouring of the ingots, would be present uniformly over the entire product and there would be considerable similarity in the shape and thickness of the scabs. EXPERIMENTAL WORK Our experimental work was conducted on 200-ton heats of semikilled plate steel tapped into an oval ladle 15 ft. high. All ingots were top-cast direct into 24 by 54 by 82-in. molds, straight-sided, set on fat stools. Two separate studies were made about one year apart, each study extending

Jan 1, 1943

By B. Trentini

In the spectacular development of pure oxygen steel-making, the process using the vertical lance converter LD, is at the present time the most widely employed. Proper control of slag composition during the steel-making process appears to be essential in achieving satisfactory blowing from both the metallic yield and metallurgical points of view. The paper illustrates the primary importance of the presence of a large quantity of metal droplets in the slag during the process. In the case of both phosphorus and hematite pig iron, it can be deduced from the phase diagrams and confirmed by experimentation that nonhomogeneous slags are one of the causes of slag overflowing during the blow. The problem is however a complex one and further physicochemical studies appear necessary. Finally, the new continuous steelmakingprocess developed by IRSID is described. PEOPLE who knew Henri Marion Howe have said that he took great pleasure in speculating on the future of metallurgical processes. It is therefore not inappropriate to devote, in his memory, some description and discussion to processes unknown to the world of his time, in particular oxygen steelmaking and continuous steelmaking. The first industrial application to steelmaking of tonnage oxygen produced by air liquefaction was made in Germany just before the war and consisted in enriching the air blown through the bottom of a basic Begsemer converter in order to melt a higher proportion of scrap and to produce steels with lower nitrogen content than is achieved with conventional practice. While this process was being developed after the war, mostly in Western Europe, steelmakers were becoming increasingly familiar with the technique of blowing pure oxygen from the top, first by means of consumable steel pipes, with or without refractory shielding, and later by water-cooled lances, designed for the purpose and affording longer life. The field was then open for the wide use of pure oxygen in steelmaking, either in existing processes such as open-hearth or electric furnace, or in new processes. These new processes can be broadly classified according to the category of furnace employed. In the case of the vertical converter taken as the first category, bottom-blowing of pure oxygen causes extremely rapid wear of the refractory tuyeres, and although various expedients have been tried to overcome this drawback (such as mixing oxygen with CO2 or H2O or using high pressure oxygen), they have had to be abandoned. The solution for vertical converters has been found in top-blowing with a vertical water-cooled lance; this is known as the LD process or basic oxygen converter process.

Jan 1, 1969

By A. T. Tye

Regarding the results of preferential flotation at Cananea, Weinig has stated that "The concentrating mill of the Cananea Consolidated Copper Company at Cananea, Mexico, furnishes an excellent example of modern flotation practice. The complete figures are given because they present so forcibly the advantages of modern selective flotation."l L. 0. Howard notes that "Perhaps the outstanding example so far published of improverrients in results through the use of selective flotation is that at Cananea, Mexico."" The following notes indicate the conditions under which the results were obtained at Cananea; also the effect of preferential flotation at the concentrator and at the smelter. In the majority of cases the full benefit of selective flotation is not fully realized, as the concentrates are shipped from the mill to smelters owned by other companies. The saving made at a certain concentrator by this method of flotation may be well understood but the saving resulting at the smelter from the results of preferential flotation at the mill is not so apparent, as the data are contained in the smelting records of some other company. Even at the smelter the great gains following preferential flotation may not be noted, as a variety of ores and concentrates from various sources are received and the difference from the changed concentrator operations of a certain mill may be obscured. As noted by Professor Weinig and Professor Howard, the results obtained at Cananea brought about a veritable metallurgical revolution at the smelter. There are probably plants at which a better preferential separation is being made than at Cananea. Many ores contain barren iron pyrite which, when depressed, does not carry copper into the tailing. Some concentrators use clean uncontaminated water for milling and in others the ore is ground much finer than at Cananea. All of these items are concerned in perfect separation. The details of preferential flotation at Cananea, therefore, are not presented on account of the perfection of the

Jan 1, 1928

By J. T. Eash, E. M. Wise

Many of the platinum metal alloys are hot-forged in the early stages of reduction from ingot and substantial quantities of platinum alloys are commercially employed at very high temperatures in ammonia oxidation units, orifices for forming glass rods and fibers and as cathodes in long-life thermionic amplifiers. They are used also for electrical heating resistors, safety blowout disks, thermocouples and crucibles. The tensile properties at elevated temperatures are important in many of these situations but data on the subject are limited. Creep data also are important, but will not be covered at this time. Scope and Conclusions Tensile tests were carried out at room temperature and elevated temperatures up to 1100" C. on previously well annealed samples of platinum. palladium and several of their important alloys with compositions shown in Table 1. The results are presented graphically in Figs. 1 to 4. The tensile strengths of platinum and the platinum-base alloys (with the exception of the 10 per cent rhodium-platinum alloy) at 1100" C. are from 16.6 to 18.8 per cent of the strengths of the same alloys (well annealed) at room temperature. The strength ratio of the 10 per cent rhodium-platinum alloy is 22.3 per cent, which is appreciably higher than that of the other materials tested. The tensile strengths of palladium and the palladium alloy at 1100" C. are from 10 to 11.2 per cent of the room-temperature values. The elongations of platinum and its alloys tend to increase at temperatures above 600" to 800" C., while the two samples of pure palladium show a maximum at 600" C.

Jan 1, 1938

By J. T. Eash, E. M. Wise

Many of the platinum metal alloys are hot-forged in the early stages of reduction from ingot and substantial quantities of platinum alloys are commercially employed at very high temperatures in ammonia oxidation units, orifices for forming glass rods and fibers and as cathodes in long-life thermionic amplifiers. They are used also for electrical heating resistors, safety blowout disks, thermocouples and crucibles. The tensile properties at elevated temperatures are important in many of these situations but data on the subject are limited. Creep data also are important, but will not be covered at this time. Scope and Conclusions Tensile tests were carried out at room temperature and elevated temperatures up to 1100" C. on previously well annealed samples of platinum. palladium and several of their important alloys with compositions shown in Table 1. The results are presented graphically in Figs. 1 to 4. The tensile strengths of platinum and the platinum-base alloys (with the exception of the 10 per cent rhodium-platinum alloy) at 1100" C. are from 16.6 to 18.8 per cent of the strengths of the same alloys (well annealed) at room temperature. The strength ratio of the 10 per cent rhodium-platinum alloy is 22.3 per cent, which is appreciably higher than that of the other materials tested. The tensile strengths of palladium and the palladium alloy at 1100" C. are from 10 to 11.2 per cent of the room-temperature values. The elongations of platinum and its alloys tend to increase at temperatures above 600" to 800" C., while the two samples of pure palladium show a maximum at 600" C.

Jan 1, 1938

By H. D. Outmans

The mechanics of filtration are described by a theoretical-empirical nonlinear diffusion equation which, under certain circumstances, may,be linearized and then solved explicitly. For filtration under static conditions linearization leads to a boundary value problem analogous to a heat flow problem with a known explicit solution. The corresponding solution for static filtration is compared with published experimental data. Under dynamic conditions filtration takes place in three successive stages. During each of these the rate of filtration and/or the thickness of the filter cake are different functions of the filtration time. The proposed mechanism explains the observed high resistance of dynamically deposited filter cakes against erosion and also the connection between filtration rate and viscosity of the drilling fluid. Several of the quantities governing dynamic filtration have no counterpart in the static filtration mechanism. The static filtration rate is, therefore, not a reliable measure for the dynamic rate and vice versa. INTRODUCTION Filtration under simulated borehole conditions, i.e.. either from a static suspension or from a suspension flowing parallel to the filter cake (dynamic filtration), has been the subject of several laboratory studies.1-7 This experimental and theoretical work showed that many aspects of the filtration mechanism cannot be explained by an elementary filtration theory based on the assumption that the filter cake is incompressible. For a more satisfactory theory compressibility should be taken into account. This has been done. at least to some extent, in the filtration theory developed for the chemical industry. Surveying the literature (see Ref. 8 for a bibliography) it becomes apparent that, although several properties of filter cakes deposited from many different suspensions have been measured, including compressibility, the filtration equations are essentially empirical in nature. No attempt has been made, for instance, to develop filtration theory along the lines of consolidation theory.12 This theory, upon which a highly successful development in soil mechanics rests, would appear to be an excellent starting point for a filtration theory since the compressibility concept is an essential part of it. As we will use this theory in the following development it is well to state the four assumptions on which it is based: 1. The fluid flow through a compressible porous medium is governed by Darcy's law. 2. The rate of change in fluid content of an element of the porous medium is proportional to the rate of change of solid pressure between the particles. 3. The solid particles are incompressible within the range of pressures considered. 4. The total pressure on a surface normal to the line of flow is equal to the sum of the fluid pressure and the pressure between the particles (solid pressure) at that surface. To calculate the rate of filtration and other quantities of interest it is necessary to know the filter cake compressibility and the permeability as a function of the solid pressure. It has not been possible to calculate these functions from theoretical considerations and they will therefore be introduced in this paper as empirical expressions. Both are determined in a compression cell where the cake is subjected to a mechanical load. Permeability and compressibility are measured after the solid pressure has stabilized, i.e., after the excess fluid pressure has been dissipated and the uniform pressure is transmitted entirely by the solids. The permeability and compressibility thus determined are not the same as during filtration in the borehole, under either static or dynamic conditions, because then, due to frictional drag, the solid pressure and hence also the permeability and compressibility vary along a line normal to the direction of the mean flow and can only be defined locally. DERIVATION OF THE FILTRATION EQUATION FOR COMPRESSIBLE FILTER CAKES As the filter cake in the borehole is thin compared to the radius of the hole the filtration may be considered as linear. Taking the x-axis normal to the wall, with its origin at the formation, we have, according to Darcy's law,

J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—The fact that the experimental work has been applied to copper rather than iron and that the paper is presented to the Iron and Steel Division, I regard as rather significant. It shows the unity of metallurgy and the fallacy of trying to cut it up by metals. This result for the solubility of sulphur in molten copper correlates with Professor Schuhmann's finding that the published data on the other side of the copper-sulphur miscibility gap are also in error. I should like to ask the author to say a little bit more about the sulphur capacity of the slag. T. Rosenqvist (author's reply)-—I hope that Dr. Chipman will find the derivation of the expression for sulphur capacity more clearly explained in the printed version of the paper than in the oral discussion at the meeting. I feel that this quantity, which actually is the ratio of two activities, can be measured more easily than the individual activities. Even if the ratio CaO/CaS is chosen as the standard state, the expression can be used for any slag, even for slags completely free of lime, and it represents a way to put the desulphurizing power of all slag constituents into one bag. Some doubt has been expressed as to whether oxygen ions really exist in calcium oxide and in molten slags. From a thermodynamic view point that question is of minor importance. The term oxygen ion activity, or any activity for that matter, is defined rigorously by the equation: activity = exp u/RT, where u is the change in free energy connected with the transfer of one mol of ions from the standard state into the slag. Whatever happens to the ion in the slag is of no concern to the thermodynamicist. Regardless of whether the ion is "free" in the slag or not, or whether it is present in a very small amount, its activity can always be expressed, and for a thermo- dynamic calculation that is all we need. However, ionic activities will only be of some real value if they are simple functions of the slag composition, or can be measured easily. Concerning the real nature of the oxygen in the slag, my feeling is that the oxygen atom has a rather multiplex nature depending on how strongly it is tied by covalent forces or polarized by the other atoms or ions present. The oxides of iron, cobalt, and nickel differ from calcium oxide and blast furnace slags as to the amount of free electrons that can give rise to electronic conductivity. In slags we know that the conductivity is mostly ionic. The fact that reversible emf's can be obtained with oxygen electrodes in certain salt melts, indicates a significant amount of oxygen ions in these melts. But extended work, e.g. polaragraphic studies and measurements of transference number; are needed to obtain quantitative information about the real structure of the slags. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—-With reference to the ion, it might be well to remember Dr. Moses Gomberg. All of his life he had no use for the ionization theory and he contributed greatly to the field of chemistry on the assumption there was no such thing as ions. I do not think we have to worry about whether the oxygen is ionic or not. I think one thing specifically should be brought to your attention and this I think is one of the important contributions of Dr. Rosenqvist. He pointed out what we know as oxygen potentials or what is described as oxygen potentials. I have used this concept for a long period of time and I want to state that if this concept is properly applied, it vitiates much of what we have in the literature, or makes our usual ideas regarding oxidation seem primitive. That one thing is more valuable than almost all the rest of the discussion as a fundamental basis on which to build a reasonable in-

Jan 1, 1952