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By Paul C. Ragland, P. Geoffrey Feiss

The Piedmont province of the southern Appalachians is the focus of interest for many exploration geologists. In the past, only those deposits with significant surface exposure were exploited. Thus, few deposits have been found and relatively little exploration has been conducted in recent years. Modern geochemical and geophysical techniques can alleviate this problem of concentrating on exposed ore bodies by allowing us to "look through" the soil and saprolite to detect the presence of significant mineralization at depth. This paper will attempt to evaluate the feasibility and effectiveness of several geochemical exploration techniques in the Piedmont province of Cabarrus and Stanly counties, N.C. The area chosen for study is shown in [Fig. 1], lying almost wholly within the Mt. Pleasant quadrangle, N.C. The area is on the eastern boundary between the Charlotte belt, a zone of plutonic and intermediate grade metamorphic rocks, and the Carolina Slate belt, a series of complexly interbedded volcanic and sedimentary rocks of predominantly low metamorphic grade. The area is considered to be an early Paleozoic active, continental margin. l As is typical of most of the piedmont, outcrop is sparse. [Figure 2] is a sketch map of the general geology of the area under study, showing the Charlotte belt rocks in the northwestern quadrant and slate belt rocks to the east. Within the area are a number of old mines and prospects, the most famous of which are the Furniss and Phoenix mines in Cabarrus County. All are reported to have contained Au and Cu. Ag and Pb were reported from some. A summary of the deposits is given in [Table 1]. Data used in this study are from three Master's theses completed at the University of North Carolina at Chapel Hi11. 3, 5, 6 In separate studies, well waters, 5 B-zone soils,3 and vein and float from the area were sampled and analyzed. Each study concluded separately that geochemical anomalies in the vicinity of the ores justify use of that specific sampling technique in a geochemical exploration program. However, no comparative study of the methods has been made. It is our intention

Jan 1, 1980

By Thomas F. Downing

When examining a coal property it is customary for the engineer to take channel samples at several coal faces. In doing so the extraneous matter, or partings, which can be removed by hand, or mechanically, with the facilities at hand, or proposed, is rejected. Where there is doubt concerning a stratum it is usually rejected from the main sample but part is taken for separate analysis. The samples are forwarded to a chemist for proximate analyses and determination of British thermal units, and, sometimes, ash fusion. Consideration is given all available commercial analyses but frequently the owner presents only the favorable ones. From the results thus obtained a general evaluation is made, monies are loaned or expended, markets are determined, and realization is estimated. In many instances, such grades are not substantiated and it is time we looked deeper for a basis which will prove more practical. Institute committees are working hard on analytic and use classifications and much valuable information has already been assembled and distributed. However, no single grade can be applied to any particular bed or region. Much study has been given the Pittsburgh No. 8 seam, yet that bed is subject to material differences in a single section;i. e., some strata of a face may differ from others in structure and analysis, particularly in sulfur content. From some localities it yields a good carbonization fuel, while in others it is chemically unfit for such use. Traveling south to the Logan, W. Va., field we find the Cedar Grove (Island Creek) seam a hard, gray splint coal., In the same field, and not far distant, the same bed changes, both structurally and chemically, and consists of excellent gas coal. In Illinois the moisture content of a bed may vary greatly in different localities. We have seen mines in which part of the coal is excellent for special purpose use but is spoiled by the product from another part of the same mine. Many other illustrations could be given but these are sufficient to show that application of any grading of coal must be distinctly local. The actual designation of grade can be given only after detail study of the component parts of the seam, or seams, on the property under considera-

Jan 1, 1932

By Clyde E. Williams

Estimates indicate a life of known Lake Superior iron ore reserves of 20 to 30 years. Although some believe the future ore supply will come from foreign sources and will be brought to interior points via the projected Great Lakes-St. Lawrence waterway, and others fear a displacement of the interior steel-producing districts to the Atlantic seaboard, the author has faith that American engineering skill will make possible the use of lean ores from the Lake Superior district. Three general types of Lake Superior ores and ore formations, that represent possible reserves and require beneficiation, are: (1) the wash ores of the western Mesabi range, (2) the partly leached hematitic formations, and (3) the oxidized but largely unleached iron formations. The total tonnage represented by (1) and (2) is not large, but the recovery of iron from present washery tailings would bring on the market the equivalent of nearly one million tons of wash ore, annually. Group 3 comprises the magnetic iron formation of the eastern Mesabi range, the hematitic formations including the taconites of the Mesabi range, and the iron formations of all the other ranges. These formations represent our future supply of iron ore. Their treatment requires intensive research because the bulk of the iron oxide and silica minerals exist in a finely disseminated condition. The possibilities of the adaptation of tables, oil flotation, and other processes warrant extensive study. Cheaper method of agglomeration of the concentrate is essential. Recent developments in better preparation and sizing of blast-furnace charges indicate that substitution of agglomerated ore for fines will increase furnace efficiency and output. If agglomerated beneficiated ore can be shown to rate a per-unit premium for iron contents over the base rate or a premium for structure, the payment of these would greatly assist in enlarging our iron ore supply. Since present methods of taxation of ore reserves, which encourage the rapid depletion of rich ores, will result in using up our rich ores and later on putting domestic producers at a disadvantage in competing with' foreign producers, it would seem highly provident to conserve our rich ores and to increase the use of beneficiated ores as soon as possible.

Jan 1, 1931

By Morris Muskat

In preparing a well for pumping, observations are often made of the fluid level in the well bore or bottom-hole pressures at various times before equilibrium has set in. From a qualitative point of view one may immediately infer that if the rise in the bottom-hole pressure or fluid level is rapid the permeability of the sand about the well bore is large, and converse conclusions may be drawn if the rise is slow. However, a more quantitative estimate will give additional information of value, as will be shown in this paper. To derive such an estimate we may proceed as follows. Let h be the fluid height, above the sand face, at time t, and let yo be the average density of the fluid that enters the bore. The bottom-hole pressure, for a fluid height h will therefore be p = rogh, neglecting, of course, the friction drop in the well bore, while the fluid is rising, as may be justifiably done for most pumping wells. If a is the free area of the open-flow string—assumed to be uniform— the rate of production from the sand during the rise of fluid will be: where the last part of the equation merely indicates that, in general, the production rate Q must be considered as a function of the back pressure, and is determined by it alone. In fact, equation 1 shows that if the rate of rise of the pressure or fluid level is determined as a function of the height of rise, or p, for a number of values of the latter, this functional relation between Q and p will be immediately given. Conversely, if we know this functional relation, the rate of increase of p or h may be predicted, or, by observing the rate of rise of p or h some of the constants of the sand may be determined. Thus we may approximate the production from a well in a pumping state by that of a dead

Jan 1, 1937

By Keith Leonard Sutherland

THIS paper is a study of the differential flotation of the sulphide minerals in the presence of salts of silver, lead and zinc. In practice, accidental activation due to these salts is more important than their use as reagents to replace copper sulphate. The general method of investigation has been based upon contact tests, the temperature of 35°C. being chosen in conformity with earlier work. Potassium ethyl xanthate and potassium amyl xanthate were selected as collectors and pure sulphide minerals were used. The experimental procedure has been outlined in earlier papers and all solutions were kept carbonate-free.'' Contact, or spreading of an air bubble, at a mineral surface indicates the presence of an adsorbed collector film. PURITY OF REAGENTS The xanthates were purified in the usual manner.1 Neither the cyanide nor the sodium hydroxide solutions contained sufficient carbonate to give a precipitate with barium chloride solution. The silver sulphate was prepared from pure silver nitrate by evaporation with concentrated sulphuric acid until there was no evidence of brown fumes. This solution was diluted and the difficultly soluble sulphate washed with water so that unchanged nitrate was dissolved. The resultant crystal-line powder was pure white. The lead and zinc salts were prepared by dissolving especially pure lead and zinc in C.P. nitric and sulphuric acid solution and the crystals drained. The standard solutions were checked by titration. It was felt desirable to use the sulphate radical wherever possible, but since lead sulphate was insufficiently soluble for the purpose of the experiments, it was necessary to use some other lead salt. A.R. copper sulphate was used without further purification. RESULTS The results are presented in the accompanying figures; the areas of noncontact (nonflotation) are shaded in Figs. 8, 9, 10 and 11; in the remainder they lie to the right of the curve. Zinc Sulphate The curves in Fig. I are to be compared with those for Fig. 2, for which zinc sulphate is absent. This comparison shows that the influence of the zinc ion is usually small. Its influence is more marked, however, for chalcopyrite in the absence of cyanide. The influence of zinc sulphate is also marked for copper-activated sphalerite, for which tests were made only in the absence of cyanide. The results are of importance in the separation of pyrite from copper-activated sphalerite when zinc sulphate is added in the lead flotation section (p. 204 of ref. I). Sphalerite does not adsorb the collector (i.e., become floatable) under the conditions chosen.

Jan 1, 1942

By Keith Leonard Sutherland

THIS paper is a study of the differential flotation of the sulphide minerals in the presence of salts of silver, lead and zinc. In practice, accidental activation due to these salts is more important than their use as reagents to replace copper sulphate. The general method of investigation has been based upon contact tests, the temperature of 35°C. being chosen in conformity with earlier work. Potassium ethyl xanthate and potassium amyl xanthate were selected as collectors and pure sulphide minerals were used. The experimental procedure has been outlined in earlier papers and all solutions were kept carbonate -free.1,4 Contact, or spreading of an air bubble, at a mineral surface indicates the presence of an adsorbed collector film. PURITY OF REAGENTS The xanthates were purified in the usual manner.1 Neither the cyanide nor the sodium hydroxide solutions contained sufficient carbonate to give a precipitate with barium chloride solution. The silver sulphate was prepared from pure silver nitrate by evaporation with concentrated sulphuric acid until there was no evidence of brown fumes. This solution was diluted and the difficultly soluble sulphate washed with water so that unchanged nitrate was dissolved. The resultant crystalline powder was pure white. The lead and zinc salts were prepared by dissolving especially pure lead and zinc in C.P. nitric and sulphuric acid solution and the crystals drained. The standard solutions were checked by titration. It was felt desirable to use the sulphate radical wherever possible, but since lead sulphate was insufficiently soluble for the purpose of the experiments, it was necessary to use some other lead salt. A.R. copper sulphate was used without further purification. RESULTS The results are presented in the accompanying figures; the areas of noncontact (nonflotation) are shaded in Figs. 8, 9, 10 and 11; in the remainder they lie to the right of the curve. Zinc Sulphate The curves in Fig. I are to be compared with those for Fig. 2, for which zinc sulphate is absent. This comparison shows that the influence of the zinc ion is usually small. Its influence is more marked, however, for chalcopyrite in the absence of cyanide. The influence of zinc sulphate is also marked for copper-activated sphalerite, for which tests were made only in the absence of cyanide. The results are of importance in the separation of pyrite from copper-activated sphalerite when, zinc sulphate is added in the lead flotation section (p. 204 of ref. I). Sphalerite does not adsorb the collector (i.e., become floatable) under the conditions chosen.

Jan 1, 1942

By Gerhard Derge

METALLURGISTS have used borax as a fluxing agent traditionally, but until recently elemental boron has played an insignificant role as an alloying element. Neither the metal nor its compounds have been regarded as important metallurgical materials and there is a surprising lack of knowledge concerning their metallurgical behavior. The new applications to steelmaking of both boron and borates, which arose in part from wartime incentives and restrictions, have been seriously handicapped by this lack of data. For example, rasorite, a naturally occurring sodium borate, has been shown to be an effective substitute for aluminum as a ladle deoxidizer in rimming steels.1 Likewise, the effectiveness of boron as an alloying agent has been demonstrated, 2,3 giving deep hardening when used in restricted amounts. The exploitation of both of these uses has been retarded by the difficulty of attaining suitable metallurgical control. Recognizing that the most important information required was a knowledge of the equilibrium between boron and oxygen dissolved in liquid iron, Gurry4 calculated this relation from the best thermal data available. However, estimates of the entropy of melting of boron, the activity coefficient of boron in liquid iron and the activity coefficient of B203 in slag were involved, and experimental work on this problem was obviously desirable. The experiments to be described were planned to establish the boron-oxygen relations in liquid iron and to demonstrate at the same time the ferroborate slag compositions in equilibrium with various amounts of oxygen in liquid iron. Accordingly, slags containing varying proportions of iron and boron oxides were held in contact with molten iron, and samples of both slag and metal were analyzed. The limitations upon the accuracy of the data will be considered, but in a practical sense the oxygen levels that can be attained in iron by iron borate slags, and the amounts of boron in iron at these oxygen levels were established. EXPERIMENTAL PROCEDURE No entirely suitable refractory was found for the mixtures of iron oxide and boron oxide used as slags. Crucibles of silica, magnesia, Ramix, beryllia, and zirconia were all tried unsuccessfully. The most satisfactory method discovered for handling them was the rotating-crucible technique, which creates a parabolic crucible of liquid iron 5,6 Even this was not entirely successful, for at steelmaking temperatures (1600°C.) the slags had such a low surface tension that they crept up to the refractory and slowly dissolved it. These difficulties made it impossible to maintain a constant slag composition for an unlimited period of time. However, by using the rotating

Jan 1, 1946

By Gerhard Derge

Metallurgists have used borax as a fluxing agent traditionally, but until recently elemental boron has played an insignificant role as an alloying element. Neither the metal nor its compounds have been regarded as important metallurgical materials and there is a surprising lack of knowledge concerning their metallurgical behavior. The new applications to steel-making of both boron and borates, which arose in part from wartime incentives and restrictions, have been seriously handicapped by this lack of data. For example, rasorite, a naturally occurring sodium borate, has been shown to be an effective substitute for aluminum as a ladle deoxi-dizer in rimming steels.' Likewise, the effectiveness of boron as an alloying agent has been demonstrated,2,3 giving deep hardening when used in restricted amounts. The exploitation of both of these uses has been retarded by the difficulty of attaining suitable metallurgical control. Recognizing that the most important information required was a knowledge of the equilibrium between boron and oxygen dissolved in liquid iron. Gurry4 calculated this relation from the best thermal data available. However, estimates of the entropy of melting of boron, the activity coefficient of boron in liquid iron and the activity coefficient of B2O3 in slag were involved, and experimental work on this problem was obviously desirable. The experiments to be described were planned to establish the boron-oxygen relations in liquid iron and to demonstrate at the same time the ferroborate slag compositions in equilibrium with various amounts of oxygen in liquid iron. Accordingly, slags containing varying proportions of iron and boron oxides were held in contact with molten iron, and samples of both slag and metal were analyzed. The limitations upon the accuracy of the data will be considered, but in a practical sense the oxygen levels that can be attained in iron by iron borate slags, and the amounts of boron in iron at these oxygen levels were established. Experimental Procedure No entirely suitable refractory was found for the mixtures of iron oxide and boron oxide used as slags. Crucibles of silica, magnesia, Ramix, beryllia, and zirconia were all tried unsuccessfully. The must satisfactory method discovered for handling them was the rotating-crucible technique, which creates a parabolic crucible of liquid iron.5,6 Even this was not entirely successful, for at steelmaking temperatures (1600°C.) the slags had such a low surface tension that they crept up to the refractory and slowly dissolved it. These difficulties made it impossible to maintain a constant slag composition for an unlimited period Of time. However, by using the rotating technique, short runs could be made in

Jan 1, 1947

By Gerhard Derge

Metallurgists have used borax as a fluxing agent traditionally, but until recently elemental boron has played an insignificant role as an alloying element. Neither the metal nor its compounds have been regarded as important metallurgical materials and there is a surprising lack of knowledge concerning their metallurgical behavior. The new applications to steel-making of both boron and borates, which arose in part from wartime incentives and restrictions, have been seriously handicapped by this lack of data. For example, rasorite, a naturally occurring sodium borate, has been shown to be an effective substitute for aluminum as a ladle deoxi-dizer in rimming steels.' Likewise, the effectiveness of boron as an alloying agent has been demonstrated,2,3 giving deep hardening when used in restricted amounts. The exploitation of both of these uses has been retarded by the difficulty of attaining suitable metallurgical control. Recognizing that the most important information required was a knowledge of the equilibrium between boron and oxygen dissolved in liquid iron. Gurry4 calculated this relation from the best thermal data available. However, estimates of the entropy of melting of boron, the activity coefficient of boron in liquid iron and the activity coefficient of B2O3 in slag were involved, and experimental work on this problem was obviously desirable. The experiments to be described were planned to establish the boron-oxygen relations in liquid iron and to demonstrate at the same time the ferroborate slag compositions in equilibrium with various amounts of oxygen in liquid iron. Accordingly, slags containing varying proportions of iron and boron oxides were held in contact with molten iron, and samples of both slag and metal were analyzed. The limitations upon the accuracy of the data will be considered, but in a practical sense the oxygen levels that can be attained in iron by iron borate slags, and the amounts of boron in iron at these oxygen levels were established. Experimental Procedure No entirely suitable refractory was found for the mixtures of iron oxide and boron oxide used as slags. Crucibles of silica, magnesia, Ramix, beryllia, and zirconia were all tried unsuccessfully. The must satisfactory method discovered for handling them was the rotating-crucible technique, which creates a parabolic crucible of liquid iron.5,6 Even this was not entirely successful, for at steelmaking temperatures (1600°C.) the slags had such a low surface tension that they crept up to the refractory and slowly dissolved it. These difficulties made it impossible to maintain a constant slag composition for an unlimited period Of time. However, by using the rotating technique, short runs could be made in

Jan 1, 1947

By M. Sagheer

This paper gives a report of the laboratory work investigating the fundamental flotation characteristics of chromite and its commonly associated mineral, serpentine. Floatability curves, showing floatability of chromite at different concentrations of sodium oleate and pH, were obtained by pick-up method. One of the difficulties encountered in flotation of chromite in presence of serpentine has been attributed to dissolved metal ions. The influence of metal ions, dissolved in pulp filtrate, on floatability of pure chromite and serpentine has been studied and it has been shown that Mg, Ca and Fe ions depress chromite. A considerable amount of work applying bubble pick-up method was carried out to counteract the depressing action of metal ions. Various methods and reagents were applied in this connection. Validity of each method and reagent has been discussed. Probably due to the abundance of high-grade chrome ores, very little has been published concerning the flotation of chromite. As improvements in mineral beneficiation are realized, more attention is being directed to low-grade ores previously considered unusable. Currently, gravity concentration is the principal process applied to upgrade chrome ores, but this cannot be used for finely disseminated ore because of the substantial losses in the fines,1,2,3 To avoid these losses, flotation can be applied to material which is too fine for satisfactory gravity concent ration, and it is probable that a combination

Jan 1, 1967

By Henry Faul

Measurement of radioactivity of rocks and ores has developed into a complete method of geophysical exploration. The problem falls into three natural categories: (1) surface radiation measurement in the field and underground; (2) radioactivity logging of drillholes; and (3) laboratory analysis of samples. Portable counters are used in the field for tracing radioactive formations and for quanti tative estimates of radioactive content of surface rock. Wartime advances in battery design make it possible to construct small precision counters that can be carried easily. Even the smallest conventional diamond drillholes can be logged, and actual content of the radioactive element can be measured. The exact grade of very thin active layers or veins can be estimated only approximately. Samples may be analyzed for their alpha, beta or gamma activity, and beta assaying is the best suited to rapid routine operation. Simple calibration with standard samples is sufficient for rough work, but a density correction is necessary when greater precision is required. Samples with high emanating power should be fixed and stored for three weeks to reestablish the radium-radon equilibrium prior to precision assaying. Carno-tite can be fixed by sintering or molding with plastics. Among the important new developments, a low-voltage Geiger tube has been 'designed recently, and crystal scintillation counters hold great promise for high-efficiency gamma-ray measurement. Introduction During the last few years we have witnessed an unprecedented rise in the demand for radioactive minerals, coming as a direct consequence of the discovery of nuclear fission and subsequent developments, the full impact of which is by no means in sight even now. It remains certain, however, that radioactive minerals, and especially those which can be used as ores of uranium and thorium, will continue to be of great interest not only to the prospector and mine operator but also to the various inspection parties envisioned by most of the schemes advanced for the control of nuclear energy on a world-wide basis. It is clear, therefore, that the measurement of radioactivity in rocks in the field as well as in samples in the laboratory has become a method of geophysical exploration of some importance. If we consider the recent technological advances in the general fields of nuclear physics and electronics it seems proper to review the present status of the methods and procedures of radiological exploration. General Considerations Equilibrium If we take a fixed amount of uranium that has just been purified, some of it will immediately start decaying into its first daughter element which in turn decays into its own daughter and so on down the line until the last daughter is reached—a stable isotope of lead. The rate at which a radioactive element decays is frequently expressed as the half-life, which is the length of time required for the decay of half the atoms in a given amount. The half-life is inversely proportional to the decay constanl X which is defined as the number of atoms which decay in one unit of time divided by

Jan 1, 1949

By Henry Faul

Measurement of radioactivity of rocks and ores has developed into a complete method of geophysical exploration. The problem falls into three natural categories: (1) surface radiation measurement in the field and underground; (2) radioactivity logging of drillholes; and (3) laboratory analysis of samples. Portable counters are used in the field for tracing radioactive formations and for quanti tative estimates of radioactive content of surface rock. Wartime advances in battery design make it possible to construct small precision counters that can be carried easily. Even the smallest conventional diamond drillholes can be logged, and actual content of the radioactive element can be measured. The exact grade of very thin active layers or veins can be estimated only approximately. Samples may be analyzed for their alpha, beta or gamma activity, and beta assaying is the best suited to rapid routine operation. Simple calibration with standard samples is sufficient for rough work, but a density correction is necessary when greater precision is required. Samples with high emanating power should be fixed and stored for three weeks to reestablish the radium-radon equilibrium prior to precision assaying. Carno-tite can be fixed by sintering or molding with plastics. Among the important new developments, a low-voltage Geiger tube has been 'designed recently, and crystal scintillation counters hold great promise for high-efficiency gamma-ray measurement. Introduction During the last few years we have witnessed an unprecedented rise in the demand for radioactive minerals, coming as a direct consequence of the discovery of nuclear fission and subsequent developments, the full impact of which is by no means in sight even now. It remains certain, however, that radioactive minerals, and especially those which can be used as ores of uranium and thorium, will continue to be of great interest not only to the prospector and mine operator but also to the various inspection parties envisioned by most of the schemes advanced for the control of nuclear energy on a world-wide basis. It is clear, therefore, that the measurement of radioactivity in rocks in the field as well as in samples in the laboratory has become a method of geophysical exploration of some importance. If we consider the recent technological advances in the general fields of nuclear physics and electronics it seems proper to review the present status of the methods and procedures of radiological exploration. General Considerations Equilibrium If we take a fixed amount of uranium that has just been purified, some of it will immediately start decaying into its first daughter element which in turn decays into its own daughter and so on down the line until the last daughter is reached—a stable isotope of lead. The rate at which a radioactive element decays is frequently expressed as the half-life, which is the length of time required for the decay of half the atoms in a given amount. The half-life is inversely proportional to the decay constanl X which is defined as the number of atoms which decay in one unit of time divided by

Jan 1, 1949

By T. S. Lundy, R. E. Pawel, F. R. Winslow, C. J. McHargue

The volume-diffusion coefficients of Nb-95 and Ta-182 in niobium have been measured over the temperature range 878° to 2400°C. High-temperature specimens (T 21500°C) were sectioned by conventional lathe and grinding techniques while low-temperature specimens were sectioned by an anodizing and stripping technique previously described. Over a range of more than ten orders of magnitude in diffusivity, the self-diffusion data is well-represented by the equation: D = (1.1+ 0.2) exp [- (96,000 * 900)/RT ] cm2/sec Upward deviations from this line are explained by short-circuit diffusion in combination with the loss of resolution of the sectioning techniques. Oxygen contamination within the range 100 to 450 ppm was found to have little or no effect on the self-diffusivitj 01 niobium. In a limited number of measurements, the diffusivity of Ta-182 in niobium was found to be about half that of Nb-95 in niobium. These data may be described by D = (I.0+0.90.5)exp [- (99,300 * 2400) /RT ] PREVIOUSLY reported studies of self-diffusion in niobium were by Resnick and Castleman1 and Peart, Graham, and Tomlin.2 The data of Resnick and Castleman over a temperature range 1585" to 2120°C show considerable scatter but. can be represented by D = (12.4 *0.8) exp [-(105,000+3OOO)/RT] cm2/sec The limited data of Peart, Graham, and Tomlin follow the equation D = 1.3 exp (-95,00O/RT) cm2/sec In view of recent diffusion data for ß zirconium3 and 0 titanium4 in which Arrhenius-type plots do not yield straight lines and of the potential high- temperature uses of niobium and its alloys, we thought it important to investigate the diffusion behavior of this bcc refractory metal over a large temperature range. This has recently been done for molybdenum,5 chromium,6 vanadium,"" and tantalum.9 Niobium was a particularly suitable material for this study largely because of the development of an anodizing and stripping sectioning technique which enables diffusivities as small as l0-19' sq cm per sec to be determined accurately.10 In addition to self-diffusion data, data were obtained for the diffusion of Ta-182 in niobium and for the effect of varying oxygen content on self-diffusion. I) EXPERIMENTAL PROCEDURE Materials. The niobium was obtained from three sources: 1) melting stock from Shieldalloy Corp., 2) electron-beam melted single crystals, 1/2 in. diameter, from Semi-Elements, Inc., and 3) oxygen-doped, electron-beam melted single crystals from Materials Research Corp. The melting stock was electron-beam melted and specimens 5/8 in. diameter by 1/2 in. long were machined from the center of the bar. The analysis supplied by the vendor and an interstitial analysis of one of the specimens are given in Table I. The single crystals (type 2 above) were cut with a jeweler's saw to specimens about 3/8 in. long. The interstitial analysis of this material is given in Table 11. This material was used

Jan 1, 1965

By Chas. A. Ashburnea

THE appliances which have been proposed, and the modifications in the construction of boiler-furnaces which have been made for the prevention of smoke, and the utilization of what are ordinarily called the waste products of combustion, have been innumerable.† †There is now open in London an exhibition "of apparatus of all kinds devised to prevent smoke."

Jan 1, 1882

By Charles E. Wait

IN order to secure cupels uniform in size, density, etc., I have arranged a machine which has proved quite satisfactory, and is so simple and inexpensive as to be within the reach of nearly everyone. It has been in operation here about four years, and with it all cupels used in the assay department of the School of Mines have been made. As shown in the accompanying figure, it consists of a common letter-press, the movable platen of which has been removed. In place of the plate, there is attached to the screw a plunger, which turns with the screw, moving up and down, and making the depression in the cupel. The ring holding the bone-ash is held in place directly underneath the plunger by a wooden guide fastened to the base of the press. There is also fastened to the top of the guide for the ring, at a distance above the base of the press equal to the height of the cupel-ring, a piece of mood about § inch thick, under which the ring will just slide into place, and through which there is cut a circular hole exactly fitting the plunger, guiding it in its downward movement always in the same vertical line; this last guide not only directs the plunger, but also prevents the lifting of the ring by the plunger, upon the raising of the latter.

Jan 1, 1886

By W. A. McCurdy, Joseph W. Leonard, William F. Lawrence

INTRODUCTION Utilization from the Point of View of the Preparation Engineer The primary interest of the coal preparation engineer is in process design, operation, and maintenance to produce an acceptable product that can be sold at the greatest possible profit. Because of emphasis upon these interests, attention to other potential values of coal is sometimes neglected. The intent of this chapter is to alert the preparation engineer to the utilization possibilities of the product as well as the tributary coal flow moving through a modern coal preparation plant. The basis for any unrealized potential derives directly from the coal seam itself. Most coal seams consist of coal bands and benches sandwiched together in layers that differ visually from each other in physical structure and luster. Randomly selected physical and chemical ranges determined from layers of coal in a single seam can easily differ by as much as 30 Hardgrove grindability indices, 0.30 of a specific gravity point, 20 percentage points of ash, 6 percentage points of dry volatile matter, and 10 percentage points of total su1fur.l Similar wide variations exist for calorific value, seam moisture content, and, undoubtedly, for any other conceivable coal test parameter that might be used for comparative purposes. These observations all point to the long-established fact that coal is not homogeneous, as conventional analytical methods might tend to indicate, but is instead a highly heterogeneous substance.

Jan 1, 1979

By J. A. Knox, R. M. Lasater, J. M. Tinsley

Chemical squeeze treatments have been used to provide temporary relief from certain production problems. The chemical fracture-squeeze technique, combining the effects of a fracturing treatment and a squeeze operation, has been more successful than conventional squeeze operations. Knowledge derived from well stimulation and reservoir engineering research provides a means for predicting the theoretical effective life of such a treatment. Analysis of theoretical equations and concepts developed allows selection of improved treatment techniques based on specific formation conditioins. Theory used in this analysis was developed as an extension of previous electrical model studies made to establish the expected flow and pressure profiles adjacent to a fracture system. The chemical fracture squeeze technique can be utilized in the economic application of corrosion inhibitors, emulsion breakers and paraffin and scale inhibitors. Application of this technique is shown to be effective. The slow return rate of injected chemicals, controlled by the resultant flow profiles and treatment variables, permits extended periods of chemical effectiveness. Results of field treatments are given, showing that the concepts outlined above for chemical fracture-squeeze treatments are valid and that applying this technique can help alleviate many current production problems. INTRODUCTION Much progress has been made in the last 10 to 15 years in developing chemicals for use in stimulating wells, maintaining production and protecting well equipment from damage due to corrosion. Not too many years ago, some wells seemed to dry up or wear out. In many cases the wells were produced as long as possible without any attempt at maintaining productivity. Even with the advent of new and better stimulation techniques, a rapid decline in production was observed. Methods of removing and, in some instances, preventing damage have been developed. Among thosc factors responsible for uneconomical production are scale, paraffin, corrosion, bacteria, water blocks and emulsions. Soluble scale-prevention chemicals have been developed1,2 that can be placed in a formation along with frac- turing sand. As the water produces back across this bed, the solid material dissolves slowly and can provide long-term protection from scale. However, bottom-hole temperature and salinity of produced water vary widely and both these factors influence the rate of solubility. Scale inhibitor composition is also a controlling factor. Some of the solid material may be crushed, increasing the surface area exposed to water and increasing the rate at which it dissolves. Some of the material may never be contacted by water and can be lost. However, this type of treatment has been very successful in many instances and has helped maintain economical production for extended periods of time. Liquid scale inhibitors, which are more widely applicable and more stable, have been developed in recent years; however, because they are liquids, their use has been restricted to treatment down the annulus, using metering pumps to provide proper concentrations in the produced fluid. This has prevented use in wells containing packers, in dually completed wells and in gas-lift and flowing wells. Wells that operate with an open annulus may also experience severe corrosion problems due to introduction of oxygen. Paraffin inhibitors3 have been developed that can be fractured into a well as particulate solids to be slowly dissolved in the produced fluid. These materials are not usually effective in wells with a bottom-hole temperature in excess of 120F since solubility rate may be too fast if that temperature is exceeded or if aromatic content of the oils is unusually high. Corrosion inhibitors have been developed that can be fractured' into a well for long-term feedback, but development of a material with proper solubility or feed rate has been difficult. Corrosion inhibitors are available in many different forms. Liquids have been lubricated down the annulus or sticks or pellets dropped down tubing. Inhibitor squeeze treatments5 devcloped a few years ago led to development of inhibitors with particularly strong film-forming properties.6,7 This technique basically involves displacing a highly concentrated solution of the inhibitor into the formation through the tubing. Kerver and Hanson8 studied the adsorption properties of inhibitors on various types of formations. They showed that, even though the inhibitor was displaced radially into the true permeability, it could be produced back for a long period of time because of slow desorption from the rock. Methods developed for monitoring the return of these inhibitors generally have established 1 to 6 months as the effective limit before retreatment is necessary.9 Inhibitors displaced into the interstices of the formation sometimes cause emulsions that either hamper production or cause treating problems on the surface.

By J. L. Huitt, S. R. Darin

The use of a partial monolayer of propping agent to obtain a high flow capacity for a hydraulically induced fracture is discussed. From the results of laboratory work it was shown that a modified form of the Kozeny-Carman relation could be used to describe the flow in the partial monolayer propped fracture. With equations presented in the paper, the density pattern of the propping agent (number of particles per unit of fracture surface) that results in the maximum flow capacity for the fracture can be determined. The maxitnum flow capacity obtained with a partial monolayer is often an order of magnitude greater than the flow capacity obtained in greater width fractures containing multilayers of the propping agent. INTRODUCTION One of the predominant factors controlling the success of a hydraulic fracturing operation is the propping of the fracture. The trend in hydraulic fracturing recently has been an increase in the ratio of propping agent-to-fluid. The primary purpose of this increased ratio is to sustain a propped fracture of greater width. It was shown in a recent study' that for some formations low concentrations of propping agent would result in "closing" or "healing" of the fracture. In some cases, in an effort to insure sufficient propping agent concentration, the fracturing operation is designed to obtain a pack of the propping agent in the fracture. The placing of a pack of propping agent in the fracture provides a fracture of maximum width; however, the width alone does not control the flow capacity of the fracture. The flow capacity is dependent on the permeability of the fracture, as well as the fracture width. Thus, increasing the permeability to obtain larger flow capacities is as important as obtaining a greater width fracture. By increasing the concentration and particle diameter of the propping agent, fractures of sufficient flow capacities are obtainable for effective well stimulation in a number of formations. However, in some of the recovery techniques, the fracture capacity obtained by commonly used practices in fracturing is inadequate. One such recovery technique is gravity drainage via a horizontal fracture placed near the base of the productive zone. For this recovery technique, the fracture capacity desired is usually one to two orders of magnitude greater than the fracture capacity normally obtained in fractures propped with the size of sand commonly used (20-40 mesh). By the use of particles of larger diameter, the permeability of a pack2 is increased; however, even a multilayer pack results in a fracture flow capacity lower than that desired for some formations. For example, a fracture of 1/4-in. width, packed with 8-12 mesh sand of about 2,000 darcies permeability, would result in a fracture flow capacity (permeability X fracture width) of only 40,000 md-ft. If the fracture flow capacity needed is an order of magnitude greater than that cited in the example, an approach different from the formation of a pack in the fracture is needed. One approach is a partial monolayer of large-diameter propping agent. In working with this type of fracture system, it was found that the flow problems were unique to the system; therefore, the study discussed in this paper was made. THEORY AND RELATED STUDIES Previous studies, although related to that described in this paper, have not pertained directly to the flow in a fracture propped with a partial monolayer of propping agent. However, studies such as flow between parallel plates,' flow in packed columns,' fracture flow capacity' and flow in simulated fractures reduce the scope of this flow problem considerably. A fracture propped with a partial monolayer of dropping agent may be considered to be between two extremes — between an open fracture and a bed of particles packed In a conduit of fracture geometry. Thus, it seems appropriate to review the extreme cases.

By George R. St. Pierre, John Chipman

METALLURGISTS have been studying the chem-ical behavior of sulfur in steelmaking for many years in order to have a better control of the sulfur content of finished steel. During the refining period in the open hearth, molten steel is separated from a gas phase by molten slag. Chemical reactions occur principally at the slag-metal interface and at the slag-gas interface. A need for physical-chemical investigations of reactions between sulfur-bearing gases and steelmaking slags was recognized some time ago.'.' From the early work, it can be qualitatively concluded that increased sulfur content and low partial pressure of oxygen in the gas phase favor the passage of sulfur from gas to slag. Using radioactive sulfur S Koch and Fink' have demonstrated the rapid rate of exchange of sulfur between gas and slag in an open hearth furnace. Gurry and Darken and Darken and Shields (as reported by Derge and Marshall') have equilibrated lime-iron oxide slags with SO—O2 gas mixtures. The major conclusion from the reported results is that sulfur content increases with increasing lime content in lime-iron oxide slags equilibrated with a gas of high oxygen pressure (10-2). The data were interpreted as indicating the presence of SO, and S,O, ions. Richardson and Fincham' have conducted the most extensive experimental study of sulfur equilibria between gas and slag. Their results confirmed many of the conclusions drawn from calculations of Richardson" and Withers. Richardson and Fincham's data fitted very well into the sulfur scheme represented by the reactions 1/2 s2 (g) + (0) melt - 1/202(g)+ (S) melt [II 1/2 S, (g) + 3/2 O (g) + (0) melt - (SO,) melt. [2] At oxygen pressures greater than 10 to 10 they found that reaction Eq. 2 was predominant while reaction Eq. 1 was controlling at oxygen pressures less than 10." to 10.". The slag compositions and gas mixtures used in their investigations were different from those used in the present study. Wherever possible, comparison has been made between their results and these, and agreement is excellent. It is evident that the distribution of sulfur between slag and gas depends upon the oxygen pressure of the gas. In FeO slags, a change in oxygen pressure produces a change in ferric oxide content, and a knowledge of this equilibrium is a prerequisite to studies of sulfur distribution. The data are found in the work of Darken and Gurry" on the FeO system and the more recent experiments of Gurry and Darken" and of Larson and Chipman" on FeO slags containing lime and silica. The effect of oxygen pressure on the ratio Fe /(Fe" + Fe ), the so-called j-ratio, reported by these investigators will be used in interpreting the results which follow. Experimental Method The purpose of the experimental program was to determine the equilibrium sulfur content in slags exposed to gases of known oxygen and sulfur pres- sures. The slag compositions selected for study were from the lime-silica-iron oxide system. Additions of magnesia were made to some of the slags. Apparatus—The apparatus used by Larson and Chipman was modified slightly to accommodate the addition of SO2 to the gas mixtures. As in their work, slag samples of 0.5 to 2.0 g were held at temperature (lcc) in platinum crucibles under a steady stream of gas, 100 to 200 ml per min, for several hours and then rapidly lowered to the bottom of the furnace where they were quenched in mercury. Preparation and Analysis of Gas Mixtures—Mixtures of SO,-CO were prepared from Virginia Smelting Co. Extra Dry liquid SO, and Pure Co. CO,. After removing traces of water vapor with an-hydrone, the CO, was passed over graphite at 1200°C, at which temperature the conversion to

Jan 1, 1957

By Linn Bradley, W. W. Strong, H. D. Egbert

Marked differences of opinion have been expressed by engineers interested in cleaning iron blast-furnace gases for use in hot-blast stoves and under boilers, in reference to the advantages of a hot-dry method over a cold-wet method. One point at issue involves the sensible heat energy in the moisture contained in the gas. Some advocates of the cold-wet methods claim that the condensation and resultant removal of the greater portion of this contained moisture by wet scrubbing, spraying or similar methods, results in a saving of some of this sensible heat energy, by reason of the fact that water vapor has a high capacity for sensible heat energy and may carry from the exit of a hot-blast stove, for example, more heat units than are sacrificed or lost when the gas is cleaned by this cold-wet method. Other advantages claimed for the latter method are: That gas burns more readily when it is free from moisture in any form; that because gas is made denser by cooling and removing the moisture it has a higher calorific value than hot gas carrying moisture; and that higher flame temperatures are obtained when the gas is cleaned by the cold-wet method. A search through the available literature fails to disclose any extensive calculations or records of conditions obtained in practice, bearing upon these phases of gas cleaning. This paper deals with these problems from the standpoint of the economy of using a gas of higher flame temperatures, of improved stove design, and of economy in the gas-cleaning department. Calculations have been made which show that by cleaning the gases by a cold-wet method the sensible heat energy of the blast-furnace gases is greatly reduced; and, in general, this loss of heat energy is far greater than that lost from the stoves or boilers due to the sensible heat capacity of the water vapor if carried away by the exit gases. By making use of the

Jan 1, 1917