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By Brahm Prakash, R. Schuhmann

Chemical conditions for flotation and nonflotation of quartz with oleic acid as collector and barium, calcium, aluminum, iron, and tin as activators were studied using a simple vacuum-flotation technique in glass-stoppered graduates. The detailed study of barium activation led to an interpretation based on ideal Langmuirian chemi-sorption. FLOTATION of quartz is of practical importance as something to be avoided in soap-floating many types of ores. Clean, unactivated quartz is not floated with fatty acids and soaps, such as oleic acid and sodium oleate, in the quantities normally used for flotation. However, data in the literature indicate that almost any multivalent cation will activate quartz if given an opportunity. Thus, a common problem is to prevent activation of quartz by the various inorganic cations inevitably present in flotation pulps. Wark and his coworkers1 have demonstrated the reversibility of the chemical reactions and adsorptions involved in the activation, depression, and collection of the common sulphide minerals. The procedure in much of their work was to bring a mineral surface to equilibrium with solutions of known pH, collector concentration, and activator concentration, and then to test the floatability of the mineral by contact-angle measurement. From the data, graphs were constructed with pH and reagent concentrations as coordinates. These graphs show fields of flotation and fields of nonflotation, separated by narrow transition regions whose locations are shown by so-called contact curves. From the shapes and locations of the contact curves, which roughly separate fields of flotation from fields of nonflotation, a quantitative understanding of the interaction of the reagents with each other and with the minerals often can be deduced. The study of quartz flotation to be described in this paper follows in broad lines the approach of Wark and coworkers. That is, pH, activator concentration, and collector concentration were varied to find equilibrium conditions of flotation and non- flotation, and the results are presented graphically by means of contact curves. However, instead of testing for floatability by measuring the contact angle on a polished surface, a simple vacuum flotation technique was developed and used. Purified oleic acid was the collector and terpineol the frother. Barium activation was studied in some detail, and exploratory studies were made of activation with calcium, aluminum, ferric iron, and stannic tin. Preparation of Materials Quartz: Large lumps of high-grade vein quartz were crushed dry in a cone crusher and rolls. The —20, +28-mesh portion was screened out and used in the subsequent steps. This material was passed through a high-intensity magnetic separator to discard iron, then leached twice with hot concentrated HCl and washed repeatedly with distilled water. The cleaned sand was then wet ground with porcelain balls in a porcelain pebble mill, deslimed repeatedly by settling and decantation to discard —800-mesh material, and again washed with hot HCl followed by distilled water. The resulting stock of quartz was stored under water. Chemical analysis gave 99.8 pct SiO2. Table I gives the size analysis of the quartz used for flotation tests. Calculations from these data, using shape factors given by Gaudin and Hukki9 indicate a specific surface of about 500 cm2 per g. Blank flotation tests in distilled water, and in water with added frother, showed the prepared quartz to be completely nonfloatable and thus indicated the absence of organic contamination. Oleic Acid: The preparation of oleic acid was based on fractional vacuum distillation of methyl oleate2,3 followed by regeneration of oleic acid, and finally fractional crystallization of oleic acid from acetone solutions at low temperatures." The pure oleic acid was stored in a refrigerator. The iodine number of the oleic acid was found to be 90.0 (theoretical 89.93). Oleic acid was used in the form of a dilute water solution of sodium oleate, after preliminary flotation tests showed no effects of form of addition and order of addition of reagents when an adequate conditioning time (that is, 30 min) was provided. Other Reagents: Sodium hydroxide solutions low in carbonate were prepared by first making 1:1

Jan 1, 1951

By R. V. Hughes, J. N. Breston

Conclusions drawn by previous research workers with reSPect to the relation between Pressure gradients and/or velocity and oil recovery obtained by laboratory water flood tests have been in disagreement probably due to variable procedures and unnatural conditions and materials. The Bradford Laboratory of the Pennsylvania Grade Crude Oil Association as part of its secondary recovery research program has conducted nineteen water floods on two long cores of widely differing characteristics in an attempt to clarify this relationship and make it an aid in predicting flooding pressures in the field. Unlike previous research procedures the present experiments were conducted with the aim of duplicating field conditions as closely as possible by using long unextracted consolidated cores, a live crude, and natural brines for both flooding and, connate water content. Also, the pressure gradients and flooding velocities were representative of field conditions where similar sands were being flooded. Eleven floods on one core and eight floods on the other core showed increased recoveries and lower residual oil saturation with increased flood pressure gradients and flood velocities. A marked decrease in recovery was obtained from both cores at very low flood velocities. This pressure versus recovery relationship is shown to hold up to the point of water breakthrough and also up to the 100 and 1 produced water to oil ratio point. INTRODUCTION The possibility of water flooding oil sands was suggested by Carl1 of the Pennsylvania Geological Survey in 1880. It is not known when the practice was tried intentionally for the first time, but its beneficial effects were noted in the annual production rate of the Bradford field as early as 1907. The practice was illegal in Pennsylvania until 1921. Early water floods in the Bradford field usually consisted of shooting or splitting the casing secretly to permit subsurface waters to enter the producing sands under hydrostatic head. As it was noted that the benefits of water flooding seemed to be proportional to the quantity of water dumped into the well many also began to utilize surface sources after the practice became legal. It was probably during the middle 20's before many producers realized that the pressurehead of the water upon the producing sand determined the rate and quantity of water that would enter the sand. Hence, rate and quantity of production appeared to be a direct function of input pressures. By 1927 a few producers had ventured the installation of pressure pumps in order to increase water-input rates and production through the combination of hydrostatic and hydraulic pressures. The adoption of pressure flooding and the "five-spot" drilling pattern in the Bradford field were essentially simultaneous. Water-input pressures in 1930 seldom exceeded 300 p.s.i. at the well head or 1100 p.s.i. at the sand face. Since that time, water-flood producers in the Bradford-Allegany fields have gone to higher and higher pressure until today 600 p.s.i. at the well heads is called a low pressure flood. Many high pressure floods now operate at 1300-1400 p.s.i. at the well head. The limiting and advisable pressure at the sand face has been pronounced as that pressure just under what is required to lift the overburden or to cause formation parting: According to this rule any water flood operation utilizing well-head pressures nearly equal in pounds per sq. in. to 1.1 times the average depth in feet to the top of the producing sand would be considered as a high-pressure flood. Despite the higher pressure trends in the Bradford-Allegany field operations and the results of early laboratory water flooding research, the desirability and benefits of high input pressures are still questioned by many operators, particularly in midwestern water flood operations. The present paper recounts a series of 19 laboratory water floods using two long, consolidated cores of widely differing characteristics saturated with live crude and flooded with oil field brines in an effort to simulate field conditions under • various pressure gradients and flooding velocities. For both cores, higher recoveries and lower residual oil saturations were obtained at higher pressure gradients and flood velocities. This relationship is shown to hold up to the water breakthrough point and also up to the 100 to 1 produced water to oil ratio point.

Jan 1, 1949

By C. A. Heiland

I. Description of reflection equipments.................. 412 A. Design features of present types.................. 412 B. Reflection equipment designed by writer.............. 418 11. Characteristics of reflection seismographs............... 421 A. Types of coupling in electromagnetic seismographs.......... 421 B. Action of pickup, amplifier and galvanometer............. 424 C. Combined action of pickups, amplifiers and oscillographs....... 433 D. Static and dynamic constants................... 434 E. Desirable values for static and dynamic constants.......... 435 111. Calibration of reflection apparatus.................. 442 A. Dynamic tests without shaking table................ 442 B. Calibration methods....................... 445 C. Various other tests........................ 451 INTRODUCTION In the past five years, the reflection method of seismic prospecting has been developed to a high degree of perfection. Its success in mapping oil structure is due to the unique and definite nature of the depth data obtained. While articles on the principle and results of this method continue to appear in increasing number, there is virtually nothing published about the instruments used in this work. Several years ago, the writer started an experimental and theoretical investigation with the object of determining which characteristics would be best adapted to the problem at hand. As a result, an equipment was developed which has proved its usefulness in a great number of field tests. W. E. Pugh, now with the Empire Oil and Refining Co., joined the writer, in 1931 and 1932, in the laboratory experiments and field tests. In 1933, a paper was written on Certain Instrument and Field Problems in Reflection Seismology, and submitted to the Institute. The part of that paper dealing with field tests was published as Contribution 34 (reprinted in this volume, p. 455). Since then, considerably more labora-

Jan 1, 1934

By Charles H. Moore

In the study of the properties of rutile pigments it became apparent several years ago that certain physical and optical properties could not be determined on particles of pigmentary size. Since reflected light is the dominant type which reaches the eye from small particles, the true color of pure rutile was not known. Most rutile pig-ments are acicular in habit, elongated parallel to the "c" axis. It was considered important to know the nature and tone of light transmitted, for example, by a basal plate. Further, as shown by spectrophotometric curves, there is a very strong absorption of light of 4000 A as measured on particles with random orientation. It would be interesting to see whether this absorption position varied with predetermined and selected orientations. Also, since the behavior of titanium pigments in a vehicle is important, a knowledge of the surface wettability of single crystals by various media should prove very fruitful. Finally, the optical properties of rutile are such that it should show, in a single pure crystal, greater fire and brilliance than the diamond. Mineralogists had long speculated that this would be the case and curiosity was strong to produce a single crystal large enough to cut. In light of the above, a project was initiated for the formation of single crystals of rutile. Method of Formation of Rutile Single Crystals Fortunately, purification of TiO2 produced from both titanium tetra-chloride and titanyl sulphate solutions had reached the stage where spectro-graphically pure starting material could be made. Spectrographic analysis of the feed material used in the initial experiments is compared with the present feed material in Table 1. It is apparent that the present large scale purification is approximately as good as the original experimental, small scale purification. Verneuil1 produced synthetic ruby and corundum in 1904 by the well-known flame fusion process, which today bears his name. Except for mechanical improvements the present commercial production of synthetics by flame fusion is essentially unchanged from his initial method. His burner consisted of an inner orifice through which was fed the feed material and oxygen. Surrounding this was a larger outer orifice through which was fed hydrogen at lower pressure. This arrangement consists then of a lance of oxygen burning in an atmosphere of hydrogen. The proportions of hydrogen to oxygen usually used in corundum production is about 3:1, providing there is sufficient temperature to reach the 2050.°C required for the fusion of alumina. From work done in the Titanium Division Laboratories2 and from the published work of Erlich3 it was known that rutile appears to lose oxygen near its melting point and that it would not be possible to grow single crystals in a strongly reducing environment. Consequently, in order to determine whether single crystals could be grown at all, an Airco oxygen-acetylene torch with

Jan 1, 1950

By C. Elbaum

If a thin layer of liquid gallium is spread on a surface of solid aluminum, the gallium penetrates high-angle grain boundaries at a very rapid rate and separation along these boundaries follows. An experiment was carried out to investigate this phenomenon. A well-annealed specimen of aluminum 99.994 pct pure, consisting of several large grains was used, Fig. 1. The dimensions of the sample were 25 mm wide by 2.5 mm thick and all the grain boundaries extended through the entire thickness of the plate. This sample was prepared by strain-annealing and, as can be seen in Fig. 1, contained one long, straight boundary. An examination of the crystal orientations showed this boundary to be a coherent twin boundary. The angular misorientations between the grains forming the other boundaries were all in excess of 20 deg. A thin layer of liquid gallium was spread on one side of the specimen at about 30°C (the melting point of gallium is 29.7"C). After the application of the liquid the temperature was lowered to about 27°C. The gallium remained liquid at this temperature and it can be seen from the A1-Ga phase diagram1 that the liquid was probably saturated with aluminum.

Jan 1, 1960

By William A. Johnson

The mathematical analysis of diffusion curves in solid metals is carried out ordinarily by analogy with the flow of heat in a continuous medium and no account is taken of the fact that the materials involved are composed of discrete particles that move discrete distances at irregular intervals. It is possible to treat the problem on the basis of simple assumed atomic mechanisms, in which case, because of the small scale of the elementary process compared to the gross effects observed experimentally, the two procedures lead to the same expression for the variation of concentration with distance. Thus, for engineering purposes, the usual methods are quite satisfactory. If, on the other hand, our purpose is to go beyond the mere collection of data, however desirable this may be, it is necessary to recognize and understand the factors that are of fundamental importance. One factor that has not hitherto been considered when dealing with solid metals is the difference in atomic weights of the isotopes of a single metal. While all the atoms of a given element are alike chemically, their weights may vary by a small but significant amount, and atoms of different weights may have different diffusion rates. With gases this variation in isotopic weight produces a change in the rate of diffusion by a factor inversely proportional to the square root of mass. While, except for the lightest gases, this is not a large effect, it is, for example, sufficient to permit a considerable concentration of one isotope at the expense of others. If metals exhibit a similar phenomenon, some modification of the analysis of the diffusion process will be required, since the different isotopes of a given metal will have different probabilities of moving and the heat-flow analogy will contain a fundamental error. This situation cannot be rectified by using a diffusion coefficient based on the average probability of moving, and it can be shown that even when the diffusion coefficient is independent of composition, the diffusion curve will not agree with the simple theory except in the rare cases where only one isotope exists; e.g., gold. If, however, the mass effect in the solid state were no larger than in the gaseous, the errors arising therefrom in the analysis of ordinary diffusion curves would be quite negligible. Nevertheless, our desire to obtain all possible information concerning the details of the diffusion process, and the possibility of diffusion in the solid state as a means for separating isotopes are cogent reasons for undertaking an experimental study to determine whether isotopes of different masses diffuse at different rates. Experimental Procedure If isotopes of different masses diffuse at different rates, the ratio of the concentration of one relative to another will vary with the distance from the diffusion inter-

Jan 1, 1946

By William A. Johnson

The mathematical analysis of diffusion curves in solid metals is carried out ordinarily by analogy with the flow of heat in a continuous medium and no account is taken of the fact that the materials involved are composed of discrete particles that move discrete distances at irregular intervals. It is possible to treat the problem on the basis of simple assumed atomic mechanisms, in which case, because of the small scale of the elementary process compared to the gross effects observed experimentally, the two procedures lead to the same expression for the variation of concentration with distance. Thus, for engineering purposes, the usual methods are quite satisfactory. If, on the other hand, our purpose is to go beyond the mere collection of data, however desirable this may be, it is necessary to recognize and understand the factors that are of fundamental importance. One factor that has not hitherto been considered when dealing with solid metals is the difference in atomic weights of the isotopes of a single metal. While all the atoms of a given element are alike chemically, their weights may vary by a small but significant amount, and atoms of different weights may have different diffusion rates. With gases this variation in isotopic weight produces a change in the rate of diffusion by a factor inversely proportional to the square root of mass. While, except for the lightest gases, this is not a large effect, it is, for example, sufficient to permit a considerable concentration of one isotope at the expense of others. If metals exhibit a similar phenomenon, some modification of the analysis of the diffusion process will be required, since the different isotopes of a given metal will have different probabilities of moving and the heat-flow analogy will contain a fundamental error. This situation cannot be rectified by using a diffusion coefficient based on the average probability of moving, and it can be shown that even when the diffusion coefficient is independent of composition, the diffusion curve will not agree with the simple theory except in the rare cases where only one isotope exists; e.g., gold. If, however, the mass effect in the solid state were no larger than in the gaseous, the errors arising therefrom in the analysis of ordinary diffusion curves would be quite negligible. Nevertheless, our desire to obtain all possible information concerning the details of the diffusion process, and the possibility of diffusion in the solid state as a means for separating isotopes are cogent reasons for undertaking an experimental study to determine whether isotopes of different masses diffuse at different rates. Experimental Procedure If isotopes of different masses diffuse at different rates, the ratio of the concentration of one relative to another will vary with the distance from the diffusion inter-

Jan 1, 1946

Discussion of the paper of C. W. WASHBURNE, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 93,. September, 1914, pp. 2365 to 2378. ROSWELL H. JOHNSON, Pittsburgh, Pa.-It seems to me rather important to bear in mind one thing which is sometimes lost sight of, that the marine sedimentary rocks are laid down in water. We have to start with an initial charge of water. That being so, and the surface tension between the water and the -oil being as slight as it is, as referred to by Mr. Washburne,. the phenomena of capillarity are bound to be most important as between the liquid surface and the gas surface. So far as the liquid-gas surface is concerned, capillarity, in my opinion, is of the utmost importance, and it seems to me this paper of Mr. Washburne's is of great value to us for that reason. Starting out as we have, with our attention concentrated upon gravitational sorting, we have had to wait for the discussion of movement furnished by Munn, and this discussion of capillarity by Washburne, for a more balanced view of the situation. It seems to me that in the accumulation of oil and gas we have a problem of the interworking of gravitational sorting, capillarity, viscosity, immiscibility, and movement. All five things seem to me to be important. I would have expected Mr. Washburne to have given a fuller treatment of the relation of movement to capillarity. In my own experiments I find that gravitation and capillarity alone seem remarkably impotent when everything is at rest, but if I furnish a little movement, gravitation and capillarity step in and accomplish a great many results that one would not expect. Take a horizontal tube and fill a portion at the middle with an ordinary sand saturated with oil, and then put water and sand in each end, and the tube may remain at rest a very long time without that oil distributing itself along the top of the tube. But with a little motion that oil will gradually work up to the upper side. So gravitation and capillarity alone are rather impotent unless they get this element of movement. It would not be necessary to have very extensive movement, but some degree of movement is essential. Now if natural gas, in addition to the method of origin by the action of bacteria on organic matter in mud, may also arise by pressure at great depth, as the overburden is added, a great deal of motion may result. I think more motion is produced in this way than by the descent of meteoric waters.

Jan 4, 1915

By R. E. Boehler, N. C. Ludwig

At Buffington Station, Gary, Ind., Universal Atlas Cement operates fourteen 8 x 101/2 x 155-ft cement kilns in mill 6 and two 11 x 360-ft kilns in the Harbor plant. The No. 11 and 12 kilns in mill 6 are equipped with Manitowac recuperator sections. This report describes studies in measuring exterior shell temperatures on several of these kilns and the development of a traveling radiation pyrometer with certain novel features. Preliminary Work: At first various temperature-sensing devices were placed on the steel shell: 1) crayons with calibrated melting points, 2) colored paints with temperature-calibrated pigments, 3) aluminum paints with temperature-calibrated binders, and 4) metal-stem dial thermometers. The colored paints and aluminum paints failed to indicate the temperatures correctly. The crayons and thermometers did indicate fairly correct temperatures, but it proved impossible to apply enough of these on the shell to detect all the potential areas where hot spots might develop. Furthermore, considerable labor was required to apply these sensors and read the temperatures. Consequently no further work was done with these devices. Formation of Hot Spots: In the burning or clinker-ing zone of a cement kiln, the thickness of the protective coating and thickness of the brick govern the amount of heat transmitted to the steel kiln shell. Usually the protective coating consists of 4 to 8 in. of fused cement clinker. The formation of a hot spot is usually caused by loss of coating? that is, localized areas of the coating become thin or fall away from the refractory. This is generally caused by excessive temperature in the burning zone over a fairly long period of time. It may also be caused by a sudden thermal change in the burning zone. Variations in raw feed composition and in feed rate require changes in the fuel and air rates, and when these are not appropriately altered, conditions may develop in the kiln that will result in loss of coating. Luminescence on the kiln shell indicates that a hot spot has developed to a point that usually alters the refractory's thermal conductivity properties. When this thermal weakness zone occurs in the burning zone of the kiln, constant vigilance is required to protect it by maintaining proper coating. Even so, it has been the writers' experience that within a period of several days to about four weeks the hot spot usually recurs with greater severity. This necessitates shutting down the kiln and re-bricking the affected area. One of the prerequisites of a good burnerman is the ability to maintain a protective coating despite the many variables in operation. When he knows that it is getting thin or that an area has dropped off, he reduces the firing rate and kiln speed and brings feed into the affected area in an effort to rebuild the coating. But when powdered fuel is burned, the atmosphere of the kiln may prevent the burnerman's observing the condition of the coating closely at all times without taking off the fire. It is not considered good practice to do this frequently, as it imposes a thermal shock on the coating and upsets operation of the kiln. To help the burnerman scan the shell of the kiln along the burning zone, therefore, a radiation pyrometer, connected to a potentiometric recorder, was mounted on a slowly moving steel cable. The theory of operation, construction details, and adaptability of the radiation pyrometer are included in an excellent monograph' and also in a textbook.' Shell temperatures of the Atlas Cement kilns were measured with a Brown Instruments Div. low intermediate range Radiamatic unit, of range 200" to 1200°F, and a circular chart Electronik potentio-metric recorder, of range 500" to 1000°F. In Bulletin 59095M the supplier publishes standard calibration data (millivolts vs degrees Fahrenheit) for this radiation pyrometer, These data, however, apply only to flat surfaces having emissivities of unity. Calibration of Radiation Pyrometer for Use on Curved Surfaces: When applied to surface temperature measurements, the radiation pyrometer reading depends on the nature of the surface, the material of which it is composed, and also to some extent on the temperature of the surroundings. Although the present radiation pyrometer is designed to give a calibrated response under ideal (black body) conditions when used commercially, it must be calibrated empirically. The calibration procedure, given below, follows that described by Dike (Ref. 1, pp. 38-39). Calibration tests on plane and curved surfaces showed that the response of the radiation pyrometer was very

Jan 1, 1961

By A. L. Holley

THERE are regularly manufactured in the eleven Bessemer steel rail mills of the United States, 119 patterns* of steel rails, of 27 different weights per yard. This list does not include patterns which, although still largely inn use, are regarded by experts as obsolete, and which would swell the number to nearly 300; nor does it include all, the patterns for which rolls are kept on hand to fill a possible demand; nor does it include extra pattern,- rolled in one finishing groove by opening or closing the rolls so as to get different weights with the same contours. The list embraces only those separate patterns which are subject to current orders. How thoroughly modern these patterns are, is shown by the fact that of the whole 119, there are but five patterns of conspicuously bad shape; all the rest more or less completely illustrate the standard features,-a heavy bead,. light web and flanges, and a good angle :to hold the fish-plate. Sixty-two per cent. of the patterns have the "Chanute" head, which was not designed until 1874.† Sixty-four per cent. of the 119 patterns are embraced under five weights per yard,; three only of these vary from standard type; there am thus 76 patterns, all of them modern and standard, to represent five different weights, for which five patterns would perfectly answer. Of the 60-lb. rails, there is only one of the pear-head type, while a dozen of the bevelled head templets cannot be distinguished from each other * From all the works 188 patterns were sent to me as standard. Of these I found 119 different shapes and 69 duplicates. † Since this paper was read I have seen at the Bethlehem Iron. Works the templet of a 68-pound Lehigh Valley rail, with the bevelled head, usually called the "Chanute" head, and marked "Templet of 1872." This is shown on Plate II. I learn that iron rails, with bevelled heads, were rolled at Bethlehem prior to 1870.

Jan 1, 1881

By Galen Clevenger

THE losses of gold and silver occurring during the conversion of the precipitate, resulting from the cyanide process, into bullion may occur in two ways: first, there may be mechanical losses during the handling of the precipitate up to the time that it is charged into the melting furnace; and second, there may be losses after the precipitate reaches the melting furnace. Much of the loss during the handling of the pre-cipitate can be eliminated, and in fact, in modern plants this loss is known to be very small; particularly since preliminary acid treatment of the precipitate with the attendant extra operations has been abandoned in all but certain plants where gold predominates and this extra step is still deemed necessary. The losses in the melting furnace are from dusting and volatilization; losses in the furnace bottom and linings; floor sweepings; and slag and matte. The gold and silver in the: products which do not: go out of the flue are readily recoverable by standard methods, and while there may be considerable gold and silver tied up at times, the ultimate loss with careful "work should be small. The losses resulting from volatilization and dusting in connection with the melting of the silver slime from copper refineries have been determined by standard methods, and the possible recovery: definitely estab-lished through the installation and operation of electro-static precipitation units. This subject has not been thoroughly investigated in connection with the melting of`. cyanide precipitate; at least, there are no published accounts of such tests. Experiments have been made in the past to determine melting losses by weighing and assaying the precipitate, but this method gives results which are uncertain on account of the difficulty of accurately sampling and assaying cyanide precipitate. Attempts to ascertain these losses by bubbling a measured sample of the gas through cyanide solution or, other absorbent have likewise failed to give depend-able results.

Jan 1, 1922

By R. V. Norris

The removal of mine-water by hoisting in tanks instead of pumping, while somewhat a reversion to the methods of the ancients, has come very rapidly into favor in the anthracite region of Pennsylvania during the past few years. In fact, so much so, that at the present time there are at least eight large collieries at which all the water is hoisted, and six more plants are in preparation. The particulars of the plants in operation and under construction, as far as decided on, are given in the tables on pages 107 and 108. Besides these, the Delaware, Lackawanna and Western R.R. Co. is constructing a hoist of large capacity for a depth approximating 500 feet, to be located in the Keyser Valley, near Scranton. The hoists will be driven by electric motors, geared directly to the sheaves. The Lehigh Valley Coal Company is planning a large hoist for the Packer collieries in the Shenandoah district, but no work has been done on this as yet. The earliest regular hoisting, I believe, mas done by means of semi-cylindrical tanks (Fig. 1) at the Nanticoke collieries of the Susquehanna Coal Company. These tanks were attached under the regular shaft-carriages, taking in water through six large clack-valves in the bottom, and discharging through an endgate opened by a lever which was operated by a guide-piece on the shaft head-frame. These tanks were designed July, 1880, by the late J. H. Bowden, one of the very early members of the Institute. Similar tanks are still used in emergencies at the Nos. 1, 2, 3 and 6 shafts of the company. The objections to. their use were: that water could only be hoisted during the night-shift, or when the shafts were not in use for hoisting coal, thus requiring a very large sump, and greatly limiting the water capacity of the plants; that the alternate wetting and drying

Jan 1, 1904

By C. E. Lundin, D. T. Klodt

The binary alloy systems, Y-Ti, Y-Zr, and Y-Hf, have been investigated throughout their entire composition regions. There is no compound formation in any of the systems, and each system is characterized by a single eutectic reaction. The eutectic compositions and temperatures are as follows: A eutectoid reaction pct Y and 870°C occurs in the Y-Ti system, whereas a peritectoid reaction,: pct Y and 880°C occurs in the Y-Zr system. Peri-tectic-type reactions at temperatures above the eutectic levels are postulated for the yttrium and hafnium transfovmations. The development of the technology of yttrium has been given considerable attention during the past few years, and studies of binary phase equilibria have, of course, taken a prominent position in this development. In many respects yttrium, in the third group of metals of the periodic table, is similar to the adjacent group of metals, titanium, zirconium, and hafnium, and the knowledge of the phase relationships of yttrium with these metals is basic to their technology. MATERIALS AND EXPERIMENTAL PROCEDURES Materials. The metals for this investigation were supplied by the General Electric Co., Aircraft Nuclear Propulsion Department. The yttrium was in the form of an arc-melted ingot, and the other metals were in the form of high-purity, iodide-Process crystal bar. Table I lists the purities of these materials. Alloy Preparation. Melting was done by conventional techniques in a nonconsumable electrode arc furnace in an atmosphere of purified argon. Melting conditions for each binary system were the same. Each alloy button was inverted and remelted several times to assure homogeneity. Accurate weights of the charges and resultant alloy buttons were obtained to indicate deviations from intended compositions. No chemical analyses were obtained since melting weight losses were consistently in the range of 0.1 to 0.2 pct of the total weight. 10- or 20-g buttons for each 5.0 wt pct composition increment were melted to survey the three individual alloy systems. Additional alloys differing in composition by 1.0 or 0.1 wt pct increments were also melted to study selected regions of the systems. Metallograpllic Techniques. Standard metallo-graphic techniques were followed for mounting and rough grinding. Preliminary polishing was accomplished using 6-u diamond paste as an abrasive on a Metcloth Lap. Final polishing was done on a Microcloth-covered wheel using 1-u diamond abrasive paste. Purified kerosene was used as a lubricant for both polishing stages. • sothermal- Annealing. Alloys were sectioned for as-cast structlure examinations and then homogenized in preparation for isothermal-annealing treatments. Homo{:enization was accomplished by cold pressing the alloy buttons followed by 72-hr anneals at 1100c. The alloys were encapsulated in Vycor or quartz for the homogenization treatments or for isothermal anneals. Resistance-wound or resistance-element tube furnaces were used for the annealing treatments. The homogenized alloy buttons were cold rolled until cracking occurred or until a -in. specimen thickness was obtained. Small -in. square) specimens for the isothermal anneals were then sawed from the alloys. Each specimen was wrapped in tantalum foil before being sealed in the capsule. Temperatures during the anneals were controlled The time at temperature necessary to equilibrate the structures during the anneals was determined for each alloy system by holding triplicate specimens of alloys at a constant temperature for three different periotls. The specimens were quenched and examined microscopically to determine the number and amounts of phases present in the micro-structure as a function of time. Melting Studies. Eutectic temperatures of the three alloy systems were established from the results of incipient-melting studies conducted on as-cast alloys. Specimens to be melted were suspended on a tungsten wire inside a graphite cylinder placed in a glass vacuum chamber. An optical pyrometer was used to follow the temperature of the specimen as it was inductively heated in a high vacuum. The temperatures were corrected for emissivity losses by standardizing the pyrometer with known-melting-point metals. Accuracy of the temperature measurements is estimated to be + 10°C. The melting point of the yttrium was determined to be 1550°C by this technique. The invariant-temperature levels were also checked by an anneal-quench technique. This technique consists of annealing a series of

Jan 1, 1962

By Adrian C. Dorenfeld, Theodore Balberyszski, Strathmore R. B. Cooke

This paper reports results of studies of sulfidiza-tion of base-metal oxides and silicates with gaseous sulfur, hydrogen sulfide gas and pyrite and of their subsequent flotation with xanthate collectors. It has been established that a 100% conversion of the oxides of lead, zinc, copper and manganese into their respective sulfides is possible and is a function of reaction time and temperature. Sulfidization of chrysocolla (with malachite and azurite inclusions) resulted in a product containing covellite, chalcocite and digenite in proportions depending on conditions of sulfidization. Reacting cassiterite with gaseous sulfur, H2S or pyrite at various reaction temperatures resulted in its partial conversion to a tin sulfide. Flotation of the products of sulfidization indicated that their behavior is similar to that of natural sulfide minerals, the recovery being a function of the con-version of the oxides to their respective sulfides. The gradual depletion of high-grade sulfide mineral deposits has turned the attention of the mineral industry to the recovery of metals from the oxides and silicates. Anionic (fatty acid) and cationic collectors have in some cases made flotation of nonsulfides possible, although, in general, flotation of oxide ores is not as yet an economic process. Consequently, many attempts have been made to sulfidize the surface of the relevant oxide mineral and thus make it amenable to to In recent years, Bautista and sollenberger4 have investigated the conversion of a number of oxides to sulfides by reacting them with molten sulfur. This paper presents the results of .investigations carried out at the School of Mineral and Metallurgical Engineering at the University of Minnesota to study the flotation characteristics of some sulfidized minerals. It is divided into two parts: The first describes the sulfidization of a number of oxides and a silicate, and the second presents the flotation behavior of the products of sulfidization. SULFIDIZATION OF METAL OXIDES AND SILICATES Experimental Procedure: SULFIDIZATION WITH HYDROGEN SULFIDE GAS — Sulfidization with H2S gas was carried out in a horizontal tube furnace (Fig. 1). The temperature of the furnace was regulated by means of a Variac and determined with a chromel-alumel thermocouple. The constant temperature zone in the furnace was about 6 in. in length, and it was within this zone that the experiments were carried out. The gases employed were supplied from standard compressed gas cylinders, and passed through a glass-wool filtering tower before entering the Pyrex reaction tube. Gaseous products were bubbled through a water tower (used as a flow indicator) and excess H2S was burned off at the end of the outlet tube. Samples of reagents or minerals were placed in a 3-in. Alundum boat and inserted within the constant temperature zone of the furnace. Nitrogen gas (6 ppm O2 content) was passed through the tubes at room temperature to remove air in the tube, and continued to pass while the furnace was heating up. When the required temperature was reached, H2S was allowed to enter the tube and the supply of nitrogen was shut off. At the end of the reaction period, the reverse procedure was carried out, the samples being cooled to room temperature in a nitrogen atmosphere. The flow rate of H2S gas was maintained fairly constant in all experiments, although the rate was not determined. SULFIDIZATION WITH SULFUR POWDER - To study the sulfidization of minerals with sulfur (liquid or gaseous), samples of the mineral, together with a measured quantity of sulfur powder, were placed in a stainless steel (SS316) reaction vessel (Fig. 2). The reaction vessel was heated in a vertical resistance coil furnace, the temperature being regulated through a Variac. At the end of the experiment the vessel was cooled to room temperature before the sample was removed. Cooled products were leached with CS2 to remove any free sulfur. SULFIDIZATION OF TIN CONCENTRATES - Fifty gram samples of sulfidized tin ore were prepared by mixing -48 mesh Bolivian tin concentrate with -48 mesh Ottawa sand in various proportions and sulfi-dizing these samples with H2S in the horizontal tube

Jan 1, 1969

By O. Bergmann, R. E. Lueders, R. R. Ellefson, H. M. Brennecke, D. S. Davies

A new hydrometallurgical process has been developed to recover copper from sulfide ores. Copper is leached in a staged reactor system utilizing nitric and sulfuric acids at 105OC. Iron is removed from the pregnant liquor as a jarosite, and cathode copper is electrowon directly from the purified pregnant liquor. The spent electrolyte is recycled. Nitrogen oxides evolved from the leach are reconverted to nitric acid and are also recycled. Sulfur is rejected as So, jarosite, and gypsum. The process is highly versatile and can recover precious metals, molybdenum, and zinc when these elements are present. Continuous, integrated, semi-pilot plant operations using chalcopyrite ores demonstrated 99% copper leaching and production of cathode grade copper. Economic evaluation shows that the process is competitive with pyrometallurgical and other hydrometallurgical processes.

Jan 1, 1982

By John Wulff, Robert Kamm, Steinberg Morris

In powder metallurgy it has often been observed that shrinkage may occur in one direction and growth in another during sintering. Even in long-time sintering experiments the rate of shrinkage may be different in different parts of the compact. In the fabrication of some parts requiring a constant permeability it is even questionable in some cases whether pressing from one direction should be attempted. These observations require for their interpretation a more detailed study of green or pressed density than has heretofore been available. Usually average density measurements of the whole compact are made and in some cases carefully cut sections are measured. A different approach to the problem was first mentioned by Rakowskil and also used by Balshin.2 Balshin's diagram is reproduced in Fig I and schematically shows the result of pressing three layers of metal powder with fine intervening layers of graphite. The retarding effect of the die walls and a qualitative example of the density distribution is evident. More quantitative information about the distribution of density within a cold-pressed powder compact would be useful in showing the variation in density in as as influenced by the type of poKder, shape of die, lubricatioll during the process, and other variables. Furthermore, information about the cracking of cold-pressed compacts may be obtained from an analysis of the stress distribution within a, powder compact, and some information about the stress distribution can be obtained in turn from the derlsity and strain distributions. A more detailed report on some of the present experiments appears in reference 3. Present Investigation In order to ascertain the density gradients in cold-pressed metal powders, a deformable lead grid within the powder was employed. After pressing in cylindrical di" the ejected compact was radiographed, giving a pattern of the deformed grid. From the radiograph density and deformation from point to point is readily measured. From the radiograph strain distribution and stress trajectories were also determined. The latter also permits the determination of the coefficient of friction at the die wall. This technique indicates that the densest Part of a compact pressed from one side is at the top outer circumference and the least dense region at the bottom circumfercnce near the stationary plunger. For Some heights of compacts the density at the axis is such that the lower density is at the top rather than at the bottom. SO irregular a density distribution is due primarily to die-wall friction. As the ratio - diameter to height of compact is increased the die walls play a correspondingly smaller role. More uniform density

Jan 1, 1947

By John Wulff, Steinberg Morris, Robert Kamm

In powder metallurgy it has often been observed that shrinkage may occur in one direction and growth in another during sintering. Even in long-time sintering experiments the rate of shrinkage may be different in different parts of the compact. In the fabrication of some parts requiring a constant permeability it is even questionable in some cases whether pressing from one direction should be attempted. These observations require for their interpretation a more detailed study of green or pressed density than has heretofore been available. Usually average density measurements of the whole compact are made and in some cases carefully cut sections are measured. A different approach to the problem was first mentioned by Rakowskil and also used by Balshin.2 Balshin's diagram is reproduced in Fig I and schematically shows the result of pressing three layers of metal powder with fine intervening layers of graphite. The retarding effect of the die walls and a qualitative example of the density distribution is evident. More quantitative information about the distribution of density within a cold-pressed powder compact would be useful in showing the variation in density in as as influenced by the type of poKder, shape of die, lubricatioll during the process, and other variables. Furthermore, information about the cracking of cold-pressed compacts may be obtained from an analysis of the stress distribution within a, powder compact, and some information about the stress distribution can be obtained in turn from the derlsity and strain distributions. A more detailed report on some of the present experiments appears in reference 3. Present Investigation In order to ascertain the density gradients in cold-pressed metal powders, a deformable lead grid within the powder was employed. After pressing in cylindrical di" the ejected compact was radiographed, giving a pattern of the deformed grid. From the radiograph density and deformation from point to point is readily measured. From the radiograph strain distribution and stress trajectories were also determined. The latter also permits the determination of the coefficient of friction at the die wall. This technique indicates that the densest Part of a compact pressed from one side is at the top outer circumference and the least dense region at the bottom circumfercnce near the stationary plunger. For Some heights of compacts the density at the axis is such that the lower density is at the top rather than at the bottom. SO irregular a density distribution is due primarily to die-wall friction. As the ratio - diameter to height of compact is increased the die walls play a correspondingly smaller role. More uniform density

Jan 1, 1947

By Rollin E. Hook, Attwell M. Adair

The response of CrzO3 and C~304 to various heat treatments was studied in are-melted iodide chromizim over the temperature range 1000" to 1750°C. These oxides, which are present as impurity phases in this material, were identified by X-ray diffraction teclzniques which were supplemented by optical metallop-aphy. As a function of increasing temperature, Crs04 is first observable in samples annealed at 1300°C and coexists with Cr2O3 (the low-temperature oxide) over a temperature range exceeding 200°C. As the temperature decreases, Cr3O4 dissolves with the concomitant precipttation of Cr2Y2. Both oxides precipitate predominantly at pain boundaries. The reactions which occur are involved with at least ternary equilibria, possibly due to iron which is present as an impurity in arc-melted iodide chromium. HILTY, Forgeng, and Folkman' reported in their investigation of the Fe-Cr-0 system that Cr3O4 (with about 8 pct Fe substituted for chromium) is a primary phase found in alloys with 9 or more pct Cr. They reported that this phase is stable only at high temperatures and that below the liquidus Cr3O4 is disproportionated into Cr2O3 and chromium-rich metal for both Fe-Cr-O alloys and in oxygen saturated pure chromium. Further, they proposed that CrsO4 forms by a peritectic reaction between Cr2O3 and the liquid. On the other hand, Hook, Garrett, and Adair2 found in their investigation of impurity phases formed in "pure" chromium (material consolidated from iodide chromium crystals) that Cr3O4 forms intergranularly and is stable as low as 1500°C which is 375OC below the melting point of chromium. The purpose of the research described herein is to determine the temperature range of stability of Cr3O4, and to show the nature of its decomposition. This further investigation indicates that Cr3O4 undoubtedly occurs in this material as low as 1300°C. The chromium studied was consolidated and fabricated from iodide chromium crystals (ICr-5) and contained Fe r 135 ppm, Si = 20 to 100 ppm, and 0 = 35 to 137 ppm. A complete chemical analysis is given elsewhere.' Annealing was conducted in 1 atm of purified helium and all samples were rapidly cooled (-200°C per sec) by withdrawing them from the furnace hot zone under a high flow rate of helium. The details of the electrolytic-etching technique and electrolytic-digestion techniques for preparation of insoluble residues for X-ray examination are given elsewhere also.' EXPERIMENTAL RESULTS The Starting Material. The as-swaged rod (final swaging done at 900°C) had a wrought grain structure and contained a dispersion of CrzO3 inclusions of maximum particle size of about 2 or 3 p, Fig. 1. The microstructure also contained a dispersed

Jan 1, 1964

By J. S. Bryner

In the study of metallographic specimens in the electron microscope, there is need for a method of locating the same field in both the light microscope and the electron microscope. This need arises chiefly from the fact that in the electron microscope the magnification and degree of resolution are so much higher, and the field so much smaller than in the light rnicroscope that it is often difficult, if not impossible, to identify positively what is being observed. The difficulty is increased by the fact that, because a transparent film replica of the metal surface must be used in the electron microscope, micro-constituents can be identified not by their color but only by their texture and contours. For these reasons it is desirable to obtain a series of photographs showing the same field in both microscopes in order that the appearance of common microstructures and micro-constituents in the electron microscope may be identified and catalogued for future reference. The need for a method of locating the same field in both microscopes arises also when it becomes desirable to enlarge in the electron microscope for more detailed study a particular interesting structure observed in the light microscope. Using the standard polystyrene-silicalJ replica technique, in which the silica film replica is fished from the ethyl bromide on a 1/8 in. diam zoo-mesh specimen screen, the possibilities of locating a particular area on the film in the electron microscope are rather remote. The desired structure may be obscured by the wires of the specimen screen or unrecognizable at the high magnification. A solution to the problem would be provided if a specially designed specimen screen, containing an opening which could be absolutely identified and quickly located in the electron microscope, could be fastened to the silica film replica in such a position that the desired field on the specimen would be located at the identifiable opening in the specimen screen. The design for such a specimen screen, a method for producing it, and a technique for fastening it to the silica film replica are described below. Description OF Method The Specimen Screen A simple design for a specimen screen containing an opening easy to identify and locate in the electron microscope is one with two lines of openings at right angles in the form of a cross. Such a screen is shown in Fig I. The opening at the center of the cross is identified easily and can be located quickly in the light microscope and in the objective image of the electron microscope. The specially designed specimen screens for this work were produced in quantity by electroforming. On both sides of a polished strip of copper I X 3 X 1/8 in., twenty patterns of the cross of openings were punched with a diamond point micro-hardness tester, using a load of magnitude

Jan 1, 1949

By Carl Swartz

FOR many years kettles used in the melting and refining of lead and other nonferrous metals and alloys have been made of cast iron. The logic of this probably lies in the fact that cast iron has been known as a material of construction for vessels of this type much longer than steel, and satisfactory fabrication from it has been more easily accomplished and better understood. As the capacity of lead refineries has increased, it has been only natural to increase the size of kettles. Today kettles of 150 to 250 tons are not uncommon. As the size of the kettles increased and better shapes were designed, the uniformity of material of construction became more important. Records kept over comparatively long periods of time have shown that the length of service of kettles has not been uniform. Many causes contribute to this and the importance of each has not yet been evaluated. Kettle design, kettle setting, method of firing and material of construction have been changed from time to time to obtain better service, but the variation in length of service is still great. A kettle may fail during the first few heats or may last through more than one thousand heats. The purpose of this article is not to present the conclusions of a finished piece of research on kettle manufacture and use, but to present a series of observations made over considerable time in the hope that others will publish data and that all may be correlated into a logical scheme which will result in better service and longer kettle life.

Jan 1, 1931