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By David J. Mack, T. V. Philip

The effects on the Cu-A1 eutectoid transformation of the addition of a third element from the second long period and from Group IIB of the periodic table, were studied by isothermal transfomation techniques. The valency of the third element shows the most pronounced effect on the eutectoid decomposition. With some exceptions, the atomic size factor of the third element shows some consistent effects on pearlite nucleation and growth. The atomic concentration or the electronegative valency of the third element shows wo consistent effect on the eutectoid decomposition. Addition of the third element helps spheroidization of pearlite. SINCE the pioneering work of Davenport and Bainl on the eutectoid decomposition in steel by the isothermal transformation technique, an enormous amount of data has been accumulated on the eutectoid transformation characteristics of commercial steels. While the eutectoid reaction in steel is of tremendous industrial importance, it appears to be quite unique among the eutectoid reactions. Though the metal-lographic structures developed in the Fe-C and Cu-A1 eutectoids are similar, it is now evident that the two eutectoid reactions are quite dissimilar. The eutectoid decomposition in the Cu-A1 system is more complicated partly due to the appearance of transitional phases in addition to the equilibrium phases. * The first isothermal studies of aluminum bronzes were made by Smith and Lindlief2 and later by Mack,3 Klier, and Grymko,4 and recently Hayne 5,6 A few other systems, structurally analogous to the above, have been studied by the same technique.7-10 Kasberg and Mack1' studied the effects of iron on the transformation of commercial aluminum bronze. The effects of manganese and nickel on this aluminum bronze and those of iron, manganese, and nickel on the binary Cu-A1 eutectoid have been recently studied.12 The object of the present investigation was to study, by isothermal transformation techniques, the effects (with respect to the fundamental factors of alloy formation) of the addition of a third element on the transformation of a Cu-Al eutectoid alloy, 11.8 pct Al. The third elements chosen for the purpose were silver, cadmium, indium, tin, and antimony from the second long period, and beryllium, zinc, and cadmium from group 11B of the periodic table. They were added in nominal amounts of 0.5, 1.0, and 2.5 pct by weight to a eutectoid Cu-A1 alloy. These third elements were expected to show the effects of electron valency, atomic size factor, and electronegative valency effects on the binary eutectoid transformation. PFLEPARATION OF ALLOYS AND PROCEDURE All alloys were made as 400-g heats by induction melting in a graphite crucible with a graphite lid. The molten alloy with a layer of graphite powder on top was stirred at regular intervals by a graphite rod. When the melt was judged to have acquired sufficient superheat, a pinch of common salt was sprinkled on top and any crust scraped off to one side. It was then chill cast into a 5/8 in. rod. The alloys with silver were prepared by remelt-ing the high-purity Cu-A1 eutectoid alloy used by Mack3 with high-purity silver (99.99 pct pure from Hardy and Harmon, Inc.). In the preparation of all the other alloys, polished electrolytic copper shot (from Belmont Smelting and Refining Co.) and high-purity aluminum (99.99 pct pure from Aluminum Co. of America) were used.

Jan 1, 1962

By Charles Prasky

ABOUT five years ago the Bureau of Mines began a study, at Minneapolis, of the various methods for beneficiating the low-grade manganese deposits of the Cuyuna range. Several samples of green carbonate slate from the Cuyuna range, containing about 7 pct Mn and about 28 pct Fe, were obtained for this study. The component minerals in the carbonate slate formation were so intimately associated that mineral dressing methods were not suitable for concentrating manganese to a ferrograde product. Although upgrading of manganese and iron minerals has been effected by flotation methods, it appears that manganese cannot be separated from iron except by chemical means. Because the flotation studies at Minneapolis were carried out simultaneously with the hydrometallurgical studies, only crude slate was available for process testing. An important economic consideration in selecting any one of the several chemical methods proposed for recovering ferrograde manganese is the availability of the chemical reagent. Fortunately, large tonnages of sulfur are available on the Cuyuna range in low-grade pyrite and pyrrhotite deposits that are readily concentrated by flotation to a suitable feed for a sulfide roasting furnace as indicated by a Bureau of Mines investigation in 195 0-1951.1 The roasted residue from the sulfide concentrates is a potential source of marketable iron oxide. Therefore, if these sulfide deposits were employed in recovering manganese, utilization of two heretofore unused mineral deposits would be accomplished. Laboratory investigations of several proposed leaching processes were made as a preliminary step in the investigation of hydrometallurgical methods for the treatment of Cuyuna carbonate slate using sulfur as a chemical reagent. From results obtained in the laboratory tests, these leaching processes did not appear entirely suitable for treating Cuyuna carbonate slate. The method developed at the North Central Experiment Station and selected for a more intensive pilot-plant investigation has been termed the differential high-temperature sulfatizing process. Essentially, this sulfatizing process consists of the following steps, described in the order in which the small-scale pilot-plant investigations were made. The first and perhaps most significant step in the process consists of a sulfate roast. Carbonate slate is roasted in an atmosphere of sulfur dioxide gas and air. The overall chemical reaction for converting manganese carbonate to a sulfate at a high temperature in a sulfur dioxide atmosphere follows MnCO8 + SO2 + 1/2 0, = MnSO4 + CO2 (H077°O = —64,180 cal per g mol) .' The need for concentrated sulfuric acid is avoided. Fine grinding is not essential. Removal of carbon dioxide from the slate during roasting produces a more porous structure and permits easier permeation by the sulfatizing gas mixture. The temperature limits for this conversion of manganese have been established as 600" and 850°C. Iron sulfate is unstable and is not formed at these temperatures; phosphorus is not converted to a water-soluble form; and polythionates are not formed. The second step in the process consists simply of a water leach of the sulfatized product. Manganese sulfate in the sulfatized product is dissolved in water. Iron, phosphorus, and calcium remain in the leach residue as water-insoluble products. The third and final step consists of the recovery of ferrograde manganese oxide from manganese sulfate leach solution. Water is evaporated from the leach solution, and impure monohydrate crystals of manganese sulfate are recovered. The moist crystals are formed into pellets or extrusions and thermally decomposed to produce a ferrograde manganese

Jan 1, 1958

By Linn Bradley

Introduction 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 2, 1917

By N. F. Dyson, T. R. Scott, M. R. Thornber, W. E. Ewers, M. Bussell

Leach liquors derived from the processing of nickel ores are generally highly contaminated and contain appreciable free acid. Methods are described for obtaining a commercial grade of concentrate from such solutions using pyrrhotite as the seed material to abstract nick- el, cobalt, etc. from solution. At temperatures in excess of 160° C., recoveries of 99% can be obtained from contaminated solutions where the free acidity is as high as 0.5 M in sulphuric acid. At lower temperatures down to 80° C., high recoveries can also be obtained either by adding H2S to the system with appropriate adjustment of the free acidity or by using "activated" pyrrhotite or artificial FeS in the system without prior addition of H2S. The methods are applicable to liquors derived from either oxide or sulphide ores, and the products are suitable for smelting or other known processes used to obtain pure metals. The mechanism of the reaction appears to vary with the operating temperature, and the results ye therefore discussed in the light of electron probe and optical microscopic studies.

Jan 1, 1973

By E. K. C. Williams, Nathaniel Arbiter

INTRODUCTION The surface processes involved in preparing ores for flotation and for operations depending on their flocculation/dispersion characteristics * vary widely in agitation dependence. Most of the reagents used for these purposes are added to grinding circuits, pump sumps, launders, or directly to flotation cells with the turbulent flow conditions usually adequate both for mixing reagents and for surface reactions without special conditioners. However, some reagent systems do require specific control of agitation intensities and reaction times, the more important of these being the following: 1. Activation of ZnS with CuSO4. With the usual conditions pH about 10, with collector added with the CuSO4, Cu 2+ is almost completely precipitated as basic compounds and as collector salt. As a result the levels of reagent in solution are extremely low which probably accounts for the need for separate conditioning. The agitation intensities are at about the 0.01 HP/ton level.** 2. Flocculation with natural or synthetic polymers. In this case the agitation problem is two-fold; first, to insure adequate initial mixing of the viscous stock solution of the

Jan 1, 1980

By R. L. Curfman

From January 1, 1965 through July 5, 1970, the very difficult potash ore body of Texasgulf Inc. near Moab, Utah was mined by conventional methods. The mine was gassy, the temperature was high and structural conditions precluded a satisfactory or economical extraction ratio due to the undulating configuration of the ore horizon. In 1966, 67, and 68, alternative mining methods were considered, among which was solution mining of the ore body. Cost studies indicated that the use of crystallizers to evaporate the large amounts of water attendant to solution mining offered no chance of economic success. In 1969 additional testwork and cost studies were carried out utilizing solar evaporation. These studies showed economic potential and justified additional investigation. As a result of these studies, Texasgulf now gathers potash solids from these solar evaporation ponds, (Fig. l), after pumping them from the underground mine as brine. The investigations were concentrated in four basic areas : (1) area evaporation rates and crystal growth habits; (2) underground solution tests including heat transfer rates; (3) accelerated evaporation tests to provide material for metallurgical testing, and (4) tests of evaporation pond lining materials and application techniques, along with area surveys to ascertain if sufficient earth was available in the near vicinity to con-

Jan 1, 1974

By W. J. Slatosky

W. 0. Philbrook (Cairiegie Institute of Technologyogv—Mr. Slatosky has presented an interesting and constructive paper that represents another step along the way of converting steelmaking from an art to a science. I am confident that his computer will be practical and successful and that with a very few months of experience it will provide a significantly better degree of control than his record of 65 pct of heats within range obtained with the slide-rule calculator . A paper such as this, with a lot of symbols and condensed mathematics, is difficult to comprehend quickly. Since I have had an opportunity to study it carefully, perhaps my evaluation of its validity and accomplishments will save time for others. Mr. Slatosky has correctly used standard principles of stoichiometry and heat balances, which are available to anybody, but he has also brought to them two original contributions: 1) He has developed from operating data some empirical relations for predicting the final FeO content of the slag (at 0.5 pct C end-point) as a function of slag basicity, lance height, and scrap, ore, and scale in the charge. This improves the accuracy of prediction of temperature or scrap requirement compared with assuming an arbitrary, constant FeO content at the end of each heat. There is no assurance yet that exactly the same relations will hold for other furnaces or practices, but similar correlations can be expected. 2) He has combined calculations that are ordinarily carried out laboriously as a number of individual steps into a single, simple linear equation that can readily be fed into a machine. This involved a tremendous amount of painstaking detail work as well as the imagination to see the possibility and work out the steps. While his particular Eqs. [3] and [6] are valid only for the furnace design, charge weight, and blowing time used at Aliquippa Works, only a few numerical values have to be changed to adapt it for other conditions. In order to arrive at a useable solution, Mr. Slatosky had to make some basic assumptions about the process that are similar to those used by others. He neglected variation in some process variables and assumed an arbitrary average value for waste gas analysis and temperature for want of more exact information at the present time. All of these judgments are clearly stated. In addition, some thermody-namic data presently available are not adequate for the job, notably in relation to heats of formation and sensible heat in slag, and some expedient has to be adopted to get around the difficulty. Other people might prefer slightly different judgments about these details and hence obtain somewhat different numerical solutions. This is not of serious importance, however, because the errors accumulate in the "heat loss" term and are largely self-compensating for a constant heat time. Although the extended Eq. l(a) in Appendix I was set up as a rate equation originally, for convenience in using an analogue computer as stated in the paper, the time dependence was removed by later mathematical manipulations and assumptions about the process. The final result is an integration of element and energy balances from initial to final states; this procedure is as legitimate here as in any other form of heat-balance calculation. The formal handling of stoichiometry and thermochemistry appears to be correct, and it is assumed that any arithmetical errors would have come to light in applying the calculations to furnace practice. Mr. Slatosky's approach is not necessarily unique, in that other people might start with apparently different equations or prefer another form of final equation for another type of computer. However, he has presented an accomplished result that appears to be a theoretically sound and practically useful way of applying scientific principles and rapid computation for better control of steelmaking. His success will undoubtedly encourage himself and others to improve on the mathematical model and its use as better informatioq becomes available. John F. Elliott (Massachusetts Institute of Teck-t2ology)-The last comment by Mr. Richards that a calculator is quite unnecessary for an L-D operation ?-equi??es a rebuttal. The L-D furnace is a very high capacity process which places a premium on close control. When one is making steel at rates between 100 and 200 tons per hr, one cannot afford the luxury of an extra 5 or 10 min at the end of a heat correcting for an error that should never have been made in the first place. Mr. Slatosky's paper is a very sound application of the simple principles of stoichiometry and the energy balance. It is a satisfactory and valuable start, but only the start of the development of methods of control for this process. An analysis of the process shows that it should be very suitable to control by a computer. This is especially the case when various grades of steel are to be made. In fact, it would seem that the organizations who are planning new and bigger installations of L-D vessels should consider carefully the advantages that would stem from computer control of a vessel with the operator present to do little more

Jan 1, 1962

By J. A. Solomon, H. E. Shafer

As a result of the great demand for metallic aluminum and the scarcity of domestic bauxite, numerous processes have been proposed and developed to extract the oxide of this metal (Al2o3) from clays, shales, and other low-grade raw materials.1-4 An exploratory study was made to extract alumina with sulfuric acid from relatively impure coal-associated draw-slate and to establish an optimum calcination temperature for maximum recovery. Draw-slate is the term used to describe the hard, slaty material directly overlying many coal seams and may range from a few inches to a few feet in thickness. Alumina content of these draw-slates may range from as low as 15% to over 35%. Although the following results are limited in scope, some of the data should prove beneficial for further work. Coal-associated clay, shale, and gob heretofore have been considered nuisance products; any successful alumina extraction process would greatly enhance the worth of these almost limitless resources. This research demonstrated that an optimum calcination temperature for alumina extraction could be established for a coal-associated draw-slate and that this temperature was lower than those suggested in previous work with unspecified clay types. It should be noted that slightly higher acid concentrations and somewhat finer particle sizes were used in this series of tests as compared to previous work. EXPERIMENTAL WORK Essentially, alumina extraction proceeded in four steps: 1) grinding, 2) calcining, 3) acid leaching, and 4) precipitating of aluminum sulfate. An initial series of reference tests to determine the optimum temperature of solubility for alumina was run using relatively pure kaolin. Kaolin forming clays are hydrous aluminum silicates of the approximate composition 2H2O A12O3 2SiO and kaolinite is the mineral that predominates in most kaolins. 5 The kaolin was ground to -30 mesh and subsequently calcined at temperatures ranging from 100°C to 700°C. Each sample was calcined for 1 hr in a muffle furnace and in turn subjected to sulfuric-acid leaching (H2SO4, 9 molar) for a 2-hr period. The filtrates were analyzed for the amount of dissolved alumina recovered.637 Also, each sample of leached or barren residue was

Jan 1, 1968

By Prof John E. Church

It is a well-known fact that under similar conditions a ton of pig iron can be made from any ore with less fuel when charcoal is used than when coke or anthracite is employed for heating. The cause of this superiority is entirely undiscovered, and no explanation has yet been offered which has won even temporary acceptance. Such as they are the hypotheses heretofore presented are of two general kinds, and they come from those two divisions of the working force which are so often antagonistic in all professions, the scientific and the practical men. The theory of the scientific men is drawn from the chemical reactions which are known to go on in the furnace, and it is well expressed in a recent paper by Prof. Akerman, of the Stockholm (Sweden) School of Mines. It makes the superiority of charcoal as a fuel in the blast furnace to depend upon its quick and thorough reduction of carbonic acid. This property belongs to charcoal in virtue of its porous structure. Its cells have a diameter of only one twenty-four hundredth of an inch, and one grain of charcoal has been computed to have a surface of two and four-tenths square feet. According to the theory in question, carbonic acid is formed by the first impact of the air upon the fuel; but in charcoal furnaces the acid is immediately reduced to oxide by taking the necessary amount of carbon into combination, and the gas reaches its highest reducing power even in the near vicinity of the tuyeres. Coke, being harder, does not produce so strong a reducing gas in that part of the furnace. Carbonic acid is formed as in the case of charcoal, and remains longer before its reduction to oxide is completed. Anthracite is the

Jan 1, 1879

By Albert Sauveur

IN an important paper on The Critical Ranges of Pure Iron1 presented at the May, 1913, meeting of the Iron and Steel Institute, Professor Carpenter reports and illustrates the results obtained by him in determining the critical points of some very pure electrolytic iron sheet about 0.01 in. thick. The iron strip was rolled into the form of a cylinder 1; in. long and fn in. wide, weighing 42 g., the thermo-couple being inserted in a small hole in the center. The points Ac3 and Ar3 were readily detected, as well as the point Art, but the point Act was absent from every heating curve. The author concluded from this occurrence that the conception of A2 as an independent allotropic change must be abandoned. At the October, 1913, meeting of the American Institute of Mining Engineers, Dr. G. K. Burgess and J. J. Crowe read a paper on The Critical Ranges A2 and A3 of Pure Iron2 in which they described some extremely important experiments conducted by them at the Bureau of Standards, Washington, D. C. They tested Professor Carpenter's electrolytic iron and detected a sharp and well-defined absorption of heat corresponding to the point Act. Professor Carpenter's failure to detect this point is explained by them on the ground that unless the iron be in a single piece entirely surrounding and in contact with the thermo-couple junction, the thermo-couple will integrate the irregular progress of the heat through the sample and the curves will lose their sharpness. In discussing Messrs. Burgess and Crowe's paper, Professor Carpenter accepted this explanation as probably accounting for the absence of Act in his heating curves.

Jan 2, 1914

By D. Harker, W. E. Seymour

CERTAIN alloys of iron and nickel, when rolled and annealed, possess a preferred crystal orientation: (001) in the rolling plane and [loo] in the rolling direction, when recrystallized at 850" to 1050°C after approximately 98 pct cold reduction. Since the preferred orientation makes a direction of easiest magnetization coincide with the rolling direction, these alloys, especially a 50 pct iron in nickel alloy, have found wide application in the electrical industry' for choke coils and special types of transformers. The rate of the recrystallization reaction was studied at temperatures ranging from 500° to 600°C. The heat of activation for the reaction was calculated from the observed rates, and crystal orientation determinations were made before and after re-crystallization. A vacuum melted iron-nickel alloy* analyzing 49.6 pct nickel, 0.018 pct carbon, and 0.30 pct manganese was used for the experiments. The alloy was cold-rolled 98 pct into strips 1/2 in. wide by 0.002 in. thick. Specimens 1 in. long were sealed under a vacuum (approximately 10-8 mm Hg) in 1/2 in. ID pyrex glass tubes. For heat treatment these tubes were fastened to Nicrohm wires and submerged in a molten salt bath controlled to ±2°C. (The maximum measurement error was within 3°C.) The time at temperature was varied logarithmically from one sample to another, and runs were made at 500°, 525", 550" and 575°C. A molten lead bath was used for a run at 600°C which was controlled to the same accuracy. To determine the extent of recrystallization after a particular time at a given temperature, a method was used suggested by the work of Decker, Asp, and Harker.3,4 This method employs an X-ray spectrometer whereby X rays are diffracted from crystallites whose diffracting atom planes are parallel to the rolling plane of the specimen. The intensities of the diffracted rays are measured by a Geiger counter. The counter can be rotated through a range of angle, and can be motor driven through this range at a speed of 2" per min. The measured intensities are plotted vs. angle by a potentiometer recorder. In a 50 pct iron-nickel alloy it was found that only (200) reflections were obtained from the rolling plane with recrystallized material, and that only (220) reflections were obtained from the rolling plane with unrecrystallized material. No other reflections were obtained under these conditions over a range of Bragg angle of 0 to 45" using either type of specimen. As a consequence, the intensity of the (200) reflections from the rolling plane was taken to indicate the amount of recrystallized ma-terial present in a specimen, and the corresponding intensity of the (220) reflections was taken to indicate the amount of unrecrystallized material present. To insure flatness and proper alignment of the reflecting specimen in the spectrometer, the sample was laid in a slot 1/2 in. wide x 0.001 in. deep which was machined in a 3/4x2x1/2 in. steel carrier. The specimen then was taped down with cellophane tape. This steel cradle was mounted vertically in the specimen holder of the spectrometer so that the bottom edge of the carrier rested against a horizontal shoulder. Intensity data used in plotting the percent of recrystallized material vs. time at temperature were obtained by directly counting the diffracted beam of nickel filtered copper Ka radiation used throughout the work. The X-ray spectrometer was employed also in obtaining pole figure data to be used for orientation determinations. At the beginning of this investigation a transmission pole figure holder was used." As a thickness of 0.002 in. of this alloy was found to be opaque to the copper Ka radiation, it was necessary to reduce the thickness of the pole figure specimen. A cold-worked sample was etched in a 50 pct HCl solution for 5 min and was found to transmit a

Jan 1, 1951

Dr. Oldshue has provided a useful summary of a voluminous subject and my task will be to select and direct attention to those areas of mixing theory and practice which are germane to mineral processing in general, and to fine particle treatment in particular. Pulp mixing in impeller actuated reactors occurs in mineral processing in several different applications: (1) emulsification of reagents; (2) mixing pulp with 'reagents as in conditioning for subsequent operations (such as flotation, flocculation or agglomeration) ; (3) high intensity agitation, as in (a) disintegrating and dispersing aggregates, and (b) aggregating particles as in shear flocculation or in selective agglomeration; (4) hydrometallurgy; (5) hydrometallurgy with gas phase (e.g., Arbiter process); . (6) flotation in sub-aeration machines. Attention is invited to 3 above in which two opposite effects can be induced by proper choice of chemical treatment and hydrodynamic conditions. Successful processes for treating mineral fines require excellent aggregate dispersion in order to fully accomplish the liberation stage. Some processes depend further upon selective aggregation following dispersion. The term “dispersion” is often used in different senses which for present purposes will be clarified at the bottom of the next page.

Jan 1, 1979

Florida State Geological Survey, Tallahassee, Fla Herman Gunter, State Geologist A list of publications will be sent upon request Citizens of the state may obtain publications available without cost, others may have them for postage, or they can be sent express collect Twenty Annual Reports have been issued from 1908 up to and including the 21st-22nd Annual Report (1931). Only three are now available; 4th Annual Report (1912), 15th (1924) and 18th (1927) Reports since 1921 contain statistics on mineral production. All reports contain papers on various subjects, many of which are still available separately, and are so indicated in the list of publications. Seven bulletins have also been issued, principally of interest to paleontologists Bulletin 7, The Pensacola terrace and associated beaches and bars in Florida (1931), is of more general interest Bulletins will be sent upon receipt of postage. Thirteen Press Bulletins, most of which are available, have also been issued, but are of minor interest

Jan 1, 1933

By Klaus Detert, Joseph Ziebs

The progress of primary recrystallization has been studied in alloys of nickel with 0.01, 0.1, and 1.0 at. pct Ta. It can be shown that in one particular alloy containing 0.1 Ta and 0.02 02 a large grain structure (0.5 mm diameter) could he developed by primary recrystallization in thin sheetswhich were cold-worked to 97.5 pct reduction in thickness. Electron transmission microscopy demmstrates that this phenonmena was linked to the occurrence of fine precipitates at subboundaries. A discussion of how fine precipitates can exert under certain circumstances a rather distinct retarding effect on nucleation rate is included. IN a former investigation, the recrystallization and texture formation in a series of binary nickel alloys including pure nickel were studied.' Nickel alloys with some tantalum added displayed peculiarities during primary recrystallization which have been studied in more detail by the present investigation. The alloys were prepared by powder-metallurgy techniques similar to the previous investigations.' Pure metal powders were thoroughly mixed to obtain alloys with 0.01, 0.1, and 1.0 at. pct Ta, referred to as alloy A, B, or C, respectively. The metallic impurities were kept below 0.005 at. pct except iron and cobalt with slightly higher values, by using highly purified nickel and tantalum powders.' The mixtures were pressed into bars and sintered at a temperature of 1300°C. The sintering atmosphere was either high vacuum, dry hydrogen, or wet hydrogen. The sintered rectangular bars were rolled 60 pct to a thickness of 3 mm, then annealed under dry hydrogen at 1000°C and again cold-rolled to about 97.5 pct reduction of thickness. After this heavy deformation, the sheet thickness was 0.07 5 mm. In order to study primary recrystallization which occurred in measurable times between 400" and 600°C, samples of the rolled sheets were annealed in a salt bath at various temperatures for various times in order to study the progress of recrystallization by hardness measurements and microscopic examination. For optical observation, the samples were polished and etched in a solution of 65 cu cm HNO3, and 18 cu cm acetic acid in 20 to 100 cu cm H2O, depending of the particular sample and annealing treatment. For transmission electron microscopic observations, thin foils were prepared by the combined window and Bollmann techniques.273 The electrolyte consisted of 23 pct perchloric acid and 77 pct acetic acid held at 15°C. Polishing was performed at a current density of 0.4 amp per sq cm. The examination of the thin films was accomplished by a Siemens Elmiscope-type electron microscope operating with an accelerating voltage of 100 kv. RESULTS The progress of primary recrystallization was very accurately followed in these alloys in order to establish the time when recrystallization started and ended during an isothermal anneal. Table I gives some of the data obtained by these studies. The time for beginning is a mean value, where somewhat less than 5 pct of the matrix has recrys-tallized. The end of recrystallization is the time when at least 95 pct of the matrix has recrystal-lized. Listed are three different B alloys, with 0.1 Ta distinguished by different sintering atmospheres which influence the rate of primary recrystallization. By the above method, the state of the grain structure when primary recrystallization was completed, but grain coarsening had not started, could be clearly defined. The average grain diameter of the recrystallized matrix is also given in Table I. The grain size did not depend on the temperature of the isothermal anneal. With one exception the grain size of the primary recrystallized matrix was found to be rather fine

Jan 1, 1965

By John C. Calhoun, R. C. Newman

A report is made of experimental work performed on the capillary retention of water within porous solid systems, the displacement being accomplished with air and various organic liquids. A portion of the experiments were designed to measure the lowering of vapor pressure of water within a porous solid with subsequent conversion of such vapor pressure data to capillary pressure values. The form of the capillary pressure curve at high capillary pressures has been elucidated from this data. Certain theoretical approaches are presented to indicate the correlation between work done by previous investigators. The present work is correlated also with theory. Surface area values are calculated for the various core systems studied. INTRODUCTION Leverettl in 1941 presented a paper which gave the essential concepts of capillary behavior in porous solids. His presentation included both theoretical and experimental aspects of the problem. He defined the term "capillary pressure" and applied it to an ideal porous system. His work included the definition of a dimensionless quantity which was a function of fluid saturation and which could be correlated with porosity and permeability for clean, unconsolidated sands. His experimental work was performed by the drainage of water from packed columns of unconsolidated sands. Subsequently, other authors have presented experimental techniques which permit the determination of capillary pressure data on small core samples. Data have been presented on porous systems other than unconsolidated sand and with the use of liquids other than water. Notable among these are the works of Hassler, Brunner and Deahl,2 Bruce and Welge,³ Amyx and Yuster, and Purcell. Others have indicated the applicability of such data to field problems without regard to the theoretical aspects of the capillary pressure saturation function. Within the recent published literature there have also been reported studies of the correlations between capillary pressure data and other fundamental properties of porous solids. It was the intent of the present reported work to investigate the behavior noted by water and various other liquids within porous systems in an attempt to amplify existing correlations between capillary properties, surface properties, and other fundamental characteristics of porous systems. The experimental work described here was performed as two different investigations but due to its nature it is reported as separate phases of the same general topic. CAPILLARY PRESSURE AND VAPOR PRESSURE LOWERING It has long been recognized that the vapor pressure above the curved surface of a liquid is a function of the curvature of the liquid surface." The capillary pressure is also a function of the curvature of the liquid surface. Both capillary pressure values and vapor pressure lowering are, therefore, functions of the liquid saturation of a porous solid. A quantitative relationship between the vapor pressure lowering and the capillary pressure can be simply developed by considering a porous solid system containing water in equilibrium with its vapor. The capillary pressure at any height within the system is defined as Pc= Pv -P1.......(1) where PI is the pressure in the vapor phase and PI is the pressure in the liquid phase. Consider that both the water and its vapor are continuous phases within the system and that at any point the two phases are in equilibrium. The gradients in the liquid and vapor columns within the porous system are: PI = plgdh dPv = pvgdh By integrating these gradients from the point where h = 0 to the height h, values of PI and PI at the point h are found. Let the point where h = 0 be that where Pc = 0. At this point also Pv is equal to Pve, the equilibrium vapor pressure of the liquid above a flat surface. From the first of these integrations since p is independent of height: P = p1gh + P, From the second, by substituting pv = PvM/RT, where M is the molecular RT weight: Pv M Pvo- RT gh By combining the two last equations to eliminate h, one obtains: P1 RT Pv Substituting, values for Pv and Pi in equation (1) gives PyRT RT Pv which is approximately Pc=RT/Mp1 In Pvo/Pv .......(2) This equation relates the vapor pressure above a curved surface with the capillary pressure across the curved surface in terms of measurable quantities. The equivalent of this equation is given by Freundlich."

Jan 1, 1949

By John C. Calhoun, R. C. Newman

A report is made of experimental work performed on the capillary retention of water within porous solid systems, the displacement being accomplished with air and various organic liquids. A portion of the experiments were designed to measure the lowering of vapor pressure of water within a porous solid with subsequent conversion of such vapor pressure data to capillary pressure values. The form of the capillary pressure curve at high capillary pressures has been elucidated from this data. Certain theoretical approaches are presented to indicate the correlation between work done by previous investigators. The present work is correlated also with theory. Surface area values are calculated for the various core systems studied. INTRODUCTION Leverettl in 1941 presented a paper which gave the essential concepts of capillary behavior in porous solids. His presentation included both theoretical and experimental aspects of the problem. He defined the term "capillary pressure" and applied it to an ideal porous system. His work included the definition of a dimensionless quantity which was a function of fluid saturation and which could be correlated with porosity and permeability for clean, unconsolidated sands. His experimental work was performed by the drainage of water from packed columns of unconsolidated sands. Subsequently, other authors have presented experimental techniques which permit the determination of capillary pressure data on small core samples. Data have been presented on porous systems other than unconsolidated sand and with the use of liquids other than water. Notable among these are the works of Hassler, Brunner and Deahl,2 Bruce and Welge,³ Amyx and Yuster, and Purcell. Others have indicated the applicability of such data to field problems without regard to the theoretical aspects of the capillary pressure saturation function. Within the recent published literature there have also been reported studies of the correlations between capillary pressure data and other fundamental properties of porous solids. It was the intent of the present reported work to investigate the behavior noted by water and various other liquids within porous systems in an attempt to amplify existing correlations between capillary properties, surface properties, and other fundamental characteristics of porous systems. The experimental work described here was performed as two different investigations but due to its nature it is reported as separate phases of the same general topic. CAPILLARY PRESSURE AND VAPOR PRESSURE LOWERING It has long been recognized that the vapor pressure above the curved surface of a liquid is a function of the curvature of the liquid surface." The capillary pressure is also a function of the curvature of the liquid surface. Both capillary pressure values and vapor pressure lowering are, therefore, functions of the liquid saturation of a porous solid. A quantitative relationship between the vapor pressure lowering and the capillary pressure can be simply developed by considering a porous solid system containing water in equilibrium with its vapor. The capillary pressure at any height within the system is defined as Pc= Pv -P1.......(1) where PI is the pressure in the vapor phase and PI is the pressure in the liquid phase. Consider that both the water and its vapor are continuous phases within the system and that at any point the two phases are in equilibrium. The gradients in the liquid and vapor columns within the porous system are: PI = plgdh dPv = pvgdh By integrating these gradients from the point where h = 0 to the height h, values of PI and PI at the point h are found. Let the point where h = 0 be that where Pc = 0. At this point also Pv is equal to Pve, the equilibrium vapor pressure of the liquid above a flat surface. From the first of these integrations since p is independent of height: P = p1gh + P, From the second, by substituting pv = PvM/RT, where M is the molecular RT weight: Pv M Pvo- RT gh By combining the two last equations to eliminate h, one obtains: P1 RT Pv Substituting, values for Pv and Pi in equation (1) gives PyRT RT Pv which is approximately Pc=RT/Mp1 In Pvo/Pv .......(2) This equation relates the vapor pressure above a curved surface with the capillary pressure across the curved surface in terms of measurable quantities. The equivalent of this equation is given by Freundlich."

Jan 1, 1949

By G. W. Land, A. F. Duzy

There have been some problems associated with hot coal, defined as oxidizing coal heating toward ignition temperature, in shipments from the US to overseas markets. This paper will provide, first, a brief review, together with a selective bibliography. Second, a thorough discussion of coal oxidation is covered. Third, potential effects of storage are presented and, lastly, methods are suggested for the safe storage and bulk transfer of coal. The scope includes coal storage for power plants.

Jan 1, 1986

By N. Christensen, B. Augland, T. H. Johansen

Samples of an Fe-Nb alloy were brought to equilibriurtr with hydrogen-methane mixtures in the temperature range from 950° to 1050°C, and subsequently analyzed on their carbon contents. The solubility pvoduct L = [%Nb] [%C] may be represented by the equation Approximate solubilities indirectly assessed through hardness measurements have been included from a previous report. These data are shown to be in a fair agreement with the present solubility measurements. IN an investigation based on hardness measurements by de Kazinczy, Ms, and pachleitnerl the molal heat of solution of NbC was estimated to 11.5 kcal per mole. This value was considered rather small, and an investigation using a similar technique was carried out. The results indicated a heat of solution about 35 kcal per mole.2 At this stage it was decided to determine the solubility under conditions of true equilibrium . During the course of this work a similar investigation was published by Smith. 3 His heat of solution, 41.6 kcal per mole, is not very different from the value resulting from the present work (42.5 kcal per mole). Our solubility product, on the other hand, is at considerable variance with that reported by Smith. Possible reasons for these differences are discussed below. Mori, Tokizane, and saheki 7 have studied the behavior of niobium in commercial steels, with special attention to the formation of niobium carbide, nitride, and sulfide. Assuming a carbide composition Nbco.87 based on X-ray diffraction and chemical analysis of residues extracted from Fe-Nb-C-S alloys, the molal heat of solution of niobium carbide was estimated to 35.2 kcal per mole. MATERIALS AND EQUIPMENT The chemical analysis of the materials is given in Table I. Electrolytic iron* was used in the preparation of

Jan 1, 1968

By Douglas Ashmead

In his paper Mr. Braley makes no mention of the bacteriological aspects of the problem. It is now quite well established that certain bacteria play a major role in formation of acid mine waters, and it is a simple matter in the laboratory to show that under sterile conditions the rate of acid production from a pyrites suspension is only about one quarter of that obtained from a similar suspension inoculated with drainage from a mine producing an acidic pit water. Under sterile conditions the oxidation is due to direct chemical action and, from the evidence just given and from much other evidence, this increase under nonsterile conditions is due to certain bacteria. Experiments recently completed, and shortly to be published, have shown that this bacteriological oxidation can be prevented by the maintenance of pH conditions above 4. It was found that to raise this pH above 4 at the beginning of the experiments was not sufficient but that, due to the continuing chemical oxidation, alkali had to be added daily to maintain the pH conditions above 4. The amount of alkali added, however, over a fixed period, was only about one quarter of the alkaline equivalent of the acid produced when pH conditions were not controlled over an equal period. The opinion expressed by Mr. Braley that sodium hydroxide has little or no effect on the rate of oxidation of pyrites is not substantiated by the above experiments. The writer does not claim that these results show a practical solution to the problems, especially in abandoned workings, but feels that the application of an alkaline coating, such as lime wash, to exposed accessible workings might be well worth trying. S. A. Braley (author's reply)—In 1919 Powell and Parrl suggested that bacteria, or some catalytic agent, hastened the oxidation of pyritic or marcastic sulfur in coal. Carpenter and Herndon (1933)' attributed the action of Thiobacillus thiooxidans. Colmer and Hinkle (1947)3 observed an organism similar to T. thiooxidans and another organism that oxidized iron. Leathen and Braley 9rst discovered this organism in 1947 in a sample of water from the overflow of the Bradenville mine (Westmoreland County, Pennsylvania). They characterized the organism in 1954" and gave it the name Ferrobacillus ferrooxidans. Although Temple and Colmer (1951)' had suggested the name Thiobacillus ferrooxidans, since they claimed it oxidized both ferrous iron and thiosulfate, we have found that pure cultures of the organism do not oxidize thiosulfate, hence the name F. ferrooxidans. In 1955 Ashmead7 isolated an organism, similar to the one called Thiobacillus ferrooxidans by Temple and Hinkle, from acid mine water in Scotland. It is probable that this organism was F. ferrooxidans. In 1954 Bryner, Beck, Davis, and Wilsonh reported microorganisms in effluents from copper mine refuse. These organisms appeared to be similar but were not in pure culture. In view of this history of bacterial investigation of acid mine water and our own ten years of experience, we do not agree with Mr. Ashmead that bacteria play a major role in acid formation. We do not find that any of these bacteria will directly oxidize pyritic material. They do, however, augment the chemical formation of sulfuric acid by atmospheric oxidation. In two papers in 1953% eathen, Braley, and McIntyre discuss the role of bacteria in acid formation and postulate the mechanism through which they operate. Mr. Ashmead in his discussion of my paper has assumed that this work was carried on in the presence of acid mine water in which bacteria would be present. This was not the case. Strictly sterile conditions were not maintained, but the organisms present in mine drainages were definitely absent in these experiments. We believe that we have demonstrated that alkalis do not inhibit the chemical oxidation of pyritic material. This is also indicated by Mr. Ashmead's discussion in which he says that alkali must be added daily due to the continuing chemical oxidation. It is interesting to note that Mr. Ashmead finds that maintenance of pH above 4.00 decreases the activity of the bacteria. We have found also that a decrease in pH below 2.8 also inhibits its activity. Table XIII of published data'" illustrates the decrease in activity with increased acidity, although pH values are not given. These values are in comparison with uninoculated controls and show the marked increase in acidity up to 22 weeks but a decline at 29 weeks, at which time the experiment was terminated. It is probable that after a longer period only chemical oxidation would have continued. From our studiesv we have postulated that the iron oxidizing bacterium (Ferrobacillus ferrooxidans) oxidizes the ferrous iron, resulting from chemical oxidation, to ferric iron. The ferric iron then aids the atmospheric oxidation of the sulfuritic material and is itself reduced to ferrous iron, which in turn acts as food for the autotrophic bacteria. Study of the physiologic properties of F. ferrooxidans shows that its preferred pH is about 3.00 and its activity decreases with variation in either direction. It is extremely inactive above pH 4.00 and below 2.5. This inactivity above 4.00 is indicated by Mr. Ashmead's observations. These properties of F. ferrooxidans then correlate perfectly with our hypothesis. Ferrous iron is oxidized very slowly by atmospheric oxygen in highly acid sohtion and since the bacteria become inactive, acid is formed only by atmospheric oxidation. At a pH of 4.00 or above iron is more readily oxidized by atmospheric oxygen, but the bacterial activity is decreased. However, with a pH above 4.00 the ferric iron is removed from the field of activity since its soluble sulfate hy-drolyzes and precipitates the iron as ferric hydroxide or a basic sulfate. As we have shown in the paper under discussion, the alkali does not inhibit the chemical oxidation, and thus the acid formation continues. This

Jan 1, 1957

By A. A. Smith, J. S. Smart

THE controlled amounts of phosphorus, arsenic, sulphur or selenium found in commercial coppers perform a variety of highly useful functions. Indeed, a large segment of modem copper technology is essentially dependent upon the presence of one or more of these elements. Consequently, the literature contains many references to their effects but the scope is broad and has been only partly covered. New data are presented herewith directed toward a better understanding of the basic behavior of these elements in copper, with particular emphasis on the composition range 0 to 0.05 per cent. These data are a part of a general program of research on the effects of impurities on the properties of oxygen-bearing and oxygen-free copper, other portions of which have been reported previously.1-2-3 Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,1, 2 and the binary alloys employed are synthesized from high-purity copper in order to eliminate interference from the effects of extraneous impurities. Alloys of selected composition were first prepared in the oxygen-free form by continuously casting the melts in the form of 3/8-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 850°C. from a surface scale. Test wires were drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at o.3125, 0.257, o.204 and o.162 in., and a final cold reduction of 95 per cent t0 0.081 in. Oxygen-bearing slugs made by remelting were hot-rolled to 5/16 in., drawn to 0.162 in., annealed for 30 min. at 600°C. and cold-drawn 95 per cent to 0.081inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 5/16-in. rod, and processed to wire with only the last three intermediate anneals listed above, all of these having been conducted in commercial nitrogen. In addition, the conductivity anneals on these alloys were also performed in the same atmosphere, and the small amount of oxygen present as an impurity in the gas resulted in some loss of accuracy at temperatures of 700° to 800°C., as will be shown later. Subsequently, the anneals for all oxygen-free alloys were conducted in hydrogen to prevent oxidation, and purified nitrogen was employed only for oxygen-bearing samples. All conductivity anneals were of one hour duration followed by a rapid quench in 10 per cent H2SO4. EFFECT OF PHOSPHORUS The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1945