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By J. Rogers, H. F. A. Hergt, K. L. Sutherland

In 1938 Ralston4 reviewed the many attempts to find a satisfactory collector for the separation of cassiterite from its ores and in 1944 Dean and Ambrose2 summarized some further attempts. Generally, soaps and amines are effective but nonselective collectors. We have discovered that reagents containing either the polar group — SO4- or — SO3- are excellent collectors for cassiterite and promise to be selective. The response to these reagents of cassiterite and of minerals commonly associated with it was studied, using the captive-bubble technique. Using these fundamental data, the practicability of separation and concentration of tin was investigated by flotation tests in a 2000-gram Denver cell. Experimental Methods Reagents All inorganic reagents were of Analar grade. The preparation and purification of sodium cetyl sulphate, cetyl trimethyl-ammonium bromide, laurylamine and cetylamine have been previously described.5 The other collectors were commercial surface-active agents, which were used without purification. Tests Captive-bubble Tests and Cylinder Flotation Tests have been previously de- scribed.5,10 The full lines shown in the figures relating solution composition to contact (flotation) distinguish solutions in which contact (flotation) is possible from those in which it is not. The curve is derived by successive approximation and the accuracy is ±0.2 pH units and ± 5 mg. per liter of collector or depressant. Solution compositions for which it was shown experimentally that contact or flotation is possible are marked by a circle, those for which it is not possible, by a cross, and those for which it is doubtful by a cross within a circle. It is assumed that at all other solution compositions within (without) the curve, contact or flotation is possible (not possible). After testing in the collector solution, the mineral was removed, washed, and tested by the captive-bubble method in water, or floated in a cylinder with frother only. In this way the composition of solutions in which a mineral was conditioned but in which properties of the collector solution prevented contact or flotation can be defined. The composition of solutions in which conditioning was possible lie between the full and broken curve, and the experimental results are indicated by a square. The curves show the limits of composition of solutions in which flotation in a cell would be possible but many factors other than those considered in these the determine recovery and grade of a given mineral in practice. Flotation Tests in 500 and 2000-gram Denver SUbmachines,—Melboume tap water, containing 12 parts calcium, 6 parts

Jan 1, 1947

By C. A. Heiland

The following summary is written for the benefit of the practical operator in the nonmetallic field who wishes to know what geophysics has done and may be expected to do in his line of work. His problem is quite different from that of the geophysicist who has operated with various or all methods and has followed the literature, and who is assumed to be familiar with the geologic possibilities and limitations of each method. This article is not written for the latter, although he may be interested in the four or five hitherto unpublished surveys described. To the operator, on the other hand, geophysics is only secondary. His problem is to determine which geophysical method is best suited to his special needs. If he wanted to know, however, which method could be used to locate a certain material of given physical properties, building stone, for instance, he would have to wade through a tremendous amount of geophysical literature, bibliographies and articles, before he could find what he wanted. Therefore, the purpose of this summary is to present the geological problems first and then to discuss the comparative merits of the geophysical methods that can be, or have been, applied. Choice of Geophysical Methods in Oil, Civil and Mining Engineering In the first two of these fields, the geological problems are not nearly so complex as in the metal and nonmetallic mining fields. The selection of the correct geophysical method in these fields is not nearly so difficult for the operator. For oil prospecting, his problems have been discussed exhaustively by E. DeGolyer.(1) † In civil engineering (foundation and ground-water work), the usefulness of electrical methods has been so well established that there is hardly any choice of other methods at present. The situation may be changed in the future with the perfection of the seismic reflection method for shallow depths. In the mining field the operator and often the geophysicist himself finds difficulty in determining which method is best suited for a given

Jan 1, 1934

By R. N. Upadhyay, M. Maleki, I. Fatt

Conventional laboratory core analysis tests on samples of two limestone reservoir rocks indicate that about 20 per cent of PV is in dead-end pores. These tests (electric logging formation factor, mercury injection capillary pressure and miscible displacement) were carried out on 1/4-in. diameter test plugs. Test results show a clear dilference between these samples and sandstone or homogeneous limestone reservoir rock. Although the amount of dead-end pore space can be only roughly estimated, the presence of such pore space seems clearly indicated. Pressure transient studies also show presence of deadend PV. Although they do not give quantitative results, pressure transient data yield a reasonable estimate of the size of the neck connecting dead-end pores to the main flow channels. INTRODUCTION Equations conventionally used to describe reservoir flow behavior contain the implicit assumption that all connected pore spaces contributed to both porosity and permeability. Several authors3-7 have pointed out the changes in pressure transient behavior and in electric log interpretation that may result if this assumption is incorrect and, instead, dead-end or cul-de-sac pores are present. There is a need for laboratory tests that can detect presence of dead-end pores in core samples. With such information on hand the petroleum engineer can make more rational use of the mathematical tools now available for analysis of reservoir flow behavior. This paper describes laboratory studies designed to detect and, if possible, give a quantitative measure of dead-end PV in laboratory-size core plugs. Three reservoir rocks were used, two of which were limestones suspected of having deadend pore spaces and a well-known sandstone, used as a comparison standard, in which there is believed to be little or no dead-end pore space. All the studies were designed to measure the natural dead-end PV; i.e., the pore space which is dead-ended because of rock structure. During multiphase flow in a rock without dead-end pores, some parts of one of the phases can become surrounded by the other, thereby giving (for certain flow behavior) an effective dead-end pV8,9. Such behavior will not be described here.

Jan 1, 1967

By H. T. Kennedy

The fact that intrusion of water into oil wells can be prevented by treating the sand adjacent to the well seems to have been only recently recognized. Swan1 mentions the process of solidifying naphthalene in strata. R. Van A. Mills2 recommends the use of materials such as sodium silicate and sodium carbonate, which react with oil-field water to form solid plugging agents. When a well is drilled in a new field the oil sands are found essentially devoid of water (Fig. 1). Unless a completely impermeable break exists over wide areas in the field, no water is found above the lower limit of the oil zone and no oil is found below the upper limit of the water zone. After considerable oil has been taken from the well, however, it is almost universal experience that water intrusion occurs. This intrusion may be of two kinds. The water may follow a path parallel to the bedding planes of the producing formation through loose streaks in the pay sand, as shown in Fig. 2, or the water level of the field may rise and enter the well by coning (Fig. 3). Water entering from the side is called "edge water," and that coming in from the bottom is called "bottom water.'' Effectiveness of any method for shutting off water depends not only on the effective treatment of the sand adjacent to the well but on

Jan 1, 1936

By H. T. Kennedy

The fact that intrusion of water into oil wells can be prevented by treating the sand adjacent to the well seems to have been only recently recognized. Swan1 mentions the process of solidifying naphthalene in strata. R. Van A. Mills2 recommends the use of materials such as sodium silicate and sodium carbonate, which react with oil-field water to form solid plugging agents. When a well is drilled in a new field the oil sands are found essentially devoid of water (Fig. 1). Unless a completely impermeable break exists over wide areas in the field, no water is found above the lower limit of the oil zone and no oil is found below the upper limit of the water zone. After considerable oil has been taken from the well, however, it is almost universal experience that water intrusion occurs. This intrusion may be of two kinds. The water may follow a path parallel to the bedding planes of the producing formation through loose streaks in the pay sand, as shown in Fig. 2, or the water level of the field may rise and enter the well by coning (Fig. 3). Water entering from the side is called "edge water," and that coming in from the bottom is called "bottom water.'' Effectiveness of any method for shutting off water depends not only on the effective treatment of the sand adjacent to the well but on

Jan 1, 1936

By J. F. Smith, J. R. Ogren, N. J. Magnani

The uapor pressrcres of magnesium over binary alloys of magnesium with twelve of the yare-earth eletnetzts have been measured by the Knudsen effuion method in the temperature range 675° to 910°K. These vapor-pressure measurments were combined with data concerning the tevtrlitzul magnesium solubility and the vapor pressure of pure magnesinm to evaluale the standuvd free energies of pluase jormation. These free-etzergy values indicate that the CsCl structures of the heacy rave earths tend to be somewhat less stable than those of the light rare earths. This dif-]eying- behaviov covrelates with differences which have been obsevz~ed in other alloy systetns wherein a phuse appeurs, disappeavs, or changes crystal stvucture as the atomic number of the rare-earth com-ponent is changed. This behauior also appears to correlate with the struclurul rariations within the rare-earth elements themselves, and it is speculated that cariations in the spatial extent of the 4f orbitals are responsihle. STUDIES of the phase relationships and crystal structures in the binary systems between rare-earth metals (lanthanons) and magnesium are extensive but far from complete. However, the currently available information1-10 does produce a rather interesting pattern. This is illustrated in Table I. If one excludes europium and ytterbium from consideration because of their generally atypical behavior, it can be seen from the table that the phase relationships in the magnesium-rich regions show a distinctly different pattern for the lighter lanthanons as compared to the heavier lanthanons. For the lighter lanthanons, LnMg2 phases occur from lanthanum to gadolinium with the cubic MgCu2 structure, LnMg3 phases occur from lanthanum to terbium with the BiLi3 structure, and magnesium-rich phases occur from lanthanum to gadolinium with stoi-chiometries between Ln5Mg42 and LnMg12. In contrast, for the heavier lanthanons, those LnMg2 structures which have been examined have the hexagonal MgZn2 structure, LnMg3 phases have not been observed beyond terbium, and the magnesium-rich phases occur with the a manganese structure near a stoichiometry of Ln5MgZ4. The heavy lanthanon-magnesium systems thus appear to be analogous to the Y-Mg system""2 wherein YMg has the CsCl structure, YMg2 has the MgZn2 structure, and the region Y4Mgz5-Y5Mg24 has the a manganese structure, and no other intermediate phases are observed. Similarity in alloying behavior between yttrium and the heavy lanthanons occurs commonly, and on this basis it seems likely that LnMg2 phases will be found with the MgZn2 structure in the binary systems of dysprosium, thulium, and lutetium with magnesium when the appropriate investigations are made. In the case of the magnesium-rich phases of the lighter lanthanons, only the Ce-Mg phase relationships have been investigated thoroughly and in detail, and until similar investigations are made for the other systems there will remain questions as to which magnesium-rich stoichiometries represent equilibrium phases and what systematic variations occur in the sequence from lanthanum to gadolinium. Thus the data in Table I show that only the LnMg phases occur with the same crystallographic structure throughout the sequence from lanthanum to lutetium. It was speculated that the relative stability of these LnMg phases might vary from one lanthanon to the next in such a way as to presage the differences which occur among the more magnesium-rich lanthanon-magnesium phases. On this basis the present investigation of the thermodynamics of phase formation was Gndertaken for the LnMg phases. PROCEDURE AND RESULTS A generalized phase diagram for the lanthanon-rich portion of a lanthanon-magnesium alloy system is shown in Fig. 1 where ß represents a high-temperature bcc

Jan 1, 1968

By Russell Dayton

THE metallurgical polarization microscope has been utilized in several researches in the last few years, thus attaining a fair degree of prominence, but little has been written in a manner suitable to a metallurgist concern-ing the theory of this instrument. In this investigation the theory was carefully studied, and the results are presented here in a detailed manner, yet as simply as possible. The theory is discussed with particular reference to the three chief functions of the instrument: (1) determination of anisotropy; (2) effect of strain; and (3) identification of inclusions. Each of these is investigated experimentally, with especial attention to the mechanism of producing any effect. Where possible, the discussion is supplemented by photomicrographs. The instrument used had numerous defects as a polarization microscope; these and their remedies are discussed. In the microscopic study of transparent mineral sections (chal-cography) the use of polarized light has aided tremendously in the identification of a mineral. The determination of strain in transparent substances (photoelasticity) by the use of polarized light has lately become a commercial process, used in testing finished glass articles. The success of the use of polarized light with opaque materials has not been so great. The magnitude of the effects obtained is much less than that of the corresponding effects with transparent materials, and the mechanical difficulties are much greater. Konigsberger,(1)? in 1909, was the first to apply polarized light to the microscopic study of

Jan 1, 1935

By R. E. Ogilvie, J. I. Goldstein

The a and y solubility limits in the Fe-Ni phase diagram have been redetermined at temperatures above 500°C. Both a diffusion-couple and a quench and anneal technique were used. The solubility limits were measured with an electron-probe micro-analyzer. The nickel concentration at the phase boundary is increased below 700°C and the a solid-solubility range is much larger than had been previously measured. The solubility limits are also extrapolated to 300°C. It is suggested that the solubility of nickel in a FeNi reaches a maximum in the temperature interval 400o to 500°C. THE equilibrium diagram has been of great use in the field of meteoritics, where the phase relations between kamacite (a) and taenite (?) in metallic meteorites can be described by means of the Fe-Ni diagram. The study of metallic meteorites by electron-probe microanalysis has cast some doubt on the accuracy of the presently available Fe-Ni diagrams.1, 2 Recent thermodynamic studies of the Fe-Ni system also suggest that the diagram may be in error.3 For these reasons the high-temperature (800o to 500°C) part of the diagram was redetermined. INTRODUCTION The currently accepted Fe-Ni diagram is that of Owen and Liu.4 Above 910°C, there is a region of complete solid solubility, ? (fee). Below 910°C, the a (bee) phase is stable in pure iron. The effect of increasing amounts of nickel is to stabilize the y phase. The phases that form when Fe-Ni alloys are heated or cooled bear little relation to the equilibrium diagram. If an alloy is cooled from the y state and held at a temperature within the a + y field, no evidence has been found for the occurrence of the y - a transformation.5 If the alloy is cooled to low enough temperatures the y phase breaks down into a supersaturated bee phase called a2. In fact, in alloys over 27 pet Ni the y phase is retained at room temperature.6 The a, phase has the same composition as the original y. The temperature at which a2 forms, the M, temperature, has been determined experimentally.' A state of equilibrium can be approached by cooling below M, to form a2 and then reheating the alloy into the two-phase region of the diagram. The y phase will then begin to precipitate out of the a2 phase and grow. The growth of the phase, however, is quite slow. Using the interdiffusion coefficients -Da of Goldstein et al.,8 it is estimated that it takes about 1 year to grow a 10-µ-wide region of ? at 700°C in a 5 pet Ni alloy. Owen and Liu4 used the technique just described to form the equilibrium phases. The phases present were determined by means of X-ray analysis. The accuracy of their diagram depends on the number of alloys available near the phase boundary at a given temperature. In this study two different techniques were used to determine the a/a + ? and ?/a + ? solubility limits. The inherent accuracy of both techniques was greatly improved over that used by previous investigators because the phase-boundary compositions were measured with an electron-probe microanalyzer. PROCEDURE The two methods used to determine the Fe-Ni diagram are the diffusion couple (D.C.) and the quench-and-anneal (Q.+A.) techniques. In the first method, diffusion couples whose diffusion path goes through a two-phase region of the phase diagram were used. A description of the technique used for making the diffusion couples has been described in a previous paper.' After the diffusion treatment a discontinuity in the resultant concentration vs distance profile was measured. The nickel concentrations in the a and ? phases at the interface of the discontinuity are the solubility limits of the a and ? phases in the phase diagram at the diffusion temperature. If the interface com-

Jan 1, 1965

By F. N. Rhines, B. H. Alexander

MUCH attention has been directed to the effects of grain size upon the properties of alloys, but there has been scant study either of the conditions that determine the pattern and dimensions of den-drites in metal systems, or of the influence of their shape and size upon the overall properties of cast-ings. The aim of the research that is about to be described has been to investigate the effect of vari-ous factors upon the mode of formation of dendrites in alloys by measurements of the distance between adjacent dendrite arms (dendrite spacing). Early investigators, including Grignonl and Tschernoff,2 showed that a metal dendrite is com-posed of a tree-like system of stalks and branches arranged in a simple geometrical pattern. North-cott and Thomas3 demonstrated that, in the face-centered cubic solid solutions of copper-base, these stalks and side arms all lie in (100) directions in the crystal. Several investigators, including Sauveur and Chou,0 Sauveur and Reed,' and Martin and Mar-tina have reported that the addition to steel of alloy-ing elements, such as nickel, chromium, and molybdenum, not only makes the dendrites easier to reveal by etching, but makes them coarser. The latter authors8 proposed that the coarsening of the dendrites is roughly proportional to the increase in the temperature range of freezing, caused by adding the alloying elements. Sauveur and Chou6 showed, in addition, that the dendrites are coarsened by a decreased rate of cooling of the casting. Measurement of Dendrite Arm Spacing Among the physical conditions that could be ex-pected to have an influence upon the dendrite arm spacing, that appears in a cast metal, are: composi-tion, rate of freezing, crystal structure, and type of constitution. The relationships obtaining between these variables and the dendrite dimensions have been examined, in the present research, by measur- ing the arm spacing in a wide variety of alloys, listed in tables II through VI. Alloy compositions are recorded in the tables by showing the symbol of the major metal followed by the percentage and symbol of the alloying agent; thus, "Al-10Ag" is an aluminum-base alloy containing 10 pct of silver. Although none of the alloys were analyzed, an im-pression of their degree of purity may be obtained from that of their component metals given in table I. Five hundred grams of each alloy was made by melting in small clay-graphite crucibles in an elec-tric muffle furnace. After alloying the temperature was adjusted to 50" to 75°C above the liquidus and the melts were poured into cast iron molds, at room temperature, the molds having a wall thickness of 1 in. and a cavity 11/2 in. sq in cross-section. Each ingot, thus cast, was sectioned at mid-height and the sectioned surface was polished and etched for metallographic examination. Dendrite spacing meas-urements were made at three positions, namely, ad-jacent to the mold wall, midway between the wall and the center of the ingot, and at the center (desig-nated e, m, and c respectively, in the tables). A typical series of microstructures is presented in fig. 1. For each measurement, the average was taken of the dendrite spacing of several grains covering a zone about 2 mm wide. Only those grains which had a major dendrite axis nearly in the plane of polish were selected in order to eliminate corrections for orientation differences from grain to grain. Although the dendrite spacings were measured to the nearest thousandth of a millimeter, the values listed in the tables are thought to be significant only to the nearest hundredth of a millimeter. The larg-est difference in readings found, when various ob-servers rated the same specimens, was 0.012 mm; the largest difference between corresponding meas-urements upon duplicate specimens was 0.027 mm.

Jan 1, 1951

Lester Guttman (General Electric Research Lab-boratory)—Seybolt has measured the thermodynamic activity of silicon in dilute solution in a iron. The anomaly which appears at 800 °C in the approximate range 1 to 6 wt pct Si is most naturally attributed, as Seybolt has done, to the existence of a region of

Jan 1, 1960

By H. W. Hitzrot

THE new 4800-ton fine-grinding plant at the Hollinger Consolidated Gold Mines property at Timmins, in the Porcupine district of northern Ontario, went into operation in November 1937, and represents the culmination of an experimental program. The plant is a moderately low rectangular building of hollow tile on a steel frame, large enough to house four 7 by 15-ft. ball mills, with a 12 by 27-ft. classifier beside each mill. At one end is space for the addition of another mill and classifier or a mill and classifier for the regrinding of table concentrates. This regrinding is now done in the old grinding department of the main mill building. Also within the new building are the four 6-in. sand pumps for lifting the product from the low-dis- charge ball mills up to the classifier feed launders and the containers and appurtenances of a complete dust-collecting system. Together with the usual overhead crane, these constitute the major units of equipment within the new plant. The location is at the lower end of the main mill buildings toward the old tailings pond, now so neatly leveled off and sodded to rival the very best of our own W.P.A. projects. Close by the new grinding plant is a large dome-shaped structure-the new fine-ore bin designed arid built by Mr. Longmore and the Hollinger milling and engineering staffs. There are four separate automatically loaded inclined belt conveyors leading up from the bottom of the bin to the grinding plant. Each belt is equipped with a recording weightometer, in the grinding building. The whole structure and the machinery within it give the impression of permanence and a carefully integrated design with close attention to details, giving the operators every advantage for consistently good work. The many ideas and opinions behind this achievement were all ably organized and executed by the Hollinger milling and engineering staffs, anti not a few were directly initiated by them. Excellent cooperation was afforded by the Hollinger staff to the engineers helping to conduct the grinding and classification test program. It was the author's privilege

Jan 1, 1939

By Thomas T. Read

MINING, which is at least twenty centuries old, was at first, and long, wholly a practical art. Little more than two centuries have elapsed since the inception of the idea that general education and a knowledge of natural science would be of advantage to those engaged in the mining industry. Though schools of mining began to develop in Europe early in the eighteenth century the concept of educational preparation for technical conduct of the industry was slow in winning general acceptance in the industry itself. John Hays Hammond, in his autobiography, recalls that when he sought employment with a mining company after he had graduated from Yale and Freiberg he had to assure its executive, before being even considered for employment, that he did not consider that he had learned anything about mining. This was as late as 1880. Existence in the industry of a prejudice against education of the academic type is perhaps an explanation why inadequate provision has been made by the mining industry for the continuing education of technical employees after they enter employment, although engineering education prior to engaging in industry has now won general acceptance. I am familiar with the existence of "loop" courses for engineering graduates in metallurgical plants, of schemes for giving mining graduates "practical experience," and of the interest in vocational courses for workmen which sprang up in the period of labor shortage during and immediately following World War I (but which quickly died when the depression of 1921 again made experienced workmen available in sufficient supply), having been chairman of a committee appointed by the Mineral Industry Education Division to make a survey of existing provisions for post-employment training for engineers in our industry. The results of that survey, reported elsewhere, dearly indicate that it is inadequate as to amount; the aim of this paper is to present evidence for belief that it is also inadequate in quality. To avoid becoming too involved, no reference will be made here to post-employment vocational training for workmen, which is a subject differing so much from post-employment education for engineers as to require separate treatment. Neither will postgraduate education for metallurgical engineers be discussed, because a distinction must then be made between training for research work and for plant operation, whereas mining engineers engage almost exclusively in operations. Since the situation in the coal-mining industry has been discussed at several recent meetings, that also will be passed over, and what follows should be taken as a discussion applying exclusively to the metal-mining industry. PROFESSIONAL DEVELOPMENT In the operations field (both in mining and metallurgy) the work to which a beginner is assigned is seldom closely related to previous academic- education. The contrast is almost as great as between

Jan 1, 1941

By Zay Jeffries

IT has been known for a number of years that certain aluminum alloys could be hardened by quenching from a temperature of about 500° C. Immediately after quenching the total increase in hardness is not marked, but the hardness increases gradually so that after about 4 days, it has reached a maximum. The actual increase in hardness probably continues for weeks or even months, but in order to detect the differences after 4 days, it is necessary to make tests at rather long intervals. So far as is known to the authors, Alfred Wilm was the first to discover these properties in aluminum alloys.1 The aluminum-copper alloys are amenable to this treatment and the addition of magnesium makes the heat-treatment effect more pronounced. Until recently heat treatment of aluminum alloys has been confined to the worked alloys in the form of sheet or extruded products. The alloy that has been most used in this connection is known commercially as duralumin and has about the following composition: copper not exceeding, 6 per cent.; magnesium not exceeding, 2 per cent.; manganese not exceeding, 1 per cent.; commercial aluminum,2 balance. A typically good alloy in this range consists of: copper, 4 per cent.; magnesium, 0.5 per cent.; manganese, 1 per cent.; commercial aluminum, balance. This alloy can be rolled into sheets or extruded; and in this condition it can be heated in the ordinary furnace atmosphere to a temperature near 500° C. and quenched in water. After about 4 days it will have the following physical properties: tensile strength 55,000 to 60,000 lb. per sq. in. (3866 to 4218 kg. per sq. cm.); elongation in 2 in., 15 to 20 per cent. No harmful effects of the furnace gases or even the air, if the heating is affected in an electric furnace in an air atmosphere,

Jan 9, 1919

By R. T. McLamore

Lack of sufficient native permeability or skin damage caused while drilling wells for in situ leach mining projects may necessitate stimulating injection and production we1ls to increase the leaching rate to economic levels. Such stimulation processes could include acidization, hydraulic fracturing, or explosive fracturing. This paper describes an explosive fracturing process that is being developed primarily to stimulate the production of oil and gas wells, but may be useful in in situ leach mining projects as well. The process utilizes a liquid explosive that has unique safety features. The chemicals that form the explosive are subdivided into two pumpable, non- detonable components. Technology has been developed to pump these two components independently but simultaneously into the well and blend them together downhole to form the explosive. As such, surface facilities and personnel are not exposed to explosive hazards. The explosive formulations utilized in the process have been subjected to numerous safety and characterization tests and been qualified for use in deep wells with temperatures and pressures up to 250°F and 10,000 psi. The explosive composition can be varied to produce an explosive ranging, energetically, from a blasting agent to a high explosive that can be detonated after injection into a borehole, a porous media or into thin naturally occurring fractures within the roc

Jan 1, 1974

By N. Schapiro, R. J. Gray, G. D. Coe

A petrographic and chemical investigation was conducted to determine the occurrence and distribution of the organic and inorganic forms of sulfur in various size and specific gravity fractions of a high volatile, A-rank, Pittsburgh seam coal. The investigation was conducted to aid in the resolution of the problem of how metallurgical coke of lower sulfur content can be produced from high sulfur coals. The Pittsburgh raw coal contains about 2.4% S in two dominant forms: pyritic and organic. Pyritic sulfur constitutes about 57% of the total sulfur in the raw coal and occurs in macroscopic and microscopic-size particles. A plant cleaning process mechanically separates between 50 and 60% of the pyritic sulfur, mainly the macroscopic particles. The organic sulfur constitutes 41% of the total sulfur in the raw coal and 55% of the sulfur in the washed coal. Thus, organic sulfur is not reduced by physical methods of separation. Organic sulfur occurs in all the coal entities, but in general, increases as the exinoid content of the coal increases. In this study, it was found that carbonizing certain selected low gravity coal fractions containing an average of 0.45% pyritic sulfur and 1.01% organic sulfur produced cokes containing an average of 0.22% pyritic sulfur and 0.91% organic sulfur. However, the organic sulfur in the coke is probably derived in part from the heating of pyrite in the presence of carbon. Thus, the total sulfur in the coal carbonized is the most important factor affecting the sulfur content of the coke produced. Concentration of microscopic pyritic and organic sulfur in the middling-type coal indicates the necessity for rejecting as much of this material as is economically feasible. Most of the sulfur introduced into the blast furnace originates from the coke. Although the sulfur content of the hot metal can be controlled by the addition of flux, the flux used restricts the productivity of the furnace by displacing ore and requires first to be smelted; therefore, low sulfur coke is highly desirable. Since the sulfur content of coke is dependent upon the sulfur content of the coals from which the coke is produced, low sulfur coals are required to produce low sulfur coke. In the western Pennsylvania area, large quantities of good coking coal are available from the Pittsburgh seam, but this coal unfortunately contains relatively large quantities of sulfur. To provide information that might be useful in reducing the sulfur content of this coal in the cleaning process, an investigation was conducted to determine the physical and chemical forms in which this sulfur occurs and with what petrographic components it might be associated. The Pittsburgh seam coal, like most other coals, contains two dominant forms of sulfur: one occurs as the minerals pyrite and/or marcasite and is referred to as pyritic sulfur; the other is combined with the coal substance and is called organic sulfur. Pyritic sulfur is amenable to physical methods of separation, whereas organic sulfur is not. Pyritic sulfur particles must be freed from the surrounding coal if they are to be removed in the washing process. Generally, this requires crushing; the required degree of crushing being a function of the size and distribution of the pyrite. The present investigation was conducted to 1) determine the size, distribution and association of sulfur-bearing minerals in the coal and 2) to determine whether the organic sulfur has a preferential association with specific coal entities. If a preferential association exists, this knowledge may be useful in devising a method for organic sulfur reduction. In addition, a study was made to determine the extent to which pyritic and organic forms of sulfur in the coal contribute to the sulfur in the coke produced from this coal. A representative 3%-ton sample of raw coal was crushed to —3 in. and screened into square-mesh sizes: 3 to 1 in., 1 to % in., % to % in., % in. to 10 mesh, 10 to 35 mesh, and 35 to 200 mesh. Separate samples of the -200-mesh fraction and the all-size composite were also collected. Each size fraction (except the -200 mesh) was fractionated on heavy liquids of the following specific gravities: 1.280, 1.300, 1.325, 1.350, 1.375, 1.400, 1.425, 1.450,

Jan 1, 1963

By W. F. Holbrook, C. E. Wood, E. P. Barrett

The Blast Furnace Studies Section, Metallurgieal Division, Bureau of Mines, has been working for several years on the mechanism of desulphurization of iron and steel by slags. The usual assumption that desulphurization takes place by diffusion of FeS from metal into slag and subsequent reaction of this FeS with CaO to produce CaS has seemed to us inconsistent with a number of experimental results we have obtained. We undertook, for example, to determine the proportion of sulphur in a slag present as FeS. An entirely satisfactory method of doing this has not yet been evolved. The results of extraction with metallic antimony led to an interesting conclusion, however. FeS is readily soluble in metallic antimony, either physically or by chemical reaction. On the other hand, CaS was found to be insoluble. Hence it would appear that by rapid extraction of the slag with antimony we might expect to determine the distribution of sulphur between iron and calcium. The results showed that much of the sulphur was present as FeS. In some instances the extraction of sulphur as FeS was almost quantitative. For example, in a slag containing 3.8 grams Fe and 3.7 grams S, extraction removed 1.18 grams S and 2.12 grams Fe. If all the iron present in the antimony had been FeS, 1.21 grams S would have been extracted. In another slag with 8.6 grams Fe and 0.06 gram S present, 0.14 gram Fe and 0.08 gram S were extracted. This was obviously extraction of sulphur as FeS within the analytical error and showed that FeS was present either in solution or as a dispersion. Attempts to determine the solubility of FeS and CaS in slag by quenching and ultramicroscopic investigation have indicated that the solubility of FeS is very low, and that reactions in the slag are probably not to be considered as homogeneous. A more detailed report on these theoretical considerations will be made at a later date.

Jan 1, 1940

By W. F. Holbrook, C. E. Wood, E. P. Barrett

The Blast Furnace Studies Section, Metallurgieal Division, Bureau of Mines, has been working for several years on the mechanism of desulphurization of iron and steel by slags. The usual assumption that desulphurization takes place by diffusion of FeS from metal into slag and subsequent reaction of this FeS with CaO to produce CaS has seemed to us inconsistent with a number of experimental results we have obtained. We undertook, for example, to determine the proportion of sulphur in a slag present as FeS. An entirely satisfactory method of doing this has not yet been evolved. The results of extraction with metallic antimony led to an interesting conclusion, however. FeS is readily soluble in metallic antimony, either physically or by chemical reaction. On the other hand, CaS was found to be insoluble. Hence it would appear that by rapid extraction of the slag with antimony we might expect to determine the distribution of sulphur between iron and calcium. The results showed that much of the sulphur was present as FeS. In some instances the extraction of sulphur as FeS was almost quantitative. For example, in a slag containing 3.8 grams Fe and 3.7 grams S, extraction removed 1.18 grams S and 2.12 grams Fe. If all the iron present in the antimony had been FeS, 1.21 grams S would have been extracted. In another slag with 8.6 grams Fe and 0.06 gram S present, 0.14 gram Fe and 0.08 gram S were extracted. This was obviously extraction of sulphur as FeS within the analytical error and showed that FeS was present either in solution or as a dispersion. Attempts to determine the solubility of FeS and CaS in slag by quenching and ultramicroscopic investigation have indicated that the solubility of FeS is very low, and that reactions in the slag are probably not to be considered as homogeneous. A more detailed report on these theoretical considerations will be made at a later date.

Jan 1, 1940

By Donald L. Ball

The equilibrium of boron nitride, gaseous nitrogen, and solute boron was investigated in Fe, Fe-C, and Fe-Si rnelts by the Sieverts technique. The free ellergy of dissociation of boron nitride, involving -the implied standard states, was evaluated in the range 1400" to 1600°C as: ?Fo = 38,000 - 23.5T, cal ber mole The solute-solute interaction coefficients eBB, ecB , and eg were determined as 0.058, 0.22, and 0.078, respectively. BORON is an important ingredient in some types of steel and cast iron. It was employed at a particularly high level, 0.01 wt pet, in the as-cast malleable iron "CentraSteel".1 In this material, the boron concentration was critical in order to assure graphite, and avoid primary cementite, in the as-cast structure. One possible function of the boron in this alloy was the nucleation of graphite through the agency of boron nitride, which, conceivably, precipitated from the melt during cooling. A research program was instituted to assess the validity of this proposed mechanism. The first undertaking, reported here, was a determination of the thermodynamic possibility of boron nitride precipitation. Data available in the literature on the activity coefficient of solute boron in iron-base melts are inadequate for the present purpose. They will be reviewed briefly, however, so that comparison can be made, when

Jan 1, 1968

By H. W. Weart, D. J. Mack

SINCE the first recognition of eutectic solidification as the simultaneous formation of 2 solids from one liquid,1 many complex structures thus produced have been observed. Despite many attempts to ascertain it, however, the detailed mechanism by which these structures develop remains obscure. In an attempt to clarify the origin of eutectic structures, the study described in this paper was undertaken. The broad objective of the study was to investigate the effect of different solidification conditions on the structure of single eutectic grains. It was expected that the eutectic structure would thereby be isolated for study, but preliminary experiments revealed another structure within each grain. When a literature surveye revealed only 1 previous mention of the subgrain structure,' it was decided to determine the origin of the structure and to study its response to various growth conditions. Before presenting the details of the investigation, it is apropos to distinguish carefully among the 3 structures produced during eutectic solidification. This is especially desirable in view of the apparent confusion existing in the literature concerning the structures in a eutectic specimen. The confusion is due largely to the existence of the subgrain structure noted above which is easily mistaken for the grain structure. In the following paragraphs, an effort is made to distinguish the 3 structures by briefly describing their origin during solidification, even though the results are thereby anticipated slightly. The 3 structures produced during eutectic solidification are the grain structure, the colony structure, and the eutectic structure, each one contained by the one preceding it. The grain structure is analogous to the polycrystalline structure of a metal or inle-phase alloy in that each grain grows from a single nucleus. A somewhat broader interpretation is needed here, however, because of the presence of 2 phases in each grain. Since in most eutec-tics particles of 1 phase are dispersed in a matrix of the other, a grain may be taken to be the region in which the matrix phase is monocrystalline.*

Jan 1, 1959

By A. L. Galpin

INTRODUCTION For many tailings ponds, particularly those having substantial watershed areas, the control of pond water levels will be a major factor influencing the operation of the pond and the design and construction of the dam retaining the pond. This paper summarizes the basic factors affecting the control of water in tailings ponds, methods of water control, and methods of estimating the variables involved. The influences that pond water levels can have on the design, construction, and stability of tailings dams are explained in order to emphasize the importance of water control in the overall planning of mine tailings disposal systems. Two examples of pond water control planning conclude the paper. BASIC FACTORS The principal factors influencing the control of water in tailings ponds are illustrated on Fig. 1. Fig. 1 (a) shows the general disposition of the tailings solids and water in the pond; the solids settle from the slurry to form "slimes", deposits sloping down into the pond from the points of discharge; these slimes hold volumes of water in the voids between solid particles; water in excess of this "retained" water forms a pool of "free" water laying over the slimes deposits. In some cases, tailings solids (and water) go to the tailings dam for its construction. Fig. 1 (b) indicates those ways additional to tailings disposal in which the pond gains or loses water. These include surface and sub-surface runoff from the pond watershed, water reclaimed from the pond for ore processing, evaporation, and seepage. Seepage losses sometimes include water draining from tailings sand placed in the dam, but a portion of the total seepage flow is often collected and returned to the pond in order to avoid downstream pollution and to recover water for re-use. PRINCIPAL REQUIREMENTS In relation to the control of water in a tailings pond, the first requirement is usually to maintain a pool sufficiently large to ensure adequate clarification of the free water prior to its reclaim for use in the mill, or its discharge from the pond.

Jan 1, 1972