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By Roger C. Malan

The Monument Valley and White Canyon districts are in northeastern Arizona and southeastern Utah. Exploration and mining for uranium has been conducted in these districts since the late 1940's. In July 1965, ore reserves plus ore production at 174 properties were approximately 3.3 million tons of ore containing about 19 million pounds U3O8, of which about 10 per cent remained in reserves. The two largest mines, Monument No. 2 and Happy Jack, together account for about 45 per cent of the sum of production and reserves. Approximately half the deposits in these districts contain less than 1000 tons of ore. Nearly 5000 feet of Permian, Triassic, and Jurassic sedimentary rocks, mainly continental in origin, are exposed in these districts. All the important uranium deposits are in the Shinarump, the basal member of the Chinle Formation of Triassic age. The Shinarump lies on a widespread unconformity. It is composed of fluvial sediments, generally less than 100 feet thick, that were deposited by streams flowing from a source to the south. Most of the deposits are in an arcuate belt, convex to the west. This belt, 3 to 12 miles wide, extends from Monument Valley northward nearly 130 miles. It is along the western flank of the ancient Monument Valley-Monticello upland, an area that was slightly uplifted at the beginning and again at the end of deposition of the Shinarump. Erosion and subsequent reworking of the Shinarump sediments in the vicinity of this upland are postulated to have made possible the transportation, in solution, of the uranium contained in these sediments. The soluble uranium probably was carried by migrating ground water into sites favorable for precipitation in Shinarump beds bordering the upland. Thus, the original very small amounts of dispersed uranium in the early Shinarump sediments were accreted in the favorable belt where the accumulations of carbonaceous plant remains and their decay products provided a persistent reducing environment.

Jan 1, 1968

By M. F. Goudge

LIMESTONE surpasses any other rock or mineral in the number and diversity of its uses and in the quantity consumed fur industrial purposes. Either in the raw state or when calcined to lime it enters directly or indirectly into the manufacture of a great variety of products and its sphere of usefulness is continually expanding. The term "limestone" as here employed includes all varieties from high-calcium limestone, consisting almost entirely of the mineral calcite, to the highly magnesian variety, largely dolomite. Lime is also discussed .because lime is simply calcined limestone and often the material may be used in either the calcined or natural state. Limestone has been of service to man since prehistoric times but only in the last hundred years has it become one of the most important raw materials in industry. In every industrial country it comprises the greater part of the total stone produc-

Jan 1, 1937

By A. V. De Forest

INSPECTION and test methods of great diversity have been used from the most ancient times to select raw material, control its manufacture, and appraise its finished properties and value. The "miller thumb," expert in grading flour, the vintner's sense of taste, the goldsmith's micro-wear test on a touchstone, the enquiring sniff over the doubtful egg -these are all nondestructive inspection methods, accurate and depend- able, but not readily reduced to numbers in the c.g.s. system. A horse trader inspecting a possible purchase is interested in more than age, size, weight, color. heredity, speed, or drawbar pull which can be reduced to figures. Behavior, temperament, stamina, health-past, present and future---are just as important as the numerically determinate constants.

Jan 1, 1940

By A. Lucian Walker

SILVER is not only of paramount importance to millions of people as a medium of savings and to other millions as a medium of exchange, but it is also valuable and useful in industry. Mexico continues to be the largest producer of this metal, followed by the United States, Canada, and Peru. The largest consumers are China and India, which normally absorb about two-thirds of the world's mine production, hoarding it as savings. The imports by these countries exert a powerful influence upon the price, yet neither country is on the silver standard. China having abandoned it in 1935 and India in 1893, when the rupee was definitely linked to the pound sterling. Other nations such as Persia, Ethiopia, Mexico, and many of the South American countries either have been on the silver standard or have used silver as their chief circulating medium, and most large nations use it for subsidiary coins, this use accounting for 20 to 30 million ounces annually. The arts and industries have consumed 35 to 40 million ounces each year.

Jan 1, 1937

By H. A. Wheeler

IT may surprise some of our members to learn, among the industries based on the mineral resources of the United States that of clay now ranks third, being exceeded in value of product only by pig-iron and coal. The present annual value of clay-products exceeds the value of the outputs of gold and silver, and also exceeds the combined values of copper, lead, zinc, aluminum, mercury, antimony and nickel. These facts are shown in Table I. which gives the statistics for the year 1902

Jan 1, 1905

By C. van der Poel, R. L. Chuoke P. van Meurs

When an initially planar interface between two im-ttitcihle liquids is displaced at constant rate, U, nor-mat to the front, instability will occur for all rates greater than a critical rate. U, given by provided the Fourier decomposition of the spatial pertmrbcrtiott or deformation of the moving displacetment front contains modes with wavelengths. A, greater than a critical wavelength, given by tit there expressions, p, p and k, with the subscripts I and 2 distinguishing the two 1iquids under consideration, are density, viscosity and effective pemeability coefficients respectively; g is the absolute value of the acceleration due to gravity; and cos (zz') is the direction cosit7e between the vertical carlesian coordinate z' (positive upward) and the z coordinate norma1 to the initially plane macroscopic interface taken positive in the direction from Liquid I to Liquid 2. U is the average volumetric velocity (injected volume of liquid pet. unit time per unit of area normal to Z) and is positive for Liquid I displacing Liquid 2, negative for the reversc displacement and r2 is an effective inter-fucial tension (for displacements between parrallel plates, t0= s the ordinary bulk interfacial tension). further, there is a wavelength of maximum instability given by For natural perturbations, this wavelength will preclotninate and characterize the form of the instability as a quasi-sinusoidal deformation, i.e., viscous fitzgers of peak-to-peak separatiotr, A,,. Comparison of experitient with theory rei'eals tltat these considerations are recsonably valid for displacements in hoth parallel plate chantzels and nnconsoli-clutt'd glass ptnvder packs. These results are. tij particular interest for interpretation of data from laboratory experiments with regard to fielil applica/iotz.s. It is quite possible for A,, although st7zall relative to the large lateral dimension of the reservoir, to rxceed the greatr.st lateral extent of the lahoratory sample or model. If it does, frontal displace- ment occurs in the laboratory experiments, and oil INTRODUCTION Thc puposes of this paper are to present theoretical and experimental evidence for occurrence of macroscopic instabilities in displacement of one viscous fluid by another immiscible with it through a uniform porous medium and to compare available experimental data with some predictions of a theory of instability developed by the first author. The instabilities are referred to as macroscopic in the sense that spatially quasi-sinusoidal, growing fingers of the displacing liquid are formed, the width and peak-to-peak separation (wavelength) of which is large relative to a characteristic length of the particular permeable medium such as grain size. Visual models of two kinds have been used to obtain observations: displacement of oil by water-glycerine solutions through the flow channel formed by closely spaced parallel plates and displacement of oil by water with and without initial interstitial water through unconsolidated glass powder packs, employing the technique of matching indices of refraction. In all cases we have observed macroscopic instabilities or fingers under conditions predicted by the theory to be favorable for their occurrence. The phenomenon discussed here is not the production of streamers due to gross inhomogeneities such as permeability stratification of the porous medium. It is our object to show, on the contrary, that a quantitative prediction of finger spacing is possible in a porous medium known to be macroscopically homogeneous and isotropic throughout. The importance of the phenomenon in its influence on the configuration of oil and water with respect to oil production behavior was noted earlier by Engel-berts and Klinkenberg' who coined the term "viscous fingering". THEORY Necessary and Sufficient Conditions ior Instability anc Initial Kinematics There are several levels of increasing complexity in the theoretical description of instabiIity of fluid displacements in permeable media. Of these, the simplest description, ;tdapted to low permeability systems, is selected for presentation.' More inclusivc tlescriptions are reserved for separate publication.

By Kefton H. Teague

This paper deals with the practical application of the Dutch State Mines cyclone separator for fine-coal cleaning. The more important operating variables are discussed, and results of a number of continuous-scale tests on various fine coals with a 6-in. cyclone separator are given. Descriptions of the Cyanamid Pilot Plant and the 50 tph Cyclone Separator Plant at the Emma Washery in Holland are included.

Jan 1, 1950

By Henry S. Washington

I. INTRODUCTION. DURING the last twenty years or so the chemical investigation of rocks has made great advances, and it is now generally recognized that a knowledge of the chemical composition is as essential as that of the texture or mineral composition-if not more so-for the proper classification of rocks and study of their origin and relationships. Rock-analyses have vastly increased in numbers and, what is of greater importance, in quality. New and improved methods permit of greater accuracy than was possible in the early days, and the list of chemical constituents frequently determined has risen from the seven or eight of the greater part of the nineteenth century to twenty or more. Indeed, rock-analyses with determinations of so many constituents are now commonly made by the chemists of the United States and Australia, while in Germany, Great Britain, France, and Italy the rarer constituents are determined more frequently than formerly. As a consequence of this modern, accurate work, it has been discovered that some elements which were formerly supposed to be rare are of wide-spread occurrence and are often present in considerable amount. The fact is further being developed that the elements tend to show certain relations of occurrence or abundance in connection with each other. This is a fact which is applicable to the rarer elements, and which also finds a broad geological and petrological expression in the recognition of petrographic provinces. We are beginning to obtain some definite, though as yet rudimentary, knowledge of the distribution of the elements among igneous rocks. Some of the results along these lines obtained by study of the vast accumulation of analytical data now available are well known to petrologists, while others do not seem to be so gener-

Sep 1, 1908

By Heinrich Ries

I. INTRODUCTION. THE facts is presented in this paper, based chiefly on recon¬naissance made, during the summer of 1903, by myself and my assistant, Mr. R.. C. Brooks, cover practically all that portion of Texas lying east of the 99th meridian. The work was undertaken for the University of Texas Mineral Survey, and was to have been extended over the entire State, but the sudden termination of the survey prevented even the official publication of the results already obtained. Most of the mineral resources of Texas were fully treated by the First Geological Survey, but the clay-industry was tit that time little developed, so that only a few scattered notes concerning it are to be found in the Survey reports. The extensive exploitation of the clay-deposits, however, has emphasized their commercial importance, and has also made accessible many facts of exceptional interest concerning their geologic conditions. The erection of new plants for the utilization of clay-products is usually preceded by more or less prospecting, which, by reason of the scarcity of outcrops, and the geologic and topographic conditions of eastern and southeastern Texas, is often slow and difficult work. This is especially true in the Tertiary and Pleistocene areas, where the structural conditions much resemble those of the Atlantic coastal plain, the deposits being mostly lenticular in form, and surrounded by beds of sand. II. GENERAL GEOLOGY OF THE CLAY-DEPOSITS. The accompanying sketch-map, Fig. 1, shows the location of nearly all the deposits examined, their relation to the geology of the State, and the type of clay found in each. The geology is based on the published work of Hill, Cummins, Tail, Adams, Hayes and Kennedy, but the boundaries have unfortunately not been determined over the entire region covered by the map, and, in many areas, are only approximate. It will be seen that the clay-deposits range from Carboniferous to Pleistocene in age, the older deposits being found in the northwestern part of the area, while those of Cretaceous and Tertiary age lie to the east, southeast and south. The Pleistocene clays are found in part in a belt along the coast, and in part along many of the larger rivers, where they often underlie extensive terraces.

Sep 1, 1906

By G. R. Speich, L. Zwell, H. A. Wriedt

HORNBOGEN1 has recently shown that it is possible to measure the degree of segregation accompanying cellular precipitation in ferritic Fe-Zn alloys by measuring the lattice parameter of the ferrite phase within the cell. In extending this work to study a wider range of composition and to evaluate the free-energy change accompanying the growth of the cells, the lattice parameter and the boundary of the a! phase in Fe-Zn alloys were redetermined to check the earlier work of Schramm.2 This appeared to be necessary since the Fe-Zn diagram has been drastically revised since the work of Schramm. Stadelmaier and Bridgers3 have recently shown that, contrary to prior belief: the y iron field is closed and the a phase boundary extends to an a + T + L peritectic at 782°C where peritectic a contains 42 at, pet Zn. The phase T in equilibrium with the a solid solution has a composition near Fe3Zn10 and a cubic 081 type structure.' The alloys were prepared by two different methods. In the first method carbonyl iron powder (400 mesh, 99.8 pet pure) and high-purity zinc powder (200 mesh, 99.99 pet pure) were mixed in a ball mill and then pressed in a die at 40,000 psi pressure to make compacts with a diameter of 5/8 in. and a thickness of l/4 in. These were sealed in evacuated quartz capsules, gradually heated to 1100°C over a period of 1 week (3 days at 600°C) 3 days at 800°C, 1 day at (1100°C), and then quenched in iced brine. For the alloys containing 23.4 and 30.1 at. pet Zn, the final homogenization anneals were performed at 1000" and 850°C) respectively, to prevent melting. In the second method, alloys were prepared by saturating high-purity iron millings (0.001 in. thick, 99.9 pet pure) in zinc vapor. For each alloy the impregnation was conducted at a fixed vapor pressure of zinc and a fixed temperature between 750' and 800°C. When saturated, the millings were quenched in water. The compositions of the alloys prepared by both methods are shown in Table I. The lattice parameters of the ferritic solid solutions were determined by comparing the 26 values of their 310, peaks (using Co Ka) or of their 211 , peaks (using Cr Ka) with those of corresponding peaks for high-purity a iron. The 20 values were measured at room temperature with an X-ray dif-fractometer (G.E.-XRD5). By using a fiducial value of 2.8664Å for the lattice parameter of pure a iron at 25oC,5 the lattice parameters of the zinc-bearing

Jan 1, 1964

By Frederic Dewey

(New York Meeting, February, 1913) This old and well-known method of determining, silver is, in bullion work, so far superior to the furnace-assay that it is looked upon with reverential awe by many, if not by most, users, and its-ease of execution, with proper equipment, commends it highly where much commercial bullion work on silver is required. The method is so thoroughly well known that a, description of it here may seem to be unnecessary, but many thousands of determinations are annually made by it in the U. S. Mint Service and its practice is there reduced to an art. This is necessary both for the sake of economy of time, acid because high-grade work with it requires constant practice. It is useless for a person who uses it only occasionally to expect to attain high accuracy with it, without spending more time upon a determination than is warranted in a busy commercial laboratory. It is always employed in the Mint service whenever possible, but its chief field is in the determination of silver in standard silver (ingots and coin), which is 900 fine in silver and 100 fine in copper, and I shall first briefly outline its use on this metal and then take up various points in detail, especially as related to the accuracy of the results obtained.

Jan 4, 1913

By Sam Tour

SOME years ago, the writer described heat checks or thermal cracks that occur in die-casting dies.1 The life of dies was considered in relation to the casting temperature, the material used for the die, and the heat to be absorbed by the die per unit volume of casting made. The mech-anism of the action that results in thermal failure of dies was described. In the present paper the writer proposes to describe some additional observations in regard to heat checking, make one or two suggestions as to the method or methods for further attack of the problem, and give the results obtained on some work carried out along these lines.

Jan 1, 1934

By H. H. Hausner, O. V. Roman, F. V. Lenel, G. S. Ansell

The radial shrinkage during sintering of cylindrical compacts and loose aggregates of copper powder was measured. It was found to be nonuni-form from top to bottom of the samples and to depend upon the method of supporting them. The non-uniformity is due to the effect of gravity forces during sintering. Since gravity has an effect in sintering without externally applied stresses, no sharp dividing line can be drawn between conventional sintering and hot pressing. RECENT investigations of the sintering behavior of compacts1 and of loose powder aggregates2 have indicated that forces, other than those arising from surface tension effects, may play a role in shrinkage. In compacts it was shown that residual stresses from the pressing operation influence shrinkage behavior. In loose powder aggregates gravity forces due to the weight of the powder affect the ratio of shrinkage in the vertical and the horizontal direction. The main effort in the work reported here was to show that gravity plays a role also in the sintering of compacts. A few additional experiments were made confirming the effect of gravity in the sintering of loose powder aggregates. EXPERIMENTAL PROCEDURE Compacts and loose powder aggregates were prepared from irregularly shaped, electrolytic copper powder. Prior to use the powders were reduced 30 min at 400°C in dry hydrogen to remove surface oxides. Then the -325 mesh size fraction was separated from the -100 + 325 mesh fraction. The compacts were pressed at a pressure of 10,000 psi from 50 g of powder in a hardened steel die, 1 in. in diam. The height of the compacts was 0.725 i 0.005 in. An effort was made to get as uniform a green density distribution in the compacts as possible. The walls of the die were lubricated with a suspension of 3 pct of zinc stearate in acetone and the compacts were pressed using double action by first pressing the powder at 1200 psi with the die barrel supported, then removing the sup- ports and pressing to final pressure of 10,000 psi with the die barrel floating. The pressure was maintained for 10 sec. The compacts were sintered at a temperature of 925°C, generally for 1 hr. In order to maintain uniform temperature they were sintered in boats made from cylindrical copper blocks. The blocks were 2 in. in diam, either 2 or 2 1/2 in. long and, split to form the body of the boat and a lid. The body of the boat contained a cavity 1 3/8 in. wide, 1 in. deep and either 2 1/8 or 1 3/8 in. long. The longer cavity accomodated two samples, the shorter one only one sample. The uniformity of temperature distribution within the boats was checked with thermocouples welded to the top and bottom of the samples. The maximum variation between top and bottom temperatures was i 1/2°C. The actual sintering temperature was held constant within ±2°C. In order to determine the effect of gravity forces, i.e., the weight of the compacts, upon shrinkage, they were supported in the following ways during sintering: a) Full Bottom Support. The compacts rested either on a flat alundum disk or on alundum powders. b) Partial Bottom Support. The compacts rested on a graphite cylinder, 0.3 in. in diam which formed a projection on a larger graphite disk. It is difficult to balance the compact on the small projection. To avoid having the compact tip, a small hole was drilled through the compact and through the graphite disk and its projection. The graphite disk was then suspended from the lid of the boat by a thin iron wire which passed through the holes in the disk and the compact. c) Top Support, first type. A hole 3/32 in. in diam was drilled diametrically through the green compact 3/16 in. from the top of the compact. The compact was sintered suspended from an alundum rod (thermocouple protection sleeve) inserted into the hole. d) Top Support, second type. A hole was drilled axially through the center of the compact. The upper part of the hole from the top surface of the compact one fourth of the way down was 1/16 in. in diam; the lower part of the hole from the bottom surface three fourth of the way up was 3/32 in. in diam. The compact was suspended from the lid of the boat by an iron wire passing through the upper part of the hole and then tied into a knot. The loose powder aggregates were made by filling l in. deep, l in. diam cylindrical graphite molds with -325 mesh powder. To achieve uniform density in all the loose powder aggregates, the powders were settled in the molds by placing the

Jan 1, 1963

By Frances H. Clark

DEVELOPMENTS in powder metallurgy have been disappointing in 1943. If any new part has gone into large-scale production, knowledge of it has been restricted by considerations of national security. Nor have any outstanding papers appeared to advance the theory of the subject during this period.

Jan 1, 1944

THERE have been two important accomplishments of the Truman administration; the Hoover Commission report on inefficiency and waste in government and the report of the Paley Commission on the natural resources of the United States. Both reports are in the interest of the American people and should transcend the boundaries of political parties. Both reports are starting points for the formulation of policies which must be continuously revised to meet changing conditions. Regardless of the outcome of the election the principles embodied in these two great documents must be kept alive. The Paley report is right in our own bailiwick of mineral raw materials and it behooves us to study it carefully as our responsibility to posterity. To those in the mining industry who have limited their field of observation to moving rock or to metal prices it may come as a surprise that our production of such staples as copper, lead, and zinc has fallen behind increased requirements to the point that substantial tonnages must be imported. Iron ore is next on the list and everybody knows that such metals as tin, tungsten, chromium, manganese, nickel, and cobalt are imported almost exclusively. The crisis in raw materials pointed up by the Paley report has been reported annually by Elmer Pehrson and others to small gatherings at the Mineral Economics Division sessions at the Annual Meeting for as long as we can remember. In September 1949, the United Nations Economic and Social Council held an international resource conference at Lake Success which disclosed these same grave conclusions: - Consumption of raw materials is multiplying at an alarming rate, faster than discoveries or replacements are being made. - Production has been wasteful and utilization lavishly beyond enginee¬ing and practical requirements. - Industrialized nations are depleted and many raw materials consumed by industry are not found in the industrialized countries. - Nations formerly exporters of raw materials are increasingly building their own consuming industries. - Political forces in the world are limiting access to raw materials. The Paley Commission selecting the quarter century, 1950 to 1975, to project raw material requirements for the United States, pointed out obstacles to meeting these requirements, and made recommendations for procurement. It is not important that we disagree that cobalt consumption will reach 344 pct of present, or fluorspar 187 pct when iron and ferroalloys are only expected to increase 75 pct. What is important it that the fabulous appetite of the United States for mineral raw materials has consumed more since World War I than was consumed by the entire world in all recorded history prior to 1914. And, unless the people of the United States are satisfied to remain at their present standard of living (which is unthinkable) this consumption is correctly plotted by the Paley Commission as continuing to expand. If the U. S. is to continue on a course of progress, it must procure raw materials wherever it can at the lowest possible cost. Natural resources are clearly an area in which the broadest cooperation between industry and government must exist to achieve efficient exploitation, economic consumption, and expansion of sources of supply. The message of the Paley report requires action comparable to that of the North Atlantic Pact. Its implication is as significant as military preparedness. It is a world problem. It is a mining engineering problem. Don't let it die!

Jan 1, 1952

By R. W. Raymond

EDWARD COOPER, was born in New York City, October 26, 1824. His father, Peter Cooper, to say nothing of manifold reasons for fame as an inventor and philanthropist, deserves to be remembered as a pioneer in the establishment of public schools; and it is not surprising that he sent his son to one of the democratic institutions in which he was himself so ardently interested. From the public school Edward Cooper went to Columbia. College, where he made the acquaintance of Abram S. Hewitt, who was first his tutor, afterwards his traveling companion, brother-in-law, business partner and life-long friend.* For twenty years I was the consulting engineer of the firm of Cooper & Hewitt, and also connected with the work of the Cooper Union, in which they were both deeply interested and faithfully active. On the basis of the intimate knowledge thus gained, I venture an estimate of Edward Cooper's character and career which, if not fully comprehensive, may facilitate a juster estimate than would be reached by the strident of those data which the modesty of the man permitted to be placed upon public record. Edward Cooper's mind was one of the most active, accurate and subtle with which I have ever come into contact: He had inherited from his father a sunny, benevolent temperament, and' the irresistible impulse to attack all new problems which challenged his attention. His thorough education had 'indeed made him wiser than his father, both in philanthropy and in technical inventions. He could condemn and reject a proposition which Peter Cooper would have embraced, in a splendid, though ignorant, faith that nothing was impossible to an. American, and that the word ? impossible " was simply a label,

Jul 1, 1906

By Fred P. Peters

T. D. Yensen.*—As my information is of a negative nature, I think it belongs under this paper. We are particularly interested in magnetic materials and we would like very much on occasions to make use of powder metallurgy. We have tried repeatedly to use powder metallurgy in preparing our nickel alloys but always. with negative results; that is, we cannot get as good magnetic properties by powder metallurgy as we can by starting with a molten material. We have tried by all possible means to make materials' like 50 per cent iron-nickel alloys by powder metallurgy. The compacts can be regularly lorged and rolled but no matter what we do in the way of annealing, the magnetic properties come out very much poorer than if we start with molten material. F. V. Lenel. †—I want to mention one characteristic of articles made from metal powders which distinguishes them from die castings; that is, their wear resistance. Die castings usually are made from zinc or aluminum alloys and a few copper-zinc alloys; all of them are comparatively soft and not very wear resistant. I know of a number of cases where powder metallurgy rather than the die-casting method was used for producing a certain part because higher wear resistance was needed than could be attained in die castings. A, J. LanghammeR.*—The subject of powder metallurgy is somewhat difficult to discuss, and portray, in the time that his been allotted. Most of you would rightly be bored if we went into details. However, I will cite one incident that possibly will help illustrate some of the potentials. Last summer I was in Washington and met Navy officials for the purpose of studying the possibility of making a certain part by powder metallurgy. The part is highly intricate and I happened to remark that the material cost would be high; that is, the cost on one raw material. Promptly a high-ranking Navy officer said: "Mr. Langhammer, if you must pay x dollars a pound for the raw material, but achieve the desired results, the cost of the finished part would still be low."

Jan 1, 1945

By N. A. Gokcen

EQUILIBRIA in the reactions between gases and liquid metals have been the subject of many interesting investigations. The experimental realization of true equilibrium, however, is questionable in certain cases due to the lack of conclusive studies in reaction rates. It -will be shown here that a systematic interpretation of rate studies with the analysis of prevailing experimental conditions leads to valuable practical information. The reactions of particular interest are: H2(g) +S(inFe) - H2S(g) [1] H2(g) +O (inFe) =H2O(g) [21 2H2(g) + SiO2(s) = 2H2O(g) + - (inFe) [3] The usual and perhaps the most convenient method of investigation may be illustrated with reaction 1. A stream of gas mixture consisting of H2 + H2S is passed over or bubbled through the liquid metal at constant temperature. The ratio of H2S/H2 in the entrant mixture is fixed in each experimental run, and, therefore, the composition of melt varies until the establishment of equilibrium. The purpose of this paper is to derive a formula expressing the minimum time required for the establishment of equilibrium and to compare the calculated values from such a formula with the available data. Equations Reaction 1 is used for the purpose of illustrating the derivation. Let E represent the equilibrium and X the nonequilibrium sulphur in weight percent at any time t in minutes. For the sake of simplicity, it is first assumed that E > X although the results are of general applicability without restriction. It has been shown by Morris and Williams' that within a difference of 1 pct S or less, i.e., E-X5 1.00, the value of K'1 = Ph2s/Ph2.S% is very nearly constant. The maximum ratio of available Ph2s/Ph2 = H,S/H,, from which sulphur can be absorbed by metal, is equal to H2S/H2 in equilibrium with E (which equals H2S/H2 in the entrant gas), minus H,S/H, in equilibrium with X. Thus: Available H2S/H2 = EK'1 - XK'1 [4] Eq. 4 expresses that sulphur can be absorbed by metal from the H2S/H2 in the entrant gas until the gas leaving the metal assumes a value of H2S/H2 which is in equilibrium with the dissolved sulphur X at that time. H,S constitutes up to approximately 1 pct of the gas mixture. Its disassociation into H2 and SL is about 1 pct at 1600°C, hence, the H2S/H2 impinging on the surface of metal is very close to that in the entrant gas. The rate of flow of hydrogen entering the reaction chamber is kept constant experi-

Jan 1, 1954

By N. A. D. Parlee, I. D. Shah, W. C. Phelps

THIS note reports on a continuation of a program on the thermodynamics of Fe-S-X systems in the "steel-burning" temperature range begun by Bock, Barloga, and parlee.' Small coils of 0.039-in.-diameter pure iron (Ferrovac-E) wire were equilibrated with Fe-S-0 melts in ingot iron crucibles under argon at 1324°C in the assembly shown in Fig. 1, the lower part of which was heated in a large Globar furnace. Fig. 1 shows (R) the coiled iron wire sample, (M) the Fe-S-0 melt prepared from desired proportions of ferrous sulfide and ferric oxide, (K) the iron crucible, (I) a mullite guide tube, (J) an alumina crucible, (L) alundum sand, (N) crushed mullite, (Q) hollow cylinders of K30 brick, (C) a steel rod, (B), (El, (F), (G), (P), and (O), details of brass water-cooled head, and (H) a mullite tube 2-3/4 in. ID and 26 in. long. The rod (C) bearing the sample could be removed at will and be replaced by a tube for sampling the melt, or by a thermocouple for comparing the melt temperature with a control thermocouple not far from the 2-3/4-in. mullite tube. After equilibration the iron coils were treated with acid to remove the outer layer of metal and then they were analyzed for sulfur by a standard combustion method. The melt samples were analyzed for oxygen by a variation of Lander's2 hydrogen-reduction method for mattes, and for sulfur by the ASTM combustion-iodometric method NO. E 30-47. When the results of some forty-two runs were examined it was found that the sulfur and oxygen contents of the equilibrated melts showed good consistency, in that the plotted compositions fell along the smooth curve shown in Fig. 2. The points on this curve represent the experimental compositions of melts in equilibrium with ?-iron (Fe-S-0) solid solutions. These solid solutions are saturated with sulfur and oxygen with respect to the melt and therefore have the same sulfur and oxygen activities as the melt. The curve drawn through the points therefore delineates the ? liquidus. It falls in such a position as to roughly confirm the liquidus curves of Hilty and crafts3 at 1200" and 1300°C which are

Jan 1, 1965

By S. S. Lisnyak, B. D. Lichter

An important question in the study of the "hot corrosion" phenomenon (i.e., accelerated oxidation of Ni-Cr-base and Co-Cr-base "superalloys" in the presence of sulfur) is the condition of formation and physico-chemical properties of different sulfides in the system Ni-Co-Cr-S. seyboltl has observed the presence of ((chromium-rich" sulfides of compositions M3S4, and M2S3 in the scales of superalloys after hot corrosion; however, as he points out, much confusion exists as to the identity of sulfides found on Ni-Cr and Co-Cr alloys. According to the literature,&apos; ternary sulfides, e.g., NiCr2S4, (monoclinic structure) and CoCr2S4 (spinel structure) exist in these systems. Therefore, it is likely that these compounds are found in the scale of alloys undergoing hot corrosion. At present this possibility has not been discussed in the literature. Accordingly, we have begun investigation on the properties of ternary sulfides and their mutual interaction. The magnetic and electrical properties of pure NiCr2S4 and pure CoCr2S2 have been previously determined."-&apos; In the present work we have studied the interaction between these sulfides at high temperatures by means of X-ray diffraction and magnetic susceptibility. The measurements were carried out at room temperature after appropriate thermai treatment of samples at high temperatures. For alloys containing the three elements nickel, chromium, and cobalt this interaction may be of importance in the study of the hot corrosion phenomenon. The compounds NiCr2S4 and CoCr2S4 were prepared from stoichiometric amounts of the elements and CoS in the case of CoCr2S4. Samples were mixed and sealed in evacuated silica tubes, slowly heated to 900&apos; to 100O°C, and held at temperature for a total of 120 hr (NiCr2S4) or 80 hr (CoCr2S4) with intermediate re-grinding~. X-ray diffraction showed a pure spinel structure for CoCr2S4 and a monoclinic structure for NiCr2S4. Samples of mixtures of the two ternary sulfides were prepared with different compositions, see Table I. Samples were heated for a total of 80 hr at 900&apos;C in evacuated silica tubes, with one intermediate regrind-ing. The capsules were slow-cooled to room temperature in the furnace. Samples for X-ray diffraction were prepared by placing powder on a glass slide with vaseline. Dif- fractometer traces were obtained on a G.E. XRD-5 diffractometer using a chromium tube and vanadium filter (40 kv and 31 ma). The size of the spinel unit cell was determined from the eight highest angle peaks (80 deg < 2b < 160 deg). Calculated lattice parameters were plotted vs cos B . ctn 0 and extrapolated to 6 = 90 deg. Measurements of the magnetic susceptibility were carried out at room temperature using the Faraday method in a magnetic field of 3000 G and using a Cahn RG automatic microbalance. The system was calibrated from the well-established susceptibilities of platinum and palladium: (Xpt = 0.968 x 10-6 g-1 and Xpd 7 5.04 x 10~6 g-1). The weight of samples were approximately 0.200 g. X-ray diffraction patterns for unsintered mixtures showed Bragg peaks from both the spinel (CoCr2S4) and monoclinic (NiCr2S4) structures. After sintering no monoclinic peaks were observed in samples containing up to 40 mol pct NiCr2S4. However, the spinel peaks were displaced to higher angles with increasing

Jan 1, 1970