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By C. D. Stahl, E. E. Templeton, R. F. Nielsen

It has been customary, in predicting saturation changes, to use the Leverett fractional flow formula", obtained by eliminating the unknown pressure gradient from the generalized Darcy equations for the separate phases. The formula presents difficulties in the case of counterflow, since the "fractional" flow may be negative, greater than unity, or, in the case of a closed system, infinite. Recently, it has been shown by several authors that the corresponding equations (with capillary pressure and gravity terms) for actual flow of the phase may be used just as well. These equations are in agreement with Pirson's1 statement that, if the two mobilities differ considerably from each other in a closed system, the flow is largely governed by the lower value. The present study was undertaken because of an apparent lack of experimental data on gravity counter-/low with which to test the theory. A 4-ft sand-packed tube in a vertical position was employed. Electrodes for determining saturations by resistivity were spaced along the tube, one phase being always an aqueous salt solution. Air, heptane, naphtha, or Bradford crude oil was used for the other phase. A reasonably uniform initial saturation was set up by pumping the phases through the system, alter which the tube was shut in and saturation profiles obtained at definite intervals. Cumulative flows over certain horizontal levels were obtained by integration of the distributions; hence, differentiation of the cumulative flows with respect to time gave instantaneous flow rates. To compare experimental and theoretical flow values, capillary pressures were assumed given by the final saturation-distribution curve. The upper part corresponds to the "drainage" region and the lower part to the "imbibition" region, where trapping of the nonwetting phase occurred. While calculations indicated that the capillary pressure saturation function and, probably, the relative permeability saturation functions changed during the segregation, the relation of the measured rates to saturation distributions are in general accord with the frontal-advance equation. It appears that the Darcy equations, as modified for the separate phases, are generally valid for counterflow due to density differences. The usual method of predicting saturation changes, which involves a continuity equation and the elimination of the unknown pressure gradient from the flow equations, should therefore be applicable. However, the need for advance knowledge of drainage and and imbibition "capillary pressures" and relative permeabilities during various stages presents difficulties. INTRODUCTION The present study was undertaken because of a seeming lack of experimental data relating to vertical counterflow of fluids of different densities in porous media. In particular, it was desired to determine whether data obtained from these laboratory tests were in accordance with certain mathematical treatments of counterflow which have been proposed. The gravity "correction" has been incorporated into the flow equations (and, hence, into displacement theory) nearly as long as both have been used. field4 and laboratory5 data have generally borne out the validity of the theory as applied, for instance, to downward displacement by gas, with all fluids moving downward. However, the modifications for counterflow have only recently been pointed out. 2-3 It has been customary to use fractional flow rates instead of actual flow rates in displacement calcuIations. In the case of counterflow, this results in negative values, values greater than unity and, when rates are equal and opposite, in infinite values. As pointed out by Sheldon, et a1,3 and by Fayers and sheldon,2 actual flow rates may be used just as well. The fact that these may be of opposite signs for the two fluids does not present any difficulty.

By E. N. Cameron

GRAPHITE has been included in U. S. lists of strategic minerals since the problem of mineral deficiencies was revealed during World War I. Since 1918 the domestic graphite industry has led a precarious existence, and there has been much uncertainty as to the amounts of usable graphite of various grades that would be available from domestic sources in time of emergency. In 1950-1951 therefore, the writer, assisted by Paul L. Weis, undertook a review of domestic graphite sources for the U. S. Geological Survey.' The conclusions of this study are presented here, with a discussion of some technologic and politico-economic factors bearing upon the problem. Uses of Graphite: Natural graphite as marketed exhibits a wide range of properties, which determine the uses to which it is put. The most essential uses are in the manufacture of crucibles and related refractory articles, in lubricants and packing materials, and in the manufacture of batteries, foundry facings, pencils, and carbon brushes. Numerous specifications covering the mineral in its various applications must be met by producers and processors of graphite. The problem of supply is therefore not simply one of procuring a sufficient total tonnage, but the more difficult problem of procuring enough of each different grade to meet foreseeable needs. The amount of graphite required by American industry is not large. Ordinarily only a few thousand tons of strategic grades are consumed annually, yet the elimination of this small tonnage would have serious effects in several industries. Strategic Graphite: Since World War I, 60 to 100 pct of the country's annual supply of graphite has been furnished from imports. At present, natural amorphous graphite for use in pencils and batteries is produced largely from American-owned mines in Mexico. Graphite for foundry facings is obtained from a number of sources. Neither grade is a serious problem. High purity graphite for carbon brushes and for pencil leads, however, is imported, largely from Ceylon, in the form of amorphous lump graphite. Most of the flake graphite used for crucibles and related refractory articles is likewise imported, largely from Madagascar, and much of the lubricant and packing grade graphite used by industry is obtained from the same source. The strateg'ic grades of graphite are therefore amorphous lump of the Ceylon type, crucible flake, and flake suitable for lubricants and packing. Ceylon lump and Madagascar flake have for many years been accepted as standard by domestic consumers of graphite, and various essential manufacturing processes are geared to the use of graphite from these sources. Ceylon graphite as marketed is classified into several grades based on particle size and purity. Processing methods are said to be simple, but the products marketed are carefully graded and are consistent in their characteristics, an important matter to the consumer. Nearly all the graphite produced in Ceylon is from veins. Resources are reported to be large, labor is cheap, production costs are low, and world competition is slight—factors accounting for the commercial success of the graphite mining industry in Ceylon. Madagascar is reported to have deposits of the Ceylon type, but its output consists almost entirely of flake. Madagascar graphite as received in the U. S. is further processed by importing organizations, and a large number of grades are produced to meet industry requirements, especially those for crucible flake and for lubricant and packing grade flake. Madagascar crucible flake as marketed is noted for coarseness, uniformity, toughness, clean-

Jan 1, 1957

By Charles W. Chesterman

Perlite is a glassy volcanic rock which will, upon rapid controlled heating, expand or "pop" into a frothy material of low bulk density, valued as a lightweight aggregate. The term perlite also is applied to the expanded product. The chemical composition of perlite ranges from that of rhyolite to that of andesite; the water content ranges from 2 to 5%. Most perlite is pale gray, but some is black, brown, or even green. Inclusions in perlite are common and include phenocrysts of quartz, feldspar, biotite, and hornblende, and miscellaneous rock fragments. Occurrences of perlite are restricted to areas of Tertiary and Quaternary volcanic rocks. Perlite occurs as flows associated with thick accumulations of pyroclastic debris and other flow rocks, as dikes, sills, domes, and as selvages of intrusive bodies of volcanic rock. Individual flows of perlite range in thickness from a few feet to as much as 100 ft and commonly cover several square miles. Dikes and sills of perlite generally are small, but domes generally are substantial in size and may be as much as several miles in diameter. Most perlite deposits are large enough and topographically situated so as to lend themselves to low-cost open pit mining methods. Conventional equipment is employed in the mining of perlite. Although milling procedures may appear to be simple, care is exercised in order to produce a carefully sized product and to minimize the production of excessive quantities of fine materials, which have limited use and are considered as waste. Perlite is processed, or "popped," in one of two basic types of furnaces: horizontal rotary or vertical stationary. Both types of furnaces include product collection and dust control systems. Many commercial deposits of perlite are known to occur throughout the world, and although no exact estimate of reserves is available, there appears to be an adequate supply to meet current and future worldwide requirements. End Uses The uses of expanded perlite are many and varied and are based primarily upon its physical and chemical properties. Because of its (1) low bulk density, which generally ranges between 2 and 20 lb per cu ft; (2) low thermal conductivity "K" factor (Btu per hr per sq ft per OF per in, of thickness), which ranges between 0.267 for loosely packed perlite (bulk density of 4.48 lb per cu ft) to 1.25 for perlite gypsum plaster; (3) high resistance to fire; and (4) low sound transmission, expanded perlite is used to a great advantage as aggregate and insulating material in the construction industry. Early uses of perlite were related exclusively to the construction industry, which now consumes about 60% of the domestic production. The primary use of perlite now is as aggregate in insulation boards. Other uses of perlite in 1971 were as aggregate for plaster, horticultural aggregate, low-temperature insulation (cryogenics), and concrete. Because of its low thermal conductivity ("K" factor), high adsorption of sound, low bulk density, and fire resistance, perlite aggregate plasters hold many advantages over conventional plaster. Perlite aggregate plaster lends itself to machine applications, dries quickly, and has relatively high elasticity which reduces cracking after drying. These same features make perlite useful as aggregate in portland cement concrete and asphalt concrete for construction wherever weight reduction, insulation, and acoustics are of prime importance. Perlite-portland cement concrete offers up to 20 times more thermal insulation than conventional concrete, and because of this it finds wide application in roof decks and floor fill in multistory buildings, in

Jan 1, 1975

By J. A. Hafford, J. K. Kerver, J. G. Richardson, P. M. Blair, J. S. Osoba

This paper presents the results of laboratory measurements of relative permeabilities to oil and gas on small core samples of reservoir rock by five methods, and describes the influences of such factors as boundary effect, hysteresis, and rate upon these measurements. The five methods used were the "Penn State," the "single core dynamic," the "gas drive," the "stationary liquid," and the "Hassler" techniques. In those methods in which the results are subject to error hecause of the boundary effect, the error may be minimized hy the use of high rates of flow. In order to avoid complexities introduced by hysteresis, it is necessary to approach each saturation unidirectionally. Observed deviations of relative permeabilities with rate can be explained as a manifestation of the boundary effect, and disappear as the boundary effect vanishes. The results indicate that all five methods yield essentially the same relative permeabilities to gas. Of the four methods applicable to the determination of relative permeability to oil, three, the Penn State, single core dynamic, and gas drive, gave relative permeabilities to oil which were in close agreement. The Hassler method gave relative permeabilities to oil which were consistently lower than the results obtained by the other methods. INTRODUCTION The relationship between the effective permeability of a reservoir rock to each of the fluids flowing through it and the corresponding fluid saturation is an important characteristic of the reservoir rock. Knowledge of this characteristic is and gas reservoirs and of the ultimate recovery to be expected extremely important in the prediction of the behavior of oil under various operating conditions. These effective permeabilities are usually expressed as the "relative permeability" to a fluid phase, defined as the ratio of the effective permeability to the permeability of the rock to a single phase at 100 per cent saturation. Relative permeability-saturation relations are not the same for all kinds of reservoir rock, but may vary from formation to formation, and within the different portions of a heterogeneous formation. In studying the performance of a specific reservoir, it is necessary, then, that the relative permeability characteristics of the individual portions of the reservoir be measured. These measurements may be made in the laboratory on small core samples from the reservoir. Various techniques have been proposed for the measurement in the laboratory of relative permeability-saturation relations. In varying degree, difficulties attend the use of all of the methods which have been proposed. It is the purpose of this paper to discuss the factors which influence the measurement of relative permeability, the difficulties encountered in several methods, and to present comparative results obtained by the use of various techniques. FACTORS WHICH INFLUENCE THE MEASUREMENT OF RELATIVE PERMEABILITY It is necessary that the relative permeability data measured in the laboratory yield the same relative permeability-saturation relationships that would govern the flow of fluids through the sample if it were to occupy its original position in the reservoir. Since the core sample upon which the laboratory measurements are made is not surrounded by similar core material as it was in the reservoir, an error in measuring the relative permeabilities may arise from the "boundary effect" which results from a discontinuity in capillary properties of the system at the effluent end of the core. Again, the rates of

Jan 1, 1951

By O. J. Neslage, R. W. Jenkins

MINE operators today are paying increased attention to the mechanization of drilling operations as an important factor in increasing efficiency and decreasing costs. Recent progress in the design of drill jibs for mounting on drill carriages, or jumbos, has done much to advance the mechanization of mining methods. This progress has introduced new opportunities in the application of "jib jumbos" that are worth serious consideration. An attempt will be made here to classify the various types of jumbos and drill mountings available for level development and flat stope work, t6 indicate applications, and to measure their effectiveness in relation to their cost. The data here are based on a wide variety of field usage, and are offered only to point up, in a general way, the relative efficiency in proportion to cost. It should be remembered that any contemplated jumbo installation must be studied to determine what type of installation is most suitable, considering ground conditions, loading, timbering and haulage equipment, service available, and attitude of manpower. Early Drill Carriages: The advantages of some sort of a drill carriage were recognized at the time rock drills were introduced. In drift or heading operations where a fairly standard drill round and cross section were anticipated, as well as in flat bedded deposits where standard slabbing rounds were used, track and crawler-mounted drills found an early application. These first drill jumbos were little more than drill carriers, designed locally and manufactured with materials at hand. Of comparatively simple construction, function, and low capital cost, they usually consisted of a hinged column which supported one or more drills on arms or universal bars. When the column was pivoted vertically, the drills were moved into position. Screw jack extensions reached from the column to the roof and floor to hold the drill rigid. In some cases, particularly in tunnel jumbos, enough weight was carried that rail clamps or roof jacks were sufficient. Many of these column and arm-type jumbos, usually equipped with air and water manifolds, steel racks, and staging for drillers, are still in use today. Some have employed air or hydraulic extensions for securing the columns. They offer the equip-saving advantage of having all the necessary out, ment together, and they un be moved i and t. set up and torn down as a unit. Boom-type Jumbos: When the advantages of to column-type jumbo were seen, operators could to realize the further gains possible. More time could be saved with mechanical assistance to position api drill vertically. A rack on the column and a pinion on the arm for raising and lowering the drill in the manner of a quarry bar were tried with some success. The most outstanding solution to the vertical handling problem was reached with the boom-type of jumbo. Here two or more machines were mounted on a cross arm at the end of a boom that was pivoted at the rear of the track. This was raised and lowered by various mechanical aids. Occasionally air or hydraulic power was used. Nearly all of today's wagon drills use this boom-type principle. Boom jumbos represent a savings in time and physical effort expended in raising and lowering the drills. The boom must be balanced by the roof of the truck which is secured by rail clamps or type jacks. The most successful application of areawhere this of jumbo has been in the Tri-State area where multiple long-feed machines are used on caterpillar-mounted, boom-type jumbos for slabbing

Jan 1, 1951

By Walton J. Greer, System By John E. Owen

The guard electrode system measures the resistivity of formations by employing a thin disk of current which is caused to flow perpendicular to the bore hole. The control of this current disk is obtained in a brute force manner through the use of relatively long equipotential electrodes above and below the measuring electrode. The log obtained from the system is free of "lag," "plateau," "shadow," "reflection" and other distortions evident on conventional logs. The proportionate contributions of the hole size and invaded zone resistivity to the apparent resistivity reading are reduced when the mud and filtrate resistivities are lower. Thus, the guard system favors the use of conductive muds. The mathematical development of the theory is given in an appendix. Equations are derived to evaluate the effects of mud resistivity, hole size, invaded zone resistivity and depth, and the true formation resistivity. Sample logs from several provinces are reproduced and compared with conventional electric logs to illsutrate the much greater detailed lithology that can be presented by the guard electrode system. INTRODUCTION With increased ability of those in the petroleum industry to analyze formation characteristics from electrical resistivity data, there has become apparent the need for more precise measures of that parameter. The measurement of the resistivity of a homogeneous and isotropic material can be made simply when the body of the material is infinite in all dimensions and the measuring electrodes can be placed within the body. In such a case, the current leaving an electrode follows a spherical distribution and the mathematical expression for the potential level at any distance from that electrode can readily be derived.'.' If it is considered that the active electrodes are within a bore hole filled with mud of a resistivity different from that of the formation. the current does not flow in a spherical pattern near the current source or sink, and the calculations of potential levels become more difficult. The additional consideration of a section of formation invaded by mud filtrates, and thus having resistivity different from either that of the mud, the adjacent formations or of the undisturbed formation, makes the mathematical problem extremely complex. Should the vertical dimensions of the formations be considered as finite. the problem becomes so complex as to preclude reasonable solution. Yet, even these considerations have not described adequately the conditions encountered in a large proportion of the wells to be studied. In efforts to evaluate the effects of the various conditions. combinations of twn, three. and four electrode logging con- figurations of the conventional types have been used. The resulting logs have left much to be desired in some provinces. It has become apparent that the use of such configurations will not result in adequate measurements being made, particularly in cases where the formation is composed of thin sections. If all the current of a resistivity measuring circuit is made to flow through the formation opposite the exploring electrode, many of the shortcomings of the conventional measuring system are eliminated. In the guard electrode method of electrical well logging to be discussed in this paper, the current is so controlled by causing it to flow in a thin disk normal to the axis of the logging tool. EARLY HISTORY The guard electrode method of electrical well logging in its early years was a joint development by the Geophysical Research Corp. and the Amerada Petroleum Corp. The method was first experimentally investigated by means of model studies. The results of these studies indicated that current focusing systems properly applied to electrical well logging

Jan 1, 1951

By M. Cohen, P. E. Beaubien, D. Caplan

Addition of 1 pct Mn to Fe-26 CY ca/(ses a12 increase in scaling rate at 870° and 1090°C. Whereas only the rhombohedral oxide, formrs on tire manganese-free alloy, with manganese present major amounts of the spinel .Mn0 . Pro-duced through which diffusion is more rapid. At 1090°C the scale formed OH Mn is highly, irregular due to blistering and sintering, This is a second cause of faster oxidation Since much of the blistered oxide does not participate as part of the protective layer. The oxide phases that form at different times depend on the degree to which the surface metal has become depleted, in manganese by preferential oxidation. PREVIOUS work has demonstrated that the oxide scales formed on chromium steels at high temperature consist of both spinel and rhombohedra1 phases and may contain considerably more manganese, especially in the spinel phase, than is present initially in the alloy.' It has further been observed that a binary Fe-26 Cr alloy scaled less rapidly than an equivalent commercial steel and formed no spinel.' However, it is not established if manganese in chromium alloys actually promotes formation of spinel nor if it affects oxidation resistance. It seemed expedient to try to evaluate the specific effect of manganese by oxidizing an Fe-26 Cr alloy containing a small manganese addition under the same experimental conditions as used for the manganese-free alloy.' EXPERIMENTAL Table I shows the composition in weight percent of the Fe-26 Cr-1 Mn alloy and of the Fe-26 Cr alloy used as reference. The alloy with manganese was prepared from the vacuum-melted Fe-26 Cr alloy by remelting in vacuum with the proper manganese addition. The ingot was rolled to strip and specimens 1.1 by 0.035 by 5 cm and 1.1 by 0.5 by 4 cm cut out or machined. As previously described2 the specimens were smoothed by abrading through 600-grit Sic paper, electropolished in acetic-perchloric acid (20 to 1) to remove 10 p of metal, annealed at 1100°C in 20 torr of purified argon, and electropolished to remove a further 10 p of metal. They were then either rinsed in water and methanol and blotted dry or immediately etched for 45 sec in deoxy-genated 4 N HC1 under cathodic polarization at 10 pa per sq cm. Oxidation runs were carried out in a vertical tube furnace in a flow of purified oxygen at 1 atm while the weight increase was recorded continuously on a* automatic balance.3 Alter 98 hr at 870.C or 20 hr at 1090"C the specimens were removed to flowing argon and observed microscopically for evidence of spalling as they cooled. Subsequently they were examined by X-ray diffraction, the oxides analyzed chemically, and metallographic cross settions prepared. RESULTS Figs. 1 and 2 show the oxidation curves of Fe-26 Cr-1 Mn at 870' and 1090C. The Fe-26 Cr reference runs are shown as dashed curves. Experimental details of the six runs are included in Table 11. The first 20 hr of run 1 is repeated in Fig. 2 to show the effect of temperature. At 8'70°C the weight gain for Fe-Cr-Mn is about twice that of Fe-Cr (curve 1 vs curve 2, Fig. 1). Both alloys show regular oxidation curves. On parabolic coordinates (right-hand scale of Fig. 1) the

Jan 1, 1965

By W. O. Philbrook, K. Natesan

A mathematical model was derived for the temperature change in a particle undergoing heterogeneous chemical reaction and heal exchange with a stream of fluid. The model has been applied specifically to the exothermic oxidation of spherical particles of zinc sulfide. Very good agreement was obtained between the theoretical prediclion and experimental observation. It was found that at no stage of the reaction was the particle subjected to a state of thermal instability. In studies of gas-solid reactions, it is generally assumed that the gaseous and the solid phases are at the same temperature throughout the reaction period. This is not strictly true since most of the reactions are either exothermic or endothermic in nature. This paper deals only with heterogeneous gas-solid reactions of noncatalytic type. In the case of exothermic reactions (e.g., roasting of sulfides), there may result an increase in temperature of the particle due to the release of the heat of reaction, and this increase in temperature may enhance the reaction rate and thus cause further release of heat. Such a "spiralling" effect may lead to a thermally unstable situation within the particle. On the other hand, in the case of endothermic reactions (e.g., calcination of limestone), there may occur a decrease in temperature of the particle as the reaction proceeds, leading to a virtual "quenching" of the reaction front. A general discussion of autothermic processes with emphasis on properties and reactor design is given by Van Heerden. 1 Levesque and cubicciotti 2 observed self heating of the sample in the oxidation of thorium. Anous et al. 3 observed self cooling of the sample in their dehydration studies on chrome alum. Cannon and Denbigh, 4 and Ong et al.5 reported self heating of the sample in their studies of the kinetics of oxidation of zinc sulfide. A typical plot of heat generation and heat loss rates with reaction temperature is shown in Fig. 1.'14 The Sigmoid curve represents the heat generation rate while the straight lines represent the heat loss rate. The main objectives of this analysis are to estimate the temperature increase of a single particle undergoing an exothermic reaction and to study the possibility of a thermally unstable situation within the particle. Also, a study of the dependence of the tempera- ture increase on different process variables has been attempted. A "she ll-by-shell" method has been proposed to analyze the problem. The shells may be made as small as necessary, and equations may be set up for heat transfer by various mechanisms. Such equations will have to be solved for each shell, with the boundary conditions for ith shell being obtained from the (i - 1)th shell, using a high speed digital computer. The oxidation of spherical particles of zinc sulfide is considered for this analysis, but the treatment is general enough to be applicable to other reactions and particle shapes. The oxidation reaction can be written as AH =« -115 kcal/mole ZnS [1] Such a reaction has been found to proceed in a topo-chemical manner; i.e., as the reaction proceeds, a progressively thicker outer shell of zinc oxide is formed, while the inner core of unreacted sulfide decreases. It has been found experimentally, both in the present work and in the previous investigations,4-6 that the particle retains its original dimensions. Therefore, at any given time, the particle may be

Jan 1, 1970

By John B. Knaebel

The annual Jackling Award Lecture, sponsored by the Society of Mining Engineers of AIME, is intended to honor and commemorate one of the greatest mine-makers of all time, an innovator whose vision and determination made ore out of waste rock. He ushered in a new philosophy of mining which revolutionized some segments of the industry and notably affected our economy generally. To have been asked to given the Jackling Lecture this year is an honor that I scarcely deserve, but which I have accepted in humble gratitude. Although it is true that "many a mine has made the man," it is also true that while ore bodies are found, mines are made. That statement has been hammered into my skull many times by a man whose own career exemplifies its truth, a man who has been first and last a steadfast friend, who for a while was my boss and mentor, and who as one of this country's great mining geologists has laid his hand to the making of many a mine. I will doubly cherish the memory of the honor bestowed upon me because the presentation of the Jackling Award was made by this man. After the Lord made Dick Hunt he threw away the mold. Metals and other mineral products are essential ingredients of the social economy of the modern world. No well informed and thoughtful person can doubt that they will be indispensable to mankind as long as the fabric of civilization as we know it today can be held together. They are mined from ore bodies, which, unlike some other kinds of bodies, are physically inorganic and wholly incapable of reproducing themselves. Since in time they become mined out, an endless procession of new producers must be made by someone if the fundamental needs, to say nothing of the not so fundamental whims of an affluent society, are to be gratified. In saying that these mines must be made, I mean exactly that. It is my purpose to comment upon some of the problems we must cope with in making them. I shall try to avoid dwelling needlessly upon aspects of new mine development with which most people in this business are thoroughly familiar, and will attempt to discuss in a useful way some of the newer and more significant features of the economic climate in which these endeavors must be conducted. To begin with, an Almighty force put the ore into the ground, and selected the places in which to put it. Mankind was not consulted. Beyond that stage, however, mankind must find the ore deposits and contrive to extract their contents and put them into useful service. In doing this, he must use tools and techniques devised by man to overcome obstacles created in part by nature, but also in part by man himself. And most importantly of all, in making the tools and applying the techniques, he must use people. In the whole process the most pliable ingredient at hand-and also the most unpredictable-is people. Mines play out, and men die. As time goes on, we will have new mines, and they must be made by new men. The Environmental Dilemma It is perhaps timely to touch first upon the newest and in many ways the most potent consideration affecting the feasibility of developing new mines-the problems related to protection of the environment and to the

Jan 1, 1973

By H. Warlimont

Precipitation of cementite plates from carbon-rich austenite gives rise to localized formation of martensite in the matrix next to the precipitate upon quenching. The growth of this martensite is urmsually restricted. A distinct lattice relationship is found between this martensite and the cementite phase. It is concluded that the martensite is nacleated in the region of lowest carbon concentration at the austenite-cementite integace, with low-energy matching to the cementite lattice. The restriction of the growth of the martensite phase to the vicinity of the cementite plates can be explained by misfit in the austenite -martensite glissile interface and the uphill carbon gradient in the austenite. The investigation was carried out by light- and electron-microscopy and by electron-diffraction of thin foils. THE precipitation of cementite from carbon-rich austenite gives rise to a localized formation of martensite in the matrix next to the precipitate upon quenching. This behavior has been described previously by A. B. Greninger and A. R. Troiano1 for a 1.78 pct C steel ("pseudomorphic martensite"), and by A. Hultgren2 for a Fe-0.99 pct C—5.20 pct Mn steel. By measuring the axial ratio of the martensite phase,' it was found that the carbon content of this martensite was lower than that of the martensite which formed without prior partial transformation to cementite. Therefore, it was concluded that lowering of the carbon concentration in the matrix next to the precipitate raised the M, temperature locally and thus led to nucleation of martensite at the ce-mentite-austenite interface. However, the restriction of the growth of the martensite phase to the vicinity of the cementite plates cannot be explained by localized carbon impoverishment alone. Under ordinary conditions a martensite plate which has been nucleated in a favorable site can continue to grow until it encounters a physical barrier, or until it encounters a compositional barrier in the matrix, where the total free-energy change for the reaction is not negative, since it has been shown by numerous experiments that the activation energy for growth of ordinary martensite is virtually zero.' An investigation was conducted by transmission electron microscopy and electron diffraction to study this extraordinary martensite. It was expected that crystallographic in addition to compo- sitional conditions caused this abnormal mode of martensite formation. MATERIAL AND PROCEDURE An Fe-C-Mn alloy containing 1.15 pct C and 5.1 pct Mn was used for most of the experiments. For metallographic work, specimens 15 by 15 by 3 mm were used. For preparation of thin films, the initial specimen size was 15 by 15 by 0.7 mm. The heat treatment of each specimen consisted of austenitizing for 1/2hr at 1100'~ in an argon atmosphere, subsequent isothermal holding in a lead bath at one of a series of different temperatures, and, finally, quenching into brine at room temperature. For metallographic examination, the specimens were mounted in bakelite (slight tempering effects resulted from the heat in the mounting press) ground, polished, and etched in nital. Thin films for transmission electron microscopy and electron diffraction were obtained by grinding the specimens to approximately 0.2 mm thickness and subsequent electrolytical thinning. The orientation relationships were evaluated from sets of electron micrographs and selected-area electron diffraction patterns of single units of the transformation products and the adjacent matrix. RESULTS In the alloy which was used for the experiments, proeutectoid carbide precipitates over a wide tem-

Jan 1, 1962

By J. K. Kerver, J. S. Osoba, J. G. Richardson, P. M. Blair, J. A. Hafford

This paper presents the results of laboratory measurements of relative permeabilities to oil and gas on small core samples of reservoir rock by five methods, and describes the influences of such factors as boundary effect, hysteresis, and rate upon these measurements. The five methods used were the "Penn State," the "single core dynamic," the "gas drive," the "stationary liquid," and the "Hassler" techniques. In those methods in which the results are subject to error hecause of the boundary effect, the error may be minimized hy the use of high rates of flow. In order to avoid complexities introduced by hysteresis, it is necessary to approach each saturation unidirectionally. Observed deviations of relative permeabilities with rate can be explained as a manifestation of the boundary effect, and disappear as the boundary effect vanishes. The results indicate that all five methods yield essentially the same relative permeabilities to gas. Of the four methods applicable to the determination of relative permeability to oil, three, the Penn State, single core dynamic, and gas drive, gave relative permeabilities to oil which were in close agreement. The Hassler method gave relative permeabilities to oil which were consistently lower than the results obtained by the other methods. INTRODUCTION The relationship between the effective permeability of a reservoir rock to each of the fluids flowing through it and the corresponding fluid saturation is an important characteristic of the reservoir rock. Knowledge of this characteristic is and gas reservoirs and of the ultimate recovery to be expected extremely important in the prediction of the behavior of oil under various operating conditions. These effective permeabilities are usually expressed as the "relative permeability" to a fluid phase, defined as the ratio of the effective permeability to the permeability of the rock to a single phase at 100 per cent saturation. Relative permeability-saturation relations are not the same for all kinds of reservoir rock, but may vary from formation to formation, and within the different portions of a heterogeneous formation. In studying the performance of a specific reservoir, it is necessary, then, that the relative permeability characteristics of the individual portions of the reservoir be measured. These measurements may be made in the laboratory on small core samples from the reservoir. Various techniques have been proposed for the measurement in the laboratory of relative permeability-saturation relations. In varying degree, difficulties attend the use of all of the methods which have been proposed. It is the purpose of this paper to discuss the factors which influence the measurement of relative permeability, the difficulties encountered in several methods, and to present comparative results obtained by the use of various techniques. FACTORS WHICH INFLUENCE THE MEASUREMENT OF RELATIVE PERMEABILITY It is necessary that the relative permeability data measured in the laboratory yield the same relative permeability-saturation relationships that would govern the flow of fluids through the sample if it were to occupy its original position in the reservoir. Since the core sample upon which the laboratory measurements are made is not surrounded by similar core material as it was in the reservoir, an error in measuring the relative permeabilities may arise from the "boundary effect" which results from a discontinuity in capillary properties of the system at the effluent end of the core. Again, the rates of

Jan 1, 1951

By Paul J. Bennett, James E. Castle

The sillimanite family of minerals, including kyanite, sillimanite, and andalusite, are anhydrous aluminum silicates with the formula A12O3-SiO2. Dumortierite and topaz are also included in this group because they are closely allied in composition and thermal behavior. However, neither are mined commercially today. They are typical metamorphic minerals which are found in metamorphic rocks on every continent. Sillimanite minerals are prized chiefly for their refractoriness and are important components in a broad range of acid refractory products, especially in mortars and castables. World production of sillimanite minerals is currently about 400,000 tpy and has been increasing at the rate of 3 to 8% a year for many years (Anon., 1972). While these minerals have widespread occurrence, the consumption of sillimanite minerals is concentrated in the relatively few highly industrialized areas where refractories are manufactured, and which in turn are typically close to the major iron and steel producing regions of the world. Thus northern Europe,. England, the United States, and Japan are the principal consumers of refractories and sillimanite minerals. Of these countries only the US is a significant producer. Uses of Kyanite The following specifications are typical for the domestic kyanite industry: Raw Kyanite Concentrates Chemical Analysis 56% AI2O3 min 0.1% CaO max 42% SiO2 0.1% MgO max 1% Acid soluble 0.3% combined Fe2O3 alkali max 1.2% TiO2 max Available Sizes 35, 48, 100, 200, and 325 mesh The largest use for domestic kyanite, both raw and calcined, is in the manufacture of refractory mortars, cements, castables, and plastic ramming mixes. In these applications kyanite constitutes from 10 to 40% of the mixture, the balance being refractory clays and coarser grog materials. A certain proportion of raw kyanite is used to offset the shrinking of the clay binder, whereas the calcined kyanite is used in the coarser sizes for body. Certain high grade refractory shapes and kiln furniture are composed chiefly of graded sizes of calcined kyanite bonded with a little ball clay. In most applications, however, kyanite is used only to fortify the mix or as a minor ingredient. Some manufacturers of mullite brick use domestic calcined kyanite for the fine-grained portion of the brick, but seldom in quantities exceeding 10% by weight. Kyanite is used by ceramic manufacturers of wall tile and sanitary ware to offset shrinkage and cracking after firing. Indian kyanite has traditionally been used to make the coarse grog sizes needed for the manufacture of mullite brick, and for the grog portions of mortar, cement, and castable mixes. It has been largely replaced, however, by synthetic mullite, high fired flint, and diaspore clay or calcined bauxite for other applications. Indian kyanite has been available in lump as well as in granules and concentrates, as are sillimanite materials from India and South Africa. Andalusite is available as 8 mesh granules and as fines with chemical analyses not unlike those of domestic kyanites. From time to time and from place to place minor amounts of other aluminum silicate minerals such as dumortierite, topaz, and pyrophyllite have been made available at various prices and specifications, but have not been significant factors in the refractory industry. A mixture of kyanite and sillimanite of relatively fine grain-size and of low iron content was at one time offered to the molding sand industry by the Du Pont Co. as a byproduct from their deposits of heavy

Jan 1, 1983

By System By John E. Owen, Walton J. Greer

The guard electrode system measures the resistivity of formations by employing a thin disk of current which is caused to flow perpendicular to the bore hole. The control of this current disk is obtained in a brute force manner through the use of relatively long equipotential electrodes above and below the measuring electrode. The log obtained from the system is free of "lag," "plateau," "shadow," "reflection" and other distortions evident on conventional logs. The proportionate contributions of the hole size and invaded zone resistivity to the apparent resistivity reading are reduced when the mud and filtrate resistivities are lower. Thus, the guard system favors the use of conductive muds. The mathematical development of the theory is given in an appendix. Equations are derived to evaluate the effects of mud resistivity, hole size, invaded zone resistivity and depth, and the true formation resistivity. Sample logs from several provinces are reproduced and compared with conventional electric logs to illsutrate the much greater detailed lithology that can be presented by the guard electrode system. INTRODUCTION With increased ability of those in the petroleum industry to analyze formation characteristics from electrical resistivity data, there has become apparent the need for more precise measures of that parameter. The measurement of the resistivity of a homogeneous and isotropic material can be made simply when the body of the material is infinite in all dimensions and the measuring electrodes can be placed within the body. In such a case, the current leaving an electrode follows a spherical distribution and the mathematical expression for the potential level at any distance from that electrode can readily be derived.'.' If it is considered that the active electrodes are within a bore hole filled with mud of a resistivity different from that of the formation. the current does not flow in a spherical pattern near the current source or sink, and the calculations of potential levels become more difficult. The additional consideration of a section of formation invaded by mud filtrates, and thus having resistivity different from either that of the mud, the adjacent formations or of the undisturbed formation, makes the mathematical problem extremely complex. Should the vertical dimensions of the formations be considered as finite. the problem becomes so complex as to preclude reasonable solution. Yet, even these considerations have not described adequately the conditions encountered in a large proportion of the wells to be studied. In efforts to evaluate the effects of the various conditions. combinations of twn, three. and four electrode logging con- figurations of the conventional types have been used. The resulting logs have left much to be desired in some provinces. It has become apparent that the use of such configurations will not result in adequate measurements being made, particularly in cases where the formation is composed of thin sections. If all the current of a resistivity measuring circuit is made to flow through the formation opposite the exploring electrode, many of the shortcomings of the conventional measuring system are eliminated. In the guard electrode method of electrical well logging to be discussed in this paper, the current is so controlled by causing it to flow in a thin disk normal to the axis of the logging tool. EARLY HISTORY The guard electrode method of electrical well logging in its early years was a joint development by the Geophysical Research Corp. and the Amerada Petroleum Corp. The method was first experimentally investigated by means of model studies. The results of these studies indicated that current focusing systems properly applied to electrical well logging

Jan 1, 1951

By R. W. Jenkins, O. J. Neslage

MINE operators today are paying increased attention to the mechanization of drilling operations as an important factor in increasing efficiency and decreasing costs. Recent progress in the design of drill jibs for mounting on drill carriages, or jumbos, has done much to advance the mechanization of mining methods. This progress has introduced new opportunities in the application of "jib jumbos" that are worth serious consideration. An attempt will be made here to classify the various types of jumbos and drill mountings available for level development and flat stope work, t6 indicate applications, and to measure their effectiveness in relation to their cost. The data here are based on a wide variety of field usage, and are offered only to point up, in a general way, the relative efficiency in proportion to cost. It should be remembered that any contemplated jumbo installation must be studied to determine what type of installation is most suitable, considering ground conditions, loading, timbering and haulage equipment, service available, and attitude of manpower. Early Drill Carriages: The advantages of some sort of a drill carriage were recognized at the time rock drills were introduced. In drift or heading operations where a fairly standard drill round and cross section were anticipated, as well as in flat bedded deposits where standard slabbing rounds were used, track and crawler-mounted drills found an early application. These first drill jumbos were little more than drill carriers, designed locally and manufactured with materials at hand. Of comparatively simple construction, function, and low capital cost, they usually consisted of a hinged column which supported one or more drills on arms or universal bars. When the column was pivoted vertically, the drills were moved into position. Screw jack extensions reached from the column to the roof and floor to hold the drill rigid. In some cases, particularly in tunnel jumbos, enough weight was carried that rail clamps or roof jacks were sufficient. Many of these column and arm-type jumbos, usually equipped with air and water manifolds, steel racks, and staging for drillers, are still in use today. Some have employed air or hydraulic extensions for securing the columns. They offer the equip-saving advantage of having all the necessary out, ment together, and they un be moved i and t. set up and torn down as a unit. Boom-type Jumbos: When the advantages of to column-type jumbo were seen, operators could to realize the further gains possible. More time could be saved with mechanical assistance to position api drill vertically. A rack on the column and a pinion on the arm for raising and lowering the drill in the manner of a quarry bar were tried with some success. The most outstanding solution to the vertical handling problem was reached with the boom-type of jumbo. Here two or more machines were mounted on a cross arm at the end of a boom that was pivoted at the rear of the track. This was raised and lowered by various mechanical aids. Occasionally air or hydraulic power was used. Nearly all of today's wagon drills use this boom-type principle. Boom jumbos represent a savings in time and physical effort expended in raising and lowering the drills. The boom must be balanced by the roof of the truck which is secured by rail clamps or type jacks. The most successful application of areawhere this of jumbo has been in the Tri-State area where multiple long-feed machines are used on caterpillar-mounted, boom-type jumbos for slabbing

Jan 1, 1951

By T. Rosenqvist

From the chemical, metallurgical, and mineralogical points of view, the importance of thermodynamic data for metal-sulphides and sulphur dissolved in molten metal has long been realized. Such data will give a basis for thermo-dynamic calculations of processes such as roasting and the distribution of sulphur between molten metal and slags. Furthermore, it will help us understand the chemical forces which tie sulphur to the metal and to the melt. Thermodynamic studies of solid sulphides and the equilibria between solid sulphides and metals have been carried out in a rather large number of cases by several investigators. An excellent review of this work is given by Kelley.1 On the other hand, very little is known about the thermodynamic properties of molten sulphides and of sulphur dissolved in molten metal. The only system which previously has been investigated in this respect is the iron/sulphur system. The purpose of the present investigation was primarily to obtain further data for metalisulphur melts and the system silver/sulphur was chosen, not because this system was expected to be of special interest in itself, but because the silver/sulphur system is a typical example of a metal/sulphur system. Because of the low melting temperatures, the work could be carried out without appreciable furnace and refractory difficulties. The sulphur in this system possesses a rather high escaping tendency compared to most other metal/sulphur systems. By the method employed (reaction with hydrogen to form hydrogen sulphide) this gives ratios Ph2s/Ph2 up to 0.30, which may be determined accurately. 'rhermodynamic investigations of the heterogeneous reaction Ag2S +H2 —+ 2Ag + H2S have previously been carried out by Pelabon,2 Keyes and Felsing,3 Jellineb and Zakowski,4 Wat-anabe,6 and Britzke and Kapustinsky.6 Their results are in rather poor agreement. Experimental Part PRINCIPLE In the present invehgation the escaping tendency of sulphur from the condensed phase was determined by the reaction: S + H2 = H2S The ratio Ph2s/Ph2 is at constant temperature, directly proportional to the escaping tendency of sulphur and to its chemical activity in the condensed phase. (This ratio will subsequently be denoted by H2S/H2.) From this ratio and its variation with temperature and with change in the com- position of the condensed phase, thermodyrlamic quantities such as free energy and heat of reaction can be derived. The apparatus used is shown in Fig 1. The silver/sulphur alloy was placed in a crucible inside a refractory tube and mounted inside the furnace to the left. The tube was a part of a closed, gas-tight system in which the gas mixture could circulate until equilibrium was established. Circulation was maintained by the glass propeller to the right, driven by an external magnet, and promoted by the chimney action of the furnace. The gas passed up through the furnace, down into the crucible where it came in contact with the alloy, passed rapidly up through a narrow tube and out of the hot zone. After equilibrium was established between the gas and the condensed phase, the composition of the gas mixture was determined from its density. In its circulation, the gas mixture passed through a chamber (lower right on Fig 1) containing a buoyancy-balance, where the density of the gas was determined by magnetic balancing. From the measured density,

Jan 1, 1950

By E. I. Organick, B. H. Golding

A simple correlation is presented for the prediction of saturation pressures in condensate-gas and volatile-oil mixtures. Saturation pressure is related directly to the composition of the mixture with the aid of two generalized composition characteristics, B, the molal average boiling point, and W, the modified weight average equivalent molecular weight. The need for hydrocarbon equilibrium constants is entirely eliminated. Only the values of the two conlposition parameters need be obtained, and these are calculated in a simple and reproducible manner from the stream analysis of the mixture and the ASTM distillation for the heavy ends. The correlation is given .in the form of a set of 14 working charts in which saturation pressures, either retrograde dew points or bubble points, are plotted cs temperature, forming partial phase envelopes for mixtures having discrete values of the composition parameters, B and Wul. A locus of critical states on each chart intersects the partial phase envelopes, distinguishing retrograde dew point pressures from bubble pressures. A comparison Between experimental and predicted saturation pressures reveals that: the probable error of the predicted values, when considering the data as a whole (214 experimental points), is five per cent; for high gasjoil ratio condensate fluids (approximately 40.000 or more cu ft/bbl) the probable error is about 8 per cent. In either case, however, the probable error is comparable with the overall uncertainty of the data from which the correlation is derived. INTRODUCTION There is a present need for a simplified, yet reasonably accurate method for predicting upper phase boundaries of reservoir fluids. In the case of high gas/oil ratio fluids, namely the so-called highly volatile oils and the condensate gases, no simple method, accurate within 5 to 10 per cent, is now available by which bubble point and retrograde dew point pressures may be predicted. In order to calculate the upper phase boundary of a volatile reservoir fluid, using correlations now available, it is necessary to find and employ the proper K-values (equilibrium volatility ratios of the hydrocarbons in that fluid). This process of finding the Proper K-values usually involves a double trial and error computation. Since the K-values are in themselves dependent upon the composition of the fluid, their use in the calculation of a saturation pressure actually represents an unnecessary complication. The correlation described in this paper relates saturation pressure directly to the stream composition, entirely eliminating the need for K-values. The only data required to calculate the Stream composition are obtained from the customary low temperature fractional analyses of separator gas and liquidt and from the ASTM distillation of the c,+ fraction of the separator liquid. A considerable simplification in the procedure for predicting saturation pressures is thereby effected without significant loss in accuracy. BASIS FOR A CORRELATION Empirical relationships between the saturation pressure and the composition of the fluid in question have already been partially explored by one of the authors.V n particular, a relationship between the critical pressure for a hydrocarbon mixture and its composition was developed. The critical pressure is in reality a saturation pressure, as it repregents a limiting case either of a dew point or of a buhhle point pressure for any given mixture. It was found that the critical pressure may be correlated as a function of two generalized composition characteristics or variables. One characteristic expressed a molal average prop-erty, the other a weight average property of the mixture. Specifically, the molal average boiling point (MABP, or B as it

Jan 1, 1952

By G. J. Wilson

Difficulties experienced in correlating vertical and lateral locations of subsurface features that are encountered in directional wells prompted critical review of the tangential method of computing directional surveys. Inherent discrepancies were indicated to cause small incremental but significantly large cumulative errors in computed vertical depth and horizontal departure. A radius of curvature method, developed for planning and analyzing directional wells, was studied as a means of more accurately calculating survey data. Errors incurred in the tangential method were not present in the radius of curvature method. Conflicting assumptions in calculating dog-leg severity by the tangential method were resolved by a new procedure that was derived from the radius of curvature method. Results of the investigation showed the radius of curvature method to be an improved method for computing directional surveys. Introduction Many improvements in directional drilling tools and techniques have been made in the past 10 years,' but the method of computing survey data has remained virtually unchanged. While use of computers greatly aids the process of calculation' and eliminates many human errors, manual and computer calculations are still made with the assumption that the wellbore consists of straight-line segments. This paper points out discrepancies in the method and presents an improved method in which the wellbore is assumed to be curved. Tangential Method The method presently used to calculate vertical depth, horizontal departure and direction coordinates with measured values of well depth, inclination angle and direction angle is termed the tangential method. This term stems from performing calculations with a series of straight-line segments, with each segment assumed to be tangent to the wellbore at a corresponding survey point. A segment is defined by inclination and direction angles measured at only the lower or deeper end. Consequently, a discrepancy or error is introduced for each segment. Errors are not of extreme magnitude, but cumulatively are significant due to the need to define as accurately as possible the vertical and lateral location of subsurface features such as pay tops, fluid contacts and fault cuts encountered in expensive directional well bores. In Fig. 1, the curved-line segment ab represents a portion of the actual borehole as viewed in the vertical plane. Points a and b are survey stations and +, is the inclination angle at point b. The curved-line segment ab is assumed to be the straight-line segment arb of a length equal to ab and tangent at point b to the curved-line segment. Lengths a'c' and c'b are equal to a'b cos +, and a'b sin +,, respectively. Point a already has been fixed by calcillations performed with survey data obtained at point a, and calculated lengths m'c' and c'b are projected as lengths from point a, rather than from point a'. Point b1 is thus fixed and assumed to represent the actual point b. Calculated length ac" is shorter than actual length ac, and calculated length c"bl is longer than actual length cb. Since b1 is the point from which the next deeper segment will be projected, errors are cumulative. Cumulative error continues to increase as long as the inclination angle continues to increase. When the inclination angle decreases (Fig. 2), calculated length ac" is longer than actual length ac, and calculated length c"bl is shorter than actual length cb. These errors also are cumulative, but differences between calculated and actual lengths are opposite in mathematical sign to differences demonstrated in

Jan 1, 1969

By William R. Barton

Iron and steel slag represent man's most successful attempt to date to profitably utilize a solid waste. Its consumption represents a solution to a solid waste problem and also represents tonnage of natural aggregates that will not have to be mined with concomitant disturbance of the land. Slag has been produced as long as iron has been made; but until a little more than 50 years ago, it was mostly a waste product to be disposed of with as little effort and cost as possible. Huge piles of waste slag were generated over the years of iron and steelmaking. Sporadic use was found for small amounts starting with slag (from Catalan forges) used for road bases by the Roman Empire. The first recorded sustained commercial use was, as is often the case in man's history, for making war. Some profit- conscious munitions maker in the 16th century realized that he could make cannon balls of slag instead of the more precious iron. Other small-volume uses gradually developed: cast building blocks, slag-lime mortars and cements, slag wool, ballast, road base, and, finally, in concrete. But it was not until after World War II that the true potential of blast-furnace slag as a construction aggregate was really recognized. Now nearly all blast-furnace slag produced is used, and much of the earlier stock- piles in the U. S. have been reduced or entirely consumed. Steel slag for aggregate use has been in commerce for only the past 10 years, and use has increased rapidly (10-50% per year) during the past 5 years as blast-furnace slag supplies became depleted. However, much remains to be accomplished in determining character and optimum conditions of use for various types of steel slags before such slags will realize their full use potential. Although slag represents only 2% of construction aggregate materials used in the U.S., its production involves certain features that make its production record far more important than national tonnage figures would indicate. Its source is in iron and steel production and concomitantly slag availability is restricted to those areas where iron or steel is produced. In such areas, it often represents one of the principal aggregates marketed and, because of special properties that make slag a selected aggregate for certain uses, the tonnage imbalance may be overcome by the importance of its contribution to quality or special characteristics of end products. The location and number (Fig. 1) of slag plants handling this annual production is governed by the geographic makeup of the iron producing industry. Prior to the period marked by World War 11, most blast furnaces were in the Great Lakes area-Pittsburgh, Cleveland, Chicago, Gary, Buffalo, Detroit, Youngstown, and Toledo, with exceptions at Baltimore, Bethlehem, and Birmingham. Since that time, iron and steel facilities have been established in Texas, Utah, and California. Today 85 slag plants in 15 states provide employment for almost 2000 persons. The slag plants also recover almost 4 million tons of slag-encrusted iron each year for return to the blast furnaces. Much of the success in developing uses for slag can be attributed to the efforts of the National Slag Association founded in 1918. Since then, it has conducted numerous field and laboratory investigations to demonstrate the properties and uses for slag and slag products. These investigations have resulted in total recognition of blast-furnace slag as a construction material of consequence. The American Society for Testing & Materials Designation C125 recognizes blast-furnace slag as "the nonmetallic product consisting essentially of silicates and aluminosilicates of

Jan 1, 1975

By A. E. Powers

YEARS of experience and research have shown that molybdenum, tungsten, and vanadium are among the most useful and effective elements in augmenting the high-temperature strength of heat-treatable, ferritic steels. Grün, for example, in conducting an early survey of the strengthening effects of various elements in annealed, low-carbon steel at 750° and 930°F (400° and 500°C), found molybdenum and vanadium to be the most effective.' Holtmann comprehensively studied the strengthening effects of molybdenum and vanadium in quenched and tempered steels at 930°F as a function of microstructure and carbon content.' He found creep strength to be related to the saturation of the austenite at the austenitizing temperature, such that strength is increased by alloying until the y loop is reached—the terminus of complete austenitization. Beyond this degree of alloying, the inability to heat treat will result in lower strength, at least for low and moderate creep temperatures. Tungsten, owing to higher cost than molybdenum, has been little used in ferritic high-temperature steels. As a result, very few investigations have been made of its high-temperature strengthening ability, and reliable data on its effectiveness are not available. Grün rated tungsten far less effective than molybdenum at 930°F (500°C) on a weight-percentage basis.' However, Tammann has found that tungsten is as effective as molybdenum in raising the recrystallization temperature of iron. For this reason Smith, in a review of the subject, has advocated a re-examination of the influence of tungsten on the high-temperature strength of steel.' In any study of the effects of alloying additions on high-temperature properties, recognition must be made of the many variables involved, some of which can be controlled but have been ignored in innumerable investigations of the past, and some of which are difficult or even impossible to control. One cannot, for example, assign a definite strengthening index to any one alloying element, for this will be dependent upon the microstructure (heat treatment and mechanical treatment), testing con- ditions (temperature, time, and stress), and the complete composition of the steel (accompanying alloying elements, impurities, etc.). One ever-appear ing variable, hardness or tensile strength at room temperature, may be eliminated by heat treating all of the alloys to a single hardness level. An attempt may be made to control the variable of primary quenched structure by oil or water quenching the test specimen. The control of such variables may not be possible in cases of widely varying compositions, but at least such deviations should be recognized. Material and Procedure The alloys, made as 30-lb ingots in an induction furnace, all had the same base composition of about 0.18 pct C, 0.85 pct Mn, and 0.48 pct Si. They were grouped as follows: Mo Group—Containing up to 5.2 pct Mo. W Group-Containing up to 6.0 pct W. V Group—Containing up to 3.3 pct V. Mo-V Group—Containing up to 2.7 pct Mo and up to 1.4 pct V. Mo-W Group—Containing up to 2.5 pct Mo and up to 2.5 pct W. The steels, listed in Table I, were forged to ¾ in. sq bars and the material for the high-temperature, rupture-test specimens was further swaged to %-in. round bars.

Jan 1, 1957

By N. J. Grant, B. C. Giessen, R. Koch

The system Nh-Ir was investigated over the complete concentration range by metallography and X-my techniques, using forty one alloys. The solubility limits of terminal and intermediate phases and the solidus temperatures were determined. Five intermediate phases were found: a Nb3Ir, cubic, Cr3O type; tetragonal, ofecr thorhomhic, isostruc-turn1 with (ta-Rh); and a Nhlr3. cubic, AuCu, type. a Nb3lr and a Nbfr3 melt congruently; three eutectic and three pentectic reactions occur. The phase diagram of the Nb-Ir system had not been fully treated in the literature; only surveys of intermediate phases were found.1"5 In this study, the details of the phase boundaries were investigated as well as the crystallography of the intermediate phases. EXPERIMENTAL METHODS The experimental procedures such as arc melting of powder compacts, heat treatments, solidus measurements, X-ray, and metallographic observation were identical with those used in the work on the Nb-Rh phase diagram.&apos; They will therefore not be repeated here except where the conditions differed. The purity of the niobium powder was as stated in Ref. 6; the iridium powder of 99.9+ pct purity from J. Bishop and Co., Malvern, Penn., did not contain impurities exceeding 100 ppm, except rhodium (200 ppm). The melting points and vapor pressures of both elements are very similar. This fact contributed to a very small weight loss on melting and facilitated preparation of homogeneous alloys. As shown in Ref. 6 for Nb-Rh, no oxygen pick-up exceeding 200 ppm had to be considered; this was regarded as valid also for Nb-Ir. A total of forty one alloys were used in the determination of the phase diagram; their concentrations are shown in Fig. l, which presents the phase diagram. The concentration limits as determined by the weight-loss method averaged <0.2 at. pct, and never exceeded 0.5 at. pct. Heat treatments were carried out as described in Ref. 6. Depending on the concentration, only tantalum, tungsten, or iridium containers were employed, avoiding oxide crucibles altogether. Alloys from 0 to 25 and from 65 to 100 at. pct Ir were homogenized at 2095°C for 15 hr, intermediate compositions from 25 to 65 at. pct Ir for 65 hr at 1780°C. A typical annealing-time schedule is presented in Table I. Solidus points were measured as described in Ref. 6 with the modification that samples rich in niobium were held between pieces of tantalum foil and samples of high iridium concentrations were held between rhenium platelets or in iridium wire. After each run it was ascertained metallographically that no reaction with the holder had occurred. Rhenium was selected as holder material after it had been shown in separate tests that the melting points of Re-Ir alloys rise continuously from 2440°C. Metallographic examination was carried out as described in Ref. 6, and the same procedure and etchants were used successfully. While metallographic discrimination between a Nb3lr and o was easily possible, X-ray diffraction was necessary to separate al and ct2. X-ray powder patterns were taken and evaluated as for Nb-Rh6 yielding the error limits indicated in Table 111, to be introduced later. For the determination of the invariant reactions and phase boundaries, the same techniques as for Nb-Rh6 applied. The general accuracy of invariant concentrations is regarded as somewhat higher than for Nb-Rh due to the small slope of most solvus lines.

Jan 1, 1964