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By R. S. Bradley, B. K. Miller

The principal producing areas of fire clay in Missouri are: (I) the east central district, which includes Audrain, Callaway, Montgomery, Warren, and Boone Counties (Fig. I); (2) the St. Louis district, which includes St. Louis and St. Louis County; (3) the north central Ozark district, which includes Franklin, Gasconade, Osage, Maries, Phelps, and Crawford Counties. Most of the semiplastic‡ fire clay is found in Audrain, Callaway, Montgomery and St. Louis Counties, and in St. Louis. Flint fire clay is found in Callaway, Audrain, and Montgomery Counties and in most of the north centra! Ozark district. High-alumina diaspore clay is found only in the north central Ozark district, except a few deposits found in Montgomery County. This paper is concerned with the semi-plastic fire clay that occurs in the east central Missouri district near Mexico, Audrain County, Missouri, which is mined by the open-pit method as practiced by the A. P. Green Fire Brick Co. About one-fourth of the semiplastic fire clay in that district is mined in shaft mines, and three-fourths in open pits.

Jan 1, 1942

By H. E. Dunn, C. M. Cosman, J. H. Brennan

Up to the beginning of World War I, the American ferro-alloy industry was in its infancy and largely dependent on Europe. During that War, capacity was over expanded. Later recovery and commercial and scientific development have resulted in an industry which in 1957 produced 1.8 million tons of ferro-alloys. THE ferro-alloy industry is today an important element of the industrial structure of the United States. Its output is valued at almost half a billion dollars annually and its products are basic not only to National defense but also to the peacetime standard of living. This has not always been so. The ferro-alloy industry from late in the last century has grown from small beginnings, nurtured by the demand for stronger, tougher materials; by the search for steels capable of absorbing severe impact loads and resisting corrosive media and high temperatures; and also by the need for electrical and electronic specialties. Conversely, the ferro-alloy industry has grown because it developed improved steels and alloys by extensive research, and because it was able to show to steel makers the advantages accruing from the more extensive and the more economical use of alloying elements. The industry has grown in scope from producing a few grades of ferro-alloys of the more common metals-manganese, chromium, vanadium, silicon, titanium, tungsten, and molybdenum-until there are today some 150 compositions of ferro-alloys available to the steel maker, including such elements as columbium, zirconium, and boron. In 1912 the industry produced 360,000 tons of alloys valued at about $12,000,000, while 1957 production figures show an output of 1.8 million tons worth $440,000,000. In the United States, the history of an industry is largely the history of the companies making up this industry; hence, this paper will briefly trace the development of the most important ferro-alloy-producing companies. Quite varied have been the reasons that caused the different companies to move into the ferro-alloy field; the Willson Aluminum Co., seeking methods of producing aluminum, succeeded with the production of calcium carbide, and their developing electric furnace skills led them to the production of ferro-silicon and ferrochromium alloys. Willson was the predecessor of the Electro Metallurgical Co. of Union Carbide. Two Pittsburgh undertakers, interested in vanadium as an alloying agent for steel, set about to find a mine and, ranging as far as Peru, fathered American Vanadium Co., the predecessor of Vanadium Corp. of America Experiments of the

Jan 1, 1961

By A. Goldberg, T. E. Tietz, J. E. Dorn

Introduction The concept that the flow stress for plastic deformation of metals in the work hardening range is a function of the instantaneous values of the strain, strain rate and test temperature was promulgated by Ludwick' many years ago. This thought has been more or less a guiding principle throughout the immediate period of development and growth of mechanical metallurgy. It has been tacitly assumed or knowingly applied to many investigations on the plastic behavior of metals. Spurred by the theoretical interest and practical importance of the plastic behavior of metals, many investigators have attempted to determine empirical, semi-empirical, and theoretical equations2-l8 relating the flow stress with the strain, strain rate, and temperature. Although the applications of such equations have been extensive, the experimental verification of the existence of a mechanical equation of state is weak. Furthermore, some of the available evidence on plastic flow appears to suggest that no simple functional relation between stress, strain-rate, strain and temperature can exist. The mechanical equation of state demands that Where a = true stress = loadlinstantaneous area e = true strain _ Instantaneous gauge length ~ initial gauge length i = true strain rate T = temperature This formulation implies that da is an exact differential. Therefore the flow stress (a) is a function of the instantaneous values of the strain (c) the strain rate (i) and the temperature (T), independent of the previous mechanical or thermal history. Having reached a certain strain, strain rate, and temperature, by any path whatsoever, a definite and fixed value of the flow stress should be obtained. One check on the validity of the mechanical equation of state is easily obtained. Consider the following three tests on the stress-strain curve at constant temperature: A. Strain at rate :I B. Strain at rate it C. Strain at rate 11 to el and continue test at &. A graphical representation of possible results of such tests are shown in Fig I. If, for strains greater than el, test (C) data coincide exactly with the data from test (B), as shown in Fig ra, a limited verification of the mechanical equation of state is obtained for the range of strain rates from il to iz. But if the data from test (C) differ from those of (g) beyond strain t\ where the strain rate is changed from il to k2, the mechanical equation of state is not

Jan 1, 1949

By Gerhard Derge

THE chemical and physical properties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use, These processes are carried out at high temperatures and involve such complex chemical systems that fundamental scientific knowledge of the properties and behavior of these slags is inadequate. Various hypotheses have been proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenck1 and the recent papers of Chipman and co-authors.2-5 Another proposal is that these compounds dissociate by completes or partial ionization, the evidence for which has been reviewed by Martin and Derge.7 Whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: I, Studies of solidified slag samples by X-ray diffraction, petrography, and similar methods that can be used at room temperature, The correlation of this information with the high-temperature properties of the molten slag is uncertain, 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature, However, even these data present problems of interpretation because they require a complete knowledge of the metal phase, 3, Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret, Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information, The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems CaO-SiO2 and CaO-A1203-Si02 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1946

By Grover J. Holt

In order to provide a clear picture of the development of the sink-and-float process of concentration as applied to the iron ores of Minnesota, a few pertinent facts should be brought out concerning the ores and the products of concentration. Iron ore is primarily a cheap commodity handled in immense quantities. The price of iron ore at present, based on a natural iron content of 51.5 per cent, varies from $2.55 to $2.70 per gross ton f.0.b. cars at the mine or washing plant in Minnesota. Last year 92,000,000 gross tons were shipped from the Lake Superior district (Minnesota, Michigan, and Wisconsin) to the furnaces. Concentrated iron ores have no greater value per unit of iron content than ores that can be mined and shipped direct from the shafts or open pits. For years only the higher grades of concentrating ores could be treated and sold in competition with the immense reserves of direct shipping ore available. These higher-grade "straight wash" ores required only the simplest treatment; namely, the washing out of fine sand from coarse ore particles. As the exhaustion of the " straight wash " ore is reached, rock is found replacing part of this sand, and the ore no longer responds to the former sizing treatment. Substantial tonnages of this marginal (jig ore) remained to be treated. Because of the limitations placed on concentrates by the furnaces—namely, low price of product and minimum amount of fines—iron-ore concentration oil has been and must continue to be a one-pass process. Only an increase in price or a change in structure of concentrates allowed by the ore consumer will encourage departure from this practice. Faced with the necessity of handling large tonnages, with the limitations mentioned, iron-ore research men have found their search for new and more efficient methods of treatment seriously handicapped and removed from the field of fine crushing. Sink-and-float treatment appeared to offer the best field in coarse concentration and has been proved by several plants to be well adapted to our problem. The use of ferrosilicon as a medium solid was decided upon. In our present practice, the ferrosilicon metal, carrying about 83 per cent iron, 15 per cent silicon and 2 per cent carbon and nonmagnetics, is crushed to pass 65 mesh and used without further sizing. When mixed with water the specific gravity of the medium may be controlled to within 0.02 per cent above or below the required gravity. Table I shows examples of a change in solid content of the medium for varying gravities. the I is based on clean ferrosilicon, whereas some contamination is always present in the mill circuit, tending to

Jan 1, 1947

By H. L. Gilbert, H. A. Johansen, R. G. Nelson

High purity electrolytic chromium plate has been hydrogen-reduced and arc-melted under inert atmosphere to give sound ingots. These ingots may be hot forged to break the as-cast structure and then worked at 500°C to finished form. An intermediate and final high temperature anneal gives best ductility and grain refinement. HE increasing interest in refractory metals for I use in high temperature gas turbines, jets, and rockets has led to great efforts in exploiting the fifth and sixth groups of transition elements. Much of the interest has centered upon production of metals that can be worked and fabricated by normal means to produce various engine parts or components having the high temperature characteristics of oxidation resistance and high creep strength required for such uses. If these pure elements do not exhibit all of the desired characteristics, it may be possible to obtain a high purity alloy that will. Since, in all cases, development of these transition elements has depended to a large extent upon removal of oxygen and nitrogen as a means for producing ductile metal, the hypothesis has been accepted that oxygen is the normal embrittling material in a high grade electrolytic chromium metal. Various methods have been employed in an effort to remove this oxygen by direct or indirect attack.' Many workers have endeavored to produce pure chromium through reduction of the oxide by carbon or active metals, while others have recommended fusion electrolysis of chromium salts or reduction of these salts by active metals, such as sodium or calcium. Hydrogen reduction of the oxide or chloride and thermal dissociation of the iodide have been reported to give high purity metal. Experimental Work The U. S. Bureau of Mines, Northwest Electro-development Laboratory, has systematically re-examined the more promising methods and developed two which produce metal having ductility at temperatures lower than heretofore described. It has been found' that oxide-free chromium chlorides in a NaCl-KCl carrier salt may be mag- nesium-reduced and the byproduct salts distilled off in vacuo to give a high purity chromium sponge. Fusion analysis conducted under the supervision of W. W. Horton of Knolls Atomic Power Laboratory showed the oxygen and nitrogen both to be below 10 parts per million on a selected sample. A small amount of carbon is carried over in the final metal from the chlorination and reduction steps which are carried out in graphite crucibles. This trace of carbon is not detrimental to hot ductility. A more practical method for producing ductile metal is through hydrogen reduction of high purity electrolytic chromium. Normal electrolytic chromium will, if "developed" for a few minutes at 1100°C in high vacuum, be found by the method of Adcock:; to contain about 1 pct chromium sesquioxide (Cr2O3). This small amount of oxygen may be effectively reduced by hydrogen.2, 4 The method employed was to crush electrolytic chromium plate in a gyratory crusher to pass 60-mesh; finer crushing appears to offer no advantage. A nitric acid leach removed the iron picked up during crushing. The leached powder was rinsed until neutral with distilled water and vacuum-dried.

Jan 1, 1954

By E. J. Ripling, S. I. Liu

IT has been shown in a number of recent publications that much information on the mechanical behavior of metals can be gleaned by first deforming test specimens under one set of conditions, and then evaluating the effect of this deformation by means of a subsequent tensile test. A straining procedure of this type has been applied to study the flow behaviors of a number of metals.1, 2 In these studies the prestraining and testing were both tensile strains, while the straining temperature was varied between the prestraining and testing steps. These data indicate that there is a more or less general flow behavior exhibited by all metals which are pre-stretched at one temperature and then tested in tension at a second temperature. Prestraining a metal at a high temperature produces a lower yield strength during the subsequent low temperature strain than would the same total strain at the lower temperature. On reversing the order of the strains, low temperature prestraining produces a higher yield strength during the subsequent high temperature straining than would a single high temperature strain of the same magnitude. Unlike the flow behaviors, the fracturing characteristics of metals when prestrained under one set of conditions and tested under a second set of conditions is quite material dependent. The fracture behavior of a number of steels2" as well as of a commercially pure zinc,4 have been investigated by these two-step tests and was found to depend upon the position of the transition temperature with respect to the prestraining and testing conditions. Since these fracturing phenomena are complicated by the appearance of the transition temperature, it has been difficult to reliably define the basic effect of a two-step straining procedure in fracturing. Metals crystallizing in the face-centered cubic system do not exhibit transition temperature effects so that the mechanical characteristics obtained on these materials could serve as a base for two-step straining behaviors. Consequently groups of specimens of the aluminum alloy 24s-T4 were prestrained various amounts at room temperature in either tension or compression after which these strained specimens were further strained to failure, or tested in tension, at either room or some lower temperature. Other groups of 24S-T4 specimens were prestretched at various low temperatures after which these were tested in tension at room temperature. These straining techniques then made it possible to compare the behaviors of aluminum with the behaviors previously presented for steels. Material and Procedure The commercial aluminum alloy 24S-T4 in the form of 3/4 in. rods was used in this investigation. The material was subjected to the following treatments before machining: 1—resolution treating at 920" & 10°F for 45 min, 2—quenching in water at room temperature, and 3—aging at room temperature for four days. The re-heat treated material was then machined to either of the specimen shapes shown in Fig. 1. Fig. la shows the threaded-end specimen used for prestraining in compression. Fig. 1b shows the specimen used for both prestrain in tension and final testing. The material subjected to precompression in the form of the specimen shown in Fig. la was re-machined to the specimen shape in Fig. 1b for final testing. Prestraining in tension and final testing were done without any intermediate machining. All straining was performed on a 10,000 1b Riehle tensile testing machine. Tensile strains were conducted in a specially designed concentric fixture which produced an eccentricity of less than 0.001 in." The change in diameter at the minimum section of

Jan 1, 1954

By Will Mitchell, Ford F. Miskell, C. L. Sollenberger

THE taconites in general are hard, tough ores, difficult to grind. Liberation of iron mineral constituents usually is accomplished by grinding the ore through at least 100 mesh, and often it has been found necessary to grind substantially through 325 mesh to achieve satisfactory recovery and grade in the concentration process. Because of the fineness of grind required and the enormous tonnages of material contemplated for treatment in the future, costs resulting from grinding media wear and power consumption, together with capital investment required for comminution, approach astronomical figures. Economy in any one of these elements per ton of material ground could very well reflect a considerable saving to the ferrous industry in yearly costs. With this in mind, the Research Laboratories of Allis-Chalmers Manufacturing Co. have launched a program to discover means of effecting this economy. The initial phase of the work as described here deals with a heat treatment of crushed raw ore, followed by thermal shock in cooling, for the preparation of rod mill feed. Several investigators 1-5 have noted an improvement in the grindabilities of ores treated in this manner. One investigator2 subjected low grade iron ores to heat treatment in an electric furnace. Basing his conclusions on screen analyses of crushed products, he observed that treated ore was more easily crushed than the untreated. He reported that observation of the treated and untreated ore through a microscope revealed cracks following the grain boundaries in treated ore, whereas no cracks were present in untreated ore. However, few if any have quantified the improvement in terms of total hp hours saved, reduction of wear of grinding media, or reduction of capital costs of grinding equipment involved. By means of Bond rod mill and ball mill grindabilities6 and by comparative wear tests, the conditions maintained during this investigation have been definitely evaluated. Heat treatment experiments have been made on a batch scale in a muffle furnace, followed by continuous scale experiments in a rotary kiln under various conditions of temperature, atmosphere, retention time, and quenching to determine the combination that would give the greatest improvement in the grindability of a taconite without affecting adversely the magnetic susceptibility of the magnetite. From these data, relative costs have been calculated for grinding both untreated and heat treated ore on a basis of plant capacity of 120 tons per hour. Heat requirements for a rotary kiln, as well as the kiln capacity required for the treatment, have been estimated. For these tests 50 tons of ore were obtained from the Aurora mine of the Erie Mining Co., Hibbing, Minn. The ore was reported' to have been selected from the magnetic portion of the lower chert horizons. An average chemical analysis of this portion is shown in Table I and an approximate mineralogical analysis is shown in Table II. No attempt was made to differentiate between the various silicates because the compositions vary widely on the different horizons and depend on the degree of oxidation. Minnesotite, however, is the predominant silicate. The siderite grains were dispersed throughout the ore but were essentially associated with the rock-forming minerals. In a series of preliminary tests in which batches of -6 mesh ore were heat-treated in a muffle fur-

Jan 1, 1952

By J. W. Freeman, R. F. Decker

A microstructural investigation was pursued to establish the mechanism of the pronounced benefits of traces of boron and zirconium on creep properties of a 55 Ni-20 Cr-15 (20-4 MO-3 Ti-3 A1 alloy at 1600°F. The mechanism of improvement of creep properties was found to be a pronounced stabilizing effect of traces of boron and zirconium on the grain boundaries of the alloy. The alloy with low boron and zirconium was subject to rapzd agglomeration of M23 C6 and in the grain boundaries, followed by depletion of y ' and intergranular microcracking at the grain boundaries transverse to applied stress. Brittle fracture then occurred by linking of microcracks. However, additions of zirconium, boron, and boron plus zirconium decreased this tendency in that order, allowing longer creep exposure and higher creep defor.mations before fracture occurred. VERY little information has been published describing the mechanism by which trace amounts of boron or zirconium improve the creep properties of complex nickel-base heat-resistant alloys, although the effect is now well recognized.1-4 Because the phenomenon is so important to properties and the effects are so striking, a study was made of the mechanism in a 55 Ni-20 Cr-15 Co-4 Mo-3 Ti-3 A1 alloy. It was believed that such a mechanistic approach would increase knowledge in theory of alloying and give a more basic understanding of alloy design to resist creep. The basic premise of the study was that boron or zirconium would alter the microstructural characteristics controlling creep and fracture to the extent that the effects could be identified by light and electron microscopy and by electron diffraction techniques. Characteristic of the microstructure of the Ti + Al-bearing nickel-base alloys is the dispersed precipitation of the intermetallic compound Ni,(Al, Ti), the ? ' phase, which is generally con- sidered to be the major source of high creep resistance.5-7 In addition, carbide phases have been identified8-10 and these can alter creep properties markedly.11 Since both the ?' and carbide transformations have been found to control properties, careful attention was paid to the effect of boron and zirconium on these transformations.

Jan 1, 1961

By Robert M. Asimow, Bisuddhi Riddhagni

THE use of back-reflection Laue photographs for crystal orientation is standard in many research projects. The time required for the orientation of any given crystal depends largely on luck and the skill of the investigator. In any case, where large numbers of crystals are used, this time can be quite considerable when the standard methods involving a Greninger chart and Wulff net are employed. For this reason the technique described below was developed. This new procedure applicable for cubic crystals (without preparation of new charts) largely eliminates the skill and luck factors and makes possible the determination of orientation in minutes. The procedure works in the following way: the Laue photograph is examined and arbitrarily an important hyperbola is picked out. An important hyperbola is defined as one which contains some spots through which several hyperbolas pass. Such a hyperbola inevitably corresponds to a low-index zone axis. The angles between the reflection planes causing all the spots on this hyperbola can be read directly from a Greninger chart in the usual manner. If the hyperbola contains more than five spots, these interplanar angles will positively identify the zone axis and the indices of each of the reflecting planes. However, initially since neither the zone axis nor the Miller indices of a diffraction spot are known, there are a very large number of possibilities that must be considered. Using tables of interplanar angles to check out every possibility would be quite tedious, so that this approach is not generally used. Instead, various poles are plotted on a stereographic projection. In the cubic system, however, it is possible to plot out once and for all the angles between all planes of a particular zone axis up to some upper limit of Miller indices. This has been done for all low-index zone axes in Fig. 1. Given these charts, it is quite a simple matter to identify the spots of the unknown hyperbola. All that is necessary is to plot the angles read off the Greninger chart to the same scale as Fig. l(b) on a strip of paper. Then this strip can be slid along each zone axis of Fig. l(a) until a good fit is obtained. Once this is accomplished, the Miller indices of each spot are given and thus the orientation problem is solved. To check, it is possible to pick a second hyperbola and see whether a compatible solution is obtained. This is most conveniently done by picking for the second hyperbola one that contains a spot common with the first. If the specimen axis is chosen parallel to the incident X-ray beam, then usually the [ loo] hyperbola will appear on the film as one of the more important hyperbolas and consequently will be either chosen initially or as a check. Using the [100] hyperbola, after the (001) or (011) spots have been identified, the latitude and longitude of the specimen axis can be read directly from the Greninger chart so that it is unnecessary to use a Wulff net for the entire orientation procedure. This makes the operation not only quicker but more accurate. Of course, if neither the first nor second hyperbolas correspond to [loo] then a third hyperbola can be chosen.

Jan 1, 1967

By Grover J. Holt

In order to provide a clear picture of the development of the sink-and-float process of concentration as applied to the iron ores of Minnesota, a few pertinent facts should be brought out concerning the ores and the products of concentration. Iron ore is primarily a cheap commodity handled in immense quantities. The price of iron ore at present, based on a natural iron content of 51.5 per cent, varies from $2.55 to $2.70 per gross ton f.0.b. cars at the mine or washing plant in Minnesota. Last year 92,000,000 gross tons were shipped from the Lake Superior district (Minnesota, Michigan, and Wisconsin) to the furnaces. Concentrated iron ores have no greater value per unit of iron content than ores that can be mined and shipped direct from the shafts or open pits. For years only the higher grades of concentrating ores could be treated and sold in competition with the immense reserves of direct shipping ore available. These higher-grade "straight wash" ores required only the simplest treatment; namely, the washing out of fine sand from coarse ore particles. As the exhaustion of the " straight wash " ore is reached, rock is found replacing part of this sand, and the ore no longer responds to the former sizing treatment. Substantial tonnages of this marginal (jig ore) remained to be treated. Because of the limitations placed on concentrates by the furnaces—namely, low price of product and minimum amount of fines—iron-ore concentration oil has been and must continue to be a one-pass process. Only an increase in price or a change in structure of concentrates allowed by the ore consumer will encourage departure from this practice. Faced with the necessity of handling large tonnages, with the limitations mentioned, iron-ore research men have found their search for new and more efficient methods of treatment seriously handicapped and removed from the field of fine crushing. Sink-and-float treatment appeared to offer the best field in coarse concentration and has been proved by several plants to be well adapted to our problem. The use of ferrosilicon as a medium solid was decided upon. In our present practice, the ferrosilicon metal, carrying about 83 per cent iron, 15 per cent silicon and 2 per cent carbon and nonmagnetics, is crushed to pass 65 mesh and used without further sizing. When mixed with water the specific gravity of the medium may be controlled to within 0.02 per cent above or below the required gravity. Table I shows examples of a change in solid content of the medium for varying gravities. the I is based on clean ferrosilicon, whereas some contamination is always present in the mill circuit, tending to

Jan 1, 1947

By C. A. Siebert, O. S. Duffendack, A. W. Herbenar

IN metallurgical problems involving the study of equilibrium in binary systems, the ,existence of an additional vapor phase, due to the presence of a volatile component in the alloy, has often been neglected. This is well indicated by the modified form of the phase rule, usually accepted in condensed systems in which pressure is not considered as a degree of freedom. In many cases the vapor pressure of the volatile component is exceedingly small and for all purposes can be considered negligible, in which case this form of the phase rule is applicable. However, alloys containing Hg, Cd, Zn, or Mg, tend to show very marked equilibrium vapor pressure, even in the solid state, and therefore present cases where the modified form of the phase rule no longer holds true. A quantitative determination of the vapor pressure of zinc in alpha brasses is not only of practical interest because of the loss of zinc in the processing of these alloys, but also of theoretical interest in that such measurements provide a means of applying the principles of theoretical physics and physical chemistry to problems of applied metallurgy. A number of investigators have reported vapor pressure measurements of zinc in alpha brasses. Hargreaves1 made extensive measurements which were used by Birchenall and Mehl² and Guttman³ for the determination of activity coefficients of zinc in alpha brasses. Hargreaves1 used a differentially heated quartz tube and measured the condensation temperature at one end corresponding to the temperature of the heated brass at the other end. Birchenall and Cheng outlined the condensation method of obtaining vapor pressure of zinc and Cd over some of their silver alloys." The primary object of the present investigation was to increase the range and accuracy of the vapor pressure data for the alpha brasses. Preparation of Alloys: Six alloys were prepared from Bunkerhill zinc and O.F.H.C. copper, both of 99.99 pct purity. The cast ingots were annealed for 24 hr at 550°C, scalped, cold rolled 40 pct and annealed for 50 hr at 550°C. The annealed bars were then surface ground and degasified for 30 min at approximately 550°C in an induction heated vacuum furnace. The surface of the bars was removed before milling the bars into relatively fine chips for chemical analysis and samples for the equilibrium cell. The analyses of the six alloys are given in table I. Experimental Method: The vapor pressure of zinc over the various alloys at a number of temperatures was determined from absorption spectra data. The spark source was produced by means of a high tension discharge between two electrodes of pure zinc. The design of the absorption vessel is shown in fig. 1. The vessel was constructed of transparent quartz which transmits the whole of the visible spectrum and the ultraviolet down to a wave length of 2000 A. The thickness of the vapor space was set at 0.8 mm so as to permit a relatively wide range of measurements without altering the vapor space, and thereby necessitating recalibration of the vessel. The furnace used for heating the absorption vessel consisted of a split wound furnace as shown in fig. 2. The spectrograph used in obtaining the transmitted zinc spectra was a double prism type especially designed for a region of 2500-3500 A. A step diaphragm used in conjunction with a tungsten filament provided the necessary intensity patterns required for calibration of the photographic plates.

Jan 1, 1951

By H. A. Deans

A three-parameter mathematical model for one-dimensional flow in porous media is developed. The objective of the model is to predict accurately the longitudinal dispersion associated with the flow of either gases or liquids over a wide range of Reynolds number. A qualitative analysis of the model parameters is given. Published experimental pulse-response curves are compared with results predicted by the model. Several general types of problems are given for which the model can be used. INTRODUCTION The problem of multicomponent single-phase flow through porous media is encountered in the study of petroleum reservoirs, gas chromatographic and ion-exchange columns, industrial fixed-bed con-tacters and elsewhere. These particular examples span the wide range of flow conditions possible; Reynolds numbers of less than l0-4 are not unusual in oil-production problems, while values in excess of 103 are common in large fixed-bed operations. The study of flow-dependent transport phenomena is complicated both by the changes in the character of the flow over this range, and by the irregularity of the flow boundaries inherent to porous media. Dispersion is one of the important phenomena known to depend fundamentally on flow conditions as well as on fluid and medium properties. As used in this paper, the term "dispersion" refers to the observed mixing of fluid elements of different composition which occurs in flow systems. The actual mechanism may be one or more of a number listed below. Only dispersion in the direction of the mean flow (referred to as axial or longitudinal dispersion, or mixing) is considered here, although lateral dispersion arises as part of certain coupled mechanisms. MECHANISMS FOR LONGITUDINAL DISPERSION A number of distinct mechanisms are known3,5,7,8 to contribute to the phenomenon of longitudinal dispersion. The more important of these are as follows. 1. Molecular diffusion in the flow direction. 2. Turbulent (cell) mixing. 3. Lateral transport processes coupled with velocity and/or residence time distributions, including: (a) "Taylor" diffusion caused by the interaction of velocity profiles in individual voids with lateral molecular diffusion; (b) separation and remixing or interdiffusion of streams having different velocities around particles; and (c) the couplipg of gross velocity profiles, caused by viscous instability or inhomogeneous porosity, with lateral dispersion. 4. Finite mass-transfer rate between a porous matrix and the flowing phase, and finite diffusion rate inside elements of the porous matrix. It is a well documented fact that these mechanisms, whether acting individually or in combinations, produce essentially similar integral effects. The observed dispersion can be described approximately by solutions of the diffusion equation with a properly chosen dispersion coefficient. Necessary conditions for equivalence between dispersion and diffusion are discussed by Klinkenberg and Sjenitzer.7 Apparently these conditions are not satisfied exactly in many real systems. "Best fit" solutions of the diffusion equation often depart appreciably from measured breakthrough curves for the usual pulse- or step-forced experimental systems. In particular, pulse response curves usually show some degree of asymmetry and "tailing" which cannot be reproduced by the one-parameter diffusion model. The three-parameter model proposed herein attempts to produce these effects in a realistic manner. Asymmetry and tailing are predicted for certain sets of parameter values, while for other sets the new model agrees with the diffusion model. VELOCITY DEPENDENCE OF DISPERSION Molecular diffusion apparently controls at sufficiently low Reynolds number in both gas and liquid systems.*l3 At Re > 20, turbulent cell mixing is dominant for gases flowing at low pressure; the data of McHenry and Wilhelm8 show that the mixing cell is approximately 1 particle diameter long in random sphere packs. on the other hand, the data

By N. S. Bornstein, M. A. DeCrescente

ThE nickel and cobalt base superalloys employed in gas turbine engines under some conditions' oxidize at an accelerated rate when exposed at elevated temperatures to atmospheres containing minor quantities of sea salt. It is generally agreed by investigators in the field that the major steps comprising this phenomena of accelerated oxidation, also called hot corrosion or more commonly, sulfidation, are a) a slag composed primarily of Na2S04 is formed on turbine components, b) the protective oxide scale is rendered ineffectual, c) the slag reacts with. the substrate to form metal sulfides, and d) the substrate is rapidly oxidized. Sodium sulfate, a minor constituent of sea salt, is formed within the gas turbine engine from the reactions between NaC1, the major constituent of sea salt, and the oxides of sulfur.' Depending upon concentration, engine compression ratio, and temperature, the Na2S04 will be present in the gaseous or condensed state. It has been determined that in order for sulfi-dation to occur the Na2S04 must be present in the condensed state.' Although a number of sulfidation mechanisms have been postulated, there is no consistent explanation of oxide scale breakdown and subsequent catastrophic oxidation. Some investigators believe that after oxide scale breakdown, the Na2SO4 reacts with the substrate to form lower-valent sulfur compounds. The accelerated rate of oxidation is due to oxidation of a nickel-sulfide phase." Other investigators believe that sulfur from the fused salt reacts with chromium in the alloy to form chromium-rich sulfides; thereby depleting the alloy of an element which imparts oxidation resistance.3,4 This publication will demonstrate that the accelerated rate of oxidation associated with sul-fidation is due to interactions between Na20, a con-stituent of NazSO.,, ancl the substrate. The aim of this study was to separate and determine the effect of compounds of sulfur and sodium on the oxidation kinetics of various nickel-base superalloys, in order to elucidate the sulfidation mechanism. The work reported herein is sponsored in part by the Naval Ship and Development Center-Investigation of EXPERIMENTAL PROCEDURE The nickel base alloys B-1900, U-700, and Waspaloy were chosen for this study. The nominal compositions are presented in Table I. The specimens, approximately 1 in. by 1 in. by 0.060 in. received in the "as cast" condition were polished with 600 grit emery, washed, and rinsed with acetone immediately prior to oxidation experiments. Sulfida-tion attack was duplicated in the laboratory by apply-ing a saturated aqueous solution of Na2S04 onto the al loy substrate and subsequently exposing the specimens in oxygen at elevated temperature. The method of Na2S04 application is described elsewhere in detail.6 In another set of experiments the affected substrate microstructure associated with sulfidation was reproduced free of the normal oxide scale, by reacting and diffusing elemental sulfur into the alloy. The experimental procedure is also described elsewhere in detail. All oxidation studies were performed using an Ainsworth thermobalance type RV-AU-1, which is readable to 0.01 mg and is reproducible to ±0.03 mg. The specimens, introduced into a heated furnace, were exposed in the temperature range 800" to 1000°C

Jan 1, 1970

By C. F. Rust

Experimental evidence is presented showing that reproducible formation resistivity factor measurements and resistivity index determinations on reservoir core samples map be made utilizing either the two- or four-electrode methods. Equipment is described which permits the application of either technique to the core specimen without loss of time and with a minimum amount of effort. Since electrical resistivity measurements on reservoir rocks are important not only in electric log interpretations, but also in the study of fundamental rock parameters, it was considered desirable to compare the applicability of both techniques of resistivity measurement. INTRODUCTION The techniques employed in the measurement of electrical resistivity on reservoir rocks, as practiced in the petroleum industry, may be reduced to two fundamental methods: one utilizing two electrodes only, usually referred to as the two-electrode method; the other using two additional electrodes and commonly known as the four-electrode method. In the former, the core sample whose resistivity is to be measured is mounted between two electrodes, usually metal discs, which serve to pass a current of known magnitude through the saniple. The potential drop across the sample, measured between these same two electrodes, and the core dimensions furnish the necessary data to compute he resistivity of the sample. In the four-electrode technique the end plates, again usually ol metal, still serve as current electrodes. Additional probes or electrodes dispersed along the sample are utilized to measure the potential drop. Both methods are used in practice1,2 and it is the purpose of this paper to compare the two techniques as applied to the determination of formation reiistivity factors and the resistivity index exponent n, in Archie's empirical equation I = p/po = Sw 11. To evaluate the two techniques it is desirable to point out the experimental precautions which must be taken to insure reliable results. It is evident from the electrode arrangements of the two- and the four-electrode methods that, for a given sample, the volume of sample included by the four-electrode method is less than the volume included by the two-electrode method. One of the prime difficulties associated with the two-electrode method is the possible occurrence of an abnormally high resistance between the electrodes and the brine-saturated sample, which results in erroneous resistivity values for the core sample itself. Attempts to alleviate this difficulty meet varying degrees of success. Methods used in the past employ such absorbent materials as brine-saturated Kleenex: chamois, or felt. A technique described by Morgan, Wyllie, and Fulton,1 appears to be more satisfactory. Their method consists of spraying or painting the end areas of a core sample with conductive silver paint. This technique reduces contact resistances between the porous medium and the electrodes to a value which is generally negligible as compared to the resistance of the sample itself. In the four-electrode method these requirements are not as stringent since separate probes are used to measure the potential difference acrozs a portion of the sample. In this case, contact resistance occurring at the current electrode; are of no consequence. and those appearing at the potential

Jan 1, 1952

By George C. Lipsey

FOR many years the mining of coal and other minerals occurring in sedimentary formation has been planned according to information obtained by diamond drilling. Placer mines have used churn drills for sampling and estimating deposits, and some metal mines have used the method either wholly or in part. The diamond drill method, therefore, although not entirely new, has come into more prominence in the last few years. Several large-scale developments now being planned or in the production stage have used this method in varying degree. This paper will describe the operations of the Howe Sound Exploration Co., Ltd. at Snow Lake, Manitoba, where a gold mine was developed and equipped for mining and milling wholly on the basis of diamond drilling results. The property has been in operation nearly 3 years, so that results can be compared with the estimates and assumptions made from the diamond drilling. In developing the subject it is necessary to outline as briefly as possible the normal method of mining, from discovery to production stage. Table I sets forth these various stages, the methods of financing, the percentage of total cost, and the relative time interval required for each section of the work. The plan presented in this table cannot be applied to all mining developments, but it gives a basis on which to work. In Stages 2 and 3 the investment is moderate, and if the property does not respond favorably the options or interests can be terminated. Stage 4 represents a sizeable investment, and it is more difficult to drop the property after this part of the operation is completed. Stages 2, 3, and 4 may be repeated several times by different groups or companies before Stage 5 is reached, but when Stage 5 has been started the total capital investment must be provided and there can be no turning back. It will be noted that there is a total of 116 units of investment in the overall cost if one company proceeds with Stages 2, 3, 4, and 5 in order. Stage 4, however, consumes time which is important when markets are being considered. Bringing a property into production when metal prices are low is much more difficult than when the prices are high, and if this stage can be set aside production is attained more quickly. When Stage 4 is eliminated the total becomes 86 units of cost for Stages 2, 3, and 5, but an adjustment of 14 units must be added to Stage 5. These 14 units represent the useable value of Stage 4. Thus Stage 4 represents an investment of 30 units if carried on before Stage 5, but 14 units if included with Stage 5. This is accounted for by the fact that development work can be accomplished more cheaply under Stage 5, since everything that is done is planned on a production basis with permanent services. Stage 4 must of necessity be governed by expenditures, and a great many temporary services, including housing and power plants, must be provided. The prospect shaft is a small one, and drifts,

Jan 1, 1952

By B. K. Miller, R. S. Bradley

The principal producing areas of fire clay in Missouri are: (I) the east central district, which includes Audrain, Callaway, Montgomery, Warren, and Boone Counties (Fig. I); (2) the St. Louis district, which includes St. Louis and St. Louis County; (3) the north central Ozark district, which includes Franklin, Gasconade, Osage, Maries, Phelps, and Crawford Counties. Most of the semiplastic‡ fire clay is found in Audrain, Callaway, Montgomery and St. Louis Counties, and in St. Louis. Flint fire clay is found in Callaway, Audrain, and Montgomery Counties and in most of the north centra! Ozark district. High-alumina diaspore clay is found only in the north central Ozark district, except a few deposits found in Montgomery County. This paper is concerned with the semi-plastic fire clay that occurs in the east central Missouri district near Mexico, Audrain County, Missouri, which is mined by the open-pit method as practiced by the A. P. Green Fire Brick Co. About one-fourth of the semiplastic fire clay in that district is mined in shaft mines, and three-fourths in open pits.

Jan 1, 1942

By S. H. Gelles

Samples of poly crystalline zinc of 99.999+ pct purity were observed metallographically after having been exposed to hydrostatic pressures of up to 27 kbars. The deforrnation produced by this treatment was analyzed using X-ray and metallogaphic techniques. Basal-plane slip occurred universally in all grains exumined at the lowest pressure used (8 kbars). At pressures of >23 kbars, {1012} twin nucleation and growth were noted as well as slip. Formation of bend planes, complex kink bands, and recrystallization at the gain boundaries were also observed in this pressure range. These observations are discussed in reference to the expected deformation behavior of zinc under high hydrostatic pressure. It has been shown over the past few years1'3 that anisotropic, poly crystalline metals can be made to deform plastically by the application of a hydrostatic pressure. The effect is greater 1) the larger the anisotropy of linear compressibility and 2) the smaller the stress level needed to produce plastic deformation. Zinc having both very anisotropic linear compressibilities and a very low critical resolved shear stress (CRSS) for basal-plane slip has been shown to exhibit large amounts of plastic deformation when subjected to a hydrostatic pressure.2,3 At pressures up to 15 kbars, grain boundary migration and slip on one set of glide planes have been reported.' After exposing samples to 20 kbars pressure, grain boundary migration, single slip, multiple slip, and twinning have been noted.' The identification of the deformation modes operative under these conditions has not been reported. It was the purpose of this research to identify the deformation modes induced in poly crystal line zinc by the action of a hydrostatic stress and to study the strain accommodation at grain boundaries. Hydrostatic pressure could affect the operational modes of deformation by altering the Peierls-Nabarro stress. This may be roughly approximated by the relationship4

Jan 1, 1967

By John Wulff, Richard P. Seelig

THE importance of the pressing operation in the forming of articles by powder metallurgy depends to a great extent on the type of product to be made. While in some few cases the pressing is merely a means of compacting loose powder particles into a solid mass preliminary to a sintering treatment in most applications it constitutes a molding operation with the purpose of shaping the raw material in powder form into a certain predetermined, accurately defined part not altered in shape by sub- sequent sintering. In still other cases, no pressing at all but sintering in molds gives useful articles. A limited number of products are made by the simultaneous application of pressure and heat. The factors that control the product of the pressing operation are raw material, lubricant, type, size and shape of die and compact, magnitude and time of application of pressure, as well as temperature of pressing. All such factors need to be con- trolled; yet, depending on the function of the pressing operation, greater emphasis may be placed on processing factors other than the pressing operation. In any complete discussion of pressing, subsequent sintering cannot be disregarded. For the sake of brevity, the present paper has been limited to the mechanics of pressing and only occasionally refers to sintering. For the same reason, hot-pressing has been omitted as beyond the scope of this paper. In any survey of the literature on the pressing of metal powders, the 1938 paper of Balshin1 on the theory of the process of pressing deserves mention. The first attempts at an interpretation of pressing phenomena were made by Balshin1 and Rakovski.2 The experimental results of both are of great interest. Since the experimental results are not described, the work was repeated, using our own interpretation of the possible techniques, and is reported in the following pages. The basic theory of Balshin,1 based on a hydro- dynamic analogy, however, leads to but another way of plotting density and pres- sure against height of a pressed compact. Since it does not give any new insight into the phenomena, nor account for the influence of side-wall friction, a discussion of the theory has been omitted from this paper. DENSITY GRADIENTS IN COMPACTS The process of pressing metal powders in a die (disregarding for this consideration the powder filling and ejection operations) may be divided into three phases: (I) packing, (2) elastic and plastic deformation, (3) cold-working with or without fragmentation. It must be emphasized that these three steps do not follow each other in sequence; on the contrary, in practice

Jan 1, 1946

By Eric R. Jette, A. G. H. Anderson

During the period from 1910 to 1920, there was a lively interest in the subject of grain growth and many papers were published, followed by interesting discussions. Questions dealing with the fundamentals of grain growth—why and how it occurs—were treated in papers by Howe,' .Jeffries,² Sauveur,² Chappell,4 Beilby,5 Mathewson and Phillips,6 Mc Adam,7 Carpenter and Elam,8 Stead and Carpenter,9 Ruder,l0 as well as others. Since that decade, much indeed has been done regarding the practical control of grain size, and it is now possible to order material having a size sperified in the American Society for Testing Materials classification. Also, one hears the term "spliced boundaries" used in connection with certain tungsten lamp filamentsl1 wherein it is important to prevent "sagging" between consecutive turns of the helix.12 This practical use of a certain knowledge as to the things that influence or even control grain growth should not be taken as an indication that the subject has been thoroughly explored and that nothing more can be learned from fundamental studies. It is with this thought in mind that a report of some observations and experiments on abnormal grain growth is believed justified. Abnormal grain growth is met with in heat-treating high-carbon steels in the austenitic range,'? in the hardening treatments of high-speed steels,14'15 and in the low-temperature annealing of strained low-carbon steels as in sheet and wire material. Entirely aside from these instances of exaggerated grain growth, which some might consider as freakish, it is thought that abnormal growth is simply a case where the growth forces and the forces tending to prevent growth are almost, but not quite, evenly balanced. Information relative to grain-growth characteristics in general may be obtained from a study of abnormal growth conditions, which may be looked upon as vantage points. Reflection will show at once that if growth forces are great in comparison to inertia or resistance to growth, many crystals start to grow and, for that reason, none becomes very large, whereas if inertia is

Jan 1, 1938