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By Robert Glass Cleland

THE THIRD and most important item on the Phelps Dodge agenda for the development of new ore supplies involved the site of the company's initial venture into Arizona, the old mining camp of Morenci. By the purchase of the Arizona Copper Company's holdings in 1921, Phelps Dodge had obtained control of virtually the entire Morenci district, including town, public utilities, and, above all, the huge mineralized area that had once been divided between numerous competing companies. Because of this rigid concentration of ownership in the hands of one organization, Phelps Dodge was able to plan and successfully carry out a program of greater magnitude than any Arizona mining company had previously under- taken. The immense deposit of low-grade ore, usually referred to as the Clay Orebody, had been known to the mining companies of Morenci for many years. Pioneer exploratory work, both by the Arizona Copper Company and later by Phelps Dodge, revealed that the deposit, mostly of light-gray porphyry rock, lay under a hard capping from two hundred to five hundred feet thick. An intensive drilling

Jan 1, 1952

By R. Schuhmann, G. W. Powell

The concept of local equilibrium is examined and, in particular, the applicability of the concept to two-phase binary diffusion couples is discussed. It is concluded that, if binary solid solutions are treated thermodynamically as ternary solutions, vacancies being the third component, then recent experimental observations of nonequilibrium interface compositions (i.e., compositions different from the phase diagram values) are consistent with a state of complete dynamic equilibrium at the interface. CLASSICAL approaches to diffusion and to other irreversible processes often utilize a postulate of "local equilibrium". That is, one assumes even in the presence of gradients, fluxes, and time changes of properties, a) that the Second Law can be formulated locally, and b) that thermodynamic equations of state among intensive properties are identical with those for equilibrium phases. A direct consequence of this assumption, for example, is that one would calculate the total entropy of a nonequilibrium phase simply by integrating the entropy density (eu per unit volume) over the volume of the phase, assuming that entropy density is the same function of energy and particle density as for equilibrium phases. In the study of diffusion and of diffusion-controlled phase transformations, metallurgists take this concept of local equilibrium for granted and utilize it automatically. In fact, experimental evidence of all kinds is overwhelming that "local equilibrium" is a valid limiting law, approached more and more closely as gradients and rates of change approach zero. On the other hand, we have neither experimental nor statistical thermodynamic proof that this principle of "local equilibrium" should remain rigorously valid at high gradients and for rapid processes. Theoretically, in fact, one would expect deviations because interactions between adjacent volume increments of material affect the evaluation of entropy. Also one observes experimentally structural and small energetic differences between equilibrium and nonequilibrium phases. The purpose of this paper is to present a thermodynamic framework for the study and correlation of deviations from strict local equilibrium in isothermal diffusion and related processes. This procedure, in effect, preserves the principle of local equilibrium by thermodynamically assigning the deviations from static equilibrium properties to a defect component. Although this theory is entirely phenomenological, the possibility does exist of correlating the theory with experimental observations of defects under favorable circumstances. The most immediate application appears to be to the equilibria at the interfaces in two-phase binary diffusion couples. A recent pertinent work by Eifert et al.1 has shown that the concentrations of aluminum in the a(fcc) and B(bcc) phases at the 0-8 interface in Cu:Cu-12.5 wt pct A1 diffusion couples are greater than those given by the phase diagram. It is postulated by these authors that the supersaturation of the o phase at the interface provides the driving force for the a-to-B lattice transformation; the excess free energy of the a phase, ?Gaxs, arising from the greater-than-equilibrium aluminum concentration is about 3 cal per g-atom. On the basis of the schematic free energy-composition diagram shown in Fig. 1, Eifert et al. concluded that the thermodynamic situation at the interface is one of the partial equilibrium; that is, = for the more mobile aluminum whereas will be reexamined in the latter part of this paper. THERMODYNAMIC PROPERTIES OF DEFECTS A rigorous analysis of the thermodynamics of defects requires an added degree of freedom in the Phase Rule sense, because the standard formulations of solution thermodynamics (partial molal properties of components, free energy minimization, equality of chemical potentials, and so forth) involve the implicit

Jan 1, 1970

Discussions of the papers of DORSET A. LYON and SAMUEL S. ARENTZ, RICHARD D. DIVINE, H. A. WENTWORTH, and S. E. BRETHERTON, presented at the Salt Lake meeting August, 1914, and printed in Bulletins Nos. 91 and 92, July and August, 1914. GEORGE W. RITER, Salt Lake City, Utah.-We have every reason to believe that oil flotation Will soon come into general use as a final guard against slimes losses in concentrating mills, not only in the case of zinc ores, but also in the case of other semi-precious ores. It also promises much as a primary process for the concentration of minerals that are not adapted to gravity methods. Moreover, modifications of the process involving selective or preferential flotation are gradually becoming understood, and will make it possible to eliminate pyrite and other minerals occurring as undesirable impurities in zinc concentrates. And what perhaps is of equal importance, further modifications promise an effective method of separating zinc blende from ores that are chiefly valuable for copper, lead, anti precious metals, thereby making an asset out of zinc which has heretofore been a liability. The tendency of certain pulverized minerals to float on water, especially after having been in contact with grease, has been known to mill-men for a long time, and was formerly something to be deplored and to be striven against. All at once, this tendency has become a saving grace; and now, like tardy converts to a new faith, we are zealous advocates of something we once despised. I was once employed at a mine in the Tintic mining district of Utah¬the old Eureka Hill property-where ores that were too low in value to Warrant being sent to copper or lead smelters were treated in a combination mill. The ores contained gold, silver, lead, copper, zinc, manganese, arsenic, etc., in varying quantities and in varying mineral forms, mingled in a quartz and calcite gangue. The material was stamped fine and then concentrated on Frue vanners so as to make a smelting concentrate, after which the tailings were thickened and treated in amalgamating pans for the recovery of non-concentratable precious metals. In the amalgamating pans, under the influence of heat and agitation, a dark greasy froth or scum sometimes formed on the surface of the ore mixture. This froth or scum was composed mainly of mineral sulphides, and its occurrence might have meant only casual losses in the previous concentration, except that the phenomenon was accompanied by faulty amalgamation of the precious metals and by excessive losses in the mill tailings. Grease and oil, present by accident, were the cause of the trouble.

Jan 11, 1914

By J. T. Berling, J. B. Conway

MANY studies have been devoted to the correlation of low-cycle fatigue behavior. Several of these have also been concerned with the identification of an effective approach to the prediction of low-cycle fatigue behavior from short-term tensile data. Perhaps the first such approach was that reported by coffin1 in the form: where is the plastic strain range, Nf is the number of cycles to failure, and c is a constant characteristic of a material. In this analysis by Coffin it was reasoned that in a short-term tensile test the value of Nf could be considered as equal to a , in which case the value of c is interpreted as the tensile ductility, f, measured in such a test. If, therefore, the Coffin equation is assumed to be applicable to a given material, it is a simple matter to predict the low-cycle fatigue behavior. Once the tensile ductility is known, this point is located at Nf = 1/4 on a log-log plot of vs Nf and a line is drawn through this point with a slope of to yield a prediction for the fatigue life. Actually, while this equation is quite useful it is not generally applicable, for experiment has shown that the value of —$ does not reflect the relationship between and Nf for all materials or even for a given material over all temperature ranges. An equation similar to the Coffin equation was prepared almost simultaneously by Manson.2 This expression had the form: In this case the exponent on Nf was not assigned any particular numerical value in accord with the various values of this exponent which had been observed for different materials and at different test conditions. Because of this characteristic it will be recognized that little use can be made of this expression in predicting low-cycle fatigue results. A fairly effective expression for use in predicting fatigue behavior was proposed by Manson3 based on a study of numerous sets of experimental results. This relation (Method of Universal Slopes) makes use of modulus of elasticity, ultimate strength, and tensile ductility, and assumes an exponent on Nf equal to 0.6 in representing the plastic strain range contribution to total strain range. While this equation of Man-Son does not yield completely accurate results it must be recognized as being the best means available at

Jan 1, 1970

By R. W. Raymond

Through the courtesy of Mr. James H. Mayo, a member of the Institute, who is in charge of the operations of the Mindrinetti Company in the Saramacca district of Dutch Guiana, I have received specimeris of certain peculiar pseudomorphs of limonite after pyrite, which occur abundantly in the auriferous deposits of that. region.* I am indebted to Mr. H. Tweddle, a geiltleman- connected with the same company, for some particulars of interest con-

Jan 1, 1899

By W. J. Wrazej

THE measurements on the formation of multi-layered scales on pure iron1 and the metal -lographic examination of the produced layer of FeO, Fe,O,, and Fe2O3 shown in micrographs2 throw much interesting light on this apparently well-known subject. Professor Paidassi announced2 that in a few months7 time further results are going to be published with regard to the growth of Fe2O3 and Fe2O3 layers on an Armco iron as a function of temperature. Because of the very thin layers of Fe2O3 which are shown by Paidassi (Fig. 10 of ref. 2) when samples were scaled in air at 700°C for 4 hr and because this is not in agreement with the present author's previous observations, the following experiment was recently carried out. Polished cylindrical samples 13/64 in. in diam and 1/4 in. long from electrolytic iron used for spectro-graphic work (Hilger, H.S. Iron rods, F.693) and an Armco iron sample 1/4 in. in diam of the same length were suspended in a muffle furnace on Nichrome wire and annealed in air for 4 hr at 700°C 5OC. Because of the known easy peeling off of the Fe2O3 layer which is mainly in the form of powder (purple red dust on the surface) the samples were protected against any draft and shock. After annealing, the samples were cooled in air and placed in the mount-

Jan 1, 1954

By George H. Rupp

THE Sunrise iron mine of The Colorado Fuel and Iron Corporation is in Platte County, Wyoming, about 110 miles north of Cheyenne. It is served by the company-owned Colorado and Wyoming Railway, which connects with the Chicago, Burlington and Quincy and the Colorado and Southern railways at Guernsey, Wyoming, a distance of 6 miles from the mine. The original Sunrise claims were staked mainly by United States Army officers and soldiers stationed at old Fort Laramie, because of small showings of copper in the Carboniferous limestones that form a horizontal capping overlying the Huronian iron ore. A small copper smelter was operated for about three years at Fairbanks, now an abandoned town on the North Platte River. As many of the copper shafts and test pits near the present Sunrise mine were deepened, they penetrated the capping and encountered iron ore or gray sericitic schist, and were abandoned. Evidence of an early interest in iron ore was found when the Chicago claim was stripped for mining. A narrow, winding crevice was discovered, which led downward 20 ft. through the capping to the underlying soft red hematite, in which a room 10 by 14 by 7 ft. had been excavated. Stone hammers and wedges and a few rusted pieces of iron were found on the floor, and the evidence is conclusive that the excavation was used up to rather recent times by Sioux Indian medicine men, to provide war paint. GEOLOGY AND ORE The Sunrise district is in the Hartville uplift, an anticlinal area in which pre-Cambrian rocks similar to those of the Black Hills and the Laramie Mountains are brought to the surface. The lowest part of the pre-Cambrian series exposed is a great thickness of pink, crystalline, Huronian dolomites with thin unstratified beds of schist and quartzite. The upper part of the series consists mostly of gray or green schists but includes a few lenticular beds of jasper and a banded iron formation con-

Jan 1, 1939

By Walter S. Weeks, Vitaly S. Grishkevich

Considerable difference of opinion seems to exist as to whether the rate of air flow when a fan is placed on a given duct should be determined by the use of static pressure or total pressure characteristics. A little study will show that both methods are correct. Assume that a fan is connected to a duct by an expansion piece as shown in Fig. 1, and that steady flow is established. Considering the atmospheric pressure as zero pressure, let the static head at the outlet of the fan be h and the velocity at this point be vl. The total head at the outlet is then h + „"• The total head at this point must be equal to the total head at the end of the duct plus the losses that have occurred between the two points. Left be the friction loss in the straight duct, s the shock loss in the dif- fuser, and v2 the velocity at the end of the duct. Then ig. 1.—Fan on duct. A curve showing the value of the left-hand side of the equation for different rates of flow is the total pressure characteristic of the fan, while a curve showing the value of the right-hand side is the total pressure characteristic of the duct. If these two curves are plotted on the same chart, the intersection indicates the rate of flow when steady flow is established. We may look at this problem in another way. The static pressure at the outlet of the fan is the static pressure of the fan and it is also the static resistance of the duct from that point to the end. The friction in the straight duct is f. If the duct were the same area as the fan outlet, would be the static resistance of the whole duct system. In the present case, however, this resistance is decreased by the change of velocity head into static head in the expansion piece. If conversion were perfect, the static pressure recovered would be

Jan 1, 1931

By I. Fatt

Networks of resistors are used as analog computers to obtain relative permeability and resistivity index curves for networks of tubes. These curves have all of the characteristics of those obtained on porous media and, therefore demonstrate the validity of the network of tubes model. INTRODUCTION In paper I' of this series the network model was shown to give information on the structure of porous media that could not be obtained from the bundle of tubes model. The agreement between the capillary pressure characteristics of a network of tubes and those of typical porous media does not prove the validity of the network made. The bundle of tubes model, although it gives less information, also shows this agreement. In this paper the flow properties of a network of tubes are shown to be in agreement with flow properties of porous media. The flow properties of the bundle of tubes model are not in adequate agreement with those of porous media. The dynamic properties of porous media, such as fluid permeability and electrical conductivity, have been found experimentally to be more sensitive functions of structure and pore size distribution than are the static properties such as porosity and capillary pressure characteristics. The network model can, therefore, be best tested by comparing the dynamic properties of a network of tubes with the observed properties of porous media. All static and dynamic properties of a completely valid model must agree with the observed properties. The most commonly measured sensitive dynamic properties are the relative fluid permeability and the relative electrical resistivity. Experimental measurements of these dynamic properties on sandstone, sintered glass, sintered alumina, and soil are reported in the petroleum and soil science literature. These properties were chosen, therefore, for the test of the network model. In the network model, relative permeability is the permeability of the network when some of the tubes are not conducting fluid, relative to the permeability when all tubes are conducting fluid. Similarly, the relative resistivity is the electrical resistivity of the network of tubes when some of the tubes are filled with a nonconductor. relative to the resistivity when all tubes are filled with the electrical conducting fluid. Single Size Tube Network The simplest porous medium is one in which all pores are of the same size. Such media can be approached by packing beds or columns of uniform size particles of sand, glass, or metal. The model of such medium in this study is a network of single size tubes. The network form, the ß factor, is usually not known for real porous media. If the validity of the network model can be established, then the study of the flow properties

Jan 1, 1957

By Charles R. Keyes, D. F. Riddell

For a period of several years, and in a large number of oases, the Metallurgical Laboratories of the New Mexico School of Mines were employed in umpire work. During this time many important local problems mere solved. Against the results of careful chemical analyses of ores, assay-returns mere often checked. In many cases the assay-methods of mine and custom-smelter were compared, and both often found faulty for the ore concerned. A wide range of ores was covered. Many of the chemical analyses and assays were made by Dr. F. C. Lincoln, Professor of Metallurgy, now of the Montana State School of Mines. A varied series of instructive assays was prepared by Prof. R. B. Brinsmade, now of the West Virginia State University. Single assays and given series of tests were undertaken by H. T. Goodjohn, now chief chemist to the Cia. Metalurgica de Torreon, Coahuila, Mexico; by H. J. Hub-bard, now superintendent of the Butters Divisadero Mines, Jocoro, San Salvador, C. A.; by E. D. Morton, now superintendent of the Arizona & Nevada Copper Mining Co., at Lunning, Nev.; and by A. W. Edelen, now superintendent of the Angangueo Unit of the American Smelting & Refining Co., in Michoacan, Mexico. A critical comparison of assay-methods that were found to be followed in the case of certain gouge-ores mined in the Mimbres range in New Mexico, and about which there had been much controversy, was made by D. F. Riddell, then Acting Professor of Assaying, and now superintendent of the Providentia Mines Co. of Parral, in Chihuahua, Mexico. To him is due the credit of much that is contained in the following notes, which he has generously permitted to be used in advance of the publication of the complete results.

Jan 1, 1912

The discovery of nickel at the Wallace Mine in 1846, recorded in the Report of Progress of the Geological Survey of Canada, 1.848-49, was not the first find in the Sudbury mining district. As long ago as 1770 a company had been formed to work the rich deposits of, copper whose existence was then known. .But it was during the first mentioned year that, incited thereto by fresh finds and a favorable report by Mr. W. E. Logan, then Provincial Geologist, two [ ] groups of Canadians organized "The Montreal Mining Company and "The Upper Canada Mining Company." By the former company the Bruce Mines Location' was purchased and work was immediately commenced upon it. The Wallace Mine acquired by the Upper Canada Mining Company, was abandoned after a shaft had been sunk and a few test pits opened.

Jan 1, 1907

By H. S. McQueen

THE central Ozark region of Missouri has inter-ested geologists and mining engineers for many years. Of particular interest are the mineralized sink-hole type deposits, some of which have produced large quantities of iron ore. Deposits of coal are also known in this part of the State, and in mode of occur-rence are similar to the iron ore deposits. Occurring in the same general area, and often associated with coal, are deposits of high-grade non-plastic flint fire clay, and high alumina or diaspore clay. At present these clays are the most important materials being mined from the sink-hole type deposits. Deposits of high-grade flint fire clay have been known to occur in this region for many years, the Kelley pit near Rolla, Phelps County, being discovered in drilling for iron ore shortly after the close of the Civil War. Mining operations had disclosed at an early date masses of rough, open-textured "sandy" clay associated with the flint fire clay. Some of the hard flint clay also con-tained rounded shot-like particles of "sand." Both types of clay were considered of inferior grade and unsuited to the manufacture of fire brick. These clays were discarded in mining as value-less, in some instances being used for road metal. Some knowledge of the high alumina content of this sandy material had been obtained by 1908 1, and by 1917 the high alumina content was gen- erally known, and commercial shipments of what is now called diaspore clay were being made. These deposits of diaspore clay associated with flint fire clay form the only known deposits of commercial importance in North America. The production of diaspore and flint fire clay at present exceeds that of any former year. Statistics covering the production and value of the former were not collected prior to 1922, and the figures given below do not cover the tonnage of clay mined by companies and used in their own plants, so that the total produc-tion probably is much larger than that indicated. The figures were collected by the U. S. Geological Survey and the U. S. Bureau of Mines in cooperation with the Missouri Bureau of Geology and Mines.

Jan 6, 1928

By Charles R. Keyes

Discussion of the paper of Charles R. Keyes, Bi-Monthly Bulletin, No. 19, January, 1908, pp. 1 to 31. BERNARD MACDONALD, Guanajuato, Mexico (communication to the Secretary*) :-Mr. Keyes's paper is very interesting to me because of my personal experience with the development of the ore-deposits of Lake Valley. Seeing that many of the important facts connected with the early history of the development of these mines are either now unknown, or have become more or less distorted, and thinking that it would be interesting as well as valuable to have these recorded as a historical supplement to Mr. Keyes's elaborate paper, I present the following narrative: In February, 1881, soon after the Atchison, Topeka & Santa Fé railroad made connection with the Southern Pacific at Denting, N. M., the Lake Valley properties were brought to the attention of New York and Philadelphia capitalists by John A. Miller, of Silver City, N. M. At that time silver was $1.10 all ounce and silver-mining was very attractive. Vast fortunes were being made in Leadville and other Colorado camps, and Tombstone was pouring out its millions. Lake Valley, like all' other mining-camps in their early history, had its drawbacks, but the railroad, then passing within 14 miles of it, mitigated many of these. The camp lay in the foot-hills of the Black range, in which the Apaches had their stronghold, and raided, when it suited their convenience, the surrounding country, killing the prospectors and pioneer settlers and stealing their cattle. This band of Indians was joined by the outlaws and desperadoes from the frontiers of Texas, Arizona, and Mexico, who collectively defied the United States soldiers, restrained, as the latter were, by the mollycoddles from the East. The brutality of the Indian raids through Arizona and New Mexico in those days would scarcely be believed now, but they stain in deep

Feb 1, 1909

By Morris Muskat, James M. McDowell

A report is given of electrical analog experiments on the effect of casing perforation completions on well productivity for ideal uniform reservoirs under steady state homogeneous fluid flow conditions. Graphical results are presented for the effect of perforations of different densities and various degrees of penetration into the formation surrounding the casing or cement sheath. The latter range from perforations which terminate flush with the casing to those which extend into the formation a distance equal to the casing diameter. For the special case where the perforations terminate immediately beyond the casing with semi-spherical protrusions the electrical analog results correct and supersede previously reported theoretical calculations. It is found that the penetration of the perforations into the surrounding productive section may so increase the resultant productivity as to approach or even exceed that for open hole completions. INTRODUCTION A theoretical analysis of the effect of casing perforation on well completion, without additional penetration of the formation, was reported several years ago.' In this treatment the perforations were represented by mathematical sinks and no explicit account was taken of the imperviousness to flow of the casing in which the perforations were made. This procedure was justified by consideration of the mutual interference between the sinks, which seemed to indicate that the analytical method automatically eliminated flow across the casing radius between the perforations. However, both further theoretical investigation and the electrical analog measurements described below showed that this assumption in the previously developed theory was not valid and that the calculated well capacities would considerably exceed the correct values. § Even if this simplifying assumption were retained the generalization of the theory to situations where the perforations extend into the producing formation would be extremely difficult. On the other hand, the electrolytic model analog of this type of steady-state homogenous fluid system is, in principle, so simple that it has not been worthwhile to attempt to develop the exact analysis even for the more limited case of strict casing perforation. The whole problem has therefore been studied anew by electrical models to cover the range from holes in the casing which terminate flush with the casing surface to such as extend into the surrounding rock to a depth equal to the casing diameter. It is to be expected that the productivity of a well completed with casing radius* rw, perforated with holes of radius Tp, and extending to depths d into the surrounding rock, would depend primarily on the dimensionless geometrical parameters Te Tw TP d of the system, such as —, —, — , and —, where re is the Tw, a a rw external boundary radius and a is the mean vertical separation between the perforations. It will also depend, of course, on the number of perforation lines or total perforation density. While such parameters automatically control analytical treatments, it would require a very extensive series of model experiments to fully disclose their functional effect on the well productivity. For practical purposes, however, a rather limited range of the variables suffices to give the effects of interest. Accordingly, in the experimental study reported here the casing diameter has been kept fixed? at six in., the perforation diameter has been taken as either one-fourth in. or one-half in., their density has been varied from one to eight per ft, and their penetration into the formation has ranged from zero to six in., with a primary scaling factor of one to six. EXPERIMENTAL METHOD AND RESEARCH Although electrolytic model experiments have been made for years, there still seems to be some question as to what set of conditions will give the best results. For this reason a number of electrode materials and electrolytes were tried. Those chosen for the final experiments were copper electrodes and a weak copper sulphate solution as the electrolyte. This 'Assuming that the casing has been cemented with a uniform and impermeable cement sheath, the effective casing radius is to be interpreted as the external radius of the cement annulus. It is also assumed here that the casing is set through the complete producing section that it is perforated throughout with a uniform density and that tie formation has a a and isotropic permeability. As noted later, however, a uniform scale change permits reinterpreting the primary measurements to correspond to a casing diameter of 12 in.

Jan 1, 1950

By A.J. PHILLIPS, Wm. B. Price

ADMIRALTY nickel is a new corrosion-resisting and heat-resisting white metal alloy composed of 70 per cent. copper, 29 per cent. nickel and 1 per cent. tin. It has been given the trade name "Adnic." In 1924, Win. B. Price1 described this alloy and its successful use as a diaphragm metal. The physical properties of Adnic at ordinary and elevated temperatures were given in Mining & Metallury.2 A patent3 was granted on Adnic, April 28, 1925. Work was first started on this alloy during December, 1921. An investigation of the patent situation in this country and abroad, and also a search of the literature, did not reveal any work on the ternary diagram, copper-nickel-tin; and the only wrought copper-nickel-tin alloy found was that known as "Newloy," composed of copper, 64 per cent.; nickel, 35 per cent.; tin, 1 per cent. This was being manufactured and sold by Wm.. Gallimore & Sons, Ltd., Sheffield, England, for unplated spoon and fork stock, and first came to our attention in January, 1922. The preliminary work in connection with the development of Adnic was started by casting four, binary copper-nickel alloys of the compositions shown in Table 1. Various amounts of tin were added to each of these mixtures, to produce the series of ternary copper-nickel-tin alloys also given in Table 1. A 200-gm. sample of each of these was cast by melting in a clay graphite crucible and allowing the melt to slowly cool with the furnace. A longitudinal section from each of these castings was polished and etched for-examination. The castings were not homogeneous solid solutions, but showed the usual cored structure associated with cast alloys. However, from an examination of these sections we roughly determined

Jan 1, 1928

By F. Forward, H. Veltman, A. Vizsolyi

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963

By J. H. Frye, J. W. Caum

One of the most important methods of increasing the hardness of metals is alloying. In spite of the widespread use of alloys, the fundamental mechanism of alloy hardening is little understood. This is true even of the simplest form of alloy, the primary substitutional solid solution in which solute atoms substitute for solvent atoms at random in the crystal lattice of the latter. A fundamental understanding of the mechanism of solid-solution hardening would be important, both because of the widespread use of alloys of this type and because of the light that might be thrown on the mechanism of hardening in more complicated alloys. The present investigation covers the hardness of primary substitutional solid solutions of zinc, gallium, germanium, and arsenic in copper. All of these are B subgroup elements from the third period of the periodic table. Cu, Zn, Ga, Ge, and As are in groups I, 11, 111, IV, and V, respectively, and lie just to the right of the transition elements. Because of their cost, it is unlikely that Ga-Cu and Ge-Cu solutions will ever be of commercial importance, but the intent of this study has been to discover some of the fundamentals of solid-sdstion hardening and it has been demonstrated that such a study is far more likely to be fruitful if alloys are made up on the basis of position of the constituent elements in the periodic table than if commercially important alloys are used. Many investigations have been made of the hardness of substitutional solid solutions, but lack of attention to purity of the metals, infrequent grain-size control, and the use of varying testing techniques have virtually invalidated any comparisons. The purpose of most investigations has been to solve immediate problems and not to solve the primary problem: Why do solid solutions usually have a greater hardness than pure metals? Previous Work Theories have been advanced to account for the hardness of solid solutions, but relatively little experimental work has been done. Perhaps the first experimental work of merit was that of Norbury1 on copper alloys. He showed that for several alloys there was a correspondence between the hardness of one atomic per cent solutions and atomic volume of the solutions. More recently Brick, Martin, and Anger2 have investigated the effect of various solute elements on the hardness of copper. They concluded that the hardening effect of these solutes depended "primarily on the difference in atomic volume of solute and solvent or, relatedly, upon the parameter change of the solvent or the extent of solid solubility." They also observed the effect of these elements on hardness and texture developed by rolling and by annealing of rolled material. Austin3 examined the hardness and response to heat-treatment of various iron solid solutions. Frye and Hume-Rothery4 measured the hardness of a number of silver solid solutions containing approximately 1 References are at the end of the paper.

Jan 1, 1943

By J. H. Frye, J. W. Caum

One of the most important methods of increasing the hardness of metals is alloying. In spite of the widespread use of alloys, the fundamental mechanism of alloy hardening is little understood. This is true even of the simplest form of alloy, the primary substitutional solid solution in which solute atoms substitute for solvent atoms at random in the crystal lattice of the latter. A fundamental understanding of the mechanism of solid-solution hardening would be important, both because of the widespread use of alloys of this type and because of the light that might be thrown on the mechanism of hardening in more complicated alloys. The present investigation covers the hardness of primary substitutional solid solutions of zinc, gallium, germanium, and arsenic in copper. All of these are B subgroup elements from the third period of the periodic table. Cu, Zn, Ga, Ge, and As are in groups I, 11, 111, IV, and V, respectively, and lie just to the right of the transition elements. Because of their cost, it is unlikely that Ga-Cu and Ge-Cu solutions will ever be of commercial importance, but the intent of this study has been to discover some of the fundamentals of solid-sdstion hardening and it has been demonstrated that such a study is far more likely to be fruitful if alloys are made up on the basis of position of the constituent elements in the periodic table than if commercially important alloys are used. Many investigations have been made of the hardness of substitutional solid solutions, but lack of attention to purity of the metals, infrequent grain-size control, and the use of varying testing techniques have virtually invalidated any comparisons. The purpose of most investigations has been to solve immediate problems and not to solve the primary problem: Why do solid solutions usually have a greater hardness than pure metals? Previous Work Theories have been advanced to account for the hardness of solid solutions, but relatively little experimental work has been done. Perhaps the first experimental work of merit was that of Norbury1 on copper alloys. He showed that for several alloys there was a correspondence between the hardness of one atomic per cent solutions and atomic volume of the solutions. More recently Brick, Martin, and Anger2 have investigated the effect of various solute elements on the hardness of copper. They concluded that the hardening effect of these solutes depended "primarily on the difference in atomic volume of solute and solvent or, relatedly, upon the parameter change of the solvent or the extent of solid solubility." They also observed the effect of these elements on hardness and texture developed by rolling and by annealing of rolled material. Austin3 examined the hardness and response to heat-treatment of various iron solid solutions. Frye and Hume-Rothery4 measured the hardness of a number of silver solid solutions containing approximately 1 References are at the end of the paper.

Jan 1, 1943

By Arthur Knapp

The law of supply and demand is, in general terms, that law which governs the price of any commodity in an unrestricted competitive market. There are several variables which, for the purpose of this discussion, will be defined only as they apply to the petroleum industry: Production: The volume of petroleum that is moved from leases. Stocks: The volume of petroleum that is in the hands of the tank farm and pipeline companies. Inventory: The value of the stocks at the market. Consumption: The indicated delivery of oil to others than those who hold stocks. Demand: The potential absorbing power of the consuming market. Demand is the expression of the needs of the consumer and may depend on the economic value of the oil to the consumer. In times of low prices, the demand is the same as the consumption but during periods of high prices or deficiency in supply, the demand may be greater than consumption. A general expression of the law is as follows: production or consumption Some relation between stocks and or controls price or demand inventory The Law as Applied to Crude-oil Market The above general expression of the law shows that there are six relations between variables that must be investigated in any attempt to establish the exact status of price control at any time. Production vs. Consumption If stocks of crude oil were very low, so that the flow of oil to the market was directly from the producer to the consumer and not, in a large measure, through stocks, some relation between production and consumption would be proportional to price changes. We have no criterion whereby we can tell, at present, what volume of stocks and production

Jan 1, 1924

By Walter W. Bradley, OLAF P. JENKINS

IN April of this year the California State Division of Mines (formerly known as the State Mining Bureau) observed its 50th anniversary. The Division serves as a bureau of information and, an encyclopaedia of California's economic minerals. Its primary function is to make economic surveys of the mineral resources of California, their development and utilization. Geological studies also constitute a related part of the work as being necessary in tracing and out- lining ore deposits and the most likely areas in which to find them. The results of the Bureau's data-gathering are published in the form of annual reports of the State Mineralogist, and in bulletins on specific substances. The Division is just completing a series of reports on the mineral resources of the State arranged by counties.. It is now starting .a new series of reports arranged according to substances particularly the so-called non- metallic commercial groups. Of these the following are now available: clays, barite, and mineral paint. These will be followed by reports on feldspar and silica, diatomaceous earth, limestone and others

Jan 1, 1930