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By L. S. Darken

A quadratic formalism is developed lor the representation of the excess free energy, and of the activity coefficients of each component of a ternary system in the vicinity of a single component selected as solvent. This formalism, in contrast to the e formalism, is thermodynamically consistent at .finite concentrations. Numerous specific systems are used as illustrations, with cross checks where possible; these systems are Fe-C-X systems in the vicinity of 1600°C and include practically all those for which reliable data are available. It is shown that this formalism is usually quite adequate to rebresent available data up to a solute concentration of 20 to 30 at. pet. It is hoped that the formalism here presented may prove useful for the treatment and tabulation of data on ternary and multi-component solutions. SINCE, as discussed in a prior paper,' we do not as yet have an adequate basic understanding of the nature of binary metallic solutions, we cannot hope to be in better position for ternary and multicomponent systems. However, the accumulation of thermodynamic data on ternary and multicomponent metallic solutions has led to an urgent need for a rational formalism for the presentation and use of such data. Notable attempts to represent the isothermal isobaric thermodynamics of ternary solutions were made by Benedict et 01.' and by Wohl.3 These attempts were directed toward developing an analytic expression adequate to encompass the entire ternary triangle, primarily for organic systems; they generally involve the power-series approach, which has been shown' to be inappropriate, in general, even for binary metallic systems. On the other hand, interest in the thermodynamics of ternary and multicomponent metallic solutions has tended to focus either on general thermodynamic relations4-10 over wide compositional ranges, or on cases where one or more components have been at rather low concentration. This latter approach has been followed by Wagner,= by chipman,11 and by Alcock and Richardson,12 and more recently in many publications by the same and other authors. It has already been shown' that the thermodynamic behavior of binary metallic systems is, in general, relatively simple only in the terminal regions. Hence, it would appear that any approach, at this time, to a simple formalism for ternary and multicomponent systems must, a fortiori, be limited to the vicinity of the major component or solvent. The present treatment is aimed to be useful for a given solvent with moderate solute concentrations ranging up to 20 or 25 at. pet and in exceptional cases to considerably higher concentrations. In order to achieve even this modest objective, it is necessary that any appropriate formalism have built into it 1) a thermodynamic consistency (at least within the desired degree of approximation), and 2) an approach at infinite dilution to Raoult's law for the solvent and to Henry's law for each solute. Let us first formulate the condition of thermodynamic consistency for a ternary system. Under isothermal isobaric conditions, we may write for the molal value G of any extensive function dG - C1 dN1 + G2 dN2 + G3 dN3 [l] where the G's are the corresponding partial molal quantities and the N's are the atom fractions. Taking component 1 as the solvent, this relation may be rewritten in terms of the independent variables N2 and N3

Jan 1, 1968

By Wayne L. Worrell

Thermodynamic data for the stable carbides and oxides of chromium, molybdenum, and tungsten have been critically eualuuted and are used to determine the stable condensed phases at 1 atm total pressure in each metal-carbon-oxygen system. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures neces.see)*y to oblain these metals by corbolhermic redlrction under reduced pressures. USING recently reported data for the carbides and oxides of chromium, molybdenum, and tungsten, the stable phases in the Group VI metal-carbon-oxygen systems at specific temperatures and pressures can be determined. The thermodynamically stable regions in each metal-carbon-oxygen system can be completely pictured using a Pourbaix-Ellingham diagram in which the two coordinates are oxygen potential (-RT In Po2) and temperature. Worrell and chipman' have described and constructed such diagrams for the metal-carbon-oxygen systems of vanadium, columbium, and tantalum. Downing2 has used similar diagrams to provide a description of the reactions in submerged arc furnaces. One of the examples which he cited was the Cr-C-O system; however, an improved diagram is presented in this paper using recently obtained data for the carbides of chromium. Although some of the oxides and carbides of the Group VI metals exist over slight ranges of composition,3 all solid phases are represented as stoi-chiometric compounds in the subsequent diagrams. Any error introduced into the calculated equilibria by neglecting the compositional variation of these phases is less than the uncertainty in the thermodynamic data. In a Pourbaix-Ellingham diagram for a three-component system, the phase rule requires that at equilibrium four condensed phases specify a point, three condensed phases determine a line, and two condensed phases define an area. To obtain a well-defined area at high oxygen potentials and teniperatures, the initial carbon to oxygen mole ratio is specified to be more than sufficient to reduce the oxide but not enough to convert all the metal to carbide. Thus, the lowest regions in the subse- quent Pourbaix-Ellingham diagrams represent areas in which the metal and its carbide are the stable condensed phases. Cr-C-O SYSTEM A) Thermodynamic Data. To simplify the subsequent calculations, all thermodynamic data are presented in the form of linear Gibbs-energy-of-formation* equations which were derived for the temperature range 505° to 2000°K and are reasonably accurate over the entire temperature ranges of the diagrams. The thermodynamic data for the compounds occurring in the Cr-C-O system are summarized in Table I. Several volatile chromium oxides have been reported,4 but their influence is negligible in the Cr-C-O system. Thermodynamic data for CO and CO2 were taken from the compilation of Coughlin.5 The only solid chromium oxide sufficiently stable to exist below 1800°K in the Cr-C-O system is Cr2Os.11 The Gibbs-energy-of-formation equation for Cr2O3 was obtained by revising the data tabulated in Coughlin,5 using the heat of formation of ah' and the high-temperature thermal data for chromium.7 In 1953 Richardson8 re-evaluated the original work of Kelley and coworkers,9 who measured the thermodynamic properties of the chromium carbides. However, the high-temperature equilibrium results of Boericke9 yield values for ?G°f of Cr2O3 which are 2 kcal more positive than the accepted data. His results for the chromium carbides are based on the same questionable equilibria. Gleiser10 recently determined the Gibbs energy of formation of Cr3C2 and the equation in Table I was calculated from her data and the thermal data of Kelley and coworkers.9 Thermodynamic data for the Cr7C3 and Cr23C6 carbides were obtained by combining the Cr3C2 data

Jan 1, 1965

By R. L. Bleifuss

The object of this study was to evaluate the oxidized taconites of the western Mesabi iron range and to establish a correlation between the various basic taconite types and their concentratability. The initial work included a study of the original mineralogical and stratigraphic facies of the fresh taconite and traced the oxidation and leaching patterns developed during the conversion of this material to oxidized taconite. Subsequent studies have extended this work to include the semitaconites and also the wash and heavy media ore types widely developed in the area. Each basic original mineralogical facies or taconite type produces during alteration an equivalent secondary oxidized facies which has a unique mineralogical composition and texture. These control the concentratability of the oxidized taconites. Actually the influence of the original mineralogical composition of the iron formation extends even further and determines whether the most likely product of oxidation and leaching will be a wash ore or a heavy media ore and even to the direct shipping ores where the ratio of hematite to goethite is largely determined by the original taconite type. The relationship between original taconite, oxidized taconite, semitaconites, and wash and heavy media ores is briefly summarized in Table I. The terms are not precise and in some instances tend to overlap. The table is intended to point out only the essential differences between the various materials. The original taconite was dominantly composed of mixtures of magnetite, iron carbonate, iron silicate, and quartz (chert). In a few thin stratigraphic units, hematite was present as an original constituent. The alteration of the original taconite to oxidized taconite has resulted from the circulation of ground waters through an initial fracture system related to minor structures in the iron formation. The chemical reactions have involved the oxidation and decomposition of original minerals such as magnetite, iron carbonate, and iron silicates to hematite or goethite. The alteration at this early stage is characterized by pseudomorphic replacement of the original minerals by oxidation products although retaining the major textural features of the original taconite. There was very little secondary migration of iron at this stage and the total iron content of the rock has been only slightly increased. Further alteration of this material to form a semi-taconite, a wash or a heavy media ore, involves extensive removal of silica in solution and significant redistribution of iron units. Wash and heavy media ores are developed by the growth of coarse secondary iron layers, dominantly goethite, coupled with the removal of silica in solution and decomposition of the cherty layers. This paper is concerned primarily with the materials classified as oxidized taconites which are characterized by oxidation of the original mineral constituents with little secondary enrichment. The area studied, shown on the index map, Fig. 1, extends some 30 miles along the strike of the Biwabik formation roughly from Hibbing to Coleraine. This study was greatly facilitated by the basic stratigraphic and mineralogical studies of Gruner1 and white2. The bulk of the material in this presentation represents a portion of the author's contribution to a study sponsored by the Great Northern Railway on the oxidized taconites of the western Mesabi.3 METHOD OF APPROACH A total of 106 drill holes, representing some 30,000 ft of drilling, were examined and sampled. The drill holes were logged and some 1500 composite samples were prepared for chemical analysis and bench scale metallurgical tests. These samples were analyzed for total iron and ferrous iron; and magnetite iron was determined by a standard Davis tube test at minus 200 mesh. Standard reduction roast tests using 150-gram samples of minus 10 mesh material were made on these 1500 composite samples with a mixture of H2, CO2, N2, and H2O at a temperature of 650°C. This roasted material was pulverized through 150 mesh and concentrated in the Davis tube. The iron recoveries and concentrate grades obtained on the roasted products were used to assess the concentratability of the oxidized taconites. Detailed mineralogical work was done on thin sec-

Jan 1, 1964

DAVID WHITE,* Washington, D. C.-This paper is very timely since the Philippine Islands are presumably open to the enterprise of the American driller, whereas much of the territory in that part of the world is closed to us. The United States has ambitious plans for the operation of a great merchant marine, which is to be oil burning in the main, and it takes but a glance at the world map to see the strategic advantage of oil supplies in the Philippines for such marine operations. It is a little difficult to understand why more attention has not been given to the Philippines, in spite of the difficulties attending development in these islands. A number of American oil companies are, I believe, at the present moment taking an interest in the possibilities of the Philippines. Important factors in the formulation of opinion regarding the importance of the oil deposits of the Philippines, as brought out by Mr. Pratt,1 are the point of view and the breadth of experience of the examining geologist. The average oil geologist, whose experience has been mainly in the Appalachian region, the Mid-continent, or Louisiana, or possibly even in California, on seeing the narrowness of the basins, the closeness of the folding, and the presence of igneous rocks here and there, would be likely to draw unfavorable conclusions as to the possibilities of the Philippine Islands. Geologists visiting that region should be familiar with the geological conditions of oil occurrence in Japan, Formosa, the East Indies, or in the Baku district, and their conclusions should be formulated with the knowledge and understanding of the occurrence of oil in those regions rather than in the United States.

Jan 8, 1920

By Edward I. Salkovitz

THE determination of the orientation of metal single crystals and the studies of plastic deformation are greatly facilitated by the use of the stereographic projection. To draw a standard projection of the crystal it is necessary to have a tabulation of the angles between the various crystal-lographic planes of the particular crystal studied. Bozorth' has published such a table for the cubic system which can be found in many reference books; such convenient tabulation for the hexagonal metals, however, does not appear to be in the literature, although scores of workers have calculated these angles. Therefore, Table I of angles for magnesium, zinc, and cadmium has been compiled. Since the c/a ratio is different for each of these metals, three separate calculations are necessary. The angles 4 between (HKIL) and (hkil) were calculated by means of the formula: Hh+Kk+½(Hk + hK)1+~3aLl cos The c/a ratios were calculated from data given in the 1948 edition of Metals Handbook. Fig. 1 is a typical (0001) standard projection of zinc. For all practical purposes, it serves for cadmium as well, as can be seen from the table. For magnesium, however, it is necessary to construct another net. R. M. Bozorth: Physical Review. (1925) 26, 390.

Jan 1, 1952

By E. C. Truesdale, W. K. Waring

The Research,Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kids of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein' some years ago: ZnO + CO = Zn + CO2 [i] C + COj = 2CO [2] Each of these reactions is dependent upon the other for the supply of CO and COz, respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + He = Zn + HZO 13] C + Hz0 = CO + He U3 While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse Ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction is still the faster. He also says (p. 48), "At temperatures . . . be- -tween 1100' and 1300°C., . . . the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates.'' In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier's statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of ' a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented.*

Jan 1, 1944

By W. A. Backofen, R. L. Fleischer

Single crystal, bicrystal, and polycrystal tensile tests of aluminum at 4.2°K, 77°K, and 300°K have been used to examine the role of grain boundaries in the deformation process. Results indicate that a grain boundary may affect the extent and slope of easy glide. The stage II hardening rate, on the other hand, is independent of the presence or absence of grain boundaries. This conclusion allows the size of the region of multiple slip caused by an incompatible grain boundary to be determined. For the size of bicyystal sample used in this study, multiple slip occurs in about half of the cross section. PREVIOUS studies of the stress-strain characteristics of bicrystals of face-centered-cubic metals have been limited to aluminuml-5 at room temperature. Recent results, however, indicate that the stress-strain curves of single crystals of such metals may be separated into at least three stages6 in which different deformation processes are occurring7 provided testing is done at sufficiently low temperatures.' Since for aluminum a well-defined stage II develops only below room temperature, previous studies have not been able to relate effects of grain boundaries to all of the three stages of deformation. It is therefore to be expected that low-temperature deformation of aluminum single crystals and bicrystals should clarify the effects of grain boundaries on the different processes of deformation. EXPERIMENTAL PROCEDURE Single crystals and bicrystals were grown from the melt by the standard techniqueg with aluminum reported by Alcoa to be 99.993 pct pure. Ridges in the boat were used to guide the grain boundary during growth, assuring that the boundary would bisect the sample.10 The rate of furnace motion during growth was 1.0 cm per hr. During growth zone purification resulted, as evidenced by the ability of the first material to freeze to recrystallize at room temperature following severe deformation. Samples were approximately 4.4 X 6.6 mm in cross section and 103.5 mm in length between grips. Samples were annealed at 635" i 5°C for 40 hr and furnace cooled over a 7-hr period. They were then electropolished in a solution of 5 parts methanol to 1 part perchloric acid at a current density of 15 amp per sq dm for about 30 min at temperatures below 0°C. Tensile testing was performed at 295" (room temperature), 77" (sample in liquid nitrogen), and 4.2"K (sample in liquid helium) on the hard-type machine indicated schematically in Fig. 1. The machine con- sists basically of a tube surrounding a rod; one end of the sample is attached to each member, and the rod is pulled up the tube to extend the sample. The rod is rigidly mounted and is moved vertically by a system described by asinski." The pulling force is measured continuously by an electrical strain gage load cell, and the relative displacement of the tube and rod is also recorded continuously by a soft cantilever beam with electrical strain gages. Maximum stress and strain sensitivities were ±2g per sq mm and * 3-10-5. In all tests the strain rate was approximately 5.10-5 per sec. The thin wires in the tensile apparatus introduce softness, which may be corrected for, however, by measuring load vs displacement with the sample replaced by an elastic member. For loads greater than 15 kg the spring constant is 1.875.106 g per cm. The flexible wires also served to reduce substantially the large shearing forces which may arise in the case of grips having horizontal rigidity.'' As in any gripping system, however, bending moments will arise in the course of deformation by single slip. Engineering stress, s = (load)/(original cross-sectional area), and strain, E = (increase in length)/ (original length), are used for stress-strain curves unless otherwise indicated. Tables list resolved shear stress, T=mo and shear strain ? = dm, where m is the usual Schmid resolved shear stress factor for the primary slip system at the start of deformation. The first group of samples to be described forms an isoaxial set, all of the crystals making up the single crystals or bicrystals having the same tensile axis, the orientation of which is indicated by the cross in Fig. 2. For this orientation the primary slip plane and slip direction make angles of 45 deg with the tensile axis and the Schmid factor m has its maximum possible value of 0.5. Rotations about the tensile axis are indexed by means of an angle 0 between the small-area surface of the samples and the projection of the primary slip direction onto the cross section, as defined in Fig. 3. In single crystals, values of 0 were 0 and 90 deg, while in bicrystals 0 values were (0 deg, 180 deg), (90 deg, 270 deg), and (0 deg, 90 deg) as indicated in Fig. 4.

Jan 1, 1961

By R. T. Bayliss

Although every mill-man of even limited experience in the amalgamation of gold-ores is probably aware that copper plates will in time become coated by the accumulation of gold-amalgam, it may be that many do not know to what extent this accumulation occurs in the treatment of ores dissimilar to those with which they are familiar, and under conditions foreign to those with which they have to contend in any given locality. The writer, therefore, feels relieved from the necessity of offering an apology for dealing with such an elementary subject, believing that certain facts in reference thereto, which have recently come under his personal observation, will be interesting to many, and possibly instructive to some persons engaged in the amalgamation of gold-ores. The facts hereinafter stated were observed in the 50-stamp "combination"-mill, owned by the Montana Mining Company, Limited, of England, operating the Drum Lummon mine, situated at Marysville, Montana. The material treated in this mill consists of quartz and ores of somewhat variable character, containing gold and silver in native form, as well as in chemical union with the sulphides of iron and copper. There is also present a little lead, some arsenic and antimony, and a little zinc. The last fair minerals, however, are of irregular occurrence, and but sparingly distributed throughout the ore, and yield only a trace in the analysis of the average material in this mill. The free gold, which is in a condition of fine division, and rarely visible to the naked eye, carries silver as an alloy; and the native silver, which is only occasionally observed, is present in the richer ores in wireand in leaf-form. Of the two precious metals, the ore worked during the past three years and ten months, the period under review, contained about 1/2-ounce of gold, and from 7 to 12 ounces of silver, per ton of 2000 pounds.

Jan 1, 1897

By G. H. Kennedy, H. E. Criner

CYCLONE thickeners are "hydraulic centrifuges" designed either to produce a maximum practical separation between the water and solids of a feed slurry or to classify the slurry solids according to particle settling rate. The possibilities of utilizing the thickener to "close" plant water circuits have been investigated. Since the thickener becomes an integral part of the plant water circuit when installed, the basic means by which the solids content of all circulating water systems must be controlled is reviewed. All coal not separated from the circulating water by means of dewatering screens or settling devices must be bled from the plant at the same rate as they are being fed or created by degradation. If this were not true, the circulated volume would finally be completely filled with solids. If the rate of bleed is low, the solids concentration in the bleed and circulating water generally will be high. To keep a reasonable circulating water concentration, large amounts of fresh water must be supplied and the bleed rate must be high. These conditions are usually undesirable because of the difficulty in securing fresh water, the loss of large quantities of coal, and the pollution of nearby streams. Thickeners are the primary stage in the separation of the water contained in the bleed from the coal. Since a thickener, when operating with reasonable efficiency, usually cannot be expected to deliver an underflow containing less than 50 pct water, secondary dewatering devices such as a slurry screen or vacuum filter must be used to separate additional water from the bleed. The surface area required by the filter or screen will be nearly proportional to the total water which must be handled, and therefore the thickener becomes necessary to hold down the original cost. The water separated from the coal is then returned to the plant circuit to maintain the water balance and thus becomes the source of fresh water. It is not necessary to return clear water to the plant to maintain control of the circulating water concentration. It is only necessary that the bleed dewatering devices remove coal in all sizes at a rate equal to that at which these sizes are entering the circulating water. However, practically speaking, in order to maintain low solids concentration, it is usually necessary that the thickener have good recovery characteristics on bituminous coals in those sizes down to 400-mesh. The thickener can remove the smaller sizes from the closed-circuit system at the "solids in" rate and prevent their "build up" in the circulating water as shown in Fig. 1. With the portion of the feed water going directly to the underflow, comes the very fine solids not concentrated by the cyclone. All the larger solids are removed from the feed and delivered in a concentrated condition at the underflow. To apply thickeners with some reasonable assurance that operating requirements will be met, it is necessary to know the rate at which solids of all sizes must be removed from the circulating water and to know the thickener characteristics. The required removal rate of fine solids not recovered by other dewatering devices may be estimated from the size distribution and tonnage of the plant feed with a reasonable allowance for degradation in the circulating water system. A more reliable estimate may be secured by sampling the plant bleed water during a constant load period.

Jan 1, 1952

By Sir Robert Hadfield

Introduction.-I esteem it a great honor to be asked by this Institute to give them an address chiefly devoted to metallurgy. While it is with great regret that I find myself unable to be present to deliver this in person, I take this opportunity of wishing your society every success in its continued career of usefulness to the metallurgists of the great Republic. To be elected, eight years ago, along with Dr. J. E. Stead, F. R. S., as one of your Honorary Members, was a privilege which I greatly esteemed, for I consider that no society in America has done so much as ours for the advancement of metallurgy. Those who have Served our Society.-Where many have served so well, it is difficult, without appearing to make unavoidable distinctions, to select names from those of your members who have done so much for the cause we have at heart-the advance and progress of metallurgy. As typical, however, and not in any way meant as a complete list, there are among others the following names which in the past and to-day stand out prominently in this science of ferrous metallurgy. With most of those now mentioned I have personally come in contact, or by correspondence in some few cases, and have exchanged views, since I first came over to America 30 years ago. Holley; Jones; Weeks; Andrew Carnegie; Thomas Carnegie; Fritz; Sterry Hunt;. Egleston; Maunsel White and Taylor, who did so much for high-speed tool steel, and helped to revolutionize machine-shop practice; W. J. Taylor; Robert Hunt; Alfred Hunt of Pittsburg, who did so much in the early history of aluminum, and, alas! did. not live to see the wonderful progress which has been made in that particular branch of metallurgical industry; James Douglas; C. B. Dudley; Birkinbine; Howe; Metcalf; Barus; Langley; Raymond; P. H. Dudley; H. H. Campbell; W. R. Webster; E. D. Campbell; Talbot; Spilsbury; Gayley; Dinkey, under whose supervision and responsibility modern armor has been so successfully produced in this country, which the writer can testify from personal knowledge of , test results possesses very high Figure of Merit; Schwab; Kennedy; Wellman; Garrison; Wood; Moldenke; Webster; Swank; Unger; Richards; Sauveur; Strat-

Jan 5, 1914

By Alex Boozenny

The results of potential measurements between 1) a titaniurn electrode in NaCl-TiCl, melts and a graphite-cizlorine reference electrode and 2) a titanium electrode in NaC1-Nu "melts and a graphite-chlorine reference electrode show that the following relationship expresses the equilibrium relationship between the TiCl, and the dissolved metallic sodium concentrations, expressed in mole fraction units, in dilute NaCl welts at 850°C. The results of potential measurenments between a graphite electrode in NaCl-TiCl, melts that were saturated with TiCl, and a graphite-chlorine reference electrode, when combined with the standard free energy data given in literature, gave the following expression for the equilibrium relationship between the TiCl, and TiCl, concentrations, expressed in mole fraction units, in dilute NaCl melts at 850°C. These relationships are for melts in equilibrium with pure titanium. In impure systems, less sodiurn and more TiCI, can be copresent with a given concentration of TiCl,. AFTER 10 years of existence, the titanium metal industry still relies on the original Kroll and the sodium reduction processes for the only important means of converting titanium-bearing ores to titanium metal via production of titanium tetrachloride as an intermediate. Through years of modification and development these two processes have evolved to a point where any further major economic advances in the field of titanium metal production must be achieved through implementation of processes which are distinct departures from simple magnesium or sodium reduction of titanium tetrachloride. Concurrently with the refinement of the Kroll and sodium reduction processes, industries and government have sponsored research and development in the field of producing titanium by electrolysis of oxides,' carbides,' and halides3'4 in fused salt media. However, the incomplete understanding of the physical chemistry of fused salt systems has in many cases hindered the development of promising new titanium production processes to the point where they will have a clear advantage over the processes presently employed. Fortunately the volume of information on fused salt physical and electrochemistry is increasing at an accelerating pace. The first approaches tbward investigating the electrochemical behavior of fused salt systems have been the measurements of equilibrium potentials of metals immersed in melts containing their halides.' Some work on the kinetics of fused salt electrochemical processes has been reported.'09" Some descriptions of the structural composition of fused salt systems are also available. The work described herein is a continuation of the study of metal electrode potentials in fused salts. Specifically, this contribution to the growing store of fused salt chemistry information presents a description of the equilibrium relationships between the concentrations of titanium dichloride, titanium trichloride, and metallic sodium in fused sodium chloride. The investigation of the titanium dichloride-titanium trichloride equilibrium relationships is not completely new. Kellog and Krye and Melgren and opie15 have presented the results of chemical analysis of salts containing titanium chlorides. Flengas and lngrahaml' have published the results of an investigation of these equilibrium relationships obtained by measurement of electrode potentials in a fused NaCl-KC1 mixture. The investigation described herein differed from that of Flengas and Ingraham principally in the use of straight NaCl as the solvent in place of the more costly and more difficult to purify mixture. This investigation was conducted in three parts. First, the equilibrium potentials of titanium in sodium chloride containing known concentrations of titanium dichloride were measured. A graphite-chlorine electrode was employed as reference. Second, the equilibrium potentials of titanium immersed in sodium chloride containing known concentrations of elemental sodium were measured. Third, the equilibrium potentials of graphite immersed in titanium tetrachloride-saturated sodium chloride containing known concentrations of titanium trichloride were measured. The results of these three related investigations are presented in the above order. The results are combined with the thermodynamic properties of titanium chlorides and sodium chloride, obtained from literature, to give the titanium dichloride-titanium trichloride-elemental sodium equilibrium concentration relationships. In the test, whenever a melt contains titanium chlorides in predominantly divalent form, the melt

Jan 1, 1962

With one shaft almost completed and another shaft being sunk, the scope of the Saskatchewan potash area is beginning to come into focus. Some 18 companies have reportedly leased more than four million acres to explore potash possibilities. PCA, farthest along, is located about 15 miles southeast of Saskatoon, and IMC has its project underway near Esterhazy in the eastern edge of the province. U. S. Borax and Chemical Corp. is also reported exploring the area. The field lies in the middle Devonian geological formation which was probed by oil companies along the 200-mile area across the province. Extensive examination began after World War II and deep drilling was started a few years later.

Jan 5, 1958

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

By crystallographic and X-ray methods, the existence and isonzorphism of Ti3Rh5 and Hf3Rhs were confirmed. Both phases are of the orthorhombic Ge3Rh5 type; lattice parameters and refined positional parameters are given. The structure is related both to the filled-up NiAs-B8 and Cu-AI types. An analogous phase with zirconium does not exist; the effect of ternary substitutions for titanium ad hafnium suggests a size factor limit to be active. A recent survey of phase diagrams of the T4 metals titanium, zirconium, and hafnium with the T, noble metals rhodium and iridium indicated the existence of the A3B5 phases Ti3Rhs, ZrsRhs, and HfsRhs. Ti3Rhs and Hf3Rh5 were found to be isostructural, based on the line-rich powder patterns which had not been analyzed. Zr3Rh5 was considered to have a substructure of the NbRu type (orthorhombically distorted B2-CsCl type).&apos; Because, in combinations with other transition metals, hafnium and zirconium are generally more likely to form isostructural phases than hafnium and titanium (with the significant exception of the Ti2Ni-"E93" type phases based on T4 metals2), the reversal of this relation for the A3B5 phases was of interest. As shown in the following, the nonexistence of Zr3Rhs has been established, the structures of Ti3Rh5 and Hf3Rh5 have been worked out, and crystal chemical relationships and stability criteria are reported. EXPERIMENTAL METHODS AND RESULTS Alloy Preparation and Phase Diagram Work. Alloys were prepared from high-purity (99.99+ pct) elements by arc-meltin3,4.Heat-treated alloys were annealed in a vacuum of 3 x X torr for 24 hr at 1300DC. Metal-lographic samples were etched electrolytically in concentrated HCl with 5 v ac for 5 min.3 X-ray diffraction powder patterns were taken on a GE XRD-5 dif-fractometer with Cum radiation at low scanning rates (0.2 deg per min for 28). It was confirmed that Ti3Rhs and Hf3Rh5 have similar diffraction patterns, and that an alloy with the composition Zr3Rhs has a different pattern. Six Zr-Fh alloys with 59 to 69 at. pct Rh were therefore prepared and investigated in the as-cast state by X-ray diffraction and metallography. Alloys at 59 and 61 at. pct Rh were found to be a single phase, with the distorted B2-CsC1 type structure typical for the off-stoichio- metric region of the phase (Zr,-,Rh,)Rh. This phase forms a eutectic with ZrRhs at about 66 at. pct Rh: accordingly, alloys between 61 and 69 pct at. pct Rh consisted of two phases. There is no evidence for the existence of Zr3Rh5. Based on the results in Rafs. 1 and 5, on the present work on Zr-Rh, and on several additional alloys investigated, the portions between the AB and AB3 stoi-chiometry for Ti-Rh, Zr-Rh, and Hf-Rh are as follows: Further, several ternary alloys near Ti3Rhs and Hf,Rhs were prepared in which it was attempted to replace titanium and hafnium partly by zirconium, niobium, tantalum, and germanium. The results will be discussed in a later section. Structure Determination of Ti3Rh5. Since Ti3Rh5 and Hf3Rh5 are isostructural, the following discussion will largely deal with the former. Although the powder pattern of TisRhs is complex, as found previously,1 it could be indexed by comparison with other structures of A3Bs stoichiometry. Ti3Rh5 was found to be isostructural with Ge3Rh5, whose orthorhombic structure had been elucidated by Geller.9 As both the sizes and atomic numbers of germanium and titanium are comparable, the unit cell volume and the peak intensities could be expected to be similar; however, significant differences exist in the atomic positions, as will be shown. All lines in the powder patterns of Ti3Rh5 and Hf3Rhj could be indexed with primitive orthorhombic unit cells with the lattice constants: The fractional errors are 10 The low-angle portion of the indexed powder pattern of Ti3Rh with sin2 8 < 0.30 is listed in Table I. The extinction laws Okl only with k = 2n and hOl only with h - 2n are compatible with the space group Pbo2 and the more symmetrical space group Phnm of Ge3Rh5. Finally, the positional parameters of Ti3Rh5 and HfsRhs were refined under the assumption that titanium and hafnium occupy the germanium positions in Ge3Rh5. Integrated intensities were obtained from the diffraction patterns by planimetry. Intensities of overlapping reflections were separated by an iteration process incorporated into the least-squares positional refinement program according to a method described previously. The intensities of Ge3Rh5 were used in the first separation cycle, while the atomic parameters of Ge3Rh5 were used as starting values in the first refinement cycle. Absorption due to specimen

Jan 1, 1970

By James F. Kemp

In earlier gears, the custom prevailed of regarding the anthracite basins as cases of folding with slight development of faulting. Folding is so pronounced and, in the eastern and western Middle Fields, at times so violent, that the inference was a natural one and led to the widespread impression that practically all the disturbances of the seams could be explained in this way. The cross-sections and maps prepared forty or more years ago for the Second Geological Survey of P ennsylvania, by Mr. Ashburner under Prof. J. P. Lesley, exhibit little else than folds.&apos; So far as I can discover faults fail in the charts, except in one small case in the Henry colliery near Plainsville on the outskirts of Wilkes-Barre. Some years ago, while spending a day or two in Wilkes-Barr, under the guidance of R. V. Norris, I looked over some recent and accurate cross-sections of a numbcr of the large collieries and was deeply impressed with the peculiar behavior of some of the seams and the intervening shales. Thus, a seam might present a small, more or less overturned fold, rising 30 to 50 ft. (9 to 15m.) above its general course, and yet the movement would be taken up in the overlying shales, so as hardly to be noticeable in the seams next above or below. These and similar anomalies, especially when shown with the accuracy of engineer&apos;s surveys, possess great scientific and practical interest, bearing as they do, not alone on coal mining, but on theoretical geology and the actual behavior of strata under great compressive stresses. In preparation for the semicentennial meeting of the Institute, an effort was therefore made to secure some of the most interesting sections for presentation to the members. The collection of illustrations here shown is mainly due to Douglas Bunting of the local committee, to whom and to the contributing companies acknowledgments are due. The illustrations are taken from all four of the main basins, but are chiefly from the portions nearest Wilkes-Barre. The first are in the

Jan 1, 1922

By E. G. Dean

A method of top slicing has been devised at the Miami Copper Co.&apos;s mine at Miami, Aria., which differs radically in some ways from the customary methods of top slicing. The area of that section of the orebody in which top slicing is used is about 800 ft. square. The ore, while for the most part soft, is, nevertheless, considerably harder than the capping. The latter is siliceous, seldom containing any clay or other binding material, and breaks into fine particles so that it runs like sand if given the opportunity. Because of these facts, and because the ore is above the average grade of the mine ore, it has been mined by top slicing. Haulage levels are opened up 150 ft. apart, vertically, with two sub-levels between at 50-ft. intervals, to facilitate the putting up of ore chutes. These sublevels are used during slicing for distributing air in the ventilation system. On the haulage level the drifts are spaced on 50-ft. centers, and raises along these drifts are also spaced on 50-ft. centers, except the incline raises as hereafter noted. The raises are cribbed where necessary. Where the wear will be excessive, 1/4-in. iron plates are spiked to the top of every third set of cribbing, for its protection. When top slicing was first used, an attempt was made to carry a slicing face from fifty to several hundred feet long. Timber and other supplies were brought in through long drifts from an auxiliary shaft. Great difficulty was experienced in keeping these drifts open, the side pressure breaking the posts and the top weight breaking both caps and posts. Furthermore, the men could not work efficiently while these drifts were being repaired. The slicing faces advanced irregularly, due to varying conditions, and in many ways the results were not all that could be desired. It was then decided to divide the slicing area into blocks 200 ft. square and this was later changed to 250 ft. square. At the center of each block a two-compartment raise is put up as a supply raise, the compartments being 2 ft. 6 in. and 4 ft. by 4 ft. 4 in., the smaller being used as a manway. Station sets of 12 by 12 timber with

Jan 1, 1917

By Marston G. Fleming

E. C. Peterson (Anaconda Copper Mining CO., Darwin, Calif.)—A study of this quite comprehensible and interesting paper by Dr. Fleming brings to mind several observations in the practical application of alkalinity and related factors to the actual practice of lead mineral flotation. Soda ash has long been a widely used and a very helpful alkaline conditioning agent in the flotation of galena from the usual run of lead-zinc ores. Soda ash is one of the common "standard" conditioning agents tried in any laboratory investigation of lead-zinc ores because it has so often proved helpful to galena flotation. However, the use of soda ash in the actual flotation of oxidized lead ores is certainly not widespread. In the flotation of certain lead-zinc ores from the Park City district of Utah, it was found in the usual cyanide-zinc sulphate-xanthate circuit that soda ash had an effect of producing a very condensed and flat froth regardless of the many frothers tried and that substitution of lime for soda ash to produce the same pH (8.0 to 8.4) improved the froth condition. However, the flotation of coarse particles of galena became so critical that some would pass through into the tailing, but caustic soda as a substitute for either soda ash or lime produced a very desirable froth condition in the same pH range and greatly improved the metallurgical outcome. Milling was carried out in typically "hard water" from watersheds of limestone and other calcareous rocks and the ore also apparently contributed magnesium and calcium salts to the pulp. Certain lead-zinc ores of Mexico have shown their greatest flotation response in circuits conditioned with sodium bicarbonate, and such actual mill use was also believed to be related to the water necessarily used in milling. On other lead-zinc ores the optimum has been obtained in actual milling treatment by use of caustic soda in both circuits of the operation. In flotation of oxidized lead ores in which sulphidi-zation is employed by addition of sodium sulphide, very high pH&apos;s exist in the flotation circuit. With the usual oxide lead ores, demanding 5 to 15 lb of sodium sulphide per ton of ore, pH&apos;s in the circuit (closed and open water-circuits) may range from 9.5 to 12, and for ores that contain much anglesite or a high percentage of iron oxide minerals, sodium sulphide consumption may reach as much as 30 lb per ton of ore and the resultant pH will be correspondingly higher. Yet in such flotation treatment employing either xanthate or oil (high-sulphur crude oil or diesel oils) as the collector, satisfactory to excellent grades of concentrate and lead recovery are obtained. Although there have been great studies and accomplishments in the investigations of flotation fundamentals and flotation theory, and although an investigation to determine the effect of all factors entering into the actual plant flotation of sulphide and oxide ores must become very complicated, as Mr. Fleming has mentioned in his caution regarding the drawing of general conclusions for other ores, it seems that it would be of greater interest if the techniques and investigations could, with time, approach the conditions of actual practice and lead the way to improved and more efficient flotation plant performance. Marston G. Fleming (author&apos;s reply)—The gulf between fundamental flotation research and plant operation is, perhaps, less wide than Mr. Peterson suggests. For example, the work described in my paper developed from an extensive investigation of a complex lead-vanadium ore from southwest Africa. This investigation started as a standard ore-testing problem but, at almost every stage, results were obtained which could not be interpreted in terms of previous experience. A program of fundamental research was therefore undertaken and was closely interlocked with the ore testing. This coordinated investigation resulted in a flotation process which has now been proved by two years of successful plant operation, and although the grade and mineralogical constitution of ore as well as smelter requirements have altered more than could have been anticipated, our knowledge of the fundamental character of the problem has made it possible to meet each change in conditions with much more confidence than would have been the case had we neglected this aspect of the investigation.

Jan 1, 1954

By H. D. Wilde

At the Sugarland and Raccoon Bend fields in the Gulf Coast area, all wells are drilled with rotary tools and the casing is always set in cement that is placed by the circulation method. After the cement is set, the rotary mud that fills the hole is not withdrawn or bailed out; consequently, it is not customary to give the cementing job a direct test either by putting pressure on the hole to see whether the cement will hold or by observing whether an effective water shut-off is secured. About three years ago, this company started the practice of coring the cement left in the bottom of the casing and examining the core thus secured. If the core was hard and strong, the cementing job was judged a success but if the core was incoherent, soft, and crumbly, the job was considered a failure. Of course, there were intermediate types of cores and it was not always a simple matter from this examination to decide whether the job was a success or failure. After about two years, a summary of the core examinations that had been made indicated that of cementing jobs made at depths of 1000 ft. or less, 60 per cent.. were failures; of those between 1000 and 2000 ft., 80 per cent. were failures, and of those between 3000 to 6200 ft., 100 per cent. were failures. This sta,rtling table emphasized the need of the study of the conditions under which the wells were cemented and of adopting means to reduce the percentage of failures. In addition to these core tests, two wells gave direct evidence that the cementing jobs were not always successful. In one, a four-year-old well at Goose Creek, the casing was perforated, and when fluid was circulated some of the old cement wss brought to the surface. Most of it was powdery and the few chunks that were brought up were soft and crumbly. The other was a well at Raccoon Bend which during a blow-out brought a number of chalky, soft and crumbly pieces of cement to the surface. Suggested Explanations of Cementing Failures Efforts were made at once to explain the causes of these cementing failures. As all of the cements used were of a high grade and gave

Jan 1, 1930

By W. T. Thom

All engineering education is faced by certain basic problems, three of which seem to have particular present importance in geological engineering training in general, and in respect to training for oil field geo-exploratory work in particular. Problem i The first of these problems has to do with present and future educational objectives and with the numbers and qualities of the men who should be coming out of our geo-exploratory training programs. Before the war we needed ever-increasing numbers of graduates at the Bachelor&apos;s level and a very much smaller number of men who had reached the Doctorate degree. Now, with more difficult, more extensive, and more costly exploratory work; with a rapid expansion of company "staff" activities, and with the initiation of many new research organizations and laboratories; it is clear that men of exceptional ability will be more and more in demand, and that the schools will need to carry a greater proportion of their students through to the Ph.D, degree. Problem 2 Assuming that the mineral industries will need an increasing supply of well-qualified Ph.D.s for future geoexploratory work (staff, line and research), can the schools expect to provide this supply of able Ph.D.s merely by expanding the proportion of B.S. and B.A. majors who go on through to the doctorate stage of training? And the answer is definitely "No"—as the situation stands at present. Most A.B. graduates are years short of the preparations in basic science and elementary engineering prerequisite to effective graduate study in the geoexploratory fields (paleontology ex-cepted), and similarly many of the annual crop of B.S. graduates lack adequate training in English; in ancient and modern history; and in the modern principles of labor and public relations. Indeed, several basic problems of undergraduate curricular organization and integration remain to be solved before most recipients of a Bachelor&apos;s degree will have that sound and broad educational foundation prerequisite to graduate training on a really effective basis. It is for these reasons that we have continued to experiment with our geological engineering program at Princeton, in an endeavor to provide a pilot-plant demonstration of a suitably broad and flexible undergraduate curriculum. Problem 3 But assuming that the schools can and do get undergraduate curricula set up in proper phase and scale to meet needed enrollment quotas for graduate training, what about the most urgent part of our whole mineral-industry educational problem? What about finding and bringing into mineral-industry training those youngsters of superior ability who are, by potential or known inclination, especially well-qualified for geoexploratory work?

Jan 1, 1949

By William Reynolds

This paper deals with the results of a study of the application and development of mining machines for cutting out and removing dirt bands in bituminous coal beds. Face Preparation When one or more dirt bands1 occur in a seam of coal, the problem of elimination of impurities becomes manifest. The degree of completeness to which these impurities arc removed at the face has an important bearing upon labor costs, haulage costs and outside cleaning costs, and often the ash content of the product is markedly affected. Yet, because the present-day miller is paid for the number of tons he loads he often lacks interest in the quality of the coal. To insure a clean product, a system of penalties for dirty coal is enforced, but control of extraneous impurity content in the loaded coal is often inadequate and ineffectual when coal and banded impurity are shot as one. It seems only logical that to reduce the amount of impurities by proper face preparation before the men are permitted to load the coal is the most efficient method of preparation. Many mines with one or more bands of impurities in their seams are able to mine a desirable product with a comparatively small amount of surface preparation. In fact, three companies in West Virginia have recently changed their methods of fact* preparation, with most gratifying results. The first company (in the Kanawha field) after changing its cutting practice with the hope of relieving a sales problem, was rewarded by an approximate 3 per cent drop in ash in the product. Another company, operating in the same field, reduced its ash approximately 4 per cent by a change in cutting practice. The third company (in the Pocahontas field) found the wet washer inadequate in producing a marketable coal, and installed new cutting machines. Three cuts are now being made in each working place, and the results arc so satisfactory that the cleaning plant has been abandoned.

Jan 1, 1938

By William Reynolds

This paper deals with the results of a study of the application and development of mining machines for cutting out and removing dirt bands in bituminous coal beds. Face Preparation When one or more dirt bands1 occur in a seam of coal, the problem of elimination of impurities becomes manifest. The degree of completeness to which these impurities arc removed at the face has an important bearing upon labor costs, haulage costs and outside cleaning costs, and often the ash content of the product is markedly affected. Yet, because the present-day miller is paid for the number of tons he loads he often lacks interest in the quality of the coal. To insure a clean product, a system of penalties for dirty coal is enforced, but control of extraneous impurity content in the loaded coal is often inadequate and ineffectual when coal and banded impurity are shot as one. It seems only logical that to reduce the amount of impurities by proper face preparation before the men are permitted to load the coal is the most efficient method of preparation. Many mines with one or more bands of impurities in their seams are able to mine a desirable product with a comparatively small amount of surface preparation. In fact, three companies in West Virginia have recently changed their methods of fact* preparation, with most gratifying results. The first company (in the Kanawha field) after changing its cutting practice with the hope of relieving a sales problem, was rewarded by an approximate 3 per cent drop in ash in the product. Another company, operating in the same field, reduced its ash approximately 4 per cent by a change in cutting practice. The third company (in the Pocahontas field) found the wet washer inadequate in producing a marketable coal, and installed new cutting machines. Three cuts are now being made in each working place, and the results arc so satisfactory that the cleaning plant has been abandoned.

Jan 1, 1938