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By C. W. Sherman, John Chipman

IN the mathematical statement of the law of mass action, the activity of each substance consumed or produced in a reaction is used to obtain a numerical constant which is characteristic of the equilibrium of that reaction at the given temperature. The activity in many cases is equal to, or proportional to, the concentration. If this is the case, any units denoting concentrations, such as weight percentage or mol fraction, may be substituted in the equilibrium expression. It is even permissible to use mixed units provided only that each unit is that used in defining the activity of the corresponding substance. The indiscriminate use of concentration units in writing equilibrium constants sometimes leads to very erroneous results. On the other hand, what appear to be contradictory results from similar investigations often might be resolved if the activity is the quantity that is used to determine the equilibrium constant for the reaction in question. De-sulphurization serves as an important illustration. Sulphur in lron and Steel The control of the sulphur content of the finished product is one of the oldest and broadest problems in the metallurgy of iron and steel. In general, this control must be exercised through the action of a slag, and for this reason experimental studies of the distribution of sulphur between slag and metal have assumed considerable importance. Under slags of the type found in the basic open-hearth furnace the ratio (% S)/[% S] does not in general exceed about 8. Under blast-furnace conditions, however, de-sulphurization ratios of 50 to 100 are readily obtained, and under laboratory conditions using similar slags, the ratio may be as high as 400. The fact that blast-furnace metal is much more readily desulphurized than is molten steel rests upon two distinct phenomena. The first of these is connected with the slag reaction. In the open-hearth furnace, the equilibrium in the following reaction places a definite limit on the sulphur content of the slag: S + 0-- = 0 + S- - where the symbols underlined indicate elements dissolved in the liquid metal, while slag constituents are represented as ions. The high oxygen content of the open-hearth bath prevents this reaction from proceeding far enough to effect good desul-phurization. In the blast-furnace process, however, the oxygen activity is limited by the presence of carbon in the metal and in the coke bed and the controlling reaction becomes: S_+O- + C_=S- + CO(gas) [2] The second phenomenon which contributes to the easier desulphurization of blast-furnace metal is the effect of high concentrations of other elements. These elements, notably carbon, silicon, and phosphorus, increase the thermodynamic activity of sulphur several fold. As a result of this increase, the escaping tendency of sulphur from the metal phase is increased and its removal facilitated. Previous Studies It becomes, therefore, a matter of importance to determine the effects of various elements upon the activity of sulphur in the melt. The experimental approach to this problem has been made through the equilibrium between sulphur in the melt and gaseous atmospheres containing hydrogen and hydrogen sulphide. The reaction and its equilibrium constant are written as follows: S + H2(gas) =H2S(gas);K1 = -- [3] Pn2 • as where the symbol a, represents the activity of the sulphur in solution in the metal. The understanding of the chemical behavior of sulphur in steel and pig iron rests on a firm knowledge of the binary system Fe-S. A number of studies of the equilibrium have given closely agreeing results from which the activity and free energy of the dissolved sulphur may be found. The recent paper by Sherman, Elvander, and Chipman1 includes a discussion and quantitative comparison of the results of several of the significant researchesr-" on dilute solutions of sulphur in iron. The results of this study indicate that the relationship between the ratio Ph,s/p+ and the percentage of sulphur in solution is not a linear one. This

Jan 1, 1953

By R. F. Mehl, C. S. Barrett, A. H. Geisler

THE studies of the mechanism of precipitation and of the resulting property changes in aluminum-silver alloys1-3 have presented some new concepts of the aging reaction-concepts that may be fundamental in establishing a complete quantitative theory of age-hardening. With both aluminum-copper and aluminum-silver alloys, thin platelike aggregates form parallel to the Widmanstätten planes of precipitation.1,4 These platelets grow in lateral dimensions and in thickness with aging time until they are thick enough to produce an X-ray diffraction line pattern. Their structure is that of a transition lattice which is coherent with the matrix, since the atomic spacings in the matrix and the precipitate are the same on each side of their common interface.2,4 The equilibrium precipitate forms later from and at the expense of the transition lattice. Since age-hardening occurs during the formation and growth of the transition lattice, the major contributor to the hardening no doubt is the stress condition in the matrix resulting from the matrix holding the precipitate in the coherent condition. The development of these stresses also appears to be responsible for an increase in the electrical resistance superimposed on the normal decrease resulting from a change in the concentration of the matrix during aging.3 The two consecutive reactions constituting the aging process are accompanied by characteristic microstructural alterations. The initial precipitation process results in the formation of a Widmanstätten figure, while the later transformation of the transition lattice to the equilibrium lattice is accompanied by a coalescence, in the case of aluminum-copper alloys,5 and by the appearance of light areas at the grain boundaries with aluminum-silver alloys showing a structural rearrangement of matrix and precipitate.3 This latter reaction is similar microscopically to the so-called "discontinuous precipitation." Possibly discontinuous precipitation is a process that often if not always follows true precipitation of a coherent lattice and during which the transformation of the coherent transition lattice to the equilibrium lattice takes place accompanied by matrix recrystallization.3 EXPERIMENTAL PROCEDURE The alloys were made using 99.97 per cent Al or distilled magnesium, with

Jan 1, 1943

By T. F. Kassner

The dissolution kinetics of type 304 stainless steel in the Bi-Sn eutectic alloy have been investigated under the well-defined hydrodynamic conditions produced by the rotating-disc sample geometry. In addition, the mutual solubilities of iron, chromium, nickel, and manganese from 304 stainless steel in the eutectic alloy were determined over the temperature range 450" to 985°C. The convective -diffusion model for mass transport from a rotating disc was used to interpret the experinlental dissolution data. The dissolution process was found to be liquid-diffusion-controlled under specific conditions of temperature and Reynolds number. Liquid penetration into the 304 stainless steel resulted in a reduction of the di,ffusion-controlled mass flux and thus precluded the calculation of the diffusion coeficients of the four components from 304 stainless steel in the Bi-Sn eutectic alloy. The convective-diffusion model for diffusional limitations of electrode reactions and mass transport at the tationssurface of a rotating disc set forth by Levich 1,2 has found wide applicability in the investigation of electrochemical and dissolution phenomena in aqueous systems. Riddiford 3 and Rosner have reviewed the model and also include numerous references on work of this nature. More recently the rotating-disc system has been applied to the investigation of hetereogeneous reactions in liquid-metal systems. Shurygin and Kryuk 5 have measured the dissolution rates of carbon discs in molten Fe-C, Fe-Si, Fe-P, and Fe-Ni alloys. Shurygin and shantarin6 also studied the dissolution kinetics of iron, molybdenum, chromium, and tungsten, and the carbides of chromium and tungsten in Fe-C solutions with a rotating-disc sample geometry. In these systems it was possible to distinguish between diffusion and reaction control mainly through experimental confirmation of the velocity dependence of the dissolution rate predicted by the model. However in the absence of dependable solubility data and the virtual lack of diffusion data in these systems, a quantitative check of the magnitude and the temperature dependence of the rate was not possible. In many instances, estimates of the activation energy for solute diffusion and the diffusion coefficient based upon the experimental dissolution data are not credible. A recent study by this author7 has resulted in a critical test of the model in a liquid-metal system. The solution rates of tantalum discs in liquid tin were measured over a wide range of temperature and velocity conditions. In addition, the solubility and diffusion coefficient of tantalum in liquid tin were determined as a function of temperature. The latter data were used with the model to predict both the magnitude and the temperature dependence of the dissolution flux. In that work it was also deemed necessary to reevaluate the solution to the convective diffusion equation to incorporate the effect of the lower range of Schmidt numbers encountered in liquid-metal systems. Good agreement between the model and the experimental dissolution data in the region of diffusion control was obtained in the Ta-Sn system. The Bi-Sn eutectic alloy is used as a seal between the reactor head and the reactor vessel in the Experimental Breeder Reactor-11. The alloy is fused periodically prior to fuel-handling operations. In that connection, it was necessary to investigate the compatibility of the liquid alloy with the type 304 stainless-steel containment material. The results of a rotating-disc study in this multicomponent system are presented. EXPERIMENTAL METHOD The 5.08-cm-diam discs were machined from 0.317-cm-thick plate. Chemical analysis information for the type 304 SS material is given in Table I. The discs were ground flat on metallographic paper and given a final polish on Linde B abrasive. A thin support rod was threaded into the disc and the region around the threads was fused under an inert gas. The support rod was fitted with a quartz protection tube and then was attached to a supporting shaft which passed through a rotary push-pull vacuum seal. The disc and supporting shafts were dynamically balanced prior to insertion into the furnace tube. The apparatus is shown schematically in Fig. 1. The 58 pct Bi-42 pct Sn eutectic alloy melts were prepared from 99.995 pct pure Bi and Sn by fusing the components in a 7-cm-ID Pyrex crucible. The system in which the melts were made was evacuated to a pressure of 1 x 10-6 Torr and back-filled with purified argon several times before melting the charge. The ingot was reweighed and placed in a slightly larger-diameter Vycor crucible used in the dissolution runs. A run was started by lowering the disc into the liquid

Jan 1, 1968

By P. Crowther, G. J. Lamprecht

The solubilities of silver, zinc, and cerium in liquid sodium, in the temperature ranges 100 to 270°C, 190° to 550°C, and 120" to 460°C, respectively, have been determined. From the solubility data the heat the entropy the partial molal enthalpy of mixing the excess entropy and the partial molal free energy of solution for the systems Nu-Ag and Na-Zn have been calculated. For the system Na-Ce the observed negative is discussed in terms of the solubility of the oxide Ce2O3. In an earlier publication the results obtained in the study of the solubility of tin' in liquid sodium are presented, as well as the detailed analytical procedures used. 1) REAGENTS Spectroscopically pure metals as supplied by Johnson Matthey and Co, were used to produce the following tracers: 253-day Ag110, 245-day zn65, and 325-day ce141. The tracers were prepared by irradiation in a thermal neutron flux of 4 x 10 13 neutrons cm-2 sek-1. To obtain a uniform amount of the required specific activity, needed for each solubility experiment, the radioactive metal was diluted with the corresponding inactive metal, by melting them together in an inert atmosphere. The liquid sodium used contained 11 ±2 ppm of O,1 determined by the vacuum distillation method.' The oxygen was assumed to be present as the oxide NaD. 2) THE SYSTEMS: SODIUM-SILVER AND SODIUM-ZINC Plots were made of the log of the mole fraction of silver, Fig. 1, and of zinc, Fig. 2, dissolved in the liquid sodium vs reciprocal absolute temperature. The equations for the solubilities, based on the least-squares fit to each plot, are: where Xi is the mole fraction metal dissolved in sodium, T is the absolute temperature, and s is the standard deviation in the value of log Xi. The heats and the entropies lution were calculated from the solubility data by In neither of the two cases was any intermetallic compound formed between sodium and the solute metal as was the case for tin.' Thus, for the silver and zinc systems the pure metal was taken as the reference phase. Since the solids in equilibrium with the liquid sodium were the pure metals, one can calculate the partial molal enthalpy of mixing and

Jan 1, 1969

By James Douglas

IN discussing the waste upon which hinges, or is supposed to hinge, so largely the preservation of our national resources, the conclusions reached would be more reliable if actual ex¬perience were consulted, and fewer deductions were drawn from general statements, which are often the product of the imagination. It cannot be questioned that the value of by-products has not been sufficiently appreciated by us, and that our, tardiness in recovering the useful ingredients of the escaping gas of our coke-ovens is one of the most glaring instances of shortcoming in that direction. And yet even for that sin there is some palliation in the immature condition of affiliated industries. I presume that it is admitted, without argument, that, except under very exceptional conditions, all the elements cannot be recovered from most of the ores or natural products. which we treat. While it is a shame that the by-products from our coke-ovens should be dissipated, Edward W. Parker's report to the U. S. Geological Survey for 1906' supplies a fairly good excuse in justification of this appalling waste. He says (pp. 773 to 774.)

May 1, 1909

By F. W. Luersson

High carbon, low phosphorus steel can now be made from pig iron containing 0.7 pct P or more, in a commercial sized open hearth furnace. No external heat is required for refining, and steel produced is identical with basic open hearth steel. THE classical Thomas process, which requires liquid pig iron containing over 11/2 pct P, yields a product relatively high in phosphorzs and nitrogen. Unless large quantities of recarburizers are added to the refined steel, the product is low in carbon content. Thus, the Thomas process is not well suited to American raw materials, and its product is often not acceptable according to the standards set by American industry. The shortcomings of the Thomas process have long been recognized; with the advent of low cost oxygen, studies were initiated to develop pneumatic processes which would conceivably overcome the inherent objections to Thomas steelmaking. Several such modified basic pneumatic processes have been tested experimentally in commercial trials during the past decade. Probably the most widely publicized of these developments has been the oxygen converter process as practiced in Austrial,2 and in Canada.8 n this process, oxygen is substituted for air and introduced above the liquid bath in order to increase the heat available to the metallurgical system. This avoids the need for high phosphorus raw materials and gives a product low in nitrogen. In this process, the phosphorus content in the final product depends, to a considerable extent, on the total amount of that element in the burden. The rotary furnace4 which is now in commercial operation at Domnarvet Steelworks, Sweden, is producing low phosphorus steel from iron containing 1.8 to 2 pct P. One or more early slags are removed and by this means high carbon steels of open hearth quality can be produced. At this stage of development there is some question as to the applicability of the rotary process to large heats. Another development has been the use of oxygen in combination with either steam6 or carbon dioxide yn the basic bessemer, thus avoiding the introduction of nitrogen gas into the refining system and giving a product relatively low in nitrogen content. A double slag process has been used in Europe7 in conjunction with a regular Thomas converter, by means of which it is possible to obtain a phosphorus content in the product approaching that obtained in basic open hearth steels. The Turbo-Hearth process:' which uses the side blowing principle so as to produce low nitrogen steel from normal American pig irons, has been developed experimentally in this country. A process fitted to U. S. raw materials All of the preceding processes, with the exception of the rotary furnace, suffer from the common shortcoming that they cannot be adapted to the production of high-carbon, low-phosphorus steels unless large proportions of recarburizers are added. In 1947, a program was initiated by the Inland Steel Company1' to study an oxygen steelmaking process specifically designed to utilize the full range of phosphorus analyses encountered in American pig irons and to give finai products with phosphorus and nitrogen contents comparable to steel produced by the basic open hearth process. Some of the objectives of the proposed process are: 1) the process should be able to accommodate molten pig iron conta;rl;rrg up to 1 pct P., 2) sne process should be subject to close control of carbon analysis, 3) the process should be capable of producing high carbon

Jan 1, 1958

By Walter Crafts, D. C. Hilty

The liquidus diagram for the iron field of the Fe-S-O system has been derived experimentally. The solubility of oxygen in molten Fe-S alloys has been measured at several temperatures and found first to decrease slightly and then increase rapidly with increasing sulphur content. IT is well-known that the types, distribution, and amount of inclusions in any given steel are closely allied with the oxygen and sulphur contents of the metal, so that the term "deoxidation" as conventionally applied in steelmaking refers not only to the control of oxygen and oxide inclusions but to collateral modification of sulphide inclusions as well. Inclusions commonly occur in steel as mixtures of oxides and sulphides, sometimes closely associated and sometimes apparently completely divorced. Their effects on the properties of the metal may vary widely depending on their types and distribution as well as on their quantity. The mechanism by which inclusions form, however, and the means for controlling it are exceedingly complex and not well understood. Nevertheless, as described by Benedicts and Lofquist' and by Wentrup' all oxide and sulphide inclusions, excluding mechanically entrained matter, must result from specific modifications of the basic equilibria of the Fe-S-O system. In an investigation of the mechanism of deoxidation and inclusion formation being carried out at the Union Carbide and Carbon Research Laboratories, it became evident that quantitative data for the fundamental Fe-S-O system were essential to a better understanding of the problem. Consequently, the liquidus surface of the portion of the Fe-S-O diagram of interest in steelmaking has been determined, and the solubility of oxygen in liquid iron containing sulphur has been measured. Fe-S-O Diagram The portion of the Fe-S-O diagram of specific interest in steelmaking is the Fe-FeS-FeO corner. Of the contiguous binary diagrams for this partial system, only those for Fe-FeO and Fe-FeS are known with reasonable certainty.3 Several attempts to derive the FeO-FeS diagram have been made, chief among them being the work of Giani as reported by Oberhoffer,4 and, more recently, that of Vogel and Fulling." Although both Giani and Vogel and Fulling published diagrams for the FeO-FeS system, their observations indicated that the oxide component approximated Fe3O4 rather than FeO, so that there is doubt whether the system is truly binary. Benedicts and Lofquist and also Wentrup published qualitative sketches of the ternary diagram based on the assumption that it was of the type described by Marsh for a ternary system in which two of the contiguous binary systems are simple eutectic systems and the third exhibits a solubility gap in the liquid. Apparently, however, the only previous effort to establish the diagram experimentally was that of Vogel and Fülling whose results are reproduced in Fig. 1. Although defining approximately the limits of the miscibility gap and the location of the ternary eutectic, point E in Fig. I, Vogel and Fülling's diagram must be considered only semiquantitative. It was derived from a limited number of observations mainly along two quasi-binary sections, and the directions of the tie-lines and the location of the critical point, K in Fig. 1, were estimated by computation. Experimental Procedure The experimental technique employed for the present investigation involved melting mixtures of ferrous sulphide and ferric oxide in contact with iron. Since it was considered that in this part of the system the vapor pressures of sulphur and SO, are so low that they would not affect the results significantly, the melting was carried out in a current of argon to sweep out products of any initial re-

Jan 1, 1953

By W. O. Philbrook, H. E. Burner, F. S. Manning

The equation of continuity for the hydrogen reduction of hematite in a fixed bed of closely-sized particles is solved assuming a flat velocity profile, negligible temperature gradients, md negligible axial diffusion. A kinetic expression from the literature is used which assumes the reduction process is controlled at the oxide-metal interface. The integral fractional conversion is computed, and the importance of particle diameter, flow mte, temperature, bulk axial diffusion, and inter- and intra-particle mass trarnsfer is predicted. Comparison with experimental data suggests one or more additional undefined variable(s) is significant. Equipment modifications are suggested for fidture experimentcll work. WITH the increasing desire to "design" the ore feed of a blast furnace, it has become necessary to define more quantitatively the process variables and to evaluate the extent of their control upon the reduction process. The bulk of the work reported in the literature has centered about the reduction of single particles; however, the blast furnace process more closely resembles reduction of a fixed bed than that of single particles. To simplify this analysis, the isothermal reduction by hydrogen of a natural hematite in a fixed bed of closely-sized particles is examined. With appropriate modifications in the kinetic and flow rate expressions, the approach employed should be extensible to mixtures of carbon monoxide, hydrogen, and inert nitrogen, and to adi-abatic conditions, thus approaching the blast furnace process more closely. The fixed bed variables which are investigated in this study are particle diameter, flow rate, temperature, and bulk axial diffusion, as well as inter-and intra-particle mass transfer. Of particular interest is the effect of particle size upon fractional conversion for a bed operating under constant pressure drop. The constant pressure drop concept bears a close resemblance to the blast furnace process, where regions of larger particles may provide a greater permeability to divert most of the reducing gas flow from the regions of smaller ore particles. Under such conditions one would expect qualitatively that, for sufficiently small particle sizes where the flow rate is small and the total surface area is large, the reduction rate would be limited by the gas flow rate. Initially the gas entering the bed reacts very rapidly and the composition approaches the equilibrium conversion value a short distance from the reactor inlet. This concentration "wave-front" then moves up the bed as the flow of reducing gas is continued, leaving in its wake an ever increasing layer of reduced particles. Providing that the reducing gas leaves the bed at equilibrium concentrations, conversion is expected to increase with an increase in flow rate, and hence with an increase in particle diemater. Conversely, for sufficiently large particles the flow rate will be high but the surface area available for reaction will limit the reduction rate. Since the total surface area decreases with an increase in particle size, conversion, in this case, is expected to decrease as the particle diameter is increased. It is clear then that between these two extremes an optimum particle diameter must exist. THEORETICAL DEVELOPMENT Above the temperature where wiistite is stable (about 560°C) the reduction of hematite proceeds through the series Fe2O3/Fe3O4/FeO/Fe. On the basis of microstructural studies and earlier work, Edström1 has postulated a mechanism for the reduction of an ideal hematite lattice: 1) Iron phase formation at the boundary between wiistite, iron, and gas (for sufficiently porous iron). 2) Diffusion of iron across a wustite layer. 3) Phase boundary reaction of Fe3O4 to FeO. 4) Diffusion across a dense magnetite layer. 5) Phase-boundary reaction of Fe2O3 to Fe3O4. According to the mechanism postulated, gaseous reaction product has to be removed only at the boundaries between wüstite and iron or gas, the only possible exception being enveloped Fe3O4 specks. On this basis McKewan2,3 has proposed that one may consider the hematite reduction process as a simple two-phase system of oxide/metal. If, for FeO and Fe3O4 layers of negligible thickness, the hypothesis is made that the rate of formation of a

Jan 1, 1963

By Charles H. Fulton

THE Engineering Education group began its sessions Tuesday morning, Feb. 16, as a Committee and wound up the day as the Institute's fifth " Division." C.II. Fulton presided. The first paper for discussion was entitled "Teaching Management in Engineering Schools,"' by Eugene McAuliffe, president of the Union Pacific Coal Co., space for which may be found later in these pages. In it, Mr. McAuliffe argued that an engineering student should be taught the knowledge of men, much as a medical school teaches surgery. He then went on to indicate, out of the wealth of his administrative experience, the problems an executive needs to be equipped to handle, and said that every student engineer should look on himself as a potential manager.

Jan 1, 1932

By Richard S. McCaffery, Clarence H. Lorig, Joseph F. Oesterle, Ira N. Goff, Oscar O. Fritsche

This paper is the report of an investigation to determine the relations between the viscosity, temperature and composition of that portion of the silica-alumina-lime-magnesia system(l) within which blast-furnace slags are found. The work reported in this paper was made possible by a grant of funds from Engineering Foundation. It is a part of a project, the determination of properties and structure of iron blast-furnace slags, upon which the laboratories of the University of Wisconsin have been at work for some years. Three papers have been published, which have marked the progress of the study of iron blast-furnace slags at Wisconsin. The first,(2) Desul-furizing Power of Iron Blast-furnace Slags, discussed the solubility of sulfur in slags that contained no magnesia and discussed the viscosity. The second, (3) The Constitution of Iron Blast-furnace Slags, developed the constitutions of slags in the four-component system, silica-alumina-lime-magnesia, and pointed out an explanation of slag structure. Composition of Iron Blast-furnace Slags,(l) which was the third paper, gave a method of calculating the percentages of the various compounds present in slags when the amount of oxide was given and also an interpretation of quaternary equilibrium. Illustrations were given of the mineral composition of blast-furnace slags and some applications of composition results were shown. Because of their relative ease of measurement, the viscosity-temperature relation for slags was selected as a factor which would be useful in correlating the physical properties of molten slags to furnace operation. With this in mind the viscosities of slags whose compositions are in that portion of the quaternary system, silica-alumina-lime-magnesia, in which blast-furnace slags occur, were thoroughly investigated.

Jan 1, 1932

By H. W. Schreiber, G. R. Castle

INTRODUCTION The small mining company faces the dilemma of how to finance the development of its properties. Many of these small companies don't have the financial resources to pay for development costs from their own funds and frequently they do not even have the financial strength to permit them to borrow the money needed for development. A project financing can sometimes be arranged in such a way as to solve this dilemma. A typical project financing will not provide the answer to the "little guy's" problem because most project financings require that the sponsors of the project provide completion undertakings and sometimes other undertakings. These undertakings are often a prerequisite to obtaining financing, and if the sponsor is not financially strong enough to provide the comfort that the lenders require, then the sponsor will have difficulty obtaining financing no matter what undertakings are offered. However, with a little imagination and the right set of circumstances, a project financing can sometimes provide the solution to the small mining company's problem. The Strathcona Sound Project is unusually suited as a case study because the sponsor, Mineral Resources International Limited,(MRI) was able to arrange a project financing for the development of the project even though the lenders probably would not have been willing to loan a similar amount of money direct to MRI based on the full faith and credit of MRI's balance sheet. The way that MRI was able to arrange this financing makes for an interesting story. THE CASE In early 1974, MRI owned 100% of a small to medium sized zinc - lead - silver massive sulfide deposit (Property) located 475 miles north of the Arctic Circle less than two miles from deep water on Strathcona Sound which is a shipping zone in the Canadian Arctic. The Property was situated at a desolate location except for an Eskimo settlement (Arctic Bay) which was about 20 miles west of the Property. In other words, the project required that complete infrastructure would need to be installed in this far northern location. Independent reserve and feasibility studies (Study) had been completed on the Property which confirmed a total of 6,825,000 tons of reserves classified and summarized as shown below on Table I: [ ] These reserves were based on 229 diamond drill holes totalling 58,909 feet and were established on a cut-off grade of 7% zinc and a minimum mining height of seven feet. The overall mining recovery rate was estimated at not less than 85% and not more than 90%. The feasibility study indicated that it would cost an estimated $45,044,000 to develop an underground mine, a concentrator, a town-site, a power plant, storage facility, loading dock, a tailings disposal area and an airstrip on the Property with an annual capacity of 525,000 tons of ore per year. The construction period was expected to take two years and projected capital costs were broken down as set forth below on Table II:

Jan 1, 1985

By B. B. Zavoico

After showing continued and very satisfactory progress until the close of 1931, the oil industry of the Soviet, Union experienced very great difficulties, and since 1932 has not only failed to complete its assigned quotas but has fallen farther and farther behind them, and in fact during 1932 and 1933 Russian production has been below production in 1931. In 1934 the total crude oil production of 169,200,000 bbl. exceeded that of the former peak year, 1931, when 156,100,000 bbl. were produced. The production during 1934 amounted to 78.65 per cent of the plan. The failure to complete the plan has been due to the inability of the oil trusts to develop new fields; the fields that have been producing since 1917 still account for between 75 to 80 per cent of total production. The failure of the Soviet Government to develop new fields has been due to unsatisfactory organization of the geological work, to the extremely slow drilling of wells and their exploitation, and to the very much delayed development of the few areas that have been discovered. The official overestimation of the proven reserves of the country has undoubtedly been an important factor in giving the Soviet industry too much confidence when actually such reserves have been small. The official Soviet estimate of proven reserves of Russia is now placed at 21,000,000,000, bbl., while in fact such reserves, if estimated on a conservative basis, do not exceed 4,200,000,000 bbl., as will be shown later in this review. The refinery branch of the industry also showed unsatisfactory results with a recovery of gasoline, both straight-run and cracked, of only some 16 per cent of the total runs to stills. In fact, the showing of the refineries has been so unsatisfactory that the exports of gasoline have been greatly curtailed from 1933 to 1934, dropping to 10,000,000 bbl. in 1934 from 12,230,000 bbl. in 1933. With the indicated increase in domestic demand, together with but slightly increased refining capacity, the volume of available gasoline for export probably will be reduced to about 6,000,000 bbl. during 1935. The geographic distribution of constructed refineries has been unsatisfactory and the crude oils from Baku had to be transported by tankers

Jan 1, 1935

By Thomas C. Wilder

ALTHOUGH there is an abundance of thermodynamic information available in the literature today, no experimental data on the standard molar properties of formation of zinc oxide have ever been reported for the temperature range 419.5" to 908°C. This is the temperature range for which zinc metal is a liquid. so that the formation reaction is: Data have been reported for Reaction [I] where zinc is a solid or a gas. Maier. Parks, and nderson' measured the electromotive force of the cell: in order to obtain the free energy of the reaction: over a limited temperature range. With the known properties of H2O, those of ZnO were calculated. These workers found that t;j of ZnO is -75,930 ± 150 cal per gfw and Mtf is-83,000 300 cal per gfw at 25°C. akolkin made similar measurements to obtain ilF7 and AH; of -75,870 and -82,540 cal per dw respectively at the same temperature. Truesdale and arirlg and Kitchener and 1gnatowicz4 measured the equilibrium of the reactions: respectively, in order to determine Ff of ZnO from the known values of CO, CO2, and H/X The thermodynamic properties of ZnO, presumably taken from the above investigations, are tabulated by Kubaschewski and vans' and Wicks and Block" The latter reference also gives values for the range where zinc is a liquid. These numbers are probably acquired from the known extremities of the range plus Cp data of the components. In the present work the electromotive force of the cell: was measured in order to calculate the properties of ZnO from the well known values of NiO for the temperature range where zinc is a liquid. In Cell [B] the cathode reaction is: and at the anode: The overall reaction is: for which the free energy change is: where is the electromotive force in volts of cell [B] after correction for the Pt-Ta thermocouple. The standard molar free energy of formation of NiO is very well known as a function of temperature. Kiukkola and agner's data are used in most tabulations. The error is probably less than I00 cal per gfw, The latter authors were the first to use solid mixed oxide electrolytes in galvanic cells. Their work with NiO and other oxides was performed with cells similar to Cell [B] using a variety of reference electrodes of fixed oxygen potential. There may be a small composition range for which either NiO, ZnO or both exist. If nonstoichiometry does exist for these oxides, then the properties described herein are those for the metal saturated compositions. The simple cell design was the same as described elsewheres except that the molten metal electrode was about 125 g of pure zinc including a small (0.25 to 0.50 g) amount of ZnO. The mixture of pure nickel and NiO powders making up the reference electrode was contained in a tube of the ZrOl + CaO electrolyte which was immersed in the molten zinc. A platinum contact was made to the reference electrode; tantalum to the zinc. A refractory cement plug was necessary at the open end of the electrolyte tube in order to prevent zinc vapor from contaminating the reference electrode. Experimental details such as the vessel containing the cell, furnace, temperature control and measurement, and electromotive force determinations of the cell have all been outlined previously. The temperature was varied randomly in the range between the freezing and boiling points of zinc. After each temperature change, time was allowed for the drift at the new temperature to be less than +;"c whereupon a series of three cell readings was taken at least 10

Jan 1, 1970

By J. S. UNGER

A LARGE proportion of the coke used is made in the by-product oven from the high-volatile coals mined in the adjacent district. At the beginning it was feared good by-product blast-furnace coke could not be made with our coals. By experimenting with various mixtures of coals, coking time, oven design, and coking temperatures, much has already been accomplished. The results show that a hard, dense coke, not easily broken by handling, can be produced. In its present state it is not all that could be desired, but it is being constantly improved. Such coke has been used alone as the fuel on several of the blast furnaces producing the highest daily production in the Pittsburgh district. Many of the coals in the Pittsburgh district when coked in the by-product oven yield a gas which contains a high percentage of sulfur, which is objection- able for many metallurgical operations. As this fuel is gradually replacing the ideal fuel, natural gas, which is becoming less plentiful, studies are being made of the best methods for purification. Some metallurgists believe sulfur to be a very injurious element in steel. Recent investigations by Government bureaus, scientific bodies and private firms, seem to indicate that a reasonable amount of sulfur may exist in steel without detriment. Without wishing to provoke any metallurgical controversy on the subject of sulfur, the fact remains that the daily purification

Jan 1, 1926

By N. Tiner

IN an article on magnesium and its alloys, Gann and Winston1 stated that manganese has a limited solubility in the liquid state. W. Schmidt2 showed a diagram according to Joseph Ruhrmann indicating that the solubility of manganese in liquid magnesium falls from about 2.65 per cent at 790°C. to about 0.5 per cent at 695°C. The curve was extrapolated to show zero solubility at the melting point of pure magnesium (Fig. I): This work suggested that at the lowest manganese contents it was not possible to detect either a eutectic or the formation of a solid solution, so that manganese was stated to be present in the structure as large individual crystals. Two years after the presentation of these results, Gann3 brought evidence to show that some manganese is capable of dissolving to form a solid solution, any excess of manganese present then assuming chiefly the form of small blue-gray particles scattered throughout the primary magnesium crystals, occasionally in clusters but seldom at the boundaries. He presented micrographs of cast alloys containing o.1, 0.4 and 1.0 per cent manganese that show a small amount of coring around the individual particles due to solid solution, and indicate that the location of the manganese particles is closely associated with the original dendritic structure of the primary crystallization. He also pointed out that the amount of manganese that can be dissolved in magnesium depends on the amount of other alloying elements present, the effect of the second alloying element being to decrease the amount of manganese retained in the alloy. E. Schmid and G. Siebe14 have determined the solid solubility of manganese and its variation with temperature by means of precision X-ray diffraction measurements. They found that the solubility is 3.4 per cent at 645°C and decreases to practically zero at 200°C. It is apparent that the X-ray diffraction measurements of Schmid and Siebel are not in agreement with the results of Ruhrmann as presented by Schmidt. This disagreement, and also the lack of data on magnesium-aluminum-manganese and magnesium-zinc-manganese systems, led the author to the present investigation, to determine accurately the liquid solubility of manganese and its variation with temperature. EXPERIMENTAL METHOD The experimental method for making solubility determinations consists of saturating the molten magnesium or the alloys with manganese at various temperatures and analyzing the dip samples taken from these melts. Melting is carried out in a cylindrical steel pot heated by an electric resistance furnace. The pot had a metallic outside coating to protect the steel against oxidation, and a graphite inside lining to prevent the contamination of the melt by prolonged contact with iron. The inside diameter of the pot was 4 in. and the depth 12 inches.

Jan 1, 1945

By F. C. von der Weid

The mining district of Sao Fidelis, in the northern part of the State of Rio de Janeiro, is situated on the Paraiba River, where it crosses the Serra do Mar (Mountain of the Sea), in the center of a mountainous country having numerous graphitic outcrops. For a long time, these outcrops were irregularly explored by local people, who had little means and no technical advice. A few years ago, the Cia. Brasileira de Minerasgo de Grafite took over the control of some of the more important outcrops and entrusted to me the task of studying the ores and establishing a flowsheet for a pilot plant to be situated in São Fidelis—the ore to be concentrated being mostly of a very high grade. Mineralization and Ores The rocks of the district are mostly gneiss and crystalline schists, with occasional interstratification of dolomitic limestone belonging to the Archean Brazilian Fundamental Complex. The general direction of the beds is roughly between 60" and 80°E., with variable dip, generally nearly vertical. Mostly, direction and dip of the graphitic outcrops is concordant with the embanking gneisses or schists. These outcrops seem to be aligned in two or three parallel zones (Pádua, São Fidelis, Mac- abu), the Sao Fidelis zone being the best known and the most important to date. Two outcrops of the São Fidelis zone, Saudade and Sao Benedito, are now being exploited. Mining has been carried out, so far, on a small scale. The mineralization consists of a vein of nearly massive graphite in a very compact, partially granitized gneiss, with vertical dip. The vein is most irregular, with nests and lenses irregularly distributed along the fracture plane. The ore consists chiefly (particularly in Sao Benedito) of massive graphite appearing and disappearing along the main direction of the vein, forming a succession of irregular lenses in a sort of rosary design. The average width is more or less one foot, with variations from zero to 6 feet. The lode minerals are quartz, a little feldspar and garnet (the latter having its origin perhaps in the embedding gneisses), with rare ferruginous clays on the outcrops. In Saudade a little pyrite, pyrrhotite and chalcopyrite is found occasionally, as well as a carbonaceous mineral, very light, black and shiny, with conchoidal fracture, looking like a sort of jet. The composition of this mineral has not yet been established, but it seems to be very complex. The mineralization seems to be hydro-thermal at a rather low temperature, perhaps mesothermal. The paragenesis, according to samples from Saudade, seems to be as follows, the earlier minerals being listed first: pyrrhotite, pyrite, chalcopyrite, with quartz concomitant to the three and graphite formed later. Age of the mineralization is still uncertain, owing to the very in-

Jan 1, 1948

By F. C. von der Weid

The mining district of Sao Fidelis, in the northern part of the State of Rio de Janeiro, is situated on the Paraiba River, where it crosses the Serra do Mar (Mountain of the Sea), in the center of a mountainous country having numerous graphitic outcrops. For a long time, these outcrops were irregularly explored by local people, who had little means and no technical advice. A few years ago, the Cia. Brasileira de Minerasgo de Grafite took over the control of some of the more important outcrops and entrusted to me the task of studying the ores and establishing a flowsheet for a pilot plant to be situated in São Fidelis—the ore to be concentrated being mostly of a very high grade. Mineralization and Ores The rocks of the district are mostly gneiss and crystalline schists, with occasional interstratification of dolomitic limestone belonging to the Archean Brazilian Fundamental Complex. The general direction of the beds is roughly between 60" and 80°E., with variable dip, generally nearly vertical. Mostly, direction and dip of the graphitic outcrops is concordant with the embanking gneisses or schists. These outcrops seem to be aligned in two or three parallel zones (Pádua, São Fidelis, Mac- abu), the Sao Fidelis zone being the best known and the most important to date. Two outcrops of the São Fidelis zone, Saudade and Sao Benedito, are now being exploited. Mining has been carried out, so far, on a small scale. The mineralization consists of a vein of nearly massive graphite in a very compact, partially granitized gneiss, with vertical dip. The vein is most irregular, with nests and lenses irregularly distributed along the fracture plane. The ore consists chiefly (particularly in Sao Benedito) of massive graphite appearing and disappearing along the main direction of the vein, forming a succession of irregular lenses in a sort of rosary design. The average width is more or less one foot, with variations from zero to 6 feet. The lode minerals are quartz, a little feldspar and garnet (the latter having its origin perhaps in the embedding gneisses), with rare ferruginous clays on the outcrops. In Saudade a little pyrite, pyrrhotite and chalcopyrite is found occasionally, as well as a carbonaceous mineral, very light, black and shiny, with conchoidal fracture, looking like a sort of jet. The composition of this mineral has not yet been established, but it seems to be very complex. The mineralization seems to be hydro-thermal at a rather low temperature, perhaps mesothermal. The paragenesis, according to samples from Saudade, seems to be as follows, the earlier minerals being listed first: pyrrhotite, pyrite, chalcopyrite, with quartz concomitant to the three and graphite formed later. Age of the mineralization is still uncertain, owing to the very in-

Jan 1, 1948

R. W. Raymond, New York, N. Y,:—Since the presentation of my note on this subject at the New York Meeting, Professor Louis has pointed out an error in my statement of his conception of " pitch "—namely, he understands the pitch, in the restricted sense which he proposes, to be the angle of inclination of the axis of an ore-body, measured on the vertical plane drawn through the body; whereas, I represented him as proposing to define " pitch " as the angle of inclination of an oblique body, measured on the plane of the dip, in the direction of the strike. The difference will appear upon consideration of the accompanying isometric projection, Fig. 1, in which ABCD represents the plane of the inclosing ore-deposit (vein or bed), and AC the axis of the oblique ore-shoot. ABE is the angle of the dip, as universally understood; and ACE

Jan 1, 1909

Papers in Classes A-Metal Mining, B-Milling and Concentration, H-Industrial Minerals, and I-Mining Geology are distributed in MINING TECHNOLOGY, which is issued every other month. Papers in Classes C-Iron and Steel Division, D Nonferrous Metallurgy and E-Institute of Metals Division are distributed in METALS TECHNOLOGY, which is issued twice quarterly. Papers in Class G Petroleum Division are distributed in PETROLEUM TECHNOLOGY, which is issued every other month. TECHNICAL PUBLICATIONS in Classes F-Coal Division, J Mineral Industry Education Division, Mining Administration, and L-Geophysics, are issued as separate pamphlets. Contributions are papers that when printed or mimeographed are available, but only on request.

Jan 1, 1946

By J. E. Graham, A. H. Glenn

Oil operators engaged in drilling on the Continental Shelf of Louisiana and Texas are in agreement that adverse weather and wave action are two of the greatest hazards to the safety and efficiency of their work. It was ami-pated when the offshore operations commenced that such would be the case, and experience to date has verified this assumption. Because atmospheric conditions and wave action involve tremendous amounts of energy it is highly unlikely that it will be possible to control any but the most localized weather and wave phenomena within the foreseeable future. Thus. as long as the offshore operations involve the movement of small craft and barges over exposed waters, and the transfer of personnel and heavy equipment from these craft to either fixed structures or larger craft at close quarters, the weather and wave problem will remain. Taking into consideration the persistence of the wave and weather problem and the improbability of achieving a direct solution, the Humble Oil & Refining Company, in planning its offshore campaign investigated the possibility of forecasting wave and weather conditions in order to provide warnings of dangerous conditions and increase efficiency in day-to-day planning of work. It was recognized that predictions of wave and weather conditions based on meteorology and oceanography, both geophysical sciences, are not 100 per cent accurate and application of forecasts in the offshore work was dependent on whether they provided information which was sufficiently greater in accuracy than the layman's guess to be worth the expenditure involved. During World War 11. meteorology and oceanography were used with success in reducing danger resulting from environmental conditions and increasing efficiency of operations exposed to the elements. This success was partially the result. of improvement in the scientific techniques involved and the procurement and distribution of observational data, and partially due to the large scope of the military operations which meant that a reduction of losses of a relatively small percentage of the total cost amounted to a large figure expressed in terms of dollars. Since the offshore drilling involves an extremely large financial investment, it was considered that the experience of the Armed Services in successfully employing meteorology and oceanography might be duplicated in the oil industry. In addition. the oil industry's successful experience in utilizing seismology, geology, and terrestrial magnetism; all geophysical sciences, indicated that meteorology and oceanography, also of the family of geophysical sciences and sharing their scientific assets and liabilities, might be profitably put to use. Since the immediate problem involving the sciences of meteorology and oceanography in the offshore campaign is wave action, a program was inaugurated within the Humble Oil & Refining Company during June 1947. the purpose of which was to ascertain the applicability and limitations of wave forecasting in the offshore campaign. A summary of the effective wave forecasting techniques developed during the war was prepared in the form of a forecasting manual for the Continental Shelf off Grand Isle, Louisiana, by Bates and Glenn. After completion of this manual, experimental forecasts were prepared daily over a two-month period by Graham and Thompson to determine the accuracy of the forecasts. It was considered that the accuracy of the experimental forecasts justified a more extensive test under actual operating conditions in the offshore work and the firm of A. H. Glenn and Associates was set up under the sponsorship of the Humble Oil & Refining Company to work with the Humble Grand Isle District in providing forecasts of wave and weather conditions over a one-year period. This paper discusses the service now provided to the Grand Isle District, its applicability and limitations. TYPE OF FORECASTS REQUIRED It was apparent before the commence-mence of the forecasting service that a specialized type of forecast was required. Many of the weather elements of interest to the general public, such as rain and temperature, are of minor concern to offshore operators. On the other hand, such elements as wave height and wind speed and direction are of great concern in the offshore operations since variations in wave height of a few feet in the critical range divide safe from hazardous working conditions. To be of utility. a forecasting service for the offshore work must provide detailed forecasts of the elements which affect the operation. With this in mind, it was decided that forecasts would include the following information: average wave heights to the nearest foot, wind speeds within a range of approximately 5 miles per hour, and wind directions within 221 degrees. Since the procedure for forecasting these elements involves thorough analysis of weather data, it was decided to include a generalized forecast of weather conditions such as rain and cloud cover, although these are of secondary importance.

Jan 1, 1949