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By Renato G. Bautista, Robert A. Hard

A comparative study has been made of the ex-tractability of several of the transitim metals from thiocyanate sohtions using methyl isobutyl ketone as the organic solvent. Extractions were made of scandium (III), chromium (III), manganese (II), iron (III), and cobalt (II), of which only the scandium , iron, and cobalt were readily extracted. All extractions were made at pH 2 and at 25.5 °C. A series of extraction experiments was made on scandium, iron, and cobalt to determine the effect of thiocyanate cmcentration added as the ammonium and also as the calcium salt. Also determined was the effect of metal ion concentratim and ionic strength on the distribution ratio. Analyses of the organic extracts indicated the scandium and iron were extracted principally in the uncharged trithiocyanate form, while the extractable form of the cobalt contained the cobaltotetrathiocyanate anion. THE chemical separation of metal complexes in solution by solvent extraction has in recent years been developed for large scale separation as well as bench scale work in the laboratory. It has also found increased application in analytical chemistry. Its extension to extractive metallurgy as a unit operation is best illustrated in the recovery of uranium and vanadium from their leached liquor.5-8 The extractability of some thiocyanate systems have been extensively investigated. The rate earths have been separated from one another using butanol as a olvent. Scandium was effectively extracted in ethyl ether using ammonium thiocyanate as the com-plexing agent.'' Similarly, the separation of hafnium from zirconium has been reported using ether""' or hexone13 as the organic solvent. The extractability of various metal thiocyanates in ethyl ether is given by 0ck.l Sharp and Wilkinson15 prepared nickel-free cobalt slats by thiocyanate extraction. The mechanism of extraction of titanium (IV) thiocyanate with methyl isobutyl ketone was determined by elafosse.''" The characterization of cobalt (TI) thiocyanate complex using methyl isobutyl ketone as the solvent at near neutral aqueous solution and the spectrometric studies of the ex-tractable cobalt complex has been made by Hard." It is noteworthy to mention at this point that the fundamental characteristic of ketone (oxonium) solvent extraction is that the extractable species are uncharged ion pairs solvated by the ketone molecules, but probably still partially hydrated.

Jan 1, 1963

By F. Hass, N. W. Lord

This paper gives the results of experiments conducted in the metallurgical laboratory of the Ohio State University with the objects of determining: First, the calorific powers of a number of coals in general use in Ohio; and second, how far ordinary analytical methods could be used as a basis for computing these values. Incidentally a test of the performance of the calorimeter was involved. The chemical work has been carried on in the department for some time, so that the whole investigation has extended over three or four years. The Mahler calorimeter was purchased from L. Golaz in Paris, and is practically identical with the one described and figured by Mahler in his monograph "Contribution a l'Etude des Combustibles," from the Bulletin de la Société d' Encouragement pour l'lndustrie Nationale. A figure and description is also given by William Kent in The Mineral Industry for 1892, page 97. There were furnished with the instrument three thermometers covering a range of from 7°.5 C. to 31° C. Thermometer "A" (17°.5 to 31°) was carefully calibrated by reading the ends of a thread of mercury in sixteen positions covering the whole scale, supplementing this by readings of longer threads and deducing the errors of scale by the method published by Prof. Holman in the Technology Quarterly of September, 1887. The maximum error of a single reading was found to be 0°.0042 C. Thermometer "B" (13° to 25°) was compared directly with " A " over the scale common to both, and a variation was found of 0°.0145 C. for 7°.5 (or 0°.002 for l°) of the scale. Thermometer " C" ('7°.5 to 19°.0) was omitted from the cornparison, as it was rarely used, being only required where measurements were made at low temperatures. From the

Jan 1, 1898

By A. G. Guy

In a special type of electrodiffusion experiment the entire specimen is at constant temperature. The vacancies are then created at one end of the specimen and flow to the other end where they are destroyed. The energy required to operate the corresponding sources and sinks results in a super saturation of vacancies at one end of the specimen and an under -saturation at the other end. This gradient in vacancy concentration produces a chemical-diffusion flux, J(D), of vacancies in addition to the flux, J(E), caused by the electric current. Using the experimental data of Ch. Herzig,5 it is shown that a super saturation of 1 pct can cause J(D) to be about 25 pct of J(E), and thus account for the anomalous behavior of short specimens. THERE are advantages in a phenomenological treatment as contrasted to an atomistic one. For example, there are many reactions involving the element copper that are quantitatively and usefully understood from a phenomenological viewpoint, even though electron theory is not yet able to predict whether copper should be fcc or cph.' Similarly, the lack of a complete atomic theory of vacancies need not prevent the development of a treatment based on thermodynamics and chemical kinetics. In the following discussion, models will be used for the vacancies and for the mechanisms by which they move or are created or destroyed, but the phenomenological treatments are not dependent on the details of these models. The important product of a phenomenological analysis is an equation that describes the relation among the measurable quantities determining the behavior of the system. Based on such an equation, experiments can be performed to study these quantities in detail. Eventually atomic theory will supply an adequate theoretical base for the phenomena in question. A chemical species whose chemical potential was invariant during reactions in binary and ternary systems of varying composition would indeed be an anomaly. Yet this is the role that has frequently been assigned to the vacancies in pure metals, in dilute solutions, and even in ordinary alloys. The weight of available evidence supports the view that supersatu-rations of vacancies are on the order of 1 pct in usual diffusion processes.' Although it may seem strange that such a small deviation from equilibrium could significantly affect the thermodynamic properties of the vacancies, it is well known that the driving force for an ordinary chemical reaction is the departure of the components from their equilibrium state. Similarly, the reaction of vacancies that results in the formation of pores in various types of diffusion3 can reasonably be attributed to the supersaturation of vacancies. In the present paper, it will be shown that small degrees of supersaturation can significantly affect the kinetics of the diffusion process itself. ISOTHERMAL ELECTRODIFFUSION Two different experimental techniques are convenient for studying the behavior of vacancies in a pure metal in the presence of an electric field. Gilder and Lazarus4 studied self-electrodiffusion in a gold specimen in which only the central portion was at high temperatures. In this case the significant vacancy sources operate inside the specimen in the presence of a temperature gradient. In the laboratory of Th. Heumann a method has been devised for studying self-electrodiffusion at constant temperature.5 In principle, there is then no effect of thermodiffusion. It will now be shown why in this case the significant ATungsten disks \^^ ^^ ^Gold disks^^ ^^"T>.... "TTZA ? Up Iy'7 markers ///// ////// initial plane p I y/y/y of joining \I 7//// V7//A_________I_________V//// -I 0 +I Distance from center of specimen (a) -— Direction of flow of electrons —Direction of flw of vacancies %yy} Matano I z~irkendall /%W, vy/A inlerfacej "interface ///// -} HfiK- +/ 0 Distance from center of specimen (6) Fig. 1—-Schematic illustration of the essential features of isothermal self-electrodiffusion. (a) Initial condition of specimen. (b) Condition of specimen after electrodiffusion.

Jan 1, 1970

By Albert Sauveur

IT WAS in June, 1889, that I was first admitted to the society of educated men. The admission ticket had been signed, on the recommendation of my old and beloved teacher, Bobby Richards, by General Francis A. Walker at the time President of the Massachusetts Institute of Technology, an institution familiarly known as M. I. T. I immediately proceeded to take advantage of that privilege by departing for Steelton, Pennsylvania, where I understood I was eagerly awaited by the educated officials of the Pennsylvania Steel Company. I was some. what disappointed at the casualness of my reception and at being tucked away in that preserve closet of steel works known as the chemical laboratory. At Steelton I met Major Bent who was president of the company. When I say "met," that is a figure of speech as my acquaintance with him was confined to my being shown

Jan 1, 1937

By John S. Brown

The northeastern United States embraces that area of the Appalachian Mountains, and adjacent territory, beginning on the south at the Potomac River. It thus extends from the flat-lying Paleozoic terrane of the Appalachian plateau on the west, across the folded Paleozoics of the Great Valley and adjacent ridges (Paleozoic and Precambrian), over the Piedmont and New England metamorphic complex (mixed Paleozoic and igenous rocks), broken by the great Triassic rift remnants, onto the subdued coastal plain of Cretaceous and Tertiary sediments. Although not noted as a metal mining region, the area does contain numerous substantial and several outstanding mines, chiefly of the more prosaic metals, particularly iron, zinc, and copper, as well as many minor occurrences of these and a few additional items. These deposits occur to some extent in every subdivision of the area. The region to date (1966) has produced almost 500,000,000 tons of medium to lowgrade iron ore, especially magnetite, including ilmenitic magnetite; 50,000,000 tons of highgrade zinc ore; and 5,000,000 tons of lowgrade copper. In the past, it has yielded small amounts of chromite and nickel, and at present is a large producer of titanium. Precious metals are conspicuously absent, and so also are the Tertiary or Mesozoic igneous phenomena so commonly associated with mines of the West. Hence, a survey of the extensive mineralization · of this region should be instructive

Jan 1, 1968

By P. Pietrokowsky

lntermediate phases in the binary metal alloy systems Ti-Zn, Ti-Hg, Zr-Zn, Zr-Cd, and Zr-Hg have been investigated by X-ray powder diffraction methods. Gamma-TiBHg and Zr3Hg have a beta tungsten structure; TiHg and ZrHg are analogous to ordered AuCu (L l0 type); delta-TixHg and ZrHg, are isomorphous with ordered AuCu,, (L l2 type); ZrZnz is face-centered cubic (C 15 type); TiZna crystallizes in a C 14 type structure; and Zrll-, occurs in cubic and tetragonal modifications in which a random distribution of atoms exists. Additional information for the intermediate phase TiZn, is presented. THE physical metallurgy of titanium and zir-conium when alloyed with elements in subgroup 11-B of the periodic table has received comparatively little attention in the literature. Laves and Wallbaum' reported the existence of several intermediate phases in the system Ti-Zn. They identified TiZn as a CsCl (B 2) structure and described TiZn, as an ordered Cu,Au (L 1, type) crystal structure. Gebhardt' investigated very limited zinc-rich regions in the systems Ti-Zn and Zr-Zn. Phase relationships in these partial constitution diagrams were deduced from the results of thermal analysis and metallography, X-ray results being inconclusive. The first zinc-rich intermediate phase in either system was not identified. More recently, Anderson, Boyle, and Ramsey" have had occasion to refer to a partial Ti-Zn phase diagram (unpublished data) covering the region 0 to 10 atomic pct Ti, wherein two intermediate phases corresponding approximately to TiZn,, and TiZn,, were indicated. The metals used in this investigation and typical analyses as determined by the suppliers are given in Table I. The iodide-process zirconium which was used was not hafnium free. Experimental Methods Alloy Preparation: The relative ease with which titanium and zirconium combine with other elements places extensive restrictions on the methods by which alloying can be achieved. The direct current electric arc melting procedure was found to be unsatisfactory for preparing these binary alloys and for this reason solid state diffusion methods were utilized. The iodide process titanium and zirconium rods were filed by hand. Fines were subjected to a magnetic separation and classified as to size as either finer than 200 mesh or coarser than 200 but finer than 80 mesh. Powder mixtures of various binary combinations of titanium and zirconium with zinc and cadmium were compacted in a 12 mm diameter die and then placed in Vycor or quartz vials which were evacuated and sealed. The mercury alloys were prepared in a similar manner; the proper weight of liquid mercury being placed in a vial with minus 200 mesh titanium or zirconium. These ampoules were then heat treated at various temperatures and times depending on the characteristics of the particular alloy system. Upon completion of the heat treatment the ampoules were cooled rapidly and the specimens weighed. The loss in weight varied from 1 to 3 pct (except as noted in the text) and for this reason the calculated compositions were accepted as a fair measure of the actual alloy compositions. X-Ray Dif raction Techniques: Powder diffraction experiments were conducted at room temperature with a 143.2 mm Debye-Scherrer X-ray camera in which the film was placed in the Straumanis arrangement. When copper radiation was used, a nickel filter was employed, and for the cobalt target a filter of iron oxide was used. In both cases, the /i? filter was placed between the X-ray target and the powder specimen which was mounted on a glass fiber. The lack of information based on optical metallography placed reliance on the results obtained from the X-ray experiments for determination of

Jan 1, 1955

By Euzebio De Oliveira

ONE of a recent batch of samples from the Serra da Baliza, in the state of Parana, Brazil, contained asphalt and a dark heavy oil; and workmen on the railway from Porto União to Uruguay discovered asphalt, coming from eruptives that outcrop along the Rio de Peixe. The occurrence f asphalt in the triassic eruptives of southern Brazil, however, has been known a long time, according to Dr. Gonzaga de Campos. It is generally believed that the Botacatú sandstone is always a hard vitrified rock, from the metamorphic action f. the overflowing eruptive contacts. In this region, however, the contact metamorphism is almost nil; the sandstone is slightly hardened in a narrow zone about 20 to 30 cm. wide. In many places, the sandstone is so friable as to be easily reduced to sand, which is used-.in, mortar for building in Guara-puava and Palmas. South and west from Porto União,. this bench of sandstone is about. 50 m. thick, and is capped by a heavy bed. f basic eruptives, many of which are amygdaloids. Dr. Geo: P. Merrill, after studying the triassic eruptives collected by the Coal Commission, reached the conclusion that. "All these rocks are of typical basalt-diabases, not in any essential different other than in structure. An interesting mineralogical phase is its paucity in olivine, which in many cases is completely lacking. Professor Hussak, who carefully studied these rocks and their accessory minerals, decided that in the dikes they are granular (diabase) and, that in the lava sheets, porphyritic (augite-porphyrite or melaphyre), and that the latter pass evidently to normal diabases and are always typical of effusive rocks. The examination f many slides from dikes and sheets leads us to adopt the opinion of Professor Hussak; the rocks of the dikes are of ophitic structure, while that of the sheets show a great variety f structure and may vary from almost granular to basaltic. The great paucity in olivine had been noted by Hussak, who classes as melaphyres, the porphyritic triassic rocks in Brazil which contain olivine.

Jan 4, 1921

By S. R. Maloof, W. R. Mitchell, J. A. Mullendore

Preliminary experimental evidence is presented to show that the metallic impurities aluminum, iron, and silicon, and beryllium oxide as found in commercially pure hot-pressed beryllium powder can be reduced to lower Concentrations by Zone -Purification techniques. The reduction in the concentration of aluminum to extremely low levels (10 PPm) is noteworthy, since earlier work demonstrated that aluminum is a major factor contributing to the hot-tearing of beryllium during fusion welding. On the basis of present findings, a method is suggested for producing beryllium metal of improved weldability. EXPERIMENTAL research now being conducted on the purification of beryllium indicates that several of the metallic impurities and beryllium oxide can be reduced to lower concentrations by employing standard horizontal zone-refining techniques. For the preliminary work, commercially-pure hot-pressed beryllium having a purity of 97.84 pct was used. The chemical composition is given in Table I. The hot-pressed beryllium was machined into bars 5/8 by 5/8 by 4 to 6 in. in length. Beryllium-oxide boats which had been conditioned by prior heating in a vacuum of 10"5 mm of Hg at 1100°C for 3 hr were used to hold the beryllium while it was zone melted. The boat with its charge, along with a smaller beryllium-oxide boat containing scrap beryllium to be used for gettering purposes, was loaded into a quartz tube and evacuated to 10-6 mm of Hg. Alter alternately evacuating and flushing three times with purified argon, the furnace tube was backfilled to a pressure of 1/6 atm of A and sealed off by means of a vacuum-tight stopcock. It was then removed from the pumping equipment and mounted on the traveling carriage of the zone-refining apparatus. Heating was accomplished with a 10 kw 450 kc induc- tion heating unit using an induction coil consisting of two turns of 3/16-in. diam copper tubing. Before starting to zone melt, the atmosphere in the furnace tube was gettered by heating the scrap beryllium in the smaller boat to above its melting point and holding at temperature for several minutes. The carriage was then shifted so as to locate one end of the beryllium ingot in the large boat within the induction coil. A molten zone approximately 3/4 to 1 in. was established by loading directly into the ingot. The molten zone was moved very slowly along the length of the ingot. Before each pass was made the procedure for evacuating, flushing, and backfilling, and so forth was repeatedI' Speeds of 1 1/2 and 3 in- per hr were used with up to twelve zone passes. The appearance of a typical zone-refined ingot is shown in Fig. 1. After zone refining, the grains in the ingot appear to be elongated in the direction of zone travel, whilst before, they are essentially equi-axed. A microexamination revealed the presence of a network in the beryllium grains as seen in Fig. 2. Laue spots in back reflection pictures taken of the sample were not sharp, indicating the presence of subgrains in the structure. As can be seen, however, many of the network boundaries cross beryllium grain boundaries. It has been shown by Martin and Moore1 that beryllium solidifies as a bcc structure which then transforms to the hexagonal structure at about 1250oC.It is believed that the observed network is merely the outline of the bcc structure which formed from the melt and are not subgrain boundaries. In order to eliminate surface contaminants, approximately 1/16 of an inch of material was removed from the outer skin of each ingot after zone refining.

Jan 1, 1962

IN THE past, we have, perhaps, been somewhat careless in our furnace practice, in the use of high-grade material, lowering the production costs through demanding high-grade ores, increasing the size of units, and eliminating heat losses by collecting and returning unused heat to our furnaces. Further economies would seem to be possible through keeping out of the furnace those materials that appear to serve no useful purpose and carry with them heat that should be used in reduction operations. In the manufacture of pig iron, about three tons of inert nitrogen pass through the furnace for each ton of iron produced. This nitrogen serves no useful purpose in the chemical actions involved, but when discharged into the atmosphere it carries away a considerable quantity of heat. Can not this loss be eliminated, at least in part, through the use of more oxygen in the blast? Many metallurgical chemists, during the past 20 years, have stated that they thought it can and have urged that the plan be tried. Others have expressed doubt, not being able to visualize how more oxygen could be used in present practice; they have regarded it as impracticable, without trying to conceive of an entirely new practice based on a new reagent. That more experimental work has not been done is due to the fact that no cheap oxygen has been available, but the committee believes that there is strong reason to expect that, should a demand exist, 99 per cent. oxygen may be made at a cost not to exceed $3 per ton. The theoretical studies of the committee have indicated such marked economy by using oxygenated air in various operations that its members strongly recommend experimental work to verify the anticipated economies. The committee has developed plans for experimentally determining the effects of oxygen-enriched air on the operation of an iron, blast furnace. A furnace with a height of 30 ft. has been built and it is recommended that the plans be put in, effect as the first step in the research.

Jan 11, 1924

By Robert S. Archer

THE proper material of construction for a given purpose is that material which meets the requirements satisfactorily at the lowest ultirnatc cost. It is consistent with this principle that most aluminum castings are made of an alloy containing about 8 per cent. copper. This alloy possesses mechanical properties satisfactory for general engineering purposes together with manufacturing characteristics leading to the production of finished castings at low cost. It is to the aluminum industry what gray iron is to the iron and steel industry. Just as some services require "semi-steel," malleable castings or steel castings instead of gray iron, there is a certain and growing demand for aluminum castings of superior strength or ductility, or both. Since the beginning of .the industry producers and others have sought to develop alloys or processes by which such castings could be made. Out of these efforts have emerged many alloy compositions and special processes, of which only a few have had sufficient merit to survive. It is the purpose of this paper to describe those which seem to the authors to offer the greatest promise for the production on a commercial scale of aluminum castings of superior mechanical properties, with special reference to heat-treated castings. The suitability of an alloy or process for actual manufacture is affected by so many factors that the problem of appraisal is not a simple one. Since this is such an important part of the whole subject it is proposed to discuss briefly some of the requirements. The final verdict is of course the result of commercial trial and experience. It will therefore, perhaps, be profitable to employ a somewhat historical method of treatment in discussing the subject of alloy development. The alloys or processes to be used in the production of aluminum castings are to be considered from the standpoint of their effects on both the utility and the cost of the finished casting. Specific gravity and mechanical properties come under the first head, while the properties

Jan 1, 1927

By B. E. Sundquist

The various methods based on solution models for obtaining free energies of mixing from miscibility-gap data have been applied to a number of binary-alloy systems. For nine of these systems there exist experimental thermodynamic data that permit a comparison of the results to experiment. It was found that the method of van der Toorn and Tiedema almost invariably leads to results that are physically unacceptable and that vary drastically with small changes in the miscibility-gap parameters. The subregular solution model is found in all cases, except the Al-Zn, Fe-Cr, and Cu-Pb systems, to exaggerate the free energy of mixing by 30 pct or more. The model developed by Lumsden is found to give results that are often in excellent agreement with experiment and which exaggerate the free energy of mixing by no more than 30 pct. These results and others give evidence that the Lumsden treatment of the effect of unequal atomic sizes and of imperfect configurational randomness due to deviations of AB bond energies from the mean of AA and BB bond energies is adequate for most systems. ANALYTIC expressions are frequently proposed for the dependence on composition of the activities of the components of a solution. Because the development of solution theory is incomplete, these expressions contain parameters which must be determined by experiment. The measurement of activities is often difficult and consequently such measurements are less readily available than are measurements of phase equilibria which, under certain conditions, can also be used to evaluate these parameters. For example, suppose it is known that two structurally dissimilar phases, each of known composition, in an n-com-ponent system are at equilibrium at a given temperature and pressure. n equations can be set up in terms of these parameters expressing the equality of the chemical potential of each component in the two phases. In addition, one can write the Gibbs-Duhem equation for each phase that also contains these parameters. Thus, if these n + 2 equations contain n + 2 parameters, these parameters can be determined (at the temperature in question) from the phase diagram alone. If the average number of parameters in each expression for the activity of a given component in a given phase is V then there will be 2nV parameters involved. Equating 2nV to n + 2 shows that, for n + 2, V = 1. If the temperature dependence of each parameter were to be expressed in some explicit form one could use equilibrium conditions at a number of temperatures to increase V. The situation is much improved when the two phases in equilibrium are structurally similar. It can then be assumed that, stably or metastably, two phases will become one at higher temperatures. Thus the number of parameters involved becomes nV instead of 2nV. Hence, V = 2 for n = 2 using only one temperature. (It is implied here that the activity expressions used are valid over the entire composition range.) In this investigation only the equilibrium of two structurally similar, two-component phases (miscibility-gap systems) will be considered. The various proposed solution models will be applied to a number of these systems and the results compared with available experimental results. All of the analytic expressions that have been proposed for the free energy of mixing of a two-component system are of the form where ?Gmix is the free energy of mixing per mole of solution, N1 and N2 are the mole fractions of components 1 and 2, respectively, and f(Ni, T) is some function of composition and temperature. In the "ideal" solution model f = 0. In the "regular" solution model f = a constant. Since these two models permit only a symmetric equilibrium diagram they will not be considered further here. The simplest model that permits a nonsymmetric miscibility envelope is the so-called "subregular" solution model proposed by Hardy.1 This model gives where the Ci(T) are functions of temperature only. The same expression for f is obtained from the "linear a function" model proposed by Darken and Gurry2 and applied to miscibility-gap systems by Wriedt.3 This model requires that the a function defined by be a linear function of composition (yi is the activity coefficient of component i). This model is not purely hypothetical for it has been found2 to hold true for a number of systems. It is readily shown3 that the f(Nl, T) obtained from this model is of the form given in Eq. [2]. It will be noted that the subregular solution model contains only two parameters and hence both of them can be determined at any desired temperature below the critical temperature, Tc, for a miscibility-gap systems in the manner described previously. At T, the two constants can be determined by equating the second and third derivatives of ?Cmix with composition to zero. Another two-parameter model was proposed by Lumsden4 who set

Jan 1, 1967

By E. M. Norris

Phosphate deposits are distributed widely over the earth's surface. Of the known areas of deposit, eight fields are of particular interest because of their vast reserves of high grade phosphatic material and the volume of their production that goes to the world's great consuming areas. These fields, in the order of their present economic importance, are situated respectively in Florida, French Morocco, Kola Peninsula of U.S.S.R., Tunisia and Algeria, Tennessee, Montana-Idaho-Wyoming-Utah, Ocean and Naru Islands in the Gilbert group, and in Egypt. The Rocky Mountain deposits have a comparatively low ranking in the phosphate trade of today, but this field contains one of the largest known reserves of phosphatic material, associated with which are recoverable trace minerals, which are of increasing importance in our national economy. The first discoveries of phosphate rock in the western states were recorded in Cache1 and Rich2 counties in Utah, respectively in 1889 and 1897. Mining operations were begun on these deposits near Montpelier, Idaho, in 1906. During the latter year geological studies of the phosphate beds were started by Weeks and Ferrier of the U. S. Geological Survey. These studies have been continued to the present day by a distinguished roster of the Survey's technicians. As a result of this systematic exploratory program, the Survey has published a series of bulletins, papers, and maps, which provide the mining public with a comprehensive study of the exposed

Jan 1, 1949

By Richard H. Rein, John Chipman

The activity of SiO2, in the entire liquid system SiO2-CaO-Mg0-A12O3 at 1600°C is calculated from the distribution of silicon between these slags and Fe-Si-C alloys saturated with either graphite or silicon carbide, the activity coefficient of silicon in these alloys, and the requisite thermodynamic data. The activities of the other components in the ternary systems SiO2-CaO-A12O3, SiO2-MgO-CaO, SiO2-MgO -A12O3 are computed from these data by the IrON blast-furnace slags can be regarded as consisting of the four major oxide components, SO2, CaO, MgO, and A12O3 along with minor proportions of other oxides and of sulfur. The purpose of this study is to measure the activity of silica in the liquid solutions of these four oxides at iron-making Gibbs-Duhem equation with the aid of the known free energies of several of the interoxide compounds and the accepted phase diagrams. Based on these activities, new data are Presented for the free energy of formation of a number of the interoxide compounds. The free energy of mixing the liquid metasilicates of CaO and MgO shows slight positive deviations from the ideal. temperatures and to obtain activities of the other components by application of the Gibbs-Duhem equation and the properties of several interoxide compounds. Recent investigations on the activity of silica in the SiO2-CaO-A12O3 system1-3 and recogntion of a serious error in older data for the free energy of formation of SiO2 (Ref. 4) have succeeded in bringing a fair degree of concordance into the results of different investigators. In the present study, the activity of silica is obtained from the silicon-distribution experiments described in a previous paper,' the revised activity coefficient of silicon

Jan 1, 1965

By AIME AIME

COMMITTEES. LOCAL COMMITTEE.-R. C. Crawford, Chairman; Harrison W. Craver, Secretary; Julian Kennedy, Taylor Allderdice, E. W. Pargny, Charles L. Miller, W. H. Rea, S. A. Taylor, M. E. Wadsworth, W. A1. Henderon, A. C. Dinkey, W. L, Jones, E. L. Messier, George Mesta, J. H. Jones, G. H. Riley, S. L. Goodale, D. W. McNaugher. LADIES' COMMITTEE.-Mrs. Taylor Allderdice, Chairman; Mrs. Julian Kennedy, Mr. R. C. Crawford, Mrs. E. M. Herr, Airs. J. W. Marsh, Mrs. T. A. Mellon, Mrs. G. P. Bassett, Jr., Airs. D. M. Clemson, Mr. Charles L. Miller, Mrs. V. L. P. Shriver, Mrs. W. A. Bostwick, Mrs. A. C.. Dinkey, Mrs. A. P. Childs, Jr., Mrs. F. R. Dravo, Mrs. Hermon Griffin, Mrs. W. H. Nimmick, Mrs. F. H. Lloyd, Mrs. S. G. Cooper, Mrs. S. H. Church, Mrs. E. N. Ohl. The Institute Headquarters was established at the Hotel Schenley, where a bureau of information was maintained for the benefit of the visiting members and guests of the party during the time of the meeting. TECHNICAL SESSIONS. The first session, held Tuesday evening, Mar. 1, 1910, in the large lecture hall of the Carnegie Institute, was called to order by Harrison W. Craver, Secretary of the Local Committee. Mr. Craver introduced Dr. John A. Brashear, who extended to the members and guests a hearty welcome to the city of Pittsburg, to which David W. Brunton, President of the Institute, responded. The following papers were presented in oral abstract by the authors: Biographical Notice of Dr. Charles B. Dudley, by Dr. R. W. Raymond, New York, N. Y. Biographical Notice of William Metcalf, by Col. II. P. Bope, Pittsburg, Pa. Development of Hindered Settling Apparatus, by Robert H. Richards, Boston, Mass. (Illustrated by lantern-slides.) A Few Mining Districts in the Argentine Republic, South America, by Z. S. Beyl. (Illustrated by lantern. slides.)

Apr 1, 1910

By Robert G. Johnson, Richard J. Prosen

THE present work was done in connection with a program for investigating metal-to-ceramic braze techniques using the well-known reactivity of titanium with certain ceramic oxides. The investigation extended over the range of 0 to 30 pct Ti. The indium was obtained from the Indium Corp. of America and was specified to be 99.97 pct pure. The titanium was supplied by Metals Disintegrating Co. and was stated to be 99.5 pct pure. Each 2 to 4 g quantity of the alloy compositions studied was prepared using a mixture of 300 mesh powders pressed into pellet form. The pellets were heated in thin-walled molybdenum crucibles using a resistance-wound furnace in a vacuum less than 10-4 mm of Hg. Little reaction occurred between the molten alloy and the crucibles at the temperatures and short time intervals used. Only slight spectroscopic traces of molybdenum were found in the melt after a typical period of heating. The points shown on the phase diagram of Fig. 1 represent thermal arrest measurements. The phase boundaries shown are consistent with the thermal arrest and X-ray data obtained. The temperatures were determined using a Pt-Pt 10 pct Rh thermocouple with the junction spot-welded to a short molybdenum rod. The rod was almost completely immersed in the liquid metal, so that good thermal contact with the melt was achieved. The small mass of the crucible and its contents made it possible to obtain many heating and cooling curves in a few minutes time, an advantage which helped to minimize the effects of indium evaporation at the higher temperatures. A Brown strip chart recorder was used to display the thermal arrest curves. To check the technique, the melting point of 99.999 pure Al was measured and found to be within 1 of 660.2c, the accepted melting point. The upper limit of temperature with this technique was about 900°C beyond which the evaporation rate of indium became great enough to alter appreciably the alloy composition during the runs. A peritectic transition was found at 796°+ 5°C from 1.5 to 30 wt pct Ti. It was not found at 0.5 or 1.0 pct. A small super-cooling effect was observed. The melting-point transition to the B + L phase was found up to 20 pct Ti but not at 25 pct. Within the 1 deg accuracy of the measurement, the transition temperature was that of pure indium, 156°C. The liquidus line to the left of the 1.5 titanium point was located only approximately. The two crossed circle points at 1.0 and 0.5 pct Ti place a lower limit on the liquidus line and were determined by observing visually the cessation of vibrations in the melt caused by the damping effect as B-phase crystals were formed during cooling. The B-phase boundary was found at 23.8 pct Ti by X-ray analyses of small single crystals of the B phase isolated from 2 pct Ti melts. The compound was found to be Jetragonal with lattice dimensions of c = 3.052A and a = 10.094W. From the unit cell dimensions and the measured density of 6.42 i 0.05 g per cc, the compound was determined to be In4Ti3 which has 23.8 pct Ti. The calculated density of 6.44 g per cc is obtained assuming 2 mol

Jan 1, 1962

By Arthur La Motte

I NDUSTRIAL explosives, as distinguished from military explosives, include high explosives and blasting powder. The high explosives which are best known are straight dynamite, gelatin dynamite, ammonia dynamite and permissibles. There are two kinds of blasting powder, saltpetre blasting powder and nitrate of soda blasting powder. Blasting powders are mechanical mixtures of nitrate of potash or nitrate of soda with sulfur and charcoal, highly compressed, granulated and glazed. They ignite from a spark and burn with relative slowness, the rate of burning and hence the rate of conversion into gases depending upon the size of the granulation and upon the degree of. confinement under which the powder is placed. High explosives, on the other hand, are chemical compounds which detonate; that is, when the explosive is subjected to a violent shock, provided in practice by a blasting cap or an electric blasting cap, the molecule of the essential ingredient, usually nitroglycerin, is disrupted and the energy and heat released cause any other explosive ingredients which may be present, such as ammoniuin nitrate or T.N.T., to decompose with a resultant evolution of gases at an extremely rapid rate varying from 6000 to 20,000 ft. per second.

Jan 1, 1924

By G. T. Jackson

The Alaska Gastineau Mining Co.'s mine is located at Perseverance, about 4 mi. east of Juheau, Alaska. Its property consists of a group of claims, the lode system traversing these claims for a distance of 11,000 ft. (3352 m.). It is shown in Fig. 1. The ore deposits occur in what is known as the Juneau gold belt. This gold belt can be traced for about 50 mi. northwest of Juneau and 40 mi. southeast. It consists of a single band, several hundred feet wide, in which stringers and veins of quartz, carrying gold, occur in a slate formation near its contact with some altered volcanic rock known as greenstone. The Perseverance orebody consists of stringer lodes, having a strike northwest and southeast, dipping about 60° to the northeast. These

Jan 1, 1920

By J. W. Downey, M. V. Nevitt

The phase boundaries for the 950" isothermal sections in the ternary systems Zr-Co-0 and `Zr-Ni-0 have been determined for the composition range from 50 to 100 at. pct Zr. The two systems show very similar phase relations, having no extensive solid solution phase fields. Each contains a ternary phase. These phases are apparently isostructural, but their structure has not been determined. Some aspects of the phase relations are discussed in terms of the alloying behavior of transition metals. THE work described in this paper is the outgrowth of a recent study of the occurrence of phases having the Ti2Ni-type structure (structure-type E9,) in certain ternary systems involving Ti, Zr, or Hf with another transition metal and O.", In the Zr-CO-0 and Zr-Ni-0 systems no Ti2Ni-type phases were found to occur. However, there are several interesting aspects of the phase relations in the two systems which have significance from the point of view of the alloying behavior of transition metals. The results of this investigation may also have some importance in studies of the oxidation of Zr-Co and Zr-Ni alloys. In both the Zr-Co-0 and Zr-Ni-0 systems only the 950" isothermal sections were investigated and, as a further restriction, the study was limited to the composition range from 50 to 100 at. pct Zr. A tentative Zr-Co binary diagram has been published by Larsen, Williams, and Pehin. In the composition range pertinent to the present work they report a eutectic at 980°C and 75.9 at. pct Zr, the products of which are the terminal solid solution based on /3 Zr and the compound Zr2Co, and a eutectic at 1080" and 64.8 at. pct Zr whose products are Zr,Co and ZrCo. The solid solution based on /3 Zr is shown to decompose eutectoidally at 826°C into a Zr and Zr2Co. The limits of solubility of Co in a and /3 Zr have not been established. The structure of Zr2Co is not identified in the publication just cited. Dwight has reported that ZrCo has the CsC1-type strcture. The Zr-rich portion of the Zr-Ni diagram has been determined by Hayes, Roberson, and Paasche." The phase relations are very similar to those of the ZrCo system. A eutectic reaction whose products are /3 Zr containing 2.9 at. pct Ni and Zr,Ni occurs at 961°c, and a eutectic between Zr,Ni and ZrNi is found at 985". The solid solution based on /3 Zr decomposes eutectoidally at 808°C. The solubility of Ni in a Zr is not known accurately but is believed to be very small. Smith, Kirkpatrick, Bailey, and Williams7 have found that Zr2Ni has a tetragonal structure of the A1,Cu-type and that ZrNi is orthorhombic. Domagala and McPherson8 have published a constitution diagram for the system Zr-ZrO,. At 950" their diagram indicates that the solid solution of 0 in 0 Zr is stable from 0 to 0.5 at. pct while the phase field of 0 in a Zr extends from 6 to 29 at. pct. These solubility limits were adopted in the present study and no binary Zr-0 alloys were made. No previous data on the phase diagrams of the ternary systems are known to exist. EXPERIMENTAL PROCEDURE The experimental details involved in the preparation of alloys in this laboratory by arc melting have been described in several previous papers"3 and they will not be repeated here. Information concerning the purity of the metals used is given in Table I. Oxygen was added in the form of reagent grade ZrO,. All of the cast specimens in both alloy systems were annealed in air-atmosphere tube furnaces at 950 3' for 72 hr and water quenched. The specimens were protected from oxidation by wrapping them in Mo foil and sealing them in quartz tubes that had been evacuated at room temperature to a pressure of 1 x 10B mm of Hg. The phase boundaries were determined by metallography, and identification of the phases was accomplished primarily by X-ray diffraction methods which employed a powder camera having a diameter of 114.6 mm. The diffraction techniques which are in use in this laboratory have been previously described.' An etchant that proved satisfactory for most of the alloys consisted of 5 pct by vol of AgNO

Jan 1, 1962

For handling rough rock, the shovel-train system is unexcelled. The ideal application is a physically large, but not excessively deep, open-pit mine from which the coarsely blasted ore and waste must be transported distances in excess of three miles. If, in addition, a high production rate is to be maintained, railroad haulage will probably afford a lower cost per ton transportation than will any other haulage method. Relatively gentle grades must be employed- usually 3% for uphill hauls and 4% for downhill hauls. The greater the differences in elevation the greater are the railroad track grade space requirements. By way of illustration, a 3% ramp out of a pit only 300 ft deep must be almost two miles long. Mainline track locations should be selected carefully so that the frequency of movements during the life of the mining operation is minimized. This applies both to ore and to waste haulageways. Such moves are not only expensive but difficult to execute without adversely affecting production rates. The large mine affords greater opportunities for judicious location of semi-permanent trackage.

Jan 10, 1967

By John Jermain Porter

PAGE. I. INtroduction............ 191 I1. Derivation of Formula foR Fuel-RequiRements.... 192 1. Heat Available in the Hearth........193 a. Method of Calculation..193 b. Data for the Determination of Critical Temperature.. 195 2. Heat Necessary in the Hearth ...... 197 a. To Care for Slag..197 b. To Care for Pig-Iron...198 c. To Reduce Silicon........198 d. For Other Items.........199 3. The Effects of Rate of Driving ..... 199 4. Loss of Carbon Between Throat and Hearth.....201 a. Solubility of Coke..201 b. Carbon-Loss Due to Flux....201 c. Effects of Reducibility of Ore..202 5. The Formula as Used........203 III. The LImitations of the Formula........ 204 1. Through Effects of Irregular Furnace-Work.....204 2. Through Ratio Between Heat-Requirements in Shaft and Hearth. 20.5 IV. The Formula Applied to Actual Furnace-Records,.. 209 1. Description of Furnace-Stock........ 209 2. Furnace Dam..........210 3. Application of Formula..211 4. Average Furnace-Practice..213 V. Sources of Error........... 214 VI. SuggesTions for Practical Methods of Fuel-Economy... 215 VII. Efficiency as a Factor in Furnace-Management.... 219 1. The Efficiency Principle........ 219 2. The Application to the Blast-Furnace..220 I. Introduction. The heat-balance of the blast-furnace has been a favorite subject for discussion for many years. and its study has contributed much to our knowledge. and still possesses a certain academic interest. As a means of accounting for differences in fuel-consumption, however. it has failed utterly. and it is evident that we must look elsewhere for the means of accomplishing this end.

Jan 1, 1912