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By W. S. Tower

STEEL is the basic metal, the main metallic prop of the modern industrial world, a good gage for measuring the state of our complex economy. Any who had doubts on that score should have had them dispelled by the many evidences of public concern over the affairs of the steel industry in recent months. I do not need to relate the various criticisms of the industry, nor the questions about its policies and performance which have come in a rising flood, especially from unthinking and irresponsible sources. But judged from the standpoint of production, or from plans to improve and expand facilities, or from technical progress, the facts about the steel industry are proof of

Jan 1, 1948

By P. W. George, G. A. Hellstrand

In 1915, H. A. Guess, Vice President of American Smelting & Refining Co., in charge of its Mining Department, learned that the Anglo-Newfoundland Development Co., Ltd., a pulpwood and paper-mill enterprise, had found upon its large concession in Newfoundland, and had opened up by shaft to the third level and some drifting, a lenticular orebody indicating about 100,000 tons, as an extremely fine-grained sulfide ore, averaging about 0.05 oz. Au, 4 oz. Ag, 1.5 per cent Cu, 10 per cent Pb, 18 per cent Zn; and that having sent parcels of this ore to Minerals Separation, Ltd., and various other metallurgical testing concerns without obtaining any success in commercial separations thereof, had discontinued work thereon and let the workings fill. Mr. Guess wrote to the general manager of that company and obtained a few hundred pounds of the typical ore, which he sent to his company's metallurgical testing laboratory at Flat River, Mo., outlining various flotation tests desired thereon, in an endeavor to obtain separation into a commercial lead concentrate and a zinc concentrate. But the art of flotation had not then progressed far enough to treat such ore, the galena and zinc blende being so fine grained that grinding to about 300 mesh was required to release the mineral particles in their gangue. Mr. Guess had flotation and other tests continued upon this ore from time to time with whatever new reagents and flotation devices were evolved as time went on, and finally, in 1925, he succeeded in effecting in his company's testing plant, then at Wallace, Idaho, separations into lead concentrates and zinc concentrates of satisfactory commercial grade. Mr. Guess then proceeded to unwater, examine and sample the property and made with the owners a partnership operating agreement upon the mine itself and a considerable area surrounding it, and in the early summer of 1926 began to prospect for additional orebodies, utilizing for such prospecting geophysical methods under the direction of Hans Lundberg, methods which up to that time had been little used in mining in the western hemisphere. This geophysical work found two large flat-lying orebodies of a type precisely similar to the smaller body of the original discovery. The larger orebody, some 3500 ft. west of the original

Jan 1, 1935

By George H. Ashley

The Legislature of the Commonwealth of Pennsylvania at its last session passed a new act dealing with barrier pillars, which may have a wide interest in other states. In the past the laws of Pennsylvania have required that the superintendent of a mine "shall not permit the mining of coal within 50 ft. of any abandoned mine containing a dangerous accumulation of water, until said danger has been removed by driving a passageway to tap and drain off said water, as provided for in this act: Provided, That the thickness of the barrier pillars shall be greater aid shall be in proportion of one foot of pillar thickness to each one and one-quarter feet of water head, if in the judgment of the engineer of the property and that of the district inspector it is necessary for the safety of the persons working in the mine." Thus it has happened that a thickness of several hundred feet has necessarily been left in pillars in mining. It has seemed to many in the mining industry that this left an unnecessary amount of coal in pillars, and did not provide that the pillar be left equally on the two sides of the mine. As a result the General Assembly of 1927 by Joint Resolution authorized the Governor to appoint a Commission of "seven prominent citizens, of whom four shall be recognized mining engineers, one shall be a hydraulic engineer, one a geologist of recognized standing in his profession, and one a State mine inspector from the bituminous coal mining district, to investigate and report upon barrier pillars in the bituminous coal region." The Governor appointed the following Commission: Morris Coulter, Clearfield Bituminous Coal Corp., Indiana, Pa.; A. E. Roberts, Monroe Coal Mining Co., Revloc, Pa.; George T. Lewis, Westmoreland Coal Co., Irwin, Pa.; Morris Knowles, hydraulic engineer, Pittsburgh, Pa.; Thomas A. Mather, State Inspector of Mines, Tyrone, Pa.; A. B. Jessup, Anthracite Coal Operators Association, Jeddo, Pa.; George H. Ashley, State Geologist, Harrisburg, Pa. Mr. Coulter was elected Chairman and Mr. Ashley, Secretary. This Commission held meetings in Harrisburg, Johnstown and Pittsburgh. It obtained and considered the laws and experiences of other states and European countries. Some of its members conferred at length with the directors and other members of the U. S. Bureau

Jan 1, 1930

Executive HENRY A. BUEHLER, Chairman ERLE V. DAVELER EDGAR RICKARD JOHN M. LOVEJOY WILLIAM WRAITH J. V. W. REYNDERS, Consultant Finance HENRY KRUMB, Chairman E. E. ELLIS PAUL D. MERICA H. G. MOULTON, Consultant Admissions RALPH M. ROOSEVELT, Chairman GEORGE D. BARRON DONALD M. LIDDELL WILBER JUDSONW. D. B. MOTTER, JR.

Jan 1, 1934

University of Alabama University, Alabama Mining and Metallurgical Society WILLIAM S. SPRINGER, President ROBERT E. MEAD, Secretary J. R. CUDWORTH, Faculty Sponsor MILTON H. FIES, Counselor University of Arizona Tucson, Arizona Miners' Society PERCY E. COE, President W. JAMES THOMAS, Secretary E. P. MATHEWSON, Faculty Sponsor B. R. HATCHER, Counselor

Jan 1, 1937

By O. D. Gonzalez

ThIS communication presents the results of a determination of the permeabilities of hydrogen and deuterium in a iron from 360° to 560°C. Recently Heu-mann and primas' have given values of the diffusivity and solubility in a iron of the two isotopes from which the permeability can be calculated. The work reported in the present communication, however, is a direct measurement of the rate of permeation of the isotopes through an identical iron specimen under the same conditions, so that systematic errors can be minimized in the calculation of the ratio of the permeabilities—the value which is usually of main importance in establishing limits for isotopic differences in diffusive processes. Experimentally the procedure used was the usual one: a steady-state flow of gas produced by a pressure difference across an iron membrane was observed as the pressure rise with time in a previously evacuated, calibrated volume connected to the outlet side of the membrane, while a constant pressure of gas was maintained on the opposite inlet side. The membrane was a cylindrical tube 9.38 cm long, 0.730 cm inside diam, 0.187 cm wall thickness, fabricated of 99.95 pct vacuum-melted National Research Corp. iron (less than 0.003 pct C). One end was sealed by a heliarc-welded iron (99.95 pctj lid of 0.147 cm thickness; the other end of the tube was welded to a 304 stainless-steel tube (0.318 cm ID and 0.318 cm wall) which connects to a vacuum system and to the calibrated volume including a dibutylphthalate manometer. The temperature of the iron membrane was maintained constant to ±0.l°C and was measured with an iron-constantan thermocouple which was calibrated against a standard Pt/Pt-Rh thermocouple: the temperature variation along the length of the membrane did not exceed ±0.5°C. Hydrogen was allowed to pass through the membrane assembly for 72 hr at 615°C before permeability measurements were begun. The system was tested at temperature before and after the experiments by a substitution of helium for hydrogen in the inlet side; under these conditions the pressure rise observed in the outlet side was negligible at all times. The gases used for the permeability measurements were 99.95 pct Matheson prepurified H2 and 99.7 pct D2 (0.3 pct HD) from the Isomet Corp. The gases were dried with liquid N2 before use. In Fig. 1 the logarithms of observed flows, jt, for a pressure difference of 73.4 cm Hg are plotted against T-1 Each point in Fig. 1 represents the slope determined by a least-square evaluation of a plot of the pressure in the outlet side of the membrane against time, including at least two separate sets of observations. Each point in the figure has an uncertainty of ±0.6 pct arising from the experimental uncertainty in the pressure and time measurements. The standard deviation of the observed pressures from the straight lines in all cases is less than the experimental precision of the measurements. The observed flow, jt, includes a small but not negligible flow through the stainless-steel connection.

Jan 1, 1968

By L. J. Erck

H EAVY-MEDIA separation continues to be the favored process for concentrating the coarser fractions by elimination of undesirable tailing and middling fractions. The first vessel used for heavy-media separation was the closed-top cone. Further developments then led to the Akins spiral separator which fulfilled the requirements for improving metallurgica1 separation as well as gaining mechanical advantages. During the last season there has been a substantial influx of separator designs for further improvements of metallurgical separation based on the heavy- media method as well as attempting to garner further mechanical advantages with reduction in power consumption to boot. The newest of these designs was the Hardinge counter-current separator which was introduced into the field last spring in two plants. Both Hardinge separators proved satisfactory in operation and substantiat-

Jan 1, 1950

By D. W. Fuerstenau

MEASUREMENT of zeta potentials is a useful tool to study the surface chemistry of minerals under flotation conditions.1,2 Because there is continued interest in this approach, the apparatus for obtaining zeta potentials of nonconducting solids by the streaming potential method is outlined here. Fig. 1 illustrates the streaming potential apparatus." The streaming potential cell or plug consists of two 24/40 standard ground joints (4) joined with a piece of pyrex tubing 60 mm long and 12 mm in diam (5). The electrodes are made of bright platinum disks 19 mm in diam and 1 mm thick through which 0.5-mm holes have been drilled (6). To the surface of each is welded a piece of 80-mesh platinum gauze. Each electrode is permanently mounted on the ends of the inner parts of the two standard joints by means of a platinum wire (7) which connects it to the tungsten seal at the end of the cell (8). For ease in cleaning and handling the apparatus, the streaming cell is fastened to the 500-ml reservoir flasks (1) by means of two 18/9 ball and socket joints (2). This particular arrangement permits passage of the solution in either direction through the plug of particles. Flow of solution can be stopped by a stopcock (3). One of the reservoir flasks has a large opening to permit insertion of either a thermometer or a pair of electrodes for measuring pH of solutions within the system. In making the experiments, the plug is filled with 48 to 65-mesh particles, but a layer of 28 to 35-mesh particles is placed at each electrode to prevent any of the finer particles from passing through holes in the electrodes. The assembled apparatus is shown schematically in Fig. 2. To eliminate CO2 from the solutions, all experiments are conducted in a nitrogen atmosphere. Nitrogen, used to drive solutions through the plug, is passed through a bottle of concentrated KOH solution to remove CO2 (9). A 9-liter ballast reservoir (10) is used to maintain a more nearly uniform pressure. A series of stopcocks controls the direction of flow nitrogen to the flasks (11). Tubes of as-carite prevent backflow of CO2 into the system (12). Driving pressure, which can be set at any desired value, is measured with either a water manometer (13) or a mercury manometer (14). Reservoir flasks have side arms for making pressure corrections for the difference in water levels in the flasks. Streaming potentials are measured by the circuit illustrated in Fig. 2. The electrodes from the plug are connected through mercury wells (15) to a reversing switch (16), which reverses the polarity of the electrodes depending on the direction of flow of solution through the plug. The streaming potential is measured with a Leeds and Northrup type K2 potentiometer (17). Proper choice of null instrument is important because Eq. 1 assumes that the current which escapes through the measuring instruments is negligible. An ordinary galvanometer cannot be used to determine the null point because

Jan 1, 1957

By W. R. Hudspeth

AS an outgrowth of its spodumene recovery operation at Kings Mountain, N. C., Foote Mineral Co. has been recovering a heavy mineral by-product. Foote leased this idle plant in 1951, reactivated it, using a new spodumene recovery process, and purchased plant and properties in October 1951. While the operation at Kings Mountain is primarily concerned with the production of spodumene concentrate, pilot plant work determined that the pegmatites also contained heavy minerals including cassiterite. Plans were made to recover the heavy minerals as a by-product and the flowsheet incorporated these facilities when the mill was modified for the new spodumene recovery process. The orebodies consist of spodumene, feldspar, quartz and mica. Apatite, tourmaline, and beryl are present in small quantities. The wall rock is pre- dominantly hornblende shist. The heavy minerals, including cassiterite, columbite, pyrrhotite, monazite, pyrite, and rutile represent about 0.2 pct of the ore. The fine-grained heavy minerals are disseminated throughout the dikes, apparently unassociated with the spodumene. The pegmatites are quarried and secondary breakage is by mud-capping and block-holing. Power shovels load into trucks transporting the ore to a coarse ore bin. A Telesmith 10x36-in. apron feeder delivers the ore to an 18x36 in. Traylor Jaw crusher adjusted to discharge -3 in. product to a primary conveyor. The conveyor delivers to a 4x5-ft Tyrock single deck vibrating screen using 3/4 in. cloth. The screen undersize is elevated to the crushed ore bin. Screen oversize goes to an Allis-Chalmers Hydrocone Crusher fitted with 4 in. concave and set to deliver approximately 66 pct minus 3/4 in. The crusher discharge returns to the primary conveyor. The crushing and screening installation has a capacity of about 60 tons per hour. Spirals The crushed ore is delivered at a rate of 350 tons per day to two 6x8-ft Hardinge Pebble Mills, equipped with 20 mesh Ton-Cap trommel screens. The screen oversize is pumped to a 12-in. hydroclone for primary desliming. The hydroclone underfl spirals. There is no heavy mineral loss in the hydro-clone overflow. The spirals bank consists of eight 5-turn Model 24-A Humphreys Spirals. The top port and the last four ports of each spiral are blanked, the remaining nine port splitters are adjusted to remove about 5 pct feed weight. The heavy mineral rougher concentrates are upgraded on a Deister Overstrom table. The spiral concentrates contain approximately 4 pct heavy mineral, and the spiral reject, which goes to another section of the plant for spodumene recovery, contains about 0.03 pct heavy mineral. There is an interesting feature in the spirals installation. An adjustable splitter mounted on the discharge boxes splits out a mica fines product containing very little heavy mineral. The mica product is cleaned by spiralling and screening. Thus the spirals recover two products; mica, and a heavy mineral rougher concentrate. Table Treatment The rougher spiral concentrate goes to a Deister Plato table, modified to receive a Deister-Overstrom No. 6 rubber cover with sand riffles. The table is operated with a 5/8 in. stroke, 270 strokes per minute, and a slope of 1/2 in. per ft from feed to tailings side. There is no slope adjustment from motion to concentrate end. Wash water consumption is relatively high, since the large spodumene grains tend to report with the fine heavy minerals. A middling band about 4 in. wide is maintained in order to produce clean concentrate. The middling, representing about 10 pct of table feed, is recirculated by air-lift. A band of concentrate grade coarse spodumene occurs just below the middling. This is removed and delivered to concentrate storage. The table tailing, containing approximately 0.7 pct heavy minerals, is returned to the spodumene feed preparation circuit. The heavy mineral table concentrates are approximately 45 pct cassiterite, 33 pct columbite, 14 pct pyrrhotite and 8 pct monazite, together, with some rutile, pyrite, and copper from blasting wire. Concentrate is collected at 24 hour intervals. and dried. If the concentrate remains in wet storage appreciably longer surface oxidation takes place which seriously interferes with the subsequent magnetic separation process. About 150 lb of heavy mineral concentrate is produced per 24 hours and shipped to the company's plant at Exton, Pa. for final separation into tin and columbium concentrates.

Jan 1, 1952

FREderick H. Davis, Electrical Engineer of the Westinghouse Electric and Manufacturing Co., in charge of the plant at Bodie, Cal. (communication to the Secretary): I beg to offer, to complete the information conveyed in Mr. Leggett's paper, the following report of tests of the electrical efficiency of the power-transmission he has described:

Jan 1, 1895

By G. V. Jere, C. C. Patel

Chlorination of the various constituents of ilmenite by different chlorinating agents in presence of various reducing agents, have been considered on the basis of the standard free energy and standard enthalpy changes as a function of temperature. The standard free energy change considerations show that it is beneficial to chlorinate ilmenite by chlorine in the presence of carbon and also that iron constituent of ilmenite can be preferentially chlorinated by clzlorine, titanium tetrachloride or their mixture. These findilzgs have been corroborated from the published work. METALLURGICAL processes involving the use of titanium tetrachloride have gained in importance because of the use of the latter in the manufacture of titanium metal. Since ilmenite is more abundant in nature than any other titanium mineral, the future of the metallurgical processes depends on the utilization of ilmenite for the production of titanium tetrachloride. In these laboratories, investigations have been carried out on the chlorination of ilmenite under a variety of conditions.1'2 During these studies, it was noticed that 1) preferential chlorination of iron was effected at low temperatures (400° to 600°C) and at low carbon content (6 to 7 pct), 2) carbonyl chloride retarded the chlorination of iron oxides and titania perceptibly, while 3) carbon-tetrachloride, compounds of sulphur and some other catalysts favored the chlorination. Moles3 has found that oxides of iron are chlorinated in preference to titania at high temperatures, while wilcox4 has claimed the preferential chlorination of titania between 1200" and 1500°C. It has been shown in this paper that preferential chlorination of titania claimed by Wilcox is not likely to occur. Daubenspeck and coworkers5,6 have claimed the preferential chlorination of iron by chlorine or by a mixture of titanium tetrachloride and chlorine between 700° and 1050°C in the absence of carbon. Even when plain titanium tetrachloride is employed as the chlorinating agent, pascaud7 noticed the preferential chlorination of iron and other oxides. The purpose of this paper is to explain from thermodynamical considerations, the various chlorination reactions studied so far. ILMENITE CONSTITUENTS AND THEIR CHLORINATION PRODUCTS Although the general composition of the ilmenite mineral is represented as FeTiO,, most of the ilmenites found in nature have variable quantities of TiO2 (44.6 to 64 pct), FeO (4.7 to 36 pct) and Fe2O3 (6.9 to 28 pct).8 The higher content of ferric iron in ilmenites was attributed by Millerg to the presence of arizonite (Fe2O3.3TiO2). But the X-ray studies by Overholt, Vaw, and odd" have shown that arizonite is a mixture of haematite, ilmenite, anatase, and rutile. Except for the anatase, similar views have been advanced by Lynd, Sigurdson, North, and Anderson8 from magnetic, X-ray, and optical and electron microscope studies. The ilmenite ores can, therefore, be assumed to consist of mineral aggregates of ilmenite, rutile and haematite. From the free energy of formation of ilmenite (FeTiO3), it has been shown by Kelley, Todd, and King11 that ilmenite is stable even up to its melting point (1367°C) and would not undergo decomposition into its constituent oxides. Schomate, Naylor, and Boericke12 have found that in the presence of a reducing agent the iron constituent of ilmenite is selectively reduced. The reaction of chlorine with ilmenite in presence of a reducing agent can, therefore, be synonymous with that of the reaction of chlorine with the constituents of ilmenite, viz., TiO2, FeO, and Fe2O3. Most of the reaction products of chlorination of ilmenite in the presence of reducing agents will be in equilibrium with their dissociation products, depending on the temperature. The titanium tetrachloride is, however, quite stable up to 1500°C due to its covalent nature. The equilibrium for the ferric chloride system has been investigated by Kangro and Bernstorff, 13, schafer14 and Kangro and petersen,15 and the results are summarized in Fig. 1, curves a, b, and c respectively. From these results, it is clear that the ferric chloride disociates as follows: 324° to 700°C FeaCl6(g) ?2FeCl2(c) + Cl2(g) [1] 324°to 900°C Fe2Cl6(g) =2 Fe Cl2 Reaction [I] (curve a) occurs in the forward direction to about 6 pct at 400°C but falls off very rapidly with increase in temperature and beyond 600°C, it is practically negligible, perhaps due to the formation of the stable monomer, FeC13(g). As the temperature is further increased, the amount of FeCl,(g) in-

Jan 1, 1961

By J. M. Silliman

Several years ago, having occasion to determine the amount of some very slight atmospheric depressions, I devised and had constructed by a skilful tinsmith the manometer shown in the accompanying drawing. It consists of a cylindrical vessel of tin, 6.6 inches in diameter, through the sides of which, at a distance of about six inches from the top, passes an air-tube D, its upper extremity terminating 3.5 inches from the top. Within the vessel is a combined cylipdrical

Jan 1, 1889

By A. E. Jenkins, O. C. Roberts, D. G. C. Robertson

Using an inverted-cone coil at 450 kHz, it has been possible to levitate iron (FeS), cobalt (CoS), and nickel (NiS) sulfides. Important nontransition metal sulfides such as ZnS, PbS, and Cu2S have proven impossible to levitate although Cu-Fe-S ternary alloys containing 30 wt pct S and up to 10 wt pct Cu, and Cu-Co-S and Cu-Ni-S ternary alloys containing 30 wt pct Cu have been levitated. The levitation technique has been used in preliminary experiments on the vaporization from liquid sulfides and the reaction of liquid metal-sulfur alloys with oxidizing atmospheres. The course of the reactions with pure oxygen were followed using highspeed photography and two-color pyrometry. ELECTROMAGNETIC levitation is now established as a basic laboratory technique in high-temperature research but its application has been restricted mainly to metals and alloys. Applications have included alloy preparation,' metal purification,2'3 determination of liquid metal densities and emissivities,4,5 and studies of metal supercooling,4 alloy thermodynamics,6 and vaporization phenomena.7-9 The application of the technique to compounds has not been considered previously. The successful investigation of the reactions between dilute iron alloys and oxidizing atmospheres10'1 has prompted the current physico-chemical studies involving levitated metal sulfide drops and flowing inert or oxidizing atmospheres. This paper presents the results of such a study and provides a basis for future studies involving a wide range of other compounds of metallurgical interest. The successful levitation of many metal sulfides and mattes provides a method of studying the oxidation reactions fundamental to flash-smelting and similar pyrometallurgi-cal operations under closely controlled laboratory conditions. In addition the system allows the use of a controlled atmosphere (e.g., a gas stream of a certain H2/H2S ratio) with a particular chemical potential to study the relevant thermodynamic equilibria or the mass transfer processes between the atmosphere and the levitated drop under conditions where the hydrodynamics of the system can be closely defined. The optimum frequency for the levitation melting of metals in an inverted-cone coil type inductor is within the radio frequency range 400 to 500 kHz. At frequencies lower than 10 kHz the rate of heat generation is usually insufficient to melt the levitated charge' or where melting is achieved, "dripping" from the charge is encountered.'' At frequencies above 2 mHz the levitation force decreases. Metals, alloys and preheated elemental semiconductors such as germanium and silicon, have been levitated but the levitation of only a few metal compounds has been reported. Jostsons13 and the authors have levitated liquid titanium-oxygen alloys containing 50 at. pct 0 while clark14 has reported the levitation of mixtures of FeS and MnS for short periods. With a "cold crucible" inductor sterling15 has melted ferrites by preheating them by induction in a 4 mHz field and melting at a lower frequency. However this second type of inductor has been designed purely for the melting of materials without contamination; there is only a small gas film between the charge and the inductor and the electromagnetic levitation effect is of secondary importance. For this reason further discussion will be restricted to the use of the coil type inductor. The assessment of the suitability of a particular metal compound for levitation is based upon the following two criteria: i) thermal stability, and ii) physical "levitability". In this paper these two criteria will be considered separately. The thermal stability of a solid or liquid metal compound with respect to a gaseous environment depends upon its chemical reactivity with that environment or, in the case of an inert atmosphere considered here, its volatility. The physical criterion as to whether or not a particular compound can be levitated is based upon a comparison between those physical properties of the compound determining "levitability" which are defined by the fundamental equations of levitation theory as developed by Okress et a1.,16 and the properties of the metals. Since it is not practical to cover the vast field of metal compounds, further discussion will concentrate on the metal sulfides but the treatment would be applicable to any metal compound. THE THERMAL STABILITY OF METAL SULFIDES The temperatures usually encountered during levitation in inert atmospheres cover the range 1400" to 2000°C. The stabilities of the condensed states of the sulfides under these conditions are considered in relation to the periodic classification by reference to Table I. Two general classes of sulfides emerge. The solid sulfides of elements of group IIB and of groups further to the right are volatile while those sulfides of group IB and of groups further to the left are nonvolatile solids. The sulfides described as volatile may be dismissed as unsuitable for levitation. The stabilities of the more favorable nonvolatile sulfides under the anticipated conditions must be studied more closely From Table I it is seen that the alkali metal sulfides exist as liquids in the temperature range of in-

Jan 1, 1970

By Ronald K. Linde

Metastable Ag-Cu solid solutions at two compositions beyond the maximum limits of solubility obtainable by quenching from the solid state were obtained by rapid quenching from the liquid state. The process of transformation of the metastable solid solutions into the equilibrium phases was studied by means of X-ray diffraction intensity measurements and electrical-resistance measurements; metallographic examination was also performed. Results are compared with those for an alloy quenched from the solid state at a composition which exists as a solid solution at elevated temperatures. Activation energies for the trans-formation were computed to be 33,600 * 2500 and 33,100 * 2000 cal per g mole for the 60.1 and 75.0 at. pct Ag;Cu compositions, respectively THE kinetics of precipitation in supersaturated solid solutions obtained by quenching from high temperature has been thoroughly studied in many alloys, and detailed investigations of the early stages of nucleation and subsequent growth of the equilibrium phases have been carried out. All of these studies have been made on alloys quenched from the solid state, however, and it is the purpose of this paper to present some of the results on the kinetics of transformation of metastable solid solutions in Ag-Cu binary alloys whose compositions lie outside of the solid-state limits of solubility. Limits of solubility in the solid state can be increased by rapid quenching from the liquid state. This was first demonstrated by Falkenhagen and Hofmann, who obtained appreciable increases in solubility limits of the elements of the first transition series in aluminum by rapid cooling of liquid alloys through contact with a copper mold maintained at liquid nitrogen temperature.' The same basic idea of cooling a liquid alloy by conduction onto a substrate rather than by convection of a gas or liquid (conventional quenching) has been recently revived and extended to very high rates of cooling by Duwez and his collaborators. The new technique was first applied to Ag-Cu alloys because the existence of a eutectic in this system is not predicted by the Hume-Rothery rules of alloy phase formation. Rapid quenching from the liquid state resulted in metastable solid solutions at all concentrations. The kinetics of decomposition of these metastable solid solutions containing 60.1 at. pct Ag;Cu (eutectic composition) and 75.0 at. pct Ag;Cu is the subject of the present paper. EXPERIMENTAL TECHNIQUES Alloys were made in 10- to 20-g heats using silver of purity 99.99 pet and copper of purity >99.999 pct. Components were weighed accurately to 0.1 mg and melted by induction heating in an alumina crucible under an atmosphere of hydrogen. Weight losses amounted to less than 0.02 ~ct in all cases. Rapid cooling from the liquid state was achieved in an apparatus of the type described by Pietrokowsky. 3 In this technique a freely falling drop of molten alloy is caught between a stationary anvil and a fast moving piston, both anvil and piston being lined with copper. The resulting foils were approximately circular (about 2 cm in diam) and from about 50 to 150 u in thickness, depending on the pressure driving the piston. Metallographic samples were prepared for polishing by edge-mounting foils in Quickmount. The mostef-fective etching procedure was found to be: 10 parts NH4OH (concentrated), 1 part H2O2 (30 pct), 5 parts H2O, swab for 5 to 10 sec. The transformation of the metastable alloys to equilibrium was followed by X-ray diffraction and electrical-resistivity measurements. The peak intensity and the integrated intensity of suitable Bragg reflections of the metastable and stable solid solutions were studied with a Norelco dif-fractometer, using nickel-filtered copper KO radiation. The peaks were step-scanned at intervals of 0.05 deg. Using either a Kelvin bridge or a null circuit with a Leeds and Northrup K-2 potentiometer, the changes in electrical resistance due to phase transformation were measured for specimens cut into strips about 20 mm long and 4 mm wide. All resistivity measurements were carried out at liquid-nitrogen temperature. The isothermal heat treatment was accomplished by sealing the samples in argon-filled aluminum containers with stainless-steel O-rings. Containers were then suspended in wax baths with temperatures in the

Jan 1, 1967

By P. Marier, T. R. lngraham

The kinetics of the sulfation of MnO,, MnzO3, and Mn3O4 in SO,, SO3, and O, mixtures was examined and the descending order of sulfation rates at temperatures near 400°C was found to be Mn,O3 > MnO, > Mn3O4. The respective activation energies for the thermal decomposition of MnO, and Mn,O, are 39 and 47 kcal. At 900°C, the thernzal decomposition of MnSO, to MnzO3 is slower than that to Mn3O4. The respective activation energies are 62 and 51 kcal, respectitely. MANGANESE is used to improve the hot workability of steel in the proportions of approximately 13.5 Ib of ferromanganese per ton of steel produced. This requirement accounts for about 95 pct of its large industrial market in North America. The remaining 5 pct is used in the battery and chemical industries. In most North American ores, the percentage of manganese and the manganese-to-iron ratio are not suitable for the direct production of ferromanganese. Hence, most of the North American requirements for manganese are satisfied by importing ore. Typically, many of the studies done on native low-grade manganese resources have been directed toward the production of ore substittes" and the recovery of manganese from open-hearth slags.3 Of the wide variety of processes which have been proposed, the most popular involve compounds in the Mn-S-O system. The thermodynamic properties of manganese and its compounds were reviewed by ah' in 1960 and, more recently, lngrahams discussed the thermodynamics of some of the reactions involved in the Mn-S-O system at normal roasting temperatures. The conditions for producing manganese sulfide during the reduction roasting of manganese sulfate are discussed by Fuller and Edlund.9 A novel scheme was proposed recently by zimmerley7 for utilizing waste sulfur dioxide from stack gases to recover the manganese from ocean-mined manganese nodules. Very little of the work published on manganese compounds has been related to reaction rates. Singleton et 1.' studied the rates of reaction on the MnO-C and Mn7C3-3MnO systems and observed linear and parabolic kinetics respectively in the systems. Tatievskaya et a1.' studied the low-temperature reduction of Mn&, MnO,, and Mn& in HZ and CO, and reported activation energies in the range 1628 kcal. In this paper, the rates of some of the decomposition and formation reactions involving MnSO4, MnOz, MnzO3, and Mn3O4 will be examined after the conditions for the thermodynamic stability of the individual compounds have been designated. CONDITIONS FOR STABILITY OF MnSO4, MnOz, MnZO3, AND Mn3O4 The areas of stability for h'hSO4, MnOz, MnzO3, and h3O4 were established from the data of Mah4 and Ingrahams and are shown in the predominance area diagram,10 logpq- logpsq, in Fig. 1. The diagram is drawn for two temperatures, 700°K, solid lines, and 1100°K, dotted lines. The sketch for the lower temperature includes the conditions likely to prevail in the Zimmerley patent7 when manganese nodules react with sulfur dioxide and that for the higher temperature indicates the conditions for recovering MnzO3 or Mn3O4 from MnSO4 during a roasting reaction. From the fact that the boundary between the areas of stability of MnOz and hSO4 at 700°K is parallel to the abscissa, it is evident that MnOz and SO2 should react together to produce MnSO4, irrespective of the oxygen pressure in the system. If the source of sulfur for sulfation were from waste flue gases, it is likely that the oxygen content of the gas stream would be more than sufficient to oxidize any MnsO4 to MnzO3, 107 atm of O2 required, or even to convert any Mnz03 to MnOz, 0.02 atm OZ required, prior to sulfation. At 1100°K, the diagram indicates that MnSO4 may be converted directly to either MnzO3 of Mn3O4, depending upon the prevailing partial pressure of oxygen. When the gas stream contains more than 1 pct Oz, logpq = -2, only MnzO3 would be recovered from an experiment done under equilibrium conditions. At oxygen partial pressures of less than 1 pct, one would expect to bring about a reversible exchange between MnSO4 and Mn3O4 by appropriate adjustment of the partial pressure of SOZ. These various reactions will be described in the subsequent kinetic experiments.

Jan 1, 1969

By R. E. Frounfelker, W. M. Hirthe

INVESTIGATORS in the areas of plasticity, crystal growth, and stress analysis have a need for crys-tallographic data such as the interplanar angles. This information is utilized in the form of a stereo-graphic projection from which orientation determinations can be made. Calculations of mechanical properties, such as the critical resolved shear stress, require values for the angles between directions as well as the interplanar angles. Only a limited amount of this data is available for tetragonal crystals. The equations for these angles are relatively simple but because of the large numbers of angles involved and the infinite number of structures that could be investigated, it was decided to program these calculations on a high speed digital computer. The angle, 8, between two crystal planes (h1 k1 l1)

Jan 1, 1962

By AIME

WILLIAM WALLACE MEIN, known to his intimates as "Will" or "Billy", is a mining engineer who has taken the fundamentals of successful mining--operating, engineering, and financial-and applied them to the founding of new industries. Born in Nevada City, Calif., in 1873, Will Mein grew up in an atmosphere of mining, and began to develop his sound judgment in a practical way before starting his formal technical education. As a young man he supplemented his early observations by helping his father, Captain "Tom" Mein, on mining work in California and Alaska. He then went with his father to the Rand, and after a period of milling experience as operator and shift boss he became, in 1894, manager of the chlorination of gold ores at the Robinson mine.

Jan 1, 1947

By F. Clerf

Blast-furnace practice in France is determined more or less by the character of the ores used. Some French ores are siliceous and others are calcareous, therefore by proper burdening a self-fluxing mix can be used. This is not always done, as, for instance, at the Caen furnaces of the Société Métallurgique de Normandie, where the Soumont ore of Normandy is used, which is a carbonate. This ore is crushed and calcined at the mines, yielding a product that is porous and well sized for blast-furnace consumption. The lines of the Caen furnaces are given in Fig. 1. Originally these furnaces had 16 tuyeres; six are plucked and these tuyeres are set in the lower part of the bosh. Operating data on these furnaces are given in Table 1. Table 1.—Operating Data, Caen Furnaces Kg. Lb. Blast-furnace burden per ton of iron: Soumont ore....................................... 200&2100 (44004650) Limestone...................................... 900-1000 (2000-2200) Basic Bessemer slag (bearing phosphorus).............. 100 (220) Scale.............................................. 35 (77) Manganese ores.................................... Coke.............................................. 1100-1200 (2420-2640) Coke analysis: Ash, per cent............. 9.5 H2O, per cent............. 4.0-10.0 Flue dust (approx.), kg. per metric ton.... 200 (440 lb.) Blast volume, cu. m. per hr.............. 83,000 (49,000 cu. ft. per min.) Preesure, lb............................ 12 Blast heat, deg. C....................... 650 (1200" F.) Top temperature, deg. C................ 250 (445O F.) Top-gas analysis, per cent............... CO2 9.3 CO 30.3 O2 0.3 H2 3.0 Production per 24 hr. about 510 tons. MINETTE ORES The most important ore deposits in France are in the west of Lorraine. They are called the "minette" ores and are of two classes-—siliceous and

Jan 1, 1937

By R. Schuhmann, J. Th. Overbeek, P. L. De Bruyn

W. E. Ewers (Commonwealth Scientific and Industrial Research organization, Melbourne, Australia)— Any attempt to elucidate further the meaning of the contact angle, particularly if it deals with the magnitudes of those mysterious quantities rsa and YRL, is certain to receive attention from those interested in the fundamentals of flotation. It is imperative, therefore, that attention should be drawn to a serious defect in the treatment by de Bruyn, Overbeek, and Schuhmann. Their Eq. 5 dy = — ld/u — Th2odiH2n states correctly the relationship between the change in surface free energy dy, the surface excesses Tx and Th2o of the components x and H2O and the changes du, and dph2o in the chemical potentials of these components. This equation applies for constant pressure and con- stant temperature and for the interface of the solid in contact with the solution of X. The relation remains valid when 1.1 is defined so that TH2O becomes zero and the equation becomes dr = — r:dur [17] From this equation de Bruyn et al. correctly concluded that increased adsorption of the collector at the liquid solid interface would reduce the interfacial energy ysl. Their second conclusion, however, that an increase in the contact angle, corresponding to a greater decrease in rsa than in rsL can be attributed to greater adsorption of X at the solid-air interface than at the solid-liquid interface is quite unjustified. The portion of the solid surface from which the collector solution has been displaced by air must be considered in terms of the equilibria between the gaseous phase and the surface. If the pressure and temperature

Jan 1, 1955

By John Naughton

At the General Electric ResearchLabora-tories, we have been interested in the iron-manganese system and the effect of hydrogen on the properties of these alloys. Dr. H. H. Uhlig previously has presented some of these results.' We wish now to offer some other of the data that have a bearing on the subject of this symposium. In the determination of hydrogen in the iron-manganese system by any heating Method we are presented with the problem of the evaporation of volatile manganese and the consequent adsorption of hydrogen by this evaporated metal. It seems wise. therefore, to extract gas at as low a temperature as feasible. Consequently we chose the vacuum or hot extraction method for the analyses of these alloys. The apparatus used is shown in Fig. I. The design is a modification of the apparatus described by Holm and Thompson. To limit loss of hydrogen, samples are stored in a chamber immersed in liquid air. We recommend this procedure whenever there is a question of loss of hydrogen at room temperature. Thence they are moved to the quartz furnace by means of a small magnet, where they are heated by induction to 700' to 800°C. The extracted gas is removed by the circulating pump and placed in the known volume VI (or V2). The circulating pump has been described.3 It is so designed that in spite of the fact that the outlet portion of the pump is part of the known volume, this volume is affected neither by the speed of pumping nor by the pressure of stored gas. The pump also serves to circulate the gases for analysis. The analytical system consists of a

Jan 1, 1945