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By C. Schlumberger, M. Schlumberger

In order to explore electrically a terrain composed of a succession of horizontal beds, a current of known intensity i is caused to flow between two grounds A and B, and the resultant drop of potential , caused by the resistance of the earth, is measured between two given points in the soil, M and N. In practice it is convenient to choose the two points M and N so that they lie on the line AB and their midpoint coincides with the middle 0, of that line, although this is not imperative. When the lengths L and I of the two lines AB and MN are varied, equations are obtained which may be solved for the resistivity p of the subsoil at various depths. Recall briefly that the formula 4 x l gives the average resistivity, in the horizontal direction, of a layer of earth which extends to a depth1 about equal to L/4. This elementary concept is adequate for numerous practical applications. Nevertheless, it must be said that, in many cases, a rigorous mathematical analysis may be made, provided it is always a question of homogeneous, superposed horizontal beds. The authors expect to publish, later on, appropriate methods of calculation for some specific cases.

Jan 1, 1932

By C. Altstetter

THE work herein reported is restricted to the carbides which occur in quenched and tempered AISI 43XX steels with carbon contents up to 0.40 pct and silicon additions of up to 3 pct. In view of the instability and extremely small size of the carbides formed at low tempering temperatures, the technique for successfully preparing specimens for X-ray diffraction will be outlined. The alloys listed in Table I were obtained through the courtesy of the United States Steel Corp. in the form of 1/2-in. rounds forged from 100 lb. induction furnace heats (except for 4337 which was a commercial heat). The stock was normalized and then swaged and drawn to 15 mil wire with anneals at 1200F between passes. The wire was austenitized for 45 min in evacuated vycor capsules and quenched into iced brine with simultaneous smashing of the capsule. Tempering was done in air with a water quench after tempering. The carbides were extracted in a simple cell using a solution of 1M KC1 and 0.5 pct citric acid with an initial current density of 0.1 amp per sq cm. One end of a short length of wire was immersed in the solution, and the current at constant voltage was noted as a function of time. After about an hour the current dropped sharply because of the decrease in specimen cross-section. At this point it was found that the dissolution could be stopped and that the very fine wire which then resulted was just large enough to permit handling of the extracted precipitate still clinging to it, yet so small that it diffracted and absorbed only a negligible amount of the X-radiation. This rod of residue with a convenient handle of undissolved wire was rinsed in distilled water. alcohol, and acetone. Then it was dipped in a thin solution of cellulose-acetate cement and dried in vacuum. The resulting specimen was straight, uniform in density, easily handled, but most important, was completely sealed and never exposed to air. Furthermore, the residue had never been subjected to strong acids or rough handling such as in the extraction-replica technique or in the complete extraction to a powdered residue. It was found that improperly coated specimens were pyrophoric, turning to oxide with a dull red glow as they were exposed to air and yielding patterns of Fe2O3 and Fe3O4. The steels containing 3 pct Si were especially difficult to prepare for this reason. The specimens were put in a 57 mm Straumanis camera with double pinholes or slits and irradiated with filtered-chromium radiation. Readable patterns were obtained in less than an hour. A preliminary finding of some note was that for both tempered and as-quenched specimens of steels 4337 and 4337 (1.5 Si). M23C6 patterns were found along with the patterns of other constituents of the residues. This result was somewhat surprising in that previous investigators had reported that this carbide did not appear in a 0.38 pct C, 0.48 pct Mo steel1 or in chromium steels of less than about 10 pct Cr.2 Although the total amount of carbide-forming alloying elements is less than 2 pct, due to their mutual interaction and the action of the plastic deformation in promoting equilibrium, this carbide was able to form even in the steel containing 1.5 pct Si. M23C6 was not detected in the 4337 (3.0 Si) steel and the lower-carbon steels were not investigated in this condition. It is very likely then that the steels studied herein underwent a fourth stage of tempering during the anneals at 1200°F. This result has significance in that even a small amount of undissolved M23C6 in a low-carbon, low-alloy steel would exert a large effect on its hardenability. Its presence would also influence the mechanical properties by decreasing the carbon content of the matrix. Annealing in vacuum for 1 to 4 hr in the austenite field removed all traces of MZ3C+ The results on carbide precipitation during tempering, summarized in Table I, are in agreement with those of Klingler et al.3 for the higher carbon steels. For the AISI 4337 steels it is noteworthy that in the steels with added silicon the E carbide persists to longer times and higher temperatures and that silicon delays the formation of cementite. The results for the lowzr-carbon steels parallel those of the higher-carbon grade. The appearance of E carbide in the AISI 4315 is significant. There is considerable disagreem-nt in the literature as to whether this carbide forms in the tempering of steels containing less than about 0.2 pct C. Following the detection of E carbide in a 0.18 pct C plain-carbon steel,4 its occurrence in a steel containing chromium and molybdenum should be expected. The fact that the low-carbon steels have the same carbide-precipitation sequence as the high-carbon steels has bearing on the larger problem of the exact tempering reactions in all steels. Following the suggestion of Roberts et al.,' the first stage has been generally assumed to result in a metastable equilibrium of c carbide and martensite of about 0.25 pct C. From this it was concluded that a steel having less than 0.25 pct C should then be under-saturated with respect to c carbide and should not precipitate this carbide upon tempering. In view of the experimental findings of c carbide in steels hav-

Jan 1, 1962

By Joseph W. Richards

ALTHOUGH bad grammar, the above query is probably, at the present moment, good sense. Why was the Institute started and why does it continue to exist? The small group of men who worked out the original idea felt keenly the necessity of mining engineers and metallurgists getting together in order to discuss their professional problems. That necessity still exists but it does not strike the present generation of engineers so keenly because they have always had the Institute: they do not know what it is to be without it. The Institute is a great graduate school of mining and metallurgy. All of its members who have something to say worth saying are the teachers; all the rest may be learners or critics. No university or technical school can match the experience and information which the authors of its papers possess, no institution of learning has a body of potential listeners so extensive and so vitally interested.

Jan 1, 1921

By Ulrich H. Roesler

RECENTLY, C. Zener1 published a new thermo-dynamic treatment of the a/y transformation in iron alloys. His interpretation differs from the previous theories2-0 ainly through the separation of the free energy difference, Ga—G, into two additive

Jan 1, 1957

President H. M. Howe, Boston, Mass. (communication to the Secretary): Le Chatelier's pyrometer is certainly a most convenient and accurate instrument for the laboratory, and one that may be used under some conditions in the mill. I have used it for several years and with great satisfaction. Like Prof. Roberts-Austen and unlike Herr Blass, I have always found that its indications remain constant over long periods. Like Prof. Roberts-Austen, also, I find it possible, in a quiet place, to read with extreme accuracy ; and, by the use of a telescope, I can read temperatures to within a degree, for some delicate determinations which I have in hand. Variations in the temperature of the room affect the readings of the instrument far less than one would expect. When the current is cut off, the mirror does not always return exactly to the same place; in other words, the zero shifts appreciably, and must be determined often, indeed every few hours if accuracy be desired. In some cases I have had it determined within a very few minutes of every important reading. To this end a switch should he introduced, so that the circuit may be broken readily. With this arrangement we can determine accurately the position of the zero within a very few seconds of the time of taking any especially important reading. The chief causes of the variation of the zero which I have noticed are as follows: a. The suspension may not be tight enough, so that the momentum of the galvanometer frame as it swings makes its supporting wires slip in their bearings. b. Changes in the position of neighboring iron objects may deflect the mirror. c. Changes in the temperature of the room may, perhaps, change the torsion of the suspension wires, and so shift the mirror. d. Dust may attach itself to the galvanometer frame, and by friction against the surrounding fixed parts of the galvanometer, may

Jan 1, 1895

CARACAS PETROLEUM Established February 24, 1957 Official year begins in January Harry J Sykes, Chairman G J Clarke, Vice-Chairman Robert S Longwell, Vice-Chairman David L Stepanek, Treasurer Robert C Newman, Secretary Texas Petroleum Co Apartado 267 Caracas, Venezuela

Jan 1, 1960

By Augustus Locke

WHY should I, a geologist, be coming before you to talk about finding ore? Certainly, the great discoveries of the past have not been made by geologists, but by men of very different tastes and training. If, in the year 1800, the course of ore discovery could have been foreseen, there would have been no reason to put it into the hands of geologists or other men of technical preparation. It was not geologists but explorers, Indian fighters, prospectors, manual laborers, and hardy financiers, who initiated the American mining industry. Then why this association of geological technique with ore finding? Why this feeling that the way to find ore is to apply to the problem what we call geo- logical principles? Well, to put it broadly, the old method has run out on us. It no longer works. Or, to put it another way, the cost of finding ore by the old method has mounted so high that one old district after another has become, practically speaking, dead, and various other old districts that are still going apparently at full strength are actually beginning to limp, and, with the cost of discovery mounting yearly, to fear, more than they will acknowledge, that the end is approaching.

Jan 1, 1926

By R. B. Snow

THIS paper describes a technique of polishing and etching specimens of open-hearth furnace slags or hearth aggregates for identification of the crystalline constituents-lime (CaO), tricalcium silicate (3CaO•SiO2), dicalcium silicate (2CaO-SiO2), monticellite (CaO•MgO-SiO2), or forsterite (2MgO•SiO2), with especial emphasis on the mineral merwinite (3CaO-MgO.2SiO2). With proper standardization, this identification does not require the use of the petrographic microscope. The composition of basic open-hearth slags and furnace bottoms falls, almost without exception, within systems containing CaO, MgO, "FeO," MnO and SiO2, in which the number of basic molecules so greatly exceeds the orthosilicate ratio (two molecules of base to one of silica) that free basic oxides, and combinations between them such as aluminates or ferrites, are present in cooled specimens. Orthosilicates of (CaO + MgO) are the most common in such specimens, since in nearly all cases, except premelt slags, the molecular ratio of (CaO + MgO) to SiO2 is more than 2 to r. When sufficient lime is available it combines with the silica to form dicalcium silicate (2CaO•SiO2), which contains little, if any, MgO, FeO or MnO in solid solution whereas the latter oxides combine to form the oxide solid solution known as periclase. If the lime present is insufficient to form dicalcium silicate (2CaO•SiO2) it combines with MgO to form either merwinite (3CaO•MgO.2SiO2) or monticellite (CaO-MgO•SiO2); these minerals take little if any FeO or MnO into solid solution and the remaining MgO, FeO and MnO combine as periclase. This generalization seems to be valid for basic slags and furnace bottoms, since minerals such as CaO-MnO•SiO2 and CaO-FeO-SiO2 are found only in slags in which the lime-silica ratio is less than 2 and are not observed in specimens from furnace bottoms. The identification of crystalline constituents in such materials, especially of fine crystals in the groundmass, is difficult under the petrographic microscope. They are often masked by their neighbors because of their small size in relation to the thickness of the thin section and because of the presence of opaque or colored constituents. The indices of retraction and the optical sign of the mineral are sometimes difficult to determine because of the small size or because of twinning or of inclusions within the crystal. Moreover, the positive identification of merwinite (3CaO•MgO.2SiO2) from its optical properties is usually difficult in the presence of dicalcium silicate (2CaO•SiO2). CaO, MgO, 3CaO•SiO2 and 2CaO•SiO2 in open-hearth slags have been identified for a number of years in the U.S. Steel Corporation Laboratory by the usual

Jan 1, 1947

By W. Philippoff

ALTHOUGH Gaudin1 and more recently Sutherland2 have calculated the probability of collision of a falling mineral particle with a rising bubble, there is no published information concerning the details of the mechanism of attachment of a collector-coated particle to a bubble. During the past year the writer has developed a theory for the mechanism of attachment, which has been substantiated experimentally.' Funds for the investigation and for some of the equipment used have been supplied by the Mines Experiment Station of the University of Minnesota. Motion picture studies of the phenomena involved in the collision between mineral particles and bubbles, such as those of Spedden and Hannan,3 show that the contact can be completed within 0.3 millisec. Formulas developed for rigid bodies have hitherto been used' for the calculation of the motion of bubble and particle, but it is obvious that a bubble cannot be regarded as a rigid body. On the contrary, Spedden and Hannan's pictures show a great degree of deformation during the collision. The time of attachment was calculated as the time the particle drifted past the bubble. Time of Collision The theory presented in this paper enables calculation of the time of collision; using the concept that the bubble, or more generally, a liquid-air interface, acts as an elastic body. The elasticity, defined as the restoring force on a mechanical deformation, is caused by, the surface tension and is the result of the principle of the minimum of free surface energy. It is well known that an elasticity together with a mass determines a frequency of vibration. The vibrations of jets and drops caused by the elasticity of the interface are known to comply exactly with the classical theory of capillarity.5 However, the vibrations of isolated bubbles, as distinct from foams, have not been investigated previously. The following equation, presented elsewhere,' has been deduced for these frequencies: [3fB = 9.20•'./V•Vn- (n-1) • (n+2) /8[1]] in which fB is the frequency of a harmonic of the bubble in cycles per second, V the volume of the bubble in cc, n a number determining the order of the harmonic, and n = 2 the basic vibration. The first (basic) harmonic describes a change of the spherical bubble to an ellipsoidal bubble. The higher harmonics are more complicated, for the circumference of the bubble is divided approximately into as many parts' as the order of the harmonic. As an example, Spedden and Hannan's published motion picture of, a vibrating bubble corresponds to the sixth harmonic. Eq 1 shows that only the first and third harmonics are simple multiples (1 and 3), all the others being irrational fractions of the basic frequency. This means that the shape of the vibration can change with time and is in general unsymmetric in respect to the time axis. Such conditions prevail when there is a distributed elasticity or mass, as in the case of vibrating membranes or rods. The constant 9.20 is valid for water at room temperature, but a general solution involving the physical constants of the liquid has not been found. The case of the floating particle is much easier to treat I than that of the bubble. It can be assumed that the elasticity is caused exclusively by the interface and that the mass is concentrated in the particle together with some adhering water. The following expression for the frequency of a system, of one degree of freedom can be applied: [1E/m[2] fP = 27] Here f, is the frequency of the particle vibration in cycles per second, E the elasticity in dynes per cm, and m the mass in grams. The classical theory of impact phenomena gives the time of collision during the striking of a spring (in this case the surface of the bubble) by a mass, as: [t~ = 2/f = 7r\/m/E[3]] It is now possible to develop an expression for the elasticity of a floating cylindrical particle. The force equilibrium of a cylinder floating end on at the air-liquid interface is given by the well-known equation (Poisson' 1831) [aP = 4 D2.pL•g•h +7rD•y sin a[4]] which accounts for the buoyancy and the action of the surface tension where P is the force acting on the particle in dynes (weight-buoyancy), D the diameter of the cylinder in cm, pL the density of the liquid in grams per cc, g the acceleration of gravity = 981 cm per sec2, h the depression of the cylinder below the surface of-the liquid in cm, y the surface tension in dynes per cm and a the supporting angle' or the one required to insure equilibrium, a being smaller than the contact angle ?. Although demonstrated by Poisson, it has not

Jan 1, 1952

The following is an incomplete list of members and guests who called at Institute headquarters during the period July 10, 1919, to Aug. 10, 1919. Howard C. Arnold, Washington, Pa. J. S. Lane, New York City, N. Y. L. M. Banks, Denver, Colo. H. W. Lawrie, Washington, D. C. George S. Blair, Pittsburgh, Pa. J. L. McAllen, Latouche, Alaska. Richard H. Catlett, Newark, N. J. David F. McFarland, Urbana, Ill. George L. Clark, Council Bluffs, Iowa. James F. Magee, Lancaster, Pa. Capt. Frederick S. Cook, Portland, Ore. A. G. McGregor, Warren, Ariz. John J. Croston, Atlanta, Ga. Emory M. Marshall, Santa Fe, N. M. Thomas Davis, Seattle, Wash. Benjamin L. Miller, Bethlehem, Pa. J. C. Dick, Salt Lake Cite, Utah. 2d Lieut. C. 0. Noble, U. S. Army. Chris. G. Dobson, Vancouver, B. C. Irving Perrine, Hutchinson, Kans. H. S. Emlaw, Grand Rapids, Mich. Fred S. Porter, Seattle, Washington. F. A. Fahrenwald, Cleveland, Ohio. Capt. H. R. Robbins, Peking, China Lieut. James L. Head, St. Louis, Mo. Joseph P. Ruth, Jr., Denver, Colo. A. A. Holland, Napanu, Canada. William A. Simkins, San Francisco, Calif. W. E. Hopper, Washington, D. C. T .V. Smirnoff, Siberia. Harry Hotchkin, Chicago, Ill. Harrison Souder, Cornwall, Pa. L. L. Hutchison, Tulsa., Okla. F. J. Sur, Denver, Colo. Paul S. King, Wilmington, Del. Harry Wolf, Denver, Colo. George K. Anderson, Jr., lies accepted a position as manager for Wight & Co., producers of air-cooled blast-furnace slag, at Longdale, Va. J. M. Armstrong, with the Caribbean Petroleum Co., has been transferred from Philadelphia to Maracaibo, Venezuela. Fred Sherman Baker, who has been with the Oriental Consolidated Mining Co., at Unsankinko, Chosen, Korea, is now at Columbia City, Ind. Ray J. Barber has removed from Roxbury, Mass., to New York City, and is now consulting engineer for the Roxbury Cold Mines, Inc.

Jan 9, 1919

By J. V. W. REYNDERS

NOT only is your toastmaster silver-tongued in his references 'to myself, but he is also quite in the habit of "saying it in silver." I have analyzed with some care his statistics of the world's silver production, which have been distributed here along with the menu, although frankly from the point of view of most of us, the distribution rather than the production of silver is of immediate concern. Unlike the performers by whom we have been entertained between courses, the rest of us on the program will have to do without costume or musical accompaniment, which as my friend Rains can testify puts an artist under severe strain. I am entitled by right of office and of precedent to receive your attention for ten minutes. The Governor, who appears on the program as a speaker; however, has asked me for five minutes of my time, and Senator Thomas has insinuated that he would appreciate one-half of the remainder, wherefore, I must ask your close attention to the very brief remarks that I am able to make under such restricted circumstances. To begin with, I want you to believe that I am approaching the task set by your toastmaster with misgivings. In looking over the Institute records relating to the Salt Lake City meeting of 1914 for some precedent as to what I ought to say, I found but one reference-and that of the following indefinite char¬acter-" and Friday night there was a hilarious banquet to 350 members and guests."

Jan 1, 1925

By J. L. Gillson

The big mass of anorthosite in the Lake Sanford district and the bodies of titaniferous magnetite that occur in a small area near the south margin of the mass have been described repeatedly, and the puzzling problems of the genesis of the rocks and ores have stimulated the deductive reasoning of geologists for a hundred years. Some of these men have taken a leading part in describing the anorthosite rock and forming hypotheses concerning its origin; some have contributed most to the study of the ore deposits; and some have made classical Studies introducing a basic approach to the problems of the anorthosite rock and genesis of the titaniferous magnetites. Much of the writing on the problems of rock and ore genesis has been based on physical-chemical reasoning rather than on field and microscope observations of the rocks and ores. Most of these geologists conclude that the anorthosite was formed by true magmatic crystallization, involving previous settling or squeezing out of ferromagnesian minerals from the parent magma. The associated gabbro is a separate segregation or later intrusion, and the lighter colored and finer grained facies of the anorthosite is either a chilled border zone of the anorthosite or the result of granulation by crushing of the coarse, dark blue rock of the main mass. This blue rock, called the Marcy type, is named after the highest peak in the range. The finer grained and lighter colored rock is called the Whiteface, after another mountain appropriately named for a cliff colored by this facies of the anorthosite.

Mar 1, 1956

[59H1-Water Law and Its Significance to the Mining Industry by Wells A Hutchins 59H2-Relation of Land Subsidence to Groundwater Withdrawals in the Upper Gulf Coast Region, Texas by Leonard A Wood and A G Winslow 59F3-Hydraulic Mining of Gilsonite and Its Application to Coal Mining by J H Baker 59H4-Recovery of Phosphates by In Situ Fluid Mining by Sylvain J Pirson 59F5-Coal Cleaning Plant Design for Minimum Operating Labor by Wm M Bertholf and John D Price 59F6-Coke Combustibility A Neglected Characteristic by J D Price 59B7-Union Carbide's Uranium Operation at Maybell, Colorado by K W Lentz and F T Temple 59H8-A Rapid Method for Estimating Alumina in Feldspathic Sands by Hugh H Bein 59H9-Water Laws as Related to Dredging in Idaho by Robert A Lothrop, Richard B Porter, and Robert P Porter 58B19-Separation and Washing of Alumina Process Residue by Morton Handelman 59B11-Feed Preparation and Froth Modification for Fatty Acid Flotation by Carl C Martin and Burt C Mariacher 59B12-Design Requirements for Tailing Disposal in the Southwest by E Vern Given 59B13-Semi-Dome Shaped Buildings for Bulk Storage by Edward E Ives and William L Payne]

Jan 1, 1961

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members) The following is a partial list of members and guests who called at Institute headquarters during the period Mar. 10, 1917, to Apr. 10, 1917. Frederick R. Ahbe, Athens, Pa. Frank M. Leland, San Francisco, Cal. J. L. W. Birkinbine, Philadelphia, Pa. Edwin Ludlow, Lansford, Pa. Samuel D. Bridge, Monterrey, Mex. E. P. Mathewson, Toronto, Canada. J. R. Buchanan, Pasadena, Cal. E. V. Matlack, Webster Grove, Mo. G. M. Colvocoresses, Humboldt, Ariz. E. C. Potter, Clearwater, Mont. F. G. Cottrell, Washington, D. C. R. B. Stanford, Bluefields, Nicaragua. H. N. Eavenson, Gary, W. Va. R. S. Ransom, Jr., Newark, N. J. H. T. Fisher, Englewood, N. J.. M. L. Requa, San Francisco, Cal. E. P. Fleming, Salt Lake City, Utah. John A. Rice, El Paso, Tex. F. L. Garrison, Philadelphia, Pa. W. E. Rice, Ringwood, N. J. W. M. Grant, So. Bethlehem, Pa. Lewis A. Riley, Philadelphia, Pa. J. F. Hanst, Negaunee, Mich. Hallet R. Robbins, Vancouver, B. C. H. D. Hibbard, Plainfield, N. J. Allen H. Rogers, Boston, Mass. B. B. Hood, Chrome, N. J. A. A. Stevenson, Philadelphia, Pa. Henry M. Howe, Bedford Hills, N. Y. Wm. Huff Wagner, Johnstown, Pa. Hennen Jennings, Washington, D. C. E. E. Watts, Denver, Colo. Oscar Lachmund, Greenwood, B. C. Samuel S. Wyer, Columbus, Ohio. H. W. Aldrich, after ten years of service with the Anaconda Copper Mining Co., at Anaconda, has resigned and accepted a position as general superintendent for the Ladysmith Smelting Works, at Ladysmith, B. C. Charles E. Bunker, formerly superintendent of the Keystone mine, has been appointed superintendent of the Bunker Hill mine near Amador City, Cal.

Jan 5, 1917

By Persifor Frazer

The rocks which cover the east flank of the South Mountain are chloritic schists typical in character. A specimen of this rock from near the Bechtel shaft, Hamilton Ban Township, Adams County, Pa., was selected and analyzed in my laboratory by Mr. C. Hanford Henderson, with the following results: Ignition,........2.740 CaO,..........7.040 SiO,,..........41.280 MgO,.......... 7.486 AI,O,,.........18.480 K,O,..........2.208 Fe,Os,.........9.440 Na,O,.........3.523 FeO,......... 8.200 100. As one penetrates the range by moving westvard, these schists are replaced either by epidotie quartz or by orthofelsite. In the former case, a belt of copper-bearing rock is traversed, but not in the latter case. Inasmuch as this junction of the chloritic schists on the southeast and orthofelsite on the northwest, separated by the epidotic quartz, is several times repeated, we find two or three copper belts arranged in general parallelism to the axis of the chain, because the copper horizon is generally at this junction. Thus, in going west from Fairfield, after entering the low spurs on the South Mountain, one is fairly within the chlorite measures. At the " Virginia Mills " a chlorite schist comes in with a dip of S. 1.5 E.-74 Half a mile up Middle Creek, large numbers of fragments of chlorite schist, decoruposed epidotic matter, and quartz are encountered. The former rock, where in place, dips E. 40" S.-57o. About 4000 feet west of the intersection of this road with the so-called Tape-Worm Railroad, near the house of one Singly, large masses of chloritie schist are found loose on the road. A hundred yards farther west, near a triangle in the road, the latter is less in quantity and much epidotic quartz appears, after which a very large display of orthofelsite succeeds on the left bank of Middle Creek. All these last-mentioned rocks, however, are in fragments. Crossing the stream again a few hundred yards farther On, the chlorite fragments at first preponderate, and then large numbers of both rocks

Jan 1, 1884

By Allan T. Gwathmey, J. Bruce Wagner, Kenneth R. Lawless

Between 250°and 550°C in oxygen pressures of 10 to 760 mm Hg, the relative oxide thicknesses formed per unit time on the (100), (111), (110), and (320), decreased in this order. The predominant oxide orientation was (001)Fe3O4 and [110] Fe304 A small amount of a-Fe2O3 which exhibited a fiber pattern was observed in all oxides except those formed at 250°c in low oxygen pressures. IN order to understand the properties and behavior of thin films, particularly their role in oxidation reactions, there is needed more experimental information on their structure, composition, and kinetics of formation on clean surfaces of known geometry. The present study was undertaken to obtain such information for thin oxide films formed on single crystals of a body centered cubic metal, iron. Crystals in the form of spheres were used in order to expose all possible crystal planes to the reactant gases simultaneously. Using this procedure the relative rates of oxidation of all planes could be estimated, and those exhibiting, maximum or minimum oxidation rates could be selected for a more intensive study of composition and expitaxy. Since the three types of information were obtained from the same experiment using a single crystal substrate, any differences between rate, composition, and expitaxy on the several planes may be attributed to the influence of the substrate structure. EXPERIMENTAL The starting material for this study was Armco iron rods, 6 in. long and 3/8 or 1/2 in. in diam. The analysis was reported to be 99.8 pct Fe, with major impurities listed as carbon 0.018 pct, manganese 0.027 pct, phosphorous 0.005 pct, sulfur 0.029 pct, silicon 0.005 pct, and copper 0.11 pct. These rods were cleaned with ether and heated in an atmosphere of moist hydrogen at 950°C for three days. The purpose of this treatment was to decarburize the iron and to provide a consistent, uniform grain size for the growth of single crystals. Crystals in the form of rods, up to 1/2 in. in diam and 2 in. long, were prepared by a method similar to that reported by Leidheiser and Buck.2 Spherical crystals, 3/8 and 1/2 in. in diam and having a handle about 1/4 in. in diam by 112 in. long, were machined from the single-crystal rods. After machining, each crystal was etched in aqueous nitric acid to remove the cold-worked metal at the surface. Before each experiment, the crystal was polished mechanically with metallographic papers through number 4/0, and electropolished in a perchloric acid-acetic anhydride mixture by the method of Jacquet and Rocquet.3 The crystal was washed in running distilled water for at least 5 min. The excess water was blotted with a soft paper tissue, and the crystal was placed in an all-glass reaction vessel (See Fig. 1). The crystal was heated at 550°C in hydrogen for at least 8 hr prior to the oxidation in order to reduce any surface oxides and to help relieve any stresses in the metal. For the structure and composition studies, flat faces were cut parallel to (loo), (111), and (110) planes on the iron crystal spheres. The orientation of these faces was checked by a back-reflection X-ray diffraction technique. The faces were within 2 deg of the desired orientation. The flat faces were treated as described above except that prior to electropolishing they were given an additional polish on metallographic felt saturated with twenty-minute levigated alumina. After the crystal was heated in hydrogen for at least 8 hr, the temperature was adjusted to the desired value, and the hydrogen was evacuated. Commercial oxygen which had been purified by successively passing through tubes containing magnesium perchlorate, Ascarite and magnesium perchlorate was admitted to the desired pressure as measured by a mercury manometer. A resistance-wound furnace surrounded the oxidation chamber, and a temperature controller maintained the temperature within ±3°C. The furnace was provided with a small window for observing the crystal. The changes in thickness of the oxide films were followed by observing the interference colors. The oxidation was allowed to proceed until the desired oxide thickness was attained on a given crystal plane. The experiment was terminated by evacuating the oxidation

Jan 1, 1962

By E. Miller, K. L. Komarek, M. Ettenberg

The activity of aluminum in solid Co-A1 alloys has been measured by an isopiestic technique between 850° and 1200°C from 45 to 80 at. pct Al. The activity shows a Precipitous decrease around the stoichzornetric composition of CoAl. Free energies of mixing have been calculated over a limited composition range. Considering an antistructure-vacancy defect mechanism, the degree of intrinsic disorder, a , in CoAl was related to the alunminum activity. Excellent agreement between the calculated and experimental activity curves was obtained for a = 1.25 x 10-4. ThERMODYNAMIC properties of solid aluminum-transition metal alloy are being studied in an investigation of disordering in ordered compounds. In a continuing series of investigations, activities of solid Fe-1,' Ni-A1, kd r-A13 alloys have been measured. From the results for Fe-A1 and Ni-A1, the degree of intrinsic disorder for the equiatomic compounds was calculated2 using equations derived by Wagner and chottk. From the results for Cr-A1 the degree of intrinsic disorder was calculated from equations derived by Orr.' In this paper, the results of the study of Co-A1 alloys are described. Published activity data in the Co-A1 system has been limited to liquid alloys at 1600°C.° A heat capacity study7 of stoichiometric CoAl indicated that a second-order phase transformation occurs at 790° C, attributed to an order-disorder reaction. Oelsen and Middel,' employing the calorimetric mixing of pure liquid metals, obtained heats of formation for compositions from 6 to 90 at. pct Co. Heats of formation for 50 and 78 at. pct Co alloys have also been measured by acid solution calrimetr. The Co-A1 phase diagram, as compiled by Hansen and Anderko,lo is in good agreement with more recent X-ray evidence. The method for measuring activities of aluminum in this study is essentially that employed in the studies of the Fe-1,' i-Al, and r-A13 systems. This isopiestic method entails placing cobalt specimens, in a temperature gradient, in a sealed alumina system containing a pure liquid aluminum source of fixed vapor pressure. The specimens are equilibrated, cooled to room temperature, and their final compositions determined. From the measured temperature of the specimens and the known vapor pressure of pure aluminum the activities of aluminum in the alloy can be calculated. EXPERIMENTAL PROCEDURE The cobalt was 3-mil-thick sheet of 99.9 pct purity (herritt Gordon Mines Ltd., anada). The major impurities were 0.1 pct Ni, 0.014 pct C, 0.018 pct Fe, 0.004 pct S, and 0.005 pct Cu. The aluminum metal had a purity of 99.99 pct (Aluminum Corp. of America) and all alumina parts were 99.7 pct A1,O3 (Triangle RR Grade, Morganite Refractories, Inc.) with major impurities 0.05 pct SiOz, 0.1 pct Fe203, 0.2 pct NazO, and 0.05 pCt K20. Runs 1 to 3 were made with annular cobalt specimens (12 mm ID by 21 mm OD) punched from the sheet. The specimens were deburred and degreased in carbon tetrachloride and in acetone. The samples, each weighing about 150 mg, were then positioned along an alumina rod, a in. OD by 14 in. long, separated by alumina spacers, i in. ID by | in. OD by & in. long. The lower end of the rod was placed in a hole drilled in the center of an 80-g aluminum cylinder. This assembly was put into an alumina crucible, 1+ in. ID by 13 in. OD by 3+ in. high, and the position of each sample was measured to within 50.5 mm relative to the bottom of the crucible. An alumina tube, 28.5 mm ID by 35.5 mm OD by 14 in. long, closed at the top, was slipped over the whole assembly, so that it fitted snugly into the bottom crucible. The entire reaction assembly was tied with molybdenum wire and lowered into a mullite tube, closed at the bottom. A quartz thermocouple tube, closed at one end, containing a t/Pt-10 pct Rh thermocouple, calibrated according to the specifications of the National Bureau of standards,'' was placed along the reaction assembly inside the mullite tube. The temperature of each specimen could be determined by gradually raising the thermocouple and measuring the temperature gradient along the reaction assembly. The combined error in temperature measurement and sample position resulted in a total error of Q°C in the recorded temperature of each sample. The mullite tube was sealed at the top by a water-cooled brass head, connected to a conventional glass vacuum system. The aluminum reservoir is heated to its melting point sealing the alumina system containing the samples. During this process the pressure is maintained below 0.01 li Hg. During subsequent heating to establish the proper temperature gradient and throughout the entire run the pressure is maintained below 2 1 Hg by means of a two-stage mechanical pump. Equilibration runs lasted from 4 to 6 weeks and were terminated by air cooling. The temperature of the liquid aluminum reservoir was brought below its melting point in less than 20 min. For runs 4 and 5, alloy buttons with 49 and 69 at. pct A1 were prepared from the initial high-purity metals by arc melting under purified argon. The alloy buttons were comminuted to powder with an alumina mortar and pestle until the powder passed through a 400-mesh screen, particle size 0.0014 in. Portions of this powder weighing between 50 and 200 mg were placed in small alumina trays, 25 by 15 by 5 mm, which were then

Jan 1, 1969

By Henry Wurtz

Jan 1, 1880

By M. E. Wadsworth, A. S. Peck

Infrared spectra disclose that oleic acid will not adsorb on the surface of pure beryl unless the mineral is first activated with HF. The adsorption of oleic acid on HF activated beryl is attributed to the hydrogen bonding of oleic acid monomers to F-surface bridging sites. These sites are formed as a result of the reaction of HF with chemisorbed water or surface hydroxyl. Characteristic infrared spectra of physically adsorbed oleic acid are correlated with flotation at different pH at temperatures of 25°C and 75°C for colloidal and -60-mesh particles. The usual mode of occurrence of the beryllium mineral beryl, Be3A12Si6O18, is in granite pegmatites as pale green, white, or yellow crystals. A dark green gem variety, emerald, may be found in the wall rock of pegmatite veins or in mica schist. The most important beryl deposits in the United States are in the Black Hills District of South Dakota, and several mountain ranges of central and west-central Utah contain potential commercial sources of this mineral. Several papers have been published concerning the flotation of beryl with different conditioning reagents. Kennedy and O'Meara1 reported on the essential use of HF in the flotation of beryl from different ores. The use of calcium hypochlorite to separate HF activated beryl from feldspar after flotation with an amine collector was made by Runke.2 A report on the activation of beryl with different cations using sodium oleate collector was presented by Viswa-nathan and co-workers.3 Flotation of beryl with sulfonate collector and different activating salts was employed by Fuerstenau and Bhappu.4 The role of the surface charge or zeta potential in the flotation of beryl with different collectors and salts was also extensively investigated.5"7 Previous infrared investigations by the authors8 disclosed that the orthosilicate beryllium mineral, phenacite, reacts with oleic acid to form a chemisorbed oleate monolayer on the mineral surface. Thus, chemisorption is the effective mode of adsorption in the phenacite-oleate acid flotation system. In contrast, neither chemisorption or physical adsorption of oleic acid occur on the surface of pure beryl as evidenced in this study. Efforts were subsequently made to determine the mechanism of activation and collector adsorption for HF pretreated beryl. EXPERIMENTAL PROCEDURES Large, white, terminated crystals of beryl were obtained from Madagascar through Ward's Co., Monterey, Calif. The crystals were broken into -60-mesh fragments in a porcelain mortar. Part of this prepared material was ground to a powder with a Fisher Grinder using an agate mortar and pestle. The powder was transferred to a graduated cylinder and mixed with 500 ml of distilled water. After 5 min, the colloidal suspension was separated from the settled particles by decantation and used as a stock for infrared test determinations. Adsorption tests were performed by first transferring 20 ml of colloidal suspension to 50 ml glass centrifuge tubes. The solids were then centrifuged out and the liquid was discarded. Then, the solids were pretreated with one molar HC1 or one molar HF. After 15 min, the solids were again centrifuged out. The mineral solids were washed free of residual acid by repeated centrifuging and water washing operations. Then, 20 ml of distilled water was added to the solids, and the resultant suspension was used for test purposes. In the preparation of mineral for flotation tests, 1.5 g of -60-mesh beryl was deslimed by removing the colloidal fraction by three successive water washes and decantations. Then, the coarse particles were pretreated with either one molar HCl or one molar HF for 15 min. The mineral was next washed free of acid with distilled water, and 20 ml of distilled water was added to the beryl prior to collector conditioning. The conditioning of mineral with collector was performed in 50 ml centrifuge tubes to which either NaOH or HC1 was added for pH modification. One drop (6.0 mg) of U.S.P. reagent grade oleic acid or 2 ml of 0.01 molar sodium oleate was added to the pulp and stirred at about 1500 rpm for 3 min at a

Jan 1, 1968

By N. A. D. Parlee, I. D. Shah

ThIS reports on some work done on the solubility and diffusivity of oxygen in liquid silver. Solubility. Improvements in the measurement of the solubility of oxygen in silver and silver alloys were made because precise data were needed for calculating diffusion coefficients of oxygen in these alloys. The apparatus and the procedure used were similar to those of Parlee and Sacris.' The main improvement was in the temperature-measuring technique. A MV30 mullite protection tube containing a calibrated Pt-Pt, 10 pct Rh thermocouple was inserted in the reaction tube from the top through a vacuum-tight swage-lok fitting. The protection tube was well-immersed in the liquid silver, which was heated by induction. A Leeds and Northrup potentiometer was used in connection with the thermocouple. All runs reported were made at 1 atm. The temperature range investigated varied from 940" to 1200°C. The ternary point in Ag-0 phase diagram2 is at 939°C and 0.32 wt pct O. This point was reinvestigated using the above-described apparatus and was found to be at 939°C and 0.315 wt pct 0. It was determined by observing the sudden evolution of oxygen at this point while the solubility measurements were made. The point was easily reproducible if precautions were taken to keep the liquid silver essentially in equilibrium with oxygen and to lower the temperature very slowly. All of the results of this new solubility investigation are plotted in Fig. 1. They are represented by the "least-squares" line shown in the figure and the following equation for solubility at po2 = 1 atm: log% O =695.4/T - 1.086 This equation differs only slightly from that proposed by Parlee and sacrisl and that of Diaz, Masson, and Richardson.3 The points of Parlee and Sacris, using an optical pyrometer, are shown for comparison.

Jan 1, 1968