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By Leonard B. Gulbransen, John R. Lewis, W. Martin Fassell, J. Hugh Hamilton

T. E. Leontis (The Dow Chemical Co., Midland, Mich.)—This paper is of particular interest to me because of my own work with F. N. Rhines on the oxidation of magnesium and magnesium alloys a few years ago. The authors are to be complimented on their development of an accurate and reproducible technique for measuring ignition temperatures and on their comprehensive study of the many variables that affect the ignition temperature of magnesium. It is indeed gratifying to see that they have obtained a good correlation between ignition temperatures and the oxidation rates reported by us. The correlation is valid not only with composition within one alloy system but also between alloy systems; that is, alloying elements which effect the greatest increase in oxidation rate also produce the greatest decrease in ignition temperature. There are a few points upon which I would like to comment. In attempting to correlate ignition-temperature data, one must be sure that the same definition of this quantity is used by all investigators. It does not appear to me that such is the case in the authors' comparison of their data with the theoretically calculated values of Eyring and Zwolinski. The equation derived by these investigators defines the ignition temperature, To, as the temperature at the gadoxide interface, whereas the present authors use the metal temperature as the criterion for ignition. The contradiction in the effect of oxide-scale thickness on ignition temperature between the predictions of the Eyring-Zwolinski equation and the observations reported in this paper indicate that some variable has not been taken into consideration. Could that be the geometry and size of the specimen? There is a marked difference in the type of specimen used in this investigation and that used in our work which formed the basis of Eyring and Zwol-inski's theoretical treatment. Another factor which plays an important role in ignition is the vapor pressure or the rate of vaporization. Combustion can safely be assumed to take place in the vapor phase by the reaction between vaporized magnesium and oxygen. Thus, a more accurate theoretical analysis may be made on the basis of the rate of vaporization which may be the controlling rate of the process. The effect of a large number of alloying elements on the ignition temperature has been reported in this paper, but beryllium was not included. Practical experience dictates that beryllium markedly decreases the burning tendency of magnesium. I was wondering if the authors plan to study the effect of beryllium in their future work. The authors predict that concentrations of sulphur dioxide in the furnace atmosphere greater than 5.8 pct would be expected to increase the ignition temperature to values still higher than those they measured. I would like to mention that large concentrations of sulphur dioxide markedly increase the rate of combustion of magnesium once ignition has started. Although it has been shown in the paper that the ignition temperature of magnesium in oxygen increases with increasing sulphur dioxide content up to about 1 to 2 pct, in practice relatively low-melting commercial cast alloys (AZ63A and AZ92A) are being continuously heat treated at temperatures just below the melting point in air containing 0.5 to 0.75 pct SO*. In regard to the change in color of the oxide scale observed on magnesium and magnesium alloys just prior to ignition, I would like to mention that in our work alloying elements were found to color the usually white magnesium oxide even though ignition did not occur. For example, the oxide formed on Mg-A1 alloys was gray, increasing in intensity with aluminum content in the alloy. Finally, I might suggest that the authors indicate their source of the value of 0.8 g per cc for the density of MgO as it is formed on magnesium upon oxidation at elevated temperatures. W. M. Fassell, Jr. (authors' reply)—The comments by Dr. Leontis are very excellent ones and I will attempt to answer them in order. First, the problem of ignition of magnesium is a rather difficult one since many factors are involved. Concerning the comparison of the To in the Eyring-Zwolinski equation, eq 4, with the experimentally determined values, it will be noted that the calculated and experimental values of the ignition temperature in Table I are not self-consistent. In the case of the 1.78 pct A1-Mg alloy the calculated value is 49°C below the experimental value; for the 3.81 pct A1-Mg alloy, 122°C below the experimental value; for Mg with 5x10-' cm film, 19°C above the experimental value; for Mg with 2x10-I cm film, 28 °C below the experimental value. Thus, if it were merely a matter of difference of location of temperature measurement the calculated ignition temperature would always be below the experimental value, the difference being due to the thermal gradient through the oxide film. The possibility of a thermal gradient in the magnesium metal must be considered. From Carslaw and Jaeger,'Y t can be shown that the maximum temperature gradient that could exist between the oxide-metal interface and the center of the sample is of the order of O.Ol°C. The geometry and size of the specimen could certainly have some effect on the ignition temperature. The equation for ignition that has been proposed in reference 14 is of the following type containing terms to account for this and other factors: M dT AHv(T) =Cp--------------\-J(.T—TB) + ZAHl-M A dx where AH is the heat of reaction, v(T) is the velocity of the reaction at temperature, Cp is the heat capacity of sample, M is the mass of sample, A is the area of sample, t is time, J is the total coefficient of heat transfer outward from the reaction zone, TR is the temperature of the bath or furnace, and AH,, is the heat associated with any phase change involved. Prior to the instant of ignition, the vapor pressure of magnesium is of no special significance. After ignition, neither eq 4 nor the above equation is applicable. The actual combination of magnesium cannot safely be assumed to take place in the vapor phase. While experimental data is lacking to support a hypothesis that ignition does or does not occur in the vapor phase, some observation on the pressure ignition experiments may be of interest. At high oxygen pressures, once ignition has occurred, the reaction of magnesium with oxygen approaches near explosive violence, the entire sample being consumed in probably less than 1 sec. At atmospheric pressure it usually requires 15 to 20 sec. Thus it appears that the oxygen concentration becomes the rate determining factor. Further, if burning magnesium is observed through darkened glass (Lincoln Super-visibility Shade No. 12) the magnesium sample is very much hotter than the "smoke" and the outline of the sample is retained perfectly. No "flame" is visible above the metal. No work was done on Mg-Be alloys. We do, however, intend to study this problem in the near future.

Jan 1, 1952

By D. M. Schuster, E. Scala

The elastic effects occurring in the matrix of a composite reinforced by discontinuous fibers were studied by means of photoelastic techniques. A hirefringent plastic was employed as the matrix material with high-strength a Al2O3 whiskers as the reinforcing fibers. It was found that for whiskers aligned parallel to the tensile load direction: (I) Matrix reinforcement occurred along the length of the whisker to within about 5 diameters of the whisker tip for a length to diameter ratio, L/D, of 40. (2) Significant stress concentrations were created in regions immediately surrounding the tips; the fine as-formed tapered ends exhibited the minimum stress concentration whereas the square-ended whisker produced relatively high values, K r 2.5 for L/D = 40. (3) The axial and radial stress distributions could he determined quantitatively; the stress distribution at the whisker-matrix interface was in general agreement with theoretical calculations. (4) The highest source of stress concentration occurred at points of fracture in whiskers which had ruptured after incorporation into the composite. Whiskers aligned perpendicular to the load direction neither reinforced nor caused appreciahle stress concentrations in the matrix. ThE properties of composites have generally been formulated empirically on the basis of macroscopic tests. There are still many questions concerning the mechanical and chemical interactions occurring at the interface between the reinforcing fiber and its matrix. Continuously reinforced plastics and dispersion-hardened metals represent the two extremes of composite reinforcement. Whether artificially produced or formed in situ, the whisker composite falls between these two extremes and is an example of discontinuous fiber reinforcement. The effect of fiber shape, size, surface condition, and end configuration on the stress distribution in the matrix is important since the presence of stress concentrations, especially in any high-strength, thin-wall structure, could become the cause of catastrophic failure. DOW,' in his theoretical discussion of discontinuous fiber reinforcement, has pointed out that appreciable stress concentrations occur at the tips or ends of the reinforcing fibers. It is the purpose of this study to examine directly, by means of the photoelastic technique, the stresses which occur in the vicinity of a discontinuity or whisker tip and to measure qualitatively and quantitatively the effects of whisker geometry when embedded in a birefringent matrix material. The use of sapphire (a A1,O3) whiskers was decided upon as the reinforcing agent because of their high elastic modulus (E- 60 X 106 psi) and in some cases strengths in excess of one and a half million psi. Sapphire whiskers are of further practical interest since they retain large fractions of their strength up to temperatures approaching the melting point (3720oF).2 The whiskers were grown, by the vapor-phase reaction commonly employed,3 as part of this study to insure a physically uniform supply. Tensile and bend tests were performed to verify that the whiskers were of the expected ultra-high strength. The high-strength whiskers can be identified and selected from the combustion boats by surface perfection, shape, and size; otherwise, strength values can vary by a factor of ten or more. Macroscopic defects are quite common on the surface of large bladed whiskers and the principal experiments were conducted with hexagonal whiskers of about 0.002 in. diameter and lengths ranging from 0.1 to 0.4 in. Upon completion of these two phases of the experiment, several birefringent resins were evaluated. A plastic, developed by Zandman,4 which is supplied by the Budd Co., was found most suitable and was used as the matrix material for the whisker composite throughout the study. It has a sensitivity of 60.5 lb per in. order, calibrated in tension and cures without introducing residual stresses. Young's modulus for this matrix material is 430,000 psi in the fully cured condition. Since good wetting and bonding between the sapphire and the matrix material is essential to the interpretation of the results, a wettability test was performed. The contact angle was measured to be 168 deg where perfect wetting is defined as 180 deg; therefore, the Budd Plastic wets the sapphire

Jan 1, 1964

By Elmer Weber, W. M. Baldwin

Solid lead obeys a single parabolic weight increase vs. time law. In contrast, liquid lead undergoes three successive parabolic weight increases vs. time laws, the first of which has a low constant relative to the latter two. The conversion times for the change from one parabola to the next decrease with increasing temperature. IN recent reports on the subject,1,2 it was noted that zirconium and titanium scale in air by a complex mechanism. The scale first forming on the metal is protective to the extent that it gives a low constant, K, for Tammann's, and Pilling and Bedworth's parabolic equation: w² = Kt [1] relating weight increase, w, due to chemical reaction of the metal with the air, and time, t. After hundreds of hours of apparent stability in some cases the first scale yields to another that offers little protection to the metal. This transition from one scale to another, from a slow parabolic oxidation reaction to a fast one, was not due to impurities in the atmosphere or incidental effects (changing environment, etc.) but was a specific behavior of the metal itself, the transition occurring at definite times (dependent on temperature) and showing other reproducible traits. In view of this behavior how can long-time service behavior be predicted from short-time laboratory tests, not only in the case of these metals, but in any case? Certainly a systematic study of the type of scaling behavior described above—wherever it is found—would help to answer this question. The present paper is a report on the behavior as it is found in lead—the only metal to the authors' knowledge for which the behavior has been described at all, if inadequately, for our present purpose.* At least four oxides of lead are known, of which one occurs in two allotropic forms. They are ß (red) tetragonal PbO stable up to 486°C;8 a (yellow) orthorhombic PbO stable from 486°C up to its dissociation temperature in air at about 2300°C;9 minium or Pb3O4 which from the dissociation pressure data given in Fig. 1 decomposes to PbO at 540°C in air; lead sesquioxide or Pb2O3,; and lead dioxide or PbO2 which, according to Fig. 1, decomposes in air at 400°C to minium. In view of the high dissociation temperature of PbO, lead will scale up to at least its boiling point. Further, it is known that oxygen is almost insoluble in liquid lead.'V his implies a fair probability that an oxide scale would not dissolve in the molten metal and would afford the same protection to lead in the liquid state as in the solid. All of the oxides of lead for which specific gravity data are available are more voluminous than an equivalent weight of metal or a lower oxide from which they might form, hence the scales will be in compression. Lead oxides are known to be ductile, so it would be anticipated that they would form coherent nonporous scales. It is not surprising to learn, then, that both solid and liquid lead scale according to the Tammann, and Pilling and Bed-worth law.14,15 (Gruhl states that at 600°C and above lead oxidizes linearly with time because of "spitting" of the scale.) The parabolic constants K reported by various investigators3,14-16 are badly scattered, however, as shown in Fig. 2. The oxides formed on solid lead were described as being reddish-brown but were not chemically identified by Pilling and Bedworth.15 Gruhl's descripdin³ of the appearance of the scales On his liquid samples indicates that a (yellow orthorhombic) PbO is formed initially on the specimens but gives Way eventually—at least at temperatures below 486 °C— to .ß (red tetraunal) PbO, and that below 540°C minium—Pb3O4 :is firmed at an even later time as an overlay on either the red or yellow PbO. Fig. 3 is a graphical interpretation of Gruhl's description. Gruhl does not indicate any change in the parabolic scaling rate as yellow PbO converts to red. He does indicate that minium reduces the scaling rate, al-

Jan 1, 1953

By KENNETH CITTISGHAM

During the year 1945, the total number of wells drilled in Ohio, including the. non¬productive wells, was 1034. For the 10-year period ending with 1945, the average completions per year were 1125, the least number being 910 in 1938, and the maximum 1561 in 1941. The proportion of dry holes in 1945 was 37 per cent?about the same as for the year 1944 but exceeding the 10-year average, which was 34 per cent. The number of oil wells completed exceeded the number drilled in 1944 by about 30 per cent, the average initial per well being the same in both years. Gas-well completions were approximately 10 per Cent less than in 1944, with the average initial per well about 5 per cent greater. The difference in number of oil and gas wells in the two years was in Berea and Clinton completions, as the number of oil wells increased about 30 per cent, owing to greater activity in the two sands named, while the number of gas wells decreased because of fewer completions therein.

Jan 1, 1946

By Earl E. Hunner

At the end of the year 1914, the main North Star incline shaft had reached the 6300-ft. level, and encountered a vein dipping southwest, or exactly opposite to the North Star. Subsequent development failed to find the North Star vein continuing beyond this intersection, so the 6300-ft. level proved to be the bottom level of the North Star vein, and very little ore was found below the 5300-ft. level. The new vein was called No. 1 vein. Development work carried on for the next 10 years discovered a third vein, called No. 2, branching off about 1200-ft. to the east, with a north-south strike and a west dip. No. 1 vein had about 900 ft. of backs above the 6300-ft. level before reaching the boundary line of the property, and No. 2 vein died out about 800 ft. above. During these 10 years, the money spent on development was increased from $54,000 in 1914 to $184,000 in 1924; the ore reserves steadily diminished until it was evident that the mine must close down unless by some means a large tonnage of ore could be developed quickly. Problems and Plans In order to understand what follows, the general layout and equipment of the mine as it was at this time must be briefly described. Fig. 6 indicates the relative positions of the shafts. The North Star (incline) shaft extends from the surface to the 6300-ft. level following the vein, with an average pitch of 26", between limits of 11" to 38. There is at present no hoisting equipment in this shaft between the 2700 and 4000-ft. levels. The Central (vertical) shaft connects with the North Star shaft at the 4000-ft. level, at a vertical depth of 1600 ft. In two compartments of this shaft 4-ton skips made a vertical turn of 15 ft. radius at the 4000-ft. level and ran down the incline to the 6300-ft. level. A cage operated in the third compartment to the 4000-ft. level. Men and supplies were transferred to a truck running on a third track down the incline shaft to the 6300, operated by an electric hoist on the 4000-ft. station. When the shifts changed double-deck cages were substituted for the skips in the vertical shaft, but they stopped at the 4000-ft. station. The truck to 6300 carried 22 men, and it required 8 min. to make a trip down and back. This arrangement was satisfactory as long as a fairly large proportion of the work was

Jan 1, 1930

By AIME AIME

THIS year the Chairman of the Institute's Iron and Steel Division is THIS William Anderson Haven, better known to the membership generally as Bill Haven. The Division Chairman is an individual endowed with a broad perspective of the ferrous metal industry he result of his earlier experiences as a successful operating man in the working and management of blast furnaces and his later experiences as an engineering-consulting executive concerned with the design and erection of and steel works throughout the world. William A. Haven was born to iron steel in the Pittsburgh district on ;. 1, 1888, and in due time--or in 1909 graduated from Penn State with a Bachelor degree in industrial chemistry.

Jan 1, 1944

By M. E. Hassan, J. C. Calhoun, R. F. Nielson

An apparatus was constructed for the measurement of inter-facial tensions over a range of temperatures and pressures. This apparatus utilized the pendent drop method, and resembles in construction similar apparatus recently described in the literature and in use in some petroleum research laboratories. The interfacial tensions of benzene, propane, n-pentane, n-hexane. n-octane. and iso-octane against water were measured at temperatures ranging from 26" to 82" C and at pressures ranging from 1 to 204 atm. Values of interfacial tensions for the henzene-water system and their variations with temperature and pressure are generally in good agreement with value? of previous investigations. The data in all cases showed a slight decrease of interfacial tension with pressure at constant temperature in the range studied. The effect of pressure became less as the pressure was increased, with an indication of a reversal of the effect at higher pressures. There was a decrease of interfacial tension with temperature at constant pressure in all cases, as would normally be expected. This rate of decrease became greater the higher the temperature. A general equation is presented for the interfacial tensions as a function of presPurp and temperature over the range studied, and the constants calculated for each system. A definite trend was found in the effect of molecular weight on the interfacial tension at a given temperature and pressure, for the homologous series from propane to n-octane. Data for n-decane from the literature fitted well into this trend. INTRODUCTION It has been recognized for many years that surface forces play an active part in the production history of an oil reservoir as well as in determining the amount of unrecoverable oil. The magnitudes of these forces are governed by the values of the interfacial tensions. These vary greatly with composition, pressure, and temperature. The effect of composition is greater than that of pressure and temperature over the ranges normally encountered. In fact, because of the variety of compounds present in a crude, no attempt has yet been made to correlate crude composition with its surface tension or with its interfacial tension against water. The amount of dissolved methane greatly affects the surface properties of an oil, and there are "surface-active" compounds in crudes which have a much greater effect on boundary tensions than do equal amounts of hydrocarbons. The purpose of the present work was partly to contribute data that would eventually be used in correlations applicable

Jan 1, 1953

By H. A. BURK

THE ores of the Tonopah, district are hard, compact and' highly siliceous. They contain from .1 to 2, per cent. of sulfide material, of which argentite is the valuable mineral; occasionally pyrargyrite is found in the richer ore. The sulfide is, chiefly pyrite with small amounts of chalcopyrite,. and sometimes sphalerite. The ore also contains a small amount of gold-about 1 per cent. by weight of the silver present. The major gangue constituent is quartz but frequently considerable rhodonite-called by the miners pink manganese-is present. For primary crushing, jaw and gyratory crushers are used. These crushers are of such capacity that, in most cases, one 8-hr. shift will supply the mill for 24 hr. The Extension Co., at the Victor ore house, passes the ore through a 13 by. 24-in. Blake type McFarland crusher set at 13 in., and at the No. 29 re house, a 14 by 24-in. Blake type Traylor crusher is used. The ore is thus crushed to stamping size in one reduction. The capacity of each crusher is about 40 tons per hr.; the power consumption is 0.6 kw. per ton.

Jan 1, 1921

By Helmut Thielsch

IN recent years an ever increasing amount of interest has been directed toward research studying the principles and various applications of sonic and supersonic waves. Though still in their early stages of practical development, sonic vibrations are already used in the emulsification and degasification of liquids. Metals exposed to sonic or ultrasonic vibrations while solidifying show a considerable amount of grain refinement. Often sound waves are applied instead of radiography to test engineering materials for internal cracks and flaws.1 In the field of pure research these waves are used in dispersion and also in coagulation of particles or liquids in gaseous or, under certain conditions, in other liquid systems. In the settling and thickening of slurries considerable time is necessary to compress the solid particles and to squeeze out the liquid to obtain as low a dilution (liquid to solid ratio) as possible. Various methods have been developed to increase the amount of coagulation of the very fine solids (colloidal or semicolloidal) and to shorten the over-all time. The addition of small amounts of electrolytes and the warming of the suspension represent merely the more important techniques. Some of the effects of supersonic vibrations have been reported previously.2,6 From preliminary studies, therefore, it was hoped that by application of sonic vibrations it would be possible to reduce the time required to thicken such materials to a specific dilution, as well as to thicken to lower ultimate dilutions than could be obtained by quiescent settling alone. By increasing the volume thickened per unit time-i.e., improving the plant efficiency-great savings in equipment and time would be obtained for industrial processes. Also, faster settling rates should result if coagulation of particles could be increased. Experiments have been conducted for a period of several months in the Allis-Chalmers laboratory to study the effect of sonic vibrations on settling of particles of different sizes and concentrations. APPARATUS The sedimentation apparatus used in these experiments is illustrated in Figs. I and 2. The essential features are the stationary field coil and the movable voice coil. Both windings are placed around a solid iron core. A leather diaphragm connected to the steel frame holds the voice coil in place. A brass rod is fastened to the voice coil with a metal disk connected to the other end. This disk is sealed to the lucite cylinder with a flexible rubber diaphragm. The lucite tube is 17 in. long; its inner diameter is 2 ½in. and the wall thickness is ¼ in. The tube is calibrated on the outside in 10 c.c. divisions for a total of 1000 cubic centimeters.

Jan 1, 1946

By B. B. Zavoico

During 1936 the Russian oil industry made very satisfactory progress and, while not all difficulties of organization have been ironed out, the country is now assured of a supply of petroleum products in sufficient quantities and of quality demanded by modern motor equipment. The year 1937 promises to better by a wide margin the good showing of 1936. The statistics given in this paper for the first time take into consideration the varying gravities of crude oils of the several Russian oil fields instead of using a flat conversion factor of 7 bbl. per metric ton. It was found from the detailed study that the generally used average conversion factor should be increased from 7 to 7.25 bbl. per metric ton, the figure varying, of course, with the gravity of oil in the individual fields. Crude-oil production during 1936 is estimated at 201,500,000 bbl. as compared with 182,970,000 bbl. produced in 1935, an increase of 9.4 per cent. The greatest increase was again recorded in the Baku district, which increased its production by 10.9 per cent, from 141,257,000 bbl. in 1935 to 158,300,000 in 1936. Grozny district maintained its production at a level of about 23,000,000 bbl., but its old fields continued to decline and production was sustained by the development of newer fields. A great advance was made in drilling speeds and the total footage in 1936 reached 6,694,200 ft. as compared with 4,926,600 ft. drilled in 1935, an increase of 26.4 per cent. In older deep fields, producers were being completed at over 8000 ft.—a great depth for Russian drillers but two years ago. Several major discoveries were made in 1936. Northeast Caucasus.—Izberbash, east from Grozny and on the Caspian Sea, was the outstanding discovery, the initial production of the discovery well being around 3000 bbl. per day from about 5000 ft. The importance of the field is due to the large area of the structure, half of which, however, is under the sea, and also to its strategic location on the shores of the Caspian and near a trunk pipe line to the Grozny refining center. An active development program is being pursued in Izberbash and its 1937 production quota is set at 7,500,000 bbl. Achi-Su field, near Izberbash, also discovered during 1936, while not as prolific as Izberbash, is thought to cover a very large area and the small

Jan 1, 1937

By William M. Kester

INTRODUCTION The Coal Research Bureau of the School of Mines at West Virginia University is presently conducting laboratory-scale tests to determine the technical feasibility of beneficiating pulverized coal and coal fines with high-intensity electromagnetic fields. Interest in magnetic processes for cleaning fine coals was stimulated by results obtained by Yurovsky, et a1 in 1958.1 This work, while not new in concept,2,3 indicated that pulverized coal which had been thermally treated in a rotary drum in the presence of superheated steam and air underwent thermo- chemical reactions. Films of the ferromagnetic minerals magnetite (Fe2O3), hematite (Fe3O4), and pyrrhotite (FeS[3]) were reported to be formed on the surfaces of the pyrite grains associated with fine coal during the foregoing treatment at temperatures ranging from 120 to 360°C. After thermal treatment the coal was magnetically separated in an experimental magnetic device having a field strength of 10,000 oersteds.

Jan 5, 1965

By A. E. Back, S. F. Ravitz

When manganese ores are leached with sulphur dioxide, a large part of any zinc in the ore usually is extracted with the manganese.1 In the dithionate process,2,3 in which the manganese ore is leached with dilute sulphur dioxide gas and the manganese is subsequently precipitated by adding lime to the pregnant solution, the zinc is precipitated with the manganese. These facts suggested the possibility of applying the dithionate process to the recovery of zinc from oxidized ores or calcined sulphide concentrates. Accordingly, an investigation was begun, and preliminary tests were made on several ores and concentrates. The results were encouraging, but the need to devote available funds and personnel to other projects made it necessary to drop the work before the various factors involved in the process could be studied in detail. A brief mention of the process,4 however, elicited a number of inquiries, so that it appeared desirable to report the results of the preliminary work. The dithionate process as applied to zinc may be summarized briefly as follows: The ore or calcined concentrate is leached with dilute SO2 gas to dissolve the zinc, largely as zinc sulphate, in accordance with the following equation in which [ZnO] represents the "oxide zinc" in the ore or calcine: [ZnO] + SO2(g) + 1/2 O2 = Zn++SO4— [1] If, in the leaching step, the ore or calcine is suspended in calcium dithionate solution, the sulphate ion, as it is formed, is precipitated immediately as calcium sulphate, which is subsequently filtered off with the insoluble ore residue: Zn++SO4— + Ca++S2O6— = CaSO4(s) + Zn++S2O6- [2] An alternative procedure is to suspend the ore in water, filter off the insoluble ore residue after leaching, add calcium dithionate to the resulting zinc sulphate solution, and then filter off the calcium sulphate precipitate. In either event the zinc is obtained in the form of a pregnant solution of zinc dithionate, from which it can be precipitated as relatively pure zinc hydroxide by adding milk of lime: Zn++S2O6— + Ca(OH), = Zn(OH)2(s) + Ca++S2O6- [3] The zinc hydroxide precipitate is calcined to form the final zinc oxide product: Zn(OH)2 = ZnO(s) + H2O(g) [4] Theoretically the process is completely cyclic with respect to dithionate ion, the calcium dithionate required for reaction 2 being replaced by that formed in reaction 3. In practice, of course, small amounts of dithionate would be lost in the various filter cakes, depending on the economic washing limits. In the leaching step, however, some of the SO2 is oxidized to dithionale instead of sulphate, accord- ing to the following overall reaction: ZnO + 2SO2(g) + 1/2 O2(g) = Zn++S2O6-, [5] so that the dithionate losses are made up, at least in part. Ores and Concentrates Tested The analyses of the ores and concentrates tested are summarized in Table 1, which also includes the analyses of the calcines produced from the concentrates. The concentrates were roasted in a laboratory muffle furnace at the temperatures indicated until evolution of SO2 could no longer be detected; shallow clay dishes ordinarily were used; but calcines 2a and 2c were prepared in iron dishes, with the result that these two calcines were badly contaminated with iron scale. The "complex" concentrate, sample 1, consisted essentially of sphalerite grains containing inclusions of pyrite and other sulphide minerals too minute to be liberated by grinding within economic limits. In the " marmatitic" concentrate, sample 2, the iron was present largely as marmatite (that is, as iron sulphide in solid solution in zinc sulphide) rather than as pyrite inclusions. The zinc was present largely as the carbonate in the two "oxidized" ores, samples 3 and 4, and as the silicate in the "willemite" ore, sample 5. Leaching Tests The leaching cell was a 3-liter glass beaker placed in an electrically heated water bath manually controlled to maintain a temperature of 35°C in the leach slurry. The slurry was agitated by means of a flat paddle-type stirrer

Jan 1, 1950

By J. M. Sands

Production of oil in Oklahoma during 1927 amounted to 273,256,900 bbl. (Table l), an increase of nearly 100,000,000 bbl. over the previous year. All of the major fields declined with the exception of those of the Seminole district which produced 136,105,000 bbl., almost one-half of the total production of the state. Because of this large new production, most of the development in the state during the year took place in that district. The Seminole City pool located in T.-9-N., R.-6-E., was the first of these pools to be developed. The Indian Territory Illuminating Oil Co. brought in the first well in this field in March, 1926, for 1100 bbl. This well is located in Sec. 24-T.-9-N., R-6-E., and produced from the Hunton lime reached at depth of 3900 ft. The first Wilcox production was developed by the Independent Oil & Gas Co. and R. S. Garland in Sec. 26, T.-9-N, R-6-E. This well was being drilled for production in the Hunton lime but was dry in this horizon and was deepened to the Wilcox sand in July, 1926, and at the total depth of 4069 ft. developed a maximum production of 8000 bbl. daily. It held up in wonderful manner and was the cause of not only the development of this pool but the prospecting of the whole district for the Wilcox sand. This led to the discovery of the other major pools in that district. Seminole City pool reached a peak production of 264,500 bbl. on February 22, 1927, and slowly declined so that by December it had a daily average of 56,200 bbl. from 321 wells. The second pool in this district to be discovered was the Searight pool which was discovered by F. J. Searight et al. in Sec. 33, T-10, R-6, in April, 1926. The first well was drilled to the Hunton lime encountered at 4115 ft., and came in for 1300 bbl. daily. During August, 1926, the second well was drilled on the same farm through the Hunton lime to the Wilcox sand which was encountered at 4360 ft. It came in for an initial production of 4000 bbl. daily. This started active drilling in this field for the Wilcox sand. The field had a peak production of 40,621 bbl. on June 15, 1927, and declined to a daily average of 22,300 bbl. from 73 wells during December.

Jan 1, 1928

SULPHUR is a very well known mineral and apparently is produced in many places. It is engendered from an unctuous earthy and powerfully hot substance so that it is considered among experienced workers to bear a resemblance to the element of fire. This is called by these same men the masculine seed and the prime agent of Nature in the composition of metals. Because of its great dryness and heat it has, as experience shows, affinity with fire, which is easily introduced in it when brought near. And once introduced the fire is quenched only with difficulty before its unctuousness is wholly consumed. Although it shows itself to us of such a hot and dry nature, we must not think that sulphur is a substance so pure that it can stand by itself or that in order to attain its form it has no need of its portion and part of moisture like every other mixture. This is shown to us by its easy fusion, in which it resembles the metals. This thing is found in many places and in many varieties of color; some are white, others yellow and orange, and some others between gray and black. They also say that some red is found. It does not occur in that arrangement of veins like other minerals, but most liberal Nature makes whole mountains of it as is seen in the Aeolian islands, [26] near Sicily, in Etna or Moncibello which is the island of Sicily, at Pozzuoli, in the territory of Rome, in the Sienese domain at San Filippo, and in many other similar places. It is a substance that has a very strong odor and is most unpleasant to smell. It is very fixed in its substance so that it is never corrupted by time, by boiling, or by the moisture of water. For although it may stand in water a long time it never becomes soft nor does it ever decrease or increase in weight. It is brittle and easily crushed very fine. It is said that a trace of garlic rubbed on the mortar helps anyone who wishes to reduce it to impalpability. Its ores have a form more like earth than like stone although they some¬times have the color of a certain soft rock. The places where it is found are easily recognized by the great odor that they give out and by the very hot baths that often spring forth near it. What I have already told you about quicksilver that is contrary to the

Jan 1, 1942

By A. U. Seybolt, J. L. Walter

The effects of the addition of 0.5 pct ThO2 (by volume) on the grain structure and texture of heavily rolled tungsten sheet were studied. Powder metallurgy ingots were rolled to sheet, 0.001 in. thick, and samples were annealed at temperatures from 1200" to 2500°C. The heating rate to the anneal temperature was varied from 3°C per min to 6500°C per min. The orientations of the largest grains were determined by X-ray diffraction. The disposition and loss of the ThO2 particles were determined by electron transmission microscopy and the activation energy for remozlal of the thorium was measured by mass spec-troscopy. Heating rates below about 800 C per min produced large, highly elongated grains. Higher heating rates produced much smaller, less elongated grains. The grain structure and texture of the slowly heated samples were identical to the structures and textures of heavily rolled tungsten foil conventionally doped with aluminum, silicon, and potassium but the recrystallization temperature was about 200°C lower. There was stringer-like dispersion of larger ThO2, particles superimposed on a uniform dispersion of fine particles. The particles increased in size and decreased in number with time at temperature. The loss of particles was accompanied by formation of grain boundary voids and surface pits. The activation energy for removal of the ThO2 was about 40 kcal per mole. THE addition of small amounts of aluminum, silicon, and potassium to tungsten has a profound effect on the grain structure of heavily rolled sheet1 or drawn wire."4 Thus, "doped" tungsten sheet, rolled to 0.001 in. and recrystallized, develops a structure consisting of large, highly elongated grains of a specific preferred orientation.' It has been shown that the elongated grain structure was caused by a dispersion of particles, identified as mullite (Al6si2O13),1,4 in strings parallel to the rolling direction in sheet or to the wire axis. Identical results were obtained for iron which was doped with glass and rolled to 99 pct reduction of thickness and recrystallized.5 Again, the glass particles were disposed in strings parallel to the rolling direction. The strings retarded boundary migration in the lateral direction but grain growth was able to proceed relatively unhindered along the direction parallel to the strings.1,5 In both the doped tungsten and the glass-doped iron, the particles were highly plastic during the high-temperature deformation. Since mullite melts at about 1800°C and the glass employed melts at about 810ºC, the particles were probably molten during the recrystallization anneals (above 1800°C for the doped tungsten and 850°C for the glass-doped iron). There are indications in the literature that particles not plastic at hot-working temperatures (up to about 1550°C for tungsten) may also impart elongated grain structures by primary recrystallization of worked alloys. Examples are dispersions of tantalum carbide in chromium,6 and ThO2 in nickel where elongation ratios of recrystallization grains of up to 20:l were obtained.7 Strings of ThO2 particles in W-ThO2 wire have been seen by Rieck.8 In view of the available evidence, it was of interest to extend the previous studies of doped tungsten and glass-doped iron to include W-ThO2 sheet materials. Of specific interest was the grain structure, preferred orientation, recrystallization temperature, and disposition of the thoria particles. EXPERIMENTAL PROCEDURE A) Material Preparation. About 380 g of blue tungsten oxide (approximate composition WO3) was wet with a sufficient amount of aqueous solution of Th(N03)4 to provide 0.5 vol pct ThO2. The wet mixture was stirred to distribute the doping material uniformly throughout the powder. Stirring was continued while the mixture was heated until it was completely dry. The dried, doped mixture was then reduced to tungsten powder by heating at 850°C for 2 hr in a stream of dry hydrogen. The doped tungsten powder was hydropressed in a rubber sack at pressures of 50,000 psi to produce an ingot approximately 2 cm diam by about 5 cm long. Next, the pressed cylinder was heated in hydrogen for 2 hr at 1350°C to render it strong enough for machining. The cylinder was machined to a square cross section of 1.6 by 1.6 cm with rounded corners. Finally, the bar was heated for 2 hr at 2150°C in hydrogen to provide a sufficiently dense mate rial to withstand the hot-rolling operation. Prior to rolling, the ingot was reduced in thickness by about 20 pct by forging at 1550°C. This served to increase the density of the material and to widen it slightly for better rolling characteristics. The forged ingot was then rolled at 1550°C to a reduction of 45 pct of thickness, following which the rolling temperature was reduced to 1300°C and the slab rolled, with several reheats, to 0.050 in. Further reduction was accomplished at 800°C in tungsten sheet packs to a total reduction of about 99.85 pct. B) Annealing Treatment and Observation of Structure. Small samples of the rolled foil were annealed in one of two ways. Some of the samples were suspended in a covered tungsten can and annealed at temperatures from 1200" to 2200°C for various times in vacuum of l0-7 to 10-6 mm Hg. The can was heated by induction and temperatures were determined by optical pyrometry

Jan 1, 1970

By J. P. Smith

Permian salt measures carry extensive lenses of soluble potash salts in north central Germany. Potash deposits of Oligocene age are found in the Upper Rhine Graben of Alsace (France), and in the Catalonian Basin of Spain. These deposits are found in a wide range of structural settings. Reserves are large, and the production of potash salts is an important phase in the economy of each of these countries.

Jan 1, 1950

In the January Bulletin a list was published of Societies' publications, magazines, etc., which were duplicates and were discarded at the time of-the consolidation of the libraries of the three Founder Societies. A second list published herewith includes text books which are duplicates and which will be disposed of about April 1, 1916, by the Board of Directors of the Institute through the, Library Committee.. If, meanwhile, members desire to secure some of these books, they are asked to communicate at once with the Secretary as. this is an unusual opportunity to secure books at an extremely low price. Airy, George Biddell.-Magnetism, London, 1870, Bd. Alberti, Friedrich von.-Halurgische geologic. Erster Band. Zweiter Band. Stuttgart, 1852, Bd. American Iron and Steel Association.-Ann. Rep. of the Sec'y. Statistics of American and, Foreign Iron Trades, 1877. Phila., 1877, Bd. Same, for year 1878. Phila., 1879, Bd. American. Telephone and Telegraph Co.-Ann. Rep. of Directors to Stockholders, 1911. N. Y., 1912, paper. Armagnat, H.-Induction Coils. Trans. by Otis Allen Kenyon, N. Y., 1908, Bd. Armstrong Cork Co. Insulation Dept. Nonpareil Corkboard Insulation. Pittsburgh, 1909, Bd. Associazione fra gli Industriali Metallurgici Italian.-The Metallurgic industry of Italy. Description of some of the principal works. Milan, 1911, Bd.

Jan 2, 1916

By Robert E. Sorenson

EXPLORATION for deep-seated orebodies in the Silver Belt area of the Coeur d'Alene mining district is complicated by meager surface expressions of diagnostic criteria, lack of knowledge of the significance of specific alteration phenomena, and the great expense involved in the exploration for ore shoots, the tops of which often occur near sea level elevation or below and as much as 4000 ft or more below the surface. Except for the early studies of Ransome and Calkins in 1903 and 1904,[1] little geological work was done in the Coeur d'Alene district for many years, and it is only during the last 15 to 20 years that complete and careful geological mapping has been applied to most of the mines in the area. Much early information, which now would prove invaluable, is lost in hundreds of miles of caved and inaccessible mine openings not mapped by mining geologists. In more recent years mining geology has become a tool of greater use in the district, and some measurable progress is being made in the accumulation of observations that are adding gradually to the knowledge of ore deposits in the district.

Jan 7, 1951

By H. C. Brassfield, R. E. Fryxell, E. C. Duderstadt, E. A. Aitken, P. K. Conn

Permeation rates of hydrogen through are-cast tungsten were measured at temperatures from 1300" to 2600°C with hydrogen pressure differentials of 1 and 0.1 atm across isothermal membranes. Rates were nearly Proportional to square root of pressure, were inversely ProPortional to membrane thickness, and were temperature-dependent according to the equation: p = permeation coefficient in cu cm (stp)-mm per sq cm-min-atmlr2, R = gas constant in cal per mole-OK, T = absolute temperature in OK. Permeation rates of oxygen through tungsten were deternlined in the range 1965" to 2300°C and at calculated oxygen (02) pressures of 3.3 x 10-4 to 2.2 x at?n using sealed capsules containing Kmown quantities of tungsten oxide. Permeation coefficients obtained in this manner had a temperature dependency in the range of 40 to 45 kcal per mole of permeating species. Permeation coefficients for oxygen were higher than those for hydrogen in the temperature range studied. This is probably the result of oxygen solubility being much greater than hydrogen solubility at these temperatures at a gzven pressure. The purpose of this investigation was to determine experimentally the permeabilities of hydrogen and oxygen through polycrystalline tungsten at temperatures ranging from 1300° to 2600°C. Permeation rates of hydrogen through tungsten have been measured at temperatures up to 925°C,but no previous measurements have been reported for the temperature range covered in this investigation. Some diffusion measurements3&apos;&apos; and solubility measurements3 have been made for hydrogen at temperatures below 2200°C. No previous permeability studies of oxygen through tungsten are known to the authors; however, efforts have been made to determine diffusion rates5-&apos; and solubilities PERMEATION THEQRY Permeation has been defined by ortton" as the overall steady-state flow process from the gas phase on one side of a membrane or wall to the gas phase on the other side and includes the steps of adsorption, solution, diffusion, exsolution, and desorption; in a given temperature range, any of these processes may be rate-controlling. For diatomic gases, which dissociate prior to diffusion, the quantity of gas which permeates through a membrane or wall at a given temperature is directly proportional to the surface area of the membrane, the length of time of permeation, and the difference between the square roots of the pressures on each side of the membrane, and it is inversely proportional to the thickness of the membrane when diffusion-controlled, thus: q = total amount of gas permeating a membrane, p = temperature-de pendent permeation coefficient, A = area of membrane exposed, / = time, p i = gas pressure of high-pressure side, p2 = gas pressure of low-pressure side, d = thickness of membrane. When the surface reactions are not rate-controlling steps and the solution of the gas in the metal follows Henry&apos;s law, the permeation coefficient, P, is equal to the product of diffusivity and solubility. The permeation coefficient is also temperature-dependent according to the equation: Po = permeation constant, Q = activation energy, R = gas constant, T = absolute temperature. MATERIALS The tungsten materials used in this investigation were greater than 99.9 pct pure. The interstitial impurities ranged from < 1 to 50 pprn C, 7 to 35 ppm O, less than 15 pprn N, and undetectable quantities of hydrogen. Previous high-temperature studies of are-cast tungsten have shown that thermal treatment similar to that which the hydrogen permeation cells experienced reduces the carbon content from starting levels of 50 to 60 ppm to about 30 ppm. Metallic impurities were in the low (1 to 50) ppm range. The argon gas used in this investigation contained about 8 ppm N. None of the following gases were

Jan 1, 1968

By Leslie C. Richards

The competitive position of producers of industrial minerals depends upon the delivered price of their product. Freight charges are a major factor in the sales to consumers. A comparison of freight rates on movements of limestone and silica rock in the Pacific Northwest shows a wide variance in mills per ton mile for like hauls, thereby favoring some localities over others.

Jan 1, 1950