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By O. W. Ellis

The question of the influence of gases upon the properties of copper has received the attention of a number of investigators, among whom Sieverts,' Iwase,2 Lobley and Jepson3 stand preeminent. Solubility of Gases in Copper Sieverts and Iwasé concerned themselves with the solubility of a variety of gases in the metal in the solid and liquid states. They determined the absorption coefficients of these gases and in all cases found a sharp change in solubility at the melting point of the metal. In this respect they disagree with Lobley and Jepson, who have based their opinions upon the appearance of small ingots of the metal which had been fused in an atmosphere of one or other of three gases and had then been rapidly cooled, while surrounded by gas, to the freezing point (rate—possibly 30" to 60" C. per sec.). The ingots that had been fused and cooled under nitrogen and carbon monoxide were free from blowholes and it was assumed that these gases were not absorbed in amounts much in excess of those which would dissolve in the solid metal; the ingots similarly treated under hydrogen were full of blowholes and it was assumed in this case that gas was ejected on solidification of the copper. The effect of varying the rate of freezing upon the character of the test ingots was not examined by these investigators; otherwise, it is felt, their views might have been subject to modification. Sieverts' most important contribution is that the solubility of a gas in any metal is proportional to the square root of its pressure or concentration. Knowing then the absorption coefficients of the various gases in copper, it should be possible to determine the analysis of the

Jan 1, 1929

By J. B. Morgan

The mechanical behavior of MgCu2 from 20 o to 725°C has been determined by "brittle-ring" tensite-test techniques, axial compression, and bending experiments. Compressive ductility begins at 450°C (0.65 T/Tm) and slowly increases with increasing temperature white the tensile ductility is characterized by an abrupt brittle-ductile transition at 600°C (0.8T/Tm). The compressive strength increases eightfold from room temperature to 400°C with a "normal" decrease as the temperature is further increased. The tensile strength goes through a rather abrupt threefold increase above 600°C with a subsequent decrease at higher temperatures. The slip system is (111)[110] and the twinning system is (111)[112]. At high temperatures MgCu2 is quite rate-sensitive, and dynamic yield points are observed that are extremely orientation-dependent. The high-temperature creep behavior under constant load is characterized by an increasing strain-rate with time. The general characteristics of the mechanical behavior make it possible to classify MgCu2 with those materials in which initial mobile dislocation density and the dislocation velocity-stress dependence are significant in determining mechanical response. Mgcu2 is the C15 prototype of the cubic Laves phase. Its range of homogeneity extends from 32.8 to 35.5 at. pct Mg at 500°C and narrows at lower temperatures. The lattice parameter is reported to vary from 7.02 to 7.05A,1 and the compound is completely ordered to the melting point of 819°C. MgCu2 has a brassy metallic appearance, is extremely brittle, and many of its physical properties are intermediate between those of the constituent elements: the electrical resistivity is 3.5 x 10-6 ohm-cm, Young's modulus is 10x 106 psi, the shear modulus is 6 x l06 psi, and the thermal coefficient of expansion is 18.7 x 10-6 cm per cm per "C from 20" to 250°C. Usually, properties of intermetallic compounds as functions of temperature have been determined by hardness, compression, or impact behavior, and almost all of these experiments have been performed on polycrystalline materials. Tammann and Dahl,2 for instance, determined the onset of ductility in a series of binary intermetallics by ball-hardness measurements and found the onset to range between 0.71 and 0.96 T/T,. Lowrie's3 investigations included some tensile properties, and he found ductility beginning around 0.65 T/Tm for most materials examined. His work did include some data on polycrystalline, nonstoichiometric MgCu2, however. The present work is an attempt to extend the examination of the particular compound MgCu2 in single-crystal form in order to aid the formation of general concepts about mechanical be-

Jan 1, 1965

By John E. Greenawalt

In view of the increasing importance of sintering in the beneficiation of iron ores preparatory to their reduction in the blast furnace, the writer believes the time is opportune for an up-to-date, though brief, discussion of the general principles of sintering, as well as a discussion of some of the recent improvements and mechanical developments that have been achieved in this industry, its present trend and future possibilities. Sintering may be defined as the agglomeration of fine mineral particles into a porous mass by incipient fusion caused by heat produced by combustion within the mass itself. Its first successful application, in connection with the treatment of lead sulphide ores, was known as blast roasting. In this process the lead ore was given a preliminary roasting in a reverber-atory furnace, then the incandescent mass was placed in a pot with a grate and an updraft was applied. It was soon discovered that much better results were obtained by cooling the ore, moistening it, and placing it upon an incandescent layer of fuel previously placed upon a grate, and then applying the updraft blast of air until the charge was converted into a more or less agglomerated mass. The fuel was sulphur and the process one of desulphurization, which was the principal result desired. The application of downdraft to blast roasting brought about tremendous results; the principal one of which was that an air blast of high pressure could be passed through a layer of ore deposited on a grate, or on a grate covered by a layer of coarse porous material, without disturbing the particles of which the layer is composed. The air current is compelled to filter through the pores of the charge, whereas if the same pressure applied to the top surface of the charge with downdraft were applied to the bottom of the charge with updraft, the charge would be completely blow11 off the grate. Another result of reversing the draft was that a flame could readily be applied to the top surface of the charge for igniting purposes. Broadly speaking, sintering is an oxidizing or burning process, therefore the volume of air passing through the charge is the all-important factor. The air must pass through with sufficient rapidity to produce the necessary heat, and if sufficiently rapid the combustiorl will take place

Jan 1, 1938

By B. C. Allen, W. D. Kingery

Surface tension and its temperature dependence have been determined for pure liquid Fe, Cu, Co, Ni, and Sn and for Fe-C, Co-C, and Ni-C alloys. The temperature coefficient of surface tension is negative for all these liquids. The surface tension and wetting behavior of tin and tin-titanium alloys on A120,, Si,N,, MoSi,, and Sic, as well as the behavior of titanium-containing nickel alloys on A1 20, have been determined over a wide temperature range. For all the solids investigated titanium additims markedly lower the contact angle. Some limits for the solid-surface energies have been calculated from liquid surface tension and wetting behavior. SURFACE tension and interface energy are important variables in a number of metallurgical and ceramic phenomena, and have been discussed at some length in connection with determining micro-structure of polyphase systems,' solid-state sintering,' thermal etching of grain boundaries, heats of solution and fine powders,'1 grain-growth phenomena,' the mechanical behavior of fine foils and fibers, nucleation, soldering and brazing,' and other phenomenz of academic or practical interest However, until recently few quantitative data have been available for high-temperature systems. Among available data are some indicating positive temperature coefficients for the surface tension of liquid copper,*,11,'2 cast iron,l3 and iron-carbon14 alloys. Although carbon was found to be not surface active in iron at 1570" some preliminary studies had indicated the possibility of a positive temperature coefficient for the eutectic composition at lower temperatures.16 One part of the present study has been largely concerned with determining the temperature coefficient of surface tension for several metals at elevated temperatures, In addition to surface-tension studies, the wetting behavior of alloys containing titanium has been investigated over a wide temperature range. Previous measurements indicated that titanium was selectively adsorbed from nickel at a liquid nickel-solid alumina interface,17 and the use of titanium hydride or titanium-alloy techniques for metal-ceramic soldering is well known. In the present study, previous data have been extended to new alloy systems, and measurements have been carried out with other oxidation-resistant ceramics. EXPERIMENTAL The sessile-drop method was employed to measure liquid surface tension and contact angle between liquid and solid, utilizing apparatus and techniques which have been described previously.'g The shape of a sessile drop depends on equilibrium between forces of surface tension tending to form a spherical surface of minimum area and forces of gravity tending to flatten the drop. Typical sessile drops are shown in Fig. 1. From precise measurements of maximum drop diameter and drop height the surface tension and drop volume were calculated. Four solid materials were employed as supporting plaques for the liquid-metal drops. Aluminum oxide (99.9 pct, J, T. Baker, reagent grade) was pressed and sintered at 1800°C. Molybdenum-disilicide powder (99.0 pct, Electro Metallurgical Co.) was pressed and sintered at 1650°C. Plaques were cut from silicon carbide (99.4 pct, hot-pressed at Alfred University) and silicon nitride (95.1 pct, with Al, Fe, 0 as major impurities, Norton Co.) rods. All plaques were polished, cleaned, and dried prior to use. A number of metals and alloys were employed. Chemical analyses of vacuum-melted ingots of iron, nickel, cobalt (National Research Corp.), commercial nickel-base alloys, electrolytic copper (International Smelting and Refining Co.), and tin (Mal-linckrodt Chemical Works) are given in Table I. Alloys were prepared in the laboratory by vacuum melting the base metal with either titanium hydride (Metal Hydrides, Xnc.) or spectroscopic-grade carbon (National Carbon Corp.). Nickel-titanium alloys contained between 0.001 and 0.005 pct oxygen and the ferromagnetic metal-carbon alloys contained 0.001 pct. Cylindrical metal specimens (1 to 2.5 g) were machined and bevelled at the bottom to insure a uniform advancing contact angle on melting. Before use the samples were acid-etched, cleaned with acetone, and rinsed in petrol ether.

Jan 1, 1960

By J. E. Ryan

TRONA, Calif., is a miniature urban community of some 3500 people, located on the northwest shore of dry Searles Lake in the extreme northwest corner of San Bernardino County, approximately 186 miles north and east of Los Angeles. Since it is situated on the Mojave Desert, a typically desert climate prevails with wide variations in temperature between day and night, extreme daytime summer heat, and cool to cold winters. Rainfall averages somewhat less than 4 in. per year, and dust storms are common. The rate of evaporation, .however, is great, amounting to 6 to 9 ft of water per year. The extremely low humidity makes the summer heat of 110°F tolerable with only a mild, temporary discomfort. Nature of Deposit During the periods when Searles Basin was flooded, the waters that passed through Indian Wells Valley spread out to form a broad, shallow lake providing, in effect, a settling basin for suspended sediment. The drainage into the deeper and more isolated Searles Basin thus was clarified to a great degree before concentration began. Today, the elevation of the dry surface of Searles Lake is 1618 ft, and the salt deposit measures 5x7 miles. At the eastern and northeastern margins of the main playa zone and just at the foot of the alluvial slope of sand and coarser wash from the Slate Range mountains, a rim of crusted salts rises a few feet above the level of the flat. The deposit is a saline efflorescence composed of salts that were presumably brought up with rising ground waters to be deposited at the surface by solar evaporation. This deposit consists chiefly of trona, and it is after this Trona Reef that the town Trona was named. Strip mining operations have been conducted in the past at infrequent intervals for the recovery of crude trona salts. The main focal point of interest in Searles Lake from a commercial standpoint is the main salt body located almost centrally in the basin. The exposed portion of this porous saline deposit covers approximately 12 sq miles and averages 71 ft deep. Its interstitial voids, which constitute 50 pct of the total volume, are permeated with a brine, which is in equilibrium with the soluble salt deposits. The brine is the raw material for the operations of the American Potash and Chemical Corp. plant at Trona, shown in Fig. 1. The soluble salt deposits are of interest for their potential values in future technologic development. The brine, which is stratified according to slight differences in density, stands usually within 6 in. of the surface of this exposed, firm, salt body. The surface is usually dry and will support the weight of heavy mobile units and drilling equipment. Occasionally, however, surface waters from the higher watersheds encroach upon the main salt body during infrequent periods of precipitation on the surrounding mountains. This water dissolves surface salt, becomes a dilute brine, and has been observed to stand as high as 18 in. above the salt surface when undisturbed. Windstorms will shift the water back and forth across the lake surface. The exposed salt body is surrounded by additional submerged areas of commercial soluble salt deposits covering some 20 sq miles, hidden from view by marginal playa mud. These vary in depth up to as much as 30 ft. Thus, the outline of exposed and submerged salt deposits of commercial value is estimated to cover a total area of 32 sq miles, which is roughly circular but slightly elongated from northwest to southeast. It has been estimated that each square mile contains about 100 million tons% f alkali salts. The results of drill borings in the past 15 years have brought to light the interesting fact that the main salt body lies superimposed on an impervious mud deposit from 10 to 15 ft thick containing relatively little soluble salt. Under this deposit lies a second soluble salt body 35 ft deep. The lower salt body is interspersed with numerous insoluble mud lenses and its composition is considerably different from that of the primary, or main salt deposit. Recent drill borings have not penetrated beyond 300 ft. They have, however, revealed that underlying the lower salt body, the mud sediments carry deposited minerals of trona, nahcolite, mirabilite and much less soluble carbonates or sulphates of calcium and/ or magnesium. This structure is shown in Fig. 2. Current Lake Survey Program Several hundred holes have been drilled in the deposit. However, to carry out a thorough and carefully correlated study of the composition of the soluble salts and other minerals in the dry lake basin, a drilling program was inaugurated recently and is now nearing completion. In this survey, pattern drill holes are sunk at regular lh-mile intervals to a depth of approximately 150 ft. Drilling equipment consists of a No. 51 C. P.

Jan 1, 1952

By Albert A. Smith

The creep properties of metals have assumed increasing importance in recent years and many investigations have been made on various phases of the problem. In the past year the annual lectures of the Institute of Metals Division1 and the Iron and Steel Division2 were concerned with this subject, and are excellent reviews. For many years the creep properties of lead and lead alloys have been investigated at the Central Research Laboratories of the American Smelting and Refining Co., and it is hoped that the present paper will contribute knowledge of some of the factors that influence creep. Lead, being a metal that recrys-tallizes readily at room temperature, is an excellent material upon which to investigate creep phenomena because of the simplicity of the apparatus needed, and it might be expected that results would apply to some extent to elevated-temperature tests of other metals. Material The creep tests of this investigation were all made on high-purity lead (99.9998+ Pb) in which the only impurity that could be detected by spectrographic and chemical means was approximately 0.0001 per cent Fe. Flat strips, 0.750 in. wide by 0. 100 in. thick, were prepared by extruding 2-in. dia. cast billets at a temperature of 250°C. This gave a material of 2 to 3 mm. average grain size with a tensile strength of j.400 lb. per sq. in. when tested at a straining rate of 5 per cent per minute. With this extremely soft material, great care was necessary in handling the specimens, to avoid distortion and subsequent recrystallization. The creep tests at 30°C. were conducted in a constant-temperature room, specially built for the purpose in the basement of an office building in which there was no moving machinery, and no vibration was detectable under the most severe conditions of shock in the adjacent surroundings. The room was well insulated and heated electrically, control being by means of a de Khotinsky regulator operating a relay. Maximum temperature variation over a period of several years has been ± 1/2°C. Specimens of the extruded strip, 16 in. long, were used for test purposes with no reduced gauge section, thus eliminating any distortion due to machining. The method of clamping and supporting the specimens is shown diagrammatically in Fig. 1. The gauge marker for the measurement of extension consisted of an aluminum strip, 0.050 in. thick by 0.75 in. wide, one end of which was ground and sanded to a precise knife-edge and fastened to the specimen by suitable pins. After the strip was fastened in place a fine scratch was inscribed just below the knife-edge by means of a sharp teasing needle. Just below this gauge scratch a short vertical mark was made so that the same point could be located and read each time. Several hundred specimens have been prepared by this method, and it was found that with experi-

Jan 1, 1941

By O. W. Ellis

The question of the influence of gases upon the properties of copper has received the attention of a number of investigators, among whom Sieverts,' Iwase,2 Lobley and Jepson3 stand preeminent. Solubility of Gases in Copper Sieverts and Iwasé concerned themselves with the solubility of a variety of gases in the metal in the solid and liquid states. They determined the absorption coefficients of these gases and in all cases found a sharp change in solubility at the melting point of the metal. In this respect they disagree with Lobley and Jepson, who have based their opinions upon the appearance of small ingots of the metal which had been fused in an atmosphere of one or other of three gases and had then been rapidly cooled, while surrounded by gas, to the freezing point (rate—possibly 30" to 60" C. per sec.). The ingots that had been fused and cooled under nitrogen and carbon monoxide were free from blowholes and it was assumed that these gases were not absorbed in amounts much in excess of those which would dissolve in the solid metal; the ingots similarly treated under hydrogen were full of blowholes and it was assumed in this case that gas was ejected on solidification of the copper. The effect of varying the rate of freezing upon the character of the test ingots was not examined by these investigators; otherwise, it is felt, their views might have been subject to modification. Sieverts' most important contribution is that the solubility of a gas in any metal is proportional to the square root of its pressure or concentration. Knowing then the absorption coefficients of the various gases in copper, it should be possible to determine the analysis of the

Jan 1, 1929

By H. S. George

On one occasion when it seemed desirable to reveal under the microscope not only the metallic structure of an alloy, but certain small non-metallic inclusions that are ordinarily obliterated by etching, it was discovered that, by partly eclipsing the illuminating pencil of light rays, the residual light was thrown on the object from one side and the structure was brought out in relief. At the same time, the non-metallic inclusions were retained in clear view. In this first demonstration of lighting obliquely through the objective a card was thrust part way into the light beam between the arc iris and the light filter; the shadow of the card on the filter served to locate its position. Next several stiff-paper disks of various diameters were mounted on flexible wires; some plasticine on the other end of the wires made it easy to adjust and maintain a disk at any desired position in the light beam. To facilitate manipulation, an assortment of disks was mounted on a wheel, as shown in Fig. 1. The purpose of partly eclipsing the light beam was discussed in an earlier paper.' There it was pointed out that the usual methods of illuminating opaque objects for microscopic examination lend an unnatural appearance to the view, while the new method, which has been termed conical illumination, revels the true relationship of constituents by simulating natural lighting. In nature, all objects are lighted diffusely, or by light predominating from one direction, or by a combination of diffuse and directed light. Under these conditions, objects appear to have three dimensions—they possess relief. The kind of illumination known to metallographists as vertical or axial results in an unnatural appearance, as a large proportion of the illuminating rays are parallel to the line connecting the eye with the object, a condition almost never met in nature. Microconstituents

Jan 1, 1924

By P. B. Bucky

IN previous publications1 it was shown that a scalar model of any weighty structure, where the stresses produced are mainly due to gravita-tional forces, will behave similarly to its prototype if the model and proto-type material are the same arid the model is placed in a centrifugal field of force (substituted for the gravitational field) which has been increased in the same proportion as the linear model scale is decreased. This principle is now being applied to a study of the behavior of mine structures in an attempt to determine the laws that control them. The importance of using models as a means of solving mining problems has been discussed previously, yet it may be well to reiterate here that this method of research and type of solution have been productive of far-reaching results in other engineering fields, notably those of hydraulics and aerodynamics. Model research is a comparatively cheap and time-saving method of checking practical experience. Up to the present time the best guide to what will happen underground has been the judgment of the man who has observed most and been longest acquainted with the local conditions. His experimental work underground is limited by the elements of cost, time and danger, while failure is seldom permissible. In a model, as in a test tube, all elements that affect the solution of a problem are under definite control. Each element may be varied independently at will and its effects noted. Experimental work on a small-scale model may there¬fore be performed at a comparatively small expenditure of time and money, instead of on a full scale in the mine, where the cost, time, and danger elements are necessarily great. The experiments described in this paper are to be considered as part of a progress report and a continuation of Technical Paper 425. One object of the research program is to make each experiment point the way for further research on that particular phase of the general problem. The results and conclusions presented here are therefore not to be considered as final, but are to be interpreted as

Jan 1, 1933

THE problem of picking the best students for an engineering college can no longer, be considered as simply one of determining the amount of general ability, but rather of finding special aptitudes for scientific work, according to Carl C. Brigham~ a Princeton University professor, who has been conducting researches on methods of selecting engineering undergraduates at Cooper Union, an evening school in New York City. When we first began this investigation seven years ago," says Dr. Brigham, "we thought the whole job would be done a soon as we had found a good method of measuring general intelligence. Today we feel that we are still about five years away from a solution, but on somewhat firmer footing than when we were looking for general ability.

Jan 1, 1928

By Charles W. Merrill

IF we follow the threads of the mining problems, upon which I have touched, we find them all leading to one great fundamental desideratum. The people of this State, of this Nation, and of this world must be brought to a better understanding of the basic nature of our industry-must be made more mineral-minded. It is my belief 'that there is not a man present among this earnest gathering of those interested in the mining industry, who has not a deep-seated and heartfelt desire that the existing unprecedented welfare and prosperity of the whole mass of American people be maintained not merely through our own generation but through the generations of our children and their children. In the decades to come there can be no question of the keenness of the foreign competition which we are doomed to meet, and in this great international contest that Nation which has the best balanced program of development and that broadness of vision in its governmental direction, which recognizes the necessity of a sympathetic attitude toward the upbuilding of such a broad pro- gram will be the Nation which will maintain and pre- serve that welfare of all of its people.

Jan 1, 1929

By MORTON WEBB

Discussion of the paper of Max Boehmer, presented at the Pittsburg meeting, March, 1910, and printed in Bulletin. No. 38, February, 1910, pp. 119 to 122. W. MORTON WEBB, Germiston, Transvaal, South Africa (communication to the Secretary*):-The experience of Mr. Boehmer in the Leadville district and his reputation as an engineer assure the interest of anything he may write on the ore-bodies of that district; and all engineers who have operated in Leadville will agree that the theory of the origin of the Leadville deposits, as given by Mr. Emmons in his famous monograph, does not adequately explain the genesis of all the deposits. The solution of the problem does not, however, appear to be quite so simple as Mr. Boehmer would make it; and the advance pamphlet issued by the U. S. Geological Survey, pending the completion of the main report, shows that there is still much ground for controversy. No doubt the later eruptives had a greater influence on the deposition of the ore-bodies than was thought at the time of the first investigation by the Survey; but it has always appeared to me that the influence exerted by these dikes was more in the nature of a physical than a chemical one. The weight of evidence in recent years is mostly in the direction of ascension rather than lateral secretion; and one of the strongest evidences is the fact that most of the ore-bodies lie under one of the comparatively impervious layers which help to make up the structure of these hills. On Iron hill I have found a very persistent white porphyry sheet, split off from the overlying porphyry and lying from 30 to 60 ft. below the main white porphyry and blue limestone contact. This sheet varies from a few to 50 ft. in thickness, and where found adds another "contact" to that region ; some of the largest ore-bodies on Iron hill lie immediately under this sheet. Above this is the main white porphyry and * Received Mar. 3, 1910.

Feb 1, 1911

By ANTON GRAY

In considering the possibilities and costs of discovering minerals by exploration. mineral occurrences may be classified roughly according to the size of the target they offer to the various methods that have been used to search them out. This classification is advantageous because the methods of search which might be expected to give results in one case may be totally inapplicable in others. Mineral deposits for the most part have been found in groups, or districts, in which the individual deposits occur under the same general geological conditions and usually contain more or less the same metals. There are, also, what are apparently isolated de- posits, although if the truth were fully known many of these probably would not be isolated. These districts, such as the Belgian Congo copper fields, the California Mother Lode, and the Linares lead district of Spain, form the first division of my classification. The second division is formed of the individual deposits of these districts, for example, Kambove mine in the Congo, the Kennedy-Argonaut vein in California, and the Cruz vein at Linares. The third division consists of the separate ore bodies that make up the deposits

Jan 1, 1949

By Charles L. Mantell, Kurt Straler

The hydrogen reduction of Cr2O3 to chromium metal was found to be feasible at very low water-vapor concentrations, corresponding to dew points of -38° to -24°C, over a temperature range of 1130" to 1490°C. Hydrogen reduction under these conditions was predicted by the calculated equilibrium curves which also indicated that CrzOs is reduced directly to chromium without forming the intermediate oxide, CrO. This reduction path was confirmed by X-ray diffraction analysis. The percent reduction of Cr2O3 at each reaction temperature was constant with time, suggesting an inhibiting effect of water vapor. A small increase in the residual water-vapor concentration of a single temperature, 1490°C, strongly retarded the rate of reduction This effect was expressed by an empim'cal equation which indicated a direct relationship between "distance from equilibrium" and the rate of reduction. me effect of temperature over the range of 1130" to 1490°C was expressed in an Arvhenius plot of log rate vs reciprocal absolute temperature. From this curve the apparent enthalpy of activation was found to be 29,600 cal. Based on the hypothesis that the rate of reductiun is contvolled at the oxide-metal interface, an over-all rate equation consistent with the experimental data and the thery of absolute reaction rates was formulated. A simplification of this expression to an Arrhenius equation was justified by the overriding effect of temperature on the rate of reaction for the minimum water-vapor concentration range. MOST of the metals in Subgroup V1 of the periodic table can be prepared commercially by direct reduction of their oxides by hydrogen or carbon monoxide, at temperatures considerably below the melting points of both the metals and their oxides. Chromium is an exception, being generally reduced from its ore, Cr2O3 . FeO, by silicon in an electric arc furnace which operates above the melting point of the Fe-Cr alloy or above the melting point of chro- mium if a chromium oxide be the starting material. In reduction of chromium oxide by hydrogen, either reduction does not occur at all or the rate of reduction is extremely slow. Theoretical considerations based on the high, exothermic, free energy of formation of Cr2O3 compared to the oxides of the other Subgroup VI metals, molybdenum, tungsten, and uranium, would also suggest a slow rate of reaction and a high activation energy. Interest in the direct gaseous reduction of fine-powdered ores in fluidized beds was considered justification for examination of this reaction. In order to develop a basis for a continuing study of the commercial feasibility of the direct gaseous reduction of chromite, a study of the kinetics of the reduction of Cr2O3 with hydrogen was undertaken. To the authors' knowledge no accurate kinetic data for this reaction have been obtained. Neither has an activation energy been determined nor has an attempt been made to establish a mechanism of reaction. LITERATURE Maier10 compared the data of I. Y. Granaat,6 H. von Wartenburg and S. Aoyama, and G. Grube and M. Flad7 with that derived from calorimetric and ther-modynamic properties for the equilibria for the reduction of Cr2O3 with hydrogen. These results, plotted as the log of the equilibrium constant vs absolute temperature for the reduction of Cr2O3 and the intermediate oxide, CrO, to chromium, show agreement between the differently derived data. In both cases the equilibrium constants were extremely low. Maier showed that, over a temperature range of 1000° to 2000°K, Cr2O3 is more readily reducible than CrO. Granat assumed that CrO was preferentially formed from Cr2o3 above 1100°C. Grube and Flad's analysis of their reaction products in the 895" to 1000°C range indicated the coexistence of only Cr2O3 and chromium. The hydrogen reduction of the other Subgroup VI metals, molybdenum, tungsten, and uranium, shows that reduction of the higher oxide proceeds through all of the intermediate oxides before being reduced to the metal. Since evidence pointed to an anomaly in the reduction behavior of Cr2O3, the authors investigated the reduction path of Cr2Os.to chromium. This was done theoretically with more recently available free-energy data and experimentally by X-ray diffraction analysis. This work reinforces Maier's conclusion.

Jan 1, 1964

By Milton E. Wadsworth, R. Ted Wimber

Cobalt sulfate solutions containing ammonium acetate and chloroplatinic acid were reduced by hydrogen in a pyrex-glass lined autoclave in the temperature range of 170o to 232°C and hydrogen partial pressure range of 115 to 830 psia. The reduction rate was directly proportional to the hydrogen partial pressure and surface area of the pyrex glass and was independent of the quantity of chloroplatinic acid added initially. Experiments involving the variation of the relative concentration of ammonium acetate indicated that the reducible cobalt complex was probably the diacetate complex of cobalt, Co(AC)4H20, or a new mononcetate complex Co Ac, which was in solubility equilibrium with a pink precipitate of CO(AC)-4HzO. THE reaction in which a metal is dissolved by an acid to produce gaseous hydrogen and a salt solution was discovered early in the history of chemistry. In 1859 Beketoff found experimentally that this reaction could be reversed; i.e., a salt solution could be reduced by gaseous hydrogen to produce a metal and an acid. A review of work done on this phenomenon since that time may be found elsewhere., The hydrogen reduction of a cobalt salt solution is facilitated by complexing the cobalt ion. An ammonia complex of cobalt has been reduced commercially in the recovery of cobalt metal. A new reducible complex of cobalt was discovered5 when it was found that a co-baltous sulfate solution containing ammonium acetate could be reduced by hydrogen at temperatures in the region of 200°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature below its normal boiling point, a violet color became apparent, indicating complex formation. The nature of this complex was investigated5 by the addition of NH4Ac to a CoSO4 solution maintained at 85o. During the first additions of NH, Ac, the pH of the solution remained fairly constant at about 5.85. However, as the ratio of NH,Ac to CoSO, approached two, the pH rose and then leveled off at about 6.05. The absorption spectra of a Co(Ac), solution and a CoSO,, NH Ac solution were obtained at 85°C and were compared and found to be the same. These findings suggested that the diacetate complex of cobalt, Co(Ac),.4H20, was formed at 85°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature above about 165o, a finely divided pink precipitate appeared. The X-ray diffraction pattern of this precipitate indicated that it was Co(Ac), - 4H,O. In addition, it was discovered that when chloroplatinic acid, H,PtCl;, was added initially to the cobalt sulfate-ammonium acetate solution, a faster reduction was obtained. The roles of the solution complex, pink precipitate and chloroplatinic acid in the reduction process were then investigated. APPARATUS The experimental work was carried out in a two-liter stainless-steel autoclave. Adetailed description of the autoclave and the auxiliary equipment used in maintaining constant temperature and pressure may be found elsewhere.= Because the stainless steel was corroded, and also because it acted as a hydrogena-tion catalyst, an all-glass liner was fabricated such that the solution came only into contact with flame-polished pyrex glass. EXPERIMENTAL PROCEDURE The solutions used in the experimental work were prepared by dissolving reagent grade chemicals in distilled water. Although variation of the brand of ammonium acetate appeared to have no effect on the experimental results, CoSO, 7H O from the J. T. Baker Chemical Co. of Phillipsburg, N. J.,was found to give faster reductions than that prepared by Allied Chemical and Dye Corp., N. Y. The former was used throughout the course of the experimental work and was weighed up at the outset of each experiment. The ammonium acetate was dissolved to form a 6M stock solution, which was stored under refrigeration. A 10 pct solution of chloroplatinic acid (J. T. Baker Chemical Co.) was diluted to a 1.15 x 1Q2 M stock solution, which was standardized by precipitation of K,PtCl, as outlined by Scott. The appropriate volume of the chloroplatinic acid, H,PtCl,, solution was pipetted into the clean, dry glass liner. The cobalt sulfate-ammonium acetate solution, which had previously been saturated with

Jan 1, 1962

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

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

Jan 1, 1943

By Milton H. Fies

Although pig iron from iron ore and red cedar charcoal preceded the mining of coal by many years, for tradition says that Alabama iron was used to shoe the horses of Andrew Jackson's soldiers, coal was not produced until 1830. In that year, coal was mined in Tuscaloosa County, in the vicinity of what is now the University of Alabama, and shipped on flat boats (obviously during the wet season, for there were many shoals) down the Warrior River to Mobile. About that time, the first railroad, the Decatur & Tecumseh, was being constructed in northern Alabama to overcome the obstructions to freight traffic caused by the now well-known Muscle Shoals in the Tennessee River. This railroad was patterned after a railroad at Mauch Chunk, Pa., which was used for hauling anthracite from the Panther Creek valley. The Alabama railroad, which required about four years to complete, was 46 miles long and was used solely for the transportation of cotton. Although it was a failure, it demonstrated the practicability of the undertaking, and the succeeding railroads, which were begun in 1834, 1848, 1852, and 1853, added immeasurably to the development of the coal resources of the state. Between the years 1830 and 1860, practically all the coal mined in the state was dug from the outcrop near the river or from the river beds, and shipped by boat to Mobile. Transporting coal down the Warrior River was an undertaking of great risk, required much skill, and frequently had heavy losses. It is recorded that this coal was sold to the gas company in Mobile in 1844; it was most likely mined from the Black Creek Seam. In 1914, on the completion of Lock 17, the Warrior River became a navigable stream from 9 miles above Cordova, Ala., to Mobile and offers a great opportunity for the future development of the coal resources of the state. Coke for foundry use was first made in Alabama in 1855. It was 21 years later, however, in 1876, that pig iron was made from Alabama ore with Alabama coal.

Jan 1, 1925

By J. A. Wilcox

A NEW LINE of specialists has arisen as a result of the trend toward labor socialization and collectivism in all branches of industry. These men are the ones who will govern the destiny of many companies and the labor policy of our government in coming years. They must be men of integrity and of rather exceptional qualifications; men who can foresee the trend of labor relations with business, and who are willing to sacrifice the immediate fruits of technical training for manual labor and study. They must take their place in industry, not with the idea of following the orthodox line of advancement, but knowing that they must stay at the bottom until they have learned to understand the viewpoints, the work, the advantages and the disadvantages of each classification of labor. They must not be of a radical nature or become easily biased, and they must study. You will say I am looking for a superman and in one sense that is true, but the business man and our government are both in the market even now for this type of man, and with the proper training and background, many of our young technicians can readily enter this field of work.

Jan 1, 1942

By L. A. Bromley, A. W. Petersen

The van Arkel-deBoer method for producing ductile titanium by thermal decomposition of Til, vapor and deposition on an electrically heated filament is modified by film boiling Til liquid on a heated filament, resulting in similar titanium deposition on the filament and liberation of gaseous iodine. The deposition rate is higher and the energy requirement smaller than in the van Arkel process. Many problems must be solved before the process is commercially feasible. TITANIUM of 99.9 pct purity, called ductile titanium, has been produced by a modification of the van Arkel-deBoer&apos; method. In the van Arkel-deBoer method, an electrically heated wire is suspended from two electrodes, which are placed in a container holding TiI, vapor at a low&apos; vapor pressure (usually <5 mm Hg). The vapor diffuses to the hot wire, usually maintained at 1100" to 1600°C,&apos; and decomposes according to the reaction liberating gaseous atomic iodine and depositing solid crystalline titanium on the wire. Estimations based on the data of Runnalls and Pidgeon,&apos; indicate that the rate-control ling step is the diffusion of atomic iodine away from the wire. There appears to be nearly thermodynamic equilibrium at the wire with TiI, and iodine as the main gaseous species. TiI, is almost certainly an important gaseous species in the cooler regions.&apos; The liberated iodine diffuses to a heated source of crude titanium and reacts to form more TiI, vapor, which again diffuses to the hot wire and completes the cyclic process. The foregoing process may be modified by suspending the hot wire in liquid TiI,, instead of the vapor, and obtaining film boiling. This type of boiling is characterized by the formation of a continuous film of vapor over the wire surface. Since only vapor contacts the wire sul.face, the temperature of this surface may be raised as high as desirable, within the limit of mechanical strength requirements for the wire. By properly adjusting the input voltage. the temperature of the wire may be maintained above U0C"C; and by evacuating the vessel holding the liquid TiI, and maintaining a suitable condenser temperature, the vapor pressure of TiI, may be held low. Thus, the conditions of operation of the van Arkel-deBoer method may be approximated with film boiling; and hence, it is postulated that ductile titanium may be produced by this method. Preparation of Til, There are many methods available for the preparation of TiI,; that used in this research was prepared by the direct reaction of titanium sponge in controlled amounts with liquid iodine. Although no difficulty was encountered with this reaction, it has since been pointed out that this method is sometimes dangerous and should be used with caution. The resulting TiI, was purified by distillation. First Film Boiling Experiments Apparatus: The apparatus shown in Fig. 1 was used for film boiling TiI, on short wire filaments. The current to the filament was supplied through a bank of three 5 kva transformers connected in parallel. The current was controlled by adjusting the voltage over a 0 to 67.5 v range with a 7 kva variable transformer on the low voltage side of the bank of transformers. The current and voltage were measured by Weston meters. The sealed-in-glass tungsten electrodes were hard-soldered to the filament for the film boiling of TiI,. The bottom part of the reactor, containing TiI,, was wrapped with ni-chrome heating wires to maintain the TiI, in the liquid state. An ice or liquid nitrogen trap, for solidifying I, vapor and any TiI, not condensed, was attached to the low pressure side of the air-cooled condenser. A Megavac vacuum pump was used. Procedure: A 0.010 in. diam tungsten filament was hard-soldered to the tungsten electrodes. TiI, was melted (mp 156°C) and poured into the reactor chamber; the top of the reactor chamber, containing the electrodes, was replaced. Freezing of the TiI, was prevented by controlling the current to the ni-chrome wires wrapped around the reactor with a 1 kva variable transformer. The mechanical vacuum pump was started and the system evacuated to about 2 mm Hg TiI, vapor pressure. The current to the filament was turned on and the impressed voltage slowly increased with the variable transformer. A sudden drop in current at nearly constant im-

Jan 1, 1957

By Sidney Powers

CONTENTS PAGE Distribution of fields 4 History of development 6 Origin of oil 7 Structure, accumulation and migration 8 Reservoir rocks 9 Methods of drilling and exploration 10 Oil-field statistics : 12 Description by regions: United States: Appalachian region ; 12 East-central states 17 Kansas 18 Oklahoma : 19 Texas : 24 Arkansas : 32 Louisiana 33 Mississippi ....... 34 Rocky Mountain region : 34 California 37 Canada 41 Mexico 43 Cuba 46 Bibliography 46 THE purpose of this brief account- of the occurrence of petroleum in North America is to make available to those who have a knowledge of geology, but who are not engaged in the petroleum industry, a few salient facts about the location of oil and gas fields, their productivity, the important structural types of accumulation and the age of the rocks containing petroleum. A few useful data and statistics are furnished, yet not complete statistics that are available elsewhere. Geology has been treated in simple terms because the reader is presumed to have little interest in the names of formations and of oil sands. Mineral deposits are more or less analogous. Whether oil or metals, minerals are found in rocks, largely in sedimentary rocks which carry water or have at one time carried it. A genetic or accumula-

Jan 1, 1931