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By Benjamin N. Webber

THE peninsula of Nicoya contains virtually all of the known manganese deposits of Costa Rica. These are south and west of the Tempisque River, which flows across the peninsula near its juncture with the mainland. This peninsula forms the westernmost part of the province of Guana¬caste, which is the northern of the two Pacific Coast provinces of Costa Rica. The larger villages are connected by ox-cart roads and trails. The area may be covered on horseback without difficulty except during the rainy season, when rivers are in flood and difficult to ford. This is particularly true of the Rio Seco-Guayjiniquil area, where there are no inhabitants and few open trails through the tropical jungle. Santa Cruz and Sardinal are served by the Taca Airlines, two planes a week from San Jose and Puntarenas. The port of Puntarenas has excellent loading facilities but none are available nearer the manganese districts; there ore must be lightered to vessels standing offshore. PHYSIOGRAPHY In Costa Rica there are three physiographic divisions: (I) the central plateau (Mesa Central), a somewhat dissected lava platform upon which are superimposed volcanic peaks, some of which are still active; (2) the Atlantic lowlands and (3) the Pacific lowlands. The peninsula of Nicoya and the larger part of the province of Guanacaste lie within the Pacific low lands. The term "lowland" indicates relation to the central plateau, as the peninsula of Nicoya is largely mountainous. The mountains of Nicoya form the southern extremity of a range of low hills, which are almost continuous along the Costa Rican coast to the Nicaraguan border. The coast line shows evidence of subsidence. The Gulf of Nicoya obviously is the drowned valley of the Tempisque River. The west coast of Nicoya shows many rocks, shoals, bays, inlets and small islands as evidence of a sea encroachment. The altitude of the manganese deposits ranges from 0 to 800 ft. Topography is of the mature type of wide valleys and low ,hills, often with abrupt slopes. The climate is tropical and humid; rainfall of 125 in. falls largely between Sept. I and Jan. I. Vegetation often is very dense, the Rio Seco-Guayjiniquil area being truly tropical jungle, containing many hardwoods. HISTORY AND PRODUCTION The production of manganese ore in Costa Rica apparently dates from the first World War. It reached a peak of about 10,000 tons in the year 1919, then declined rapidly. Evidence of this period of prospecting has rotted away or been swallowed by the jungle. The war now in progress apparently revived the interest in Costa Rican manganese and has encouraged further prospecting. Deposits long known have been redenounced and trails have been cut through the jungle to them. Many new deposits have been discovered in the last

Jan 1, 1942

By F. Weinberg

It has been suggested, for some time, that the behavior of metals under high-temperature creep conditions is strongly influenced by the behavior of the grain boundaries present in the material. This has led to a number of investigations1-6 in which attempts were made to measure the properties of the grain boundaries themselves, both to determine their contribution to the creep process and to obtain further knowledge of their intrinsic structure and properties. The present investigation was undertaken to extend the observed data under more closely controlled experimental conditions and to attempt to clarify sonie of the discrepancies in the literature. A brief report of the preliminary results has been published.7 EXPERIMENTAL PROCEDURE For the present investigation, controlled orientation specimens were used having plane boundaries which terminated at the specimen surface. Trierys-tal specimens were used instead of the bicrystal type of Puttick and King,' in order to simplify the gripping technique required to apply a shear stress along the boundary. The aluminum used was obtained from the Aluminum Francaise and was of 99.994 pct purity, containing 0.002 pct each of Cu, Fe, and Si. The aluminum tricrystals were grown horizontally from the melt, in graphite boats, and in an argon atmosphere, following the technique developed by Chalmers.' The orientation of the tricrystals was controlled by using seed crystals separated by mica inserts. Thermal conditions were adjusted to produce tricrystals having boundaries which were macroscopically straight, parallel to the growth direction, and perpendicular to the top surface. Following growth, the tricrystals were carefully cut with a jeweller's saw to the test specimen shapes shown in Fig. l(a) and l(b). In Fig. 1(a), the boundaries subjected to shear stresses are indicated AB and CD: Points A and C are the ends of the mica inserts separating the seed crystals; points B and D are at lateral cuts made in the specimen. It was found that the slots left by the mica inserts at A and C had to be enlarged slightly, by cutting, to ensure that the boundary terminated freely at these points. A shear stress was applied to the boundarks by gripping the upper two legs in file-faced Inconel grips and suspending a weight from the lower part of the specimen held in similar grips, as shown schematically in the diagram. The test specimens shown in Fig. 1(b) were cut from long

Jan 1, 1959

By Arthur W. Sheafer

MR. ECKLEY B. COXE, in his able and interesting paper on " The Preparation of Small Sizes of Anthracite,"* read and discussed at the Glen Summit Meeting, October, 1891, refers to the reputed immense amount of coal contained in the culm-banks, which are the unsightly accompaniment of every mining operation in the anthracite coal-regions. Mr. Coxe thinks the available amount and value greatly exaggerated, giving among his reasons (1) the spoiling of the culm by mixing with other refuse; (2) its deterioration; (3) its destruction by fire ; and (4) frequent failures to realize expectations as to the size of the banks. These points are undoubtedly important factors in determining the advisability of working any individual bank, but they have a varying influence in the several regions, some prevailing more in one than in another. Although the amount of fuel lying waste in these banks is still an uncertain and undetermined quantity, yet no one can visit the Schuylkill region without being impressed with the fact that a considerable amount of culm, too valuable to be left merely to the mercy of the elements, surrounds and encumbers each site of an old or present colliery operation. The rapid increase in the number of washeries, and the demand for leases on old culm-banks, shows that, in the Schuylkill region at least, the question of deterioration doès not play an important part. The proportion of coal to refuse, the relative percentage of the sev-

Jan 1, 1895

By Carle Hayward

THE effect of copper on steel has been studied by numerous investigators. Before modern testing methods had been developed, blacksmiths noted red shortness in iron, the cause for which was ascribed to the presence of copper. Numerous papers have been published on the corrosion of steels containing various amounts of copper, and a few writers have discussed the effect of copper on the mechanical properties of steel. The purpose of the investigation described in the following paper was to obtain additional data on the mechanical properties of medium-carbon steel containing small quantities of copper. Among those who have published results of mechanical tests on copper steels are Ball,1 who states that copper increases the tensile strength and 'hardness but lowers the elongation. Stead2 states that copper steels closely resemble nickel steels containing equivalent percentages of nickel,, as regards tensile strength, resistance to shock, corrosion and hardness. Wigham 5 found that copper in small amounts had no injurious effect on steel. Breuil4 found that with 1 per cent. carbon, copper lessened the brittleness of steel and in low-carbon steel it increased the tensile strength and lowered the ductility slightly. H. H. Campbell 5 states that copper up to 0.25 per cent. slightly raises the elastic limit, elongation and reduction of area.

Jan 1, 1918

By Bruce A. Kennedy

The long awaited new Mining Engineering Handbook is taking shape under the leadership of A. B. Cummins, Chairman of the Editorial Advisory Board for the SME Mining Engineering Handbook, and Ivan Given, Editor-in-Chief. The last Mining Engineers' Handbook, the Peele edition, published by John Wiley and Sons, was last revised in 1941. This book was and still is a virtual mine of information although a good deal of its content, especially the cost tables, is becoming rather antiquated. The new one-volume work will contain approximately 1600 pages and be divided into 36 sections. A brief summary of the sections follows: The Place and Contribution of Mining, Mining Costs: Mining Geology-Minerals and Mineral Deposits; Minerals Discovery-Prospecting and Exploration Methods and Equipment; Site Exploration and Selection; Minerals-Mining Design; Soil and Rock Mechanics; Design of Excavations; Opening and Development: Underground Mining Systems and Equipment; Roof and Ground Control; Groundwater and Groundwater Control: Open-Pit and Strip-Mining Systems and Equipment: Underwater and Ocean Mining; Fragmentation-Cutting, Drilling, Blasting; Underground Haulage: Hoists and Hoisting Systems; Surface Haulage, Hoisting. Lowering Pumping and Drainage; Ventilation: Mine Surveying; Ore and Coal Processing; Mill Design; Industrial Minerals-Specifications and Markets: Power; Maintenance plant and Equipment; Supply Service; Health and Safety; Reclamation and Surface Restoration: Administration and Management; Operations Optimization (Systems Engineering) : Mint, Costs and Control: Mine Examination. Valuation. Reports; Engineering Terms: and Consulting Engineering.

Jan 1, 1970

By A. W. Schlechten, A. H. Larson

Equilibrium H2S/H2 ratios were determined as functions of temperature (500o to 900°C) and composition in a hydrogen-circulation apparatus. Within the composition range studied there exists a two-phase region of "Zr3S4" and "ZrS2". The upper composition limit of this two-phase region is hounded by a disulfide phase and is practically constant over the temperature range investigated. The lower composition limit of this two-phase region is bounded a "Zr3S4 " phase and varies appreciably with tem- perature. The upper composition limit of the homogeneous region of the disulfide phase is not definitely determined, but it appears to he bounded by the stoichiometric composition of ZrS2. The lower composition limit of the homogeneous region of the Zr3S4 phase could not he determined due to the extremely low values of the equilibrium H2S/H2 ratios. Various thermodynamic quantities are evaluated from the data. PUBLISHED free-energy data for the Zr-S system are practically nonexistent. Strotzer, Biltz, and Meisel1 measured the sulfur pressures for the reaction 2ZrS2(s) + S2(g) = ZrS3(s) in the temperature range 783" to 874°C. The average heat of reaction calculated from the temperature dependence of the sulfur pressure is -47 keal. It should be noted, however, that according to these investigators, the two-phase region as determined by sulfur pressure constancy under isothermal conditions extended from approximately ZrS2, 3 to ZrS2.7. From consideration of X-ray data they concluded that the homogeneous regions of the disulfide and trisulfide phases are ZrS1.8-2.0 and ZrS2.8-3.2, respectively. Hahn and coworkers2 have made a structure study of the zirconium sulfide phases. They summarized the zirconium sulfide phases as follows: the compounds ZrS3 and ZrS2 with narrow homogeneous regions, a "Zr3S4" phase with a homogeneous region roughly within the limits of ZrSl.5 and ZrSo.9, the compounds ZrS and Zr4S3, and a "Zr3S2" phase with a homogeneous region within the limits ZrSo.8 and ZrSo.5. It is noted that the compounds ZrS and Zr4S3 are only formed in the gaseous state through sublimation of a phase which has the approximate composition of the compound. This paper describes the determination of the stability of the zirconium sulfide phases by a hydrogen-reduction method in which hydrogen is circulated over the heated sulfide until equilibrium is attained. The resulting H2S-H2 mixture is then analyzed. Partial molar free energies, enthalpies,

Jan 1, 1964

By A. H. Lee

Discussion of the paper of H. P. HOWLAND, printed in Bulletin No. 111, March, 1916, pp. 627 to 650. A. H. LEE, Buffalo, N. Y. (communication to the Secretary*). The statements and results recorded in Mr. Howland's paper can be accounted for by the use of coke with a low sulphur content (0.60 and under). This allows the furnaces to be run on a small volume of acid slag, which it is presumed was done in Mr. Howland's practice. H. A. Brassert has admitted that this was the largest factor in low fuel consumption in his practice. Where the coke contains from 1.00 to 1.25 per cent. of sulphur the situation is quite different and I doubt whether the results mentioned by Mr. Howland could be obtained under such circumstances. ` N. M. LANGDON, Mancelona, Mich. (communication to the Secretary + ).-Gruner's ideal working (which is but a statement of the law first enunciated by Bell) as given in Gordon's Translation of Studies of Blast Furnace Phenomena, "supposes that the reduction of the oxide of iron is effected by the CO only, without intervention of solid carbon." This ideal, if reached, would mean theoretically perfect or 100 per cent. efficiency of reduction. The workings of the large number of furnaces as given in Bell's and Gruner's great works do not show that this standard of perfection ever was reached. This problem has been worked out by the writer for a number of furnaces, and his results, as well as those given by others, all show a failure to reach perfection. Some furnaces, however, approach nearer to perfection than others. The "ideal" as given by Gruner was not stated as a solved problem in blast-furnace practice, but as an ideal to the attainment of which furnace managers should strive. A study of the factors involved from every angle is interesting and instructive and the paper on this subject contributed by H. P. Howland is no exception to the rule. This article is fairly open to criticism, not because of the unique method of presenting the subject, but for the reason that, as the writer conceives, erroneous assumptions are taken which lead naturally to incorrect conclusions.

Jan 7, 1916

By Samuel Daniels

THE Al-Cu-Ni-Mg alloy is much benefited by heat treatment and, in such con¬dition, is preferable to the Al-Cu-Fe-Mg alloy either as cast or as heat-treated, when both are reheated to temperatures of from 400° to 600° F. and compared, cold, with respect to strength and to hardness. The main differences between the alloys do not arise until the reheating temperature exceeds 400° F., above which they gradually soften. This softening is characterized metallographically by the appearance of intragranular precipitate. The Al-Cu-Ni-Mg alloy is weakest and least hard after being reheated at 600° F., the AI-Cu-Fe-Mg alloy at about 700° F. The former starts to reharden at 700° F., the latter at 800° F. There is a tendency for both alloys to lose strength and hardness with prolongation of time at the reheating temperatures of 500° and of 700° F. The Al-Cu-Ni-Mg alloy is considerably stronger and harder than the Al-Cu-Fe-Mg alloy when both are heat-treated and reheated for long periods of time at 500° and 700° F. Although the latter can be made harder initially than the AI-Cu-Ni-Mg alloy by suitable quenching and aging, heat treatment, in general, favors the retention of this initial (strength and) hardness after reheating to a much greater degree in the Al-Cu-Ni-Mg alloy. The percentage of elongation of the two materials in any condition is very small. CERTAIN aluminum alloys have been used for pistons and other parts operating at temperatures up to 650° F. because of their lightness, high thermal conductivity and specific heat, fair strength and hardness at elevated temperatures, excellent machineability, and moderate resistance o corrosion. In the piston, the inertia forces and the bearing loading and with this the vibration are decreased. The piston head functions at a lower temperature (about 200° F. below one of cast iron), so that, because of the lessened tendency toward carbonization and detonation, higher compression ratios may be used. On the other hand, the aluminum alloys do not have the wearing and bearing qualities of cast iron; also they have a large coefficient of expansion, allowance for which must be made in the design.

Jan 2, 1926

By O. George Specht, Carl A. Zapffe

In recent print, some remarkably contradictory statements have appeared regarding the importance to be attached to sponge Iron,1-6 a metallurgical commodity whose history goes back at least to the time of Diodorus Siculus in the fourth century B.C. This disagreement, however, expresses the lack of a satisfactory method for producing sponge iron rather than defection in the commodity. The blast furnace is admitted to have certain inherent disadvantages, such as a general unsuitability for magnetite and the heating and blowing of vast quantities of undesirable nitrogen, so that a workable sponge-iron process remains attractive. In this respect, low-temperature gaseous reduction shows especial promise; but confusion persists regarding the factors involved. The present paper, therefore, has three principal divisions: (I) an exhaustive examination of all previous work on low-temperature gaseous reduction, (2) experi- mentation on the reduction of a magnetite with hydrogen, and (3) development of certain thermodynamic relationships in reduction, with a summarized depiction of the factors in the general process. PREVIOUS INVESTIGATIONS Gaseous media used in the reduction processes under discussion can be classified in three types: (I) H2, (2) CO, and (3) other gases. In the second, the CO is often admixed with H2. The third principally comprises hydrogeniferous gases, such as natural gas and producer gas, and in addition includes chlorine. Because hydrogen therefore features in all three, a study of hydrogen reduction based on investigations using pure hydrogen alone may be incomplete. The present paper reviews the three groups of investigations in the listed order, paying particular attention to hydrogen reduction. For the benefit of future workers, an exhaustive bibliography has been prepared and similarly classified. Group I: Reduction with Hydrogen Equilibria Although the present problem is specifically one of kinetics, a first consideration is the equilibrium of the system, since the reactions to be studied comprise that equilibrium, and their direction and end points are defined by it. The historic development of these researches is interesting and informative.

Jan 1, 1947

By O. George Specht, Carl A. Zapffe

In recent print, some remarkably contradictory statements have appeared regarding the importance to be attached to sponge Iron,1-6 a metallurgical commodity whose history goes back at least to the time of Diodorus Siculus in the fourth century B.C. This disagreement, however, expresses the lack of a satisfactory method for producing sponge iron rather than defection in the commodity. The blast furnace is admitted to have certain inherent disadvantages, such as a general unsuitability for magnetite and the heating and blowing of vast quantities of undesirable nitrogen, so that a workable sponge-iron process remains attractive. In this respect, low-temperature gaseous reduction shows especial promise; but confusion persists regarding the factors involved. The present paper, therefore, has three principal divisions: (I) an exhaustive examination of all previous work on low-temperature gaseous reduction, (2) experi- mentation on the reduction of a magnetite with hydrogen, and (3) development of certain thermodynamic relationships in reduction, with a summarized depiction of the factors in the general process. PREVIOUS INVESTIGATIONS Gaseous media used in the reduction processes under discussion can be classified in three types: (I) H2, (2) CO, and (3) other gases. In the second, the CO is often admixed with H2. The third principally comprises hydrogeniferous gases, such as natural gas and producer gas, and in addition includes chlorine. Because hydrogen therefore features in all three, a study of hydrogen reduction based on investigations using pure hydrogen alone may be incomplete. The present paper reviews the three groups of investigations in the listed order, paying particular attention to hydrogen reduction. For the benefit of future workers, an exhaustive bibliography has been prepared and similarly classified. Group I: Reduction with Hydrogen Equilibria Although the present problem is specifically one of kinetics, a first consideration is the equilibrium of the system, since the reactions to be studied comprise that equilibrium, and their direction and end points are defined by it. The historic development of these researches is interesting and informative.

Jan 1, 1947

By B. H. Kear, S. M. Copley

A dynamic theory of precipitation hardening in alloys containing cohevenl, stvess-.free, ordered particles is developed. The yield stvess is predicted from the stress dependence of the plastic strain vale, which is related to a derived dislocation velocity-stress function. The theory is shown to predict the magnilude and temperature dependence of the yield stress of a commercial nickel-base superalloy as well as many details of its slip structure. GLEITER and Hornbogen have developed a theory of the yield stress in alloys hardened by coherent, stress-free ordered ptrticles based on the observation that dislocations (b = a/2 (110)) glide in pairs.' When a dislocation pair shears through an ordered particle, the glide motion of the leading dislocation is impeded since it must create antiphase boundary (APB), whereas the motion of the trailing dislocation is assisted because it annihilates APB produced by the first one. Taking into account the APB energy, the size, and spacing of the particles, G-H predict the observed yielding behavior in Ni/18.8 Cr/6.2 A1 alloys composed of a matrix phase y '(nickel-solid solution) and particles of y' (basically Ni3A1). The G-H theory, as well as all previous theories of hardening by coherent ordered particles, do not include the details of dislocation motion; the present dynamic theory is an attempt to overcome this limitation. In the dynamic theory, the yield stress is predicted from the stress dependence of the plastic strain rate, which is related to a derived dislocation velocity-stress function. This function can be evaluated if the structure of the alloy, the APB energy of the ordered phase, and the characteristic drag or frictional stresses of the matrix and precipitate phases are known. The theory is shown to account for the observed temperature dependence of the yield stress in a commercial nickel-base superalloy. 1) NICKEL-BASE SUPERALLOYS Although their compositions are complex, the nickel-base superalloys have remarkably simple structures. A detailed examination of the commercial superalloy

Jan 1, 1968

By D. G. Westlake, E. S. Fisher

The habit planes for zirconium hydride precipitation in crystals of a zirconium have been determined at various hydrogen concentrations. The (10 • 0)planes are the predominant habit planes; some (10 • 5) and (10 -1) planes were observed after charging conditions which pevmitted formation of a surface layer of hydride. No platelets zrlere observed parallel to any of the twinning planes. Mechanisms for em-brittlement due to hydride precipitation are discussed. LANGERON and Lehr1 found, in 1956, that zirconium hydride precipitates in zirconium in platelets lying parallel to (10.0) slip planes. In 1960, Kunz and Bibbz reported observing the platelets in three different families of twinning planes, (10.2) {11.1), and {11.2), but never in the slip planes. The present study was undertaken to ascertain the cause of these seemingly contradictory results. EXPERIMENTAL Two specimens of iodide zirconium were used in the experiments. Specimen I was a single crystal, while specimen II contained three grains. Grain growth was accomplished by the technique of Lange-ron and Lehr. Three faces were ground on specimen I; the first was 2 deg from the (00.1) basal plane, a second was 2 deg from the (10.0) prism plane, and a third was 4 deg from the (12.0) plane. One face was ground on specimen II such that the poles of the surfaces of crystals A, B, and C were as shown in Fig. 1. After the faces were ground on 600 grit silicon carbide paper, they were chemically polished by dipping in a solution of 8 parts hydrofluoric acid, 50 parts nitric acid, and 50 parts water. This removed all cold worked metal from the surface. The samples were charged to various levels of hydrogen content by heating in hydrogen gas which had been purified by reaction with uranium powder. The various charging conditions are shown in Table I. Specimen I was heated to the reaction temperature at the indicated hydrogen pressure and allowed to react until essentially all the hydrogen was used up. Then the temperature was raised for homogenization. Specimen II was charged by making periodic addi-

Jan 1, 1962

By M. J. Hordon, M. A. Wright

The well-defined increase in fatigue life observed o many metals cyclicly strained at vacuum levels below 10-1 to 10-3 torr has been attributed to the critical retardation of oxygen or water vapor chemisorption at the crack tip during crack propagation.1-3 In the absence of strongly adsorbed surface films, crack re-welding during cyclic compression or dislocation escape from the plastic zone around the crack tip has been proposed to account for the observed decrease in the rate of crack growth. The increase in the critical pressure required for the transition in crack growth rate with temperature experimentally determined for aluminum was found to be generally in accord with the adsorption rate model.4 However, although the adsorption mechanism would also predict an increase in transition pressure and fatigue life with increase in cyclic loading rate, and such effects were noted by Snowden5 for lead and Hordon3 for aluminum, the opposite results were reported by Kramer et al.B in studies on aluminum. The present note describes some recent measurements of the fatigue properties of 1100-H14 aluminum at low pressures to determine the specific effect of cyclic strain frequency in the transition pressure range. Flat cantilever-type specimens of 1100-H14 aluminum shaped to produce a uniform strain gradient along the gage length were tested in reverse plane bending at constant deflection amplitudes in two independent multi-specimen vacuum fatigue systems. One series of tests using 2-in. gage length specimens was conducted in an ion pumped apparatus with 107 torr and 50 cps capacity, denoted as Unit I, utilizing fixed mechanical cams to impose the strain amplitude. An independent test series using shorter 1-in. gage length specimens was conducted in a cryopumped apparatus designed for extremely low pressures below 10-10 torr, denoted as Unit II, using an electromechanical vibrator at non-resonant frequencies up to 150 cps to provide the deflection. Both vacuum fatigue units and associated test procedures have been described previously.3'7

Jan 1, 1969

By P. W. Bakarian

Previous determinationl,2,3 of the texture of magnesium and its alloys have shown only slight variations in the principal features of the structure. This investigation presents pole figures for magnesium and two of its alloys, in which differences of some magnitude will be shown. Schmid and Wassermann have considered the texture of magnesium in analogy with that of zinc—also a hexagonal lattice. Whereas the zinc texture is said to be derived primarily through basal slip and secondarily through {IO2}† twinning, the {102} twinning is considered impossible at the later stages of the rolling in magnesium because of its smaller axial ratio. This state of affairs appears reasonable for pure magnesium, but for alloy textures the situation is more complex. A double orientation similar to that found in zinc has been reported by J. D. Hanawalt,4 and the addition of small amounts of calcium to magnesium and its alloys to produce a double texture was noted by J. C. McDonald.5 The pole figures of this investigation, using an improved X-ray technique, show these various textures. The dependence of directional properties of rolled sheet on modifications of texture is well recognized. Correlation of physical properties with existing texture should be even more significant if quantitative valuations are attached to the various areas on the pole figures. Such a quantitative technique is developed herein. Experimental Method Two alloys were used, besides high-purity magnesium. In each case, the metal was extruded to bars 1/2 in. thick and hot-rolled to a thickness of about 0.075 in. It had been established previously that such a reduction was more than sufficient to eliminate the extruded structure. The rolling proceeded in the same direction as that of the extrusion, without any cross rolling. The temperatures corresponded to normal commercial practice, averaging around 600°F. A unique method of preparing the sample was developed in this work. Instead of using a flat specimen, a stem of the metal was cut out of the rolled sheet in the desired direction (rolling direction) as shown in Fig. I. From a sheet of 0.075 to 0.065-in. gauge, the stem was cut to a square cross section with a jeweler's saw, rounded with a file and polishing paper to a diameter of 0.060 in. and evenly etched in dilute hydrochloric acid to a diameter of 0.038 + 0.001 in. In this way, a cylinder of the original sheet with its axis in the desired direction was produced. By using this type of specimen for the pin-point pictures, any variance in the absorption of the diffracted beam at the various angular settings of the specimen, was completely eliminated.*

Jan 1, 1942

By P. W. Bakarian

Previous determinationl,2,3 of the texture of magnesium and its alloys have shown only slight variations in the principal features of the structure. This investigation presents pole figures for magnesium and two of its alloys, in which differences of some magnitude will be shown. Schmid and Wassermann have considered the texture of magnesium in analogy with that of zinc—also a hexagonal lattice. Whereas the zinc texture is said to be derived primarily through basal slip and secondarily through {IO2}† twinning, the {102} twinning is considered impossible at the later stages of the rolling in magnesium because of its smaller axial ratio. This state of affairs appears reasonable for pure magnesium, but for alloy textures the situation is more complex. A double orientation similar to that found in zinc has been reported by J. D. Hanawalt,4 and the addition of small amounts of calcium to magnesium and its alloys to produce a double texture was noted by J. C. McDonald.5 The pole figures of this investigation, using an improved X-ray technique, show these various textures. The dependence of directional properties of rolled sheet on modifications of texture is well recognized. Correlation of physical properties with existing texture should be even more significant if quantitative valuations are attached to the various areas on the pole figures. Such a quantitative technique is developed herein. Experimental Method Two alloys were used, besides high-purity magnesium. In each case, the metal was extruded to bars 1/2 in. thick and hot-rolled to a thickness of about 0.075 in. It had been established previously that such a reduction was more than sufficient to eliminate the extruded structure. The rolling proceeded in the same direction as that of the extrusion, without any cross rolling. The temperatures corresponded to normal commercial practice, averaging around 600°F. A unique method of preparing the sample was developed in this work. Instead of using a flat specimen, a stem of the metal was cut out of the rolled sheet in the desired direction (rolling direction) as shown in Fig. I. From a sheet of 0.075 to 0.065-in. gauge, the stem was cut to a square cross section with a jeweler's saw, rounded with a file and polishing paper to a diameter of 0.060 in. and evenly etched in dilute hydrochloric acid to a diameter of 0.038 + 0.001 in. In this way, a cylinder of the original sheet with its axis in the desired direction was produced. By using this type of specimen for the pin-point pictures, any variance in the absorption of the diffracted beam at the various angular settings of the specimen, was completely eliminated.*

Jan 1, 1942

By J. T. Hayward

Studies of the forces and conditions governing the recovery of petroleum from natural reservoirs indicate that a low gas-oil ratio increases ultimate recovery, retards the encroachment of water and tends to reduce lifting costs. Methods for controlling and reducing gas-oil ratios in producing wells consequently have been given considerable attention during the past few years. However, during this same period, the production from wells in nearly all fields has been fixed by proration agreements and it is the opinion of the writer that where a well is required to produce steadily at a predetermined rate, less than its "potential" or maximum capacity, the gas-oil ratio will depend only upon the rate of production, and will be independent of the method of production and of the design of equipment in the well. If no change in the rate of production is contemplated, efforts directed to improving the gas-oil ratio by altering the diameter of the flow string, changing the position of the choke, assisting the flow with gas-lift or pump, etc., will be unsuccessful. This viewpoint is not new. It was presented by H. N. Marsh and B. H. Robinson in 1929,' but it has not been generally accepted. Although engineers believe that the rate of withdrawal and not the equip ment used governs the water-oil ratio, a similar opinion regarding the gas-oil ratio is not so commonly admitted. The rates of flow of oil and gas into the base of an oil well depend upon the following conditions: 1. The characterist-ics of the oil and gas. 2. The characteristics of the underground reservoir. 3. Temperature and pressure conditions in the reservoir. 4. The back-pressure held against the face of the sand. In operating a well, the only one of these conditions over which control may be exercised through operating procedure and the use of equipment above the sand is the back-pressure at the face of the sand. Strictly speaking, the back-pressure varies over the face of the sand, owing

Jan 1, 1932

By James F. Kemp

Discussion of the paper of D. Foster Hewett, Bulletin To. 27, March, 1909, pp. 291 to 310. JAMES F. KEMP, New York, N. Y.:-Mr. Hewett's paper is one of exceptional interest, because it not only adds an important contribution regarding one of the rarer, valuable elements, but also because it introduces compounds hitherto unknown and in associations no less novel. While we have occasionally dis¬covered and recorded asphaltite in metalliferous deposits, for example in the Joplin and Granby districts, we have not seen a metallic ore in a deposit essentially asphaltite. The source and method of introduction afford a subject well worth serious reflection. Vanadium was first discovered and recognized as a distinct element in the slags obtained in smelting the titaniferous magnetites at Taberg, Sweden. For a long time, therefore, we looked upon the titaniferous magnetites as its hone. Analyses proved, years ago, that it was present in the ores of this type in New Jersey and in the Adirondacks. It was quite rarely determined, but when looked for it was, I think, invariably found, although the Amount seldom exceeded 0.5 per cent. of V,05., In just what combination it exists in the titaniferous ores is uncertain. One might imagine V2O3 replacing some of the Fe2O3 of magnetite; or, since in the lead series vanadates and phosphates are closely akin, one might wonder if a lime-vanadate could take the place of apatite. Yet no lime-vanadate has been found in nature, and apatite itself is usually rare in the titaniferous ores. When percentage-curves are plotted for a series of analyses of the ores, the line of vanadic oxide shows a curious sympathetic behavior with the line of chromic oxide;' but the data are somewhat limited, and no compound has sug¬gested itself which throws light on the matter. Dr. W. F. Hillebrand has discussed the occurrence and dis-

Oct 1, 1909

By Edwin T. Myskowski, Alfred H. Hesse

THE development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly i00 per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi¬tion is accompanied by a change in volume of as much as S per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potters have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to g0 per cent Mn. is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparation of Alloys.-The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 Cu-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to ½ in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.-The tensile specimens, 0.313-in. diameter (1.25-in. gauge length), which were enclosed in evacuated Pyrex

Jan 1, 1942

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-' to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6'9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3'5'7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5'7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f '([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1' Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962

By B. A. Joyce, R. W. Bicknell, R. J. Bennett, P. J. Etter

Epitaxial layers of silicon have been grown on single-crystal quartz and alumina by two types of chemical reaction the hydrogen reduction of trichlorosilane and b) the pyrolysis of silane. These reaction systems are described. The cqsfallography of the two systems, as determined by electron and X-ray diffraction, is discussed, and epitaxial mechanisms suggested. The electrical behavior is briefly considered, and the design and properties of field-evert devices fabricated in the epilaxial material are also discussed. RECENT work carried out in these laboratories" has shown that it is possible to obtain epitaxial deposits of silicon on single-crystal quartz and alumina. The purpose of this paper is to describe the method of preparation of these layers using both the hydrogen reduction of trichlorosilane and the pyroly-sis of silane, to compare the crystallographic behavior of films on the two substrates, and to present some initial results of the electrical behavior of silicon layers on alumina. The structural study has been carried out using electron and X-ray diffraction and electron microscopy. The electrical assessment has been made in terms of conductivity and mobility determinations by the van der pauw3 technique, and by measurements on metal-oxide-semiconductor assemblies. 1) FILM PREPARATION Both quartz and alumina substrates, approximately 1 sq cm in area and 0.4 mm thick. were prepared from slices cut parallel to within a few degrees of (11.0), (10.0), and (00.1), and polished mechanically down to about 0.3 p diamond grade. Chemical polishing of alumina slices, using phosphoric acid at elevated temperatures, has also been used; epitaxial silicon layers have been grown on these substrates, but the process is not entirely reliable, possibly because the large strain present in the Verneuil-grown alumina crystal affects the chemically prepared surface. The two reaction systems are fairly conventional and are described briefly below. a) Trichlorosilane-Hydrogen System. The apparatus is shown schematically in Fig. 1. The substrate was heated by induction, with a fused-quartz encapsulated graphite hemicylinder as susceptor. The procedure for carrying out a deposition was to heat the substrate to reaction temperature in a stream of

Jan 1, 1965