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Jan 1, 1941

Jan 1, 1948

Established as a Division March 24, 1922 John R McMillan, '56, Chairman Claude R Hocott, '55, Past Chairman Thomas C Frick, '56, Vice-Chairman D W Akins, '57, Vice-Chairman Joe B Alford, Executive Secretary 800 Fidelity Union Building Dallas 1, Texas T A Pollard, Treasurer

Jan 1, 1954

Jan 1, 1907

POSITIONS VACANT (Under this heading will be published notes sent to the Secretary of the Institute by members or other persons.) Assayer and chemist with experience in gold and silver work and refining; used to handling a force of men. Large property in Northern Ontario. Send reference, record of practice, age, married or single, and salary expected. Apply Position 54. Metallurgical chemist wanted, competent to make the following analyses: cupola, gray iron; air:-furnace iron; pig iron of various kinds; coal; coke; sand of all descriptions; materials used in modern foundry practice; steel, and bronzes of all kinds; oils for fuel in Diesel engines and lubricating purposes; materials used in a modern machine shop, in fact, all materials likely to be used in a foundry, machine shop and forge shop. No. 55.

Jan 12, 1915

By W. A. Backofen, B. C. Wonsiewicz

The Plasticity transition in magnesium was studied by plane-strain compression of single crystals and polycrystalline material at temperatures from about 20" to 307°C. Reduction of single crystals along the c axis was accommodated by twinning on {1011) and retwinning on (10 12}, followed by basal shear in the doubly twinned volume. Deformation in that mode can result in sufficient independent shears for arbitrary shape change. Fracture in c axis compression, below about 100°C, has been related to excessive shear caused by unloading from the stress for {1011} twinning (-50 ksi at 20°C) to that for slip within the twin (-3 ksi); ductility follows from heating because the stress difference is lowered and the twin volume, in which elastic strain energy is dissipated on unloading, is increased. The stress for (1011) twinning is strongly temperature-dependent but not given by a critical resolved shear stress law. The latter is attributed to the influence of stress concentration from prior intersecting shear on nonbasal planes, the former to the temperature dependence of the preliminary slip. THE basic symmetry of hcp crystals has the effect of limiting the number of independent slip systems and making twinning an important deformation mechanism. The general result in wrought polycrystalline aggregates is a more or less sharply developed texture (or preferred orientation) which underlies a strong anisotropy in mechanical behavior. Knowing how the one influences the other is essential background for the use of such materials. Magnesium was of interest in this work because of the unexplained plasticity transition that it undergoes somewhere in the neighborhood of 200°c.''~ At lower temperatures plastic deformation before fracture in polycrystalline material is limited, while at higher temperatures extensive deformation is possible. The transition temperature commonly determines the lower limit of the range in which magnesium is worked. The limited ductility can be traced to a lack of independent crystallographic shears. A minimum of five are required for arbitrary shape change.' Around room temperature, however, slip on all known systems provides only four.' In each case, the slip direction is in the (0001) basal plane so that slip does not allow strain along the c axis. With increasing temperature, more slip occurs on the ( 1011) pyramidal plane and the ( 1010) prism plane but without change in direction.'?' Thus, that development alone cannot explain the transition temperature.

Jan 1, 1968

By J. M. Bugbee

The engineer and the conservationist agree that effective water drive is the desirable reservoir production mechanism. Water drive may result either from the expansion of edge water, the reservoir water bordering an oil pool, or from the artesian flow of edge water from the outcrop. Thus, the extent of the reservoir has an important bearing upon both the rate and the ultimate quantity of water influx to an oil pool. Lens-type reservoirs are generally recognizable, but the complete structure of the more important domal types, having possible limitations from crestal and synclinal faulting, is not well understood. The delineation from cores, electrical logs and exploitation phenomena of the crestal portions of reservoirs is increasingly exact. This paper suggests that inference from these factual pictures, combined with the scattered well and geophysical data of the synclines and with consideration of the dynamics of structural formation, may be applied to solving the complete geologic structure. Since faulting on the domes and in the synclines may effectively seal and thus limit the size of a reservoir and bar additional water influx, consideration of geologic structure and its possible effects is essential to complete analysis and prediction of reservoir performance. Introduction Implicit in reservoir studies is the fact that the oil must be displaced from the reservoir rock by some other fluid, either gas or water, and this understanding yields the terms descriptive of the major reservoir production mechanisms, gas expansion and water drive' Three recent papers1-2-3 make clear the economic and conservation preeminence of Water drive as a production mechanism; in fact, the title of the latest of these is " Production under Effective Water Drive as a Standard for Conservation Practice." There appears to be an assumption at times among analysts that the effectiveness of a water drive is solely dependent on the rate of oil production; that is, if water drive appears to be insufficient or lacking, a lower oil-recovery rate would increase or reveal it. This assumption might result from the fact that the analysis has been wholly developed during the period of production curtailment; that is, since 1929. The writer takes it that the recurrent phrase in De Golyer's paper,3 "some degree of water drive," is related to this assumption. In California, an extraordinary phrase, "inactive water drive," is rather common and the connotation of uncertainty regarding our knowledge of reservoir performance is evident. Wyckoff2 speaks of the type of reservoir and performance as follows: "In general, reservoirs may be any one or a combination of domal, faulted, lenticular, or stratigraphic traps. Insofar as the dynamic performance of such reservoirs is concerned, the particular type merely determines whether regional flow is symmetrical as in a uniformly developed domal or lenticular type, or one-sided as in many stratigraphic or faulted traps." But whether the flow is

Jan 1, 1943

By J. M. Bugbee

The engineer and the conservationist agree that effective water drive is the desirable reservoir production mechanism. Water drive may result either from the expansion of edge water, the reservoir water bordering an oil pool, or from the artesian flow of edge water from the outcrop. Thus, the extent of the reservoir has an important bearing upon both the rate and the ultimate quantity of water influx to an oil pool. Lens-type reservoirs are generally recognizable, but the complete structure of the more important domal types, having possible limitations from crestal and synclinal faulting, is not well understood. The delineation from cores, electrical logs and exploitation phenomena of the crestal portions of reservoirs is increasingly exact. This paper suggests that inference from these factual pictures, combined with the scattered well and geophysical data of the synclines and with consideration of the dynamics of structural formation, may be applied to solving the complete geologic structure. Since faulting on the domes and in the synclines may effectively seal and thus limit the size of a reservoir and bar additional water influx, consideration of geologic structure and its possible effects is essential to complete analysis and prediction of reservoir performance. Introduction Implicit in reservoir studies is the fact that the oil must be displaced from the reservoir rock by some other fluid, either gas or water, and this understanding yields the terms descriptive of the major reservoir production mechanisms, gas expansion and water drive' Three recent papers1-2-3 make clear the economic and conservation preeminence of Water drive as a production mechanism; in fact, the title of the latest of these is " Production under Effective Water Drive as a Standard for Conservation Practice." There appears to be an assumption at times among analysts that the effectiveness of a water drive is solely dependent on the rate of oil production; that is, if water drive appears to be insufficient or lacking, a lower oil-recovery rate would increase or reveal it. This assumption might result from the fact that the analysis has been wholly developed during the period of production curtailment; that is, since 1929. The writer takes it that the recurrent phrase in De Golyer's paper,3 "some degree of water drive," is related to this assumption. In California, an extraordinary phrase, "inactive water drive," is rather common and the connotation of uncertainty regarding our knowledge of reservoir performance is evident. Wyckoff2 speaks of the type of reservoir and performance as follows: "In general, reservoirs may be any one or a combination of domal, faulted, lenticular, or stratigraphic traps. Insofar as the dynamic performance of such reservoirs is concerned, the particular type merely determines whether regional flow is symmetrical as in a uniformly developed domal or lenticular type, or one-sided as in many stratigraphic or faulted traps." But whether the flow is

Jan 1, 1943

By Frank Tolonen

IRON-ORE beneficiation is becoming of vital importance to the Lake Superior region, since only a few decades will be needed to exhaust the direct shipping ores even if generous allowances are made for discoveries of new orebodies. If the region is to continue as the chief source of ore to the steel industry of the United States, it must concentrate or otherwise beneficiate the enormous tonnages of available iron formations. A beginning along this line has already been made. About one-fifth of the total shipment, even now, is the product of some sort of concentrating process, while another fifth is improved in physical structure by crushing, screening, drying, sintering, or some other similar method. The amount of material amenable to these processes is limited, however; and, in order to be able to utilize the billions of tons of iron formations that cannot be so beneficiated, an intensive study of their nature and concentration possi-bilities is necessary. As long as high-grade ores are available in ample quantities, ore dressing is economically impossible, but as soon as the supply nears exhaustion it becomes necessary. At first the products of ore dressing must meet as nearly as possible the same specifications as the rich ores in order to be adapted to the reduction processes already established. The future requirements as to quality will depend on the one hand upon the ability of the ore dresser to eliminate undesired constituents and charac-teristics in the material, and on the other upon the adaptation of the reduction processes to the product that can be economically supplied. A better understanding of the blast furnace and other reduction reactions, and improvements in the preparation of raw materials, should enable the Michigan districts to continue to supply ore for a long time to come. The study and testing of the iron formations necessary to bring a utilization of the low-grade ores, though requiring time and effort on the part of all concerned, should not be postponed, especially since the economic situation forces the use of the highest grade ore in preference to the leaner material.

Jan 1, 1933

By Newell G. Alford

Forecasts of future timber consumption in soft-coal mining are handicapped by the lack of adequate experience records for estimating properly the timber requirements of the industry. Data were obtained from plants where records are kept or from operators who collected the information and to these were added composite figures for the continental United States in 1905 and 19191 and for central and western Pennsylvania and for Illinois in 1922.2 The result, representing slightly over 928,000,000 net tons, is shown in Table 1. Some of the companies furnishing data were unable to segregate the timber into classes of use but for those who did, Table 2 shows the board feet of posts and cross ban used per ton of coal mined and the percentage of the total timber consumed that was used in roof support. The wide variation in amounts of timber per ton of coal mined is the result of

Jan 1, 1924

By Erland Johnson

BRINE was discovered at Avery Island, La., in 1790, but it was not until 1862 that rock salt was found about 13 ft below surface-the first discovery of rock salt on the continent. Maximum elevation of the island is 152 ft and elevation at the shaft 31 ft. The mining level is 530 ft below elevation at the shaft and the shallowest salt about 12 ft below surface. A shaft was sunk in 1869 when the mining operation started. In 1898 the present shaft was sunk, and the mine has been operated by International Salt Co. ever since.

Jan 6, 1957

By M. Prats, D. G. Russell

The performance of a well in a bounded, layered reservoir with interlayer crossflow has been investigated mathematically. The system studied comprises a centrally located well in a bounded cylindrical reservoir composed of two layers of contrasting physical properties. The reservoir contains a single fluid of small and constant compressibility. In the case of a well producing at constant pressure, the production rate of the crossflow system declines exponentially after the early transient behavior dies out. For wells which produce with constant rate, the pressure-time relationship is linear following the transient. For very early production time, the production rate of the two-layer crossflow system behaves as that of the two-layer stratified system (the case in which the layers are in communication at the well only). Except for early time, in most practical cases the performance of a two-layer reservoir with cross-flow can be duplicated by that of a single-layer reservoir. The equivalent single-layer reservoir must have the same pore volume and the same drainage and wellbore radii as in the two-layer case. In addition, the equivalent reservoir must have a "kh" (permeability x thickness) product equal to the sum of the "kh" products of the respective layers in the crossflow system. If the porosity and permeability distributions are known, the production and pressure behavior of a well with and without crossflow can be predicted. From a comparison of the observed pressure or production performance of a well and the theoretical behavior, the occurrence of interlayer crossflow can be detected. INTRODUCTION When flow is possible across the bedding plane from a low-permeability layer into an adjacent layer of moderate or high permeability, the earlier depletion of the more permeable layer will cause such flow to occur. If this situation exists, the oil recovery from tight layers can be appreciable; thus, the economic ramifications of interlayer crossflow are apparent. The possible importance and extent of flow between adjacent and connected layers — whether resulting from capillary, gravitational, or viscous forces — have been the subject of considerable speculation for many years. Jacquard1 presented a rigorous analysis of the crossflow due to single-fluid expansion occurring between two adjacent and connected layers when the well produces at constant rate. His presentation was entirely mathematical, however, and no numerical results from evaluation of the mathematical solutions were presented. Our objectives in the preparation and presentation of the present paper are essentially twofold— (1) to analyze the behavior of a well which produces a single compressible fluid from a bounded, layered reservoir with interlayer crossflow, and (2) to present practical numerical results and simplified formulas to facilitate engineering analysis of reservoirs with crossflow. The constant-terminal-pressure case was analyzed rigorously, whereas the constant-terminal-rate case was treated only for semisteady-state conditions. DESCRIPTION OF THE IDEALIZED TWO-LAYER RESERVOIR The reservoir to be studied is assumed to be bounded and cylindrical in shape, with a completely penetrating well at its center. The reservoir is composed of two adjacent horizontal layers between which fluid is free to flow. Each layer is assumed to be homogeneous, isotropic and completely filled with a fluid of small and constant compressibility. The total thickness of the reservoir is small enough

By J. R. Mihalisin

Phase changes in as-cast alloys in the Ni2 CoCr-Ni, Ti-NSAl system containing 0.1 wt pct C were studied after heat treatment at 1650°F. It was found that a vegion of CrCo-type s was developed in this system after I1000 hr. The tendency for s formation was dePendent upon the aluminum and litanium content, the s -forming tendency generally becoming more pro-nounced as the latter two elements are increased. s lended to form in interdendritic regioues and was associated with solutioning- of- carbide phases. Electron- vacancy computations for prediction of s formation on these alloys mere in sufficient agreement with what was observed experimentally to indicate that the method should be of value in assessing a-forming potential in cast alloys. However, the correlation of electrotz- vacancy numbers may not be as favorable in cast as cormpared to wrought alloys. THE increasing use of high-temperature alloys for longer times at higher temperatures has resulted in a real need for obtaining information on the phase changes taking place in these alloys since these changes often have a direct effect on properties. This paper reports on a study of the phase changes in Ni-Cr-Co-Al-Ti alloys after prolonged heating at 1650°F. The alloys were selected from the pseudo-ternary system Ni2CoCr-Ni3Ti-Ni3Al and this system was chosen because it is the basis of many of the newer cast commercial superalloys. The attempt here was not to define accurately the boundaries of s formation in the NizCoCr-Ni3Ti-Ni3Al system but to delineate the phase transformations taking place upon heating alloys covering a wide range of chemistries in this system. An addition of carbon was made to all alloys to further simulate commercial alloys. It was hoped that the information generated in this manner would be of more direct use to superalloy designers than an equilibrium diagram approach since commercial alloys generally have outlived their usefulness when equilibrium is attained. EXPERIMENTAL PROCEDURE The alloys were vacuum-melted from carbonyl-nickel pellet, vacuum-grade chromium, electrolytic cobalt, high-purity aluminum and titanium, and spec-trographic-grade carbon.

Jan 1, 1968

By W. C. Ellis, E. S. Greiner, M. E. Fine

Discontinuous changes of Young's modulus, internal friction, coefficient of expansion, electrical resistivity, and thermoelectric power are evidence for a transition in chromium near 37OC. Although the X-ray diffraction pattern gives no clue, a difference between the thermal expansivity and the temperature dependence of the lattice parameter suggests a crystal-lographic change. Young's modulus data disclosed another transition near THE thermal dependence of a number of proper- ties of chromium indicates a transition occurring over a temperature range near room temperature. Bridgman' noted this first from a minimum in the electrical resistivity near 12°C. In a sample of greater purity, Sochtig' observed the minimum at 41 °C. Erfling3 reported an inflection in the thermal expansivity curve at 36°C. These temperature-dependence curves are reversible with no hysteresis being detected. No discontinuity or inflection has been observed in the heat capacity' or the paramagnetic susceptibility.' Likewise, no one has noted a change in crystal symmetry. In the present investigation Young's modulus, internal friction, coefficient of expansion, electrical resistivity, illustrated in Fig. 1, lattice constant, Fig. 2, thermal electromotive force, Fig. 3, and paramagnetic susceptibility, Fig. 4, were measured over an extended temperature range. The samples were prepared in two ways: (1) By cold pressing a sintered electrolytic powder compact,' and (2) by electroforming from an aqueous solution. The electroformed samples were prepared by R. A. Ehrhardt and G. Bittrich by plating on copper or nickel tubes from an aqueous solution according to the method of Brenner, Burkhead, and Jennings.' The pressed powder samples (method 1) were finally annealed at 1400°C in purified helium: the electroformed samples, packed in powdered chromium, were vacuum-annealed at 1000°C. From the composition of the original powder' the purity of the pressed powder samples is estimated to be 99.8 pct Cr. Spectrochemical analysis furnished by E. K. Jaycox, revealed only slight traces of impurities in the electroformed sample (less than 0.001 pct), neither iron nor nickel being detected. Chromium deposited by this method is reported to contain approximately 0.05 pct 0.- Methods and Data Young's Modulus: For measurement of Young's modulus, an annealed, pressed powder sample, 0.114 x0.237x1.845 in., and an electroformed sample, 0.10 in. od, 0.01 in. id, and 1.86 in. long, were prepared. The resonant frequencies of the rod samples in forced longitudinal vibration were measured at a series of temperatures from —192" to 200°C by a method previously de~cribed.6,7 Because the samples were nonferromagnetic, iron- silicon or molybdenum permalloy tips (0.013 in. thick) were soldered to the ends. The softening temperature of the solder limited the temperature of measurement. Young's modulus, E,, of chromium at temperature, T, may be calculated from the resonant frequency of the composite rod, f,; the thickness of the tips, t; the length of the chromium sample at 25°C, l,.; the density of chromium at 25°C, pc (7.20 g per cc);5 and the thermal expansivity, Al/l25. Modulus differences for two temperatures, ET and E, are accurate to +0.002x10" dynes per cm2. ET = 4PAlc+2tyf Young's modulus at 25°C, Fig. la, is 28.2~10" dynes per cm' (40.8xlO" si) in wrought chromium (upper curve). The modulus of the electroformed sample is apparently lower due to cracks. From the modulus measurements two transitions were observed: one with a critical temperature at 37°C, the other at —152°C. Internal Friction: The internal friction, 1/Q, was determined from the width, Af, of the strain amplitude-frequency curve at 0.707 times the strain amplitude at resonance;' the internal friction, 1/Q, then equals Af/f. Fig. lb shows a sharp peak in internal friction at 38°C. The internal friction of the electroformed sample had a similar maximum. Thermal Expansion: The expansivity measurements, shown in Fig. 2, covering the temperature range —195" to +400°C were made by D. MacNair in an interferometric dilatometer8 sing a sample consisting of three pyramids 0.25 in. high prepared from wrought electrolytic chromium. Below —120°C the experimental points deviated up to ±2x10 from the drawn expansivity curve in Fig. 2 because of decreased precision of the quartz wedge thermometer at low temperatures. Near 38°C the thermal expansivity curve, Fig. 2, goes through an inflection corresponding to a minimum in the coefficient of expansion, Fig. ld, and a relative volume decrease on heating. Electrical Resistivity: The variation of electrical resistivity with temperature measured by the po-tentiometric method is also shown in Fig. l. The resistivity of the wrought chromium (upper curve) at 20°C is 13.6 microhm-cm; of electroformed chromium (lower curve) 12.8 microhm-cm. The lower value reflects higher purity and agrees closely with a published value." A minimum at 40°C occurs in the resistivity curves of both samples. No conclusive evidence for a transition near — 150°C was observed, but the points, Fig. 1, appear to deviate from a smooth curve between —120" and —160°C.

Jan 1, 1952

By H. M. Howe

§ 24. Introduction.—This paper discusses the chief existing data as to the temperature, in iron-carbon alloys, of Ae3, the upper limit of the transformation range when in equilibrium, as distinguished from Ac3, the temperature at which the end of the transformation is noted in heating up, and from Ar3, that at which its beginning is noted in cooling down. The former is in fact carried above Ae3 and the latter below Ae3 by lag. I touch incidentally on the influence of manganese on Ae3 (§ 29, p. 614). The sections, tables, and illustrations are numbered consecutively with those in the accompanying papers by Howe and Levy on Determination of the Position of Ae3 in Carbon-Iron Alloys, and by Burgess, Crowe, and Rawdon on Thermal and Microscopical Examination of Professor Howe's Standard Commercial Steels, to which the present paper forms a sequel. § 25. The contradictoriness of our present evidence is shown by grouping it together in Fig. 14. For instance, both Goerens and Meyer (Series 2) and Meuthen (Series 12) used practically stationary temperature, and thus reduced the influence of lag very greatly; yet Ae3 for 0.32 carbon steel according to the former investigators is 894", but according to Meuthen it is at or below 770°, a discrepancy of 124" or more. In view of our ability to measure these high temperatures within a few degrees, the existence of such a discrepancy is as unwelcome as it seems needless. I attack the thankless task of bringing some order out of this chaos. In Part 11. (§§ 29 to 39) I consider the chief causes of error. In Part III. (§§ 40 to 48) I apply certain corrections to some of the existing data, review those data, weight them, and calculate a prob-

Jan 1, 1914

By G. Das, S. V. Radcliffe

The substructural features developed in tungsten as a function of annealing temperature (up to 2200°C) and type of material [undoped and doped powder metallurgy (PM) tungsten and electron beam melted tungsten] have been investigated by transmission electron microscopy. For doped PM tungsten wires, characteristic "par-ticulate" substructural features developed rapidly with increase in annealing temperature above 700°C. The features consisted of parallel rows of elongated or circular shapes (500 to 1000A diam) lying along the direction of the wire axis and were identified as internal voids by diffraction contrast experiments. In recrystallized doped PM rod, larger voids were observed and were identified by precision dark field analysis to be cubic in shape and bounded by (100) planes. In marked contrast with both the doped PM materials, recrystallized undoped PM rod exhibited only very occasional and randomly arranged voids. Furthermore, no voids were observed in either material after electron beam melting. The high concentration of voids in the doped PM materials is attributed primarily to vaporization of doping additions or their pvoducts situated at the original grain boundaries , whereas the few voids in undoped material are considered to be traces of microporosity which were not eliminated during sintering. A tentative mechanism is suggested for the dezlelopment of the voids in relation to the processing sequences (sintering and working) and to the subsequent annealing. In recent years, a characteristic substructural feature consisting of rows of small elongated or circular regions of light contrast lying along the direction of working has been seen in thin foil electron microscopy studies of annealed sheet, wire, and rod tungsten. These features were present in the published micrographs of sheet by Weissmann et al.1 and of wire by Meieran and Thomas2, although the authors did not draw attention to them. Wronski and Fourdeux3 observed similar features in sintered rod tungsten (it was not specified whether or not the material was doped*) and interpreted them on the basis of their ap- particles, based on extraction replica evidence from the fracture surface of the initial hot-rolled slab material from which the sheet was prepared. No diffraction contrast experiments on the features were reported in any of these studies. The present investigation was undertaken with the primary objectives of: a) identifying the nature of these substructural features in tungsten by electron diffraction contrast experiments, since the contrast for voids can be expected to differ from that for crystalline or glassy particles, and b) elucidating the origin of the features and their development. For the latter purpose, doped and undoped powder metallurgy tungsten was obtained as rod and wire to represent different stages of reduction during final processing. These materials were examined both in the as-processed condition and after annealing to successively higher temperatures. In addition, the same doped and undoped materials were examined after vacuum melting in rod form. I) MATERIALS AND PROCEDURE Doped powder metallurgy (PM) tungsten wire (commercial purity 99.9 pct W) was obtained in the as-drawn and surface ground condition (0.030 in. diam "ground seal rod"). Doped and undoped tungsten rod (0.075 in. diam) representing an earlier stage of final processing was obtained from the same commercial source (Refractory Metals Division, General Electric Co.). Lengths of both the doped and undoped rod materials were single-pass melted in an electron-beam zone refiner to examine the effect of vacuum melting on the substructure. Annealing was carried out in a tungsten crucible in a tantalum strip resistance furnace under a vacuum of l0-15 mm Hg. Longitudinal sections of the wire and rod materials were examined by light and electron microscopy. The preparation of thin foils suitable for electron transmission from 0.030 in. diam tungsten wire and the rod specimens was carried out by means of a high-precision microjet technique developed to provide lack of jet stability and precise control of the area thinned. The method is described in detail elsewhere.' The foils were examined in a JEM 6A electron microscope using a goniometer stage (±20 deg tilt, 360 deg rotation) and operated at 100 kV. To minimize contamination problems a 200 µ condenser aperture was used in conjunction with a useful beam current of 50 µA. II) RESULTS AND DISCUSSION A) Diffraction Contrast Analysis. In order to determine the optimum conditions for the development of the substructural feature, a series of isochronal 30 min annealing experiments were carried out on specimens of the doped PM tungsten wire. The transmission electron microscopy analysis showed that the as-drawn wire, Fig. 1(a), consists of 'fibers' whose long axis is closely parallel to the wire axis of (110). The fiber width averages some 0.5 µ. Dense disloca-

Jan 1, 1969

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By C. M. Wayman, J. F. Breedis

The crystallography of the martensitic transformation in the Fe-30 Ni alloy was reinvestigated. The scatter in the habit Plane as determined from measurements on the mid-rib plane was smaller than reported previously, and the orientation relationship was determined from a martensite plate having known direction cosines. From agreement with crystallographic theory and from observations of the morphnlogy of the martensite plates, it is suggested that the mid-rib plane represents the starting region of the transformation. THE crystallography of the martensitic transformation in the iron-nickel system has been the subject of many investigations.&apos;-7 However, for iron alloys containing approximately 30 wt pct Ni, a wide scatter in the reported habit planes exists. In only one instance has a Laue determination of the orientation relationship been made, but the habit plane of the martensite plate studied was not determined experimentally. Because the most successful thermodynamic and kinetic analyses8 of the martensite transformation have been based on Fe-30 Ni alloys, it was considered desirable to reinvestigate the crystallographic features of the transformation in this alloy. Lieberman9 suggested that the most significant information for use in a theoretical treatment involves the determination of all the crystallographic observables from a single plate of the product phase. This was first done in essence by Greninger and Troiano10 for Fe-22 wt pct Ni-0.8 wt pct C, and is the method followed in this investigation. Some theoretical approaches11-13 in describing the martensitic transformation consider the overall transformation distortion to be comprised of a Bain distortion, or lattice deformation (PI, which produces the structure change, and a lattice invariant deformation (G), such as twinning, which together leave the interface or habit plane un-distorted. The incorporation of a rigid body rotation (R) results in a transformation distortion (E) such that the interface plane is left both undistorted and unrotated. In matrix notation, E = RPG where the lattice invariant deformation has "taken place" in the austenite. Bowles and Mackenzie14-16 in formulating a theoretical approach proposed an adjustable scaler quantity, denoted as 6, which represents a uniform dilation in the interface plane. This dilation acts to adjust the lattice spacings of the parent and product structures at the plane of contact. Using the dilation parameter as a variable, these authors were able to account for a continuous variation of habit planes in steels along a curve in the stereogram between {225}A and {259}A. she invariant line strain14 of the transformation is 6 RP, and the corresponding transformation distortion is E/6.) With the dilation parameter known, the invariant line is computed as the triple coincidence of the habit plane, the shear plane of the lattice invariant deformation, and the initial Bain cone.14 The contraction axis for the Bain distortion can be taken9&apos;17 as [010]A, and the correct permutation of the habit plane indices used. Kelly and Nutting 18 have established the shear plane (of twinning) in the tetragonal martensite of Fe-22 Ni-0.8C to be {112)M by means of transmission electron microscopy. The reasonable shear system is then {112}M which is equivalent to {011}A <01l>A. The as-

Jan 1, 1962

By R. H. Martinson, E. Teghtsoonian

The effects of magnesium-rich surface layers of varying thickness on the mechanical properties of LiF have been studied. The yield stress, critical tensile stress, and work-hardening slope increase linearly with layer thickness, while the strain to fracture decreases yapidly with increasing layev thickness. The results of tension tests, supplemente!d by metallogvaphic evidence, indicate that the yield stress and the critical tensile stress of LiF are not determined by surface-source operation. DESPITE many studies, which have recently been reviewed,&apos; certain fundamental aspects of the plasticity of LiF remain obscure. For instance, one question still awaiting a satisfactory resolution is: does the nucleation and/or multiplication of dislocations in LiF occur preferentially near the crystal surface? It is now well-known that mobile dislocation half-loops are readily introduced into LiF by surface damage and that the mechanical properties of LiF are affected by such surface damage. However, it is not known whether, in the absence of large numbers of artificially introduced surface sources, dislocations arise more easily near the crystal surface than in the crystal interior. It is also not known to what extent existing mobile dislocations multiply preferentially near the crystal surface. The present work is an experimental study of these matters. A short investigation of the effect of magnesium -alloyed surface layers on the deformation of LiF single crystals has been published by Westwood.~ Some relevant conclusions drawn from this research are restated here for purposes of comparison with the present work. 1) Tests on as-cleaved, chemically polished, coated and uncoated specimens show that a coating can restrict the operation of artificially introduced surface sources, thereby raising the yield stress. A coating also decreases the initial rate of work hardening of as-cleaved LiF crystals by reducing the number of active dislocation sources, so that mutual dislocation interference effects are lessened. 2) A catastrophic breakthrough of groups of edge dislocations piled up against the coating can cause stress drops in the stress-strain curve. 3) A surface coating can act as a stable barrier to the egress of dislocations, causing pile-up,

Jan 1, 1965

By H. A. Bright, H. C. Vacher, J. G. Thompson

The methods employed for the determination of oxides and oxygen in ferrous materials may be roughly classed in two groups, "wet" methods and "hot" methods, the first group including the iodine, electrolytic, mercuric chloride, hydrochloric acid, nitric acid, and chlorine methods; the second group including the vacuum-fusion and hydrogen-reduction methods. The wet methods depend upon preferential solubility in a selected medium to separate the metallic portion of the sample from the oxygen-containing constituents. Subsequent analysis of the insoluble residue permits the isolation and separate determination of individual oxides and compounds. The hot methods depend upon the reduction of the oxide constituents of the sample by means of carbon or hydrogen at elevated temperatures. With the exception of the recently developed fractional vacuum-fusion method, the hot methods do not identify individual oxides and compounds but yield only a single value representing the sum of the oxygen contents of several or all of the oxide constituents present. With such diversity in the principles and aims of the different groups, it is not surprising that concordance of results by different methods has usually been difficult to obtain. The present cooperative attempt to define more rigorously than has been possible heretofore the accuracy and limits of usefulness of the various methods, originated in correspondence between Dr. John Johnston, Director of Research of the United States Steel Corporation, and other interested metallurgists. The plan was, briefly, to submit identical samples to a number of laboratories for analysis by different methods and to collate the results of these analyses. The project was endorsed by the Iron and Steel Division of the American Institute of Mining and Metallurgical Engineers at the annual meeting in February, 1933, and has been conducted under the joint sponsorship of the Iron and Steel Division and the National Bureau of Standards. The latter organization undertook

Jan 1, 1937