Search Documents

By N. J. Grant, K. M. Zwilsky

A series of copper-alumina dispersion strengthened alloys were prepared using three different copper and two different alumina powder sizes. Improvements in strength of up to ten times that of pure copper were found in room-temperature as well as elevated-temperature stress-rupture tests. Conductivity values remained from 70 to 90 pct that of pure copper. The best alloys were based on the finest metal powder (1 p) and contained from 7.5 to 10-0 vol pet of 0.018 or 0,033 p alumina. DISPERSION strengthening of metals consists of strengthening a metal matrix by the addition of oxides or other refractory constituents, followed by strain hardening, in order to reinforce the base material and extend its temperature range of application. Since the discovery of SAP by lrmannl and Von zeerleder2 in 1949, many investigators have reported data obtained on a variety of metal-inert oxide alloys.3-7 The present work deals with the mechanical mixing of copper and alumina powders. While several techniques of introducing the second phase have been investigated to date, mechanical mixing so far has been recognized as the simplest, least expensive, and most universally applicable technique that can be used to obtain an ultrafine dispersion of inert particles. In the present case, the effects of changing the metal particle size, the oxide particle size and the volume percent of oxide were investigated. This work is an extension of a previous study.6 EXPERIMENTAL PROCEDURE The starting materials were three different grades of copper powder and two different alumina powders. The three metallic powders were -74 µ(- 200 mesh) electrolytic copper powder consisting of irregular equiaxed particles having a normal screen distribution and analyzing 99.5 pct Cu, and two powders having a 5-µ and 1-µ particle size, average, respectively. The latter powders were produced by the hydrogen reduction of purified sulfate solutions at elevated temperature and pressure and were furnished by the Sherritt Gordon Mines, Ltd. The alumina used was obtained from Godfrey L. Cabot Co., under the trade name of Alon C, one batch of powder having a particle size of 0.018 µ, the other a particle size of 0.033 µ. The crystal structure of these alumina powders was found to be cubic gamma. Each batch of powder was mixed in a Waring Blendor for a total of 15 min, followed by a low-temperature reduction in hydrogen and vacuum compacting in cylinders which were hydrostatically pressed at 35,000 psi to give a compact that could be handled conveniently. Six of the compacts were hydrogen sintered at 900°C while the remaining four were sintered at 1000°C. Subsequently, all compacts were hot extruded at 760°C with a reduction of area ratio of approximately 20 to 1. Evaluation of alloys included density and resistivity measurements, room-temperature tensile tests, stress-rupture tests at 450°C plus one other temperature per alloy, hardness tests, microstruc-tural examination, X-ray analysis of the dispersed phase after dissolving the metal phase, and oxidation studies on two of the alloys. A vacuum-melted, wrought copper rod was tested together with these alloys for comparison purposes. RESULTS Table I is a summary of the compositions, sintering temperatures, densities and conductivity values of the ten alloys prepared. All alumina additions are given in volume percent, and will be referred to as

Jan 1, 1962

By Robert A. Rapp, Jan E. Verfurth

From the measurement of internal-oxidation band widths in Ag-In and Cu-A1 alloys, products for the solubility No and the diffusivity Do of oxygen in silver and apparent NODo products in copper have been obtained over a range of temperature. The NODO products for silver are in agreement with the product of the individually determined No and Do values of Eichenauer and Müller. Although interstitial diffusion of oxygen in silver is expected, the temperature-independent factor Do of the diffusion coefficient does not agree well with the theory of Wert and Zener. For Cu-A1 alloys internal oxidation does not follow the expression derived for ideal kinetics, since the apparent NODo product calculated from internal-oxidation measurements is a function of the alloy content in the specimen. Thus, unequivocal values for No or DO or even the product NODO in copper are not available from the literature. RELIABLE values for the saturation solubility NO and diffusivity DO of oxygen in fcc metals are lacking and difficult to determine, partially because internal-friction measurements are not applicable. Permeability experiments and Sieverts7-type adsorption -desorption methods3 have met with difficulty; however, Eichenauer and Müller4 have recently reported on the solubility and diffusivity of oxygen in silver as determined by the latter technique . Rhines, Johnson, and Anderson,5 and independently Meijering and Druyvesteyn,' introduced the possibility of deriving values for the product NODO in a metal from measurements of the widths of internal-oxidation zones (subscales) formed during the internal oxidation of alloys. In addition to these authors, several other investigators7-9 have made such measurements in various silver and copper alloys at various temperatures, mostly using me- chanically polished specimen surfaces. The purpose of this investigation was to determine over a range of temperature the calculated products NODO in silver and copper from systematic measurements of the widths of internally oxidized zones in Ag-In and Cu-A1 alloys, using specimens with electro-etched surfaces. Consider the internal oxidation of a dilute solid-solution alloy in which the base metal is not oxidized. If diffusion of oxygen is the rate-controlling step, then the depth 5 of the internal-oxidation zone is given by where y is a dimensionless parameter and t the oxidation time. Based on the solution of the diffusion equation, wagnerl0 has shown that under certain conditions several mathematical simplifications may be used in the evaluation of y, so that Eq. [I] may be expressed for the case that y « 1, and y(Do/DB) 1, where N(so)the is the equilibrium solubility (mole fraction) of oxygen in the solvent metal for the given oxidizing atmosphere, is the mole fraction of the solute metal in the bulk alloy, 4 is the diffusivity of the solute in the base metal, and v is the ratio of oxygen atoms to solute atoms in the precipitated oxide BO,. Rearranging Eq. [2] Maak' has derived an expression analogous to Eq. [3] for the case that an external-oxide scale, in addition to an internal-oxidation zone, is formed. For this combined external and internal oxidation for the case that 5/2 where 5 is the distance of the internal-oxidation front from the original external s.urface, and X is the distance of the external oxide/metal interface from the original external interface. The function F is defined by the expression

Jan 1, 1964

By R. H. Doremus, E. F. Koch

The first carbide phase that precipitates at 120°C from a iron containing about 0.02 wt pct, C was studied with the electron microscope. In both strained and unstrained material the carbide particles appeared to form on the dislocations in the iron, in agreement with the results of the kinetic study in part II. The structure of the carbide was tentatively identified as an expanded a-iron lattice (body-centered tetragonal) with about 0.7 wt pct C. This phase appeared to be metastable and apparently transformed into cementite or epsilon carbide when the iron was over-aged. WhEN a iron containing less than about 0.025 wt pct C is quenched from 700°C to room temperature the carbon is retained in solid solution and precipitates out slowly with time. The morphology and structure of the precipitating phase are still in doubt, two different carbide phases, epsilon carbide and cementite, have been identified, but there is considerable disagreement about the time and temperature at which they appear.1-4 Epsilon carbide seems to form at lower temperatures than cementite, although one group of investigators4 found only the latter phase over a wide range of aging temperatures. Usually these two phases have been identified after aging times much longer than needed to drain the carbon from supersaturated solution, at least for aging temperatures below 200oC. The precipitated carbides have been observed with the electron microscope,'-5 but again most results have come from samples aged much longer than necessary to reduce the carbon concentration in solution to a low value. In this study the carbide phases were observed in earlier stages of precipitation with the electron microscope, in order to learn more about the shape, size, and distribution of the carbide particles. Samples strained small amounts before aging, as well as unstrained samples, were studied, and the structure of the carbide phase was tentatively identified. EXPERIMENTAL "Ferrovac E" vacuum-melted iron, from which the wires for kinetic studies were also made (Refs. 6 and 7 and the following paper) was used for this work. An analysis of this material is given in Table I; it agrees well with the manufacturer's values. The number of inclusions in the iron was very small, as can be seen in the optical micrograph in the following paper. Pieces of iron about 1 mm thick and 5 to 10 mm in diam were used for all the studies except for those in which the sample was strained before aging; then the specimen was a rod 3 to 6 mm in diam and 20 cm long. The samples were held at about 700°C in wet hydrogen for at least an hour to remove residual carbon and nitrogen, after which they were heated to 950" (in the y region) and cooled to room temperature in the furnace. This treatment gave an average grain diam of more than 1 mm, so that the effect of grain boundaries on the precipitation process was negligible. The samples were carburized at 710°C for about 2 hr in hydrogen that had passed over toluene held at -30°C; then they were rapidly quenched into water. From chemical analysis this treatment gave a carbon concentration of from 0.012 to 0.016 wt pct, which is less than the solubility of carbon at this temperature. After quenching, the samples were aged at 120 "C in an oil bath for vari-

Jan 1, 1961

By Nicholas J. Grant, Rolf Nordheim, Bill C. Gissen

The system Cb-Re was examined in detail utilizing pure metals, careful melting techniques, and heat treatments. Metallographic and X-my methods were utilized for phase identification. In addition to soli-dus determinations, the composition limits and mode of formation of the intermetallic compounds 0 and X were determined. The binary constitution diagram Cb-Re has been the subject of a number of investigations.'-7 Two intermetallic phases have been described and tentative diagrams have been proposed. It was the aim of this investigation to obtain a complete and more accurate diagram through the use of purer alloys and improved techniques. The diagram worked out by Knapton7 was published after our experiments were concluded. EXPERIMENTAL METHODS The starting materials were Re powder of 99.95 pct purity, supplied by the Chase Brass and Copper Co., and Cb rondelles of 99.6 pct purity, supplied by the Electro Metallurgical Co. Typical analyses are given in Table I. The alloys were prepared from compacted Re powder and Cb rondelles; for critical compositions master alloys were used. The melts varied from 5 to 50 g and were melted nonconsumably in an Heraeus arc furnace, under ti-tanium-gettered laboratory grade argon. It was necessary to invert the buttons and remelt, followed by crushing and further remeltings, the number of which depended on the nature of the fracture of the alloy. The weight of each alloy was carefully checked after each melting operation. It was found that significant weight losses occurred only when loose Re powder was used. These losses amounted to a maximum of 3 wt pct in such instances, but did not occur after the charge was once molten, regardless of the composition. Typical loss of weight after 4 remelts, including crushing, amounted to 0.2 wt pct. Oxygen pickup during successive melting cycles did not appear to be significant, since the weight gain values never exceeded 0.01 wt pct. Control of the composition of the alloys was not too difficult; however, the problem of homogenization was a far greater one. Optimum alloying conditions were finally achieved by a combination of master alloy production and repeated crushing and remelting cycles. The compositions of the alloys utilized to determine the constitution diagram are listed in Table 11. The weight balance method was used ultimately as the sole analytical method, since repeated checks indicated that it was accurate to 0.2 pct, if the weight losses were small. The results were double-checked by a metallographic study of the homogeneity of the samples, since this was presumed to be the more serious factor. Heat treatments at 1200°C or lower were accomplished by sealing the specimens in Vycor tubes, heating in a Globar furnace, followed by air cooling. This was considered to be an adequate quench because of the very low temperatures involved. For temperatures of 1200" to 1900°, alloys were homogenized and heat treated in a tungsten-filament resistance vacuum furnace. From 1900" to 2750" a tantalum-tube resistance furnace was utilized, operating under a vacuum of 105 mm Hg. The temperature measurements up to 1200" were made by means of platinum-platinum 10 pct Rh thermocouples, with an accuracy of 5°C. For temperature measurements greater than 1200°C, optical pyrometers were used. They were calibrated against a standardized instru-

Jan 1, 1962

By George Mixter

MINING, in contrast to manufacturing, deals with a wasting asset. That which is taken out of the ground is gone, the property is depleted to that extent, and will eventually become exhausted of profitable ore. So the life of a mining company is dependent upon the ability of its management to develop improved methods to permit extraction at a profit of the lower-grade ores which remain, to extend by intelligent exploration the limits of its known ore bodies, and to find and acquire new properties to take the place of those that, for one reason or another, are no longer operated. Its history is a story of constant change, of the working out of properties here and the acquisition and development of properties there, to maintain the vitality of the whole. It is a story of estimating with the tools and the knowledge available the location and extent of hidden ore bodies and of devising the means of extracting

Jan 1, 1948

By C. H. Samans, G. F. Tisinai

HARDENING and embrittlement of the ferritic chromium stainless steels at temperatures near 885 °F have been known for a long time.' However, no satisfactory explanation has been given. Both ordering and precipitation hardening have been suggested. Fisher, Dulis, and Carroll2 discovered a chromium-rich body-centered-cubic precipitate in embrittled alloys. Subsequently, Williams' and Wright4 also have found evidence of this body-centered-cubic constituent. William's hardness, electrical resistance, and magnetic studies led to his proposal of a new constitutional diagram for the Fe-Cr alloys. The new feature of this diagram is the eutec-toidal decomposition, below about 970°F, of the s phase into two stable body-centered-cubic solid solutions, one rich in iron and the other rich in chromium. An observation of Heger5 that the amount of s phase has increased and the amount of chromium-rich body-centered-cubic phase decreased in the interval 5000 to 32,600 hr at 900°F, even though the alloy increased in hardness, casts some doubt on this diagram. If precipitation hardening causes the embrittlement, the precipitate probably is always coherent with the matrix, since no evidence of overaging has been reported. It cannot be stated positively, however, that Fisher's body-centered-cubic constituent is the embrittling phase. According to Preston's data,6 such a chromium-rich phase should have a parameter less than about 0.5 pct larger than that of the iron-rich matrix lattice. Moreover, the constitutional relationships whereby Fisher's constituent forms, and whether it is stable, metastable, or a transition phase, are not yet completely clear. The recent studies of Wright4 and of Lommel,7 as well as the earlier studies of Becket8 and of Hochmann,9 have shown that 885°F hardening occurs in relatively pure Fe-Cr alloys. No evidence of its occurrence or absence in chromium itself has been reported. The rate of hardening in high purity alloys seems appreciably slower than that in alloys containing larger amounts of impurities (chiefly carbon and nitrogen). This may be due merely to the absence of hardening and straining effects from precipitated carbides and/or nitrides. These observations on high purity alloys make it seem unlikely that 885 °F hardening is caused by a constituent containing other than iron and chromium atoms, e.g., carbides and/or nitrides. Wright,4 Lommel,7 and Lena and Hawkes10 emonstrated the accelerating effects of a finely dispersed precipitate of (probably) chromium nitride on the hardening reaction. This appears to be evidence that lattice straining increases the rate of nucleation of the hardening constituent. Some new observations on 885°F hardening are reported here. They show an effect of preheat treatment that should contribute to a better understanding of the 885°F hardening phenomenon. They also clarify a discrepancy which exists in the literature. Some investigators have reported most rapid hardening at 885", whereas others have reported it at 930°F. The present work also shows that 885°F hardening does not occur in electrolytic chromium, and that any long range ordering type of reaction affecting any sizeable part of the volume is unlikely. Materials Studied Table I shows the currlposition of the alloys used in this investigation. In these alloys carbon and nitrogen are present in roughly similar amounts. Presumably both elements precipitate, as carbides and/or nitrides, during the heat treatments given.

Jan 1, 1958

By D. B. Smith, John Chipman

THIS investigation was undertaken as a prerequisite to the study of sulphur activities in the liquid system Fe-Cu-Ni, a continuation of the work of Sherman, Elvander, and Chipman,¹ using the same equipment and the same experimental technique. Temperature measurements are made with a disappearing filament optical pyrometer, sighting through a prism onto the surface of the melt which is heated by induction. To obtain true temperatures by this means, a calibration is necessary, since, in the absence of true black-body conditions, the observed temperature is always lower than the true temperature. This calibration is actually an emissivity correction, since the emissivity is a function of both temperature and melt composition. The original furnace was used with a deeper metal bath to provide sufficient depth of immersion for the thermocouple which was inserted through the sampling hole. The atmosphere was a 50-50 mixture or argon and hydrogen passing through the furnace at a rate of 1000 ml per min, and preheated by means of a molybdenum resistance coil. It was assumed that the rapid gas flow effectively eliminated any error which might have resulted from the presence of metallic vapor. The charge in each case consisted of about 300 g of metal, contained in a high purity, dense alumina crucible. At each melt composition, readings of the optical pyrometer and of a thermocouple immersed in the molten metal were taken simultaneously. Calibration curves of optical vs. true temperature were then made for each melt composition investigated. Thermocouples were made of 0.010 in. platinum and platinum-10 pct rhodium. They were checked against the melting point of chemically pure copper. Silica protection tubes with an outer diameter of approximately 1/8 in. were used. The depth of immersion of the tip in the molten metal was approximately 1 14 in. The life of these small thermocouples was relatively short, varying from approximately 1 min at 1550°C to 10 min or longer at 1300°C. Melts containing iron corroded the protection tubes more than those without iron present. Measurements taken while heating checked those taken while cooling, indicating the absence of a temperature gradient between the molten metal and the thermocouple. Results The temperature range of the. measurements on copper-free metals extended from the melting point to 1600°C. For copper the upper limit was 1380°C, and the data were extrapolated linearly for comparison with observations on the other metals and alloys at 1535°C. Examples of typical calibration curves for various melt compositions are shown in Fig. 1. These curves, besides providing a calibration system for the given experimental conditions, also give a basis for the calculation of true emissivities at the effective wavelength of the pyrometer, 0.65 micron. The starting point of the calculations is the value of the emissivity of iron at its melting point. Taking the melting point of electrolytic iron under hydrogen as 1535°C, and using the corresponding emissivity value of 0.43, as determined by Dastur and Gokcen,² the emissivities can be determined as functions of composition (and temperature, if desired). The relationship used is the Wien equation: ln(Ea)=C2/?(1/T1-1/Ta where E is the emissivity; a, the transmissivity of the optical system; C,, the fundamental constant, 14,380 micron-degrees; A, the wave length of light used (0.65 micron); Tt, the true temperature, OK; and T., the apparent temperature, OK. At the melting point of iron the observed temperature was 1358"; this gives 0.62 for the transmissivity, which compares with 0.65 in the similar system used by Dastur and Gokcen. The emissivities of all the compositions investigated were determined at 1535°C, after obtaining from each calibration curve the corresponding temperature. These results

Jan 1, 1953

Year of Election 1959 Andrew Fletcher, New York, N Y "For his outstanding leadership in the lead and zinc mining industries, and for his able and devoted services to the Institute as its Treasurer and President, and as a Director for many years " 1917 Herbert Hoover, New York, N Y 1955 George M Humphrey, Cleveland, Ohio 1950 Zay Jeffries, Ptttsfield, Mass 1942 Essington Lewis, Melbourne, Vic, Australia 1959 John M Lovejoy, New York, N Y "For his distinguished service to the Institute, for his outstanding contributions in furthering the professional status of petroleum engineers, for his pioneering in application of engineering to petroleum production, and for his outstanding record of public service on behalf of the petroleum industry " 1957 Donald H McLaughlin, San Francisco, California 1957 C H Mathewson, New Haven, Connecticut 1938 Albert M Portevin, Parts, France 1957 Fred Searls, Jr, New York, N Y

Jan 1, 1960

By F. von Gemmingen, E. J. Fasiska, L. Zwell

EARLIER studies of the dependence of creep on structure1 and of the dependence of creep rupture on creep behavior2 did not include detailed discussion of the phases present in the specimens under examination. It is of interest to determine the nature and amounts of such phases present since it is well known that these are dependent on composition, heat treatment and creep conditions.3 This investigation has therefore been undertaken to identify these constituents and to determine their relative amounts. This report presents the results of this investigation and describes an improved "extraction replica" technique developed in the course of the work. The composition of the Type 316 austenitic stainless steels studied in this investigation is given in Table I. The specimens were solution treated at 2000°F for 1/2 hr and water quenched. Those specimens subjected to prestrain at room temperature Methods for extracting precipitate particles from materials for electron and X-ray diffraction analysis have been described by Fisher,4 Smith and Nutting: and Booker and coworkers.6'7 Electrolytic extraction methods have been described by Andrews and Hughes.8 The first two methods have been used at this Laboratory, but have not proved satisfactory for many problems requiring X-ray diffraction analysis. It has been difficult to remove the replicas or to avoid tearing them during removal. These difficulties are overcome by backing the replica with a water-soluble plastic such as Dupont 51-05 Elvanol (polyvinyl alcohol). The backing increases the thickness of the replica so that it can be mechanically stripped from unloosened particles without folding or tearing. This procedure eliminates the stripping of wet replicas, which usually have a low tear strength. By stripping replicas after drying, it is possible to extract partially loosened particles which otherwise would remain imbedded in the metal. The modified method is as follows: after the specimen is polished, it is etched for 60 min in modified glyceregia consisting of 30 ml glycerol, 7 ml nitric acid, and 4 ml of hydrochloric acid. The sample is then washed, air dried, and coated with a 20 pct Baker and Adamson 1611 collodion (85 pct amyl acetate by volume) film. After the collodion film is dry (about 15 min), the sample is again etched in the modified glyceregia for 50 min, washed with isopropyl alcohol (to prevent dissolving the collodion) and air dried. A very thick coat of polyvinyl alcohol (about 50 pct solution "Elvanol Dupont 51-05" in water) is poured over the sample and is permitted to dry for about 24 hr. The composite film containing the precipitates is then stripped from the specimen and floated, polyvinyl alcohol side down, in water (at about 50°C) until the polyvinyl alcohol dissolves. This usually takes about 15 min. Should any of the polyvinyl alcohol remain on the replica, it does not give a crystalline diffraction pattern and therefore does not hinder identification of the precipitates. The extraction replica, floating in water, is picked up on a glass fiber and mounted in the Debye-Scherrer camera for X-ray diffraction analysis. Concentration of the etchant, and also etching time, had to be increased for several of the samples. Fig. 1 shows two extraction replicas taken from different areas of spec. M74-37; X-ray analysis showed a strong diffraction pattern of M23C6 and a medium one of u phase. A

Jan 1, 1962

By C. A. Fisher

THE discovery of petroleum in Pennsylvania in 1859 marked the birth of an industry of paramount importance. Spreading from - Oil Creek, this remarkable industry may be said to have embraced the earth in a little more than half a century. Those who made the discovery little realized its deep significance or far reaching influence on our national life. For over sixty years, during which time this nation has created and developed the oil industry to a high state of efficiency and' carried its activities to all parts of the world, we have' at all times been the leaders in the production of crude oil and in the development of its technology. During the unprecedented growth and expanse of the oil industry there has been an increasing dependency of our basic industries on, petroleum, until at present it has become essential to our national existence. To meet the ever increasing demand for petroleum and its products, we have explored, at one time or another, for their oil possibilities, practically all parts of the sedimentary rock area in the United States. Furthermore, detailed surface and, in many places, subsurface studies have been made of all the promising regions; over 640,000 jewells have 'been drilled for. oil since the beginning of the industry; $12,000,000,000 have been spent in this work; seventeen major fields exceeding 100,000 bbl. daily production and more than a thousand minor pools have been opened up, and 8,000,000,000 bbl. 'of oil have been produced, or an amount nearly equal to the estimated future reserves of the United States made in 1921.

Jan 1, 1925

OFFICERS AND DIRECTORS For the year ending February, 1932 PRESIDENT ROBERT E. TALLY JEROME, ARIZ. FREDERICK W. BRADLEY SAN FRANCISCO, CAL. WILLIAM H. BASSETT,P WATERBURY, CONN KARL EILERS NEW YORK N. Y.

Jan 1, 1929

By W. F. Hosford, E. W. Kelley

Deformation studies have been conducted at room temperature on single crystals of magnesium and magnesium alloys with thorium and with lithium. Single crystals oriented to suppress shear on the easily activated basal slip systems were deformed by plane-strain compression. Compression along the C axis was accommodated by {1011} banding. Compression perpendicular to the unconstrained c axis activated {1012} twinning, and, after virtually complete twinning, deformation continued by {1011) banding in the twinned material. Compression perpendicular to the constrained c axis was accommodated by the simultaneous operation of (1012) twinning against the constraint and (1011 ) banding. Although this orientation was favorable for {1010)(1210) prism and {1011}(1~10) pyramidal slip, these modes were not observed in pure magnesium or in Mg-0.5 pct Th. However, {10i0)(1~10) prism slip was observed in crystals of Mg-4 pct Li during compression perpendicular to the constrained c axis. Fracture in all materials occurred parallel to (1124) or {l~il) depending on the orientation and composition of the specimen. THE mechanical behavior of the hcp metals is strongly anisotropic. Although several slip systems have been reported the slip is cpmmonly in the directions of closest packing, the (1210),' and this does not produce strains parallel to the c axis. Hence the inherent anisotropy. The deformation mode most easily activated in magnesium at room temperature is (0001)(1210)- basal slip. Also {1010}(1~10) prism slip and {1011)(1210) pyramidal slip have been reported, primarily at elevated temperatures.2"4 However, at room temperature the shear stresses to activate the prism and pyramidal modes are roughly a hundredfold greater than that required for basal slip.'j4 Thus prism and pyramidal slip may be expected only under special conditions of loading. Strains normal to the basal plane can be produced by twinning, however. Many twinning modes have been reported for magnesium,' with (1012) twinning the most common and relatively easy to activate. Magnesium can deform by (1012) twinning when stressed along the c axis jn tension, but not in compression. In contrast, (1011) twinning is activated by compression along the c axis and not by tension. In addition to primary twinning, secondary twinning or slip can occur within the reoriented material of primary twins.' In general at least five independent shear systems must be active to bring about an arbitrary shape change such as that in the individual grains of a deforming polycrystalline material.' Because basal slip can_ provide only two independent shear systems and (1012) twinning can only accommodate an extension of the c axis, other deformation modes must be active in magnesium for an arbitrary shape change to occur. The purpose of this investigation has therefore been to study the various deformation modes in magnesium at room temperature, with special emphasis on those modes that are less easily activated. The effect of the alloying elements, thorium and lithium, has also been investigated. In polycrystalline aggregates, unambiguous identification of deformation modes is extremely difficult and the direct evaluation of the resolved shear stresses to activate them is not feasible. On the other hand, uni-axial tension and compression experiments on single crystals may not activate some of the- deformation modes because basal slip and/or {1012) twinning cannot be suppressed in most orientations. However, it should be possible to activate all possible deformation modes using oriented single crystals and plane-strain compression. Identification of active deformation systems and evaluation of the resolved shear stresses required to activate them should be facilitated. Wonsiewicz and Backofen have recently completed an investigation of the plasticity of pure magnesium crystals at various temperatures utilizing plane-strain compression and selected crystal orientations. This technique has also been used in the present work. The seven orientations selected for study are indicated in Table I. Plane-strain compression along the c axis (orientations A and B) should activate some deformation mode _other than basal, prism, or pyramidal slip, or (1012) twinning. In orientations C and D, prism or pyramidal slip would be expected to take place. When the compressive load is applied perpendicular to an unconstrained c axis (orientations E and F) the three slip modes should be suppressed but not (10i2) twinning. In orientation G, basal slip should occur.

Jan 1, 1969

By T. P. Floridis, J. H. Young

The need for close control of the phosphorus content of steels has led to numerous investigations on the equilibria of the dephosphorization reactions. Winkler and chipman1 have established the general conditions for effective dephosphorization of steel. They are high slag basicity, high oxygen potential, and low temperature. Other investigators have made additional contributions to the understanding of the dephosphorization process. The current status of the understanding of the dephosphorization of steel is concisely presented by Bodsworth2 and by Ward. The investigation reported in this communication was undertaken with the purpose of establishing the effect of additions of barium oxide and calcium fluoride on the dephosphorizing capacity of slags. Esin and Gel'd4 proposed that barium oxide, being more basic than calcium oxide, should cause an increase in dephosphorizing capacity when added to steelmaking slags, or when used as a substitute for calcium oxide. Derge5 has also proposed that in the future conventional slags might be replaced by BaO-Al2O3 slags. There is, however, no experimental evidence confirming the effect of barium oxide on the dephosphorizing capacity of slags. The effect of calcium fluoride on the dephosphorization of steel is not clearly understood. It is generally recognized that additions of calcium fluoride are beneficial. It is not clear, however, whether calcium fluoride affects the equilibrium of the dephosphorization reaction, or whether it simply causes an increase in the fluidity of the slag and, consequently, faster approach to equilibrium. The experimental procedure consisted in equilibrating synthetic molten slags with liquid copper at 1550°C under a gas stream containing argon, hydrogen, and water vapor. In all experiments the argon to hydrogen ratio was approximately 4:1, and the hydrogen to water ratio was 5.42:l. Molybdenum crucibles were used as containers for the slag and metal. Under the above-described conditions of temperature and composition of atmosphere, there was no observable attack of the crucibles by the metal, slag, or atmosphere. Copper was used instead of iron, because iron attacks molybdenum. The equilibration was made in a tubular furnace consisting of a recrystallized alumina tube. The alumina tube was heated by electrical resistance. A Pt-40 pct Rh wire winding was used for most runs. A silicon carbide tubular resistor was also used for some runs. Temperatures were measured with a Pt-Pt-Rh (10 pct Rh) thermocouple and kept constant within ±5°C. Equilibrium was approached from both sides, i.e., by adding the phosphorus either as oxide in the slag or as a phosphorus-rich alloy of phosphorus and copper. The holding time at the equilibrium temperature was 6 hr. At the end of each run the crucibles were rapidly cooled and removed from the furnace. The slag and metal were separated and analyzed. The experimental results are shown in Table I. The phosphorus content of the slag is expressed both as percent phosphorus pentoxide and as percent phosphorus. The basicity ratio is computed by dividing the number of moles of basic oxides-oxides of barium, calcium, magnesium, and sodium—by the number of moles of acidic oxides- oxides of aluminum, phosphorus, and silicon. Calcium fluoride is not included in the computation of the basicity ratio; i.e., calcium fluoride is assumed to be neither basic nor acidic. The distribution ratio of phosphorus—percentage of phosphorus in the slag divided by the percentage of phosphorus in the metal- is plotted in Fig. 1 against the basicity ratio. The results indicate that slags containing barium oxide have greater dephosphorizing capacity than slags containing calcium oxide. The high dephosphorizing capacity of slags containing sodium oxide and the low dephosphorizing capacity of magnesia-containing slags which already have been reported in the literature2 are confirmed by the results of this investigation. It appears that calcium fluoride has a beneficial effect on the distribution of phosphorus between slag and metal in acid slags only. Although the obtained distribution ratios between the phosphorus contents of slag and copper are not directly applicable to the dephosphorization of steel, they are sufficient for evaluating the effect of slag additions on the dephosphorizing capacity of slags in general. An increase in the ratio of distribution of phosphorus between slag and metal indicates lowering

Jan 1, 1968

By H. Guyod

The response of the Guard Electrode sonde (LL3) and the Laterolog (LL7) can be mathematically computed only for cases that do not represent realistic conditions. A resistance network analogue that simulates a number of typical—although idealized—formations was used instead to obtain, for both devices, a large number of resistivity logs and current distribution maps. From these data, charts were prepared for estimating true resistivities under a number of conditions. Some of these charts and current distribution maps are presented. INTRODUCTION Two main benefits are expected from a resistivity log: (1) obtaining geological information for mapping and other purposes, and (2) obtaining petrophysical data, based on true rock resistivity. The geological information can be derived from any resistivity curve having sufficient vertical detail, but true rock resistivities frequently are difficult to determine with desired accuracy because we do not have sufficient interpretation data. This is particularly true for the records given by the Laterolog tools. The object of this paper is to throw some light on the factors affecting the responses of these tools so that better resistivity data can be obtained from Laterologs. LATEROLOGS Laterolog measuring systems are of two types: the LL3 sonde, frequently called "Guard", and the LL7 sonde. Both measure the resistance between a single exploring electrode placed in the borehole and a faraway return electrode whose influence will be assumed here to be negligible. Although the principles of these tools have already been outlined,1-3 it is desirable to review them briefly in this article. LL3 Fig. 1, left side, represents a long cylindrical, vertical current electrode placed in a medium of uniform resistivity. The current leaving the center section of the electrode flows essentially along horizontal lines, delineating a surface having the shape of a biconcave lens. It is the elec- trical resistance offered to this particular group of current lines that is measured by the Guard tool. This is done in practice by having a long cylindrical electrode consisting of three sections physically and electrically separated by thin insulating washers, as shown in the center of the figure, and keeping the three sections at the same potential. It is obvious, for all practical purposes, that the current and potential distributions about this electrode are the same, as if we had a continuous electrode of same dimensions. Because the three sections are electrically separated, the resistance seen by the center section E can be independently measured. This section will be called the exploring electrbde, or E electrode. Its height generally is from a few inches to 1 ft. The outer sections are the guards G, which are several feet long. The combined length of the three sections is from 10 to 12 ft for the tools currently used in the petroleum industry. Let V denote the potential difference between E and the faraway return electrode, and I be the current flowing between these two electrodes. The resistance (Re) seen by the exploring electrode is VII, and the corresponding apparent resistivity is Ra = k(Re),............(1) where k is the tool calibration factor. The previous description establishes that the Guard tool uses that central portion of the sonde from which, in a uniform medium, the current follows essentially horizontal paths. When the formation being logged is fairly uniform, and when its resistivity is of the same order as

Jan 1, 1965

PRESIDENT AND DIRECTOR CHESTER A. FULTON NEW YORK, N. Y. PAST PRESIDENTS AND DIRECTORS EUCENE MCAULIFFE OMAHA, NEBR. C. H. MATHEWSON NEW HAVEN, CONN. TREASURER AND DIRECTOR ANDREW FLETCHER NEW, YORK, N. Y.

Jan 1, 1944

By R. B. Rosene, G. L. Foster, A. R. Hendrickson

he properties of some of the common fracturing oils, such as sand-falling rate, fluid loss and viscasity, are a function of the three major constituents of the oil. These are: asphaltic material, parafin waxes and a base oil. The base oil can be either high or low viscosity. Asphaltic material increases viscosity by thickening the oil, decreasing the rate of fall of sand through the oil. at temperatures up to 200" F. When large arnorrnts of parafin wax are present, much of the wax i.s not dissolved, but is present in the form of rnicroscopic crystals. 7'his, of course is limited to temperatures below the melting points of waxe.s. As a result, parafin waxes clo not function primarily as thickener.7, but rother as bullting materials. The functiori of wax, without asphaltic material, in a low viscosity base oil is uniquely unlike that of wax with asphalt coexistent in the oil. The resulting difierence in wax crystal size governs the sand-falling rate to a large extent. An ideal type of fracturing oil is one containing neither asphalt nor waxes. In such cases, the viscosity and resulting low sand-falling rate are apparently due to soluble resin- ous hydrocarbons, which are compatible with formation oils. INTRODUCTION Since the introduction of hydraulic fracturing as a method of stimulating production from oil and gas wells, a variety of fluids have been employed to open the fractures and carry the propping agent. Such fluids include gels, emulsions, and oils. In the latter category, the use of refined oils has increased tremendously, and it is probably safe to assume that such oils represent more than one-half of the total fluid used in fracturing. The general acceptance of refined oils for fracturing can be accounted for on the basis of their relatively low cost and general applicability. To minimize transportation costs, such refined oils are generally obtained within the local areas of operation. As a result there are several kinds of oil used in different areas, with a wide variation in the basic composition. These types may vary from a fair grade of lubricating stock to a highly viscous cut-back asphalt. or road oil. Originally, little attention was paid to the composition of the oils used for fracturing, and any oil which would carry sand was considered satisfactory. Recently, however, service companies and well operators have become more concerned with the type of oils used for fracturing. With this in mind, the present work was undertaken to evaluate and compare many widely used fracturing oils to determine which constituents were most desirable for fracturing purposes. Some of the important properties of fracturing fluids are sand-falling rate, viscosity, and fluid loss. Other properties, that are actually of no less importance, include flash point, pour point, emulsifying tendencies with formation brines, and compatability with the formation oils. This discussion has been limited, however, to the first mentioned properties in order to give some idea of the general composition of the refined oils, how they function, and why. PROPERTIES OF FRACTURING OILS The properties of fracturing oils are a function of the three major constituents of the oil. These may be designated as: (1) asphaltic material, (2) paraffin waxes and (3) a base oil, which may be of either high or low viscosity. The asphaltic material clas-

Jan 1, 1956

By John A. Church

IN May, 1878, I had the honor of presenting to the Institute, at the Chattanooga meeting, some observations upon the heat of the Comstock Lode, and since then the subject has attracted some attention and criticism, in the course of which, I have observed errors of apprehension which I beg leave to correct now. Mr. John Arthur Phillips discussed it before the Geological Society, his paper being printed in the Quarterly Journal for August, 1879.* His criticism is based upon that part of my paper in which I quote a number of analyses of the mine waters, to illustrate the fact that the heat does not come from the oxidation of pyrite. I pointed out that these waters contain only an insignificant proportion of sulphuric acid, and not enough to account for even one per cent. Of * A Contribution to the History of Mineral Veins. By J. Arthur Phillips, Esq., F.G.S. Quarterly Journal of the Geological Society for August, 1879.

Jan 1, 1880

By H. C. Rickaby

BY August 1944 Canada expects to be shipping 56 percent hematite ore from its new Steep Rock iron mine, via Port Arthur on Lake Superior, to the steelmaking centers in Canada and the United States. This is indeed welcome news to steel men, especially if they operate open hearth furnaces, as the Steep Rock ore is a high-grade lump and will be valuable as charge and feed ore. But better news is the fact that this first big producer of high-grade hematite ore in Canada, since the exhaustion of the Helen mine in the Michipicoten area north of Lake Superior in 1918, has a proved ore body of 16,757,000 long tons and a probable ore body of 14,000,000 long tons, thus giving an over-all total of 30,757,000 long tons and assuring production for a number of years to come.

Jan 1, 1943

By B. Lustman

IT has been known for a number of years that the addition of certain alkaline-earth and rare-earth metals to nickel-chromium base electric resistance alloys causes marked increase in their oxidation resistance as measured in an intermittent oxidation test similar to the ASTM—B 76-39 test. However, the mechanism whereby such additions confer protection is still unknown. On the basis of the experimental observation that the increase in life in intermittent tests of nickel-base alloys is proportional to the atomic radius of the added element, Hessen-bruchl has proposed that the added metal ions occupy holes in the oxide lattice which prevent diffusion of nickel ions in the oxide. Horn2 has postulated that the effect of such additions is to accelerate the rate of diffusion of chromium atoms in the metal and thus to favor the formation of Cr2O3 scales. Hickman and Gulbransen3 concluded from electron diffraction observation that the addition of the elements in question results in the formation of a barrier to the diffusion of nickel ions to the surface. In connection with some experiments conducted to develop a test for the resistance to oxidation of alloys in massive form under conditions of intermittent heating and cooling, some features of the oxidation of nickel-chromium base alloys were revealed which may serve to elucidate the mechanism of protection conferred by rare-earth and alkaline-earth elements. Specimens of cylindrical shape 0.360 in. diam x 0.37 in. long were placed in alumina thimbles and inserted into and withdrawn from a Globar-heated furnace operating at 2150°F at 7.5-min intervals. The weight of oxygen absorbed as well as the weight of oxide spalled were measured at intervals. With the particular experimental conditions used, the specimens in a 7.5-min cycle were at temperature for 2 min which corresponds to the heating time of the ASTM test. The weight changes of similar specimens under conditions of continuous heating in air at 2150°F were also measured. The specimens after oxidation were examined metal- lographically and samples of the spalled oxide collected for X-ray diffraction identification of the phases. The specimens used were from the same lot of material used by Hickman and Gulbransen3 and had the compositions shown in table 1. Included in table I are results of ASTM life tests on the materials in the form of wires. These materials, their composition and the ASTM life test data thereon were all supplied by F. E. Bash of the Driver-Harris Co. It may be noted that alloy 13246 of 80 pct nickel, 20 pct chromium nominal composition showed the shortest life in the ASTM test; alloy 12246 with the addition of small amounts of the elements zirconium, calcium, and aluminum, intermediate life; and alloy 12046 with the further addition of silicon, the longest life. In fig. 1 are shown the results of intermittent oxidation tests made on bulk specimens at 2150°F as well as continuous tests conducted at the same temperature. Duplicate tests were made on each specimen. The ordinate scale, inches of metal oxidized, was derived from the experimentally observed weight gain of oxygen by assuming the scale to be entirely Cr2O3. It may be noted that the metal-loss curves during intermittent oxidation show a constant or continuously increasing rate of weight

Jan 1, 1951

By Y. L. Yao

A scale based on existing data for the mutual solid solubilities of metals in binary systems has been compiled. This scale is useful for estimating the relative magnitude of two solubilities, provided that these two metals do not form a continuous series of solid solutions. In his classic work on the theory of metallic solid solutions, Hume-Rothery proposed that, other things being equal, a metal of lower valency should be regarded as more likely to dissolve one of higher valency than vice versa. He called this the "relative valency effect". Later he found that the application of this general principle was limited to the three univalent metals: copper, silver, and gold. In dealing with alloys of these metals with metals of higher valency, Hume-Rothery stated, it is usually found that the solid solution of the univalent metal is of the greater extent.&apos; The question of whether there is a systematic trend in comparing the relative magnitude of mutual solubilities, if valency is not considered a criterion, naturally arises. The present paper proposes a "mutual solid solubility" scale on an empirical basis. The order of its arrangement is determined by the relative magnitude of mutual solid solubilities. Some applications of and inferences from this scale are given. ORIGIN AND SCOPE OF THE SCALE An extensive survey of over 400 binary phase diagrams shows that, with certain exceptions and within certain limitations, metals can be arranged in the following order: Na Zn Cd Ga Bi Ge Sb As Hg Sn Si Mg Li Ba In Tl Pb Al Ca Be Mn Cr Re W Mo Cu V Ta Fe Ru Cb Co Ti Hf Ni Os Zr Ir Pt Au U Rh Ce Pd Ag Th so that a metal higher on the scale tends to have a higher solubility in a metal lower on the scale than vice versa. some experimental solubility data are given in Table I. These data, unless otherwise specified, are taken from Hansen and Anderko.6 Throughout this paper, the term "solubility of A in B" is taken to mean the maximum solid solubility of A in B in atomic percent, while the maximum solid solubility of B in A in atomic percent is called "reciprocal solubility". The exceptions found in the above-mentioned survey are: Al-Ag system, 20.34 at. pct Al in Ag, 23.8 Ag in Al; Mg-Pb system, 5.9 Mg in Pb, 7.75 Pb in Mg; As-Sn system, vanishingly small amount of As in Sn, a large As primary solid solution; Cd-Hg system, Cd in Hg <Hg in Cd; Mg-T1 system, 5(?) Mg in ßT1, 15.4 T1 in Mg; W-Ti system, -21 W in ßTi, -25 Ti in W; Zr-Ag system, probably small amount of Zr in Ag, 20 Ag in ßZr.7 Considering the large number of examples, the exceptions are few. It is remarkable that metals may be so arranged without considering other factors such as size, crystal structure, electronic structure, and so forth. A limitation to the use of the scale is the fact that it cannot be tested for two metals forming a continuous series of solid solutions. It is interesting to point out that when the continuous solid solutions have a miscibility gap the critical composition is

Jan 1, 1961