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By H. K. Work, H. T. Clark

The instrument for the rapid determination of carbon in steel, described in this paper, was developed originally to facilitate the operation of the pilot-sized open-hearth furnace in the Jones & Laughlin Research and Eevelopment Laboratory. In this small furnace, with its shallow bath, the drop in carbon is accelerated, and a rapid, reliable test for carbon content is indispensable. This problem becomes rather acute when it is desired to finish heats at a carbon content higher than can be estimated with any degree of accuracy by the fracture test. Several independent methods for determining carbon were investigated, therefore, and it was found that a relatively simple magnetic device could be made to give reproducible results. A laboratory instrument was designed and set up for the use of the furnace operators. It was tested exhaustively in the laboratory and was used with considerable success for following the carbon content in the furnace bath. As soon as sufficient data had been compiled to indicate that the instrument might have a wider application, a more rugged model was constructed and placed in the mill to be tested on commercial heats. Finally, about a year ago, instruments were furnished to the plant open-hearth shops, and these have been in use since that time. As a matter of convenience, the instrument has been named the "Carbanalyzer," and will be referred to by this designation in the following pages. $ Eaklier Investigations While by far the greatest number of magnetic investigations in which the carbon content of ferromagnetic materials was considered have had to do with the evaluation of the magnetic properties of steels of known

Jan 1, 1940

By Jim D. Mote, Eugenia M. Howard, Willis L. Barmore, John E. Dorn

The effect of stress and temperature on the creep rate of Ag-33 at. pct A1 and Ag-33 at. pct Al-1 at. pct Zn for prismatic slip was determined over a range of temperatures from 440º to 700°K. The alloys exhibited a brief initial inverted transient creep over which the creep rate increased slightly to a steady-state value which depended only on the stress and temperature, regardless of the previous strain history. The steady-state creep rates were found to be given by: where the activation energy is independent of the stress and strain and agrees fairly well with that estimated for diffusion. The observed creep behavior was shown to be in qualitative agreement with a model based on the stress-induced local disordering in the vicinity of a dislocation. OVER the past fifteen years, considerable progress has been made in correlating the experimen-entally observed plastic behavior of pure metals over each temperature range with one or more of a series of theoretical strain-rate controlling dislocation mechanisms. Despite the current interest in the plastic behavior of intermediate phases and inter metallic compounds, however, very little has been done in identifying the operative dislocation mechanisms in these materials. It is anticipated that the plastic behavior of intermediate phases can be rationalized in terms of the same dislocation mechanisms that are appropriate to pure metals and a solid solutions, provided the additional complexities arising from crystal structure, bonding, long-range order, short-range order, and defect lattices are taken into account. As part of a more extensive investigation on the plastic behavior of intermediate phases, Mote, Tanaka, and Dorn1 recently reported on the effect of temperature on the yield strength for prismatic slip in the hexagonal Ag-33 at. pct A1 intermediate phase as recorded in Fig. 1: Over Region I the deformation was observed to take place as a result of the thermally-activated Peierls mechanism, and over Region II the athermal disordering mechanism applied. The experimental data at that time, however, were not sufficiently extensive to identify the thermally activated mechanisms operative over Region III. It is the purpose of this investigation to attempt to identify the mechanisms that are operative over this high-temperature region. It will be shown that the same mechanism operates all over Region Ill, although the activation energy for this mechanism is in good agreement with that for diffusion, the process cannot be attributed either to the motion of jogged screw dislocations or the climb of edge dislocations. The results, however, are in good qualitative agreement with stress-induced disordering localized at dislocations. EXPERIMENTAL PROCEDURE The alloys studied in this investigation were prepared from silver, aluminum, and zinc (each of purity greater than 99.995 pet) by induction melting under an argon atmosphere and chill casting in a copper mold. Rectangular bar single crystal specimens (1/4 by 1/8 in. in cross-sect ion) of Ag-33 at. pct Al were grown in vacuum by a modified Bridgman technique. Similar Ag-33 at. pct Zn specimens were produced by an identical technique employing an argon atmosphere. The specimens were so oriented that the angle 90-Xo between the tensile axis and the normal to the prismatic plane and the angle A, between the tensile axis and the slip direction were 45 ± 1 deg. The effect of a change in temperature on the creep rate and a change in stress on the creep rate were determined over the temperature range

Jan 1, 1963

By J. C. Melrose, W. R. Foster, J. G. Savins, E. R. Parish

Many differences can be imagined between gas-oil flow in which the gas is supplied at the face of the core and gas-oil flow in which the flowing gas was originally dissolved in the oil. If capillary pressure characteristics and flow requirements control gas saturation distribution, the gas would be expected to be located at preferred sites within the porous medium as determined by pore sizes. On the other hand, during solution gas drive the gas first appears as bubbles through a nuclea-tion process. Nothing in self-nucleation theory specifies at which sites the first bubbles should be formed. In all probability they will be randomly distributed throughout the porous medium. Furthermore, it is not at all certain that even at low rates of production the gas will redistribute itself after nucleation to the channels normally occupied by gas in simple gas flow. Stewart, et at, have shown that at least for some limestone samples, oil recoveries could not be predicted for all rates of production using any one set of relative gas and oil permeabilities. An important factor in controlling recoveries during solution gas drive was the rate of bubble formation, higher rates giving higher recoveries. Stewart, et al, attributed the increase in recovery to a better distribution of the gas phase in heterogeneous limestone samples than is obtained by simple external gas drive. Differences in recovery from these causes were not reported for sandstone cores. In the experiments to be reported here, oil recovery, pressure and producing GOR history were measured during solution gas drive for a 5-ft sandstone core. The results were compared with predictions from the Muskat method for computing solution gas-drive behavior using external gas-drive relative permeability. The effects of changing the rate of production and oil viscosity were studied. At high laboratory rates of average pressure decline, two observations were made which would not have been predicted by Muskat's depletion theory: (1) oil recovery increased with increasing rate of production for a given viscosity oil, and (2) oil recovery increased with increasing oil viscosity for a given high rate of production. Both of these observations are explained as consequences of diffusion control of gas saturations superimposed on the normal gas-oil flow requirements, Fur- thermore, discontinuous gas phase flow appears to be significant during solution gas drive. The laboratory tests were performed at rates of average pressure decline many times greater than the maximum possible rate of average pressure decline in an actual oil field. It is, therefore, not possible to draw any direct conclusions regarding the effect of rate on recovery for the solution gas-drive mechanism under actual field conditions. However, at the lower laboratory rates, recoveries were nearly independent of rate and could be predicted by the Muskat method, using external gas-drive relative permeability data. These results suggest that at normal oilfield rates the effect of rate on recovery for the solution gas-drive mechanism is negligible. EXPERIMENTAL PROCEDURES The core material for the pressure depletion studies was Bandera sandstone from an outcrop in the Mid-Continent. This sandstone was selected because of its low permeability (about 10 md), which would permit the development of substantial pressure gradients in the corn at moderate flow rates. The core was 5-ft long and 2-in. in diameter. Its properties are listed in Table 1. Relative gas-to-oil permeability ratios were measured by an external gas-drive method2. The results are shown for a short 2-in. core and for the 5-ft core in Fig. 8. Oils used in the pressure depletion experiments were kerosene and a highly refined white oil (standard white oil No. 3) with gas-free viscosities of 1.8 and 25 cp, respectively. The gas was a naturally occurring methane from Gough field, Inglewood, Calif. The oil viscosities, gas solubilities and formation volume factors are plotted as functions of pressure at 75°F in Figs. 1 and 2. Methane viscosities and compressibilities were obtained from the literature"'. A core mounting was required which could withstand up to 2,500 psi internal pressure. This was obtained by first encasing the core completely in a plastic resin (Scotch Cast, manufactured by Minnesota Mining & Manufacturing Co.) The plastic covered core was then inserted into a steel pipe equipped with screw caps so that the plastic coating could be pressured from

By R. W. Fountain, J. Chipman

THE solubility of nitrogen in iron and steel has been of considerable interest due to the role of nitrogen in strain-aging and in quench-aging. It is generally considered that quench-aging is the result of precipitation of carbide and nitride particles from supersaturated solid solution, while strain-aging results from the segregation of carbon and nitrogen atoms to dislocations.1-9 The rate of strain-aging is controlled primarily by the amount of carbon and nitrogen in solution and the temperature. In experiments on strain-aging of pure iron with only carbon or nitrogen as impurities, Fast" has shown that even after 40 hr at 50°C carbon did not give any strain-aging while

Jan 1, 1959

By Arnulf Muan, Klaus Schwerdtfeger, L. S. Darken

The equilibrium ratios CO/CO, of. a gas pharse coexislitrg with selected oxide phase assemblages of the system "FeO"-MnO-SiO2 and metallic iron have been determined at 1150°C. The data obtained are combined wilh the thermodynamic data on fayalite (Fe2SiOi) and "FeO"-MnO solid solutions to derive the actiuity-coiHpQsiUon relations for the various oxide components of the olivine (Fe2SiO4-,lIn2Si04) and pyroxenoid (standard free energies of formation of ferrosilile (FeSiO,), tephroite , and rhodonite from their oxides have been evaluated. In the Appendicc~s by Darken and Schivcerdtjeger the ideal solution law for solid deri oed. THE quaternary system Fe-Mn-Si-0 is of interest in many important phases of iron- and steelmaking. For instance, reduction in the blast furnace of ores containing Fe-Mn silicates, deoxidation of liquid steel with Mn-Si alloys, formation and subsequent alterations of oxide inclusions in steels, and the oxidation of manganese- and silicon-containing steels during processing are all governed largely by the thermodynamic relations existing in the system Fe-Mn-Si-O. Although the equilibria between liquid iron and Fe-Mn silicates have been studied in detail previously,' experimental data are lacking for equilibria among the solid phases. The present paper provides such data for a selected temperature, 1150°C. I) PREVIOUS WORK The general feature of subsolidus phase relations in the system iron oxide-manganese oxide-silica under strongly reducing conditions is known.' Fig. 1 represents an isothermal section at 1150°C. The phases present, in addition to silica, are three solid-solution series, viz.. the oxide solid-solution series "Fe0"-MnO (manganowiistite), the orthosilicate solid-solution series Fe2SiO4-Mn2SiO4 (olivine), and the metasilicate solid-solution series FeSi03-MnSi03 (pyroxenoid). The "FeO"-MnO solid solution is continuous between the two end members wustite and manganositeV3 as is the orthosilicate series between the two end members Fe2SiO4 and Mn2 SiO4. 4 The metasilicate solid solution, on the other hand, extends only part way from the MnSi0.l end member toward FeSiO because the latter end member is unstable relative to the phase assemblage fayalite + silica. The letters a through m in Fig. 1 identify end members of the individual solid phases dealt with [for instance, c designates fayalite (FeZSiO4) in equilibrium with wustite, e designates fayalite in equilibrium with silica, and so forth]. In addition to the phase relations there are some thermodynamic data available for the end members of the silicate solid solutions and for the "FeO" -MnO solid solution. The free energy of formation of fayalite (Fe2Si04) from its oxide components has been studied by several investigators. Unfortunately, the data obtained show considerable discrepancies. According to recent tabulations by Kelley, the change in standard free energy Affn for the reaction

Jan 1, 1967

By Gerhard Derge

The rapidity of oxygen steelmaking has created renewed interesl in the mechanisms and kinetics of the various processes involved. These studies can now be approached with increased confidence because of the more adequate thermodynamics, physical chernislry, and relevant engineering infornzation available. These combine to offer promise of useful control and automation if the details of each specific problem can be sufficiently well-defined. The hot filament microscope provides new insig-hi into many of these problems by direct observation at temperature, allowing the appraisal of the relative importance of thermal gradients, convection, and intermediate phases. All of these have a direct bearing on the overall rates and control of most pyrometallurgical processes. It is one of the special privileges of the Howe Lecturer to become better acquainted with this distinguished man. All of us interested in the metallurgy of iron and steel have developed some sense of his widespread influence by the annual reference to his work in these Memorial Lectures. Each lecturer since 1923 has been able to identify his personal specialty with the broad interests of Professor Howe. This has become even more rewarding with the background information from Professor Gensamer's monograph, "Henry Marion Howe's Contributions to Metallurgy, which brings out his happy combination of intellectual and professional activities. Beyond this, I found my personal bond with Professor Howe in his book on The Metallurgy of Sleel first published in 1891.' After a detailed discussion of the dephosphorizing action of slags, he relates the mineral species identified in the frozen sample to the chemistry of the fused slag with the question, "Is it not most philosophic to hold that these independent entities were wholly integrated in the initial magma; that their presence in it was wholly

Jan 1, 1968

By P. M. Robinson, J. S. LI. Leach

The heats of solution oj' indiurrr, tin, lend, nrzd tellurium have been calculated from the measured heat effects when mechanical mixtres of indium and telLuium tin and tellurium, and lead and tellurium were added to liquid bismuth. The results are in good agreement xith publislzed values.s for the separate sollction of each eleltzent in bismuth. The heats oj solution of cadmium and tellurium calculated from the rneasuved heat effects on adding trechanical mixtures of these elements do not ugree zc,itl the published values jbv the separate solution of each element. It is shown that at 623°K Ile interaction between cadmium and tellurium dissolved in liquid bismuth is strong enough to led lo preciPitation of solid CdTc. The heats oj- jor-mation of CdTe at 273" nd 623°K (1)-c crilculated fi-or the measured heat ejlfecls. The calcnlaled az'erage deviation from the Kopp-l\'ez?,zunrz rule fov solid CdTe is less than 0.06 cat per g-atom- C over this lertzperalure range. Tlze importance 0.f these oDserl.ations to the determination of heals of formation hy metal solution calorimetry is considered. LIQUID metal solution calorimetry is a convenient method for determining the heats of formation of solid compounds. In this technique the heat of formation is the difference between the measured heat effects on dissolution of the compounds and of mechanical mixtures of the components in the liquid metal.' The heat of solution of the mechanical mixture may be calculated from the measured heat effect. At infinite dilution of the solutes, this heat of solution is equal to the sum of the heats of solution of the separate components. If the heat of solution of one of the components is known, the value for the other can be derived; if both are known, they may be used to check the accuracy of the calorimetric technique. The heats of formation of the tellurides of cadmium, indium, tin, and lead have recently been measured by metal solution alorimetr. The heats of solution of indium, tin, lead, and tellurium at infinite dilution in liquid bismuth at 623"K, calculated from the measured heat effects on solution of the mechanical mixtures, are in good agreement with the published values. The heats of solution of cadmium and of tellurium calculated from the measured heat effect on solution in bismuth at 623'K of mechanical mixtures of cadmium and tellurium, however, do not agree with values estimated from the literature. 1) EXPERIMENTAL PROCEDURE AND RESULTS The Heats of Solution of Indium, Tin, Lead, and Tellurium in Bismuth. The heat effects were measured when mechanical mixtures corresponding to the compounds In,Te, InTe, In2Te3, In2Te5, SnTe, and PbTe were dissolved in bismuth. The calorimetric procedure and the method of calculation have been described elsewhere.' The heats of solution of the mechanical mixtures were obtained by subtracting the change in heat content per gram-atom of the sample between the addition temperature (273°K) and the bath temperature (623"K), (H623°K - H273°K)S, from the measured heat effects. The calorimeter was calibrated with pure bismuth. The reported values of the measured heat effects are based on (HGoK - ^273oK)Bi = 4.96 kcal per g-atom.3 The measured heat effects are found to be linear functions of the solute concentrations of the bath in the dilute solution range. The values, extrapolated to infinite dilution, are listed in Table I, together with the heats of solution of the mechanical mixtures calculated using the published values of (H 623°K - H273°k)s for indium, tin, lead,3 and tellrium. All the error limits quoted in this work represent the spread of values obtained. The heats of solution in liquid bismuth at 623°K of mechanical mixtures of indium and tellurium in four different proportions were determined. Values of the heats of solution of the two components were then calculated from the resulting four simultaneous equations: The heats of solution at infinite dilution of tin and lead in liquid bismuth at 623°K were calculated from the heats of solution of the mechanical mixtures of tin and tellurium and of lead and tellurium using the heat of solution of tellurium calculated above. These values of the heats of solution are listed in Table I1 together with some published values for comparison.

Jan 1, 1967

By J. E. Coyne, L. E. Tanner, J. E. Boyd

In recent investigations of the isothermal transformations of the retained 0 phase in a titanium alloy having 13 pct V, 11 pct Cr, and 3 to 4 pct Al, there have been indications that the w transition phase is the initial decomposition product at temperatures below about 950°C (510 c).' This metastable phase, found in a number of titanium-base alloys rich in stabilizing elements and known to have an adverse effect on their ductility and toughness, is not easily observed by the usual experimental techniques. Since wis coherent with the /3 matrix,495 distinct interphase boundaries are not revealed metallographically. However, in some cases, an etching effect (i-e., a "mottled" /3 surface) poorly resolved by light microscopy has been found to correspond with the presence of w.6 X-ray diffraction examination has generally been the most suc- cessful means for identifying this phase and crys-tallographic determinations have been made.4'5 Dynamic elastic modulus7 and electrical resistivity measurementse have also aided in the identification of w. In the current study, the electron microscope was utilized to examine microstructures in aged Ti-13V-11Cr-3A1 that were unresolvable by light microscopy techniques. Using negative parlodion replicas (shadowed with chromium at 27 1/2 deg) examination was made of various transformation

Jan 1, 1962

By W. Rostoker, S. A. Spachner

FOLLOWING the discovery of the w transition phase in certain titanium-chromium alloys by Frost, Parris, Doig, and Schwartz, much interest has centered on the alloys in which this phase is found and its mode of precipitation. The w phase has been found in alloys of Ti-Cr, Ti-Fe, Ti-Mn, Ti-MO,2 and Ti-v.3 The temperature-time-transformation characteristics have, as yet, not been determined for most of these. In this study, such transformation characteristics have been investigated for two heat-treatable titanium alloys known to exhibit transition phase phenomena. The alloys chosen, Ti-8Cr and Ti-13M0, are representative of two classes of binary equilibrium systems. In the

Jan 1, 1959

By Gilbert L. Eggert

The effects of reactor irradiation on age hardening in a Cu-2 wt pct Be alloy have been investigated in two neutron-energy ranges. During some of the irradiations, specimens were exposed to high-energy fission neutrons which passed through a boron-10 shield; during other bombardments, the boron-10 was omitted and specimens were irradiated in a reactor thermal column, or the fuel configuration was modified to increase the thermal-neutron flux at a location in the core. Differences in length, X-ray diffraction angle, and hardness indicated that low-energy neutron irradiation made a small contribution to changes in the measured properties. The influence of defects generated by knock-om with less than the Brinkman critical energy or by prompt (n,y) recoil is suggested as the cause of this effect. EXPERIMENTS designed to test the effects of reactor irradiation on the properties of age-hardening alloys have to the present time employed fluxes un-differentiated according to neutron energy. Billing-ton and Siegell in 1950 were the first to perform such an experiment and to compare the results with those obtained by thermal aging. These authors concluded that precipitation in a Cu-2 wt pct Be alloy was not enhanced by the radiation. However, 4 years later, Murray and Taylor,2 working with specimens of the same Cu-2 wt pct Be alloy, reported that an increase in density, hardness, and resistivity which followed reactor irradiation resembled changes associated with thermal aging at about 100°C. (It should be noted that these authors reported that higher aging temperatures caused a decrease in resistivity.) cupp3 reported hardness results similar to those of Murray and Taylor. Koppenaal4 showed that irradiation-enhanced precipitation and irradiation defect hardening were not simply additive but that they acted separately in an irradiated alloy. Kernohan et a1.,5 working with Ni-Be, offered evidence that beryllium was removed from solid solution by reactor irradiation and suggested that the mechanism was one of increased diffusion through the use of vacancies in the structure. piercy6 also found that more precipitate particles were formed by fission-neutron irradiation of a Cu-Co alloy which contained a small amount of particles before irradiation. He proposed that the additional particles were caused by an appreciable amount of diffusion during the final cooling of displacement spikes. The retrogression of extant precipitate particles found by Murray and Taylor2 and Boltax7 as well as piercy6 indicated that nuclei were dissolved within a high-energy spike region and, upon resolidification of the perturbed volume, new nuclei precipitate and grow by enhanced diffusion. Bleiberg et al.' and Konobeevski et al.' explained phase changes obtained by irradiating fissionable alloys in terms of retrogression and re-precipitation in regions of high-energy spikes. Parsons and Balluffi10 used electron microscopy to verify that crystallization did indeed occur in displacement spikes which were formed in amorphous germanium by fast-neutron irradiation. The concept that low-energy neutron irradiation might cause structure-sensitive property changes in semiconductors by atomic recoil associated with the (n, y) reaction was first proposed by Schweinler" and walker." This thesis was tested by Cleland and crawford" and found to be valid. Coltman et al.14 exposed a variety of pure metals to thermal-neutron irradiation at cryogenic temperatures and attributed the resulting resistivity changes to the action of defects created by (n, y) recoil. The present work was undertaken to extend the concepts of Schweinler," walker," and Coltman et al.I4 to the case of an age-hardening alloy and to determine whether or not the action of defects produced by thermal-neutron irradiation would en-hance age hardening. EXPERIMENTAL PROCEDURE Omeea West Reactor Irradiations.* Thermal-

Jan 1, 1965

By E. B. Olds, B. P. Burt

The mines of the Consolidated Gopper-mines Corporation are at Kimberly, in the Robinson mining district, White Pine County, Nevada. The blanket-like ore body is a disseminated copper deposit occurring in monzonite porphyry and, in general, is thoroughly fractured, altered, and soft. Contained in the porphyry ores of the extreme westerly end of the ore body are pendants of hard garnetized limestone. A younger monzonite porphyry underlies the ore-bearing porphyry, which in turn rests on limestone and shale. Block caving is the standard method of mining. Because of the undulating top and bottom contours of the ore body, the main haulage level was selected and driven at an elevation calculated to be the most economic depth below the major tonnage sections of ore. Fig. I shows a general section of the Emma Nevada ore body taken through its long axis, which lies roughly in an east-west direction. Mine openings in either type of porphyry require heavy timbering and constant maintenance and repair, particularly in horizons at or near the ore body contact. Where the ore lies close to the haulage level, slusher hoists and scrapers are used to transport horizontally the ore to the main haulage drift (Fig. 2). For the extraction of high-lying ores, a system of branch raises is used; and the ore is mined by gravity. Slushing methods are used also on the high-lying ore-body fringes. Slusher drifts are often driven from the fringe branch raises that have already served their purpose, in order to minimize the cost of the preparatory work in mining the thinner portions of the ore body (Figs. 3 and 4). When a block of ore is developed and undercut, it is economical to mine it as rapidly as the ore will cave efficiently; and this procedure often presents safety problems because of men with equipment working in a relatively congested area. The single-track main haulage drift is about 11/2 miles long, and lateral haulage drifts are driven under the ore body at intervals determined by the height of the ore body above the haulage level. In order to minimize repair and maintenance, the

Jan 1, 1949

By Craig R. Barreft, Oleg D. Sherby

The steady-state creep characteristics of pure polycrystalline copper were studied in the temperature range 400" to 950°C and in the stress range 400 to 7000 psi. Tests were conducted in dry deoxidized hydrogen and all specimens exhibited high ductility before fracture. Two activation energies for creep were established as a function of temperature. Above about T/T, = 0.65, the activation energy for creep was 48,000 cal per mole whereas between 0.5 and 0.65 T, it was 28,000 cal per mole. The observed temperature dependence of the activation energy for creep follows the same trend as exhibited by the self-diffusion coefficient of copper in copper single crystals and silver in silver single crystals. It is therefore believed that the rate-cmtrolling mechanism in creep of copper in the stress and temperature range studied is diffusion-dependent and is probably associated with a dislocation-climb process. The low activation-energy region is attributed to enhanced volume difFusion from the presence of dislocations which act as short-circuit paths for diffusion. THERE is extensive experimental evidence1,2 that the activation energy for creep, Q,, for pure poly-crystalline metals tested at temperatures above one half the absolute melting temperature (0.5 Tm) is a constant and equal to the activation energy for volume self-diffusion, Qsd This equality is generally interpreted as meaning that creep in this temperature range is controlled by a dislocation-climb process. The existence of high-temperature creep activation energies not equal to the respective self-diffusion values has been suggested both theoretically3"5 and experimentally.6-8 Two examples of apparent nonequality between Q, and Qsd have been reported for the cases of silver7 and copper,' where activation energies for creep much lower than those for self-diffusion persist to rela- tively high temperatures (up to 0.6 T,). These observations suggest that dislocation climb may not be the only important process in the high-temperature deformation of these metals. That dislocation climb does indeed occur relatively slowly in these two metals due to their low stacking-fault energy has been suggested by many investigators.9-10 Although the creep behavior of copper has been studied extensively at low temperatures, the high-temperature activation energy for creep is not well-defined. The data of Feltham and Meakin8 indicated that Q, is temperature-dependent above one half the melting temperature, equaling a value of -30,000 cal per mole at temperatures up to 550°C and increasing to a value of -49,000 cal per mole at 700°C. No data has been reported above 700°C. The value of 49,000 cal per mole is very near the value of Qsd for copper reported by Kuper et al." as 47,100 cal per mole. In view of the lack of high-temperature creep data and the apparent temperature dependence of Q, for copper the present investigation was undertaken to determine the value of Q, over the temperature range of 400" to 950°C. It was hoped that such a study would clearly document the temperature dependence of Q, and yield significant information as to the nature of the rate-controlling creep mechanisms. MATERIALS AND PROCEDURES The material used in this investigation was high-purity OFHC copper. After rolling and recrystal-lization treatments spectrographic and chemical analyses showed only 0.0008 pct Ag, 0.0002 pctCa, 0.0002 pct H2, and 0.002 pct O2 as trace impurities indicating a purity of greater then 99.995 pct. Specimens were machined from cold-rolled sheet and the gage sections polished with 2/0 emery paper prior to annealing treatments. Annealing was done in both vacuum and dry deoxidized hydrogen atmospheres. No variation in creep strength was found as a result of the different annealing atmospheres. The final annealing temperature was either 700°, 800°, or 1000°C depending on the temperature range to be studied. These treatments resulted in average grain diameters of 0.03, 0.4, and 1.0 mm, respectively. The precise mechanical-thermal history of these

Jan 1, 1964

By Murray Kaufman

Using en; 41 for a base alloy, 15 modifications were made in sheet form. The elements Al, Ti, C, Mo, Co, and Cb were varied. The effects on the phases formed and their temperature dependence, the aging characteristics, tensile and stress-rup- ture properties, and weld cracking were determined. The A1-Ti content and balance is the most important factor influencing the major sCrengthening phases [Ni,Ti and Ni,(Al, Ti)] and, consequently, mechanical properties. THE mechanical properties, fabricating and joining characteristics, dimensional stability, and so forth, of alloys containing secondary phases are largely determined by the phases present, their distribution, and their temperature dependence. The phases in the basic ternary and quaternary Ni-Cr-Al-Ti combina- tions have been investigated thoroughly.'* The phase behavior of many commercial nickel-base alloys has been determined also. In some cases, for example U500, 5 the effect on mechanical properties has been found. However, little systematic work has been done to clarify the action of each of the important alloying elements in controlling the phases formed in complex commercial alloys and their behavior. The effect of molybdenum on the carbides formed in M252 was investigated by Beattie and verSnyder.6 Application of the results provided by that work

Jan 1, 1963

By M. R. Tek, M. L. Katz

The flow of fluids in stratified porous systems, in which adjacent layers of the system are in communication over part or all of their common interface, in many instances involves crossflow between layers. A theoretical study has been made of the unsteady-state flow of slightly compressible fluids during depletion of bounded stratified porous systems. Consideration has been restricted to single-phase flow, with negligible capillary and gravity effects. Analytical expressions have been derived for pressure distribution and for (luxes at the producing face in two-layer systems with complete fluid communication between layers. These expressions occur in the form of double Fourier and Fourier-Bessel series. The method of extending the solution to any number of layers is demonstrated by deriving the equation for pressure distribution in a three-layer system. On the basis of the exact results for two-layer systems, certain generalizations regarding the behavior of stratified systems in general are presented. The performance of stratified systems, in terms of cumulative flux as a function of time, is shown to lie at all times between bounds established from single-layer theory. The upper bound is given by treating the system as a single layer with arithmetic average physical properties. The corresponding lower bound is the summation of the fluxes from each layer as treated individually. Variation in performance of stratified systems between the upper and lower bounds is determined by the extent to which crossflow occurs in the system. The principal parameters affecting the amount of crossflow are the vertical permeability of the system, the ratio of system thickness to "radius of drainage" and, for radial systems, the ratio of system thickness to interior radius. At very early times, the system performance is near the lower bound. As time and the radius of drainage increase, the per- formance tends toward the upper bound. INTRODUCTION One of the principal problems confronting the reservoir engineer today is the incorporation of the effect of reservoir heterogeneity into predictions of reservoir performance. The first part of this problem is the characterization of the actual reservoir heterogeneity in a mathematically useful manner.1, 2 It is then necessary to calculate the effect of this heterogeneity on the system performance. It is frequently possible to estimate this effect by comparison with the known behavior of an idealized system. One such idealized system is the stratified or "layer-cake" model. Many studies have been made of the behavior of stratified systems, from both a theoretical and experimental standpoint. The great majority of the theoretical studies have been concerned with systems of separated layers, with no fluid crossflow. Among the more noteworthy of such theoretical papers is that recently published by Lefkovits, et al,3 in which a comprehensive analysis was presented for the behavior of bounded stratified systems which are unconnected except at the wellbore. Three recent references have dealt with stratified systems including the effect of crossflow. Jacquard4 has presented mathematical derivations pertaining to depletion of two layer systems producing at constant rate. A doctoral dissertation by Katz5 contains analytical solutions and tables of results for pressure distribution and fluid flux during constant-terminal-pressure depletion of two-layer and three-layer systems with crossflow, together with tables of eigenvalues necessary in the computations. The dissertation also presents results from experimental studies of stratified systems using a heat-transfer analog model. This paper is largely based on the material in this dissertation. A third paper has been presented by Russell and Prats6 since completion of the work resented herein, containing mathematical derivations for and discussion of the behavior

By A. G. Jordan, W. Jeitschko, Paul A. Beck

The occurrence qf the V phase structure /Zr,Co,Ge, type) in ternary syste7ns (titanium, zivconium, niobium, lanta1urn) -(nickel, cobalt, iron)-(silicon, germanium) was incestigated. Nine V silicides and four V gertrlanides were found and their lattice constants are reporled. The lattice constants of twenty-one preri-ously identified E phases (TiNiSi type) are given. The average atomic volumes of these phases are discussed in relation to similar binary phases. ThE occurrence of a phase Ti4Ni4Si7 was first reported by Westbrook. DiCerbo, and peat' who gave it the name "V phase". They also reported the existence of an E phase TiNiSi. Subsequently a systematic study was undertaken in this laboratory to explore the occurrence of E' and V phases3 in related ternary systems. In the meantime the crystal structure of the E phase TiNiSi 4 and of the V phase Zr4CO4Ge 75,6 was determined. In the present paper the details of the V phase investigation and the lattice constants of the E and V phases are presented. V PHASES Alloy specimens of approximately 10 to 15 g were prepared by arc melting under argon (99.996 pct Ar) atmosphere. The starting materials were all of purity higher than 99.9 pct, with the exception of cobalt. which contained 0.14 pct Fe as the only major impurity. The weight losses were in all cases less than 2 pct, in most cases less than 1 pct. The samples were encapsulated in fused silica tubes with sufficient argon to yield about 1 atm pressure at the annealing temperature. After the homogenization anneal. Table I. the specimens were water-quenched. A representative portion of each specimen was then examined metallographically (etchant: 20 pct HNO,. 10 pct HF. 25 pct glycerine, 45 pct H20). Only minor amounts of second- and third-phase particles were observed in the specimens listed in Table I, with the exception of alloys Zr4Fe4Si7 and Ta,Fe,Si,. which contained an estimated 10 pct by volume of foreign phases. X-ray powder photographs were taken with a Seeman-Bohlin type focusing camera and Fe-KO radiation. Of the thirty possible combinations of elements in the ternary systems (titanium, zirconium. vanadium. niobium. tantalum)-(iron. cobalt, nickel)-(silicon. germanium) thirteen V phases could be identified. In the remaining seventeen ternary systems and also in the systems Cr-Ni-Si and (M0.W)-(Ni.Co)-Si no V phase was found at the composition 4:4:7 after annealing at temperatures between 900" and 1200'C. For the determination of the lattice constants of the V phases Debye-Scherrer photographs were taken using the asymmetric film arrangement and CrKcr radiation (ka1, = 2.28962A). Using the positional parameters, as determined6 for Zr,Co,Ge,. Table 11. intensity calculations were carried out for each of the V phases with the aid of a computer program.: Thus unequivocal indexing of the diffraction patterns was greatly facilitated. The lattice constants. Table I. were then computed by a least-squares fit of the high-angle lines with f (0) = cos2 Q as extrapolation function. Only few. if any. very weak impurity lines were observed, with the exception of the three iron alloys Zr,Fe,Si7. Zr4Fe,Ge7. and Ta,Fe,Si7. The agreement

Jan 1, 1970

By R. F. Mehl, J. K. Stanley

THE recrystallization of cold-worked metals is studied ordinarily by determining the temperatures required for complete recrystallization to occur within a given arbitrary time period, usually within 15 min. to 2 hr. The results obtained are conventionally assembled in a three-dimensional diagram relating this temperature to the amount of cold-work (percentage deformation) and the resultant grain size, though sometimes other modes of representation are employed.1 Such three-dimensional diagrams are not complete, for the number of variables exceeds the number represented. The process of recrystallization is characterized by a time-rate, a fact that is not portrayed upon ordinary recrystallization diagrams. It is known that recrystallization consists in the formation of new nuclei and the growth of these nuclei, a process that continues until the matrix is completely consumed and the original set of grains entirely replaced by the new. This knowledge is old.2 Truly heterogeneous reactions invariably proceed by nucleation and growth; the decomposition of eutectoid solid solutions provides an example about which much is known,3 and freezing, originally studied by Tammann, provides the classic example. Although recrystallization is not a heterogeneous reaction .within the orthodox meaning of the term, the mechanism of the process is the same. As in eutectoid inversion and freezing, it should be possible to study the rate of isothermal recrystallization as a function of time, and it should also be possible to analyze the isothermal reaction curve into the component rates of nucleation and growth that determine them.* Other methods, not employing the rates of nucleation and growth, have been used to represent the rates of such reactions, but these in general have been artificial and have not led to progress.4,5? The theory of recrystallization is not in advanced state; if recrystallization data were obtained, in terms of the rate of isothermal recrystallization, and in terms of the rate of nucleation and the rate of growth of recrystallized grains, and in particular if the temperature coefficients of these rates were measured accurately, an adequate theory should be more readily developed.27 Such an effort requires proper experimental technique, but especially requires suitable methods of mathematical analysis to convert measurements made upon a surface of polish into values for the rate of nucleation and the rate of growth and to combine these into a rate of isothermal recrystallization. These methods are now

Jan 1, 1942

By J. B. Cohen, B. W. Howlett, M. B. Bever

The partial molar heats of solution at infinite dilution in tin of aluminum at 300° and 350°C and of gallium, indium, and thallium at 240°, 300°, and 350°C have been measured by tin solution calori-metry. Aluminum, gallium, and thallium are endo-thermic on solution; indium is exothermic. Any temperature dependence of the heats of solution lies within the experimental scatter. Over the dilute ranges investigated, only aluminum has a measurable change in its heat of solution with composition. HEATS of solution of one element in another reflect the interaction between them. The investigation of partial molar heats of solution in dilute alloys is of particular interest as the properties of the solvent are altered to only a limited extent by the presence of the solute and also as the interaction between solute atoms is small. When the heats of solution of a related series of elements in a solvent are known, a systematic comparison may be made. In the investigation reported here, the partial molar heats of solution of the Group III elements aluminum, gallium, indium, and thallium in dilute solution in tin were measured. This work follows an investigation of the heats of solution in tin of the Group IB elements.' EXPERIMENTAL PROCEDURES Materials. Samples of gallium, indium, and thallium were obtained from Johnson, Mathey and Co., Ltd. Indium and thallium were supplied as wire, 1.6 mm in diam; gallium was in the form of irregular pieces. The supplier reported the following minimum purities: gallium—99.95 pct; indium—99.99 pct; thallium—99.99 pct. The aluminum, obtained from Alcoa Research Laboratories, was reported to be 99.995 pct pure. The tin was supplied by Baker and Co., Inc.; the reported analysis indicated a tin content of at least 99.96 pct with lead as principal impurity. Calorimeter. this description will cover only the essential features of the calorimeter with special attention to modifications made since an earlier description was published.' A Dewar flask containing the tin bath was held in a constant-temperature bath of a near-eutectic mixture of lithium, sodium, and potassium nitrates. This bath, which was stirred vigorously, was heated by a primary resistance winding in the container wall and by a secondary winding immersed in the salt. The voltage supplied to both windings was stabilized. The temperature of the salt bath was controlled by means of a platinum resistance thermometer in one arm of a Wheatstone bridge. The light from a mirror galvanometer in the bridge circuit fell on a photocell which controlled the current in a saturable reactor in series with the secondary winding. In this manner, the temperature of the salt bath was controlled to ±0.003°C and that of the tin bath to at least ±0.002°C. Each of these temperatures was measured by two iron-constantan thermocouples in series, coiled in a helix to minimize heat loss and immersed in the salt and tin baths in protective sheaths. The temperature of the laboratory was kept constant to ± 1°C during a run. Specimens were dropped into the tin bath from an addition arm held at O°C which was part of the cal-orimetric system. The system was evacuated to about 0.02 1 to minimize oxidation and to reduce transfer of heat. The bath was stirred by a glass stirrer introduced through a double Wilson seal. The samples were scraped clean before weighing, which was carried out as rapidly as possible. Each sample was immediately placed in the evacuated addition arm to minimize contamination. These precautions were especially necessary with aluminum. After the runs with gallium and thallium at all temperatures and with indium at 240° and 350°C (Series I) were completed and before the runs with indium at 300°C and aluminum at 300° and 350°C (Series 11) were begun the following changes were made. The shape of the Dewar flask was changed so as to result in a lower surface to volume ratio of the bath and at the same time the amount of tin was reduced from 500 to 400 g. The paddle type stirrer was replaced by a helical screw and the rate of stirring was increased to about 150 to 200 rpm.

Jan 1, 1962

By Jean Howard

THERE are two mechanisms by which secondary crystals can develop in bcc alloys, namely 1) impurity inhibition and 2) strip-thickness inhibition. This paper reports some studies of each mechanism; the alloys were Si-Fe, A1-Fe, Cr-Fe, Mo-Fe, and Ge-Fe, as well as iron itself. All the alloys, which were of interest as part of a program of work on soft magnetic materials, were made by a powder-metallurgy process, using carbonyl iron (Grade MCP) as the starting material. Earlier phases of the work have already been published. Work described previously1 shows how the oxygen content of the sintering. atmosphere can be used to produce silica in the material which acts as a grain-growth inhibitor. Since then it has been found more convenient to make use of the oxide in the iron powder to control the silica content of the material. The compacts are sintered in vacuum which allows a direct reaction to take place between the iron oxide and the silicon. Details are given elsewhere.4 By this method, and by suitable adjustment of the rolling schedule, material with cube-on-edge secondary crystals has been produced in thicknesses from 0.1 to 0.001 in. in iron containing from 2-1/2 to 4-1/2 pct Si. It was also found possible to process 6-1/2 pct Si-Fe to 0.001 in. This was achieved by refinement of the sintered-compact grain size by using fine-particle silicon (i.e., <200 mesh). The brittleness of the material necessitated hot rolling to 0.020 in., from which thickness cold rolling was possible. If the conditions of sintering and the cold-rolling schedule were correct (i.e., as given elsewhere4 for 3-1/4 pct Si-Fe) secondary crystals of (110) [001.] orientation could be developed. The size of the secondary" crvstals" could not be

Jan 1, 1965

By L. W. Holm

This study shows that in the presence of foam, gas and liquid flow separately through porous media representative of reservoir rock. These results were obtained by using tracer techniques to measure the flow of the gas and liquid comprising the foam. Foam does not flow through the porous medium as a body even when the liquid and gas are combined outside the system and injected as foam. Instead, the liquid and gas forming the foam separate as the foam films break and then re-form in the porous system. Liquid moves through the porous medium via the film network of the bubbles and gas moves progressively through the system by breaking and re-forming bubbles throughout the length of the flow path. The flow rates of the gas and liquid are a function of the number and strength of the films in the porous medium. There is no free flow of gas; i.e., no continuous gas phase. On the basis of these results, foam can be expected to improve a water flood or gas drive by decreasing the permeability of the reseruoir rock to a displacing liquid or gas. This improves the mobility ratio and thus the conformance of the flood. INTRODUCTION Foam is formed when gas and a solution of a surface active agent are injected into a porous medium either simultaneously or intermittently. During the past few years, several papers have been published on the subject of foam flow in Dorous media. Foam has been used successfully in the removal of capillary water blocks from producing formations.&apos;&apos;2 The use of foam in gas storage reservoirs to reduce gas leaks and to increase storage capacity has been considered in recent years. Foam has also been investigated as an oil displacing agent,3-5 and as an agent to improve the mobility ratio in a waterflood.6-10 However, the mechanism by which the gas and liquid phases comprising the foam flow through a porous medium has nor been described adequately. Normally, when two immiscible phases (gas and liquid) flow concurrently through a porous medium, each phase follows separate paths or channels. At given saturations of the two phases, a certain number of channels are available to each phase, and as saturations change, the number and configuration of the channels available for each phase also change. The effective permeability of each phase is a function of the saturation of that phase only, and the flow of each phase can be described by Darcy&apos;s law. When foam is present, the effective permeability of the porous medium to each phase is greatly reduced compaced with permeabilities measured in the absence of foam.6,11-13 Based upon the observed flow of surfactant solutions and gas in capillaries, it has been concluded that the gas and liquid may flow separately or they may flow combined as foam. At least four mechanisms have been postulated to explain how fluids flow with foam present: 1. A large portion of the gas is trapped in the porous medium and a small fraction flows as free gas, following Darcy&apos;s law.9 2. The foam structure moves as a body; the rate of gas flow is the same as the rate of liquid flow. 6,13 3. Gas flows as a discontinuous phase by breaking and re-forming films. Liquid flows as a free phase.12 4. A portion of the liquid and gas move as a foam body while excess surfactant solution moves as a free phase.14 It also has been suggested that different flow mechanisms exist for high quality (dry) foams made from dilute surfactant solutions and for foams made from more concentrated solutions. Studies conducted on the flow of foam through capillaries have shown that a plug-type flow occurs and that foam flows as a body.6,15 Fried also has described the flow of foam through porous media as

Jan 1, 1969

By H. P. Greenwald, H. C. Howarth

The rapidly increasing use in coal mines of portable auxiliary fans, which are generally &apos;blowers" employed in connection with canvas tubing, raises questions concerning the hazards of such equipment, especially where the practices are opposed to established methods of ventilating face workings. Half a dozen or more coal-mine explosions and some fires have been attributed to the use of auxiliary fans; moreover, competent mining engineers have found many dangerous installations and methods of use-for example, intermittent running of the fans in gassy mines with consequent accumulations of firedamp at the faces. These facts have led the U. S. Bureau of Mines to issue this recommendation: "In the interest of safety, the Bureau of Mines, Department of Commerce, recommends that auxiliary fans or blowers should not be used in coal mines as a substitute for methods of regular and continuous coursing of the air to every face in the mine." The comparatively recent introduction of new types of mining machines, mechanical loaders, face conveyors, and slabbing machines has encouraged the trial of new systems of face mining, all of which have for their object the rapid advance of the faces. Although the latter has certain economic advantages, in gassy mines the rate at which gas is given off is generally found to increase in proportion to the speed of advance into new territory, which in turn increases the difficulties of efficient ventilation of the face workings. Some of the systems of advance mining being tried in connection with new mechanizing methods practically compel the use of blower fans and tubing, as single narrow places arc now driven 300 ft. or more without crosscuts. In some instances a series of parallel headings are driven without crosscuts pre-

Jan 1, 1928