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By Rex B. McLellan, W. A. Oates, William W. Dunn

Vapor transport experiments have been carried out in order to determine the saturation solubility of carbon in cobalt and nickel with respect to graphite over a large temperature range. Some of the uncertainty existing in the thermodynamics of these systems has been removed and accurate estimates of the heat and entropy of solution of carbon in nickel and cobalt have been deduced. The relatitle partial entropies of carbon are considered to be predominantly vibrational in origin. ALTHOUGH the thermodynamic properties of solid solutions of carbon in cobalt and in nickel have been investigated previously, the results of these investigations show a marked lack of agreement amongst themselves. In this investigation simple vapor transport experiments have been undertaken in order to measure the temperature variation of the saturation solubility of carbon in nickel and cobalt with the object of removing to some degree the uncertainties in the thermodynamics of these systems. In the case of the C-Co system, early measurements of the saturation solubility of graphite in Co show results at the same temperature differing by almost an order of magnitude.1-5 Recently Schenck, Frohberg, and Jaspert6 measured the equilibrium between CH4-H2 mixtures and C-Co solid solutions at five temperatures ranging from 850° to 1050°C. Their values of the activity of carbon in the solid solution, deduced from a knowledge of the chemical potential of carbon atoms in the gas, varies linearly with composition at each temperature and the authors concluded that the solutions were Henryan. The saturation solubilities deduced from Schenck, Frohberg, and Jaspert's measurements are in good agreement with the solubility determined at 1000°C by Rao and Nicholson7 and the value at 1000°C deduced from the measurements of smith8 on the equilibrium between CO/CO2 mixtures and C-Co solutions. The object of this investigation was to check the results of Schenck, Frohberg, and Jaspert and also to extend the range of solubility data to higher temperatures. In the case of the C-Ni system, there is fairly good agreement between the values given by schaefer9 for the saturation solubility of carbon C, in nickel, the value given at 1000°C by Rao and Nicholson,7 and that deduced from Smith's8 measurements of the equilibrium between C-Ni solutions and CO/CO2 mixtures at 1000°C. The values of C, deduced from Schenck, Frohberg, and Jaspert's6 measurements of the carbon activity in nickel are also in fairly good agreement. However, there is a large discrepancy between the above set of measurements and those of Lander, Kern, and Beach," who measured the carbon solubility of nickel in equilibrium with graphite by depositing an excess of graphite on the surface of Ni-foils from a gaseous mixture and subsequently diffusing in the carbon. These results are considerably higher than those mentioned above. The determinations6 of carbon activity a, in nickel from the CH4-H2 equilibrium showed that at all the temperatures investigated, the ac-values varied linearly with concentration up to about a, = 0.6 and then began to increase with concentration much more rapidly. On the basis of auxiliary experiments in which C-Ni solutions were equilibrated with graphite, Schenck, Frohberg, and Jaspert concluded that their CH4-H2 solid equilibrations at high values of a, were spurious and a, behaved linearly with composition up to the saturation limit (a, = 1). The short linear extrapolations of Schenck, Frohberg, and Jaspert's a, data yield values of C, in good agreement with those of Lander, Kern, and Beach." The solubility data for nickel discussed here is presented in Fig. 1 in the form of plots of ln[Cc/(l - 2cc)] vs 1/T. The discrepancies mentioned are clearly seen. In this investigation a vapor transport method is used to measure C, over as wide a temperature range

Jan 1, 1969

By P. S. Kotval, H. Hahell

PRECIPITATION of M23C6 carbides at grain boundaries in austenitic steels and nickel base superalloys has received considerable attention. Hatwell and Berghezan,1 in a study using carbon extraction replicas, observed that dendritic growth of the M23C6 carbide phase occurred at grain boundaries in austenitic steels. Merrick and Nicholson2 have observed that in thin foils of "Nimonic 75" alloy the precipitation of M23C6 carbide was discontinuous at grain boundaries. Lewis and Hattersley3 have suggested that the type of M23C6 precipitation observed in Ni-Cr austenites represented the early stages of discontinuous precipitation. In a more recent study, Singhal and Martin4 have concluded that grain boundary M23C6 precipitation involves the migration of an austenite grain boundary by a mechanism very similar to that proposed by Tu and Turnbull.5 Tu and Turnbull's suggestion essentially involves grain boundary migration under the driving force arising from the difference between the surface free energies of the opposite sides of the plate. Thus, Singhal and Martin's observation4 implies that the first stage of discontinuous precipitation has taken place and that the grain boundary has provided a diffusion short circuit for the sub-stitutional solute atoms (principally chromium) which assist the preferential growth of the M23C6 plate in contact with the grain boundary. However, no evidence of the characteristic cellular morphology typical of discontinuous precipitation was found in Singhal and Martin's studies. Presumably, this is due to the low volume fraction (i.e., low supersaturation of solute) of the precipitating carbide reported by Singhal and Martin.4 Recently, Raymond6 has studied precipitation of the M23C6 carbide in Incoloy alloy 825 and shown that the growth of this phase is perpendicular to grain boundaries at 1400°F and in the plane of the grain boundary at 1700°F. The former aging condition resulting in discontinuous or "cellular" precipitation. Raymond has suggested an explanation for this behavior based on the relative rates of chromium diffusion by volume and grain boundary diffusion at the two different aging temperatures. In the course of a recent investigation on precipitation behavior in several ' strengthened superalloys, precipitation of M23C6 carbide at grain boundaries was studied. Under conditions of a high degree of supersaturation, the M23C6 carbide precipitates in the discontinuous or cellular morphology in Waspalloy (Ni-18.51 Cr-2.0 Fe-3.53 Mo-1.16 Al-2.78 Ti-0.09 C). This note presents electron microscopy observations of this mode of precipitation and its effect on mechanical properties. Specimens of Waspalloy after "solution" heat treatment at 1950°F show essentially single phase matrix with a few residual particles of "primary" MC carbide. In normal commercial heat treatments, precipitation of Ni3(Al,Ti) ordered fcc r' phase occurs throughout the matrix and M23C6 precipitates as globular particles at the grain boundaries. In these commercial heat treatments the degree of supersaturation during precipitation is low. However, if specimens of Waspalloy are quenched from the solution heat treatment temperature of 1950°F and then aged at an aging temperature where the degree of supersaturation is high, discontinuous precipitation of M23C6 occurs. Figs. 1 and 2 show thin foil micrographs of Waspalloy, solution heat treated at 1950°F, water quenched, and aged at 1292° and 1598°F, respectively, for 500 Fig. 1—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 500 hr at 1292°F. Magnification 15,500 times. Fig. 2—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 114 hr at 1598° F. Magnification 13,000 times.

Jan 1, 1970

By J. F. Butler

Boron nitride, BN, has been identified in boron low-carbon steels by means of light microscopy, electron microscopy and diffraction, and chemical analysis. This boron nitride is responsible for strain aging suppression in these steels through the removal of nitrogen from solution; however, small oxidizing potentials which result in deboronization In the austenitic temperature range also result in boron nitride decomposition and the subsequent occurrence of nitrogen strain aging. THE addition of boron to low-carbon steels is an effective means of eliminating the detrimental effects of strain aging;',' however, the mechanism by which boron suppresses strain aging has not been established. In studying the effect of heat treatment on the strain aging of boron low-carbon steels, Butler3 found that no detectable nitrogen was present in the ferrite solid solution after various heat treatments even though the total nitrogen analyses of the steels were 0.003 pct N. Apparently the function of boron in suppressing strain aging is the removal of nitrogen from solution to form a relatively stable second phase. A clue to the identity of this phase was found by Speight4 who extracted from an aluminum-killed boron steel an acid insoluble residue which contained boron and nitrogen in proportions corresponding to the compound, BN. Shyne and Morgan5 found that the addition of nitrogen to a hardenable boron steel lowered its hardenability in a manner which suggest-d the presence of nucleating particles (presumably BN) even at high austenitizing temperatures. Although this indirect evidence for the presence of boron nitride in boron steels has been found, the compound was not identified metallographically as a separate phase in these steels. Because boron has an affinity for oxygen comparable to that of silicon,5 boron steels must be thoroughly killed with aluminum in order to prevent the reaction of boron with oxygen.7 The affinity of boron for oxygen also is demonstrated through the ease of deboronization of a boron steel in an oxidizing atmosphere. Digges, Irish, and Carwile8 found that a mixture of wet natural gas and air caused both deboronixation and decarburization of a boron steel at 1900°F. The boron content rose at the surface of the steel due to the formation of boron oxide. Shyne and Morgan9 encountered deboronization at much lower oxygen potentials; loss of boron occurred in steels treated at 1750o F under argon purified to 0.0014 pct 0, even though decarburization did not occur. Boron oxide, B2O3, is much more stable than the nitride, BN, as is indicated by the standard free energies of formation at 980oC: -235 kcal per mol of B2O3 (liquid) and -28 kcal per mol of BN (crystal). It is evident that the oxygen potential must be kept low in the presence of BN in order to prevent its decomposition and the subsequent formation of B2O3' The purpose of the work described in this paper was to identify the nitride phase responsible for the removal of nitrogen from solution and to study its stability under oxidizing conditions. IDENTIFICATION OF BN In order to identify the phase containing boron and nitrogen, several alloys high in boron and nitrogen were made up in a small vacuum furnace. In alloys 3 and 4, Table I, electrolytic iron was used as a charge material. Boron additions were made in the form of 18 pct B ferro-boron after the iron was molten. In the case of alloy 3, the charge was solidified at this point; for alloy 4, nitrogen at 1 atm pressure was admitted over the melt before it was

Jan 1, 1962

By W. A. Backofen, D. Lee

The deformation of textured sheet of titanium and several of its all-a (hcp) alloys was investigated with two kinds of experiments: tension testing along different directions in the plane of the sheet, and combined-stress loading along the principal axes of anisotropy (the rolling and transverse directions). Texture and plastic anisotropy were evaluated with pole figures and by measurement, as a function of orientation, of the tensile transverse-strain ratio, or R parameter. The results as a whole can be rationalized qualitatively with the present understanding of deformation mechanisms in titanium. Quantitative agreement between the orientation dependence of tensile yield strength and the Predictions of continuum ANISOTROPY in the properties of engineering materials is more the rule than the exception because anisotropy in structure is so common, and the one generally follows the other. Two broad categories of structural anisotropy are represented by mechanical fibering and crystallographic texture. The former is important in many aspects of fracture.' The latter has more significance for yielding and plastic deformation, theory, using the R measurements, was relatively poor. However, in tension-tension quadrants of the yield-locus diagrams, the difference between theory and experiment was hardly more than 10 pct. The maximum texture-hardening effect was found in a 4Al-1/4O2 alloy to be nearly 50 pct. In the compression-compression quadrant, {1012} deformation twinning prevented the locus from expanding much beyond the Position predicted for isotropic material. With increasing temperature the trend in R was downwards, approaching unity (isotropy) near the a-transus temperature; an accompanying development was large amounts of neck-free extension. which are of special concern in this paper. The tendency has been to view crystallographic texture more as a liability or curio than as an asset. The prominent exception is found in silicon-ferrite sheet for power-transformer cores, which is processed to develop a new optimum texture for high electrical efficiency. Yet it should be possible to find other examples, involving other kinds of properties. More specifically, there is good analytical reason to expect improved combined-stress yielding resistance in suitably textured material,2,3 and it has now been shown by experiment that texture hardening or softening is a potentially useful phenomenon in certain engineering devices and processes.'-I To date, work has included measurements of the transverse (width to thickness) strain ratios in the

Jan 1, 1967

By E. Miller, K. L. Komarek

Equatiorzs have been derived which related maximum solid solubilities in semicondcting compounds having retvograde solidus curves with 1iqllidus data. Liquidus curves in Lke Pb-Te, Pb-Se, ard PB-S systetris have been defermined by thertrzal aralyses. Fvotrz expevimental maximum solibilities ia CdTe, PbTe, uxd PbS vetvograde tetrperatures hale beep1 calculated. TIze resllts support the concept that under certaiz conditiots pronounced itjlections in the liquidis curves arc indzcatiz:e of retropade solidus curves and that the tenlperatltre of the lmaximum solid solubility will be close to the temperature of the point of inflection in the liquidus curve. The maximum solid solihility within a gvoup of homologous cottrpoods SeetlLs to increase with increasing flatness ol the liquidus curvres. The phenomenon of retrograde solubility in metals, i.e., maximum solubility in a solid terminal phase in equilibrium with a liquid phase, has been theoretically predicted by Van aar' in his calculations of hypothetical binary phase diagrams. It was not until 1926, however, that retrograde solubility was experimentally verified in the Zn-Cd system.' Since then many sys- tems with retrograde solubility have been found, so that at present approximately fifty binary diagrams with a retrograde solidus curve are known.3 Meijering4 has critically appraised the accumulated data and has presented calculations which alloy predictions as to whether or not a solidus line will be retrograde. Interest in retrograde solubility increased when it was found that the solidus curves of germanium and silicon alloyed with a great many doping elements are retrrade. The problem was treated thermody-namically by odkinson,% d all available data on solid solutions in germanium and silicon were summarized by Trumbore.7 Although it is to be expected that intermetallic compounds will also exhibit retrograde solubility, experimental evidence is much more limited. Until now retrograde solidus curves have been reported for the compounds de,' be, Ps:" ne," SnSe," and SnS.13 All these compounds are semiconductors, and the solidus curves were usually obtained by determining the carrier concentration at room temperature of samples equilibrated at elevated temperatures and then quenched. It has been hown,'' however, that it is not always possible to quench in the equilibrium compositions from above a certain temperature. Theoretical discussions have either explicitly excluded intermetallic compounds4 or not treated them with respect to retrograde slubilit.j In the following a thermodynamic treatment of retrograde solu-

Jan 1, 1967

By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale forma¬tion) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. EXPERIMENTAL PROCEDURE Silver.-The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By Merton C. Flemings, Harold D. Brody

Analyses that include diffusion of solute in the solid phase are formulated to describe solute redistribution in dendritic solidification of metallic alloys. The analyses are based on conditions that include negligible undercooling before nucleation of solid phases, negligible increase of solute in advance of the tips of growing dendrites, complete diffusion within the liquid over distances the order of dendrite spacings, and a plate-like dendrite morphology. The classical nonequilibrium freezing equation, Cs = kCo(I - fS)k-l accurately describes solute redistribution between dendrite arms for the solidification processes considered, provided diffusion in the solid is negligible. To account for the effect of diffusion in the solid, an analytic expression is given which is similar inform to the classical expression. 172 addition, a numerical-analysis procedure is etnployed to examine in more detail the effect of diffusion both during and after solidification. The analyses are intended for application to solidification of castings and ingots to describe a) final solute distribution after solidification and cooling to room temperature (microsegregation) and b) local fraction solid as a function of ternperatcre within the solidifying casting or ingol. SOLUTE redistribution in cellular and dendritic solidification has been discussed quantitatively in recent papers'-3 and in a series of earlier work.4-6 However, none of the analyses developed have permitted close correlation of theory with final solute distribution (microsegregation) observed in castings and ingots. In this paper, discussion is given of approximations which may reasonably be made in mathematical treatment of microsegregation, and analyses are presented based on these approximations. Numerical results are given for Al-Cu alloys. In a second paper the analyses will be compared with exeriment.7 CLASSICAL ANALYSIS The classical quantitative treatment of solute redistribution within a closed "volume element" has been derived repeatedly, for example by Gulliver,4 Scheil,' and Pfann.' This "classical nonequilibrium solidification equation" is written for constant partition ratio: where Cs = interface composition of the solid when the weight-fraction solid within the "volume element" is fs (weight fraction, wt pct); k = equilibrium partition ratio; Co = initial alloy composition within the volume element (weight fraction, wt pct). Assumptions of Eq. [11 are: 1) There is negligible undercooling before nuclea-tion, or from curvature or kinetic effects. 2) There is no mass flow in or out of the volume

Jan 1, 1967

By J. D. Grace

Screening by centrifugal force is a unique subject, for all vibrating screens, with but one exception, depend on gravity alone to pass material through a sizing mesh or screen cloth. Centrifugal screening is one of the greatest advancements made in screening since the development of vibrating screens. It makes possible sizing in a range previously im-practical by mechanical methods. The centrifugal screen is specially designed for fine sizing from No. 4 separations to finer than No. 100 separations. Centrifugal force provides a positive control of factors that make fine particle separation practical and effective as opposed to gravity which is a fixed force acting only in a fixed direction, The centrifugal screen provides a control of the force of material against the screening surface, and also controls the distance of departure of the material from the surface and its rate of return. The centrifugal screen has a rotating drum that becomes a natural fan blowing air outward through the material being screened and carrying float dust and fines through the apertures with it. Screening by centrifugal force is an unique subject, for with the exception of only one vibrating screen presently on the market, all vibrating screens depend upon gravity to pass material through a sizing mesh or screen cloth. This one screen that sizes by centrifugal force and utilizes gravity only to convey material along the screen, is the Symons V-Screen. The requirements of the industrial minerals industry to meet ever-increasing stringent fine sizing specifications by a practical mechanical method accentuates the weakness of gravity, a fixed force acting in a fixed direction, as a prime force for fine sizing. It was apparent a force other than gravity was needed. This led to the development of a centrifugal screen to meet modern demands for practical fine sizing operations. Gyratory-type screens in use today were originally designed in a day when a 1/4-in. separation was normally considered fine sizing and 1/8-in. separations were extremely fine sizing. Although gyratory-type screens are sometimes used for separating below 1/8-in., they are not practical screens for this purpose. They were not designed to do this type of work. A growing demand for a practical means of making positive mechanical separations in a range of from 1/8 in. downward led to the development of the vibrating screen. These screens utilize higher speeds and lower amplitudes of vibration than

Jan 1, 1967

By L. L. Melton, D. L. Lord, B. W. Hulsey

A mathematical model d1.20p/4L = A(8v)8 derived from the Blasius equation is proposed to be applicable to turbulent flow through straight cylindrical pipe for time-independent fluids which produce a diameter family of straight parallel lines on a log (dp/4L) vs log (8v/d) plot or stress-flow diagram. Such a correlation should permit scale-up with data taken from one pipe diameter for Newtonian, inelastic non-Newtonian and viscoelastic fluids, such as dilute polymer fracturing fluids, which produce considerable frictional pressure reductions. The Newtonian diameter exponent value 1.20 is shown to be empirically valid for turbulent non-Newtonian flow by application of numerical analysis methods. Multiple regression analysis is applied to a logarithmic linearization of the proposed model. An improved data fit results from further linearization achieved by taking linear terms from a generalized Taylor's series expansion about the multiple regression coefficients. Extensive experimental data obtained in five pipe diameters with water, sodium carboxymethyl-celIulose solutions, guar gum solutions, bentonite clay suspensions and calcium carbonate slurries are presented. Except for calcium carbonate slurries, which were investigated rather than time-dependent cement slurries, the fluids studied contain drilling or fracturing fluid additives. The behavior exhibited by these fluids is considered typical of most fluids encountered in drilling, cementing and fracturing operations. INTRODUCTION Considerable difficulties have been encountered in predicting turbulent flow pressure drops produced by non-Newtonian fluids flowing through straight cylindrical pipe. Correlations previously presented require extensive experimental data which represent several pipe diameters and a wide flow rate range to estimate the necessary scale-up parameters.l-7 One must implement either elaborate experimental apparatus or spend considerable time and effort to gather these data. Presented here is a correlation method which should minimize the experimental effort and data analysis normally required by utilizing flow data taken with only one pipe diameter. Turbulent flow data (up-stream and down-stream pressure and volumetric flow rates) were collected for five pipe diameters through operation of a small pipeline system having an electronic data acquisition and digitizing system. A mathematical model derived from the Blasius equation was utilized to describe the functional relationship between pressure drop and the two independent variables, diameter and average flow velocity. A correlation, which should produce a valid single-pipe scale-up, resulted from a computer-implemented statistical and numerical data analysis for several time-independent non-Newtonian fluids.

By M. R. Tek, K. H. Coats, D. L. Katz

The performance of a gas reservoir su,bject to water drive is often affected by interference due to gas procluction or injection in neighboring reservoirs adjacent to a common aquifer. Field data available on production-pressure behavior of several reservoirs indicate that prediction of reservoir performence must include the effects due to mutual interference. A method developed to predict the performance of two or more interfering gas reservoirs, subject to specified production-iniection .rchedule.s, is presented. The method involves the comhinatiorz of the theory of unsteady-state water movernent with appropriate meterial balance consideration.s. The procedure which extends M. Mortada's treatment for interfering oil reservoirs makes use of his dimen-.sionless pressure drop quantities. prevented graphically in the literature. In order to evaluale the predictive accuracy and practical field applicability of the theory, the method has been applied to analyze the performance of two actual gas reservoirs in mutual interference. The calculations were performed on an IBA4 704 computer. The predicted performances were alro calcltlated with the interference effects ignored. The results show that considerably better agreement between calculated and observed behavior ic. obtained when the interference effects are included. INTRODUCTION Fluid communication between any number of oil or gas reservoirs adjacent to a common aquifer results in mutual interference effects on their production-pressure behavior. The theory, application and interpretation of pressure build-up behavior of oil wells, drawdown tests on oil or gas-producing formations and behavior of several storage reservoirs indicate ample experimental evidence of mutual interference. A method developed to compute the behavior of interfering oil reservoirs was published several years ago by Mortada.4 Studies conducted during the recent years on underground storage of natural gas clearly indicated the need for extending Mortada's work to the case of interfering gas reservoirs. The adoption of appropriate material balance equations in conjunction with the unsteady-state pressure interference theory yields pressure-explicit equations. Their solution, their application to a specific case history and an over-all evaluation of the developed method through the comparison of predicted and observed field performances were the main objectives of this study. DEVELOPMENT OF MATHEMATICAL RELATIONS The diffusivity Eq. 1 governs planar, radial, unsteady-state compressible liquid flow through a porous medium. ?p/?r2+1/r ?p/?r=µFc/k ?p/?t (1) The 1iterature1,2,3 contains derivations and solutions of

By W. H. McFarland

The mechanical properties have been determined for a large number of alloy-free martensitic steels with carbon contents ranging from 0.08 to 0.20 pct and with manganese contents of about 0.4 to 0.5 pet. These steels were tested 1) as water-quenched, 2) after quenching, temper rolling, and tinning, and 3) after tempering treatments which involved temperatures from 400o to 1300oF and times from 1 min to 8 hr. The majority of these tests represent steel from commercial-size coils, i.e., strip 32 in. wide, coil weights up to 20,000 16, and steel thicknesses from 0.0055 to 0.024 in. As a result of these treatments, it has been shown that as-quenched low-carbon alloy-free steels can be produced with tensile strengths ranging from 140,000 to 220,000 psi and tensile elongations from 3.0 to 4.0 pet in 2 in. The tensile strength of the as-quenched martensites can be represented by the equation, tensile strength (ksi) = 119 + 560 (wt pet C). The response to tempering of these steels is related to previous work by Muir, Averbach, and Cohen and by Grange and Baughman. Strain aging of low-carbon martensite has also been investigated. If low-carbon steels are defined as those steels with a maximum carbon content of 0.2 pet, it is found that the literature on low-carbon, alloy-free martensites contains little data on the mechanical properties of these steels. However, the following facts concerning low-carbon alloy-free martensites seem firmly established:'-' 1) The major factors in controlling the strength of the martensite appear to be a) fine structure, b) the internal strain resulting from the transformation, and, particularly, c) the amount of carbon in solid solution. 2) In low-carbon steels, the martensite is auto-tempered and is in the form of needles with only minor amounts of internal twinning, whereas the martensite in high-carbon steels forms as plates which are internally twinned on a fine scale. 3) Care must be taken in comparing the results of work that has been done on low-carbon steels with varying amounts of alloying elements to data on plain carbon steels. As has been noted by Irvine, Pickering, and Garstone,6 alloying elements generally lower the martensite start temperature and, thereby, decrease the amount of auto tempering obtained during the quench. This makes it difficult to

Jan 1, 1965

By John R. Gould

A mathematical treatment of multiple-pass floating-zone refining of semiconductors, including the evaporation of solutes from the melt at reduced pressure, is presented. Vapor pressures and evaporation rate constants for phosphorus, arsenic, and antimony in germanium have been determined from floating-zone experiments conducted at 10 mm Hg. Rate sensi-tivity of arsenic in germanium has been examined over the range of 1 to 10 in. per hr growth rate. The equilibrium value of the segregation coefficient of arsenic in germanium, as determined by an extrapolation of these data, was found to be 0.09. PFANN has treated the segregation of nonvolatile solutes in the zone-melting process, Bradshaw and Mlavsky2 considered the evaporation of solutes in a vacuum during the growth of crystals by pulling from the melt, and van den Boomgaard3 has shown that it is possible to bring a volatile impurity element homogeneously into an ingot by means of zone-melting under a constant pressure of that element. This paper is concerned with the volatilization of solutes during zone - melting in a vacuum. The mathematical analysis by Lord4 of multiple-pass zone melting is extended to include evaporation of solutes. A method is presented in which evaluations of vapor pressures, evaporation rate constants, and distribution coefficients may be derived from the variation of solute concentration in the floating-zone refining of germanium at 105 mm Hg. EXPERIMENTAL Ingots of zone refined germanium, approximately 1/4 in. in diam and 10 to 12 in. in length, were subjected to several floating-zone passes at 105 mm Hg in order to provide intrinsic material for these studies. These ingots were then seeded in a [Ill] direction and solid-doped to a constant impurity concentration of approximately 1015 atoms per cmS in a forming gas ambient (10 pct H - 90 pct A) at 1/2 atm gage. The resulting crystals were subjected to repeated floating-zone passes at 105 mm Hg and a concentration profile along the length made after termination of each pass. Concentrations were determined from four-point probe resistivity measurements, and proper precautions were taken to prevent contamination during handling. A constant zone length, crystal cross section, and growth rate were maintained during zoning. A stationary coil and moving crystal system were employed for floating-zone growth with neither the section of crystal above nor below the melt rotated.

Jan 1, 1962

By S. S. Nosseir

INTRODUCTION General Quebec Cartier Mining Co. (QCM) , Canadian subsidiary of U . S. Steel Corporation, operates two iron ore concentrators at the North Shore of Quebec, Canada. In its own operation at Mount-Wright, over 45 million tons per year of crude ore are ground, fully autogenous in six 32' x 11-1/2 Dominion Engineering mills. At Fire Lake/Lac Jeannine operation, property of Sidbec Normines Incorporated (SNI), over 11 million tons per year of crude ore are now ground, fully autogenous, in twelve 18' x 5' Hardinge mills. The Lac Jeannine concentrator was originally constructed by Q.C.M. in 1960 and. was since operated, in beneficiating the Lac Jeannine ore deposit until fully depleted in 1977, at an annual capacity of 18 million tons of crude per year. In 1976, the new company, Sidbec Normines, was incorporated by Sidbec Corporation, British Steel Corporation and Quebec Cartier Mining Co., in proportional holding of approximately 51 to 41 to 8 percent respectively. Since the acquisition of the Fire Lake ore deposit and Jeannine concentrator by the new company, QCM has continued managing the mine and concentrator operaions for S idbec Normines Inc . Flow-Sheet Design Jeannine concentrator comprises twelve identical mill lines grinding the ROM from 8" top size to 14 mesh nominal size range. Driven by 600 H.P. motor at 13.4 RPM corresponding to 73% critical speed, each mill is operated in a closed circuit with two 5' x 12' vibrating screens dressed with 2.5 x 25 mm slot opening cloth. The ground product or screen undersize at an average grade of 33.4% Fe is beneficiated by gravity separation to produce 66.5% Fe concentrate grade at 42.7% weight recovery. At the rougher stage, each mill line con-tains 128 Humphrey 13- 1/2" pitch spirals which produce a final tailing, middling and concentrate products. The rougher concentrate - so produced - is classified by 64 Humphrey pocket sizers into an underflow, which is a final concentrate product and an overflow which is further upgraded by 64 cleaner spirals. The cleaner concentrate together with the pocket sizer 's underflow are dewatered on a 13'[6] horizontal filter. The rougher middling together with the cleaner tailing are recycled in a closed circuit with the spirals. The rougher tailing after dewatering by hydrocyclones is disposed of by a

Jan 1, 1982

By A. G. Guy, T. B. Lindemer

A second intepation of the Fick law has been developed and applied to three-place data generated from the Gosting and Fujita solution of the diffusion equation. This integration provides new mathematical techniques for the analysis of experimental data. Through use of the synthetic data it is shown that for concentration-independent interdifiusion coefficients these techniques permit a more accurate determination of the coefficients than does the usual Boltzmann-Alatano analysis. Another technique, applicable to the most general concentration-dependent diffusion coefficients , can be used to determine whether given sets of coefficients are consistent with the experimental ternary concentration-distance curves. DURING the past 10 years the subject of three-component diffusion has advanced from the stage of a laboratory curiosity to the status of an accepted portion of physical metallurgy.1 In the course of this development the underlying treatment for two-component sys- tems was extended and generalized to accommodate the added component, but fundamentally the analyses currently employed for ternary systems are analogous to those previously developed for binary systems. There are several indications that an improved analysis is needed for the ternary case. First, the two cross coefficients, D312 and D321 are typically an order of magnitude smaller than the direct coefficients and consequently are difficult to determine with adequate precision. Second, instead of a single concentration-penetration curve (as in binary diffusion), there are four such curves in the usual determination of ternary diffusion coefficients. These curves have definite theoretical interrelationships, but actual experimental curves exhibit significant departures from these relationships. Finally, the amount of data needed to adequately describe the diffusion behavior of a ternary system is so large that radically new methods are needed to facilitate the gathering of these data. ICirkaldy2j4 has proposed several possible analyses of ternary diffusion data, including some of the methods in current use. A "second-integration" procedure proposed by him4 differed in important respects from that presented here and was not carried to the point of application. Two other methods have been explored by the authors and will be published separately; these are a numerical analysis technique and a method for the analysis of a single ternary diffusion couple. Still other analyses are being explored by various investigators. At present it seems likely that the final analysis of ternary diffusion that evolves will be a composite

Jan 1, 1968

By Welton J. Crook

Unless present, in considerable praportion, metals of the precious-metal group—other than gold and silver—are not readily detected by the methods of fire assaying usually applied to ores and metallurgical products. Platinum, when present in small quantity, will ordinarily be reported as silver unless special methods of parting are used. Other elements occurring in the gold itself are all fluxed and slagged in the assay operation and if analyses are made on bullions the melting and slagging operations to which the bullion has been subjected may eliminate most of the associated elements. On the other hand, the analysis of precipitate from the cyanide treatment of gold ores may reveal the presence of many unexpected elements, such as tungsten and molybdenum. It is uncertain, however, whether many of the elements present in the precipitate are derived from the ore gangue or from the gold itself. No very general survey of the distribution of metallic elements in gold seems to have been made. Rose and Newman,l in connection with the composition of native gold, say in part as follows: Gold is occasionally found alloyed with copper and sometimes also with iron, bismuth, lead, mercury, tin, antimony, palladium or rhodium. Rhodium gold from Mexico was found to be of the specific gravity 15.5 to 16.8 and contained 34 to 43 per cent of rhodium. The native alloy of palladium, gold, and silver from Porpez contains 85.98 per cent of gold, 9.85 per cent palladium and 4.17 per cent silver. Mal-donitk, from Victoria, contains gold 64.5 per cent, bismuth 35.5 per cent (Louis). Dana2 says that native gold is usually alloyed with silver in varying amounts, and that sometimes it also contains traces of copper and iron. Rare varieties contain palladium, rhodium and bismuth. Other authors, for instance Zeigler3 and Clark,4 give similar information. Most references on the subject agree that ordinary native golds contain, in common, the elements silver, copper and iron. After completion of the work of which this paper is a record, the conclusion is reached that all ordinary native gold probably does contain these elements and, although in certain cases other elements may be found to be present, that it is difficult to

Jan 1, 1943

By Welton J. Crook

Unless present, in considerable praportion, metals of the precious-metal group—other than gold and silver—are not readily detected by the methods of fire assaying usually applied to ores and metallurgical products. Platinum, when present in small quantity, will ordinarily be reported as silver unless special methods of parting are used. Other elements occurring in the gold itself are all fluxed and slagged in the assay operation and if analyses are made on bullions the melting and slagging operations to which the bullion has been subjected may eliminate most of the associated elements. On the other hand, the analysis of precipitate from the cyanide treatment of gold ores may reveal the presence of many unexpected elements, such as tungsten and molybdenum. It is uncertain, however, whether many of the elements present in the precipitate are derived from the ore gangue or from the gold itself. No very general survey of the distribution of metallic elements in gold seems to have been made. Rose and Newman,l in connection with the composition of native gold, say in part as follows: Gold is occasionally found alloyed with copper and sometimes also with iron, bismuth, lead, mercury, tin, antimony, palladium or rhodium. Rhodium gold from Mexico was found to be of the specific gravity 15.5 to 16.8 and contained 34 to 43 per cent of rhodium. The native alloy of palladium, gold, and silver from Porpez contains 85.98 per cent of gold, 9.85 per cent palladium and 4.17 per cent silver. Mal-donitk, from Victoria, contains gold 64.5 per cent, bismuth 35.5 per cent (Louis). Dana2 says that native gold is usually alloyed with silver in varying amounts, and that sometimes it also contains traces of copper and iron. Rare varieties contain palladium, rhodium and bismuth. Other authors, for instance Zeigler3 and Clark,4 give similar information. Most references on the subject agree that ordinary native golds contain, in common, the elements silver, copper and iron. After completion of the work of which this paper is a record, the conclusion is reached that all ordinary native gold probably does contain these elements and, although in certain cases other elements may be found to be present, that it is difficult to

Jan 1, 1943

By Walter C. Lawson

The first plans were made in 1930 for the mining by open-pit methods of the low-grade disseminated ore body now known as the Morenci open pit. It was not until 1937, however, that final plans were completed and the decision reached to go ahead with the actual development. Many advances were made in open-pit mining equipment during that period of seven years, therefore the ways and means of attack actually used were very different from those originally contemplated. Diesel-operated bulldozers, big trucks, full-revolving electric shovels and electric churn drills constitute the major equipment finally purchased for this modern stripping operation. Neither the bulldozers nor the big trucks were considered in the early operating plans, for at that time bulldozers had not been used in mining operations and the trucks as yet were undesigned. The full-revolving shovel and the churn drills were not new developments in open-pit equipment, but both had undergone remarkable manufacturing transition, emerging far more efficient and far more dependable than their predecessors. Even the ordinary drilling steel had been fundamentally changed. It was now threaded so that the dulled cutting bits could be detached and replaced, thus eliminating the costly transportation of long bars to the drill shop for resharpening. The decision to use trucks in the preliminary stripping operations was based on the desirability of this type of transportation to economically prepare the pit for rail haulage, coupled with the success that the contractors had had with them on other big excavation jobs. There are at present no plans for the use of trucks beyond the preliminary work, inasmuch as rail haulage will give lower costs after roadbeds and benches are once established. For many years to come, both ore and waste haulage will be over favorable grades. The average length of ore haul between the pit and an assembly yard will be about two miles. From there the crushers will be 1? miles with a connecting track grade of 0.4 per cent. The upper ore benches of the pit will be reached from the yard by a series of four switchbacks over a ruling grade of 4.0 per cent compensated for curvature. Tracks to the dumps will be on 0.2 per cent grades.

Jan 1, 1940

By Walter C. Lawson

The first plans were made in 1930 for the mining by open-pit methods of the low-grade disseminated ore body now known as the Morenci open pit. It was not until 1937, however, that final plans were completed and the decision reached to go ahead with the actual development. Many advances were made in open-pit mining equipment during that period of seven years, therefore the ways and means of attack actually used were very different from those originally contemplated. Diesel-operated bulldozers, big trucks, full-revolving electric shovels and electric churn drills constitute the major equipment finally purchased for this modern stripping operation. Neither the bulldozers nor the big trucks were considered in the early operating plans, for at that time bulldozers had not been used in mining operations and the trucks as yet were undesigned. The full-revolving shovel and the churn drills were not new developments in open-pit equipment, but both had undergone remarkable manufacturing transition, emerging far more efficient and far more dependable than their predecessors. Even the ordinary drilling steel had been fundamentally changed. It was now threaded so that the dulled cutting bits could be detached and replaced, thus eliminating the costly transportation of long bars to the drill shop for resharpening. The decision to use trucks in the preliminary stripping operations was based on the desirability of this type of transportation to economically prepare the pit for rail haulage, coupled with the success that the contractors had had with them on other big excavation jobs. There are at present no plans for the use of trucks beyond the preliminary work, inasmuch as rail haulage will give lower costs after roadbeds and benches are once established. For many years to come, both ore and waste haulage will be over favorable grades. The average length of ore haul between the pit and an assembly yard will be about two miles. From there the crushers will be 1? miles with a connecting track grade of 0.4 per cent. The upper ore benches of the pit will be reached from the yard by a series of four switchbacks over a ruling grade of 4.0 per cent compensated for curvature. Tracks to the dumps will be on 0.2 per cent grades.

Jan 1, 1940

By Vernon Taylor

CANADA'S oil production is obtained almost entirely from the Turner Valley gas and oil field, in the Province of Alberta. This field, about 30 miles southwest of the city of Calgary and approximately 115 miles north of the United States border, supplied 92 per cent of production in Canada during 1937. In 1938 considerable development took place in this field and total production for the year amounted to 6,688,716 bbl., an increase of 3,922,146 bbl. over the production in 1937, which increased the percentage of production to approximately 97 per cent of Canada's total. In the British Empire, Canada's production is thus comparable to that of Bahrein Island and Burma, each of which produced approxi-mately 7,800,000 bbl. in 1937, being second to Trinidad's production of 15,500,000 bbl. The total production of the British Empire in that year amounted to 2.07 per cent of the world's total. HISTORY Development of the Turner Valley field commenced in 1913, when a well was started near a gas seepage on the banks of the South Fork of Sheep River in the central part of the Valley. This well found small quantities of a light crude oil in beds of Upper Cretaceous age and pre-cipitated a wild boom in 1913-1914 which ended with the beginning of the Great War in 1914. A small amount of drilling was done in the years from 1914 to 1922 and a few wells found small crude-oil production in the upper sands. In 1922 a few wells were started, including the Royalite Oil Company's No. 4 well (R, Fig. 1), which became the discovery well of naphtha pro-duction from the Paleozoic limestone. In October 1924, this well was completed at a depth of 3740 ft., being approximately 300 ft, in the lime-stone, with an initial flow of 600 bbl. of 72° A.P.I. gravity naphtha and 20,000 M cu. ft. of gas per day. Intense activity was not started until the latter part of 1928, when the Okalta No. 1 well (Q, Fig. 1) was drilled, with an initial production of 500 bbl. of naphtha per day. This well was only 1 ¼ miles from Royalite No. 4, but it was approximately 1300 ft.

Jan 1, 1939

By R. G. Davies

WeERTMANI has shown that the high temperature steady state creep rate, i, in lead and indium-base alloys obeys an equation of the form where AH is the activation energy, o the applied stress, n the stress exponent, and R and T have their usual meanings. He observed a variation in n from 4.5 for pure metals to 3 for concentrated alloys, which he interpreted as due to Change in creep mechanism from the climb of dislocations in pure metals to a micro-creep mechanism in the alloys. The Cottrell-Jaswon microcreep mechanism of the moving dislocation taking its impurity atmosphere with it was considered to be the most likely process, although short-range order and the segregation of solute atoms to a stacking fault will also give a stress exponent of 3. Steady state creep has been investigated in a Au - 27 at. pct Cu alloy at temperatures above 1/2 TIM where TIM the absolute melting temperature. As the oxidation resistance of this alloy is excellent all tests were carried out in air with a furnace built to give a temperature variation of less than 1°C along the 60 mm gage length. A lever-arm arrangement applied the stress with a load being adjusted between each creep test to maintain a constant stress. As each test produced less than 0.5 pct creep strain, the variation in stress during the test was negligible. The creep strain was measured by a transducer at the end of one of the alloy-steel grips, with the out of balance potential being finally recorded on a variable speed chart recorder. A typical creep curve is shown in Fig. 1. The results, Fig. 2, confirm that n is nearer to 3 than to 4.5; the creep mechanism could be any of those given above. The activation energy, AH, which is independent of stress, is consistent with a diffusion controlled process; the activation energies for the self-diffusion of gold and for the diffusion of gold into Copper are both -45 kcal per ml., There is now considerable evidence, that, when the steady state creep is dependent upon diffusion, irrespective of the actual creep mechanism, the activation energy is independent of the stress. The author would like to acknowledge the financial assistance provided by the International Atomic Energy Agency, Vienna, and the Argentine Atomic Energy Commission.

Jan 1, 1962