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By M. R. Tek

A new method for correlating the data on multiphase flow through vertical pipe is presented. The correlation is based on a "two-phase f factor" concept which was developed and successfully applied to horizontal multiphase flow by Bertuzzi, Tek and Poettmann. Field data previously published on several flowing and gas-lift wells have been used as the basis for the developed correlation. The application of the method to actual two-phase flow problems indicate that this method is capable of predicting the pressure distribution in vertical multiphase flow strings well within the accuracy range usually desired for common engineering and design calculations. A new working chart developed for calculation of two-phase pressure gradients and a graphical step-by-step procedure for the computation of pressure distribution are presented along with an example problem. INTRODUCTION Multiphase flow through vertical pipe is encountered in many engineering installations. In petroleum, chemical process, nuclear engineering and many other industries, problems associated with simultaneous flow of two or more phases through vertical pipe have been of interest for a long time. This interest has increased considerably during recent years due to applications to new processes in petroleum production and refining and to problems of steam generation and heat removal from nuclear reactors. One prominent example of vertical two-phase flow is provided by the gas-lift process where oil, water and gas flow simultaneously. If the pressure profile in a gas-lift well can be predicted within reasonable accuracy, it would be possible to get good estimates of the power required to lift the oil, the optimum depth, the pressure and the rate at which to inject gas. Furthermore, the effect of production rate and tubing sizes on these quantities can be evaluated before any design decision is made on the installation and operation of the flow string. The majority of experimental work available in the literature deals with two-component systems where individual phase flow rates in and out of the pipe remain constant. The general problem of prediction of pressure drops in multiphase flow systems is very complicated. The co-existence of numerous flow patterns of widely different geometry and mechanism, conditions of surface instability and the nature of force fields acting upon the system are among the major difficulties commonly encountered. The classical approach of fluid dynamics which would be based upon the formulation and solution of Navier-Stokes equations has been found by many investigators completely devoid of any hope of success-—not only because of inherent nonlinearities but also because of insurmountable analytical difficulties standirng in the way of setting up the boundary conditions. The presence and effect of interfacial forces on mu1tiphase flow systems further complicate the theoretical approach. For these reasons, many investigators choose to adopt semi-empirical if not purely empirical approaches in order to obtain solutions of engineering utility. A prominent practical solution has been given by Poettmann and Carpenter' in the form of an empirical correlation. In their paper, total flowing densities of fluids and solubility effects of gas in oil have been taken into account for the correlation of field data covering a wide range of operating conditions for oil wells. They treated the gas. oil and water as a single phase of combined propcrties and correlated the multiphase friction factor as a function of the product (pvd), i.e., density X velocity X diameter of the flow string. However, because the product (pvd) is dimensional while the frictior factor is dimensionless, the generality of their result's is somewhat restricted. It seems that the omission 01 viscosity effect may be one of the reasons for the scatter of data as shown in their correlation chart. The concepts of the "two-phase f factor" and the "two-phase Reynolds' number function" were recently developed and successfully applied to correlate horizontal multphase flow by Bertuzzi, Tek and Poettmann.' Recently, two new methods of correlation by Tek and Chan' have been presented on simultaneous flow of liquid and gas through vertical pipe. These two methods of correlation and the working equations in field units necessary for their application are included in this paper. The extension of the conccpt of two-phasc Reynolds' number function successfully developed for horizontal flow into vertical multiphase flow systems, development and evaluation of working charts permitting calculation of two-phase pressure gradients and

By C. Y. Ang, C. Wert

Quench aging of supersaturated solid solutions of nitrogen in columbium takes place in reasonable times in the temperature range 300&apos; to 500°C. Changes in internal friction, hardness, and electrical resistivity are found to accompany this change. THERE is practically no detailed information in the literature concerning interstitial solid solutions in either columbium or tantalum. The fact that both of these metals are used extensively commercially in both pure and alloyed states makes studies of their properties of value. While the plan is to study both these metals and their alloys extensively, so far only a small number of measurements have been made. This paper presents data obtained in the initial investigations of columbium. The principal interstitial impurities of columbium are likely to be hydrogen, carbon, oxygen, and nitrogen. The first of these, hydrogen, is outside the scope of internal friction measurements at present and nothing quantitative is known about the initial hydrogen content of the specimens. However, it is believed that it is completely absent after the preliminary heat treatments are carried out. The carbon content of the original samples is low and can be reduced still further during sample preparation. Oxygen is normally present to some extent in columbium and can also be added or removed easily. Nitrogen is also normally present in small amounts and can also be controlled within limits. Since it is not possible yet to remove all the nitrogen from columbium and since it is possible to remove essentially all the oxygen and carbon, initial measurements were made on the alloy system nitrogen in columbium. In this sense then, the alloys are true binary alloys. Little is known about the effects of nitrogen on the physical and metallurgical properties of columbium, so it was necessary to perform some rather elementary measurements on the specimens. These measurements are described briefly in the next section and are discussed in detail in later sections. Scope of the Work That internal friction is associated with diffusion of nitrogen in columbium has been known for some time. It is similar in nature to that for carbon and nitrogen in a-iron. In these latter cases, the information obtained from internal friction has been useful metallurgically.&apos; and it is not too much to expect useful information from similar studies on columbium containing nitrogen. The technique of internal friction measurements is adequately described by Ke2 At a frequency of 1 cps the internal friction peak for nitrogen in columbium occurs at 300°C and that for oxygen at 160°C." So that all the measurements will be meaningful metallurgically, the internal friction has been calibrated by making a measurement of the damping at the two peaks and a measurement of oxygen and nitrogen content by chemical analysis. A comparison of the two gives the following calibration factor: To go from damping capacity expressed in terms of 1/Q to weight percent of oxygen and nitrogen in solid solution in columbium, multiply the peak values of internal friction by about 4 and 3 respectively." Data from which these factors were calculated are presented in Table I. The increase of electrical resistance of columbium caused by the addition of oxygen and nitrogen as interstitial impurities has been quantitatively determined. At room temperature the percentage increase is small for small additions of impurities (<0.1 wt pct); as the temperature is lowered it becomes an increasingly larger factor of the total resistance. An empirical relation has been established to express the resistivity at — 195°C in terms of weight percent of oxygen and nitrogen in solid solution. It is easy to make supersaturated solid solutions of nitrogen in columbium and to observe aging phenomena. The optimum aging temperature, as in the case for carbon and nitrogen in a-iron, occurs at the temperature for which the time necessary for a single place-change in diffusion is about 1 to 10 millisec. This means for nitrogen in columbium that significant property changes should take place for this alloy at about 400" to 500°C in reasonable time intervals. Results of such aging experiments are

Jan 1, 1954

By D. T. Peters, J. C. Bisseliches, J. W. Spretnak

The pain boundary relaxation phenomenon in high-purity copper, 0FHC copper, and a precipitation-hardenable alloy o-fCu-2 uit pct Co has been studied by internal ,friction and elastic aftereffect techniques. The data were analyzed by assuming the broad distribution of relaxation times observed obeys a lognormal distribution law which enables calculation of the relaxation strength. Grain size had no effect on relaxation strength, although the peak width increased with increasing grain size and decreasing temperature. A double grain boundary peak was produced in high-purity copper by annealing to produce secondary recrystallization. The activation energy measured for 99.999 pct Cu is 37.5 * 3 kcal per mol and 46.5 kcal per mole for OFHC copper. A small peak in the Cu-Co alloy at about 220°C at 1 cps was deduced to be the grain boundary peak. Its height increased and its activation energy decreased with increasing aging time. Except for erratic peak positions the observations were consistent with the theory of pain boundary sliding. BEFORE the mechanism of the grain boundary internal friction peak in metals can be satisfactorily explained, the detailed characteristics of the relaxation process must be documented. Of interest are the effect of grain size on relaxation strength, the high-temperature background, and peak width and position. The effect on the grain boundary peak of a precipitate at grain boundaries and of the change in distribution of the particles with aging time must also be explained by any existing or forthcoming theory. The model which has received the most attention was proposed by KG&apos; and zener2 and proposes that the anelastic strain results from sliding of adjacent crystals at grain boundaries. The sliding is limited by the interlocking of grain corners. It follows, according to this model, that the relaxation strength is independent of and the relaxation time is proportional to the grain size. The proportionality between grain size, D, and relaxation time, t, has been confirmed by K&&apos; and Bisseliches . In this case, the internal-friction peaks of various specimens can be superimposed by plotting Q-&apos; as a function of the parameter vD exp H/RT where v is the frequency and H the activation energy. However, the data of Starr et 01.&apos; and Leak6 fit better to a parameter containing D to an exponent near two. A meaningful relationship is not always deducible from the shift of peak temperature with grain size. KG7 demonstrated that a twofold variation in grain size obtained by varying the amount of cold work followed by identical recrystallization anneals will cause a peak shift that is too large to be accounted for even by an exponent of two. Since the decreased grain boundary area existing with a larger grain size is exactly compensated for by an increased sliding distance, the relaxation strength should not decrease with increasing grain size. The height of the internal-friction peak has generally been observed to be rather insensitive to grain size as long as the average grain diameter does not approach the specimen diameter. Exceptions have been reported by Koster, Bangert, and Lang8 for copper, and by Leak6 for iron. The observations for copper could well have been confused by the presence df 0.3 pct0. The possibility that the peaks may simply be increasing in width with increasing grain size and that the relaxation strength, which is proportional to the area under the peak, may remain constant was not examined. his point has been checked in this investigation using high-purity copper. Atomic mechanisms to account for damping by sliding at grain boundaries have been proposed by KG7 and Mott. KG predicts the activation energy to be identical to that for self-diffusion. Mott&apos;s "island" model suggests the activation energy is nL where n is the number of atoms in an island and L is the latent heat of fusion per atom. Other authors have felt that a value equal to the activa-

Jan 1, 1964

By David Cornell, D. L. Katz

Procedures for computing turbulent flow of gas in steady state near the well bore and a graphical method for predicting unsteady state laminar flow at distances from the well have been combined to compute pressure gradients in gas reservoirs. Methods are discussed for predicting single and multiple transients at constant flow rate in an infinite reservoir, predicting constant How rate. in a finite reservoir, reproducing and interpreting back pressure test data, and prediction of the behavior of a closed-in gas well. An example of the graphical method is given for a single transient and the results are compared to a published analytical solution. A typical calculation of the pressure gradient in a reservoir and the production of gas is made .starting with data from a hack pressure test. INTRODUCTION The calculation of pressure gradients throughouse a ga-reservoir at any point in its production history is a complex problem involving turbulent flow near the well bore and unsteady state flow of the gas from the reservoir. The problem is complicated further by the variety of boundary conditions that may be imposed upon the flow. Such boundary conditions include finite or infinite reservoirs. constant or variable rates of production, constant or varying bottom hole pressures, complex initial pressure distributions throughout the reservoir, and pressure maintenance through cycling. In addition to these problems there are the practical difficulties associated with natural gas reservoir analysis These might include: (1) variation. in the permeability and porosity throughout the formation. (2) variations in the thickness of the formation, (3) communication of the producing formation with other producing zones. (4) radial variations in permeability due to influx of drilling fluid. acidizing. or the buildup of liquid in the formation around the well, (5) partial penetration of the producing zone. (6) water flood, and many others. These problems will be considered eventually. In the mean- time, it is necessary to present methods of handling the case of radial flow through a homogeneous, regular, producing stratum to a single well uncomplicated by other factors. The idealized case of steady state, radial flow from a natural gas reservoir was studied by Elenbaas and Katz5 and by Mac-Koberts.&apos; An analysis of the unsteady flow of gases through porous media has been made by Aronofsky and Jenkins&apos; for the one dimensional laminar case with the boundary conditions of constant downstream pressure and uniform initial pressure. Solutions for the partial differential equation for unsteady state radial flow of liquids through porous media have been given by Van Everdingen and Hurst" for the constant bottom hole pressure and constant production rate cases for laminar flow in a reservoir initially at a constant pressure. The analogous heat transfer equation has been treated by Perry and Berggren9 for the case of quenching a cylindrical hole in an infinite medium to a constant temperature. The back pressure curve, which involves the variation of the bottom hole pressure as it is determined by the behavior of the reservoir as a whole. has been studied by Rawlins and Schellhardt,10 Binck-lev,&apos; Baumel and Breitung,&apos; and others. No complete. adequate treatment has been given for the unsteady state, radial flow of gases into a cylindrical hole from a porous medium with or without the presence of turbulent flow and for any set of boundary conditions. If one relies only on analytical solutions of the basic equations, a new solution must be obtained for each new boundary condition. Furthermore, the complexity of the mathematical expressions for boundary conditions other than the very simple cases limits the use of analytical solutions. Graphical methods exist, however. that are general in nature, accurate, and readily employed. The analysis of steady and unsteady, laminar and turbulent, radial flow for various boundary conditions with application to specific natural gas well problems by means of graphical procedures forms the content of this paper. STEADY STATE RADIAL FLOW EQUATION FOR LAMINAR AND TURBULENT FLOW A steady state radial flow equation for laminar and turbulent flow through unconsolidated sands has been given by Muskat as discussion of the work by Elenbaas and Katz.5 This equation is based on the properties of unconsolidated

Jan 1, 1953

By J. Chupak, D. J. Salley, G. L. Simard

DITHIOPHOSPHATES and xanthates are the principal collectors for sulphide minerals, and consequently any knowledge of mineral-collector systems of this type is of value. In the present investigation an attempt was made to obtain information on the interaction of a typical dithiophosphate with galena. In carrying out this study, radioiso-topes, so much discussed in the past few years,&apos;, &apos; were extensively employed. By using radioactive dithiophosphate synthesized from radioactive phosphorus, a rapid and sensitive analytical procedure G. L. SIMARD is in the Research Division, Stamford Research Labs., American Cyanamid Co., Stamford, Conn.; J. CHUPAK, formerly in the Research Division, Stamford Research Labs., is now at Camp Detrick, Frederick, Md.; and D. J. SALLEY is in the Research Division, Stamford Research Labs. AlME New York Meeting, Feb. 1950. TP 2815 B. Discussion (2 copies) may be sent to Transactions AlME before April 30, 1950. Manuscript received Oct. 17, 1949. was at hand. This permitted determination of such important quantities as the rate of uptake of dithiophosphate by the mineral, the amount existing at equilibrium on the mineral surface and in the solution, and the desorption of the agent from the surface. Such measurements were possible even on single crystals of galena. In addition the exchange of dithiophosphate between the solution and the sorbed phase was examined, a matter which could be accomplished only by the use of isotopes. It is desired to point out at this time that throughout this paper the term "sorption" has been employed to designate the uptake of agent by mineral, without implication as to the nature of the process by which the uptake was accomplished. Experimental Materials: Galena: The galena was from the Tri-State district. For studies on ground mineral four preparations were used during the course of the investigation. These were prepared from selected large crystals by wet grinding in order to reduce surface oxidation. Alcohol was chosen as a convenient medium for this purpose. The ground mineral was then fractionated by sedimentation in alcohol, dried by evacuation, and stored in a nitrogen-filled desiccator. Data on the preparations are tabulated in table I. The size analysis indicated that the areas of the preparations were of comparable magnitude, even though the absolute values may be somewhat incorrect. Dithiophosphates: Nonradioactive dithiophbsphate (di-isopropyl or di-secondary butyl) was obtained by purification of a commercial product. An aqueous acid solution of the agent was extracted with petroleum ether, the ether layer dried, and the dithiophosphate precipitated as ammonium salt with anhydrous ammonia. Several repetitions of this process resulted in a nearly colorless, flaky product of good purity. (General formula (RO,)PSSNH,). Radioactive dithiophosphate was synthesized by heating radioactive elementary red phosphorus* • For early experiments (1943 to 1944), the elementary red phosphorus was obtained from the cyclotron group at the Crocker Radiation Laboratory of the University of California. Berkeley, through the courtesy of Dr. Joseph W. Hamilton. For more recent work (1946 to 1949). the elementary radioactive Phosphorus has been supplied by the Oak Ridge National Labarotories on allocation from the U. S. Atomic Energy Commission. with sulphur at 270" to 300°C to produce radioactive P,S,. The latter was then treated with the desired purified alcohol (isopropyl or secondary butyl) at 60" to 80°C to form the dithiophosphoric acid derivative. Purification was effected in the same manner as for the nonradioactive material. The effectiveness of the purification method was established by the isotopic dilution method." The same technique was used to show that only negligible decomposition of neutral or of carbonate solutions of the dithiophosphate took place over a period of a day; this was true whether or not galena was suspended in the solutions. Procedures: Radioactivity: The activity of a solution was obtained by counting with a small glass-jacketed, silvered Geiger counter, using a conventional scaling circuit.&apos; Crystals and other solids were counted under a bell-shaped, mica-window counter tube. Sufficient counts were made so that the probable error of counting was of the order of +I-3 pct. The specific activity in terms of counts per minute

Jan 1, 1951

By J. H. Swisher

In measuvements of the solubility of nitrogen in fer-rilic Fe-P alloys, tile nitrogen solubility is found to be Less in pIrospliorus-bearing alloys than in pure iron. The reduction in solubility is about 20 pct in a 1.0 wt pct P alloy at 1300°C and about 30 pct in a 0.23 wt pct P alloy at 440°C. Diffusion coefficient measurements at 1150 and 585°C show that phosphorus also decreases the nitrogen diffusivity in iron. In previous work on the Fe-P-N system, phosphorus was found to reduce the nitrogen solubility in liquid iron slightly.&apos; Indirect evidence for similar behavior in a Fe at low temperature was obtained by Dickenscheid and Brauner.&apos; These authors found that phosphorus reduces the height of the internal-friction peak due to dissolved nitrogen. The results of Dickenscheid and Brauner were confirmed by J. C. Swartz of this Laboratory in a single internal-friction experiment using the same specimen stock as in the solubility measurements described below. In the present investigation, the solubility of nitrogen in a fer rite-stabilized Fe-1.0 wt pct P alloy was measured in the temperature range from 800" to 1300°C. Additional experiments were performed in the temperature range from 440° to 585°C, using an Fe-0.23 wt pct P alloy and NH3-H2 gas mixtures. EXPERIMENTAL The experiments were performed in a vertical tube furnace wound with platinum wire. For experimental temperatures of 800°C and above, a mixture of 5 pct Hz in N2 was used as the reacting gas. The gas mixture was prepurified from oxygen by passage over platinized asbestos at 450°C, and subsequently over anhydrone to remove water. Flow rates of the gases were measured with capillary flow meters. The temperature was measured before and after each experiment with a Pt/Pt-10 pct Rh thermocouple. The specimens used for the high-temperature solubility measurements were in the form of rectangular plates, 0.534 by 1.6 by 3.8 cm. The specimens were cleaned in trichloroethylene and annealed for 2 hr in hydrogen at the beginning of each experiment. In measuring the nitrogen solubility, the specimens were held in the reacting gas until equilibrated, then cooled in a water-cooled copper block at the bottom of the furnace. The time needed for equilibration at 1150°C was determined by measuring the average nitrogen content of the 1.0 pct P alloy as a function of reaction time. As will be described, the nitrogen diffusivity in the alloy at 1150°C is only slightly less than its calculated diffusivity in pure iron. At temperatures other than 1150°C, the reaction time used in measuring the nitrogen solubility was about twice the calculated equilibration time for pure iron at the same temperature. With a few exceptions, the procedure for the low-temperature solubility measurements was the same as that described above. The compositions of the NH3-H2 gas mixtures were determined by collecting gas samples from the gas train and analyzing them for NH3 by titration with HC1. The specimen thicknesses were less than those used for the high-temperature experiments, eg., 0.124 and 0.051 cm for measurements at 585° and 440°C, respectively. Nitrogen concentrations were obtained by chemical analysis, using the Kjeldahl method. The Fe-P alloys were made by adding ferrophos-phorus to electrolytic Plastiron (Type 104 A). Commercial ferrophosphorus, containing 3 pct Mn and 0.35 pct Si as the major impurities, was first purified by melting under an FeO slag. In a separate heat, the electrolytic iron was melted and vacuum-carbon-deoxidized prior to making the ferrophosphorus addition. The principal impurities and their concentrations in weight percent in the 1.0 pct P alloy are as follows: Mn, 0.01; Si, <0.01; C, 0.01; 0, 0.003; and N, 0.0012. The impurity levels in the 0.23 pct P alloy are con-

Jan 1, 1968

By C. Zener, J. H. Hollomon

IT Is commonly recognized that a given material may be described as ductile or brittle only with reference to the conditions of test. Thus under the usual test conditions quartz is brittle, but under high pressures it is ductile. Salts that are brittle at room temperature become ductile at elevated temperatures. Pitch, brittle with respect o rapid loads, flows at low rates of loading. Pearlitic steel, ductile under the usual conditions of test, may be embrittled under the proper conditions of combined stresses, temperature, and rate of loading. EARLIER INVESTIGATIONS A clear analysis of the conditions necessary for plastic flow and for fracture was first given by Ludwik,1 who introduced two types of stress, the "flow stress" and the "stress at fracture." These stresses may refer to tensile or to shear stresses, or, in fact, to any type of stress. Ludwik considered these two stresses to be independent of one another, functions of the conditions of test and of the prior history of the material. For the purpose of analysis, both a flow stress and a stress at fracture can be envisaged as functions of strain over the entire range from zero to infinite strain. Thus, the material is brittle if the stress at fracture is less than the flow stress and ductile if the reverse is true. According to Ludwik&apos;s analysis, the problem of determining the effects of combined stresses, of temperature and of strain rate upon the behavior of metals reduces to a problem of determining the effect of these variables upon the flow stress and upon the stress at fracture. In the present paper, methods are described for determining the effects of two of these variables, temperature and strain rate, and examples are given of the dependence or now stress and stress at fracture, upon these two variables. The effect of combined stresses will be discussed in a succeeding paper. The flow stress may be determined from a load-diameter curve. Load-diameter curves were obtained over a wide range of temperature and over the limited range of strain rates obtainable with the lever-type Riehle machine used. The. curves were then converted to an extremely wide range of strain rate by making use of the equivalence of the effects of changes in strain rate and changes in temperature, previously proposed2 and demonstrated&apos; by the authors. According to this principle of equivalence, strain rate E and temperature T affect the flow stress only through a single parameter p of the form: p = EeQ/RT [I] In this equation, R is the gas constant (2 cal. per gram mol per deg. C.), and Q is a heat of activation, which varies from material to material, and may depend upon the strain, but not upon the strain rate or the temperature. There is associated with every value of p a flow-stress curve. Combinations of strain rate and of temperature that give the same p have the same flow-stress curve. Therefore, merely by changing the temperature of test, the effect of changing the strain rate may be obtained. Thus, under isothermal conditions, the material will behave the same at

Jan 1, 1944

By John F. Elliott, John R. Rawling

The rate of reduction of silica to silicon by carbon at 1550° to 1700°C in iron blast-furnace type slag-metal systems has been investigated. In the tower portion of the temperature range oxygen transport in the metal boundary layer at the slag-tal interface is probably rate limiting. A second step, which apparently involves a chemical process in the slag at the slag-metal interface, appears to be rate limiting when the oxygen-transport limitation is avoided. Above 1650°C rate control of the reduction by carbon probably is mixed between the two steps. INVESTIGATIONS1.2 into the equilibrium distribution of silicon between graphite-saturated slags and metals typical of iron blast-furnace practice show that, under the experimental conditions specified, the reduction of silica to silicon is relatively slow compared with the rates of other slag-metal reactions under similar conditions. For this reason, the reduction of silica in blast-furnace slag-metal systems was considered to be an interesting subject for further study. Investigations of the kinetics of the reaction3-5 suggest that several possible steps may be rate controlling, and that the rate-controlling step depends not only on the physical state of the systems but also on the configuration of the apparatus. The main objects of the investigation reported here were to sug- gest plausible reaction paths for the reduction of silica under the experimental conditions chosen and to determine the step or steps which control the rate of reduction of silica. EXPERIMENTAL Two types of experiments involving the reduction of silica from the slag were carried out. In the first, the only reducing agent present was carbon (graphite), for which the over-all reaction is (SiO2) +2C(gr) —Si + 2Co(g) [l] The second type was a graphite-saturated ferro-silicon-iron concentration cell. In it silica in the slag could be reduced either by carbon according to Eq. [I], or by a reaction of electrochemical nature in which silicon was oxidized at the ferrosilicon-slag interface and silica was reduced at the slag-iron interface without the formation of CO. The two types of experiment are described below. Reduction of Silica with Carbon as the Only Available Reducing Agent. The reduction of silica was accomplished by allowing a liquid lime-alumina-silica slag and graphite-saturated iron to react in an induction-heated graphite crucible. The crucible was 2.25 in. diameter and 5 in. deep; it was fitted with a graphite stirrer which penetrated through the slag and into the metal, Fig. 1. The slag and metal charges weighed 350 g each. Pure carbon monoxide at a pressure of 1 atm was maintained above the melt by passing the purified gas through the crucible at a rate of 0.5 liter per min. The gas did not stir either the slag or metal. Temperature measurements were made by sighting an optical pyrometer down the hollow stirrer rod into a 1/4-in. hole drilled in the stirrer blade. The crucible temperature was maintained within *15"C of the required value by manual control of the power supply to the

Jan 1, 1965

By L. C. Brown, E. B. Hawbolt

The formation of grain boundary precipitates has been studied in Ag-5.64 wt pcl Al alloys at 688°C. Large-grain specinzerzs were used and the boundary misorientation measured by X-ray diffraction. At low-angle grain boundrrries Primary sideplates form. u)hile abore a 17-deg misorientation lenticular precipitates predominate. Growth of the lenticular precipitates was studied on individual grain boundaries using a statistical technique. The thickening and lengthening rates appeared to be independent of &apos;pain boundary misorientation, indicating that grain boundary diffusion was not significant in this system. The precipitates grew urith constant shape, with both the length and thickness increasing parabolically with time. The parabolic lengthening rates were unexpected since previous theory and experimerztal results had indicated linear growth. By approximating the shape of the precipitate to that of an oblate spheroid grouling with constant shape an equivalent diffusion coefficienl was calculated. The zlalue obtained was in good agreement with nleasurements obtained fron, diffusiorz couples. IF a single-phase alloy is heated or cooled to a temperature such that the phase becomes supersaturated, there is a tendency for a second phase to precipitate from it in order to remove the supersaturation. Precipitation takes place initially on grain boundaries due to preferred heterogeneous nucleation, but subsequently Widmans kitten plates may form in the grain interiors if the grain size and supersaturation are sufficient. The type of grain boundary precipitate formed depends on the nature of the boundary. Aaronson1 and clark2 have shown that grain boundary misorientation can be characterized by the simple parameter R, where and X, Y, and Z represent the minimum rotations about three orthogonal axes required to bring the two lattices forming the grain boundary into coincidence. The maximum value for R is 60 deg. In using this parameter the orientation of the grain boundary itself is, of course, neglected. However it was found in both Fe-si3 and A1-Ag2 that the precipitate shape depended only on the parameter R. Clark found that the vast majority of precipitates formed were allo-triomorphs— lens-shaped precipitates that grew along the grain boundaries. At low-angle boundaries, however, (R < 15 deg) Widmanstatten sideplates nucleated at the grain boundaries and grew into the adjacent grains. It has been reported that the rate of growth of grain boundary precipitates is controlled by diffusion within the supersaturated phase.&apos; The theories which have been developed for growth rates have assumed the diffusion coefficient constant over the composition range of the supersaturated phase. This is a fairly good approximation if the composition range involved is not large. Thickening rates have been calculated using the theory developed by Zener4 and by Frank5 for the growth of planar precipitates. A parabolic growth law

Jan 1, 1968

By K. M. Kolobova, E. Z. Kurmayev, A. Z. Menshikov, S. A. Nemnonov, V. A. Trapeznikov

The present work represents a review of our intestigations into the X-ray spectra of solids, which have been carried out by us along two lines of upproach: 1) St@ of the electronic structure of high -rnelting compounds of transition metals; 2) stzddy of the interatomic binding forces by the fine structure of absorption spectra under varying temperature and concentration conditions. With this in mind, int>estigations hare been made into the emission and absorption spectra of the K-series of atoms of transition elements in alloys and compounds. In the problem concerned with the electronic structure of high-melting compounds of transition metals, considerable importance is attached to the question of ascertaining the role played by 3d4sp electrons of metal and 2p electrons of metalloid in the formation of chemical bonds and of giving, on the strength of this data, an explanation of the properties which seem to be contradictory at first sight: good conductivity inherent in metals and high brittleness and high-melting characteristics typical of covalent compounds. Over the last few decades this question has attracted the attention of many investigators whose studies were devoted to this type of compound. Many works, both of theoretical1-3 and experimental4- l5 nature , have contributed much to the elucidation of the physical character of the phenomenon referred to. Alongside the investigations in the field of electric resistance, Hall effect, paramagnetic susceptibility, electronic heat capacity, and the temperature of transformation into a superconducting state, we should particularly emphasize the studies on X-ray spectra, which have played a significant role in the development of the zonal theory for high-melting compounds. This fact has become highly evident after the theoretical calculation of the energy spectrum has been made and the density of states curve in Tic, TiN, and Ti0 has been plotted by Ern and Switendick3 who used the method of augmented plane waves. Correlation of the results of the theoretical calculation of the band structure in the compounds listed above with the data obtained by X-ray spectroscopy studies showed that X-ray spectra can be a source of valuable information on the electronic structure of high-melting compounds within a wide range of ener- gies. It is well known that X-ray emission spectra basically give a direct picture of the occupied excited states above the Fermi level of a solid (valence band, conduction band) and that the absorption spectra (region of initial absorption) give a similar picture of states corresponding to the unoccupied levels near the Fermi surface. Full information on the density distribution of electronic states by energies can be obtained by combining the emission and absorption spectra. Such an opportunity arises from investigation

Jan 1, 1970

By Walter V. Knopp, Laurence Delisle

The aim of this work was the preparation of nickel-steels from elemental metal powders by powder metallurgy techniques. It was known that plain carbon steels could be made from a mixtufe of iron powder and graphite and that the effect of carbon on iron in powder form was of the same nature as that produced in fusion metallurgy. The problem in making nickel steels from elemental powders consisted therefore in finding out whether sufficient diffusion of the nickel and other incidental metals . normally present in such steels could be induced in the solid state to modify the properties of plain carbon steels made from powders and produce the beneficial effect of alloying. The composition selected originally was that of an S.A.E. 2330 steel. Metal powders, in the proportion correspending to that composition, were mixed with graphite, pressed, and heated at different temperatures for different periods of time, to produce bonding of the metal particles and mutual diffusion of the various elements without melting. Temperatures up to 1325°C and sintering periods as long as 6 hr were first investigated because it was expected.that such conditions would produce maximum diffusion with an accompanying improvement in the properties of the alloy. It was found that, although diffusion proceeded to a large extent under the conditions investigated, it would not be complete unless sintering were carried out at a high temperature for much longer than 6 hr. Relatively high temperatures and long sintering times are objectionable from a practical point of view, particularly when a low COSt material is to be produced, because they necessitate the use of special, costly equipment. Work could be done to improve the diffusion of iron and nickel by changing conditions other than the sintering temperature and time, that is, finer primary or alloy powders could be used. However, a marked change in the properties of the steel had been observed even with only partial diffusion. It was thought, therefore, that instead of trying to improve the diffusion, advantage might be taken of its incompleteness to produce a special structure consisting, in the unquenched condition, of a hard constituent, rich in nickel, dispersed in a tough pearlitic matrix. Steels with such a structure, not readily obtainable by fusion, should have desirable mechanical properties. Besides, it should be possible to prepare them from elemelltal powders under economical conditions. This latter alternative was therefore adopted for the second phase of this work. This report is divided into four parts: I. General Procedure. 2. Effect of Sintering Temperature. 3. Effect of Varying the Nickel Content. 4. Effect of Alloying Elements. General Procedure The general technique of cold pressing as used in powder metallurgy was applied.

Jan 1, 1949

By H. Sigurdson, C. H. Moore

Extensive studies have been carried out on electric furnace and blast furnace slags obtained in the winning of iron from its ores. These slags normally consist of elements of the gangue minerals present in the ores, as well as the added flux materials. In consequence, melts of CaO, MgO, Al2O3 and SiO2 can be considered as representing typical slag compositions. When a slag of this composition cools, it usually crystallizes according to predictions possible from an equilibrium diagram of these constituents, providing the melt is not undercooled to form glass. The melt is either viscous or fluid, depending upon the ratio of binary cations to silica, and crystallizes easily or forms a glass for the same reasons. If the melt is not overheated so that carbides of the metal components of the slag are formed and if the composition of the slag is so adjusted that it has a high fluidity, liquid equilibrium is attained and the slag can be held in a liquid state for extended periods of time. Upon tapping, the slag crystallizes into minerals, the type and proportion of which are determined by the melt composition. Since equilibrium is attained, the holding period is not critical. In melts containing a large increment of titanium, however, the normal slag procedures are not applicable. Titanium, as one of the atomic transition elements, is, at elevated temperatures, capable of being reduced to form metalloid compounds much more readily than the refractory oxides present in normal slags. In consequence, an oxide melt containing titanium never reaches equilibrium in a reducing environment, but continues to shift its composition until cooled. If melts of this nature are cooled and samples submitted to metal-lographic and X ray analysis the course of reaction and crystallization in this type of slag can be determined. Preparation of Slag The slags investigated fell into the system CaO-MgO-TiO2-Al2O3-SiO2 and were produced from ilmenite ores reduced by carbon in an electric furnace. Since the equilibrium series1 and the laboratory smelting of ilmenite2 are described in two of the accompanying papers, detailed description of the smelting procedure is not required here. However, certain essentials must be mentioned. Two types of melts were used to produce slags studied in this investigation. The first series of smelts made to determine proper flux addition were produced in a 4 lb Ajax induction furnace. The charge, consisting of ore with the proper flux addition, was heated in a graphite crucible until fluid, held fluid for a sufficient time period to obtain 1-5 pct FeO content, and poured. Because of the small size of the charge only the final sample of these melts could be examined. In the melts made in the 50 lb arc furnace, however, grab samples taken at 10 min. intervals between time of initial melting and final pouring were available for examination. These samples allowed a much clearer picture of the course of reaction and crystallization. amounts of ferrous oxide and reduced titanium compounds is opaque to transmitted light. Therefore, all petro-graphic studies had to be made on polished slag sections. A representative sample of slag was cut or broken, mounted in a thermosetting plastic, ground flat using 400 grit silicon carbide, the coarse scratches removed with 600 grit silicon carbide and polished on billiard cloth using levigated alumina. Rouge was avoided because of the entrainment of the red particles in pores in the slag, causing a possible confusion with some of the mineral phases. In order to prevent sample projection above the plastic surface red bakelite was used to hold the sample, and backed up with clear lucite. In this manner sample labels could be permanently retained in the mounting. The polished samples were examined on a Bausch and Lomb metallograph at magnifications of 250 X, 500 X, 1000 X and 1800 X. The instrument was equipped for examination of specimens under bright field illumination and with crossed nicols. A magenta tint plate to aid in color tone differentiation was also used. Petrology of Slags In order to determine the composition and mineral relatinos of a previously unreported system petrologically, it is essential that the starting composition, reaction temperature and final composition be known. The chemical composition of the ilmenite ore used in these smelts is given in Table 1, and the complete analysis of a typical high titanium, low iron slag is given in Table 2. In the winning of TiO2 from ilmenite by a smelting process it is necessary to produce a slag which will melt at an economically feasible temperature, remain molten as the iron is removed by reduction, be fluid enough to be readily removed from the furnace, contain a high percentage of TiO2 and a low percentage of reduced titanium com-

Jan 1, 1950

By Charles Fulton

EXPERIMENTAL work on the process was begun on a laboratory scale at Cleveland, Ohio, in 1914, and transferred to East St. Louis, Ill. in 1916, where a commercial sized furnace was in technical operation until January, 1918. The essential steps of the process are as follows: Oxidized zinc ore or roasted zinc concentrate is mixed with crushed coke and coal-tar pitch and formed into briquets 9.25 in. (23.5 cm.) in diameter and 21 in. (53 cm.) long in a manner similar to that used in the manufacture of graphite or carbon electrodes, except that much less care and time are required. The composition varies with the nature of the ore; in one case, the composition was 100 parts ore, 70 parts coke, and 18 to 20 parts pitch. These briquets maintain their form and volume during and after the distillation of the zinc. This object is gained by using coke as the matrix and coal-tar pitch as the binder; this pitch becomes coke on heating and unites the ore particle and the original coke particle into a continuous mass. The briquet is an electrical conductor but only to such, a degree that it can be used as a resistor. The size of the ore, as in the present practice of zinc metallurgy, ranges from fine material, such as flotation concentrate, to coarse table and fine jig concentrate. The process is not restricted to any particular kind of ore, but is applicable to pure high-grade ores, ores high in iron, and complex zinc lead ores, since the residue from the distillation is held immovably in place within the briquet. In the case of complex zinc-lead ores, the distillation is conducted with a carefully regulated temperature so that a high percentage of lead is retained in the distilled briquet, which may then be smelted for its lead content. In present zinc smelting practice, the reduction fuel is from 40 to 50 per cent. of the weight of the ore. In the briquet, it is from 60 to 85 per cent. of the ore; but unless the ore is exceptionally high in residue, the distilled briquet

Jan 9, 1919

By I. Cornet

INTRODUCTION WITH the greatly expanding use of magnesium during the war, it appeared necessary to the War Metallurgy Committee that the notch sensitivity of magnesium alloy extrusions be further investigated and the influence of various factors upon notch sensitivity be noted. Accordingly, the National Defense Research Committee of the Office of Scientific Research and Development placed a research contract with the University of California, supervised by the War Metallurgy Committee. The work discussed herein was done under "Restricted" Project NRC-21, reported in Dec. 1943 1; it has been released for publication by the O.S.R.D. SCOPE OF THE INVESTIGATION The notch sensitivity of various magnesium alloy extrusions was determined under axial tension, and also under several conditions of nonaxial tension. Hardness, grain size and other metallographic features were observed; stress-strain data were obtained, and the chemical compositions of the alloys were determined, in order to correlate these quantities with the notch sensitivity. Notch sensitivity under axial tensile load was determined for a few specimens which had been cold worked to various degrees by tensile prestraining. Magnesium alloy extrusions studied included Dowmetal 0, X, J, and M. For comparison, extrusions of aluminum alloy 24S-T, cast bars of aluminum alloy I22-T2, and cast bars of magnesium alloy C were also tested, The specified chemical composition of these alloys is given in Table I. All bars tested were within specification limits of composition. Investigation of the tensile notch sensitivity of various magnesium alloy extrusions, under conditions of axial and eccentric load, showed little or no correlation with stress-strain or other conventional data. Since the many uncontrolled variables present might mask significant relationships, one alloy was selected for intensive study. Magnesium 0 alloy extrusions were subjected to experimental heat treatments, and the changing hardness, tensile strength, microstructure, and notch sensitivity observed. EXPERIMENTAL TECHNIQUES AND PROCEDURES Tensile Testing Bars used for axial loading were machined with 3/8 in.- and with 1/4-in. minimum diam, and included specimens with 6o° V notches (Fig I and 2). Each V-notched specimen was roughed out carefully and then finished with a honed tool. These V-notched bars were sampled frequently, sectioned, polished, and examined at 500 X magnification to control

Jan 1, 1948

By Chas. Y. Clayton, Francis B. Foley, W. E. Remmers

DuRing the summer of 1919, the late Dr. Henry M. Howe, then Chairman of the Division of Engineering of the National Research Council, organized a committee to obtain a better insight into the behavior of carbon steels under the influence of various treatments by a proper control of the time and temperature factors. During part of 1919 and 1920, work in connection with this investigation was carried on at Dr. Howe&apos;s laboratory at Bedford Hills, N. Y. During 1921 there was an enforced hiatus in the work, occasioned by the illness which resulted in Dr. Howe&apos;s death in 1922. At that time one of the present authors compiled the results of the work which had been done and this was published in 1923.&apos; Following the publication of this work, it seemed desirable to carry on in the same manner an investigation of steel of C 0.75 per cent., which steel had not been as fully treated as had the other steels of C 0.34 and 0.52 per cent., used in the published work. Furthermore, certain unusual results have been obtained in the treatment of C 0.52 per cent. steel by quenching and drawing, and repetition of this part of the work seemed advisable. This has been done during the past year at the School of Mines and Metallurgy of the University of Missouri at Rolla, Mo., by a cooperative undertaking of the School and the Bureau of Mines, working in conjunction with the Committee on Heat Treatment of Carbon Steels of the National Research Council. The present paper is a report of the results obtained in this work.

Jan 1, 1926

By J. H. Nead

Discussion of the paper of J. H. NEAD, presented at the New York meeting, February, 1916, and printed in Bulletin No. 108, December, 1915, pp. 2341 to 2357. E. D. CAMPBELL, Ann Arbor, Mich.-Any one at all familar with research work can at once see that Mr. Nead has condensed into his tables and curves the results of a carefully planned set of experiments which must have involved a great amount of work on his part. He deserves much credit for the way in which he has carried out these experiments, for it is to the results of such systematic experimentation that we must look for further knowledge of the underlying causes which determine the physical properties of steel. It will probably be many years before we have sufficient knowledge of all the factors of the problem of the constitution of steel, but every set of carefully carried out experiments such as Mr. Nead has made adds something to our knowledge and brings us a little nearer to the final solution of the problem.

Jan 5, 1916

By N. Jaffee, J. E. Dorn

An activation energy of 27,400 5 1000 cal per mole was obtained for the creep of poly crystaLline aluminum over the temperature range of 273° to 350°K, at strains varying from 0.003 to 0.230. Stresses varied fronz 2250 to 6000 psi, strain rates from 0.1145 x 10-5 to 29.5 x 10~s min.-1. A strain temperature-compensated time correlatzon was oblained indicating that the structure was depedent solely upon the strain at a given stress; X-ray diffraction analyses and tensile tests on precrept specimens verified this. PREVIOUS investigations1 have revealed that the apparent activation energies for creep of high-purity polycrystalline aluminum are insensitive to the applied stress, strain, and strain rate. On the other hand, the apparent activation energy is dependent on the temperature1,2 as shown by the data reproduced in Fig. 1. Each plateau of this curve is associated with a unique rate-controlling dislocation mechanism for thermally activated creep. It is now very well-established that over the high-temperature range, where the activation energy is about 35,500 cal per mole, the creep rate is controlled by the dislocation climb mechanism. 3 Over the intermediate range of temperatures, from about 260° to 370°K, another unique activation energy, namely 28,000 cal per mole, is obtained. Current evidence strongly supports the contention that cross slip is the rate controlling mechanism for creep in this case: 1) Crystal recovery can occur by a number of mechanisms prominent among which are climb and cross slip. Astrom,4 using the Borelius micro-calorimeter, reported rapid crystal recovery of cold-worked polycrystalline A1 at 340° to 370°K giving an activation energy of 28,000 cal per mole and additional recovery at 455° to 478°K giving an activation energy of 3 6,000 cal per mole. Whereas the latter recovery process was clearly associated with the dislocation climb mechanism, the former, 28,000 cal per mole process could have arisen as a result of the cross-slip mechanism. 2) Single crystals of high-purity A1 favorably oriented for octahedral glide exhibit an activation energy for creep of about 3400 cal per mole over the range from 0° to 400°K and that of about 28,O:O cal per mole over the range from 600° to 775°K . Whereas the lower activation energy process is accompanied by the development of sharp slip-band traces, the 28,000 cal per mole process was uniquely characterized by extensive cross slip. 3) Theoretical calculations by Seeger and schoeck6 suggest an apparent activation energy for cross slip in A1 of about 24,000 cal per mole and another theoretical estimate by Friedel 7 gives the observed 28,000 cal per mole as the theoretical activation energy. It is therefore consistent with this evidence to, at least tentatively, ascribe the 28,000 cal per mole creep process in A1 to the operation of cross slip as the rate controlling mechanism. Although creep has been rather well-explored in the dislocation climb range, very little, excepting perhaps the activation energy, is known about creep in the cross slip range. This investigation was undertaken, therefore, to reconfirm the activation energy for creep in polycrystalline A1 in the intermediate temperature range and to study the strain-time relationship for creep at a constant stress in the cross slip region. EXPERIMENTAL PROCEDURE AND TECHNIQUE The three types of high-purity A1 alloy specimens described in Table I were used in this investigation. Specimens were milled from 0.100 in. thick cold-rolled sheets with their tensile axes in the rolling direction following which they were given a recrys-tallization and grain growth heat treatment at temperatures well above those which were subsequently employed in the creep tests.

Jan 1, 1962

By J. B. Wagstaff, R. A. Buchanan, J. F. Elliott

High speed photography through blast-furnace tuyeres showed coke particles moving rapidly. Model studies showed a raceway was formed and gave quantitative results which were correlated with actual blast furnaces. Another study showed the similarity between hanging and the flooding of a packed column. This was explored by models. THE combustion zone before the tuyere in an iron blast furnace is a vital region because here are generated: 1—most of the gases on which the furnace depends to carry out its basic operation of reducing iron ore to the metallic state, and 2—the major fraction of the heat required in the nearby regions of the furnace for the various reduction reactions, the fusion of the slag, and the melting of the iron. Since the greater part of the coke is consumed in this region, the descent of the burden must be greatly affected by the characteristics of the tuyere zone. This region then would seem to be a profitable field for study. Fortunately, a view into this important zone is available to the operator through the tuyere peep sight. Here he sees relatively dark pieces of coke "dancing" in the blast. What he sees is of considerable help in interpreting the behavior of the furnace at a given time but the very rapidly moving particles and the intense radiation obscures what is happening very deep in the zone. This investigation was initiated in the hope that a better understanding of the combustion region could be obtained by using a high speed camera with a maximum speed of 3000 frames per sec. It seemed the best practical method of "slowing down" this characteristically violent action within the highly luminous field. Model studies and tuyere probing also have been used to aid in explaining the observed phenomena. Above the combustion zone, but below the fusion zone, there is probably a region in which the coke is comparatively stationary. Here are zones in which the gases must flow up through the granular bed counter to descending liquid slag and metal. There is no easy way to observe this zone in a blast furnace, but model studies have been of some help in explaining the nature of the zone and the laws governing the flow of the fluids involved. The whole problem is difficult and involved and any approach to a complete solution may require long investigation. This preliminary report has been written, therefore, because it is believed that appreciable progress has already been made that would be of interest to others. Tuyere Studies, Chemistry and Kinetics It is well known from the early work of Kinney and coworkers1,2 that combustion of carbon before the tuyeres appears to occur in two zones: Zone A: C + O, = CO2; AH77°F. = — 14,108 Btu per lb of carbon [I] Zone B: CO2 + C = 2CO; H77°F = + 6,183 Btu per lb of carbon [2] Zone A (Fig. 1) is close to the tip of the tuyere and zone B is somewhat farther back; there being a transition region in which both reactions occur. It is interesting to estimate the rate at which coke is burned before a tuyere with a wind rate of 90,000 cfm in a modern furnace having 18 tuyeres. Approximately 0.55 lb of carbon is consumed by eq 1 per tuyere per sec. A like amount disappears by eq 2 for a total consumption of 1.11 Ib per sec per tuyere. Assuming the coke is 85 pct C and has a bulk density of 30 lb per cu ft, this figure can be converted to a total of 1.30 lb of coke with a bulk volume of 0.043 cu ft disappearing per sec per tuyere. At the temperatures prevailing in the combustion zone (according to Kozlovich,³ he maximum is about 3400°F), the rate at which carbon is con-

Jan 1, 1953

By R. E. Ogilvie, J. I. Goldstein

The a and y solubility limits in the Fe-Ni phase diagram have been redetermined at temperatures above 500°C. Both a diffusion-couple and a quench and anneal technique were used. The solubility limits were measured with an electron-probe micro-analyzer. The nickel concentration at the phase boundary is increased below 700°C and the a solid-solubility range is much larger than had been previously measured. The solubility limits are also extrapolated to 300°C. It is suggested that the solubility of nickel in a FeNi reaches a maximum in the temperature interval 400o to 500°C. THE equilibrium diagram has been of great use in the field of meteoritics, where the phase relations between kamacite (a) and taenite (?) in metallic meteorites can be described by means of the Fe-Ni diagram. The study of metallic meteorites by electron-probe microanalysis has cast some doubt on the accuracy of the presently available Fe-Ni diagrams.1, 2 Recent thermodynamic studies of the Fe-Ni system also suggest that the diagram may be in error.3 For these reasons the high-temperature (800o to 500°C) part of the diagram was redetermined. INTRODUCTION The currently accepted Fe-Ni diagram is that of Owen and Liu.4 Above 910°C, there is a region of complete solid solubility, ? (fee). Below 910°C, the a (bee) phase is stable in pure iron. The effect of increasing amounts of nickel is to stabilize the y phase. The phases that form when Fe-Ni alloys are heated or cooled bear little relation to the equilibrium diagram. If an alloy is cooled from the y state and held at a temperature within the a + y field, no evidence has been found for the occurrence of the y - a transformation.5 If the alloy is cooled to low enough temperatures the y phase breaks down into a supersaturated bee phase called a2. In fact, in alloys over 27 pet Ni the y phase is retained at room temperature.6 The a, phase has the same composition as the original y. The temperature at which a2 forms, the M, temperature, has been determined experimentally.&apos; A state of equilibrium can be approached by cooling below M, to form a2 and then reheating the alloy into the two-phase region of the diagram. The y phase will then begin to precipitate out of the a2 phase and grow. The growth of the phase, however, is quite slow. Using the interdiffusion coefficients -Da of Goldstein et al.,8 it is estimated that it takes about 1 year to grow a 10-µ-wide region of ? at 700°C in a 5 pet Ni alloy. Owen and Liu4 used the technique just described to form the equilibrium phases. The phases present were determined by means of X-ray analysis. The accuracy of their diagram depends on the number of alloys available near the phase boundary at a given temperature. In this study two different techniques were used to determine the a/a + ? and ?/a + ? solubility limits. The inherent accuracy of both techniques was greatly improved over that used by previous investigators because the phase-boundary compositions were measured with an electron-probe microanalyzer. PROCEDURE The two methods used to determine the Fe-Ni diagram are the diffusion couple (D.C.) and the quench-and-anneal (Q.+A.) techniques. In the first method, diffusion couples whose diffusion path goes through a two-phase region of the phase diagram were used. A description of the technique used for making the diffusion couples has been described in a previous paper.&apos; After the diffusion treatment a discontinuity in the resultant concentration vs distance profile was measured. The nickel concentrations in the a and ? phases at the interface of the discontinuity are the solubility limits of the a and ? phases in the phase diagram at the diffusion temperature. If the interface com-

Jan 1, 1965

By J. Brett, S. Friedman

A study of the diffusion of nickel into both fibrous and recrystallized 0.065-in.-diam silica-alumina doped tungsten wire at 1200°C has been conducted. The diffusion profiles were determined by chemical dissolulion of successive circumferential layers and spectro-photometric determination of nickel in the etchant. It was shown that the diffusion of nickel into tungsten is markedly structure-sensitive. No significant amount of nickel could be introduced at 1200°C into tungsten which had first been recrystallized at temperatures of 2300°C, leading to an upper limit estimate for the bulk diffusivity of nickel in tungsten of 10-11 sq cm per sec at 1200°C. However, nickel did diffuse into initially fibrous wires, caused re crystallization, and was alsays present at the advancing recrystallization front. The accumulation of nickel in an initially fibrous region ceases when the recrystallization front arrives. The characteristics of the resulting diffusion profiles are explained in terms of the relation between diffusion processes and micro structural changes. WHILE it is well-known that the presence of nickel and certain other metals causes low-temperature recrystallization of the cold-worked fibrous structure of doped tungsten,&apos;&apos;&apos; the character of the phenomenon is not well understood. Recently it was shown that the recrystallization reaction can be induced at low temperatures by the presence of solid nickel on the surface of doped wire, but not by exposure to nickel vapors.3 Once recrystallization was initiated, a continued source of nickel was required for propagation of the recrystallization front. The phenomenon appeared to be a complicated solid-state reaction since, in addition to the change in structure of the tungsten from fibrous to equiaxed grains, diffusion of nickel from the surface into the recrystallized and fibrous structures was occurring with possible chemical reaction between nickel and tungsten at the surface and interaction of nickel with the dopants which ordinarily stabilize the fibrous structure within the wire. The objective of the present work was to study the diffusion of nickel into fibrous and recrystallized tungsten structures in order to clarify the relationship of the diffusion process to nickel-induced recrystallization. Studies of interdiffusion in the Ni-W system4"7 have been principally concerned with the mobility of tungsten in nickel. Information on diffusion of nickel in tungsten is meager, and there seem to be no studies of the mobility of nickel in tungsten which elucidate the structural aspects of the phenomenon. The present experiments were designed to determine the diffusivity of nickel at 1200°C in fibrous tungsten, in large-grained tungsten prerecrystallized at high tem- perature, and in tungsten recrystallized at 1200°C due to the presence of nickel. Although the concentration profiles were determined in these experiments, unexpected changes in boundary conditions or complex diffusion paths complicated the analysis of these profiles so that the interpretation could not be readily expressed in terms of simple diffusivities. EXPERIMENTAL PROCEDURE The experiments were conducted on Sylvania 0.065-in.-diam silica-alumina doped commercial tungsten wire, hereafter designated as ordinary doped wire. A special lot of 0.065-in.-diam silica-alumina doped low-nickel wire was also used. Impurity analyses of the wire are given in Table I. The experimental design is shown in Fig. 1. All heat treatments were conducted in vacuum. Two groups of ordinary doped wire were prepared for diffusion with nickel. One group in the as-received (fibrous) condition was elec-tropolished, nickel-plated, and annealed at 1200°C for 20 and 40 hr, or was exposed to nickel vapor at 1200°C for 20 and 40 hr. The second group was recrystallized to an equiaxed grain structure at 2300°C for 3 hr, electropolished, nickel-plated, or exposed to nickel vapor for anneals at 1200°C for 20 and 40 hr.

Jan 1, 1969