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By Arnulf Muan, Carlos Landolt

Equilibria involving Cu-Pt alloys, copper oxides, and atmospheres of known ox2gen pressures have been determined at 1000' and 1200 C. The data obtained have been used to calculate activity-composition relations in the alloys. A moderate negative deviation from ideality is found. At high copper concentrations, the results of the present study are in good agreement with those of previous investigators, whereas at low copper concentrations the activities obtained in this investigation are slightly higher than those reported previously. The present study is part of a research program dealing with the determination of phase relations and thermodynamic properties of copper-containing systems at high temperatures. The information available for such systems is very scanty, particularly for copper oxides and their combinations with other oxide components. Platinum is commonly used as a container in studies of oxide equilibria. To evaluate quantitatively the extent of reaction between the oxide and the container, a knowledge of activity-composition relations in Cu-Pt alloys is necessary. Such data are not available for Cu-Pt alloys in the temperature range of particular interest in the present research program, and particularly for alloys low in copper. Studies of various aspects of the systems Cu-Pt and Cu-0 have been reported in previous literature. The system Cu-Pt is known1 to form a continuous solid-solution series above 812.C, whereas ordered phases are present in certain composition ranges at lower temperatures. Thermodynamic data for the system have been reviewed by Hultgren et al.,' who presented free energies of mixing at 65Oo C, mainly derived from electromotive force cell measurements by Weibke and Matthes.3 Enthalpies of mixing at 640°C have been obtained by Oriani and Murphy4 with liquid tin calorime-try. Their results differ considerably from those derived from the temperature dependence of the data of Weibke and Matthes. Thermodynamic data for the disordered alloys have been obtained by Assayag,5 and more recently by Schmahl and Minzl,6 by Myles and Darby,7 and by McCormack, Myers, and Saxer.8 The two latter sets of data7'' became available after the present study was completed. In the system Cu-0+ two oxides are stable at high temperatures, CuO and CuzO+ each having only minor deviations from stoichiometry. Equilibria in the liquidus temperature region of the system Cu2O-CuO have been studied by Roberts and systemsmyth,9'10CuzO-CuO by Vogel and ocher,I1 by Osterwald,12 and recently the the present authors.13 The system is of the eutectic type with a eutectic temperature of 1083.C The composition of the eutectic liquid corresponds to Xcu0 = °.44, and the oxygen pressure of the coexisting gas phase is Po2 = 0.55 atm.13 Equilibrium oxygen pressures for coexistence of solid CuO and solid Cu2O have been determined by Schmahl and Muller,l4 by Gadalla, Ford, and white,l5 by Bidwell,16 and recently by the present authors.13 There is reasonably good agreement among the various sets of data. Free energies of formation of Cu2O(s) from the elements have been derived by Tretyakov,17 by Bidwell,16 by Kiukkola and wagner,18 by Pal'guev and Neuimin," and by Steele and Alcock,20 There is particularly good agreement among the latter three1'-20 sets of data. THEORETICAL BASIS Consider a subsolidus isothermal section of the system Cu-Pt-0, as shown in Fig. 1. Two phase as-

Jan 1, 1970

G. D. Kneip, Jr., and J. 0. Betterton, Jr. (Union Carbide & Carbon Corp., Oak Ridge, Tenn.)—The authors have contributed to the theory of zone melting by considering the effects of the solidification of the final zone on the distribution curves for the finite length bar. However, they do not consider in sufficient detail the restrictions imposed by the particular metals involved. Eq. 4 has the analytical solution which is equivalent to Pfann's' equation for normal solidification of the final zone. For distribution coefficients less than one, it is apparent from this form of the equation that, as the solidification approaches completion, the concentration attains extremely large values which are inconsistent with the density of physical materials. The necessary restrictions then are that the solute concentration cannot exceed the density of the alloy, or more frequently, the solubility limit in the solid phase. Secondly, the distribution coefficient cannot be constant from 0 to 100 pet solute unless the liquidus and solidus coincide over this whole region. It would thus be more correct to impose limits on the solubility such as would be indicated by a typical eutectic diagram. Furthermore, in this case the assumption that the distribution coefficient remains constant is more likely to be realized. Eq. 4 should then be replaced by the following C,,(x) =k/L-x [ ?11 3 C11 (x)Ddx - ?11 4 Cn(x)dx= k[Cn (L-l)/k] [ L-x/l]x-1 L-l = x = L-l [kCenterlie/Cn (L-l)]1/k-1 The typical shape for the distribution curve in the final zone is indicated schematically in Fig. 12 for the simple eutectic case. The solidification proceeds according to Pfann's' expression until the concentration reaches the maximum solubility in the solid phasc. At this point, the concentration changes abruptly to the eutectic composition and remains at this value for the duration of the solidification. The width of the flat region, and the back reflection of this effect into the concentration curve on subsequent passes, depends upon the ratio of the eutectic concentration to the original concentration, upon the distribution coefficient, and upon the number of passes. Similar effects on the concentration curves in the first zone length would be expected in many systems for which the distribution coefficient is greater than one, and where the maximum solubility is not too much larger than the original concentration. The discussers agree with the authors that the assumption that the liquid is uniform in concentration should be considered with caution. Kneip and Better-ton' have shown, however, that in floating zone refining of zirconium, using induction heating, the distribution of iron agrees with theory which assumes a uniform liquid composition. Hence, in this case, the experimentally realized distribution coefficient agrees with the present phase diagram within the experimental uncertainty. L. Burris, Jr., C. H. Stockman, and I. G. Dillon (authors' reply)—The authors are happy to have received the comments of G. D. Kneip, Jr., and J. 0. Betterton, Jr., which provide additional insight into the zone refining process. It is true that the equations developed are inapplicable if the solute solubility in the solid phase is exceeded. However, this restriction on the use of the equations was clearly stated in the paper. A closer approach to

Jan 1, 1957

By W. A. Tiller, W. C. Johnston

The solute distribution ahead of an advancing solid-liquid interface is controlled by varying the momentum boundary layer thickness in the liquid adjacent to the interface. Single pass zone-melting experiments on Pb-Sn alloys are described in which the liquid is caused to rotate in the plane of the solid-liquid interface due to the influence of a magnetic .field rotating in this plane. The variation of the diffusion boundary layer thickness with field strength is determined. DURING the freezing of an alloy a partitioning of solute occurs at the solid-liquid interface, the magnitude depending upon the difference in the solid and liquid solubilities at the interface temperature. Because the diffusion coefficient is so small in the liquid relative to normal freezing rates, either a pileup or a depletion of solute occurs at the interface when the partition coefficient, kO, is either less than or greater than unity, respectively. This solute distribution is completely characterized by i) the solute concentration in the liquid far from the interface, C) the ratio of freezing velocityf, to diffusion coefficient, D, iii) the partition coefficient, ko, and iv) the thickness of the diffusion boundary layer, 6,, at the interface (this assumes that an electric field is not applied across the interface). For a particular system, C ko and D are fixed so that the character of the solute distribution can be changed only by a variation of either f or 6c. As is well known, the freezing velocity can be changed by varying the thermal environment of the alloy. Whereas, the thickness of the solute rich layer can be changed by varying the fluid flow conditions in the liquid. It is the purpose of this paper to describe a technique for controlling the fluid flow conditions in the liquid. During most solidification experiments the driving force for fluid flow arises from either mechanical mixing, thermal convection or electromagnetic mixing. The momentum boundary layer thickness, 6m at the solid-liquid interface, within which negligible movement of the liquid occurs, has been calculated for the special case of mechanical mixing where crystals are solidified by the Czochralski technique.l,2 The calculation of 6m for the case of thermal convection has also been made.3 In some calculations it has been assumed that the momentum boundary layer thickness, 6,, may be equated to the thickness of the diffusion boundary layer 6c, at the interface. However, as may be seen from Appendix I this is only true in very special cases and in general where a is a constant of magnitude determined by the particular liquid alloy. Neither calculations nor experimental data exist for the dependence of upon electromagnetic mixing. In this paper experiments are described in which the liquid is caused to rotate in the plane of the interface due to the torque developed on it by a magnetic field, H, rotating in this plane. The variation of is controlled by the variation of H. A magnetic field rotating in a plane perpendicular to the interface has been used for the purification of aluminum. Experimentally, we determined the variation of 5C with H by using the zone-melting technique of pfann5and a theoretical relationship of Burton et a1.2 pfann5 has shown that, after the passage of one molten zone through a long cylindrical charge of uniform concentration, CO, the solute distribution, C,, in the solid is as shown in Fig. 1. The equation describing this distribution is

Jan 1, 1962

By S. H. Moll, R. E. Ogilvie

The investigation of solid-state diffusion phenomena may lead to much information concerning binary alloys. In particular, a study of the concentration gradients present in multiphase diffusion couples can lead to the determination of the solubility limits of the single-phase fields in the phase diagram. The specific concentration gradient which results from the heat treatment of a diffusion couple depends not only upon the time and temperature of diffusion, but also upon the number of phases existing in equilibrium at the diffusion temperature. Such concentration gradients possess sharp discontinuities whose terminal points correspond to the solubilities existing at the limits of the two-phase field in the phase diagram at the diffusion temperature. In general, there will be a discontinuity in the concentration curve for each two-phase field which exists in the phase diagram between the concentration limits of the couple. A number of investigators have analyzed the gradients present in multiphase diffusion couples. 1-8 The iron-titanium phase diagram exhibits a y loop in the temperature range from 900" to 1400°C, and the limit of the a + y field lies at some composition which is less than 1 wt pct Ti for any temperature. It was felt that a diffusion study could yield values not only for the diffusion coefficients involved, but also for the chemical solubilities in the phase diagram. The concentration gradients were analyzed by an X-ray absorption technique developed by Ogilvie.6 The absorption of a monochromatic X-ray beam is measured in steps parallel to the diffusion direction and the resulting intensity gradients are transformed into concentration gradients by applying the laws of X-ray absorption in a binary system. This technique has been applied by ogilvie6 to the systems Ni-Au, Cu-Au, Fe-Cr, and Ni-Cr; by Gelles7 to the systems Be-Fe, and Be-Ni and by Hilliarde to the system Al-Zn. Linear X-Ray Absorption Analysis—The use of X-ray absorption analysis as a tool for determining concentration gradients arises from the fact that the beam is absorbed according to the quantity and species of elements present in the sample and not according to their state of aggregation. This method is more advantageous than the chemical analysis of machined layers since it is less time consuming and less expensive and can analyze a very small area. IF a homogeneous binary alloy (A + B) is analyzed with two different monochromatic X-ray beams I0(2) and lo(2) the following relation between the transmitted intensities, the intrinsic absorption coefficients of A and B for the two different radiations and the weight fraction of each element may be derived.' In (I/Io) (a+b) xa(u/p)a(2) + xb(u/p)8(2) Eq. [1] is independent of specimen thickness and density, but requires that either element A or B possess an absorption edge between the wavelength limits of the two monochromatic beams. I, is evaluated for each radiation by measuring the transmitted intensity through a varying number of foils of a suitable absorber. A plot of the natural logarithm of the transmitted intensity as a function of the number of foils, when extrapolated to zero foils, yields the value of I,. If a plot of the ratio in Eq. [ I] is calculated as a function of xA, then a master curve results. From

Jan 1, 1960

By W. Ivanick, Frank W. Glaser

ORDERING reactions of Fe-Si compositions in the a region have been mentioned in a number of review articles.7-8 However, little is known in regard to the critical temperature, T at which this transformation takes place. Greiner and Stoughton,' in a study of the constitution of iron-rich Fe-Si alloys below 800°C, placed the onset of order at a composition of about 4 to 5 wt pct (7.5 to 9.5 atomic pct) Si. They observed that at this composition the ductility and strength begin to decrease sharply and brittleness develops. During X-ray studies they observed only the appearance of superlattice lines for compositions containing 12.5 atomic pct Si. More recent X-ray diffraction studies- etected the appearance of superstructure lines (corresponding to the calculated positions of [Ill] and [ZOO] reflections) for alloys containing 9.5 atomic pct. This fact confirms Greiner and Stoughton's original hypothesis in regard to the onset of order at compositions containing about 7.5 to 9.5 atomic pct Si. The physical properties.of Fe-Si alloys containing more than 10 atomic pct Si have been studied only to a limited extent. Their extreme brittleness and difficulties of sample preparation render them of little industrial use in comparison with alloys in the 0 to 10 atomic pct Si range. The properties of Fe-Si alloys reported to date are mostly properties measured at room temperature on ordered compositions It appears that because of experimental difficulties fully disordered alloys could not be produced in the critical composition ranges and their properties could therefore not be reported. In Figs. la, lb, and lc, a summary of physical properties of Fe-Si alloys, measured during recent investigations of the influence of silicon additions to iron, is presented. No mention of determination of the critical temperature, T for disorder could be found in the literature. The following is an account of work done in an attempt to: 1) produce the disordered state of various Fe-Si alloys and establish the critical temperature, T for disordering, and 2) compare the electrical and thermal conductivity characteristics of the ordered and disordered phases as functions of composition. Materials, Preparation of Test Samples, and Testing Methods Fe-Si alloys with high silicon contents (about 10 atomic pct) are usually prepared using powder metallurgy techniques. This method insures accurate compositions and high purity through the use of protective atmospheres during solid state diffusion alloying of the mixed powders."" Iron and silicon powders were mixed in the desired proportions, cold or hot pressed, and then homogenized at 1150°C for periods ranging from 6 to 12 hr under a protective getter and in a hydrogen atmosphere. Fully homogenized samples were quenched in water from various and successively higher temperatures to establish the critical temperature for disorder. Temperatures were determined using Pt—Pt-Rh thermocouples in contact with the test samples. Test bars were approximately 0.6x1.25x7.5 cm. Electrical measurements were made at room temperature by determining the potential drop over a 1.5 cm span for a current of 10 amp. Densities of the samples were determined by immersion. High temperature electrical resistivities were measured using previously described techniques.'" Specific heat conductivity up to 200°C was measured by heating one end of the test bar and water-cooling the other; heat conductivity was then obtained by subtracting the rate at which heat entered the water from the

Jan 1, 1957

By M. R. J. Wyllie

Eight laboratory-prepared aqueous base drilling muds representing common mud types, and 15 aqueous base drilling muds sampled in the field, have been used in an experimental investigation of the relationship between the streaming potential developed across a mud filter cake and the differential pressure causing filtrate flow. It has been established that the relationship is of the form, ES = kPy, where Es is the streaming potential, P the differential pressure and k and y are constants for any particular mud system at constant temperature. Beyond a certain minimum thickness this relationship is independent of filter cake thickness. Experiment has shown that both k and y are temperature dependent parameters and that in certain mud systems there is a critical value of P above which the simple relationship Es = kPY ceases to hold. The constant k tends to be a function of the mud resistivity at 77ºF, but the exponent y has not been found to be related to any commonly measured mud property. Certain field experiments are described which serve to demonstrate that the total SP (self potential) developed opposite a formation may be quantitatively accounted for as the algebraic sum of an electrochemical potential and an electrokinetic potential. A chart to permit the simple use of mean solution activities in the interpretation of electrochemical SP data is given and its use described. Various field methods for computing the electrokinetic SP component of the total SP are considered and rejected as being unduly complicated and inaccurate. It is shown that the employment of low resistivity drilling muds is essential if optimum accuracy is desired in the use of the S.P. curve for the purpose of computing connate water salinities by the electrochemical SP method. The use of such low resistivity drilling muds is accordingly recommended. INTRODUCTION In a previous paper' a quantitative analysis of the electrochemical compovent of the SP (self potential) curve was made and it was shown that the electrochemical* emf, E, could be expressed as E = ZtRT/F In a,/a,, where t is the transference number of the chloride ion, R is the gas constant, T the absolute temperature of the formation water and mud, a, the mean activity of the connate water (assumed to be sodium chloride) and a, the mean activity of the mud (as sodium chloride). The essential accuracy of this expression was confirmed by an investigation 2 of the SP kicks opposite sands of known water salinity. The logs examined had been routine runs in oil wells in a number of Mid-Continent states. Further confirmation of the original analysis of the electrochemical SP is implicit in the paper by Tixier3 wherein a relationship between the SP and the ratio of connate water and mud resistivities, based only on field data, is given. Allowing for the fact that mud and connate water resistivities were used instead of activities, and that electrokinetic effects were ignored, the constant reported by Tixier is essentially 2tRT/F. The error involved in the universal substitution of resistivities for activities will receive further reference below. Possible reasons for the fact that the electrochemical properties of shales do not appear to be significantly dependent upon either the nature or the quantity of cation exchange materials, such as clays, they contain has been considered at some length by Wyllie and Patnode.4 In the same paper, the probable effects of shale thickness and compaction on electrochemical efficiency, and hence the inherent difficulty of obtaining reliable laboratory-scale data, were also pointed out. However, it is

Jan 1, 1951

By R. G. Gifkins

Mean boundary migration depended linearly upon creep extension under various conditions. Prolonged annealing or air-casting increased the proportion of immobile boundaries at a given stage of tests. Grain growth during annealing followed a power law. The linking of migration and sliding in creep and models for migration are examined; activation energies are calculated from these models. Segregation of oxygen to boundaries appears to be a controlling factor. THE idea that boundary migration and boundary sliding during creep are linked has often been suggested,'-5 especially when evidence has been obtained for an alternation between the two processes. In simple bicrystals sliding can occur without any migration6 but in more complex bicrystals7 it is observed. McLean' and Couling and Roberts 5 made measurements of both sliding and migration; McLean concluded that there was no linking of the two processes whereas Couling and Roberts supported the idea. McLean' also developed a model for migration during creep and annealing. The present work was initiated as part of a study of the recrystallization of lead during creep9 but has been extended to examine some aspects of the mechanism of migration. MATERIALS AND METHODS Specially refined high-purity lead* was used; the total of impurities, excluding oxygen, was 0.0008 wt pct. Oxygen was removed as far as possible by melting in vacuo, treating at 550" to 600°C with hydrogen and then casting at 450°C under a vacuum of 10-2 mm Hg; the oxygen was then believed to be 0.00005 wt pct. Specimens were made from extruded strip and then annealed at the required temperature in an air oven, controlled to 5 lac. They were then polished in a mixture of acetic acid and hydrogen peroxide. At this stage some specimens were etched to give grain contrast and their grain sizes determined by the intercept method. Migration of boundaries during creep was measured on the surface of polished (not etched) specimens, directly loaded at room temperature (22°C) or 50°C (52"C) to initial stresses of 300 to 700 1b per sq in. Twenty six vacuum-cast hydrogen-reduced specimens were used and, in addition, two specimens were from material air cast after hydrogen reduction ("partial" air cast) and two from air-cast material not treated with hydrogen ("full" air cast). Duplicates were made in the majority of tests. At intervals through the creep tests, specimens were unloaded and the migration measured, normal to the direction of migration at the point of measurement, for each boundary along standard traverses. Usually between 110 to 180 boundaries were measured at each of some twelve stages of the tests. Migration was measured on the projected image (X100) using prism illumination. Fig. 1 illustrates the method of measurement and shows the kind of variation of migration found from boundary to boundary and along particular boundaries. Fig. 2 gives an example of more extensive migration. The mean value of distance migrated was generally reproducible to *10 pct but occasional points gave a scatter of *20 pct. The correctibn applied by McLean8 to allow for the contribution sliding makes to the apparent distance of migration could not be used, for the sliding at most boundaries was too small to measure with the equipment available. There were two reasons for supposing the correction unnecessary in the present work;

Jan 1, 1960

By G. V. Jere, V. Krishnan, C. C. Patel

Standard free energy and standard enthalpy changes as a function of temperature have been calculated for the chlorination reactions of different oxides constituting columbite and tantalite. The tallies of standard lee-energy change (F) indicate the possibility of pvefeential chlorination of different oxides but the ease 0.f chlorination of columbium pentoxide at about 250°C and the chlorinating tendency of columbium pentachloride in promoting the chlorination of tantalum and other metal oxides, p7-evetzt the separation of columbiu?n and tantalum from other oxides and pom each othel.. It is likely that low temperatuves of chlorination and continuous 1err2oval of columbium pentachloride from the ..eaction zone may help partial separation of columbium from tantalum as well as from titanium. The standavd enthaply change (AH?) values shotr that 1ou.-temperature chlorination around 300" to 500°C is likely to sustain the chlorination , without external heating. COLUMBIUM (niobium) and tantalum metals, their alloys and interstitial compounds are finding extensive uses in nuclear reactors and high-temperature equipment.la-3 These metals also find uses in chemical process plants, electrical rectifiers and capacitors and as "getters" in electronic tubes.la With the development of Kroll process of reduction of volatilized titanium tetrachloride by magnesium for the production of titanium metal, chlorine metallurgy is receiving greater attention. Chlorine metallurgy has several advantages, the foremost amongst them are: the ease of chloride formation, separation of the different constituents of minerals by selective chlorination, and the reduction of the chlorides in vapor phase to the respective metals. Recently, Si-bert, Kolk, and Steinberg4 have considered a number of methods for the preparation of columbium metal and the most promising is found to be the halide reduction. Since the minerals columbite and tantalite are comparatively abundant in nature, the future of the metallurgical processes depends on the utilization of these minerals for the production of columbium and tantalum chlorides by chlorination. In this paper, an attempt has been made to interpret thermodynamically the chlorination of individual oxides constituting columbite and tantalite, with the help of the recent thermodynamic data.5-8 For this purpose, standard free energy and standard enthalpy changes of the chlorination reactions of the oxides with chlorine, both in absence and presence of carbon as the reductant, have been calculated as a function of temperature and represented graphically. Similar calculations for the reactions employing carbon tetrachloride and carbonyl chloride as chlorinating agents have also been incorporated in this paper. REPORTED WORK ON CHLORINATION Cuvelliezg has patented a process for the separation of columbium and tantalum from their concentrate, wherein 75 pct Cb05 is claimed to be chlorinated at 1050°C in the course of 7 hr using chlorine or chlorine containing nonreducing gases, the products of reaction being CbC1, or CbOC1,. At this temperature, Ta,05 is claimed to remain unaffected. It is further claimed1° that at higher temperatures, the proportion of Ta205 chlorinated increases while that of Cb205 diminishes. During the studies on the action of chlorine on individual metal oxides, Kangro and Jahn" have observed that Ta,05 is not chlorinated even at 1200" in the stream of chlorine, while 75 pct of Cb,05 is converted into CbOC1, around 900 to 1100°C. The chlorination of Cb205 by chlorine in the presence of carbon, investigated by Lind and Ingle,' and

Jan 1, 1962

By L. J. Kashar

By means of a continuum-mechanics approach, the following equation for calculuting the pressure for axisymmetric cold forging has been derived: where P is the extrusion pressure; K and n are the strength coefficient and the strain-hardening exponent of the steel, respectively; a and b are strain factors, primarily dependent on the die design; and R is the extrusion ratio. Data from compression and backward-extrusion tests performed at a crosshead speed of 0.5 in. per min on a nonwork-hardening material pure lead) and on a work-hardening material (1018 steel) indicate that the predicted extrusion pressures obtained from the derived equation agree very closely with the actual extrusion pressures. Therefore, the equation can be used to predict backward-extrusion pressures from standard mechanical-test data. The decision to cold-forge a part is based on several considerations, most of them related to economics. However, the production feasibility is usually determined by the pressure needed to extrude the part and the availability of tooling that can repeatedly sustain this pressure for over several hundred thousand cycles. A major contribution to the cold forging of steel would result from the development of steels that could be forged at reduced pressures and from the development of techniques that permit the accurate prediction of the pressure necessary to cold-forge the part. The ability to predict extrusion pressures is necessary to properly design the tooling required for the cold-forging process. Attempts to theoretically predict the cold-forging pressure, especially for work-hardening materials, have been unsuccessful in previous investigations of the cold-forging process.1-3 Many empirical relations have, therefore, been proposed relating the extrusion pressure to the chemical composition,' the extrusion ratio,2 the tensile strength,273 and hard- ness, 2 and the yield strength3 of the material being extruded. However, these empirical relations are valid only for the specific conditions used in their development, and, in some cases, the empirical relations had a scatter band greater than * 10 pct. A study of the extrusion process was undertaken with the objective of developing predictor equations for extrusion pressure by using a continuum-mechanics approach to the problem of metal flow. The derivation of such an equation is summarized in this paper, and data are presented that confirm the validity of the derived equation. DERIVATION OF THE EXTRUSION EQUATION If the extrusion of a material through a die is considered in terms of a work balance, it has been shown that it is possible to derive an equation relating the work necessary to move the material through the die to the deformation work undergone by the material. The work done, W, in moving the material is given by where F is the extrusion force, I, is the distance the material was moved, A, is the original cross-sectional area of the material, P is the extrusion pressure acting on A,, Ap is the cross-sectional area of the extrusion punch, and Pp is the punch pressure acting on Ap. The deformation work, WD, is given by where V is the volume of metal deformed, ay is the flow stress of the metal, and E is the total strain undergone in the extrusion. If there are no frictional losses, the work done, W, is equal to the deformation work, WD; therefore, Since the volume of a metal does not change during deformation,

Jan 1, 1968

By V. O. Struebing, K. A. Johnson, F. H. Ellinger, C. C. Land

The system Pu-Ce-(Pu,Ce)Co2 has been investigated by thermal, micrographic, and X-ray diffraction methods. The principal characteristics of this system were found to be: 1) a "eutectic" valley extending across the phase diagram from the 6 Pu/Pu3 Co eutectic at 408°C to the 7 Ce/Ce24Co11 eutectic at 42Z°C, the maximum temperature in the valley being 443°C; 2) three ternary inter mediate phases, each having an appreciable mutual solid solubility for plutonium and cerium; 3) eleven four-phase equilibria comprising one eutectic, four peritectics, and six Class II reactions; 4) a pseudobinary section between the ternary phase A and the y Ce solid solution, and another such section between the 6 Pu solid solution and the 77 phase (Pu3 CO) containing cerium in solid solution. ALLOYS of plutonium that are completely molten at temperatures in the vicinity of 500°C are of interest for use in the liquid state as fast reactor fuels. Since exploratory work1,2 on Pu-Ce-Co alloys had indicated that a "eutectic" valley extended across the ternary system between the Pu-co[6 Pu/n (Pu3co)] and the Ce-CO[? Ce/? (ce24co11)] binary eutectics, thus allowing alloys of any plutonium concentration to be selected within the temperature limitation, the present investigation was begun for the purpose of accurately defining the "eutectic" valley. However, when the existence of three ternary intermediate phases and the consequent complexity of the liquid-solid equilibria were discovered, the investigation was expanded to cover the complete system, except for the corner between the isomorphous series PuCo2-CeCo2 and pure cobalt. 1) EXPERIMENTAL The purities of the alloy components are given in Table I. Alloy buttons, each weighing about 5 g, were prepared by arc melting the accurately weighed components (±0.1 mg) under a purified He-Ar atmosphere. Weight loss as a result of melting was usually less than 1 part in 1000; therefore, the buttons were not chemically analyzed. One half of each button was re-melted by induction heating in vacuo in a magnesia crucible and furnace-cooled, so as to produce a somewhat coarser microstructure than that of the rapidly cooled arc-melted button. About 20 g of each alloy to be examined by thermal analysis were remelted in vacuo in a tantalum crucible of the inverted thermocouple well type. The thermal, X-ray diffraction, heat treating, and micrographic methods used in this investigation were essentially the same as have been described in earlier reports.3,4 Two etchants for these alloys were found to be satisfactory: A) 8 (parts by volume) orthophosphoric acid, 5 ethanol, and 5 glycol; B) 7 tetraphosphoric acid, 36 water, and 57 2-ethoxyethanol. Etchant A was used at 5 to 6 v for 15 to 20 sec, and etchant B was used at 10 v for 10 sec. 2) THE LIMITING BINARY SYSTEMS 2.1) Plutonium-Cerium. The phase relationships of this system have been investigated by Ellinger, Land, and Cramer,5 and by Selle and Etter.6 The over-all agreement of their phase diagrams is good, but there are some discrepancies in the positions of some phase

Jan 1, 1967

By P. G. Shewman, T. L. Wilson

Using published surface-diffusion (D,) data and published sintering equations, it is shouln that surface difusion should dominate the neck-growth stage of intering for all materials in which D, has been measured (six metals and A1as). Also, grain boundary diffusion can be expected to contribute appreciably to shrinkage and possibly to neck growth below some critical temperature of the order of 70 pct 01- the absolute melting temperatuve. In view of the widespread conclusion in previous sintering work that volume diffusion dowzinates neck gvowth, experiments were conducted using spherical copper powders to test this conclusion. Scaling studies on neck growth at 950°and 1020°C clearly demonstrated that suyface diffusion dorninates. Kinetic studies on shrinkage gave more equivocal results that indicated an increasing role of' grain boundary transport at lower temperatures. Five diarszeters from 100 to 300 u were used in the scaling sludy and a temperature range of -650' 10 950 C was covered in the shrinkage studies. All experiments were conducted in dvy hydrogen. In 1949, Kuczynski published his now classic paper on the determination of the transport mechanism in sintering from the time laws of neck growth. In the interim, these laws have been applied to many systems and slightly modified by several authors. Essentially all these authors concluded that, for crystal- line materials, the dominant transport mechanism in neck growth is volume diffusion. This stems from the observation that the neck radius increases about as t"5 and that the activation energy approximates that for lattice diffusion. A related but independent series of studies stems from Mullins' rigorous analysis of the growth of the groove formed where a grain boundary meets a free surface." xperimental work stemming from this analysis has shown that for each crystalline material studied (Au, Ag, Cu, Ni, Fe, Pt, Al2O3) surface diffusion was clearly the dominant transport mechanism for groove widths up to the order 10 to 20 p. The ratio of the quantity of material being carried by lattice diffusion to that carried by surface diffusion increases linearly with the groove width, so surface diffusion is dominant for all widths under 10 to 20 u. The analysis of the relative contributions of surface and volume diffusion to grain boundary grooving, and to neck growth in sintering, shows that they are quite similar. Thus, using the available surface-diffusion data and the approximate equations of Kuczynski, or the more rigorous recent equations of Nichols and Mullins, 3 it can be shown that the small necks between particles must grow almost entirely by surface diffusion. The purpose of this study was to re-examine the basis for the conclusion that the neck-growth stage of sintering proceeds by volume diffusion. Using spherical copper powders, of several different diameters, precise experimental measurements were made of both neck growth and shrinkage. Application of Herring's scaling laws to the neck-growth data clearly indicated that neck growth occurred by surface transport, even though the neck radius increased as or Using the recent analysis of Mullins and Nichols as well as published data on surface diffusion, it is shown that the observed time law, as well as actual rate of neck growth, can be satisfactorily explained by a surface-diffusion mechanism.

Jan 1, 1967

By Henry Louis

THE work performed by the Royal Commission on Mining Subsidence is likely to prove of permanent value, less perhaps for the conclusions it has reached and for the recommendations it has based upon these than for the admirable exposition which it affords of the law concerning mining subsidence and of the legal status of the person who has suffered damage by reason of such subsidence, as also of him whose working has caused the damage. The Commission was appointed by Royal Warrant in the middle of 1925 and delivered its final report in the middle of 1927. The terms of reference to the Commission were as follows: "To consider the operation of the law relating to the support of the surface of the land, and of buildings or works on or under the surface, by underlying or adjacent minerals; to enquire into the extent and gravity of the damage caused by subsidence owing to the extraction of minerals and the incidence of the resulting liability; and to report what steps should be taken, by legislation or otherwise, to remedy, equitably to all persons concerned, any defects or hardships that may be found to arise in existing conditions."

Jan 1, 1929

By C. G. Dunn

James, Jones, and Leak (JJL) conclude that growth-rate and orientation-distribution data obtained in a steep thermal gradient should be used with caution to account for isothermally produced recrystallization textures. I agree. However, it is not clear whether they conclude a) that the orientation dependence of rate of growth of secondaries in (commercial) silicon iron depends on both temperature and a temperature gradient or b) that, in applying rate data obtained in a steep thermal gradient, the isothermal annealing temperature must be close to the temperature for which the rate data apply. Also, it is not clear what tem-

Jan 1, 1967

A New Ingersoll-Rand Turbo Blower The Ingersoll-Rand Co. has added to its Turbo Compressors and Blowers a low-pressure machine t o handle volumes from 3,000 to 35,000 cu. ft. per minute at from 1-2 ½ lb. These are particularly adapted to such service as foundry cupola blowing, atomizing oil for oil burners, supplying blast to heating and annealing furnaces of various kinds, blowing air for water-gas generators, pneumatic conveying and ventilating. They are of the single stage, double flow type and are furnished either electric motor, steam turbine or water wheel driven.

Jan 6, 1916

Beyer Barometric Condenser The Ingersoll-Rand Co. is now offering to the trade complete steam­condensing plants for all service conditions. This equipment includes the Beyer barometric condenser, for' which the company has secured the patent rights, Imperial duplex and Ingersoll-Rogler straight-line reciprocating dry vacuum pumps and, where required, Cameron simplex and centrifugal pumps. The Beyer barometric condenser is of the counter-current type, in which air and cooling water flow in opposite directions. The steam inlet is at the bottom of the condensing v el, the water inlet above and the air-removal opening at the top. The sheets of cooling water over owing the pool at the inlet point meet the entering steam. The two are brought into intimate contact by conical baffle plates which assist the water to absorb to its full capacity the latent heat of the steam. The non-condensable air liberated in the condensing action rises through the falling water to the removal point at the top, being cooled to practically the temperature of the incoming water. It is also to be noted that ample opportunity is given for the removal of the air content of the water before

Jan 8, 1916

By M. Mortada

Nonsteady-state flow of slightly compressible liquids in porous media of non-uniform properties has been the subject of a number of recent studies. Most of these studies considered one-dimensional flow in systems with cylindrical geometry and with the properties of the porous medium varying with radial distance only. A. Houpeurt' studied the problem in its general form by examining the solutions of the differential equation, In Eq. 1, the permeability k and the porosity + are arbitrary functions of radial distance. Houpeurt concluded that, except for special forms of the functions k and the problem is not well suited for mathematical treatment, but lends itself to high-speed digital computation. Carslaw and Jaeger' discussed the solution of Eq. 1 for the case in which the permeability varies as a power of the radial distance. P. Albert3 studied analytically the pseudo steady-state solutions in systems of finite radial extent and non-uniform properties. He also obtained some numerical solutions for nonsteady-state flow using a high-speed computer. William Hurst4 examined the interference pressure drop due to a point sink located in an infinite system consisting of two permeability regions in series. In this case, the permeability changed at a radial distance r from the point sink. INTERFERENCE BETWEEN OIL FIELDS IN A NON-UNIFORM AQUIFER The interference pressure drop for oil fields located in an extensive aquifer of uniform properties is discussed in a number of places in the literature. This work considers the interference pressure drop for oil fields located in a non-uniform extensive aquifer comprising two regions of different properties as shown in Fig. 1. Region I of the aquifer extends from which is the radius of Oil Field A, to ar,,, where a>1. It has permeability k,, porosity +, and effective compressibility c,. Oil Field B is located in Region II which extends from ar, to infinity and has different properties from those of Region I, but the same formation thickness h. Region II has permeability k2, porosity and effective compressibility c2. The choice of this type of aquifer should not imply that it is of frequent occurrence. It is chosen primarily to illustrate the effects of non-uniform aquifer properties on oilfield interference. It is of interest to point out that a non-uniform radial aquifer in which both the permeability and the porosity are inversely proportional to the radial distance can be treated in a manner similar to a linear aquifer of uniform properties. The situation where only the permeability varies as the inverse of the radial distance is also amenable to analytical treatment. Both aquifers behave quite differently from a radial aquifer with uniform properties so far as the water influx and the interference pressure drop are concerned. METHOD OF SOLUTION The expression for the interference pressure drop in Oil Field B due to a constant rate of water influx in Oil Field A is developed in the Appendix. This is accomplished by the simultaneous solution of two partial differential equations describing the pressure in Regions I and 11. The two differential equations are solved subject to the following conditions: (1) at r,, the pressure gradient is constant; (2) at ar the pressure and

By J. R. Kyte, L. A. Rapoport

The material balance equation for partiai or complete 1:trter-drivc reser1,oir.s been re-arranged to include a pressure irrferferencr ternr. This pressure interfernce term was ohtained from the theory established hy Morinda. A .successful progranl deissed to solve the resrclritlg c,qrration in a few hours on a nleelitr .sizeti, digital compuier. No prior knowdelge of the properties of the eqrrifer is required in the solution. 7' ri~rl calculations areatle using various assumed con!binuiions of value of the constant expretsing the qquifer properties correspoinds to the best fit ohtained between observed and calculated field history. Details of the method of calculaion are illus trated by an example. INTKCDUCTICN A method 01' calculating the material balance equation for a partial water-drive reservoir completed in an aquifer has been described in the literature." Pressure interference i'rc,m other pools iocated in the same nquiucr is not taken into account in this solution. When present, the pres- sure interference effect must be included in order to make a complete performance analysis. A correction for this effect has been developed using the theory cstahlished by Mor-tada.' Manual calculation of the material balance for water-drive reservoirs is a formidable task. Such manual ca1culation when interference eflects are includcd would be impossible to completc in any reasonable time period. However, a medium-sized stored program, digltal conlputer can he used satisfactorily. The method is described in the following sections. THECKETICAL CONSIDEKATIOhS The material balance equation for a reservoir producing by partial or total water drive, as proposed by Van Everdingen, This relationship is linear for Z/a from which thc slopc, Z, and the intercept, N, can be obtained by the least-squares method from the data points. It is not necessary lo know the aquifer properties to uktain oplimum values tor 2nd IV. Various assumptions are made tor At,,: where 11 is production time, seconds (oilfield between the equal successive time intervals into which the history is divided. t,, h It, times the number of equal time periods from i.e.. the total dimen-sionless time interval from It is noted that the dinlensionless time interval, At,,, involves all the relevant aquifer properties. Accordingly, any assunlption of is an assumption of the combined aquifer properties which pertain to the solution of the equation. Deviations of the data points from a straight line arc calculated for each assumption of and the value of A, correspond ing to the minimunl deviation is chosen as the optimum solution. This method is described in Ref. 1 and 2. Thc material balance solution is usually made with an initial assumption that the reservoir being studied is located in an infinite aquifer from which there are no other withdrawals. Deviation of the points by amounts greater than can be attributed to inaccuracies in field data may be the result of: (1) boundary effects of a limited aquifer, (2) pressure interference from othcr pools completed in the .sarne aquifer, and (3) a combination of these effects. Differentiation of these effects can be made only on the basis of geologic data. Pressure interference from other fields will result in a pressure drop at the original oil-water boundary having an interference component, The measured instantaneous pressure drops at the oil-water

By G. R. St. Pierre, A. J. Wilhelem

In connection with the reduction of hematite or magnetite to metallic iron, it appeared desirable to study the rate of reduction of each oxide to the next lower oxide under conditions which excluded all other condensed phases. For this purpose, pellets of Fe,O,, Fe,O,, and oFeOo were prepared. A gas train for the preparation of Ar-Hz-H20 mixtures was employed to establish a continuous flow of a controlled atmosphere over a pellet suspended on a balance. In this manner the following individual reduction steps could be studied: For example, pellets of hematite were reduced solely to magnetite by adjusting the gas atmosphere such that it was oxidizing to wustite. In other words, the reaction was complete when the hematite pellet had been totally converted to magnetite. The pellets were prepared from Baker Chemical ferric oxide. The ferric oxide powder was moistened and handrolled. Air sintering at 950°C produced Fe,0, pellets with a density of 3.65 g per cm3. The pellets ranged in size from 0.6 to 1.2 cm diam. The magnetite and

Jan 1, 1962

By C. G. Dunn, P. K. Koh

The primary recrystallization textures of 11 single crystals cold rolled 70 pct were determined. The effect of crystal orientation on recrystallization behavior was investigated also and found to be large. An exception was found to the relationship that strong components of the recrystolliza-tion texture are rotated from the cold rolled texture by 30° about <110> axes, but generally this relationship was found to hold quite well. Evidence supporting oriented nucleotion was found and discussed in terms of probable active slip systems and <110> edge dislocations. THE present paper is one of a series&apos;.&apos; on recrys-tallization phenomena in cold rolled 31/4 Si-Fe single crystals and is mainly concerned with the textures produced on recrystallizing from stable end orientations. Data for the cold rolled textures of the crystals used have been reported by Koh and Dunn." Their results showed that the sharpness of the cold rolled textures varied throughout the range of stable end orientations and that the tendency to re-crystallize was related to the sharpness of the cold rolled texture, wherein the rate of recrystallization increased and the size of recrystallization grains decreased with decreasing sharpness of the cold rolled texture. In the project under consideration the cold rolled crystals involved a range of initial orientations that, together with those studied earlier,&apos; provide information on several points. The first point is whether the recrystallization texture from a (111) [112] cold rolled texture, a stable end orientation that can be approached from different directions, correlates in any way with the initial orientation before cold rolling, or whether the recrystallization texture is entirely determined by the observable features of the cold rolled texture. The second point involves a preliminary study to see if the main components of the recrystallization textures correlate with the most probable active slip systems. The third point is to determine what effect departure from slip on one slip system has on the tendency to recrystallize. Experimental Procedure Nine specimens from a previous investigation and two additional ones from thicker stock (lot D) but of similar composition to the others were used in the present work. The latter two crystals, like the nine, were cold rolled to a reduction in thickness of 70 pct and the amount of widening was determined. Depending on their primary recrystallization behavior, the cold rolled crystals were given short or long anneals at temperatures of 980°C or higher. Table I summarizes the data on initial orientations, the textures obtained by cold rolling, and the anneals given to provide samples for the present work. Fine grained specimens were thinned to 0.002 in. thickness and placed in an integrating specimen holder. Chart recordings using a transmission X-ray method and MoKa radiation were obtained for diffraction from (110) planes. This method,&apos;,3 which gives data for all of the pole figure except a central region of 30" radius, proved sufficient to give generally five, and sometimes six, of the six possible pole concentration areas of any one component of the texture. These data, therefore, were generally adequate for a positive identification of each component present. The first texture obtained for specimen B-2 was poorly defined because of too coarse a grain structure and therefore too few crystals in each component for satisfactory X-ray reflections. The same

Jan 1, 1957

By H. I. Smith

WHEN Spain established colonies on the North American continent, some of her land grants, in what is now the United States, reserved to the Crown deposits of gold, silver, and mercury. Later mineral rights were reserved under some of the English Crown charters involving land in the eastern part of North America, with provisions for the payment of royalties thereon to the Crown. Reservation of mineral deposits to the United States Government was instituted by an ordinance of Congress on May 20, 1785, which applied to such deposits in the Northwest Territory, then north of the Ohio River and east of the Mississippi River, and provided that there should be reserved "one third of all gold, silver, lead, and copper mines, to be sold or otherwise disposed of as Congress shall hereafter direct." Little was known then of the mineral resources of the country; the Great Lakes copper region had just come into the possession of the United States by treaty and much of the western mineral land still belonged to France and Spain. The policy of leasing mineral deposits was enacted by Congress under the act of March 3, 1807, which provided that "the President of the United States shall be, and is hereby, authorized to lease any lead mine which has been or may hereafter be discovered in the Indiana Territory, for a term not exceeding five years," and in the same year the Government reserved 345,600 acres of land in northern Illinois, valuable for lead. In 1816 Congress provided that in all cases where a tract of public land containing a lead mine or salt spring was applied for by settlers on the public domain, no permission to work the mine or spring would be granted without the approbation of the President of the United States. By the act of March 1, 1847 (9 Stat. 146), the control of mineral lands was transferred, with all records, from the War Department to the Treasury Department, and by the act of March 3, 1849 (9 Stat. 395), supervisory powers over lead and other mines of the United States were transferred to the Secretary of the Interior. Following the discovery of gold in California in 1848, President Polk advocated the leasing of mineral lands acquired from Mexico under the treaty of 1848. However, owing to the lack of communication and transportation facilities and the consequent difficulty of checking on production and operations, leasing was found impracticable. Mining was permitted to be carried on in each district under rules made by the miners themselves and patterned after the Mexican mining system. To meet the situation, Congress enacted mining laws in 1866, 1870, and 1872, which provided for possession by location and for private ownership, after discovery, by patent of essentially all mineral deposits belonging to the United States, except coal. Many other acts were passed by Congress applying to specific regions and states, reserving salt, lead, or other minerals, some of which provided for the leasing of such deposits. However, very few if any leases were issued thereunder. Not until 1901 (31 Stat. 745) were the mining laws extended to include salt, and in 1910 they were revised to specify salines and associated products. At the turn of the century, it became more and more evident that the mining laws developed for metallic minerals were not practical for the development and conservation of oil and gas, coal, potash, phosphate, or oil shale. Following withdrawals by the Secretary of the Interior as authorized by the act of June 25, 1910, the Department of the Interior recommended leasing legislation; however, it was not until February 25, 1920, that the Mineral Leasing Act was passed by Congress. This act authorized leasing all public lands potentially valuable for oil, gas, coal, phosphate, sodium, or oil shale. The Organic Act, creating the Geological Survey in 1879, imposed upon its director the duty of classifying the public lands.&apos; The early years of the Survey were devoted largely to the accumulation of fundamental data and, with only minor exceptions, land classification was not seriously undertaken until 1906. Since that year, it has been actively pursued with respect particularly to leasable minerals and water power values. On March 3, 1873 (17 Stat. 607) Congress authorized the sale of coal lands of limited acreage to individuals at $10 to $20 an acre, depending on the distance from a railroad, and in 1907 a new scale of prices was adopted by the Secretary of the Interior, based, more logically, on the quality and thickness of the coal deposits, their depth below the earth&apos;s surface, and their accessibility. At that time it was much cheaper and easier to obtain incidental title to coal rights under the homestead laws at $1.25 an acre. On March 3, 1909, the first separation act (35 Stat. 844) became a law. It authorized patents, with a reservation of the coal and mining rights involved to the United States, to persons who in good faith had entered public lands under the non-mineral land laws prior to withdrawal, classification, claim, or report that such lands were valuable for coal. It solved the problem only partially, and the practice thereupon adopted by the department of making coal withdrawals "from all forms of entry" instead of "from coal entry" expedited the more complete solution effected by later acts. By the act of June 22, 1910 (36.Stat. 583) withdrawn and classified coal lands were declared subject to entry under the homestead, desert land, and Carey acts, provided a waiver of the coal rights accompanied the application, and by the act of April 30, 1912 (37 Stat. 105) the same privilege was extended to State selections and isolated tracts. The act of August 24, 1912 (37 Stat. 496) extended the separation policy to lands withdrawn for oil and gas in Utah, and finally the act of July 17, 1914 (38 Stat. 509) extended it to all nonmineral filings on public lands theretofore or thereafter

Jan 1, 1955