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By T. F. Bower, M. C. Flemings, H. D. Brody

A series of experiments are reported which show thai reasonable assumptions for analysis of solute redistribution in solidification of castings and ingols illclr(de: negligible undercooling before nuclcation of solid phases, negligible increase of solute in advance of the tips of growing dendrites, complete diffusion within the Liquid oer distances the order, of dentrite arm spacings, platelike dentrite t/o?$holog?.. Qzmli/ali,e and periment is obtained JOY Al-Cu alloys front measurements of amount of nonequilibrium second phase, minimum solute content at the centers dentrites arms (after solidification), and 3) change in minimum solute content in dentrite arms during solidification. In a previous paper' analyses were given describing solute redistribution in dendritic solidification. The analyses were undertaken primarily to permit prediction of "severity of microsegregation" in a casting or ingot after solidification and cooling to room temperature, but can also be used to predict "local fraction solid' as a function of temperature in the solidifying alloy. Numerical results were given for Al-Cu alloys. The aims of this paper are to examine the validity of some of the assumptions of that analysis, and to compare predictions of the theory with experiments. All experiments reported are on Al-Cu alloys, the bulk on Al-4.5 pct Cu alloy. EXPERIMENTS Experiments conducted were on small ingots, 41/2 in. in diam by about 10 in. high. solidified in a controlled thermal environment (i.e., in a resistance-heated, re-circulating air furnace, whose temperature could be controlled to 1°C). In one series of experiments, the ingots were solidified very slowly (solidification time was varied from 8 to 1000 hr) and at constant rate of heat extraction. In a second series of experiments the ingots were solidified ( 'unidirectionally". Fig. 1 is a sketch of the method of making the two different types of ingots. The unidirectionally solidified ingots were fully columnar, and the slowly solidified ingots had equiaxed structures, Fig. 2. In making the slowly solidified ingots, the mold employed was carbon steel, coated with inert refractory. Typically the mold and its environment were heated to 700°C. The molten alloy was then poured into the mold and the temperature of the system equilibrated above the liquidus. The environment of the mold was next cooled with a controller responding to a differential thermocouple that measured the difference between the temperature of the melt and the temperature of the mold environment. The differential thermocouple consisted of one chromel-alumel junction in the melt connected in opposition with a second junction in the furnace. The potential across the differential thermocouple was input to the controller which acted to keep this potential at a set. constant value; hence the temperature difference between the two junctions was maintained nearly constant. Major resistance to heat flow in the above apparatus was between the metal surface and the furnace atmosphere, not in the metal itself. By maintaining a constant temperature difference between the metal and the furnace atmosphere, the controller maintained an essentially constant rate of heat extraction during solidification, regardless of amount of heat released by the metal per unit temperature change. When the metal temperature dropped just below the eutectic temperature. the ingot was removed from the furnace and water-quenched. The unidirectionally solidified ingots were cast in a similar mold to the foregoing except that provision was made to extract heat through the bottom face of the mold by passing air or water through the mold base, Fig. 1. For these experiments, metal and mold temperature were again equilibrated above the liquidus. Temperature of the mold environment was then held

Jan 1, 1967

By R. J. Blackwell, J. R. Rayne, W. M. Terry

This paper presents results of an experimental investigation of factors that control the efficiency with which oil is displaced from porous media by a miscible fluid. The study was made to elucidate the relevant processes both on microscopic level (within individual or between neighboring pore spaces) and on macroscopic level (within a large sand body). Mixing of miscible fluids on the microscopic level was studied in sand-packed tubes. It was found that molecular diffusion is the dominant dispersion mechanism for reservoir conditions of rate, length and pore sizes. Macroscopic channeling was studied for various mobility ratios in reservoir mode1s scaled to relate viscous, gravitational, and diffusional forces. The formation of channels was due to viscous firzgering, gravity segregation and variations in permeability. With adverse mobility ratios, it was found for reservoirs of realistic widths that diffusion will not be effective in preventing the formation and growth of fingers, even in homogeneous sands. At sufficiently low rates channeling was eliminated by gravity segregation in tilted reservoirs. The dependence of recovery on mobility ratio, length-to-width ratio, flow rate and angle of dip is presented. INTRODUCTION Oil recovery by solvent flooding is finding increasing application in the field. While the process promises high recoveries from the region swept by solvent, under adverse conditions only a small fraction of the reservoir volume may be swept at the time solvent breaks through to the producing well. Further, the high cost of the solvent encourages its use only as a bank whose size must be kept at a minimum. Thus, two important questions arise: (1) what fraction of the reservoir can be swept, practically, by solvent? and (2) what is the minimum size solvent bank that can be used to carry out the displacement? The answers to these questions require knowledge of both macroscopic channeling processes and microscopic mixing processes. The studies described here were carried out to gain this knowledge. Microscopic mechanisms which cause mixing will be discussed first, because an understanding of these mechanisms is necessary for proper interpretation of the experimental work on channeling described later. INVESTIGATION OF MICROSCOPIC DISPLACEMENT PHENOMENA FOR MISCIBLE FLUIDS The questions to be resolved concerning microscopic displacement behavior are: (1) how much mixing occurs between oil and solvent in the direction of flow? and (2) does the solvent completely flush the oil from the pore spaces in the region invaded by solvent? The classic work of Sir Geoffrey Taylor' and its extension by Aris2 have shown that it is possible from theory to describe the amount of mixing in single straight capillaries when solvent displaces a fluid of equal viscosity and equal density. Aris showed that the lengths of the mixing zones, 81, corresponding to the 10 per cent and 90 per cent concentration levels of the solvent can be calculated from the formula, 81 = 3.62 \/Kt, .........(1) where 8l is the length of the mixing zone, cm; t is the time, sec; and K is the effective dispersion coefficient, cm2/sec, given by K/D = 1 + (1/48) (au/D)2......(2) where a is the radius of the capillary, cm; D is the molecular diffusivity, cm2/sec; u is the average velocity

By M. P. Tixier, F. Segesman

Explanations bused on theory and laboratory tests tire offered for certain unusual features of SP logs which may befog their interpretation, namely the "sawtooth" SP and the reduction or increase of SP with time. The sawtooth SP is frequently seen in SP recordings of thick, very permeable watcr. sands of the Louisiana Gulf Coast. Using SP data from a resistor network analog, this anomaly is explained on the basis of a thin shale streak within the sand. under which the invading filtrate accumulates by gravity segregcitiorr. The electromotive force then appearing across the shale streak gives rise to the anomalous SP. Reduction of the SP on successive logging runs Ira often been observed in very permeable sands when as indicated by the resistivity curves, the invasion depth has been reduced to practically zero. Laboratory results verify that this phenomenon may be due, to the presence of air electromotive force, across the mod rake when the fluids on either side differ in activity. Also, there is, in some cases; an increase of SP deflection on successive logging runs, because the emf initially present across the mud cake disappears as the somewhat saline water just behind the mud cake is progressively flushed out by the invading filtrate.. Field example and laboratory data are presented. I N T R ODUCT1ON Some unusual features are frequently observed on certain SP logs which make interpretation difficult. The purpose of this paper is to offer explanations of several cases of interest. All of these arc related to the conditions of invasion. The cases to be discussed are as follows. 1. The sawtooth SP anomaly which is frequently seen within the thick, highly permeable saltwater sands of the Louisiuana Gulf Coast 1. Reduction of the SP deflection from the usual sand line in very permeable sections when the depth of invasion is practically nil. As will be explained, such a reduction is attributable to a membrane electromotive force across the mud cake. 3. An increase of the SP with time just after the iormation is drilled as a result of progressive flushing of the invaded zone. FUNDAMENTALS OF SP PHENOMENA An explanation of SP phenomena must begin with the following basic ideas. 1. The SP log derives its character from ohmic potential differences in the hole produced by currents flowing through the mud.' These currents are driven by electromotive forces which are primarily electrochemical in origin. Other possible types of SP-producing electromotive forces may be disregarded for the purposes of this paper. 2. The electrochemical emf's associated with permeable formations are now understood to consist of liquid-junction emf's and membrane emf's.',' As schematically shown by thc battery symbols in Fig. 1, the liquid-junction emf, E,,,, exists at the contact between waters of different chemical activities, a,,,, (mud filtrate) and tr,,. (formation water); the shale membrane emf, lS.sn. exists across the adjacent shales whcn they separate waters of different activities. The emf's just cited are additivc in producing SP currents (arrowed circles of Fig. I). Thus, neglecting for the moment any possible membrane emf across thc mud cake, the total electrochemical emf, E,, will be given by their sum, where K,., -! K,q,, = 12 + 59, or 71 at 75 °F. In the log interpretations the SP of a thick sand (i.e.. the static SP) is generally related to the activities of the filtrate and formation water through Eq. 1. by setting the static SP equal to - E,.

By W. A. Backofen, D. Lee

Titanium of commercial purity (RC-70) and two all-a (hcp) alloys (4Al-1/4O2 and 5Al-2.5Sn) were tested in sheet form under conditions of combined-stress loading. Plane-strain compression and plane -strain tension together with uniaxial compression and tension provided information for constructing the tension-tension and compression-compression quadvants of the plane-stress yield locus. Coordinate values were obtained from yield-strength measurements; the slope at each point was based on a plastic-strain ratio. The materials represented a wide range of plastic anisotropy, which was reflected in correspondingly varied departures of the yield locus from that for iso-tropy. The tension-tension and compression-compression quadrants were not identical. If the uniaxial yield strength is insensitive to direction and the sign of the applied stress, the Mises or perhaps the Tresca criterion is adequate for predicting the onset of yielding under combined-stress loading. The prediction is not so straightforward in plastically anisotropic material. Depending upon details of texture, combined-stress yielding resistance may be substantially different from that indicated by the usual criteria.' However. a continuum theory of yielding under such conditions is available for reasonably direct application.2,3 Whether or not it can be used successfully must, of course, depend upon how closely the conditions of the theory are satisfied in the material in question. In its present form the theory contains no provision for Bauschinger-type effects, nor does it allow for the consequences that might grow out of deformation by more than one mechanism, e.g., by slip and twinning.4 With those limitations, more importance must be attached to experimental information about the yield surface for anisotropic materials. Studies of the yield surface have generally been confined to states of plane stress (tension-tension and tension-compression) established in thin-wall tubes by externally applied forces and internal pressure. That approach would be entirely suitable for anisotropic materials if they were available in tube form or in sufficient bulk to be machined into test specimens. 6-9 It would not serve for the textured and anisotropic sheets of much current engineering interest, unless sheet could be formed into high-pressure tubing without structural change. Since there would seem to be little chance of the latter, practical alternatives are needed. One such alternative is the subject of this paper. It involves the use of a few selected but relatively simple uniaxial loading tests on sheet specimens. The underlying idea is presented here with some details relating to application and a few results bearing on how well it has worked. THE BASIS OF TESTING Conventional Measurements. Yielding for a general case of anisotropy is described by the plane-stress locus in Fig. 1. Reference directions in the sheet specimen are related to the stress coordinates as shown with the insert: x is the rolling direction, y the transverse direction, and z the through-thickness direction. The four reference-direction yield strengths (t, tension; c, compression), Xt, Xc, Yt, and Yc, are all different. Nine paths that can be followed in uniaxial loading experiments are identified. Paths 1, 2, 3, and 4 represent conventional tension and compression testing to establish Xt, Yt,.Xc, and Yc. Useful information also comes from the ratio of the transverse plastic-strain components associated with yielding and flow in conventional tension or compression. A condition to be satisfied in locus construction is that the plastic-strain vector be everywhere normal to the locus.10 The projection of the vector which would

Jan 1, 1967

By F. V. Lenel, G. S. Ansell

The creep behavior of an aluminum -aluminum oxide alloy, A T 400, fabricated by compacting an atomized aluminum powder, extruding the compact, cold working, and recrystallizing the extrusion, was investigated. This alloy has a dispersion spacing of 1 . Previously Ansell and Weertman determined the steady-state creep rate of a recrystallized aluminum-aluminum oxide SAP-type alloy, MD 2100, with a 0.48-p dispersion. This alloy was found to have a steady-state creep rate of less than 10-6 min-1, too small to be measured accurately. By employing a more sensitive method of measuring creep rate, it was possible to determine the steady-state creep rate of AT 400 alloy, which is somewhat faster than that of MD 2100, at a series of temperature and applied stresses. Above a stress of Burger's vector, A = dispersion spacing, u = is a shear modulus) the rate follms an equation of the type: Steady-state creep rate K = A exp. where A is a constant, Q is the activation energy for sey-diffusion, and is the applied stress. At stresses lower than the steady-state creep rate drops off sharply and is no longer in agreement with this equation. This behavior is in good agreement with that predicted by the model for dispersion strengthened alloys in the stress and temperature range investigated. The absolute value of the creep rate is, however, four orders of magnitude lower than that predicted if the normal number of active dislocation sources are assumed to be present. It is concluded that in this SAP-type alloy the usual three-dimensional dislocation network is not present. Instead, short dislocation segments extending from one dispersed particle and terminating at a neighboring particle may act as dislocation sources. With this provision the creep model proposed by Ansell and Weertman reasonably accounts for the creep behavior which was observed. RECENTLY, Ansell and Weertman1 proposed a dislocation model from which they derived creep equations to describe the steady-state creep behavior of dispersion - strengthened alloys. Following Schoeck,2 they assumed that the rate controlling process for steady-state creep is the climb of dislocations over the dispersed particles. In order to verify their creep model, Ansell and Weertman determined the steady-state creep behavior of an aluminum-aluminum oxide SAP-type alloy, MD-2100, in both the fine-grained as-extruded, and coarse-grained recrystallized conditions. Since the grain size was the order of the dispersion-spacing, their model was not applicable for the as-ex- truded alloy. It should, however, be applicable to the coarse-grained recrystallized alloy. The results they obtained were rather unexpected. No meas-ureable steady-state creep was observed for the recrystallized MD-2100 alloy. If their model is correct, and if the second-phase particles act solely to hinder dislocation motion, then some measureable steady-state creep would have been expected. On this basis, they postulated that, in this SAP-type alloy, the main effect of the fine dispersion was to inactivate dislocation sources rather than to hinder the movement of dislocations. In order to understand more fully this unusual creep behavior, and to determine the validity of the model proposed,' the steady-state creep behavior of an aluminum-aluminum oxide recrystallized SAP-type alloy, with a somewhat coarser dispersion spacing, was investigated. The results of this study are presented in this paper.

Jan 1, 1962

By B. H. Bergstram, C. L. Sollenberger

When glass spheres are crushed by slow compression loading, the outer lune-shaped fragments resulting from the fracture consistently fly outward at high velocity. About 45 pct of the strain energy fed into the sphere-platen system reappears in the form of the kinetic energy possessed by these fragments. These measurements were obtained from high-speed photographs. This kinetic energy can be utilized for addtional comminution if the fragments are allowed to impact against a suitable structure. Comminution theory has advanced considerably in recent years by the study of this unit operation under laboratory conditions. Some of the parameters have been isolated, but the experimental measurements of the pertinent quantities, such as energy, particle size, etc., are still only made prior to and after the conclusion of a fracture sequence. The catastrophic fracture process itself has not been adequately studied from a comminution point of view. It has recently been suggested by Gilvarry that the fragments which result from the free crushing of a single glass sphere by slow compression contain a considerable amount of kinetic energy after fracture. This kinetic energy, if properly directed, possibly can be partially utilized to cause additional fracture. In this paper a hypothesis will be presented which suggests that this kinetic energy is necessarily present and that its dissipation is the process by which a large part of the thermal energy imparted to the crushed product is generated. Evidence supporting the existence of kinetic energy and its utilization for secondary fracture will also be presented. THEORETICAL A previous paper4 has shown that the load-deformation curve of a system composed of an elastic sphere gripped by a pair of parallel platens, can be predicted by a consideration of the theories of Hertz as summarized by Timoshenko.' The deformation A, of one half of the system is given by which states that the deformation is a function of the mutually applied load, P, the radius of the sphere, R; and the respective physical properties of Poisson's ratio, v, and Young's modulus of elasticity, Y. The shape of experimental load-deformation curves conform to this relationship. The energy input to the sphere-platen system, can be predicted from the integral of the load acting through the appropriate distance, dA. Since dA can be evaluated in terms of P from the derivative of Eq. 1, this integral can be integrated between limits of 0 and P. The test sphere, however, is loaded at not one but at two points of contact, i.e., at both ends of a diameter, and hence the total energy input, E, is twice the energy input at each end, or The energy input to the system calculated from this equation corresponds to the energy computed from the measured area under the load-deformation curve. Timoshenko, considering the impact of two perfectly elastic spheres, has shown that the inter-penetration distance A is given by - m f (D (^ * ^t w as modified for the special case where one sphere is of infinite radius, i.e., its surface is a plane; where M is the mass of the finite sphere of radius R, and V is the velocity of approach at the start of an impact and also equals the final velocity of separation for perfectly elastic bodies. Because A is also a function of the load and the elastic properties, as shown in Eq. 1, the velocity, V, can also be calculated in terms of the elastic properties and maximum load, P, or

Jan 1, 1961

By J. H. Reynolds

The possibility of using a semiconductor, metal, semiconductor structure as a light detector is discussed. A brief theoretical argument is presented which predicts that this structure should have pho-toresponse characteristics similur to those of a metal-semiconductor diode, but with the magnitude of the current increased by a transistor gain factor. Measurements made at low frequencies on a particulur S-M-S device agree u~th this prediction aizd shoul that significant gain factors are attainable. The current gain is substantially higher than that predicted for the metal base transistor. It is proposed that the operation of these units is more closely approxinzated by the metal-gate model which predicts higher current gains. A qualitative discussion of its high-frequency performance indicates that detection of light modulated at microwave frequencies by a S-M-S deuice is possible. ADVANCES in the technology of chemical vapor deposition'-4 have made it possible to form a S-M-S structure consisting of a thin metallic layer sandwiched between layers of single-crystal semiconductor. It has been proposed5-7 that, if the metal layer is made sufficiently thin, this structure could be used in an amplifier having several advantages over presently available transistors including higher-frequency performance. Calculations8 predict that the maximum gain-bandwidth product is nearly an order of magnitude higher than that of a bipolar transistor having the same geometry. Maximum oscillating frequencies in the microwave range are predicted. Electrical measurements made on S-M-S devices have shown that, although the theoretical frequency characteristics are not presently attainable, current and power gain is obtained. Another possible application of the S-M-S structure is its use in a light detector. This structure is a three-layer relative of the metal-semiconductor diode. Light detection using M-S diodes is the subject of considerable present interest. They are known to have a short response time and the ability to detect light having a photon energy below the semiconductor bandgap. In this paper, the mechanism by which S-M-S photocurrent is generated is discussed. An expression is derived which shows that the response characteristics are similar to those of a M-S diode, but that the magnitude of the current is increased due to the transistorlike behavior of the device. The results of low-frequency response measurements on a particular S-M-S structure are presented. These agree with the theoretical predictions and show that significant gain factors are attainable. A qualitative discussion of the high-frequency characteristics is presented which predicts that detection of light at microwave frequencies by a S-M-S device is possible. THEORY In this discussion, the photocurrent, iT, measured across terminals attached to the semiconductor emitter and collector layers is related to the current pho-toemitted from the metal base layer. The latter will be referred to as the primary photocurrent. The behavior of the primary photocurrent is determined by the characteristics of the two metal-semiconductor diodes. The diode photoemission is illustrated in Fig. 1, which shows the emitter and collector potential barriers. The metal thickness has been greatly exaggerated. As will be discussed later, the actual barrier shape can be much more complex, but this diagram illustrates the essential features of the photoemission process. An absorbed photon having an energy greater than the barrier height can emit an electron into the emitter or collector. Since this process is discussed

Jan 1, 1968

By E. T. Turkdogan, L. S. Darken

Using the quadratic formalism, thermodynamic equations are derived for the composition dependence of the heat and entropy of mixing. The applicability of these equations is confirmed by available experimental data on the activities and heats of mixing for binary metallic systems of Group ZZB elements. In a recent paper arkeen' introduced a quadratic formalism describing the composition dependence of the activity coefficient in the terminal regions of binary metallic solutions. That is, in the terminal region, which may extend to as much as 60 at. pct, the logarithm of the activity coefficient, log y,, of component 2 is a linear function of (1 - N,)' where N2 is the atom fraction of component 2. Similarly, for the other component, log yl is a linear function of (1 - N,)'. A number of iron-base binary liquid alloys were shown to obey this quadratic formalism. arkeen' extended this formalism also to any corner of a ternary system and showed that the activity coefficients of the components 1, 2 and 3 (1 is taken as the solvent) can be represented by quadratic terms involving five parameters, four of the binaries and one for the ternary system. Numerous examples given by arkeen' demonstrated the general applicability of the quadratic formalism to iron-base systems over a wide composition range. In this paper further examples are given of binary liquid systems (Group IIB elements, Zn, Cd, and Hg) and of several solid solutions, again demonstrating the appropriateness of this concept. A further purpose of this paper is to extend the quadratic formalism to the enthalpy and excess entropy of binary metallic solutions and to test the equations so found using available experimental data. QUADRATIC FORMALISM FOR HEATS AND ENTROPIES OF MIXING OF BINARY METALLIC SOLUTIONS The following equations, reproduced from Darken's paper, are for the two terminal regions of binary systems. at infinite dilution and a's are temperature dependent parameters to be determined from the experimental data. Although the quadratic formalism is an assumed representation of the data, Eqs. [I] to [4] are thermo-dynamically consistent with the Gibbs-Duhem relation and satisfy Raoult's and Henry's laws as limiting cases. As pointed out previously,' the following form of the Gibbs-Duhem equation facilitates the integration in general but particularly in regions I and 11, where each of the derivatives is constant. The partial molar enthalpy of solution i, (and i; the value of i, at infinite dilution) are related to the activity coefficients y, and y," by the thermodynamic relation Differentiating Eq. [l ] with respect to 1/T and substituting the above thermodynamic relation gives for region (I) It is reasonable to assume that over a temperature range of experimental interest, the enthalpy of mixing is essentially independent of temperature, implying from Eq. [7] that the derivative da,,/d(l/) is also independent of temperature. On the basis of this argument, the temperature dependence of a has the form where £ and S have the units of enthalpy and entropy respectively; they are characteristic parameters for a terminal region of a binary system, e.g. for region (I), C12, S12 and for region (II), d:,,, S2,. Using this equation gives for dff ,/ d(l/), From Eqs. [7] and [9] an expre_ssion is obtained for the composition dependence of L,. Similar calculations are made for El and the results are summarized below for the two terminal regions. For region (I), The corresponding expressions for the molar heat of solution, AHM, are readily obtained from the above equations for the two terminal regions: For region (I),

Jan 1, 1969

By R. E. Holmes, T. W. Leland

The solution to the unsteady-state mass- and heat-transfer equations describing the adsorption of a dilute component from a gas stream flowing through a packed bed is readily applicable to the design of hydrocarbon recovery units. The solution to these equations depends on the assumption of a linear equilibrium equation to relate concentrations on the surface to concentrations in the gas. This assumption is shown to be justifiable for components which are very dilute in the gas stream. This approach permits the prediction of the effects of bed shape and size, cycle time, and gas mass velocity on the recovery of each component. It also allows the time and gas flow rate needed for regeneration to be determined. The equations involve a constant for each component and another constant characterized by the type of adsorbent. These constants must be evaluated from operating data. Values of these constants determined for silica gel are presented. This paper points out the type of experitrrental data needed for a thorough design of hydrocarbon adsorption units. INTRODUCTION The growing importance of adsorption processes to recover hydrocarbons from natural-gas streams has created an urgent need for better methods to design and predict the performance of these processes. Since the original use of solid adsorbents in natural-gas processing was for dehydration, most of the current design methods for hydrocarbon recovery re extensions of those developed earlier for dehydration. These methods are based on an adsorptivity or bed loading factor defined as the amount of a particular component adsorbed per unit weight or per unit volume of the packed bed. The recovery of a given component is then expressed as an empirical function of its adsorptivity on a given adsorbent. In spite of the simplicity and initial utility of these methods, they are not completely satisfactory in that they do not predict the effect of the dimensions of the bed in relation to flow rate and cycle time, and do not predict the distribution of various components along the length of the bed. It is possible, however, to make a considerable improvement in the design of these processes by applying the basic equations of mass and heat transfer applicable to gases containing small concentrations of adsorbing components flowing through granular beds. These equations have been developed and solved by Anzelius,' Furnas,% nd Hougen and Marshall." where G = mass velocity of the inert constituents (assumed to be methane), lb/hr-sq ft, y = weight of an adsorbing component in the gas per unit weight of inert, lb of a given constituent per lb of methane, x = bed length, ft, p, = packed bed density, lb/cu ft, P, = gas density, Ib/cu ft, f = void fraction in the bed, t = time, hours, and w = weight of a given component adsorbed per unit weight of adsorbate free solid, Ib/lb pure adsorbent. The term on the left side of Eq. 1 represents the flow rate per unit bed volume of a component entering less the flow rate per unit bed volume of that component leaving the differential bed length. The terms on the right side represent, respectively, the accumulation rates per unit bed volume on the solid and in the gas phase within the differential bed section. The last term is negligible for this application since pgfv is quite small in comparison with p, and G. The partial differential is determined by the mass-transfer rate between gas and solid in the differential section.

J. B. Cohen (AVCO Mfg. Co.)-The model presented by the authors is only one of several possible mechanisms for low-temperature aging. It is true that the motion of dislocations to the copper atoms, followed by diffusion along the dislocation lines, is one such mechanism. However, the details of such a process which would :result in copper-rich platelets on (100) planes in the f.c.c. matrix are not clear. Furthermore, there is at least one other mechanism that may be used to e.xplain the authors' results, so that the data do not clearly favor the Turnbull model. The zones may form by "normal" diffusion. The diffusion constants would be higher at room temperature than extrapolated data would suggest due to vacancies trapped in the specimens in the quench. The diffusivity would then be multiplied by the ratio of the number of vacancies present at the solution temperature to that present at room temperature. These vacancies could remain in the alloy specimen for long times at room temerature, due to interaction with the copper atoms. ' The activation energy for diffusion is smaller than that for bulk diffusion at elevated temperatures for it is only that for the motion of vacancies existing after the quench; after these are used up, the aging process effectively ceases. It is somewhat questionable if the laws governing transformation kinetics can be directly applied to changes in elastic moduli, especially in the case of aging where the structure and the composition of the zones may be changing during aging, If such laws are assumed, it is possible to explain the exponential factor of % with this vacancy model. It is probable that the structure of the zones and the matrix match only on (100) planes. Certainly the precipitates that form in this system after various aging treatments show orientation relationships similar to those of the zones. Strains on the edges of the zone may set up fields which do not allow the zone to grow in an edgewise manner. The exponent in the growth of a thin plate in a direction perpendicular to its face would be %. It may also be that copper atoms are attracted to dislocations. If this is the rate-controllin factor in the growth process Ifthisthen an exponent of % or % may arise. The writer would like to know if the authors have tried plotting l/a; proportional to as might be expected for "dislocation drainage." R. H. Doremus (General Electric Research Laboratory)—An important new method for following the growth of Guinier-Preston zones is presented in this paper, and I wish to congratulate the authors on their experiments. Their interpretation of the results, however, is doubtful in certain respects. To determine the exponent m in Eq. [4] the authors plotted -log at against t to various powers (their Fig. 6). The initial value of frequency used for these plots was found by extrapolating the data to zero time. In Fig. A the data from their Fig. 2 are plotted against a linear, rather than logarithmic, time scale. To obtain graphs similar to their Fig. 6 for these data one must use an initial frequency of about 52720; such a plot for m = % is shown in Fig. B. The straight line in Fig. B fits the data in an intermediate range only. The curve drawn in Fig. A was mapped from this line; comparison of

Jan 1, 1960

By W. O. Philbrook

An engineering analysis indicates that the coke rate in present blast-furnace practice is set not by chemical or thermal needs but to give adequate charge permeability for economical driving rates. An equation showing interrelations among pressure drop, gas flow, and charge characteristics has been derived. Flooding conditions and the location of the fusion zone are discussed. Maximum ore size is probably limited by chemical re-ducibility rather than by heat transfer. THE intention of this paper is to show that the ].imitations on the production rate and coke requirement of the iron blast furnace are not primarily chemical or thermal in nature but are related to characteristics of the burden and operation that govern gas flow, heat transfer, and stock movement. A semiquantitative analysis will be developed in terms of standard engineering principles to give a useful picture of the relative importance of physical and mechanical factors in contrast with the chemical features of the process that are more commonly emphasized. Most of the details of calculation have been omitted in the interest of brevity and to avoid submerging the rnain points in a sea of arithmetic. Numerical values have been arrived at by objective methods from reported operating data or by reasonable estimates of material properties where exact data are lacking and then tested to see how well they fit practice, rather than by working backward to find what assumptions are needed to give the desired answers. The analysis is oversimplified in many ways because exact engineering relations have not yet been studied for bed distributions as complex as are known to exist in the blast-furnace stock column. One objective of this paper is to show that the blast furnace, in spite of its complexity, can be at- tacked by engineering methods in the hope that this viewpoint will stimulate the kind of research needed for a more exact treatment. The basic ideas and many of the conclusions presented are qualitatively well known. A careful literature survey to credit the source of all observations not original to the author would indeed be voluminous, and such has not been attempted. T. L. Joseph's Howe Memorial Lecture' gives an excellent background of what is known about the internal workings of a blast furnace. Other important reference works or sources of specific information will be noted. It is hoped that the present paper will contribute something new, in method of attack and interpretation, that will aid in a clearer understanding of how to operate the blast furnace to best advantage. Factors Limiting Production and Coke Rates The rate of combustion of coke in a blast furnace, as in any fuel bed, is exactly proportional to the rate at which air is supplied. It is axiomatic, then, that the production rate of a furnace is limited by the rate at which it will take wind, i.e., burn coke, and the amount of coke that must be burned at the tuyeres to make a ton of iron of suitable composition. These two possible limiting factors will be considered briefly in the order mentioned. One common restriction on wind rate is flue-dust production. Since the volume of top gas is nearly proportional to the blast volume (by a factor of about 1.35 on a dry basis), an increased wind rate causes a correspondingly increased linear velocity of top gas in the throat of the furnace. The higher

Jan 1, 1955

By Donald Ofte, L. J. Wittenberg

The absolute viscosity coefficients and activation energies for viscous flow of bismuth, lead, and zinc are reported. The viscosities were measured in an oscillating cup viscosimeter from nearly 1000°C to within 1 deg of the melting point of zinc; 2 deg of the melting point of lead; and in the supercooled condition of bismuth, 9 deg below the melting point. Two methods of relating the change in the viscosity coeflicient with temperature were compared. From the plot of the logarithm of viscosity (77) as a function of reciprocal absolute temperature (1/T), the equations of the lines which fit the data are: AS a part of the Reactor Fuels and Materials Research program at Mound Laboratory, precise measurements of the physical properties of liquid metals are of interest because the desirability for a low vapor pressure liquid coolant in high-temperature nuclear power plants has focused attention on the properties of the liquid metals.' Also, a clearer understanding of the liquid metal state can be achieved when better measurements are available. For these reasons, the viscosity values of certain liquid metals have been determined. The viscosities of the liquid metals, bismuth, lead, and zinc are measured in an oscillating cup viscosi-meter. In this apparatus the liquid is sealed in a right-circular cylindrical cup which is attached to a torsion fiber so that the system forms a torsion pendulum. The damping effect of the molten metal upon the normal oscillations of the torsion pendulum is a function of the viscosity of the liquid. This method is advantageous because of the small amount of sample required (8 to 10 cc), the ease of remote operation of the apparatus in a vacuum system, and the containment of the liquid metal in a hermetically sealed, nonreactive, tantalum crucible. With the liquid metal sealed in the crucible, loss of liquid by vaporization and chemical reactions with atmospheric gases are prevented. Additionally, an absolute viscosity determination is obtained which avoids the sources of possible error in a relative measurement. The difficulties in a relative method include the repetitious cup calibrations, and the uncertainty inherent in the practice of calibration of the apparatus at room temperature and extrapolation to the high temperatures necessary for the investigation of most liquid metals. The oscillating cup viscosimeter was first described by Meyer in 1891.2 The first complete mathematical treatment offering an absolute measurement of viscosity with this type of apparatus was proposed by Andrade and chiong3 in 1936 for an oscillating sphere filled with a liquid. This solution was modified to include a right circular cylinder by Hopkins and Toye4 in 1950, and R. Roscoe5 in 1958. Roscoe's treatment for the calculation of the viscosity of a liquid at a particular temperature from the logarithmic decrement and period of oscillation of the torsion pendulum was used in this investigation. A detailed description of the method of calculating the viscosity from these measurements has been reported earlier.' This calculation has been programmed for the IBM 704 and IBM 1620 computers for expedition of the otherwise laborious calculations. APPARATUS The cutaway view of the apparatus in Fig. 1 shows the suspension system within the high vacuum enclosure. The low residual gas pressure. maintained between 1 x 10-4 and 5 X 10-6 mm Hg during a determination, avoided both air drag on the pendulum and

Jan 1, 1963

By N. K. Chen, R. Maddin

In the extension of molybdenum single crystals at room temperature, the slip planes were found to be of the type (1101; the slip direction <111>. Theories of plasticity of body-centered cubic metals have been examined, and an explanation based upon planes of highest atomic density seems plausible to explain the plastic behavior of molybdenum single crystals. IN body-centered cubic metals, slip has been reported to occur on several planes; these are of the type {110), {112), and (123). Andrade has correlated&apos; the operative slip planes in body-centered cubic metals with the testing temperature relative to the melting point. In this correlation, if T is the absolute temperature at which slip takes place and Tm the absolute melting point, then the acting slip planes in body-centered cubic metals may be arranged as shown in Table I. However, deviations from this correlation have been reported in iron and iron-silicon alloys2 and also in molybdenum deformed at a temperature around 2400°C." In the case of iron and other body-centered cubic metals or alloys in which all three slip planes have been reported to be active at any one temperature, the crystallographic mechanism of slip is not well understood. Numerous investigators in this field have assumed that the resolved shear stress is a deciding factor. Such considerations were given by Gough in his experiments with repeated torsion of iron single crystals4 and recently by Opinsky and Smoluchowski in their study of iron-silicon alloys," and will be dealt with later in this report. A third possibility is that slip lines in body-centered cubic metals may be formed by alternate slip on nonparallel (110) planes and not by slip on any plane of higher indices. This was advanced by Elam in the case of ß brass." Since (1101 planes are planes of highest atomic density in the body-centered cubic structure, this hypothesis would be in accordance with the plastic behavior of metals in other systems, namely, face-centered cubic and hexagonal close-packed. Experimental evidence in support of this hypothesis is lacking. Nevertheless the work of Barrett, Ansel, and Meh12 has definitely demonstrated that the slip resistance on {110} planes in iron is very much smaller compared with that on (112) and (123) planes. In the present investigation, molybdenum single crystals were carefully documented as to the operative slip planes and lattice reorientations after plastic extension at room temperature. In three crystals studied, (110) planes were found to be active invariably rather than the (112) planes, which were previously reported for molybdenum at this temperature&apos; and predicted by Andrade&apos;s theory.&apos; In two other cases (112) and (123) planes seemed to operate together with (110) planes as active slip planes. However, it is believed, after careful analysis of crystallite and lattice rotations, that slip on (112) and (123) planes may be spurious. Particular reference will be made to the formation of asterism, lattice rotation, and crystallite rotation in an attempt to show that slip apparently observed on {1121} and (123) planes is actually slip on nonparallel {110} planes. Materials and Treatment Sintered molybdenum rods ? in. in diam, obtained from the Fansteel Metallurgical Co., were reported to have a purity of 99.9 pct.* One specimen, Mo-13, ¼ in. in diam, was supplied by Westinghouse Electric Corp. Single crystals were prepared, using the technique devised by Chen, Maddin, and Pond." Mo-13 was ¼ in. in diam x 7 in. long with a reduced gage section of 0.200 in. in diam x 3 in. long. The center of

Jan 1, 1952

By J. G. Kura, P. D. Frost, L. W. Eastwood

THE preparation and general properties of mag-nesium-lithium base alloys have been described in earlier papers.l,2 Lithium forms solid solutions with pure magnesium, lowers its density, and improves its formability. The improved isotropy and better formability of these alloys are attributed to the ability of lithium to convert the magnesium lattice from hexagonal (alpha phase) to body-centered-cubic (beta phase) structure. This change in structure is, however, accompanied by some limitations which make it difficult, if not impossible, to combine all the desirable properties in one composition. The most important of these limitations is the tendency of the high-strength alloys to overage and lose strength at temperatures of the order of 150" to 200°F. A study was made of the effects of composition and heat treatment on the age-hardening character- istics of the alloys. Stability of properties was determined by hardness and tensile testing of the alloys at room temperature after various periods of exposure to elevated temperatures. Precipitation-hardening curves are shown for a number of magnesium-lithium-zinc alloys in fig. 1. All the alloys were solution treated at 700°F and aged at 200°F. The reason for using the drastic quench, toluene at —105°F, was to reduce the rapid precipitation of the hardening phase which takes place at room temperature. Previous experience has shown that a hardness of about 90 to 95 Rockwell E is indicative of yield strengths in the range of 35,000 to 40,000 psi. This is a desirable strength level for magnesium-lithium base alloys with specific gravities of the order of 1.65 or less. Although the hardness level is raised by large zinc contents, a corresponding decrease in the cold formability of these alloys occurs with increasing zinc content. Thus, alloys containing up to about 10 pct Zn and having hardnesses of the order of 70 to 75 Rockwell E may be bent over a very small radius; however, the 16 pct Zn alloy requires a bend radius of more than 8T. The hardness relationships illustrated in fig. 1 can be explained by the partial phase diagram shown in fig. 2. The zinc-free magnesium-lithium alloys are entirely body-centered cubic (100 pct beta phase) when the lithium content of the binary is 10.3 pct or higher. When zinc is added, the boundary between the beta and alpha-plus-beta fields at 700°F is shifted to lower lithium contents. In addition, the solubility of zinc at 700°F decreases with decreasing lithium content. It is shown by a study of micro-structures that the limit of solid solubility of zinc in the 6Mg/Li* matrix at 700°F is about 19 pct. It is believed from a study of the aging curves that this limit is about 2 to 3 pct at 200°F. Zinc additions up to about 2 pct increase the hardness and strength of the magnesium-lithium base solid solution. Larger additions of zinc effect further hardness increases, but precipitate during prolonged aging at 200°F. Alloys having 14 to 20 pct Zn precipitation harden extremely rapidly during quenching, even when quenched in toluene at —105° F. The high-zinc alloys overage at 200°F but are capable of maintaining reasonably high hardnesses for periods up to 1000 hr.

Jan 1, 1951

By M. H. Childs, K. E. Merklin

Blast furnace feed specifications are being revolutionized because of the large increase in iron pellet production from low-grade ores of the Lake Superior region. Recent laboratory findings aimed at a better understanding of factors influencing the physical quality of pellets produced from taconite concentrates are reviewed. Tests for determining better product quality, the effects of additives, and production factors are discussed. The current revolution in specifications for blast furnace feed is typified to a great extent by the recent tremendous growth in iron ore pellet production from low grade ores of the Lake Superior region. Indeed, pellets are responsible, at least in part, for many of the stringent new requirements that are being placed on the suppliers of furnace raw materials. As the tonnage of pellets going to the steel mills increases, more and more attention is being turned to the detailed characteristics that make this product an ideal blast furnace feed. Control of quality in pellets is similar to that of any other product. A basic understanding of the factors that are encountered in their production, from the crude ore through to the finished product, is required, along with careful process supervision and frequent quality checks. Normally, chemical grade is not a problem. This usually can be controlled within the desired specifications by minor operating variations in the con- centrator. While future changes in requirements may result in the need for self-fluxing pellets1 or other chemical changes, today&apos;s quality demands center primarily around the physical characteristics of the pellets. It is in this area that many of the recent laboratory studies have proven helpful to the operating plants. A better understanding of the physical factors involved in pelletizing has provided the basis for a continuing program of quality improvement. Tigerschiold and Ilmoni2 and Cooke with various associates are responsible for the development of much of the basic understanding of the pelletiz-ing process. These earlier findings have served as a most useful background for this work. LABORATORY PROCEDURES Magnetite concentrates produced from eastern Mesabi Range magnetic taconites were used for all of the work reported herein. The sizing and chemical analysis of a random sample are shown in Table t Additives usually are mixed with the concentrates in taconite plants before pelletizing to improve the strength characteristics of the unfired balls. Ben-tonite, soda ash, and coal are in common use. The bentonite used in these studies was of the Wyoming sodium type; the soda ash was a standard commercia1 brand. Anthrafines were used where coal was called for. The procedure for making batches of balls at the Hibbing Laboratory is as follows: In an especially designed mulling equipment 2800 g of dry ore are mixed for 10 min with the desired additives. Water is added and mixing continued for 1 1/2 min. The charge is removed from the muller and put through a mechanical shredder to break down any lumps that may have formed. sixty previously formed seed balls are placed in the balling drum, which is in fact a 6 x 16-in. diam airplane tire turning at 53 Wm. Two thousand grams of the shredded concentrate and additive mix are fed by hand into the tire at a con-

Jan 1, 1961

By Robert A. Rapp, Jan E. Verfurth

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

Jan 1, 1964

By I. A. Lesk

The various materials utilized in the construction of integrated circuits, and the resultant materials interfaces, are discussed with emphasis on a materials system that is compatible with all types of integrated circuits and minimizes the number of different interfaces. Problems with interfaces may originate in the silicon, on its surface, and between other materials within the integrated-circuit package independent of the silicon. ThE difference between integrated-circuit theory and practice may generally be spelled out in terms of the difficulties in fabricating a desired structure. There are, of course, problems in forming the requisite materials, of the necessary composition and geometry, where needed. A distinct class of problem, however, is associated with interfaces— generally between different materials, but occasionally between regions of the same material. We require that each interfacial system perform its proper electrical, mechanical, and thermal function, and do so in an unchanging manner with time under the most severe operating conditions. In a practical sense, we deal in nonideal systems, such that it is generally not possible to form an interface exactly the way it was intended, even if we allow for a knowledge of the practical limitations of the fabrication system. Another way of looking at this situation is to realize that, when we form a group of interfaces under apparently the same experimental conditions, there are often differences of important consequence between them. Very high-magnification pictures, such as are obtained by an electron microscope, reveal fine structure that often differs over the area of a given sample, as well as from sample to sample. Low-magnification pictures look better, but don&apos;t eliminate the problem. The trend towards integrated circuits, and away from circuits fabricated utilizing separate components, is very strong in many areas of electronics. A typical silicon monolithic integrated circuit, still in place in the wafer on which it was fabricated, is shown in Fig. 1. The increased reliability which is being experienced through the use of integrated circuits can, to a large extent, be credited to the reduced complexity of the interface system that is present in the electronic system. A glance at Fig. 1, however, with all of its epitaxial and diffused p-n junctions, and interconnect system, shows that interfaces have been far from eliminated. Fig. 2, depicting a schematic cross-sectional view of a (partial) typical integrated circuit, illustrates in detail the numerous interfaces that occur in this type of structure. Besides the individual circuit elements, there are interfaces for isolation, and, Fig. 3, even a crossover requires a series of interfaces. What has been accomplished, however, irrespective of whether or not the total number of interfaces in the circuit is increased or decreased, is that the variety of interfaces is very much reduced. This is because there are fewer materials involved. Since the expense incurred in an R & D program to improve reliability is pretty much directly proportional to the variety of interfaces involved, it is economically advisable to work with integrated circuits for highest reliability. That is not to say that circuits built using standard components could not be made as reliable as integrated circuits, but that the expense involved because of the more complex over-all interface system would be much greater. Although electronic performance utilizing integrated circuits with all silicon elements (i.e., transistors, diodes, resistors, capacitors) is adequate for many applications, there are numerous instances where thin-film passive elements must

Jan 1, 1965

By A. D. LeClaire

This paper claims to provide a description of diffusion processes in solids which is said to be a reformulation of Fick&apos;s Laws and therefore, presumably, is supposed to be as general as those laws. In fact, it appears to provide no more than an atomic model of a rather restricted type leading even to results in conflict with experiment. The restriction lies in the assumption, carried throughout the paper, that even in a chemical gradient the jump frequency i of an atom of species i is a function only of the composition on the plane from which it jumps, i.e., ?i = ?i(cl, c2 ...). This means that atom jumps in opposite directions from a site would occur with equal probability. There would then be no tendency for atoms to migrate preferentially in one direction along the gradient, so the model is incapable of accommodating the well established phenomenon of atom drift in a chemical gradient.10-" A more general model that does not suffer this difficulty was discussed in a paper13 I wrote in 1958, and the results therein already contain as a special case those given by Dr. DeHoff. The simplest sufficiently general assumption is to suppose that ?i is a function ?i(a1 a2,...; wl, w2, ..-) of the concentration aj and ? ?j at the site from which and to which, respectively, a jump is made. Any such function can always be expressed as a function of the sum and difference of its arguments. Thus d is the jump distance and g a geometrical constant. Obviously this is zero, i.e., no drift, if ??ri/??j = 0. X is written in this form, revealing two components of the total drift, because it can be shown that only the second component, depending on ??&apos;i/???(?j -aj), actually contributes to the net diffusion flux Ji. This component can be shown,13 by a straightforward ther-modynamic transcription, to be responsible for the so called "thermodynamic factor" in the Darken approximation for a chemical diffusion coefficient is the activity coefficient of i. Because the jump rate ?i in DeHoff&apos;s approximation has no dependence on the concentration gradient it does not seem possible to derive the Darken equation from his Eq. [6] without the further rather arbitrary assumption that ?i = const ri. It is to be noted too that the author&apos;s derivation of Eq. [12] is only valid when ?i is in fact a function only of the cj at the plane from which the atom jumps—for only then is ci?i a unique function of position and therefore of A. Author&apos;s Reply R. T. DeHoff I am indebted to Dr. LeClaire for his penetrating discussion of my paper, "A Reformulation of Fick&apos;s First Law". I concede that it does appear initially that the relationship presented in my paper could be derived from the detail atomic model of random walk and atom drift presented in Dr. LeClaire&apos;s approach. However, there are some important differences in concept and viewpoint which deserve further amplification. Dr. LeClaire&apos;s description is penetrating, detailed, and fundamental. His approach describes an extremely complex phenomenon, the displacement of atoms in a multicomponent gradient, at a sophisticated level. For precisely these reasons, his analysis has not proved to be useful for experimental studies that have practical objectives. For example, in order to obtain the information required to complete the analysis of the jump frequency distribution in a ternary system, the following series of experiments would, I believe, be required: 1) chemical (gradient) experiments, covering the composition range;

Jan 1, 1970

By S. C. Sircar, D. R. Wiles

The rate has been studied of the hydrogen reduction of nickel ions in acetate -buffered solutions, using a nickel catalyst. At temperatures between 130°and 160°C, the rate is found to be proportional to the catalyst area, the nickel ion concentration, and the hydrogen pressure. The effect of hydrogen ions is to reduce the observed rate, likely by causing the reverse reaction (dissolution) to proceed. The experimental activation energy was found to be 25 kcal per mole. THE precipitation of metals and lower oxides from solution by hydrogen reduction has been quite actively investigated during the past few years.1 In the case of nickel, the kinetics of the precipitation have been studied in ammonia solution2 but extension of this study to acid solutions has not attracted much interest, largely because of the unfavorable thermodynamics at all but the lowest acidities. For example, Schaufelberger foundg that only 10 pct reduction of nickel could be effected in sulphate solutions. One kinetic study of the reduction of Ni++ has been reported by Knacke, Pawlek, and Sussmuth,4 in which the order of the reaction was found to be one in nickel ion and one-half in hydrogen pressure. No mention was made as to the part played by the nickel catalyst, or by the pH of the solution. Moreover, the activation energy reported (4 .12 kcal per mole) is so low as to lead to some question as to whether diffusion might be playing a major role in determining the kinetics. We have recently completed a study5 of the kinetics of the hydrogen precipitation of nickel from acetate-buffered acidic solutions whose results confirm and amplify those of Knacke et al. EXPERIMENTAL PROCEDURES The work was done in a high-pressure autoclavee by the usual technique of removing small samples of the solution for analysis. Nickel analysis was done colorimetrically by the dimethylglyoxime method.&apos; The catalyst used was carbonyl nickel powder (Standard A powder of the Mond Nickel Co., Ltd.) which was found to be composed of spheres of less than 350 mesh. The surface area of the powder was determined in this laboratory by the B. E. T. method to be 1.85 sq m (m2) per g. The catalyst was added to the solution only after the proper temperature and pressure had been reached. Agitation of the baffled system was by a turbine-type impeller, rotated at speeds between 400 and 750 rpm. The reduction rate was found to be independent of the stirring rate, so it was assumed that diffusion in the liquid does not limit the rate. In typical experiments, the nickel concentration was unchanged during an induction period of variable length. The concentration then decreased sharply, and gradually levelled off to approach the final equilibrium value. In some cases, notably at high stirring rates, the nickel concentration was found to increase considerably during the induction period, and then to decrease. In all cases, the rate was determined from the slope of the tangent to the rate curve as the concentration first decreased below the initial value. This is seen in Fig. 1. The rate measurements were found to be reproducible to within about 5 and to be quite independent of the nature or duration of the induction period. The range of conditions used is given in Table I.

Jan 1, 1961

By N. A. D. Parlee, I. D. Shah

The solubilities of oxygen in liquid Ag-Au, Ag-Pt, and Ag-Pd alloys have been determined in the range of 940° to 1200°C at 1 atm pressure of oxygen using an improved Sieverts technique. The additions of gold (0 to 57 pct), platinum (0 to 27 pct), and palladium (0 to 22 pct) to liquid silver continuously decrease the solubility of oxygen in liquid silver. Activity coefficients and interaction coefficients of oxygen in these alloys and have been calculated. The interaction coefficientscan be described by the following equations: Approximate second-order interaction coefficients (pM have been calculated. The contribution of the product, pMxNM, to In yo only becomes significant at high alloy concentrations. RECENTLY several investigators1"3 have redeter-mined the solubility of oxygen in liquid silver. In general the recent findings1" for Po, = 1 atm are in good agreement with the equation:4 log %O = 695.4/T + 1.086 [1] It is established1, 2 that the solubility of oxygen follows Sieverts&apos; law reasonably well, at least up to 1 atm partial pressure of oxygen. It should be noted that a very slight deviation from Sieverts&apos; law has been reported by Lupis and Elliott.3 Only recently has the solubility of oxygen in Ag-X binary liquid systems received much attention, and only the Ag-Cu, Ag-Au, Ag-Pt, and Ag-Pd systems have been studied. Par lee, Sacris, and zoellners reported that the solubility of oxygen in liquid silver increases progressively with the small additions of copper (0 to 0.5 pct) up to the point where the copper oxide phase appears. Lupis and ~lliott~ have reported that the solubilities of oxygen in liquid silver decrease progressively with the additions of gold, platinum, and palladium. However, their investigation was limited to 0 to 5 pct of these alloying elements, a range too limited to satisfy the requirements of the research program of this laboratory, where the solubilities of oxygen in the range of 0 to 30 pct were required for the calculation of chemical diffusion coefficients of oxygen in these alloys. The present paper deals only with the solubilities of oxygen in these alloys while another paper will deal with the diffusion of oxygen in these alloys. EXPERIMENTAL METHOD A Sieverts technique was employed which involved an improved design of the reaction tube, Fig. 1, as described briefly in a previous communication.4 Liquid melts (70 to 100 g) were held in Norton Alun-dum crucibles. The induction furnace used had a maximum output of 2.5 kw with very fine control. This induction system had excellent stability and the final equilibrium temperatures measured by calibrated Pt-Pt, 10 pct Rh thermocouples are believed to be within ±2C. These thermocouples were checked against the melting point of pure gold wire, and the results agreed with standard tables (±l°C). Each run involved a careful sequence of operations. The sample was heated to and held at about 900°C in vacuum for 3 to 4 hr with the thermocouple in a retracted position. After melting, the melts were usually exposed to a small amount of oxygen (0.5 to 2.0 cu cm) and then degassed slowly for 1 to 2 min to remove any oxidizable volatile impurities such as carbon and sulfur as CO, CO2, SO2, and SO forth. Argon gas was then allowed to enter the system. The protection tube containing the thermocouple was then

Jan 1, 1969