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By R. P. Alger, M. P. Tixier, D. R. Tanguy

In the combination induction-electrical log used at present in the field, the induction logging tool is appropriate for the investigation of moderately invaded formations. A new induction sonde with a radius and investigation about twice as large has been developed recently for the case of deep invasion. It has very nearly the same vertical resolution as the present sonde so that thin beds are defined as accurately as before. The characteristics of the new tool are described, the corresponding interpretation charts are given and field examples are discussed. The design of the sonic logging tool has been modified to improve the calibration and the reliability. The fact that porosity can be accurately recorded by means of the sonic log has prompted new interpretation procedures for saturation estimation, wherein the data concerning the various permeable beds in a given well are correlated. One approach consists of plotting transit time vs true resistivity, with an appropriate scale. With this approach, saturations can be estimated conveniently even in cases where formation water resistivity is not well known. In another approach, a comparison is made of the values of the formation waters computed from the re- sistivity and sonic logs. Using the concept of continuity, this procedure makes possible a quick determination of zones of saturation in shaly sands and/or in case of appreciable variations of formation salinities with depth. It has been found that the comparison of porosity from the sonic log with the apparent porosity computed from a short-investigation resistivity log may reveal, in many cases, the presence of residual oil and thus detect potentially productive formations; this procedure is valuable when the true formation resistivity and the resistivity of the formation water are in doubt. INTRODUCTION During the past year, the efficiency of log interpretation has been vastly improved. The improvements have largely resulted from the introduction of a deep-investigation induction device and from the application of new interpretation techniques that utilize sonic vs resistivity readings. Since the new interpretation techniques depend, in part, upon good values of true formation resistivity, the new induction log will be discussed under Part I. The sonic interpretation techniques will be studied under Part 11. Early in 1959, the 6FF40 induction equipment was introduced in the field. This device was designed for a better approach to true formation resistivities in deeply invaded zones. The greatly improved radial investigation of the 6FF40 equipment has been achieved without sacrificing vertical resolution. The first combination induction-electrical log, the 5FF40, was introduced as a standard tool in 1956 for the logging of wells drilled with fresh muds. The tool has received wide industry acceptance in the United States. 'The 5FF40 induction log has a radial investigation sufficient to overcome average depths of mud filtrate invasion. At 5d invasion, for example, the 5FF40 induction log will read about 1.4 R. in a water sand where R., = 10R,. At 10d invasion, such induction log would read 2.45 R. in the same water sand. In either case, the effects of invasion would not be sufficiently great to cause a water sand to be mistaken for a shale-free oil- or gas-producing zone. Some formations, however, invade deeply — in excess of 10d. Such water zones could be mistaken for oil-or gas-saturated sands unless the porosity balance' can clearly make the distinction. It is for these deeply invaded formations that the 6FF40 was developed. CHARACTERISTICS OF THE 6FF40 Radial Investigation Characteristics To describe the comparative responses of the 5FF40

By C. Gatlin, M. E. Chenevert

The effects of bedding plane orientation on the elastic constants and the yield strengths of three laminated rocks (one sandstone and two shales) and one isotropic rock (a limestone) were studied. The directional dependence of the elastic properties of these rocks was experimentally evaluated using a triaxial compression cell and auxiliary stress-strain measuring equipment. Symmetry of Poisson's ratios within the bedding plane suggested that horizontal isotropy exists, but the bedding planes do give rise to an appreciable difference between properties in the horizontal and vertical directions. For the three bedded rocks studied, Young's modulus was lower normal to bedding than along bedding. Yield strengths were determined at confining pressures from 0 to 12,000 psi in a triaxial compression cell. The rocks studied showed strength reductions as high as 40 per cent when the test specimen was oriented at 20°-30° to the bedding planes. The mechanical behavior of these rocks suggested that the rock properties of shear strength and/or coefficient of internal friction can vary with direction, depending on the particular rock tested. Tensile strengths were also measured and found to be lowest when failure occurred along bedding. This work shows that bedded formations exhibit sizable directional variations in both their elastic constants and yield strengths. It is suggested that these variations may be accounted for by using the "elastic laminate" model and the "variable coefficients" failure model. INTRODUCTION The nature of rock deformation at elevated pressures has been studied by many workers; papers by Handin,l,2 and Robinson3 illustrate the present state of knowledge. Most investigators have either chosen rocks which were as isotropic as possible (in order to avoid complications of data interpretation and analysis) or they have oriented their samples so that the effects of anisotropies (such as bedding planes) have been avoided. Of the studies performed, few were concerned specifically with mechanical anisotrop-ies. Griggs4 has presented limited data for specimens cut parallel, normal, and 45° to the bedding plane; he relates the strength anisotropy observed to the fabric (bedding) anisotropy. His tests were primarily concerned with large deformations (20 per cent strain); thus, no directional values of the elastic constants were reported. Handin has reported the results of similar experiments. Bott5has discussed rock strength anisotropies due to faults, cleavage, or bedding. He was concerned primari ly with determining the shear stress on such planes and did not mention the effect of friction. Jaeger6 later generalized Bott's work by taking friction into account and presented a limited theory for the failure of rocks having a "single plane of weakness", and also for rocks having a constant coefficient of friction, and a shear strength which varies with bedding plane orientation. Donath and Cohen,7 and Donathg have evaluated rock strengths from shale and slate specimens cut normal and parallel to bedding. A dependence of cohesive strength (7,) on the specimen orientation was also shown. Adler9 has also studied this problem and lists similar results. He assumes that all bedded rocks behave according to Jaeger's single-plane-of-weakness theory. Kalinin and Belorussov10 list results for strength tests parallel and perpendicular to bedding and use this information as a basis for hole deviation analysis. From the literature it is apparent that sedimentary rocks have been tested under widely varying conditions of stress; however, the assumption of isotropy is generally, but not always, made. Since geologic sedimentation often deposits sediments in very definite lavers.,. it seems that more svstema tic attention should be given to the possible effects of this natural bedding. Bedding, as used here, refers to visible regularities of grain size or orientation resulting from depositional processes. The mechanical strength anisotropies, which bedding may present, is not the only anisotronic property to be considered, since the elastic

Jan 1, 1966

By J. B. Cheatham, C. E. Murphey

Presently, computer control of Borobolic direction cannot be obtained during drilling, and most straight-holc drilling methods attempt to resist hole deviation rather than control direction. Many of the theories advanced as possible explanations of the cause of hole deviation are Summarized berein. A new correlation of physical partables is introduced to indicate bow factors such iis drill collar stiffness clearance and hit weight influence borehole deviation, .A methord is proposed for predicting the rate of change of hole angle when drilling conditions are changed. INTRODUCTION Control of borehole direction during drilling can be difficult and costly. Unintentional crooked holes are often lrilleti in dipping formations and many times directional drilling is required when the surface location is not directly above the target area —- for example, at offshore and mountainous locations. Prilllng progress can be greatly hindered in either air or liquid drilling when it be comes necessary to use low bit weight to prevent excessive hole angle build-up. If hole inclination becomes too great, drill pipe drag becomes excessive and fishing risks are increased, logging is more difficult and problems of differential sticking, key seating and fatigue failures may be encountered. Dog-legs and key seats are more serious problems than steep inclination angles: therefore, reducing rate of direction change is preferred to attempting to maintain absolutely vertical holes. Consequently, a straight inclineti hole is preferable to a nearly vertical crooked hole containing numerous dog-legs. In this paper, theories of the cause of hole deviation and analyses of drill string behavior under down-hole conclitions are summarized. Methods for computing hole deviation are presented und systems for resisting deviation as well as neans for provic!ing control of holt- direction are iliscusseI. A new correlation of physical variables is introduced tu indicate how factors such as drill collar stiffness, clearance and bit weight influence borehole deviation. A method is oroposeti for predicting the rate of change of hole anFrle when drilling conditions are clianged. IIEVIEU' OF PREVIOUS WORK ON HOIaE DEVIATION Significant progress in the theoretical analysis of hole deviation problems has been made in the past 1 5 years. The pioneering work has been primarily a result of the efforts of Lubinski and Woods.l-5 In 1950, Lubinski 1 considered the buckling of a drill string in a straig:rt vertical hole, a problem also considered by Willers6 in 1941. It wns concluded that very low bit weights must be used to prevent hole deviation resulting from drill collar buckling. The use of conventional stabilizers was proposed2 in 1951 by Mac Donald and Lubinski as a method for permitting greater Sit weights to he carried without drill collar buckling. These authors pointed out that a 2° nearly vertical spiral hole can cause severe key seatinp, and drill pine near, wilereas n 3 straight inclined hole with deviation all in one direction, while not vertical, will not result in serious drillirig or producing problems. Studies were continued with an investigation of straight inclined holes by Lubinski and Woods3 in 1953. In this paper they concluded that perfectlv vertical holes cannot be drilled even in isotropic forriations unless extremely low bit P-eights are used. .l'l~ey postulated that constant drilling conditions produce holes of constant inclination angle and varying conditions cause the hole to drill at a neiv equilibrium angle. This analysis was not concerned with drill string buckling since it was based on an equilibrium solution in which the ~irill string Was presumed to lie along the lower side of the hole abcrve the point of tangency. Weight of the drill collars below the point of tangency tends to force the hole toyard the vertical, whereas the weight on hit tends to force the hole aurav from the vertica l. The concept of an anisotropic formation Lvas introduced as an empirical method for explaining actual drilling data and as a means for extrapolating known deviation data to otiier conditions of hit

Jan 1, 1967

By L. W. Holm

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

Jan 1, 1969

By R. G. Garlick, H. B. Probst

Tungsten single-crystal specimens of various orientations were deformed in tension at room temperature. Slip traces indicated both (112)(111) and (110) (111) slip; however, about 10 pct plastic dejormation was required bejore these traces could he seen. Resolzled shear-stress considerations indicated that at least some of the particular systems observed were not those on which slip initiated hut were secondary systems. This is highly probable, considering the high plastic strains involved. Analysis of the stress data with respect to possible slip systems indicated that slip must have been initiated at stresses below the proportional-limit stresses measured. ALTHOUGH there is general agreement that slip deformation in fcc and hep metals takes place on the plane of close packing and in the direction of close packing, there is no such agreement for slip in bcc metals. It is generally agreed that the close-packed direction (111) is the slip direction, but investigations have led to conflicting descriptions of the slip plane. As Hoke and Maddin1 point out, there are essentially four points of view. 1) Deformation in bcc metals is composite shear on (112) and (110) planes or on nonparallel (110) planes, and any apparent slip on other planes can be accounted for completely by slip on these planes. Chen and Maddin have reported this to be the possible case for molybdenum." 2) Slip occurs in the (111) direction and is limited to {110), {112), and (123) planes (the three closest packed planes of the lattice). 3) Slip occurs in a (111) direction, but not necessarily on planes of close packing (banal slip). 4) Slip occurs in those directions and on those planes for which ß, the ratio of Burgers vector to interplanar spacing, is a minimum. The slip systems of the bcc metal tungsten have never been fully determined, although several investigators have reported pertinent results.3"7 The present work was initiated to determine the active slip systems in tungsten at room temperature, the critical resolved shear stresses associ- ated with these systems, and the orientation dependency of operative systems. These features of tungsten deformation at room temperature have never been reported in the literature. The authors find this somewhat surprising, particularly in view of the availability of tungsten single crystals since the advent of electron-beam zone-melting techniques and the widespread interest in refractory metals. It would seem apparent that such work has been attempted but the results have not been reported, possibly due to the conflict with deformation theory. The results of the present work conflict with any straightforward description of deformation based on the proposed explanations of slip in bcc metals. Although these conflicts have not been resolved, a presentation of the problem seems in order and should be of value to others working in this field. MATERIALS AND PROCEDURE Single-crystal tungsten rods of 1/8-in. diameter were grown from undoped commercial rod by one-pass electron-beam zone melting in apparatus previously described by witzke.8 Representative analyses of the rod before and after melting are given in Table I. There was no detectable zoning of impurities during melting. Buttonhead tensile specimens, as shown in Fig. 1, were machined from single crystals. Two flats 90 deg apart were ground in the gage length of each specimen. These flat surfaces facilitated the analysis of slip traces. No attempt was made to position these flats with respect to the crystal orientation. The worked surface layer of the machined specimens was removed by electrolytic polishing in a NaOH solution. Tensile-axis orientations were determined by standard Laue back-reflection techniques. The sharpness of the Laue spots indicated that the crystals were free of strain.

Jan 1, 1964

By H. J. Ramey

A general solution is presented for the transient temperature distribution caused by radial movement of a cylindrical heat source through a homogeneous medium of infinite extent. This problem represents a highly simplified model of the movement of a combustion front during the thermal recovery of oil. Numerical solutions are presented for a heat source moving at a constant velocity, and a velocity inversely proportional to the radial location of the heat source. Numerical solutions are presented for both finite and infinite vertical thickness of the heat source, i.e., with and without vertical heat losses. The numerical solutions are used to estimate the fuel concentration needed to maintain a combustion front during the thermal recovery of oil. The sensible heat carried to the combustion front by the injected gas stream is discussed in regard to the fuel concentration. Numerical solutions for a heat source (combustion front) of finite vertical thickness indicate the field conditions that may be necessary to sustain the temperature of a combustion front above the ignition temperature of the fuel over considerable distances from an injection well. The results also have implications in regard to the quantity of heat required during ignition. The results of this computation apply to a highly idealized model of a thermal recovery process. But the results may be used as a guide in engineering consideration of the thermal recovery process. INTRODUCTIO N The thermal recovery of crude oil has received considerable attention since the publication by Kuhn and Kochl of laboratory and field tests of this method of oil recovery. Other publications2,3,4,5,6, since that time have dealt with various features of the thermal recovery of oil and have illustrated the extremely complex nature of this process. Vogel and Krueger7 described an electric analog computer designed to solve a moving heat source problem which was analogous to movement of a combustion front during the thermal recovery of oil. The heat source was maintained at constant temperature and was a cylindrical source of infinite height (no vertical heat loss) moving radially at either constant velocity, or at a velocity inversely proportional to the radial location of the heat source. Jenkins and Ramey2 presented analytical solutions to a similar heat conduction problem and pointed out the possible importance of vertical heat losses. The following presents a general solution to the transient heat conduction problem introduced by Jenkins and Ramey4 as well as numerical solutions for a wide range of conditions possibly similar to those that might exist during field operation of the analogous thermal recovery process. DESCRIPTION OF PROBLEM The problem considered in this paper is determination of transient temperature distribution caused by a cylindrical heat source of infinite or finite vertical height, moving radially through an isotropic medium of infinite extent. It is further assumed that the heat flux generated at the surface of the moving heat source may be a function of time such that the fuel concentration required may be constant, or permitted to vary, and that heat is generated at the surface of the heat source only. In regard to the thermal recovery of oil the assumption that heat is generated at the surface of the front is equivalent to assuming that the thickness of the combustion zone is infinitely small, or that the reaction rate between fuel and oxidant gas is infinite. The last assumption does not appear stringent. See laboratory information published by Martin, et al3 Under these assumptions the temperature distribution throughout an infinite medium caused by a heat source moving radially with an arbitrary velocity may be described by The heat generation function or heat flux at the surface of the source, +(t), is Note that the fuel concentration may be defined as a function of time. Eq. 1 is derived in the Appendix.

By H. A. Wriedt

Zinc-vapor pressures in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C were measured by an isopiestic method. Thermody-na?nic properties of zinc in these solutions were derived directly and those of iron with a Gibbs-Duhem integration. Zirzc and iron exhibit large, positive, and moderately temperature-sensitive deviations from ideality. Excess enthalpies and Gibbs energies are positive in the ranges studied. It has been establzshed in relating published phase equilibria to the Gibbs energies of forming solid solutions that positive departures from ideality also exist in the fcc solutions. Tlze stability, as defined by Darken, of the bcc solutions is small but positive at 703.5"C. Its decrease with decreasing temperature indicates that a miscibility gap may exist in the stable or metastable bcc solutions at lower temperatures. The changes of thertnodynanlic properties relatable to changes in magnetic state are minor compared to other changes due to alloying. The accuracy with which the relation between lattice parameter and composition of the bcc solutions is known has been improved. Zinc increases the lattice parameter of a iron by O.ZOZA per unit atom action zinc to at least NZn = 0.25. TO our knowledge, only Ciganl has previously investigated thermodynamic properties of the bcc solutions of the Fe-Zn system. He measured zinc-vapor pressures in the temperature range from about 320" to 360°C by an effusion technique. We have measured the vapor pressures of zinc in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C by an isopiestic technique. This investigation and the pursuant thermodynamic computations are part of a program for studying several properties of these solid solutions. In the appendix we report a remeasurement of the relation at room temperature between the lattice parameter and zinc content. Related work not reported herein embraces measuring the diffusivity2 of zinc in ferrite at 700" to 900°C and the Curie point temperature3 as functions of composition. EXPERIMENTAL METHOD AND APPARATUS Purified iron at a series of constant temperatures was saturated with zinc at a series of constant zinc-vapor pressures, the range of conditions being so limited that the equilibrated solid solutions were ferri-tic. The equilibration was conducted in long capsules, Fig. 1, that had been evacuated, gettered with titanium, and sealed. The purified iron, part of a vacuum-melted ingot of electrolytic-iron stock (Glidden Co. 1044-grade), had the impurity contents listed in Table I. It was used in the form of millings about 0.001 in. thick. A zinc of 99.999 pct purity (United Mineral and Chemical Corp.) and later one of 99.9999 pct purity (Cominco Products, Inc.) were used, with no observed difference in results. Sufficient zinc was placed in the capsule (separate from the iron and kept at a different temperature) to supply the vapor phase and the iron alloy, while leaving a pool of pure liquid zinc throughout the run. The imposed temperature of the residual zinc pool fixed the vapor pressure of zinc throughout the capsule; condensation was avoided at other locations by making this the lowest temperature in the capsule. Two common complications of nonisothermal systems were, we believe, effectively absent from ours: first, molecular species other than monatomic have no appreciable concentration in zinc vapor at 700" to 900~~: second, the development of zinc-pressure differentials in the capsules was suppressed by use of relatively large-diameter tubing and the absence of diluents in the zinc vapor other than desorbed impurities. The specimens and zinc pool were located at two isothermal zones (each ranging within 1°C over several inches) of a wire-wound, 37-in.-long vertical-tube furnace. The required temperature distribution was achieved by external adjustment of the currents in three electrically isolated windings. The temperatures of the isothermal zones were controlled independently by ther-

Jan 1, 1968

By H. C. Brassfield, R. E. Fryxell, E. C. Duderstadt, E. A. Aitken, P. K. Conn

Permeation rates of hydrogen through are-cast tungsten were measured at temperatures from 1300" to 2600°C with hydrogen pressure differentials of 1 and 0.1 atm across isothermal membranes. Rates were nearly Proportional to square root of pressure, were inversely ProPortional to membrane thickness, and were temperature-dependent according to the equation: p = permeation coefficient in cu cm (stp)-mm per sq cm-min-atmlr2, R = gas constant in cal per mole-OK, T = absolute temperature in OK. Permeation rates of oxygen through tungsten were deternlined in the range 1965" to 2300°C and at calculated oxygen (02) pressures of 3.3 x 10-4 to 2.2 x at?n using sealed capsules containing Kmown quantities of tungsten oxide. Permeation coefficients obtained in this manner had a temperature dependency in the range of 40 to 45 kcal per mole of permeating species. Permeation coefficients for oxygen were higher than those for hydrogen in the temperature range studied. This is probably the result of oxygen solubility being much greater than hydrogen solubility at these temperatures at a gzven pressure. The purpose of this investigation was to determine experimentally the permeabilities of hydrogen and oxygen through polycrystalline tungsten at temperatures ranging from 1300° to 2600°C. Permeation rates of hydrogen through tungsten have been measured at temperatures up to 925°C,but no previous measurements have been reported for the temperature range covered in this investigation. Some diffusion measurements3&apos;&apos; and solubility measurements3 have been made for hydrogen at temperatures below 2200°C. No previous permeability studies of oxygen through tungsten are known to the authors; however, efforts have been made to determine diffusion rates5-&apos; and solubilities PERMEATION THEQRY Permeation has been defined by ortton" as the overall steady-state flow process from the gas phase on one side of a membrane or wall to the gas phase on the other side and includes the steps of adsorption, solution, diffusion, exsolution, and desorption; in a given temperature range, any of these processes may be rate-controlling. For diatomic gases, which dissociate prior to diffusion, the quantity of gas which permeates through a membrane or wall at a given temperature is directly proportional to the surface area of the membrane, the length of time of permeation, and the difference between the square roots of the pressures on each side of the membrane, and it is inversely proportional to the thickness of the membrane when diffusion-controlled, thus: q = total amount of gas permeating a membrane, p = temperature-de pendent permeation coefficient, A = area of membrane exposed, / = time, p i = gas pressure of high-pressure side, p2 = gas pressure of low-pressure side, d = thickness of membrane. When the surface reactions are not rate-controlling steps and the solution of the gas in the metal follows Henry&apos;s law, the permeation coefficient, P, is equal to the product of diffusivity and solubility. The permeation coefficient is also temperature-dependent according to the equation: Po = permeation constant, Q = activation energy, R = gas constant, T = absolute temperature. MATERIALS The tungsten materials used in this investigation were greater than 99.9 pct pure. The interstitial impurities ranged from < 1 to 50 pprn C, 7 to 35 ppm O, less than 15 pprn N, and undetectable quantities of hydrogen. Previous high-temperature studies of are-cast tungsten have shown that thermal treatment similar to that which the hydrogen permeation cells experienced reduces the carbon content from starting levels of 50 to 60 ppm to about 30 ppm. Metallic impurities were in the low (1 to 50) ppm range. The argon gas used in this investigation contained about 8 ppm N. None of the following gases were

Jan 1, 1968

By B. K. Larkin, H. R. Bailey

A model Of heat flow in an underground combustion process is studied. This model includes convection effects and thus is more general than previous studies which considered conduction as the only mechanistn for heat transfer. Both linear (tube run) and radial (field application) geometries are considered. The effects of ignition heaters, vertical losses and finite source width are considered for the linear case. The results are in the form of equations and are presented in graphical form for a number of cases. Convection effects increase frontal temperatures about 25 per cent over those computed for conductive transfer for typical field operating conditions. This increase in temperature is a result of heat being transported toward the front by the injection gas. Even greater temperature increases are realized as the per cent oxygen in the injection gas decreases. It is well known that compression costs are of considerable importance in estimating the economic feasibility of underground combustion. By assuming an ignition temperature for the combustion fuel, predictions of limiting conditions on fuel density and injection rate necessary to sustain the combustion zone are made. For typical field conditions, at least 0.75 lb/cu ft of fuel are needed with air as the injection gas. If the injection gas is 10 per cent oxygen and 90 per cent nitrogen, this figure is 0.69 lb/cu ft. INTRODUCTION The possibility of increasing oil recovery by underground combustion has been considered for many years. Recent field tests indicate that the underground combustion process is technically feasible. The economic feasibility depends to a large extent on the amount of air which must be injected to sustain combustion. Prediction of the success of employing underground combustion in a particular reservoir must be based on existing field tests, laboratory tube runs"&apos; and solutions of mathematical or analog models. Vogel and Krueger5 devised an electrical analog of the heat transfer problem in an underground combus-ion process. They considered the problem of heat conduction from a cylindrical source with increasing radius assuming no vertical losses. Bailey and Larkin and Ramey solved the corresponding problem including vertical losses by considering a mathematical model of the conduction process. Ref. 9, 10 and 11 also present information related to the subject study. The present paper generalizes these results to include both conduction and convection mechanisms for heat flow. A model of the conduction-convection process is described. The partial differential equations governing this model are written and solved for a number of cases of interest. The formulas are evaluated and the results are presented graphically. A CONDUCTION-CONVECTION MODEL Description of the Model A number of models are employed in this paper, each of which approximate a particular physical situation depending on the geometry, i.e., linear or radial flow, the type of vertical heat losses, the nature of the source, etc. The geometry for both the linear and radial case is shown in Fig. 1. A particular linear model is described in this section, and variations from this model are described in later sections of the paper. Consider a homogeneous, semi-infinite porous prism with lateral sides insulated as shown in Fig. 1. The left end, x = 0, is heated for a time t, with a plane heater supplying a constant heat flux and during this time; gas (nitrogen) is passed through the pores of the prism at a constant mass flux. At time t, the heater is turned off and air is injected in place of the nitrogen. This causes combustion to take place, and a uniform source of width 1 is formed which moves at a constant velocity v, to the right. The frontal velocity v, is related to the gas velocity v,, through stoichiometric considerations

By L. F. Mondolfo, B. E. Sundquist

The crystallographic orientation relationships resulting when lead is nucleated from the liquid by Ni, Cu, Ag, and Ge were determined. For each nucleating agent several definite orientatioz relationships were found. These relationships seemed to be controlled by good symmetry relations and low crystallographic disregistry between mating planes. For any given nucleating agent the under colling for nucleation was found fairly constant and independent of the orientation relationship and consequent disregistry. It was also found that, upon re melting and refreezing the Pb, the orientation relationship was changed. These findings prove that crystallographic disregistry is not the controlling factor in heterogeneous nucleation from the liquid. The results of this investigation tend to confirm the theory presented in a preceding paper that heterogeneous nucleation starts with the formation of an adsorbed layer of nucleated metal on the nucleat-ing impurity. Evidence is given that cavities in the nucleating agent act as centers of nucleation. IT has long been known&apos; that solid extraneous particles are active in catalyzing phase transformations that occur in a system, particularly condensation and crystallization. It is well established that these heterogeneities act as catalysts by providing surfaces upon which nuclei of the precipitating phase can form with activation energies smaller than those required for homogeneous nucleation. Numerous investigations have shown that in this process of heterogeneous nucleation: a) the nucleus forms with one, or several, definite crystallographic orientation relationships with the nucleating phase2-4 and b) that there is a small range of undercoolings or super saturations characteristic of the nucleation of a given solid on a given Substrate.5-10 Turnbull and vonnegut11 have developed a theory based on theories developed by Volmer12 and Turn-bull and Fisher1= for heterogeneous nucleation from gases and liquids, that relates the super saturation or undercooling required for nucleation to the dis-registry between the lattices of the nucleus and the nucleating agent. This theory predicts that nucleation should occur with the orientation relationship between the nucleus and nucleating agent that minimizes the disregistry. Further, it predicts that the undercooling or super saturation necessary for nucleation should be a function of the disregistry. Numerous investigations have dealt with the orientation relationships resulting from the condensation of vapors onto crystalline solid substrates2,3 and a few with the nucleation of one phase by a second phase in solidification4,14. Others have dealt with the supersaturation8-10 and undercooling5-7 associated with nucleation in condensation and solidification respectively. However, there is virtually no report that gives both of these factors for the same system. In this investigation a study was made of the undercoolings and orientation relationships resulting when Pb is nucleated from the liquid by Ni, Cu, Ag, and Ge. It was the purpose of this investigation to check the Turnbull-Vonnegut theory, i.e., the importance of crystallographic disregistry between nucleating catalyst and nucleated metal. The results indicate that disregistry is not an important factor in nucleation and that the nucleation process is probably somewhat more complex than current theories suggest. EXPERMENTAL PROCEDURE Small single crystals of nickel, copper, silver, and germanium were prepared from materials of four to five nines purity, and the Pb used was also 99.999+ pet pure. Cu and Ag single crystals were prepared by sealing small chips of Cu or Ag in an evacuated quartz capsule and heating the capsule at 2000°F for 1 hr before cooling. Nickel crystals of 200 diam were also prepared in evacuated quartz capsules, but melting was done by heating the capsules in an oxy-acetylene flame for a few minutes. These spheres were invariably polycrystalline so

Jan 1, 1962

By J. A. Elias, A. J. Heckler

A simplified method is described for the prepauatior~ of comnposite samples for determination of one quadrant of an X-ray pole figure of a sheet material by the Schulz reflection method. Other special conzposite sampling methods were used to investigate specific areas of the pole figures. Plotting nets for these sampling plans were drawn by a computer. Step-scanning techniques were used to obtain detailed information about specific regions of a pole figure. Satisfactory pole figures were obtained for large-grained (0.5 to 1 in. diam) sheet materials. COMPOSITE sampling techniques for preparing one quadrant of an X-ray pole figure have been reported by a number of authors.&apos;-5 All of these methods are similar in that they use a composite sample prepared by stacking and holding together coupons cut from a sheet material. The schulze reflection technique is applicable to the composite sample so that only minor corrections are needed for defocusing and absorption effects. Also, a relatively large area of a sheet is sampled through the use of multiple cross sectional pieces. In general, sampling methods necessary to obtain a composite-type specimen have been formidable enough to discourage their use in routine pole figure determinations. This paper presents a versatile sampling technique which is simpler than those previously described along with an accurate method for obtaining stereographic plotting nets for any orientation of a composite specimen surface. A step-scanning technique is used to obtain more quantitative determinations of specific regions in pole figures, and the composite technique is satisfactorily applied to determine pole figures of very large grained sheet materials. REVIEW OF PREVIOUS TECHNIQUES Mueller and ~nott&apos; first proposed a technique for obtaining one complete quadrant of an X-ray pole figure by using a sheet sample and six different composite samples in which the individual coupons were aligned and held together by two types of jigs. Data from the seven different samples were overlapped to obtain a single quadrant. ~eieran~ and Lopata and ~ula~ obtained a complete quadrant of a pole figure from a single sample prepared by forming a cube from coupons cut from a sheet. These coupons were bonded together using an epoxy cement, and a cut was made at 54.7 deg to the normal, transverse, and rolling directions of the sheet, Fig. I. The normal direction of the cut face projects into one quadrant of a stereographic projection at equal angles to the three principal orthogonal reference directions mentioned above. X-ray reflection data obtained along a spiral path in physical space could then be plotted on a stereographic net offset 54.7 deg from the normal, as shown in Fig. 2. A rotation about an axis representing the surface normal is designated as a, and a rotation about an axis lying in the plane of the surface is 4. From Fig. 2 it is apparent that a tilting angle of no more than 55 deg @ is necessary to obtain the complete quadrant. ~eber~ devised an improved sampling technique by cutting coupons 45 deg to the rolling direction of a sheet, stacking and bonding these with an epoxy cement at an angle of 54.7 deg to a reference plane, and finally grinding and lapping a flat specimen surface parallel to this plane. An important consideration of this technique and that of Lopata and ~ula~ is variation in the diffracting power of the specimen surface due to the bonding medium. While any composite-type sample will have some such variation due to boundaries between coupons, the problem can be minimized by elimination of the bonding medium and by avoiding prolonged etching times which could lead to significant inter lame llar attack of the coupon faces. EXPERIMENTAL TECHNIQUE We were working concurrently though independently on a technique similar to ~eber&apos;s,&apos; but which does not

Jan 1, 1968

By S. B. Twiss, P. R. Basford

The relationship between areas of iron powders, briquettes, and sintered compacts and tensile strength has been determined. It has been found necessary to distinguish between two types of areas which exist in such powders—a macroscopic area due to the shape and size of particles and a microscopic area due to pores and cracks in the surface. Only the macroscopic area, specifically the area due to particle irregularity, contributes to tensile strength; the microscopic area cannot be forced into contact with adjacent particles ond does not participate in bond formation. Of the two methods of area measurement employed in this study—permeability to liquids and gas-phase adsorption—only the former is useful for determining the roughness factor. A measure of this roughness, (area measured by permeability to liquid) -f- (orea of powder with the same size distribution, but made up of spherical particles), is shown to be uniquely related to tensile strength at constant density. The other important factors in determining the strength of sintered-metal compacts are the density and presence or absence of surface oxide. THE manufacture of metal parts by the process of powder metallurgy is an important and rapidly growing industry. Progress has been rapid and continuous, largely because of the excellent research in the field. Nevertheless, the process remains inherently complex and empirical. Several investigators have shown that the properties of the final compact must depend on many variables; namely, shape,&apos; size distribution,"-" nd compositiona of the original particles, the pressure necessary to compress to the desired density, the density of the compact, the time and temperature of sintering, and so on. Through the application of some new techniques to the study of powders and compacts, and the correlation of a number of observations of known variables, the present paper attempts to clarify and simplify the underlying theory of the powder-metallurgy process. Any theory must start with the obvious fact that the strength of a compact, its most useful property, is due to the formation of welded areas between adjacent particles, and attempt to deduce what effect other variables will have on (a) the area and (b) the intrinsic strength of these welds. Such welded areas can be demonstrated by electron micrographs, as in Fig. 1. It was believed that (a) could be most directly studied by means of surface-area measurements on the original powders and on the compacts made from them; the area decrease should be related closely to the welded area. A representative group of eleven iron powders from commercial sources, and made by a variety of processes, was chosen for this study. In addition to the surface-area measurements, correlations were established between the tensile strength and all the known variables which might possibly affect it. The results are quite unexpected. They indicate that the situation is much simpler than the authors had anticipated. The strength of the sintered compact is determined, indeed, by no more than three variables; viz., the irregularity of the original particles, the density of the compact and, in exceptional cases, the amount of surface oxide. All three had been recognized previously as having some effect on the tensile strength, but in the absence of the special techniques and interpretations to be developed here, there could be no suspicion that they were the only relevant variables. Materials and Methods Material—All the iron powders were commercial products obtained from the Amplex Division of Chrysler Corporation. Powders A, B, C, and J were very pure electrolytic iron. Powder D was made from oxidized scrap reduced by heating with an excess of cast iron. Powder E was a high-grade iron ore reduced by hydrogen. Powder I was prepared by atomizing molten cast iron in an air blast, quenching the droplets in cold water, and crushing the coarse powder. Mill scale (oxide) is added and the mixture heated to reduce the high carbon content. The other powders were all prepared by reduction of iron oxides, such as mill scale. They

Jan 1, 1959

By R. A. Salathiel, A. D. Kaiser, P. H. Monaghan, B. E. Morgan

The productivities of many hydrocarbon-bearing for-rnntions appear to be reduced during drilling, completing and repairing operations. The reason for these othcarwise unexplainable low productivities may be a drastic reduction of formation permeability immediately surrounding the borehole. A possible cause of the reduced permeability is swelling and dispersion of clays present in porous media when contacted by fresh water or mud filtrates. Hence, the invasion of fresh water or mud filtrate into hydrocarbon-bearing formations that contain clays may cause low productivities as a result of formation damage. Present laboratory investigations have yielded results which supplement existing literature on formation damage. An expanded-type clay, montmorillonite, way found in hydrocarbon-bearing formations not previously analyzed. When sand columns and formation cores containing montmorillonite were contacted by fresh water, their oil permeabilities were reduced. This reduction in oil permeability way restored partially but not completely by a repair procedure, i.e., flooding with kerosene containing organic agents or flooding with water containing electrolytes. Hence, where montmorillonite is present in formations, prevention of formation danzage was indicated to be the only complete solution to the problem. To prevernt formation damage, results suggested use of an approximately 1 per cent solution of calcium chloride or stronger solutions of sodium or potassium chloride. In conventional rotary drilling operations the wall of the hole is exposed to drilling mud for days, weeks, and in some instances for as long as several months. During this time, drilling mud filtrate seeps slowly into formations surrounding the hole. The permeability and stability of many formations, especially those containing clayey materials, are impaired by the mud filtrate. Often interaction between the mud filtrate and the formation causes drilling and production difficulties. Serious reduction in productivity of oil and gas formations during drilling, completing and repairing wells has been noted often in recent years. Cases are known of development wells which produced only small volumes of fluid upon completion. However, after a period had elapsed, they began to produce oil or gas in commercial quantities. In other cases, results of drill-stem tests taken during the drilling of deep wells have indicated good production should be obtained from shallow formations. Later difficulty has been experienced in obtaining production from these shallow formations which had remained in contact with drilling muds for an extended time. In yet other cases wells have failed to attain the productivities expected from previous performance after the use of drilling mud as a circulating fluid during workover operations. It is evident from the field behavior cited that the productivities of certain oil- and gas-bearing formations have been damaged by exposure to drilling muds. This reduction in well productivity, called "formation damage", causes serious consequences. In development wells, expensive remedial operations are incurred. In wildcat wells, good formations may appear to be marginal or even non-productive. The importance of formation damage has been recognized by a number of investigators1-s who have considered the effects of fresh water, saline solutions and aqueous mud filtrates on the permeabilities of formations. A general conclusion from such studies is that interaction between water and formation clays reduces permeability of reservoir rock and that the permeability decreases as salinity of the water decreases. Data in these references, however, concern the permeability change with only a single fluid present. A more pertinent and direct consideration in the production of oil and gas from wells is the permeability change when two fluids, oil and water, are present. Recognizing this, Nowak and Kreuger2 and Bertness1" considered several ways in which mud filtrates and saline solutions caused reductions in the oil permeability of formation cores. Investigations discussed here were designed to supplement information in the literature on changes in oil

By S. W. Kennedy, M. Cohen, L. D. Calvert

A high-temperature X-ray diffraction method has been used to study the composition and the kinetics of formation of oxide scales at 800 °C on iron and pure iron-nickel alloys containing 25.6, 75, and 84 pct Ni. This technique has been combined with chemical analysis, and metallographic examination, and determination of weight-gain time curves. The 75 and 84 pct Ni alloys form a three-layer scale consisting of porous NiO next to the metal, a spinel layer, and a -Fe203 on the outside. The 25 pct Ni alloy produces a scale of spinel and Fe,O,, in which, however, traces of FeO and NiO are observed near to the metal. On all the nickel alloys the Fe20, is orieqted with the (107) plane parallel to the surfaces. The exposed surface of the Fe20, is in the form of needles whose axis is perpendicular to the specimen surface. Although the alloys show nonuniform oxidation rates as determined from weight-gain measurements, the X-ray data indicate that the total scale and individml scale layers grow uniformly and parabolically. Deep subscale formation is observed in the 25 pct Ni alloy only. This appeared to be associated with cracking of the scale and penetration of the oxygen along the grain boundaries. ALTHOUGH film formation has been investigated by high-temperature electron-diffraction techniques, for example by Gulbransenl and Hickman,&apos; there have apparently been no investigations of scaling by methods permitting study of the scale during formation at the reaction temperature. Methods involving quenching of scales are based on the working assumption that no significant changes take place on cooling. In general, however, compounds may disproportionate, and the different thermal expansions of constituents may cause disruption of the scale on cooling. In particular, some scales cannot be quenched without spalling. These difficulties are avoided by X-ray diffraction examination at the temperature of formation. High-temperature diffraction procedures also provide a method of determining the kinetics of formation of each phase separately in a multicom-ponent scale. The scaling of binary iron-nickel alloys Containing up to 30 pct Ni at a temperature of 800°C has been studied by Benard and Moreau using cooled specimen~,~ whilst Foley, Druck, and Fryxel14 made an electron-diffraction study of cooled oxide films formed on an iron 42 pci Ni alloy. In the present work the scaling of three iron-nickel alloys containing 25.6, 75, and 84 pct by weight of nickel, at 800°C in oxygen at atmospheric pressure was investigated by X-ray diffraction techniques using a Norelco Geiger-counter diffrac-tometer. The oxidation of iron was investigated for comparison. In addition normal metallographic examinations and chemical and X-ray analyses were made, and weight-gain time curves obtained. EXPERIMENTAL Materials Used—The analyses of the alloys were as follows: Percent by Weight Nickel 25.6 pct 75.4 pct 83.2 pct Aluminum 0.004 None found 0.002 Cobalt — 0.05 0.05 Chromium — — — Silicon — 0.01 None found Carbon All less than 0.05 pct The chemical analysis of the iron was: Al— 0.002 i 0.001 pct, C—0.007 pct, Cr less than 0.001 pct, Cu—0.002 ± 0.001 pct, Mn—0.003 ± 0.001 pct, N—0.0002 pct, 0-0.013 pct, P—less than 0.0002 pct, Pb—not detected, S—0.0017 pct, Si—0.0095 pct, Sn—none detected. This iron was the same as that used to make the alloys and was obtained from the same source-Vacuum Metals Corp. One specimen of pure iron from The British Iron and Steel Research Association was used for preliminary investigation. Specimens were machined to shape from cast rod, polished (the final polish being with 600 Sic paper), degreased in trichlorethylene, washed, and etched. The etching and neutralizing procedure adopted by

Jan 1, 1960

By S. K. Mitra

A refinement of the Seeger model for intersection process is investigated which is in better agreement with experimental observations than the original. It is shown that, in single crystals, the strain hardening in Stage II is mainly due to the short-mnge interactions when intersection is the rate-controlling process. It is also demonstrated that the creep curves, as predicted by this theory, are in good agreement with the experimental observations. MOTT: Cottrell? and Seeger have developed an approximate theory for plastic deformation of single crystals over the range of variables where the strain rate is controlled by the rate of intersection of dislocations. Although it is now generally agreed that the low temperature deformation of many pure metals is controlled by the intersection mechanism, various dictates of the over-simplified Seeger model are not in good agreement with all the experimental facts. It is the purpose of this paper to reveal that by appropriate extensions of the Seeger model, particularly those suggested by Basinski: a much more reliable theory results. The refined model to be presented here will be shown to account, in a satisfactory way, for the effect of stress, temperature, and strain on the creep rate under constant stress and for the effect of temperature and strain on the flow stress in constant strain-rate tests. EXPERIMENTAL METHOD To Check the theoretical deductions, both creep and tension tests were conducted on single crystals of high-purity Al (99.994 pct Al) so oriented that both the active slip plane and the Burger&apos;s vector of the operative dislocations on that plane made angles of about 45 deg to the tension axis. Single crystals of aluminum (5/8 in. by 1/10 in. by 8 in.) were grown in a graphite mold under an inert atmosphere using the Bridgman method. The chemical composition of the aluminum is given in Table I. A common seed was used for all crystals and their orientation is shown in Fig 3. The extensometry consisted of two differential transformers with matched outputs mounted so as to measure the extension in a 2 in. gage length. The amplified difference in output of the two transformers was recorded by a potentiometer. The amplification was calibrated before each run so that one chart division of the recording potentiometer indicated a 105 shear strain on the specimen. Stresses were measured to the nearest 1 x l04 dynes per sq cm. ACTIVATION VOLUME The concept of Basinski that the activation volume is not constant but is a function of the force that aids thermal fluctuation in effecting the cutting of dislocations will be adopted in this section. The force acting due to an applied shear stress on the dislocation being intersected is where L is the mean spacing between the forest dislocations, is the Burger&apos;s vector and T is the back stress. A detailed discussion about the origin of back stress will be taken up later in this report. As shown by Basinski, the activation energy, U, that must be supplied by a thermal fluctuation in order to effect intersection, is equal to where x is the distance through which the dislocation must be translated for complete intersection, and Fm is the maximum force encountered in intersection. When the applied stress is decreased abrupt ly F also decreases and the activation energy increases correspondingly as documented in Eqs. [ 1 ] and [2]. The Seeger equation for the strain rate when the deformation is controlled by rate of intersection of where the shear strain rate (per sec) N = the number of points per unit vol at which intersection can take place

Jan 1, 1962

By B. C. Allen

Grain-boundary gvoocing was studied irz chronziu?n. molybdenum, tungsten, and the solid-solution alloys, Cr-35Re. Mo-33Re, and W-25Re at 0.6 to 0.9 of the absolute liquidus temperature under an inevt atmosphere , foveign nzetal zlapor, and liquid metal. The controlling mechanism of matter transport was deduced frolr groove size and shape. kinetics of growth, and cotnparisoz with theoretical relatiotzships derived by Mullins. Grooves in chowzizon formed prittzarily by volume diffusion tkrongk kelium or argon at 1 atm pressure and by e1)apovation-condensatiotz in a static vacuum. Groozles in the other nzetals and alloys forrned priniarily by sirface diffusion, the coefficients of which were calculated. Carbon was found to decrease the acti7:ation energy for surface diffusion on molybdenun. Sitrface diffusizities weve sinzilav for iWo-0.0ZC and Mo-33Re. The presence of about 1 -?nm pressure of silver or tin vapor did not affect the neckanis)n of grooz;e formation. In liquid titz or silz:er, pain bolindary gvooves formed by zolume diffusion in the liquid. BASED on theories of ullins," the mechanisms of grain-boundary grooving have been determined for low-melting metals such as copper in an inert atmospheres or in liquid lead.4 The purpose of this investigation was to study grain-boundary grooving in the refractory Group VI-A metals, chromium, molybdenum, and tungsten, and the bcc solid-solution alloys, r-35e, 0-33e,= and -25e,&apos; at 0.6 to 0.9 of included to see whether Mullins&apos; theories were applicable to them as well. EXPERIMENTAL WORK The materials chromium, molybdenum, tungsten, Cr-35Re, Mo-33Re, and W-25Re were in the form of 0.050-cm-thick sheet assaying 99.98 pct or better. The nominal carbon level was generally 30 ppm. The oxygen + nitrogen + hydrogen content was -50 ppm. Mo-33Re and W-25Re were prepared by powder-metallurgy methods and supplied by Chase Brass and Copper Co. The remaining materials were arc-cast. Chromium and Cr-35Re were prepared at Battelle by arc melting, extruding, swaging, and rolling. Mo-0.003C was supplied by Climax Molybdenum Co., and Mo-0.02C and tungsten by Universal Cyclops Corp. As a source of liquid metals, tin and silver granules assaying 99.98 pct were used. Spectrographic analyses indicated the presence of -100 ppm each of iron and silicon. Vacuum melting reduced the combined gas content to c5 ppm (2.60,, 0.9N2, 0.4H2 in tin and l.602, 0.7N2, and c0.04H2 in silver). Specimens were prepared for grain-boundary grooving. Coupons 0.5 by 1.5 cm with a small hole in one end, or substrates 1.5 by 1.5 cm, were cut from sheet. The specimens were annealed in containers of the same material to provide a vapor-solid equilibrium as well as to protect them from gaseous impurities. Outgassing was done at 2 x 10"5 mm for 15 to 30 min at 1150°C for chromium and Cr-35Re, 1750°C for molybdenum and Mo-33Re, and 2600°C for tungsten and W-25Re. Then recrystallization to a stable grain size of about 0.5 mm was accomplished by annealing at least 1 hr at 1600°C for chromium, 1800°C for Cr-35Re, 2350°C for molybdenum, and 2300°C for Mo-33Re in a rhenium-element resistance furnace under 1 atm of static argon or helium. The atmosphere was gettered by tantalum radiation shielding. Tungsten and

Jan 1, 1967

By Franklin J. Hill, Theodore D. Tiemann

Sized fractions of Wisconsin Gogebic taconite were reduced with hydrogen over the temperature range from 600° to 1000°C. In general, the degree and rate of reduction increase with temperature. Particle size has no observable effect except in the smaller fractions at 900°C and above, where reduction is impeded, possibly due to the siliceous nature of the ore. Gaseous diffusion appears to be significant as a rate controlling factor at certain stages. THE depletion of high grade iron ore reserves in the United States has established the need to utilize all available iron ore deposits, both in long range planning and from the viewpoint of national emergency. This has led to extensive research and development in this field. The beneficiation of Wisconsin Gogebic taconite ore has been previously studied by investigators at the University of Wiscconsin, 1 the United States Bureau of Mines,, Battelle Memorial Institute, 3 and others. Methods investigated have included concentration by flotation processes, magnetic and gravity separation, magnetic roasting and various combinations of them. The foregoing studies have been concerned with the production of an enriched ore suitable for blast furnace use. If the ore could first be reduced to metallic iron and then beneficiated, the product could be used directly in the open hearth or electric steel-making furnace. The by-passing of the blast furnace should enhance the economic feasibility of the beneficiating process. The work reported here,4 was undertaken to establish data on the hydrogen reduction of Wisconsin taconite that would eventually lead to the development of an economic direct reduction process for this and perhaps other low grade siliceous ores. The volume of work on direct reduction can be judged by the fact that 240 direct reduction processes were patented in the United States alone up to 1951, 5 and numerous additional processes have since been developed. Some of the factors contributing to direct reduction development are: 1) The increasing capital cost of the blast furnace and its accessory equipment. 2) The decreasing availability of high grade domestic ore. 3) The high cost of steel scrap for use in the open hearth and electric furnaces. In general, direct reduction processes can be divided into two types; those using a solid reductant (coal, peat, lignite) usually carried out in a kiln, and those using a gaseous reductant (H2, CO) in a shaft furnace or a fluidized bed retort. As there is no low cost coal readily available in northern Wisconsin but natural gas could be quite easily obtained, it is believed a gaseous reductant process would offer the greater feasibility for use on Wisconsin taconite. It is hoped that this preliminary work will beof interest to other investigators in this increasingly important field. TACONITE ORE The ore used in the investigation was obtained originally from the U. S. Bureau of Mines, and consisted of a representative composite made up from trench samples of the Norrie, Pabst, Plymouth, Pence, and Yale members of the Wisconsin Gogebic range iron formation. Chemically, the ore contains approximately 52 pct SiO, and 30 pct Fe. X-ray diffraction and other studies indicate the principal minerals to be quartz (SiO2), hematite (Fe2O3), and goethite (Fe2O3. H2O). Minor amounts of iron containing silicates, siderite (FecO3), and magnetite (FeO-Fe2O3) are present. The iron minerals and quartz are so finely disseminated that the ore requires grinding to less than 200 mesh (74 µ) for essential liberation.l,2 The iron content of each of the several size fractions studied is shown in Table I. EXPERIMENTAL METHOD The method used throughout the investigation was based on that developed by the U. S. Bureau of Mines in Minneaopolis6,7 in which the course of reduction is followed by the loss in weight of the ore sample. More specifically, a 100-g sample of the size frac-

Jan 1, 1962

By C. E. Taylor, L. V. Fegan

With on-stream electrical-resistance measurement as a basis, Bethlehem Steel developed a system for the completely automatic control of moisture in the feed to pelletizing. This system was later successfully adapted to the sintering process, with automatic control of moisture serving to maintain the air permeability required for effective burnthrough. Control of moisture content is an important factor in the agglomeration processes by which iron ores are converted into either pellets or sinter for use in blast furnace burdens. In both pelletizing and sintering the iron ore feed must be mixed with the proper amount of water so that capillary attraction and surface tension forces can be utilized to cause the ore particles to coalesce and form larger agglomerates. The success or failure of the entire pelletizing or sintering process depends on maintaining the proper moisture. Therefore, continuous automatic control of moisture is one of the conditions for the automation and optimum use of both pelletizing and sintering processes. In pelletizing, variation in moisture can cause ball size to change and is a common cause of cycling which results in a fluctuating feed to induration. Excessive moisture can cause lumps to form at the cutter bar and contributes to the formation of buildup on the green pellet screens. Green pellets with excess moisture deform and reduce bed permeability. In sintering, accurate control of moisture is also important because moisture must be within the limits that give the bed the required permeability for good burnthrough. In response to these problems, a moisture meter, based on the principle of electrical resistance measurement, was developed. This moisture meter has been a key factor in the development of systems for providing uniform feed of concentrates in most of Bethlehem&apos;s pelletizing and sintering plants. The automatic moisture control system for pelletizing was successfully plant-tested and resulted in the following: (1) Control of moisture in the green pellets to +0.2%. (2) Up to 50% reduction of bentonite consumption. (3) Control of unscreened green pellets so that 85% of the furnace product at Cornwall was within the size range of -5/8 +3/8 in. (4) Improved quality of product with a tumble test of 94 and a "Q" index of 90 as the result of feeding a consistently uniform feed to a shaft furnace. In sintering, where sinter-mix temperature change and variable feed could cause errors in moisture measurement, the system was designed to maintain the correct moisture under virtually all plant operating conditions. It was successfully plant-tested and is now in use in most of Bethlehem&apos;s sintering plants. The system achieves: (1) Control of moisture within the desired limits for optimum production. (2) Continuous measurement and control of moisture even with intermittent feeding of mix, so that attention by the operator is seldom required. The two automatic control systems provide smoother startup, minimize upsets and contribute to the consistent control of process variables in pelletizing and sintering. MOISTURE-CONTROL SYSTEM FOR PELLETIZING Fig. 1 shows the general arrangement of the system for automatic control of moisture in pelletizing.1 In this system a bin level controller, using a single probe which regulates filter speed, maintains a uniform low concentrate level in the bin.&apos; The moisture meter, comprised of an analyzer and control components, continuously measures the moisture in the bed and adds water to adjust to the desired level. The meter is placed in an open-loop (feed-forward) control, i.e., water addition occurs downstream from the probes. Filter vacuum must be set so as to produce a filtercake moisture which is below the optimum for pelletizing. Bentonite is added after the

Jan 1, 1969

By R. H. Oliver

The purposes, types, preparation, and testing of flocculants are discussed. A flocculation compendium is included, indicating choice of flocculant for a given set of conditions. An economic evaluation of the process is presented. Solid-liquid separation is a major expense in most mineral processing flowsheets today. Proper use of flocculation can often lower the overall cost of a solid-liquid separation by reducing the size of sedimentation or filtration equipment. PURPOSE OF FLOCCULATION When is use of a flocculant justified in terms of overall process economy? 1) when it results in process improvement, such as producing a clear liquor for electrolysis, precipitation, ion exchange, or solvent extraction; 2) when it results in satisfying requirements of pollution abatement ordinances; 3) when it results in increased recovery of values that would otherwise be lost; or 4) when it results in considerable savings in capital expenditure due to use of smaller equipment. When can the use of a flocculant adversely effect overall process economy? 1) when it results in increased filter cake moisture, 2) when it results in decreased filtration rates, 3) when it results in considerable bulking of sedimentation underflow, 4) when it contaminates either the supernatant or sludge, or 5) when the cost of using the flocculant is greater than the savings due to its use. First step in consideration of flocculants for a given application is establishment of desired goals in terms of increased clarity of effluent, increased recovery of solids, or decreased size of equipment. The most economical solution to a solid-liquid separation problem is that combination of equipment and flocculant costs which meets the established goals at the lowest total annual expenditure. This economic decision can be made only after technical data has been obtained as outlined in next four sections. TYPES OF FLOCCULATION Flocculation is a process wherein individual particles are united into more or less tightly bound agglomerates or flocs, thereby increasing effective particle size of solids suspended in a liquid. Degree of flocculation of a suspension of finely divided solids in a liquid is controlled by a combination of probability of collision between particles and probability of adhesion after the collision has occurred.&apos; Probability of collision can be increased commercially through use of a paddle-type flocculator, combination flocculator, and clarifier or flocculating-type feedwell. Probability of adhesion usually can be increased by addition of a reagent known as a flocculant. Reagents act as flocculants through one or a combination of three possible mechanisms. The first is electrolytic neutralization of inter molecular repulsive force due to Zeta potential. This neutralization enables Van der Waal&apos;s cohesive force to hold the particles together after they collide.&apos; The second is the precipitation, within a definite pH range, of voluminous metallic hydroxide flocs which entrap fine particles. This process is known as coagulation.14 Third is the bridging of two or more particles by either natural or synthetic long-chain, high-molecular-weight organic polymers. This bridging is accomplished by adsorption of two particles at different sites on the same molecule or by bonding of two molecules, each adsorbed to a different particle. Considerable effort has been expended in explaining the action of these polyelec-trolytes and detailed accounts are available in the literature. CHOICE OF FLOCCULANTS It is impossible, at the present time, to specify the optimum type or amount of flocculant for a given application from a knowledge of the material to be treated. The standard procedure is to choose reagents or combination of reagents most likely to be effective on the slurry; then test them.&apos; The accompanying Flocculation Compendium (Table I) contains details of all currently available reagents sold as flocculants and it should be used when selecting the group of reagents for tests. This selection can be based on information listed in columns 4 and 5. Column 4 presents industries in which each floc-

Jan 1, 1961

By F. P. Bullen

Empirical relationships between fracture stress, orientation angle, and diameter of crystal have been determined at 77°K. Orientation ranges of markedly different behavior were found—a law of constant normal stress&apos; of value a (diameter)-1/2 for the fracture of ductile crystals, and a condition of shear stress (or strain) for more brittle crystals. The observations are not consistent with current theories. An interpretation is advanced which is also applicable to observations on the effect of prestrain at room temperature on the subsequent fracture stress at 77°K and to the effect of cyclic stressing on the cleavage strength.&apos;&apos; The law of constunt normal stress&apos; and the brittle ductile transition are also explained. The interpretation is more consistent with the initiation of cracks by intersecting dislocations than with theories based on stress -concentration by dislocation arrays. ZINC single crystals are particularly suited to the study of cleavage because fracture occurs on the basal plane over a wide range of crystal orientations. Analysis of the conditions of stress and strain at fracture in crystals of different orientations should indicate which parameters control the cleavage process. Unfortunately, controversy has arisen over the correct empirical relationship between tensile fracture stress and orientation. Schmid&apos;s observations1,2 favored a &apos;law of constant normal stress&apos;, as observed in other materials.2 For zinc, however, the observed values are far below the theoretical strength and cannot represent the true limit of cohesion between neighboring atomic planes. Hence, the interpretation of such a &apos;law&apos; is not straightforward. Deruyttere and Greenough3,4 found a complex variation between tensile fracture stress and orientation; this variation did not agree with a &apos;law of constant normal stress&apos;. Two theories have been advanced to account for their observations: a) the propagation of cracks from low-angle boundaries,5 and b) the release of energy from piled-up dislocations during crack-propagation.4 The present work resolves the apparent discrepancy between the observations and shows that neither of the above theories are applicable to the tensile fracture of zinc single crystals. A phenomenological explanation, along the lines suggested by Gilman,&apos; is advanced and successfully applied to previously unexplained effects. EXPERIMENTAL DETAILS &apos;Crown Special&apos; redistilled zinc was used, except for one comparison series op tests using &apos;Tadanac&apos; electrolytic zinc. Crystals of 1 mm diam, subsequently called &apos;1 mm crystals&apos;, were grown from the melt in vacuo in precision-bore Pyrex tubes internally coated with graphite. Several specimens 1 in. long were cut from each crystal and chemically polished. Jigs were used to minimize handling strains, and crystals were mounted in the Polanyi machine the day prior to testing to allow recovery from any such strains. One-mm crystals were chemically polished for long periods to obtain 0.1 mm (approx) crystals. One-mm crystals were cemented into miniature gimbals by &apos;Araldite&apos; casting resin. The Appendix gives the reasons for using gimbals and the results obtained by other methods. More complete details of all techniques are given elsewhere.7 The symbols and terminology used are as follows: X = orientation angle (angle between tensile axis and line of greatest slope in the basal plane). T = tensile stress (on true cross-section) S,N = shear and normal stress (components of T with respect to the basal plane) ? = shear strain D = crystal diameter. The subscript &apos;f&apos; will be used to denote values at fracture. PART I-ANNEALED CRYSTALS EXPERIMENTAL OBSERVATIONS One-mm crystals were used to establish the variation of fracture stress at 77°K with orientation at fracture (Xf), Fig. 1. For 18 deg = Xf = 55 deg, a &apos;law of constant normal stress&apos; was observed. For Xf > 55 deg, the fracture condition approximated to a constant shear stress. At Xf< 18 deg, twinning occurred before fracture so that the results were not typical of homogeneous single crystals,4,8— such specimens will not be considered herein. The dependences of fracture stress upon Xf were of similar type for 6 mm,* 1 mm, and 0.1 mm crystals,

Jan 1, 1963