Search Documents

By M. V. Lowry

This paper outlines the economic considerations that led to the recent installation of a thickener at St. Joseph LeadCo.'s Balmat, N.Y. mill. To incorporate storage of concentrates, they decided upon a single, unusually deep tank to be used for both storage and thickening. The abnormally high rake lift required was achieved by the novel feature of having the entire drive platform raise and lower. Initial operating problems are described along with the satisfactory solutions. Total costs for concentrate handling before and after installation of the storage thickeners are compared. In Northern New York State, the St. Joseph Lead Co. conducts a 2100 tpd zinc mining and milling operation at its Balmat Plant. Conventional crushing, grinding, and flotation is used to produce a zinc concentrate. For 32 years, from 1930 through 1962, the plant operated with the concentrates going directly from flotation to the filtering, drying, and loading facilities. All of the concentrate handling equipment, therefore, had to operate 24 hrs per day. It also had to accommodate wide fluctuations in tonnage, due to variations in the grade of ore. Many problems were thereby encountered in filtering and drying, but it was never concluded that the cost could be justified for installing a conventional, large diameter thickener. Finally, in 1963, they installed an unconventional thickener that is unusual in several respects. The tank depth is 16 ft instead of the normal 8 ft. The rakes are raised and lowered by having the main drive gear located on a movable platform. Automatic controls are programmed to raise the drive platform and rakes during one shift of storage. During the next two shifts of withdrawal, the controls are programmed to lower the drive platform and rakes. After three years of operating this unique storage-thickener, the conclusion is that a correct choice was made from several alternative schemes for storing concentrates. The various considerations involved in the final selection will here be analyzed, and the design features and installation details will be de- scribed. Operating problems and modifications made to the equipment will next be considered, and finally the effects upon filtering, drying, and loading will be reported. SELECTION CONSIDERATIONS Even without a thickener, concentrate handling had become reasonably efficient at the Balmat Mill by the year 1962. A tonnage that varied between 6 and 25 tph was being handled fairly satisfactorily. The filter cake moisture of 8%% seemed quite respectable, except that two large filters were usually in service. Three filters often had to be operated in order to prevent excessive filter overflow with consequent loss of values. This situation occurred when zinc concentrates from flotation exceeded 20 tph and when filter cloth blinding developed. Over the years, numerous small improvements had been effected, such as: selection of a filter cloth with better flow characteristics; addition of flocculant to the filter feed; and, in 1953, the smallest of three drum filters was replaced by a five disc, 8' 10" diam filter with a bottom agitator and snap blow. As another example of fairly efficient operation, the oil-fired dryer was doing a seemingly satisfactory job of further reducing the moisture content to an average of 3%. However, there were often considerable dust losses when the tonnage suddenly dropped off to 6 tph. At high tonnage rates, the resulting high moistures of 4% and 5% caused difficulties due to concentrates sticking and freezing in chutes leading to the box car loaders. (Drying of concentrates is justified because of the high freight rate for the long shipping distance to the company owned smelter at Josephtown, Pa. near Pittsburgh.) It was long realized that installation of a thickener would permit the subsequent steps of concentrate handling to proceed more smoothly and would alleviate the problems existing in the filtering, drying, and loading operations. It was also realized that even a slightly lower filter cake moisture could mean considerable savings in fuel oil. However, all these factors were never quite sufficient to warrant the expense of a thickener until three more considerations were added to the picture. First, the advent of flocculants meant that a thickener of relatively small area could now be considered. Secondly, a complete renovation of the zinc flotation circuit was made between 1957 and 1961. The

Jan 1, 1967

By R. C. Ku, A. J. McEvily, T. L. Johnston

The microplastic response of a series ofas-quenched Fe-Ni-C martensites has been measured at 77°K. At strains less than JO'3 the flow stress is governed primarily by the transformation-induced dislocation structure of the martensite. Only at strains in excess of 10-3 is the influence of carbon manifested in the flow stress. At these macroscopic strains, typically 10-2, the solid-solution hardening is proportional to (wt pct C)1/3, and, in an alloy containing 0.39 wt pct C, amounts to 50 pct of the flow stress. THE technological significance of high-strength ferrous martensite has stimulated many investigations of its structure and properties. Although our knowledge of the characteristics of martensite has increased immensely, especially with the advent of high-resolution techniques, an understanding of the basic strengthening mechanism still remains elusive. The purpose of the present paper is to consider certain aspects of micro-plastic behavior of Fe-Ni-C martensite which we feel can help to resolve this important problem. Such alloys are particularly suitable for experimental investigation because their compositions can be adjusted to reduce the M, to a temperature low enough essentially to eliminate the diffusion of carbon in the freshly formed martensite.1 The mechanical properties in this condition are of interest inasmuch as they reflect a state that is free of the important but complicating influence of precipitation processes. In this virgin martensite the carbon is distributed as it was inherited from the parent austenite; i.e., it is present interstitially, and gives rise to tetragonality through strain-induced ordering.' In order to determine the source of strength of such alloys, Winchell and Cohen1 investigated the low-temperature macroscopic stress-strain behavior of a series of virgin martensites of increasing carbon content but of common M, temperature (-35°C). They found that the flow stress increased rapidly with carbon content up to 0.4 wt pct; beyond this point the flow stress increased at a much slower rate. It was concluded that martensite is inherently strong. To account quantitatively for the strength of virgin or as- quenched martensite in terms of the role of carbon, Winchell and cohen3 suggested that the carbon atoms, trapped in their original positions by the diffusionless martensite transformation, interfere with dislocation motion according to a model akin to that of Mott and Nabarro. 4 In this treatment, individual carbon atoms are considered to constitute centers of elastic strain and thereby generate an average stress resisting the motion of dislocations throughout the lattice. The additional stress necessary to move dislocations, over and above that necessary for motion in a carbon-free martensite, is given by where L is an effective length of dislocation capable of motion. L was assumed to be limited to the spacing between the twins that are an essential structural element of Fe-Ni-C martensites. They assumtd the spacing to be invariant and of the order of 100A. However, recent work5 has shown that L is variable and can be in excess of 1000Å, so that the assignment of an appropriate value of L is not straightforward. In contrast to the above conclusion that there is an intrinsically high resistance to plastic flow, it has been suggested by Polakowski6 that freshly quenched martensite is in fact "soft" in the sense that dislocations are initially free to move upon application of stress. The high indentation hardness and macroscopic yield stress of ferrous martensites are then a consequence of rapid strain hardening that depends upon carbon in solution. Consistent with this point of view are the results of Beau lieu and Dubé who measured the rate of recovery of internal friction as a function of aging (tempering) temperature in a freshly quenched steel containing 0.90 wt pct C, 0.37 wt pct Mn, 0.1 wt pct Cr, and 0.07 wt pct Ni. The kinetics were clearly consistent with the idea that many dislocations are unpinned in the as-quenched state and that during aging they become progressively pinned by carbon at a rate controlled by carbon diffusion in the body-centered martensite lattice. In order to provide a basis upon which to distinguish between the "hard" and "soft" interpretations indicated above, we have made studies of the initial stages of plastic deformation in Fe-Ni-C martensites similar to those'used by Winchell and Cohen. It will be shown that the results support the contention that dislocation segments in as-quenched material are indeed

Jan 1, 1967

By W. A. Oates, J. A. Lambert, P. T. GaIIagher

Monte Carlo methods have been used to compute the arrangements of interstitial atoms dissolved in tetrahedral sites in bcc lattices. It is assumed that the presence of an interstitial atom "blocks " a certain number of neighboring sites and prevents their occupancy. Sites "blocked" by more than one filled site are allowed for. The computed values of. the mean occupation number (defined as the ratio of the total number of sites blocked to the number of solute atoms are used to calculate the configurational entropies of the solutions. These entropies are compared with those resulting from previous theoretical studies of this problem and also with available experin~ental data for the p Zr-H, Nb-H, V-H, and Ta-H systems. Evidence is also given that the "blocking" explanation of low limiting compositions in these systems, rather than this being due to initial limitations on the number of sites available, is probably correct. THE ideal partial configurational entropy of mixing of an interstitial solute in a metal is given by: where p is the number of interstitial sites per metal atom and Xi is the atomic fraction of the interstitial. For the bcc lattice. which we shall be concerned with in this paper, the interstitial positions are shown in Fig. 1. It can be seen that for the tetrahedral sites, p=6. whereas for the octahedral sites, p = 3. Different emphasis has been placed on the relative importance of energy and entropy effects in determining deviations from ideality in interstitial solid solutions. In some cases the same system, e.g., Fe-C, has been described by the contradictory regular and athermal solution models indicating that the enthalpy and entropy functions, derived from equilibrium data, are frequently not accu.rate enough to differentiate between these treatments. However, for certain metal-hydrogen solutions the equilibrium data is available over sufficiently wide ranges of temperature and composition to permit a reasonably accurate determination of the compositional variation of the heats and entropies. Hoch&apos; has attempted to interpret the results of interstitial solid solutions in terms of a regular solution model. In the case of the Ta-H system where 13 = 6, this model entails fitting the experimental relative partial entropies of solution, asH, to the equation: where ASgs is the relative partial excess entropy of solution of hydrogen. Hoch found that the results of Mallett and Koeh1 could be fitted to this equation with an approximately constant value of AF up to XH = 0.25. However, it is apparent from the solubility isotherms in this system which become asymptotic to the composition TaH that, since (Xh /6 - ~Xh ) becomes infinite only at TaH6, it is necessary that AS<&apos; tends to infinity at TaH. In other words, the low saturation composition of TaH, instead of the anticipated TaH,, eliminates the possibility of applying regular solution theory to such systems. Rather large negative excess configurational entropies must exist at higher hydrogen concentrations in order to explain the lower saturation values. To account for these low limiting compositions and excess entropies two distinctly different approaches have been followed. Rees and many others1-l2 have assumed that not all interstitial sites are crystallographically equivalent with respect to the interstitial addition; that is, in Eq. [I] p is less than the value anticipated from geometrical considerations. To describe, say, a bcc metal-hydrogen system with a limiting composition of MH by this approach one would consider that p = 1 in the first instance instead of p = 6.&apos;j3 In some cases, nonintegral values of B have been taken in order to improve the fit with the experimental data over limited ranges of composition. The other approach which has been used to explain the low saturation compositions is to assume that, although all sites are available for occupancy, strong repulsive interactions exist between the neighboring interstitial atoms, and hence occupancy of any site excludes or blocks a certain number of neighboring sites from being occupied. Earliest treatments of this concept considered the exclusion of an integral number, of nearest-neighbor sites from being occupied at all concentrations. In this case, the partial configurational entropy is given by: These early treatments failed to allow for the overlap of the blocked sites which will arise at all but the very lowest concentrations. More recently attempts have been made to calculate the effect of this decrease in the number of blocked sites on the configurational entropy. Using the quasichemical treatment of interstitial solid solutions as given by Lacher and assuming that an infinite repulsive interaction energy existed between the solute atoms. atom obtained an approximate configurational entropy applicable to the blocking with overlap case:

Jan 1, 1970

By Axel Hultgren

In ingots of silicon-killed carbon steel-made without addition of aluminum, transparent spherical or nearly spherical inclusions, up to about 0.15-mm diameter, are generally present. They may be glassy or crystallized, wholly or partially In steels of high carbon contents they consist of silica,4,12 in steels of lower carbon contents and, in consequence, higher oxygen contents, of iron-manganese-silicate with higher iron and manganese contents the lower the carbon content. Small silicate inclusions, about 0.01 mm or smaller, may occur, just as sulphide inclusions do, in portions that have been the last or nearly the last to freeze,l0,12,17 this location being verified by primary etching.10 Hence, it may be concluded that they have separated from liquid steel that has become enriched in oxygen through segregation during freezing. Silicate inclusions with a diameter larger than about 0.02 mm appear, at least in ingots of moderate size, to be distributed at random in relation to the primary structure and therefore may be assumed to have existed as droplets in the liquid steel before freezing started at the point in question. The average size of such large inclusions has been found to increase toward the axis1&apos; and their amount to increase from the top downward in the axial region.2,10 It has been assumed that this accumulation is a result of the droplets being brought down by the slowly settling metal crystals.2 It has been suggested that large silicate inclusions generally form,6 or may form,&apos;&apos; by coagulation of smaller ones, or by small drops being caught by larger ones during the rising of the latter.9 The occasional occurrence of a large inclusion surrounded by a swarm of small ones has been taken as a proof of this mechanism but, as suggested later, may be explained in another way. It has been pointed out that an inclusion droplet in the liquid steel may grow at the expense of an adjacent one, which implies diffusion of soluble inclusion-forming elements in the liquid steel.&apos;= Further, it has been pointed out that, on cooling in ladle or mold, the metal-silicate equilibrium is displaced in the direction of separation of silicate. Thus inclusions may grow in size and amount.2,3,8,12,13,17,19,20 The exposure of the liquid steel to the oxygen of the air during tapping and pouring, and the consequent reaction, has been mentioned as a source of the formation of inclusions19.20 but this possibility has not received particular attention. Further, the admixture of furnace slag during tapping1 or of refractory material from various sourcesl,20 has been considered. The inclusions due to the latter may be recognized, however, through their resistamce to hydrofluoric acid, imparted by the alumina content. Silicate inclusions are often referred to as the natural and inevitable product of reaction on adding silicon or silicon

Jan 1, 1949

By O. D. Gonzalez, R. A. Oriani

The migration of hydrogen and of deuterium dissolved in a iron and in nickel induced by an applied electrical potential has been measured over a range of temperature. In all cases the intevstitial solute migrates to the cathode. The deduced charges of transport are positive, independent of or slightly dependent on temperature, and markedly larger for the beavier mass. These results are interpreted as showing predominating momenlum transfer between electron holes and the acticated complex of the elementary diffusion act. THE migration of components of a metallic system under the action of an applied electrical potential is called electromigration or electratransport. This phenomenon has been known since 1861 and is becoming of increasing interest to metal scientists because of the opportunity it offers to explore the connections between mass transport and electron transport. Until recently, reliable data have been very scarce because of the difficulties inherent in the measurements. In addition, theoretical understanding has been either nonexistent or rudimentary and at present this situation is only moderately improved. Whereas the prevalent notion had been (and is still widely held) that electromigration directly reflects the state of ionization of a component in its equilibrium state in the metal, it is now becoming clear that the major, if not the sole, factor is the momentum transfer between the charge carriers, themselves in motion because of the applied field, and the metallic components in their activated state. It becomes important therefore to obtain reliable data over a range of temperature on electrornigration in systems where only one component moves, that is, either in pure metals (vacancy motion) or in interstitial solid solutions. Our choice of systems was dictated by our measurements&apos; of the Soret effect in solid solutions of hydrogen and deuterium in iron and nickel. Indeed, the main reason for making measurements on electromigration at all is that we suspected a mechanistic connection between thermal diffusion and electromigration. In our former paper&apos; we proposed that what is common to both phenomena is the momentum transfer between the charge carriers in the metal and the atom as it jumps from one equilibrium position to another. In Soret diffusion, however, there is in addition the dissipation of the energy of the jumping atom via pho-nons. We have since found that similar ideas for this interconnection have been developed by Fiks.2 In the present paper we will discuss in more detail our understanding of the mechanism of electromigration itself, but we turn first to a presentation of the experiments and results. EXPERIMENTS AND RESULTS Let us consider a metallic system in which only one component, m , can diffuse at the temperature in question, and to which are applied simultaneously an electrical potential gradient, grad cp, and a chemical potential gradient, grad p,. One may write3 for the material flux Jm and the electronic charge flux Je by applying the condition, grad = 0, to Eq. [I] and evaluating grad(um/T) for the isothermal case and for activity coefficient independent of composition over the relevant composition range. ere, c is the concentration and D the diffusivity of the mobile component. The experimental technique that we have used to measure Z* for the isotopes of hydrogen individually dissolved in each of two transition metals has been developed from a method used by Wagner and Heller.4 (A somewhat similar method was also used by Herold.5) A wire or thin rod of the metal under study connects two volumes of gaseous hydrogen at identical pressures; hence grad um = 0. A direct current is made to pass through the specimen, serving to maintain the specimen at the desired temperature and also to produce the electromigration of the hydrogen dissolved in the metal in equilibrium with the gaseous hydrogen. Under these conditions, the flux of hydrogen from one volume to the other is given, from Eq. [I] for grad( um/T) =0by

Jan 1, 1968

By L. S. Darken

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of &apos;association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples&apos;-4 or thermogravimetric measurements. 5,8 Darken and Gurry&apos;s1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth&apos;s neutron-diffraction experiments. Roth&apos;s model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1&apos; used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.&apos; Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3&apos; states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By W. A. Jr. Slippy, E. P. Dahlberg, R. B. Reed-Hill

A large room-temperature mechanical-hysteresis effect under cyclic tensile loading was observed in zivconium specimens prestrained at 77°K so as to form large numbers of (1121) twins. The observed hysteresis loss was a maximum when the prestrain was just under 1 pct It also depended strongly on the maximum applied cyclic stress, but only moderately on loading rate and temperature (-72°to 100°C). The phenotnena have also been studied in terms of the elastic aftereffect where the data has been found to cotlforln closely to the functional relationship between strain and time, c = -RT/a In tank ft. t to)/Zr, for strains cts large as about 10-4 This eyication can be derived directly from the strain-rate equation There may be important commercial implications to the present discovery since it appears that within rather wide limits it may be possible to obtain any desired magnitude of damping capacity in zirconium melal. The damping propevties may also be given directional characteristics. It is shown that the observed anelaslic phenomena can he explained on the assumiplion that they are the resuilt of stress-induced twin-boundary movements in which the average twin increases its thickness by only a few percent. In polycrystalline zirconium, a grain is least favorably oriented for slip when its basal plane, containing the (1130) slip directions, lies nearly perpendicular to the principle normal stress. Mechanical twinning is favored by this orientation and under simple tensile deformation at room temperature the primary twinning mode is {1012).&apos; The (1012) twinning shear is small (0.17) so that, during deformation, twin growth does not greatly enhance ductility. At 77°K, on the other hand, the predominant twinning mode shifts to {1121), and many thin (1121) twins can form at small strains.&apos; Twins thus nucleated can grow readily during subsequent room-temperature deformation and permit easy deformation in unfavorably oriented grains. In addition, the (1131) twinning shear is large: 0.63. These facts have lead to a process&apos; for greatly improving the room-temperature ductility of zirconium when it contains a sizable fraction of grains with basal planes nearly normal to the stress axis. Optimum results are obtained by slightly less than 1 pct prestrain. The effect is large so that a 50 pct elongation increase is readily attained. A large room-temperature mechanical-hysteresis effect has also been observed in zirconium specimens prestrained at 77°K. The present paper is concerned with some aspects of this effect which the experimental observations strongly indicate is primarily the result of strain-induced {1121) twin-boundary movements. This clearly suggests that mechanical twins formed by plastic deformation can cause anelastic effects similar to those previously observed2 for annealing twins and twins associated with phase transformations. EXPERIMENTAL PROCEDURES All specimens were prepared from arc-melted sponge zirconium plate stock as previously described,3 which has a preferred orientation with basal planes aligned parallel to and uniformly distributed around the rolling direction. Both lonti-tudinal and transverse tensile specimens, with axes parallel and transverse, respectively, to the plate rolling direction, were cut from this plate. In a longitudinal specimen most grains are favorably oriented for slip, while in a transverse specimen a large fraction are unfavorably oriented. Prestraining at 77°K was performed in two ways. In one, annealed zirconium plate stock was cooled in liquid nitrogen and then rolled in the transverse plate direction to strains varying from 0.5 to 12 pct. Cylindrical 1/8-in.-diameter by 1-1/4-in.-gage-length tensile specimens were machined from this material. In the other, previously machined tensile specimens were prestrained in tension at 77°K between 0.2 and 3.8 pct. Type FA 25-12 SR4 strain gages were cemented to all specimen gage sections. All tests were performed on an Instron testing machine of 10,000-lb capacity. EXPERIMENTAL RESULTS Fig. 1 shows a typical two-cycle room-temperature stress-strain diagram for a specimen prestrained 0.65 pct by rolling at 77°K. The maximum stress in both cycles was 14,500 psi. Note that in the first cycle the loading and unloading curves are unsymmetrical so that a residual strain, er, remains after unloading. In the second cycle the stress-strain curves form a nearly symmetrical hystere-

Jan 1, 1965

By A. L. Barnes, A. M. Rowe

A heat transfer study was made of hot gas injection into oil shale through wells interconnected by vertical fractures. This analysis involved the simultaneous numerical solution of a nonlinear, second-order partial differential equation that describes two-dimensional conduction heat transfer in oil shale and a nonlinear first-order partial differential equation that describes convection heat transfer in the fractures. Three nonlinear, temperature-dependent coefficients were used in this work; they are thermal conductivity, thermal capacity and retorting endothermic heat losses of oil shale. Vertical fractures were considered to be of finite height. Although vertical conduction heat transfer was not considered, an estimate of the error resulting from this limitation was made. The effects of injected gas temperature, injection rate, system geometry, cyclic injection and time upon retorting efficiency were investigated. Results from this study show that the rate of retorting oil shale is a direct function of both injection temperature and rate, and the theoretical producing air-oil ratio:(AOR) is an inverse function of temperature. Retorting rates are constant until "breakthrough" of the 700 F isotherm at the producing well, assuming constant injection parameters. Retorting rates for bounded systems are higher than the analogous unbounded systems and likewise AOR&apos;s are less. The use of an alternating injection-soak routine with high injection rates is less efficient than continuous injection at lower rates. These results indicate that injection temperatures on the order of 2000F or greater may give theoretical AOR&apos;s in the economic range. INTRODUCTION Over half of the known oil shale reserves are located in the U.S., and most of them lie in the Piceance Creek basin of Western Colorado. The Colorado oil shale outcrops on the edges of the Piceance Creek Basin. At the outcrops the shale beds are relatively thin, from 25 to 50 ft thick. In the center of the basin the oil shale is as great as 2,000 ft thick and is covered with 1,000 ft of overburden. It has been estimated that there are over 1,000 billion bbl of oil in shales having an oil content over 15 gal/ton in this basin. Oil shale does not contain free oil but an organic matter called kerogen. Kerogen yields petroleum hydrocarbons by destructive distillation. It must be heated to approximately 700F, at which temperature it decomposes into shale oil, gases and coke. The U.S. Bureau of Mines and, more recently, oil companies have conducted considerable research on surface retorting methods to economically recover oil from this shale. Another approach to exploit the oil shale deposits, in particular that portion having 1,000 ft of overburden, is to retort the oil shale in place and produce the liquid and gaseous hydrocarbons through wells drilled into the shale. Some research has been done on this approach.l,2 There are several variations to the in situ retorting approach. These variations fall into one of two groups, depending upon the geometry of the system: (1) retorting in a highly fractured or broken up matrix; (2) retorting from single fractures between production and injection wells. The latter is the group studied. Several investigators,3-6 using various assumptions, have studied flow of heat through horizontal systems. The objective of this work was to make a heat transfer study of in situ retorting oil shale by hot gas injection through wells interconnected by single vertical fractures of finite height. The oil shale thermal conductivity, thermal capacity and retorting endothermic heat losses were considered to be functions of temperature. A knowledge of the

Jan 1, 1969

By W. C. Leslie

The textures of cold-rolled and of annealed iron are compared with those of an iron-0.8 pct copper alloy in which the amount of precipitation after cold rolling was controlled. Previously published pole figures -for cold-rolled and for annealed iron are confirmed. The effects of precipztatiotz after cold rolling are to retain the cold-rolled texture after annealing, to inhibit the formation of the usual allnealing texture, and to produce elongated recrys-tallized ferrite grains. It is suggested that the inhibition of new textures by precipitation after cold rolling is a general phenomenon. A great deal of attention has been paid to the development of texture during the secondary or tertiary recrystallization of ferritic alloys, but very little work seems to have been done on the control of texture during primary recrystallization. If such control were attained, it might be possible to simplify the processing of oriented materials or to change the characteristics of current cold-rolled and an-nealed products. From previous experience, it seemed likely that texture could be controlled by recrystallizing a supersaturated solid solution. Green, Liebmann, and Yoshidal found that the formation of preferred orientation in aluminum (40 deg rotation about <111> relative to the deformed matrix) was inhibited when iron was retained in supersaturated solid solution in the strained aluminum. The authors attributed this inhibition to iron atoms in solid solution. There is, however, an alternative explanation. Green et al, took a highly supersaturated solution of iron in strained aluminum and heated it to an unspecified temperature for recrystallization. It is probable that precipitation occurred prior to and during recrystallization, and it is proposed that the inhibiting agent is this precipitate, rather than the iron atoms in solid solution. It is important to note that precipitation before cold work is ineffective; the effective precipitate is that formed after cold working and either before or during recrystallization. The location and distribution of the precipitate are critical. Precipitation in such a manner has been found to have profound effects upon kinetics of recrystallization and the microstruc-ture of the recrystallized alloys.2-4 It would be surprising, indeed, if this were accomplished with no change in texture. Because of the relative simplicity of the system, and because of previous experience,4-7 it was decided to determine the effect of precipitation on texture in an alloy of iron and copper. Bush and Lindsay5 found an unspecified change in texture in cold-rolled and annealed low-carbon rimmed steel sheets when the copper content exceeded 0.1 pct. MATERIALS In earlier work, the rate of recrystallization of a low-carbon steel was greatly decreased by 0.80 pct copper, and, after the proper treatment, the recrystallized ferrite grains were greatly elongated.4 Accordingly, it was decided to investigate the effect of precipitation on texture at this level of copper content. The iron and the iron-copper alloy were made from high-quality electrolytic iron and OFHC copper, vacuum-melted in MgO crucibles, cast, hot-rolled to 0.2 in., then machined to 0.150 in. The compositions are given in Table I. The plates were heated to 925°C and brine quenched, twice. This produced a ferrite grain size of ASTM 0 in the iron and ASTM 1 in the Fe-Cu alloy. Disk specimens were cut from the heat-treated plates, repeatedly polished and etched, then used to determine (110) and (200) pole figures by reflection. Despite the complication of large grain size, these pole figures strongly indicated a random texture. PROCEDURES The copper content in solid solution in ferrite before cold rolling and recrystallization, and hence, the amount that could precipitate during the recrys-tallization anneal, was controlled at three levels by heat treatment. The specimens as quenched from 925° C were presumed to have all the copper, 0.80 pct, in solid solution. Other samples of the quenched alloy were aged 5 hr at 700°C to retain about 0.5 pct Cu in solid solution.6 A third set of quenched specimens was reheated to 700°C, then slowly cooled in steps, to reduce the amount of copper in solid solution to a very low level. All specimens were cold-rolled 90 pct, from 0.150 to 0.015 in. thick. The rolling was done in one direction only, i.e., the strip was not reversed between passes, with a jig on the table of the mill to keep the short specimens at 90 deg to the rolls. The rolls were 5 in. in diameter and speed was 35 ft. per min. Machine oil was used as a lubricant. In a supersaturated alloy, the maximum effect of the copper precipitate on microstructure and on recrystallization can be developed by a treatment at 500°C, after cold rolling and before recrystallization.&apos;

Jan 1, 1962

By D. C. Seidel, E. F. Fitzhugh

The Colorado School of Mines Research Foundation has developed a hydrometallurgical process for recovering nickel from oxidized ores, including both the iron-rich laterites and magnesium-rich, soft silicates. Known as the HSO-HTCP (Hydrothermal Sulfidization Oxidation-High Temperature Cementation in Pulp) Process, the system consists of feed preparation, sulfidization, oxidation, precipitation (cementation), and calcination and melting. This paper deals primarily with the sulfidization and oxidation phases of the process. Nickel sulfide ores lend themselves readily to concentration before smelting or pressure leaching, but neither of the major oxidized ore types — the iron-rich laterites and magnesium-rich, soft silicates-has been directly concentrated. Upgrading of crude ore in current practice is limited to cobbing lumps of the harder, lower grade rock (protore) from the softer, enriched silicate ore, because only a small percentage of the nickel in these ores occurs in discrete, contrasting mineral particles. There is no apparent mineralogical contrast in the superficial, iron-rich lateritic ores and, in fact, there is no firm assurance that the nickel atoms are within the lattices of the limonite minerals, or else irregularly adsorbed on the limonite. Within underlying, "rotten rock" silicates, occasional veinlets of gamierite and related nickeliferous silicates are found.&apos; The gamierite veinlets, however, are only incidental, and the majority of the nickel atoms occur as erratic replacements of magnesium atoms in the micaceous chlorites of the ore mass. Pyrometallurgical processes account for nearly all the nickel currently being recovered from oxidized ores. Plants in New Caledonia, Oregon, Japan, Brazil and Greece smelt the ores to make ferronickels or a sulfide matte,2 and the ammoniacal leaching3 at Nicaro, Cuba, is preceded by a reducing roasL4 The only fully hydrometallurgical installation has been the politically ill-fated Freeport Nickel Co. enterprise, and this process was limited to lateritic ores.5p6 A hydrometallurgical technique which might handle both laterite and the typically richer silicate ores has been an enticing goal. The technique described here was developed at the Colorado School of Mines Research Foundation, Inc. on behalf of the Republic Steel Corp. It uses sulfur, heat, air and metallic iron to recover nickel from these ores. Inasmuch as the ores are treated as aqueous slurries, the cost of drying a plant feed that normally carried 30% or more moisture is eliminated, and there are no dust problems. Patent applications have been filed by Republic Steel Corp. on the procedures used for getting the metal into solution and on the subsequent recovery without liquids-so l ids separation of the slurry. It is referred to as the HSO-HTCP Process (Hydrothermal Sulfidization Oxidation — High Temperature Cementation in Pulp). THE PROCESS FLOWSHEET The results of various experimental studies have been combined to form the continuous flowsheet illustrated in Fig. 1. This flowsheet serves as a general pattern showing the sequence of the operations which include: (1) feed preparation; (2) sulfidization; (3) oxidation; (4) precipitation (cementation); and (5) calcination and melting. This paper deals primarily with the sulfidization and oxidation phases of the process. Feed preparation: In general, the silicate ores can be considered as earthy rather than hard, and preparation might be carried out before the addition of water in a trommel, or with water in a scrubber or log washer. This breaks up the earthy particles, allowing the hard lumps to be separated by screening. The oversize material from most ores is relatively barren and may be discarded. If there is occasion to control the iron-magnesium ratio in the plant feed, laterite, which normally breaks up readily into fine sized particles, and silicates are mixed in suitable proportions. The fine product slurry from the initial steps is mixed with elemental sulfur and fed to a conventional ball mill, although the amount of actual grinding that takes place is relatively small. The object of milling is to complete the disintegration to natural particle size and to produce an intimate mixture of the ore and elemental sulfur. This pulp, which is almost entirely -200 mesh, has a pH of about 7.0 and normally can

Jan 1, 1969

By B. Ramaswami, U. F. Kocks, B. Chalmers

This paper describes the tempetrature, solute (gold), and orientalion dependence of the plastic rleforlirnlion of silver single crystals. The virgin flow stress, To, and its temperatutre dependence incrense with increase in solute concentration. el decreases with decrease in temperature below room teiirperature and with increase in solute coucentralion. The dependence of 011 on temperature arid solute sontenl is due to the dependence of Ts on the two variables. An increase in ts, due to either the temperature or the solute conlent, results in a decrease of e11 in crystals of single-slip orientation and an increase of 011 in crystals of&apos; (100) find (111) orientation. is orientation-dependent and at all the temperatures and in all the materials studied. The Leveling off of the engineering stress-strain curve in crystals of (100) 07-ientotion at a stress tl, is associated with extensive cross slib. The temperature and strain -rate dependence of tl are similar to those of indicating that a rate process is the cause 01 this phenomenon. The plastic deformation of silrer crystals of (110) orientation is multiple to that of crystals of single-slip orientation. THE work hardening of fcc crystals has been the subject of intensive investigations in the past 15 years. The effect of orientation, deformation temperature, solutes, second phase or precipitates, strain rate, etc., has been studied in a number of fcc metals.&apos;-5 In spite of the considerable amount of work reported on the dependence of work hardening on the orientation, temperature, and solute concentration, certain aspects of the plastic deformation of fcc crystals have not been clarified. For instance, with the exception of a few investigations,6-8 where crystals of multiple-slip orientations have been studied, almost all the studies have been on crystals of single-slip orientations. Hence, a major portion of this study has been devoted to the dependence of plastic deformation on the multiplicity of slip systems and the enhanced possibility of dislocation interactions resulting from such multiplicity. Further, the abnormally low rate of work hardening observed at large strains at certain temperatures in crystals of the (100) orienta-tion 6-8has not been explained satisfactorily. It is the aim of this study to clarify this aspect of the orientation and temperature dependence of the plastic deformation of fcc single crystals. The work-hardening characteristics of single crystals of aluminum of ( 110) orientation have been studied at room temperatur "&apos;12 and above." They have not been studied at temperatures where the virgin flow stress is dependent on temperature or where, in Seeger&apos;s terminology is important. The work hardening of single crystals of (110) orientation is of interest for another reason. As shown in Table I, the dislocation reactions that are possible in the (110) orientation are similar in certain respects to those that are possible in the (100) orientation. Hence, the deformation of single crystals of silver of (110) orientation was studied in the temperature range 100° to 900°K at intervals of 200°K. The effect of solute concentration on the plastic deformation of fcc single crystals of single-slip orientation has been studied by several investiaators.> In all of these investigations—with the exception of Ref. 20—single crystals of identical orientation have not been used, with the result that the orientation dependence of plastic deformation is superimposed on the effect of the solute. In addition, the effect of the solute on the work-hardening characteristics of single crystals of multiple-slip orientations has not been studied by the previous

Jan 1, 1965

By L. C. Michels, O. G. Ricketts

The disorientations between s?nall grains, whose growth has been arrested at an early stage of recrys-tallization, and the deformed matrix in cold-rolled aluminum single crystals were determined using transmission Kikuchi line and electron diffraction patterns. The orientations of the recrystallized grains were found to be random, and the disorientations of these grains with the matrix weve found to be intermediate to large. This leads to the conclusion that the observed vecrystallization began in small areas of large disorientation present in the cold-worked structure. heavily cold-worked thin sections of aluminunz single crystals and of polycrystalline aluminum and nickel were produced directly by a mechanical technique. The specinlens thus prepared were heated with the electron beam to bring about vecrystallization during observation in the electron microscope. Motion pictures taken du.ring heating and the electvon, microg.raphs taken both before and aftev heating allowed the recrystallization process to be traced to its ovigin. Re cvystallized grains originated in very s,mall regions of the cold-worked structure and developed through rapid migration of high-angle boundaries. The boundaries either were present as such in the matrix or were formed out of dense dislocation networks. SIGNIFICANT advances have been made in recent years in the study of nucleation of recrystallization using the technique of transmission electron microscopy of thin metal foils. Bollman1 in a study of heavily rolled polycrystalline nickel found support for the Cahn-Cottrell2,3 theory of nucleation. According to this theory nuclei form by the initially slow growth of subgrains formed through polygonization. During this initial period of slow growth (the incubation period) the migrating boundary of the subgrain increases its disorientation with the cold-worked matrix and thereby increases its mobility to become a rapidly migrating high-angle boundary. Bailey4,5 investigated the annealing behavior of several metals deformed both in tension and by rolling and concluded that recrystallization took place through the migration of high-angle boundaries. With low deformations these boundaries were present in the metal before deformation. With high deformation it was not possible to tell whether the boundaries were pieces of the original grain boundaries or were produced either during deformation or by polygonization during ameal- ing. Direct observation during heating of metal foils indicated that subgrains form by polygonization and grow at an uneven rate. The grain size obtained decreased with decreasing foil thickness indicating that the foil surface resists boundary motion. Votava,6 in heating stage experiments on rolled copper, observed nuclei to appear suddenly and grow in jumps of differing magnitude. However, he found no special dislocation configurations where the nuclei appeared. Fujita,7 as a result of a study of subgrain growth in heavily worked aluminum, concluded that the boundary of a recrystallized grain initially forms from the boundary of a group of subgrains. This occurred by a process of deposition of vacancies and dislocations in the group boundary as the boundaries within the group disappear. HU8,9 directly observed a similar process in heating stage experiments on 70 pct rolled Si-Fe single crystals. The growth of subgrains appeared to proceed by a coalescence mechanism. The observed fading away of the boundary between two subgrains was explained by the moving out of dislocations from the disappearing boundary into the connecting or intersecting boundaries around the subgrains. The subgrain size and degree of disorientation with the surrounding structure were thus increased. With the increase in disorientation occurred a corresponding increase in boundary mobility, which eventually allowed the boundary to migrate rapidly. This process was observed to occur within "microbands" consisting of parallel narrow segments disoriented by a few degrees present in the as-rolled structure. The conclusion of Rzepski and Montuelle10 that growth is preceded by the coalescence of blocks through disappearance of their common boundaries supports this view. In contrast to Hu&apos;s coalescence model for nucleation were the conclusions of Walter and ~och.""~ Working with the same material as Hu, of the same orientation and rolled to the same reduction, they concluded that nucleation occurred by the Cahn-Cottrell mechanism. They observed, in agreement with Hu, that recrystallization began in the "microband" regions which they referred to as "transition" bands. Bartuska13 studied subgrain growth in heavily rolled nickel using a beam heating method in the electron microscope. He concluded that nuclei for recrystallization form from the largest most perfect subgrains present in the cold-worked structure by rapid intermittent migration of parts of subboundaries. In rare instances he observed subgrain growth by coalescence. EXPERIMENTAL PROCEDURE The materials used in this study were 99.999 pct A1 supplied by A.I.A.G. Metals, Inc., and 99.999 pct Ni supplied by Johnson and Matthey and Co., Ltd. The Hitachi HU-11 electron microscope, with uniaxial

Jan 1, 1968

By H. H. Kellogg

Available high-fernperatzwe equilibrium measurements and other thermochernical data have been critically reciewed for sulfation reactions of the type: Recommended values for log K and ?Fo as junctions of temperature are given for thirty-six suck reactions involving twenty-six different metals. Methods of calculation and choice between conflict-ing data are discussed. SELECTIVE sulfation now enjoys a considerable renaissance as a metallurgical unit process due, in large part, to the available of the fluid-bed re- actor—a device capable of the close control of temperature and gas composition necessary for a successful sulfation process. An additional need, however, if sulfation chemistry is to be approached in a scientific manner, is a reliable body of data on the equilibrium and kinetics of sulfation reactions in simple and complex systems. This paper offers a critical review and compilation of equilibrium data on pure sulfates (simple systems). The last such review, by K. K. Kelley in 1935:30 has proven itself most useful, but the existence of many new data makes necessary a re-evaluation of the available information. METHODS OF CALCULATION For a simple sulfation reaction such as MS04(c) = MO(c) + SO3 [1] there are two approaches one may take toward establishing the value of ?Fo or K as a function of

Jan 1, 1964

By Francis Cameron

Gloomy predictions that domestic mineral reserves are approaching exhaustion are unwarranted and may be harmful, this author contends. Specific mineral forecasting errors in the Paley Report are cited to support this contention, and steps that can be taken to insure a progressive mineral industry capable of keeping pace with the major raw material needs of the nation through advancing technology are suggested. Mining is both exciting and rewarding —although at times somewhat frustrating— and we all can have real pride in our industry, in its people, and in its accomplishments. It is, however, with concern that I have noted a deterioration in this Country in what might be called mining&apos;s stature and in the growth of a belief in many quarters that our mineral reserves are rapidly approaching exhaustion. In other words, there is a popular image that we are fast becoming a "have not" nation in many respects and that the domestic mining industry can no longer be considered, in the vernacular of Wall Street to offer much in the way of "growth potential." I do not subscribe to this hypothesis, nor do I be-li4ve that the record of the mining industry bears this out. However, let me add that we can, in time, talk ourselves into this frame of mind and we can hasten the day when this very well might come about by unnecessary and unwise legislation or regulation. My remarks today are basically designed to give my reasons for refuting this negative philosophy and to review our record. With your help, I know we can improve our image, and the public&apos;s recognition of our industry&apos;s peculiar problems. The progress of our civilization over the centuries has been fundamentally based upon proper use of raw materials, both agricultural and mineral, and upon energy, human or otherwise. As the standard of living has progressed century by century, the demands for mineral raw materials have increased in an irregular, but steadily rising progression. Fortunately, those minerals on which we depend most, i.e., iron, coal, petroleum, copper, aluminum, lead, and zinc have been neither too difficult to find nor to process into useful form. Iron, the most useful of all metals, is present in various amounts in most rock types and soils. Gold, seemingly the most generally desired (but certainly not the most useful of all metals), occurs in sea water in a far greater total tonnage than has been won from all of the world&apos;s known gold mines. If the latter is true, then why do we not see large installations treating sea water for the recovery of its gold content? The answer, of course, is that even the French, who seem, from their recent actions, to value gold above all else, have not devised a way of doing this at a profit. Theoretically, it is possible, but not with today&apos;s technology at a cost which would justify the effort. Man has exploited only those mineral concentrations which accidents of nature have placed within his so far limited means of finding and utilizing. What we geologists and engineers refer to as an orebody is nothing more than a concentration of minerals, exploitable with available knowledge, that will yield a value greater than the value attached to the energy and capital required to produce it. What is "ore" and what is not "ore" is, in the end, a matter of economics. The economic problem stems from the physical and chemical character of mineral deposits. The good Lord stacked the cards heavily in favor of rising costs by limiting the amount of the higher grade ores easily available. As the best and most accessible ores are depleted, it becomes necessary to work harder and with greater ingenuity to produce more from less accessible and lower grade resources. The quantity of mineral raw materials we can have in the future will be determined largely by what we can afford to pay for them in terms of human effort, capital outlay and production energies. We will always have the problem of cost with us and our only real means of keeping ahead of rising costs is by continually improving our technical abilities. We, in this country at least, no longer have open to us large and unexplored virgin wildernesses in which a pick-and-shovel prospector might uncover an untouched mineral bonanza. The rest of the world also has few conventional frontiers left in which the explorer-prospector is free to roam. We do, however, have enormous land areas unexplored, and untouched po-

Jan 1, 1969

By A. M. Sarem, J. M. Campbell

Molecular refraction is introduced as a new and improved third parameter for prediction of the PVT behavior of hydrocarbon systems. This parameter, characterizing the complex as well as the pure hydrocarbon systems (1) is a direct measure of London dispersion forces which affect the PVT behavior; (2) can be measured directly, accurately and easily for complex as well as pure hydrocarbon systems; (3) varies significantly between the reference substances thus allowing accurate interpolation of PVT properties; and (4) has a fundamentally sound basis. Molal average molecular refraction was used with the pseudocritical mixing rule proposed by Leland and Mueller to predict the molal volume of liquid and vapor for 84 published data points on nC4-nCI0, Cl-nC5, Cl-nC4-nC10 systems in the region of coexisting vapor-liquid and at the critical point. The same technique was applied to predict the densities of liquid hydrocarbon mixtures in the two-phase and single-phase regions near the critical point for seven different systems each having different properties of the heptanes-plus fraction, but all simulating the fluids of either gas-condensate or volatile oil reservoirs. A modification of the Leland-Mueller mixing rule for the determination of pseudocritical properties is also presented which yields more accurate liquid density predictions than the original form when used with the proposed third parameter. INTRODUCTION The PVT behavior of multicomponent systems has received widespread attention in the literature in recent years. A large portion of the reported work has stemmed from attempts to overcome the inherent difficulties encountered when using the standard compressibility-factor chart which shows 2 as a function of reduced temperature T, and and reduced pressure p,. This chart assumes that z, is constant for all systems. The error in this assumption is not pronounced for pipeline-type gases high in methane and low in heavy ends, particularly when contained at moderate pressures. For such gases the error in the calculated z is usually less than 2 to 3 per cent. However, the reliability of this approach becomes somewhat nebulous for gas condensate and volatile oil systems at high pressure. One logical approach has been to recognize the variation of 2,. This idea was first suggested by Meissner and Seferianl and used by Lyderson, Greenkorn and Hougen2 to prepare extensive tables of thermodynamic properties. Other third parameters have been proposed by Stockmeyer, Kihara, Riedel, Lightfoot, Bloomer and Pitzer. These were tested by Satter and Campbel13 for many gas mixtures and it was shown that they were inter-related. All of these third parameters have a common fault — they cannot be directly evaluated for the heptanes-plus fraction. Consequently, one necessary requisite of an improved method for predicting the density of multicomponent hydrocarbon systems, was development of a third parameter that could be evaluated for that fraction. PREVIOUS MULTICOMPONENT DENSITY PREDICTION METHODS Sage and Lacey4 suggested a method of using partial molal volumes for computing the density of hydrocarbon gas mixture for pressures to 3,000 psi. In this technique, they approximate the complex multicomponent gaseous mixtures by a quarternary system of methane, ethane, propane and butane. Sage, Hicks and Lacey5 suggest a method of using partial molal volumes for computing the density of hydrocarbon liquids. The results agree within 3 per cent of the experimental values. However, the composition range is limited to about 10 per cent by weight of methane. Consequently, this correlation does not cover the low-molecular-weight liquid similar to natural gasoline and high-pressure gas condensates.

Jan 1, 1966

By E. P. Klier, Jane Jellison

The course of the transformations on cooling in a series of Cu-A1 alloys has been followed by means of thermal analysis, X-ray diffraction, and optical metallogrAphy. Specimen size was found to have a pronounced effect on the time of completion of the pearlite transformation due to modification in the unmber of nuclei. The ordeving transformation zvas observed for all cooling rates for all alloys studied, and is considered insuppvessible. At intermediate cooling&apos; rates, a transitional struchire for 011 alloy compositions and based ox the bainite reaction was observed. The alloys of aluminum and copper possess a eu-tectoidal region at from about 9.4 to 16 pct Al. Above the critical temperature, the disordered bcc phase, 0, is stable. At subcritical temperatures, the 0 phase decomposes under equilibrium conditions into the stable phases, a and y,. At the eutectoid composition, these phases develop a lamellar pearlite structure, in appearance much like that found in steels. During rapid quenching from supercritical temperatures, the diffusion processes required for the formation of the equilibrium phases are suppressed, and the 0 transforms to an acicular martensitic phase, designated B or y&apos; depending on the aluminum content, or to a mixture of the two. Early investigators of this system concentrated on determining the equilibrium phase diagram, &apos;&apos;&apos; the structure of the equilibrium phases,3 and later the isothermal decomposition of the 0 phase at subcritical temperatures, or the decomposition of the martensite on tempering. Other work which treated the nonequilibrium transformations concentrated largely on the martensite transformations and the structure of the b and y&apos; phases.15"17 Since the pearlite and martensite transformations in this system resemble those in steels, the one being formed by nucleation and growth of adjacent lamellae of the equilibrium phases, and the other by a diffusionless, shear-type transformation, the present study has been undertaken to investigate the structures formed on continuous cooling, with the objective of constructing cooling transformation diagrams analogous to those derived for alloy steel systems. In particular it was desired to determine whether parallels between the A1-Cu and iron-iron carbide systems on continuous cooling extended to encompass the intermediate phase, namely the bainite structures, which form by a combined martensitic-diffusion mechanism,&apos;&apos; but which are supersaturated with respect to the equilibrium phase upon which their crystal structure is based. To this end the transformations in representative alloys of the Cu-A1 B eutectoid system have been followed, using the methods of thermal analysis, X-ray diffraction, and optical microscopy. EXPERIMENTAL PROCEDURE Materials. The materials tested were those used by Klier and Grmko 5 in their study of the isothermal decomposition of these alloys. The alloys were melted in graphite crucibles and chill-cast into 5 by 2 by 1/4 in. ingots. The ingots were then hot-rolled to sheets 1/8, 1/16, and 1/32 in. thick. The compositions are given in Table I. Specimen Preparation. Specimens for thermal analysis were in the form of small squares approximately 1/4 in. on a side. For the 11.9 and 13.5 Al-Cu alloys, the sheet thickness was 1/16 in. and for the 10.5 A1-Cu alloy the 1/32-in. sheet was used. One lead of a chromel-alumel thermocouple was spot-welded to either face of the square with the specimen itself thus forming the hot junction of the thermocouple. Specimens for X-ray analysis were prepared as filings from martensitic sheet stock and were sealed in glass ampoules under 1/2 atm of argon. Metallographic examination of the powder specimens was carried out on a portion of the heat-treated filings mounted in lucite. All specimens were examined metallographic ally after etching

Jan 1, 1965

By Don L. Kendall, Martin G. Buehler

A simple physical model has been developed to fit carrier-removal data in silicon irradiated near room temperature with reactor spectrum neutrons. Commonly observed donor and acceptor defect energy levels are assumed to be introduced linearly with neutron fluence. The donor levels (in ev) are Ev + 0.16, Ev + 0.27, and Ev + 0.31 and the acceptor levels are Ec - 0.55, Ec - 0.40, and Ec - 0.1 7, where Ev and Ec are the valence and conduction band energies, respectively. The introduction rates of each level are adjusted to fit literature initial carrier-removal rate data. When normalized with respect to the Ev +0.27 level, the relative values of introduction rates are 5.3, 1.0, 3.1, 1.0, 2.0, and 20.0, respectively for the six levels indicated above. To fit p-f (hole concentration vs neutron fluence) and n-f (electron concentration us neutron fluence) data, the introduction rates are multiplied by a factor which preserves the relative values given above. This factor depends upon irradiation temperature, reactor energy spectrum, neutron fluence calibration, and oxygen content of silicon. An extensive study of the effect of neutrons on carrier-removal in silicon irradiated with reactor spectrum neutrons (E > 10 kev) has been given by Stein and Gereth1 (SG) and Curtis, Bass, and Germano&apos; (CBG). They measured initial carrier-removal rates for both p- and n-type silicon over an impurity range typical of silicon devices. In this work, we attempt to fit a simple theory to this data to establish a usable relationship between hole and electron concentration, p and n, respectively, and neutron fluence f. The p-f and n-f relations are needed to assist in the design of neutron tolerant silicon devices and are needed to clarify presently used empirical resistivity-fluence relationships.3 Neutron damage in silicon produces a variety of defects ranging from simple point defects to defect clusters. For the purpose of this treatment, we assume that simple point defects dominate carrier-removal effects. In contrast to this view, stein4 has proposed that defect clusters are responsible for a significant portion of carrier-removal effects. In the following section, it is shown that the carrier-removal effect in n-type silicon with an electron concentration less than 1015 cm-3 can be explained adequately by assuming that the divacancy is the dominant defect and that its introduction rate is independent of the electron concentration. For electron concentrations greater than 1015 cm-= an additional acceptor defect center is needed, and for simplicity the A-center (vacancy-oxygen pair) has been chosen. Although the E-center (vacancy-phosphorus pair) can account for some of the results, the A-center was chosen because the E-center requires a more involved treatment which the presently available data do not justify. In p-type silicon three radiation-induced donor levels are assumed, namely the divacancy and two other centers of unspecified nature located at Ev + 0.16 ev and Ev to 0.31 ev. The donor divacancy at Ev + 0.27 ev is assumed to be introduced at the same rate in p-type as in n-type. However, this rate is too low to fit p-type initial carrier-removal data. The dominant centers in p-type silicon are assumed to be the Ev + 0.16 ev and Ev + 0.31 ev levels where the latter is not the divacancy. The introduction rates are chosen to fit initial carrier-removal rate data. Assuming that the introduction rates are independent of Fermi level, the ratio between them is fixed for subsequent p-f and n-f calculations. Using the same ratios, the initial carrier-removal rate data1,2 as well as p-f and n-f data1,5 can be fit provided the absolute value of the introduction rates are adjusted to account for irradiation temperature, reactor energy spectrum, neutron fluence calculation, and the oxygen content of silicon. THEORETICAL ANALYSIS This analysis is basically the same as that used by Hi116 to analyze electron damage in silicon except we express the degree to which an impurity level is ionized not in terms of the Fermi level, but in terms of carrier concentration. Landis and pearson7 have used the latter approach to analyze y-damage in silicon. Neutron-induced defects responsible for carrier-removal at room temperature are assumed to be simple point defects with no interaction between defects so that they may be represented by discrete energy levels. It is also assumed that no constituent of a defect complex is used up and defects stabilize shortly after irradiation. Defects are assumed to be introduced linearly with fluence according to the product Rtf where Rt is the defect introduction rate and f the neutron fluence. Taking into account the ionization of defects according to Fermi statistics, and considering charge neutrality where minority carriers are neglected, the n-f relation is where no is the preirradiation electron concentration. The parameter Nt is the electron concentration at which the ionized defect concentration is one-half the total defect concentration (Rtf) or where Et is the defect energy level. For silicon at 300°K, ni = 1.45 X 1010 cm-3 and Ei = Ev+ 0.542 ev which was determined using Ec — Ev = 1.11 ev and me* = 1.07 mo and mh* = 0.558m0. The spin degeneracy factor, which usually appears as a number multiplying the Nt/n term of Eq. [1], is taken as unity. In effect, this factor has been incorporated into the defect en-

Jan 1, 1970

By Donald E. Meyer

High current-low voltage EB-gun evaporation in an oil-free ultra-high vacuum system was found to be necessary, though not sufficient, for stability (300°C, 106 v per on) of aluminium gate MOSFET&apos;s and MOS capacitors not stabilized by a phosphorous glaze. five characteristics of the equipment used: 1) Vacuum purification of the aluminum charge, 2) Ionization of the evaporant by the electron beam, 3) X-ray formation, 4) Residual gases during evaporation, and 5) Metal film structure were studied as Possibly significant in MOS fabrication. EVAPORATION of contact metals common to the semiconductor industry historically has been accomplished with oil diffusion pump systems and various resistance heated evaporant sources as dictated by the type of metal evaporated. To meet a need for greater reliability of semiconductor devices, other metallization methods were developed. A good example would be application of the moly-gold contact system to integrated circuits with deposition by RF or triode sputtering.&apos; More recently, fabrication of stable metal-oxide-silicon devices and circuits has put new demands on metallization. The purity of the thin metal films composing MOS structures is critical, particularly at the metal-oxide interface, and ultra-high vacuum metallization using sputter-ion pumping and electron beam gun (EB-gun) evaporation are well suited for the task. At this laboratory aluminum has been the most common contact-gate metal for both MOS capacitors and MOSFET&apos;s. In the earliest work with MOS capacitors, aluminum was evaporated from wetted tungsten filaments using both diffusion pump and ion pump vacuum systems. In spite of clean oxide techniques these capacitors were unstable under bias-tempera-ture stressing. Only after a switch to EB evaporation of aluminum were stable capacitors produced. Using the same techniques it was possible to make MOSFET&apos;s with equivalent stability. Stability data for a discrete MOSFET is shown in Fig. 1. This is a "clean" oxide gate (no phosphorus stabilization or no etch back of a thicker gate) having a thickness of lOOO? thermally grown on the (111) plane. Gate length after diffusion was 0.24 mils, and the devices were hermetically sealed. Stressing conditions were 300°C and 106 v per cm applied alternately as a positive and negative field for 10 min, 50 min, and 4 hr for a total stress time of 10 hr. An initial shift in turn-on voltage of 0.1 v was detected for 10 min of positive bias. All evidence at this laboratory indicated that while EB-gun evaporation of ultra-high purity aluminum was not sufficient for 300°C stability, it did seem to be necessary. There may well then be something inherent in the EB-gun deposition used which enhanced stability, and probably no single factor existed but rather a series of factors. It is the purpose of this paper to report on some of the investigations carried out to learn more about EB-gun evaporation in ultra-high vacuum systems. EXPERIMENTAL DESCRIPTION The EB-gun was self accelerated, had a maximum power rating of 10 kw, and used a water-cooled copper crucible able to hold a 20-g aluminum charge. The electron beam was bent 180 deg and focused by an electromagnet which also provided movement of the beam across the crucible. Normal power conditions in this work were 9 kv and 300 to 600 mamp. The gun can be described as high-cur rent/low-voltage and was quite different in its mechanism of operation from EB-guns with much higher acceleration potentials. An oil-free vacuum system capable of 5 x 10- l0torr, a quartz crystal rate and thickness monitor and a quadruple mass spectrometer completed the evaporation system, Fig. 2. A typical evaporation cycle consisted of a 3 to 4 hr pumpdown to the upper l0-9 range and evaporation at l0? per sec with the pressure in the bell jar not rising above 1 x 10"7 torr. Thickness control was 5 pct or less and could be automatically monitored and controlled. Five phenomena associated with the EB evaporation and considered as possible contributors to Ma performance included a purification effect, ionization of evaporating aluminum, X-rays, constitution of vacuum ambient during evaporation, and film structure dependence upon evaporation rate. These phenomena are now discussed. Vacuum Purification. The design of the EB-gun permitted purification of the aluminum charge by vacuum outgassing. Particular features included an efficiently water-cooled copper hearth with a capacity of over 20 g of aluminum and the capability for sweeping the beam across the charge. Such capacity meant that aluminum had to be added only after about every fifth evaporation. A new charge was not required each evaporation as is necessary with filament evaporation. An oxide "scum" which appeared on the charge could be completely cleared from the top hemisphere of the charge by sweeping with the beam prior to opening the shutter. An indication of the purifying effect was obtained by a series of analytical measurements on incoming aluminum, after melting but with little vacuum out-gassing, after 30 min outgassing, and the evaporated film itself. Either a solids (spark source) mass spectrometer or an emission spectrometer were used for analyzing the aluminum charge. Analysis of the evapo-

Jan 1, 1970

By O. R. Wagner, R. O. Leach

Immiscible displacement tests were performed in a consolidated sandstone core over the interfacial tension range from less thdn 0.01 to 5 dynes/cm to better define how interfacial tension (IFTJ reduction can lead to increased oil recovery. Data obtained were displacement efficiency at breakthbrough vs IFT for both drainage and imbibition conditions. These tests simulate water flooding under oil-wet and water-wet conditions, respectively. Results of the study have shown that displacement efficiency under both oil-wet and water-wet conditions can be markedly improved by a sufficient reduction in IFT. In the particular porous media used and for the low pressure gradients employed, the IFT must be reduced to a value less than about 0.07 dynes/cm to achieve increased recovery at the time of breakthrough of the injected phase. Below 0.07 dynes /cm, further small reductions in IFT result in large increases in displacement efficiency. Observed increases in recovery were obtained at pressure gradients which are well below those which can exist in the interwell area of a reservoir under water flood. The effect of pressure gradient on recovery is discussed. INTRODUCTION A residual oil saturation remains in rock which has been water flooded because, under usual reservoir conditions, the driving force which can be generated is inadequate to expel oil trapped by capillary forces. Since these capillary forces can be reduced by reducing the IFT a frequently studied method of increasing oil recovery has been the use of surfactants to reduce the water-oil interfacial tension. Mungan l observed improved recovery in both water-wet and oil-wet systems at 1.1 dyne /cm IFT, finding that the amount of improvement was greater in oil-wet systems. Moore and Blum,2 working with visual flow cell micro-models, con- cluded that recovery cannot be improved in water-wet systems by injecting surfactant solutions. They calculated that, for a pressure gadient of 1 psi/ft in their model, the IFT must be reduced to 0.03 dynes/cm to release oil trapped under water-wet conditions. Berkeley et al.3 indicated that, at representative field flooding rates, the IFT must be reduced to 0.001 dyne/cm to improve recovery, Thus, there is a wide variation of opinion about the IFT levels needed to improve recovery under field conditions. These previous investigators all have used as their experimental method the addition of surfactants to the injected water. The use of surfactant solutions to reduce IFT creates two experimental problems: (1) the loss of surfactant through adsorption on reservoir rock can obscure the true IFT value which exists at the displacement front, and (2) at very low values of IFT emulsifica-tion of oil and water commonly occurs. It is difficult, therefore, to determine whether the increased recovery is caused by IFT reduction as such, or is instead caused by emulsification. Also the properties of the available surfactants limit the IFT range which can be studied. In the present study the purpose is to better define how interfacial tension reduction can lead to increased oil recovery. A matter of great interest is the amount of recovery improvement potentially achievable in this way. The study was made using very low pressure gradients which was well within the range achievable by water flooding in the interwell region of petroleum reservoirs. A unique experimental approach was chosen to avoid adsorption and emulsification problems, and to allow convenient control of IFT. The fluid phases used were the equilibrium vapor and liquid phases of the methane-n-pentane system. The interfacial tension level was varied by changing the equilibrium pressure of the methane-pentane system over the range from 1,200 psia to near the critical pressure (2,420 psia). All tests were performed at a controlled temperature of 100F. The IFT-vs-pressure relationship for the methane-pentane system was based on the data of Stegemeier and Hough,6 and on new data obtained in this study. With this experimental approach it has been possible to study displacement at lower values of IFT than have been previously investigated.

Jan 1, 1967

By N. S. Stoloff, J. N. Mushovic

Age hardening response of a Mg-Th-Zr alloy has been studied at temperatures in the range 60° to 450°C. Transmission microscopy revealed clustering of thorium atoms at low aging temperatures, supporting a previous report of GP zone formation. Peak strengthening, which is observed at 325°C, is due to the formation of a coherent, ordered, DO19 type superlattice structure, of Hobable composition Mg3Th, as plates parallel to the matrix prism planes. These plates later reveal a Laves phase structure of composition Mg2Th. The equilibrium Mg4Th phase begins to precipitate in two different forms at an early stage, competitively with the Mg2Th plates. RECENT work on the Mg-Th system indicated that, unlike most magnesium-base alloys, complex precipitation phenomena may be occurring. The partial phase diagram of the Mg-Th system indicates that an equilibrium phase, Mg5Th, is the sole intermediate phase.&apos; sturkey,&apos; however, has reported, using X-ray and electron diffraction techniques, that a metastable fcc Laves phase, Mg2Th, precedes the formation of the equilibrium compound, which he identified as closer in composition to Mg4Th. Murakami et al.3 reported that the equilibrium phase precipitates preferentially on grain boundaries and dislocations in a Mg-1.7 wt pct Th alloy; Kent and Kelly4 aged a more dilute alloy, Mg-0.5 wt pct Th, for 4 days at 220°C and found similar results. In addition, they reported that a platelike phase with a structure close to that of the magnesium matrix forms perpendicular to the basal plane and is probably ordered. Research on a Mg-4 wt pct Th alloy by electrical resistance measurements and transmission electron microscopy has suggested that GP zones may form at low aging temperatures.3 However, the electron micrographs purporting to show this phenomenon were not conclusive. In view of the fragmentary evidence concerning the nature of the precipitation processes in the various Mg-Th alloys, an aging study was undertaken to clarify the characteristics of the various precipitates which form and to correlate the mechanical properties of the system with the direct precipitate-dislocation interactions. The latter results are presented elsewhere.&apos; The purpose of this paper is, therefore, to discuss the precipitation sequence in this system. EXPERIMENTAL PROCEDURE Sheet stock (0.060 and 0.010 in. thick) of a commercial Mg-3.93 wt pct Th-0.42 wt pct Zr alloy (designated HK3lA) similar to that studied by sturkey2 was supplied through the courtesy of Dr. S. L. Couling of Dow Metal Products Co. Zirconium does not enter into any precipitation reactions,&apos; but is present primarily as a grain refiner. The alloy was chill cast, warm rolled to 0.090 in. thick stock, and then finally reduced by a combination of hot and cold rolling. The alloy chemistry is given in Table I. This material was solution treated at 580°C for 4 hr in a dry CO2 atmosphere, and then water quenched. Material in this condition was fairly clear of precipitate particles and was fully recrystallized. Aging at temperatures less than 200°C was accomplished by immersing the alloy in a silicone oil bath; for higher temperatures, aging was done in a salt pot. Age hardening treatments were conducted at 60°, 80°, 105°, 135°, 160°, 250°, 325°, 350°, and 450°C for times ranging from 5 min to 400 hr. Hardness tests were performed on chemically polished 0.060-in.-thick blanks of solution treated material which were aged at the various temperatures for increasing lengths of time. For aging temperatures above 150°C the Rockwell Superficial 30T scale was employed, while samples hardened at temperatures below 150°C were monitored with the 45T scale. Each data point consists of at least three separate readings. Yield stresses also were measured at room temperature on both 0.060 and 0.010 in. sheet specimens aged at 325°C. The aged foils were thinned by the window method in a solution of 80 pct absolute alcohol and 20 pct concentrated perchloric acid (70 pct) maintained at 0°C. A stainless steel cathode was used and the applied voltage was 10 to 15 v. Thinned samples were rinsed in distilled water and pure methanol. After the me-thanol rinse the thin foils were quickly dried between filter paper. Foils prepared by the above method were examined in a Hitachi HU11B electron microscope operating at 100 kv. RESULTS A) Hardness. The hardness data are depicted in Figs. 1 and 2. Peak strengthening occurs at 325°C after aging about 6 min, see Fig. 1. Significant strengthening is achieved also at 350°C, but aging at 450°C produces only softening. The stepped curve at 250°C indicates that a complicated precipitation process may be occurring at that temperature. Fig. 2 suggests that at least two hardening mechanisms exist since the lowest temperature hardness peaks are displaced to the left of the peaks obtained at 135° and 105°C. A great deal of scatter is observed at long times in all cases due to magnesium surface degradation caused by the silicone oil bath. B) Identification of the Strengthening Precipitates. The structure formed atlowagingtemperatures (c10O°C) was not clearly resolvable by transmission microscopy. The only bright-field evidence for a change in structure was a mottled appearance which could be observed at extinction contours, as shown in Fig. 3(a), and the disappearance of this effect when dislocations produced under the influence of the electron beam passed through the matrix, as noted in

Jan 1, 1970