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By F. H. Deily, Jean M. Quets, Milton E. Wadsworth, John R. 222-000-000-012 Lewis, D. S. Rowley, R. J. Howe

Samples of synthetic magnetite were reduced in hydrogen-water vapor atmospheres in the temperature range 450o to 900oC. The reaction was always surface controlled, indicating the final products of reaction are nonfirotective. Three separate cases have been identified from the kinetic results: Case I, reduction of magnetite to iron below 570°C; Case II, reduction of magnetite to iron above 570°C; and Case 111, reduction of magnetite to wustite above 570 oC. In Cases I and 111 the kinetics have been explained by the formation of oxygen anion vacancies in the magnetite surface followed by associated diffusional processes. In Case 11 the observed kinetics have been related to the concentration of iron cation vacancies in the wustite layer formed, followed by associated steady-state diffusional processes. The concentration of cation vacancies in the wustite is maintained constant by the magnetite-wustite equilibrium. THE reduction of the oxides of iron has been a subject of study and interest for many years. However, few attempts have been made to interpret the results in terms of the mechanism of reduction of an iron oxide by either hydrogen or carbon monoxide. Stalhane and Malmberg' using CO, H2, and CO-Hz mixtures, developed the rate expression: where m = mass of oxide reduced, t = time, k = a constant, s = surface area, P = partial pressure of of CO or H,, and P, = partial pressure of the reducing gas at equilibrium. The rate of reaction per unit area was proportional to the difference between the partial pressure of the reducing gas and its pressure at equilibrium. Hansen, Bitsianes, and Joseph2 studied the reduction of pellets of hematite to magnetite with mixtures of CO-CO,. They concluded that below 450°C the reaction proceeded according to a model in which CO reacts with the hematite surface producing an oxygen ion vacancy. The rate controlling step was then assumed to be oxygen ion diffusion through vacancies resulting in the formation of magnetite. They derived an expression giving the rate of reduction proportional to the cO/CO, ratio. Recently McKewan3 published results for the reduction of magnetite spheres in atmospheres below 570°C. He explained his results by an equation of the form where K, is the equilibrium constant for wustite-iron equilibrium attributed to the formation of wustite as an intermediate in the reduction of magnetite. According to McKewan, Kp is an equilibrium constant for H, -HO adsorption in which oxygen is deposited on the surface from the H,Oand subsequently acts as a poison for reduction by hydrogen. Sample Preparation and Experiments. In this work the authors used the same apparatus and experimental procedure employed in the hydrogen reduction of magnetite. Sintered disk samples weighing approximately 1.5 g and measuring 1.2 cm in diameter and 0.25 cm in thickness were prepared by a method described previously.4 Partial pressures of hydrogen and water vapor were controlled by bubbling hydrogen through a series of flasks containing distilled and deionized water maintained at constant temperature in an oil bath. The total flow rate of the reacting gases—hydrogen and water vapor—was approximately 0.5 liter per min. The entire external system was maintained at a temperature above the oil bath to prevent condensation of water vapor. This was accomplished by wrapping electrical resistance elements over all surfaces. The glass column containing the weighing system-a McBain balance suspended from a gold chain-was enclosed in an aluminum tube heated by nichrome resistance wire enclosed in an insulating material. The temperature of the glass column was held constant by means of a series of thermocouples connected in parallel to a Leeds and Northrup temperature controller. This was necessary since variations in temperature resulted in expansion and contraction of the glass column and could be readily observed with the cathetometer. The spring extensions were measured through a window with a gaertner cathe-

Jan 1, 1962

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'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'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 W. van der Knapp

A theoretical and experimental ana1ysis is given of the change in volume of a porous medium due to changes in external and internal pressures. The result enable one to deduce directly the effect of large increlents in stresses. It is shown that the three-dimensional representation of the volume of a nonlinear porous system is a cylindrical rules surface, the generating lines of Which have a slope according to the solid rock compressibility. Analytical expression for such a ,surface is very simple. It follows that the bulk and pore compressihilities depend only on the difference between pore fluid and external hydrostatic pressure, i.e., the effective rock frame pressure. From measurements on a number of sandstones as well as limestones it can be conduded that for practical values of this effective frame pressure the pore compressibility falls in the range between the compressibility of water and that of undersaturated crude oil. In general, pore compressibility is found to be higher the lower the porosity. For a particular limestone reservoir pore compressibility and porosity could he related by means of a simple empirical formula. Results from the described study find a direct applicxtion in material balance calculations and in prob1ems of liquid flow through porous media. Since the elastic constants of the rock bulk material enter into equatiorls for velocity of acoustic waves, the results are also of importance for calculating rates of wave propagation in these media. It is shown for sandstones with 1.5 to -10 prr cent porosity that laboratory measured porosities may differ from those lender reservoir conditions by about I per cent of their value. The difference for low porosity limestotnes can be of the order of 10 per cent. The subsidence caused by elastic deformation of reservoir rock is shown to he very small. General formulas relating pore and bulk volume to external and internal pressure can be derived, as has been shown by Biot1, Gassmann2 and Geertsma.2 Their theories describe the differential change in volume caused by a variation in pore fluid tension and external hydrostatic tension. It has been known for a long timei that the stress-strain relations of a packing of spheres are essentially noninear. Our experiments show that for almost all reservoir rocks which arc elastically deformable the relation between volume and loading is also a nonlinear one, resembling that of a packing of spheres very closely. The behavior of these media is often described by using the linear stress-strain relations for small incremental stresses and strains in the vicinity of a pre-stressed condition." The present study differs from these considerations in that it enables one to deduce the effect of large increments in the stresses directly. In analogy to the stress tensor for a homogeneous body the stress tensor for a porous body can be written in the conventional way: where the tensor components, o, and t, represent the total forces acting on the faces of a unit cube of porous material. This tensor can be split into two parts. a hydrostatic and a deviatoric part, as follows2,3,1 where the component of the hydrostatic stress system, a. equals The hydrostatic stress causes a change in volume whereas the deviatoric stress system gives rise to a change in shape only. One of the difficulties in describing changes of volume occurring in reservoir rocks is that the relations connecting these volume changes with external and internal stresses are essentially non-linear. A complete description requires the bulk volume, V,,, as well as the pore volume,V,,. to be known as a function of both the changes in pore fluid tension (v) and the hydrostatic tension on the outer boundary.

By Lawrence A. Roe

Talc, when it can be isolated as a pure mineral, has a composition of 63.36% SiO2, 31.89% MgO, and 4.75% H2O. However, as an industrial commodity, talc rarely approaches theoretical purity. Nevertheless, the impure talc products of commerce find a multitude of uses and few substitutes in many industrial applications. Minerals commonly associated with and sold together in talcose mixtures are tremolite, chlorite, dolomite, mica, and magnesite. Steatite was originally a mineralogical name applied to pure talc. In today's commerce steatite generally refers to the massive variety of talc suitable for electrical insulator manufacture. Block steatite ore can be machined into various shapes. Impure varieties of massive or block talc are still commonly referred to as soapstone. Soft massive talc, suitable for crayon manufacture, has been referred to as French chalk. It has been common practice to discuss talc, soapstone, and pyrophyllite under the same general heading. In the case of soapstone and talc, this is a natural thing since many different types of platy, soft minerals exhibiting a high degree of lubricity (commonly referred to as "slip") have been grouped together and called soapstone or talc. Further, there is a mineralogical relationship of pyrophyllite to montmorillonite and talc to hectorite. Thus, talc and pyrophyllite are sometimes referred to as clay minerals. When finely divided talc or pyrophyllite are combined with water in proportions to make a slurry, the end product does have the appearance of a clay-water mixture. Soapstone for utensils and ornaments was mined by prehistoric Indians on Santa Catalina Island, Calif. In the mid-1800s, soapstone from deposits along the western foothills of the Sierra Nevada mountains was used by white settlers for building and ornamental stone and in the linings and foundations of furnaces (Anon. 1956). Previous to 1916, the annual recorded production in California did not exceed 2000 tons. In the period 1912 to 1918, output rose sharply when the Talc City, Western, and Silver Lake mines were put into operation. From 1916 to 1935, the state's annual output of talc was in the range of 9,000 to 20,000 tons. In the mid-1930s, the use of talc in wall tile grew rapidly. In California, the production of talc grew to 63,000 tpy in 1943. The post-war building boom helped California production to grow to 120,000 tons in 1951. In 1968, production was 165,000 tons, 1969 was 145,000 tons, 1970 was 185,000 tons, and 1972 was 155,000 tons. Talc mining in New York state dates to about 1878 when a Colonel Palmer and associates opened the first commercial talc mine on the Nelson Freeman farm near Talcville, New York. In 1893, this operation was sold to the International Pulp Co. which changed its name to the International Talc Co. in 1944. Total production from seven New York mines, in 1948, was 130,000 tons. A new talc operation, the Gouverneur Talc Co. owned by the R.T. Vanderbilt Co., began operations near Balmat, N.Y., in 1948. The initial capacity of the processing plant was 200 tpd (Gillingham, 1950). Subsequent expansions have increased capacity to over 600 tpd. The Vermont talc industry began just after the start of the 20th century. Talc was discovered in the area of the present Johnson, Vt., talc mine in 1902. The American Min¬erals Co. initiated plant operations at Johnson in 1904. The Magnesia Talc Co. opened a plant at Waterbury, Vt., in 1913 (Burmeister, 1963; Trauffer, 1964) and acquired American Minerals Co. in 1923. The Waterbury mine has a long history as a producer of talc crayons. The Eastern Magnesia Talc Co. was formed in 1924 by a merger of the Eastern Talc Co.

Jan 1, 1975

By N. M. Levine, W. M. Fassell

In this laboratory study the problem of aerative conditioning to separate chalcopyrite and pyrite from cobaltite was simply effected with a sulfy-drate collector and pH by proper choice of mixing variables. It was shown that for a given impeller type and geometry, selectivity is governed by a relation between the Froude number and a modified power number multiplied by impeller tank-diameter ratio wherein the power factor is expressed as power intensity or horsepower per unit volume of contained pulp. In applying this approach to other systems, other criteria would be used in place of selectivity. The purpose of this paper is to show how solutions to problems of aerative conditioning of pulps may be enhanced by development of mixing parameters in a given system through application of a fundamental approach to agitation. The term aerative conditioning refers to a combination of processes which include mechanical gas dispersion, gas solution in the liquid phase, transport of dissolved gases and other reactants to the reaction zone, physico-chemico interaction within the liquid phase and/or at the solid surface, and, finally transport of products away from the reaction zone. Important elements of these processes are: 1) Air-Liquid Contact Area: This area limits the rate at which a given gas may dissolve in a given liquid. Thus, an aerative conditioning system should be designed for optimum gas dispersion. 2) Diffusional Factors: Such factors as concentration gradient, diffusion film thickness, and diffusivity may govern the rate at which dissolved constituents are transferred to the zone of interaction at a particle surface and the rate at which reaction products are transported therefrom. Thus, such systems would be designed for maximum turbulence to effect good mixing and to minimize diffusion film thickness. 3) Solids-Turbulent Liquid Contact Time: Sufficient time should be provided for interactions to take place at solid-liquid interfaces. The region of maximum turbulence for mechanical systems being in the impeller zone, it is important that the number of passes through this zone be optimized. This means that a proper balance should be struck be- tween flow and turbulent power to achieve optimum conditioning time. Too high a flow rate and insufficient turbulence may be improper if the reactions are diffusion limited. On the other hand, too much turbulent power and too little time in the reaction zone due to insufficient flow power may also be limiting. 4) Geometry and Impeller Design: The design of the conditioning vessel and the type of impeller employed are important factors in determining the relative distribution between flow and turbulent power and the degree of gas dispersion. Maximization of power input would be to no avail if the distribution between flow and turbulent power were improper or gas dispersion insufficient. 5. Physical Chemistry: The reactions between dissolved gases and solid surfaces may be limiting if gas solubility, activation energies and/or free energies are not favorable. J. H. Rushton, E. W. Costich, and H. J. Everett' have summarized the mechanical elements of the combination of processes listed in a fundamental mixing equation. This equation was derived by dimensional analysis and relates the physical variables for a single impeller, centered in a cylindrical, vertical axis, flat-bottomed tank. It is, where T is tank diameter in feet; H is liquid depth in feet; C is height of impeller off tank bottom in feet; S is pitch of impeller; L is length of impeller blades; W is width of impeller blades; R is number of baffles; D is impeller diameter in feet; Np is the power number, pg/dN3D5; P is power in foot-pounds per second; g is the gravitational constant, feet per second; J is width of baffles; B is number of im-

Jan 1, 1961

By J. Szekely, V. Stanek

Steady state heat transfer and fluid flow rates are predicted for the counter-current contacting of gas and solid streams. For a .fixed pressure drop across the bed the convective heat transfer rate is affected by the gas flow rate, which in turn is affected by the temperature distribution in the system. Variations in bed voidage and in particle size were found to change the predicted temperature profiles quite markedly, in particular when the thermal capacities of the gas and solid streams were equal. IN Part I we examined the effect of step and pulse changes in the inlet gas temperature on transients in the flow of gases through fixed packed beds. Here we shall discuss heat flow and fluid flow interactions in the counter-current heat exchange between packed solids and a gas stream. Counter-current heat exchange in packed beds has been extensively studied. In his now classical paper, Furnas' assumed constant property values and developed a simple analytical. expression for the temperature profiles in the gas and in the solid stream. A highly sophisticated analysis of counterflow systems, allowing for transients and interparticle conduction was developed by Amundsen. In preparing a very readable review of this topic Elliott' also presented a number of elegant solutions, including the case involving heat generation. A great deal of work has been done on the application of these concepts to the modelling of the blast furnace. However, in all this previous work the mass flow of the gas was regarded as a quantity independent of the gas-solid heat exchange process. In the following we shall consider counter-current heat exchange between a gas stream and a packed bed of solids, under conditions where the pressure drop across the bed is specified, rather than the mass flow of the gas. FORMULATION Consider a packed bed, extending from y' = 0 to y' = L, in which moving solids and a moving gas are contacted in a counterflow arrangement. Let cold solids, with an initial temperature Tsi and mass flow GA, enter at y' = L, and hot gas with an initial temperature of Tgi and mass flow Gg enter at y' = 0. In contrast to the problems considered in Part I this system has a nontrivial steady state and we shall restrict our attention to the study of the pressure drop flow relationships and the resultant temperature distributions for steady state conditions. Under these conditions the formulation of the problem requires the statement of the following: 1) heat balance on the gas 2) heat balance on the solids 3) the mechanical energy balance equation and in addition the knowledge of the equation of state, and a functional relationship between viscosity and temperature and an expression for the heat transfer coefficient in terms of the other parameters. On neglecting temperature gradients within the solids and for a constant mass flow of the gas, the solution to this problem is well known.'" The expressions for the temperature profiles of the gas and solid streams may be put in the following form: where Tg and T, denote the dimensionless gas and solid temperatures respectively, y is a dimensionless distance, and R is the ratio of the thermal masses. These quantities are defined as follows: For the particular case of equal thermal mass capacities by the gas and the solid, that is R = 1, the Eqs. [1]and[2] simplify to Eqs. (71 and[8], respectively: i.e., the resultant profiles are linear. As for most practical cases , solutions given by Eqs. [7] and [8] will contain only the inlet temperatures as parameters. For a fixed, predetermined value of C;b the above

Jan 1, 1970

By R. E. Collins

The existence of fluid migration across fixed boundaries in oil and gas reservoirs has been known for many years. Several techniques have been developed in the past for estimating The rate of migration across fixed boundaries as an aid in planninng field development and in the valuation of oilfied properties. The principal de/errc7nt to the use of these techniques lies in the rather extensive reservoir and field data required for ca1cula1ion.s of fluid migration. For this reason, a new, simplified procedure has been developed which makes possible the calculation of fluid migration with a minimum of field and resrvoir data. This new technique is based on certain. solutions of the differential equations describing flour in the reservoir which assume, for the portion of the reservoir of interest, that the formation can be approximated by a homogeneous rock of uniforrn thickness, that only a Single mobile fluid phase exists, and {hut fluid production at the well is solely a result of expun.rioti of rile resersoir fluds. The results of the, present work are compiled in a set of curves. These curves can he used to calculate both rule and cummulative fluid migration when the abovc assumptions ore ju.r/ifiril. The only data required for such calcu1ations are the production hisrories of all wells in the field, the permeability and porosity of the reservoir., the, compressibility and viscosity of the fluid. and the shape of the reservoir, INTRODUCTION The migration of fluids across fixed boundaries in oil and gas reservoirs has long been recognized as an engineering and economic problem, but no methods for estimating the extent of migration during the development stage of a reservoir have been published. The investigation reported here has been directed toward providing a simple technique for estimating the extent of such migration and has therefore been restricted to the simple case of a homogeneous reservoir of uniform thickncss containing compressible liquids. It is assumed that only a single mobile fluid phase exists and that fluid production at the wells is solely by expansion of the reservoir fluids. Obviously, few, if any. reservoirs conform to these assumptions during their entire productive life. On the other hand, most reservoirs approximate fluid expansion reservoirs during their initial stages of primary production. Consequently, the present work should be applicable during the field development of most reservoirs, regardless of whether or not they ultimately are gas cap, dissolved-gas, or water-drive reservoirs. The mathematical analysis of this problem has been outlined in the Appendix, while the results of the investigation are presented in the following discussion. DISCUSSION OF CALCULATION PROCEDURE SLNGLE Well, Ini-iimite Reservoir The procedure for calculating fluid migrations is based on solutions of the partial differentia1 equations describing the flow of a homogeneous compressible liquid in a homogeneous reservoir of uniform thickness. This differential equation has the form of the well-known diffusion equation. The equation, as applicable to our problem, is where p is fluid density, is porosity, EL is viscosity, c is compressibility,* and k is permeability; .r, y and t are the space coordinates and time. Derivation of this equation is given in the Appendix. The analytical solution of this equation for a single well of negligible radius producing at a constant rate. q, from a reservoir of infinite areal extent for a time, 1. can he readily obtained. From this solution the rate of flow and also the cumulative flow across a straight line segment of length, 1, at a perpendicular distance. 6. from the well can be computed. One end of the line must be on the perpendicular joining the well to the

By L. O. Storey

The McDermitt mine was found as a separate mercury ore-bearing occurrence approximately 305 m (1000 ft) northeasterly and in a different geologic setting from the old Cordero mine, which had been the district's major producer. The following briefly describes the discovery of the new deposit and the Placer Amex lnc. involvement. The Cordero mining property was under lease by Sierra Mineral Management from the owner Fred H. Lenway in February 1971, when the property was brought to the attention of Placer Amex Inc. (known at that time as American Exploration and Mining Co.) by Richard F. Hewlett of Sierra Mineral Management. The property was first examined by Amex geologists in the spring of 1971, who reported favorably on the project. During that year, Sierra Minerals Management had retained Dr. Larry Walters as a consultant. He proceeded to drill test mercury soils anomalies which he had found northeast of the old Cordero mine in an area overlain by recent alluvium and gravel. An area known as the D area was subsequently blocked out and ascribed a tonnage of about 18 1 kt (200,000 st) which occurs in the vicinity of the eastern edge of the currently defined McDermitt ore body. This mineralization was found in flat lying mercury-bearing lakebeds, unlike the steep structurally controlled ore which was mined in the old Cordero mine. It became apparent to Placer Amex that since the chances of much more extensive ore were good in such a geologic environment, additional exploration was warranted. A joint venture was formed in October 1972 by American Exploration and Mining Co. and Sierra Mineral Management to further explore the Cordero property. The project exploration was fully funded and managed by Amex. Sampling began by Placer Amex in the D area where an open trench had exposed the lakebed ore. Visible cinnabar could not account for the high-grade mercury assays taken from the trench, and an unknown mercury mineral was suspected. Subsequent work established the presence of a chlorine-bearing mercury sulfide which may have enriched the lakebeds as a secondary supergene mineral. Early identification of the mercury-bearing mineral corderoite (Hg3Cl2S,) aided in the geologic concepts for the ore occurrence and was helpful in exploring for the expansion of the D area. Corderoite was found occurring with cinnabar in the lakebeds, and in places it is a major contributor. Specimens of the unique ore were given to Dr. Eugene E. Foord and Dr. Pieter Berendsen at Stanford University, who subsequently identified the chemical and crystallographic makeup of the new mineral and described it for the first time as a naturally occurring substance. Metallurgical work on mercury recovery from the newly described mineral was carried out by the Placer Development Ltd. laboratories in Vancouver, and an acceptable recovery system was worked out together with a planned mill design. Step out drilling from the D area by Placer Amex Inc. encountered extensive flat lying lakebed ore. The McDermitt ore body, as subsequently defined by drilling, was found to contain 2.7 Mt (3 million st) of open pittable ore, containing approximately 5 kg/t (10 lb per st) Hg. The ore body gently dips to the north and is found lying mainly in claybeds just above an opalite breccia blanket which overlies the earlier volcanics. Some ore is also found in the opalite breccia. The mine and mill were constructed under an operating joint venture with Placer Amex Inc. and Sterling Mineral Ventures, and production began in June 1975 at the rate of 20,000 flasks per year. The mine is currently in progress.

Jan 1, 1985

By Leonard R. Weisberg

The general properties of diffusion in GaAs are reviewed. A total of .fourteen atoms have been studied to date, and activation energies for eleven reported are (in ev): Ga (5.6), As (lo), Zn (2.49), Cd (2.43), Sn (2.5). Mn (2.75). S (4.0). Se (4.2). Ag (0.33), Cu (0.52). and Li (1.0). The dijfusion of the first eight atoms, as measured by Goldstein using radiotracer techniques, established the principle of sub lattice diffusion for both host and impurity atoms, since atoms substituting for gallium have lower activation energies than those substituting for arsenic. The diffusion constant of interstitial copper has been determined for the first time by Hall and Racette using heavily doped p-type samples in which interstitial copper predominates. The anomalous behavior of zinc, which has an abrupt diffusion front and a strong dependence on zinc concentration, has recently been quantitatively explained in terms of an interstitial-substi-tutional equilibrium-diffusion mechanism. Lithium and silver diffuse mainly interstitially, while the diffusion of phosphorus is complicated by the continual formation ofGap. Junction-migration measurements indicate diiferent results than radiotracer techniques, and this is one problem that still remains, together with discrepancies in cadmium-diffusion results, and an unexplained dependence of impurity diffusion on arsenic pressure. BESIDES the usual insights into the behavior of atoms in solids, studies of diffusion in semiconductors have additional importance for device applications. In fact, the amount of diffusion studies performed on a semiconductor might serve as a simple barometer of its technological importance. Thus, the information accumulated for GaAs is not yet quite comparable to that for germanium or silicon, but considerable knowledge is available. The diffusion of at least fourteen atoms has been investigated for GaAs, and the diffusion constants have been determined for eleven of these. Interesting results were found for GaAs that elucidated problems not previously solved for germanium or silicon. For example, the interstitial-diffusion constant for the very fast diffusant, copper, was first measured in GaAs. Also, solutions for interstitial-substitu-tional equilibrium diffusion in extrinsic material were provided first for GaAs, although they are ap- plicable to germanium, silicon, and other semiconductors. Studies in GaAs firmly established the concept of sublattice diffusion, which should have application in many different compound systems. The purpose of this paper is to review briefly the general state of knowledge concerning diffusion in GaAs. First some general aspects of diffusion will be covered, and next attention will be given to the results mentioned above. Diffusion in GaAs has been measured both by radiotracer and junction-penetration techniques, and some discussion will be given of differences in the two sets of results. The comprehensive work of oldsteinl-' has served as the primary reference for the diffusion of well-behaved substitutional atoms in GaAs. Since a review has recently been presented of many of these reults, details of the diffusion data will not be repeated. Neither will any discussion be given of the experimental techniques of diffusion measurements, except to note here, in passing, the simplicity and effectiveness of the precision lapping device employed by Goldstein.' I) EXPERIMENTAL RESULTS AND DISCUSSION A) Summary of Experimental Results. Diffusion constants D = Do exp(E/kT) have been determined for eleven atoms in GaAs: a,' AS,' n,'" Cd,'" n,' n,8 s, e,' Ag,O CU," and i." These results are summarized in Table I. In addition, diffusion was investigated for phosphorus,4'12 germanium,I3 and ilicon,' but Do and E were not determined. Radiotracer techniques were used for most of the studies except for lithium, where a combination of chemical and electrical techniques was employed, and germanium and silicon, where junction-migration techniques were applied. The diffusion of zinc, manganese, sulfur, and tin was also measured using junction migration.13'14 Goldstein demon-

Jan 1, 1964

By R. J. Weege, A. W. Schillinger

Conventional underground mapping methods and diamond drilling are being applied in a study to determine the nature of the copper ore occurrences near the footwall of the Osceola lava flow top, commonly referred to as the Osceola Amygdaloid. The work to date suggests that structures formed by relatively impermeable barriers, created by flowage and injection of still-molten lava from the interior of the flow into the solidified, brecciated crust, acted as the ore receptacles. Ascending hydrothermal fluids traveling near the footwall contact were trapped and confined in these barriers which retarded the direct upward movement of the ore fluids and caused deposition of copper. Oreshoots located near the footwall appear to have been formed spatially independently from the hanging-wall oreshoots by fluids traveling simultaneously, but along different channelways. The barrier concept, as advanced by earlier writers to explain the concentration of the ore-bearing fluids into broad shoots constituting entire ore bodies, is found to be equally as applicable for the localization of smaller oreshoots within the Osceola ore body. Recently, the Calumet Division of Calumet and Hecla, Inc. completed the unwatering of the old mine workings on the Osceola amygdaloid. Two shafts were subsequently reactivated and mining commenced on the Osceola lode after an idle period of over 20 years. Early in 1961, the Calumet and Hecla Geological Dept. was assigned the task of locating additional reserves. Accordingly, an intensive mapping and underground diamond drilling program was initiated. Except for a very few years following the first mining on the amygdaloid, the Osceola lode had never been a high grade producer. It was, therefore, recognized from the onset that a concentrated effort would have to be made by the mining, milling, and geological departments to insure success of the project. Company reports contained many references to ore that had been located near the footwall of the Osceola amygdaloid. Information concerning the grade of this ore was meager, but it was known that at least some was very rich. In contrast to ore that occurred near the hanging-wall, however, the footwall copper did not appear to have a systematic distribution and a large amount of poor rock had to be removed in developing this ore. This, of course, resulted in high development costs and discouraged any extensive mining of footwall ore. The possibility of more continuity than had previously been suspected was recognized by other workers, in particular Dr. T. M. Broderick, formerly Chief Geologist of Calumet and Hecla, who suggested attempts be made on a trial basis to follow the footwall contact with the main development drift. As most mining was done on the Osceola lode before a geological department had been established by the company, and almost all of these openings are now caved, very little information concerning the geology of footwall ore was available. It was, therefore, decided that the first step in the exploration program would be to become familiar with footwall ore occurrences by mapping the geology as the openings were driven. It was possible that a mapping program would reveal the features that controlled the localization of the ore. Furthermore, if it could be shown that footwall ore was more continuous, or if its distribution was more systematic than generally believed, it would be possible to produce a high grade ore that could be blended with the lower grade hanging-wall ore. In connection with the geological program, the Michigan College of Mining and Technology Geophysical Dept. under the direction of Professor Lloyal Bacon, is making a geophysical study of the problems of locating footwall ore by electrical methods. GENERAL GEOLOGY OF MICHIGAN NATIVE COPPER DEPOSITS The native copper deposits of Michigan are located in Keweenaw, Houghton, and Ontonagon Counties. The host rocks are Keweenawan in age and are comprised of interbedded sediments and lava flows which form a belt two to four miles wide and over one hundred miles long. These rocks form part of the south limb

Jan 1, 1962

By D. R. Mash

A strong yield point with attendant enhanced mechanical properties was found in commercially pure beryllium under certain conditions of heat treatment. Beryllium specimens also responded to both quench and strain aging treatments. Based on these results, a possible means of obtaining increased normal temperature mechanical properties is suggested. COMMERCIALLY pure beryllium has been found to exhibit the yield point phenomenon and several other aging manifestations under certain conditions of heat treatment. This behavior is not surprising in view of the present accumulation of experience regarding such effects in numerous metals; but in addition to extending this experience to include beryllium, the present study is of interest because aging effects are generally associated with the presence of small amounts of solute elements. The well known lack of tensile ductility in beryllium at normal temperatures is also considered to be due to impurities in some way. In the present investigation, the view was taken that beryllium of commercial purity (greater than 98 pct) should be considered as a dilute alloy and that precipitation phenomena may well exist which could lead to enhanced mechanical properties. In connection with this possibility, published data on the variation of mechanical properties with temperature are of interest. For example, Fig. 1 illustrates the variation of ductility (percentage of elongation) and ultimate strength as a function of temperature for beryllium of various histories.* Although these curves are somewhat schematic in nature, they clearly indicate the possibility that precipitation of an unstable phase and/or aging effects occur during tests in the region 400" to 700°C. The existence of such behavior should be recognized as affecting the properties of the commercial material and perhaps can be employed advantageously. Experimental Method All testing was done at room temperature using a Baldwin universal testing machine. A microformer extensometer was used in conjunction with a micro-former-type stress-strain recorder. All tests were conducted at constant loading rate, the slowest rates being used. This corresponded to 120 lb per min in the 1200 lb full scale range and 300 lb per min in the 6000 lb full scale range. After the rate of loading was set in the elastic range of the material during the early part of the test, no further adjustments were made, allowing the test to proceed at that setting. In the plastic region of the curve above the yield region, strain rates of from 0.002 to 0.006 in. per min were regularly obtained. All experimentation was carried out on specimens machined from the same lot of beryllium, lot No. Y5036BP. Table I shows the chemical analysis as furnished by the supplier, Brush Beryllium Co., as well as the standard specifications to which commercial beryllium is produced. Both 1/4 in. thick hot pressed plate and ½ in. round hot pressed and warm extruded rods were obtained. The history of the material is reported to be as follows: 1—Beryllium metal plates, produced from a standard hot pressed QMV beryllium metal block 4x15x40 in., were cut off and finished machined to 1/4x6x12 in. flat plates. The original hot pressed block was made by hot pressing —200 mesh vacuum cast attri-tioned powder at about 1050°C under vacuum. 2—Beryllium rod was hot pressed and warm extruded. Extrusion billets were machined from the regular hot pressed blocks followed by extrusion at 425°C. The extrusion was done without jacketing, and graphite was used as a lubricant. The rods were then straightened at 720 °C, after which they were annealed at 800°C for 15 min. Both flat tensile specimens and round tensile specimens were tested. The former were machined from the plate stock into standard specimens according to specifications shown in ASTM E8-52T. The nominal cross-section was 0.25x0.500 in. and the gage length was 2 in. The round specimens were

Jan 1, 1956

By R. J. Wagner, Jim Douglas Jr., P. M. Blair

The calculation of the behavior of an oil reservoir during a water flood has long been an important problem to reservoir engineers. Buckley and Leverett derived the differential equation which describes the displacement of oil from a linear porous medium by an immiscible fluid, but this equation could not be solved by the methods of classic mathematics. Consequently, in order to integrate the equation over the length of the reservoir, they neglected the effects of capillary pressure. In the present paper, a numerical method has been developed for determining the behavior of a linear wafer flood with the inclusion of capillary pressure. The differential equation which was derived for the case of incompressible fluids is second order and non-linear. This differential equation was approximated by an implicit form of difference equation which is second order correct in both time and distance. An electronic digital computer was used to perform the numerical solution of the difference equation. INTRODUCTION The problem of calculating the flow and distribution of fluids in an oil reservoir subjected to a water flood has long challenged the reservoir engineer. The ability to solve this problem would provide a valuable tool for the design and study of field waterflooding programs. One of the first contributions in this field was made by Buckley and Leverett,'.' who developed a method of calculating waterflood performance in a linear reservoir. Their technique was limited by the practical necessity of excluding quantitative consideration of capillary pressure. It is the purpose of this paper to describe a method for calculating the behavior of a linear water flood with capillary pressure considered. This method, although limited to the linear case, should serve as a step toward the solution of the two- or three-dimensional waterflooding problem which would better describe actual reservoirs. The treatment of the problem has assumed that the reservoir is linear and homogeneous, that both oil and water -are incompressible, and that gravitational forces may be neglected, and that water is injected into one end of the reservoir and oil and water are produced from the other. Though these assumptions may not be directly applied to natural reservoirs, they are closely approached in many laboratory core tests. The physical problem has been represented mathematically by means of a differential equation and suitable boundary conditions. The inclusion of capillary pressure effects causes the differential equation to be second order and non-linear, and it is not amenable to solution in terms of known functions. Nevertheless, the problem may be solved by numerical methods. The authors have successfully calculated several cases from the start of water injection through to depletion of the hypothetical reservoir using realistic capillary pressure and relative permeability characteristics that were chosen so as to put the method to a test. DIFFERENTIAL EQUATION In two- or three-dimensional problems involving the two-phase flow of incompressible fluids through a porous medium, the equations describing the flow can be combined until only two dependent variables remain, the pressure in one phase, and the saturation of one phase. These variables appear in two simultaneous partial differential equations which are derived on the basis of the conservation of mass and Darcy's law as applied to two-phase flow. For a linear reservoir, this system of differential equations can be reduced to a single, nonlinear, second order, parabolic differential equation for one dependent variable, the saturation of one phase. For incompressible water and oil, it can be shown that the conservation of mass for the two phases requires that Where q, and q, are the water end oil flow rates per unit cross-section, s, and so their saturations, +, the porosity, and [ and T, dimensional space and time variables. Darcy's law, as extended to two-phase flow including the effect of capillary pressure,' is as follows:

By Frank J. Tolonen, Nicholas H. Manderfield, Paul Jasberg

EARLY in the study of the low grade iron formations of Michigan, wide variations in their structure and texture became evident. Because of these variations no simple method of concentration is possible, and those portions of the formations that can be exploited profitably under a given stage of metallurgical progress and existing economic conditions must be searched for carefully. Both structure and texture of the formations have an important bearing on their amenability to bene-ficiation. By structure is meant the banding planes of easy fracture, the porosity, and the degree of leaching. Texture, which includes grain sizes, shapes, and degree of interlocking, determines the amount of grinding necessary to liberate the mineral grains. Structure determines the liberation of portions richer in one mineral. Structure and texture may be termed the gross features of the formation. Earliest surveys of the formations were conducted to outline the parts that could be concentrated at % in. (3 mesh). Operators agreed on this size because anything finer required sintering or other agglomeration processes. At 3 mesh only the structural features, as defined above, would be liberated. With suitable ores concentration was easy, as any of the gravity methods could be used. Sink-and-float gave good results, but with this method only limited portions of the iron formations yielded a desilrable product.1,2 n general, the iroa content could be raised to shipping grade, but the silica content remained too high—sometimes 20 pct—instead of 9 or 10 pct. Grinding did not greatly increase the liberation ofsilica until 2010 mesh or finer was reached. To find the reason fpr this T. M. Broderick began micros~opic examin'ations of the formations in 1933.3 Procedure: The purpose of this discussion is to correlate the appearance of typical portions of the iron formations with their amenability to concentration. As liberation is essential before separation becomes possible, much of the work is based on measuring the liberation achieved by crushing and grinding. Both heavy media and magnetic tube tests were used in this work. On the basis of general structural features such as banding, degree of alteration, and leaching, a specimen was selected from each part of the iron formations studied. The specimen represents the gross features of the formation and not necessarily the particular formation quantitatively. One half of the specimen was polished for macro-study, and the remainder was used for analyses to obtain the grades represented by variations appearing in the macrosection. Specimens for microscopic examination were also prepared for each variation in gross appearance. For correlation of microstructure with liberation, the previous work by sink-and-float methods was supplemented by magnetizing roasting followed by magnetic separation. The results show the liberation of silica to be very important at the sizes used, because any silica particle with iron minerals occluded would be held in the concentrate. A magnetizing roast changes the crushing and grinding character of the sample. For partly leached soft samples the change is slight, but with harder types and those in which there is a considerable change in crystal structure of the minerals, the increase in liberation of the iron minerals may be 30 pct more than that of unroasted samples at the same crusheH size. Gogebic Range Iron Formations: The Gogebic Iron Range is located in the extreme western and southern parts of Michigan's Upper Peninsula, extending westward into Wisconsin. Samples for this study were obtained from the Ironwood formation, comprising three chief members—the Plymouth, Norrie, and Ahvil—with several intermediate slates and thick overlying slates. (The slates are not considered in this discussion because grinding finer than present practice is usually required to liberate the iron minerals.) The predominant iron mineral is hematite, about half of which is hydrated to goe-thite. Limonite occurs in some of the partly leached areas, and siderite in parts of the formation.

Jan 1, 1958

By C. Chu

A theoretical investigation has been made of the forward combustion process using a one-dimensional linear mathematical model, taking into consideration the effect of the vaporization-condensation which occurs on the leading edge of the heat wave. This work involves the solution of five coupled partial differential equations. Besides the vaporization-condensation phenomenon, these equations account for conduction, convection, combustion, heat loss, diffusion and bulk fluid flow. For the one-dimensional linear model studied, the vaporization-condensation phenomenon does not induce appreciable change in the temperature at the combustion front; and its primary effect is to create a steam plateau and to increase the length of the heated zone ahead of the combustion front. This effect becomes more pronounced at lower pressures, higher porosities or reduced gas saturations. The peak temperature and the temperature profile on the leading edge of the heat wave stabilize after a certain period. The length of the steam bank remains practically constant, although the length of the water bank increases as the heat wave advances. INTRODUCTION The existence of the vaporization-condensation phenomenon in the heat-wave process and the important role played by the phenomenon have been recognized by several investigators. Kuhn and Kochl stated that steam plateaus were frequently observed on the temperature records of their experiments. The steam plateaus were attributed primarily to the vaporization and subsequent condensation of the interstitial water existing in the oil sand. Szasz2 suggested that both lighter hydrocarbons and water are vaporized on the leading edge of the heat wave, carried forward in the gas stream, and then condensed to create banks of oil and water. Martin et al suggested that the vaporization-condensation phenomenon is one of the main mechanisms of the heat-wave process, along with thermal expansion and viscosity reduction. Wilson et al. reported the existence of a steam plateau several inches in length in their small-scale tube-run experiments. However, this important phenomenon has never been taken into consideration in the numerous theoretical analyses by various authors. 5 The purpose of this work was to study the thermal aspects of a linear heat wave, taking into consideration the vaporization-condensation on the leading edge of the wave, to determine the effect of this phenomenon on the temperature profile of the reservoir, and to investigate how this effect varies when other process variables are changed. THEORY We consider a reservoir of porous medium of cross-sectional area A, extending from x = 0 to x = L. This reservoir contains, aside from the solid matrix itself, a gas phase and a "combined liquid phase" which is a combination of two immiscible liquid phases — namely, an oil phase and a water phase. The oil present in the reservoir is assumed to consist of three fractions, a noncondensable gas, a nondistillable residuum, and a vaporizable oil fraction which may be present in both the gas phase and liquid phase. Before the heat-wave process begins, preheating has taken place and has imparted an initial temperature distribution T,(x) to the reservoir. At the start of the process, a stream of oxygen-bearing gas is introduced through the face at x = 0. This gas supports the combustion of the residual fuel and supplies the heat throughout the process. In order to develop a tractable system of equations, the model properties are postulated as follows: (1) the system is isotropic and homogeneous; (2) there is a uniform fuel content throughout the reservoir; (3) combustion takes place in a moving vertical planar region of infinitesimal thickness; (4) the temperatures of the fluids and the solid matrix are identical; (5) radiation is negligible; (6) the gas and liquid saturations are uniform throughout the reservoir and remain unchanged

Jan 1, 1965

By Tasuku Fuwa, John Chipman, David H. Kirkwood

Fe-C-Si alloys in silica crucibles were held at 1600°C in a controlled atmosphere of CO and Co2 and the approach to equilibrium was obsertsed. Results were not of sufficient precision to establish the activity and interaction coefficients. Observations 012 the equilibrium provided an average value for the standard free-energy change which differed by + 1.1 kcal from the earlier accepted value. The C-SL relation at other temperatures is calculated and shown graphically. IN the refining of steel in an acid-lined furnace, it is well known that, unlike in basic refining, a very significant amount of silicon may remain dissolved in the metal even when the carbon content approaches a final endpoint. Further, it is known that the residual silicon increases with increasing temperature. The quantitative relation between silicon and carbon can be calculated for equilibrium conditions from data already available on the Fe-C-O and the Fe-Si-O systems. Such equilibrium calculations could show us approximately the limitations within which the reaction would be expected to operate in practice. In the oxidation of a bath containing both carbon and silicon it is well known that at low temperatures silicon is preferentially oxidized first. It can be shown by calculation that at high temperatures carbon will be oxidized preferentially. It is the purpose of this paper to record direct observations on the Si-C relation by means of experiments carried out in an atmosphere of carbon monoxide for Fe-C-Si alloys contained in silica crucibles. When such a system is brought into equilibrium, at a fixed temperature, the composition of the liquid metal is governed by the following equations: Both K1 and K2 are known with a fair degree of accuracy, and may be calculated from the tabulated In general the percentage of CO2 is extremely small compared to that of CO and in the experiments to be described the partial pressure of the latter was generally only slightly below 1 atm. EXPERIMENTAL METHOD The induction furnace employed was the same as that described by Rist and chipman' and by Fuwa and chipman.2 It was modified slightly in view of the change from alumina to silica crucibles. The small silica crucible was surrounded by a thin susceptor of molybdenum sheet which in turn rested inside a zirconia crucible. Since the zirconia was subject to breakage, it was supported inside an alumina crucible. The charge consisted of 30 to 35 g of electrolytic iron along with the required amounts of refined silicon and graphite to produce a melt of required composition. Purified carbon monoxide and carbon dioxide were passed into the furnace through carefully calibrated flow meters. Two separate and independent series of experiments were carried out. In Series I (D.H.K.) the melt was held in the furnace at 1600°C for periods of time up to 6 hr. Samples were taken at intervals in silica tubes and were analyzed for carbon and silicon. The results of the last one or two samples taken from each experiment and the direction in which equilibrium appeared to be approached are shown in Table I. In Series II (T.F.) the silica crucibles were of less satisfactory strength and the melts were held at 1600° C for periods of only 2 to 4 hr. In heats number 29 to 45 inclusive, the metal was cooled in the furnace and the ingot itself served as a sample for analysis. In heat 46 and all subsequent heats, samples were withdrawn in silica tubes at the termination of the heat, and these samples were analyzed. The results of all of these experiments in which equilibrium appeared to be approached are listed in Table II.

Jan 1, 1965

By J. Fageant, W. C. Ellis

All major regions in a progressively solidified germanium ingot were related through successive orders of octahedral twinning. The occurrence of lineage structure and the generation and survival of orientations are discussed. WHEN metals solidify in a temperature gradient a preferred orientation, or casting texture, usually develops. For example, in face-centered and body-centered cubic metals, most of the solidifying crystals have a cube axis, <loo>, aligned approximately in the freezing direction.&apos; In the solidification of diamond cubic metals this is not the case, since there is a natural tendency to form twin orientations.&apos; . In this paper, twinning relationships in cast germanium are described; some conclusions with respect to nucleation and survival of new orientations are discussed. In the first experiment, an ingot of high purity germanium, % in. in diameter and 1 % in. in length, was formed by progressive solidification4 from the bottom. The ingot was cut into 21 slices, each circular and about 0.030 in. thick. The top surface of each slice was polished and etched to reveal the regions of different orientations. Orientations were determined by the Laue X-ray back-reflection method. The uncertainty in the determined orientation relationships was l" or 2" when separate slices and films were involved. Frequently, however, advantage was taken of illuminating across a boundary when the patterns of the two orientations were recorded on the same film. The uncertainty then was less than 1". Often the twin relation was evident from common zones or individual reflections. Twin relationships were recognized through comparison of the values of the nine angles between cube poles of the two orientations with those calculated for successive orders of octahedral twinning. The birth and survival of each region can be reconstructed by visual examination of the etched slices shown in Fig. 1. In slice 21, where solidification began, many regions are present; these regions were found to be twin-related. Solidification appears to have started from one nucleus formed probably at the wall of the crucible.* Subsequent ori- entations were developed by nucleation on existing solid surfaces, and only in the twin relationship. This is an example of a general process of nucleation on a surface of existing solid and may be descriptively termed oriented nuc1eation.t In germanium, and other diamond cubic substances, the orienting habit is that of twinning on an octahedral plane.&apos; " The prevalence of straight traces in the polished surfaces of succeeding slices (Fig. 1) suggests that the twinning observed in the first slice persisted throughout solidification. This was confirmed by X-ray determinations. The schematic diagram of Fig. 2 shows the twinning relationships of the major regions throughout the ingot. Since all observed relationships are describable as twinning, it is reasonable to conclude that no random nucleation occurred in the freezing of the ingot. An alternative possibility would be that nucleation of a random nature occurred, but only those nuclei in twin orientations survived in subsequent growth. This is unlikely for there would be as good a reason for the growth of randomly oriented nuclei as for the growth of the many different orientations present after several orders of twinning. The many twin components contain a wide distribution of orientations, and did grow. In fact, they are the only ones found in the solid. The conditions of solidification of this ingot were such as to discourage nucleation of crystals wholly in the liquid. The rate of solidification was 0.125 in. per min. This slow rate of heat removal afforded but small opportunity for supercooling within the liquid —a condition needed to provide enough decrease in free energy for such nucleation. When nucleation occurs on an existing solid surface, the interfacial energy between the existing and forming regions is important in determining the new stable orientation. The new orientation is expected to be one which minimizes this energy. In the diamond cubic structure, the interface for the

Jan 1, 1955

By Donald L. Johnson

REVIEWS on the applications of optical ellipsometry to the study of polycrystalline metal surfaces and oxidation-corrosion processes have been presented by Kruger and Hayfield, and white.&apos; In view of the ability of this method to measure differences in film thicknesses to below 10A, ellipsometry was used to study nitrogen chromium surface reactions during the early stages of growth. Chromium specimens in the form of a vapor-deposited film on glass substrate were exposed to purified nitrogen for selected time increments at 700°F. This temperature was selected because it gave the best combination of exposure time and thickness change. Ellipsometer readings were taken immediately after exposure to determine polarizer and analyzer angles using monochromatic light at 5000A.2 After each set of readings was obtained, the specimens were exposed for an additional increment of time in nitrogen and a new set of readings taken. Film thickness was computed from LUCy&apos;s3 equation for nonabsorbing thin films. In Lucy&apos;s derivation, two equations for computing thickness were obtained. Peterson and Bashara4 have discussed the validity for using one of these equations when an independent value of the refractive index is used. The film was assumed to be Cr2N (Ref. 5) and was determined to be optically isotropic. Optical isotropy was determined by rotating the films about the surface normal and noting that the azimuth and phase difference did not change. Since Cr2N is reported to be hexagonal, it is assumed that optical isotropy results from randomly oriented grains of very small size. The thickness was computed using refractive indexes varying from 1.6 to 2.0. The maximum variation in computed thickness over this range for a given exposure was 20 pct. The data reported are based on a refractive index of 1.8. Reference readings on the metal surface were taken just prior to nitrogen exposure. No attempt was made to deoxidize or denitride the metal surface after vapor deposition, although specimens were observed to gain approximately 2A per day in air at room temperature. Twelve experimental exposures were made on a single sample over a total accumulative time of 132 min. Additional experiments over longer time intervals were made to determine the effect of heat up and cool down during and after exposure. As a result of these experiments, the thickness computed for each exposure was increased by 4A. Time profiles based on the linear law are similar to the oxidation profiles for many metals.&apos; The rate of accumulation of the nitride film is rapid at first and slows down as the film thickness increases. The parabolic law x2 =k1t +k2 [11 gives a straight line in Fig. 1; therefore, it is concluded that the kinetic behavior is parabolic. Sey-bolt and Haman5 reported similar results for CrlN on chromium at 1000°C although the order of the thickness was much greater (10-3 cm). Analysis of thickness data based on other values of refractive index shows that the curves are shifted vertically but retain the same shape. According to Mott,7 it is expected that for thin films k2 is zero in Eq. [I]. Since the plot in Fig. 1 is linear through the origin, k2 is zero and the parabolic nature of the film growth is further indicated. The parabolic rate constant, calculated from the slope in Fig. 1, is 4.4 x 10-16 sq cm per sec. The corresponding work (+) required to bring an electron from the metal into the oxide is estimated to be 1.5 ev.7 The author thanks professor N. M. Bashara and D. W. Peterson, Electrical Materials Laboratory, University of Nebraska, for making the ellipsometer available and providing technical assistance. The Electrical Materials Laboratory is supported by the office of Naval Research, NONR 3718 (01). This work was partially supported by the Engineering Experiment Station and the Mechanical Engineering Department, University of Nebraska.

Jan 1, 1967

By Thomas C. Wilder

ALTHOUGH there is an abundance of thermodynamic information available in the literature today, no experimental data on the standard molar properties of formation of zinc oxide have ever been reported for the temperature range 419.5" to 908°C. This is the temperature range for which zinc metal is a liquid. so that the formation reaction is: Data have been reported for Reaction [I] where zinc is a solid or a gas. Maier. Parks, and nderson&apos; measured the electromotive force of the cell: in order to obtain the free energy of the reaction: over a limited temperature range. With the known properties of H2O, those of ZnO were calculated. These workers found that t;j of ZnO is -75,930 ± 150 cal per gfw and Mtf is-83,000 300 cal per gfw at 25°C. akolkin made similar measurements to obtain ilF7 and AH; of -75,870 and -82,540 cal per dw respectively at the same temperature. Truesdale and arirlg and Kitchener and 1gnatowicz4 measured the equilibrium of the reactions: respectively, in order to determine Ff of ZnO from the known values of CO, CO2, and H/X The thermodynamic properties of ZnO, presumably taken from the above investigations, are tabulated by Kubaschewski and vans&apos; and Wicks and Block" The latter reference also gives values for the range where zinc is a liquid. These numbers are probably acquired from the known extremities of the range plus Cp data of the components. In the present work the electromotive force of the cell: was measured in order to calculate the properties of ZnO from the well known values of NiO for the temperature range where zinc is a liquid. In Cell [B] the cathode reaction is: and at the anode: The overall reaction is: for which the free energy change is: where is the electromotive force in volts of cell [B] after correction for the Pt-Ta thermocouple. The standard molar free energy of formation of NiO is very well known as a function of temperature. Kiukkola and agner&apos;s data are used in most tabulations. The error is probably less than I00 cal per gfw, The latter authors were the first to use solid mixed oxide electrolytes in galvanic cells. Their work with NiO and other oxides was performed with cells similar to Cell [B] using a variety of reference electrodes of fixed oxygen potential. There may be a small composition range for which either NiO, ZnO or both exist. If nonstoichiometry does exist for these oxides, then the properties described herein are those for the metal saturated compositions. The simple cell design was the same as described elsewheres except that the molten metal electrode was about 125 g of pure zinc including a small (0.25 to 0.50 g) amount of ZnO. The mixture of pure nickel and NiO powders making up the reference electrode was contained in a tube of the ZrOl + CaO electrolyte which was immersed in the molten zinc. A platinum contact was made to the reference electrode; tantalum to the zinc. A refractory cement plug was necessary at the open end of the electrolyte tube in order to prevent zinc vapor from contaminating the reference electrode. Experimental details such as the vessel containing the cell, furnace, temperature control and measurement, and electromotive force determinations of the cell have all been outlined previously. The temperature was varied randomly in the range between the freezing and boiling points of zinc. After each temperature change, time was allowed for the drift at the new temperature to be less than +;"c whereupon a series of three cell readings was taken at least 10

Jan 1, 1970

By A. R. Marder

Fe-C alloys have been investigated at temperatures below the eutectoid transformation to determine whether the superplasticity phenomenon exists for these materials. As a result of void formation at the carbide-ferrite interfaces that led to void coalescence and premature failure, the large elongations characteristic of superplustic matem&apos;als did not develop. It had generally been assumed that the conditions for obtaining superplasticity include: a) T/Tm =0.5, b) a strain rate sensitivity of the flow stress that results in m s 0.3, and c) fine-grain structure. Although superphsticity was not observed in the alloys studied, stress-strain rate measurements indicated that an additional condition for the existence of superplasticitv in Fe-C allovs is that the fine-wain structure be equiaxed in agveement with previous results on Zn-Al al1oys. MANY investigations have been made on the hot deformation of iron-base alloys in order to obtain an understanding of the variables that may affect high-temperature strength and ductility.&apos;-6 However, only a few papers have studied the effect of carbon content on the high-temperature properties of iron-base alloys. Peretayat&apos;ko and Zaikov and Wallquist and carlen4 studied the effect of carbon on strength in the y temperature range, and recently Robbins, Shepard, and sherby6 studied the influence of carbon on the torsional behavior of iron in the a and cu-plus-cemen-tite temperature ranges. In addition to studying hot deformation behavior, current investigations have also been concerned with the phenomenon of superplasticity in nonferrous materials, and, in particular, ferrous alloys. Superplasticity is identified by the increased resistance to necking that results from a high strain rate sensitivity of the flow tress. ackofenr proposed the strain rate hardening coefficient m = d log a/d log e as a measure of strain rate sensitivity and showed that m must be "-0.3 for superplasticity to exist. In addition, a fine-grained microstrcture,- a eutectic or eutectoid ornosition,- and a test temperature in the creep range (TITm > 0.5)" have also been advanced as necessary conditions for superplasticity. Although many workers""23 investigated superplasticity associated with the allotropic transformation in iron and the eutectoid transformation in steel, and recently chadler " and orrison have studied superplasticity in the a - y phase region, no one has measured the superplastic effect in the a + cementite temperature region. Therefore, the purpose of this investiga- tion was to determine the effect of carbon content, microstructure, and test temperature on the strain rate sensitivity of Fe-C alloys at temperatures below the eulectoid transformation. EXPERIMENTAL PROCEDURE Fe-C alloys with carbon contents of 0.2, 0.4, 0.6, 0.8, and 1.0 wt pct were prepared as 100 lb 54 in. ingots by vacuum-induction melting. The compositions are listed in Table I. All the ingots were soaked at 2100°F for 2 hr prior to rolling to 4 in. plate. The minimum finishing temperature for rolling was 1800°F. The plate was sheared in 10-in. lengths and tensile bars were rough-machined prior to heat treatment. The samples were heat-treated according to the schedule in Table I1 in order to obtain a fine-grained microstructure consisting of finely dispersed carbides in a matrix of small ferrite grains. All the tensile specimens were heat-treated prior to finish machining, and tensile testing was accomplished on an Instron machine in conjunction with a clamshell furnace. The buttonhead specimen configuration is shown in Fig. 1. An inert atmosphere, helium, was maintained during testing with a steel tube shroud in a bell jar arrangement. Predried helium was continually purged over the buttonhead specimens and exhausted through ceramic fiber at the bottom of the tube to keep oxidation at a minimum and to prevent

Jan 1, 1970

T.P. 1958 D. H. DAVIS.*-Mr. Carris has ably pre¬sented the problems of coal preparation, particularly those brought about as the result of increased mechanical loading. Many mines are now crushing the run-of¬-mine raw coal through 12 or 15 in. immediately after it is dumped from the mine car and before it is handled by conveyors. At certain mines the removal of large slate mechanically has been solved by the installation of scalping screens consisting of bars or rails set at spacing of 12 to 15 in. on the top deck of the main raw-coal sizing screen. At the plants where these are in use, the plus 12 or I5-in. raw material contains 60 per cent or more free rock or slate, so that it is easier to pick coal than to pick rock. After the screening at 12 or 15 in. is accomplished, the oversize material is diverted to one side of the shaker, where a picker allows the refuse to pass off the shaker into a chute and guides the coal back onto the shaker. After the large rock has been removed, it is then advisable to reduce the size of rock by crushing before putting it onto a conveyor. A great saving in picking labor has been made by the use of such scalping screens, which in addition has maintained the plant capacity when handling a dirtier feed. The great increase in percentage of coal under 1/4 or 3/8 in., coupled with a greatly increased percentage of free impurities in this size, is the most serious problem that has been brought about by mechaniced loading. Many plants that formerly prepared good quality 1/4-in. to o or 3/8-in. to 0 slack by air¬cleaning are faced with installing facilities for wet-cleaning mechanical and heat-drying and water clarification. The change to wet prepa¬ration of fines usually affects the marketing problems for many coal companies. There will also be problems involving wastage of fine solids and stream pollution. Much work will be necessary for improvements in present practice. Pneumatic and electrostatic methods for cleaning fine coal should receive consider¬able attention in an attempt to avoid wet¬cleaning of fines. The preparation supervisor and the plant personnel should not be satisfied merely to run the cleaning-plant machinery and assume that the job will be done for them. Coal is a heterogeneous substance and in many instances is constantly changing. This is more true when full-seam methods are in use. Only persons trained to observe closely and make the necessary changes in plant operation will be able to solve the many problems that will be imposed on the preparation plants. The plants will require skillful and observant operating men. With full-seam mining methods, seams of roof coal will often be mined. Under the former mining systems these strata were not mined and frequently they contain a high per¬centage of bony and banded partings. The mining of this coal will greatly alter the washability and specific gravity characteristics of the feed to the plant. Often the percentage of 1.40 to 1.60 sp. gr. increased from 3.5 to 7.5 per cent, or nearly a 1.0 per cent increase in the ash content of the 1.60 sp. gr. float coal. Thus the cleaning problem is much more difficult, and it is unlikely the same ash content of cleaned coal can be produced as before without a decrease in recovery or the produc¬tion of a "middlings" product. Mr. Carris had this in mind when he said "The quality of the

Jan 1, 1946