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By K. Takahashi, I. Iwasaki

The methyl stretching vibrations for a series of normal xanthates, isoxanthates and normal amines were determined with the aid of an infrared spectro-photometer, and the results were compared with published information on the corresponding alcohols. The frequency shifts of methyl stretching vibrations may be attributed to the inductive effect of polar groups. The hydrogens in the shorter chain alkyl groups are somewhat polar and can be expected to interact with water molecules by hydrogen bonding. Contact angle, surface tension lowering, solubility, and critical micelle concentration appear to be related to the induced polarity of the alkyl groups. Traube's rule states that in homologous series of compounds solubility decreases and surface activity increases regularly with the size of the hydrocarbon group. Analyzing the work of transfer of a solute from solution to surface, Langmuir' interpreted this rule to mean that each CH2 group added to a molecule produced its effect independently of the others. It is also well known2 that the maximum equilibrium contact angle with sulfhydryl collectors is independent of the polar groups and of the sulfide minerals, and that it increases to a certain limit with the number of carbon atoms in the alkyl group. This observation is thought to demonstrate the orientation of the collector molecules at the sulfide surfaces. The dependence on the hydrocarbon chain length is usually explained as due to the screening of the force field of polar mineral surfaces.3-5 Here again, Langmuir's principle of independent surface action appears to be implied. Heteropolar compounds consist of nonpolar and polar groups, the former being the hydrocarbon group and the latter containing such electronegative atoms as O, N, S, P, or halogens. According to Palit6 the hydrogens in the alkyl groups are more electroposi- tive than in the paraffins owing to the negative inductive effect of the polar groups and a possibility that a hydrogen bond with water molecules ensues. Goto and Takenaka7 provided direct evidence of the inductive effect by measuring the shift of the C-H stretching vibrations of alcohols, acids, and alkyl bromides with an infrared spectrophotometer. Their approach appeared to be directly applicable to the studies of surface activity both at air-water and water-mineral interfaces encountered in flotation systems. The present article attempts to relate the C-H stretching vibrations of alkyl xanthates, alcohols, and amines with such flotation chemistry parameters as contact angle, surface tension lowering, solubility, and critical micelle concentration. MATERIALS AND METHODS Normal xanthates from methyl to octyl inclusive and the isopropyl, isobutyl, and isoamyl xanthates used in this investigation were prepared in the usual manner.8 Normal amine hydrochlorides with carbon chain lengths of 1, 2, 4, and 6 were from Distillation Products Industries, of 8 from Archer-Daniels-Midland Co., and of 10, 12, 14 and 16 from Armour and Co. Normal propylamines, pentylamines and heptylamines from Distillation Products Industries were used both as received and as hydrochloride formed by converting the amines according to the procedure described by Li9 Perkin-Elmer Model 521 and 621 infrared spectro-photometers were used to investigate the spectra in the frequency region of 3050 to 2800 cm-' with frequency scale expansion. The accuracy of the frequency readings was within + 1 cm-1. The KBr micropellet technique was used to prepare the xan-thate samples for measurements, and the halocarbon mull technique was used for amines and amine hydrochlorides. EXPERIMENTAL RESULTS Fig. 1 shows the CH3 asymmetric stretching vibrations as a function of the number of carbons in the alkyl group for normal xanthates, isoxanthates and amines. Also included in the figure are data for normal alcohols and isoalcohols taken from the article

Jan 1, 1970

By Ralph W. M. Lai, D. W. Fuerstenau

This paper presents the results of a study of the principles which control the distribution of ultrafine particles between an oil phase and an aqueous phase. Alkyl sulfonates were used to control the wettability of fine alumina particles and to stabilize the water-isooctane emulsion system in the extraction process. The effects of sulfonate chain length, sulfonate adsorption, pH, and oil-water ratio on the recovery of solids in the oil phase were investigated. Higher extraction was found under conditions which yield higher hydrophobicity and large interfacial area of the oil-water emulsion. Today there is considerable interest in developing methods for the recovery of fine particles from disseminated ores. One such method might be the extraction of fine particulate solids from aqueous suspensions into an oil phase, and one example of a successful industrial process based on oil-water distribution phenomena is the emulsion flotation process used in concentrating manganese ore.' The oil agglomeration process of Farnand, Smith, and Puddington has been suggested for concentrating tin ore. Patents 3-4 for oil flotation processes extend back to that of William Haynes in 1860. The basis of all these processes is directly related to the stabilization of emulsions with solid particles. The first extensive study of oil-water emulsions stabilized by finely divided solids was made by Pickering. Later, Briggs,6 weston, 7 Chessman and King,8 and Leja and Schulman9 experimentally demonstrated how solid particles control water-oil and oil-water systems. Hildebrand10 suggested that fine particles can stabilize an emulsion because the fine particles are partially wettable by both oil and water, that is, that the contact angle must be finite. Takakuwa and Takamori 11 recently applied emulsion inversion to the study of collector adsorption in flotation systems. At the Royal School of Mines, Shergold and Mellgren12 are currently carrying out a comprehensive study of the extraction of fine particles into an organic liquid phase. In the present study of the liquid extraction or oil flotation of ultrafine particles, the recovery of hydro-philic alumina particles of 0.1-µ average diameter was determined after separating an isooctane-water mixture (emulsion) into its two phases. Alkyl sulfonates of different chain lengths were used to change the wettability of the alumina and to effect emulsifi-cation of the oil-water mixture. The effects of the oil-water volume ratio, sulfonate adsorption, and pH on the recovery of the fine particles were investigated. Since the surface charge on an oxide such as alumina is determined by the adsorption or interaction of H+ and OH- with the surface, pH control is extremely important. Furthermore, since the zero point of charge (zpc) of alumina13-14 occurs at pH 9 to 9.4, major adsorption effects with anionic collectors in these systems will occur below pH 9. The results of the foregoing investigation are discussed in terms of the recovery of the fine particles, the oil-water ratio, contact angles, surface tension, the adsorption of sulfonate onto the solid surface, and the emulsifica-tion of oil. MATERIALS AND EXPERIMENTAL METHODS Materials: The particulate solid used in all the experiments was Linde "A" alumina, a high-purity, readily available form of a-alumina. The surface area of the alumina, as evaluated from measurements of stearic acid adsorption from benzene, was 14.5 sq m per gm, based on a value of 20.5 sq Å for the cross-sectional area of stearic acid.13 All aqueous solutions were prepared from triply distilled conductivity water. Other materials included high-purity crystals of sodium alkyl sulfonates, isooctane, and, for pH adjustments, reagent grade hydrochloric acid and sodium hydroxide-Because sulfonic acids are strong acids, they are

Jan 1, 1969

By Franklin J. Hill, Theodore D. Tiemann

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

Jan 1, 1962

By Keith R. Bock, Norman Parlee, Albert M. Barloga

Coils of pure iron and iron-carbon alloy wire (0.05 to 0.80 pct C) and sufficient sulfur to saturate the solid phase were equilibrated in evacuated or argon filled tubes. After rapid cooling, and removal of the outside nonmetallic layer, the wires were analyzed for carbon and sulfur and the data used to construct an Fe-S binary and isotherms of the Fe-C-S ternary in the range 1149° to 1427°C. THE solid solubility of sulfur in steel is of interest in connection with such phenomena as hot shortness, burning, and so forth. "Burning," the more or less permanent damage that some steels suffer when heated for forging or rolling, has been shown to be related closely to the behavior of sulfur and less closely to carbon and oxygen.' Attempts to interpret burning phenomena in steels fail because of lack of data on the Fe-C-S and the more complex systems in this family. Rosenqvist and Dunicz 2 and Turkdogan, Ignatowicz, and pearson3 have largely elucidated the Fe-S diagram in the region of interest but no information on the Fe-C-S diagram in this region appears to be available in the literature. This paper deals with the elucidation of the Fe-C-S diagram in these interesting ranges. The method employed is different from those used by previous workers2'3 on the Fe-S system. EXPERIMENTAL METHOD Pure iron wires (Ferrovac E) or iron carbon alloy wires of 1 mm in diam were cleaned with acid and acetone, coiled, and placed in silica tubes (7 mm OD and 5 mm ID) previously closed at one end. Enough sulfur was added to assure saturation of the solid iron phase. The filled tubes were either simply evacuated and sealed, or filled with argon at a reduced pressure and sealed. The argon was required at the higher temperatures to prevent collapse of the tubes. The filled and sealed tubes were placed in the middle uniform temperature zone of a Globar tube furnace and equilibrated at temperatures ranging from 2100°F (1149°C) to 2720°F (1493°C). After equilibration the tubes were removed from the furnace and quenched in air or water, the form of quenching being found to have no effect on the results. The tubes were broken open and the coils were placed in a 1 : 1 HC1 solution to remove the sulfide-rich layer. The coils were then cut into small pieces and analyzed for sulfur and carbon. In the early stages of the investigation different equilibration times ranging up to 17 hr were tried and the cores of the wires were analyzed to test for saturation. One hour appeared to be sufficient to reach maximum sulfur content at 1454°C and 2 hr sufficient at 1149°C. The practice adopted was to use at least 3 hr at the higher temperatures and at least 5 hr at the lower temperatures. The iron-carbon alloy wires used were made by carburizing pure iron wire with carbon monoxide gas in a one inch diameter ceramic tube at about 1204°C. Differing carbon contents were obtained by allowing fairly large coils to react with the gas for varying lengths of time at a flow rate of 800 cc per min. The reacting times ranged from 15 min to 4 hr depending upon the amount of carbon desired. The furnaces used were controlled by means of Leeds and Northrup Speedomax Type H instruments with D.A.T. Control attachment. Thermocouples were calibrated against the melting points of gold and copper. The temperatures recorded appear to be accurate within i2.7OC. Starting with run No. 85 and continuing with the

Jan 1, 1962

By G. Derge, Ling Yang, John Henderson

Self-diffusion coefficients of aluminum have been measured by the capillary reservoir technique in liquids of the CaO-SiO2-Al2O3 system containirg equimolar portions of CaO and SiO2, in the temperature range 1400o to 1520oC. For the melt containing 6.0 mole pct Al2O3 the results can be expressed by the equation D = [(4.3 * 0.3) x 104] exp [(-85,000 * 17,500)/RT]cm~sec-'; for the melt containing 12.5 mole pct Al2O3, by the equation D = (5.4 i 0.2) exp [(-60,000 * 10,00O)/RT] cm2sec-: A concept of the constitution of these melts has been developed which proposes that the ratios O/(Si +Al) and Al2 O3/CaO determine the dominant species present. In recent years considerable work has been done on the system CaO-SiO2-A12O3 with a view to elucidating the structure of liquids of this system. Conductivity,' electromotive force, 3 density,4 and activity5 measurements have all contributed to an understanding of the problem, but as yet there is no entirely satisfactory theory that can account for all the observed experimental results. In principle, measurements of self-diffusion coefficients should give further information which is not obtainable in other ways. Self-diffusion coefficients for calcium, silicon,6 and oxygen7 have been measured. The present investigation extends the series of self-diffusion coefficient measurements to include aluminum and develops a concept of constitution for liquids of this system which is compatible with all the observed experimental results. EXPERIMENTAL The technique used in the measurement of the self-diffusion coefficient of aluminum was the capillary-reservoir method,8 A126 being incorporated in the melt contained in the capillary and inactive aluminum in the reservoir melt. This method was chosen because it minimizes convection currents' in the diffusion zone. It has the further advantage that the boundary conditions are such that a slight modifica- tion of Anderson and saddington's8 solution of Fick's Law yields an equation which requires measurements only of the length and the initial and final average specific activities of the solidified melt within the capillary. where t is the diffusion time, Co is the average specific activity of the melt contained in the capillary at t = O, C is the average specific activity of the melt contained in the capillary at t = t, 1is the length of the capillary, and D is the self-diffusion coefficient. The equation is of somewhat different form than those previously applied to high temperature diffusion studies because the specific activity of the melt in the reservoir was negligible both before and after diffusion. The diffusion apparatus is shown schematically in Fig. 1. It consisted of a silicon carbide resistance furnace containing the inactive melt in a graphite crucible, internal dimensions 7/8 by 4 in., enclosed in a 1 1/4- by 1 1/2- by 30-in. McDanel tube. A 3/8-in. McDanel thermocouple sheath to which graphite radiation shields and a graphite protection tube were affixed, was used to hold the capillaries. By moving this sheath through a rubber seal at the top of the McDanel tube the capillaries could be lowered into or raised out of the melt. Temperature was measured with a Pt-Pt 13 pct Rh thermocouple which was calibrated periodically against a standard couple. The furnace temperature was controlled to ± 5°C through the thermocouple immersed in the melt. Temperature variation over the depth of the melt was less than ± 3°C. The inactive melts were prepared from pure native quartz, assaying better than 99.9 pct SiO2, A.R. grade A12O3 and A.R. grade CaCO,. The same quartz and CaCO3 were used in preparing the active melts, the

Jan 1, 1962

By M. R. Tek, F. F. Craig, J. O. Wilkes, C. S. Goddin

The waterflood performance of a water-wet, stratified system with crossflow is computed by a finite difference procedure. The effects of five dimensionless parameters on tile oil displacement efficiency, water saturation con-tour.7 and crossflow rates are evaluated in the absence of gravity forces. Crossflow due to viscous and capillary forces is shown to exert a significant effect on oil recovery in a field-scale model of a two-layered. water-wet sandstone reservoir. The crossflow is at a maximum in the vicinity of the front advancing in the more permeable layer. Under favorable mobility ratio conditions, the comparted oil recovery with crossflow always is interrnerliate between that predicted for a uniform reservoir and that for a layered reservoir with no crossflow. INTRODUCTION The important erects of reservoir heterogeneity on waterflood performance are commanding increased attention in the technical literature. Much of this attention is centered on two categories of layered reservoirs: those in which layers are non-communicating and those in which crossflow of fluids occurs between the layers. In the first category, the reservoir is assumed to consist of discrete layers, each uniform within itself and differing from the others only in such properties as thickness, porosity and absolute permeability. The performance within each layer is calculated by one-dimensional flow theory, and the performance of the total reservoir is obtained by summing individual layer performances. Capillary and gravity effects usually are not considered. Representative publications dealing with thi5 type of reservoir are those of Stiles,' Dykstra and Parsons,' Hiatt,3 Warren and Cosgrove' and Higgins and Leighton." Prediction of performance for reservoirs in the second category is considerably more difficult since viscous, capillary and gravitational forces all play important roles in causing crossflow between layers. A number of authors have investigated the simpler problem of two-dimensional displacement flow in a stratified system with a mobility ratio of unity and negligible capillary and gravity effects.'; Others have considered two-dimensional, non-steady-state flow of a single, slightly compressible fluid in a stratified reservoir. A limited number of laboratory oil displacement tests in layered models with crossflow have been reported. Miscible floods (with resultant zero capillary forces) in layered five-spot models were conducted by Dyes and Braun," who studied the effect of mobility ratio with zero gravity forces, and by Craig et al. 12 who studied the effect of gravity forces at constant mobility ratio. Waterfloods in layered five-spot models (with cross-tlow due to capillary, viscous and gravity forces) were conducted by Gaucher and Lindley,"' who showed the effect of gravity forces in causing underrunning of the injected water and by Carpenter, Bail and Bobek, 14 who demonstrated the reliability of Rapoport's" dimension-less parameters for scaling layered systems. Waterfloods in rectangular layered models were conducted by Richardson and Perkins."' who investigated the effect of velocity at constant mobility ratio and with zero gravity forces, and by Hutchinson," who studied the effects of varying mobility, layer permeability and layer thickness ratios. The differential equations which rigorously describe waterflooding in a heterogenous porous medium are non-linear and do not facilitate analytical solution. By using finite difference approximations it is possible to obtain a solution to any desired degree of accuracy. Such a solution, using an alternating direction implicit procedure (ADJP), is described by Douglas, Peaceman and Rachford.18 In the present study, a computer program using ADJP explores systematically the effects of important parameters on waterflood performance of a two-dimensional, two-layered, field-scale model of a water-wet sandstone system. Particular attention is given to evaluation of the water saturation contours and crossflow rates at the interface between layers to gain improved understanding of the crossflow mechanism. PROCEDURE BASIC: FLOW EQUATIONS The basic flow equations for two-dimensional, two-phase, immiscible, incon~pressible flow in a porous medium are:

Jan 1, 1967

By L. L. Handy

The most common method of identifying hydrocarbon-bearing strata in a well that penetrates many different formations involves measurement and interpretation of the electrical properties of the formations as determined by electrical logs. Even though this method is used extensively, and even though in a great many instances it is capable of indicating presence of oil or gas, situations arise for which it is extremely difficult, if not impossible, to deduce the presence of hydrocarbons. These situations may involve the following. 1. A thin formation, bounded by highly resistive formations, in which it is impossible to obtain the actual resistivity of the uninvaded zone with existing logging devices. 2. A formation in which invasion has been so extensive that a value for the uninvaded zone resistivity cannot be obtained. 3. A very shaly formation in which the resistivity index, I, is lower than that usually associated with productive formations. 4. Laminated formations comprised of thin productive sands separated by thin shale streaks in which the individual sand and shale streaks are too thin to permit measurement of uninvaded-zone resistivity with existing logging devices. 5. Productive formations in which the water saturation is high. To extend the utility of electric log interpretation to identification of hydrocarbons in all types of formations, there is strong incentive to find a method not subject to these limitations. Some time ago, in connection with research on the wettability of reservoir rock, an investigation was conducted in which the resistivities of cores were measured shortly after they were removed from a core barrel, and again after they had been extracted and restored to their original oil and brine saturation.' The resistivities after extraction were generally lower. Other tests made on the cores indicated that they were more nearly water wet after they were extracted; thus, it was assumed that the observed changes in resistivities were due to a change in wettability of the cores. Other experiments'," have shown that resistivities of rock samples are sharply dependent on wettability. These experiments have shown that oil-wet samples are more resistive than water-wet samples. To obtain an understanding of how the wetting properties of the surfaces of core material affect electrical resistivity, a series of experiments was conducted. Two groups of core samples were prepared for testing. One group contained brine, but no residual oil. The other group was saturated with brine, flooded with oil to a low water saturation, then flooded with brine to a final residual oil saturation. Resistivity measurements were made on each group. Both groups were then flooded with the original brine to which a chemical had been added that renders sand and clay surfaces preferentially oil wet, a so-called reverse-wetting agent. very little change in resistivity was observed in cores containing only water. The group containing residual oil, however, showed resistivity increases of 100 to 200 per cent. These experiments showed that the resistivity of a core containing oil could be altered by changing wet-tability of the core. Moreover, the possibility was introduced that reverse-wetting agents might be employed as the basis for a logging method for identification of oil-bearing strata. Since behavior of a porous rock containing gas and water might be expected to be similar to that of a rock containing oil and water, such a method should also be applicable to identification of gas-bearing zones. In principle the wettability of the invaded zone could be reversed without altering conductivity of the interstitial water or the hydrocarbon saturation therein. Those strata showing significantly increased invaded-zone resistivities would, therefore, contain hydrocarbons; those with no significant change would be filled only with water. Addition of a reverse-wetting agent to a hydro carbon -bearing zone which is, by nature, already preferentially oil wet would not result in an enhancement of its resistivity. It is generally believed, however, that most hydrocarbon-bearing strata are preferentially water wet.

By C. H. Li, R. J. Stokes, T. L. Johnston

The phenomenon of solid-solution strengthening has previously been studied in a number of binary alloy systems.1-8 There has been, however, very little information published concerning the strengthening effects of specific solutes in magnesium alloys. Schmid and his coworkers9,10 investigated the behavior of aluminum and zinc in binary and ternary magnesium-alloy single crystals, but this work was done before high-purity materials were readily available. Workers at the Dow Chemical companyH reported increases in the critical resolved shear stress upon alloying magnesium single crystals with zinc and indium. Recently, Hardie and parkins* investigated the extent of hardening produced by the addition of various solutes to poly crystalline magnesium. The present work was undertaken to provide data on the strengthening effects of a number of solutes in high-purity magnesium, for the purpose of supplying further experimental information which might be useful in describing a general mechanism for solid-solution strengthening. To simplify interpretation of the results, the mode of deformation was limited to basal slip, through the use of single crystals. EXPERIMENTAL PROCEDURE Magnesium and magnesium binary-alloy single crystals containing indium, cadmium, thallium, aluminum, and zinc were prepared in the form of l/2-in.-diam rods, approximately 8 in. long, using a modified Bridgman technique in which the crystals were slowly cooled from the melt in a steep temperature gradient, in an atmosphere of helium. It was found that a solid-liquid interface travel speed of about 0.7 in. per hr consistently produced single crystals. The poly crystalline starting materials for the preparation of single crystals consisted of 1/2-in.-diam extruded rods, prealloyed to the desired composition. The unalloyed magnesium and magnesium-indium extrusions were furnished by the Dow Chemical Co. The other alloys were prepared at the Rensselaer Polytechnic Institute Metallurgical Laboratories. Some preliminary studies of the strengthening effect of indium were conducted at room temperature using a constant rate of tensile loading of 1040 g per min. Stress was applied to the crystals by means of a simple 5:l lever arm. The lever was loaded by a constant rate of flow of shot into a receptacle suspended from the long arm of the lever. Plastic flow was detected by an electrical resistance strain gage cemented to the surface of the crystal normal to the minor axis of the predicted glide ellipse. The crystals were acid machined to produce tensile specimens with a reduced section between the grip ends, with an additional step in the center of the reduced section to compensate approximately for the slip-retarding effect of the strain gage. The balance of the single crystals were extended in an Instron tensile tester. This machine employs a synchronously driven screw and automatically records applied load as a function of cross-head separation. It became unnecessary therefore, to employ a strain gage to detect deformation or to acid machine a reduced section. Preparation for testing reduced merely to chemical cleaning of the surface, thus minimizing the amount of handling and probability of accidental damage to the crystals. The rate of elongation employed in all the tests was 0.002 in. per min, corresponding to a strain rate of approximately 0.0004 per min. EXPERIMENTAL RESULTS The investigation confirmed the finding of many workers that the yield strength of hexagonal metal crystals is strongly orientation-dependent. This is illustrated in Fig. 1, in which o, the tensile stress required to produce gross plastic flow in eleven unalloyed magnesium crystals stressed at a constant rate of loading is plotted as a function of sin X, cos Ao where X, is the angle between the

Jan 1, 1960

By R. H. Oliver

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

Jan 1, 1961

By E. L. Claridge, K. S. Lee

Areal sweep efficiency of oil displacement by enhanced-viscosity water exhibiting pseudoplastic behavior was measured in a Hele-Shaw model representing one-quarter of a five-spot pattern. The pseudoplasticity of polymer solutions and the velocity distribution in the five-spot pattern produced a condition under which the mobility ratio between the displacing and the displaced fluid could not be assigned a single value. Instead, the movement of the displacement front is governed by local mobility ratios which are also time dependent. The areal sweep at breakthrough with polymer solutions was poorer than the sweep obtained with Newtonian fluids of comparable viscosity. However, the areal sweep at 1 PV throughput was greatly improved as compared to flood water without polymer. It was also demonstrated that, even after the oil-cut had declined to a low value during a regular waterflood, switching to polymer flood efficiently swept out the oil remaining in the model. INTRODUCTION The behavior of fluid displacements in isotropic porous media for various patterns of injection and production wells has been extensively investigated.1-7 These investigations all concerned Newtonian fluids, i.e., the viscosity of each fluid was constant regardless of flow rate. The generally unfavorable influence on areal sweep efficiency of higher mobility of the displacing fluid as compared to the mobility of the displaced fluid has been established for both miscible and immiscible fluids. The principle was also established that a close correspondence exists between miscible and immiscible flood front behavior,2, 3 although oil recovery in a waterflood at unfavorable mobility ratio may be less than that observed in a miscible displacement at the same mobility ratio. This is true even when oil recovery is expressed on the basis of movable oil. The reason is that oil saturation only slowly achieves its final value behind the water-flood front in accordance with the Buckley-Leverett8 simultaneous flow relations. It is convenient to use miscible displacements for laboratory simulation of waterflood frontal advance since the interfacial tension forces which are negligible in proportion to viscous forces on a reservoir scale9 are thus made nonoperative in the laboratory model. For miscible displacements, the Hele-Shaw type of model adequately represents a porous medium so long as the appropriate scaling rules5-10 are observed in its design and operation. During simulation of waterflood front behavior in the laboratory by using miscible displacements, the behavior of connate water may ordinarily be disregarded since it is usually indistinguishable from flood water in this process. However, when the flood water is deliberately thickened to improve the mobility ratio between water and oil. the effect on the sweep efficiency due to generation of a connate water bank during the process must be considered. In a uniform porous medium, such a bank is generated11 and efficiently displaced by injection of thickened water.l2 The oil originally in-place at the start of the waterflood is then displaced by connate water followed by thickened water. If the flood water must be thickened to obtain a favorable mobility ratio, the mobility of the oil phase is appreciably less than that of the connate water. Hence, the oil phase is inefficiently displaced by the connate water bank, and a considerable proportion of the oil comes in contact with and is displaced by the thickened waterflood front' A recent study 12 of five-spot displacements using miscible Newtonian fluids in which connate water banks of various sizes were simulated shows that, for connate water banks as large as 40 percent of 1 PV, major improvements in sweep efficiency resulted from use of a thickened

Jan 1, 1969

By H. J. Ramey

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

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

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

By David W. James

DURING a recent investigation of the transition from a planar to a nonplanar solid/liquid interface for the systems H20-NH4F and 0-AIR,' an apparatus was developed which enabled the morphology of the ice-water interface to be examined during the transition. The slightly curved interface was viewed at a glancing angle with a Bausch and Lomb X30 stereomicro-scope. The interface was obliquely illuminated by a polarized light source. It was thus possible to differentiate between small projections or depressions at the interface, both by a shadowing effect and by the way in which they distorted the colored interference fringes across a particular crystal surface. Many attempts were made to photograph the various stages of interface breakdown. Unfortunately, the limited depth of focus of the microscope rendered the system unsuitable for photographic recording. Visual examination, however, was facilitated by continuous adjustment of the microscope focus control. The following observations of the interface transition were recorded for dilute solutions of ammonium fluoride in water. They are compared with iller's postulated morphologies shown in Fig. 1. i) The initial departure from planarity was characterized by the appearance of a large number of small depressions or "pores" in the interface. ii) The pores were arranged in wavy rows all lying roughly in the same direction within a particular grain. iii) The pores did not appear to form near to grain boundaries. iv) The pores appeared in certain grains before others. v) The transition from the pore structure to the elongated cell structure, Fig. l(d), was difficult to follow. It occurred quite rapidly and no truly irregular cell structure, Fig. l(c), was noticed. vi) The elongated cells gradually became more uniform in size and shape, with straight cell boundaries. They remained elongated, however, and no regular hexagonal cells were observed, cf. Fig. l(e). Several conclusions may be drawn from these observations. Firstly, the appearance of a poxed or, more accurately, a pore structure can be used as a criterion for the onset of constitutional supercooling. Care should, of course, be taken to distinguish between the true pore structure and artifacts caused by splashed-back liquid, particles of oxide, or inefficient decantation of liquid retained between cell boundaries, as described by Spittle et al? Secondly, and contrary to the suggestions of Tiller el l., it seems that interfacial perturbations are characterized not by curved projections but by small depressions or pores. A recent independent investigation by Biloni, Bolling, and cole5 reported in this issue indicates that the depressions might be explained in terms of dislocations intersecting the solid/liquid interface. It is possible that the dislocation concentration is reduced in the vicinity of grain boundaries. This would then explain the grain boundary depleted areas noted in (iii) above. This work was partially supported by the Air Force Office of Scientific Research, Contract No. AF 49-(638)-1029.

Jan 1, 1967

By R. L. Rickett, W. C. Leslie

The influence of deoxidation practice, prior thermal history, and aging time and temperature on the strain-aging behavior of low-carbon open-hearth steels was investigated. The criterion of aging employed was the increase in yield strength in the tensile test, after straining and aging. Composition, prior heat treatment, and aging conditions were all found to be important in governing the strain-aging characteristics of these steels. THAT deoxidation changes the strain-aging propensities of low-carbon steels has been known for a long time, but there has been little agreement, and even contradiction, between results obtained by different investigators and between results obtained in the laboratory and in the mill. This investigation was begun in the hope that some of the uncertainties connected with the strain aging of commercial steels could be eliminated. In considering this problem, it was necessary to define strain aging and to examine the methods used to measure this property. Strain aging can be defined as the changes in properties of a metal or alloy with time, after cold working. The rate at which these changes occur increases as the temperature is raised above atmospheric. The requisite plastic strain is the principal distinction between strain aging and quench aging, the latter being due to precipitation from supersaturated solid solution. Strain aging is also characterized by rapid attainment of maximum hardness at high aging temperatures and lack of softening (overaging) at low aging temperatures. Several possible criteria of strain aging have been listed by Sachsl and by Davenport and Bain.' Because changes in mechanical properties are the most easily measured and the most commonly used, consideration of methods to be used in this investigation was confined to three tests: tensile, notch-impact, and hardness. Hardness tests are the most economical and easiest to perform, but produce only one measure of strain aging. Also, as pointed out by Felmly, Hartbower, and Pellini,³ hardness changes due to aging are not pronounced for steels containing more than 0.15 pct C. Notch-impact tests require careful preparation of large numbers of specimens. Above and below the transition temperature the test lacks sensitivity; furthermore, it is extremely difficult to impart a uniform strain to the specimens, followed quickly by aging and final testing; machining must generally take place after straining. For these reasons, the tensile test was selected for use. Although this test requires a considerable expenditure of time, labor, and money in preparation of the specimens and performance of the test, more information can be gained than from any other single mechanical test, information which includes upper and lower yield points, yield-point elongation, tensile strength, strain-hardening exponent, reduction of area, and elongation. Low and Gensamer' and Schwartzbart and Low5 lso used the tensile test, taking the increase in flow stress after straining in tension and aging as a measure of strain aging. In our work, as in theirs, each specimen was strained an arbitrary amount, sufficient to pass through the

Jan 1, 1954

By Ronald J. Roman

Research pertaining to flow of solutions in leach dumps has generally been neglected. This technical note proposes a method for evaluating the flow patterns and incorporating the results into dump-leaching models. Three dump-leaching models1-3 have been proposed to scale up laboratory test data to expected field results. These models are based on the same physical picture in a dump and differ only in the importance of diffusion or surface chemical reaction rate. Selection of this rate-controlling phenomemon is based on type of ore (sulfide or oxide), physical dimensions of the particles being leached, and the leach heap itself. All three models are applicable to specific types of operations. The models are similar in the use of a size distribution analysis for the dump material and the assumption that the leach solution flows around each particle. Transport of the leaching agent to the interior of the particle takes place by diffusion [(Fig. 1)]. However, normal dumps are of a higher bulk density than the material in a laboratory column used to generate the scale up data. How does this difference in bulk density affect the scale up equations? Increasing the bulk density can be expected to give more particle-to-particle contact; therefore, individual particles will be blinded by each other. As blinding increases with bulk density increase, the particles will behave like larger particles with a coarser apparent size distribution. The extreme will occur when the bulk density reaches that of the undisturbed rock, the entire dump behaving as a single particle with the dimensions of the heap itself. Harris4 alluded to this phenomenon in his paper. An alternative method of describing the same phenomemon is to consider the flow paths of the solution. At high bulk densities leach solution no longer surrounds each particle, but flow paths are separated by several particles and channeling is said to take place. Instead of the particle radius being the maximum distance through which the leaching agent must diffuse, the maximum distance is half the separation distance of the solution flow path. Particle size distribution must then be replaced in the models by the concept of channel separation distribution. Like size distribution, channel separation distribution specifies the cumulative percentage of the rock in the dump situated less than a specified distance from a solution channel. Thus, [ ] Distribution of the solution channels is a function of how the dump was built (among other things), and therefore it cannot be determined in the laboratory. Accordingly, it becomes necessary to determine a range for d and a in existing operations or measuring these parameters before leaching starts. Howard5 gives a clue to one possible technique of measuring solution channel distributions. When his paper was published little was known about the phenomemon of leaching; the importance of this type of data was not recognized. [Fig. 2] is a Y-Y log for one hole drilled

Jan 1, 1978

THE second part of the mould for making guns is the core. Without this the space could not be made where the powder is to be and through which the ball, impelled by the fire, can pass and take flight. To make this it is necessary to take two things into consideration, because they are very important. One is what you are to make it on so that it may be supported and kept true. The other is what composition of clay will stand up during casting and yet not be very difficult to extract from the body of the finished gun. For the first, it is found that only an iron spindle of a suitable thickness is able to support the weight of the clay without bending under the heat of the fire or wobbling as it is turned on its journals or when handled. This should be a braccio or more longer than the mould of the gun and worked exactly round, straight, and well tapered like a spindle; above all every one of its joints should be well secured and solid. At the upper end a per-orated heel should be made, and lower down, exactly at the point corresponding to the length of the mould, are one or two other holes through which the little crossbars can be passed that fasten the core to the outer mould and also serve for constructing the disc. Now this iron is to be arranged on two trestles, pivoted so that it may turn truly when rotated. In order that it may not run up and down, make a little iron fork which engages a notch made with a file at the foot, and another at the head. After this, you must prepare clay for the core which is well made and tenacious ,enough not to crack. Fint take care that there are no pebbles in it and that it is composed of a small amount of cloth clippings and much sifted horse dung and some washed and clean wash ashes so that it may be of a tender and crumbly consistency in order that it may later be more easily extracted from the space inside the gun. In the same way, in order that you may be able to take out the iron piece at the same time, first cover it with ashes, and then wrap it all over with a rope of ordinary thickness, leaving a dito of the iron uncovered in every palmo length. [86] Alternatively, you may cover it all very tightly with hemp tow in the same way after it has been covered with ashes. Or heat your iron considerably and then cover it all to the thickness of a good cord with wash ashes or powdered charcoal that has been made into a paste with a little

Jan 1, 1942

By William A. Johnson

The fundamental role of diffusion in many reactions occurring in solid metals has long been recognized, and there have been careful measurements of rates of diffusion in numerous alloy systems; but our understanding of the atomic mechanism by which diffusion occurs is scarcely in an advanced state.l-3 It is doubtful that this mechanism can ever be directly ascertained; rather, all imaginable mechanisms must be examined and the one that is in best accord with such data as can be obtained from suitably chosen experiments should be selected. Because of its relative simplicity, diffusion in a system containing only one kind of atomic species—commody called self-diffusion—is of considerable theoretical interest. It may be expected that diffusion theory will not be advanced appreciably until a wide variety of diffusion experiments—of which diffusion in a chemical concentration gradient and self-diffusion are two important types—are carefully performed and inter-compared. Aside from the purely theoretical interest in self-diffusion measurements, such studies will be of considerable engineering importance. The rate of any process in a pure metal requiring the movement of atoms, of which recrystallization and creep are two familiar examples, will be understood more readily with the aid of self-diffusion data.† Self-diffusion implies the diffusion of something into its exact counterpart; the detection of such a process is patently impossible, and it is necessary to substitute for it the diffusion of one isotope (in this case radioactive) into another isotope (in this case stable) of the same chemical element. There is, however, no reason to suppose that a radioactive atom will not diffuse at the same rate as its stable isotope, for all of the isotopes of the same element have exactly the same chemical properties; neither the difference in nuclear energy nor the difference in mass would be expected to exercise an important influence in this phenomenon. In this sense, self-diffusion may be thought of as the diffusion of radioactive atoms down a radioactivity concentration gradient, just as usual diffusion is the diffusion of one kind of atom down its chemical concentration gradient. The first measurements of self-difiusion were made by von Hevesy4-6 using the radioactive lead isotope thorium B in ordinary lead. The recent development of means for producing artificial radioactive elements has made possible similar measurements on gold,7, 8 copper,2, 9 and zinc.10, 11 Many of the data that have been obtained are rather poor, and no adequate reason has been given for their poorness; it appears, however, that the unsatisfactory results are characteristic of the particular experimental procedure employed, and not of self-diffusion measurements in themselves. The experimental technique that has yielded the poorer results is the deposition of a thin layer of radioactive atoms on the surface of a specimen and the determination of the rate of inward diffusion

Jan 1, 1941

By E. A. Nichols

The purpose of this paper is to present a contour map that shows the geographical variation in geothermal gradients in the Mid-Continent and Gulf Coast oil fields. Introduction Frequently there arises the need for an estimation of the temperature to be expected at a predetermined depth in working with a wildcat or in deepening old production into 'Ones that are relatively unknown. The study of geothermal gradients in oil fields has been made previously by many investigators. One of the pioneers in this work was C. E. Van Orstrand,' who, as well as most of the other investigators, was primarily interested in the relation between temperature and depth in a given locality. Between 192r and 1929, American Petroleum Institute Research Project NO. 25 fostered a thorough study of earth temperatures.2 K. IV. French did some work in California, the results of which were published in 1939.3 In most of these studies, an attempt was made to correlate temperatures in a rather localized area. This paper will show the results of an attempt to correlate temperature gradients over rather large Portions of the Mid-Continent and Gulf Coast area. Method of Obtaining Data It has been found that for complete thermal equilibrium to be established in a well, the well must stand undisturbed for a period of several hours to several weeks, depending upon the way the well was produced prior to the shut-in period. The data in this paper were obtained in conjunction with running pressures in wells or in taking samples of reservoir fluid. Glass maximum recording thermometers were used in all but a few instances. The wells had been shut in from one hour up to I. or 12 days. Since the wells were normal producing wells, some of the shut-in times undoubtedly were insufficient for complete thermal equilibrium to have been established and the temperatures measured do not necessarily represent the true earth temperatures. They do represent the temperature conditions that will be encountered in a well that is producing oil. The data, therefore, can be useful in working with or in estimating the temperatures to be expected in producing reservoirs. In obtaining a thermal gradient by dividing the difference in temperature of the formation and the mean annual surface temperature by the depth of the formation, one is assuming the depth-temperature line to be straight. Depth-temperature curves are almost straight lines (Fig. I). However, on close examination of accurate data, a slight curvature usually is observed. Most wells yield curves with slopes increasing with increasing depth. These curves are believed to be from wells that are in and are underlain by sedimentary material. Some few curves have slopes that decrease with increasing depth. These curves are believed to be from wells that are underlain rather closely by granite or some other igneous rock. Most investigators

Jan 1, 1947

By G. B. Craig, G. L. Montgomery

A simple technique has been developed which reveals glide dislocations in zone-refined aluminum as etch pits. The technique has been tested quantitatively by making dislocation counts on aluminum single crystals deformed in pure bending. The method has the advantage of being insensitive to the orientation of the surface under examination. A number of etchants which will reveal dislocations in annealed aluminum have been reported.'-' These etchants apparently depend on decoration of the dislocations by an impurity (probably iron) and cannot, therefore, be used to reveal fresh glide dislocations. In addition, it is unlikely that screw dislocations will be etched because of their small attraction for impurity atoms. Amelinckx6 has reported that glide dislocations located along slip traces can be revealed by fluo-rated aqua regia. This work indicated that dislocations themselves, irrespective of decoration by impurity atoms, are responsible for the etch pits. However, as a result of additional etching experiments, Wyon and Marchin7 concluded that dislocations alone are not sufficient to explain the localization of etch pits on slip lines in aluminum using chemical etch-pitting techniques. In addition, their results show that glide dislocations are revealed only on surfaces approximately parallel to a (100) axis and that not all slip systems are attacked. These observations have been confirmed by the present authors. The technique described in this article is insensitive to the orientation of the surface, and reveals dislocations on all glide systems. Fig. 1 shows a deformed region in the neighborhood of a scratch. Dislocations can be seen along three slip traces. In the present work, single crystals of zone-refined aluminum are polished for from 2 to 5 min in a chemical polishing reagent held at 100°C, as described by Herenguel and second:' H2Sol 60 pct H3PO4 30 pct HNO3 10 pet The samples are then coated with a thin oxide film by annealing in air at 450°C for 1 hr and cooling in the furnace. After deformation, dislocation etch pits are developed by immersing the specimen in the same polishing solution which is now held at a temperature of 50°C. The formation of small hydrogen bubbles indicates that etching has occurred. The sample is immediately removed from the solution. Prolonged etching results in enlargement of the pits and, in regions of high dislocation density, the overlapping and loss of resolution of individual pits. It is the experience of the authors that contact with iron will ruinously contaminate the reagent. With careful etching, dislocations separated by half a micron can be resolved optically and the method has been shown to be sufficiently sensitive to reveal dislocations produced during the pre-easy glide region of deformation, Fig. 2. A few examples of glide-dislocation configurations, as revealed by this technique, are shown in Figs. 1 to 4.

Jan 1, 1964