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By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By E. P. Sadowski, L. P. Trudeau, C. R. Cupp

The apparent high radiation resistance of two varieties of maraging steel is described and an indication is given of some phenomena that require further study. Two aspects were included in this work: a) effects of neutron irradiation on the room-ternperature tensile properties of 18 Ni (250) maraging steel; b) effects of neutron irradiation on the room-temperature tensile properties and on the impact resistance of 12 pct Ni-5pct Cr-3 pct Mo maraging steel. Subsize tensile and impact test specimens were used. The 18 pct Ni steel was irradiated to a neutron fluence of 3.3 x 10 n per sq cm (>1 mev). The 12-5-3 variety was irradiated to two neutron fluence levels: 1) 1.5 x 10 per sq CTTL (>I mev) 2) 3.1 x 10'9nper sq cm (>1 mev) In all respects both varieties showed unusually high resistance to change in strength and ductility after neutron irradiation. There was no noteuorthy over-aging in fully aged specimens. The aged 18 pct Ni variety showed a 4 pct drop in yield strength upon irradiation with little or no decrease in ductility. The aged 12-5-3 variety showed a 5 pct increase in yield strength on irradiation with a very slight decrease in ductility. The impact transition of the 12-5-3 variety only increased 35 to 45 Co upon irradiation, and the shear energy fracture value for the subsized specimens decreased only half as much as expected frorn experience with conventional steels. THE development of new reactor concepts and nuclear technology now depends to a large extent on the availability of new alloys capable of operating in stringent reactor environments. One of the most important new types of metallurgical material that has been developed in recent years is the maraging steels. This type of alloy is notable for its remarkable retention of toughness at high strength levels. In the course of a research program which incorporated ambient temperature radiation effects studies to determine the mechanisms of strengthening of 18 pct nickel maraging steel,' it became evident that the resistance of the alloy to neutron-induced changes in mechanical properties should be studied. This paper is to present evidence for the apparent high radiation resistance of maraging steel. The experimental program was in two parts: a) Effect of neutron irradiation on the room-temperature tensile properties of 18 Ni (250) maraging steel. b) Effect of neutron irradiation on the room-temperature tensile properties and on the impact resistance of 12 pct Ni-5 pct Cr-3 pct Mo maraging steel, a cobalt-free alloy. EXPERIMENTAL PROCEDURE 18 Ni (250) Maraging Steel. Tensile test specimens were machined to the dimensions shown in Fig. 1 from $-in.-diam hot-rolled bar of the composition shown in Table I. All specimens were austenitized for 1 hr at 1500°F (815°C) in argon and water-quenched. Half of the specimens were then mar aged for 3 hr at 900° F (482°C) in argon. The specimens were irradiated in a fast neutron transformer rod at approximately 120°F (50°C) to a neutron fluence of 3.3 x 10 10 n per sq cm (>1 mev). The irradiation was performed in the NRX reactor of Atomic Energy of Canada, Ltd., at Chalk River, Ontario, Canada. In all cases, the thermal neutron flux was three times as high as the reported (> 1 mev) fluxes. The room-temperature tensile tests were performed with an Instron tensile testing machine operating at a crosshead speed of 0.05 in. per min. The loading frame of the machine, mounted in a hot cell, was remotely controlled. The specimens were tested either

Jan 1, 1968

By R. Wachtell

IN order to study better the phenomena at work in various phases of diffusion of the Fe/Si system when compounded and alloyed by powder metallurgy methods, several attacks have been planned. Electrical, hardness and other measurements have been discussed e1sewhere.l,2 The metallographic phenomena will be considered here. Concerning the metallography of the ferrosilicon alloys, some initial discussion is in order. As this laboratory discovered to its chagrin, there are many traps that lie in wait for even the experienced metal-lographer when he deals with alloys of high silicon content. Chief of these is probably the anomalous behavior of these materials under conventional etching techniques. We have before us, for instance, Corson's paper" of 1928, wherein is mentioned and illustrated (probably for the first time) the peculiar "barley shell" structure sometimes found in these alloys. Again in 19412 he same author reports the structure in 5-14 pct silicon irons. Houghton and Becker mention its presence' but make only tentative effort to explain it. In 1943, Hurst and Riley6 discussed the "barley shell" and declared it to be a false structure, resulting from the peculiar and characteristic film-forming propensities of the alloy. At about the same time, Wrazej7 proved correct the contentions of Hurst and Riley, establishing pretty well the mechanisms of formation and identifying the constituents involved. Hurst and Riley6 a1so describe in their paper (1943) a "cracked film" structure, also a pseudo-morph, the precise nature of which they do not suggest. Careful examination of such a film reveals that it not only cracks but begins to curl away from the surface of the metal and peel, much in the manner of flaking paint. The careful microscopist will be able to focus on the topmost edge of the flake, and, by optical sectioning, follow it down to the metal surface. We have been able, by oblique illumination of such specimens, to observe the raised segment of the film, the shadow that it casts, and the mating segment on the metal into which it fits. As late as 1946, Hurst and Riley8 found occasion to correct misinterpretation of this "cracked film" structure in a work by others on a 12 pct Si/Fe alloy. The "barley shell" and "cracked film" pseudo-morphs are not the only ones encountered in studies of these materials. A third pseudomorph, which may, however, have some structural significance is a fine striation of the surface. Closely spaced and parallel striae extend entirely across single grains. Each grain shows a different direction for the striae, and different closeness of the spacing. The regularity of this structure, and the fact that the striae do not cross from one grain to another, suggest that the structure is a film cracking controlled in some way by the crystal plane orientation of the surface being etched. In general it is wise for the metallographer dealing with these alloys to cultivate a feeling of uncertainty not only of the more complex questions of interpretation, but also of the basic question of whether that which he sees is indeed a true representation of the structure. We have taken, as a first test of the validity of a structure, its reproducibility "in situ" after repolishing and re-etching of the samples. Thus we knew the "barley shell" to be false (fig. 1) even before encountering the definitive works on the subject. The Metallography of Silicon Diffusion in Laminate Bars: As a first step in the study of the metallography of the diffusion process, we have pressed a series of laminate bars. These bars, or "sandwiches" as we have termed them, were pressed with covering layers of iron powder, and a "filler" of the Fe/Si master alloy under study. Bar dimensions were approximately %, x 3 x 1/4 in. The total

Jan 1, 1951

By H. C. Chang, N. J. Grant

Creep of very coarse grained, high purity aluminum was studied at 400° to 1100°F with an initial stress range of 50 to 1200 psi. The process of boundary sliding and migration was studied. The driving force of boundary migration under creep conditions is shown to be a combination of strain energy migrationand surface energy. A theory is presented regarding the strainenergyrole the grain boundaries play under creep conditions. From this thetheory intercrystalline failure of commercial alloys can be explained. Also from this theory an optimum grain size should exist for good high temperature properties of high purity materials. IN the investigation of the creep of very coarse grained, high purity aluminum previously reported,' the cyclic nature of the process of grain boundary sliding and migration has been established by microscopic observation of the actual creep process as well as metallographically. It was also substantiated by measuring localized strains across the grain boundaries. In addition, it was shown how extensive subgrain and fold formation may result from boundary sliding and how the slid grain boundary may become sharply wavy as a result of subgrain formation. Since the publication of those results, additional information on the process of grain boundary sliding and migration has been obtained. It is the purpose of this paper to report on the direction and driving force of boundary sliding and migration, the effect of grain size, and the effect of temperature. Finally the effect of decreasing purity (alloys 2s and 3s) on the process of boundary sliding and migration is noted. From these results, an explanation is presented for the intercrystalline failure of alloys under creep conditions. The effects of grain size on the creep properties of impure and high purity materials are discussed in the same light. The experimental procedures and technique have been presented elsewhere.' It is only necessary to state how the 2s and 3s aluminum specimens are prepared. Machined specimens were first annealed at 600°F for about 12 hr. In order to produce a large grain size the specimens were then stretched 3 to 8 pct. The specimens were marked with reference marks, electropolished, annealed at 900°F for 24 hr and at 1150°F for 12 hr, and repolished. The grain size of 2s aluminum produced by this treatment is comparable to that of high purity aluminum in the direction of its width of the specimen, i.e., there are 2 to 4 grains across the width of the specimen. However, the grains of 2s aluminum are 3 to 10 times longer in the direction of the specimen axis. On the other hand, the grain size of coarse grained 3s aluminum ranges from 10 to 20 grains across the width of the specimen due to the treatment just outlined and therefore is much smaller than that of both high purity and 2s aluminum. As in 2s aluminum, the grains are about 3 to 10 times longer in the direction of the specimen axis than in the direction of the width of the specimen. The arrangements of the grains in 2s and 3s aluminum were generally irregular; therefore it was difficult to follow the course of the grain boundaries. Results Method of Presentation: In order to show the arrangement of the grains, especially the direction and positions of the grain boundaries, traces of the grain boundaries on the four surfaces of the specimens were unfolded and mapped out after macroetching. Figs. 1 and 2 show the structural development drawings of specimens P-3 and P-8 respectively. The two flat surfaces (of which the front one faces the microscope) and the round-edged surfaces will be called the "front surface" and "back surface" and

Jan 1, 1954

By F. A. Schaufelberger

METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on page 545. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.' The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited3 to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SO2,4 which may lead to contamination with sulfur, or C0,5 which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents,7 which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere.' It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution composition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farben10 claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic, antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373ºC), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred, probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

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 E. A. Gulbransen, A. Pebler

Pressure-composition isotherms have been determinedfor the systems ZrMo2 -H2 between 0" and 900°C at hydrogen pressures between 10-4 and 760 Torr. Tkese studies plus X-ray diffraction analyses of selected compositions show that these intermetallic compounds form a complete series of hydrogen solid solutions within this temperature and pressure range. The partial molar enthalpies and entropies of solution of hydrogen in the three intermetallic compounds were calculated. The solubility of hydrogen in these Laves phases can be related to their free electron concentration. ThE reaction of hydrogen with inter metallic compounds of zirconium with Laves phase-type structure has both theoretical and practical interest. The in-termetallic compounds have structures different from any of the pure metals. In addition the electron to atom ratio of the intermetallics varies appreciably. In the nuclear materials field, these materials are of interest since intermetallic compounds may exist as precipitates in commercial zirconium alloys with transition metals. From studies on the hydrogen reaction, one can establish the stability of the intermetallic compounds relative to the hydrides of the component metals. The intermetallic compounds may also be used as getters for hydrogen and as materials for hydrogen storage. This paper will present the results of equilibrium and structural investigations of the ZrCr2-H2, the ZrV2-H2, and the ZrMo2-H2 systems for the temperature range of 0" to 900°C and the pressure range of Torr to 1 atm. A complete thermochemical analysis will be made of the measurements. Some of the results have been referred to in a survey paper' covering the types of hydrogen behavior observed in zirconium alloys. LITERATURE ZrCr2 is the only intermetallic phase in the Zr-Cr system.' It exists in two allotropic modifications. Between 900" and 1000°C the hexagonal MgZa (C14) structure transforms into the cubic MgCu2 (C15) structure. Beck4 has previously shown that the intermetallic ZrCrz takes up hydrogen into solid solution up to a composition H/ZrCr2 = 1.14 at room temperature and 1 atm hydrogen. A ZrCr2 hydride was stated to have a fcc structure. The binary Zr-V system has been investigated by williams5 although Rostoker and Yamamoto 6 had given earlier a partial phase diagram. ZrV2 was the only intermediate phase found in the system. wallbaum7 reported earlier that the compound ZrV2 hp the MgZm (CJ4) type structure with a = 5.288A and c = 8.664A. This was not comfirmed by Elliot8 nor by Matthias, Compton, and corenzwit9 who reported that ZrV2 has a cubic MgCua LC15) type structure. The latter authors gave a = 7.429A. Also, several authors do not agree on the temperature of the peri-tectic horizontal. It appears that ZrV2 may exist in several modifications. A high capacity for occluding hydrogen was reported by Beck4 who found H/ZrV2 = 1.38 at room temperature and 1 atm of hydrogen. ZrMoz is the only intermetallic phase in the Zr-Mo system.10 ZrMoa is formed by a peritectic reaction of the melt with a molybdenum-rich solid solution. ZrMo2 has the C15-type structure with a = 7.59A. MATERIALS High-purity chromium, vanadium, and molybdenum were used together with grade 1 crystal bar zirconium to prepare the alloys. Table I lists the chemical analysis and the sources for the metals. Ten-gram alloy compacts were levitated and melted in an inert argon

Jan 1, 1968

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 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 R. J. Blackwell, J. R. Rayne, J. R. Henderson, W. M. Terry, D. C. Lindley

This paper presents the results of a laboratory investigation of the efficiency of water-solvent mixtures in recovery of oil. These mixtures may have the high displacement efficiencies characteristic of solvent floods and the high sweep efficiencies characteristic of water floods. Thus, the water-solvent process may increase the number of reservoirs in which a miscible-type displacement can be used profitably. The experiments on the use of water-solvent mixtures for recovery of oil were conducted to find the general applicability of the process. These studies demonstrated that, in flowing through sands, water and solvent segregated into a solvent layer on the top and a water layer on the bottom rather than flowing through the sands as a uniform mixture. Calculations based on the simultaneous flow of the water and solvent in layers were used to predict the effective mobility of the mixtures and the optimum operation of the process in steeply dipping, homogeneous reservoirs. As most reservoirs are not suited for the operation of the process under ideal conditions, experimental studies were conducted with sand-packed models scaled to represent more realistic reservoirs. These studies included the effects on recovery of oil of rate of injection, viscosity of oil, variations of permeablity within a formation and variations in water-solvent ratio. For the range of con-ditions studied, higher recoveries of oil were obtained with water-solvent mixtures than with water or practical volumes of solvent alone. INTRODUCTION A group of intriguing—because of their great possibilities—new oil recovery methods at the disposal of the petroleum engineer are the miscible displacement processes. These processes (high-pressure gas drive, en-riched-gas drive and LPG bank driven by methane) displace all of the oil from the portions of the reservoir swept by the injection fluid. The key question confronting the engineer applying one of these techniques to a particular reservoir is, "What fraction of the reservoir can be swept by injection of a practical volume of solvent?"." Intensive laboratory studies have been made during the past several years in seeking answers to the question of the sweep efficiencies which can be expected in solvent floods.' - These studies provided the answer that low-viscosity, low-density solvents channel and by-pass oil in sands with no dip. In horizontal sands, solvent flooding becomes less efficient as the viscosity of the oil increases, the recovery of oil at solvent breakthrough decreases and larger volumes of solvent are required to achieve a given recovery. More efficient displacement of oil by solvent is observed under certain conditions in sands with dip.".' If the permeability and dip of the sand are sufficiently high, gravity segregation of low-density solvent injected updip can prevent channeling. At rates of depletion below a critical rate,"." no channeling occurs. Unfortunately, in many reservoirs, the critical rate is so low that production of oil at rates below this rate is not economically attractive. And at rates over four times the critical rate, channeling is almost as severe in sands with dip as in horizontal sands. These findings pointed out that, for solvent floods to be generally applicable in recovering oil from all types of reservoirs, new methods of improving their sweep efficiencies are needed. Simultaneous injection of water with the miscible fluid was suggested by Caudle and Dyes7 as a method for improving sweep efficiencies. They theorize that water flowing with the solvent would decrease the effective mobility of the solvent and cause it to contact more oil sand. If, indeed, the water and solvent flowed as a uniform mixture, the process should have the advantages of the high displacement efficiencies characteristic of miscible floods and the high sweep efficiencies of water floods. Thus, the method (at least in theory) would greatly increase the number of reservoirs in which miscible-type displacements would be feasible. A research program was conducted to probe the technical feasibility of the water-solvent process. It

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

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

Jan 1, 1968

By W. N. Poundstone, G. R. Spindler

A comprehensive report on extensive experimentation in degasification of the Pittsburgh Coal seam is presented. Detailed accounts of the procedures and results are given for permeability tests, vertical bore hole tests, measurement of gas flow from sealed drainage areas, horizontal rib hole tests, and water infusion tests. The removal of methane gas from coal seams in advance of mining is not a new idea with mining men—much attention has been given to the possibility for many years. In other parts of the world, a principal concern has been in the recovery and utilization of the gas and a number of successful projects have been developed in Europe and elsewhere. In this country, the principal motivation has been related to the safety aspect with some possible side benefits concerning costs and efficiency in mining as secondary objectives. To date, experimental work in this country has been largely or entirely exploratory to determine bed characteristics with respect to the liberation of combustible gases to investigate or establish the possibility of degasification in advance of mining and as an aid in projecting mine ventilation systems to provide for safe, effective and economical handling of combustible gases liberated during mining. With these objectives in mind, the School of Mines and Engineering Experiment Station at West Virginia University, in cooperation with the Christopher Coal Co. of Osage, W. Va., initiated some experimental work in May 1952 and the project has been more or less continuous since that time. The work has been centered entirely in mines of the cooperating company in Monongalia County, W. Va., and Greene County, Pa. LOCATION AND GENERAL CONDITIONS OF THE AREA The principal mining in the area involved is in the Pittsburgh coal seam which lies at the bottom of the Monongahela series of the Pennsylvanian. The Pittsburgh coal in the area is generally uniform in its structure and physical characteristics. The bed thickness averages about 7 to 8 ft and the coal has a characteristic blocky structure as the result of pronounced face cleats and definite, but somewhat less pronounced, butt cleavage. It is a medium volatile coal, averaging about 37 pct, and is marketed principally as a steam fuel and for metallurgical purposes. The Pittsburgh coal outcrops along the Monongahela River and dips gradually, but not uniformly, slightly north of west (about N75°W). The westward extensions of the bed, from the areas contiguous to the Monongahela River which have been heavily mined, constitute the principal reserves and are all well below drainage with the depth of cover increasing with the distance from the river. In general, with deeper cover, it may be expected that methane liberation will be more of a problem in future mining as compared to areas mined previously; therein lies the interest in possible de-gasification in advance of mining. Fig. 1 shows the Pittsburgh coal area in the vicinity of Morgantown in Monongalia County, W. Va., and Greene County, Pa., in which the experimental work discussed is located. Fig. 2 shows the contours on the Pittsburgh coal in the test area. It will be noted that the first two bore holes for the experiments were at the edge of a bench or terrace with considerable change in the gradient in the immediate vicinity of the test holes and that the same general condition applies to later test areas. Mining is intensively mechanized in the area and in the mines involved in the experimental work with corresponding rapid advance of working faces a typical characteristic. In the areas now mined the total methane liberation ranges from moderate to relatively heavy, but the actual face liberation is extremely variable and may range from practically

Jan 1, 1961

By H. Furman Byars

INTRODUCTION of bottom dump hauling units into the Ray, Ariz., stripping operation of the Isbell Construction Co., was motivated by several reasons, with what appears to be debatable results. The accepted theory of truck design for use in open-pit holds that end dump vehicles are the most adaptable for the work. But, because operations of the bottom dump, under certain construction and haulage conditions, proved economically feasible, the unit was put to work in the Ray copper pit. The decision to try bottom dump was reached after considerable observation of the unit in action on construction of earth filled dams, levees, airport construction and several other similar tasks. Basic tire design also motivated the choice. All things being equal, a vehicle running on low pressure single tires will outperform another operating on dual high pressure tires, providing load carrying capacities are the same. The investment required to equip a vehicle with four single tires to handle the same load as one with dual tires mounted on two axles and single front axles is about 60 pct greater. Thus, in order to reach the break even point on tire costs, single tires must operate 60 pct longer. Comparison is made with a truck outfitted with 10 16:00x25 tires. Two other factors were considered in selecting bottom dump trucks. It was felt the bottom dump principle would work well in dumping ore into a hopper where gate design fits this particular method. Also, with the absence of hydraulic dumping, ore pollution with oil is reduced. The mechanical simplicity of the unit also lent weight to its choice. Ordinary reasoning indicated maintenance costs would be low compared with other units carrying similar loads. The bottom dumping principle is not new. It dates back to the days when horses were used to haul the same kind of rig. The unit employed at Ray holds 25 cu yd struck measure, or approximately 42 short tons. Dumping is accomplished by releasing an air cylinder opening a dog holding the doors. Doors are closed by a cable system operating off a wheel wind deriving power by friction with the trailer tire. The unit is mounted on four 27.00x33 and two 14.00x24 tires on the front axle. The power unit is a 300 hp Cummins engine. Hydraulic power boosts the steering. A straight mechanical drive and friction clutch with 10 speeds is used. Conditions Not Ideal Top performance of the truck can be expected only under the conditions for which it was designed, in particular grades under 5 pct, handling fine material, and dumping where one thin layer can be placed on top of another. The machine will handle 42 tons per haul, operating at high speed, with only seconds used for dumping. On a 2 or 3 pct grade over a one mile haul,

Jan 1, 1952

By S. F. Ravitz

IN his excellent book on the Principles of Flotation, Wark&apos; makes the following significant statement concerning the theory of flotation: Two questions of first-rate importance must be considered . . . First, it must be decided whether the sulfide minerals require a collector in order that they may float, or whether as has been claimed, they possess an inherent floatability and need no collector. Second, it must be decided whether the xanthate type of collector can react with or be adsorbed by the unchanged sulfide minerals themselves, or whether, as many claim, reaction with the collector is dependent upon initial oxidation of the mineral surface. In the theory of flotation there are no two questions of greater importance than these. Ravitz and Porter&apos; presented evidence that galena can be floated without a collector, and even without any reagent, provided oxidation products are thoroughly removed from its surface. They found also that thoroughly cleaned galena floated faster when xanthate was used than when a frother alone or no reagent was used, and that, without a collector, the recovery decreased gradually upon exposure of the mineral to air. Their work, however, has met with considerable criticism. I(127).3-6 This paper is presented to answer the objections that have been raised, and to present additional data that confirm their results. EXPERIMENTAL PROCEDURE The apparatus used to provide oxygen-free conditions for flotation has been described in detail by Ravitz and Porter. An atmosphere of purified nitrogen was maintained within the apparatus; all water and solutions used were freed of dissolved air, and could be transferred where desired by the use of nitrogen pressure; nitrogen was used as the gaseous medium for flotation. The flotation cell was essentially a glass cylinder 15 cm. long and 4.6 cm. in diameter. Near the bottom was sealed a fritted glass filter, which broke up the gas into small bubbles, and 6 cm. above this filter was a side arm through which the froth overflowed. The pulp was agitated by a glass impeller, which entered the cell through a mercury seal. For each test 17 grams of galena and 75 ml. of water were placed in the cell, after which the speed of the impeller and the rate of gas flow were adjusted. Water was added gradually during the test to keep the froth level at the proper height. The mineral was prepared and cleaned in the following manner. Exceptionally pure galena was crushed by hand on a clean bucking board, screened to - 150+ 200 mesh, and deslimed on a zoo-mesh sieve with a fine spray of water. It was then boiled on a hot plate for a number of hours with several changes of the desired cleaning solution, after which both the solution and the mineral were placed in the "mineral flask" of the apparatus. The cleaning solution was drained off, and the mineral was boiled with oxygen-free water

Jan 1, 1940

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,&apos; 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&apos;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 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

By Harry Udin

IN 1948, the writer and his associates determined the surface tension of solid copper by balancing the force of surface tension in a very fine wire against an external load.&apos; At that time we, in common with other early workers, assumed that grain boundary energy in a pure metal is very small in comparison to the energy of an external surface. Accordingly, we neglected the internal surface energy of the coarse-grained specimens. Since that time, experimental evidence has accumulated showing that grain boundary energy, far from being small, is generally about one-third of the energy of an external surface.2-4 This is sufficient to introduce a significant error into our determination. The differential equation governing equilibrium is: wdl - yds, + y*ds2 [I] rather than wdl = yds as originally written. w is the balancing force in dynes, 1 the length of the specimen, sl the external and s2, the internal surface area, y the copper/ copper vapor surface tension, and y* the grain boundary tension. Fortunately, we had made for another purpose a careful study of the size and shape of the grains, and found that the boundaries, with rare exceptions, traversed the specimens and were perpendicular to the wire axis. For this case, eq 1 leads to w = rry -(n) r2y* [2] where r is the wire radius and (n is the number of grains per unit length. A count of some twenty 5-mil wires indicated that - n became 80 & 10 after a short anneal near the melting point, and remained nearly constant for as long as 96 hr at temperature. An assumption of y* = 1/3y leads to a defining eauation for r: [31 The term in the brackets may be considered a correction factor applied to eq 11 of ref. 1. Upon applying this factor, the surface tension of solid copper at its melting point is found to be 1650 & 100 dynes per cm, rather than 1370 as previously reported.&apos; The new temperature coefficient is —0.55 dynes per cm per "C. Grain boundary energy is more significant than surface energy to the physical metallurgist. It is evident from eq 2 that a series of experiments with wires of different grain size can lead to an evaluation of y*. The details of such an experiment are being worked out now. References 1 H. Udin, A. J. Shaler, and J. Wulff: The Surface Tension of Solid Copper. Trans. AIME, 185, 186-190; Journal of Metals (Feb. 1949) TP 25303. 2 G. L. C. Bailey and H. C. Watkins: Surface Energies in the System Solid Copper-Molten Lead. Proceedings Physical Society. (London) (1950) 36B, 350. 3 L. H. VanVlack: Inter granular Energy of Iron and Some Iron Alloys. Ph.D. Dissertation, Univ. of Chicago, Sept. 1950. 4 . P. Greenough: Grain Boundary Energies in Silver. R.A.E. Report, No. Met. 52. (May 1950) Fan-borough, Hants, England.

Jan 1, 1952

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 &apos;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,&apos; 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 L. S. Chabot

The bibliography of mining methods in the past few years has contained many articles dealing with the use of the diamond drill for blasthole drilling. In the Canadian mines, this method has been used with great success in stoping at Noranda, Aldermac, Waite Amulet, East Malartic and Sladen Malartic mines in the Province of Quebec. It has also been used at the Dorchester and Beattie gold mines in Duparquet, Quebec. The method has found useful application at Copper Mountain mine, British Colombia, and at Flin Flon mine in Manitoba. In the United States, the diamond drill blasthole method has been used at Cornwall Iron Ore Mines in Pennsylvania and at the Republic Steel Corporation magnetite properties in the Port Henry district of northern New York. In the Lake Superior iron district, the method has been used at the Anvil-Palms mine of Pickands, Mather and Co. at Bessemer, Mich., and is also used at the Book mine of the North Range Mining Co. at Alpha, Mich. Other companies in the district have also experimented in some degree with the method at some of their properties. This Paper is being offered as a prelimi- nary report on the use of the diamond drill method of stoping at the Book mine. Sufficient work has been done with it to prove its worth and it is the purpose of the article to present some results, operational details, equipment ideas and recommendstions which we have found in its use at our mine. Location and Description The Book mine is situated about a mile north of the village of Alpha, in the NE-NE1/4 and the SE-NE1/4 of set 12-42-33, between the Dunn mine and the Balkan-~~d~~~ mine, and about four miles southwest of the village of Crystal Falls, on the menominee Range of Michigan, The property was found to have ore near surface in sufficient quantities for open-pit operations and stripping was begun in the latter part of 1942 to prepare it for ore production in 1943. During 1943, 288,447 tons of direct shipping ore were produced from the open pit and 382,933 tons in 1944 While the mine was being operated as an open pit some 350,000 tons of lean ore were stockpiled for later treatment. This material is beilng treated in a washing and jig plant and concentrates are produced during the shipping season. The ore bodies at the Book mine are characteristic of the Menominee Range. They are found on the flanks of sharply folded anticlines which have a fairly steep pitch to the northwest. The open-pit operatiOns in 1943 and 1944 revealed two of these anticlinal structures. A detailed study and classification of the old diamond drill records, coupled with the information of some new holes drilled, has established the

Jan 1, 1949

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.&apos;-&apos; 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:&apos; 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