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By J. M. W. Mackenzie, M. H. Buckenam

Flotation experiments using stearic, oleic, linoleic, linolenic, and ricinoleic acids and naturally occuring products rich in these acids as collectors for calcite are described. The results confirm the validity of the rule of Hukki and Vartiainen relating the collecting power and unsaturation of the C18 acids. Reasons for this relationship are discussed and a close relationship between mineral depression and critical micelle concentration is reported. It has long been recognized that the unsaturated fatty acids are in general superior flotation collectors to their saturated homologues. Whereas earlier workers concentrated on saturated and monoethe-noid acids, recent investigations have centered on oleic, linoleic, linolenic, and the substituted mono-ethenoid acid: ricinoleic. From studies of the collecting properties of palmitic, oleic, linoleic, and linolenic acids on ilmenite, rutile, hematite, and magnetite, Hukki and Vartiai-nenl concluded that the collecting power of fatty acids increased with unsaturation of the hydrocarbon chain. Sun, Snow, and Purcel12 investigated the collecting properties of unsaturated fatty acids as collectors for phosphate ores and concluded that the collecting power increased with increasing unsaturation of the hydrocarbon chain up to two double bonds and that further unsaturation decreased the collecting power. More recently Sun3 studied the collecting power of the C18 fatty acids stearic, oleic, linoleic, and linolenic on 37 minerals. The results of these experiments with a few exceptions showed that the collecting power of the acids increased in the order stearic, oleic, linoleic, and linolenic. The relative collecting powers of linoleic and linolenic acids were in many cases altered by the cleanliness of the mineral surface prior to flotation. Sun concluded that linolenic acid may become oxidized by atmospheric oxygen during flotation, a reaction which would reduce its effectiveness as a collector. This deduction is supported by Gaudin and Cole4 who concluded that oleic and linoleic acids do not undergo appreciable oxidation of the double bonds during flotation but that the linolenic acid double bonds are measurably affected. The most complete investigation on the influence of hydrocarbon chain unsaturation on the collecting properties of fatty acids is that of Kivalo and Lehm~svaara.~ These workers using linolenic acid of a higher purity than Hukki and Vartiainen showed that this acid was superior to oleic and linoleic acids as a collector for magnetite. They also found that ricinoleic acid was a more effective collector for this mineral than the other acids investigated, an observation particularly apparent at high collector concentrations. Seeking to explain the superiority of the unsaturated acids these authors considered the effects of critical micelle concentration, surface activity, hydrolysis, and cross sectional area of the hydrocarbon chain in relation to unsaturation. Using what, according to the results of Caviere are erroneous surface tensions of the soap solutions of these acids, they concluded that the surface activity decreases and the critical micelle concentration increases with increasing unsaturation. In view of the data of Cavier, whose results show that surface activity of these soaps increases with unsaturation, the deductions of Kivalo and Lehmusvaara are open to criticism. The degree of hydrolysis of the soap solutions as measured by Kivalo and Lehmusvaara decreases as the unsaturation of the fatty acid increases, a result which helps to explain the superiority of unsaturated acids as collectors. In view of the superiority of unsaturated acids as collectors for many minerals, attention has been directed towards the utilization of fatty acid raw materials such as tall oils and linseed oils which contain considerable quantities of these acids. This paper describes test work to determine the effect of unsaturation of the hydrocarbon chain on the collecting properties of fatty acids on calcite, and includes comparable test work using natural products rich in unsaturated acids. TEST WORK Reagents: The pure fatty acids used were oleic, linoleic, and linolenic. Of these, oleic was supplied by British Drug Houses Ltd. and the others were produced by the Hormel Inst. When not in use these

Jan 1, 1961

By Joseph T. Singewald

AMONG the genetically interesting iron ores of the United States are those of the St. Francis Mountains near Ironton and Iron Mountain, Missouri. They are specular hematite in porphyry. The Iron Mountain and Shepherd Mountain deposits are generally spoken of as veins and those of Pilot Knob, Cedar Hill, and Russell Mountain as bedded deposits. Iron Mountain has produced nearly 4,000,000 tons of ore and Pilot Knob about 1,500,000 tons. The output of the other three localities has been insignificant. Pilot Knob is no longer worked as an iron mine, but the rock is now being crushed for use as road metal. Iron Mountain has continued as an active producer. In 1927, the property was acquired by the M. A. Hanna Co. and an extensive prospecting and exploration campaign was undertaken, so that the ultimate production of Iron Mountain will doubtless greatly exceed the figures mentioned. Previous Theories of Origin Descriptions of the deposits and theories of their origin have been concerned mainly with Iron Mountain and Pilot Knob, which represent the two contrasting types of occurrence. The Iron Mountain deposits have been considered of close magmatic origin by Whitney' in 18.54, Geijer2 in 1915, and Spurr3 in 1927. Whitney referred to them as of eruptive origin. Geijer considered them fissure fillings at magmatic temperatures. Spurr called them vein dikes formed from ore magma which was essentially fluid iron oxide. Schmidt4 in 1872 ascribed them to fissure filling by thermal chalybeate waters of meteoric origin. Nason5 in 1892 advanced essentially the same explanation. One of the best

Jan 1, 1929

By H. I. Aaronson, H. A. Domian, G. M. Pound

Zener's two-parameter theory of the y a reaction in Fe-X alloys is extended to encornpass austenite-stabilizing as well as fewite-stabilizing elements, and is then cottzbitzed with statistical thermodynamic theories of Fe-C alloys to permit development of a ther-modynamic description of the proeutectoid fewite reaction in Fe-C-X alloys. Equilibrium tielines are calculated for tile a + y rep'on from experimental data and frort extrapolations of the y/y +a equilibrium surface. Sectzovs of the y/y + 0 surface are calculaled for the tzetastable sstuation LYL u-kich alloyrtg eleitzents do not partition betzseen azrstenite andfer-rite. The finding that the metastable y/a + y curves Lie close to their equilibriuwz counterparts when X = Si, .Vo, Co, Al, and Cu but well below them when X = A/ln or Ari pr-elides a thermodunamic explanation for the expcri1?7e?ztally obserted absence of partition during the proeutec toid ferrite reartlon in the fortner alloys and for the occurrence of partition at hzgher ternperatures in the latter alloys. Cotarison ofno- patitzoa free-energy changes and y/y i a curr,es in Fe-C-X alloys with the equilibrium 11al1es of these quantities in Fe-C alloys furnishes additional qualitative insight into the irqluence of allojling elements upon the kinetics of the proeutectoicl ferrite reaction. THE introduction of a substitutional alloying element, X, appreciably complicates calculation of the thermodynamics of the formation of proeutectoid ferrite from austenite. As noted in the preceding paper,' the positional entropy of the interstitial species is the principal component of the free energy of an interstitial solid solution with which theory has so far been able to deal. One would expect, however, that other components of the free energy of this type of solid solution may be significantly altered by the addition of a substitutional alloying element. Even if the assumptions are made, by analogy to the case of Fe-C alloys,' that changes in the positional entropy of carbon represent a significant part of the thermodynamic effects of an alloying element, and that the remaining effects can be taken into account by fitting the equations developed on this basis to experimental data on Fe-C-X phase diagrams or on the activities of carbon in alloyed austenite and ferrite, the experimental information available on either of these quantities is not yet sufficiently accurate or extensive, respectively, to make such an approach useful. An attempt made by Zener on the former basis to explain the effects of alloying elements on the thermodynamics of Fe-C alloys in terms of a temperature-independent "free-energy change" (actually enthalpy hane') required to transfer 1 mole of an alloying element from austenite to ferrite, in which the "free-energy change" was determined by fitting the theoretical relationships developed to Fe-C-X phase diagrams, thus proved inadequate in part because of deficiencies in the available ternary-phase-diagram data.= Other difficulties of a more fundamental nature, however, also indicated the desirability of a different approach to the problem.3y4y6 zener6 subsequently proposed that the free-energy change associated with y — a transformation in pure iron can be decomposed into magnetic and nonmagnetic components. Alloying elements were assumed to affect those components separately. One parameter was used to describe the quantitative effect exerted on each component. These parameters were evaluated from Ms (martensite-start) temperature data and from other experimental information usually either readily available or measurable with acceptable accuracy. Zener applied this treatment only to the calculation of Fe-X phase diagrams in which X is a ferrite-stabilizing element. In the present study, this treatment is extended to include austenite-stabilizing elements, and then combined with treatments previously considered for Fe-C alloys1 to permit calculation of the thermodynamic quantities of interest in the austenite - proeutectoid ferrite transformation in Fe-C-X alloys, where a number of representative, and commonly used alloying elements are chosen for X, including Si, Mn, Co, Mo, Al, Cr, and Cu. The results are used to explain important features of the partition of alloying elements between austenite and proeutectoid ferrite, as reported in a companion paper7 on the basis of electron-probe analysis, and to provide some additional understanding of the influence of alloying elements upon the kinetics of nucleation and growth of proeutectoid ferrite. Portions of this treatment6 have been clarified in the course of a review by Kaufman and Cohen.3 The consolidated summary of these developments with which this section is begun provides a basis for further clarification of the treatment, from which extension to include austenite- as well as ferrite-stabilizing elements is a natural consequence. The division of the free-energy change associated with the 7 - a transformation in pure iron, into two independent components is formally stated as:

Jan 1, 1967

By Maurice Ewing

THE purpose of this paper is to present the results of the application of the earth-resistivity method of subsurface investigation to the problem of locating seams of anthracite coal beneath a mantle of soil and subsoil. Details are given of the successful use of this method in locating the outcrops of anthracite seams in actual prospecting. The presence of the outcrop of an anthracite seam is indicated at points where electrical resistivity tests showed relatively low readings. The reason for, this is that in some localities the resistivity of anthracite was found to be about 0.0001 megohm-cm. compared to 1 to 200 megohm-cm. for shales and sandstones. For two reasons it is believed that the data sum-marized in this paper should be of particular interest. In the first place, most of the interpretations of the resistivity survey have been checked by subsequent drilling and some by the removal of the overburden and the exposing of the anthracite seams. It is infrequent that the oppor-tunity for checking results so thoroughly is given. In the second place, the fact that recent commentators 1.2.1 on the application of geophysical methods to mining have concluded that direct prospecting for anthracite and other types of coal is not promising makes the good results obtained more significant. So far as the authors can learn, the only previous experiment with electrical methods in the Pennsylvania anthracite field was one made by Sherwin F. Kelly in 1922, when he used the self-potential method at Wilkes-Barre4. The profile he made does not show a very marked correlation with the geologic cross section. Kelly points out that stray currents from electric motors in the mines undoubtedly affected his results, but the experience of the present authors with stray currents from mining machinery suggests the possibility that the potentials measured by Kelly were due almost entirely to this effect.

Jan 1, 1936

By J. P. Pritchard, J. T. Pierce, O. G. Slay

This paper discusses the results of a technology-evaluation program to ascertain the feasibility of a piotornask-photoresist technology developed for fabrication of multiple-layer thin-film superconductive circuitry. The uehicle selected for this evaluation was a 120-bil associative data processor requiring a set of nine photomasks to define a similar number of patterned material layers of lead, tin, and polymer insulation. A total circuit area of 4 sq in. involved 2500 actitle and 12,000 passive crossings. Several short-free, electrically continuous specimens were satisfactorily completed under this program. Problems encountered in the preparation and use of the requi-ed set of Photomasks are discussed, as also are the problets of providing suitable external connections. A major retarding factor in the development of the superconducting thin-film cryotron technology for many years was the absence of batch fabrication means yielding necessary device density and count per substrate for practical applications. Early workers in the field desired only limited numbers of devices to permit careful study of discrete devices and representative circuitry integrating logic and memory capabilities. For these purposes mask stencils could be formed to selectively control the placement of materials, sequentially vapor-deposited in vacuum, to form the multilayer structure. In general a distinct pattern was required for each material layer; therefore, mechanical provisions were required to change not only the material source, but the patterning mask as well, before each deposition. All deposition steps were preferably performed in a single evacuation of the deposition chamber. Thus the means for storing, transporting, and registering masks and sources with respect to the substrate existed and were operated within the vacuum environment. In the authors' experience, the approach was and remains serviceable for preliminary device study, but was not extensible to an economical manufacturing method by virtue of the difficulties inherent in mask stencil preparation and use, and the capital investment implicit in the mechanization requirements. Since the commercial attraction of the cryotron technology stems principally from its potential for economical batch fabrication, the authors' program has placed major emphasis on fabrication methods. A highly useful method has evolved through adaptation

Jan 1, 1967

Carlisle: This is April 19, 1961. My good friend Dave Irwin is sitting on the other side of the tape recorder. We are at Rose Dhu Island, Savannah, Ga. Now, let's begin with your first job, where and what was that? Irwin: I started out to Arizona, looking for a job and wound up in Morenci. The next morning I applied at the mine office and was put on as a sampler. I worked as a sampler and as an assistant to Frank Pelton, the geologist, for a year, after which I went back to New Haven to take my last year of postgraduate work. After getting my degree, I went back to the Southwest with W. Rowland Cox and Staff, supposedly as a geologist. Q: But that was not when he was with Spurr? Irwin: That was after he had left Spurr. Henry Smith was with the Spurr end of the outfit and I happened to drop into the W. Rowland Cox end. My first job with him was to do some work on a prospect above Metcalf, Ariz., and from there I would go out on short reconnaissance trips in Arizona, New Mexico and old Mexico.

Jan 6, 1964

By A. G. Spillette, R. L. Nielsen

The purpose of this paper is to further the understanding of reservoir response to hot-water injection by desuribing a two-dimensional, mathematical model of the process. Key assumptions are that no gas phase is present, and that the injected fluid reaches thermal equilibrium instantaneously with the reservoir fluids and sand. The resulting system of three partial differential equations is solved simultaneously through the use of a "leap-frog" application of standard alternating direction implicit methods for the solution of the mass-balance equations and the method of characteristics for solution of the energy-balance equation. The utility of the mathematical model is demonstrated by comparing numerical and analytic temperature distributions for hot-water bank injection and by comparing calculated with observed field behavior. Additional calculations show that hot waterfioding can recover significantly more oil than cold waterflooding, and that a hot-water bank recovers, with less energy input, nearly as much oil us continuous injection. Introduction Consistent field success with hot fluid injection processes requires good reservoir description and a thorough understanding of recovery mechanisms. The latter is fostered by a combination of well designed experimental studies and physically sound mathematical modeling. The purpose of this paper is to further the understanding of reservoir response to hot-water injection by describing a two-dimensional mathematical technique, indicating its validity, and demonstrating its utility for studying the effects of reservoir and operating parameters. Published experimental studies of hot fluid injection processes are few." Even if extensive data were available, two considerations discourage exclusive reliance on laboratory or field work. First, because of the severity of scaling requirements," laboratory results must be interpreted with care. Second, because of the one-shot nature of field experiments — injectivity/productivity tests and pilot floods—results seldom are available over the desired range of operating conditions. These factors emphasize the need for devoting attention to mathematical modeling to complement laboratory and field work. Through the use of mathematical models, scaling uncertainties can be bridged and response can be predicted for unique combinations of reservoir and operating conditions. Numerous mathematical models developed during recent years enable us to calculate temperature distributions, thermal efficiency (or conversely, fraction of heat lost), and oil recovery behavior for hot fluid injection. Ramey" and Spillette' recently have provided reviews of these methods. Most models have concentrated on predicting temperature distributions and thermal efficiency; few have been directed at predicting oil recovery.'."1° Although these techniques are useful for estimating effects of reservoir parameters and operating conditions on process performance, results are limited by the assumptions made and by the methods of coupling independently solved fluid-flow and energy-balance equations. A computer-based method is presented for predicting total reservoir response to hot-water injection that obviates most simplifying assumptions. The model simulates fluid flow and heat transfer in two dimensions within a vertical cross-section spanning the oil sand and adjacent unproductive strata. Known numerical procedures are used to solve the governing partial differential equations. The mathematical model handles the effects of reservoir heterogeneity, gravity, capillarity, relative permeability and temperature-dependent fluid properties. In addition, a wide range of operating conditions can be modeled, including hot-water followed by cold-water injection. Mathematical Description of Hot-Water Injection Key assumptions in the mathematical model for hot-water injection are that (1) no gas phase is present and (2) the injected fluid reaches thermal equilibrium instantaneously with the reservoir fluids and sand. Relative permeability and capillary pressure are assumed independent of temperature. Darcy's law for multiphase fluid flow relates the velocities of the oil and water phases to the phase pressure gradients by the following relations:

Jan 1, 1969

Sec. 1. The membership of the Institute shall comprise six classes, namely: 1. Members; 2. Honorary Members; 3. Senior Members; 4. Associates; 5. Junior Members; 6. Rocky Mountain Members. All shall be equally entitled to the privileges of membership, excepting that no member of any class whom residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote. SEC. 2. Members: A person to be eligible for election or transfer into the claw of Member must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. This shall not apply to Rocky Mountain members.

Jan 1, 1934

By F. N. Rhines, A. H. Grobe

At elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible1 and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscaleiormation) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detai1.5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the 1-6 and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 40 alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. Experimental Procedure Silver.—The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By A. H. Grobe, F. N. Rhines

At elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible1 and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscaleiormation) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detai1.5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the 1-6 and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 40 alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. Experimental Procedure Silver.—The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By R. W. Kraft

A back- reflection precession-type X-yay camera for determining the crystallographic orientation of the crystallites of both phases in small areas of thick specimens of polyphase alloys is described ad the geometry, advantages, and limitations of the apparatus are discussed. Metallographic obseg-vations of interfacial angles (or habit planes or growth direction are made on the same specimen so that the crystallographic and metallographzc orientation data call be directly correlated. An example of the application of tile technique to a unidi-~~ectionally solidified CuA12-A1 eutectic specimen is presented. The interfacial planes ad growth directions of each phase were established, and the orientation relationship between the phases was observed and found to be approximately intermediate between two previously reported relationships. The crystallographic interfacial relationship between two solid phases is an important parameter in a variety of metallurgical phenomena because of the energy associated with the interface and because this energy is at least partly associated with the way in which the two space lattices are in contact along the interface. In order to describe the interfacial planes in the crystallites of both phases it is necessary to determine the crystallographic orientation of each phase in a specimen relative to each other, and to directly correlate these data with met-allographic measurements from which the interfacial planes can be determined on the same specimen. The back-reflection Laue technique is the easiest way to determine the orientation of thick single crystals or large grains and the method can be combined with metallographic techniques to provide the necessary data, provided the reflections from each phase can be distinguished from one another. However, if the crystallites are small or of varying orientation or if one or both phases has a unit cell with less than the maximum symmetry, many overlapping and complex Laue patterns are recorded simultaneously and it becomes impractical if not impossible to interpret the photographs. All of these complexities were present in a unidirectionally so- lidified A1-CuA12 eutectic alloy1 for which a crystallographic analysis was desired. Consequently the method described here was developed since no known X-ray or electron diffraction technique had all of the following attributes which were required. 1) Method should yield data from which the crys-tallographic orientation of every crystallite or diffracting unit in the irradiated area can be determined. 2) Method should be adaptable to the study of small areas. Depending upon the degree of preferred orientation in the specimens, it should be possible to obtain reliable data in a reasonable length of time on irradiated areas as small as 1.0 or even 0.1 mm in diam. 3) Method should permit direct correlation of crystallographic data with microscopic orientation data pertaining to crystallite axes, habit, morphology, and growth directions as determined by optical microscopy. 4) method should be such that selected areas of large specimens can be easily studied. Trepanning of a small specimen (such as an electron microscope specimen) from larger specimens was undesirable since it would greatly increase the problem of correlating the crystallographic and microscopic directional data. Requirements 3 and 4 dictated that an X-ray back-reflection pinhole technique should be used on large samples, such as metallographic specimens which had previously been examined and analyzed for their microscopic characteristics. Similarly, requirement 2 could be satisfied by choosing a collimator of appropriately small diameter. Exposure times would not be excessive provided the detector were close enough to the specimen. Because of space limitations film was chosen in preference to a Geiger counter. Requirement 1 was fulfilled by using monochromatic radiation and providing enough additional degrees of freedom in specimen rotation to compensate for Bragg law restrictions on diffracted beams. DESCRIPTION OF APPARATUS The apparatus shown in Fig. 1 consists of a pin-hole collimator, (a), projecting through a rotatable circular film in a holder, (b), which records X-ray reflections in the back-reflection region. The specimen, (c), is mounted on the end of a shaft, (d), which is provided with an adjustment, (e), so that the specimen surface can be placed accurately on

Jan 1, 1962

By Sidney Diamond, Charles Wert

The anelastic behavior of Ni-C alloys of nominal 0.5 wt pct C has been determined over a wide temperature range. The most prominent damping effect, that due to the presence of C-C pairs, was measured both above and below the Curie temperature. The effect on diffusion of the C-C pairs by magnetic spin ordering is deduced to be very small. The diffusion coefficient for C-C pairs in nickel is given by the expression ThE solid-state diffusion of both interstitial and sub-stitutional solutes in ferromagnetic solvents has been the subject of a number of investigations. Measurements of the self-diffusion of iron,"' the diffusion of nickel1,4 gold,"1 and cobalt4 into iron, the diffusion of vanadium in an Fe-V alloy,' and the diffusion of cobalt and nickel in Co-Ni alloys9 show an unusual behavior. In both the ferromagnetic and paramagnetic regions, far removed from the Curie temperature, the diffusion coefficient, D, obeys an Arrhenius relation. However, in the ferromagnetic region D is markedly lower than would be expected from an extrapolation of D from the paramagnetic region; this results in an increase in the activation energy in the ferromagnetic region. The cause of this effect for self- and substitutional diffusion is uncertain. Since substitutional diffusion is presumed to proceed by the vacancy mechanism, it has been variously suggested that the increase in activation energy below the Curie temperature is due to one of the following causes: 1) an increase in the energy of formation of a vacancy because of local demagnetization around the vacancy,2,3 2) a decrease in vacancy mobility in the ferromagnetic state,' or 3) an effect on the entropy of motion of a vacancy in the ferromagnetic state.5 Quite another explanation for the observed effect has been proposed by Borg.7 The diffusion coefficient is a function of the elastic constants of a metal. Since the temperature dependence of the elastic constants often changes at the Curie temperature, the temperature dependence of D might be expected to undergo a universal change in the vicinity of the Curie temperature. The magnitude of the change in D would, of course, depend on the magnitude of the change in the elastic constants. One might attempt to differentiate between vacancy effects and elastic effects by making measurements on interstitial alloys, in which vacancy effects play no role. Some measurements of this type have been made; this paper reports additional observations. Measurements of the diffusion of carbon in a Fe by a tracer technique8 and of the diffusion of carbon in a Co and in Co-Fe alloys by a decarburization method9 reveal a small effect, if any, on D of the magnetic change at the Curie temperature. If the effect of spin ordering is only to alter the parameters controlling formation or mobility of a vacancy, interstitial diffusion should indeed remain unchanged through the magnetic transition, as these measurements imply.

Jan 1, 1968

By L. Guttman, C. S. Barrett, J. S. Bowles

THE transformation from the face-centered cubic (Al) to the face-centered tetragonal (A6) structure in certain alloys of the indium-thallium system reported in the preceding paper1 exhibits many interesting crystallographic and metallo-graphic features, most of which presumably are similar to those of other cubic to tetragonal transformation such as, for example, the one which occurs in the chromium-manganese system,2 the one which, judging by microstructures and X-ray pat-terns,3 probably occurs in the copper-manganese system, the ones accompanying ordering in FePt,4 Copt,&apos; and AuCu,5 and the transformation near 115°C in barium titanate.6,7,8 If, as mentioned in ref. 1, the transformation is second order, the phases in equilibrium do not differ in composition, and it is both possible and likely that the mechanism is a diffusionless one. The present paper reports the results of a detailed study of the indium-thallium transformation and presents a theory for the atomic movements of the transformation which accounts for the observations. Experimental Crystallography of Transformation Markings The transformation from cubic to tetragonal in the indium-thallium alloys produces microstruc-tures of the type illustrated in fig. 1. These structures are observable either as relief effects produced on a smooth surface by the transformation, or after polishing and etching. These microstruc-tures are markedly similar to those found in copper-manganese alloys: iron-platinum alloys," and barium titanate,7,8 where it has been demonstrated that the lamellae are parallel to the (101) planes of the original cubic crystal. That the observed lamellae in indium-thallium alloys are also parallel to the (101) planes was proved by the following analyses performed on single grains in polycrystal-line samples containing 20.75 atomic pct T1. A study of the microstructures of a number of specimens revealed the fact that in many specimens the transformation markings continued unchanged in direction across the (111) interfaces of annealing twins. This at once demonstrates that the lamellae are parallel to a plane that is common to both parent and twin orientations, i.e., a plane in the zone <112>. This conclusion is compatible with the lamellae being parallel to (101) planes. To make a more complete determination of the habit plane of the lamellae, two grains were selected in which annealing twins ({Ill) twins) had been present in the high-temperature modification (cubic). The traces of the annealing twins, and of the transformation markings in both parent and twin crystals, were plotted together in stereographic projection, and a parent-twin pair of orientations was found that accounted for all lamellae as (101) planes. The projection of one of these twinned grains is reproduced in fig. 2. In view of these results the probability of there being another solution for the habit plane remote from (101) is very small, but to explore the possibility that the habit plane deviates slightly from (101), a more precise analysis was undertaken. In this, the orientation of a grain in the cubic modification was determined from a Laue back-reflection photograph taken with the sample at 90°C. The traces of the lamellae that formed in this grain on cooling were plotted in the stereographic projection

Jan 1, 1951

[Furnaces (see also Blast jurnaces) :-(Continued.) McGill, Nev., LI, 765. roasting: XLIX, 184, 188. Anaconda, Mont., XXXVII, 462, XLIX, 676. concrete hearths for, XLVI, 419. Crouse, XLVI, 413. gas, XXXVIII, 163. Heberlein, XXXVII, 634.]

Jan 1, 1918

By P. R. Hines

Diphenyl guanidine is used as an accelerator in vulcanizing rubber. Other rubber accelerators are also flotation collectors, e.g., dithiocarbamate, thiazole, and the xanthates. Urea and its derivatives are good flotation collectors,&apos; and guanidine is the nitrogen analog of urea. These two characteristics suggested testing diphenyl guanidine as a flotation collector. Diphenyl guanidine has been tried in flotation work previously, but references give no details.&apos;.&apos; Bunker Hill Co. of Kellogg, Idaho, supplied the ore sample used in these tests. The sample was typical of the ore milled in 1949 and contained 4.52 pct Pb and 1.08 pct Zn. A flotation test made by the author with potassium ethyl xanthate as a collector, the same flotation reagents, and the same grind employed in regular Bunker Hill mill practice was the standard for comparing results with the compounds and derivatives of guanidine. The compounds and derivatives of guanidine are only fair collectors of galena. However, if potassium ethyl xanthate were used in the galena float, its presence later in the sphalerite float would make it impossible to introduce another type of collector and be certain which collector contributed the result, so the compound or derivative of guanidine under test was used in both the galena and sphalerite floats in Table I. On both the galena and the sphalerite in the Bunker Hill ore, the depressing action of sodium cyanide and zinc sulfate is much greater with collectors of the guanidine type than with the xanthates. If the depressing agents are left out when a guanidine type of collector is used, but a pH of 8.6 is maintained with either lime or sodium carbonate, the depressing action is approximately the same as in the standard xanthate test. Consequently the depressing agents, sodium cyanide and zinc, were not used in the galena floats of tests 1226, 1228, and 1286, Table I, so the galena floats would be on a comparable basis with the standard xanthate test. As shown by the tests in Table I, the loss in the tail when diphenyl guanidine is used is 8.3 to 9.3 pct, as compared to 17.6 pct with potassium ethyl xanthate, or a recovery of 2.3 to 2.0 lb more zinc. Concentrate grade is 13.7 pct with potassium ethyl xanthate and increases to 22.9 and 31.8 pct with diphenyl guanidine, showing a much higher selectivity. Unless the Barrett&apos;s No. 4 coal tar creosote is considered to be a collector, no collector other than diphenyl guanidine is present in the tests, Nos. 1226, 1228, and 1286. Tests 1218, 1253, and 1263 in Table I1 were run to check the effect of the depressing agents used in flotation of the galena (sodium cyanide and zinc sulfate) upon subsequent flotation of sphalerite by diphenyl guanidine. Urea was substituted for potassium ethyl xanthate in tests 1253 and 1263 because it is a good collector for galena and a poor one for sphalerite, and the effect of the depressing agents is more marked with urea than with potassium ethyl xanthate. Test 1205 checks the effect of urea alone without any depressing agents when used for the flotation of galena. Table I1 shows that diphenyl guanidine as a collector for sphalerite is compatible with other flotation reagents used in floating galena. When the depressing agents sodium cyanide and zinc sulfate are used in the galena flotation step, the amount of lime in the sphalerite flotation must be increased (compare 1253 and 1263). Table I11 gives some of the compounds of guanidine which were tested and compared. Some of the compounds and derivatives of guanidine* are solu- * Diphenyl guanidine is in commercial production and is available on the market. ble in water and others are not. Those tested were fed dry. When an organic collector is promising, its compounds and derivatives should be tested and their comparative collecting power recorded. Eventually, in this way, it may be possible to discover some of the essential chemical characteristics of a good collector. For example, it is interesting to compare the diphenyl and dibutyl derivatives in Table IV with those of urea in Table 111, Example 3, U. S. Patent 2,664,198. All are good collectors. Table I shows some of the effects of lime on recovery of sphalerite by diphenyl guanidine. Table V

Jan 1, 1960

By A. L. Barnes

A number of reservoirs have been partially invaded by bottom water. Water flooding such reservoirs can be especially inefficient if the oil has a high viscosity because injected water will under-run the oil and emerge at producing wells without having displaced much oil. A possible means of improving water sweep efficiency would be to precede the water flood with a slug of water purposely thickened with a chemical additive. This possibility has been studied with a scaled laboratory flow model. The investigation was carried out on a model representing a 20-acre five-spot with one set of reservoir condition~. Displacements were performed with water, with viscous-water slugs of 10 and 25 per cent of the pore volume followed by water, and with all viscous water. Displacement tests were made at several rates of injection. For all cases, compared at the same producing water-oil ratio, an increase in rate resulted in an increase in volumetric sweep. The larger the quantity of viscous slug injected, the greater the crossflow of oil ahead of the displacing front and, thus, the lower the WOR during that period of a displacement. This investigation indicates that the injection of aqueous viscous slugs in this type of system would give some additional benefit over conventional flooding by (I) reducing the life of the flood, (2) reducing lifting costs and (3) increasing ultimate recovery. The benefits of a viscous-slug displacement would warrant its use if the viscous water could be created for a few cents per barrel. INTRODUCTION The most appropriate method for water flooding oil reservoirs which have been partially invaded by bottom water has been a problem of considerable interest. Such reservoirs, having good vertical permeability and unfavorable mobility ratios, are difficult to produce efficiently under normal waterflood procedures. Even though the injection wells have been plugged back above the oil-water contact and the water zone has been squeezed off, injection water will enter the formation and not only displace oil, but also much of it will displace the bottom water, thus creating a high producing water-oil ratio at the start of a flood (see Fig. 1). Since the rate of injection and the viscosity of the displacing fluid are the more easily controlled physical parameters of the reservoir, it is quite natural to study their effects on the volumetric sweep of the oil zone and on the producing water-oil ratio. Increasing the viscosity of the displacing fluid has two disadvantages—it reduces the maximum rate of injection into the reservoir, and it costs more than water. It was thought that the injection of a viscous-fluid slug, followed by water, would minimize these two disadvantages, increase the volumetric sweep of the oil zone and reduce the producing water-oil ratio. Water with an additive to increase viscosity would probably be the most effective. The primary purpose of this investigation was to determine the feasibility of injecting viscous-water slugs followed by water to improve or hasten oil recovery while reducing the producing water-oil ratios. The effect of injection rate upon recovery was also investigated. A laboratory model, scaled to a 20-acre five-spot prototype with one set of reservoir conditions, was constructed. Laboratory studies of displacements with (1) water, (2) viscous-water slugs of 10 and 25 per cent of the pore volume followed by water and (3) all viscous water were performed at several rates of injection. THEORY OF SAND MODEL SCALING There are two conventional means of determining scaling criteria. These are dimensional analysis and inspec-tional analysis. Determining scaling criteria by dimensional

By A. B. Kinzel, Walter Crafts

A PRevioUs study1 of the relations of impact strength to inclusions showed that the dynamic strength of steel is lowered by the presence of visible counted inclusions, but that other factors comprised in the term "body" have a marked influence. The previous work was carried out on selected steels from a single source, so that the body factor was purposely minimized, but even under these conditions it was found that inclusion counting or the use of the commercial inclusion rating is not satisfactory. The tensile-impact test, however, was indicated as a satisfactory measure of dynamic strength. It was further suggested that the tensile-impact test should be so standardized as to be suitable for use in specifications, and that the hardness factor should be worked out over a sufficient range to admit ready commercial use of the tensile-impact test. In accordance with these suggestions, and in view of the fact that the steels reported in the previous paper were selected and treated so as to have a minimum variation in body, hardness and structure, further work has been performed on a variety of steels which are not limited by these conditions. The word "body" is used here for want of a better term. It is simply a convenient expression which comprises the effect, of the various unknown factors that modify the dynamic strength of the steel. Thus at our present state of knowledge, the writers have chosen to consider hardness, structure and counted inclusion content as factors not comprised in the term "body," and such factors as raw materials, process of melting, fabricating, etc., as comprised in the term "body." Numerous grades of steels made in several ways have been taken from different sources and have been heat-treated to varying hardness by normalizing and by quenching and drawing. The results, therefore, may be considered to be generally applicable to current engineering steels. A certain limitation with respect to the hardness at which steel should be tested still seems necessary. The upper limit of this hardness range has

Jan 1, 1931

By H. Tabachnick, N. Hedley

The extraction of gold and silver from ores with alkaline cyanide solutions is well known. Cyanide solutions are also good solvents for many base metal minerals, particularly most of the copper minerals. Leaver and Woolf,1 who determined the solubilities of copper minerals in 0.10 pct sodium cyanide solution, showed that malachite, cuprite, chalcocite, and bornite are readily soluble in cyanide; least soluble are chalcopyrite and chrysocolla. The Mining Chemicals Laboratory of American Cyanamid Co. has studied the possibilities of using cyanide solutions for leaching base metals. In this article the authors present the results of their experiments with cyanide leaching to reduce the copper content of a zinc concentrate from 0.050 pct to the desired specification of less than 0.02 pct. Zinc Ore Sample: The sample of commercial zinc ore used in this investigation to produce zinc concentrates was ball mill feed ranging from 1/2 in. to fines. The ore was crushed to —10 mesh and riffled into 600-g charges for zinc flotation. Analysis revealed 4.54 pct Zn and 0.005 pct Cu. Examined microscopically, the ore consisted essentially of cream-colored sphalerite and carbonate gangue. It contained a small amount of pyrite, partly tarnished. The only copper mineral identified was chalcopyrite, mostly smaller than 20µ, some of which occurred as attachments on sphalerite. Flotation Procedure: Batches of zinc concentrates were made as required according to the following general procedure. A 600-g charge of —10 mesh ore was ground for 4 min at 60 pct solids in a laboratory steel rod mill. Screen sizing showed it to be all —35 mesh with 42 pct —200 mesh. The pulp was transferred to a Fagergren laboratory flotation machine, diluted to 25 pct solids and conditioned for 5 min with 0.6 lb per ton CuSO4, . -5H2O. It was then conditioned with 0.10 lb per ton Sodium Aerofloat promoter and floated for 5 min with pine oil as frother and creosote as froth stiff-ener. The pH during flotation was 8.5. A typical analysis of zinc concentrate subjected to leaching is 44.41 pct Zn and 0.051 pct Cu. The ratio of concentration was close to 10 to 1. Leaching Procedure: Aero Brand cyanide, technical calcium cyanide analyzing 49.5 pet NaCN equivalent, was used for all cyanide leaching tests. For each test three rougher concentrates floated as described were combined (total weight close to 180 g) and the water content adjusted to 150 ml. The percent solids in the pulp was thus 55. After a weighed amount of cyanide flakes had been added, the pulp was agitated on rolls for a given period, then filtered and washed. Filtrate and washed concentrate were assayed for copper content. The procedure for ammonia leaching was similar to the cyanide process. A series of tests was run in which the effects of ammonia as a solvent for copper in the zinc rougher concentrate were investigated. In each test 180 g of zinc rougher concentrate was leached with 150 ml of ammonia solution. Various strengths of ammonia and times of leaching were investigated. The results are shown in Table I. It is apparent that ammonia was a poor solvent for copper in the zinc concentrate; 60 min of agitation with a relatively strong NH:, solution extracted only 2 pct of the copper. CYANIDE LEACHING TESTS Effect of Solution Strength: The solvent effects of 0.125, 0.187, and 0.250 pct NaCN equivalent solutions were compared for leaching periods of 15 min. Residue and filtrate were assayed for copper content. The copper content of the filtrate plus wash was calculated back to the original volume of cyanide solution (150 ml). The effects of cyanide strength are given in Table II, It will be noted that 15 min leaching with 0.25 pct NaCN equivalent solution extracted 74.6 pct of the copper in the zinc concentrate. The leached product assayed 0.013 pct Cu, appreciably below the required specification of 0.020 pct. Effect of Leaching Time: Portions of zinc concentrate were leached with 0.25 pct NaCN equivalent

Jan 1, 1961

By G. D. Monk, W. C. Krumbein

The relation between permeability and the size parameters of unconsolidated sand is approached by considering sands as logarithmic frequency distributions having the basic parameters mean size and standard deviation. Sieve separates were mixed in accordance with the normal logarithmic probability law, so that the mean and standard deviation could be varied at will. Experiments were conducted in which one parameter was kept fixed and the other varied; in this manner the dependence of permeability on the individual parameters was evaluated. It was found that permeability can he expressed as the product of a power function of the mean size and an exponential function of the standard deviation. Earlier studies of the effect of size of particles on the permeability of uncon-solidated sand have shown that the permeability varies with the square of some average diameter. This was first pointed out by Hazenl in 1892 and verified by Slichter2 in 1898. Hazen&apos;s mean size was defined as the 10 percentile of the cumulative curve (i.e., size that is smaller than 90 pel cent of the distribution and larger than 10 per cent). Slichter&apos;s effective size, on the other hand, was found by Wilsey3,4 to agree with the 31 percentile. Fair and Hatch6 found that the geometric mean size of sieve separates yielded the same power function; Hulbert and Feben6 found that the permeability of sieve separates varied as the 1.89 power of the median diameter (i.e., the size associated with the 50 percentile of the cumulative curve). Relatively few studies included the effect of the "sorting" of the sediment on the permeability. It was recognized that the nature of the size distribution, in terms of the spread of the particles about the mean, affects the permeability, but no systematic investigations of this effect are known to the writers. Cloud7 demonstrated that the effect of the grain-size distribution on permeability is definitely measurable. In the present paper the authors investigate this relation analytically, and show that the effects of the size parameters on permeability may be predicted for at least a restricted set of conditions. Properties OF Sediments Recent investigations have shown that essentially all the geologically important characteristics of sediments may be expressed in terms of six measurable quanti-tities possessed by each clastic sedimentary particle. These attributes are: (I) size, (2) shape (sphericity), (3) roundness (angularity) , (4) mineralogical composition (density), (5) surface texture, (6) orientation. Each of these characteristics may be defined in several manners. Size may be expressed in terms of sieve mesh, settling velocity, volume, etc. Sphericity is a shape concept introduced by Wadell;8 it is essentially a measure of the ratio of the surface area of an equivalent sphere to the surface area of the particle. The same

Jan 1, 1943

By G. D. Monk, W. C. Krumbein

The relation between permeability and the size parameters of unconsolidated sand is approached by considering sands as logarithmic frequency distributions having the basic parameters mean size and standard deviation. Sieve separates were mixed in accordance with the normal logarithmic probability law, so that the mean and standard deviation could be varied at will. Experiments were conducted in which one parameter was kept fixed and the other varied; in this manner the dependence of permeability on the individual parameters was evaluated. It was found that permeability can he expressed as the product of a power function of the mean size and an exponential function of the standard deviation. Earlier studies of the effect of size of particles on the permeability of uncon-solidated sand have shown that the permeability varies with the square of some average diameter. This was first pointed out by Hazenl in 1892 and verified by Slichter2 in 1898. Hazen&apos;s mean size was defined as the 10 percentile of the cumulative curve (i.e., size that is smaller than 90 pel cent of the distribution and larger than 10 per cent). Slichter&apos;s effective size, on the other hand, was found by Wilsey3,4 to agree with the 31 percentile. Fair and Hatch6 found that the geometric mean size of sieve separates yielded the same power function; Hulbert and Feben6 found that the permeability of sieve separates varied as the 1.89 power of the median diameter (i.e., the size associated with the 50 percentile of the cumulative curve). Relatively few studies included the effect of the "sorting" of the sediment on the permeability. It was recognized that the nature of the size distribution, in terms of the spread of the particles about the mean, affects the permeability, but no systematic investigations of this effect are known to the writers. Cloud7 demonstrated that the effect of the grain-size distribution on permeability is definitely measurable. In the present paper the authors investigate this relation analytically, and show that the effects of the size parameters on permeability may be predicted for at least a restricted set of conditions. Properties OF Sediments Recent investigations have shown that essentially all the geologically important characteristics of sediments may be expressed in terms of six measurable quanti-tities possessed by each clastic sedimentary particle. These attributes are: (I) size, (2) shape (sphericity), (3) roundness (angularity) , (4) mineralogical composition (density), (5) surface texture, (6) orientation. Each of these characteristics may be defined in several manners. Size may be expressed in terms of sieve mesh, settling velocity, volume, etc. Sphericity is a shape concept introduced by Wadell;8 it is essentially a measure of the ratio of the surface area of an equivalent sphere to the surface area of the particle. The same

Jan 1, 1943