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By G. H. Wigton

The oxidized ores of the Chief Consolidated Mining Co., in the Tintic mining district, have never yielded to metallurgical treatment by any standard method except smelting. These ores occur in comparatively small, irregular, siliceous replacements in limestone, and carry silver, lead, and gold as the principal valuable metals. But smelting methods are unsatisfactory, as the lead smelters heavily penalize the largc amount of silica in the ore, and the copper smelters do not pay for the lead in the ore; therefore, an alternative treatment method was sought. In 1916, a metallurgical research department was organized under the direction of the writer. Many standard metallurgical methods were investigated but, on oxidized ore, none yielded extraction great enough to make its use feasible. During some chloridizing-roasting experiments in 1916, made in an assay muffle, the writer noted that large proportions of the silver, lead, and gold were volatilized from certain oxidized ores. The possibility of volatilizing the metals and collecting them in the form of a concentrated fume was then studied. But, as it was shown that satisfactory chloride-volatilization would be limited to a furnace feed with a high fusing temperature of the non-volatilizable constituents, and as the results obtained in a rotary kiln with the admixture of common salt with the ground ore were inferior to muffle tests, further volatilization experiments were discontinued until 1920. During this internal, an expcrimental sulfidizing and flotation plant was operated. After the cessation of attempts to float the oxidized minerals, chloride-volatilization experiments .were resumed. The highly infusible flotation tailing from the operation of the flotation mill was used for furnace feed. The first tests made on flotation tailing mixed with 10 per cent, common salt showed nearly complete lead and gold volatilization but considerably less volatilization of silver than in muffle tests. In attempts to increase the silver extraction, the percentage salt in the furnace feed was varied, and it soon became apparent that the use of smaller percentages of salt raised the fusion temperature of the furnace charge and thus

Jan 1, 1926

Readers of recent Bulletins have doubtless observed that the problem of improving both material and moral condition of employees is receiving close attention from influential members of the Institute. This will lend interest to certain developments and investigations that have been reported elsewhere.

Jan 5, 1918

By George A. Colligan, John M. Lo

Electrical resistivity as a function of temperature was investigated in undercooled gallium and under-cooled Ga-In alloy of eutectic compositian to examine structural changes in undercooled melts. A continuous linear extension of the resistivity was determined for 99.999 pct pure gallium when undercooled below the stable Ga(l)-liquid, and the metastable Gafl)-liquid equilibria. In icndercooled Ga-In, a significant continuous negative departure from linear resistivity behavior was observed below the eutectic temperature. All resistivity measurements were made by the four-point probe technique. ThE temperature range for investigations into the physical properties of liquids before freezing has been greatly extended with the undercooling of massive melts of pure metals and alloys. Experimental determinations of thermal and transport properties and diffraction patterns in undercooled systems should throw further light on the structural behavior of liquids. Many measurements showing prefreezing anomalies in viscosity1'5 have been regarded677 as evidence for structural groupings in the liquid state. However, the majority of viscosity results,~)~-~~ conforming to the law 17 =A exp(~/RT), do not support theories of atomic aggregation. For the system Cd-Sb, which exhibits a metastable solid phase, Fisher and Phillipsg reported that, in undercooled alloys, the activation energies for viscous flow below the stable liquidus are much higher than those above it. Similarly, Miller et a1." observed a doubling of the activation energies for electrical conductivity in undercooled Cd-ib alloys. These effects were suggested as indicative of atomic association and clustering in the liquids at lower temperatures. With the recent establishment of metastable phases in pure gallium22 and its alloys,23 attempts were made during this investigation to undercool bulk samples and to determine the temperature dependence of electrical resistivitv. Pure gallium, when undercooled below -17°C at atmospheric pressure, can crystallize to either a stable Ga(1) phase (mp, 29.78"C) or a metastable phase identi-

Jan 1, 1967

By Richard Borg

The partial molal free energy of Cd in each of the four intermediate phases, Cd3 Cu, Cd8 Cu5, Cd3Cu4, and CdCu2 is determined using the Knudsen vapor pressure technique. Measurements are made also within the two-phase regions, and thus the variation in FCd is now known across the entire phase diagram. The absolute values are all less the 2.0 kcal and increase regularly with increasing Cd concentration. The small absolute value of the free energy precludes the possibility of obtaining highly accurate values; nevertheless, the results are compatible with those previously reported for the liquid phase. Additional results are reported concerning the lattice parameters of the 6, E, and b phases. THE elements Cu and Cd combine to form four intermediate phases which are designated* and E and which include respectively the following inter metallic compounds: CdCu2, Cd3Cu4, Cd3 Cu5, and Cd3 Cu. The extent of each phase with respect to temperature and composition is shown in Fig. 1 which is the equilibrium diagram drawn according to Hansen.1 All four phases are brittle, and most probably are true intermetallic compounds. Only the crystal structure of the 6 phase has been thoroughly investigated.2,3 The structure is cubic and isotypic with y brass. The structure of Cd3 Cu has not been previously reported, It is hexagonal with a = 8.11 and c = 8.76 0.02Å and the structure is presently being determined.* The compounds Cd3 Cu4 and CdCu, have been each previously the subject of a single investigation. Cd3Cu, is presumed to be cubic4 with the space group Fd3m, whereas CdCu2 is hexagonal2 with the C14-type structure. Cu2 Cd is found by X-ray analysis to be hexagonat with lattice parameters a = 5.00A and c = 16.17Å. The material appears to be pure Cu2Cd as all reflections could be indexed on the basis of the single hexagonal structure. These values disagree with those of Kripyakevich and coworkers5 who report a = 4.96Å and c = 7.98Å. Their investi-

Jan 1, 1962

By George A. Connell

BORAX, a sodium borate and the principal sodium salt of boric acid, has been surrounded with romance and with a certain amount of mystery. Its early history is not entirely known but it has been contended that Marco Polo in his travels in the Orient introduced this material to the West during the Middle Ages. Without doubt its first source was from Central or Eastern Asia and perhaps from Tibet. The well-known fluxing properties of borax probably introduced its earliest use that of a soldering flux in the manufacture of jewelry. This use, as well as the remote location of most borate deposits, added greatly to the romance associated with the thought of borax. COMPOSITION The common element in all borates is boron but this element has never been discovered as such in any deposit, because of its great affinity for oxygen. Incidentally, this makes its manufacture extremely difficult and expensive. Elemental boron undoubtedly has many properties that make it quite valuable but the extreme cost involved in producing it from its oxidized form prevents its general use or manufacture. The common element in all borates is boron but this element has never been discovered as such in any deposit, because of its great affinity for oxygen. Incidentally, this makes its manufacture extremely difficult and expensive. Elemental boron undoubtedly has many properties that make it quite valuable but the extreme cost involved in producing it from its oxidized form prevents its general use or manufacture. The common element in all borates is boron but this element has never been discovered as such in any deposit, because of its great affinity for oxygen. Incidentally, this makes its manufacture extremely difficult and expensive. Elemental boron undoubtedly has many properties that make it quite valuable but the extreme cost involved in producing it from its oxidized form prevents its general use or manufacture of disodium tetraborate (Na2B4O7.10H2O), and, further, can be considered as the acid salt of monosodium metaborate. However, the term "acid salt" might imply that borax gives an acid reaction in solution, which is not true, since solutions of borax are decidedly alkaline, giving a pH of 9.2. Boric acid, also known as boracic acid, has the chemical formula H3BO3; it occurs in nature as the mineral sassolite. Sassolite has been

Jan 1, 1949

By G. L. F. Powell

Bulk samples of silver have beat undercooled lo a large degree in contact with crystalline siliceous and ceramic oxide materials, indicating lhat stable oxides and oxide compounds are not the heterogeneous nucleants which normally catalyze cryslallization within a feu degrees of the equilibrium freezing point. Since 400-g samples were undercooled 250°C in contact with cristobalite, it is concluded that the undercooling required for homogeneous nucleation of sil11er is greater than 250°C. Undercooling was Jacilitated by precleaning the crucibles with a high-fires -sure blast of gas. IN numerous experiments on the undercooling of metal melts it has been assumed that a solid glassy surface, being non crystal line, will have no effect in catalyzing crystal nucleation from the melt. Conversely, it is usually accepted that any crystalline surface, in contact with a metal melt, will catalyze nucleation of metal crystals from the melt at degrees of undercooling less than that at which homogeneous nucleation will occur. Both these assumptions were implicit in the claim that homogeneous nucleation was observed in experiments1'2 on the undercooling of small metal droplets (10 to 100 mp diam). The droplets were thought to be freed of suspended crystalline particles which would otherwise catalyze heterogeneous nucleation. They were supported on flakes of silica glass which were assumed to be amorphous, and therefore incapable of acting as substrates for heterogeneous nucleation. In later experiments, large samples of molten metal were undercooled to temperatures similar to those achieved by the droplet technique by melting in a fused-silica crucible3 or a boro-silicate glass slag.4 Since these samples were usually fully enclosed in glass at the moment of freezing, it seemed possible that nucleation was homogeneous when maximum degrees of undercooling were achieved, despite the large size of the samples (up to 500 g). In experiments on the undercooling of silver5 the metal was contained in vitreous silica crucibles, the

Jan 1, 1968

By P. W. Bridgman

IT is characteristic of most scientific investigators that they are not satisfied with the discovery of new facts, no matter how curious or unex-pected, but that along with the factual discovery there is a constant effort to understand. It appears that one's interest in, and satisfaction with, the discovery of an array of new experimental facts is enormously increased if one has at the same time a theory or hypothesis guiding one's expectation of what sort of new experimental discovery may lie around the corner. Conversely, as a theoretical physicist one's satisfaction with his theory is greatly enhanced if along with the development of the theory can go the discovery of new experimental facts, confirming or perhaps modifying the theory as it grows. Of course, there have been long arid stretches in the history of physics in which new data of unquestioned ultimate importance have piled up, without much inspiration or illumina-tion in the way of understanding. For 50 years spectroscopy had such an arid history, but how irksome this was felt to be is plainly shown by the almost audible relief that greeted the first success by Bohr in injecting understanding into the situation, and by the fresh rush of experimenters into this field when the prospect of understanding had once been offered. The investigations in the field of high pressure, which have occupied me for a long time,1 until the last few years have been in very much the same sort of situation as spectroscopy before the advent of Bohr. A great many kinds of data were collected for a great many solid and liquid sub-stances, and there could be no question of the importance of these data, because the uniform change of dimensions produced by hydrostatic pressure is perhaps the simplest conceivable type of alteration to which a body can be subjected. But except for a few isolated flashes, there was no theoretical illumination, so that it had to be to a large extent the enthu-siasm of the collector that kept me going. However, within the last few years the wave-mechanics theory of solids has progressed so rapidly that

Jan 1, 1938

By D. U. Deere, F. D. Patton

Introduction A close relationship exists between the geologic investigation and the stability analysis of the slopes of an open pit mine. One significant result of this relationship is that the stability analysis is no better than the assessment of pertinent geologic factors that enter into the analysis. In some slope stability problems the engineering solution becomes obvious once the geologic framework is established. In other cases, establishing the geologic framework is only the first stage in the process of analysis. However, even in these cases the geology should not be neglected once the analysis is made. The geology should be periodically reviewed when new slopes are excavated. This will help ensure that the basic assumptions for the analysis have not changed and will permit changes when new conditions are encountered. In recent years improved methods of stability analysis have been accompanied by advances in laboratory testing techniques and new knowledge of the shear strength of rock discontinuities. At the same time there have been improvements in field geological descriptions. As more experience is gained in analyzing and predicting the stability of rock slopes, the importance of certain geologic factors has become more apparent. Some of these factors were described in a paper given at the Open Pit Mining Symposium in Johannesburg, South Africa in September 1970 (I). This paper includes many of the points covered at that meeting but with additional emphasis on the significance of the major geologic structures. Other papers given at the South African symposium also considered geological and hydrogeological factors in slope stability analysis (2) (3) (4) (5) (6). This paper first describes the approach to a slope stability problem including assessment of the relative roles of field geology studies, laboratory testing, stability analyses, and continued slope monitoring studies. Next, is described a framework which has been found useful for classifying or separating the several types of slope stability problems encountered in open pit mines. The principal geologic factors in slope stability problems in rock are discussed and brief comments are made on how these factors distinguish stability problems in rock slopes from those normally encountered in soil slopes. The over-riding control of major geologic structures, especially faults, in most slope stability problems is emphasized. In this regard the relative importance of statistical studies is contrasted with knowledge of the positions of key structural

Jan 1, 1971

By L. D. Fetterolf, G. T. Mahler, W. M. Peirce, R. K. Waring

Until recently, the only commercial method of producing magnesium has been fused salt electrolysis, despite a considerable amount of experimental work on the direct reduction of magnesium oxide. In this early work, a number of investigators demonstrated that magnesium oxide would react with any one of several reducing agents to produce magnesium vapor, but that the mixture of magnesium oxide and reducing agent must be heated to a high temperature even in a vacuum. In particular, it was demonstrated that silicon and aluminum are effective reducing agents and that when either of these is used the magnesium vapor can be condensed to massive metal. In spite of this knowledge, no successful commercial reduction process was developed, at least in this country, because of the operational difficulties imposed by the requirement of high temperature and vacuum and because of the high cost of the reducing agent. The outstanding experimental work done by Pidgeon, who carefully reviewed all of the known methods of making magnesium and then selected ferrosilicon reduction, overcame some of the operational difficulties. The process developed by Pidgeon comprises briquetting a mixture of calcined dolomite and reducing agent, preheating the briquets to about 600°C. in an externally heated alloy retort, reducing the MgO with silicon in an evacuated horizontal alloy retort heated externally to about II50 C., and condensing the magnesium vapor to a solid in a cold extension of the retort projecting beyond the front of the furnace. A major advantage of Pidgeon's process is that the retort is not cooled down between charges. Earlier investigators had used apparatus that necessitated cooling and reheating of the retort between charges. Early in January 1942, when the War Production Board was considering the Pidgeon process for quickly increasing the production of magnesium, The New Jersey Zinc Co. offered to have a research investigation of the process carried on, with the hope of assisting in its further development. This offer was accepted, and a two-retort pilot plant was built at Palmerton and put in operation on Jan. 29,1942. An intensive investigation of certain phases of the process was carried out in the ensuing four months. This investigation was completed in the last part of May 1942) and the pilot plant was then shut down. Subsequently, The New Jersey Zinc Co. was requested to have further development work done on the process, and a more extensive investigation was undertaken in August 1942 under contract with the War Production Board and under the supervision of the War Metallurgy Committee. This paper describes the ,phases of the investigation that are thought to be of sufficient general interest to merit publication.

Jan 1, 1944

By J. Mote, P. Ward Flynn, J. E. Dorn

The effect of strain and strain rate on the critical resolved shear stress for prismatic slip in specially oriented single magnesium crystals was determined over a range of temperatures in an effort to identify the thermally activated strain-rate controlling dislocation process. Below about 450°K prismatic slip was preceded by twinning and fracturing. Above 450°K extensive prismatic slip was obtained followed by fracturing. Neither the Peierls&apos; mechanism nor the dislocation intersection mechanism can account for the observations. The data, however, are in good agreement with the dictates of Friedel&apos;s theory for cross slip to the prismatic plane. PREVIOUS investigations on single and polycrys-talline magnesium have resulted in the identification of the mechanisms of plastic deformation summarized in Table I. The-only well-confirmed mechanisms are {0001}, (1010}, (1011) slip plus (1012) twinning. The other twinning modes were only tentatively established and additional investigations are required to further confirm their operation. As noted in Table I, slip in this hexagonal close-packed metal invariably occurs in the direction of greatest atomic density, revealing that the Burger&apos;s vector for-active slip dislocations is always given by b = a/3<1210>. Slip is easily induced on the basal plane, and recent investigations have shown that the strain-rate controlling mechanism at low temperatures is the thermally activated intersection of the glide dislocations with dislocations threading the basal plane. In contrast, very little is known about prismatic slip. It has been reported to be active at points of stress concentration in polycrystals below

Jan 1, 1962

By A. J. de Witte

INTRODUCTION The importance of determining dips of subsurface formations in wells, especially in wildcat wells, is self-evident and need not be enlarged upon. Various dipmeter instruments have been described in technical literature1,2,3,4 over the years. The introduction of the continuous dip-meters3,4 has made the earlier types obsolete. Continuous dipmeter logs are run by at least two different major service companies. Included as part of the service are a limited number of dip calculations—usually 10—made at different levels from the log. Very frequently this is the total result of a dip survey. It is believed that dipmeter surveys would be of considerably more advantage if geologists and engineers were able to make their own calculations from the original records. Determination of dips from the dipmeter record starts with the correlation of three log curves taken at different sides of the borehole. It cannot be over-emphasized that the quality of the results hinges primarily on this correlation. Nobody should be better qualified to correlate logs than a subsurface geologist or field engineer. The next requirement is to have an easy yet accurate way of computing the dip from the correlated points. Service companies use a mechanical device for this purpose. Directions for a graphical method were given in a recent article by B. 0. Prescotts. This paper describes a different graphical technique which, in our experience, is simpler, faster and at least as accurate. The entire manipulation is carried out on the stereonet in a number of easy moves. The paper is divided into two parts. This first part contains the introductory sections and full explanation of the geometry involved. The second part reviews the reading of data from an actual field log and summarizes the practical rules for computation of dips, the whole process being illustrated by an example. Following the outlined procedure, one could calculate a good many levels in a relatively short time, thus being able in particular to check suspected anomalies such as fault zones or unconformities in as close detail as the log will permit. GENERAL EXPOSITION OF THE METHOD Prnciple of the Dipmeter The position of a plane in space is defined by the location of three points, not on a straight line. Referring to Fig. I, if a borehole traverses a bedding plane, we can determine the strike and dip of the bed by finding three points which are not in line along this plane. Such points as A, B, and C are obtained with the dipmeter. The device consists of three electrodes (or caliper arms)1, 2, and 3 spaced at 120 angles, as schematically indicated, whose readings are separately recorded (Curves 1, 11, 111, to the right). When electrode 1 passes the boundary of the bed, Curve I will kick, etc. From these curves, we know the relative distances of points A, B, C, measured along the axis of the hole. If A is at zero, then B and C are at levels d1 and d2 up the hole,

Jan 1, 1957

By G. R. Leverant, M. Gell

The high- and low-cycle fatigue poperties of MAR-M200 directionally -solidified into columnar-grained and single crystal forms were determined at 1400" and 1700°F. These results were compared with the corresponding properties of conventionally -cast MAR-M200. The low-cycle fatigue lives of the columnar-grained and single crystal materials were similar at both temperatures and were one to two orders of magnitude greater than those of conventionally-cast material. The variations in the fatigue lives among the three forms of MAR-M200 were related to the more rapid rate of intergranular muck propagation compared to that of transgranular propagation. In conventionally-cast MAR-M200, cracks were initiated in grain boundaries and crack popagation occurred rapidly along an almost continuous grain boundary path. In the columnar-grained material, crack initiation occurred on short transverse segments of grain boundaries, but crack propagation was transgranular. The fatigue lives of columnar-grained and single crystal materials were approximately the same because most of the life in both materials was spent in trans-granular propagation. For the directionally -solidified materials, the number of cycles to failure, Nf, can be related to the total strain range, , by: heT = K where n and K are 0.16 and 0.044 at 1400&apos;F and 0.29and 0.098 at 1700, respectively. In addition to intergranular crack initiation in the columnar-grained material, initiation also occurred at we-cracked MC carbides and micropores in both directionally-solidified materials. At 1400°F, fatigue life was reduced with increasing MC carbide size, but at 1700 there was no effect of carbide size. THE creep and stress-rupture properties of conventionally-cast nickel-base superalloys can be greatly improved by directional solidification into either single crystal or columnar-grained forms. The improvement in properties results from a reduction in intergranular cavitation and crack growth in the columnar-grained materials and the complete absence of this fracture mode in the single crystals. This paper describes the effect of grain boundaries on the elevated temperature fatigue properties of the nickel-base superalloy MAR-M200. The effect of cycling frequency on cracking arid fatigue life and the role of MC carbides and micropores on crack initiation are also emphasized. The fatigue properties of columnar-grained and single crystal MAR-M200 at room tem- perature,4,5 and the change in the mode of fatigue crack propagation with temperature6 have recently been described. I) EXPERIMENTAL PROCEDURE The material used in this study was the nickel-base superalloy MAR-M200, directionally-solidified into columnar-grained and single crystal forms. The columnar grains were approximately 0.5 mm in diam. The nominal composition of these materials in wt pct was 0.15C, 9Cr, 12.5W, loco, 5A1. 2Ti, lCb, 0.05Zr. 0.015B, bal Ni. They were solutionized for 1 to 4 hr at 2250°F followed by aging at 1600°F for 32 hr. which resulted in 0.2 pct offset yield stresses of 150,000? 144,000, and 95,000 psi at room temperature? 1400°, and 1700°F, respectively. The corresponding elastic moduli parallel to the testing direction were 19.2. 15.0, and 12.5 x 106 psi, respectively. Specimen design, testing procedures and alloy mi-crostructure have been described previously and will only be summarized here. Following the 1600°F aging treatment. MAR-M200 contains an ordered, cuboidal, y&apos; precipitate 0.3 1 on edge, which is coherent with the 1 matrix. The y&apos; precipitate is quite stable; even after testing at 1700°F. the precipitate is only slightly enlarged and its corners somewhat rounded. The alloy also contains a small volume fraction of micropores, and MC carbides. some of which contain preexisting cracks5 formed during casting. These cracks are always parallel to the long dimension of the carbide. Measurement of MC carbide size has been described previously.5 Axial fatigue tests were conducted in air over a wide range of strain amplitudes in both the high - and low-cycle fatigue regions, with specimen lives varying from about 10&apos; to 10&apos; cycles. Low-cycle fatigue (LCF) tests were strain-controlled with strain varied between zero and a maximum tensile value at a frequency of about 2 cpm. High-cycle fatigue (HCF) tests were stress-controlled with the stress varied between 5000 psi and a maximum tensile value less than the yield stress at a frequency of either 10 cps or 0.033 cps (2 cpm). The temperature in the gage section was controlled to 52°F. Specimen axes were within 5 deg of the [001] growth axis of the single crystals and the common [001 ] growth axis of the columnar-grained material. Specimen gage sections were electro polished prior to testing. After the standard heat treatment, three specimens were coated with a typical aluminide coating applied as a slurry. An additional specimen was given the coating heat treatment without actually being coated. In all cases: specimens were reaged at 1600°F for 32 hr after receiving the coating heat treatment at 1975&apos;F for 4 hr.

Jan 1, 1970

By A. E. Jenkins, L. A. Baker, N. A. Warner

Rates oj decarburization of levilated Fe-C droplets conlaining 5.5 to 0 pct C have been measured at 1660°C. Gas mixtures of 1, 10, and 100 pct 0, with helium diluenl were used at velocities of 12.5 and 62.5 cm per sec. Rates were independent of carbon concentration in the mell and in good agreement with the calculated rule of oxygen diffusion through the gas boundary layer. The effects of flow rale and total pressure are as predicled and the rates are approxitnalely 2.5 times those with CO2 as oxidant. The mass-transfer correlation used incorporaled the efject of natural convection as well as forced conrection. Graphile spheres are shown to oxidize at the same rate as Fe-C droplets under the same experimental codlions. It is concluded that, for high carbon concentrations in the melt, the rate of- decarburizalion is controlled wholly by the rate of gaseous diffusion. Rate measurements with pure CO, are reported for low carbon concentrations where CO bubbles nucleate within the droplet. Under these circumstances the decarburi-zation decreased with carbon concentration and it is proposed that carbon diffusion is significant in conlrolling the decnvburization rate. In an earlier paper1 decarburization rate measurements were reported for levitated Fe-C alloys at 1660°C but with CO2 as the oxidant. The decarburization rate was found to be independent of carbon concentration in the melt but slightly affected by total pressure. The authors were unable to explain the slight pressure effect but in all other respects the results were consistent with control by diffusion in the gas boundary layer. Subsequent work has been directed at finding the reason for the slight pressure effect and whether the kinetics with oxygen as oxidant parallel those with CO2. Recently Ito and Sano2 have shown that with water vapor-argon atmospheres the decarburization rate is gaseous diffusion controlled until an oxide film appears on the surface. In this work the melts were contained in crucibles. MASS TRANSFER IN THE GAS PHASE In the earlier analysis1 only forced-convection mass transfer was considered. Subsequent recognition of the existence of some free-convection mass transfer explained the observed small effect of total pressure on the decarburization rate. Steinberger and Treybal3 and Kinard, Manning, and Manning4 have developed correlations involving the linear addition of the contribution of radial diffusion, free and forced convection. Steinberger and Treybal&apos;s correlation was chosen as the most applicable to the present work since it correlated most of the data available in the literature and handled the low Reynolds number region exceptionally well. The correlation for (Gr&apos;Sc) < 108 is where Nu&apos; is the Nusselt number for mass transfer based upon the total surface of a sphere in an infinite medium, G&apos; is the mean Grashof number for mass transfer defined by Eq. [2], Sc is the Schmidt number (µ/pDAB)f, Re is the sphere Reynolds number (dpu,pf/µf), p is the viscosity of the gas (poise), p is the density of the gas (g cm-3), Dab is the binary diffusivity for the system A-B (sq cm sec-&apos;), dp is the sphere diameter (cm), u is the approach velocity of the gas (cm sec-I), and subscript f denotes the property value is computed at the film temperature Tf defined by Tf = +1/2(To + Tr) where To is the specimen temperature and T, is the approach gas temperature (oK). Natural convection occurs when inhomogeneities exist in gas density. These may be caused by concentration gradients, temperature gradients, or both. In the present work the temperature gradient between the sphere and the bulk gas was very large and in some cases, for example the runs with pure oxygen, the concentration gradient was also appreciable. The Grashof number defined by Mathers, Madden, and piret5 was used since it took account of both temperature and concentration gradients: where Gr&apos; is the Grashof number for mass transfer (p2fgd3|-yA-yA|/µ2f), Gr is the Grashof number for heat transfer (p2f gd3p|To - T,]/µ2fTf), Pr is the Prandtl number (cpµ/k)f, g is the acceleration due to gravity (cm sec-&apos;f, a is the concentration densification coefficient (1/p)(ap/ayA)T, yA is the mole fraction of component A at the gas-metal interface, yA is the mole fraction of component A in the bulk gas stream, cp is the heat capacity of the gas per unit mass at constant pressure (cal g-I OK-&apos;), and k is the thermal conductivity of the gas (cal cm-&apos; sec-1 OK-1). Mathers et al. tested this combined Grashof number

Jan 1, 1968

By R. L. Slobod, C. Gatlin

This .study defines the basic mechanism of the mis-cible displacerrzent of oil and writer from porous Medici by various water-driven alcohol .slugs. Three distinct alcohol slug processes were .studied. Considerable data concerning the quanity of alcohol required for oil recovery were also obtained. All data were obtained in a 1-in. diameter, 100-ft long, unconsolidated core. The porosity of this system was 35 per cent. and the permeability was approxitrlately 4 darcies. Total core pore volume wax 5,716 cc. All displacements were conducted at a constant injection rate of 5 to 6 cc//min, which corresponds to a frontal advance of 5 ro 6 ft/hr. The first portion of this paper is concerned with 111 use of one alcohol—isopropyl—a\. the slug material. Isopropyl alcohol (IPA) is completely miscible with both oil rind water; however, miscibility of the threc-component systems, oil-water-IPA, requires a relutively. high concentration of IPA. Hence, the displocement is not of the misoible type unless the IPA concentration is maintained above some critical value. A slug of IPA equal to only 13.5 per cent of the pore volume was jound to be sufficient to obtain complete recover?, of residua1 naphtha. In later studies two distinct process variations were developed. The firsr of these utilized methyl alcohol (MA) and IPA as slug materials. It was shown that methyl alcohol may he substituted for IPA at the front and rear of the slug with no loss of oil recovery. A .slug of 4 per cent MA-4 per cent IPA-4 per cent MA was sufficient for complere oil recovery. Because MA is considerably cheaper than IPA, this represents an important step toward economic application. A .second process variation used normal butyl alcohol (nBA) and MA as the composite slug, the nBA segnzent being injected first. This technique requires the smallest total slug size (approximately 10 per cent) of all processes studied. The high cost of nBA, however, precludes commercial application. It is possible that this basic process, subject to changes of alcohol type, may lead to a commrercicil process. INTRODUCTION Within the last 10 years, considerable study has been devoted to the general mechanics of miscible phase dis- placements in porous media. These studies have. in general, dealt with two-component displacernent. All reported field trials to date have been modified gas drives of one type or another. These utilize either lean gas at high pressure, rich gas at lower pressure or an LPG slug. The irreducible water content of the reservoir remains immobile during these processes. Although these techniques hold great promise. certain drawbacks do exist. Poor areal sweep efficiency, inherent in any displacement having a highly unfavorable mobility ratio, is one disadvantage. Furthermore, the miscibility of all processes which use gas is dependent on pressure. These pressure limitations may prohibit application to shallow reservoirs. There are also many areas where large quantities of LPG and natural gas are not readily available. These factors emphasize the need for improved techniques. The alcohol slug process is also a miscible-phase displacement process. It differs from the previously mentioned two-component techniques, however, in that both the reservoir oil and water are displaced by the slug. This behavior is a consequence of the miscibility of certain oil-water-alcohol systems. In the simplest case, a relatively small volume (slug) of an alcohol (such as isopropyl) is injected into the system. Water is then used to drive the slug through the medium. Thus. three components—-alcohol. oil and connate water-—exist at the front side of the slug. Miscibility is obtained at some alcohol concentration, this being dependent on the solubility of the particular system. Miscibility is maintained within the slug until the alcohol concentration falls below that value required to maintain miscibility. When miscibility is lost, the process reverts to a water flood. Certain inherent benefits of this technique are apparent. High pressures are not necessary to obtain miscibility in these liquid systems. Furthermore, water is a more desirable driving agent than gas because of the improved mobility ratio and the attendant improvement in areal sweep efficiency. The main disadvantage is, of course, the relatively high cost of alcohols. The use of an alcohol slug to recover reservoir oil is not a new idea." &apos; However, this process has received only limited study, presumably due to the lack of industrial interest caused by the seemingly prohibitive cost of alcohols. The main purpose of this study was to investigate the mechanism of the displacement of oil and water by various alcohol slugs and to develop process modifications aimed toward possible commercial application.

By J. E. Smith, P. B. Crawford, B. L. Laudrum

A method is presented by which the displacement efficiency of a steam-injection process may be determined. The method consists of a determination of the position of the steam front at a particular time and the application of the Buckley-Leverett theory to the hot and cold regions of the reservoir with the appropriate hot or cold fluid properties. A uniform, linear flow system is assumed for this study. The method is applied to a number of reservoir conditions. The primary properties which affect the results of a steam-injection process are the oil viscosities at steam and reservoir temperatures, injection rate, pay thickness and oil saturation. The efficiency of steam injection is compared with that of water injection for a 10-acre, linearly flooded reservoir. In reservoirs where the oil viscosity is about 35 times the water viscosity, the steam process yields recoveries about 20 per cent higher than the water flood. Where the oil viscosity is near 500 cp, the steam process may recover from three to four times as much oil as a water flood. INTRODUCTION In a previous paper,&apos; a method was suggested for evaluating a steam-injection process. Emphasis was placed upon the determination of the steam-front position in the reservoir at various times. In the present paper, the displacement process is studied in more detail. The approach is essentially that employed by Jordan, Rayne and Marshall3 in their study of hot-water injection. The steam-injection process is quite complex, and an exact description of the process has not been found; however, a qualitative description can be made. When a quantity of steam is injected into a relatively cold reservoir, the leading edge of the steam front continaally flows into cool sand, and some steam condenses. As more and more steam condenses, a bank of condensed water will form which is augmented by displaced connate water. The reservoir may be divided in three regions—(1) a region containing displaced fluids at reservoir temperatures, (2) a region contain- ing water at reservoir temperature and (3) a region occupied by steam. The reasons for the lack of a region of hot water or oil of any appreciable size have been discussed.&apos; A method has been presented by which the location of the steam front can be determined even when heat losses to the regions surrounding the reservoir are sizable compared with the amount of heat injected. It remains to show the effectiveness of steam injection in increasing the ultimate oil recovery. To illustrate the technique for determining the increase in displacement efficiency and, hence, the increase in ultimate production, two sets of hypothetical reservoir conditions will be studied in detail.

By A. R. Rosenfield, G. T. Hahn

The effects of adding 0.025 volume fraction of uniformly dispersed Tho2, particles (particle size -380A) to iron have been examined. The two-phase alloy is shown to have a lower transition temperature and higher cleavage stress than either the base metal or a solid-solution alloy (Fe-3Si). Enhanced cleavage resistance is thought to be a consequence of particles limiting the effective slip distance of dislocations and thus the ability of Pile-ups to act as stress concentrations. Further calculations predict that the highest cleavage strengths are attained with uniform dispersions, where the particle size is kept small (-250A) and the volume fraction is relatively large (-2 to 3 pct). ALTHOUGH a fine dispersion of second-phase particles is known to impart strength to an alloy, the possibility that it might also impart ductility has only recently been explored. Outstanding progress has been made in the production of ductile tungsten alloys containing Tho21,2or (Hf, Zr)C,= but the contribution of the dispersion to ductility has neither been optimized nor fully analyzed. The basis for such an analysis has now been developed1,5 and is discussed briefly below. Experiments on iron are also described that attempt to isolate one of the possible ductilizing mechanisms and test its effectiveness. In analyzing these experiments, it is important to remember that cleavage obeys a stress criterion, and that either a lower ductile-to-brittle transition temperature or a higher cleavage stress is evidence of enhanced resistance to cleavage. DUCTILIZING MECHANISMS Slip Blockage. Cleavage fracture of polycrystals may be initiated at the intersection of a slip band (or twin) and a neighboring grain or a large (-1 to 5 µ) particle. The slip band generates a stress concentration at its head, and either the grain boundary fractures, the particle fractures, or cleavage is initiated in a neighboring grain. Experimental evidence for this viewpoint is found in metallographic studies8-8 and from the observation that cleavage is usually preceded by yielding.8-11 The potency of a slip band as a stress concentrator

Jan 1, 1968

By D. A. Woodford

In a constant-load creep test, if the density of nlobile dislocations is assumed constant for strains exceeding that corvesponding to the minimum creep rate, it is shown that the creep rate may be approximated by the equation where E is the nominal strain, o0. is the initial stress, and a&apos; the stress fov unit dislocation velocity. The constant C contains the mean density of mobile dislocations and n is a measure of the stress sensitivity of dislocation celocity. This equation is shoum to be applicable to published data on an alloy steel and on nickel. The degree of plastic instability and hence the creep ductility is dependent on the calue of n for these materials. When instability becomes gross and local macroscopic necking occurs, the assumptions are no longer valid. On the basis of this equation, and the strain-time relation derived from it, a method of predicting the creep behavior at different stresses is suggested. MOst analyses of creep data have been concerned with time-dependent transient creep or time-independ- ent secondary creep in constant-stress tests. The far more widely used constant-load test has been neglected in terms of a mechanistic approach. In general, since the strains involved are usually small, the same laws for transient creep may be applied to both types of tests. However, there is no steady-state creep in a constant-load test since the stress increases continuously. Any apparent steady state observed on a strain-time plot is either fortuitous or illusory, and is generally revealed as a continuously varying creep rate on a carefully constructed strain rate vs time plot.* Transient creep may be understood in terms of a simple differential equation representing the change in mobile dislocation density with time:&apos; where p is the density of mobile dislocations. The first term on the right is related to first-order kinetics of dislocation multiDlication and the second to second-order kinetics of exhaustion. On the basis of this equation, several authors2-4 have found good agreement with experimental transient creep curves for a number of materials. When k1p = k2p2, a steady-state creep

Jan 1, 1968

By G. E. Keller

In connection with the work of Committee D5, Coal and Coke, of the American Society for Testing and Materials in developing new standards and improving old standards, series of tests were made to check the variance of sample preparation and analysis of American coals. Table I in the "Tentative Method of Preparing Coal Samples for Analysis - 02013-62T" is rather complicated, and the tests were designed to develop data for the simplification of this table. An allowance of 20% of the total variance of sampling and analysis for the sample preparation and analysis steps was used. Also, instead of coals being grouped into ash ranges, they were grouped as washed and raw (unwashed) coals. As a result of these tests, a simplified Table I for Tentative Standard 02013 has been proposed. A standard test for laboratories to check their variance of sample preparation and analysis has been developed. Committee D5 on Coal and Coke of the American Society for Testing and Materials has been making a study of all standards applying to coal for the purpose of improving and bringing them up to date and for breaking some of the existing standards covering a number of tests into single standards. As an illustration, sample preparation is now partly covered in ASTM Designation D492-48, Sampling Coals Classified According to Ash Content, and partly in ASTM Designation D271-58, Laboratory Sampling and Analysis of Coal and Coke. The latter contains, in addition to parts of sample preparation, methods for determining Moisture, Ash, Volatile Matter, etc. Although revision of sampling methods and sample preparation methods are now assigned separately, it is possible that they may end up as one standard. One of the first new Tentative Standards developed as the result of these studies was ASTM Designation D2013, Tentative Method of Preparing Coal Samples for Analysis. Although this method is quite an im- provement over that in the old standards and gives very specific instructions, Table I (attached) is quite complicated and rather hard to understand. In order to take advantage of reduced quantities or weights, it is necessary to know the ash content within rather narrow limits before sample preparation and no distinction is made as to whether the coal is cleaned or uncleaned. No limits of accuracy are assigned to the sample preparation and analysis. The total over-all accuracy of sampling, preparation and ash determination as given in D492-48 has been specified for commercial sampling procedure as follows: "This procedure is intended for an accuracy such that if a large number of samples were taken from a single lot of coal, the test results in 95 out of 100 cases would fall within ? 10 per cent of the average ash content of the sample." Although Appendix 11, Method for Determining the Over-All Variance of Reduction and Analysis in the Tentative Methods for Mechanical Sampling of Coal, ASTM Designation D2234-63T, does give a method for determing the over-all accuracy of preparation and analysis expressed as variance and also the F test, it does not permit the determination of the variance at the various stages of reduction or of the ash determination. It was decided in 1961 to ask a number of laboratories to run a series of tests for the purpose of determining the variance at various stages of reduction and analysis with the view of simplifying Table I of the Tentative Standard D2013-62-T. This paper is a record of this series of tests with recommendations which resulted from the tests. At the same time and preceding these tests the International Organization for Standardization under Committee TC/27 WG 7 was studying the same problem. Tomlinson1 of England and Dr. paul2 of West Germany had made studies giving quite a bit of information. Also Schwerd and coryel13 published some information which was the main basis for the Mechanical Division provision in ASTM Tentative Standard D2013-62T, Table I. In checking with the various laboratories which offered to cooperate in these tests, none was found which used mechanical division through the entire preparation procedure. It was then decided to use riffles at all stages with the thought that if riffles gave satisfactory variances, approved mechanical

Jan 1, 1965

By M. E. Wadsworth, J. S. Cho

The kinetics of silicate adsorption from aqueous colloidal (SO2 . nH2O) silicate sols on thoria (ThO 2) surfaces were determined at 100, 150 and 200°C in an autoclave system. The amount of chemisorbed silica on the thoria surface was determined by means of infrared spectroscopy. First order kinetics were observed in all cases with the anomalous result that the first order rate constant was found to vary with the initial amount of silica added to the system. These results have been correlated quantitatively by means of a strain model of adsorption involving two types of surface silicate bonding, both of which may be readily observed in the infrared spectrum. Initial adsorption occurs rapidly to produce one type of surface silicate followed by a slow transition to a second type of surface bonding, the latter transition representing the slow step in the adsorption process. Initial interest in silicate adsorption on thoria arose from the dispersive effect silica has on finely divided thoria in aqueous suspensions. Spaepen et al studied the equilibrium adsorption of silica on thoria and noted increased adsorption up to approximately 215°C with a notable decrease in adsorption at temperatures above 215°C. Similar results were observed by Cho and Wadsworth2 who identified two types of surface silica by infrared spectroscopy. At temperatures of 100°C and above, rapid initial adsorption occurred producing a surface species with maximum infrared absorbance at 9.4 After extended periods of time, the 9.4 species converted to a more strongly bonded surface silicate with maximum infrared absorbance at 10.3. The latter was very strongly bonded and difficult to remove by desorption in hot distilled water, while the 9.4 species could be removed more readily by similar treatment. The 9.4 and 10.3-p species were distinguishable from free unadsorbed silica which had maximum infrared absorbance at 9.1 The kinetics of the formation of the strongly chemisorbed silica (10.3) on thoria as determined by infrared examination are presented in this study. EXPERIMENTAL PROCEDURE As a source of silicate, Ludox SM (16.36% SiO2) or Ludox HS (30.25% SO2), DU Pont colloidal silica in aqueous suspensions, was added directly to a thoria slurry made up of one liter of distilled water and one gram of thoria. The thoria used was designated D-16-650 and was received from the Chemical Technology Div. of Union Carbide Nuclear Co. It was prepared by firing thorium oxalate at 650°C. The D-16 thoria had a surface area of 32.4 ± 0.6 sq m per g as determined by nitrogen adsorption.* This thoria &apos;Determined by Unlon Carbide Nuclear Co., ORNL. had a total adsorption capacity for silicate of approximately 19.4 mg of silica per gram of thoria.1 This amounts to approximately one SiO2 molecule for every surface thoria site. In all cases in this study.

Jan 1, 1963

By Roman Šejnoha, Karel Mazanec

A pronounced tendency for delayed fracture zoas observed in the martensite structure of low-alloy steels in the as-quenched condition. Cracks of predominantly intercrystalline nature nucleated and propagated at stresses substantially lower than the short-titne tensile strength of- the steels, and were observed even in hydrogen-free speciunens. The occurrence of delayed fractures in the as-quenched condition is interpreted as a supevposition of the effect of free dislocations generated during the martensite transforlnation, and of a weakening of the prior austenite grain boundaries caused by dynamic shocks exerted on the boundaries by growing martensite plates. AN important metallurgical problem, connected with the production and use of high-strength steels, is delayed fracture in martensitic structures. Such fractures occur in quenched steels as a result of prolonged loading with external stresses far lower than the short-time tensile strength of the steel. The same effect can be produced by sufficiently high internal stresses: it is well-known that quenched structures will in some cases crack intergranularly at room temperature if not tempered quickly enough even in the absence of any externally applied stress. In Troiano&apos;s papers1,2 on delayed fractures in high-strength steels, the fundamental role of hydrogen migrating under the influence of multiaxial stress towards the nuclei of cracks was found. Fig. 1 shows the typical relationship between stress and the time to fracture found by Troiano in hydrogen-charged high-strength steels. On the other hand, Shurakov 3,4 explains the realization of delayed fractures in martensite as due to a "quasi-viscous" behavior of the austenite grain boundaries immediately after the martensitic transformation. 1) MATERIALS AND EXPERIMENTAL METHODS Two low-alloy steels of commercial purity were used for the experiments reported in this paper. Their chemical composition is shown in Table I. The heats were melted in a laboratory furnace, cast to ingots, forged to bars of 3/4 in. diameter, and annealed. Machined test pieces were heat-treated as follows: Ni-Cr-Mo steel held at 900°C for 30 min and quenched in oil; Mn-Si-Cr steel held at 900°C for 30 min and quenched in water. For the delayed-fracture tests, notched cylindrical test pieces, Fig. 2, stressed in torsion, and unnotched cylindrical tensile-test pieces, 1/4 in. diameter, were used. The specimens were normally loaded with a constant static load 45 min after quenching for the torsional tests and 10 min

Jan 1, 1965