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By C. J. Rosa, W. C. Hagel

An attempt is made to determine the diffusion coefficients of oxygen ions in hypostoichiometric zirconium oxide. A phenomenological theory is developed for three-phase, unidirectional volume diffusion of a gaseous species from a planar source. Knowledge about oxygen diffusion in a and ß zirconium and experimentally measured rates of movements of interfaces permit the evaluation of oxygen ion diffusivi-ties in ZrO2-x. The results conform to the relationship: sq cm per sec, for the temperature range of 875" to 1050° C. DIFFUSION coefficients of oxygen ions in stoichio-metric oxides have been studied by many investigators. The obtained results not only supplement the knowledge about the lattice-defect structures of oxides and conduction mechanisms but also provide information of technological importance. Rate processes such as oxide sintering, high-temperature creep deformation, and oxidation of metals and their alloys are directly dependent on diffusion phenomena. Unfortunately, diffusion coefficients obtained from studies on stoichio-metric oxides cannot be treated without restraints when applied to oxidation kinetics, if precise evaluations of oxidation rates are desired. Oxides formed on metals are usually nonstoichiometric and exhibit nonuniform distribution of either cation or anion vacancies across their thicknesses. Debuigne and Lehr1 extended Danckwerts'2 mathematical analyses and furnished a semitheoretical treatment for evaluating oxygen diffusion coefficients in zirconium oxide in terms of weight gain measurements during oxidation of zirconium in the temperature range 400° to 850°C. Their calculations are based on theoretical partitioning3 of the total amount of oxygen between a zirconium and its oxide phase. An inherent discrepancy appears to continue throughout their calculations. The amount of oxygen confined to the oxide phase should be corrected by multiplying the calculated oxide thickness by the inverse of Pilling-Bedworth ratio, if expansion of zirconium dioxide is taken into account. The purpose of the present investigation is to provide a new semitheoretical treatment for evaluating diffusion coefficients of moving species in hypostoichiometric oxide. The analyses are relevant to unidirectional volume diffusion. Although the presented method is quite general, its applicability will be discussed in terms of kinetic measurements from oxidation of zirconium at temperatures above the a/ß transition, for reasons stated in the later part of this paper. EXPERIMENTAL Pure, 99.93 wt pct, zirconium samples of approximately 2 by 1 by 0.35 cm were exposed to oxygen for various times at four temperature levels: 875°, 950°, 1000°, and 1050°C. High-purity, better than 99.9 vol pct oxygen was passed through a cold trap and columns containing anhydrous CaSO4 to remove residual water vapor. Before exposing to oxygen at a pressure of 500 Torr, specimens were subjected to wet abrasion on 200- through 600-grit Sic papers and polished with 1—p diamond dust. Prior to oxidizing, all zirconium samples were vacuum-annealed at 10-6 mm Hg for about 15 min at the test temperature. The temperature variation across the uniform heat zone was ±2°C from the preset value. Final polishing, for phase thicknesses measurements, was performed by using 8- and 1-p diamond dust and followed by vibrator polishing with 0.05-µ ? Al2O3 solution. Measurements of phase thicknesses were made by projection on a metallographic viewing screen. Conventional powder X-ray analyses for the oxide were employed. RESULTS Fig. 1 is an example of the cross section of oxidized zirconium. Designations of phases given below this figure are the same as those used in the three-phase diffusion system represented by Fig. 5 in the following section. Zirconium oxidized for longer exposure times showed two types of oxides: white oxide at the surface and an underlaying layer of gray oxide. X-ray powder patterns of these oxides at room tern-

Jan 1, 1969

By John R. Low

A number of cases of low-temperature, intergranu2ar brittle fracture of metals containing small amounts of certain impurities, have now been identified. Some degree of understanding of this phenomenon exists for the simpler binary systems of a metal and a single impurity, but the profound effects of other impurities and alloying elements in modifying this type of behavior remain unexplained. Current research in this area is reviewed and some of the newer techniques of investigation which should make possible a more quantitative study of the structure and composition of grain boundaries in impure metals are described. To indicate the subject matter of this lecture, we may begin by reviewing the experimental observations concerning low-temperature intergranular brittleness in impure metals, particularly those examples in which the embrittlement appears to result from what has been called "equilibrium grain boundary segregation."' These are the systems in which it has been impossible, at least up to now, to detect the presence of any second phase film at the brittle interfaces. When second phase films are present they are usually readily detectable by fractographic methods, often appearing as epitaxial films in geometric or dendritic patterns. An example is shown in Fig. 1 for the case grain boundary carbides in a sensitized stainless steel which failed by intergranular brittle fracture at 78?k2 In contrast to this type of embrittlement there are numerous examples of low-temperature intergranular embrittlement in which the fractographs are essentially featureless, for example, that of an oxygen-embrittled iron shown in Fig. 2. The only second phase particles visible are the small, widely separated, round oxide particles typical of the bulk material. The fracture surface is extremely smooth and the fracture path appears to follow the intergranular interface without deviation. This type of fractograph also implies that crack propagation has occurred without plastic deformation at the crack tip, since localized slip or twinning ahead of the crack would be expected to distort the interface and be readily visible in the fractograph. Such indications are occasionally seen in these fractographs, but are not characteristic. A second example of this type of fractograph is shown in Fig. 3, which is from a temper-embrittled, carbon-free, Fe-Cr-Ni alloy containing Sb, broken at 1OO?C.3 The similarity to the oxygen embrittled iron case will be apparent. In the case of the temper embrittled Cr-Ni ferrite containing antimony, it is possible to remove the embrittlement by suitable thermal treatment. The grain boundaries may then be examined by thin film transmission in the electron microscope for the material in both the nonembrittled condition and in the embrittled condition. Two boundaries are shown in dark-field transmission in Fig. 4, one in the nonembrittled

Jan 1, 1970

By John Mathews

IT is twenty years since the writer made his first molybdenum steels and others were making them commercially five years earlier but the prevailing opinion seems to be that molybdenum steels are new; from time to time the daily press speaks of important discoveries in Europe and intimates that American steel makers have much to learn in regard to alloy steels. The earlier experiments were largely confined to the use of relatively high percentages of molybdenum in tool steels and permanent magnet steels. Recent developments deal with the types of alloy structural steels used for airplane, automobile, and other engineering requirements; in these, the molybdenum content is usually less than 1 per cent. The earlier types generally have been unsuccessful commercially, but the newer types of steels are becoming of increasing importance. The war showed our dependence on foreign sources for alloying metals; molybdenum alone is widely distributed in the United States and seemingly abundant. Many deposits are not now of commercial interest, owing to location and relatively small amount of ore available, but other deposits are being developed and a stable source of supply seems well assured. In tool and magnet steels, it was early found that 1 part of molybdenum was equivalent to from 2 to 2.5 parts of tungsten. The permanent magnet steels investigated by Madame Curie,1 in 1898, contained from 3.36 to 4.05 per cent. molybdenum; in 1902, Dr. E. L. French and the writer thoroughly tested steels containing from 2:0 to 4.0 per cent. These steels gave satisfactory tests for permanence, but were low in residual density and much more sensitive to hardening than the corresponding tungsten products. We discontinued work with them, therefore, and have no advice that such steels have been used commercially here or abroad.

Jan 2, 1921

By Arthur B. Cummins, Henry Mulryan

DIATOMITE is a hydrous or opaline form of silica, commonly known as diatomaceous earth, diatomaceous silica or kieselguhr. The term "infusorial earth" has lost its original meaning and today is incorrect in view of the distinctions between diatoms and infusoria. Various locality and variety names are obsolete but some retain local significance. Moler and Celite are trade names that have become associated with diatomite products from certain deposits in Denmark and near Lompoc, California. COMPOSITION Diatomite is essentially silica with some combined water (2 to 10 pct). Frequently it contains organic matter (from traces up to over 30 pct) and varying amounts of inorganic impurities such as sand, cryptocrystalline silica, clay, volcanic ash, calcium carbonate, magnesia and soluble salts. In the natural or crude state, diatomite contains from 10 to 65 pct or more of free water. Table I gives analyses of several diatomites from deposits of different types. PROPERTIES Pure varieties, either massive or stratified, are friable and porous, of low apparent density, and somewhat chalklike in appearance. Varieties containing organic matter vary from sedimentary oozes to peatlike materials. Impure varieties may be more or less claylike, sandy, calcareous or cherty. Compacted types approach porcellanite and silicified shales. COLOR-white, cream, gray, tan, brown, greenish to nearly black. HARDNES-light-weight varieties appear 1 to 1.5 because of porosity, but microscopic particles are 4.5 to 6.5. SPECIFIC GRAVITY-1.9 to 2.35. APPARENT DENSITY---dry block form, 20 to 40 lb per cu ft; dry powder, 5 to 16 lb per cu ft. CRYSTAL SYSTEM-generally amorphous (isotropic by X-ray diffraction) but frequently showing faint cristobalite pattern.67.68,70 MELTING POINT-1400° to 1650°C. STREAK-white. LUSTER

Jan 1, 1949

By Allen J. Johnson

With a realization of the rapidly increasing importance of automatic stokers as a medium for domestic heating, the Anthracite Institute Laboratory has conducted extensive investigations, over a period of several years, to determine the various outstanding characteristics of stoker design and performance. The purpose of this paper is to summarize these findings as a guide to current practices. Stokees Investigated One or more models of the underfeed stokers listed below were included in the various phases of this investigation: Beckley Gilkoal Burnwell Iron Fireman Combustioneer Motor Stokor Electric Furnace Man Norristown Super-stoker Erie Heat Generator Whitney Fire Ball (Tests Incomplete.) Fuel Saver Principles of Construction.—The operating principle of the leading makes of underfeed stokers is similar (Fig. 1). A plunger1 or slowly revolving worm2, conveys the buckwheat or rice sizes of anthracite to the center of a specially constructed tuyere pot where air is admitted to the coal through suitable ports of varying design. As the fuel burns, it is slowly forced to the outside circumference of the tuyere by the pressure of the incoming coal; eventually the ash falls over the edge of the pot, either entirely by gravity or aided by mechanical sweepers. In at least one model, the entire firepot revolves. While various special details have been included in the design of a number of stokers, they do not affect the general principles as described above, and therefore have not been included in this discussion.

Jan 1, 1936

By Allen J. Johnson

With a realization of the rapidly increasing importance of automatic stokers as a medium for domestic heating, the Anthracite Institute Laboratory has conducted extensive investigations, over a period of several years, to determine the various outstanding characteristics of stoker design and performance. The purpose of this paper is to summarize these findings as a guide to current practices. Stokees Investigated One or more models of the underfeed stokers listed below were included in the various phases of this investigation: Beckley Gilkoal Burnwell Iron Fireman Combustioneer Motor Stokor Electric Furnace Man Norristown Super-stoker Erie Heat Generator Whitney Fire Ball (Tests Incomplete.) Fuel Saver Principles of Construction.—The operating principle of the leading makes of underfeed stokers is similar (Fig. 1). A plunger1 or slowly revolving worm2, conveys the buckwheat or rice sizes of anthracite to the center of a specially constructed tuyere pot where air is admitted to the coal through suitable ports of varying design. As the fuel burns, it is slowly forced to the outside circumference of the tuyere by the pressure of the incoming coal; eventually the ash falls over the edge of the pot, either entirely by gravity or aided by mechanical sweepers. In at least one model, the entire firepot revolves. While various special details have been included in the design of a number of stokers, they do not affect the general principles as described above, and therefore have not been included in this discussion.

Jan 1, 1936

By R. A. Morse, P. M. Bridges, L. E. Wilsey, Howard N. Hall, P. L. Terwilliger

Theoretical and experimental investigations of a constant pressure gravity drainage system are reported. Experimental data are presented to show that recovery to gas breakthrough by gravity drainage is inversely proportional to rate. The gravity drainage reference rate, which is numerically equal to the so-called "maximum theoretical rate of gravity drainage" is shown to have no particular significance from a recovery standpoint. Before this rate can be used as a basis of comparison for recoveries, it is necessary that the relative permeability and capillary pressure characteristics and displacing fluid viscosities be identical for the systems compared. A method is presented by which accurate prediction of the performance of a gravity drainage system can be made. Close agreement between experimental and calculated drainage performance shows that steady state relative permeability and static capillary pressure data can be used to describe fluid displacement behavior. The very wide range of liquid recoveries before gas breakthrough which result from production rate variation alone demonstrates the importance of this factor in planning depletion of a gravity drainage reservoir. Calculated results are presented which show that little additional recovery can be expected from a high pressure gravity drainage system between the times of gas breakthrough and attainment of such high gas/liquid ratios as to make further pressure maintenance impractical. INTRODUCTION It bas been recognized for some time that gravity forces play an important part in the recovery of oil from some types of reservoirs. Field experience has shown that under certain conditions, gravity drainage can result in very high oil recov- eries. Qualitative reasoning has led most engineers to the general conclusions that: (1) Where gravity drainage is important, the reservoir pressure should be maintained by gas injection at the crest of the structure to prevent shrinkage of the oil in place and to keep a low viscosity so the oil can drain at the fastest possible rate. (2) Recovery by gravity drainage is rate sensitive. A survey of the literature indicates that while considerable work has been done on the effects of gravity in oil production problems, no satisfactory method of calculating the performance of gravity drainage reservoirs has been reported.1,2,3,4,5 In the absence of any proven method of calculating reservoir performance, the level at which pressure should be maintained and the rate of production for most efficient operation has been open to debate. The limits and general character of the recovery us rate relationships are apparent from the following: As rates of production approach zero, oil will drain by virtue of its own weight fast enough that the saturation distribution is always approximately the same as the original static capillary distribution. That is, at the gas-oil contact the liquid saturation goes from 100 per cent to a value of perhaps 10 to 30 per cent in a very short distance, so that as production continues. a relatively sharp gas-oil contact moves down-structure, leaving a very low residual oil saturation in the originally oil saturated zone. At very high rates of production, the oil that drains by virtue of its own weight is negligible and recovery will approach that of a horizontal gas drive, leaving a much higher residual oil saturation. At intermediate rates of production. recovery should be between these extreme*. Despite the lack of quantitative methods, tentative agreement had been reached on the question of optimum producing rate. It has been generally concluded that rather sharp decrease in recovery would occur at rates of production above the "maximum rate of gravity drainage" and hence this rate should not be exceeded. The "maximum rate of gravity drainage" is defined as the rate of production from a 100 per cent

Jan 1, 1951

By L. E. Wilsey, R. A. Morse, P. L. Terwilliger, Howard N. Hall, P. M. Bridges

Theoretical and experimental investigations of a constant pressure gravity drainage system are reported. Experimental data are presented to show that recovery to gas breakthrough by gravity drainage is inversely proportional to rate. The gravity drainage reference rate, which is numerically equal to the so-called "maximum theoretical rate of gravity drainage" is shown to have no particular significance from a recovery standpoint. Before this rate can be used as a basis of comparison for recoveries, it is necessary that the relative permeability and capillary pressure characteristics and displacing fluid viscosities be identical for the systems compared. A method is presented by which accurate prediction of the performance of a gravity drainage system can be made. Close agreement between experimental and calculated drainage performance shows that steady state relative permeability and static capillary pressure data can be used to describe fluid displacement behavior. The very wide range of liquid recoveries before gas breakthrough which result from production rate variation alone demonstrates the importance of this factor in planning depletion of a gravity drainage reservoir. Calculated results are presented which show that little additional recovery can be expected from a high pressure gravity drainage system between the times of gas breakthrough and attainment of such high gas/liquid ratios as to make further pressure maintenance impractical. INTRODUCTION It bas been recognized for some time that gravity forces play an important part in the recovery of oil from some types of reservoirs. Field experience has shown that under certain conditions, gravity drainage can result in very high oil recov- eries. Qualitative reasoning has led most engineers to the general conclusions that: (1) Where gravity drainage is important, the reservoir pressure should be maintained by gas injection at the crest of the structure to prevent shrinkage of the oil in place and to keep a low viscosity so the oil can drain at the fastest possible rate. (2) Recovery by gravity drainage is rate sensitive. A survey of the literature indicates that while considerable work has been done on the effects of gravity in oil production problems, no satisfactory method of calculating the performance of gravity drainage reservoirs has been reported.1,2,3,4,5 In the absence of any proven method of calculating reservoir performance, the level at which pressure should be maintained and the rate of production for most efficient operation has been open to debate. The limits and general character of the recovery us rate relationships are apparent from the following: As rates of production approach zero, oil will drain by virtue of its own weight fast enough that the saturation distribution is always approximately the same as the original static capillary distribution. That is, at the gas-oil contact the liquid saturation goes from 100 per cent to a value of perhaps 10 to 30 per cent in a very short distance, so that as production continues. a relatively sharp gas-oil contact moves down-structure, leaving a very low residual oil saturation in the originally oil saturated zone. At very high rates of production, the oil that drains by virtue of its own weight is negligible and recovery will approach that of a horizontal gas drive, leaving a much higher residual oil saturation. At intermediate rates of production. recovery should be between these extreme*. Despite the lack of quantitative methods, tentative agreement had been reached on the question of optimum producing rate. It has been generally concluded that rather sharp decrease in recovery would occur at rates of production above the "maximum rate of gravity drainage" and hence this rate should not be exceeded. The "maximum rate of gravity drainage" is defined as the rate of production from a 100 per cent

Jan 1, 1951

By J. B. Morrow, D. H. Davis

THERE are two general approaches to the problem of increasing profits from an operation. One is to lower expense; the other is to raise income. Mechanical preparation of coal may be used for either purpose but a prudent consideration of many details must precede any decision lest the results be negative instead of positive. It is quite possible that any net gain will result from a combination of the two. Since mechanically prepared coal invariably is a better product qualitatively than a hand-picked coal from the same mine, it is a reason- able expectation that the customer will be willing to increase the producer's income by paying a higher price. Or there may be the possibility that a combination of mechanical mining plus mechanical cleaning will give a lower over-all production cost for the coal in the railroad car. More likely, there will be found a combination of these two factors. From the customer's point of view, the competitive delivered cost per B.t.u. considered in relation to such incidental factors as dust nuisance, handling properties, ash disposal, and ash fusibility determines what he will pay. In a bulk tonnage product such as coal, freight is a very considerable part of the delivered fuel cost, and obviously freight paid on incombustible ash has no economic attractions. INCENTIVE FOR CLEANING Coal is prepared in four major ways: 1 (I) by screening or sizing, (a) by mixing or blending, (3) by cleaning, including hand picking and mechanical cleaning, (4) by dustless treatment. By a combination of any or all of these methods, coal can be prepared to standard specifications. It is easily possible to have good cleaning and still get a poor final product because of faulty screening or mixing,

Jan 1, 1943

By Theodor Zuschlag

Electrical prospecting is the art of exploring the structure of the subsoil in regard to conductivity variations and interpreting the results of such exploration as to their geological meaning. Electrical prospecting has been applied during the last few years with outstanding success, not only to prospecting1 for ore but also to structural studies.2 Both applications have proved helpful to the geologist, and the latter application especially promises to become of still greater importance in the future. The mapping of structures is the most important function of the oil geologist. Oil is lighter than water, therefore in water-bearing beds it will migrate upward until the migration is stopped by a bed impermeable to the oil. Geologic structures such as domes, anticlines, faults and terraces, offer good prospects in the search for oil accumulations and can be traced easily by electrical prospecting, provided they are composed of a series of sedimentary layers of which at least one possesses fair electrical conductivity and follows the general trend of the structure. Conditions for Successful Mapping The first condition, fair electrical conductivity, is met in almost any oil-bearing series, because generally the electrical resistance of a sedimentary bed is identical with the resistance of the more or less saline waters, filling partly or entirely the pores of the rocks.3 Briefly, the electrical resistivity of a bed can be expressed for all practical purposes by the product R X P, where R is the specific resistance of the waters in the rock pores and P a factor depending upon the percentage of water by volume in the rock. The specific resistance of any solution can be computed from the chemical analysis, being primarily a function of the

Jan 1, 1932

By C. H. Cheng, C. E. Birchenall

The fundamental problem in the thermodynamics of solid solutions is the determinatiorl or calculation of the activities of the components as a function of temperature and composition. Since the theory of metals is not suficiently developed to allow a priori calculation of these quantities, they must be obtained from experiment. C. Wagner1 has reviewed the literature of this subject for the period before 1940. Although several important and extensive studies have been made in the meantime, the number of systems to which any sort of quantitative information can be assigned is vanish-ingly small. These data have become of great potential importance in studies of the structure of solid solutions2 and intermetallic compounds, the nature of the diffusion process,3,4 and perhaps even the mechanism of mechanical deformation.5 For these reasons, it. seems very worthwhile to extend the experimental data in this field. Although there is little use in duplicating Wagner's review, attention should be directed to the most recently reported investigations. A brief enumeration of the methods of measurement previously employed also should be valuable. The most direct method is the determination of the partial pressure of the components in the vapor phase in equilibrium with the solution. Both equilibrium and kinetic methods have been tried in metal systems, but almost exclusively on liquid phases. Only in the ease of carbon in iron alloys and in the copper-zinc system have extensive measure- ments been made which include solid phases. When one of the components is an element, such as nitrogen or carbon, which forms compounds which are very volatile and stable at normal temperatures and pressures (CH4, Co2, CO NH3), it is frequently possible to equilibrate mixtures containing these (such as CH4-H2, CO2-CO, NH3-H2) independently with the elernents (C, X) and with the metal (Fe, Ni, etc.). Such measurernents have been made for carbon in iron, iron-silicon, and iron-manganese alloys by Smith6 and in iron and iron-nickel alloys by Toensing.7 Differences between carbon activity values at the same temperature and carbon content when carboil is introduced from CH4-H2 rnixtures or CO-CO. mixtures indicate that the effects of hydrogen and oxygen in the system are not negligible, and one can only hope that the true value lies somewhere between these sets of results, probably nearer the CH4-H2 data since hydrogen is less soluble in iron than oxygen. This is essentially an equilibrium method, although flowing gas is employed. A kirletic method has been employed which consists of sweeping an inert gas (generally hydrogen) over the alloy at a series of rates, condensing the metal vapor out,, and analyzing it. The metal content can be extrapolated to zero flow rate (equilibrium). Wejnarth's8 work on Cd-Mg and Zn-Mg is a good example of this frequently used method. A variant of this consists of equilibrating a known volume of inert gas with the alloy, sweeping it out quickly, and analyzing for metal. In common with the above method, it has the disadvantage that the "inert" gas is generally somewhat soluble in the alloy. Moreover, the former continuously displaces the system from equilihrium and may give low values if solid diffusion is involved. The dew point method applied by Hargreaves9 to the alpha and beta brasses and by Schneider and Stolll0 to A1-Zn avoids the introduction of another component to the system, but is useful only in systems in which one component is much more volatile than the other. The alloy sealed in one end of an evacuated silica tube is heated to the desired temperature. The temperature of the other end is lowered until droplets of the volatile component condense. When the temperature is raised slightly, the droplets will evaporate. By careful adjustment of temperature, the range between evaporation and condensation can be narrowed appreciably. An independent determination of the vapor pressure of the . pure volatile component is necessary to give the partial pressure over the alloy. This is the method employed here to determine the vapor pressures of zinc and cadmium over their silver alloys up to 34 pct in cadmium and 76 pct in zinc. The former involves only the a solid solution, but the latter covers the a, ß, y, and e fields. In recent determinations, Herbenar, Siebert, and Duffenbarkl1 used the

Jan 1, 1950

By W. T. Roberts, N. G. Turner

A study of the fatigue properties of several grades of commercially pure titanium has established that the strain-aging process is of minor importance in the development of a fatigue limit and a relatively high fatigue strength ratio. Metallographic observations and damping measurements at room temperature indicate that striations are able to spread from grain to grain only at stress levels above the fatigue limit. This suggests that the fatigue limit represents the stress above which large-scale dislocation unlocking takes place. Fatigue tests on annealed material at - 60" and - 196" c showed that under conditions when a thermally activated diffusion process would be suppressed the fatigue limit is not eliminated. Prestraining at room temperature did not have a detrimental effect on fatigue strength at room temperature but a decrease was recorded at — 60°C. This is further evidence that initial dislocation locking is a important strengthening mechanism. TITANIUM and titanium alloys have S-N curves with a definite fatigue limit, and a high ratio of fatigue limit to UTS can be attained. Other materials which show similar fatigue characteristics are mild steel and some Al-Mg alloys. The fatigue limit of these materials has been associated with their strain-aging capacity. It is well-known that commercial-purity titanium contains interstitial impurities which can give rise to a sharp yield point, and a small strain-aging effect following static strain has been demonstrated.7 This type of aging reaction is differentiated from the dynamic aging process when aging occurs during plastic deformation, and which is generally observed at elevated temperatures. In a titanium at room temperature, dislocation locking is associated with the interaction of interstitial oxygen, nitrogen, and carbon atoms with dislocations. Ehr-lich has shown that the distortion produced by introduction of these atoms into the hcp lattice has no shear stress component and hence there is no interaction between the stress field and the screw component of a dislocation. Thus the dislocations as a whole are only weakly locked. It is clear that strain-aging effects in hcp a titanium will be much less pronounced than those observed in bcc iron and steel. In recent years, the attribution of the fatigue limit solely to strain aging has been questioned. It has been pointed out that a definite fatigue limit is observed at temperatures as low as -196°C in some titanium alloys,' and strain aging is not expected to be effective at this temperature. The role of initial locking of dislocations in determining fatigue behavior has been examined in low-carbon steel by Oates and Wilson. They showed that under conditions in which the aging potential is low the factors which control the buildup of local stresses and hence affect dislocation unlocking, e.g., grain size, are important. There are indications that other metals can have a definite fatigue limit with no established strain-aging capacity, an example being magnesium12 which has the same crystal structure as a titanium. The spread of plasticity from grain to grain in hexagonal metals may be more difficult than in cubic metals because of the limited number of slip systems in the former, and this may account in part for their fatigue behavior. The present work was undertaken to elucidate the relative importance of crystal structure, strain aging, and initial dislocation locking in determining the properties of commercially pure titanium when subjected to cyclic stressing. 1) EXPERIMENTAL METHODS Three grades of commercial-purity titanium were used and a material of lower interstitial content was prepared by melting high-purity Japanese sponge titanium (referred to as H.P. Ti). The compositions and typical mechanical properties of the materials are shown in Table I. Fatigue tests were made in push-pull (zero mean stress) using an Amsler Vibraphore machine at a frequency of about 160 cps. Two types of fatigue specimen were used—one with a waisted gage length for determination of S-N curves and the other with a parallel gage length for metallographic studies and damping measurements. After careful machining and mechanical polishing, all specimens were electropolished prior to fatigue testing. The electrolyte consisted of 10 parts methyl alcohol, 6 parts 2-butoxyethanol, and 1 part perchloric acid (SG 1.54) and it was maintained at a temperature of -10" to -20°C during polishing. Tests at room temperature were normally carried out with the specimen immersed in a silicone oil bath which could be heated for elevated-temperature tests.

Jan 1, 1969

By J. W. Lacey, F. H. Brinkman, J. E. Faris

This paper presents an analysis of the high-pressure, gas-driven LPG-slug process, based on fluid flow tests in areal models. Two types of tests were made. One series was made in low-pressure models which permitted observation of fluid movement. Three completely misci-ble analog fluids were used. A second series of tests was made in high-pressure models using methane, propane and a light refined oil saturated with methane at room temperature and 1,550 psig. Under the test conditions of room temperature and a pressure level of 1,550 psig, the phase diagram for the fluids used is similar to those for many of the field systems where the process is considered for use. A method for using these laboratory data to calculate field performance of the process is outlined. As a result of this work, it is concluded that small banks of LPG (5 per cent HV or less) are not effective in increasing oil recovery in horizontal reservoirs. Znstead, where small banks are used, the driving gas quickly penetrates the LPG bank because of fingering and channeling; and from this point on, the process behaves essentially as an immiscible gas-injection project. The validity of this conclusion was substantiated by: (1) laboratory studies of the effect of rate, model size and mobility ratio on miscible displacement in areal models; and (2) calculation of field recovery, which compared closely with actual field recovery. INTRODUCTION Field applications and pilot tests of the gas-driven, LPG-bank, oil-recovery process are on the increase. Most of these tests are employing small banks (2% to 5 per cent hydrocarbon volume) of LPG, which is miscible with both the driving gas and the oil in place, in an effort to attain an effective yet economical miscible displacement of oil by gas. The expectation of miscible displacement with small banks is based on the concepts that: (1) lengths of solvent-oil mixed zones, measured during miscible displacements in long slim cores, are representative of those that will occur in the field; and (2) areal sweep efficiencies5 measured in electrolytic model studies are applicable to miscible displacement in reservoirs. Our experimental evidence indicates that the mixed-zone lengths and sweep efficiencies mentioned are not applicable to miscible displacement in reservoirs. In this paper we present an evaluation of the gas-driven, LPG-bank oil-recovery process based on fluid flow experiments in areal models. These results are used to predict the performance of a field pilot test of this process, and the results are compared with the actual test results. THE EFFECTIVENESS OF LPG BANKS The effectiveness of LPG banks of various sizes in accomplishing miscible displacement of oil by gas was determined by displacement tests in a model representing one-quarter of a confined five-spot pattern. The model, 12 X 12 X 1/4 in. in size, was packed uniformly with glass beads. It was operated at a pressure of 1,550 psig and at room temperature; the fluids used were methane, propane and refined oil saturated with methane at 1,550 psig. The saturated oil had a viscosity of 1.2 cp at room temperature. The results of these tests are shown in Fig. 1, where recovery is plotted as a function of the volume of fluid injected for: (1) an immiscible-gas drive with an oil-to-gas viscosity ratio of 85; (2) three sizes of LPG banks; and (3) two completely miscible displacements with mobility ratios of 85:1 and 10:1. (The miscible displacement data plotted are the averages of several tests.) The results show that a 2½ per cent bank of LPG does not increase oil recovery over that obtained by immiscible-gas drive. The 7 and 17 per cent banks are, respectively, about 30 and 50 per cent effective (with reference to the M = 85 miscible-displacement curve) in increasing oil recovery at the point where 2½ hydrocarbon volumes (HV) of fluid have been injected. The percentage effectiveness of the banks at a given volume of fluid injected is defined as Recovery by Bank — Recovery by Gas Drive Recovery by Miscible Recovery by Flooding Gas Drive We conclude from these results that banks of LPG smaller than about 5 per cent HV in an individual stratum will cause from little to no increase in oil recovery. This finding was substantiated by work in low-pressure models, which permitted visual observation of fluid movements. In these tests, three completely miscible fluids having the same viscosity ratios as those used in

By L. F. Bishop

The ore bodies of the Butte district1 are found in many different vein systems having many different structural characteristics; some are narrow with self-supporting ore but with weak walls; some are wide with weak or strong ore and weak walls; some of the veins dip steeply and others do not; some have well defined walls, and others, in the "horsetail" area, are mined to sample limits. Consequently, many types of stoping methods are used in mining these ores. The stoping methods used in the Anaconda Copper Mining Company's properties are the square-set and cut-and-fill. The square-set method is the principal stoping method used because, generally speaking, the ore and walls are weak, the ore is high grade, and good extraction is required. These square-set stopes may be classified as conventional, vertical slice, slot, timber rill, and Mitchell slice types. The conventional type square sets are those of various shapes and sizes, mined by horizontal slicing to the boundaries of the stopes. The rock is slid to the chute and the filling is moved by gravity. The ore and waste may be handled with a scraper when local conditions require it. The vertical-slice square-set system is the type used in narrow veins that are mined in vertical panels. The slot stopes are stopes in wide veins that employ a slot across the vein instead of a con- ventional chute to handle the ore. The timber rill is a type of square set in which the ore is mined as in inclined cut and fill but the square-set timber is used. The Mitchell slice is the type used for some broken or heavy ore blocks, or for pillar extraction between two converging slot stopes. The cut-and-fill method is used where the ore will stand without much support although the walls may be weak. The principal type of this method is the horizontal cut-and-fill, with mechanical scraping. The inclined cut-and-fill, or rill, stopes are used in some veins too narrow for scraping. The production from the various methods in use for the second six months of 1944 are shown in Table I. This paper deals mainly with the vertical slice and slot types of square-set stoping, because of their effect on production locally and their potential possibilities here and in other districts, with sufficient reference to conventional square-setting for comparison.

Jan 1, 1946

By R. W. Gurry

IN the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and 1110°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon content of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched. The mean result of concordant measurements is that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C. (1755°F.) and 1.89 per cent at 1110°C. (2030°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutectoid temperature (738°C. or 1360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature 1135°C. (2075°F.) instead of the commonly accepted value of about 1.7 per cent. EXPERIMENTAL PROCEDURE The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.1 In the empty furnace the range of temperature over a distance of 4 cm. at the heat center was 9°C. (16°F.) but at a given location the temperature remained within ±0.5°C. (0.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (1760°F.) and 1110°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with

Jan 1, 1942

By J. S. Dodge, I. M. Krieger

The laminarturbulent transition was studied for monodisperse rigid polymer latices as functions of particle diameter and concentration at several tube diameters. Breaks in the graph of friction factor US Reynolds number were used to characterize the transition; rates of shear were sufficiently high so that Newtonian behavior at the high shear limiting viscosity could be assumed. No abnormal behavior was noted at concentrations below 30 volume percent. At higher concentrations, suppression of turbulence was observed with critical Reynolds numbers rising to as high as 5,500 at 50 volume percent. No definite effect on the transition was noted due to variation of particle size or tube diameter. The type of surfactant used to stabilize the latex was found to have an important influence on the critical Reynolds number. INTRODUCTION For some polymer solutions and solid-in-liquid suspensions, the transition from laminar behavior to turbulence in pipeline flow has been reported to take place at unusually low1-5 and in some cases at higher than normal6,7 critical Reynolds numbers. Extreme values of critical Reynolds numbers (NRe*) have been found to range from 1 to 6,000, as opposed to the values of 2,000 to 3,500 which are obtained for ordinary liquids. Observations have also been reported of drag reduction in fully developed turbulent flow, i.e., a decreased value of the friction factor in the Reynolds number-friction factor plot6*10-14 in colloidal and polymeric fluids. In some cases, turbulence suppression (unusually large values of Nre*) was noted to occur preceding the drag reduction,6 while a normal transition was noted in other cases of drag reduction.14 To relate the occurrence of turbulence suppression and drag reduction to the molecular or particulate structure of the fluid, it is desirable to characterize the structural variables with some precision. For most colloidal dispersions and polymeric fluids, this is very difficult; particle sizes, shapes and stiffnesses may vary over wide ranges in the same sample. Recently, however, a colloidal fluid has become available which consists of rigid spherical particles of highly uniform diameter dispersed in a simple Newtonian liquid. These are monodisperse polymer latices, prepared by carefully controlled emulsion polymerization reactions. The purpose of this research was to study the transition to turbulence in these well-characterized colloidal fluids as a function of concentration, particle diameter and tube diameter. Typical flow curves of latices of high solids content are shown in Fig. 1. While these curves were obtained with monodisperse latices, the general shape of the curve is also typical of a polydisperse latex. It is observed that a shear-thinning region occurs for low to moderate rates of shear. At sufficiently high shearing rates a limiting Newtonian viscosity is reached. The viscosity µ diminishes with decreasing volume fraction 4 at all shear rates. For 4 less than 0.25, latices are Newtonian at all rates of shear.15 An increase in average particle size (at a given extends the Newtonian viscosity region to lower rates of shear. A third factor which influences the

By H. E. Wilborg

This chapter deals with those sands employed by the foundries for the manufacture of cores and molds used in the casting of such common metals as steel, gray iron, ductile iron, aluminum-based alloys, and copper-based alloys. Most metal is cast in "green sand" molds in which the sand mixture, consisting primarily of silica, clay, and water, forms a plastic material. This plastic material is rammed around a pattern in a split box called a flask, then the box is separated, the pattern is withdrawn, and the metal poured. These green sand molds are broken apart when the metal has solidified. The sand is then remixed and a new mold made for the next casting. To a lesser extent silica sand is mixed with resins or oils and, after forming, the mixture is hardened either by heat or chemical reaction. In any case, the foundry mold or core is used just once before being broken up and remixed for manufacturing another core or mold. By far the greatest consumption in the foundry is of those types of sand high in silica, low in clay (under 0.5%) and occurring in numerous locations thoughout the United States.

Jan 1, 1975

By Martin E. Chenevert

The early work of Terzaghi1 showed that the true stress state of a rock can be expressed by the principle of effective stress. This principle states that effective stress is equal to total applied stress minus the pore pressure. Since the introduction of this principle, a great effort has been made to measure the pore pressure of rocks so that the true stress state can be determined. For clean, permeable sandstones, it is usually found that the effective stress principle can easily be applied. Direct measurement of the pore pressure is achieved with a hydraulic pressure device and the effective stress state thereby computed. However, for fine-grained rocks which contain large amounts of clay (referred to herein as shales), pore pressure measurements are usually quite difficult because of the adsorptive forces of the clay platelets, which produce negative internal pressures. No suitable device is known for measuring internal pressures of dry shales; the effective stress approach is therefore not feasible and data are usually presented in another form. As an example, data from compressive strength tests are presented as a function of rock wetness, rather than effective confining stress. The work of Belopoloskii2 and Colback and Wiid3 are examples of such data. It was pointed out by Lambe and Whitman4 that a better way must be found to express the effective stress of argillaceous rocks. The information presented herein is an attempt to fill that need. Various authors have been able to measure moderate negative pore pressures (0-240 psi) within rather wet, argillaceous rocks by means of various pore pressure devices. In 1961 Lambe5 resented information which shows that pore pressures in argillaceous rocks are indeed negative ; he presented values of suction pressure as low as - 14 psi. Likewise,

Jan 1, 1970

A knowledge of the principles of punctuation is essential to effective and intelligible writing, for the ease and pleasure of the reader, and even his understanding, may depend upon the choice and the placing of punctuation marks. To 'punctuate' is to mark with stops or points; the word comes from the medieval Latin punctuare (punctuatus), which in turn is derived from the Latin punctum, a point. The purpose of punctuation is to show the manner in which the writing is to be understood; to indicate the relations between parts of a sentence and between successive sentences. To some extent "it does for the eye what vocal stress does for the ear", but especially it marks logical relations. Some punctuation marks, such as those indicating admiration, exclamation, and interrogation, are rhetorical as well as grammatical, but most of the common ones are logical or grammatical. My discussion will be confined to grammatical punctuation in ordinary writing. "The problem of punctuation in text matter", as George Summey * says, "is to employ words, points, and paragraph breaks in such a way as to achieve at the same time clearness, proper distribution of emphasis, and the desired kind of movement." The criticism of the punctuation of a sentence or of a group of sentences is not final until the context, within the paragraph, is read. A paragraph is a sentence or a group of' sentences forming an independent unit of the composition; it represents a unit of thought. A multiplicity of paragraphs produces a choppy effect; on the other hand, paragraphs of excessive length are tiresome, because the belaboring of one unit of thought wearies the reader. The aim should be to

Jan 1, 1931

By J. D. McBeth, G. M. Potter, Ramon Pizarro

Heap leaching is used by the Carlin Gold Mining Co., Carlin, Nev., to supplement conventional processing of gold ore by agitation-leaching and countercurrent decantation. Selected open-pit ore containing about 0.072 oz Au per ton is crushed to 3/4 inch, dumped by truck on an asphalt pad, and leached by sprinkling with dilute cyanide solution for 7 days. The heap is then drained and removed by front-end loader to tailings disposal. About 70 percent of the gold is dissolved. Leach solution from the heap joins the pregnant solution from countercurrent decantation for gold recovery by zinc precipitation. Four leach pads, each with a capacity of 1,400 tons of ore, are in use. About 10,000 tons of ore are heap leached monthly from about April through October. Heap leaching is recessed during freezing weather. Labor, equipment, and reagent requirements for heap leaching are presented.

Jan 1, 1974