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By G. A. Vissac

MoIstuRe in coal must be considered as an impurity, just the same as ash, from the standpoint of utilization of the coal. Being incombustible, it reduces directly the heating value of the coal, and in addition absorbs heat for its evaporation. Its presence means useless expenditures in handling and transportation. In coke plants, extra moisture reduces capacity and may cause damage to brick work and equipment. Accordingly, the removal of extra moisture can be considered just as important as the removal of other impurities, such as ashes, in the modern coal preparation plant. Moisture, which can be removed by heating the coal up to a temperature of 100°C, may be retained in various forms: 1. As a film, on the surface of each coal particle, and in the interstices between particles, retained by capillary forces. 2. Or "occluded" inside the coal particles. This occluded moisture may be either free moisture (as in a sponge), or hygroscopic moisture which varies with atmospheric conditions, (also called "regain"). These latter forms of moisture are particularly common in "young" coals (subbituminous and lignites); bloom coals (seam outcrops); fusain; and carbonized products. In our study of coal drying, we shall consider only the removal of free moisture, exclusive from hygroscopic moisture. Dewatering If we reserve the name of drying to the removal of water by evaporation, we must consider the initial phase of the mechanical removal of free moisture as a distinct operation covered by the term dewatering. In all cases the free water carried over the surface of the coal particles or in their interstices, or in their pores, is retained by capillary forces. Dewater-ing is accomplished by breaking or counteracting these capillary forces; removal of as much water as possible by dewatering methods is usually advisable, as the cost of these operations is generally much less than by evaporation. The most common methods of me-chanical dewatering are: 1. "Pressure piling," which reduces the interstitial spaces, accomplished in dewatering bins or over dewatering screens. 2. Or dynamic methods, such as used in centrifuges or over vibrating screens. We shall only mention the " preferential wetting" method, in which surface water can be displaced by hydrocarbons, as offering possibilities, but which, to our knowledge, has not reached yet a practical development. But we must point out that the capillary forces retaining water on the coal surfaces, decrease considerably with increased temperatures. This is the principle used in all modern dishwashing machines; by using very hot water, dishes are extracted almost dry. In line with this development, we favor the type of dryers including a dewatering section; as the coal enters the dryer and is gradually brought up to higher temperatures, its dewatering ability is increased and advantage can be taken of this conditioning, resulting in increased drying efficiencies and reductions in drying costs. Heat Drying In the final phase, the remaining moisture must be evaporated. Coal and water must be brought up to the chosen temperature of evaporation, and heat must be supplied to fill the requirements of the latent heat of evaporation of the water to be removed. Accordingly, drying becomes largely a problem of heat transfer, and drying methods can be classified accordingly, namely: 1. Radiant transfer. 2. Transfer by surface contact and conduction. 3. Transfer by hot gas contact. The first method is not applicable to coal drying; the second method is used in the old type rotary dryer. The third method, the most commonly used in modern coal dryers, will be the only one considered here; and, of course, we shall deal with continuous types of dryers only. The mechanism of complete drying is really very complex-—several phases are involved: 1. The constant rate period. 2. The uniform falling rate period. 3. The varying falling rate period. As most of our practical coal drying problems deal with wet coals (over 6 pct of moisture), and do not require complete drying (under 1.5 pct), we shall deal with the first condition only, namely the constant rate drying. Dryer Calculations Instead of presenting the algebraic formulas, we believe a concrete example will provide a clearer illustration. Assume a feed of wet coal at the rate

Jan 1, 1950

By J. M. Karpinski, R. O. Tervo

A method and equipment have been developed for measuring the impact strength of grains of brittle materials. It is shown that brittle materials develop a characteristic particle size distribution when fractured by impact. A simple mathematical model has been found to describe this distribution, and one of the parameters of the model has been designated the r value. The r value is directly proportional to impact energy and, for fixed impact energy, it becomes a useful criterion of grain strength. Data are presented on the variation of the r value as a function of sample history, initial size, energy input and number of impacts. The results are interpreted in terms of the flaw theory of brittle fracture. The view is now widely held that brittle materials comprise a strong matrix, throughout which flaws or points of weakness are scattered at random. Failure always starts at one or more of these imperfections, and planes of fracture are established by the geometry of the flaw distribution. This view has been developed extensively by Weibull 1,2 and experiments of a confirmatory nature have been reported.3,4 Thus the process of fracture or size reduction of brittle materials can be regarded as a process of elimination or creation of flaws, and the concept of strength is intimately connected with the size and history of the specimen tested. One consequence of the point of view described above is that brittle materials will fracture to yield similar size distributions, although the impact energy to produce a given amount of fracture may vary greatly from one material to another. Generally speaking, experimental investigations of brittle fracture in solids have been confined to two extreme experimental situations. On one hand, we have tests on single specimens of well-defined, but artificial, geometry and, on the other, empirical data have been obtained on the feed-product relation in a variety of mills. The first situation necessitates specimen preparation, which in the case of brittle materials is equivalent to a priori size reduction, while the second one suffers from the disadvantage that little knowledge is gained about individual fracture events. Also, the statistical significance of single specimen tests may be questioned. Our approach lies somewhere between these two extremes. We test a large population of sized specimens and yet subject each specimen to a single fracture event. In 1956 G.H. Fetterley of Norton Co., Chippawa, Ont., made the empirical observation that product size distributions obtained from impacting sized grits can be described by the following equation where R is the proportion by weight of the grain that remains on a screen having an opening x on a side, x, is a parameter having the dimensions of length, and r is a number. This equation has since been derived on a theoretical basis by Gaudin and Meloy.5 They identify x, with the initial size of the test piece and r with the number of flaws per unit length. As will be shown below, our experiments indicate that both x, and r are functions of energy and hence they should more properly be called the effective initial size and the effective number of flaws respectively. Also, our empirical data give us no basis for assuming that r represents the effective number of flaws per unit length, rather than per unit volume. METHOD AND MATERIALS The impact test machine has been designed to feed specimens, essentially one at a time, into an evacuated chamber, where they fall freely and are struck with random orientation by one or the other of a pair of flat steel vanes. The vanes are mounted at opposite ends of a steel bar, which rotates at a closely controlled angular velocity about a vertical axis. Fig. 1 shows the flat circular vacuum chamber with the cover removed, and the horizontal steel bar with the steel vanes at the ends. The cylindrical pot in which the grains are collected after impact appears at the left. Fig. 2 shows the equipment assembled for a test. The vacuum chamber occupies the central position with the variable speed drive below the table surface, the vacuum pump at the extreme left

Jan 1, 1964

By W. A. Backofen, M. L. Ebner

SINCE the early work of Gough with Hanson and Wright,l-3 the study of fatigue has been characterized by experiments on single crystals only in recent times.9-10 Now, increasing attention is given to this aspect of fatigue research for the insight that it may provide into details of mechanism. The investigations have concentrated to a large extent on the development of deformation markings on fatigued crystals, and have shown the cracks to originate in slip bands possibly preceded or accompanied by slip-band extrusions. Experiments of special interest to the present work were conducted by paterson5 on copper crystals and involved both metallographic examination and measurement of change in flow stress. Crystals were cycled in alternating tens ion-compress ion with a constant plastic shear-strain amplitude of approximately 0.8 pct, and were particularly revealing for their demonstration of hardening with accumulated strain similar to that in unidirectional straining, through an easy-glide stage I followed by a stage II of rapid hardening; deformation was not continued beyond 40 cycles, however, so that the eventual course of the hardening curve could not be decided. For the conditions used by Paterson, surface slip markings were similar to those observed in unidirectional straining, but there were no X-ray asterisms and no deformation bands on the surface. In current thinking about the nature of fracture in fatigue, two views relative to mechanism are generally acknowledged, with the reservation that both could apply simultaneously in some measure. As one possibility, fracturing across a slip plane is regarded as a result of loss of cohesion from the creation of many point defects by dislocation movement under the cyclic loading.'' On the other hand, fracture has also been taken to follow as a consequence only of the geometry of slip at a free surface, consisting of offsets and crevices which eventually become fatigue cracks.12, l3 The work of McCammon and Rosenbergl4 showing fatigue in polycrystals at 4.2oK makes clear that any long-range diffusion of point defects is unnecessary, yet studies such as those of Forsyth and stubington15 show that accelerated diffusion may be a characteristic of deformation under fatigue loading. Interest in obtaining data of possible use for resolving such questions led to the experiments described below. Copper crystals were conveniently loaded in alternating four-point bending at constant deflection, a test condition shown to approximate a constant plastic strain amplitude for a wide range of axial orientations. The method of testing was not readily adapted to extensive study of temperature effects, but an investigation of the geometry of crack formation could simply be made by orienting,the slip direction at different angles to the surface. EXPERIMENTAL PROCEDURES Single crystals were grown by a modified Bridgman method in a stationary gradient furnace under an atmosphere of purified dry nitrogen. Purity of as-grown crystals was 99.999 pct as determined by spectrographic analysis plus vacuum fusion and gravimetric analyses for oxygen and sulfur, respectively. Crystals were of reasonable perfection as evidenced by a critical resolved shear stress at 10 deg from (110) of 60 g per sq mm and half-width of a (400) X-ray diffraction line from one crystal of

Jan 1, 1960

By A. W. Bethune, L. M. Pidgeon

The equilibrium vapor pressure of zinc has been determined over the systems: ZnS(s) + Fe(s) = FeS(s) + Zn (vapor) and ZnS(s) + 2Cu(s) = Cu2S(s) + Zn (vapor) by reacting the components in an evacuated tube containing a thin copper fiber, and allowing equilibrium to be established with respect to the brass formed and the zinc in the vapor phase. The composition of the brass formed was determined and equilibrium vapor pressure values obtained from existing data. Between 850' and 1000°C, values for the first reaction ranged from 8 to 58 mm Hg; for the second reaction from 1.8 to 22 mm Hg. THE direct reduction of metallic sulphides may be indicated by an equation of the form MS + X = XS + M [1] where X is some suitable reducing agent. In the case where M is a metal of relatively high volatility, the use of vacuum will displace the equilibrium to the right at comparatively low temperatures in the face of the usually unfavorable thermochemistry. For this technique to be feasible, MS, X, and XS, must of course be nonvolatile compared to M. In this regard, zinc becomes an obvious metal both from the point of view of its volatility and the fact that most commercial ore deposits of this metal occur as the sulphide, and its direct reduction would avoid the expensive roasting process necessary prior to present day reduction methods. Two reducing agents are of interest, namely copper and iron, with the former having the added attraction of being relatively easily regenerated by oxidation in the copper converter. The possibility of these reactions has been considered before. Imbert1 patented a process whereby zinc sulphide was reduced by either copper or iron. The process as described took place at atmospheric pressure and, at the high temperatures required, the system was molten, resulting in the formation of a matte with the consequent reduction in the activities of the reactants. Peterson2 did further experimental work on these reactions and, although promising results were obtained on a small scale, attempts to increase the size of the furnace led to excessive "blue powder" formation. The early workers failed to realize the large reduction in temperature afforded by the use of vacuum and its desirable results. More recently, the direct reduction of zinc sulphide by iron has been the subject of a thermody-namic investigation by Kelley,3 and Gross and War-rington' have studied the kinetics of the reaction in the temperature range 900" to 1000°C, their experiments being conducted using vacuum and indicating that the reaction would proceed practically to completion in 1 to 3 hr, depending on the temperature. A qualitative examination of the system ZnS-Cu carried out at this University indicated that 98 pct of the theoretical zinc in the charge could be recovered in 1 hr at 1000°C when operating under reduced pressure. The purpose of this research program was to study the equilibrium of the two reactions. During the investigation, reference to the experimental work of Schenk5 was found but, due to lack of detail in the report, it was felt that it would be desirable to continue the equilibrium measurements. Selection of Method The measurement of vapor pressure of metals presents obvious problems resulting from the high temperatures which must be employed. In the present case, the production of the "reaction pressure" introduces a further difficulty since a chemical reaction must proceed before any metal vapor pressure is produced, resulting in depletion of the re-

Jan 1, 1954

By F. A. Forward, V. N. Mackiw

The paper relates to the laboratory and pilot plant studies that have been carried out by Sherritt Gordon Mines Ltd., Metallurgical Research Div., in developing the ammonia pressure leach process for extracting copper, nickel, cobalt, and sulphur from high grade nickel concentrate produced from Lynn Lake ores, and describes in some detail the chemistry of the process. IT is well known'.' 2 that copper, nickel, cobalt, zinc, ferrous iron, and a number of other metals combine with ammonia in aqueous solution to form complex ions of the form [Me(NH,)x]"+. The stability and solubility of these ions depend on the concentration of the metal ion in solution, on the amount of NH, present, and on the amount and type of anions present, e.g., OH-, C0;-, NO,, C1-, SO;-. If ammonia is partially or completely removed from such solutions, for example by boiling, the soluble ammines tend to decompose and the metals precipitate as basic salts. These properties of metal ammines have found practical application in the commercial recovery of copper, nickel, and cobalt from a variety of ores. In an operation formerly conducted at Kennecott"" the mill tailing containing 0.80 pct Cu as copper carbonate was leached by percolation with an ammonia-ammonium carbonate solution to dissolve the copper as the ammine. At Calumet and Hecla0-" With a mill tailing containing about 0.4 pct Cu as metallic copper, it has been found necessary to aerate the ammonia-ammonium carbonate leach solutions between stages to oxidize the solubilized copper. At Nicarol"-" where nickel and cobalt occur as oxides and silicates which are not soluble in ammonia, the ore is heated to decompose silicates and to selectively reduce the nickel and cobalt to metal, leaving the iron as Fe,O,, and is then leached with ammonia-ammonium carbonate solution accompanied by aeration to dissolve nickel and cobalt as ammines. In each of these leaching operations, the anion present is CO, and the metals can be precipitated from the leach solution as oxide (copper) or hydroxide and carbonate (nickel and cobalt) by boil- ing off NH, and C02 both of which are recycled to treat a subsequent ore charge. The products-—oxide, hydroxide, or carbonate—can be treated by conventional smelting, calcining, or electrolytic methods to convert them to refined metals. Thus the procedures mentioned utilize the properties of the ammines to extract copper, nickel, and cobalt from nonsulphide ores and separate them from the leach solutions. These processes have the advantage that they can be carried out in closed vessels at atmospheric pressure, that the leaching solutions are specific for the desired metals, that the metals can be recovered as relatively pure compounds by the boiling operation, and that the NH, and CO, can be recycled. Also, as the leach solutions after boiling and filtration are substantially free of metals, NH,, and CO,, they can be discarded, thus facilitating the control of the water balance in the leaching circuit. When, as is the case with Sherritt Gordon concentrates, sulphides are treated with ammonia solution in the presence of oxygen, the leach solution contains SO,--, and an entirely different set of conditions is encountered. The ammine sulphates (of nickel, for example) are more soluble than the carbonates and can be only partially decomposed by boiling. The SO, and NH, in the solutions can not be recovered by boiling. Thus, despite the more favorable leaching conditions resulting from high solubility of the ammine sulphates, the recovery of metals, NH,, and SO, from the solutions must be effected by other means. Sherritt Gordon Nickel Concentrate Treatment The Ni-Cu-Co flotation concentrate produced at Lynn Lake'" contains 12 to 16 pct Ni, 1 to 2 pct Cu, 0.2 to 0.5 pct Co, 33 to 40 pct Fe, 28 to 34 pct S, 8 to 20 pct insoluble, and less than 0.02 oz per ton precious metals. The nickel is present chiefly as pentlandite, the copper as chalcopyrite, and the iron as pyrrhotite and pyrite. Most of the cobalt is thought to be present in pentlandite, although it is known that a small amount occurs as Co-Ni-pyrite.

Jan 1, 1956

By Roscoe E. Bell

BETWEEN 1945 and 1948 the author made studies of the western phosphate industry and its potentialities. These included an appraisal of the opportunities for western development of the industry, studies of production costs, of market potentials, of transportation economics, and of industry location. This paper will be directed toward pointing up the factors which have an important bearing on the establishment of fertilizer plants in the western area. Industry Location Factors: There are, of course, an infinite number of possible organizational setups which might require consideration. However, the phosphate industry is simple enough so that studies of the most probable alternatives can be made conveniently. The salient factors which require special consideration in such a study are: (I) the location of the raw materials, (2) the location, size, and character of the present and potential markets, (3) the location of energy sources and materials required for fertilizer processing, (4) the location and capacity of present manufacturing facilities, (5) the cost of assembling the materials and energy needed in manufacturing, and (6) the cost of distributing the manufactured product. Raw Material Supplies: Rock phosphate is the raw material for the manufacturing of phosphate fertilizer. In the United States the important known deposits of this material are located in three general areas (fig. 1). The western deposits, comprising about 60 pct of the nation's supply, are in the four-state area—Idaho, Wyoming, Utah, and Montana. The Florida deposits comprise roughly 38 pct of the national supply. The Tennessee deposits, comprising about 2 pct of the national supply, have been the most important source until recent years. The western deposits, which are virtually undeveloped, have not been used to any extent to meet the nation's need for phosphate rock and phosphate fertilizer. Fertilizer Markets: The large national markets for fertilizer are in the midwestern and eastern United States (fig. 2). The principal far-western markets are along the Pacific Coast, especially in California. Until recent years the western markets have been extremely limited, whereas the markets in the eastern United States have long been established and manufacturing facilities have been provided to meet these needs (fig. 3). In recent years the western markets have expanded very rapidly, continuing to grow throughout the war years and postwar period at a similar rate. The question always arises as to whether this is a temporary war-swollen market which will shrink back to its original size as soon as the present agricultural price levels drop. In order to answer this question consideration must be given to the character of the market (fig. 4). I have considered seventeen western and midwestern states in the western market area where transportation costs from the western deposits are equal to or lower than those from Florida. They include all states west of a line drawn through Chicago, Kansas City and the western boundary of New Mexico. In the mewar period this was a small market totaling only 37,000 tons of P,O, annually. The 1946 total for this same area was approximately 200,000 tons. Considerably more fertilizer would have been used in 1946 had adequate supplies been available. Estimates of future markets are difficult to make, but we do have some indices that are useful. The

Jan 1, 1951

By Roscoe E. Bell

BETWEEN 1945 and 1948 the author made studies of the western phosphate industry and its potentialities. These included an appraisal of the opportunities for western development of the industry, studies of production costs, of market potentials, of transportation economics, and of industry location. This paper will be directed toward pointing up the factors which have an important bearing on the establishment of fertilizer plants in the western area. Industry Location Factors: There are, of course, an infinite number of possible organizational setups which might require consideration. However, the phosphate industry is simple enough so that studies of the most probable alternatives can be made conveniently. The salient factors which require special consideration in such a study are: (I) the location of the raw materials, (2) the location, size, and character of the present and potential markets, (3) the location of energy sources and materials required for fertilizer processing, (4) the location and capacity of present manufacturing facilities, (5) the cost of assembling the materials and energy needed in manufacturing, and (6) the cost of distributing the manufactured product. Raw Material Supplies: Rock phosphate is the raw material for the manufacturing of phosphate fertilizer. In the United States the important known deposits of this material are located in three general areas (fig. 1). The western deposits, comprising about 60 pct of the nation's supply, are in the four-state area—Idaho, Wyoming, Utah, and Montana. The Florida deposits comprise roughly 38 pct of the national supply. The Tennessee deposits, comprising about 2 pct of the national supply, have been the most important source until recent years. The western deposits, which are virtually undeveloped, have not been used to any extent to meet the nation's need for phosphate rock and phosphate fertilizer. Fertilizer Markets: The large national markets for fertilizer are in the midwestern and eastern United States (fig. 2). The principal far-western markets are along the Pacific Coast, especially in California. Until recent years the western markets have been extremely limited, whereas the markets in the eastern United States have long been established and manufacturing facilities have been provided to meet these needs (fig. 3). In recent years the western markets have expanded very rapidly, continuing to grow throughout the war years and postwar period at a similar rate. The question always arises as to whether this is a temporary war-swollen market which will shrink back to its original size as soon as the present agricultural price levels drop. In order to answer this question consideration must be given to the character of the market (fig. 4). I have considered seventeen western and midwestern states in the western market area where transportation costs from the western deposits are equal to or lower than those from Florida. They include all states west of a line drawn through Chicago, Kansas City and the western boundary of New Mexico. In the mewar period this was a small market totaling only 37,000 tons of P,O, annually. The 1946 total for this same area was approximately 200,000 tons. Considerably more fertilizer would have been used in 1946 had adequate supplies been available. Estimates of future markets are difficult to make, but we do have some indices that are useful. The

Jan 1, 1951

By Lawrence H. Van Vlack, Otto K. Riegger, Gerald I. Madden

The microstructural variations of periclase (MgO) in the presence of oxide liquids are examined under the steelmaking variables of: 1) temperature, 2) liquid composition, and 3) FeO additions under different oxidation levels. Attention is given to the distribution of the phases, both liquid and solid, and to the growth of individual crystalline grains. Silicate liquids penetrate more extensively between individual periclase grains than do liquids containing high percentages of Fe2O3 Higher MgO solubilities in the liquid and lower MgO contents of the solid favor more rapid grain growth. The presence of a second solid phase reduces the periclase grain growth rate and increases the amount of the solid-to-solid contact within the oxide microstructures at high temperatures. The service suitability of a refractory depends on many factors. Two are of major importance and include 1) the thermal resistance to melting, and 2) the mechanical resistance to loads at service temperatures. Neither is a simple consequence of the service temperatures because service conditions will alter compositions, produce partial melting, and induee phase changes. Consequently, the equilibrium phase relationships have been rather thoroughly studied and give a knowledge of the thermal resistance to melting, but do not give full information about the mechanical properties because two refractories with the same types and quantities of phase may have different microstructures. Although variations of microstructures with time, temperature, and composition have been subjects for extensive investigation in metals, only a limited amount of comparable microstructural work has been performed for refractory materials.' This study was an attempt to evaluate some of the consequences of service parameters upon the microstructures of refractories so that bases may be established for the analyzing of high temperature mechanical properties. Periclase (MgO) was chosen as the refractory oxide; variables included those which are encountered under steelmaking conditions such as 1) temperature, 2) liquid composition, and 3) FeO additions under various oxidation levels. Specific attention was given to the distribution of the phases, both liquid and solid, and to the growth of individual crystalline grains. The most closely related work on microstructures of polyphase materials is that of Van Vlack and Rieg-ger2 on the microstructure of magnesiowüstite [(Mg,Fe)O] in the presence of silica. In that work which pertained to solid solutions with less than 40 pct MgO, most of the quantitative work was performed on FeO microstructures. The chief conclusions concerning these relatively low-melting oxide solids were as follows: 1) the rate of crystalline grain growth is inversely proportional to the grain diameter, 2) grain growth proceeds more rapidly at higher temperatures but is slightly retarded by additional liquid content, and 3) a Silicate-containing liquid penetrates as a film between the individual magnesiowüstite grains independent of time, temperature, amount of liquid, or the MgO/ FeO ratio. The above observations are in contrast to prior work3 on the microstructure of silica in the presence of iron oxide-containing liquids where the liquid does not penetrate as a complete film between solid grains. The phase relationships for the compositions of the present work are shown in Fig. 1 which is a summary of the work of several investigators.4 Of importance is the fact that CaO forms a more stable structure with SiO2 and Al2O3 than do either MgO or FeO. The oxygen potential has little effect on periclase unless iron oxide is also present. The iron oxide is ferrous at moderately low oxygen levels, changing to ferric as the Oxygen potential is increased so the spinels, magnetite, and magesioferrite are formed.5 These two phases are relatively stable in air at steelmaking temperatures. I) EXPERIMENTAL PROCEDURE ractory were made with reagent grade Oxides. The magnesium oxide used was 99 pct MgO after ignition, and the iron oxide raw material had a minimum content of 99 pet Fe2O3. The CaO, SiO2, and A12O3 were also reagent grade raw materials. After mixing, the required compositions were pressed into pellets at a minimum pressure of 5000 psi to insure compaction of the raw materials and prevent excess void content. A silicon carbide element tube furnace was used with thermocouple control for sin-

Jan 1, 1963

By A. G. Metcalfe

Observations at temperature are used to investigate the phase changes in alloys containing more than 50 pct Co and above 1000°C. The nonsuppressible transformations in cobalt above 1120°C and in the intermetallic compound Co2Cr3 are studied. The liquidus and solidus surfaces are determined. Insufficient data is obtained to complete the constitution diagram. A REVIEW of some of the earlier work on cobalt' and on the binary systems with chromium2-4 and with molybdenum,5 showed that one likely source of differences might be attributed to the presence of phases at high temperatures which could not be retained by quenching. Consequently, the decision was made that only methods of examination at temperature should be used in this work. The correctness of this decision was confirmed during the course of the work by the investigation of the martensitic nature of the transformation in cobalt- and by the decomposition of the high temperature form of the phase Co2Cr3 on quenching.' The use of high temperature methods, including dilatometry and thermal etching led to the postula-tion of the existence of a high temperature form of cobalt with a probable hexagonal close-packed structure, transforming from cubic cobalt over a range of temperature from 1119° to 1145°C.8 One of the important pieces of evidence for this transformation was that it was observed in alloys with chromium and molybdenum which were nonmagnetic at this temperature so that confusion with magnetostriction effects was impossible. These results were not reported in this earlier paper, so that the data given here supply further evidence for the existence of a second allotropic transformation in cobalt. High temperature observations are necessarily much slower in producing results than the examination of quenched specimens at room temperature by conventional means such as X-ray diffraction or microexamination. The investigation has only covered a limited part of the field, as a result, extending from the liquidus down to about 1050°C and from the cobalt corner up to 50 pct alloying elements. The differences between the various reported diagrams for the constitution of the Co-Mo and Co-Cr systems have already been mentioned. The best available diagram in the first system is due to Sykes and Graff' which is shown in Fig. 1. Fig. 2 shows the latest Co-Cr diagram due to Elsea, Westerman, and Manning.' A comparison reveals that these are incompatible because of the disagreement with regard to the number of allotropes of cobalt. Elsea, Westerman and Manning took their liquidus and solidus curves from Wever and Haschimoto.2 The temperature horizontal in the two-phase field beneath the eutectic was placed 35" to 39°C higher than in earlier work2,4 with a new interpretation of the nature of this transformation. This interpretation also required a peritectic horizontal at about 1470°C, which has been confirmed here for an alloy with 53 pct Cr. No investigation had been made of the ternary system until after this work had been terminated, when a section at 1200°C was published." In this work a ternary compound was found by the X-ray diffraction examination of quenched alloys. This compound contained less than 50 pct Co, and was thus outside the field investigated here. However, some reactions were found dilatometrically which could not be fitted on the diagram and are now believed

Jan 1, 1954

By D. R. Wieland, A. N. Barron, A. R. Hendrickson

A definite relationship has been found between the reactivity of flowing hydrochloric acid and its shear rate in a carbonate fracture. Both flow velocity and fracture width affect the acid reaction rate. Laboratory studies were conducted on acid reactivity at different flow velocities through horizontal-linear fractures, using 15 per cent hydrochloric acid at 80' F and approximately 1,100 psi. Fracture width varied from 0.02 to 0.20 in. These data provide a new basis from which the spending time and penetration of the acid can be estimated. Equations were derived expressing the relationship between injection rate, fracture width, acid concentration, time and fracture height, for linear and radial fracture systems. Because the penetration of the acid before spending is closely related to the extent of productivity increase resulting from an acidizing treatment, these data provide a valuable insight into some of the controlling factors that must be taken into consideration during treatment preplanning. INTRODUCTION Acidizing of carbonate reservoirs to improve production characteristics has been widely practiced since 1932. Originally, it was assumed that the acid uniformly penetrated natural formation pores and flow channels, enlarging them and thereby increasing their flow capacity. Little consideration was given to the reaction rate of the acid, or how far it would penetrate away from the wellbore into the formation, before spending. It has been shown recently' that, unless fractures are present in the rock, very little penetration is attained before spending, and the benefits of the acidizing treatment are largely confined to the immediate vicinity of the well-bore. Therefore, acid treatments may be classified into two categories: (1) matrix acidizing, in which the acid flows through multiple: formation pores; and (2) fracture acidizing, in which the bulk of the acid travels through fractures in the rock, whether natural or induced. When acidizing treatments are conducted at pressures of sufficient magnitude to open and extend such fractures, it is often desirable to inject a propping agent to hold the fracture open after the treating pressure has been released, thus providing a highly conductive flow channel through the rock. In some cases where acid attack produces surface irregularities, the resulting flow passages can be sufficient to provide high conductivity without use of a propping agent. During injection, the acid dissolves the carbonate rock with which it comes in contact until it is spent. Deeper penetration of the spent acid into the formation produces no appreciable benefit (if no propping agent is used) because the unetched fracture faces will rejoin when treating pressures are released and the fracture will "heal", with negligible resultant conductivity. The spending time of the acid thus becomes important in determining how far from the wellbore the improved-conductivity zone extends. The spending time of acid after injection into carbonate rock depends on the rate at which the acid reacts with the rock. This in turn is controlled by a number of factors, as previously reported. 2-4 These include temperature, pressure, acid concentration, rock composition, injection rate and the area-volume relationship between the acid solution volume and the surface area of the formation flow channels through which it penetrates. Thus, in matrix acidizing, where an extremely large area is exposed to the acid, spending is rapid. In contrast, spending time is prolonged in open fractures, where the area-volume ratio is much lower. Thus, greatest penetration of the acid before spending will be achieved in acid-fracturing treatments where fractures are held open by hydraulic pressure. Perkins and Kern5 have presented equations for fracture-width determinations which, for hard formations such as limestone or dolomite, indicate that high injection rates and viscous fluids are required to create wide fractures. Increasing the injection rate will, in itself, produce faster reaction rates. Because this type of reaction can be considered to be first-order diffusion-controlled, '-' the rate of movement of fluid past the rock surface affects the thickness of the diffusion layer, in turn affecting the reaction rate. Staudt, et al,10 report the results of tests in which a rotating marble cylinder was immersed in acid, and the weight loss at different speeds determined. Such test conditions, however, are not truly indicative of the situation in a formation during an acid-fracturing treatment. This paper reports reaction-rate data obtained under

By N. E. Garner

Laboratory experiments were conducted to investigate the cutting of a single diamond on limestone and shale under simulated down-hole conditions. A high-pressure chamber was modified by adding a rock-rotating device so that planing tests could be run. Weight on the diamond, diamond geometry and differential pressure across the face of the rock were varied. It was found that (I) high differential pressure reduced the volume of rock cut by the diamond at a given bit weight by strengthening the rock and changing the mode of failure; (2) a finely powdered rock left in the bottom of the grooves reduced the volume cut by as much as 50 percent; and (3) orientation of a single diamond about the axis of a drill point had considerable influence on diamond cutting efficiency. INTRODUCTION Diamond bits consist of many diamonds held in a matrix provided with water courses for fluid passage to clean, cool and lubricate the diamonds as they drill formation. Each diamond contributes its share to the overall effectiveness of a bit, but a lack of understanding of the performance of a single diamond has hampered efforts to engineer improvements in diamond bits. The need for those improvements prompted this study. This paper describes the findings of a laboratory investigation of the outting action of a single diamond where the differential pressure between the wdlbore and formation, diamond geometry and vertical force on the diamond were independently varied. The tests were conducted in a pressure chamber that provided relative horizontal motion (planing) between a rock and diamond under simulated down-hole pressure conditions. EQUIPMENT HIGH-PRESSURE CHAMBER WITH ROTATING DEVICE The high-pressure chamber used in previous rock mechanics studies' was modified for this study by addition of a rock-rotating device. The modified chamber (Fig. 1) differs from the old chamber in that the rock can be rotated to provide relative horizontal movement between the rock and the penetrator which may be a small element of a diamond or a drag bit. In this study the penetrator was a single diamond. The rock sample holder inside the chamber is mounted on a thrust bearing and is connected to the external drive mechanism by a stem that passes through two seal elements. The seal elements are needed to allow formation pressure to enter the bottom of the rock sample through a small hole in the stem. The Kapseal seal elements (Tefion boots backed by O-rings) provide low friction (hand free) even at differentials of 5,000 psi. The drive mechanism is a variable-speed transmission with a speed range from 0 to 30 rpm and an output torque of 2,800 in.-lb. A right-angle-drive gear box couples the drive to the stem. The new design has two independent pressure systems (formation and borehole) to simulate down-hole rock stress environment. Formation pressure enters from the bottom of the rock through a 6-in. diameter area, and borehole pressure acts over the remaining surface. A 14-in. layer of zero fluid loss oil-base mud poured over the top of the rock and an O-ring seal on bottom allow a differential between the borehole and formation pressures. Bayol 50 was used as the hydraulic fluid in the chamber. The differentials reported here were obtained by elevating the borehole pressure while keeping the formation pressure at zero.

By R. E. Carter, C. Wagner, F. D. Richardson

By means of inert markers of radio-platinum, it has been shown that cobalt metal oxidizes by out-ward diffusion of cobalt atoms through the oxide. Oxidation rates have been measured at various temperatures and oxygen pressures and have been found to agree with the rates calculated from the Wagner equation and the authors' values for the diffusion coefficient of cobalt in the oxide. The distribution of radio-cobalt in growing oxide loyers has been accurately measured and found to be different from that predicted from the Wagner oxidation theory. Attempts have been made to measure the change of lattice parameter of the oxide with composition. SEVERAL investigators have shown that cobalt metal oxidizes according to the parabolic law,1-3 but no detailed study has been made of the oxidation mechanism. Cobaltous oxide has a metal-deficient lattice, but the defect concentration which is dependent on the oxygen pressure is only approximately known.' From the similarities in the structures of "CoO" and "FeO" and the rate laws governing the oxidation of cobalt and iron, Gulbransen- as suggested that cobalt, like iron," oxidizes by diffusion of cobaltous ions through the oxide layer. To substantiate this hypothesis, he has attempted to measure the oxidation rate of cobalt as a function of the oxygen pressure but has been able to report only that the rate depends on a "small" power of the pressure. On the other hand, Preece," Valensi,' and Arkharov' all have suggested from indirect evidence that oxygen diffuses through the COO to the metal-oxide interface. The present authors, in a previous paper,' have shown that the rate of diffusion of cobalt in cobaltous oxide is dependent on the oxygen pressure. In that investigation, they also found that cobaltous oxide disks made by complete oxidation of cobalt metal were porous at their centers (Fig. 5L, ref. 4). Both these facts strongly suggest that oxidation of the metal proceeds via outward diffusion of cations. In order to establish the mechanism unequivocally, oxidation experiments were made with inert radioactive platinum markers, and the dependence of oxidation rate on oxygen pressure was measured. In addition, an attempt was made to determine the form of the cation vacancy gradient, which the marker experiment showed must exist across a growing oxide layer. This was done by depositing radioactive Co on the surface of a cobalt disk and then measuring the tracer distribution across the oxide layer produced by partial oxidation of the metal. Finally, an X-ray examination was made in an attempt to find the expected change of lattice parameter of COO with oxygen pressure. Experimental The apparatus and materials used were substantially the same as those previously described by the authors.4 Marker Studies: The use of inert markers to follow oxidation reactions was first attempted by Pfeil" in 1929, and radioactive markers have recently been used by Davies et al.' In the investigation reported here, the markers were applied as an (NH4)2PtCI6 slurry in several thin streaks across both faces of four disks of cobalt metal 1 mm thick and 14 mm in diameter. The disks were then oxidized almost to completion at 1200°C in pure oxygen. After oxidation, they were mounted and sectioned and auto-radiographs were taken to locate the markers. Oxidation Rate: The oxidation rate of cobalt was measured at 1148°C at oxygen pressures ranging from 0.0055 to 1.0 atm and at 1000°, 1148", and 1350°C under 1 atm of oxygen. The rate was deter-

Jan 1, 1956

By C. R. Claus, G. A. Standish

Since March. 1945, the Magnolia Petroleum CO. has drilled 39 wells in Southwest Coastal Louisiana. All wells were drilled within a comparatively small radius, but the area provides a large variety of problems. The deepest well drilled was 13,518 ft, and the total depth averaged 10,977 ft. Throughout this period drilling mud control and types of mud handled were: (I) phosphate, (2) red lime (late conversion), (3) red lime starch (early conversion), (4) red lime starch oil emulsion, (5) precision controlled low alkalinity-low lime content. and (6) gel muds for completion purposes. Improvement has been obtained in effecting some or all of the following: (I) more rapid penetration, (2) reduction in drilling hazards, (3) better evaluation of cores and logs, and (4) better completions. The geological sequence of zones penetrated range from recent sediments at the grass roots through the Frio section. Anticipation of high-pressure zones and incompetent formations entails precision control of drilling mud weights, and the unconsolidated nature of the various zones requires constant attention to the filtrate, viscosity, and gel strength values. In the Chalkley field, particularly, this combination of problems exists, where the formation pressures and overburden weight density values are in very close proximity. Design of casing and drilling mud programs must be modified to fit each well. INTRODUCTION Field and research work on drilling fluids has made constant progress, enabling operators to prospect progressively deeper horizons. Numerous papers have been written on the theoretical aspects of drilling fluid devel- opment, but in the field engineers have found it difficult to evaluate the role of specific mud constitutents when dealing in terms of thousand barrel mud systems. For that reason field data is somewhat lagging in technical report writing. However, applications of new techniques in the field have usually paralleled, and in numerous instances preceded, research work. The information obtained by Magnolia Petroleum Co. in the course of drilling 39 wells within a comparatively small area in Southwest Coastal Louisiana provides an excellent opportunity of reviewing a specific example of drilling mud evolution. A large variety of problems has been coped with, the most important result being that every well was successfully drilled to its projected total depth. The discussion begins with the advent of deep drilling in this area in March, 1945, and is concluded with a resume of recent drilling operations in the Chalkley field. The primary purpose of this paper is to describe the evolution in types of drilling fluids as it occurred and its application in the solution of various drilling problems. All of this information and experience resulted in the successful drilling of the three wells in the Chalkley field, where a combination of the most sound techniques was necessary in carrying drilling operations to the projected total depths. Other operators along with service company engineers have contributed considerably through the interchange of ideas and information to this paper, but the data and conclusions which are contained are based on first-hand observation of Magnolia Petroleum Company's drilling operations. The 39 wells drilled by Magnolia Petroleum Co. average in depth 10,977 ft per well, while the maximum depth penetrated was 13,518 ft. The cost of drilling fluids have varied from $8,700 to $165,000, with the over-all drilling costs ranging from $74,000 to $543,000 per well. This wide variance illustrates the unpredictable nature of each well and the effects on over-all cost when high density muds are required to control

Jan 1, 1955

By Charles H. Grant

Some of the limiting factors relative to explosive crushing of rock and ways to overcome a few of these problems are presented. Relationships between borehole diameters, bench heights, and spacings, along with a review of the influence geometry has on energy as these are changed, are discussed. Efficiency in use of explosives and the decay of energy as it moves through rock and is absorbed and dissipated, is described, along with fragmentation as a function of spacings and energy zoning, etc. Communications are one of the major problems encountered. In an effort to provide a better understanding of the use of explosives, it is necessary to take a little different view of what explosives are, how to look at them as tools to fragment rock, and some of the problems encountered in doing so. First, take the explosive: although there are many factors involved, consider these as being reduced to only two — shock-strain imparted to the rock by the high early development of energy, and the gas effect which is a combination of heat, moles of gas formed, rate of formation of these gases which develop pressures, etc. First, consider shock energy by itself and assume there is no gas effect in the reaction. Fig. 1 illustrates a block or cube of rock, in the center of which is detonated an explosive charge which is 100% shock energy. Tensile slabbing would be seen on the surface and probably the cube of rock would generally hang together even though microcracks were formed. If the situation is reversed and an explosive whch has no shock energy and only gas effect (Fig. 2) is considered, the cube of rock would act as a pressure vessel and contain the pressure from the gas effect until it exceeded the rock-vessel strength; then the rock would break in a few large pieces. If these two kinds of energy are put together and the area of shock-strain around the explosive (Fig. 3) is considered, the two energies will be seen working together to furnish broken rock. The gas effect applies pressure to the microcracks formed from the shock energy to weaken the rock-pressure vessel and propagate these cracks to break the rock apart. It not only will be broken more finely, but will break apart at a lower pressure than the gaseffect case, since the shock energy has first weakened the rock vessel. Although tensile spalling from the shock-strain imparts momentum to the rock, the main source of displacement comes from the gas effect. The term "rock" is being used to mean any material to be blasted. These energies are absorbed by the rock in different ways. First, classify rock into two main categories: "elastic" and "plastic-acting." Elastic rock should be thought of as rock which can transmit a shock wave and is high in compressive strength, such as granite or quartzite. Since this elastic rock transmits a shock wave well, it makes good use of the shock energy from the explosive-forming cracks, etc., for the gas effect to work on. Plastic-acting rocks are rock masses which are relatively low in compressive strength and absorb shock energy at a much faster rate, thereby making poor use of the shock energy by not developing as extensive a cracked zone for the gas effect to work on. Rocks of this type are generally softer materials such as some limestones, sandstones, and porphyries. For the most part, the shockenergy part of the explosive reaction is wasted in plastic-acting rock, leaving most of the work to the gas effect. Since the ratio of gas effect to shock energy is different in different explosives, it is easy to understand why some explosives perform well in elastic rock and poorly in plastic-acting rock, and vice versa. Some of the most difficult blasting situations arise when mixtures of plastic-acting and elastic rock are encountered (Fig. 4). Fig. 4 shows an example of granite boulders cemented together with something like a decomposed quartz monzonite which is plastic-acting. The elastic granite boulders will transmit the shock-strain within itself, but when this shock tries to move through the monzonite to the next boulder, its intensity is absorbed by the monzonite and little shock-strain is placed on the adjoining boulder. In addition to this loss by absorbtion, shock reflection at the surface of the boulder will effect tensile spalling. The net effect is poor breakage of the boulders which do not have drillholes in them as they simply will be popped out with the muck. The same is true (Fig. 5) when layers and joints make

Jan 1, 1970

By S. S. Shen, M. J. Pool, P. J. Spencer, J. R. Guadagno

VERY few thermodynamic data are available for rare-earth alloys, partly because of the difficulties of obtaining the metals in sufficiently pure form and also because of their comparative scarcity up to the present time. The rare earths form a very interesting series in the periodic table in view of the progressive filling of their 4f subvalence electron shell and would be expected to provide useful information with regard to alloying characteristics of transition elements. It has been found in recent calorimetric investigations that the heats of solution of a number of the rare-earth metals in liquid tin are highly exothermic.1-4 Exceptionally strong bonding between rare-earth and tin atoms is clearly indicated in the liquid solutions. Continued thermodynamic studies of the behavior of rare earths in solution could thus contribute a great deal to present theoretical knowledge of alloying behavior and would yield an insight into bonding of a strength hitherto unencountered in liquid alloys. The determination of the heats of solution of the pure components in liquid tin is an essential preliminary to calorimetric work of this nature. Heats of solution of praseodymium, neodymium, and samarium in liquid tin at 750" ' and the heats of mixing of Pr-Nd solid solutions' have already been determined in this laboratory. The present investigations with lanthanum continue the study of rare-earth elements. Details of the construction and operation of the liquid metal solution calorimeter used in this work have been published previously by Pool and Peluso and no further description will be given here. The lanthanum used in heat of solution determinations was supplied by Lunex who quoted the purity as 99.9 pct. Their detailed analysis of the material is given in Table I. Samples of 0.0003 to 0.0005 g-atom were used for each run and great care was taken to remove all surface oxide prior to weighing. The samples were stored at all other times in a beaker of oil to prevent their otherwise rapid oxidation. The compounds LaSn (Cudu, L1P type structure) and La&, (structure not classified) were prepared from the appropriate quantities of the two pure components by arc melting under a purified argon atmosphere and once again great precautions were taken to avoid any subsequent oxidation of the specimens. Although no structural examination of the compounds was made, the consistency of thermodynarnic measurements carried out on twenty or so individual samples of each indicates that the compounds were in fact homogeneous, single phase alloys. Samples of the compounds consisting of 0.0003 to 0.002 moles were used in the calorimetric measurements. A solvent bath consisting of approximately 80 g of 99.9 pct pure Sn was used for each series of runs and its heat capacity was determined at regular intervals throughout the experiments using pure tin or tungsten calibration samples. Measurements were made of the heat of solution of lanthanum in liquid tin at 725", 750C, and 775°K and at compositions up to 2.21, 4.76, and 5.25 at. pct La at the three temperatures respectively. In every case, the heat of solution of lanthanum remained constant at its limiting value, within experimental limits, up to the highest lanthanum concentration investigated. Since no change in was observed, it was concluded that the liquid/liquid + LaSn, phase boundary had not been

Jan 1, 1969

By C. A. Hartnagel

The production of petroleum in New York in 1940, totaling 4,999,000 bbl., was only slightly under the amount produced in each of the previous three years. The year 1940 started auspiciously with a posted price on Jan. I of $2.75 a barrel. Four price reductions, beginning in May, resulted in August in a low of $1.85 a barrel, after which two increases brought the year's closing price to $2.15 a barrel. The favorable crude price at the beginning of the year stimulated an increased drilling program, especially in the water-flooding districts. In the Allegany County region, which accounts for about two-thirds of the state's oil production, 886 wells, including water-intake wells, were drilled; 200 more than in the preceding Year. During the closing months of the Year there was a marked decline in the number of wells drilled. The unfavorable position in which the industry found itself before midsummer was due largely to the loss of export markets for its high-grade lubricants, constituting approximately 25 per cent of its business. As a result of this situation, runs to refineries were curtailed as much as 30 Per cent at the middle of the Year. Improvement in market conditions toward the end of the Year found the stocks of available crude at an almost record low. Deep DRILLING with the gradual exhaustion of some of the important natural and flood-oil-produc-ing areas of the Allegany and Bradford pools, overproduction will not be a serious problem in the future. The possibility of finding new territory or deeper producing sands has been further lessened by the drilling of additional deep wells for gas in and about the present oil fields. Many of these wells drilled to the Oriskany sand-stone were over 4000 ft. deep and have tested the entire thickness of the Devonian formation, the upper 2000 ft. of which contain all the important oil-producing strata in the state. Water-flooding It is thus evident that the problem of the New york oil producers is not one of find-ing new supplies but of obtaining as much 6 oil as possible from the old developed fields that during the 60 years of their life have 1 produced I 3o,ooo,ooo bbl. of oil. Although a few floods were in operation before I9I9, when the production of oil by flooding was 1 made legal, the output for that year amounted to only 85I,000 bbl. From 1919 I on there has been an almost constant increase, which during the past four years has averaged well above 5,000,000 bbl. annually. During the last 22 years, which constitutes the period of important flooding operations, 651337,000 bbl. of oil have been produced in the state. Careful estimates indicate that between one-third and one-half of the oil fields are being flooded or are already watered out. Some of the flooded and watered-out areas include territory with unusually thick sands, which were highly productive during the early history of the fields. From a recent study of operations in the New York oil fields, it is estimated that about 65,ooo,oo bbl. of oil

Jan 1, 1941

By R. E. Robbins, H. R. Brager

THIS note describes an unusual result obtained in an electron microscope investigation of cavities produced in commercial type 304 stainless steel irradiated in a thermal reactor (ETR) at 290°C to a high neutron flu-ence, 6 x loz1 n per sq cm. The analysis of the steel used is given in Table I. The unusual result is that the calculated quantity of helium gas produced by transmutation during the irradiation, 12 ppm, is less than one-tenth the amount of gas necessary to balance the surface tension of the observed cavities produced in the steel during ETR irradiation. Therefore, the cavities would be expected to behave like voids; however, they behave like "gas filled" bubbles. The maximum quantity of helium produced in the steel by B" transmutation was 8 ppm. In addition, the amount of helium formed by (n, (1) fast neutron reactions with the major alloy constituents and nitrogen was calculated to be 4 ppm based on the tabulated differential or effective fission-averaged cross sections of elements in type 304 stainless steel irradiated in typical thermal reactors.', In previous investigations concerning commercial austenitic stainless steel irradiated in a thermal reactor, the amount of helium gas calculated to be produced by transmutation has always been significantly greater than the amount calculated on the basis that the bubbles were gas filled, PPs= 2y/R. The balance of the gas was assumed to be in bubbles smaller than could be detected on the electron micrographs. Accordingly, the bubbles were attributed to helium produced from transmutation of impurity boron by thermal neutrons. These bubbles were not uniformly dispersed in the matrix but were located principally at grain boundaries, or were radially positioned around a few precipitates located in the matrix and at the grain bundaries., 4 Voids have also been observed in austenitic stainless steel irradiated at high temperature to high neutron fluences in the EBR-I1 and Dounreay Fast Reactors. The voids were uniformly distributed throughout the matrix. The amounts of helium gas produced by transmutation during these irradiations were less than one-tenth the amounts needed to balance the surface tension of the voids formed by the fast reactor irradiation. The fast reactor results are quite analogous to those reported here for the ETR irradiated steel. Electron microscope examination of the fast reactor irradiated material after a 1 hr postirradiation annealing at 900°C disclosed that essentially all the voids had been eliminated. The authors stated that the voids had developed due to the high concentration of vacancies produced during irradiatin., 6, ' The microstructure of the ETR irradiated material as-tested at 75O°C, Fig. 1, contained about 2 X lot5 cavities per cm3 with an average diameter of 110A. With the Van der Waals b correction and y = 1500 ergs per cm2, 300 ppm He would balance the surface tension of the observed cavities. Stereoscopic examination of the electron micrographs showed that the cavities were neither preferentially located near the grain boundaries nor highly concentrated at specific regions or precipitates. The cavities were nearly uniformly distributed throughout the matrix, on dislocations and at grain boundaries. These observations imply that the cavities were not the sole results of B'O

Jan 1, 1969

By C. A. Hartnagel

The production of petroleum in New York in 1940, totaling 4,999,000 bbl., was only slightly under the amount produced in each of the previous three years. The year 1940 started auspiciously with a posted price on Jan. I of $2.75 a barrel. Four price reductions, beginning in May, resulted in August in a low of $1.85 a barrel, after which two increases brought the year's closing price to $2.15 a barrel. The favorable crude price at the beginning of the year stimulated an increased drilling program, especially in the water-flooding districts. In the Allegany County region, which accounts for about two-thirds of the state's oil production, 886 wells, including water-intake wells, were drilled; 200 more than in the preceding Year. During the closing months of the Year there was a marked decline in the number of wells drilled. The unfavorable position in which the industry found itself before midsummer was due largely to the loss of export markets for its high-grade lubricants, constituting approximately 25 per cent of its business. As a result of this situation, runs to refineries were curtailed as much as 30 Per cent at the middle of the Year. Improvement in market conditions toward the end of the Year found the stocks of available crude at an almost record low. Deep DRILLING with the gradual exhaustion of some of the important natural and flood-oil-produc-ing areas of the Allegany and Bradford pools, overproduction will not be a serious problem in the future. The possibility of finding new territory or deeper producing sands has been further lessened by the drilling of additional deep wells for gas in and about the present oil fields. Many of these wells drilled to the Oriskany sand-stone were over 4000 ft. deep and have tested the entire thickness of the Devonian formation, the upper 2000 ft. of which contain all the important oil-producing strata in the state. Water-flooding It is thus evident that the problem of the New york oil producers is not one of find-ing new supplies but of obtaining as much 6 oil as possible from the old developed fields that during the 60 years of their life have 1 produced I 3o,ooo,ooo bbl. of oil. Although a few floods were in operation before I9I9, when the production of oil by flooding was 1 made legal, the output for that year amounted to only 85I,000 bbl. From 1919 I on there has been an almost constant increase, which during the past four years has averaged well above 5,000,000 bbl. annually. During the last 22 years, which constitutes the period of important flooding operations, 651337,000 bbl. of oil have been produced in the state. Careful estimates indicate that between one-third and one-half of the oil fields are being flooded or are already watered out. Some of the flooded and watered-out areas include territory with unusually thick sands, which were highly productive during the early history of the fields. From a recent study of operations in the New York oil fields, it is estimated that about 65,ooo,oo bbl. of oil

Jan 1, 1941

By B. Ramaswami, Y. Nakada, R. Schaefer

EARLY investigations1 of the tensile properties of fcc single crystals did not reveal the easy glide region of crystals with axial orientations inside the standard stereographic triangle. With the production of high-purity metal, a region of easy glide became known1 Consequently, modern work of fcc single crystals ordinarily uses high-purity metal. In order to determine whether further purification of aluminum beyond 99.992 pct purity would result in significant alteration of the tensile properties of single-crystal specimens, metal was zone-refined and crystals grown from the purified material were compared to crystals grown from the original material. Some similar studies were made of gold and silver crystals. Aluminum. The material to be zone-refined was cast into bars 1/4 by 1/2 by 8 in. A zone, approximately 1-1/2 in. in length, was passed over each bar eighteen times at a rate of 6 in. per hr. Melting and stirring were carried out by an induction heater under a vacuum of approximately 10"5 mm Hg, the metal being held in a graphite container. he last 3 in. of each processed bar were then cut off and discarded. No quantitative determination of purity was made, but the effectiveness of the zone refining was tested by a method first suggested by Walton, Tiller, Rutter, and winegard3 depending on the relation between cell structure and impurity content. Rutter and Chalmers4 have shown that a cellular substructure is associated with the presence of impurities during solidificatibn, and have shown how solute rejection at the freezing interface can lead to such an association. Thus the observation of cells gives evidence of impurities being present. To look for cells, the last quarter of a zone-refined bar was cut off, remelted, and grown rapidly into a single crystal. It was then heavily electropolished and thermally etched.~ Cells were revealed by the presence of many parallel rows of etch pits. The same process was carried out with material from the first half of the bar, but no cells were detected. These observations give evidence that a significant amount of impurity material was moved to the "dirty" end of the zone-refined bars. Further indication of purification was obtained from recrystallization experiments. It was found that, after cold rolling to a 97 pct reduction in thickness, the material from the pure end of the bar re-crystallized at room temperature, but the material from the "dirty" end did not. Other investigators6 have previously reported that zone-refined aluminum recrystallized at room temperature. The purified material was cast into 1/4 by 1/4 in. bars, and seeded crystals were grown in a (100) orientation and in a single slip orientation where the Schmid factor is m =2. The crystals were then cut to the desired length, annealed for 24 hr at 610°C, furnace-cooled, and etched in Tucker's etch. The crystals were tested in a floor-model Instron machine, using a gage length of 4 in. and a strain rate of 1/2 pct per min. The resulting curves are shown in Fig. 1. It is seen that the differences between the curves for zone-refined and original-purity materials are small. These differences are within the scatter observed for crystals of the original purity. In particular, the zone refining does not significantly affect the onset of the different "stages" of the curves.

Jan 1, 1964

By W. W. Krysko

In order to calculate the critical particle size of lead oxide entrapped in lead, Stoke's Formula may be applied. All data were available except figures for the density of lead oxide at elevated temperatwes. The density of lead oxide was determined by means of dilatometmetrc and volumetric methods up to 1010°C. Graphs of the density of lead and lead oxide as well as the viscosity of lead are given and discussed, with the conclusion that the most unfavorable region for the separation of lead oxide from molten lead lies just above the melting point of lead. DURING previous investigations, particularly on the dedrossing of lead with aluminum1 and the oxygen solubility in lead,' the critical particle size of lead oxide which could be entrapped in solidifying lead was estimated by calculation, and it was shown that high values found for the oxygen content of lead may be due to the method of sampling and the entrapped particles of dross. Unfortunately, due to lack of data, an exact mathematical solution was not possible. The particle size which will separate under a given condition can be estimated from Stoke's Law, which states that where: d = diameter of the critical particle size ¦q = viscosity of lead in Poise V = constant velocity in cm sec-I g = 981 cm sec-2 61= specific gravity of lead 62= specific gravity of lead oxide The depth of the lead bath and the time before solidifying define the velocity. The viscosity of molten lead is known from earlier work by Krysko and is given in Table I. The specific gravity of lead is also known, see Table II. These values are according to Hofmann. A careful survey of literature revealed no values for the density of lead oxide at elevated temperatures. The present investigation was therefore conducted to provide this information. RESEARCH INVESTIGATIONS The density of lead oxide was determined from the following experiments: 1) Determination of the density of lead oxide at room temperature. 2) Dilatometric investigations on the same samples. 3) Determination of the shrinkage at the liquid-solid trans£ormation. 4) Density determinations on liquid lead oxide. 5) Time temperature curves during cooling. 1) The samples for the determination of the density of lead oxide in the solid state were prepared in the following manner. Molten lead oxide was cast into I hot mold which could be opened along the longitudinal (vertical) axis. The cast samples were cylinders of approximately 10 mm diam and approximately 80 mm length. The cylindrical hot mold was open at both ends and was placed on a large copper chill plate shortly before casting. The solidification of the lead oxides proceeded upwards without any formation of internal cavities. The sample was carefully checked with respect to density and crystalline appearance, and only the lower portions which were crystalline and free from porosity were used. The density was determined in a specially made pyknometer-like container, where the surplus liquid was squeezed out through an orifice approximately 1/10 mm in diameter. Mercury or water was used as the liquid. The densities of the samples were calculated from the weight, volume, and mean specific gravity of eight samples was 9.62 * 0.05 g cm"3 at 22"~. 2) The samples were machined to approximately 1 1/2 in. in length and fitted into a dilatometer. A

Jan 1, 1962